CN104645932A - Iron and manganese oxide composite modified zeolite as well as preparation method and application thereof - Google Patents
Iron and manganese oxide composite modified zeolite as well as preparation method and application thereof Download PDFInfo
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Abstract
本发明公开了一种铁锰氧化物复合改性沸石及其制备方法与应用。所述制备方法具体为先对天然沸石进行粉碎筛分、酸碱预处理，然后将沸石与一定浓度FeCl3溶液混合反应，制得铁氧化物改性沸石材料，将所得铁氧化物改性沸石与一定浓度MnSO4溶液混合反应，洗净、低温烘干后即可制得对Cr(Ⅵ)有较高吸附能力、较大比表面积的吸附材料。本发明采用的天然沸石、以及负载的铁氧化物、锰氧化物均为自然界中存在的化合物，无任何生物毒性，使用安全无污染。本方法原料易得、制取过程简单，反应条件温和，制取成本较低，特别适用于低浓度工业废水和突发性Cr(Ⅵ)污染事件饮用水处理，应用前景广阔。
The invention discloses an iron-manganese oxide composite modified zeolite as well as a preparation method and application thereof. The preparation method is specifically as follows: crushing and screening the natural zeolite, acid-base pretreatment, and then mixing and reacting the zeolite with a certain concentration of FeCl3 solution to obtain an iron oxide modified zeolite material, and the obtained iron oxide modified zeolite Mix and react with a certain concentration of MnSO 4 solution, wash and dry at low temperature to obtain an adsorption material with high adsorption capacity and large specific surface area for Cr(Ⅵ). The natural zeolite used in the present invention, as well as the loaded iron oxide and manganese oxide are all compounds existing in nature, without any biological toxicity, safe and pollution-free in use. The raw materials of the method are easy to obtain, the preparation process is simple, the reaction conditions are mild, and the preparation cost is low. It is especially suitable for the treatment of low-concentration industrial wastewater and drinking water in sudden Cr(VI) pollution events, and has broad application prospects.
Description
Technical field
The invention belongs to environmental protection and chemical separating field, be specifically related to composite modified zeolite of a kind of iron and manganese oxides and preparation method thereof and application.
Background technology
Chromium is one of human body unessential element, the chromium of occurring in nature is divided into trivalent and sexavalence, wherein Cr VI [Cr (VI)] is owing to having oxidisability, can react with paddy cystine, ascorbic acid and the citrate etc. in cell body, cause the cell membrane of organism and human body and nucleic acid base to damage, and produce the poisonous effects such as carcinogenic, mutagenesis.In China " standards for drinking water quality (GB5749-2006) ", in regulation drinking water, Cr (VI) must not more than 0.05mgL
-1, waste water then performs " plating pollutant emission standard (GB21900-2008) ", " urban wastewater treatment firm pollutant emission standard GB 18918-2002 " middle limit value 0.5mgL
-1requirement.
In recent years along with industry and mining development, with the heavy metal pollution Frequent Accidents that Cr (VI) is representative, as massive pollution event all occurs on the ground such as Qujing of Yunnan, Shaoguan, Guangdong, the industry such as leather, plating also can produce a large amount of containing Cr (VI) waste water in addition.The former water polluted by Cr (VI) or Industrial Wastewater Treatment are mostly for Cr (VI) concentration tens to hundreds of mgL easily
-1high-concentration waste water, conventional process has " reduction-neutralization-precipitation " or more complicated " ion-exchange-electrolysis " (treatment process method CN102815825A containing hexavalent chromium wastewater) etc.The former feature is simple and easy to do, but treatment effect less stable, the body refuse after precipitation not easily processes, and the Cr (VI) in body refuse easily again discharges and produces secondary pollution; Ion-exchange then needs to consume expensive ion exchange resin, and not only consume a large amount of electric energy during regeneration, also can produce regeneration liquid waste, use cost is higher.Evaporation concentration method operation principle is evaporated by evaporating device heavy metal electroplating wastewater, decrease in containing the low waste water of concentration of heavy metal ion, direct application evaporation concentration method energy consumption is large, only have part high-concentration waste water can adopt the conbined usage process electroplating wastewater of chromium of atmospheric evaporation device and countercurrent rinsing system, and can closed cycle be realized.Hyperfiltration adopts mechanical grading principle, pending water is removed by Physical entrapment effect, valency heavy metal is had in recoverable wastewater, facility compact, floor space is little, but the expensive and vulnerable to pollution of membrane module, strict to inflow requirement, technical requirement is high, and provide pump energy consumption needed for the necessary hydraulic pressure of counter-infiltration large, disposal ability is also restricted.Sorbing material exploitation rapidly and efficiently becomes exploitation focus (a kind of novel preparation process of modified fly ash CN1994551 for the treatment of chromate waste water; The method CN101898107A for the treatment of chromium-containing wastewater by using barite adsorbent).Wherein often contain comparatively multi-metal in flyash, in use procedure, new pollution may be caused; Barite main component is BaSO
4, Ba wherein is also one of metallic element that toxicity is larger.And zeolite is mainly by Al
2o
3siO
2the vesicular texture mineral of skeleton composition, can not discharge harmful material, the ferrimanganic element in material modified ferriferous oxide, Mn oxide is also harmless.In addition also have that Part Methods producing process is comparatively complicated or treatment effeciency is limited (based on clinoptilolite inorganic-organic hybrid type sorbent preparation method and remove the application of Cr (VI) in industrial wastewater; 101797496A).
Summary of the invention
For solving the shortcoming and defect part of prior art, primary and foremost purpose of the present invention is the preparation method providing the composite modified zeolite of a kind of iron and manganese oxides.
Another object of the present invention is to the composite modified zeolite of iron and manganese oxides providing above-mentioned preparation method to obtain.This modified zeolite material forms by having the natural zeolite of high adsorption activity, loose porous ferriferous oxide and Mn oxide, surface area is large, be rich in hydroxyl (Fe-O, Mn-O) active site position, stronger Electrostatic Absorption and Complex effect can be produced with Cr (VI), adaptable, the rate of adsorption is fast, and removal efficiency is high.
Another object of the present invention is the application of the composite modified zeolite of iron and manganese oxides providing above-mentioned preparation method to obtain.
For achieving the above object, the present invention adopts following technical scheme:
A preparation method for the composite modified zeolite of iron and manganese oxides, comprises the following steps:
(1) clean after natural zeolite mechanical crushing also screening with distilled water, under normal temperature condition, first use 0.1 ~ 0.2molL
-1naOH solution soak 5 ~ 10min, then filter; Use 0.1 ~ 0.2molL again
-1hCl solution soak 5 ~ 10min, with washed with de-ionized water 3 ~ 5min after again filtering, finally dry and obtain Wessalith CS;
(2) controlling reaction temperature is 40 ~ 45 DEG C, and the Wessalith CS that step (1) is obtained is added to 0.5molL
-1feCl
3in solution, fully mix, 25:1 ~ 75:1 adds H by volume
2o
2solution, reaction 20 ~ 30min, filters to obtain zeolite B;
(3) zeolite B step (2) obtained, with after deionized water rinsing 3 ~ 5min, is added in deionized water, at N by 1:100 weight ratio
20.2 ~ 0.5molL is added under the condition of protection atmosphere and stirring
-1mnSO
4solution, to starting to occur black fine suspension, is then warming up to 50 ~ 60 DEG C, drips the saturated ammonia aqueous solution and pH is adjusted to 7 ~ 8, fully react 20 ~ 40min; By zeolite filtration, and no longer change to leacheate pH with deionized water drip washing, be dried to constant weight and can obtain the composite modified zeolite of described iron and manganese oxides.
Preferably, step (1) described natural zeolite is using natural clinoptilolite or modenite.
Being filtered into terylene or polyvinyl filter-cloth filtering described in step (1).
Preferably, step (1) described bake out temperature is 100 ~ 105 DEG C.
Preferably, step (2) described baking temperature is 40 ~ 45 DEG C.
Preferably, step (2) described H
2o
2the concentration of solution is 30% (volume).
The composite modified zeolite of iron and manganese oxides that above-mentioned preparation method obtains, the ferriferous oxide of the composite modified zeolite of this iron and manganese oxides and Mn oxide weight ratio are 1:1 ~ 3:1, and iron and manganese oxides gross weight accounts for 15 ~ 35% of the composite modified zeolite of this iron and manganese oxides.
The composite modified zeolite of iron and manganese oxides that above-mentioned preparation method obtains in process containing the industrial wastewater of Cr (VI) or the application in processing micro-polluted drinking water that sudden Cr contamination accident causes.
Preferably, described containing Cr (VI) concentration≤10mgL in the industrial wastewater of Cr (VI)
-1, described containing Cr (VI) concentration≤1.0mgL in the micro-polluted drinking water of Cr (VI)
-1.
Preferably, described application comprises the following steps: be adjusted to 5 ~ 10 by containing the industrial wastewater of Cr (VI) or the pH of micro-polluted drinking water, then by 0.5 ~ 5gL
-1dosage add the composite modified zeolite of this iron and manganese oxides, adsorption reaction 0.3 ~ 0.6h, the water after adsorption reaction enters sedimentation basin, adds 0.5 ~ 5mgL
-1bodied ferric sulfate coagulant (hereinafter referred to as PFS) precipitate 0.3 ~ 0.5h, supernatant overflow discharge, sedimentation basin body refuse conveniently processes.
Preferably, described adsorption reaction adopts batch (-type) (SBR) or plug flow reactor (PFR).
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the composite modified zeolite surface of iron and manganese oxides of the present invention is made up of loose porous ferriferous oxide and Mn oxide, surface area is large, be rich in hydroxyl (Fe-O, Mn-O) active site position, stronger Electrostatic Absorption and Complex effect can be produced with Cr (VI), adaptable, the rate of adsorption is fast, and removal efficiency is high.
(2) natural zeolite that adopts of the present invention and the ferriferous oxide of load, Mn oxide are the compound that occurring in nature exists, and without any bio-toxicity, use safety is pollution-free.
(3) the composite modified zeolite preparation method of iron and manganese oxides of the present invention is simple, with low cost, easy to use, can apply without the need to carrying out large-scale redevelopment to existing water treatment building or adding main equipment, and it is convenient to preserve, and effect is lasting.
Accompanying drawing explanation
Fig. 1 is preparation technology's flow chart of the composite modified zeolite of a kind of iron and manganese oxides of the present invention;
Fig. 2 is that the composite modified zeolite treatment of iron and manganese oxides of the present invention is containing Cr (VI) water process chart;
Fig. 3 is the surface scan Electronic Speculum figure of natural zeolite in embodiment 1;
Fig. 4 is the surface scan Electronic Speculum figure of the composite modified zeolite of iron and manganese oxides in embodiment 1;
Fig. 5 is the X-ray diffractogram of natural zeolite and the composite modified zeolite of iron and manganese oxides in embodiment 1;
Fig. 6 be in embodiment 1 natural zeolite and the composite modified zeolite dosage of iron and manganese oxides on the impact of Cr (VI) clearance;
Fig. 7 is that the pH value of embodiment 1 containing Cr (VI) pending water is on the impact of Cr (VI) clearance.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
The invention provides the preparation method of the composite modified zeolite of a kind of iron and manganese oxides, as shown in Figure 1, comprise the following steps:
(1) clean with distilled water after natural zeolite mechanical crushing 100 ~ 150 mesh sieves being divided, under normal temperature condition, first use 0.1 ~ 0.2molL
-1naOH solution soak 5 ~ 10min, then filter; Use the molL of 0.1 ~ 0.2 again
-1hCl solution soaks 5 ~ 10min, and with washed with de-ionized water 3 ~ 5min after again filtering, last 100 ~ 105 DEG C of oven dry obtain Wessalith CS;
(2) controlling reaction temperature is 40 ~ 45 DEG C, and the Wessalith CS that step (1) is obtained is added to 0.5molL
-1feCl
3in acid solution, fully mix, 25:1 ~ 75:1 adds H by volume
2o
2(30%) solution, reaction 20 ~ 30min, filters to obtain zeolite B;
(3) zeolite B step (2) obtained, with after deionized water rinsing 3 ~ 5min, is added in deionized water, at N by 1:100 weight ratio
20.2 ~ 0.5molL is added under the condition of protection atmosphere and stirring
-1mnSO
4solution to starting to occur black fine suspension, be then slowly warming up to 50 ~ 60 DEG C, drip the saturated ammonia aqueous solution simultaneously slowly and pH is adjusted to 7 ~ 8, fully react 20 ~ 40min, make Fe
3+and Mn
2+generate iron and manganese oxides composite load respectively on zeolite microparticles surface; By zeolite filtration, and no longer change to leacheate pH with deionized water drip washing, 40 ~ 45 DEG C are dried to constant weight and can obtain the composite modified zeolite of described iron and manganese oxides.
Present invention also offers the composite modified zeolite of a kind of iron and manganese oxides, the composite modified zeolite of this iron and manganese oxides can be used for processing the industrial wastewater containing Cr (VI) or micro-polluted drinking water, concrete technology is as shown in Figure 2: pending is adjusted to 5 ~ 10 containing the industrial wastewater of Cr (VI) or the pH of micro-polluted drinking water, then by composite modified for this iron and manganese oxides zeolite by 0.5 ~ 5gL
-1dosage, add in pending water with dry type dosing method, adsorption reaction 0.3 ~ 0.6h, the water after adsorption reaction enters sedimentation basin, adds 0.5 ~ 5mgL simultaneously
-1pFS coagulant precipitation 0.3 ~ 0.5h, supernatant overflow is discharged, and sedimentation basin body refuse conveniently processes (namely by leaching test to determine to be processed as hazardous waste or household waste).Described adsorption reaction adopts batch (-type) (SBR) or plug flow reactor (PFR), adopts mechanical agitation, and stirring intensity is suitable to keep adsorbent suspension not produce being precipitated as.
Through verification experimental verification, Cr (VI) concentration is not higher than 10mgL
-1industrial wastewater after above-mentioned process, water outlet Cr (VI) can lower than 0.5mgL
-1, meet the highest permission concentration of emission of first kind pollutant in state sewage emission standard and metal plating waste water limited value of discharge standard regulation; In process Cr (VI) concentration not higher than 1.0mgL
-1micro-polluted drinking water after above-mentioned process, water outlet Cr (VI) can lower than 0.05mgL
-1, reach water hygiene safety standard limit value.
Embodiment 1
A preparation method for the composite modified zeolite of iron and manganese oxides, comprises the following steps:
(1) clean with distilled water after natural zeolite (choosing Heyuan natural mordenite zeolite) mechanical crushing, 150 mesh sieves being divided, under normal temperature, first use 0.1molL
-1naOH solution soak 10min, then use polyvinyl filter-cloth filtering, then use 0.1molL
-1hCl solution soaks 10min, uses washed with de-ionized water 5min after again filtering, and dries and obtain Wessalith CS at 105 DEG C;
(2) control reaction temperature 42 DEG C, Wessalith CS is added to 0.5molL
-1feCl
3in acid solution, adopt and fully mix, 50:1 adds H by volume
2o
2(30%) solution, filters to obtain zeolite B after reaction 20min;
(3) by zeolite B with after deionized water rinsing 5min, be added in deionized water, at N by 1:100 weight ratio
20.2molL is added under protection atmosphere and magnetic agitation condition
-1mnSO
4solution is to starting to occur black fine suspension, then 55 DEG C are slowly warming up to, slowly drip the saturated ammonia aqueous solution to pH 7.5 simultaneously, abundant reaction 30min, by zeolite filtration, and no longer change to leacheate pH with deionized water drip washing, 40 DEG C of cryogenic vacuum oven dry can obtain the composite modified zeolite of described iron and manganese oxides to constant weight.
The surface scan Electronic Speculum figure of Fig. 3 to be the surface scan Electronic Speculum figure of natural zeolite, Fig. 4 be composite modified zeolite of iron and manganese oxides.Can see from Fig. 3 and 4, the loose granule foreign of the zeolite surface after modification greatly reduces.The increase of specific area is conducive to the absorption of adsorbate on surface and duct transmission, is also conducive to combining closely of zeolite granular and iron and manganese oxides simultaneously.
Table 1 natural zeolite before modified after pore structure parameter
Can see from table 1, compared with natural zeolite, the composite modified zeolite specific area of the iron and manganese oxides not significantly increase that the present embodiment is obtained, but pore structure generation significant change, specific area and the volume of micropore obviously increase.This has mainly dissolved the non-framework ingredient impurity of part surface attachment due to alkali treatment, and dredged the pore passage structure of zeolite, modified iron and manganese oxides is attached to surface in addition, also can have an impact to pore size distribution and pore structure.
Fig. 5 is the X-ray diffractogram of natural zeolite and the composite modified zeolite of iron and manganese oxides, the X-ray diffractogram that (a) is natural zeolite, and (b) is the X-ray diffractogram of the composite modified zeolite of iron and manganese oxides.Natural zeolite crystal formation is comparatively complicated as can be seen from FIG., modification effectively eliminates surface impurity and improves surperficial crystal formation, assorted peak significantly reduces, angle value be the Mn-O diffraction maximum at the places such as 26.8 ° and 30.1 °, the Fe-O diffraction maximum at the places such as 22.60 all obviously strengthens.
Certain upper river as Raw Drinking Water is illegally stolen row due to manufacturing enterprise and is caused river Cr (VI) up to 0.8 ~ 0.9mgL
-1, the water intaking of serious threat downstream and water safety.River pH about 7 ~ 7.5, TOC is about 8 ~ 10mgL simultaneously
-1.The above-mentioned Raw Drinking Water Cr (VI) of the iron and manganese oxides composite modified zeolite emergency processing adopting the present embodiment to prepare pollutes accident, and concrete technology is as follows: after water intaking, in water channel or in regulating reservoir, dry type adds 1gL
-1the composite modified zeolite of iron and manganese oxides, adopt water channel as plug flow reactor, and fully mixing, adsorption reaction 20min, then add 2.5mgL
-1pFS coagulant after enter the follow-up coagulating sedimentation link of water factory, precipitation 0.5h, is separated by precipitation by the zeolite granular having adsorbed Cr (VI), after testing process afterwards water outlet can meet Cr (VI)≤0.05mgL
-1water quality standard for drinking water, pH Absorbable organic halogens can be reduced to 2 ~ 3mgL at 6.5 ~ 7, TOC in addition
-1.
For research zeolite dosage is on the impact of Cr (VI) clearance, the natural zeolite of the present embodiment and the obtained composite modified zeolite of iron and manganese oxides are pressed 0.5gL respectively
-1, 1gL
-1, 1.5gL
-1, 2gL
-1, 3gL
-1dosage be 1.5mgL to Cr (VI) concentration
-1, the industrial wastewater of pH7.0, T=20 ± 1 DEG C processes, and as shown in Figure 2, sorption reaction time is 30min to concrete processing technological flow, and the relation of Cr (VI) clearance and zeolite dosage as shown in Figure 6.Can see from Fig. 6, (≤1.0gL when throwing amount is lower
-1), dosage and Cr (VI) clearance are approximated to proportional relation, increase clearance tend towards stability with dosage.The composite modified zeolite dosage of iron and manganese oxides is 1.5gL
-1, natural zeolite is 3.0gL
-1time clearance reach 95.9% and 86.1% respectively.It is pointed out that (the > 3.0gL when zeolite powder dosage is larger
-1), solution appearance, in highly muddy shape, can strengthen the load of the follow-up auxiliary process such as coagulating sedimentation, filtration.
For research contains the pH value of Cr (VI) pending water to the impact of Cr (VI) clearance, be 1.5mgL by Cr (VI) concentration
-1the pH Neutralization of Industrial Wastewater of T=20 ± 1 DEG C is adjusted to 2,3,4,5,6,7,8,9 respectively, the natural zeolite of the present embodiment and the obtained composite modified zeolite of iron and manganese oxides are processed the industrial wastewater of above-mentioned different pH value respectively, concrete processing technological flow as shown in Figure 2, sorption reaction time is 60min, and dosage is 1.0gL
-1, the relation of pH Neutralization of Industrial Wastewater and Cr (VI) clearance as shown in Figure 7.Can see from Fig. 7, with the rising of pH, the clearance of Cr (VI) is slightly in rising trend.The corresponding pH of zero point charge of the composite modified zeolite of iron and manganese oxides is 8.9, close to spinel-type MnOFe
2o
3the pH8.5 that zero point charge is corresponding; As pH < 8.5, the composite modified zeolite surface of iron and manganese oxides adsorbs too much H
+and positively charged, be easy to and electronegative Cr
2o
7 2-and CrO
4 2-electrostatic adsorption occurs, and when pH raises, the composite modified zeolite surface of iron and manganese oxides is electronegative, with Cr
2o
7 2-electrostatic adsorption be suppressed, therefore advantageous pH range is 5 ~ 10.
Embodiment 2
A preparation method for the composite modified zeolite of iron and manganese oxides, the present embodiment as different from Example 1 middle institute of step (2) adds H
2o
2(30%) volume ratio is 25:1, MnSO in step (3)
4solution concentration is 0.5molL
-1, other step is identical with embodiment 1 with parameter.
The workshop waste discharge Cr (VI) of certain electroplating enterprise is up to 13 ~ 45mgL
-1, pH is 2 ~ 4.The composite modified zeolite of iron and manganese oxides adopting the present embodiment to prepare administers Cr (VI) excessive problem in above-mentioned industrial wastewater: namely first feeding lime regulates pH to 7.5, then adds 3gL
-1iron and manganese oxides modified zeolite, adsorption time is 30min, then adds 5mgL
-1pFS coagulant precipitation 30min, after quartz sand filtration, water outlet can be reduced to 0.3 ~ 0.5mgL
-1, meet discharge standard.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a preparation method for the composite modified zeolite of iron and manganese oxides, is characterized in that, comprise the following steps:
(1) clean after natural zeolite mechanical crushing also screening with distilled water, under normal temperature condition, first use 0.1 ~ 0.2molL
-1naOH solution soak 5 ~ 10min, then filter; Use 0.1 ~ 0.2molL again
-1hCl solution soak 5 ~ 10min, with washed with de-ionized water 3 ~ 5min after again filtering, finally dry and obtain Wessalith CS;
(2) controlling reaction temperature is 40 ~ 45 DEG C, and the Wessalith CS that step (1) is obtained is added to 0.5molL
-1feCl
3in solution, fully mix, 25:1 ~ 75:1 adds H by volume
2o
2solution, reaction 20 ~ 30min, filters to obtain zeolite B;
(3) zeolite B step (2) obtained, with after deionized water rinsing 3 ~ 5min, is added in deionized water, at N by 1:100 weight ratio
20.2 ~ 0.5molL is added under the condition of protection atmosphere and stirring
-1mnSO
4solution, to starting to occur black fine suspension, is then warming up to 50 ~ 60 DEG C, drips the saturated ammonia aqueous solution and pH is adjusted to 7 ~ 8, fully react 20 ~ 40min; By zeolite filtration, and no longer change to leacheate pH with deionized water drip washing, be dried to constant weight and can obtain the composite modified zeolite of described iron and manganese oxides.
2. preparation method according to claim 1, is characterized in that, step (1) described natural zeolite is using natural clinoptilolite or modenite.
3. preparation method according to claim 1, is characterized in that, step (1) described bake out temperature is 100 ~ 105 DEG C.
4. preparation method according to claim 1, is characterized in that, step (2) described baking temperature is 40 ~ 45 DEG C.
5. preparation method according to claim 1, is characterized in that, step (2) described H
2o
2the concentration of solution is 30% (volume).
6. the composite modified zeolite of iron and manganese oxides, it is characterized in that, the composite modified zeolite of this iron and manganese oxides is obtained by preparation method described in any one of Claims 1 to 5, the ferriferous oxide of the composite modified zeolite of this iron and manganese oxides and Mn oxide weight ratio are 1:1 ~ 3:1, and iron and manganese oxides gross weight accounts for 15 ~ 35% of the composite modified zeolite of this iron and manganese oxides.
7. the composite modified zeolite of iron and manganese oxides according to claim 6 in process containing the industrial wastewater of Cr (VI) or the application in processing micro-polluted drinking water that sudden Cr contamination accident causes.
8. application according to claim 7, is characterized in that, described containing Cr (VI) concentration≤10mgL in the industrial wastewater of Cr (VI)
-1, described containing Cr (VI) concentration≤1.0mgL in the micro-polluted drinking water of Cr (VI)
-1.
9. application according to claim 7, is characterized in that, comprises the following steps: be adjusted to 5 ~ 10 by containing the industrial wastewater of Cr (VI) or the pH of micro-polluted drinking water, then by 0.5 ~ 5gL
-1dosage add the composite modified zeolite of described iron and manganese oxides, adsorption reaction 0.3 ~ 0.6h, the water after adsorption reaction enters sedimentation basin, adds 0.5 ~ 5mgL
-1bodied ferric sulfate coagulant precipitation 0.3 ~ 0.5h, supernatant overflow discharge, sedimentation basin body refuse conveniently processes.
10. application according to claim 9, is characterized in that, described adsorption reaction adopts batch (-type) or plug flow reactor.
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Cited By (5)
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| CN105148885A (en) * | 2015-08-21 | 2015-12-16 | 暨南大学 | Nano-iron-manganese modified zeolite for removal of BrO3- and ClO4- and its preparation and application |
| CN106082255A (en) * | 2016-06-22 | 2016-11-09 | 河北大学 | A kind of method utilizing waterworks sludge efficiently to prepare permutite and application thereof |
| CN110102260A (en) * | 2019-05-20 | 2019-08-09 | 广东工业大学 | A kind of iron and manganese oxides-charcoal composite material and preparation method and application |
| CN113277565A (en) * | 2021-06-17 | 2021-08-20 | 中冶南方都市环保工程技术股份有限公司 | Preparation method and use method of heavy metal curing agent |
| CN115318246A (en) * | 2020-12-15 | 2022-11-11 | 青岛大学 | A kind of preparation method of novel nanometer metal oxide artificial wetland filler |
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