CN106756046A - A kind of handling process of red mud and titanium white waste liquid - Google Patents
A kind of handling process of red mud and titanium white waste liquid Download PDFInfo
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- CN106756046A CN106756046A CN201611196009.XA CN201611196009A CN106756046A CN 106756046 A CN106756046 A CN 106756046A CN 201611196009 A CN201611196009 A CN 201611196009A CN 106756046 A CN106756046 A CN 106756046A
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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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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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
- C22B59/00—Obtaining rare earth metals
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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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Abstract
The invention discloses a kind of red mud and the handling process of titanium white waste liquid.Titanium white waste liquid and red mud are first carried out mixing leaching by the technique, and qualified tailings and treatment fluid are obtained after filtering, and the scandium and vanadium in red mud are dissolved into treatment fluid.Treatment fluid carries out secondary absorption operation again, obtain qualified tail washings and saturation resin anion (R.A.) and unsaturated cationic resin, saturation resin anion (R.A.) obtains vanadic anhydride product of the purity more than 99.5% after sodium hydroxide solution desorption, ammonium salt precipitation and calcining, and unsaturated cationic resin obtains the scandium oxide product that purity is more than 99.6% after hydrochloric acid solution desorption, oxalic acid precipitation and calcining.Sodium oxide content is less than 0.5% in qualified tailings；Scandium content is less than 0.1ppm in qualified tail washings, and content of vanadium is less than 0.5ppm.The features such as present invention has that reagent consumption is low, red mud dealkalization rate is high, flow is simple, the rate of recovery of rare precious metal is high in two kinds of discarded objects, realizes waste recycling and non-waste-emission.
Description
Technical field
The present invention relates to red mud comprehensive treatment technique field, and in particular to the handling process of a kind of red mud and titanium white waste liquid.
Background technology
Red mud is the tailings that Bayer process aluminium metallurgy process is produced, and is a kind of strong basicity solid pollutant, and its process of storing up can be made
Into body of groundwater and soil pollution, the alkali content high in red mud is also that restriction red mud extracts valuable rare precious metal, prepares Building wood
The key factor of material and environment adsorbing materials.At present, acidleach operation, the acid that this process needs are used red mud extraction rare precious metal more
Concentration is high, reagent consumption is big, and the pickle liquor pH of generation is low could to be reclaimed, it is necessary to extract operation, and flow is complicated, while leached mud is in
Acidity, is more difficult by that (Li Wang, Zhu Xiao ripple Leaching Metals from Red mud carry scandium experimental study [J] non-ferrous metals（Smelting Part）,
2016, (5):36-38；Agatzini, L.S., Oustadakis, P., Tsakiridis, P.E., et al.
Titanium leaching from red mud by diluted sulfuric acid at atmospheric
pressure [J]. Journal of Hazardous Materials, 2008, 157: 579-586；Zhu Xiaobo, Lee
Hope, Guan Xuemao Leaching Metals from Red mud vanadium extraction [J] process engineering journals, 2014,14 (5): 792-796.).
Titanium white waste liquid is the waste liquid that ilmenite is produced during hydrolysis prepares titanium dioxide, is a kind of acidic liquid pollution
Thing, it is not comprehended and causes serious soil and water pollution in place, also dilute expensive containing a certain amount of scandium, vanadium etc. in titanium white waste liquid in addition
Metal.At present, the treatment on titanium white waste liquid is mainly using lime neutralization, produces neutral waste liquid and gypsum, serious waste medicine
Agent, also result in the loss (resource and extractive technique [J] of Zhang Zhongbao, Zhang Zonghua scandiums of rare precious metal in titanium white waste liquid
Yunnan metallurgy, 2006,35（5）: 23-25；Long Zhiqi, Yu Yaolun, Huang little Wei, wait a kind of from sulfate process titanium dioxide waste liquid
Middle enrichment rare earth rare element and the method patents of invention for preparing white gypsum, the A of CN 103572058).
In recent years, also there is the correlative study for red mud and titanium white waste liquid being mixed and extracting scandium and other valuable metals, but in research
During have that liquid-solid ratio is high, extraction temperature is high, scandium leaching rate is relatively low, follow-up rare precious metal concentration and separation reclaims use more
The problems such as multitple extraction and the technique of back extraction, flow are complicated, reagent consumption amount is big, it is most important that mix extraction at both valuable
Substantial amounts of acid waste liquid and acid waste residue are generated again in metal process, the waste residue is more difficult to treatment and comprehensive profit than red mud
With being not carried out non-waste-emission requirement (Tao Yang, Wang Zhijian, the Xiao Jing, in waiting red muds and titanium white waste liquid of " waste recycling "
Put forward extract technology research [J] mining and metallurgys of scandium, 2015,24（5）: 37-40；Liu Jibo, Tao Yang, Wu Xitao waits comprehensive
Close the method patents of invention of recycling waste red mud residues and titanium white waste liquid, the A of CN 103614563).
The content of the invention
The purpose of the present invention is just being directed to the weak point in the presence of above-mentioned prior art and is providing a kind of red mud and titanium
The handling process of white waste liquid, the technique has that reagent consumption is low, red mud dealkalization rate is high, flow simple, dilute expensive in two kinds of discarded objects
The features such as rate of recovery of metal is high, realizes waste recycling and non-waste-emission.
The purpose of the present invention can be realized by following technique measures：
The handling process of red mud of the invention and titanium white waste liquid is that qualified tailings, qualified tail washings and your gold obtained using waste recycling
Category byproduct, comprises the following steps that：
A, mixing are leached
By titanium white waste liquid and red mud according to the solid mass ratio 1 ~ 2.5 of liquid:1 mix, temperature be 20 ~ 50 DEG C under conditions of stirring 240 ~
360min, stirring intensity is 400 ~ 700r/min；Stirring carries out filtering to mixed ore pulp and obtains treatment fluid and qualified tail after terminating
Slag, the dealkalize rate of red mud is more than 98%, and V leaching rate is more than 70%, and scandium leaching rate is more than 80%；The direct heap of the qualified qualified tailings of tailings
Deposit and build a dam, or conduct prepares the industry such as construction material, roadbed material, environment adsorbing materials, catalysis material and soil conditioner
Raw material；
B, secondary absorption
Step a gained treatment fluids are carried out into secondary absorption operation, its process is that treatment fluid first is carried out into resin anion (R.A.) absorption, is inhaled
Resin cation absorption is carried out after attached tail washings again and obtains qualified tail washings, saturation resin anion (R.A.) and unsaturated cationic resin, wherein
Resin anion (R.A.) absorption uses macroporous type resin anion (R.A.), and absorption parameter is the mL/s of flow rate of liquid 0.2 ~ 1.6, the solid volume ratio of liquid
It is 200 ~ 500：1；Cation adsorption uses sequestering resin cation, and absorption parameter is the mL/s of flow rate of liquid 0.1 ~ 0.8, liquid
Gu volume ratio is 50 ~ 200：1；
C, segmentation desorption
Resin anion (R.A.) to step b gained adsorption saturations carries out desorption operation, and strippant is the hydrogen that mass percent is 1% ~ 4%
Sodium hydroxide solution, desorption parameter is the mL/min of flow rate of liquid 1.4 ~ 3.2, and the solid volume ratio of liquid is 2 ~ 5：1, what is obtained desorbs containing vanadium
Liquid is vanadic anhydride product of the purity more than 99.5% after ammonium salt precipitation calcining；The resin cation of adsorption saturation is solved
Operation is inhaled, strippant is the hydrochloric acid solution that mass percent is 1% ~ 4%, and desorption parameter is the mL/min of flow rate of liquid 0.8 ~ 2.4,
The solid volume ratio of liquid is 1 ~ 3：1, the stripping liquid containing scandium for obtaining is scandium oxide of the purity more than 99.6% after oxalic acid precipitation calcining
Product.
The red mud of the present invention is Bayer process red mud, and sodium oxide content is more than 6% in red mud, and content of vanadium is more than 0.1%,
Scandium content is more than 0.01%.
Titanium white waste liquid pH value of the present invention is less than 0.5, and scandium content is more than 10ppm, and content of vanadium is more than 50ppm.
The qualified tailings pH value that the present invention is obtained is 6.5 ~ 7.5, and sodium oxide content is less than 0.5%.
The qualified tail washings pH value that the present invention is obtained is 6.8 ~ 7.8, and scandium content is less than 0.1ppm, and content of vanadium is less than 0.5ppm.
More specifically：Bayer process red mud is the tailings that bauxite is obtained in strong base solution after high-temperature fusion, therein
The rare precious metals such as alkali, scandium and vanadium are more in being present in alumino-silicate in the form of wrapping up, it is more difficult to extract, need to take acidleach method ability
Effectively reclaim, but causing pickle liquor in concentrated sulfuric acid removal process needs multitple extraction-back extraction could to reclaim rare precious metal, and meeting
Acid waste residue is produced, is more difficult to process and comprehensively utilize；Titanium white waste liquid is after titaniferous strong acid solution prepares titanium dioxide through hydrolysis
The acid waste water of generation, wherein also containing rare precious metals such as vanadium and scandiums, according to after, rare precious metal can cause to damage in lime
Lose, reagent consumption amount is also high.The present invention carries out mixing leaching using red mud and titanium white waste liquid according to rational technological parameter, leaches
Liquid and leached mud control, in neutrality, to significantly reduce the reagent consumption during both distinguish processing procedure, while the leaching for producing
Slag is qualified tailings, and alkali content is less than 0.5%, meets as preparing construction material, roadbed material and environment adsorbing materials etc.
The requirement of the raw material of industry.The concentration of vanadium and scandium is increased in the neutral leachate of generation, and the element such as iron and titanium is precipitated
Into qualified tailings, therefore, can carry out being separately recovered vanadium and scandium using ion exchange resin, resin is after desorption, precipitation, calcining
The vanadic anhydride and scandium oxide product of high-purity can be obtained, adsorption tail liquid also in neutrality, without pollution, can be returned directly
Receive and utilize.
Beneficial effects of the present invention are as follows：
Due to the present invention Bayer process red mud and titanium white waste liquid are mixed using the thinking of waste recycling, non-waste-emission leach dealkalize and
Rare precious metal is extracted, the dealkalize rate of red mud can be made more than 95%, V leaching rate is more than 70%, and scandium leaching rate is more than 80%, and leached mud is
It is qualified tailings, in neutrality, sodium oxide content is less than 5%, can be inhaled directly as construction material, roadbed material and environment is prepared
The raw material of industry of enclosure material etc..Leachate is also enriched with neutrality, and rare precious metal scandium and vanadium, and titanium, iron, aluminium etc. are deposited in
In qualified tailings, be conducive to the separating-purifying of rare precious metal, therefore can be using the two sections of suctions of resin anion (R.A.) and resin cation
Attached separation and Extraction vanadium therein and scandium, can respectively obtain five oxidations of the purity more than 99.5% after desorption, precipitation, calcine technology
The scandium oxide product of two vanadium products and purity more than 99.6%, technological process is simple, does not have reagent consumption, while produce
Adsorption tail liquid also in neutrality, without pollution, can be recycled directly.
Therefore, the present invention have that reagent consumption is low, red mud dealkalization rate is high, flow is simple, rare precious metal in two kinds of discarded objects
The rate of recovery it is high the features such as, realize waste recycling and non-waste-emission.
Brief description of the drawings
Fig. 1 is process chart of the invention.
Specific embodiment
The present invention is below with reference to embodiment（Accompanying drawing）It is further described：
It is now that the technical parameter Unify legislation involved by the specific embodiment of the invention is as follows to avoid repeated description：It is described red
Mud is Bayer process red mud, and sodium oxide content is more than 6% in red mud, and content of vanadium is more than 0.1%, and scandium content is more than 0.01%；The titanium white
Waste liquid pH value is less than 0.5, and scandium content is more than 10ppm, and content of vanadium is more than 50ppm, is repeated no more in specific embodiment.
Embodiment 1
By titanium white waste liquid and red mud according to the solid mass ratio 1 ~ 1.5 of liquid:1 mixes, and it is that temperature is 20 ~ 30 DEG C, stirs to leach dissolution process
Mix the time for 240 ~ 280min, stirring intensity be 600 ~ 700r/min, stirring terminate rear mixed ore pulp carry out filtering processed
Liquid and qualified tailings, the dealkalize rate of red mud are more than 98%, and V leaching rate is more than 70%, and scandium leaching rate is more than 80%；Treatment fluid is carried out
Secondary absorption operation, its process is that treatment fluid first is carried out into resin anion (R.A.) absorption, and adsorption tail liquid carries out resin cation suction again
Attached to obtain qualified tail washings, saturation resin anion (R.A.) and unsaturated cationic resin, wherein resin anion (R.A.) absorption is cloudy using macroporous type
Ion exchange resin, absorption parameter is the mL/s of flow rate of liquid 1.0 ~ 1.6, and the solid volume ratio of liquid is 400 ~ 500：1；Cation adsorption is used
Sequestering resin cation, absorption parameter is the mL/s of flow rate of liquid 0.1 ~ 0.3, and the solid volume ratio of liquid is 50 ~ 100：1；Adsorption saturation
Resin anion (R.A.) carry out desorption operation, strippant be mass percent for 1% ~ 4% sodium hydroxide solution, desorption parameter is liquid
The mL/min of rate of flow of fluid 2.6 ~ 3.2, the solid volume ratio of liquid is 2 ~ 3：1, the stripping liquid containing vanadium for obtaining is purity after ammonium salt precipitation calcining
Vanadic anhydride product more than 99.5%；The resin cation of adsorption saturation carries out desorption operation, and strippant is mass percent
It is 1% ~ 4% hydrochloric acid solution, desorption parameter is the mL/min of flow rate of liquid 1.8 ~ 2.4, and the solid volume ratio of liquid is 1 ~ 3：1, what is obtained contains
Scandium stripping liquid is scandium oxide product of the purity more than 99.6% after being calcined through oxalic acid precipitation.The qualified tailings pH value for obtaining is
7.2 ~ 7.5, sodium oxide content be less than 0.5%, qualified tailings is directly stored up and is built a dam, or conduct prepare construction material, roadbed material,
The raw materials of industry such as environment adsorbing materials, catalysis material and soil conditioner；The qualified tail washings pH value for obtaining is 7.5 ~ 7.8, scandium
Content is less than 0.1ppm, and content of vanadium is less than 0.5ppm, can directly discharge and utilize.
Embodiment 2
By titanium white waste liquid and red mud according to the solid mass ratio 1.5 ~ 2 of liquid:1 mixes, and it is that temperature is 30 ~ 40 DEG C, stirs to leach dissolution process
Mix the time for 280 ~ 320min, stirring intensity be 500 ~ 600r/min, stirring terminate rear mixed ore pulp carry out filtering processed
Liquid and qualified tailings, the dealkalize rate of red mud are more than 98.5%, and V leaching rate is more than 72%, and scandium leaching rate is more than 83%；Treatment fluid is entered
Row secondary absorption operation, its process is that treatment fluid first is carried out into resin anion (R.A.) absorption, and adsorption tail liquid carries out resin cation again
Absorption obtains qualified tail washings, saturation resin anion (R.A.) and unsaturated cationic resin, and wherein resin anion (R.A.) absorption uses macroporous type
Resin anion (R.A.), absorption parameter is the mL/s of flow rate of liquid 0.6 ~ 1.0, and the solid volume ratio of liquid is 300 ~ 400：1；Cation adsorption is adopted
Sequestering resin cation is used, absorption parameter is the mL/s of flow rate of liquid 0.3 ~ 0.5, and the solid volume ratio of liquid is 100 ~ 150：1；Absorption
The resin anion (R.A.) of saturation carries out desorption operation, and strippant is that mass percent is 1% ~ 4% sodium hydroxide solution, desorbs parameter
It is the mL/min of flow rate of liquid 2.0 ~ 2.6, the solid volume ratio of liquid is 3 ~ 4：1, the stripping liquid containing vanadium for obtaining is precipitated after calcining through ammonium salt is
Vanadic anhydride product of the purity more than 99.6%；The resin cation of adsorption saturation carries out desorption operation, and strippant is quality hundred
Divide than the hydrochloric acid solution for 1% ~ 4%, desorption parameter is the mL/min of flow rate of liquid 1.2 ~ 1.8, and the solid volume ratio of liquid is 1 ~ 3：1, obtain
Stripping liquid containing scandium calcined through oxalic acid precipitation after be purity more than 99.7% scandium oxide product.The qualified tailings pH for obtaining
It is 6.8 ~ 7.2 to be worth, and sodium oxide content is less than 0.4%, and qualified tailings is directly stored up and built a dam, or conduct prepares construction material, roadbed material
The raw materials of industry such as material, environment adsorbing materials, catalysis material and soil conditioner；The qualified tail washings pH value for obtaining is 7.0 ~ 7.5,
Scandium content is less than 0.08ppm, and content of vanadium is less than 0.3ppm, can directly discharge and utilize.
Embodiment 3
By titanium white waste liquid and red mud according to the solid mass ratio 2 ~ 2.5 of liquid:1 mixes, and it is that temperature is 40 ~ 50 DEG C, stirs to leach dissolution process
Mix the time for 320 ~ 360min, stirring intensity be 400 ~ 500r/min, stirring terminate rear mixed ore pulp carry out filtering processed
Liquid and qualified tailings, the dealkalize rate of red mud are more than 99%, and V leaching rate is more than 75%, and scandium leaching rate is more than 85%；Treatment fluid is carried out
Secondary absorption operation, its process is that treatment fluid first is carried out into resin anion (R.A.) absorption, and adsorption tail liquid carries out resin cation suction again
Attached to obtain qualified tail washings, saturation resin anion (R.A.) and unsaturated cationic resin, wherein resin anion (R.A.) absorption is cloudy using macroporous type
Ion exchange resin, absorption parameter is the mL/s of flow rate of liquid 0.2 ~ 0.6, and the solid volume ratio of liquid is 200 ~ 300：1；Cation adsorption is used
Sequestering resin cation, absorption parameter is the mL/s of flow rate of liquid 0.5 ~ 0.8, and the solid volume ratio of liquid is 150 ~ 200：1；Absorption is full
The resin anion (R.A.) of sum carries out desorption operation, and strippant is the sodium hydroxide solution that mass percent is 1% ~ 4%, and desorption parameter is
The mL/min of flow rate of liquid 1.4 ~ 2.0, the solid volume ratio of liquid is 4 ~ 5：1, the stripping liquid containing vanadium for obtaining is pure after ammonium salt precipitation calcining
Vanadic anhydride product of the degree more than 99.6%；The resin cation of adsorption saturation carries out desorption operation, and strippant is quality percentage
Than the hydrochloric acid solution for 1% ~ 4%, desorption parameter is the mL/min of flow rate of liquid 0.8 ~ 1.2, and the solid volume ratio of liquid is 1 ~ 3：1, obtain
Stripping liquid containing scandium is scandium oxide product of the purity more than 99.7% after being calcined through oxalic acid precipitation.The qualified tailings pH value for obtaining
It is 6.5 ~ 6.8, sodium oxide content is less than 0.3%, and qualified tailings is directly stored up and built a dam, or conduct prepares construction material, roadbed material
The raw materials of industry such as material, environment adsorbing materials, catalysis material and soil conditioner；The qualified tail washings pH value for obtaining is 6.8 ~ 7.0,
Scandium content is less than 0.05ppm, and content of vanadium is less than 0.1ppm, can directly discharge and utilize.
Claims (5)
1. the handling process of a kind of red mud and titanium white waste liquid, it is characterised in that：The technique is to obtain qualified using waste recycling
Tailings, qualified tail washings and noble metal byproduct, comprise the following steps that：
A, mixing are leached
By titanium white waste liquid and red mud according to the solid mass ratio 1 ~ 2.5 of liquid:1 mix, temperature be 20 ~ 50 DEG C under conditions of stirring 240 ~
360min, stirring intensity is 400 ~ 700r/min；Stirring carries out filtering to mixed ore pulp and obtains treatment fluid and qualified tail after terminating
Slag, the dealkalize rate of red mud is more than 98%, and V leaching rate is more than 70%, and scandium leaching rate is more than 80%；The direct heap of the qualified qualified tailings of tailings
Deposit and build a dam, or conduct prepares the industry such as construction material, roadbed material, environment adsorbing materials, catalysis material and soil conditioner
Raw material；
B, secondary absorption
Step a gained treatment fluids are carried out into secondary absorption operation, its process is that treatment fluid first is carried out into resin anion (R.A.) absorption, is inhaled
Resin cation absorption is carried out after attached tail washings again and obtains qualified tail washings, saturation resin anion (R.A.) and unsaturated cationic resin, wherein
Resin anion (R.A.) absorption uses macroporous type resin anion (R.A.), and absorption parameter is the mL/s of flow rate of liquid 0.2 ~ 1.6, the solid volume ratio of liquid
It is 200 ~ 500：1；Cation adsorption uses sequestering resin cation, and absorption parameter is the mL/s of flow rate of liquid 0.1 ~ 0.8, liquid
Gu volume ratio is 50 ~ 200：1；
C, segmentation desorption
Resin anion (R.A.) to step b gained adsorption saturations carries out desorption operation, and strippant is the hydrogen that mass percent is 1% ~ 4%
Sodium hydroxide solution, desorption parameter is the mL/min of flow rate of liquid 1.4 ~ 3.2, and the solid volume ratio of liquid is 2 ~ 5：1, what is obtained desorbs containing vanadium
Liquid is vanadic anhydride product of the purity more than 99.5% after ammonium salt precipitation calcining；The resin cation of adsorption saturation is solved
Operation is inhaled, strippant is the hydrochloric acid solution that mass percent is 1% ~ 4%, and desorption parameter is the mL/min of flow rate of liquid 0.8 ~ 2.4,
The solid volume ratio of liquid is 1 ~ 3：1, the stripping liquid containing scandium for obtaining is scandium oxide of the purity more than 99.6% after oxalic acid precipitation calcining
Product.
2. the handling process of red mud according to claim 1 and titanium white waste liquid, it is characterised in that：The red mud is Bayer process
Red mud, sodium oxide content is more than 6% in red mud, and content of vanadium is more than 0.1%, and scandium content is more than 0.01%.
3. the handling process of red mud according to claim 1 and titanium white waste liquid, it is characterised in that：The titanium white waste liquid pH value
Less than 0.5, scandium content is more than 10ppm, and content of vanadium is more than 50ppm.
4. the handling process of red mud according to claim 1 and titanium white waste liquid, it is characterised in that：The qualified tailings pH value
It is 6.5 ~ 7.5, sodium oxide content is less than 0.5%.
5. the handling process of red mud according to claim 1 and titanium white waste liquid, it is characterised in that：The pH of the qualified tail washings
It is 6.8 ~ 7.8 to be worth, and scandium content is less than 0.1ppm, and content of vanadium is less than 0.5ppm.
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| CN108675762A (en) * | 2018-05-18 | 2018-10-19 | 朱文杰 | A kind of preparation method of red mud permeable brick |
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