CN105886779A - Resourceful treatment method of chromium-containing aluminum mud - Google Patents
Resourceful treatment method of chromium-containing aluminum mud Download PDFInfo
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- CN105886779A CN105886779A CN201610403435.XA CN201610403435A CN105886779A CN 105886779 A CN105886779 A CN 105886779A CN 201610403435 A CN201610403435 A CN 201610403435A CN 105886779 A CN105886779 A CN 105886779A
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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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
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
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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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
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- 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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- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a resourceful treatment method of chromium-containing aluminum mud. The resourceful treatment method comprises the steps that 1, water is added to the chromium-containing aluminum mud for mixing, and a chromium-containing (VI) aqueous solution and an aluminum-containing (III) filter cake are obtained through heating, dissolution and filtration; 2, the chromium-containing (VI) aqueous solution is subjected to electro-reduction to obtain a chromium-containing (III) aqueous solution; 3, the chromium-containing (III) aqueous solution is subjected to bipolar membrane electrodialysis treatment to obtain a NaOH solution and a chromic acid solution; 4, the NaOH solution in the step 3 is concentrated by adopting membrane distillation to obtain clear water and a concentrated NaOH solution, and the clear water is reused in the water-dissolution process in the step 1; 5, the aluminum-containing filter cake in the step 1 is dissolved in the concentrated NaOH solution in the step 4, heating reaction is performed, filtering separation is performed to obtain a NaAlO2 solution. The resourceful treatment method treats aluminum mud solid waste and achieves resource recycling of chrome and aluminum in the solid waste.
Description
Technical field
The present invention relates to chemical industrial waste thing resource process field, be specifically related to the money of a kind of chromium-contained aluminum mud
Source processing method.
Background technology
Chromium-contained aluminum mud is the by-product produced during chromium salt production, industrial general production 1t dichromic acid
Sodium about produces 30～50kg aluminum mud, containing substantial amounts of aluminum (III) and chromium (VI) in aluminum mud.At present,
The sodium dichromate factory processing mode to aluminum mud: 1, landfill；2, the factory that technique is relatively advanced
Family, uses the roasting together with chromite of aluminum mud, and major part chromium is reclaimed in extraction, and then aluminum slag is as useless
Gurry fills, though the method can reclaim major part chromium, but also has weak point, still suffers from aluminum slag
2～the chromium (VI) of about 3%.Traditional aluminum slag offal treatment mode, does not only take up a large amount of soil money
Source, and there is pollution hidden trouble, the wasting of resources and environmental pollution can be caused.
In recent years, domestic and international researcher has done numerous studies in terms of chromium-contained aluminum mud comprehensive control, including
Utilize the clay tanning extracts of aluminum and cement, phosphoric acid chemistry neutralisation except aluminum, high-temperature roasting are except chromium, flocculate by force
Agent is except chromium, reducing agent reduction are except chromium etc..But the process conditions that this kind of method has are harsh, equipment investment is high,
Some response rate are low, product quality fluctuation is big, all unsuitable commercial Application.
The patent documentation of Publication No. CN103318934A discloses a kind of chromium-contained aluminum mud and prepares high-purity
The method of aluminate, first recovery section Cr6+, then use dissolved aluminum mud, except ferrum, preparation Al (OH)3
With Cr (OH)3Mixture recovery section Cr6+, then carry out Al (OH)3With Cr (OH)3Mixture
Alkali fusion and Cr3+, finally prepare rafifinal hydrochlorate.Though this invention technique is simple, it is easy to industry
Change, but other chemical reagent need to be added.
The patent documentation of Publication No. CN104805288A discloses a kind of comprehensive utilization chromium-contained aluminum mud
Reclaim chromium and the process of aluminum, the technique isolated sodium chromate such as aluminum mud economy-combat pulp-water is washed, electrodialysis
Solution is used for producing sodium dichromate product, de-chromium process after aluminum mud, dissolve through NaOH solution, many
Secondary continuous carbon point-score obtains high-purity metallurgical-grade aluminum oxide product.
Summary of the invention
The invention provides the recycling processing method of a kind of chromium-contained aluminum mud, to the chromium in chromium-contained aluminum mud and
Aluminum is recycled.
A kind of recycling processing method of chromium-contained aluminum mud, including:
Step 1, add water in chromium-contained aluminum mud mixing, filters through rising temperature for dissolving, obtains containing chromium (VI) water
Solution and containing aluminum (III) filter cake；
Step 2, obtains containing chromium (III) aqueous solution through electroreduction containing chromium (VI) aqueous solution；
Step 3, processes through bipolar membrane electrodialysis containing chromium (III) aqueous solution, obtains NaOH solution and chromium
Acid solution；
Step 4, uses Membrane Materials to concentrate the NaOH solution in step 3, obtains clear water and concentration
NaOH solution, the water-soluble process that clear water is back in step 1；
Step 5, utilize in the NaOH solution dissolving step 1 after concentrating in step 4 containing aluminum filter cake, rise
Temperature reaction, filters isolated NaAlO2Solution.
The present invention is directed to chromium-contained aluminum mud and carry out recycling treatment, not only reduce aluminum mud solid waste, and realize
Chromium and the recycling of aluminum.
Chromium-contained aluminum mud is the primary solids garbage produced except the aluminum stage in chromium salt production, does not only take up soil
Ground, pollution environment, and serious waste resource.As chromite produces sodium dichromate (sodium dichromate),
The general 1t sodium dichromate that often produces about can produce 30～50kg aluminum mud.
As preferably, in step 1, chromium-contained aluminum mud is 1:3～9 with the mass ratio of water.
After adding suitable quantity of water dilution in chromium-contained aluminum mud, intensification stirring and dissolving, the consumption of water is too much or mistake
Few, all can affect the solute effect of chromium-contained aluminum mud.
In step 1, chromium-contained aluminum mud and water mixing heat up after stirring reaction, utilize suitable quantity of water repeated washing
More than at least 3 times, after washing liquid and product are merged, filter, obtain containing chromium (VI)
Aqueous solution and the filter cake in aluminum.
In order to promote chromium-contained aluminum mud dissolving in water, it is preferable that be warming up to 60～80 DEG C of stirring and dissolving.
Depending on mixing time is according to actual dissolving situation, it is as the criterion forming homogeneous mixed solution.
As preferably, in step 1, moisture batch adds in chromium-contained aluminum mud.
When chromium-contained aluminum mud adds water, can disposably add, it is also possible to add in batches, make aluminum mud
In chromium (VI) dissolve more abundant.
As preferably, in step 2, the electrode of electroreduction uses the plating of graphite electrode, Titanium electrode, titanium
One in ruthenium or titanium plating iridium electrode；Being separated with ion exchange membrane in electroreduction groove, electric current density is
40～300A/m2。
Bipolar Membrane is a kind of novel ion-exchange composite membranes, by cation exchange layer (N-type film), boundary
Face hydrophilic layer (Catalytic Layer) and cation exchange layer (p-type film) are composited.Make in DC electric field
Under with, water decomposition can be obtained H in film both sides by Bipolar Membrane+、OH-.Utilize this feature, will be double
The bipolar membrane electrodialysis system that pole film and anion and cation exchange membrane are combined into, can not introduce other components
In the case of, salt is converted into corresponding bronsted lowry acids and bases bronsted lowry.
In order to ensure efficiently carrying out of bipolar membrane electrodialysis, it is preferable that in step 3, Bipolar Membrane electric osmose
Analysis condition be: mass fraction be 0.1～5% conducting solution be pole liquid, reaction temperature 1～40 DEG C, electricity
Current density 200～700A/m2。
Further preferably, in step 3, the condition of bipolar membrane electrodialysis is: mass fraction is 0.5～4%
Conducting solution be pole liquid, reaction temperature 15～35 DEG C, electric current density 300～600A/m2。
Most preferably, in step 3, the condition of bipolar membrane electrodialysis is: mass fraction is 1.5～3% leads
Electricity solution is pole liquid, reaction temperature 25～35 DEG C, electric current density 400～500A/m2。
Membrane Materials process is a kind of thermal drivers process, separates hot feed liquid (heat is surveyed) by hydrophobic porous film
With through surveying (cold side), the vapour pressure surveyed because of charging is higher than the vapour pressure through side, makees in differential pressure gradients
Under with, steam molecule is surveyed by heat and is migrated to cold side through fenestra, condensed, obtains pure component.Film steams
Evaporate the combination that can regard membrane process as with still-process, be a kind of novel high efficient separation technology.
As preferably, in step 4, Membrane Materials uses hollow-fibre membrane or laminar film, and membrane material is selected
Politef (PTFE), Kynoar (PVDF), polypropylene (PP), polyethylene (PE)
In at least one.
In order to enable NaOH solution rapid concentration, it is preferable that in step 4, Membrane Materials is used
Membrane porosity is 60～95%, and aperture is 0.1～1.0 μm, and thickness is 0.04～0.25mm.
Further preferably, in step 4, Membrane Materials uses hollow-fibre membrane, and membrane porosity is 80～90%,
Aperture is 0.2～0.8 μm, and thickness is 0.1～0.2mm.
NaOH solution is concentrated to react with the filter cake containing aluminum by step 4, the reaction in step 5
Equation is as follows:
Al(OH)3+ NaOH=NaAlO2+2H2O。
When feeding intake, it then follows the stoichiometric proportion shown in above-mentioned reaction equation, the dosage of NaOH with
Calculate containing on the basis of the alumina content in aluminum filter cake.
In order to make the concentration of NaOH in NaOH solution match with containing the aluminum content in aluminum filter cake, because of
This, need to be concentrated into NaOH solution suitable concentration, selects to concentrate NaOH solution in the present invention
To saturation, described saturation is the most proper saturated, but allows certain mistake
Difference, close to saturation.
In order to make the reaction of step 5 be smoothed out, it is preferable that in step 5, be warming up to 90～110 DEG C,
Stirring reaction 2～6h.
The present invention is combined process by electroreduction technology, bipolar membrane electrodialysis technology and contains with film distillation technology
Chromium aluminum mud, in the case of not introducing other chemical reagent, not only solves the difficulty that chromium-contained aluminum mud is disposed
Inscribe, and resource has recycled the aluminum in aluminum mud and chromium resource.
Accompanying drawing explanation
Fig. 1 is the flow chart of the recycling processing method of chromium-contained aluminum mud of the present invention.
Detailed description of the invention
The flow process of the recycling processing method of the chromium-contained aluminum mud that the present invention provides is as it is shown in figure 1, aluminium chromium dosed
After mud is dissolved in water, it is filtrated to get containing aluminum filter cake and chromium-containing solution；Chromium-containing solution is through electroreduction six
Valency chromium is reduced to three prices, then obtains NaOH solution and chromic acid solution through bipolar membrane electrodialysis；
NaOH solution through Membrane Materials, the NaOH solution after being concentrated, NaOH solution after concentration and containing
Aluminum filter cake reacts, and obtains NaAlO2Solution.
Embodiment 1
The waste residue that certain chromium salt factory produces during producing sodium dichromate, moisture content about 60% (divide by quality
Number), dry aluminum mud mainly contains Al2O3、Cr2O3、Na2CrO4、SiO2And Fe2O3Deng.
(1) water-soluble: in waste residue, to add water (waste residue is 1:3 with the mass ratio of water), stir in 70 DEG C
Mixing reaction 1h, washing 3 times, filter containing chromium (VI) aqueous solution and the filter cake in aluminum repeatedly.
(2) electroreduction: be three prices through electroreduction by hexavalent chrome reduction containing chromium (VI) aqueous solution；
Electroreduction parameter: anode electrode is Ru-Ir/Ti, negative electrode is Ti plate, and electric current density is 150A/m2, electricity
Solve and groove adds ion exchange membrane, anode and negative electrode are separated.
(3) bipolar membrane electrodialysis: containing chromium (III) aqueous solution at normal temperatures at bipolar membrane electrodialysis
Reason, obtains NaOH solution and chromic acid solution；The reaction condition of bipolar membrane electrodialysis: 1% metabisulfite solution
For pole liquid, reaction temperature is 30 DEG C, and electric current density is 500A/m2。
(4) Membrane Materials: the NaOH solution that step (3) obtains through membrane distillation concentration to nearly saturated shape
State, obtains the NaOH solution of clear water and concentration, the water-soluble process that clear water is back in step 1.
Membrane Materials uses PTFE hollow-fibre membrane, and thickness is 0.2mm, and aperture is 0.4 μm, porosity
More than 80%.
(5) alkali is molten: the NaOH solution dissolving step (1) after the concentration that step (4) obtains obtains
Filter cake, in 100 DEG C stirring reaction 4h, filter separate to obtain NaAlO2Solution, the chemistry of this step is anti-
The equation is answered to be: Al (OH)3+ NaOH=NaAlO2+2H2O。
Comparative example 1
Experiment condition is same as in Example 1, the difference is that only, during step (1) is water-soluble,
Waste residue is 1:9 with the mass ratio of water, disposably washes, and the solute effect of aluminum mud relatively embodiment 1 is deteriorated.
Comparative example 2
Experiment condition is same as in Example 1, the difference is that only, reduces Bipolar Membrane in step (3)
Electrodialysis electric current density is to 400A/m2, Bipolar Membrane disposal ability reduces, at chromium (III) aqueous solution
Reason time lengthening.
Comparative example 3
Experiment condition is same as in Example 1, the difference is that only, reduces electroreduction in step (2)
Electric current density is to 50A/m2, electroreduction ability reduces, extends containing chromium (VI) the aqueous solution recovery time.
Embodiment 2
The waste residue that certain chromium salt factory produces during producing sodium dichromate, moisture content about 60% (divide by quality
Number), dry aluminum mud mainly contains Al2O3、Cr2O3、Na2CrO4、SiO2And Fe2O3Deng.
(1) water-soluble: in waste residue, to add water (waste residue is 1:3 with the mass ratio of water), stir in 70 DEG C
Mixing reaction 1h, washing 3 times, filter containing chromium (VI) aqueous solution and the filter cake in aluminum repeatedly.
(2) electroreduction: be three prices through electroreduction by hexavalent chrome reduction containing chromium (VI) aqueous solution；
Electroreduction parameter: anode electrode is Ru-Ir/Ti, negative electrode is Ti plate, and electric current density is 150A/m2, electricity
Solve and groove adds ion exchange membrane, anode and negative electrode are separated.
(3) bipolar membrane electrodialysis: containing chromium (III) aqueous solution at normal temperatures at bipolar membrane electrodialysis
Reason, obtains NaOH solution and chromic acid solution；The reaction condition of bipolar membrane electrodialysis: 1% metabisulfite solution
For pole liquid, reaction temperature is 30 DEG C, and electric current density is 500A/m2。
(4) Membrane Materials: the NaOH solution that step (3) obtains through membrane distillation concentration to nearly saturated shape
State, obtains the NaOH solution of clear water and concentration, the water-soluble process that clear water is back in step 1.Membrane Materials
Using PVDF/PTFF composite double layer hollow-fibre membrane, with the hydrophobicity of reinforcing membrane appearance, thickness is
0.2mm, aperture is 0.4 μm, and porosity is more than 80%.
(5) alkali is molten: the NaOH solution dissolving step (1) after the concentration that step (4) obtains obtains
Filter cake, in 100 DEG C stirring reaction 4h, filter separate to obtain NaAlO2Solution.
Embodiment 3
The waste residue that certain chromium salt factory produces during producing sodium dichromate, moisture content about 60% (divide by quality
Number), dry aluminum mud mainly contains Al2O3、Cr2O3、Na2CrO4、SiO2And Fe2O3Deng.
(1) water-soluble: in waste residue, to add water (waste residue is 1:3 with the mass ratio of water), stir in 60 DEG C
Mixing reaction 1h, washing 3 times, filter containing chromium (VI) aqueous solution and the filter cake in aluminum repeatedly.
(2) electroreduction: be three prices through electroreduction by hexavalent chrome reduction containing chromium (VI) aqueous solution；
Electroreduction parameter: anode electrode is Ru-Ir/Ti, negative electrode is Ti plate, and electric current density is 150A/m2, electricity
Solve and groove adds ion exchange membrane, anode and negative electrode are separated.
(3) bipolar membrane electrodialysis: containing chromium (III) aqueous solution at normal temperatures at bipolar membrane electrodialysis
Reason, obtains NaOH solution and chromic acid solution；The reaction condition of bipolar membrane electrodialysis: 1% metabisulfite solution
For pole liquid, reaction temperature is 20 DEG C, and electric current density is 400A/m2。
(4) Membrane Materials: the NaOH solution that step (3) obtains through membrane distillation concentration to nearly saturated shape
State, obtains the NaOH solution of clear water and concentration, the water-soluble process that clear water is back in step 1.Membrane Materials
Using PVDF/PTFF composite double layer hollow-fibre membrane, with the hydrophobicity of reinforcing membrane appearance, thickness is
0.2mm, aperture is 0.6 μm, and porosity is more than 70%.
(5) alkali is molten: the NaOH solution dissolving step (1) after the concentration that step (4) obtains obtains
Filter cake, in 100 DEG C stirring reaction 4h, filter separate to obtain NaAlO2Solution.
Embodiment 4
The waste residue that certain chromium salt factory produces during producing sodium dichromate, moisture content about 60% (divide by quality
Number), dry aluminum mud mainly contains Al2O3、Cr2O3、Na2CrO4、SiO2And Fe2O3Deng.
(1) water-soluble: in waste residue, to add water (waste residue is 1:3 with the mass ratio of water), stir in 80 DEG C
Mixing reaction 1h, washing 3 times, filter containing chromium (VI) aqueous solution and the filter cake in aluminum repeatedly.
(2) electroreduction: be three prices through electroreduction by hexavalent chrome reduction containing chromium (VI) aqueous solution；
Electroreduction parameter: anode electrode is Ru-Ir/Ti, negative electrode is Ti plate, and electric current density is 150A/m2, electricity
Solve and groove adds ion exchange membrane, anode and negative electrode are separated.
(3) bipolar membrane electrodialysis: containing chromium (III) aqueous solution at normal temperatures at bipolar membrane electrodialysis
Reason, obtains NaOH solution and chromic acid solution；The reaction condition of bipolar membrane electrodialysis: 1% metabisulfite solution
For pole liquid, reaction temperature is 25 DEG C, and electric current density is 500A/m2。
(4) Membrane Materials: the NaOH solution that step (3) obtains through membrane distillation concentration to nearly saturated shape
State, obtains the NaOH solution of clear water and concentration, the water-soluble process that clear water is back in step 1.Membrane Materials
Using polypropylene screen, with the hydrophobicity of reinforcing membrane appearance, thickness is 0.1mm, and aperture is 0.4 μm,
Porosity is more than 80%.
(5) alkali is molten: the NaOH solution dissolving step (1) after the concentration that step (4) obtains obtains
Filter cake, in 90 DEG C stirring reaction 4h, filter separate to obtain NaAlO2Solution.
Claims (9)
1. the recycling processing method of a chromium-contained aluminum mud, it is characterised in that including:
Step 1, add water in chromium-contained aluminum mud mixing, filters through rising temperature for dissolving, obtains containing chromium (VI) water
Solution and containing aluminum (III) filter cake；
Step 2, obtains containing chromium (III) aqueous solution through electroreduction containing chromium (VI) aqueous solution；
Step 3, processes through bipolar membrane electrodialysis containing chromium (III) aqueous solution, obtains NaOH solution and chromium
Acid solution；
Step 4, uses Membrane Materials to concentrate the NaOH solution in step 3, obtains clear water and concentration
NaOH solution, the water-soluble process that clear water is back in step 1；
Step 5, utilize in the NaOH solution dissolving step 1 after concentrating in step 4 containing aluminum filter cake, rise
Temperature reaction, filters isolated NaAlO2Solution.
2. the recycling processing method of chromium-contained aluminum mud as claimed in claim 1, it is characterised in that step
In rapid 1, chromium-contained aluminum mud is 1:3～9 with the mass ratio of water.
3. the recycling processing method of chromium-contained aluminum mud as claimed in claim 1, it is characterised in that step
In rapid 1, it is warming up to 60～80 DEG C of stirring and dissolving.
4. the recycling processing method of chromium-contained aluminum mud as claimed in claim 1, it is characterised in that step
In rapid 1, moisture batch adds in chromium-contained aluminum mud.
5. the recycling processing method of chromium-contained aluminum mud as claimed in claim 1, it is characterised in that
In step 2, the electrode of electroreduction uses graphite electrode, Titanium electrode, titanium plating ruthenium or titanium plating iridium electricity
One in extremely；Being separated with ion exchange membrane in electroreduction groove, electric current density is 40～300A/m2。
6. the recycling processing method of chromium-contained aluminum mud as claimed in claim 1, it is characterised in that
In step 3, the condition of bipolar membrane electrodialysis is: mass fraction be 0.1～5% conducting solution be pole
Liquid, reaction temperature 1～40 DEG C, electric current density 200～700A/m2。
7. the recycling processing method of chromium-contained aluminum mud as claimed in claim 1, it is characterised in that step
In rapid 4, Membrane Materials uses hollow-fibre membrane or laminar film, and membrane material is selected politef, gathered partially
At least one in fluorothene, polypropylene, polyethylene.
8. the recycling processing method of chromium-contained aluminum mud as claimed in claim 1, it is characterised in that step
In rapid 4, the membrane porosity that Membrane Materials is used is 60～95%, and aperture is 0.1～1.0 μm, and thickness is
0.04～0.25mm.
9. the recycling processing method of chromium-contained aluminum mud as claimed in claim 1, it is characterised in that step
In rapid 5, it is warming up to 90～110 DEG C, stirring reaction 2～6h.
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Cited By (3)
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| CN113249582A (en) * | 2021-05-06 | 2021-08-13 | 中南大学 | Treatment method of aluminum metallurgy solid waste |
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| CN110255675A (en) * | 2019-07-03 | 2019-09-20 | 福建师范大学泉港石化研究院 | The bipolar membrane electrodialysis process of chromium in a kind of combination oxid-reclamatiom waste water |
| CN110255675B (en) * | 2019-07-03 | 2021-08-10 | 福建师范大学泉港石化研究院 | Bipolar membrane electrodialysis method for recovering chromium in wastewater by combining oxidation |
| CN113249582A (en) * | 2021-05-06 | 2021-08-13 | 中南大学 | Treatment method of aluminum metallurgy solid waste |
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