CN109234527A - A kind of super (Asia) critical activation method and its application of gangue - Google Patents

A kind of super (Asia) critical activation method and its application of gangue Download PDF

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CN109234527A
CN109234527A CN201710855922.4A CN201710855922A CN109234527A CN 109234527 A CN109234527 A CN 109234527A CN 201710855922 A CN201710855922 A CN 201710855922A CN 109234527 A CN109234527 A CN 109234527A
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solution
gangue
solid
gallium
obtains
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CN109234527B (en
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韩丽娜
任卫国
何星星
胡江亮
常丽萍
鲍卫仁
王建成
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Taiyuan University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/24—Cements from oil shales, residues or waste other than slag
    • 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
    • C22B21/00—Obtaining aluminium
    • C22B21/0015—Obtaining aluminium by wet processes
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
    • 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
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • 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
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • Y02P40/18—Carbon capture and storage [CCS]

Abstract

The present invention relates to a kind of subcritical or overcritical activation methods of gangue, wherein by adding additive alkali into gangue and carrying out priming reaction, available active coal gangue sample under subcritical or condition of supercritical water；The invention further relates to a kind of method of comprehensive utilization of gangue, the active coal gangue sample that will be obtained through subcritical or overcritical activation and sour haptoreaction, it is not only obtained by acidleach to alumina product and white carbon black product, but also lithium, the gallium being enriched in gangue can be extracted, last filtering residue, which is used as, prepares the raw material of cement, be truly realized a kind of no pollution, zero-emission gangue waste utilization approach.The advantage of the invention is that the activation of gangue can be can be achieved under 400 DEG C or so of cryogenic conditions, and operating procedure is few, and reaction temperature is low, and the reaction time is short, and it is whole without secondary pollution, it is a kind of approach of environmentally friendly new activating coal gangue method and gangue waste utilization.

Description

A kind of super (Asia) critical activation method and its application of gangue
Technical field
The present invention relates to the activation method of gangue and its method of comprehensive utilization, and in particular to a kind of overcritical activation bastard coal The method of stone, and it is related to a kind of comprehensive Utilization Ways of gangue.
Background technique
Gangue is one kind kaolin containing coal with coal association, gangue comprehensive discharge amount account for raw coal output 10%~ 15%.Gangue " industrial waste " various as the solid, liquid, gas three disasters, its long-term stacking, which accounts for, has pressed a large amount of soil, and It polluted the water source on mining area periphery, the air of soil and surrounding, the serious ecological environment and ecoscape for destroying mining area.
Generally using sial as main component in gangue, in addition contain Fe in varying numbers2O3、CaO、MgO、K2O、Na2O、 P2O3Equal inorganic matters.In addition, the comparision contents of lithium in the gangue of Shanxi Province Pingshou coal mine, gallium are high, the especially content of gallium.Through It detects, the content of gallium is up to 38 μ g/g in raw material involved in the present invention, the production-grade (30 μ g/g) beyond gallium in coal.From While extracting sial in gangue, lithium gallium, significant are recycled.The major way of gangue high value added utilization is benefit at present Valuable element extraction is carried out with its inorganic component.But since gangue contains kaolinite, structure crystal phase is stablized, is needed gangue Raw material is just available after being activated.
The activation of gangue mainly has mechanical activation and thermal activation.Compared with mechanical activation, thermal activation is easy to operate, activation Effect is good and becomes a kind of common method.Zhao Zhen newly waits the " microwave delivered in " coal engineering " (the 7th phase of volume 47 in 2014) Method extracts the experimental study of aluminium oxide in gangue " (document 1), the gangues of 80 mesh will be crushed in microwave power 500W, 700 90min is calcined at DEG C, 40min is then leached at 65 DEG C with the hydrochloric acid that concentration is 20%, the leaching rate of aluminium oxide reaches 86%.Ji Lichun etc. " nonmetallic ore " (the 3rd phase of volume 37 in 2014) deliver " acid and alkali combination method is from low-temperature activation gangue Extract ferro-silico aluminium " (document 2), by gangue and Na2CO3Ingredient is carried out for 0.9 in mass ratio, 60min is calcined at 750 DEG C, so Afterwards clinker after cooling is reacted into 85min with the hydrochloric acid of 5mol/L at 90 DEG C in water bath with thermostatic control, the dissolution rate of aluminium reaches 82.7%.Filter residue is dissolved in the NaOH solution of 4.5mol/L, is placed in 95 DEG C of water bath with thermostatic control reaction 90min, under this condition silicon Dissolution rate reach 62.5%.From document 1 as can be seen that being the activation that directly heats of gangue, but this process needs microwave Auxiliary heating, and be to add a base to calcine jointly with gangue in document 2.
Although compared with mechanical activation, it may be seen that thermal activation has relatively good activation effect.But current institute The process of thermal activation used is to mix gangue with a certain amount of additive to calcine at high temperature.It can be seen that process of thermal activation Disadvantage is to need 700 DEG C or more of high temperature, therefore it is high to consume energy, and the reaction time is longer, and needs to make in subsequent sour treatment process With the biggish acid of concentration, acid reagent usage amount is big.In the today for advocating environmental protection and energy saving and Green Chemistry, this method is obviously It is unfavorable.
As for the extracting method of aluminium oxide, mainly there are Bayer process, soda lime sintering process and acid system, Bayer process and alkali stone at present Grey sintering process is generally used in the mineral that alumina silica ratio (mass ratio, similarly hereinafter) is greater than 3, since alumina silica ratio is generally less than 1 in gangue, It is general mainly to utilize acid system from the point of view of economy and energy consumption, i.e., the sial in gangue is dissolved into shape using hydrochloric acid or sulfuric acid At the sodium salt for the silicon and aluminium for being soluble in acid, further trans-utilization.However, the sial in gangue is mainly with kaolinite and stone The not high form of English isoreactivity exists, and structure is highly stable, and reactivity is excessively poor, it is necessary to could be anti-with acid after overactivation It answers.The activation of gangue mainly has mechanical activation and thermal activation.Xia Jupei etc. is (2015 volume 15 of " safety and environment journal " 3rd phase) " high-speed rail coal gangue acidity extraction aluminium, iron research " (document 1) delivered by coal shale in brick making using ball mill powder Mill takes the gangue of partial size 0.150mm and the dissolution rate of 75% aluminium of the sulfuric acid in 125 DEG C of heating water bath 3h, gangue to reach To 92.5%.It may be seen that such method is using mechanical activation from document, the sample after activation is in acidleach process In to use the sulfuric acid of high concentration that the dissolution rate of the aluminium oxide in gangue is just made to have reached 95.5%, but the consumption of acid Greatly, acid concentration height also brings difficulty to operation.
In recent years, supercritical fluid technique, including supercritical fluid extraction (SFE) and supercritical water oxidation (SCWO) are As up-and-coming method, it is successfully applied to the processing of solid waste.In supercritical reaction, water is by under room temperature Ionic species solution be changed into the nonionic class solution under super critical condition, temperature be higher than environment boiling point in the case where water can For extracting.At a suitable temperature, ion and polar substances will be extracted.At relatively high temperatures, apolar substance It will be easy to decompose and be extracted.In addition, supercritical water because its as nontoxic, environmentally friendly and cheap chemical reaction medium and by To extensive concern, its physical property, as viscosity, density, dielectric constant and ion product can pass through the change of pressure and temperature Change to control.
Supercritical water technology, reaction temperature used by us are low, it is only necessary to and 400 DEG C, for individual gangues, reaction temperature Degree can even be reduced to 250 DEG C.Under condition of supercritical water, gangue is reacted with the alkali of addition, the height in gangue Ridge stone has mutually been largely converted into cancrinite phase (gangue is reacted with NaOH), sodalite phase (gangue and Na2CO3Reaction) and Kaliophilite phase (gangue is reacted with KOH), and these are all readily dissolved in hydrochloric acid.In subsequent acid processing, the bastard coal after activation Shi Zhong, mainly cancrinite (sodalite or kaliophilite) are decomposed by hydrochloric acid, at this point, the most of aluminium, silicon in gangue are all with acid Root form exists in solution.And during experiment, the presence of lithium, gallium is detected in the solution, finally using richness The method of collection is collected.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of subcritical or overcritical active coal gangues While the application in aluminium oxide and silica extraction process of method and this method, contain in recovery section gangue Lithium, gallium.
In order to achieve the above-mentioned object of the invention, particular content of the invention are as follows:
A kind of subcritical or supercritical water thermal activation of gangue and the method for extracting wherein valuable element, the method packet It includes:
The lye and gangue sample are pressed solid-to-liquid ratio 1 by a) lye that configuration molar concentration is 0.5-2.0mol/L: 10-1: 20g/mL ratio mixing, stirring obtain active coal gangue precursor；
B) the active coal gangue precursor that step a) is obtained is moved in reaction kettle, at 250-450 DEG C of reaction temperature, reaction Priming reaction 5-10min under the subcritical or condition of supercritical water of pressure 3-30MPa；
C) it is separated by solid-liquid separation after priming reaction, obtained solid sample washing will be separated by solid-liquid separation, be dried to obtain work Change gangue sample, obtained filtrate will be separated by solid-liquid separation and cleaning solution merges to obtain lithium-containing solution I；
D) the active coal gangue sample for obtaining step c) lead to peracid treatment extract valuable element aluminium therein, silicon and Gallium；CO is passed through into the lithium-containing solution I that step c) is obtained2Gas carries out carbonating processing and extracts valuable element therein Lithium.
In addition, the present invention also provides a kind of method of comprehensive utilization of gangue, which comprises
The lye and gangue sample are pressed solid-to-liquid ratio 1 by a) lye that configuration molar concentration is 0.5-2.0mol/L: 10-1: 20g/ml ratio mixing, stirring obtain active coal gangue precursor；
B) the active coal gangue precursor that step a) is obtained is moved in reaction kettle, in 250-450 DEG C of reaction temperature and instead Answer priming reaction 5-10min under the subcritical or condition of supercritical water of pressure 3-30MPa；
C) it is separated by solid-liquid separation after priming reaction, obtained solid sample washing will be separated by solid-liquid separation, be dried to obtain work Change gangue sample；And obtained filtrate will be separated by solid-liquid separation and cleaning solution merges to obtain lithium-containing solution I；
D) it is 1 by solid-to-liquid ratio by the active coal gangue sample that step c) is obtained and the acid solution that concentration is 0.5-1mol/L: 6-1: 15g/ml ratio hybrid reaction 3-8h dissolves out reactant, filters residue, obtains the solution II containing aluminium, silicon and gallium, then The solution II containing aluminium, silicon and gallium is evaporated condensing crystallizing, obtains solid mixture；Wherein the concentration is 0.5- The acid solution of 1mol/L is HCl, H2SO4And HNO3It is one or more；Wherein the filtering residue is used as the original for preparing cement Material；
It e) is 1: 3-1: 6g/ by solid-to-liquid ratio by the solid mixture that step d) is obtained and the acid solution that concentration is 1-2mol/L Ml mixing, in 25-50 DEG C of leaching 10-30min, filtering obtains cohesion shape silica gel and the solution III containing aluminium plus gallium, by the cohesion The washing of shape silica gel, dry obtained white carbon black product；The acid solution that wherein concentration is 1-2mol/L is HCl, H2SO4And HNO3 It is one or more；
F) at room temperature, it is 10%- that mass percent is added in the solution III containing aluminium plus gallium obtained to step e) 20% ammonium hydroxide is filtered as the pH=6-6.5 of the solution, by filter residue and drying, obtains aluminium hydroxide and gallium hydroxide The mixed sediment of precipitating；
G) at room temperature, in the ratio of solid-to-liquid ratio 1: 15-1: 20g/ml to mixed sediment obtained in step f) 1-3mol/L NaOH solution is added, alkali soaks 0.5-1.5h, is filtered to remove the impurity such as iron therein, obtains containing the pure of aluminium plus gallium Solution IV；
H) CO is passed through into the purified solution IV containing aluminium plus gallium that step g) is obtained2Gas carries out carbonating processing, ventilation Rate is 40-60ml/min, stops ventilation, isolated a large amount of Al (OH) as the pH=8-8.5 of solution3Sediment and contain Gallium solution V；
I) CO is passed through into the lithium-containing solution I that step c) is obtained2Gas carries out carbonating processing, Ventilation Rate 40- 60ml/min stops ventilation, isolated a small amount of Al (OH) as the PH=8-8.5 of solution3Sediment and the VI of mother liquor containing lithium, By a small amount of Al (OH)3The Al (OH) that sediment and step h) are obtained3Sediment, which merges and passes through calcining, obtains oxygen Change aluminium product；The VI of mother liquor containing lithium is evaporated concentration at 100-110 DEG C, obtains Li2CO3Crystal obtains Li after calcining2O Product；
J) the Gallium solution V that step h) is obtained is evaporated concentration at 100-110 DEG C, the NaHCO that will be preferentially precipitated3Solid After being separated by filtration, CO is passed through into obtained filtrate containing gallium again2Gas, Ventilation Rate 40-60ml/min, as the PH of solution Stop ventilation when=9-9.5, obtains Ga (OH)3Sediment, the Ga (OH)3Sediment obtains Ga after calcining2O3Product.
Wherein lye described in step a) is NaOH, Na2CO3With one of KOH or a variety of；The gangue sample is excellent Selecting partial size is 0.075-0.150mm.
It is separated by solid-liquid separation in the step c) using suction filtration, then washs filter cake with secondary deionized water, and in 80- 5-12h is dried at 110 DEG C obtains active coal gangue；And filtrate and cleaning solution are recycled together and obtain lithium-containing solution I.
Advantages of the present invention
The present invention is directed to the deficiency of existing gangue Thermal activa tion, provides a kind of mild subcritical or overcritical activation Method, main advantage are embodied in:
(1) activation effect is good, and the low concentration acid for being about 1mol/L or so using only concentration just may make the dissolution of aluminium oxide Rate reaches 65-82%, and the dissolution rate of silica reaches 58-77%；
(2) reaction unit is simple, easily operated；Operating procedure is few, and activation temperature is low, it is only necessary to and 250-450 DEG C, energy consumption It is low, and activation time is short, only needs 5min；It can be seen that the temperature of supercritical water thermal activation is significantly compared to traditional process of thermal activation It reduces, consumes energy lower, and the reaction time is short, recovery rate is high；
(3) participation of whole process organic solvent-free, the feature of environmental protection is good, and discharges without noxious material；
(4) for lithium and the high gangue of gallium content, while extracting sial, also recycled the higher lithium of added value with Gallium；
(5) the present invention also provides a kind of Resource comprehensive utilization method of trade waste gangue, both reduce bastard coal The cost of stone activation, and whole pollution-free, no secondary emission, and it is truly realized the bastard coal of a kind of no pollution, zero-emission The approach of stone waste utilization is a kind of approach of environmentally friendly new activating coal gangue method and gangue waste utilization.
Detailed description of the invention
Fig. 1 is the XRD diffraction pattern of the coal shale in brick making of the embodiment of the present invention 1, activated sample and smut；
Fig. 2 is the XRD diffraction pattern of the coal shale in brick making of the embodiment of the present invention 4, activated sample and smut；
Fig. 3 is the coal shale in brick making of the embodiment of the present invention 1 by supercritical water treatment (a) and activated sample pickling (b) Silicon, aluminium, lithium and gallium dissolution rate；
Fig. 4 is the coal shale in brick making of the embodiment of the present invention 4 by supercritical water treatment (a) and activated sample pickling (b) Silicon, aluminium, lithium and gallium dissolution rate；
Specific embodiment
Embodiment 1
1) activating coal gangue: Al is accurately weighed2O3Content be 24.88% and SiO2Content be 32.40% Pingshuo Coal NaOH aqueous solution and the gangue of weighing are pressed volume matter by spoil 10g, the NaOH aqueous solution that configuration molar concentration is 2.0mol/L Amount stirs 10min than mixing in 50ml beaker for 10: 1ml/g at room temperature.Then the solution after stirring is moved into reaction kettle In, 10min is reacted under 350 DEG C, the super critical condition of 15MPa.Water cooling filters, washing, filter cake is done at 110 DEG C to room temperature Dry 10 hours.And obtained filtrate will be separated by solid-liquid separation and cleaning solution merges to obtain lithium-containing solution I；
2) acidleach mentions aluminium, silicon, gallium: by the hydrochloric acid of gangue sample and 1mol/L after activation according to solid-to-liquid ratio 1: 10g/ml 5h is reacted in mixing at room temperature, dissolves out reactant, is filtered to remove residue, obtains the solution II containing aluminium, silicon and gallium, and the filtering is residual Slag is used as the raw material for preparing cement；
3) it prepares white carbon black: by the solution containing aluminium, silicon and gallium obtained in 2), being evaporated condensing crystallizing, obtain solid Then mixture is baked to, be 1: 4g/ml addition 2mol/L hydrochloric acid according to solid-to-liquid ratio, 30min is leached at 25 DEG C, is filtered Obtain cohesion shape silica gel and solution containing aluminium plus gallium；It will the washing of cohesion shape silica gel, the obtained 2.2g white carbon black of 110 DEG C of dryings；
4) purify: be added into solution containing aluminium plus gallium obtained in 3) mass percent for 15% ammonium hydroxide to PH=6 when mistake Filter, obtains Al (OH)3With Ga (OH)3Mixed sediment；The mixed sediment soaks 0.5h with 3mol/L NaOH solution alkali, when When Ph=10, the impurity such as iron therein are filtered to remove, are passed through CO into the obtained filtrate containing aluminium plus gallium2Gas carries out carbonic acid Change processing, Ventilation Rate 40ml/min stop ventilation, isolated a large amount of Al (OH) as the pH=8 of the filtrate3It is heavy Starch and contain Gallium solution；By obtained Al (OH)3Sediment；
5) aluminium oxide and lithia are prepared: to obtaining being passed through CO in lithium-containing solution I in 1)2Gas carries out carbonating processing, Ventilation Rate is 45ml/min, stops ventilation as the PH=8 of solution, a small amount of Al (OH) is obtained by filtration3Sediment and contain lithium Mother liquor, the Al (OH) that this sediment and step 4) are obtained3In 110 DEG C of dryings after sediment merging, 1200 DEG C of calcinings are obtained 1.9g aluminium oxide；The mother liquor containing lithium is evaporated concentration at 100 DEG C, obtains Li2CO3Crystal obtains Li after calcining2O；
6) it prepares gallium oxide: being evaporated concentration at 100 DEG C containing Gallium solution for what is 4) obtained, the NaHCO that will be preferentially precipitated3 After solid is separated by filtration, then CO is passed through into filtrate2Gas, Ventilation Rate 45ml/min stop logical as the PH=9 of solution Gas obtains Ga (OH)3Precipitating, obtains Ga after calcining2O3。
By using the aluminium in inductively coupled plasma body luminescence spectrometer analysis detection solution, silicone content is obtained containing lithium The dissolution rate of aluminium oxide in solution I is 6.73%, and the dissolution rate of silica is 4.94%, and the dissolution rate of lithia is 30.11%；The dissolution rate of aluminium oxide in solution II containing aluminium, silicon and gallium is 59.01%, and the dissolution rate of silica is 65.47%, the dissolution rate of gallium oxide is 59.87%.
Embodiment 2
1) activating coal gangue: Al is accurately weighed2O3Content be 24.88% and SiO2Content be 32.40% Pingshuo Coal NaOH aqueous solution and the gangue of weighing are pressed volume matter by spoil 20g, the NaOH aqueous solution that configuration molar concentration is 2.0mol/L Amount stirs 10min than mixing in 50ml beaker for 20: 1ml/g at room temperature.Then the solution after stirring is moved into reaction kettle In, 10min is reacted under 350 DEG C, the super critical condition of 15MPa.Water cooling filters, washing, filter cake is done at 110 DEG C to room temperature Dry 10 hours.And obtained filtrate will be separated by solid-liquid separation and cleaning solution merges to obtain lithium-containing solution I；
2) acidleach mentions aluminium, silicon, gallium: by the hydrochloric acid of gangue sample and 1mol/L after activation according to solid-to-liquid ratio 1: 10g/ml 7h is reacted in mixing at room temperature, dissolves out reactant, is filtered to remove residue, obtains the solution II containing aluminium, silicon and gallium, and the filtering is residual Slag is used as the raw material for preparing cement；
3) it prepares white carbon black: by the solution containing aluminium, silicon and gallium obtained in 2), being evaporated condensing crystallizing, obtain solid Then mixture is baked to, be 1: 3g/ml addition 1mol/L hydrochloric acid according to solid-to-liquid ratio, 10min is leached at 25 DEG C, is filtered Obtain cohesion shape silica gel and solution containing aluminium plus gallium；It will the washing of cohesion shape silica gel, the obtained 4.1g white carbon black of 110 DEG C of dryings；
4) purify: be added into solution containing aluminium plus gallium obtained in 3) mass percent for 15% ammonium hydroxide to PH=6 when mistake Filter, obtains Al (OH)3With Ga (OH)3Mixed sediment；The mixed sediment soaks 0.5h with 3mol/L NaOH solution alkali, when When pH=10, the impurity such as iron therein are filtered to remove, are passed through CO into the obtained filtrate containing aluminium plus gallium2Gas carries out carbonic acid Change processing, Ventilation Rate 40ml/min stop ventilation, isolated a large amount of Al (OH) as the pH=8 of the filtrate3It is heavy Starch and contain Gallium solution；By obtained Al (OH)3Sediment；
5) aluminium oxide and lithia are prepared: to obtaining being passed through CO in lithium-containing solution I in 1)2Gas carries out carbonating processing, Ventilation Rate is 50ml/min, stops ventilation as the PH=8.5 of solution, a small amount of Al (OH) is obtained by filtration3Sediment and contain Lithium mother liquor, the Al (OH) that this sediment and step 4) are obtained3In 110 DEG C of dryings after sediment merging, 1200 DEG C of calcinings are obtained 4.5g aluminium oxide；The mother liquor containing lithium is evaporated concentration at 100 DEG C, obtains Li2CO3Crystal obtains Li after calcining2O；
6) it prepares gallium oxide: being evaporated concentration at 100 DEG C containing Gallium solution for what is 4) obtained, the NaHCO that will be preferentially precipitated3 After solid is separated by filtration, then CO is passed through into filtrate2Gas, Ventilation Rate 50ml/min stop logical as the PH=9 of solution Gas obtains Ga (OH)3Precipitating, obtains Ga after calcining2O3。
By using the aluminium in inductively coupled plasma body luminescence spectrometer analysis detection solution, silicone content is obtained containing lithium The dissolution rate of aluminium oxide in solution I is 1.99%, and the dissolution rate of silica is 0.00%, and the dissolution rate of lithia is 28.70%；The dissolution rate of aluminium oxide in solution II containing aluminium, silicon and gallium is 69.68%, and the dissolution rate of silica is 77.03%, the dissolution rate of gallium oxide is 70.01%.
Embodiment 3
1) activating coal gangue: Al is accurately weighed2O3Content be 20.79% and SiO2Content be 31.85% Pingshuo Coal KOH aqueous solution and the gangue of weighing are pressed volume mass by spoil 20g, the KOH aqueous solution that configuration molar concentration is 2.0mol/L Than mixing in 50ml beaker for 15: 1ml/g, 10min is stirred at room temperature.Then the solution after stirring is moved in reaction kettle, 10min is reacted under 250 DEG C, the super critical condition of 3MPa.Water cooling filters, washing, filter cake is dry 10 at 110 DEG C to room temperature Hour.And obtained filtrate will be separated by solid-liquid separation and cleaning solution merges to obtain lithium-containing solution I；
2) acidleach mentions aluminium, silicon, gallium: by the hydrochloric acid of gangue sample and 1mol/L after activation according to solid-to-liquid ratio 1: 30g/ml 3h is reacted in mixing at room temperature, dissolves out reactant, is filtered to remove residue, obtains the solution II containing aluminium, silicon and gallium, and the filtering is residual Slag is used as the raw material for preparing cement；
3) it prepares white carbon black: by the solution containing aluminium, silicon and gallium obtained in 2), being evaporated condensing crystallizing, obtain solid Then mixture is baked to, be 1: 5g/ml addition 1.5mol/L hydrochloric acid according to solid-to-liquid ratio, 15min, mistake are leached at 50 DEG C Filter obtains cohesion shape silica gel and solution containing aluminium plus gallium；It will the washing of cohesion shape silica gel, the obtained 3.8g white carbon black of 110 DEG C of dryings；
4) purify: be added into solution containing aluminium plus gallium obtained in 3) mass percent for 15% ammonium hydroxide to PH=6 when mistake Filter, obtains Al (OH)3With Ga (OH)3Mixed sediment；The mixed sediment soaks 0.5h with 3mol/L NaOH solution alkali, when When pH=10, the impurity such as iron therein are filtered to remove, are passed through CO into the obtained filtrate containing aluminium plus gallium2Gas carries out carbonic acid Change processing, Ventilation Rate 40ml/min stop ventilation, isolated a large amount of Al (OH) as the pH=8 of the filtrate3It is heavy Starch and contain Gallium solution；By obtained Al (OH)3Sediment；
5) aluminium oxide and lithia are prepared: to obtaining being passed through CO in lithium-containing solution I in 1)2Gas carries out carbonating processing, Ventilation Rate is 50ml/min, stops ventilation as the PH=9 of solution, a small amount of Al (OH) is obtained by filtration3Sediment and contain lithium Mother liquor, the Al (OH) that this sediment and step 4) are obtained3In 110 DEG C of dryings after sediment merging, 1200 DEG C of calcinings are obtained 3.5g aluminium oxide；The mother liquor containing lithium is evaporated concentration at 100 DEG C, obtains Li2CO3Crystal obtains Li after calcining2O；
6) it prepares gallium oxide: being evaporated concentration at 100 DEG C containing Gallium solution for what is 4) obtained, the NaHCO that will be preferentially precipitated3 After solid is separated by filtration, then CO is passed through into filtrate2Gas, Ventilation Rate 50ml/min stop as the PH=9.5 of solution Ventilation, obtains Ga (OH)3Precipitating, obtains Ga after calcining2O3.It analyzes and examines by using inductively coupled plasma body luminescence spectrometer The aluminium in solution is surveyed, silicone content show that the dissolution rate of the aluminium oxide in lithium-containing solution I is 2.92%, and the dissolution rate of silica is 12.96%, the dissolution rate of lithia is 29.05%；The dissolution rate of aluminium oxide in solution II containing aluminium, silicon and gallium is 62.80%, the dissolution rate of silica is 51.53%, and the dissolution rate of gallium oxide is 68.90%.
Embodiment 4
1) activating coal gangue: Al is accurately weighed2O3Content be 22.78% and SiO2Content be 52.93% Pingshuo Coal KOH aqueous solution and the gangue of weighing are pressed volume mass by spoil 40g, the KOH aqueous solution that configuration molar concentration is 2.0mol/L Than mixing in 50ml beaker for 15: 1ml/g, 10min is stirred at room temperature.Then the solution after stirring is moved in reaction kettle, 5min is reacted under 300 DEG C, the super critical condition of 8MPa.Water cooling filters, washing, filter cake drying 10 at 110 DEG C is small to room temperature When.And obtained filtrate will be separated by solid-liquid separation and cleaning solution merges to obtain lithium-containing solution I；
2) acidleach mentions aluminium, silicon, gallium: by the hydrochloric acid of gangue sample and 1mol/L after activation according to solid-to-liquid ratio 1: 15g/ml 8h is reacted in mixing at room temperature, dissolves out reactant, is filtered to remove residue, obtains the solution containing aluminium, silicon and gallium, the filtering residue As the raw material for preparing cement；
3) it prepares white carbon black: by the solution containing aluminium, silicon and gallium obtained in 2), being evaporated condensing crystallizing, obtain solid Then mixture is baked to, be 1: 3g/ml addition 2mol/L hydrochloric acid according to solid-to-liquid ratio, 20min is leached at 50 DEG C, is filtered Obtain cohesion shape silica gel and solution containing aluminium plus gallium；It will the washing of cohesion shape silica gel, the obtained 9.5g white carbon black of 110 DEG C of dryings；
4) purify: be added into solution containing aluminium plus gallium obtained in 3) mass percent for 15% ammonium hydroxide to PH=6 when mistake Filter, obtains Al (OH)3With Ga (OH)3Mixed sediment；The mixed sediment soaks 0.5h with 3mol/L NaOH solution alkali, when When pH=10, the impurity such as iron therein are filtered to remove, are passed through CO into the obtained filtrate containing aluminium plus gallium2Gas carries out carbonic acid Change processing, Ventilation Rate 40ml/min stop ventilation, isolated a large amount of Al (OH) as the pH=8 of the filtrate3It is heavy Starch and contain Gallium solution；By obtained Al (OH)3Sediment；
5) aluminium oxide and lithia are prepared: to obtaining being passed through CO in lithium-containing solution I in 1)2Gas carries out carbonating processing, Ventilation Rate is 60ml/min, stops ventilation as the PH=8 of solution, a small amount of Al (OH) is obtained by filtration3Sediment and contain lithium Mother liquor, the Al (OH) that this sediment and step 4) are obtained3In 110 DEG C of dryings after sediment merging, 1200 DEG C of calcinings are obtained 8.8g aluminium oxide；The mother liquor containing lithium is evaporated concentration at 100 DEG C, obtains Li2CO3Crystal obtains Li after calcining2O；
6) it prepares gallium oxide: being evaporated concentration at 100 DEG C containing Gallium solution for what is 4) obtained, the NaHCO that will be preferentially precipitated3 After solid is separated by filtration, then CO is passed through into filtrate2Gas, Ventilation Rate 60ml/min stop logical as the PH=9 of solution Gas obtains Ga (OH)3Precipitating, obtains Ga after calcining2O3。
By using the aluminium in inductively coupled plasma body luminescence spectrometer analysis detection solution, silicone content is obtained containing lithium The dissolution rate of aluminium oxide in solution I is 1.37%, and the dissolution rate of silica is 31.20%, and the dissolution rate of lithia is 18.9%；The dissolution rate of aluminium oxide in solution II containing aluminium, silicon and gallium is 81.67%, and the dissolution rate of silica is 40.26%, the dissolution rate of gallium oxide is 54.68%.

Claims (5)

1. a kind of method for comprehensive utilization of coal gangue, which comprises
The lye and gangue sample are pressed solid-to-liquid ratio 1: 10-1 by a) lye that configuration molar concentration is 0.5-2.0mol/L: The ratio of 20g/ml mixes, and stirring obtains active coal gangue precursor；
B) the active coal gangue precursor that step a) is obtained is moved in reaction kettle, in 250-450 DEG C of reaction temperature and reaction pressure Priming reaction 5-10min under the subcritical or condition of supercritical water of power 3-30MPa；
C) it is separated by solid-liquid separation after priming reaction, obtained solid sample washing will be separated by solid-liquid separation, be dried to obtain activated coal Spoil sample；And obtained filtrate will be separated by solid-liquid separation and cleaning solution merges to obtain lithium-containing solution I；
D) it is 1: 6-1 by solid-to-liquid ratio by the active coal gangue sample that step c) is obtained and the acid solution that concentration is 0.5-6mol/L: The ratio hybrid reaction 3-8h of 15g/ml dissolves out reactant, filters residue, the solution II containing aluminium, silicon and gallium is obtained, then by institute It states the solution II containing aluminium, silicon and gallium and is evaporated condensing crystallizing, obtain solid mixture；Wherein the concentration is 0.5-6mol/L Acid solution be HCl, H2SO4And HNO3It is one or more；Wherein the filtering residue is used as the raw material for preparing cement；
It e) is 1: 3-1: 6g/ml mixed by solid-to-liquid ratio by the solid mixture that step d) is obtained and the acid solution that concentration is 1-2mol/L It closes, in 25-50 DEG C of leaching 10-30min, filtering obtains cohesion shape silica gel and the solution III containing aluminium plus gallium, by the cohesion shape silicon Glue is washed, dry obtained white carbon black product；The acid solution that wherein concentration is 1-2mol/L is HCl, H2SO4And HNO3One Kind is a variety of；
F) at room temperature, it is 10%-20% that mass percent is added in the solution III containing aluminium plus gallium obtained to step e) Ammonium hydroxide be filtered as the pH=6-6.5 of the solution, by filter residue and drying, obtain the mixed of aluminium hydroxide and gallium hydroxide Close sediment；
G) at room temperature, add in the ratio of solid-to-liquid ratio 1: 15-1: 20g/ml into mixed sediment obtained in step f) Enter 1-3mol/L NaOH solution, alkali soaks 0.5-1.5h, is filtered to remove the impurity such as iron therein, obtains pure molten containing aluminium plus gallium Liquid IV；
H) CO is passed through into the purified solution IV containing aluminium plus gallium that step g) is obtained2Gas carries out carbonating processing, Ventilation Rate For 40-60ml/min, stop ventilation, isolated a large amount of Al (OH) as the pH=8-8.5 of solution3Sediment and containing gallium it is molten Liquid V；
I) CO is passed through into the lithium-containing solution I that step c) is obtained2Gas carries out carbonating processing, Ventilation Rate 40-60ml/ Min stops ventilation, isolated a small amount of Al (OH) as the PH=8-8.5 of solution3Sediment and the VI of mother liquor containing lithium, by institute State a small amount of Al (OH)3The Al (OH) that sediment and step h) are obtained3Sediment, which is merged, obtains aluminium oxide using calcining Product；The VI of mother liquor containing lithium is evaporated concentration at 100-110 DEG C, obtains Li2CO3Crystal obtains Li after calcining2O is produced Product；
J) the Gallium solution V that step h) is obtained is evaporated concentration at 100-110 DEG C, the NaHCO that will be preferentially precipitated3Solid filtering After separation, CO is passed through into isolated filtrate containing gallium again2Gas, Ventilation Rate 40-60ml/min, as the PH of solution Stop ventilation when=9-9.5, obtains Ga (OH)3Sediment, the Ga (OH)3Sediment obtains Ga after calcining2O3Product.
2. a kind of subcritical or supercritical water thermal activation of gangue and the method for extracting wherein valuable element, the method packet It includes:
The lye and gangue sample are pressed solid-to-liquid ratio 1: 10-1 by a) lye that configuration molar concentration is 0.5-2.0mol/L: The ratio of 20g/ml mixes, and stirring obtains active coal gangue precursor；
B) the active coal gangue precursor that step a) is obtained is moved in reaction kettle, at 250-450 DEG C of reaction temperature, reaction pressure Priming reaction 5-10min under the subcritical or condition of supercritical water of 3-30MPa；
C) it is separated by solid-liquid separation after priming reaction, obtained solid sample washing will be separated by solid-liquid separation, be dried to obtain activated coal Spoil sample will be separated by solid-liquid separation obtained filtrate and cleaning solution merge to obtain lithium-containing solution I；
D) the active coal gangue sample for obtaining step c) leads to peracid treatment extraction valuable element aluminium, silicon and gallium therein； CO is passed through into the lithium-containing solution I that step c) is obtained2Gas carries out carbonating processing and extracts valuable element lithium therein.
3. method according to claim 1 or 2, which is characterized in that the lye is NaOH, Na2CO3With one of KOH or It is a variety of.
4. method according to claim 1 or 2, which is characterized in that be separated by solid-liquid separation in the step c) using suction filtration, so Filter cake is washed with secondary deionized water afterwards, and dries 5-12h at 80-110 DEG C and obtains active coal gangue；And it by filtrate and washes It washs liquid and recycles together and obtain lithium-containing solution I.
5. method according to claim 1 or 2, which is characterized in that gangue sample preferable particle size described in step a) is 0.075-0.150mm。
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