CN103964603A - Method for treating heavy metal copper pollution in water - Google Patents
Method for treating heavy metal copper pollution in water Download PDFInfo
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- CN103964603A CN103964603A CN201410155085.0A CN201410155085A CN103964603A CN 103964603 A CN103964603 A CN 103964603A CN 201410155085 A CN201410155085 A CN 201410155085A CN 103964603 A CN103964603 A CN 103964603A
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Abstract
The invention relates to a treating technology for heavy metal copper pollution in water. According to the invention, by using the 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 heavy metal copper, thereby selectively adsorbing the heavy metal copper in the water solution, and then the material adsorbing the heavy metal copper is separated, namely the heavy metal copper in the water solution is removed. The treating technology provided by the invention has the advantages of simplicity in processing, high removal efficiency, low cost, good safety, reusability, zero secondary pollution and the like, has significance on removing the heavy metal copper 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 heavy metal copper ion in the aqueous solution, belong to the reparation field of polluting.
Background technology
Copper is the essential trace element of growth and development of plants, is again the multiple oxidasic moiety of plant.Plant lacks copper, the easy minus green of blade, and start and crop can not be normally solid from blade tip.Copper is the essential element that animal normal growth is grown, if food lacks copper, domestic animal easily causes the disease of " pica ".But copper is also to need one of effect of fertilizer of controlling simultaneously.Excessive copper can make crop photosynthesis weaken, branches and leaves chlorisis, and root growth is obstructed, production declining.In recent decades, mine development, three industrial wastes, all can cause the cupric of Copper In The Soil to increase, so that become secondary pollution as being widely used of Bordeaux mixture the pollution of soil, treatment of urban garbage, dirty fertilizer and cupric agricultural chemicals.The discharge of these pollutents has caused the severe contamination of environment, and extended residual is in environment, by geochemical process polluted underground water, by biogeochemical process, pollutes the whole ecosystem, agroecosystem particularly, endangers the health of animals and human beings class by food chain.Therefore study the sorption and desorption characteristic of heavy metal copper, significant to the prevention& repair of heavy metal contamination.
Resin, as a kind of novel functional high molecule material, has the advantages such as loading capacity is large, adsorption selectivity good, kind is many, is the adsorption and separation material that a class has application prospect.The resin that scholars can make new advances by changing the method preparation of its physical properties and chemical property, makes it in fractionation by adsorption direction, show wide Research Prospects.Wherein the resin containing N, S element has higher loading capacity and good adsorption 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 surface area and the good advantages such as thermostability, application at catalytic field has obtained significant achievement, and its application in fractionation by adsorption also shows good development prospect.
The present invention utilizes the meso pore silicon oxide material of resin modification to the good adsorptivity of heavy metal copper and the sedimentation effect of itself, from removing heavy metal copper ion containing the heavy metal copper aqueous solution.The meso pore silicon oxide material that 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 heavy metal copper ion, control processing condition and remove heavy metal heavy metal copper, for providing a kind of method containing heavy metal copper sewage disposal.
Have no at present the patented method that the meso pore silicon oxide material that adopts resin to modify removes heavy metal copper ion in the aqueous solution.
Summary of the invention
The method that the object of the invention is to heavy metal copper ion in the effective elimination aqueous solution.
Based on the problems referred to above, the invention provides a kind of method heavy metal cuprum polluted in water of processing, it is characterized in that the preparation of the meso pore silicon oxide material that resin is modified and the method that removes heavy metal copper in the aqueous solution, the steps include:
(1) containing the solution of heavy metal copper, introduce after filtering reactor, regulator solution pH is 1～8;
(2) regulator solution temperature is in 2～60 ℃;
(3) regulating containing copper concentration in the solution of heavy metal copper is <1000mg/L,
(4) the meso pore silicon oxide material MFT/S15-x-y synthetic resin being modified, wherein x is the mol ratio of organism and inorganics, y is the mol ratio of trimeric cyanamide and thiocarbamide in organism, the mol ratio of organism and inorganics is 1:1～20:1, the mol ratio of trimeric cyanamide and thiocarbamide is 10:1～1:10, with certain proportion, put into containing in heavy metal copper 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 desorption time at 5～120min;
(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, graphite furnace atomic absorption spectrometry is analyzed copper concentration remaining in the aqueous solution;
(9)
Wherein, the preparation method of the meso pore silicon oxide material MFT/S15-x-y that described resin is modified comprises the steps:
(1) preparation of synthetic liquid A: get the formalin of appropriate 37wt.% and appropriate deionized water, with sodium hydroxide (0.1mol/L) solution, adjust above-mentioned pH to 6.5-9.5, add afterwards a certain amount of trimeric cyanamide 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, add again appropriate (4mol/L) HCl solution and deionized water, at 25～60 ℃, stir P123 is dissolved completely, then add appropriate tetraethoxy, 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 resin is modified.
(4) MFT/S15-x-y, wherein x is the mol ratio of organism and inorganics, y is the mol ratio of trimeric cyanamide and thiocarbamide in organism.The mol ratio of organism and inorganics is 1:1～20:1, and the mol ratio of trimeric cyanamide and thiocarbamide is 10:1～1:10.
And the meso pore silicon oxide material that adopts resin to modify is while removing the method for heavy metal copper in the aqueous solution, solution temperature is 2～60 ℃, pH scope is 1～8, adsorption process oscillation frequency is 0～250r/min, processed liquid heavy metal copper ion concentration is 0～1000mg/L, the meso pore silicon oxide material amount that adds resin to modify is 0.1～10g/L, treatment time is 5～120min, then separated absorption has the meso pore silicon oxide material that the resin of heavy metal copper ion is modified, and can reach and remove more than 80% heavy metal copper in solution.
Advantage of the present invention is, meso pore silicon oxide material preparation technology that 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 heavy metal copper 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 heavy metal copper decreasing ratio (%) figure under different desorption times.
Fig. 2 is heavy metal copper decreasing ratio (%) figure under different desorbing agent additions.
Embodiment
Embodiment 1
Designed following experiment and studied the application that meso pore silicon oxide material that different desorption times modify resin removes heavy metal copper in the aqueous solution: whole reaction has adopted cillin bottle (50ml)+shaking table (200rpm) reaction system.The meso pore silicon oxide material that synthetic resin is modified is weighed in 50ml cillin bottle according to 5g/L, and the aqueous solution that absorption 25ml contains 100mg/L heavy metal copper is to 50ml cillin bottle, and heavy metal copper aqueous solution pH is 6.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 liquor, and graphite furnace atomic absorption spectrometry is analyzed heavy metal copper concentration remaining in the aqueous solution, calculates heavy metal copper decreasing ratio (seeing Fig. 1).Fig. 1 result shows, the meso pore silicon oxide material that resin is modified removes in the aqueous solution and can obtain good treatment effect in heavy metal copper 2h, and the method rapidly and efficiently.
Embodiment 2
Designed following experiment and studied the application that meso pore silicon oxide material that condition of different pH modifies resin removes heavy metal copper in the aqueous solution: whole reaction has adopted cillin bottle (50ml)+shaking table (200rpm) reaction system.The meso pore silicon oxide material that synthetic resin is modified is weighed in 50ml cillin bottle according to 5g/L, and the aqueous solution that absorption 25ml contains 100mg/L heavy metal copper is to 50ml cillin bottle, and heavy metal copper pH value of water solution scope is 1～8.Cover 25 ± 1 ℃ of constant temperature of serum cap and continue to shake (200rpm) 2h.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 liquor, and graphite furnace atomic absorption spectrometry is analyzed heavy metal copper concentration remaining in the aqueous solution, calculates heavy metal copper decreasing ratio (in Table 1).In table 1, result shows, the meso pore silicon oxide material that resin is modified in the scope of pH1～8 remove the aqueous solution in heavy metal copper all there is good treatment effect.
Heavy metal copper decreasing ratio (%) under table 1 condition of different pH
Embodiment 3
Designed following experiment and studied the application that the meso pore silicon oxide material of resin modification under Different adding amount condition removes heavy metal copper in the aqueous solution: whole reaction has adopted cillin bottle (50ml)+shaking table (200rpm) reaction system.The meso pore silicon oxide material that synthetic resin is modified is weighed in 50ml cillin bottle according to 0～10g/L, and the aqueous solution that absorption 25ml contains 100mg/L heavy metal copper is to 50ml cillin bottle, and heavy metal copper pH value of water solution is 6.Cover 25 ± 1 ℃ of constant temperature of serum cap and continue to shake (200rpm) 3h.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 liquor, and graphite furnace atomic absorption spectrometry is analyzed heavy metal copper concentration remaining in the aqueous solution, calculates heavy metal copper decreasing ratio (seeing Fig. 2).In Fig. 2, result shows, the increase of the meso pore silicon oxide material addition of modifying along with resin, removes the effect of heavy metal copper in the aqueous solution and significantly improve.
Embodiment 4
Designed following experiment and studied the effect of reusing that meso pore silicon oxide material that resin modifies removes heavy metal copper in the aqueous solution: whole reaction has adopted cillin bottle (50ml)+shaking table (200rpm) reaction system.The meso pore silicon oxide material that synthetic resin is modified is weighed in 50ml cillin bottle according to 5g/L, and the aqueous solution that absorption 25ml contains 100mg/L heavy metal copper is to 50ml cillin bottle, and heavy metal copper aqueous solution pH is 6.Cover 25 ± 1 ℃ of constant temperature of serum cap and continue to shake (200rpm) 3h.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 liquor, graphite furnace atomic absorption spectrometry is analyzed heavy metal copper concentration remaining in the aqueous solution, calculate heavy metal copper decreasing ratio, after the heavy metal copper that uses 0.5M EDTA wash-out to adsorb, reuse, the results are shown in Table 2.In table 2, result shows, the meso pore silicon oxide material that this resin is modified removes heavy metal copper in the aqueous solution and all has reusable function.
Table 2 is reused lower heavy metal copper decreasing ratio (%)
。
Claims (5)
1. process a method heavy metal cuprum polluted in water, it is characterized in that the preparation of the meso pore silicon oxide material that resin is modified and the method that removes heavy metal copper in the aqueous solution, the steps include:
Solution containing heavy metal copper is introduced reactor after filtering, and regulator solution pH is 1 ~ 8;
Regulator solution temperature is in 2 ~ 60
oc;
Regulating containing copper concentration in the solution of heavy metal copper is <1000 mg/L,
The meso pore silicon oxide material MFT/S15-x-y that synthetic resin is modified, wherein x is the mol ratio of organism and inorganics, y is the mol ratio of trimeric cyanamide and thiocarbamide in organism, the mol ratio of organism and inorganics is 1:1～20:1, the mol ratio of trimeric cyanamide and thiocarbamide is 10:1～1:10, with certain proportion, put into containing in heavy metal copper 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 desorption time at 5 ~ 120 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, graphite furnace atomic absorption spectrometry is analyzed copper concentration remaining in the aqueous solution;
Calculating heavy metal copper decreasing ratio=
.
2. process as claimed in claim 1 method heavy metal cuprum polluted in water, it is characterized in that the preparation method of the meso pore silicon oxide material MFT/S15-x-y that described resin is modified comprises the steps:
The preparation of synthetic liquid A: get the formalin of appropriate 37 wt.% and appropriate deionized water, adjust above-mentioned pH to 6.5-9.5 with sodium hydroxide (0.1mol/L) solution, add afterwards a certain amount of trimeric cyanamide and thiocarbamide, in 30 ~ 80
ounder C, stir and within 5 ~ 24 hours, form solution A;
The preparation of synthetic liquid 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 tetraethoxy, 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 resin is modified;
MFT/S15-x-y, wherein x is the mol ratio of organism and inorganics, y is the mol ratio of trimeric cyanamide and thiocarbamide in organism.
4. the mol ratio of organism and inorganics is 1:1～20:1, and the mol ratio of trimeric cyanamide and thiocarbamide is 10:1～1:10.
5. the method for heavy metal copper in the processing aqueous solution as claimed in claim 1, is characterized in that solution temperature is 2 ~ 60
oc, pH scope is 1 ~ 8, adsorption process oscillation frequency is 0 ~ 250r/min, processed liquid heavy metal copper ion concentration is 0 ~ 1000 mg/L, the meso pore silicon oxide material amount that adds resin to modify is 0.1 ~ 10 g/L, treatment time is 5 ~ 120 min, and then separated absorption has the meso pore silicon oxide material that the resin of heavy metal copper ion is modified.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410155085.0A CN103964603A (en) | 2014-04-18 | 2014-04-18 | Method for treating heavy metal copper pollution in water |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410155085.0A CN103964603A (en) | 2014-04-18 | 2014-04-18 | Method for treating heavy metal copper pollution in water |
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| CN201410155085.0A Pending CN103964603A (en) | 2014-04-18 | 2014-04-18 | Method for treating heavy metal copper pollution in water |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254830A (en) * | 2015-11-20 | 2016-01-20 | 天津大学 | Method for preparing water-soluble thiourea aldehyde heavy metal capturing agent with low formaldehyde content |
| CN109180244A (en) * | 2015-12-14 | 2019-01-11 | 宁波职业技术学院 | Using mesopore silicon oxide as the compost method of heavy metal deactivator and microbe carrier |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6482380B1 (en) * | 2000-11-22 | 2002-11-19 | The United States Of America As Represented By The Department Of Energy | Silicotitanate molecular sieve and condensed phases |
| CN101219371A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Photocatalysis oxidation treated high concentration organic trade waste |
| CN103157501A (en) * | 2013-04-07 | 2013-06-19 | 扬州大学 | Method for preparing catalyst for catalyzing organic pollutants in wet oxidation water |
-
2014
- 2014-04-18 CN CN201410155085.0A patent/CN103964603A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6482380B1 (en) * | 2000-11-22 | 2002-11-19 | The United States Of America As Represented By The Department Of Energy | Silicotitanate molecular sieve and condensed phases |
| CN101219371A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Photocatalysis oxidation treated high concentration organic trade waste |
| CN103157501A (en) * | 2013-04-07 | 2013-06-19 | 扬州大学 | Method for preparing catalyst for catalyzing organic pollutants in wet oxidation water |
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 |
|---|---|---|---|---|
| CN105254830A (en) * | 2015-11-20 | 2016-01-20 | 天津大学 | Method for preparing water-soluble thiourea aldehyde heavy metal capturing agent with low formaldehyde content |
| CN109180244A (en) * | 2015-12-14 | 2019-01-11 | 宁波职业技术学院 | Using mesopore silicon oxide as the compost method of heavy metal deactivator and microbe carrier |
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Application publication date: 20140806 |
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