CN103041815B - Preparation method of iron-supported attapulgite heterogeneous fenton catalyst - Google Patents
Preparation method of iron-supported attapulgite heterogeneous fenton catalyst Download PDFInfo
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- CN103041815B CN103041815B CN201310000494.9A CN201310000494A CN103041815B CN 103041815 B CN103041815 B CN 103041815B CN 201310000494 A CN201310000494 A CN 201310000494A CN 103041815 B CN103041815 B CN 103041815B
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Abstract
The invention discloses a preparation method of an iron-supported attapulgite heterogeneous fenton catalyst. The method comprises the process steps that A, attapulgite is taken and crushed; B, a right amount of attapulgite is immersed in an acid solution, and uniformly stirred to form a sample; C, the sample is centrifuged; an upper layer suspension is filter and dried; modified attapulgite is obtained; D, the attapulgite is ground and sieved; E, an FeCl3 solution with the concentration of 0.5-2mol/L is adopted; the attapulgite is immersed for 6-24h in a water bath; and F, the attapulgite is centrifuged or filtered, and dried and ground to the original particle size; and a finished product is prepared. The method has the advantages that iron ions are supported to the modified attapulgite through immersion and ion exchange, and the heterogeneous fenton catalyst is prepared, so that nondegradable waste water can be treated efficiently, and the problems that a pH value in homogeneous fenton is low, iron mud can be generated, and secondary pollution is caused are solved. An adsorptive property, an ion exchange property, and a strong oxidizing property of fenton reaction are exerted in waste water treatment.
Description
Technical field
That the present invention relates to is the preparation method of a kind of year heterogeneous Fenton catalyst of iron nonmetallic ore, relates in particular to the preparation method of a kind of year heterogeneous Fenton catalyst of iron attapulgite.
Background technology
In water, the source of hardly degraded organic substance is very extensive, is a difficult problem for water treatment field to its processing always.And high-level oxidation technology is owing to having the features such as the strong and non-secondary pollution of oxidability, being considered to process hardly degraded organic substance in water has the method for application prospect most.In advanced oxidation treatment technology, Fenton technology has the features such as treatment effeciency is high, cost is relatively low, easy industrialization, becomes gradually one of main method in current high-level oxidation technology.Nearly ten years, external many scholars turn to application study by Fenton technology from laboratory research gradually, for the treatment of actual used water difficult to degradate.But for common homogeneous phase Fenton system, because it only could effectively carry out under lower pH, need to repeatedly reconcile pH value to waste water, increase on foot processing cost, and the catalyst of homogeneous phase Fenton system is miscible in waste water, after finishing, reaction also can produce a large amount of iron containing sludges, post processing complexity.
For solving the bottleneck problem of Fenton system applies, iron ion immobilization is become to solid-phase catalyst, form heterogeneous Fenton system, can not be subject to the restriction of pH value, be the main development direction of current Fenton system.
Attapulgite, claims again palygorskite, is a kind of moisture zeopan clay mineral of chain layer structure, all has application extremely widely in multiple fields such as environmental protection, chemical industry, light industry, agricultural, building materials.It is cheap, has larger specific area, stronger absorption property and certain ion-exchange capacity.But the impurity content of natural attapulgite is many, sour modification can make attapulgite inner elongate and fine and close orderly crystalline substance bundle is interrupted, disperses, and impurity is removed in a large number as calcium, magnesium, manganese, and adsorption capacity, ion-exchange capacity obviously increase.
Summary of the invention
That the present invention proposes is the preparation method of a kind of year heterogeneous Fenton catalyst of iron attapulgite, its object is intended to iron ion to be firmly carried on carrier, it is a kind of dipping technique, also be a kind of ion exchange technique, iron ion is firmly carried on attapulgite after dipping and ion-exchange, is prepared into a kind of heterogeneous Fenton catalyst, can increase like this pH value scope, and catalyst can be repeatedly used, avoid producing secondary pollution.There is certain economic worth and practicality.
Technical solution of the present invention: the preparation method of a kind of year heterogeneous Fenton catalyst of iron attapulgite, comprises following processing step:
A, get attapulgite pulverize, pulverize after cross 5-20 orders;
B, get the attapulgite having filtered out in right amount and be immersed in the hydrochloric acid solution that the amount of 5-20 times of attapulgite quality is 2-10mol/L; Uniform stirring, mixing speed is 60-300r/min, obtains sample;
C, by the centrifugal 10-60min of step B sample, the rotating speed of described centrifuge is 1500-1800 r/min, centrifugal after by upper strata suspension through filtration or without centrifugal direct filtration, available quick filter paper, after filtering, sample is dried 2-3h at 103-105 ° of C, obtains attapulgite modified;
D, step C gained attapulgite was ground to 40-200 mesh sieves;
The FeCl that E, employing concentration are 0.5-2mol/L
3solution, by FeCl
3solution: the ratio of attapulgite 5:1-20:1, step D gained attapulgite is soaked to 6-24 hour in water-bath;
F, rotating speed by the attapulgite making in step e with 1500-1800 r/min, centrifugal 10-60min, or use quick Filter paper filtering, and under 103-105 ° of C condition, dry 2-3h, and be ground to the granule size described in step D, prepared by catalyst.
Beneficial effect of the present invention: the present invention on attapulgite, is prepared into catalyst by iron firm attachment, forms heterogeneous Fenton system, can high efficiency must process used water difficult to degradate.This process can reach more than 95% the clearance of the pollutants such as phenol in wastewater.The strong oxidizing property that takes full advantage of ion exchangeable, adsorptivity and the Fenton's reaction of attapulgite, does not produce secondary pollution, and catalyst can be repeatedly used, and has created considerable economic benefit and good social benefit.
The specific embodiment
Embodiment 1
A, get attapulgite pulverize, pulverize after cross 5 orders;
B, get the attapulgite having filtered out in right amount and be immersed in the hydrochloric acid solution that the amount of 10 times of attapulgite quality is 6mol/L; Uniform stirring, mixing speed is 80r/min, obtains sample;
C, step B sample is centrifugal as 1500 r/min take rotating speed, 10min, after described centrifuge centrifugal by upper strata suspension through filtering; Or without centrifugal direct filtration, available quick filter paper is dried 2h by sample after filtration under 103 ° of C conditions, obtains attapulgite modified;
D, step C gained attapulgite was ground to 100 mesh sieves;
E, employing concentration are the FeCl of 1 mol/L
3solution, by FeCl
3solution: attapulgite is 5:1 soaks step D gained attapulgite 6 hours in water-bath;
F, rotating speed by the attapulgite making in step e with 1500 r/min, centrifugal 10min, or use quick Filter paper filtering, and under 103 ° of C conditions, dry 2h, and be ground to the granule size described in step D, prepared by catalyst;
G, experiment by the attapulgite preparing for phenol synthetic water, clearance can reach 99%.
Embodiment 2
A, get attapulgite pulverize, pulverize after cross 15 orders;
B, get the attapulgite having filtered out in right amount and be immersed in the hydrochloric acid solution that the amount of 15 times of attapulgite quality is 2mol/L; Uniform stirring, mixing speed is 60r/min, obtains sample;
C, by the centrifugal 35min of step B sample, the rotating speed of described centrifuge is 1600r/min, centrifugal after by upper strata suspension through filtration; Or without centrifugal direct filtration, available quick filter paper is dried 2.5h by sample after filtration under 105 ° of C conditions, obtains attapulgite modified;
D, step C gained attapulgite was ground to 200 mesh sieves;
E, employing concentration are the FeCl of 2 mol/L
3solution, by FeCl
3solution: the ratio of attapulgite 20:1, step D gained attapulgite is soaked 24 hours in water-bath;
F, by the attapulgite making in step e with centrifugal rotational speed 1800r/min, 60min, or use quick Filter paper filtering is dried 3h, and is ground to the granule size described in step D under 105 ° of C conditions, prepared by catalyst;
G, experiment by the attapulgite preparing for phenol synthetic water, clearance can reach 99%.
Embodiment 3
A, get attapulgite pulverize, pulverize after cross 20 orders;
B, get the attapulgite having filtered out in right amount and be immersed in the hydrochloric acid solution that the amount of 20 times of attapulgite quality is 10mol/L; Uniform stirring, mixing speed is 300r/min, obtains sample;
C, by the centrifugal 60min of step B sample, the rotating speed of described centrifuge is 1800 r/min, centrifugal after by upper strata suspension through filtration; Or without centrifugal direct filtration, available quick filter paper is dried 2.5h by sample after filtration under 105 ° of C conditions, obtains attapulgite modified;
D, step C gained attapulgite was ground to 40 mesh sieves;
E, employing concentration are the FeCl of 0.5 mol/L
3solution, by FeCl
3solution: the ratio of attapulgite 10:1, step D gained attapulgite is soaked 12 hours in water-bath;
F, by the attapulgite making in step e with centrifugal rotational speed 1600 r/min, 60min, or use quick Filter paper filtering is dried 2.5h, and is ground to the granule size described in step D under 105 ° of C conditions, prepared by catalyst;
G, experiment by the attapulgite preparing for phenol synthetic water, clearance can reach 99%.
Embodiment 4
A, get attapulgite pulverize, pulverize after cross 10 orders;
B, get the attapulgite having filtered out in right amount and be immersed in the hydrochloric acid solution that the amount of 5 times of attapulgite quality is 8mol/L; Uniform stirring, mixing speed is 100r/min, obtains sample;
C, by the centrifugal 60min of step B sample, the rotating speed of described centrifuge is 1500r/min, centrifugal after by upper strata suspension through filtration; Or without centrifugal direct filtration, available quick filter paper is dried 3h by sample after filtration under 104 ° of C conditions, obtains attapulgite modified;
D, step C gained attapulgite was ground to 150 mesh sieves;
E, employing concentration are the FeCl of 2 mol/L
3solution, by FeCl
3solution: the ratio of attapulgite 15:1, step D gained attapulgite is soaked 10 hours in water-bath;
F, by the attapulgite making in step e with centrifugal rotational speed 1600 r/min, centrifugal 40min, or use quick Filter paper filtering is dried 2h, and is ground to the granule size described in step D under 105 ° of C conditions, prepared by catalyst;
G, experiment by the attapulgite preparing for phenol synthetic water, clearance can reach 99%.
Embodiment 5
A, get attapulgite pulverize, pulverize after cross 18 orders;
B, get the attapulgite having filtered out in right amount and be immersed in the hydrochloric acid solution that the amount of 5 times of attapulgite quality is 10mol/L; Uniform stirring, mixing speed is 250r/min, obtains sample;
C, by the centrifugal 30min of step B sample, the rotating speed of described centrifuge is 1560 r/min, centrifugal after by upper strata suspension through filtration; Or without centrifugal direct filtration, available quick filter paper is dried 2.5h by sample after filtration under 104 ° of C conditions, obtains attapulgite modified;
D, step C gained attapulgite was ground to 150 mesh sieves;
The FeCl that E, employing concentration are 2mol/L
3solution, by FeCl
3solution: the ratio of attapulgite 20:1, step D gained attapulgite is soaked 24 hours in water-bath;
F, by the attapulgite making in step e with centrifugal rotational speed 1800 r/min, centrifugal 60min, or use quick Filter paper filtering is dried 3h, and is ground to the granule size described in step D under 105 ° of C conditions, prepared by catalyst;
G, experiment by the attapulgite preparing for phenol synthetic water, clearance can reach 99%.
The present invention is carried on iron ion attapulgite modified upper, is prepared into heterogeneous Fenton catalyst, can high efficiency process used water difficult to degradate, has solved low pH value in homogeneous phase Fenton, can produce iron mud, brings the bottleneck problems such as secondary pollution.And iron ion load capacity is large, adhere to stablely, be not easy to separate out, catalyst can be repeatedly used.In addition, attapulgite is cheap, there is larger specific area, stronger absorption property and certain ion-exchange capacity, by ferropexy on attapulgite, as catalyst, after adding hydrogen peroxide, form heterogeneous Fenton system, can finely must bring into play the strong oxidizing property of absorption property and the Fenton's reaction of attapulgite.The heterogeneous Fenton catalyst preparation process that carries iron attapulgite comprises attapulgite modified, load iron ion two large divisions.After the modification of former concave convex rod mud acid, along with H
+to the infiltration gradually of its internal structure octahedral cations ecto-entad, in octahedron, cation is progressively substituted even completely, inner elongate and fine and close orderly crystalline substance bundle is interrupted, disperses, impurity is removed in a large number, and adsorption capacity, ion-exchange capacity obviously increase.Modification object is to increase exchange and absorption iron ion amount; Load iron ion adopts dipping and ion-exchange, and part iron ion generation secondary replaces, and enters attapulgite crystals, and the oxyhydroxide that part iron ion forms iron is attached to attapulgite's surface.The oxyhydroxide of iron can react with hydrogen peroxide, produces the hydroxyl with strong oxidizing property, hardly degraded organic substance can be carried out to oxidation Decomposition.
Above content is in conjunction with concrete preferred embodiment further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (1)
1. carry a preparation method for the heterogeneous Fenton catalyst of iron attapulgite, it is characterized in that the method comprises following processing step:
A, get attapulgite pulverize, pulverize after cross 5-20 orders;
B, get the attapulgite having filtered out in right amount and be immersed in the hydrochloric acid solution that the amount of 5-20 times of attapulgite quality is 2-10mol/L; Uniform stirring, mixing speed is 60-300r/min, obtains sample;
C, by the centrifugal 10-60min of step B sample, the rotating speed of described centrifuge is 1500-1800 r/min, centrifugal after by upper strata suspension through filtration; Or without centrifugal direct filtration, available quick filter paper is dried 2-3h by sample after filtration under 103-105 ℃ of condition, obtains attapulgite modified;
D, step C gained attapulgite was ground to 40-200 mesh sieves;
The FeCl that E, employing concentration are 0.5-2mol/L
3solution, by FeCl
3solution: the ratio of attapulgite 5:1-20:1, step D gained attapulgite is soaked to 6-24 hour in water-bath;
F, rotating speed by the attapulgite making in step e with 1500-1800 r/min, centrifugal 10-60min, or use quick Filter paper filtering, and under 103-105 ℃ of condition, dry 2-3h, and be ground to the granule size described in step D, prepared by catalyst;
Described step B, hydrochloric acid solution: the liquid-solid ratio of attapulgite is 5:1-20:1, selected acid solutions is 2-10mol/L;
Bath temperature in described step e remains on 50-100 ℃.
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| CN103230796A (en) * | 2013-04-25 | 2013-08-07 | 六安科瑞达新型材料有限公司 | Preparation method of attapulgite supported ferroferric oxide |
| CN103240122B (en) * | 2013-05-17 | 2014-10-29 | 浙江理工大学 | Preparation method of active carbon fiber loaded aminopyridine metal complex |
| CN103551204B (en) * | 2013-10-21 | 2015-04-22 | 中山大学 | Multi-stage hierarchical pore structural Fenton-like catalyst and application thereof |
| CN105268487B (en) * | 2014-07-24 | 2018-03-02 | 艾特克控股集团有限公司 | A kind of preparation method and applications of loading type ferric oxide catalyst carrier |
| CN106040244B (en) * | 2016-06-01 | 2018-07-06 | 中国科学院过程工程研究所 | It is a kind of for supported solid catalyst of Fenton's reaction and preparation method thereof |
| CN106824212A (en) * | 2017-03-10 | 2017-06-13 | 扬州大学 | A kind of CeO2/Fe2O3The preparation method of the nano environment material on load attapulgite |
| CN107335406A (en) * | 2017-06-26 | 2017-11-10 | 东北林业大学 | A kind of water treatment absorbent and preparation method thereof |
| CN108212158B (en) * | 2018-01-17 | 2020-08-14 | 上海交通大学 | Fenton catalyst and preparation method and application thereof |
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| CN110252305B (en) * | 2019-03-05 | 2020-09-15 | 中国科学院生态环境研究中心 | Preparation and application of iron-carbon micro-electrolysis material capable of maintaining long-acting catalytic activity of Fenton system |
| CN110092505A (en) * | 2019-05-26 | 2019-08-06 | 北京化工大学 | A kind of method of Concave-convex clay rod processing wastewater containing phenol |
| CN110385129A (en) * | 2019-07-04 | 2019-10-29 | 陕西省土地工程建设集团有限责任公司 | It is a kind of using mud stone as class fenton catalyst, preparation and the application of carrier |
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