CN106976946B - Method for treating diclofenac in water reduced by cobalt ion and nickel ion catalysis zero-valent zinc - Google Patents

Method for treating diclofenac in water reduced by cobalt ion and nickel ion catalysis zero-valent zinc Download PDF

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CN106976946B
CN106976946B CN201710212088.7A CN201710212088A CN106976946B CN 106976946 B CN106976946 B CN 106976946B CN 201710212088 A CN201710212088 A CN 201710212088A CN 106976946 B CN106976946 B CN 106976946B
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dcf
water
cobalt
nickel
zero
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CN106976946A (en
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韩莹
李微微
高延红
李军
王济禾
蒋贝贝
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Zhejiang University of Technology ZJUT
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C02F1/705—Reduction by metals
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

A method for treating diclofenac in water by reducing with zero-valent zinc under catalysis of cobalt ion and nickel ion comprises selecting cobalt ion (Co)2+) And nickel ion (Ni)2+) The DCF in the water is reduced by catalyzing zero-valent zinc, and the treatment method comprises the following steps: adding 400-800 mu L of 0.1 mol.L-1 cobalt chloride and nickel chloride into 40mL of ultrapure water, enabling the final concentration of the cobalt chloride and the nickel chloride in each extraction bottle to be 1-2 mmol.L-1, adjusting the pH value of the solution to be 4.0-8.0, adding 18-22 mu L of 0.1 g.L-1 DCF mother liquor to enable the initial concentration of the DCF to be 450-550 mu g.L-1, finally adding 0.4-0.8 g of zinc powder, tightly covering a bottle cover, putting into a rotary culture device, and rotating in a dark place at the rotating speed of 15-45 r.min-1. The invention effectively controls the DCF which is a substance with potential biological toxicity in water, thereby ensuring the safety of drinking water.

Description

Method for treating diclofenac in water reduced by cobalt ion and nickel ion catalysis zero-valent zinc
Technical Field
The invention relates to the field of feedwater treatment, in particular to a method for reducing diclofenac in water by cobalt ion and nickel ion catalysis zero-valent zinc.
Background
Diclofenac (DCF) is a non-steroidal anti-inflammatory drug, is one of the most used drugs in the world, and the annual demand of the global market is more than 4000 tons. The DCF has wide application range and large production capacity, and can be directly discharged by production enterprises; after the human body takes the medicine, the part which can not be absorbed by the human body can be discharged into the environment along with urine and excrement. At present, already in some countries, traces of DCF are detected in source water and in effluent water from sewage treatment plants. The content of DCF in surface water of different countries is respectively as follows: U.S. 10. mu.g.L-10.30. mu.g.L in Japan-1Germany 0.03 to 0.2. mu.g.L-1Switzerland 0.012. mu.g.L-1. The average concentration of DCF in effluent of sewage plant in Finland city is 0.40 mg.L-1. The DCF exists in the source water of China, and the DCF exists in the stream river, the pearl river and the stone well river of the pearl river water system through the water quality monitoring of the south, wherein the concentration range of the DCF is 11.6-150 ng.L-1. Given the widespread presence of DCF in water, it is highly desirable to find effective techniques to control it.
At present, the DCF removal method mainly comprises a membrane treatment process, an adsorption method, a biodegradation method and an advanced oxidation method. Nanofiltration and reverse osmosis are both effective in removing Diclofenac (DCF) from water, but this approach does not really achieve true mineralization removal of DCF. The adsorption material of the adsorption method mainly comprises activated carbon and resin. The active carbon has better adsorption effect on the diclofenac, and the removal rate can reach 98 percent. However, the activated carbon adsorption only realizes the transfer between media, does not realize the degradation and mineralization of pollutants, and has higher operation and maintenance cost. When the pH is 1 to 6, cup [4 ]]The adsorption removal rate of the aromatic modified resin to DCF exceeds 90 percent, but when the pH value exceeds 6, the content of the aromatic modified resin in the DCF is calix [4 ]]The adsorption removal rate of the aromatic modified resin to DCF is reduced sharply, and when the pH value is more than 9.0, the pH value is not less than 4]The removal rate of the aromatic modified resin to DCF is only 1%. Due to pH to cup [4 ]]The adsorption removal of DCF by the aromatic modified resin is very largeThe influence is greatly limited in practical engineering application. When DCF was treated using the activated sludge process, the concentration of DCF remained unchanged after 28 days of activated sludge degradation when the carbon source was all DCF. When using O3And UV/H2O2Low dosage of O when combined process is used to remove DCF from water3The removal rate of DCF was not high and the reaction rate was slow. In contrast, UV/H2O2The combined technology can effectively remove DCF in water, shows better oxidation capacity, but needs to add high-dose H2O2。
Disclosure of Invention
In order to overcome the defects that DCF cannot be effectively controlled and potential safety hazards exist in the existing water supply treatment mode, the invention provides a treatment method for reducing diclofenac in water by catalyzing zero-valent zinc with cobalt ions and nickel ions, which effectively controls DCF which is a substance with potential biological toxicity in water, thereby ensuring the safety of drinking water.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for treating diclofenac in water by reducing with zero-valent zinc under catalysis of cobalt ion and nickel ion comprises selecting cobalt ion (Co)2 +) And nickel ion (Ni)2+) Catalytic zero valent zinc reduces DCF in water.
Further, the process of the treatment method is as follows:
adding 400-800 mu L of 0.1 mol.L-1 cobalt chloride and nickel chloride into 40mL of ultrapure water, enabling the final concentration of the cobalt chloride and the nickel chloride in each extraction bottle to be 1-2 mmol.L-1, adjusting the pH value of the solution to be 4.0-8.0, adding 18-22 mu L of 0.1 g.L-1 DCF mother liquor to enable the initial concentration of the DCF to be 450-550 mu g.L-1, finally adding 0.4-0.8 g of zinc powder, tightly covering a bottle cover, putting into a rotary culture device, and rotating in a dark place at the rotating speed of 15-45 r.min-1.
And further, sampling at regular time, performing suction filtration on the sampled sample through a membrane of 0.22 mu m or 0.45 mu m by using a vacuum pump to separate unreacted zinc powder so as to stop the reaction, and using the obtained water sample for analysis and test of the concentration of the DCF, wherein the reaction time is 60-96 h.
Hair brushThe technical concept is as follows: in order to be applied to actual water treatment, a new simple and feasible treatment method capable of effectively removing DCF in water needs to be established. The zero-valent zinc reduction technology has wide raw material sources, is cheap and easy to obtain, but has long reaction time and low removal rate in the previous experiment. The transition metal has an unfilled d-orbital and thus has a catalytic effect, so that the transition metal ion can be used to catalyze the progress of a chemical reaction. The DCF is reduced by selecting transition metal ions to catalyze zero-valent zinc, which becomes a new and simple water treatment technology, so that cobalt ions (Co) are selected2+) And nickel ion (Ni)2+) Catalytic zero valent zinc reduces DCF in water.
The invention has the following beneficial effects: zinc in Co2+And Ni2+Can effectively remove DCF existing in water.
Drawings
Fig. 1 is a schematic diagram of the efficiency of the reductive degradation of DCF by zinc metal catalyzed by transition metal ions.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Referring to FIG. 1, a method for treating diclofenac in water by reducing zero-valent zinc with cobalt ions and nickel ions as catalyst, cobalt ions (Co) are selected2+) And nickel ion (Ni)2+) Catalytic zero valent zinc reduces DCF in water.
The processing method comprises the following steps:
adding 400-800 mu L of 0.1 mol.L-1 cobalt chloride and nickel chloride into 40mL of ultrapure water, enabling the final concentration of the cobalt chloride and the nickel chloride in each extraction bottle to be 1-2 mmol.L-1, adjusting the pH value of the solution to be 4.0-8.0, adding 18-22 mu L of 0.1 g.L-1 DCF mother liquor to enable the initial concentration of the DCF to be 450-550 mu g.L-1, finally adding 0.4-0.8 g of zinc powder, tightly covering a bottle cover, putting into a rotary culture device, and rotating in a dark place at the rotating speed of 15-45 r.min-1.
And further, sampling at regular time, performing suction filtration on the sampled sample through a membrane of 0.22 mu m or 0.45 mu m by using a vacuum pump to separate unreacted zinc powder so as to stop the reaction, and using the obtained water sample for analysis and test of the concentration of the DCF, wherein the reaction time is 60-96 h.
Example 1:
adding 400 mu L of 0.1 mol.L-1 cobalt chloride and nickel chloride into 40mL of ultrapure water, enabling the final concentration of the cobalt chloride and the nickel chloride in each extraction bottle to be 1 mmol.L-1, adjusting the pH value of the solution to be 4.0, adding 18 mu L of 0.1 g.L-1 DCF mother liquor so that the initial concentration of the DCF is 450-550 mu g.L-1, finally adding 0.4g of zinc powder, tightly covering a bottle cover, placing the bottle cover into a rotary incubator, and rotating in a dark place at the rotating speed of 15 r.min-1.
Further, sampling was performed at regular time, the sample was subjected to suction filtration using a vacuum pump through a 0.22 μm m membrane to separate unreacted zinc powder to terminate the reaction, and the obtained water sample was used for analytical test of the concentration of DCF, and the reaction time was 60 hours.
Example 2:
adding 600 mu L of 0.1 mol.L-1 cobalt chloride and nickel chloride into 40mL of ultrapure water, enabling the final concentration of the cobalt chloride and the nickel chloride in each extraction bottle to be 1.5 mmol.L-1, adjusting the pH value of the solution to be 7.0, adding 20 mu L of 0.1 g.L-1 DCF mother liquor to enable the initial concentration of the DCF to be 450-550 mu g.L-1, finally adding 0.6g of zinc powder, tightly covering a bottle cap, placing the bottle into a rotary incubator, and rotating at the rotation speed of avoiding light of 30 r.min-1.
And further, sampling at regular time, performing suction filtration on the sampled sample through a 0.45-micrometer membrane by using a vacuum pump to separate unreacted zinc powder so as to stop the reaction, and using the obtained water sample for analysis and test of the concentration of the DCF, wherein the reaction time is 80 h.
Example 3: adding 800 mu L of 0.1 mol.L-1 cobalt chloride and nickel chloride into 40mL of ultrapure water, enabling the final concentration of the cobalt chloride and the nickel chloride in each extraction bottle to be 2 mmol.L-1, adjusting the pH value of the solution to be 8.0, adding 22 mu L of 0.1 g.L-1 DCF mother liquor so that the initial concentration of the DCF is 450-550 mu g.L-1, finally adding 0.8g of zinc powder, tightly covering a bottle cover, placing the bottle cover into a rotary incubator, and rotating in a dark place at the rotating speed of 45 r.min-1.
And further, sampling at regular time, performing suction filtration on the sampled sample through a 0.45-micrometer membrane by using a vacuum pump to separate unreacted zinc powder so as to stop the reaction, and using the obtained water sample for analysis and test of the concentration of the DCF, wherein the reaction time is 96 hours.
As shown in FIG. 1, [ Zn ]]0＝10g·L-1，[DCF]＝500μg·L-1，[Ni2+]＝[Co2+]＝1mmol·L-1pH 7.0 and rotation speed 45r min-1，T＝20℃；
The reaction is carried out for 72 hours, the removal rate of DCF reduced by single zero-valent zinc is less than 25 percent, and Co is2+The removal rate of DCF reduced by catalyzing zero-valent zinc reaches 90 percent, and Ni2+The removal rate of DCF in the reduction of the zero-valent zinc is more than 98%, and the concentration of DCF is lower than the detection limit. Co alone2+And Ni2+Has no effect on the degradation of DCF in water. It can be seen that the zero-valent zinc is in Co2+And Ni2+DCF can be effectively reduced and degraded under catalysis.

Claims (2)

1. A method for treating diclofenac in water reduced by zero-valent zinc catalyzed by cobalt ions and nickel ions is characterized by comprising the following steps: selecting cobalt ion Co2+Or nickel ion Ni2+The DCF in the water is reduced by catalyzing zero-valent zinc, and the treatment method comprises the following steps:
adding 0.1 mol.L of 400 to 800 mu L into each 40mL of ultrapure water-1Cobalt chloride and nickel chloride, wherein the final concentration of the cobalt chloride and the final concentration of the nickel chloride in each extraction bottle are respectively 1-2 mmol-1Adjusting the pH of the solution to 4.0-8.0, and adding 18-22 μ L of 0.1 g.L-1The mother solution of DCF ensures that the initial concentration of DCF is 450-550 mu g.L-1Finally, 0.4-0.8 g of zinc powder is added, a bottle cap is tightly covered, and the mixture is placed into a rotary incubator for 15-45 r.min-1The rotating speed of the rotating shaft is rotated in a dark place.
2. The method for treating diclofenac in water by zero-valent zinc reduction catalyzed by cobalt ions and nickel ions according to claim 1, wherein: and (3) sampling at regular time, performing suction filtration on the sampled product through a membrane of 0.22 mu m or 0.45 mu m by using a vacuum pump to separate unreacted zinc powder so as to terminate the reaction, and using the obtained water sample for analysis and test of the concentration of the DCF, wherein the reaction time is 60-96 h.
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CN111453876A (en) * 2020-02-28 2020-07-28 浙江工业大学 Water treatment method for adsorbing tetracycline in water by using zero-valent zinc
CN113683177B (en) * 2021-07-21 2022-12-27 浙江工业大学 Water treatment method for removing diclofenac from water by catalyzing zero-valent zinc with cobaltosic oxide, cobalt hydroxide or nickel hydroxide

Citations (2)

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Publication number Priority date Publication date Assignee Title
AU2787892A (en) * 1992-02-04 1993-09-01 Board Of Regents Of The University Of Nebraska, The Highly reactive forms of zinc and reagents thereof
CN1183316A (en) * 1996-11-22 1998-06-03 大连理工大学 Quick catalytic dechlorination of poly-chloro-organocompound in water using zero-valence Fe and Pd catalyst

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
AU2787892A (en) * 1992-02-04 1993-09-01 Board Of Regents Of The University Of Nebraska, The Highly reactive forms of zinc and reagents thereof
CN1183316A (en) * 1996-11-22 1998-06-03 大连理工大学 Quick catalytic dechlorination of poly-chloro-organocompound in water using zero-valence Fe and Pd catalyst

Non-Patent Citations (2)

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"零价铁去除水中Ni2+及对有机氯脱氯的催化作用";张珍等;《浙江大学学报》;20120930;第39卷(第5期);第2页第1.2节、第4页第1.4节和第5页第3.3节 *

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