CN108569754B - Environment-friendly sewage treatment agent and use method and application thereof - Google Patents
Environment-friendly sewage treatment agent and use method and application thereof Download PDFInfo
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- CN108569754B CN108569754B CN201810424358.5A CN201810424358A CN108569754B CN 108569754 B CN108569754 B CN 108569754B CN 201810424358 A CN201810424358 A CN 201810424358A CN 108569754 B CN108569754 B CN 108569754B
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention discloses an environment-friendly sewage treatment agent and a using method and application thereof, wherein the environment-friendly sewage treatment agent comprises 0.005-0.3% of polysaccharide-metal ion catalyst, 0.1-0.6% of hydrogen peroxide and the balance of aqueous solution with the pH value of 1-14, and the polysaccharide-metal ion catalyst comprises polysaccharide and metal ion salt. The treating agent is constructed based on natural polysaccharide, has wide and easily obtained sources, simple synthesis and low cost, has good treatment effect under both acidic and alkaline conditions, and has a wider pH application range. The treating agent takes environment-friendly hydrogen peroxide as an efficient oxidant, is clean and environment-friendly, and has low cost and wide application range. The treating agent can quickly remove organic dyes in industrial sewage, solve algae pollution caused by water eutrophication, recover water to be clear and transparent, achieve the aim of water pollution treatment, and has good application prospect.
Description
Technical Field
The invention relates to the field of water pollution treatment, and relates to an environment-friendly sewage treatment agent, and a use method and application thereof.
Background
The development of chemical industry causes a great deal of organic wastewater pollution, and the living state and the ecological environment of human beings are seriously influenced. The removal of pollutants from algae pollution and industrial wastewater pollution has always been a major difficulty in sewage treatment. The traditional biochemical treatment technology is difficult to meet the requirements of relevant standards, and needs advanced oxidation technology mainly generating hydroxyl radicals for treatment. The oxidation treatment method has wide attention due to the advantages of low cost and high efficiency, has good prospects in the fields of advanced treatment of sewage, treatment of organic wastewater which is difficult to biodegrade and the like, and has great potential. Among the advanced oxidation technologies, Catalytic Wet air oxidation (CEAO) has been reported in many cases. CEWO is a chemical process in which oxygen in the air is used as an oxidant to oxidize organic contaminants in a liquid phase to inorganic substances such as carbon dioxide and water or small molecular organic substances. The reaction is accompanied by high temperature and high pressure, so that the reaction operation cost is high. To solve this problem, an oxidizing agent such as ozone or hydrogen peroxide is used instead of oxygen. Ozone oxidation can be carried out at low temperatures, but it is only suitable for treating low-concentration organic wastewater, and ozone has the disadvantages of low solubility in water and short life, which greatly limits its range of use. In contrast, hydrogen peroxide is a widely used green oxidant, is cheap and nontoxic, can not only enable the reaction to be carried out at low temperature and normal pressure, but also enable the generated hydroxyl radical to have strong oxidizing capability (the standard electrode potential is 2.8V), can oxidize most organic matters, has a fast oxidizing rate, and has wide application in the field of sewage treatment.
The Fenton oxidation treatment of wastewater is the most widely applied sewage treatment mode at present, and Fe is used2+As a homogeneous catalyst, hydrogen peroxide is used as an oxidizing agent to degrade organic matters. With Fe2+The Fenton reagent used as the catalyst has strong oxidation effect and has wide application and research in treating organic matters and organic wastewater difficult to degrade. Later researches find that other metal ions also have good catalytic effect on hydrogen peroxide, and particularly, transition metals are used as catalysts and have the advantages of high catalytic activity and low cost. At present, the metal ion salt catalyst is used more frequently, but the dissolution of the metal ions and the removal of the free metal ions have great difficulty. In addition, most of the currently studied catalysts still have some disadvantages, such as good catalytic effect under acidic conditions, but low catalytic activity under alkaline and central conditions, low catalyst stability, narrow application range, and high cost, so it is very important to find a catalyst with high catalytic efficiency, high stability, low cost, and wide pH application range.
Polysaccharide is a natural polymer material commonly existing in nature, and a polysaccharide metal complex is a hot topic in the research field of natural products at present due to the structure and the particularity of biological cereal activity. Furthermore, the polysaccharide complex compound has wide applications in the prevention and treatment of diseases, such as the prevention of ischemic anemia by the polyferose complex, the anti-oxidation treatment by the chitosan metal complex, and the uremia treatment by the absorption of urea. However, research reports at present show that the polysaccharide metal catalyst has good application in the aspect of catalytic chemical reaction synthesis, has excellent catalytic effects in catalyzing olefin monomer polymerization, unsaturated compound hydrogenation and alcohol phenol oxidation, and can also catalyze the decomposition of hydrogen peroxide.
Disclosure of Invention
In view of the above, the present invention aims to provide an environment-friendly sewage treatment agent, and a use method and an application thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
1. an environment-friendly sewage treatment agent comprises the following components in percentage by weight: 0.005-0.3% of polysaccharide-metal ion catalyst, 0.1-0.6% of hydrogen peroxide and the balance of aqueous solution with the pH value of 1-14, wherein the polysaccharide-metal ion catalyst is composed of polysaccharide and metal ion salt.
Further, the polysaccharide-metal ion catalyst is 0.02%, the hydrogen peroxide is 0.3%, and the balance is an aqueous solution with the pH of 9-12.
Further, the polysaccharide is chitosan, cyclodextrin, dextran, hyaluronic acid or starch.
Further, the polysaccharide is chitosan or hyaluronic acid.
Further, the metal element in the metal ion salt is Fe, Co, Cu, Ni, Zn, Mn, Cr or Ce.
Further, the metal element is Cu.
Further, the preparation of the polysaccharide-metal ion catalyst comprises the following steps:
1) preparing a metal ion salt solution with the concentration of 4-30g/L and a polysaccharide water solution with the concentration of 0.01-0.8 g/mL;
2) dropwise adding the metal ion salt solution obtained in the step 1) into the polysaccharide aqueous solution obtained in the step 1), and stirring at 25 ℃ to obtain a mixed solution;
3) and (3) carrying out suction filtration, methanol washing and vacuum drying on the mixed solution in the step 2) to obtain the polysaccharide-metal ion catalyst.
2. An application method of an environment-friendly sewage treatment agent comprises the step of mixing and stirring a polysaccharide-metal ion catalyst and a hydrogen peroxide solution with sewage at the same time at the temperature of 30-100 ℃ for 0-4 d.
Further, the sewage contains polycyclic aromatic hydrocarbon organic matters.
3. An application of an environment-friendly sewage treating agent in treating industrial sewage.
The invention has the beneficial effects that: in the preparation method, the sewage treatment agent with good sewage treatment effect and wide application range is prepared by controlling the reaction raw materials and the reaction conditions. The invention adopts polysaccharide metal complex as catalyst, and natural polysaccharide as ligand to complex with metal ion, compared with single ion catalyst, the catalytic process is more stable, and metal ion in polysaccharide does not exist in free ion state but exists in stable complex, which can reduce secondary pollution of metal ion in water pollution treatment.
In addition, compared with the metal organic coordination catalyst, the polysaccharide metal complex is not easy to oxidize in the air or lose catalytic activity when being affected with damp, does not corrode a metal reaction kettle, and is more economical and effective in industrial application. Moreover, the metal ion catalyst has a good catalytic effect only under acidic conditions, and is easy to generate precipitates under alkaline conditions so as to reduce or even eliminate the activity of the catalyst, thereby losing the catalytic effect.
The sewage treatment agent disclosed by the invention is wide in raw material source, low in cost, environment-friendly and clean. Compared with the prior art, the preparation method is simple, and the sewage treatment agent disclosed by the invention is simple in formula, mild in reaction condition and good in treatment effect, can effectively degrade organic wastewater pollutants, solves the problem of green alga pollution caused by water eutrophication, and has a good application prospect.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
fig. 1 is a graph of the effect of polysaccharide-metal catalyst on trypan blue degradation at pH 3.
Fig. 2 is a graph showing the effect of degrading trypan blue by the polysaccharide-metal catalyst and the copper sulfate catalyst under the condition of pH 10.
FIG. 3 is a graph showing the effect of treating alkaline wastewater with the polysaccharide-metal catalyst and the copper sulfate catalyst.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Example 1
The preparation steps of the chitosan-copper catalyst are as follows:
1) first, 1.6g of copper sulfate was added to 10mL of water to prepare a saturated copper sulfate solution, and 1g of chitosan was dissolved in 10mL of water.
2) 10mL of saturated copper sulfate solution was added dropwise to the aqueous chitosan solution, and stirred at room temperature for 48 h.
3) And (3) carrying out suction filtration on the solution obtained by the reaction, washing with methanol, and drying in vacuum to obtain the chitosan-copper catalyst.
Example 2
The preparation steps of the hyaluronic acid-copper catalyst are as follows:
1) first, 1.6g of copper sulfate was added to 10mL of water to prepare a saturated copper sulfate solution, and 1g of hyaluronic acid was dissolved in 10mL of water.
2) 10mL of a saturated solution of copper sulfate was added dropwise to the aqueous hyaluronic acid solution, and stirred at room temperature for 48 hours.
3) Dialyzing the solution obtained by the reaction, and freeze-drying to obtain the hyaluronic acid-copper catalyst.
Example 3
The method for treating sewage by using the environment-friendly sewage treating agent comprises the following steps:
the sewage treatment agent comprises the following components in percentage by weight: 0.02% of hyaluronic acid-copper (or chitosan-copper) catalyst, 0.3% of hydrogen peroxide and the balance of aqueous solution with pH of 3.
The catalyst in this example is a hyaluronic acid-copper (or chitosan-copper) catalyst, and the degradation performance of the catalyst on trypan blue (simulated sewage) is measured under the conditions of the catalyst and no catalyst, wherein the catalytic conditions are as follows: temperature: 80 ℃, pH: 3.
trypan blue 19.2mg is weighed and dissolved in 10mL of aqueous HCl solution with pH 3, 1.92mg of hyaluronic acid-copper (or chitosan-copper) catalyst is added thereto, stirred for 10min to allow the dye to reach adsorption/desorption equilibrium on the catalyst surface, then 100uL of aqueous hydrogen peroxide solution (30 vol.%) is added thereto, and an oil bath pan at 80 ℃ is added. 50uL of the sample was taken at time points and examined with an ultraviolet-visible spectrophotometer. According to the Lambert-Beer law, the concentration change of the organic matter can be quantitatively calculated according to the change of the characteristic absorption peak intensity of the organic matter. When the light absorption materials are the same and the thicknesses are the same, the change of the solution concentration can be directly expressed by the change of the absorbance, namely, the concentration of the organic matter and the absorbance are linearly related in a certain concentration range. Because trypan blue has a characteristic absorption peak at 555nm, the change of the absorbance can be used for measuring the change of the concentration of the trypan blue in the solution.
As seen from FIG. 1 (abscissa: reaction time, ordinate: ratio of trypan blue concentration value measured after a reaction time to trypan blue initial concentration), trypan blue added with hyaluronic acid-copper catalyst was degraded by nearly 100% after 2 hours of reaction, trypan blue added with chitosan-copper catalyst was degraded by nearly 100% after 4 hours of reaction, and trypan blue without hyaluronic acid-copper (or chitosan-copper) catalyst was hardly degraded. As can also be seen from fig. 1, trypan blue with the addition of hyaluronic acid-copper (or chitosan-copper) catalyst was completely degraded and the solution became colorless, while the control without the addition of catalyst had no significant change in color. Therefore, under the acidic condition, at the temperature of 80 ℃, the sewage treatment agent taking hyaluronic acid-copper (or chitosan-copper) as a catalyst has better catalytic activity on the organic dye trypan blue.
FIG. 1 is a graph showing the activity of the wastewater treatment system using hyaluronic acid-copper (or chitosan-copper) as a catalyst in degrading an aqueous solution containing trypan blue dye in this example, wherein C0The initial concentration of trypan blue, C, the concentration of the trypan blue remained in the solution after the temperature rise reaction for a period of time, and t is the reaction time. The Control group is the degradation condition of trypan blue when no catalyst is added, DY-2 is the degradation condition of trypan blue when a hyaluronic acid-copper catalyst is added, and DY-1 is the degradation condition of trypan blue when a chitosan-copper ion catalyst is added.
The hyaluronic acid-copper catalyst (or chitosan-copper) can catalyze the decomposition of hydrogen peroxide serving as a green oxidant under certain conditions to generate hydroxyl radicals, attack organic dyes and the like in industrial sewage or domestic sewage, degrade the organic dyes, mineralize the organic dyes into carbon dioxide and water, and achieve the aim of treating the sewage.
Example 4
The method for treating sewage by using the environment-friendly sewage treating agent comprises the following steps:
the sewage treatment agent comprises the following components in percentage by weight: 0.02% of hyaluronic acid-copper (or chitosan-copper) catalyst, 0.3% of hydrogen peroxide and the balance of aqueous solution with pH of 10.
The catalyst in this example is a hyaluronic acid-copper (or chitosan-copper) catalyst, and the degradation performance of the catalyst on trypan blue (simulated sewage) is measured under the conditions of the catalyst and no catalyst, wherein the catalytic conditions are temperature: 80 ℃, pH: 10.
trypan blue 19.2mg is weighed and dissolved in 10mL of aqueous NaOH solution with pH of 10, 1.92mg of hyaluronic acid-copper (or chitosan-copper or copper sulfate) catalyst is added into the solution, the solution is stirred for 10min to ensure that the dye is adsorbed/desorbed on the surface of the catalyst to be balanced, then 100uL of aqueous hydrogen peroxide solution (30 vol.%) is added into the solution, and an oil bath kettle at 80 ℃ is added.
FIG. 2 is a diagram of the sewage treatment system using hyaluronic acid-copper (or chitosan-copper or copper sulfate) as a catalyst in the present example to degrade a sewage treatment system containing trypan blueGraph comparing activity of aqueous dye solution, wherein C0The initial concentration of trypan blue, C, the concentration of the trypan blue remained in the solution after the temperature rise reaction for a period of time, and t is the reaction time. The Control group is the degradation condition of trypan blue when no catalyst is added, DY-2 is the degradation condition of trypan blue when hyaluronic acid-copper catalyst is added, DY-1 is the degradation condition of trypan blue when chitosan-copper ion catalyst is added, and DY-0 is the degradation condition of trypan blue when copper sulfate catalyst is added.
As seen from FIG. 2 (abscissa: reaction time, ordinate: ratio of trypan blue concentration value measured after a reaction time to trypan blue initial concentration), trypan blue added with chitosan-copper catalyst was degraded by nearly 100% after 8 hours of reaction, trypan blue added with hyaluronic acid-copper catalyst was degraded by nearly 50% after 8 hours of reaction, trypan blue added with copper sulfate catalyst was degraded by nearly 50% after 30 hours of reaction, and trypan blue without hyaluronic acid-copper (or chitosan-copper) catalyst was hardly degraded. As can also be seen from fig. 2, trypan blue with the addition of hyaluronic acid-copper (or chitosan-copper) catalyst was completely degraded and the solution became colorless, while the control without the addition of catalyst had no significant change in color. Therefore, under the alkaline condition, at the temperature of 80 ℃, the sewage treatment agent taking chitosan-copper as the catalyst has better catalytic activity on the organic dye trypan blue, and compared with a metal ion catalyst, the polysaccharide-metal ion catalyst can catalyze the decomposition of organic dye molecules in a short time, and has better catalytic effect.
Example 5
The method for treating sewage by using the environment-friendly sewage treating agent comprises the following steps:
the sewage treatment agent comprises the following components in percentage by weight: 0.02% of hyaluronic acid-copper (or chitosan-copper) catalyst, 0.3% of hydrogen peroxide and the balance of water.
The catalyst in this example is a hyaluronic acid-copper (or chitosan-copper) catalyst, and the degradation performance of the catalyst on trypan blue (simulated sewage) is measured under the conditions of the catalyst and no catalyst, wherein the catalytic conditions are temperature: pH 7 at 50 ℃.
Trypan blue 19.2mg is weighed and dissolved in 10mL of water, 1.92mg of hyaluronic acid-copper (or chitosan-copper) catalyst is added thereto, stirring is carried out for 10min, the dye is allowed to reach adsorption/desorption equilibrium on the catalyst surface, then 100uL of aqueous hydrogen peroxide solution (30 vol.%) is added thereto, and a 50 ℃ oil bath is added.
Example 6
The method for treating sewage by using the environment-friendly sewage treating agent comprises the following steps:
the sewage treatment agent comprises the following components in percentage by weight: 0.02% of hyaluronic acid-copper (or chitosan-copper) catalyst, 0.3% of hydrogen peroxide and the balance of aqueous solution with pH of 7.
The catalyst in this example is a hyaluronic acid-copper (or chitosan-copper) catalyst, and the degradation performance of the catalyst on trypan blue (simulated sewage) is measured under the conditions of the catalyst and no catalyst, wherein the catalytic conditions are temperature: 80 ℃, pH: 7.
trypan blue 19.2mg is weighed and dissolved in 10mL of deionized water, 1.92mg of hyaluronic acid-copper (or chitosan-copper) catalyst is added into the deionized water, the mixture is stirred for 10min to ensure that the dye is adsorbed/desorbed on the surface of the catalyst to be balanced, then 100uL of aqueous hydrogen peroxide solution (30 vol.%) is added into the mixture, and the mixture is added into an oil bath kettle at 80 ℃.
Example 7
The method for treating sewage by using the environment-friendly sewage treating agent comprises the following steps:
the sewage treatment agent comprises the following components in percentage by weight: 0.02% of chitosan-copper catalyst, 0.3% of hydrogen peroxide and the balance of sewage with pH of 8.
The catalyst in the embodiment is a chitosan-copper catalyst, the degradation performance of the algae sewage is measured under the conditions of the catalyst and no catalyst, and the catalytic conditions are as follows: at 25 ℃.
10mL of algae sewage is measured, 1.92mg of chitosan-copper catalyst is added into the algae sewage, the mixture is stirred for 10min to ensure that the dye achieves adsorption/desorption balance on the surface of the catalyst, and then 300uL of aqueous hydrogen peroxide (30 vol.%) is added into the mixture, and the mixture is stirred at room temperature.
FIG. 3 is a graph showing the catalytic effect of the sewage treatment system using chitosan-copper as the catalyst in the present example, wherein a is the catalytic effect of the sewage treatment system using copper sulfate as the catalyst in comparative example 1, b is the group of adding the catalyst and hydrogen peroxide to the sewage, c is the group of adding only hydrogen peroxide to the sewage, and d is the group of pure algae sewage. As seen from the graph 3, after 5 hours, the green algae sewage added with the chitosan-copper catalyst is changed into colorless, the green algae sewage without the catalyst is not obviously changed, the single metal ion copper sulfate catalyst has no obvious effect on sewage treatment within 5 hours, and a small amount of precipitate is generated when the copper sulfate is added, and the pH value of the sewage is measured to be alkaline, so that the free copper ions generate copper hydroxide precipitate under the alkaline condition, the effect of catalyzing hydrogen peroxide is weakened, and the sewage purification effect is influenced. Therefore, the chitosan-copper catalyst has a high catalytic effect on catalyzing the purification of green algae sewage, and compared with a metal ion catalyst, the polysaccharide-metal ion catalyst can still keep a good catalytic effect under an alkaline condition, so that the chitosan-copper catalyst has a good application prospect in the aspect of sewage treatment.
Comparative example 1
The method for treating sewage by using the metal ion type catalyst comprises the following steps:
the sewage treatment agent comprises the following components in percentage by weight: copper sulfate catalyst 0.02%, hydrogen peroxide 0.3%, and the balance of aqueous sodium hydroxide solution having a pH of 10.
The catalyst in this comparative example 1 was copper sulfate, and the degradation performance of the catalyst to trypan blue (simulated sewage) was measured under the conditions of the catalyst and no catalyst, and the catalytic conditions were as follows: temperature: 80 ℃, pH: 10.
trypan blue 19.2mg was weighed and dissolved in 10mL of aqueous NaOH having pH 10, 1.92mg of copper sulfate was added thereto, stirred for 10min to allow the dye to reach adsorption/desorption equilibrium on the catalyst surface, then 100 μ L of aqueous hydrogen peroxide (30 vol.%) was added thereto, and added to an oil bath pan at 80 ℃.
As shown in FIG. 2, DY-0 is the degradation of Trypan blue when the copper sulfate catalyst of comparative example 1 is added, the effect of the copper sulfate catalyst in degrading Trypan blue is poor under alkaline conditions, and the polysaccharide-metal catalyst of example 4 has the effect of degrading Trypan blue which is far better than that of copper sulfate, so that the effect of sewage treatment is excellent.
Comparative example 2
The method for treating sewage by using the metal ion type catalyst comprises the following steps:
the treating agent comprises the following components in percentage by weight: 0.02 percent of copper sulfate catalyst, 0.9 percent of hydrogen peroxide and the balance of sewage with the pH value of 8.
The catalyst in this comparative example is a copper sulfate catalyst, and the degradation performance of the algae wastewater is measured under the conditions of the catalyst and no catalyst, wherein the catalysis conditions are as follows: at 25 ℃.
10mL of algae sewage is measured, 1.92mg of copper sulfate catalyst is added into the algae sewage, the mixture is stirred for 10min to ensure that the dye is in adsorption/desorption equilibrium on the surface of the catalyst, and then 300 mu L of aqueous hydrogen peroxide (30 vol.%) is added into the mixture, and the mixture is stirred at room temperature.
In fig. 3, a is a wastewater treatment agent system using copper sulfate as a catalyst in comparative example 2, which catalyzes algae wastewater to purify, and compared with the wastewater treatment agent system using chitosan-copper as a catalyst in example 7, the wastewater treatment agent system using copper sulfate as a catalyst has a poor treatment effect, and the color of wastewater does not change significantly within 5 hours. Therefore, the purifying effect of the metal catalyst on the algae sewage is obviously inferior to that of the polysaccharide-metal catalyst, and the polysaccharide-metal catalyst in the embodiment 7 of the invention has good application prospect in the field of sewage treatment.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (1)
1. The using method of the environment-friendly sewage treating agent is characterized in that the environment-friendly sewage treating agent comprises the following components, by weight, 0.02% of a polysaccharide-metal ion catalyst, 0.3% of hydrogen peroxide and the balance of a water solution with the pH value of 10;
the polysaccharide-metal ion catalyst consists of polysaccharide and metal ion salt;
the polysaccharide is chitosan or hyaluronic acid;
the metal element is Cu;
the preparation of the polysaccharide-metal ion catalyst comprises the following steps:
1) preparing a metal ion salt solution with the concentration of 4-30g/L and a polysaccharide water solution with the concentration of 0.01-0.8 g/mL;
2) dropwise adding the metal ion salt solution obtained in the step 1) into the polysaccharide aqueous solution obtained in the step 1), and stirring at 25 ℃ to obtain a mixed solution;
3) carrying out suction filtration, methanol washing and vacuum drying on the mixed solution in the step 2) to obtain a polysaccharide-metal ion catalyst; the use method of the environment-friendly sewage treatment agent comprises the following steps:
and simultaneously mixing the polysaccharide-metal ion catalyst and the hydrogen peroxide solution with the sewage, stirring and treating for 0-4 d under the conditions that the temperature is 80 ℃ and the pH value is 10, wherein the sewage contains polycyclic aromatic hydrocarbon organic matters.
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