CN102502944A - Zone heterogeneous catalytic oxidation technology for removing pollutants by red-mud catalyst - Google Patents
Zone heterogeneous catalytic oxidation technology for removing pollutants by red-mud catalyst Download PDFInfo
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- CN102502944A CN102502944A CN2011103698878A CN201110369887A CN102502944A CN 102502944 A CN102502944 A CN 102502944A CN 2011103698878 A CN2011103698878 A CN 2011103698878A CN 201110369887 A CN201110369887 A CN 201110369887A CN 102502944 A CN102502944 A CN 102502944A
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Abstract
The invention aims to provide a novel ozone heterogeneous catalysis water advanced treatment technology and a preparation method of a catalyst. The catalyst can remarkably enhance the adsorption of ozone and organic pollutants on the surface of the catalyst to achieve the adsorption effect and the oxidative degradation coupling effect and finally achieve the enhanced removal of difficultly degraded organic pollutants. Compared with the ozone heterogeneous catalysis water treatment technology, the invention can remarkably improve the pollutant removal effect of the heterogeneous catalysis water treatment technology, and greatly reduces the raw material cost and the preparation cost of the catalyst at the same time; waste residue-red mud produced during the alumina preparation process is in resource utilization, and a new water treatment way using waste to treat waste and changing waste into valuables is provided.
Description
Technical field
The present invention relates to a kind of heterogeneous catalyst ozone oxidation depollution water depth treatment technology.
Background technology
In recent years, along with the extensive application of chemical industry sintetics in people's daily life and industrial and agricultural production, the kind of Persistent organic pollutants and novel pollutent, content obviously increase in the water surrounding.Increasingly sophisticated water pollution situation has proposed new challenge for China's water quality safety safeguards technique.Because conventional water treatment and the sewage treatment process given is to suspend in the water and the colloid pollution thing is main to remove, and be to organic pollutant, particularly limited to the removal ability ten minutes of Persistent organic pollutants, even powerless.Therefore, must come further to ensure water quality safety by the advanced treatment technology.Wherein, the ozone heterogeneous catalysis oxidation technology is introduced other energy and poisonous and hazardous chemical agent in technology, and catalyzer can disposablely be loaded in reactor drum, and is simple to operate, be convenient in the water technology of reality, use.But the present catalyzer ubiquity catalytic efficiency (that adopts is low, cost is high and have certain selectivity, is difficult to practical requirement.Therefore, press for economic, the catalyzer efficiently of exploitation and preparation, be applied among the ozone heterogeneous catalysis oxidation technology, to solve the removal problem of the Persistent organic pollutants of lower concentration in the tap water.
Red mud (Red Mud) contains MOXs such as a large amount of iron, aluminium, titanium, calcium as the strong basicity waste residue that produces in the aluminum oxide production process, and its essential mineral composition comprises rhombohedral iron ore (α-Fe
2O
3), pyrrhosiderite (alpha-feooh), three diaspore (Al
2O
33H
2O) and quartzy (SiO
2) etc.The basic raw material of preparation high-performance water treatment coagulant and sorbent material is not only in these mineral constituents, and is the complex body of multiple conventional heterogeneous catalyst ozone oxidation catalyst.Because China is increasing to the demand of primary aluminum, the generation of red mud presents the situation that increases year by year.Given this; Adopt the modification of appropriateness to handle; Change the distribution of red mud specific surface area and surface porosity,, can significantly improve red mud catalytic activity in the Persistent organic pollutants in the ozone heterogeneous catalysis oxidizing water for red mud provides possible avtive spot in the ozone heterogeneous catalysis process.
Summary of the invention
The present invention aims to provide a kind of novel heterogeneous catalyst ozone water advanced treatment technology and method for preparing catalyst thereof; This catalyzer can significantly be strengthened the absorption at catalyst surface of ozone and organic pollutant; Realize the coupling of adsorption and oxidative degradation, realize that finally the reinforcement of Persistent organic pollutants is removed.Compare with other heterogeneous ozone catalytic water technology; The present invention can significantly improve the depollution usefulness of ozone heterogeneous catalysis water treatment technology; Greatly reduce the raw materials cost and the preparation cost of catalyzer simultaneously; And recycling preparation waste residue-red mud of being produced in the alumina process, the water treatment new way of " treatment of wastes with processes of wastes against one another, turn waste into wealth " has been proposed.
The catalyst based heterogeneous catalyst ozone water of red mud provided by the invention advanced treatment technology; It is catalyst based to it is characterized in that (one) has developed a kind of red mud that can be used for heterogeneous catalyst ozone oxidation depollution technology; This catalyzer be with Powdered red mud serve as the preparation raw material; Adopt sulfuric acid neutral method once to be prepared from, it is catalyst based to make red mud through steps such as the grindings of stirring, wear out, dry, sieve, realizes according to the following steps: (1) preparation sulphuric acid soln; Concentration level is at 0.5mol/L, and deposits in room temperature; (2) with the former mining zero(ppm) water continuous wash of an amount of red mud 5 times, remove the ash content on red mud raw ore surface, under 70 ℃ temperature, dry;
(3) red mud after will cleaning is contained in beaker, and adds zero(ppm) water, forms the suspension liquid that concentration is about 10g/L; Under the stirring of magnetic stirring apparatus; Dropwise slowly drip above-mentioned acidic solution, and, be that 6 (± 0.2) are titration end point with pH with pH meter monitoring pH value of solution value; And keep stirring to continue 12h, aged at room temperature 24h then; Topple over and fall supernatant, the residue suspension liquid descended dry 12 hours at 70 ℃, got dried powder; (4) dried powder is ground to fine particle, sieving, (it is catalyst based that 0.15mm～0.30mm) obtains red mud.
The catalyst based heterogeneous catalyst ozone water of red mud provided by the invention advanced treatment technology is characterized in that (two) can be used for the catalyst based heterogeneous catalyst ozone oxidation of the red mud of Persistent organic pollutants depollution technology in the degradation water.This technology realizes according to the following steps: the required ozone concn of (1) technology is 1.0-3.0mg/L; (2) the catalyst based throwing amount of the required red mud of technology is 250-1500mg/L; (3) Persistent organic pollutants concentration is the 1.0mg/L level in the staying water; (4) staying water pH scope is 6.0-8.0.
Red mud among the present invention is catalyst based to be to be crucial active ingredient with the gipsite on red mud surface and quartz etc.; Catalyst based efficient absorption ozone molecule of red mud and pollutent are in its surface; Realize the interface coupling of adsorption and oxidizing reaction, realize the reinforcement of pollutent is removed.The catalyst based heterogeneous catalyst ozone oxidation of red mud depollution technology can increase substantially the utilising efficiency of ozone, and Preparation of Catalyst is easy, and self stability is high, does not produce secondary pollution, is a kind of treatment technology of water depth efficiently.
The accompanying drawing content
Fig. 1 is the removal usefulness figure of the catalyst based heterogeneous catalyst ozone oxidation of the red mud depollution technology that obtains of embodiment one to water body hardly degraded organic substance oil of mirbane; Wherein ■ representes the removal usefulness of independent ozonation technology p-nitrophenyl; ● the removal usefulness of expression red mud raw ore heterogeneous catalyst ozonation technology p-nitrophenyl, representes the removal usefulness of the catalyst based heterogeneous catalyst ozonation technology of red mud p-nitrophenyl.As can be seen from the figure; The removal effect of red mud independent ozonation technology of catalyst based O3 catalytic oxidation depollution technology and red mud raw ore O3 catalytic oxidation depollution technology p-nitrophenyl is high; And significant raising is arranged, realized the reinforcement of Persistent organic pollutants in the water body is removed.
Embodiment
Method for preparing catalyst and the application in water technology thereof in this novel heterogeneous catalyst ozone oxidation depollution water depth treatment technology are described; Technical scheme of the present invention is not limited to the following embodiment of giving an example, and also comprises the arbitrary combination between each embodiment.
Embodiment one: this embodiment red mud Quito phase O3 catalytic oxidation depollution water depth treatment technology Preparation of catalysts method is: (1) preparation sulphuric acid soln, and concentration level is at 0.5mol/L, and deposits in room temperature; (2) with after the former mining zero(ppm) water continuous wash of an amount of red mud 5 times, remove the ash content on red mud raw ore surface, under 70 ℃ temperature, dry; (3) red mud after will cleaning is contained in beaker, and adds zero(ppm) water, forms the suspension liquid that concentration is about 10g/L; Under the stirring of magnetic stirring apparatus; Dropwise slowly drip above-mentioned acidic solution, and, be that 6 (± 0.2) are titration end point with pH with pH meter monitoring pH value of solution value; And keep stirring to continue 12h, aged at room temperature 24h then; Topple over and fall supernatant, the residue suspension liquid descended dry 12 hours at 70 ℃, got dried powder; (4) dried powder is ground to fine particle, sieving, (it is catalyst based that 0.15mm～0.30mm) obtains red mud.
This embodiment O3 catalytic oxidation water treatment method: after polluted water body carries out coagulation-deposition pre-treatment earlier, carry out the catalyst based heterogeneous catalyst ozone Oxidation Treatment of red mud again, then through the aftertreatment water outlet.
Heterogeneous catalyst ozone oxidation depollution is realized according to following steps: the required ozone concn of (1) technology is 1.0-3.0mg/L; (2) the catalyst based throwing amount of the required red mud of technology is 250-1500mg/L; (3) Persistent organic pollutants concentration is the 1.0mg/L level in the staying water; (4) staying water pH scope is 6.0-8.0.
Existing ozone oxidation system of the employed red mud of this embodiment catalyst based heterogeneous catalyst ozone oxidation reaction system and water factory is identical, and polluted water body pre-treatment and aftertreatment technology adopt existing technology fully, need not water treating equipment.This embodiment O3 catalytic oxidation reactor drum can be batch reactor, also can be flow reactor or multi-cascade is used reactive system.
Embodiment two: what this embodiment and embodiment one were different is (1) sulphuric acid soln in the Preparation of catalysts step, and concentration level can be salpeter solution at 0.5mol/L, and concentration level is at 1.0mol/L.Other step and parameter are identical with embodiment one.
Embodiment three: what this embodiment and embodiment one were different is (1) sulphuric acid soln in the Preparation of catalysts step, and concentration level can be hydrochloric acid soln at 0.5mol/L, and concentration level is at 1.0mol/L.Other step and parameter are identical with embodiment one.
Embodiment four: this embodiment and embodiment one are different be in the Preparation of catalysts step in (2) red mud raw ore be block-shape morphology.Other step and parameter are identical with embodiment one.
Embodiment five: this embodiment and embodiment one are different be in the Preparation of catalysts step in (2) red mud raw ore be powder morphology.Other step and parameter are identical with embodiment one.
The catalyst based heterogeneous catalyst ozone oxidation of the red mud that this embodiment obtains depollution technology is a kind of treatment technology of water depth efficiently, and the Persistent organic pollutants oil of mirbane that exists in the water is had higher removal effect.Can find that from Fig. 1 the clearance of using the catalyst based heterogeneous catalyst ozone oxidation of red mud depollution technology p-nitrophenyl reaches more than 95%; Ozonation technology improves 45.8 percentage points separately, improves 36.4 percentage points than red mud raw ore heterogeneous catalyst ozonation technology.
Claims (10)
1. the catalyst based heterogeneous catalyst ozone oxidation of a red mud depollution that can be used for the water treatment advanced treatment is technological; It is characterized in that: red mud is catalyst based can efficiently to adsorb ozone molecule and target contaminant (oil of mirbane) and its surface; Realize the coupling of oxygenant and pollutent; Completion is removed the reinforcement of Persistent organic pollutants, significantly improves water quality, ensures water quality safety.
2. red mud according to claim 1 is catalyst based to be with the aluminium trade refuse---red mud is main preparation raw material, through sour modification handle, aging, oven dry and grinding are sieved etc., and operation is prepared the red mud catalyzer.
3. catalyst based according to the said red mud of claim 1, to compare with the raw ore red mud, the catalyst based specific surface area of red mud is bigger, is the essential mineral composition with gipsite and quartz.
4. be that according to catalyst based its surface texture featur of the said red mud of claim 1 the catalyst based specific surface area of red mud is 16.00～16.20m
2/ g, total pore volume is 0.2～0.4ml/g, mean pore size is 260.39～264.39nm.
5. be gipsite and quartz according to catalyst based its essential mineral composition of the said red mud of claim 1, its mass percent content is respectively 43% and 24%.
6. red mud according to claim 1 is catalyst based, it is characterized in that said preparation method can realize through following step:
(1) preparation sulphuric acid soln, concentration level is at 0.5mol/L, and deposits in room temperature;
(2) with after the former mining zero(ppm) water continuous wash of an amount of red mud 5 times, remove the ash content on red mud raw ore surface, under 70 ℃ temperature, dry;
(3) red mud after will cleaning is contained in beaker, and adds zero(ppm) water, forms the suspension liquid that concentration is about 10g/L; Under the stirring of magnetic stirring apparatus; Dropwise slowly drip above-mentioned acidic solution, and, be that 6 (± 0.2) are titration end point with pH with pH meter monitoring pH value of solution value; And keep stirring to continue 12h, aged at room temperature 24h then; Topple over and fall supernatant, the residue suspension liquid descended dry 12 hours at 70 ℃, got dried powder;
(4) dried powder is ground to fine particle, sieving, (it is catalyst based that 0.15mm～0.30mm) obtains red mud.
7. replaceable like the employed sulphuric acid soln of claim 2 (concentration is 0.5mol/L) is salpeter solution (concentration is 1.0mol/L).
8. replaceable like the employed sulphuric acid soln of claim 2 (concentration is 0.5mol/L) is hydrochloric acid soln (concentration is 1.0mol/L).
9. the described red mud of claim 1 Quito phase O3 catalytic oxidation technology depollution water depth treatment technology, realize through following step:
(1) the required ozone concn of technology is 1.0-3.0mg/L;
(2) the catalyst based throwing amount of the required red mud of technology is 250-1500mg/L;
(3) Persistent organic pollutants concentration is the 1.0mg/L level in the staying water;
(4) staying water pH scope is 6.0-8.0.
10. claim 1 is said can be used for red mud Quito phase O3 catalytic oxidation depollution technology that water depth is handled, and it is characterized in that this technology Persistent organic pollutants in the water body that can be used for degrading.
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| CN103537270A (en) * | 2013-09-09 | 2014-01-29 | 西安建筑科技大学 | Preparation of red mud-based polymer catalyst and application of catalyst in organic dye degradation |
| CN103566959A (en) * | 2013-03-27 | 2014-02-12 | 北京林业大学 | Preparation of heat-treatment red mud catalyst and application thereof in water treatment technologies |
| CN103570120A (en) * | 2013-03-27 | 2014-02-12 | 北京林业大学 | Preparation of ceria modified red mud catalyst and application thereof in water treatment technologies |
| CN103920494A (en) * | 2014-04-04 | 2014-07-16 | 西华大学 | Wet type catalytic oxidation catalyst preparing method and applications of prepared catalyst |
| CN105771966A (en) * | 2016-03-16 | 2016-07-20 | 桑德集团有限公司 | Solid catalyst for ozone decomposition in water and preparation method thereof and method for decomposition of ozone in water |
| CN106111138A (en) * | 2016-06-20 | 2016-11-16 | 格丰环保科技有限公司 | A kind of preparation method of catalyst based on steel slag |
| CN106800332A (en) * | 2017-01-16 | 2017-06-06 | 东北大学 | A kind of method for treating water of utilization slag catalysis ozone |
| CN108568294A (en) * | 2018-04-13 | 2018-09-25 | 哈尔滨工业大学 | A kind of light granules shape catalytic ozonation material, its preparation method and the reaction unit using the material catalysis oxidation |
| CN106076335B (en) * | 2016-06-03 | 2019-04-26 | 浙江科技学院 | A kind of preparation method and application of heterogeneous Fenton catalyst |
| CN111744476A (en) * | 2020-07-08 | 2020-10-09 | 昆明理工大学 | Preparation method and application of red mud carbon-based catalyst |
| CN111747774A (en) * | 2020-07-10 | 2020-10-09 | 武汉理工大学 | Red mud ceramic membrane support and preparation method and application thereof |
| CN115228482A (en) * | 2022-08-15 | 2022-10-25 | 广州桑尼环保科技有限公司 | Ozone catalyst taking aluminum sludge as raw material and preparation method and application thereof |
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| CN103566959A (en) * | 2013-03-27 | 2014-02-12 | 北京林业大学 | Preparation of heat-treatment red mud catalyst and application thereof in water treatment technologies |
| CN103570120A (en) * | 2013-03-27 | 2014-02-12 | 北京林业大学 | Preparation of ceria modified red mud catalyst and application thereof in water treatment technologies |
| CN103537270A (en) * | 2013-09-09 | 2014-01-29 | 西安建筑科技大学 | Preparation of red mud-based polymer catalyst and application of catalyst in organic dye degradation |
| CN103920494A (en) * | 2014-04-04 | 2014-07-16 | 西华大学 | Wet type catalytic oxidation catalyst preparing method and applications of prepared catalyst |
| CN103920494B (en) * | 2014-04-04 | 2016-01-13 | 西华大学 | The application of the catalyst of catalytic wet oxidation method for preparing catalyst and preparation |
| CN105771966A (en) * | 2016-03-16 | 2016-07-20 | 桑德集团有限公司 | Solid catalyst for ozone decomposition in water and preparation method thereof and method for decomposition of ozone in water |
| CN106076335B (en) * | 2016-06-03 | 2019-04-26 | 浙江科技学院 | A kind of preparation method and application of heterogeneous Fenton catalyst |
| CN106111138A (en) * | 2016-06-20 | 2016-11-16 | 格丰环保科技有限公司 | A kind of preparation method of catalyst based on steel slag |
| CN106111138B (en) * | 2016-06-20 | 2019-01-04 | 格丰环保科技有限公司 | A kind of preparation method of the catalyst based on steel slag |
| CN106800332A (en) * | 2017-01-16 | 2017-06-06 | 东北大学 | A kind of method for treating water of utilization slag catalysis ozone |
| CN108568294A (en) * | 2018-04-13 | 2018-09-25 | 哈尔滨工业大学 | A kind of light granules shape catalytic ozonation material, its preparation method and the reaction unit using the material catalysis oxidation |
| CN111744476A (en) * | 2020-07-08 | 2020-10-09 | 昆明理工大学 | Preparation method and application of red mud carbon-based catalyst |
| CN111744476B (en) * | 2020-07-08 | 2022-10-14 | 昆明理工大学 | Preparation method and application of red mud carbon-based catalyst |
| CN111747774A (en) * | 2020-07-10 | 2020-10-09 | 武汉理工大学 | Red mud ceramic membrane support and preparation method and application thereof |
| CN115228482A (en) * | 2022-08-15 | 2022-10-25 | 广州桑尼环保科技有限公司 | Ozone catalyst taking aluminum sludge as raw material and preparation method and application thereof |
| CN115228482B (en) * | 2022-08-15 | 2023-09-12 | 广州桑尼环保科技有限公司 | Ozone catalyst taking aluminum sludge as raw material and preparation method and application thereof |
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