CN102886240B - Adsorbent for removing toxic element arsenic in water and application thereof - Google Patents
Adsorbent for removing toxic element arsenic in water and application thereof Download PDFInfo
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- CN102886240B CN102886240B CN201210360306.9A CN201210360306A CN102886240B CN 102886240 B CN102886240 B CN 102886240B CN 201210360306 A CN201210360306 A CN 201210360306A CN 102886240 B CN102886240 B CN 102886240B
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- flyash
- adsorbent
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Abstract
The invention relates to an adsorbent for removing a toxic element arsenic in water and application thereof. The adsorbent is formed by carrying out modification on pickled coal powder ash by zirconium manganese composite oxide. The invention also provides a method for removing arsenate ions in polluted water by utilizing the adsorbent. The adsorbent disclosed by the invention overcomes the defects of characteristics of low arsenic adsorption capacity, low selectivity and poor adsorption effect, utilizes solid waste, i.e. the coal powder ash and recycles waste materials so as to fulfill the aim of treating the waste by the waste. Meanwhile, the coal powder ash has low price and a method for preparing the adsorbent is simple, and thus, the adsorbent has good economic and environmental benefits.
Description
Technical field
The present invention relates to a kind of adsorbent and application thereof, relate in particular to a kind of adsorbent and application thereof of removing poisonous element arsenic in water, belong to water-treatment technology field.
Background technology
Arsenic be ubiquity in a kind of environment, strong toxicity, can be carcinogenic element.There are some researches show, Long Term Contact arsenic, even very low concentration also can cause the pathology of organism.Long Term Contact and drink the water body being polluted by arsenic, can cause lung cancer, liver cancer and cutaneum carcinoma etc.In order to minimize the harm of arsenic, the World Health Organization (WHO) specifies that the arsenic content of drinking water must not exceed 10 μ g/L.So, remove arsenic in water body to preserve the ecological environment and human health all tool be of great significance.
At present, the arsenic main method of removing in water body has coagulant sedimentation, ion-exchange, membrane processing method and absorption method.Wherein absorption method is considered to the most promising method, and this is because absorption method has additive method and do not possess a little, as: simple to operate, cost benefit is good etc.Making adsorbent with multicomponent composite oxide modification flyash is popular in recent years method.This method uses porous and the large feature of specific area of flyash, makes flyash turn waste into wealth simultaneously, deals carefully with power plant's solid waste.And multicomponent composite oxide can obtain better adsorption effect than monobasic modified oxide.Because flyash is less expensive, multicomponent composite oxide method of modifying is simple, and adsorption capacity is higher, ideal treatment effect.So the method for preparing adsorbent this can be widely used.But flyash self is not high to the saturated adsorption capacity of pentavalent arsenic in the aqueous solution, and treatment effect is bad, addresses this problem, to make full use of flyash, be very necessary.
Summary of the invention
Technical problem to be solved by this invention is the defect that overcomes prior art, a kind of adsorbent of removing poisonous element arsenic in water is provided, and described adsorbent is high to the adsorption capacity of arsenic, treatment effect good.In addition, the present invention also will further provide the application of described adsorbent.
Technical problem of the present invention is realized by following technical scheme.
Remove an adsorbent for poisonous element arsenic in water, described adsorbent by zirconium manganese composite oxide the flyash after to pickling modify and obtain.
Above-mentioned adsorbent, described zirconium manganese oxide is by ZrOCl
28H
2o and MnSO
4h
2o is prepared from, and both mol ratios are at 1:4 to 3:2.
Above-mentioned adsorbent, the particle diameter of the flyash after described pickling is for being less than 60 μ m, and carries out pretreatment through weak acid; Described weak acid carries out pretreatment and is specially: flyash is added to deionized water, under 200r/min condition, stir, with the rare nitric acid regulator solution of 2 mol/L pH=2, maintain pH constant simultaneously, keep 200r/min rotating speed to stir 1h, by the solution filter after stirring, repeatedly rinse until the pH value of solution after rinsing is 6.5-7.5, at 105 DEG C, vacuum drying 6 h, obtain the flyash after pickling.
Above-mentioned adsorbent, the process that described zirconium manganese composite oxide is modified flyash is: in the aqueous solution, add zirconium oxychloride and manganese sulfate to generate zirconium manganese oxide, add again weak acid flyash after treatment, make zirconium manganese oxide deposit to flyash surface, obtain adsorbent.
Above-mentioned adsorbent, describedly be specially by the process that zirconium manganese composite oxide is modified flyash: zirconium oxychloride and manganese sulfate are joined in the aqueous solution, NaOH with 1 mol/L in the situation that 200r/min stirs regulates pH=7.5, continue to stir 1h, then add the flyash after cleaning, the amount of flyash and the solid-to-liquid ratio 1:20 of solution (g/mL), continue to stir 0.5h, after question response completes static 24 hours aging, filter, repeatedly rinse flyash until the pH of solution after rinsing is 7-8 by deionized water, collect the flyash after modifying, in vacuum drying chamber, with 80 DEG C of temperature vacuum drying 4 hours, obtain can adsorbed water in the adsorbent of poisonous element arsenic.
Utilize adsorbent to remove a method for arsenate ion in contaminant water, described method is utilized above-mentioned adsorbent, carries out the absorption of arsenate ion at pH under the condition that is 3-5, and adsorption temp is 20-60 DEG C, and adsorption time is 30min-120min.
Said method, when the concentration range of arsenic ion in water is 0.05-50 μ g/mL, the weight ratio of adsorbent and contaminant water is 1:2500.
The adsorbent of poisonous element arsenic in removal water of the present invention, its advantage is: (1) it utilize power plant's solid waste coal ash to prepare efficient arsenic adsorbent, the object that reach the treatment of wastes with processes of wastes against one another, turns waste into wealth for raw material; (2) preparation process is simple, with low cost; (3) high adsorption capacity of the flyash after load to arsenate ion in contaminant water, adsorption capacity higher (be 3-5 at pH value of solution, concussion 2 h, quantity of sorbent 1 g/L, when initial concentration 10 μ g/mL, the clearance of arsenic can reach 93.81%-98.08%; In pH value of solution=3, concussion 20 h, quantity of sorbent 1 g/L, when initial concentration 50 μ g/mL, saturated adsorption capacity is 38.36 mg/g).
Brief description of the drawings
SEM (SEM) photo of Fig. 1 pickling flyash;
Fig. 2 load zirconium manganese composite oxide powder coal ash scanning of materials electron microscope (SEM) photo.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in further detail.
Embodiment 1 pickling flyash
Get 10g flyash in 500 mL large beakers, add 400 mL deionized waters, be placed in vigorous stirring on magnetic stirring apparatus, then, with the nitric acid regulator solution pH=2 of 2mol/L, stir 1h, in the process stirring, ensure pH=2.Stop stirring, repeatedly rinse flyash by deionized water, the water after rinsing is neutral (pH is 6.5-7.5), and at 105 DEG C dry 6 h, make flyash after pickling.
Embodiment 2 zirconium manganese composite oxides are modified fly ash material preparation
In the conical flask of 250mL, add the deionized water of 200mL, then add respectively 4.028g ZrOCl
28H
2o and 8.451g MnSO
4h
2o, the mol ratio (Zr:Mn=1:4) of zirconium and manganese is put into vigorous stirring on magnetic stirring apparatus.To the NaOH solution that adds 1mol/L in solution, regulate pH=7.5.In order to ensure that zirconium manganese oxide fully reacts, allow solution vigorous stirring 1h, use the NaOH regulator solution pH of 1mol/L simultaneously, make pH be always 7.5.
Pickling flyash 10g prepared by embodiment 1 joins in solution, fully stirs 0.5h.Then leave standstill aging 24h.Repeatedly rinse flyash by deionized water, until filtrate clarification is bright and pH is 7-8.Collect reacted flyash and at 80 DEG C, under vacuum environment, be dried 4h, the zirconium manganese oxide of system is modified fly ash composite material.
Embodiment 3 zirconium manganese oxides are modified fly ash composite material preparation
In the conical flask of 250mL, add the deionized water of 200mL, then add respectively 12.084g ZrOCl
28H
2o and 4.226g MnSO
4h
2o, the mol ratio (Zr:Mn=3:2) of zirconium and manganese is put into vigorous stirring on magnetic stirring apparatus.
Other conditions are with embodiment 2.
Arsenate ion in embodiment 4 Adsorption contaminant water
Make adsorbent, the pentavalent arsenic ion in Adsorption contaminant water with the former ash of not processing.Adsorption experiment, at 20 DEG C, carries out in 50mL closed container, and pentavalent arsenic ion initial concentration is 5 μ g/mL--30 μ g/mL, and pH value of solution is 4, and adsorbent dosage is 0.02g, and adsorption time is 20h, and maximal absorptive capacity is 4.709mg/g.
Arsenate ion in embodiment 5 Adsorption contaminant water
Make adsorbent with the flyash after pickling in embodiment 1, adsorption conditions is with embodiment 4, and the maximal absorptive capacity of adsorbent is 3.887 mg/g.Comparative example 4, and acid cleaning process can be avoided the pollutant in former ash to be carried and enter water body.
Arsenate ion in embodiment 6 Adsorption contaminant water
Modify flyash (Zr:Mn=3:2) with zirconium manganese composite oxide in embodiment 3 and make adsorbent, the pentavalent arsenic acid ion in Adsorption contaminant water.Adsorption experiment, at 20 DEG C, carries out in 50mL closed container, and arsenate ion initial concentration is 5 μ g/mL--50 μ g/mL, and pH value of solution is 3, and adsorbent dosage is 1g/L, and adsorption time is 20h, and maximal absorptive capacity is 38.36mg/g.
Comparative example 5, visible, modify flyash can effectively improve the adsorption capacity of flyash to arsenic with zirconium manganese oxide.
Arsenate ion in embodiment 7 Adsorption contaminant water
Modify flyash (Zr:Mn=1:4) with zirconium manganese composite oxide in embodiment 2 and make adsorbent, adsorption conditions is with embodiment 6, and the maximal absorptive capacity of adsorbent is 34.45mg/g.
Comparative example 6, visible, improve the ratio of Zr and Mn, can improve the adsorption capacity of sorbing material for arsenic in water.
Arsenate ion in embodiment 8 Adsorption contaminant water
Modify flyash (Zr:Mn=3:2) with zirconium manganese oxide in embodiment 3 and make adsorbent, the arsenate ion in Adsorption contaminant water.Adsorption experiment, at 20 DEG C, carries out in 50mL closed container, and pentavalent arsenic ion initial concentration is 10 μ g/mL, and pH value of solution is 3, and adsorbent dosage is 1g/L, and adsorption time is 2h, and arsenic removal rate is 98.08%.
Arsenate ion in embodiment 9 Adsorption contaminant water
Modify flyash (Zr:Mn=3:2) with zirconium manganese composite oxide in embodiment 3 and make adsorbent, carry out respectively adsorption experiment under the condition of pH=5 and pH=9, other adsorption conditionses are with embodiment 8.Arsenic removal rate is respectively 93.81% and 76.76%.
Comparative example 8, visible, and lower pH value is conducive to zirconium manganese composite oxide and modifies arsenate ion in fly ash material Adsorption water.
Arsenate ion in embodiment 10 Adsorption contaminant water
Modify flyash (Zr:Mn=3:2) with zirconium manganese composite oxide in embodiment 3 and make adsorbent, carry out respectively adsorption experiment under earthquake 30min and 150min condition, other adsorption conditionses are with embodiment 8.Arsenic removal rate is respectively 90.90% and 98.44%.
Comparative example 8, visible, adsorbent of the present invention to arsenic ion in water be adsorbed on 120min after substantially reach adsorption equilibrium, at this moment between in scope, along with the prolongation of adsorption time, adsorption efficiency increases.
Arsenate ion in embodiment 11 Adsorption contaminant water
Modify flyash (Zr:Mn=3:2) with zirconium manganese composite oxide in embodiment 3 and make adsorbent, carry out adsorption experiment under the condition of 50 DEG C, other adsorption conditionses are with embodiment 8.Arsenic removal rate is 99.82%.
Comparative example 8, visible, and suitably improve within the specific limits temperature and be conducive to the absorption of material to arsenate ion, result demonstration, it may be the endothermic reaction for the absorption of arsenate ion in water that zirconium manganese composite oxide is modified fly ash material.
The impact of embodiment 12 coexisting ions on adsorption effect
Modify flyash (Zr:Mn=3:2) with zirconium manganese oxide in embodiment 3 and make adsorbent, to the Na that adds 500 μ g/mL in the polluted-water that contains 10 μ g/mL arsenic ions
+, K
+, Ca
2+, Mg
2+, Zn
2+, Mn
2+, Ni
2+, Cu
2+, Cd
2+, Al
3+, Fe
3+, Fe
2+, Pb
2+, Ba
2+, Zn
2+, CO
3 2-, HCO
3 -, Cl
-, NO
3 -, SO
4 2-, H
2pO
4 -ion, adsorption conditions is with embodiment 8, investigates the impact of higher concentration common ion on effect of removing arsenic, and result shows, and most common zwitterion is modified in fly ash material adsorbed water arsenate ion without impact to zirconium manganese composite oxide, but Fe
3+and H
2pO
4 -affect greatlyr, tackle in actual applications the Fe of water middle and high concentration
3+and H
2pO
4 -ion carries out pretreatment, or by increasing the consumption of adsorbent to overcome interference.
Claims (3)
1. utilize adsorbent to remove a method for arsenate ion in contaminant water, it is characterized in that, described adsorbent by zirconium manganese composite oxide the flyash after to pickling modify and obtain;
Described zirconium manganese oxide is by ZrOCl
28H
2o and MnSO
4h
2o composition, both mol ratios are at 1:4 to 3:2;
The particle diameter of the flyash after described pickling is for being less than 60 μ m and carrying out pretreatment through weak acid;
Described weak acid is the aqueous solution regulating with the rare nitric acid of 2 mol/L, and pH is 2;
Described weak acid carries out pretreatment and is specially: flyash is added to deionized water, under 200r/min condition, stir, with the rare nitric acid regulator solution of 2 mol/L pH=2, maintain pH constant simultaneously, keep 200r/min rotating speed to stir 1h, by the solution filter after stirring, repeatedly rinse until the pH value of solution after rinsing is 6.5-7.5, at 105 DEG C, vacuum drying 6 h, obtain the flyash after pickling;
The process that described zirconium manganese composite oxide is modified flyash is: first, add zirconium oxychloride and manganese sulfate in the aqueous solution, then add weak acid flyash after treatment, the zirconium manganese oxide that reaction is generated deposits to flyash surface, obtains adsorbent;
Being adsorbed under the condition that pH is 3-5 of arsenate ion carried out, and adsorption temp is 20-60 DEG C, and adsorption time is 30min-120min.
2. method according to claim 1, is characterized in that, when the concentration range of arsenic ion in water is 0.05-50 μ g/mL, the weight ratio of adsorbent and contaminant water is 1:2500.
3. method according to claim 2, it is characterized in that, describedly be specially with the operation that zirconium manganese composite oxide is modified flyash: zirconium oxychloride and manganese sulfate are joined in the aqueous solution, NaOH with 1 mol/L in the situation that 200r/min stirs regulates pH=7.5, continue to stir 1h, then add the flyash after cleaning, the solid-to-liquid ratio 1:20 g/mL of the amount of flyash and solution, continue to stir 0.5h, after question response completes static 24 hours aging, filter, repeatedly rinse flyash until the pH of solution after rinsing is 7-8 by deionized water, collect the flyash after modifying, in vacuum drying chamber, with 80 DEG C of temperature vacuum drying 4 hours, obtain can adsorbed water in the adsorbent of poisonous element arsenic.
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| CN113058540A (en) * | 2021-04-01 | 2021-07-02 | 广西大学 | Adsorption oxidant capable of reducing toxicity and mobility of arsenic and antimony in water and soil environment and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1559923A (en) * | 2004-02-17 | 2005-01-05 | 东莞理工学院 | Preparation process of multifunctional flyash sewage treatment material |
| CN102389807A (en) * | 2011-09-09 | 2012-03-28 | 杭州凯大催化金属材料有限公司 | Multi-metal supported catalyst, and preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1559923A (en) * | 2004-02-17 | 2005-01-05 | 东莞理工学院 | Preparation process of multifunctional flyash sewage treatment material |
| CN102389807A (en) * | 2011-09-09 | 2012-03-28 | 杭州凯大催化金属材料有限公司 | Multi-metal supported catalyst, and preparation and application thereof |
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