CN103964534A - Method for treating heavy metal zinc pollution in water - Google Patents
Method for treating heavy metal zinc pollution in water Download PDFInfo
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- CN103964534A CN103964534A CN201410155082.7A CN201410155082A CN103964534A CN 103964534 A CN103964534 A CN 103964534A CN 201410155082 A CN201410155082 A CN 201410155082A CN 103964534 A CN103964534 A CN 103964534A
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- heavy metal
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Abstract
The invention relates to a treating technology for heavy metal zinc 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 zinc, thereby selectively adsorbing the heavy metal zinc in the water solution, and then the material adsorbing the heavy metal zinc is separated, namely the heavy metal zinc 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 zinc 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 zinc ion in the aqueous solution, belong to the reparation field of polluting.
Background technology
Though zinc is micro elements needed by human, excess or coexist and also can bring harm to body with other poisonous metal.Heavy metal zinc is also one of essential micronutrient element of plant-growth, for the important composition composition of plurality of enzymes avtive spot, in the normal plysiochemical process of plant, play an important role, but due to the special chemical character of zinc self, it easily moves in edatope, when excessive, will have a negative impact to plant-growth.Containing Zn
2+waste water mainly comes from the industries such as plating, mining, smelting and chemical industry, Zn
2+enter environment and will cause soil and groundwater to pollute, and then HUMAN HEALTH is produced and threatened.In recent years, because constantly aggravation is smelted in the exploitation of plumbous zinc ore, and the expansion of the heavy metal pollution of area source such as feces of livestock and poultry and fertilizer and pesticide, farmland arable soil zinc pollution presents the trend that increases the weight of in various degree.Meanwhile, excessive zinc, by geochemical process polluted underground water, pollutes the whole ecosystem, particularly agroecosystem by biogeochemical process, endangers the health of animals and human beings class by food chain.Therefore study the sorption and desorption characteristic of zinc, significant to the prevention& repair of heavy metal contamination.
Heavy metal containing wastewater treatment technology mainly contains chemical method, ion exchange method, biological process and absorption method etc.Because sorbing material specific surface area is large, high adsorption capacity, be applicable to processing the water yield large, containing advantages such as the low concentration wastewaters of contents of many kinds of heavy metal ion, absorption method gets more and more people's extensive concerning always.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.Scholars can prepare the resin making new advances by the method that changes its physical properties and chemical property, make it show wide Research Prospects in fractionation by adsorption direction.Wherein containing the resin of N, S element, precious metal ion in the aqueous solution is had to higher loading capacity and good adsorption selectivity.Meso pore silicon oxide material has the duct of uniform and ordered, adjustable aperture, the larger advantage such as specific surface area and good thermostability, obtained significant achievement in the application of catalytic field, 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 zinc and the sedimentation effect of itself, from removing heavy metal zinc ion containing the heavy metal zinc aqueous solution.The meso pore silicon oxide material that resin is modified is prepared through Hydrothermal Synthesis technology, the solid of transport that obtain being dried, resistance to, easy preservation.Put into the solution containing finite concentration heavy metal zinc ion, control processing condition and remove heavy metal heavy metal zinc, for providing a kind of method containing heavy metal zinc sewage disposal.
Have no at present the patented method that the meso pore silicon oxide material that adopts resin to modify removes heavy metal zinc ion in the aqueous solution.
Summary of the invention
The object of the invention is to the method that in the effective elimination aqueous solution, heavy metal zinc pollutes.
Based on the problems referred to above, the invention provides a kind of method that heavy metal zinc in water pollutes of processing, it is characterized in that the preparation of the meso pore silicon oxide material that resin modifies and remove the method for heavy metal zinc in the aqueous solution, the steps include:
(1) introduce after filtering reactor containing the solution of heavy metal zinc, regulator solution pH is 2～10;
(2) regulator solution temperature is in 2～60 DEG C;
(3) regulating containing heavy metal zinc concentration in the solution of heavy metal zinc 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, put into containing in heavy metal zinc solution after filtration with certain proportion, 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 5～360min;
(7) reacted liquid imports in other reactors after solid-liquid separator separates;
(8) liquid of learning from else's experience after solid-liquid separator separation, graphite furnace atomic absorption spectrometry is analyzed heavy metal zinc 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, 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, at 30～80 DEG C, 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 DEG C, 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 DEG C, continue to stir after 12～24h, then ageing 48 hours at 30～80 DEG C.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.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 adopt meso pore silicon oxide material that resin modifies while removing the method for heavy metal zinc in the aqueous solution, solution temperature is 2～60 DEG C, pH scope is 2～10, adsorption process oscillation frequency is 0～250r/min, processed liquid heavy metal zinc 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 5～360min, then separate the meso pore silicon oxide material that absorption has the resin of heavy metal zinc ion to modify, can reach and remove more than 80% heavy metal zinc in solution.
Advantage of the present invention is, resin modify meso pore silicon oxide material preparation technology 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 zinc ion in removing water, there is very wide application prospect in the resource environment such as sewage disposal, purifying drinking water field.
Brief description of the drawings
Further illustrate below in conjunction with drawings and Examples.
Fig. 1 is heavy metal zinc decreasing ratio (%) figure under different desorption temperatures.
Fig. 2 is heavy metal zinc decreasing ratio (%) figure under different desorption times.
Fig. 3 is heavy metal zinc decreasing ratio (%) figure under condition of different pH.
Fig. 4 reuses lower heavy metal zinc decreasing ratio (%) figure.
Embodiment
Embodiment 1
Having designed following experiment studies the meso pore silicon oxide material that differing temps modifies resin and removes the application of heavy metal zinc in the aqueous solution: whole reaction adopts 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 3g/L, and the aqueous solution that absorption 25ml contains 50mg/L heavy metal zinc is to 50ml cillin bottle, and heavy metal zinc aqueous solution pH is 7.Cover serum cap 288～318K constant temperature and continue shake (200rpm) 120min.Bottle number is determined according to sampling number.When mensuration, get at random 3 bottles, suspension is shaken up, then remove aluminium lid, open plug.Centrifugal (6500rpm, 10-20min) separates, and gets supernatant liquor, and the heavy metal zinc concentration of remnants in the graphite furnace atomic absorption spectrometry aqueous solution, calculates heavy metal zinc decreasing ratio (seeing Fig. 1).In Fig. 1, result shows, the meso pore silicon oxide material that resin is modified in wide temperature range removes heavy metal zinc in the aqueous solution and all has good treatment effect.
Embodiment 2
Having designed following experiment studies the meso pore silicon oxide material that different desorption times modify resin and removes the application of heavy metal zinc in the aqueous solution: whole reaction adopts 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 3g/L, and the aqueous solution that absorption 25ml contains 100mg/L heavy metal zinc is to 50ml cillin bottle, and heavy metal zinc aqueous solution pH is 7.Cover 25 ± 1 DEG C of constant temperature of serum cap and continue shake (200rpm) 0～420min.Bottle number is determined according to sampling number.When mensuration, get at random 3 bottles, suspension is shaken up, then remove aluminium lid, open plug.Centrifugal (6500rpm, 10-20min) separates, and gets supernatant liquor, and graphite furnace atomic absorption spectrometry is analyzed heavy metal zinc concentration remaining in the aqueous solution, calculates heavy metal zinc decreasing ratio (seeing Fig. 2).Fig. 2 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 zinc 240min, and the method rapidly and efficiently.
Embodiment 3
Having designed following experiment studies the meso pore silicon oxide material that condition of different pH modifies resin and removes the application of heavy metal zinc in the aqueous solution: whole reaction adopts 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 3g/L, and the aqueous solution that absorption 25ml contains 100mg/L heavy metal zinc is to 50ml cillin bottle, and heavy metal zinc pH value of water solution scope is 1～10.Cover 25 ± 1 DEG C of constant temperature of serum cap and continue shake (200rpm) 4h.Bottle number is determined according to sampling number.When mensuration, get at random 3 bottles, suspension is shaken up, then remove aluminium lid, open plug.Centrifugal (6500rpm, 10-20min) separates, and gets supernatant liquor, and graphite furnace atomic absorption spectrometry is analyzed heavy metal zinc concentration remaining in the aqueous solution, calculates heavy metal zinc decreasing ratio (seeing Fig. 3).In Fig. 3, result shows, in the scope of pH2～8 resin modify meso pore silicon oxide material remove the aqueous solution in heavy metal zinc all there is good treatment effect.
Embodiment 4
Design following experiment and studied meso pore silicon oxide material that resin modifies and remove the effect of reusing of heavy metal zinc 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 zinc is to 50ml cillin bottle, and heavy metal zinc aqueous solution pH is 6.Cover 25 ± 1 DEG C of constant temperature of serum cap and continue shake (200rpm) 1.5h.Bottle number is determined according to sampling number.When mensuration, get at random 3 bottles, suspension is shaken up, then remove aluminium lid, open plug.Centrifugal (6500rpm, 10-20min) separates, and gets supernatant liquor, graphite furnace atomic absorption spectrometry is analyzed heavy metal zinc concentration remaining in the aqueous solution, calculate heavy metal zinc decreasing ratio, after the heavy metal zinc that uses 0.5M EDTA wash-out to adsorb, reuse, the results are shown in Figure 4.In Fig. 4, result shows, the meso pore silicon oxide material that this resin is modified removes heavy metal zinc in the aqueous solution and all has reusable function.
Claims (5)
1. process the method that heavy metal zinc in water pollutes, it is characterized in that the preparation of the meso pore silicon oxide material that resin modifies and remove the method for heavy metal zinc in the aqueous solution, the steps include:
Solution containing heavy metal zinc is introduced reactor after filtering, and regulator solution pH is 2 ~ 10;
Regulator solution temperature is in 2 ~ 60
oc;
Regulating containing heavy metal zinc concentration in the solution of heavy metal zinc 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, put into containing in heavy metal zinc solution after filtration with certain proportion, 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 ~ 360 min;
Reacted liquid imports in other reactors after solid-liquid separator separates;
Liquid after the solid-liquid separator of learning from else's experience separates, graphite furnace atomic absorption spectrometry is analyzed heavy metal zinc concentration remaining in the aqueous solution;
Calculating heavy metal zinc decreasing ratio=
.
2. process as claimed in claim 1 the method that in water, heavy metal zinc pollutes, it is characterized in that the preparation method of the meso pore silicon oxide material MFT/S15-x-y of resin modification 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;
By mixed with mol ratio 1:1～20:1 to solution A and solution B, 30 ~ 80
ounder C, continue to stir after 12 ~ 24 h, then in 30 ~ 80
oageing 48 hours under C.
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 zinc in the processing aqueous solution as claimed in claim 1, is characterized in that solution temperature is 2 ~ 60
oc, pH scope is 2 ~ 10, adsorption process oscillation frequency is 0 ~ 250r/min, processed liquid heavy metal zinc 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 ~ 360 min, then separates the meso pore silicon oxide material that absorption has the resin of heavy metal zinc ion to modify.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410155082.7A CN103964534A (en) | 2014-04-18 | 2014-04-18 | Method for treating heavy metal zinc pollution in water |
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| CN201410155082.7A CN103964534A (en) | 2014-04-18 | 2014-04-18 | Method for treating heavy metal zinc pollution in water |
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| CN201410155082.7A Pending CN103964534A (en) | 2014-04-18 | 2014-04-18 | Method for treating heavy metal zinc pollution in water |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105110407A (en) * | 2015-09-14 | 2015-12-02 | 浙江工商大学 | Method for recycling tungsten ions from scheelite waste mineral processing wastewater |
| CN105132943A (en) * | 2015-08-19 | 2015-12-09 | 中国科学院兰州化学物理研究所 | Dezincification carbon material applicable to nickel electrolyte |
| 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 |
| CN110665476A (en) * | 2019-11-04 | 2020-01-10 | 桂林理工大学 | Melamine-thiourea modified soybean protein microsphere, preparation method and application thereof in cadmium adsorption and detection |
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| CN1689979A (en) * | 2004-04-23 | 2005-11-02 | 邵婧鑫 | Making method of ferroaluminosilicate turbid water purifying agent |
| CN102001722A (en) * | 2010-11-04 | 2011-04-06 | 南京大学 | Method for removing phosphate from water by using zirconia-modified mesoporous silicon material |
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2014
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| US5667695A (en) * | 1994-10-24 | 1997-09-16 | Uop | Process for removing contaminant metal ions from liquid streams using metallo germanate molecular sieves |
| CN1689979A (en) * | 2004-04-23 | 2005-11-02 | 邵婧鑫 | Making method of ferroaluminosilicate turbid water purifying agent |
| CN102001722A (en) * | 2010-11-04 | 2011-04-06 | 南京大学 | Method for removing phosphate from water by using zirconia-modified mesoporous silicon material |
Non-Patent Citations (2)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105132943A (en) * | 2015-08-19 | 2015-12-09 | 中国科学院兰州化学物理研究所 | Dezincification carbon material applicable to nickel electrolyte |
| CN105110407A (en) * | 2015-09-14 | 2015-12-02 | 浙江工商大学 | Method for recycling tungsten ions from scheelite waste mineral processing wastewater |
| CN105110407B (en) * | 2015-09-14 | 2017-07-21 | 浙江工商大学 | The method that tungsten ion is reclaimed from scheelite beneficiation wastewater |
| 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 |
| CN110665476A (en) * | 2019-11-04 | 2020-01-10 | 桂林理工大学 | Melamine-thiourea modified soybean protein microsphere, preparation method and application thereof in cadmium adsorption and detection |
| CN110665476B (en) * | 2019-11-04 | 2021-12-14 | 桂林理工大学 | Melamine-thiourea modified soybean protein microsphere, preparation method and application thereof in cadmium adsorption and detection |
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Application publication date: 20140806 |