阅读说明：本技术 四氧化三钴、氢氧化钴或氢氧化镍催化零价锌去除水中双氯芬酸的水处理方法 (Water treatment method for removing diclofenac from water by catalyzing zero-valent zinc with cobaltosic oxide, cobalt hydroxide or nickel hydroxide ) 是由 韩莹 张克敏 陆青杰 郑孝苹 于 2021-07-21 设计创作，主要内容包括：本发明属于水处理领域,具体涉及一种四氧化三钴、氢氧化钴或氢氧化镍催化金属零价锌去除水中双氯芬酸的水处理方法。本发明所述方法为向含有双氯芬酸的水中,共同加入零价锌和催化剂,所述催化剂为四氧化三钴、氢氧化钴或氢氧化镍的任意一种或多种,随后放入旋转培养器中以一定转速避光旋转反应一定时间,从而使得零价锌在催化剂的催化下有效地去除水中存在的双氯芬酸。本发明方法在采用10g·L～(-1)锌粉和5mmol·L～(-1)的催化剂的混合物时,对初始浓度为500μg·L～(-1)的双氯芬酸去除率能够达到90％以上。(The invention belongs to the field of water treatment, and particularly relates to a water treatment method for removing diclofenac from water by catalyzing metal zero-valent zinc with cobaltosic oxide, cobalt hydroxide or nickel hydroxide. The method of the invention is that the zero-valent zinc and the catalyst are added together into the water containing the diclofenac acid, the catalyst is one or more of cobaltosic oxide, cobalt hydroxide or nickel hydroxide, and then the mixture is put into a rotary culture device to carry out a photophobic rotary reaction for a certain time at a certain rotating speed, so that the diclofenac acid existing in the water is effectively removed by the zero-valent zinc under the catalysis of the catalyst. The method of the invention employs 10 g.L ‑1 Zinc powder and 5 mmol. L ‑1 When the catalyst mixture (2) is used, the initial concentration is 500. mu.g.L ‑1 The diclofenac removal rate can reach more than 90 percent.)

1. A water treatment method for removing diclofenac from water by using cobaltosic oxide, cobalt hydroxide or nickel hydroxide to catalyze zero-valent zinc is characterized by comprising the following steps: adding a certain amount of zero-valent zinc and a catalyst into water containing diclofenac, wherein the catalyst is any one of cobaltosic oxide, cobalt hydroxide or nickel hydroxide, and reacting for a certain time.

2. The water treatment method for removing diclofenac from water by using cobaltosic oxide, cobalt hydroxide or nickel hydroxide to catalyze zero-valent zinc as the catalyst according to claim 1, wherein the reaction is carried out at a pH of 4-7.

3. The water treatment method for removing diclofenac from water by using cobaltosic oxide, cobalt hydroxide or nickel hydroxide to catalyze zero-valent zinc as claimed in claim 1, wherein the diclofenac content in the diclofenac-containing water is 50-2000 μ g-L^-1The addition amount of the zero-valent zinc is 5-20 g.L calculated by the volume of water containing diclofenac^-1The addition amount of the catalyst is 1-20 mmol.L calculated by the volume of water containing diclofenac^-1。

4. The method for removing diclofenac from water by using cobaltosic oxide, cobalt hydroxide or nickel hydroxide as catalyst according to claim 3, wherein the diclofenac content in the diclofenac-containing water is 100-^-1The addition amount of the zero-valent zinc is 8-15 g.L calculated by the volume of water containing diclofenac^-1The addition amount of the catalyst is 3-10 mmol.L based on the volume of water containing diclofenac^-1。

5. According to claim4 the water treatment method for removing diclofenac in water by using cobaltosic oxide, cobalt hydroxide or nickel hydroxide to catalyze zero-valent zinc, is characterized in that the diclofenac content in the diclofenac-containing water is 500 mug.L^-1The addition amount of the zero-valent zinc is 10 g.L calculated by the volume of water containing diclofenac^-1The addition amount of the catalyst is 5 mmol.L based on the volume of water containing diclofenac^-1。

6. The water treatment method for removing diclofenac from water by using cobaltosic oxide, cobalt hydroxide or nickel hydroxide to catalyze zero-valent zinc as claimed in claim 1, wherein the reaction time is 3-120 h.

7. The water treatment method for removing diclofenac from water by using cobaltosic oxide, cobalt hydroxide or nickel hydroxide to catalyze zero-valent zinc according to claim 6, wherein the reaction time is 24-100h when the catalyst is cobalt hydroxide or nickel hydroxide; when the catalyst is cobaltosic oxide, the reaction time is 3-24 h.

8. The water treatment method for removing diclofenac from water by using cobaltosic oxide, cobalt hydroxide or nickel hydroxide to catalyze zero-valent zinc as the catalyst according to claim 1, wherein the reaction is carried out in a rotary incubator.

9. The water treatment method for removing diclofenac from water by using cobaltosic oxide, cobalt hydroxide or nickel hydroxide to catalyze zero-valent zinc as claimed in claim 8, wherein the rotating speed of the rotary incubator is 20-300 r-min^-1。

10. The water treatment method for removing diclofenac from water by using cobaltosic oxide, cobalt hydroxide or nickel hydroxide to catalyze zero-valent zinc according to claim 1, wherein the zero-valent zinc is zinc powder.

Technical Field

The invention belongs to the field of water treatment, and particularly relates to a water treatment method for removing diclofenac from water by catalyzing metal zero-valent zinc with cobaltosic oxide, cobalt hydroxide or nickel hydroxide.

Background

Diclofenac (DCF) is a typical non-steroidal anti-inflammatory drug for paroxysmal pain, is one of anthranilic acid derivatives, and is one of the most commonly detected drugs in water. The traditional Chinese medicine composition is mainly used for treating rheumatism, arthritis and spondylitis and relieving various pains, is one of medicines with the largest global consumption, and is approximately 3000 more than ten thousand people use DCF every year, and the global annual consumption exceeds 940 tons. In the DCF production process, pharmaceutical factories inevitably discharge a trace amount of DCF to the environment. During the use of DCF, unabsorbed DCF is also discharged into the aqueous environment. Although the concentration of DCF in water is low, it also has an impact on the ecological environment and human health. Since DCF is widely present in the environment, its harm to the environment has attracted attention. From 2015, DCF was classified by the U.S. food and drug administration as a monitored trace contaminant. In view of the characteristics of long-term durability, low biodegradability, bio-accumulation and high toxicity of DCF, it is necessary to find a safe, environment-friendly and efficient technology to control DCF.

Because of the antibacterial property of DCF, DCF cannot be completely degraded by the conventional water treatment process. At present, methods for removing DCF in water mainly comprise methods of physical adsorption, advanced oxidation, biodegradation and catalytic reduction. The common physical adsorption methods mainly include air flotation and adsorption methods. Because the Henry coefficient of DCF can not meet the requirement of air floatation method, the Henry coefficient of blown-off substance must be greater than 3X 10³Pa·m³The air-float process therefore has a great limitation on the removal of DCF. Pilot experiments by Ternes et al show that most of DCF can be effectively adsorbed and removed by activated carbon, but the adsorption method only fixes the pollutants in the adsorbent and does not fundamentally mineralize the pollutants. The current advanced oxidation techniques for DCF removal are mainly: o is₃Oxidation, sonication and UV/H₂O₂And the like. O is₃The oxidation has good removal effect on DCF, the removal rate of low-dose ozone on DCF is very low, and the removal effect of high-dose ozone on DCF is good, but the cost is increased, and the popularization and the use are difficult. The ultrasonic method can effectively degrade DCF, but has the problems of high cost and the like. UV/H₂O₂The oxidation method can efficiently remove DCF in water but consumes H₂O₂The amount is higher. Raw materialThe biodegradation method mainly includes an activated sludge method and a membrane bioreactor method, and the activated sludge method cannot effectively remove DCF because DCF is difficult to be adsorbed on sludge. DCF is removed by the microbial film bioreactor, and the removal rate is 1.0-4.0% when the reaction lasts for 48 hours. At present, the research on DCF removal by a catalytic reduction method is not many, and De Corte et al find that a bimetallic catalyst has higher catalytic activity when used for removing DCF through synthesizing biological Pd and Pd-Au catalysts. However, catalysts supported on organisms generally have low activity, are sensitive to the environment, and are easily deactivated. Among the processes for removing chlorinated organic contaminants from water, dechlorination appears to be the most reasonable process. Catalytic hydrodechlorination proved to be a very promising process, but requires a suitable catalyst.

In view of the above, in order to be applied to actual water treatment, a new and simple treatment method capable of effectively removing DCF in water needs to be established. The zero-valent zinc reduction technology has simple operation steps, low price, no need of providing additional energy and low energy consumption, and the zero-valent zinc is rapidly developed in the aspect of removing pollutants in water and is applied to removing DCF. However, the existing technology for removing DCF in water by using zero-valent zinc has the problems of long reaction time and low removal rate, and cannot reach the satisfactory standard.

Disclosure of Invention

The invention aims to solve the problems in the prior art and provides a water treatment method for removing diclofenac from water by catalyzing zero-valent zinc with cobaltosic oxide, cobalt hydroxide or nickel hydroxide.

The invention solves the technical problem, and adopts the technical scheme that:

a water treatment method for removing diclofenac in water by using cobaltosic oxide, cobalt hydroxide or nickel hydroxide to catalyze zero-valent zinc comprises the following steps: adding a certain amount of zero-valent zinc and a catalyst which is any one or more of cobaltosic oxide, cobalt hydroxide or nickel hydroxide into water containing diclofenac acid, and then reacting for a certain time. The reaction is preferably carried out under a condition of being shielded from light, for the purpose of preventing the relevant substance from undergoing an unknown decomposition reaction or the like in the presence of light, and if the relevant substance can stably exist under light, the reaction can be carried out under a condition of not being shielded from light.

Preferably, the reaction is carried out at a pH of 4 to 7, more preferably, the reaction pH is 6 to 7, and more preferably, the reaction pH is 7.

Preferably, the diclofenac content in the water containing diclofenac is 50-2000. mu.g.L^-1More preferably, the content is 100-^-1More preferably, the content is 500. mu.g.L^-1。

Preferably, the dosage of the zero-valent zinc is 5-20 g.L based on the volume of the water containing the diclofenac^-1More preferably, the amount of the feed is 8 to 15 g.L^-1More preferably, the amount of the feed is 10 g.L^-1。

Preferably, the dosage of the catalyst is 1-20 mmol.L based on the volume of water containing diclofenac^-1More preferably, the amount of the feed is 3 to 10 mmol.L^-1More preferably, the amount of the compound is 5 mmol. multidot.L^-1。

Preferably, the reaction time is 3 to 120 hours.

Preferably, when the catalyst is cobalt hydroxide or nickel hydroxide, the reaction time is 24-100h, and more preferably 72 h.

When the catalyst is cobaltosic oxide, the reaction time is 3-24h, and the more preferable time is 6 h.

Preferably, the reaction is carried out in a rotary incubator in order to ensure the reaction by thoroughly mixing and contacting the substances in the reaction solution under the rotary condition, and therefore, other methods such as stirring and the like which can promote the thorough contact of the substances are also possible; the rotating speed of the rotary culture device is 20-300 r.min^-1More preferably, the rotation speed is 30 to 100 r.min^-1More preferably, the rotation speed is 45 r.min^-1。

Preferably, the zero-valent zinc is zinc powder.

Transition metal hydroxides or oxides are often used as catalysts for redox reactions because of the tendency of the d-electron shell of the metal cation to lose or gain electrons. In one aspect, a metal/transition metal (hydr) oxide interface can be formed with the metal, thereby providing more active sites for the hydrogen evolution reaction and generating more active hydrogen atoms. On the other hand, the transition metal (hydr) oxide can also promote the generation of hydroxyl radicals in the reaction, thereby removing DCF. Therefore, the invention adopts cobaltosic oxide, cobalt hydroxide or nickel hydroxide in the transition metal (hydrogen) oxide to catalyze zero-valent zinc to remove DCF in water. The cobaltosic oxide, the cobalt hydroxide and the nickel hydroxide are proved to be catalysts in a system for catalyzing Zn to remove DCF, and do not participate in the reaction. The catalytic action of the catalyst is mainly to catalyze the decomposition of water to generate active hydrogen, namely the equation is as follows;

H₂O+e^-→·H+OH^-

·H+·H→H₂

compared with the prior art, the invention has the following beneficial effects:

the invention provides a water treatment method for removing diclofenac in water by using cobaltosic oxide, cobalt hydroxide or nickel hydroxide to catalyze zero-valent zinc, which is to effectively remove diclofenac DCF existing in water by using the zero-valent zinc under the catalysis of the cobaltosic oxide, the cobalt hydroxide or the nickel hydroxide. In the presence of 10 g.L^-1Zinc powder and 5 mmol. L^-1The mixture of the catalyst (tricobalt tetraoxide, cobalt hydroxide or nickel hydroxide) was adjusted to an initial concentration of 500. mu.g.L^-1The DCF of (1) is subjected to a catalytic degradation reaction:

when the catalyst is nickel hydroxide, the reaction is carried out for 72 hours, the removal rate of DCF removed by reduction of zero-valent zinc reaches 90.11% under the catalysis of nickel hydroxide, and the removal rates of DCF removed by the single zero-valent zinc and the single nickel hydroxide for 72 hours are only 29.72% and 18.59%;

when the catalyst is cobalt hydroxide, the reaction is carried out for 72 hours, under the catalysis of the cobalt hydroxide, the removal rate of DCF removed by reduction of zero-valent zinc reaches 98.75%, and the removal rates of DCF removed by single zero-valent zinc and single cobalt hydroxide for 72 hours are only 29.72% and 11.11%;

when the catalyst is cobaltosic oxide, the reaction is carried out for 6 hours, under the catalysis of the cobaltosic oxide, the removal rate of DCF removed by reduction of zero-valent zinc reaches 97.65%, and the removal rates of DCF removed by single zero-valent zinc and single cobaltosic oxide for 72 hours are only 13.45% and 8.51%.

Therefore, zero-valent zinc can be used for efficiently and quickly catalyzing and degrading DCF in water under the catalysis of cobaltosic oxide, cobalt hydroxide or nickel hydroxide to remove DCF in water and further control the non-steroidal anti-inflammatory drug DCF in water, so that the safety of drinking water is guaranteed, and the method has the advantages of low cost, short time and high efficiency, and is suitable for large-scale application.

Drawings

FIG. 1 is a schematic diagram of the effectiveness of cobaltosic oxide to catalyze the removal of DCF from zero valent zinc;

FIG. 2 is a schematic diagram showing the effectiveness of cobalt hydroxide in catalyzing zero valent zinc to remove DCF;

FIG. 3 is a schematic diagram of the effectiveness of nickel hydroxide in catalyzing zero valent zinc to remove DCF;

FIG. 4 is a graph of different initial pH values of the solution versus Zn/Co₃O₄The schematic diagram of the influence result of removing DCF;

FIG. 5 shows different initial pH values of the solution versus Zn/Co (OH)₂The schematic diagram of the influence result of removing DCF;

FIG. 6 shows different initial pH values of the solution versus Zn/Ni (OH)₂The effect of removing DCF is shown schematically.

Detailed Description

The technical solution of the present invention is further specifically described below by way of specific examples in conjunction with the accompanying drawings.

Example 1:

40mL of 25 mmol. multidot.L was added to a 40mL extraction flask at room temperature (room temperature is generally 15 to 40 ℃ C., and room temperature is 20 ℃ C. in the case of this example)^-1The HEPES buffer solution (for the purpose of ensuring the pH of the reaction system to be stabilized at about 7 during the reaction) was adjusted to an initial pH of 7.0, and 0.4g (10 g. L) of the HEPES buffer solution was added thereto^-1) Zinc powder (note: the concentration is 10 g.L^-1The concentration of the substance in the final reaction solution, i.e., in terms of 10 g.L^-1Zinc powder is added in the concentration of (2), namely the concentration of the zinc powder in the reaction solution is 10 g.L^-1The same applies below), 0.2mmol (5 mmol. multidot.L)^-1) 0.4g (10 g. L) of tricobalt tetraoxide^-1) Zinc powder and 0.2mmol (5 mmol. multidot.L)^-1) To the mixture of cobaltosic oxide, and finally 20. mu.g (5)00μg·L^-1) DCF, covering the bottle cap tightly, placing into rotary incubator QB-328 for 45 r.min^-1The reaction is carried out for a certain time at a rotating speed in a dark place. And (3) 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 and cobaltosic oxide, thereby stopping the reaction, and using the obtained water sample for analysis and test of the concentration of the DCF.

FIG. 1 shows the results obtained in example 1 using 10 g.L, respectively^-1Zinc powder of (5 mmol. multidot.L)^-1Cobaltosic oxide, 10 g.L^-1Zinc powder and 5 mmol. L^-1The initial concentration of the mixture of cobaltosic oxide was 500. mu.g.L^-1The catalytic degradation profile of DCF (g).

As can be seen from FIG. 1, the reaction is carried out for 2 hours, the removal rate of DCF by zero-valent zinc under the catalysis of cobaltosic oxide is 64%, and the removal rates of DCF by the single zero-valent zinc and the single cobaltosic oxide are respectively 10% and 7.5%; the reaction is carried out for 3 hours, under the catalysis of cobaltosic oxide, the removal rate of DCF removed by zero-valent zinc is 86 percent, and the removal rates of DCF by single zero-valent zinc and single cobaltosic oxide are respectively 12 percent and 8 percent; the reaction was carried out for 6h, and under the catalysis of cobaltosic oxide, the removal rate of DCF by zero-valent zinc was 97.65%, while the removal rates of DCF by zero-valent zinc alone and cobaltosic oxide alone were 13.45% and 8.51%, respectively. Therefore, the DCF can be obtained by using the zero-valent zinc and the cobaltosic oxide independently, the DCF can be removed poorly, and the DCF can be reduced well by the zero-valent zinc under the catalysis of the cobaltosic oxide.

Example 2:

40mL of 25 mmol. multidot.L was added to a 40mL extraction flask at room temperature^-1The HEPES buffer solution (5) was added to the solution at an initial pH of 7.0 in an amount of 10 g. L^-1Zinc powder of (5 mmol. multidot.L)^-1Cobalt hydroxide, 10 g.L^-1Zinc powder and 5 mmol. L^-1To the mixture of cobalt hydroxide, and finally 500. mu.g.L of cobalt hydroxide was added^-1DCF, covering the bottle cap tightly, placing into rotary incubator QB-328 for 45 r.min^-1The reaction is carried out for a certain time at a rotating speed in a dark place. Sampling at fixed time, performing suction filtration on the sample by a vacuum pump through a 0.45 mu m membrane to separate unreacted zinc powder and cobalt hydroxide so as to stop the reaction, and using the obtained water sample for DCFAnd (4) analyzing and testing the concentration.

FIG. 2 shows the results obtained in example 2 using 10 g.L each^-1Zinc powder of (5 mmol. multidot.L)^-1Cobalt hydroxide, 10 g.L^-1Zinc powder and 5 mmol. L^-1The initial concentration of the cobalt hydroxide mixture was 500. mu.g.L^-1The catalytic degradation profile of DCF (g).

As can be seen from FIG. 2, the reaction is carried out for 48 hours, the removal rate of DCF by zero-valent zinc under the catalysis of cobalt hydroxide is 55%, and the removal rates of DCF by zero-valent zinc alone and cobalt hydroxide alone are 24% and 9.5%, respectively; the reaction is carried out for 60 hours, under the catalysis of cobalt hydroxide, the removal rate of DCF removed by zero-valent zinc is 80%, and the removal rates of DCF removed by single zero-valent zinc and single cobalt hydroxide are respectively 28% and 10%; the reaction was carried out for 72h, and under the catalysis of cobalt hydroxide, the removal rate of DCF by zero-valent zinc was 98.75%, while the removal rates of DCF by zero-valent zinc alone and cobalt hydroxide alone were 29.72% and 11.11%, respectively. Therefore, when the zero-valent zinc and the cobalt hydroxide are used independently, the DCF is poor in removal effect, and the DCF can be well reduced by the zero-valent zinc under the catalysis of the cobalt hydroxide.

Example 3:

40mL of 25 mmol. multidot.L was added to a 40mL extraction flask at room temperature^-1The HEPES buffer solution (5) was added to the solution at an initial pH of 7.0 in an amount of 10 g. L^-1Zinc powder of (5 mmol. multidot.L)^-1Nickel hydroxide, 10 g.L^-1Zinc powder and 5 mmol. L^-1To the mixture of nickel hydroxide, and finally 500. mu.g.L of nickel hydroxide was added^-1DCF, covering the bottle cap tightly, placing into rotary incubator QB-328 for 45 r.min^-1The reaction is carried out for a certain time at a rotating speed in a dark place. And (3) 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 and nickel hydroxide so as to stop the reaction, and using the obtained water sample for analyzing and testing the concentration of the DCF.

FIG. 3 shows the results obtained in example 3 using 10 g.L each^-1Zinc powder of (5 mmol. multidot.L)^-1Nickel hydroxide, 10 g.L^-1Zinc powder and 5 mmol. L^-1The initial concentration of the nickel hydroxide mixture was 500. mu.g.L^-1The catalytic degradation profile of DCF (g).

As can be seen from FIG. 3, the reaction is carried out for 24h, the removal rate of DCF by zero-valent zinc under the catalysis of nickel hydroxide is 62%, and the removal rates of DCF by zero-valent zinc alone and nickel hydroxide alone are 23% and 17%, respectively; the reaction is carried out for 48 hours, under the catalysis of nickel hydroxide, the removal rate of DCF removed by zero-valent zinc is 80%, and the removal rates of DCF removed by single zero-valent zinc and single nickel hydroxide are respectively 24% and 18%; the reaction was carried out for 72h, and under the catalysis of nickel hydroxide, the removal rate of DCF by zero-valent zinc was 90.11%, while the removal rates of DCF by zero-valent zinc alone and nickel hydroxide alone were 29.72% and 18.59%, respectively. Therefore, the DCF can be well reduced by the zero-valent zinc under the catalysis of the nickel hydroxide.

Example 4: testing different initial pH values of the solution to Zn/Co₃O₄Removing effects of DCF

Adding 40mL of buffer solution into a 40mL extraction flask, adjusting the initial pH to a specific value, and sequentially adding corresponding substances to make the concentration of each substance in the reaction solution be 10 g.L^-1Zinc powder of 5 mmol. L^-1500. mu.g.L of cobaltosic oxide^-1DCF, covering the bottle cap tightly, placing into rotary incubator QB-328 for 45 r.min^-1The reaction is carried out by rotating the rotary speed in a dark place, and the removal rate of the DCF is detected by sampling. FIG. 4 shows different initial pH vs. Zn/Co₃O₄The results of removing the influence of DCF showed that the removal effect was excellent at an initial pH of 6 to 7, good at a pH of 4, and general at a pH of 8 to 9.

Note: the buffers used to adjust the pH were (same as below):

pH 4, buffer 25 mmol. multidot.L^-1The PIPPS buffer solution of (4);

pH 6, 7, buffer 25 mmol. multidot.L^-1The HEPES buffer of (1);

pH 8, 9, buffer 25 mmol. L^-1The TAPS buffer of (1).

Example 5: test solutions different initial pH values Zn/Co (OH)₂Removing effects of DCF

Adding into a 40mL extraction flaskAdding 40mL of buffer solution, adjusting the initial pH value to a specific value, and sequentially adding corresponding substances to ensure that the concentration of each substance in the reaction solution is 10 g.L^-1Zinc powder of 5 mmol. L^-1500. mu.g.L of cobalt hydroxide^-1DCF, covering the bottle cap tightly, placing into rotary incubator QB-328 for 45 r.min^-1The reaction is carried out by rotating the rotary speed in a dark place, and the removal rate of the DCF is detected by sampling. FIG. 5 shows different initial pH vs. Zn/Co (OH)₂As a result of removing the effect of DCF, it was found that the removal effect was excellent at an initial pH of 4 to 7 and was general at a pH of 8 to 9.

Example 6: test solutions different initial pH values Zn/Ni (OH)₂Removing effects of DCF

Adding 40mL of buffer solution into a 40mL extraction flask, adjusting the initial pH to a specific value, and sequentially adding corresponding substances to make the concentration of each substance in the reaction solution be 10 g.L^-1Zinc powder of 5 mmol. L^-1500. mu.g.L of nickel hydroxide^-1DCF, covering the bottle cap tightly, placing into rotary incubator QB-328 for 45 r.min^-1The reaction is carried out by rotating the rotary speed in a dark place, and the removal rate of the DCF is detected by sampling. FIG. 6 shows different initial pH vs. Zn/Ni (OH)₂As a result of removing the effect of DCF, it was found that the removal effect was excellent at an initial pH of 4 to 7 and was general at a pH of 8 to 9.

Example 7:

40mL of buffer solution was added to a 40mL extraction flask to bring the initial pH to 6, followed by 5 g.L^-1Zinc powder and 1 mmol. L^-1Cobalt hydroxide, and finally 50. mu.g.L of cobalt hydroxide^-1DCF, covering the bottle cap tightly, placing into rotary incubator QB-328 for 20 r.min^-1The reaction is carried out for 100 hours in a dark rotating mode, and the removal rate of DCF by sampling detection reaches 92.8%.

Example 8:

40mL of buffer solution was added to a 40mL extraction flask to bring the initial pH to 4, followed by 20 g.L^-1Zinc powder and 20 mmol. L^-1Nickel hydroxide, 2 mg. L is added^-1DCF, covering the bottle cap tightly, placing into rotary incubator QB-328 for 300 r.min^-1The reaction is carried out for 24 hours in a dark rotating mode, and the removal rate of DCF by sampling detection reaches 68.62%.

Example 9:

40mL of buffer solution was added to a 40mL extraction flask to bring the initial pH to 5, followed by 6 g.L^-1Zinc powder and 2 mmol. L^-1Finally adding 80 mu g.L of cobalt hydroxide^-1DCF, covering the bottle cap tightly, placing into rotary incubator QB-328 for 30r min^-1The reaction is carried out for 120h by rotating the reaction product in a dark place, and the removal rate of DCF by sampling and detecting reaches 92.56%.

Example 10:

40mL of buffer solution was added to a 40mL extraction flask to bring the initial pH to 6, followed by 18 g.L^-1Zinc powder and 18 mmol. L^-1The cobaltosic oxide is added into the mixture, and 500 mu g.L of the cobaltosic oxide is finally added^-1DCF, covering the bottle cap tightly, placing into rotary incubator QB-328 for 200r min^-1The reaction is carried out for 12 hours in a dark rotating mode, and the removal rate of DCF by sampling detection reaches 92.62%.

Example 11:

40mL of buffer solution was added to a 40mL extraction flask to bring the initial pH to 7, followed by 8 g.L^-1Zinc powder and 3 mmol. L^-1Cobalt hydroxide, and finally 100. mu.g.L of cobalt hydroxide^-1DCF, covering the bottle cap tightly, placing into rotary incubator QB-328 for 40r min^-1The reaction is carried out for 40 hours in a dark rotating mode, and the removal rate of DCF by sampling detection reaches 72.86%.

Example 12:

40mL of buffer solution was added to a 40mL extraction flask to bring the initial pH to 7, followed by 15 g.L^-1Zinc powder and 10 mmol. L^-1Nickel hydroxide, and finally 300. mu.g.L^-1DCF, covering the bottle cap tightly, placing into rotary incubator QB-328 for 30r min^-1The reaction is carried out for 60 hours in a dark rotating mode, and the removal rate of DCF by sampling detection reaches 81.58%.

Attached: DCF degradation products

Remarking: r represents a reduction product; p represents an oxidation product

The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.