CN102502944B - 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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- CN102502944B CN102502944B CN201110369887.8A CN201110369887A CN102502944B CN 102502944 B CN102502944 B CN 102502944B CN 201110369887 A CN201110369887 A CN 201110369887A CN 102502944 B CN102502944 B CN 102502944B
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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 catalytic ozonation 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, in water surrounding, the kind of Persistent organic pollutants and emerging pollutant, content obviously increase.Increasingly sophisticated water pollution situation, has proposed new challenge to China's water quality safety safeguards technique.Because routine is to remove to suspend in water and colloid pollution thing is main to water treatment and sewage treatment process, to organic pollutant, particularly very limited to the removal ability of Persistent organic pollutants, even helpless.Therefore, must further ensure water quality safety by advanced treatment technology.Wherein, ozone heterogeneous catalysis oxidation technology is not introduced other energy and poisonous and hazardous chemical agent in technique, and catalyzer can disposablely be loaded in reactor, simple to operate, be convenient to apply in actual water technology.But currently used catalyzer ubiquity catalytic efficiency is low, cost is high and have certain selectivity, is difficult to practical requirement.Therefore,, efficiently catalyzer economic in the urgent need to exploitation and preparation, is applied among ozone heterogeneous catalysis oxidation technology, to solve the removal problem of Persistent organic pollutants of lower concentration in tap water.
Red mud (Red Mud), as the strong basicity waste residue producing in aluminum oxide production process, contains the metal oxides such as a large amount of iron, aluminium, titanium, calcium, and its essential mineral composition comprises rhombohedral iron ore (α-Fe
2o
3), pyrrhosiderite (alpha-feooh), three diaspore (Al
2o
33H
2o) and quartz (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 catalytic ozonation catalyzer.Because China is increasing to the demand of primary aluminum, the generation of red mud presents the situation increasing year by year.Given this, adopt appropriate modification, change the distribution of red mud specific surface area and surface porosity, for red mud provides possible avtive spot in ozone heterogeneous catalysis process, can significantly improve red mud catalytic activity in Persistent organic pollutants in ozone heterogeneous catalysis oxidizing water.
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, finally realize the strengthening of Persistent organic pollutants and remove.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 raw materials cost and the preparation cost of catalyzer simultaneously, and recycling prepare the waste residue-red mud producing in 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 characterized in that (one) has developed a kind of red mud that can be used for heterogeneous catalytic ozonation depollution technology catalyst based, this catalyzer is taking Powdered red mud as raw materials, adopt the method for sulfuric acid neutralization to be once prepared from, it is catalyst based that process stirs, aging, the steps such as grinding of drying, sieve make red mud, realize according to the following steps: (1) preparation sulphuric acid soln, concentration level is at 0.5mol/L, and deposits in room temperature; (2) by former appropriate red mud mining distilled water continuous wash 5 times, remove the ash content on red mud raw ore surface, at the temperature of 70 DEG C, dry;
(3) red mud after cleaning is contained in beaker, and add distilled water, form the suspension liquid that concentration is about 10g/L, under the stirring of magnetic stirring apparatus, dropwise slowly drip above-mentioned acidic solution, and monitor pH with pH meter, taking pH as 6 (± 0.2) as titration end point, and keep stirring to continue 12h, then aged at room temperature 24h; Topple over and fall supernatant liquor, residue suspension liquid is dried 12 hours at 70 DEG C, obtains dried powder; (4) dried powder is ground to fine particle, it is catalyst based that sieve (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 catalytic ozonation depollution of the red mud of Persistent organic pollutants technology in degradation water.This technology realizes according to the following steps: the required ozone concn of (1) technique is 1.0-3.0mg/L; (2) the catalyst based throwing amount of the required red mud of technique is 250-1500mg/L; (3) in staying water, Persistent organic pollutants concentration is 1.0mg/L level; (4) staying water pH scope is 6.0-8.0.
Red mud in the present invention is catalyst based is to wait as crucial active ingredient taking gibbsite and the quartz on red mud surface, the catalyst based efficient adsorption ozone molecule of red mud and pollutent are in its surface, realize the interface coupling of adsorption and oxidizing reaction, realize the strengthening of pollutent is removed.The catalyst based heterogeneous catalytic ozonation depollution of red mud technology can increase substantially the utilising efficiency of ozone, and catalyzer prepares easyly, and self stability is high, does not produce secondary pollution, is a kind of water depth treatment technology efficiently.
Accompanying drawing content
Fig. 1 is the removal usefulness figure of the catalyst based heterogeneous catalytic ozonation depollution of the red mud technology that obtains of embodiment one to water body hardly degraded organic substance oil of mirbane, wherein ■ represents the removal usefulness of independent ozonation technology p-nitrophenyl, ● represent the removal usefulness of red mud raw ore heterogeneous catalytic ozonation technology p-nitrophenyl, represents the removal usefulness of the catalyst based heterogeneous catalytic ozonation technology of red mud p-nitrophenyl.As can be seen from the figure, the removal effect of the more independent ozonation technology of the catalyst based O3 catalytic oxidation depollution of red mud technology and red mud raw ore O3 catalytic oxidation depollution technology p-nitrophenyl is high, and there is significant raising, realized the strengthening of Persistent organic pollutants in water body is removed.
Embodiment
Method for preparing catalyst and the application in water technology thereof in this novel heterogeneous catalytic ozonation depollution water depth treatment technology are described, technical solution of the present invention is not limited to following exemplified embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of present embodiment red mud base heterogeneous catalytic ozonation depollution water depth treatment technology catalyzer is: (1) preparation sulphuric acid soln, concentration level is at 0.5mol/L, and deposits in room temperature; (2) by after former appropriate red mud mining distilled water continuous wash 5 times, remove the ash content on red mud raw ore surface, at the temperature of 70 DEG C, dry; (3) red mud after cleaning is contained in beaker, and add distilled water, form the suspension liquid that concentration is about 10g/L, under the stirring of magnetic stirring apparatus, dropwise slowly drip above-mentioned acidic solution, and monitor pH with pH meter, taking pH as 6 (± 0.2) as titration end point, and keep stirring to continue 12h, then aged at room temperature 24h; Topple over and fall supernatant liquor, residue suspension liquid is dried 12 hours at 70 DEG C, obtains dried powder; (4) dried powder is ground to fine particle, it is catalyst based that sieve (0.15mm～0.30mm) obtains red mud.
Present embodiment O3 catalytic oxidation water treatment method: polluted water body first carries out after the pre-treatment of coagulation-precipitation, then carry out the catalyst based heterogeneous catalytic ozonation processing of red mud, then through aftertreatment water outlet.
Heterogeneous catalytic ozonation depollution is realized according to following steps: the required ozone concn of (1) technique is 1.0-3.0mg/L; (2) the catalyst based throwing amount of the required red mud of technique is 250-1500mg/L; (3) in staying water, Persistent organic pollutants concentration is 1.0mg/L level; (4) staying water pH scope is 6.0-8.0.
The catalyst based heterogeneous catalytic ozonation reactive system of red mud that present embodiment is used is identical with water factory existing ozone oxidation system, and polluted water body pre-treatment and aftertreatment technology adopt existing technique completely, need not water treating equipment.Present embodiment O3 catalytic oxidation reactor can be batch reactor, also can be flow reactor or multi-cascade reactive system.
Embodiment two: (1) sulphuric acid soln in the preparation process of what present embodiment was different from embodiment one is catalyzer, 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: (1) sulphuric acid soln in the preparation process of what present embodiment was different from embodiment one is catalyzer, 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: in the preparation process of what present embodiment was different from embodiment one is catalyzer, in (2), red mud raw ore is block-shape morphology.Other step and parameter are identical with embodiment one.
Embodiment five: in the preparation process of what present embodiment was different from embodiment one is catalyzer, in (2), red mud raw ore is powder morphology.Other step and parameter are identical with embodiment one.
The catalyst based heterogeneous catalytic ozonation depollution of the red mud technology that present embodiment obtains is a kind of water depth treatment technology efficiently, and the Persistent organic pollutants oil of mirbane existing in water is had to higher removal effect.From Fig. 1, can find that the clearance of applying the catalyst based heterogeneous catalytic ozonation depollution of red mud technology p-nitrophenyl reaches more than 95%, more independent ozonation technology improves 45.8 percentage points, improves 36.4 percentage points compared with red mud raw ore heterogeneous catalytic ozonation technology.
Claims (2)
1. the red mud for water treatment advanced treatment is catalyst based, it is characterized in that: the catalyst based efficient adsorption ozone molecule of red mud and target contaminant are in its surface, realize the coupling of oxygenant and catalyzer, complete the strengthening of Persistent organic pollutants is removed, significantly improve water quality, ensure water quality safety; Described red mud is catalyst based, taking red mud as main raw materials, by sour modification, aging, dry, grind and the operation of sieving to prepare red mud catalyst based; Red mud is catalyst based taking gibbsite and quartz as essential mineral composition, and its mass percent content is respectively 43% and 24%; 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; Described red mud is catalyst based preparation method can realize by following step,
(1) preparation sulphuric acid soln, concentration level is at 0.5mol/L, and deposits in room temperature;
(2) by after former appropriate red mud mining distilled water continuous wash 5 times, remove the ash content on red mud raw ore surface, at the temperature of 70 DEG C, dry;
(3) red mud after cleaning is contained in beaker, and add distilled water, the suspension liquid that formation concentration is 10g/L, under the stirring of magnetic stirring apparatus, dropwise slowly drip above-mentioned acidic solution, and monitor pH with pH meter, taking pH as 6 ± 0.2 as titration end point, and keep stirring lasting 12h; At aged at room temperature 24h, to topple over and fall supernatant liquor, residue suspension liquid is dried 12 hours at 70 DEG C, obtains dried powder;
(4) dried powder is ground to fine particle, crosses 0.15mm～0.30mm sieve, obtain red mud catalyst based.
2. right to use requires the catalyst based heterogeneous catalytic ozonation technology of the red mud polluted water deep treatment method described in 1, realizes by following step:
(1) the required ozone concn of technique is 1.0～3.0mg/L;
(2) the catalyst based throwing amount of the required red mud of technique is 250～1500mg/L;
(3) in staying water, Persistent organic pollutants concentration is 1.0mg/L level;
(4) staying water pH scope is 6.0～8.0.
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| CN103570120B (en) * | 2013-03-27 | 2015-09-23 | 北京林业大学 | A kind of preparation of cerium oxide changed red mud catalyzer and the application in water technology thereof |
| CN103537270B (en) * | 2013-09-09 | 2015-04-22 | 西安建筑科技大学 | Preparation of red mud-based polymer catalyst and application of catalyst in organic dye degradation |
| 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 |
| 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 |
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| CN111744476B (en) * | 2020-07-08 | 2022-10-14 | 昆明理工大学 | Preparation method and application of red mud carbon-based catalyst |
| CN111747774B (en) * | 2020-07-10 | 2021-05-25 | 武汉理工大学 | Red mud ceramic membrane support 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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| CN108043404A (en) * | 2017-12-20 | 2018-05-18 | 中国科学院过程工程研究所 | Catalyst of removing volatile organic compounds prepared by a kind of red mud and preparation method thereof |
| CN108043404B (en) * | 2017-12-20 | 2021-06-15 | 中国科学院过程工程研究所 | Catalyst prepared from red mud for removing volatile organic compounds and preparation method thereof |
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