CN104941572A - Red mud composite material for wastewater treatment as well as preparation method and application of red mud composite material - Google Patents
Red mud composite material for wastewater treatment as well as preparation method and application of red mud composite material Download PDFInfo
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Abstract
The invention discloses a red mud composite material for wastewater treatment as well as a preparation method and application of the red mud composite material. The preparation method comprises the following steps: pre-treatment of red mud, namely crushing and grinding dehydrated red mud and sieving through a 100-300 mesh sieve to obtain red mud powder; thermal activation pre-treatment of the red mud, namely calcining the obtained red mud powder at the temperature of 600-800 DEG C for 30-120 minutes; preparation of a nano iron-based material, namely adding a reductant into an iron salt and carrying out sufficient reaction to obtain the nano iron-based material; preparation of the red mud composite material, namely sufficiently mixing the obtained calcinated red mud powder and the obtained nano iron-based material to obtain the red mud composite material. The red mud composite material for wastewater treatment disclosed by the invention can be used for removing heavy metals in mining wastewater, urban sewage and natural water bodies; the environment problem of the red mud is partly solved; the production and usage costs of environment restoration are lowered; the approach of treating pollution with waste is realized and the red mud composite material has good environmental, economic and social benefits.
Description
Technical field
The present invention relates to technical field of waste water processing, more specifically relate to a kind of red mud composite removing various heavy in waste water and preparation method thereof and application.
Background technology
Heavy metal wastewater thereby source is wide, and the water yield is large, and persistence is seriously polluted.Heavy metal in waste water can in aquatic organism and enrichment in plant tissue, by effects such as the biological accumulations of drinking water and food chain, finally causes serious harm to health.For Xiangjiang River basin, successively there occurs Zhuzhou cadmium pollution event, the arsenic contamination accident of Yue Yangxin wall river, Liuyang cadmium pollution event.
Along with the high speed development of China's aluminum oxide industry, create a large amount of red muds.Red mud pilling, takies a large amount of soil, and the high alkalinity of red mud makes soil alkalize.When red mud dump dam break leakage accident occurs, cause tremendous economic loss to threaten to the life of the people masses simultaneously.Pollutant leakage pollution soil and surface water and underground water in red mud.But containing a large amount of aluminium, iron, silicon isoreactivity metal oxide component in red mud, be prepare the good raw material of heavy metal absorbent, can realize with the approach of useless pollution treatment.
Red mud is widely used in the soil of repairing heavy metal pollution.CN101724404 discloses a kind of modifying agent of the heavy-metal contaminated soil based on red mud and plant and chemistry combined remediation method, and its principle is that red mud can heavy metal in passivation soil.CN102941221 discloses a kind of method hindering plant absorption heavy metal, and wherein the effect of red mud is the pH value of change soil thus affects the occurrence patterns of heavy metal in soil, reduces the content of heavy metal in soil available state.CN102107208 discloses a kind of method of repairing heavy metal polluted soil in mine field, and wherein the interpolation of red mud can reduce its biological effectiveness with the plumbous zinc generation chemical reaction in soil.CN102234167 discloses a kind of solid steady method of phosphorus and heavy metal in sludge of sewage treatment plant, and after red mud calcination activation, the pH value of energy conditioning of mud, generates stable phosphorus and reduce lead in mud, zinc, cadmium exchangeable species content.CN102172106 discloses a kind of method utilizing granulating composite red mud restoration of soil polluted by heavy metal; part hydration process changed red mud material is utilized to carry out chemical modifying modification to heavy metal in soil; use in conjunction with other soil conditioners, biologically effective state content of beary metal can be reduced.
Relevant to red mud and the patent relating to heavy metal containing wastewater treatment has several as follows: CN102603027 discloses a kind of method utilizing changed red mud process Mn-bearing waste water.It utilizes sodium carbonate peroxide to red mud modification, using this changed red mud as sorbent treatment Mn-bearing waste water, can realize the qualified discharge of Mn-bearing waste water.CN101176840 discloses the application process of a kind of iron modified red mud as arsenic adsorbent.With aluminum oxide industry refuse red mud for raw material, adopt modification with Fe red mud as water quality arsenic-removing adsorption agent.But in changed red mud and water, arsenic mass ratio is very large, has limitation in the application.CN101205088 discloses the application process of a kind of seawater flushing red mud as arsenic-removing adsorption agent, and seawater flushing red mud has good adsorption effect to arsenic (V).CN103566959 discloses a kind of preparation of heat treatment red mud catalyst and the application in water technology thereof, and heat treatment can realize the optimum combination of red mud composition, and thermal activation red mud can strengthen the place to go of ozone to nitrobenzene in water.CN102674511 discloses a kind of preparation method of the composite flocculation agent for treatment of dyeing wastewater, and red mud is rich in the multiple decolouring active ingredient such as aluminium, iron after acid dissolve, and red mud is the key component of this efficient and cheap flocculant.CN101898128 discloses a kind of methods for making and using same of aluminum modified red mud defluorinating absorbent.Adopt acid aluminium salt and alkali lye to carry out modification to red mud, then through roasting, grinding, screening can obtain de-fluoridation adsorbent.From interrelated data retrieval, have not yet to see the report that red mud or changed red mud can be used for various heavy wastewater treatment.
Summary of the invention
(1) technical problem that will solve
The technical problem to be solved in the present invention is exactly how to reduce the cost removing various heavy in waste water, obtains the material of various heavy in a kind of removal waste water of high efficiency, low cost, provides preparation method and the application of above-mentioned material simultaneously.
(2) technical scheme
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method removing the red mud composite of various heavy in waste water, the method comprises the following steps:
Step one: the pretreatment of red mud: the red mud after dehydration is broken, grinding, then crosses 100-300 mesh sieve, obtains red mud powder;
Step 2: the thermal activation treatment of red mud: the red mud powder roasting that step one is obtained, sintering temperature 600 ~ 800 DEG C, roasting time 30 ~ 120 minutes;
Step 3: prepare nano-level iron sill: adding pH value regulator control solution ph in molysite aqueous solution is 3-5, and macromolecule dispersing agent is added in molysite aqueous solution, addition is 1-10g/L, under room temperature fully stirs, joins in molysite aqueous solution by borane reducing agent sodium hydride aqueous solution, the mol ratio of molysite and sodium borohydride is 1:2-5, after abundant reaction, use distilled water respectively, acetone washs, select by magnetic method, obtain nano-level iron sill;
Step 4: prepare red mud composite: the nano-level iron sill that the baking red mud powder and the step 3 that step 2 are obtained obtain fully mixes, and to obtain final product.
Preferably, in step one, described red mud (aluminum oxide industry waste residue) is Bayer process red mud, red mud from sintering process, mixed combining method red mud.The specific area of this type of red mud is 15-25m
2/ g, average pore size is 4 nanometers.Wherein, the water content of dehydration red mud is controlled not higher than 4%.
Preferably, described molysite be selected from iron chloride, frerrous chloride, ferrous sulfate, ferric sulfate one or more.
Preferably, described pH value regulator is sulfuric acid; Described macromolecule dispersing agent is polypyrrole alkane ketone.
Adopt above-mentioned molysite and reducing agent, the available nano-level iron sill of the present invention comprise in nano zero valence iron, nanoscale tri-iron tetroxide, nanoscale di-iron trioxide one or more.
The particle diameter of above-mentioned nano-level iron sill is 5-40nm, and wherein, take preferably ferrous sulfate as molysite, sodium borohydride is reducing agent, prepares nano zero valence iron sill, can realize more preferably water treatment effect.
Preparation method of the present invention, the preparation of described nano-level iron sill carries out reduction treatment with reducing agent to molysite to obtain, wherein reducing condition can be determined according to the reaction principle of molysite and reducing agent, and being specially those skilled in the art grasped, and the present invention is not particularly limited this.
Preferably, in step 4, the mass ratio that described baking red mud powder mixes with nano-level iron sill is 1 ~ 10:1, preferred 3:1.Under this amount ratio, the effective removal to various heavy in waste water can be realized.
Preferably, said method comprises the following steps:
Step one: the pretreatment of red mud: the red mud after dehydration is broken, grinding, then crosses 200 mesh sieves, obtains red mud powder;
Step 2: the thermal activation treatment of red mud: the red mud powder roasting that step one is obtained, sintering temperature 750 DEG C, roasting time 80 minutes;
Step 3: prepare nano-level iron sill: adding sulfuric acid control solution ph in ferrous sulfate aqueous solution is 4,10g/L macromolecule dispersing agent polypyrrole alkane ketone is added in ferrous sulfate aqueous solution, under room temperature fully stirs, joined by sodium borohydride aqueous solution in copperas solution, the mol ratio of ferrous sulfate and sodium borohydride is 1:3, fully after reaction, use distilled water respectively, acetone washs, and selects, obtain nanoscale zero-valent iron material by magnetic method;
Step 4: prepare red mud composite: the nano-level iron sill that the baking red mud powder and the step 3 that step 2 are obtained obtain fully mixes, and to obtain final product.
The red mud composite that the present invention protects said method to prepare simultaneously, this red mud composite can be used for removing lead, cadmium, chromium, copper, zinc, the stibium heavy metal in waste water, and removes arsenic, fluorine, the P elements in waste water, and removal effect is remarkable.
Present invention also offers the application in the treatment of waste water of above-mentioned red mud composite.
Preferably, in described wastewater treatment, the pH value range controlling water body is 6-9, and the processing time is 1-3 hour.
Preferably, in described wastewater treatment, the mass ratio of red mud composite and handled waste water is 1:30 ~ 100, preferred 1:30 ~ 80, more preferably 1:50.
(3) beneficial effect
Aluminum oxide industry waste red mud is carried out thermal activation by the present invention, add nano-level iron sill again, obtain red mud composite, with its process containing various heavy waste water, removal efficiency is high, and greatly reduce production and the use cost of sorbing material, there is very high environmental benefit, economic benefit and social benefit.
Detailed description of the invention
Below in conjunction with embodiment, embodiments of the present invention are described in further detail.Following examples for illustration of the present invention, but can not be used for limiting the scope of the invention.
Embodiment 1:
The present embodiment provide firstly a kind of red mud composite, and the preparation method of this red mud composite is as follows:
(1) thermal activation treatment of red mud: by broken for the block materials of dehydration red mud, grinding, sieve through 100 orders, by this material at high temperature roasting, temperature controls at 600 DEG C, and time controling was at 120 minutes.(2) preparation of nano-level iron sill: adding sulfuric acid control solution ph in ferrous sulfate aqueous solution is 4,10g/L macromolecule dispersing agent polypyrrole alkane ketone is added in ferrous sulfate aqueous solution, under room temperature mechanical stirs, sodium borohydride aqueous solution is joined in copperas solution, wherein, the mol ratio of ferrous sulfate and sodium borohydride is 1:3, after abundant reaction, use distilled water respectively, acetone washs, select by magnetic method, obtain nanoscale zero-valent iron material.(3) the red mud powder body material after thermal activation treatment and nano-level iron sill are fully mixed i.e. obtained red mud composite with mass ratio 1:1.
The present embodiment provides the method for carrying out wastewater treatment with above-mentioned red mud composite simultaneously, and concrete treatment step is as follows:
Get the obtained red mud composite of step (3) and pending lead waste water is 1:50 mixing in mass ratio, at room temperature stirring 2 hours, make it staticly settle, its supernatant is processed lead waste water.
Wherein, the related quality criterion of pending lead waste water and processed lead waste water is in table 1.
Embodiment 2:
The present embodiment provide firstly a kind of red mud composite, and the preparation method of this red mud composite is as follows:
(1) thermal activation treatment of red mud: by broken for the block materials of dehydration red mud, grinding, sieve through 150 orders, by this material at high temperature roasting, temperature controls at 650 DEG C, and time controling was at 100 minutes.(2) preparation of nano-level iron sill: adding sulfuric acid control solution ph in ferrous sulfate aqueous solution is 3,5g/L macromolecule dispersing agent polypyrrole alkane ketone is added in ferrous sulfate aqueous solution, under room temperature mechanical stirs, sodium borohydride aqueous solution is joined in copperas solution, wherein, the mol ratio of ferrous sulfate and sodium borohydride is 1:2, after abundant reaction, use distilled water respectively, acetone washs, select by magnetic method, obtain nanoscale zero-valent iron material; (3) the red mud powder body material after thermal activation treatment and nano-level iron sill are fully mixed i.e. obtained red mud composite with mass ratio 4:1.
The present embodiment provides the method for carrying out wastewater treatment with above-mentioned red mud composite simultaneously, and concrete treatment step is as follows:
Get the obtained red mud composite of step (3) and pending cadmium wastewater is 1:40 mixing in mass ratio, at room temperature stirring 1.5 hours, make it staticly settle, its supernatant is processed cadmium wastewater.
Wherein, the related quality criterion of pending cadmium wastewater and processed cadmium wastewater is in table 1.
Embodiment 3:
The present embodiment provide firstly a kind of red mud composite, and the preparation method of this red mud composite is as follows:
(1) thermal activation treatment of red mud: by broken for the block materials of dehydration red mud, grinding, sieve through 200 orders, by this material at high temperature roasting, temperature controls at 700 DEG C, and time controling was at 90 minutes.(2) preparation of nano-level iron sill: adding sulfuric acid control solution ph in ferrous sulfate aqueous solution is 5,8g/L macromolecule dispersing agent polypyrrole alkane ketone is added in ferrous sulfate aqueous solution, under room temperature mechanical stirs, sodium borohydride aqueous solution is joined in copperas solution, wherein, the mol ratio of ferrous sulfate and sodium borohydride is 1:4, after abundant reaction, use distilled water respectively, acetone washs, select by magnetic method, obtain nanoscale zero-valent iron material.(3) the red mud powder body material after thermal activation treatment and nano-level iron sill are fully mixed i.e. obtained red mud composite with mass ratio 2:1.
The present embodiment provides the method for carrying out wastewater treatment with above-mentioned red mud composite simultaneously, and concrete treatment step is as follows:
Get the obtained red mud composite of step (3) and pending chromate waste water is 1:30 mixing in mass ratio, at room temperature stirring 1 hour, make it staticly settle, its supernatant is processed chromate waste water.
Wherein, the related quality criterion of pending chromate waste water and processed chromate waste water is in table 1.
Embodiment 4:
The present embodiment provide firstly a kind of red mud composite, and the preparation method of this red mud composite is as follows:
(1) thermal activation treatment of red mud: by broken for the block materials of dehydration red mud, grinding, sieve through 250 orders, by this material at high temperature roasting, temperature controls at 750 DEG C, and time controling was at 80 minutes.(2) preparation of nano-level iron sill: adding sulfuric acid control solution ph in ferrous sulfate aqueous solution is 4,9g/L macromolecule dispersing agent polypyrrole alkane ketone is added in ferrous sulfate aqueous solution, under room temperature mechanical stirs, sodium borohydride aqueous solution is joined in copperas solution, wherein, the mol ratio of ferrous sulfate and sodium borohydride is 1:5, after abundant reaction, use distilled water respectively, acetone washs, select by magnetic method, obtain nanoscale zero-valent iron material; (3) the red mud powder body material after thermal activation treatment and nano-level iron sill are fully mixed i.e. obtained red mud composite with mass ratio 1:1.
The present embodiment provides the method for carrying out wastewater treatment with above-mentioned red mud composite simultaneously, and concrete treatment step is as follows:
Get the obtained red mud composite of step (3) and pending copper-containing wastewater is 1:60 mixing in mass ratio, at room temperature stirring 2.3 hours, make it staticly settle, its supernatant is processed copper-containing wastewater.
Wherein, the related quality criterion of pending copper-containing wastewater and processed copper-containing wastewater is in table 1.
Embodiment 5:
The present embodiment provide firstly a kind of red mud composite, and the preparation method of this red mud composite is as follows:
(1) thermal activation treatment of red mud: by broken for the block materials of dehydration red mud, grinding, sieve through 280 orders, by this material at high temperature roasting, temperature controls at 780 DEG C, and time controling was at 60 minutes.(2) preparation of nano-level iron sill: adding sulfuric acid control solution ph in ferrous sulfate aqueous solution is 3,2g/L macromolecule dispersing agent polypyrrole alkane ketone is added in ferrous sulfate aqueous solution, under room temperature mechanical stirs, sodium borohydride aqueous solution is joined in copperas solution, wherein, the mol ratio of ferrous sulfate and sodium borohydride is 1:3, after abundant reaction, use distilled water respectively, acetone washs, select by magnetic method, obtain nanoscale zero-valent iron material; (3) the red mud powder body material after thermal activation treatment and nano-level iron sill are fully mixed i.e. obtained red mud composite with mass ratio 2:1.
The present embodiment provides the method for carrying out wastewater treatment with above-mentioned red mud composite simultaneously, and concrete treatment step is as follows:
Get the obtained red mud composite of step (3) and pending zinc-containing water is 1:70 mixing in mass ratio, at room temperature stirring 2.5 hours, make it staticly settle, its supernatant is processed zinc-containing water.
Wherein, the related quality criterion of pending zinc-containing water and processed zinc-containing water is in table 1.
Embodiment 6:
The present embodiment provide firstly a kind of red mud composite, and the preparation method of this red mud composite is as follows:
(1) thermal activation treatment of red mud: by broken for the block materials of dehydration red mud, grinding, sieve through 300 orders, by this material at high temperature roasting, temperature controls at 800 DEG C, and time controling was at 30 minutes.(2) preparation of nano-level iron sill: adding sulfuric acid control solution ph in ferrous sulfate aqueous solution is 4,6g/L macromolecule dispersing agent polypyrrole alkane ketone is added in ferrous sulfate aqueous solution, under room temperature mechanical stirs, sodium borohydride aqueous solution is joined in copperas solution, wherein, the mol ratio of ferrous sulfate and sodium borohydride is 1:4, after abundant reaction, use distilled water respectively, acetone washs, select by magnetic method, obtain nanoscale zero-valent iron material.(3) the red mud powder body material after thermal activation treatment and nano-level iron sill are fully mixed i.e. obtained red mud composite with mass ratio 3:1.
The present embodiment provides the method for carrying out wastewater treatment with above-mentioned red mud composite simultaneously, and concrete treatment step is as follows:
Get the obtained red mud composite of step (3) and pending leaded antimony waste water is 1:80 mixing in mass ratio, at room temperature stirring 3 hours, make it staticly settle, its supernatant is processed stibium-containing wastewater.
Wherein, the related quality criterion of pending stibium-containing wastewater and processed stibium-containing wastewater is in table 1.
Experimental result: each pending heavy metal-containing waste water is as shown in table 1 below with the heavy metal wastewater thereby heavy metal concentration processed: each embodiment adopts five Duplicate Samples, averages after removing the highest and minimum.
Table 1
| Embodiment | Waste water title | Pending waste strength | Processed waste strength | Removal efficiency |
| Embodiment 1 | Containing Pb 2+Waste water | 20mg/L | 0.55mg/L | 97.25％ |
| Embodiment 2 | Containing Cd 2+Waste water | 20mg/L | 0.11mg/L | 99.45％ |
| Embodiment 3 | Containing Cr 6+Waste water | 20mg/L | 0.10mg/L | 99.50％ |
| Embodiment 4 | Containing Cu 2+Waste water | 20mg/L | 0.19mg/L | 99.05％ |
| Embodiment 5 | Containing Zn 2+Waste water | 20mg/L | 0.11mg/L | 99.45％ |
| Embodiment 6 | Containing Sb 5+Waste water | 20mg/L | 2.30mg/L | 88.50％ |
As can be seen from above experimental result, the red mud composite that the present invention removes various heavy in waste water can remove various heavy in waste water, and removal efficiency is high, can reach more than 88%.
Above embodiment is only for illustration of the present invention, but not limitation of the present invention.Although with reference to embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, various combination, amendment or equivalent replacement are carried out to technical scheme of the present invention, do not depart from the spirit and scope of technical solution of the present invention, all should be encompassed in the middle of right of the present invention.
Claims (10)
1., for a preparation method for the red mud composite of wastewater treatment, it is characterized in that, the method comprises the following steps:
Step one: the pretreatment of red mud: the red mud after dehydration is broken, grinding, then crosses 100-300 mesh sieve, obtains red mud powder;
Step 2: the thermal activation treatment of red mud: the red mud powder roasting that step one is obtained, sintering temperature 600 ~ 800 DEG C, roasting time 30 ~ 120 minutes;
Step 3: prepare nano-level iron sill: adding pH value regulator control solution ph in molysite aqueous solution is 3-5, and macromolecule dispersing agent is added in molysite aqueous solution, addition is 1-10g/L, under room temperature fully stirs, joins in molysite aqueous solution by borane reducing agent sodium hydride aqueous solution, the mol ratio of molysite and sodium borohydride is 1:2-5, after abundant reaction, use distilled water respectively, acetone washs, select by magnetic method, obtain nano-level iron sill;
Step 4: prepare red mud composite: the nano-level iron sill that the baking red mud powder and the step 3 that step 2 are obtained obtain fully mixes, and to obtain final product.
2. the preparation method of the red mud composite for wastewater treatment according to claim 1, is characterized in that, in step one, described red mud is Bayer process red mud, red mud from sintering process, mixed combining method red mud.
3. the preparation method of the red mud composite for wastewater treatment according to claim 1, is characterized in that, described molysite be selected from iron chloride, frerrous chloride, ferrous sulfate, ferric sulfate one or more.
4. the preparation method of the red mud composite for wastewater treatment according to claim 1, is characterized in that, described pH value regulator is sulfuric acid; Described macromolecule dispersing agent is polypyrrole alkane ketone.
5. the preparation method of the red mud composite for wastewater treatment according to claim 1, is characterized in that, in step 4, the mass ratio that described baking red mud powder mixes with nano-level iron sill is 1 ~ 10:1.
6. the preparation method of the red mud composite for wastewater treatment according to claim 1, it is characterized in that, the method comprises the following steps:
Step one: the pretreatment of red mud: the red mud after dehydration is broken, grinding, then crosses 200 mesh sieves, obtains red mud powder;
Step 2: the thermal activation treatment of red mud: the red mud powder roasting that step one is obtained, sintering temperature 750 DEG C, roasting time 80 minutes;
Step 3: prepare nano-level iron sill: adding sulfuric acid control solution ph in ferrous sulfate aqueous solution is 4,10g/L macromolecule dispersing agent polypyrrole alkane ketone is added in ferrous sulfate aqueous solution, under room temperature fully stirs, joined by sodium borohydride aqueous solution in copperas solution, the mol ratio of ferrous sulfate and sodium borohydride is 1:3, fully after reaction, use distilled water respectively, acetone washs, and selects, obtain nanoscale zero-valent iron material by magnetic method;
Step 4: prepare red mud composite: the nano-level iron sill that the baking red mud powder and the step 3 that step 2 are obtained obtain fully mixes, and to obtain final product.
7. the red mud composite for wastewater treatment prepared by the preparation method described in any one of claim 1-6.
8. red mud composite according to claim 7 application in the treatment of waste water.
9. red mud composite according to claim 8 application in the treatment of waste water, is characterized in that, in described wastewater treatment, the pH value range controlling water body is 6-9, and the processing time is 1-3 hour.
10. red mud composite application in the treatment of waste water according to claim 8 or claim 9, it is characterized in that, in described wastewater treatment, the mass ratio of red mud composite and handled waste water is 1:30 ~ 100.
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| CN105289487A (en) * | 2015-10-19 | 2016-02-03 | 丁玉琴 | Method for preparing red-mud-based heavy metal ion adsorbing material |
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| CN109107524B (en) * | 2018-09-28 | 2020-05-08 | 同济大学 | Red mud adsorbent and preparation method and application thereof |
| CN110040832A (en) * | 2019-06-03 | 2019-07-23 | 滨州大宗固废资源循环利用研究院有限公司 | A kind of preparation method of the polymerization aluminium silicate-sulphate ferric flocculant based on red mud |
| CN111570491A (en) * | 2020-05-14 | 2020-08-25 | 生态环境部环境规划院 | Preparation method of modified red mud composite polymer gel Cr (VI) removing filler |
| CN111872104A (en) * | 2020-07-27 | 2020-11-03 | 中国科学院重庆绿色智能技术研究院 | Method for repairing organic pollutant-heavy metal combined polluted soil by red mud |
| CN114345354A (en) * | 2022-01-05 | 2022-04-15 | 广西宏业环保节能工程有限公司 | Process for preparing reinforced neutral spherical ozone catalyst from red mud |
| CN114477382A (en) * | 2022-01-13 | 2022-05-13 | 安庆师范大学 | Preparation method and application of composite adsorption-catalysis material |
| CN114405554A (en) * | 2022-01-14 | 2022-04-29 | 广西宏业环保节能工程有限公司 | Process for preparing neutral spherical ozone catalyst from red mud |
| CN114377681A (en) * | 2022-01-21 | 2022-04-22 | 广西宏业环保节能工程有限公司 | Process for preparing spherical ozone catalyst by high-temperature modified red mud |
| CN116196884A (en) * | 2023-03-27 | 2023-06-02 | 昆明理工大学 | Manganese activated red mud catalytic oxidation adsorption material and preparation method and application thereof |
| CN116196884B (en) * | 2023-03-27 | 2024-05-24 | 昆明理工大学 | Manganese activated red mud catalytic oxidation adsorption material and preparation method and application thereof |
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