CN103962109A - Method for treating pentavalent arsenic pollution in water - Google Patents
Method for treating pentavalent arsenic pollution in water Download PDFInfo
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- CN103962109A CN103962109A CN201410155289.4A CN201410155289A CN103962109A CN 103962109 A CN103962109 A CN 103962109A CN 201410155289 A CN201410155289 A CN 201410155289A CN 103962109 A CN103962109 A CN 103962109A
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Abstract
The invention relates to a treating technology for pentavalent arsenic pollution in water. According to the invention, by using advantages of uniform and ordered aperture passages, adjustable pore diameters, larger specific surface area, excellent thermal stability and the like of a mesoporous silicon oxide material decorated by chelate resin, the mesoporous silicon oxide material decorated by the chelate resin is input into a water solution containing pentavalent arsenic, thereby selectively adsorbing the pentavalent arsenic in the water solution, and then the material adsorbing the pentavalent arsenic is separated, namely the pentavalent arsenic in the water solution is desorbed. The treating technology provided by the invention has the advantages of simplicity in process, high removing efficiency, low cost, good safety, capability of reusing, zero secondary pollution and the like, has significance on removing the pentavalent arsenic in water, and has a wide application prospect in the field of resources and environment such as sewage disposal, drinking water purification and the like.
Description
Technical field
The present invention relates to a kind of method that removes pentavalent arsenic ion in the aqueous solution, belong to the reparation field of polluting.
Background technology
Arsenic is distributed widely in the middle of the environment that we live, and belongs to transition elements, similar to the character of metalloid.Many authoritative institutions such as Shen Bei international cancer research institute are known as strong carcinogen, are one of preferential pollutants of controlling in water body, are that a class needs the strict high-risk pollutant of controlling.The arsenic of occurring in nature seldom exists with the form of element arsenic, often with trivalent arsenic (As
2o
3, NaAsO
2and AsCl
3) and pentavalent arsenic (As
2o
5, H
3as
3o
4) etc. form exist.After arsenic enters and is absorbed in human body, can destroy the redox ability of cell, affect the eubolism of cell, cause histologic lesion and body obstacle, when serious, can cause and be poisoned to death.In recent years, along with taking place frequently and the increasingly stringent (being reduced to 10ug/L by 50ug/L) of Arsenic in Drinking Water concentration standard of global arsenic contamination accident, the elimination that water body arsenic pollutes becomes one of study hotspot of global common concern.Therefore study the sorption and desorption characteristic of arsenic, significant to the prevention& repair of heavy metal pollution.
At present, Hua Fa ﹑ physico-chemical process and microbial method are to process the conventional method of using of arsenic-containing waste water.Wherein, absorption method is a kind of simple arsenic wastewater processing technology, have efficient, easy, selectively good, material source is extensive, can efficiently remove object and environment is not produced or produce the advantages such as slight secondary pollution, thereby being subject to people's common concern.Adsorbent is the key point that determines adsorption system effect, and the preparation method of adsorbent and its absorption property are of close concern to each other.Chelating resin, as a kind of novel functional high molecule material, has the advantages such as adsorption capacity is large, adsorptive selectivity good, kind is many, is the adsorption and separation material that a class has application prospect.The chelating resin that scholars can make new advances by changing the method preparation of its physical property and chemical property, makes it in adsorbing separation direction, show wide Research Prospects.Wherein the chelating resin containing N, S element has higher adsorption capacity and good adsorptive selectivity to precious metal ion in the aqueous solution.Meso pore silicon oxide material has the duct of uniform and ordered, adjustable aperture, larger specific area and the good advantages such as heat endurance, application at catalytic field has obtained significant achievement, and its application in adsorbing separation also shows good development prospect.
The present invention utilizes the meso pore silicon oxide material of chelating resin modification to the good adsorptivity of pentavalent arsenic and the sedimentation effect of itself, from removing pentavalent arsenic ion containing the pentavalent arsenic aqueous solution.The meso pore silicon oxide material that chelating resin is modified is prepared through Hydrothermal Synthesis technology, the solid of transportation that obtain being dried, resistance to, easy preservation.Put into the solution containing finite concentration pentavalent arsenic ion, control process conditions and remove heavy metal pentavalent arsenic, for providing a kind of method containing pentavalent arsenic sewage disposal.
Have no at present the patented method that the meso pore silicon oxide material that adopts chelating resin to modify removes pentavalent arsenic ion in the aqueous solution.
Summary of the invention
The object of the invention is to effectively remove pentavalent arsenic ion in the aqueous solution.
Based on the problems referred to above, the invention provides a kind of method that in water, pentavalent arsenic pollutes of processing, it is characterized in that the preparation of the meso pore silicon oxide material that chelating resin is modified and the method that removes pentavalent arsenic in the aqueous solution, the steps include:
(1) arsenic2 solution is introduced reactor after filtering, and regulator solution pH is 2～11;
(2) regulator solution temperature is in 2～60 ℃;
(3) regulating pentavalent arsenic concentration in arsenic2 solution is <1000mg/L,
(4) the meso pore silicon oxide material MFT/S15-x-y synthetic chelating resin being modified, wherein x is the mol ratio of organic matter and inorganic matter, y is the mol ratio of melamine and thiocarbamide in organic matter, the mol ratio of organic matter and inorganic matter is 1:1～20:1, the mol ratio of melamine and thiocarbamide is 10:1～1:10, with certain proportion, put into containing in pentavalent arsenic solution after filtration, keep solid-to-liquid ratio at 0.1～10g/L;
(5) introduce and stir oscillator, speed control is at 0～250rpm;
(6) control adsorption time at 5～360min;
(7) reacted liquid imports in other reactors after solid-liquid separator separation;
(8) liquid of learning from else's experience after solid-liquid separator separation, the pentavalent arsenic concentration of remnants in the hydride generation atomic fluorescence photometric analysis aqueous solution;
(9)
Wherein, the preparation method of the meso pore silicon oxide material MFT/S15-x-y that described chelating resin is modified comprises the steps:
(1) preparation of synthetic liquid A: get the formalin of appropriate 37wt.% and appropriate deionized water, with NaOH (0.1mol/L) solution, adjust above-mentioned pH to 6.5-9.5, add afterwards a certain amount of melamine and thiocarbamide, at 30～80 ℃, stir and within 5～24 hours, form solution A.
(2) preparation of synthetic liquid B: get appropriate P123 and add in beaker, then add appropriate (4mol/L) HCl solution and deionized water, stir P123 is dissolved completely at 25～60 ℃, then add appropriate ethyl orthosilicate, stir 3～12h, form solution B.
(3) solution A and solution B is mixed with mol ratio 1:1～20:1, at 30～80 ℃, continue to stir after 12～24h, then ageing 48 hours at 30～80 ℃.The white precipitate obtaining is filtered, washing, then dry, with ethanol Soxhlet extracting 24～72 hours, obtain the meso pore silicon oxide material that chelating resin is modified.
(4) MFT/S15-x-y, wherein x is the mol ratio of organic matter and inorganic matter, y is the mol ratio of melamine and thiocarbamide in organic matter.The mol ratio of organic matter and inorganic matter is 1:1～20:1, and the mol ratio of melamine and thiocarbamide is 10:1～1:10.
And the meso pore silicon oxide material that adopts chelating resin to modify is while removing the method for pentavalent arsenic in the aqueous solution, solution temperature is 2～60 ℃, pH scope is 2～11, adsorption process frequency of oscillation is 0～250r/min, processed liquid pentavalent arsenic ion concentration is 0～1000mg/L, the meso pore silicon oxide material amount that adds chelating resin to modify is 0.1～10g/L, processing time is 5～360min, then separated absorption has the meso pore silicon oxide material that the chelating resin of pentavalent arsenic ion is modified, and can reach and remove more than 80% pentavalent arsenic in solution.
Advantage of the present invention is, meso pore silicon oxide material preparation technology that chelating resin is modified is simple, removal efficiency is high, cost is low, security is good, reusable, do not cause the advantages such as secondary pollution, significant to the pentavalent arsenic ion of removing in water, in resource environment fields such as sewage disposal, purifying drinking waters, there is very wide application prospect.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, further illustrate.
Fig. 1 is pentavalent arsenic removal efficiency (%) figure under condition of different pH.
Fig. 2 is pentavalent arsenic removal efficiency (%) figure under different desorption times.
The specific embodiment
Embodiment 1
Designed following experiment and studied the application that meso pore silicon oxide material that condition of different pH modifies chelating resin removes pentavalent arsenic in the aqueous solution: whole reaction has adopted cillin bottle (50ml)+shaking table (200rpm) reaction system.The meso pore silicon oxide material that synthetic chelating resin is modified is weighed in 50ml cillin bottle according to 3g/L, and the aqueous solution that absorption 25ml contains 100mg/L pentavalent arsenic is to 50ml cillin bottle, and pentavalent arsenic pH value of water solution scope is 2～8.Cover 25 ± 1 ℃ of constant temperature of serum cap and continue to shake (200rpm) 4h.Bottle number is determined according to sampling number.During mensuration, get at random 3 bottles, suspension is shaken up, then remove aluminium lid, open plug.Centrifugal (6500rpm, 10-20min) separation, gets supernatant, and the pentavalent arsenic concentration of remnants in the hydride generation atomic fluorescence photometric analysis aqueous solution, calculates pentavalent arsenic removal efficiency (seeing Fig. 1).In Fig. 1, result shows, the meso pore silicon oxide material that chelating resin is modified in the scope of pH2～11 remove the aqueous solution in pentavalent arsenic all there is good treatment effect.
Embodiment 2
Designed following experiment and studied the application that meso pore silicon oxide material that different desorption times modify chelating resin removes pentavalent arsenic in the aqueous solution: whole reaction has adopted cillin bottle (50ml)+shaking table (200rpm) reaction system.The meso pore silicon oxide material that synthetic chelating resin is modified is weighed in 50ml cillin bottle according to 3g/L, and the aqueous solution that absorption 25ml contains 100mg/L pentavalent arsenic is to 50ml cillin bottle, and pentavalent arsenic aqueous solution pH is 7.Cover 25 ± 1 ℃ of constant temperature of serum cap and continue to shake (200rpm) 0～360min.Bottle number is determined according to sampling number.During mensuration, get at random 3 bottles, suspension is shaken up, then remove aluminium lid, open plug.Centrifugal (6500rpm, 10-20min) separation, gets supernatant, and the pentavalent arsenic concentration of remnants in the hydride generation atomic fluorescence photometric analysis aqueous solution, calculates pentavalent arsenic removal efficiency (seeing Fig. 2).Fig. 2 result shows, the meso pore silicon oxide material that chelating resin is modified removes in the aqueous solution and can obtain good treatment effect in pentavalent arsenic 300min, and the method rapidly and efficiently.
Embodiment 3
Designed following experiment and studied the application that the meso pore silicon oxide material of chelating resin modification under Different adding amount condition removes pentavalent arsenic in the aqueous solution: whole reaction has adopted cillin bottle (50ml)+shaking table (200rpm) reaction system.The meso pore silicon oxide material that synthetic chelating resin is modified is weighed in 50ml cillin bottle according to 1～10g/L, and the aqueous solution that absorption 25ml contains 100mg/L pentavalent arsenic is to 50ml cillin bottle, and pentavalent arsenic pH value of water solution is 6.Cover 25 ± 1 ℃ of constant temperature of serum cap and continue to shake (200rpm) 4h.Bottle number is determined according to sampling number.During mensuration, get at random 3 bottles, suspension is shaken up, then remove aluminium lid, open plug.Centrifugal (6500 rpm, 10-20min) separation, gets supernatant, and the pentavalent arsenic concentration of remnants in the hydride generation atomic fluorescence photometric analysis aqueous solution, calculates pentavalent arsenic removal efficiency (in Table 1).In table 1, result shows, the increase of the meso pore silicon oxide material addition of modifying along with chelating resin, removes the effect of pentavalent arsenic in the aqueous solution and significantly improve.
Pentavalent arsenic removal efficiency (%) under the different desorbing agent additions of table 1
Embodiment 4
Designed following experiment and studied the application that meso pore silicon oxide material that different temperatures modifies chelating resin removes pentavalent arsenic in the aqueous solution: whole reaction has adopted cillin bottle (50ml)+shaking table (200rpm) reaction system.The meso pore silicon oxide material that synthetic chelating resin is modified is weighed in 50ml cillin bottle according to 3g/L, and the aqueous solution that absorption 25ml contains 50mg/L pentavalent arsenic is to 50ml cillin bottle, and pentavalent arsenic aqueous solution pH is 7.Cover serum cap 278～318K constant temperature and continue to shake (200rpm) 4h.Bottle number is determined according to sampling number.During mensuration, get at random 3 bottles, suspension is shaken up, then remove aluminium lid, open plug.Centrifugal (6500rpm, 10-20min) separation, gets supernatant, and the pentavalent arsenic concentration of remnants in the hydride generation atomic fluorescence photometric analysis aqueous solution, calculates pentavalent arsenic removal efficiency (in Table 2).In table 2, result shows, the meso pore silicon oxide material that chelating resin is modified in wider temperature range remove the aqueous solution in pentavalent arsenic all there is good treatment effect.
Pentavalent arsenic removal efficiency (%) under the different desorption temperatures of table 2
Claims (5)
1. process the method that in water, pentavalent arsenic pollutes, it is characterized in that the preparation of the meso pore silicon oxide material that chelating resin is modified and the method that removes pentavalent arsenic in the aqueous solution, the steps include:
Arsenic2 solution is introduced reactor after filtering, and regulator solution pH is 2 ~ 11;
Regulator solution temperature is in 2 ~ 60
oc;
Regulating pentavalent arsenic concentration in arsenic2 solution is <1000 mg/L,
The meso pore silicon oxide material MFT/S15-x-y that synthetic chelating resin is modified, wherein x is the mol ratio of organic matter and inorganic matter, y is the mol ratio of melamine and thiocarbamide in organic matter, the mol ratio of organic matter and inorganic matter is 1:1～20:1, the mol ratio of melamine and thiocarbamide is 10:1～1:10, with certain proportion, put into containing in pentavalent arsenic solution after filtration, keep solid-to-liquid ratio at 0.1 ~ 10 g/L;
Introduce and stir oscillator, speed control is at 0 ~ 250 rpm;
Control adsorption time at 5 ~ 360 min;
Reacted liquid imports in other reactors after solid-liquid separator separation;
The liquid of learning from else's experience after solid-liquid separator separation, the pentavalent arsenic concentration of remnants in the hydride generation atomic fluorescence photometric analysis aqueous solution;
Calculating pentavalent arsenic removal efficiency=
.
2. process as claimed in claim 1 the method that in water, pentavalent arsenic pollutes, it is characterized in that the preparation method of the meso pore silicon oxide material MFT/S15-x-y that described chelating resin is modified comprises the steps:
The preparation of synthetic A: get the formalin of appropriate 37 wt.% and appropriate deionized water, adjust above-mentioned pH to 6.5-9.5 with NaOH (0.1mol/L) solution, add afterwards a certain amount of melamine and thiocarbamide, in 30 ~ 80
ounder C, stir and within 5 ~ 24 hours, form solution A;
The preparation of storing solution B: get appropriate P123 and add in beaker, then add appropriate (4 mol/L) HCl solution and deionized water, 25 ~ 60
ounder C, stir P123 is dissolved completely, then add appropriate ethyl orthosilicate, stir 3 ~ 12 h, form solution B;
Solution A and solution B is mixed with mol ratio 1:1～20:1,30 ~ 80
ounder C, continue to stir after 12 ~ 24 h, then in 30 ~ 80
ounder C, ageing is 48 hours.
3. the white precipitate obtaining is filtered, washing, then dry, with ethanol Soxhlet extracting 24 ~ 72 hours, obtain the meso pore silicon oxide material that chelating resin is modified;
MFT/S15-x-y, wherein x is the mol ratio of organic matter and inorganic matter, y is the mol ratio of melamine and thiocarbamide in organic matter.
4. the mol ratio of organic matter and inorganic matter is 1:1～20:1, and the mol ratio of melamine and thiocarbamide is 10:1～1:10.
5. the method for pentavalent arsenic in the processing aqueous solution as claimed in claim 1, is characterized in that solution temperature is 2 ~ 60
oc, pH scope is 2 ~ 11, adsorption process frequency of oscillation is 0 ~ 250r/min, processed liquid pentavalent arsenic ion concentration is 0 ~ 1000 mg/L, the meso pore silicon oxide material amount that adds chelating resin to modify is 0.1 ~ 10 g/L, processing time is 5 ~ 360 min, and then separated absorption has the meso pore silicon oxide material that the chelating resin of pentavalent arsenic ion is modified.
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|---|---|---|---|
| CN201410155289.4A CN103962109A (en) | 2014-04-18 | 2014-04-18 | Method for treating pentavalent arsenic pollution in water |
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| CN201410155289.4A CN103962109A (en) | 2014-04-18 | 2014-04-18 | Method for treating pentavalent arsenic pollution in water |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105217748A (en) * | 2015-11-05 | 2016-01-06 | 鲁东大学 | There is the preparation of Magneto separate, photochemical catalytic oxidation and adsorption arsenic-removing adsorption agent |
| CN115178242A (en) * | 2022-06-28 | 2022-10-14 | 中国地质大学（武汉） | Adsorption film for fixing pentavalent arsenic ions as well as preparation method and application thereof |
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| JPS5641645B2 (en) * | 1972-07-26 | 1981-09-29 | ||
| CN1346805A (en) * | 2000-10-09 | 2002-05-01 | 拜尔公司 | Use of monodisperse ion exchange agent for removing As/Sb |
| CN102352006A (en) * | 2011-07-20 | 2012-02-15 | 合肥工业大学 | Ultrasonic preparation method of micron spherical melamine-formaldehyde-thiourea chelating resin |
-
2014
- 2014-04-18 CN CN201410155289.4A patent/CN103962109A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5641645B2 (en) * | 1972-07-26 | 1981-09-29 | ||
| CN1346805A (en) * | 2000-10-09 | 2002-05-01 | 拜尔公司 | Use of monodisperse ion exchange agent for removing As/Sb |
| CN102352006A (en) * | 2011-07-20 | 2012-02-15 | 合肥工业大学 | Ultrasonic preparation method of micron spherical melamine-formaldehyde-thiourea chelating resin |
Non-Patent Citations (2)
| Title |
|---|
| 周乐舟等: "嵌段中孔材料 SBA- 15( SH) 的制备及应用", 《分析化学》 * |
| 黄毅等: "三聚氰胺-甲醛-硫脲树脂/SBA-15复合材料的合成及其对水溶液中Au（Ⅲ）吸附性能的研究", 《湖南师范大学自然科学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105217748A (en) * | 2015-11-05 | 2016-01-06 | 鲁东大学 | There is the preparation of Magneto separate, photochemical catalytic oxidation and adsorption arsenic-removing adsorption agent |
| CN115178242A (en) * | 2022-06-28 | 2022-10-14 | 中国地质大学（武汉） | Adsorption film for fixing pentavalent arsenic ions as well as preparation method and application thereof |
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Application publication date: 20140806 |