CN101653717A - Method of removing mercury, lead or cadmium ions in wastewater by using on-line synthesis hydrotalcite-like material - Google Patents
Method of removing mercury, lead or cadmium ions in wastewater by using on-line synthesis hydrotalcite-like material Download PDFInfo
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- CN101653717A CN101653717A CN200910018761A CN200910018761A CN101653717A CN 101653717 A CN101653717 A CN 101653717A CN 200910018761 A CN200910018761 A CN 200910018761A CN 200910018761 A CN200910018761 A CN 200910018761A CN 101653717 A CN101653717 A CN 101653717A
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Abstract
The invention relates to a method of removing mercury, lead or cadmium ions in wastewater by using on-line synthesis hydrotalcite-like material. The method comprises the following steps: preparing a mixed salt solution with magnesium and aluminium ions in a molar ratio of 1-2:1, taking the wastewater with 5.0-10.0mg/L of mercury, lead or cadmium ions, adding the mixed salt solution with magnesiumand aluminium ions in the wastewater to mix and obtain the reaction solution with the pH value of 8.5-9.0, reacting for 50-60min, performing suction filtering to obtain the solid, preparing the solidhydrotalcite-like material compound by washing and drying and finally measuring the content of mercury, lead or cadmium ions. The method of removing mercury, lead or cadmium ions in wastewater by using on-line synthesis hydrotalcite-like material omits the complicated solid-liquid separation and drying processes in adsorbing agent synthesis production by using the prior art so as to complete the adsorbing agent synthesis and the wastewater treatment simultaneously and realize the aim of treating mercury, lead or cadmium ions in wastewater cheaply and effectively; in addition, the concentrationof mercury, lead or cadmium in the wastewater treated by the method of the invention is below the permitted emission concentration of the national standard.
Description
Technical field
The present invention relates to a kind of method of removing Mercury in Wastewater, lead, cadmium ion, belong to the wastewater treating technology field, particularly in wastewater treatment process, utilize online synthesis hydrotalcite-like material compound to remove the method for Mercury in Wastewater, lead or cadmium ion.
Background technology
Along with improving constantly of modern society's industrialization degree, people are more and more to the metal waste of nature discharging, and mercurous, plumbous, the cadmium waste water that particularly produce in the industrial processes have caused the serious environmental pollution.Mercury, lead, cadmium ion have certain toxicity, enter to be difficult for being degraded removal behind the environment, but in the medium-term and long-term accumulation of environment, but also can between biologies at different levels, transmit by food chain, biological and human body are produced great toxic action.Therefore, the discharging of necessary strict control cadmium ion if let alone to be discharged into occurring in nature, certainly will cause serious pollution to the natural environment that the mankind depend on for existence.And houghite compound (HTLcs) has the layer structure that is similar to shepardite, and the basic structure formula is: [M
1-x 2+M
x 3+(OH)
2] (A
N-)
X/nYH
2O, wherein M
2+Represent the bivalent cation on the laminate.Bivalent cation on the HTLcs laminate has Modulatory character, and certain condition can be introduced divalent metals such as mercury, lead, cadmium synthetic different HTLcs in its structure down, can remove the cadmium ion in the water simultaneously.
The removal method of mercury, lead, cadmium ion and the technology such as heavy metal ion in the houghite adsorbed water are existing open, disclose a kind of high-effect, the manufacture method of reproducible deleading ion sieve that is used for that Drinking Water purifies and the application of this ion sieve as CN1064226.Deleading ion sieve is to carry on the attached titaniferous compound at silica gel, introduces an amount of lead ion, makes it maintenance through heat treatment, again with the lead ion wash-out, promptly has been covered with the specific sieve aperture that adapts with lead ion in this compound inside.During application, water body to be clean does not need any processing, can directly feed the adsorption column that this ion sieve is housed, thereby reaches the purpose of taking off plumbous purification.CN1994916 discloses a kind of steel slag composition and method for making and application of removing divalence cadmium ion in the water, and the component and the content of said slag comprise at least: mass fraction is 30%～50% CaO, 10%～30% SiO
2With 5%～40% Fe
2O
3, its steel slag composition is that the adsorbent of composition has absorption property excellence, simple to operate, nonhazardous effect, cheap, characteristics such as environmental benefit is remarkable.CN101033095 discloses a kind of modified hydrotalcite preparation method who removes Trace Mercury in the water, cadmium ion, as main modification source, hydrotalcite is carried out modification with amino acid, utilize the aqueous phase precipitation thermal crystallization to prepare modified hydrotalcite, by the control drying mode, make it structurally realize optimizing.
The method of more than removing Mercury in Wastewater, lead, cadmium ion all is to adopt first synthetic adsorbent, carries out this mode of absorption of off-line again.At first in solid absorbent synthetic, need complicated Separation of Solid and Liquid process; And in these two processes of absorption of preparation of adsorbent and cadmium ion, need two cover instrument and equipments, increased the cost of handling.
Summary of the invention
Deficiency at art methods, provide a kind of online synthesis hydrotalcite-like material to remove the method for Mercury in Wastewater, lead, cadmium ion, realize low cost, high efficiency processing Mercury in Wastewater, lead, cadmium ion, the concentration of mercury in the waste water, lead, cadmium ion is reduced to below the concentration of emission of national standard permission.
Technical scheme of the present invention is as follows:
Online synthesis hydrotalcite-like material is removed the method for Mercury in Wastewater, lead or cadmium ion, and step is as follows:
(1) contains the preparation of magnesium ion, aluminum ions mixing salt solution
Magnesium nitrate and aluminum nitrate are dissolved in the deionized water, obtain the magnalium mol ratio and be 1～2: 1 contain magnesium ion, aluminum ions mixing salt solution;
(2) get the waste water of mercurous, lead or cadmium ion, measure when wherein the concentration of mercury, lead or cadmium ion is 5.0～10.0mg/L standby; When the concentration of Mercury in Wastewater, lead or cadmium ion was higher than 10.0mg/L, thin up was to concentration to the 5.0～10.0mg/L of mercury, lead or cadmium ion;
(3) according to volume ratio 1: 1, mixed containing in the waste water that magnesium ion, aluminum ions mixing salt solution join step (2) of step (1), while dropping sodium solution, the pH value of control reactant liquor is 8.5～9.0, reacts 50～60min under the condition of magnetic agitation;
(4) suction filtration washes solid with water 3～5 times, and dry 24h under 70 ℃ gets houghite compound.Filtrate is used for the concentration of heavy metal ion analysis, measures the wherein content of mercury, lead or cadmium ion, meets the following discharging of " integrated wastewater discharge standard " discharge standard (GB8978-1996).
Preferably, the sodium hydroxide solution mass concentration is 100g/L in the step (3).
When removing mercury ions in waste water, preferred, the magnalium mol ratio of step (1) mixing salt solution is 1: 1, and the pH value of the reactant liquor in the step (3) is 8.5; The magnalium mol ratio of step (1) mixing salt solution is 1: 2, and the pH value of the reactant liquor in the step (3) is 9.0.
When lead ion or cadmium ion, preferred, the magnalium mol ratio of step (1) mixing salt solution is 1: 1 in removing waste water, and the pH value of the reactant liquor in the step (3) is 9.0; The magnalium mol ratio of step (1) mixing salt solution is 1: 2, and the pH value of the reactant liquor in the step (3) is 8.5.
The method of measuring the content of mercury, lead or cadmium ion in the method for the present invention is respectively, and the mensuration of mercury ion adopts the dithizone AAS, and the mensuration of lead ion or cadmium ion all adopts atomic absorption spectrophotometry.
Step (4) gained solid is used for the solid sample analysis, turns out to be houghite compound through infrared spectrogram and X-ray diffraction spectrogram.Structural formula [M
1-x 2+M
x 3+(OH)
2] (A
N-)
X/nYH
2O, wherein M
2+Be bivalent metal ion (magnesium, mercury, lead or cadmium), M
x 3+Be aluminium ion, A
N-Be interlayer anion (carbanion) that x refers to the content of metallic element.
Characteristics of the present invention are synthesis hydrotalcite-like materials when removing Mercury in Wastewater, lead, cadmium ion, and the gained houghite can be used for a lot of aspects: at industrial fire retardant, molecular sieve, the ion-exchanger etc. of can be used as; Aspect absorption, can be used as halogen remover, polyethylene stabilizing agent etc.
Because the structure of houghite has the Modulatory character of metal cation, when containing contents of many kinds of heavy metal ion in the waste water, they can enter the interlayer of houghite compound simultaneously, form the complicated more houghite compound of structure.
The improvement of heavy metal ion-containing waste water is the process of a complexity, the present invention utilizes the method for online synthesis hydrotalcite-like material compound to remove mercury in the water body, plumbous, cadmium ion, it is feasible that utilization of wastewater resource is become, this method has been saved complicated Separation of Solid and Liquid and drying process in the synthetic production of adsorbent in the prior art, the synthetic of adsorbent finished in a system with two discrete steps of wastewater treatment, realize low-cost, high efficiency processing Mercury in Wastewater, plumbous, cadmium ion, make the mercury in the waste water, plumbous, the concentration of cadmium ion is reduced to below the concentration of emission of national standard permission, can carry out commercial Application widely.
Description of drawings
Fig. 1 is the infrared spectrogram of the solid sample that obtains among the embodiment 1.
Fig. 2 is the X-ray diffraction spectrogram of the solid sample that obtains among the embodiment 1.
Fig. 3 is the infrared spectrogram of the solid sample that obtains among the embodiment 3.
Fig. 4 is the X-ray diffraction spectrogram of the solid sample that obtains among the embodiment 3.
Fig. 5 is the infrared spectrogram of the solid sample that obtains among the embodiment 5.
Fig. 6 is the X-ray diffraction spectrogram of the solid sample that obtains among the embodiment 5.
The specific embodiment
Below in conjunction with embodiment the present invention is further described, but is not limited thereto.Said magnalium ratio is magnesium ion, aluminum ions mol ratio among the embodiment.
Embodiment 1:
Get that to contain ion concentration of mercury be that the waste water 100mL of 10.0mg/L is in the conical flask of 300mL, rapid adding magnalium ratio is 1 mixing salt solution 100mL under magnetic agitation, wherein contain magnesium ion 6.0mmol/L, aluminium ion 6.0mmol/L, the pH value that then adds the 100g/L sodium hydrate regulator solution under vigorous stirring is 8.5, reaction 60min carries out Separation of Solid and Liquid then.The concentration of measuring mercury ion in the solution is 0.042mg/L, and clearance is 99.02%, can reach the concentration of emission that " integrated wastewater discharge standard " (GB8978-1996) allows.The solid sample that obtains is a houghite compound, and structural formula is: Hg
2Mg
4Al
2(OH)
16CO
34H
2O.
The infrared spectrogram of the solid sample that obtains in the present embodiment 1 as shown in Figure 1, the X-ray diffraction spectrogram is as shown in Figure 2.
Embodiment 2:
Processing method is identical with embodiment 1, and different is that salt-mixture magnalium ratio is 2, and aluminium ion concentration is 3.0mmol/L in the mixing salt solution, and pH is 9.0.The residual concentration of chromium in the processed waste water (VI) ion is 0.038mg/L, and clearance is 99.62%.
Embodiment 3:
Get that to contain plumbum ion concentration be that the waste water 100mL of 10.0mg/L is in the conical flask of 300mL, rapid adding magnalium ratio is 1 mixing salt solution 100mL under magnetic agitation, wherein contain magnesium ion 6.0mmol/L, aluminium ion 6.0mmol/L, the pH value that then adds sodium hydrate regulator solution under vigorous stirring is 9, carries out Separation of Solid and Liquid behind the reaction 60min.The concentration of lead ion is 0.203mg/L in the solution, and clearance is 97.97%, can reach the concentration of emission that " integrated wastewater discharge standard " (GB8978-1996) allows.The solid sample that obtains is a houghite compound, and structural formula is: Pb
2Mg
4Al
2(OH)
16CO
34H
2O.
The infrared spectrogram of the solid sample that obtains in the present embodiment 3 as shown in Figure 3, the X-ray diffraction spectrogram is as shown in Figure 4.
Embodiment 4:
Processing method is identical with embodiment 3, and different is that salt-mixture magnalium ratio is 2, and aluminium ion concentration is 3.0mmol/L in the mixing salt solution, and pH is 8.5.The residual concentration of chromium in the processed waste water (VI) ion is 0.227mg/L, and clearance is 97.73%.
Embodiment 5:
Get that to contain concentration of cadmium ions be that the waste water 100mL of 10.0mg/L is in the conical flask of 300mL, rapid adding magnalium ratio is 1 mixing salt solution 100mL under magnetic agitation, wherein contain magnesium ion 6.0mmol/L, aluminium ion 6.0mmol/L, the pH value that then adds sodium hydrate regulator solution under vigorous stirring is 9.0, carries out Separation of Solid and Liquid behind the reaction 60min.The concentration of cadmium ion is 0.087mg/L in the solution, and clearance is 99.13%, can reach the concentration of emission that " integrated wastewater discharge standard " (GB8978-1996) allows.The solid sample that obtains is a houghite compound, and structural formula is Cd
2Mg
4Al
2(OH)
16CO
34H
2O.
The infrared spectrogram of the solid sample that obtains in the present embodiment 5 as shown in Figure 5, the X-ray diffraction spectrogram is as shown in Figure 6.
The sample spectra map analysis of embodiment 1,3,5
Can see that from Fig. 1,3,5 infrared spectrograms the spectrogram of embodiment 1,3,5 three kind of sample has similar absworption peak, have the typical spectrogram of houghite.And each compound is at 700～300cm
-1The absworption peak at place is slightly different, and they are that the M-Al-OH flexural vibrations cause.This explanation embodiment 1,3,5 three kind of solid sample are houghite compounds, and each heavy metal ion has all entered in the structure of compound, by the architectural feature of houghite compound as can be known the embeddeding action of heavy metal ion in lamellar compound be that heavy metal ion is composed the principal mode deposited and the main mechanism of delay.
From Fig. 2,4,6 X-ray diffraction spectrogram as can be seen, embodiment 1,3,5 three kind of sample all have the characteristic diffraction peak of houghite compound, simultaneously low-angle diffraction maximum is more sharp-pointed, the diffraction maximum of high angle a little less than, this is one of common structure feature of lamellar compound.The baseline of collection of illustrative plates is low and more steady, and characteristic diffraction peak is sharp and narrow, and compound degree of crystallinity height is described, impurity content is low.
Embodiment 6:
Processing method is identical with embodiment 3, and different is that salt-mixture magnalium ratio is 2, and aluminium ion concentration is 3.0mmol/L in the mixing salt solution, and pH is 8.5.The residual concentration of chromium in the processed waste water (VI) ion is 0.091mg/L, and clearance is 99.13%.
Claims (5)
1. online synthesis hydrotalcite-like material is removed the method for Mercury in Wastewater, lead or cadmium ion, it is characterized in that step is as follows:
(1) magnesium nitrate and aluminum nitrate are dissolved in the deionized water, obtain the magnalium mol ratio and be 1～2: 1 contain magnesium ion, aluminum ions mixing salt solution;
(2) get the waste water of mercurous, lead or cadmium ion, measure when wherein the concentration of mercury, lead or cadmium ion is 5.0～10.0mg/L standby; When the concentration of Mercury in Wastewater, lead or cadmium ion is higher than 10.0mg/L, thin up to the concentration of mercury, lead or cadmium ion at 5.0～10.0mg/L;
(3) according to volume ratio 1: 1, mixed containing in the waste water that magnesium ion, aluminum ions mixing salt solution join step (2) of step (1), while dropping sodium solution, the pH value of control reactant liquor is 8.5～9.0, reacts 50～60min under the condition of magnetic agitation;
(4) suction filtration, washing solid 3～5 times, dry 24h under 70 ℃ gets houghite compound; Filtrate is carried out the concentration of heavy metal ion analysis, measures the wherein content of mercury, lead or cadmium ion.
2. online synthesis hydrotalcite-like material as claimed in claim 1 is removed the method for Mercury in Wastewater, lead or cadmium ion, it is characterized in that when removing mercury ions in waste water, the magnalium mol ratio of step (1) mixing salt solution is 1: 1, and the pH value of the reactant liquor in the step (3) is 8.5.
3. online synthesis hydrotalcite-like material as claimed in claim 1 is removed the method for Mercury in Wastewater, lead or cadmium ion, it is characterized in that the magnalium mol ratio of step (1) mixing salt solution is 1: 2, and the pH value of the reactant liquor in the step (3) is 9.0.
4. online synthesis hydrotalcite-like material as claimed in claim 1 is removed the method for Mercury in Wastewater, lead or cadmium ion, when it is characterized in that in removing waste water aluminium ion or cadmium ion, the magnalium mol ratio of step (1) mixing salt solution is 1: 1, and the pH value of the reactant liquor in the step (3) is 9.0.
5. online synthesis hydrotalcite-like material as claimed in claim 1 is removed the method for Mercury in Wastewater, lead or cadmium ion, it is characterized in that the magnalium mol ratio of step (1) mixing salt solution is 1: 2, and the pH value of the reactant liquor in the step (3) is 8.5.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102179253A (en) * | 2011-03-10 | 2011-09-14 | 上海大学 | Method for preparing catalyst by using electrolysis waste water and electrolysis sludge |
| CN107285369A (en) * | 2017-06-30 | 2017-10-24 | 中南大学 | A kind of method that houghite is prepared by heavy metal wastewater thereby |
| CN107337292A (en) * | 2016-11-17 | 2017-11-10 | 华北电力大学（保定） | The technological process of advanced treating desulfurization wastewater |
| CN109574084A (en) * | 2018-12-05 | 2019-04-05 | 上海宝田新型建材有限公司 | A kind of preparation method and applications of metallurgy base carbonate hydrotalcite |
| CN109852392A (en) * | 2018-12-13 | 2019-06-07 | 中国科学院南京土壤研究所 | A kind of electroplating enterprise moves composition and its application of contaminated soil of site reparation |
| CN112877719A (en) * | 2021-02-03 | 2021-06-01 | 东北大学 | Preparation method of three-dimensional flower-like Mg-Al-LDHs material |
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| CN103043691A (en) * | 2012-12-14 | 2013-04-17 | 湖南大学 | Preparation method of modified hydrotalcite and application thereof in heavy metal adsorption |
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2009
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102179253A (en) * | 2011-03-10 | 2011-09-14 | 上海大学 | Method for preparing catalyst by using electrolysis waste water and electrolysis sludge |
| CN102179253B (en) * | 2011-03-10 | 2012-08-08 | 上海大学 | Method for preparing catalyst by using electrolysis waste water and electrolysis sludge |
| CN107337292A (en) * | 2016-11-17 | 2017-11-10 | 华北电力大学（保定） | The technological process of advanced treating desulfurization wastewater |
| CN107285369A (en) * | 2017-06-30 | 2017-10-24 | 中南大学 | A kind of method that houghite is prepared by heavy metal wastewater thereby |
| CN109574084A (en) * | 2018-12-05 | 2019-04-05 | 上海宝田新型建材有限公司 | A kind of preparation method and applications of metallurgy base carbonate hydrotalcite |
| CN109574084B (en) * | 2018-12-05 | 2021-01-22 | 上海宝田新型建材有限公司 | Preparation method and application of metallurgical-base carbonate hydrotalcite |
| CN109852392A (en) * | 2018-12-13 | 2019-06-07 | 中国科学院南京土壤研究所 | A kind of electroplating enterprise moves composition and its application of contaminated soil of site reparation |
| CN112877719A (en) * | 2021-02-03 | 2021-06-01 | 东北大学 | Preparation method of three-dimensional flower-like Mg-Al-LDHs material |
| CN112877719B (en) * | 2021-02-03 | 2022-08-05 | 东北大学 | Preparation method of three-dimensional flower-like Mg-Al-LDHs material |
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