CN107487868B - Method for removing hexavalent chromium in water by synergy of nano copper oxide and bacteria - Google Patents

Method for removing hexavalent chromium in water by synergy of nano copper oxide and bacteria Download PDF

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CN107487868B
CN107487868B CN201710961492.4A CN201710961492A CN107487868B CN 107487868 B CN107487868 B CN 107487868B CN 201710961492 A CN201710961492 A CN 201710961492A CN 107487868 B CN107487868 B CN 107487868B
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hexavalent chromium
copper oxide
bacteria
nano copper
water
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CN107487868A (en
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颜旭
周沫
石岩
宋萌萌
柴立元
杨志辉
彭驰
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Central South University
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Central South University
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • C02F2101/22Chromium or chromium compounds, e.g. chromates

Abstract

The invention relates to a method for removing hexavalent chromium in water by the synergy of nano copper oxide and bacteria. Nano adsorption and biological reduction are common methods for chromium-containing wastewater, but when the hexavalent chromium in the water is removed by singly adopting a nano copper oxide or bacterial method, the removal rate is not ideal generally. The method provided by the invention fully exerts the functions of bacteria and nano copper oxide, further utilizes the nano copper oxide stimulation to improve the adsorption reduction capability of bacteria on hexavalent chromium, and synergistically and rapidly removes hexavalent chromium in wastewater, wherein the removal rate can reach 100%, and the method has an obvious effect. The method also has the advantages of small chemical substance consumption, mild reaction conditions, no secondary pollution, simple operation and the like, and has good application prospect.

Description

Method for removing hexavalent chromium in water by synergy of nano copper oxide and bacteria
Technical Field
The invention belongs to the technical field of microbial application and wastewater treatment, and relates to a method for removing hexavalent chromium in water by the synergy of nano copper oxide and bacteria.
Background
The chromium-containing compound is widely applied to leather-making, metallurgy, electroplating, printing and dyeing, photography, textile and chemical industries, and can produce a large amount of wastewater containing hexavalent chromium. Hexavalent chromium exists mainly in the form of chromate ions in water and has high carcinogenic and mutagenic abilities to organisms, so that the hexavalent chromium in water seriously harms the environment and human health. The concentration of hexavalent chromium in water discharged in production and living activities specified in the Integrated wastewater discharge Standard of China (GB 8978-1996) must not exceed 0.5mg/L, while the concentration limit value specified in the sanitary Standard of Drinking Water of China (GB5749-2006) is 0.05 mg/L. The removal of hexavalent chromium in water has received extensive attention at home and abroad.
At present, the treatment method of the chromium-containing wastewater comprises a chemical precipitation method, an adsorption method, a biological method, a membrane separation method and the like. The chemical precipitation method is suitable for high-concentration chromium-containing wastewater, but can generate a large amount of precipitated sludge, is difficult to treat and is easy to cause secondary pollution. The adsorption method and the biological method can effectively act on the chromium-containing wastewater with low concentration, can not generate a large amount of sludge, and have the advantages of simple operation, strong plasticity and the like. But the removal rate of the adsorption method and the biological method is not ideal, the concentration of chromium in the effluent is still easy to exceed the standard, the requirement is difficult to meet, and a plurality of limitations are received in practical application. The invention provides a method for removing hexavalent chromium in water by the synergy of nano copper oxide adsorption and a bacterial method, which can enable the removal rate of hexavalent chromium to reach 100 percent and is higher than the current treatment level. The method has the advantages of fast reaction, good effect, small investment, simple operation, no secondary pollution and the like, and has great application potential.
Disclosure of Invention
The invention aims to provide a method for removing hexavalent chromium in water by the synergy of nano copper oxide and bacteria. The method not only can efficiently remove chromium in the water body, but also has the advantages of small chemical substance consumption, mild reaction conditions, no secondary pollution, simple operation and the like, and has better application prospect.
The object of the present invention is achieved as follows.
A method for removing hexavalent chromium in water by synergy of nano copper oxide and bacteria is characterized in that bacteria for adsorbing and reducing hexavalent chromium in water are added into a water body containing hexavalent chromium, nano copper oxide is added at the same time, and the bacteria and the nano copper oxide are utilized to remove the hexavalent chromium in the water synergistically.
The bacteria adopted in the method are preferably Cupriavidus sp.B-8 with the preservation number of CGMCC No. 4240.
The content of hexavalent chromium in the water body to be treated in the method is 10-30 mg/L.
In the method, a single bacterial colony is activated and expanded in an LB liquid culture medium until the absorbance at 600nm is 0.8-1.0, and the obtained bacterial liquid is inoculated in a treatment system, wherein the inoculation amount is 5-15%.
In the method, the concentration of the nano copper oxide particles in the treatment system is 10-50 mg/L.
In the method, nutrient substances necessary for the growth of bacteria are added into a treatment system. Comprises 10g/L of tryptone, 5g/L of yeast extract and 10g/L of sodium chloride.
In the method, the bacteria liquid is inoculated and then shake culture is carried out for at least 36 hours. Further preferably inoculating a bacterial solution, and culturing at the temperature of 25-40 ℃, the natural pH condition and the shaking condition of 125-150 rpm; after shaking culture is carried out for at least 36 hours, centrifuging the mixed solution for 5-10 min at 12,000rpm, and obtaining supernatant, namely the aqueous solution after the synergistic treatment of the bacteria and the nano copper oxide.
The method of the invention has larger application potential and has the following advantages:
(1) the adopted nano copper oxide has wide sources, does not need further modification and optimization, and is simple and convenient to operate;
(2) the used bacteria can be cultured in a large scale, the culture period is short, the experimental operation condition is mild, and no secondary pollution is caused;
(3) the method of the synergy of the nano copper oxide and the bacteria breaks through the limitation of the traditional adsorption method and the biological method on the removal rate of the hexavalent chromium in the water, can accelerate the removal of the hexavalent chromium, even can completely remove the hexavalent chromium in the water, and has obvious effect.
The bacterial strain Cupriavidus sp.B-8 is identified as Cupriavidus, and is named as Cupriavidus sp. The strain is preserved in No. 3 of Xilu No. 1 of Beijing, Chaoyang, and China general microbiological culture Collection center (CGMCC) of China institute of sciences and microbiology, with the preservation number of CGMCC No.4240, within 22 days of 2010, 10 months and 2010.
Drawings
FIG. 1 shows the effect of removing hexavalent chromium in water by using nano-copper oxide alone in comparative example 1;
FIG. 2 the effect of the biological process alone (Cupriavidus sp.B-8) on the removal of hexavalent chromium from water in comparative example 2;
FIG. 3 shows the effect of the nano copper oxide and the bacteria (Cupriavidus sp.B-8) in the synergistic removal of hexavalent chromium in water in example 1.
Detailed Description
The following examples are intended to further illustrate the invention, but are not intended to limit the invention.
Comparative example 1
And (3) independently removing hexavalent chromium in water by adopting nano copper oxide adsorption: 5mg of nano copper oxide is added into 100mL of LB liquid culture medium, and after sterilization is carried out for 20min at 121 ℃, sterile potassium dichromate solution is added to ensure that the concentration of hexavalent chromium is 20 mg/L. The solution is subjected to oscillation reaction for 36 hours under the conditions of temperature of 30 ℃, natural pH and rotation speed of 150 rpm.
The change of the hexavalent chromium removal rate with time is shown in fig. 1, and it can be seen that the hexavalent chromium removal rate gradually increases with the progress of the reaction, the removal rate reaches 35.0% in 24 hours, then the removal rate tends to stably and slowly increase, the removal rate in 36 hours is 40.1%, the concentration of residual hexavalent chromium is 12.0mg/L, far exceeds the national standard, and the effect is not ideal.
Comparative example 2
Removing hexavalent chromium in water by adopting a biological method (Cupriavidus sp.B-8) alone: sterilizing 100mLLB liquid culture medium at 121 deg.C for 20min, adding sterile potassium dichromate solution to reach hexavalent chromium concentration of 20 mg/L. Activating and expanding Cupriavidus sp.B-8 in an LB liquid culture medium until the absorbance at 600nm is 0.8-1.0 to obtain a bacterial liquid, inoculating 10mL of the bacterial liquid into the solution containing hexavalent chromium, culturing for 36h at the temperature of 30 ℃, under the natural pH condition and under the shaking condition of 150rpm, and centrifuging the solution at 12,000rpm for 5min after the reaction is finished to obtain a supernatant, namely the treated aqueous solution.
The growth curve of the bacteria and the change of the hexavalent chromium removal rate with time in the comparative example are shown in fig. 2, and it can be seen that the hexavalent chromium removal rate slowly increases with the progress of the reaction, and when the hexavalent chromium removal rate is 35.7% in 36 hours, the residual hexavalent chromium concentration is 12.8mg/L, which far exceeds the national standard, and the effect is not good.
Example 1
Removing hexavalent chromium in water by the synergy of nano copper oxide and bacteria: adding 5mg of nano copper oxide into 100mLLB liquid culture medium, sterilizing at 121 ℃ for 20min, and adding sterile potassium dichromate solution to ensure that the concentration of hexavalent chromium is 20 mg/L. cupriavidiussp.B-8 is activated and expanded in an LB liquid culture medium until the absorbance at 600nm is 0.8-1.0 to obtain bacterial liquid, 10mL of the bacterial liquid is inoculated to the solution containing hexavalent chromium and nano copper oxide, the solution is cultured for 36 hours at the temperature of 30 ℃, the natural pH condition and the shaking condition of 150rpm, and after the reaction is finished, the solution is centrifuged for 5min at 12,000rpm to obtain supernatant, namely the treated aqueous solution.
The growth curve of the bacteria and the removal rate of hexavalent chromium in the embodiment are determined at any timeThe variation between the two is shown in fig. 3. As can be seen from comparison with the growth curve obtained in comparative example 2, the nano copper oxide promotes the growth of bacteria, as expressed in terms of biomass (OD)600) Thereby facilitating removal of hexavalent chromium. As can be seen from the change of the hexavalent chromium removal rate with time, the hexavalent chromium removal rate is rapidly increased along with the reaction, and the hexavalent chromium removal rate in 12 hours reaches 46.2 percent, which exceeds the treatment effect of single nano-copper oxide and bacteria in 36 hours, thus the method has the characteristics of rapidness and high efficiency. And then, the hexavalent chromium removal rate is continuously improved, and when the reaction is carried out for 36 hours, the hexavalent chromium removal rate reaches 100 percent, namely, the hexavalent chromium can not be detected in the treated aqueous solution and reaches the national standard. The effect is far better than the effect of the single nano copper oxide or bacteria, even higher than the sum (75.8%) of the effects of the single nano copper oxide or bacteria, which shows that the nano copper oxide and the bacteria have obvious synergistic effect on removing the hexavalent chromium, thereby obtaining unexpected obvious effect.

Claims (6)

1. A method for removing hexavalent chromium in water by synergy of nano copper oxide and bacteria is characterized in that bacteria for adsorbing and reducing hexavalent chromium in water are added into a water body containing hexavalent chromium, nano copper oxide is added at the same time, and the bacteria and the nano copper oxide are utilized to remove the hexavalent chromium in the water;
the bacteria used areCupriavidus sp.B-8, the preservation number is CGMCC No. 4240;
inoculating a bacterial liquid obtained by activating and expanding a bacterial single colony in an LB liquid culture medium until the absorbance at 600nm is 0.8-1.0 into a treatment system, wherein the inoculation amount is 5-15%;
the concentration of the nano copper oxide particles in the treatment system is 10-50 mg/L.
2. The method according to claim 1, wherein the hexavalent chromium content of the water to be treated is 10 to 30 mg/L.
3. The method of claim 1, wherein nutrients necessary for bacterial growth are added to the treatment system.
4. The method of claim 3, wherein nutrients necessary for bacterial growth, including tryptone 10g/L, yeast extract 5g/L and sodium chloride 10g/L, are added to the treatment system.
5. The method of claim 1, wherein the inoculated broth is shake-cultured for at least 36 hours.
6. The method according to claim 5, wherein the inoculated bacterial solution is cultured at a temperature of 25-40 ℃, a natural pH condition and a shaking condition of 125-150 rpm; after shaking culture is carried out for at least 36 hours, centrifuging the mixed solution for 5-10 min at 12,000rpm, and obtaining supernatant, namely the aqueous solution after the synergistic treatment of the bacteria and the nano copper oxide.
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