An industrial wastewater treatment agent and a preparation method thereof

Abstract

The application discloses an industrial wastewater treatment agent and a preparation method thereof, and belongs to the technical field of wastewater treatment. The preparation raw materials of the treatment agent comprise graphene oxide, N-methylpyrrolidone solution, sodium persulfate, acrylic acid, benzene sulfonamide, ethyl glyoxylate, microbial bacteria liquid, mercaptoethylamine, sodium carbonate, dimethylaminoethyl methacrylate, potassium persulfate and methylene acrylamide. The graphene oxide is modified twice by the method, the adsorbability of the graphene oxide is improved, the microorganisms are loaded on the modified graphene oxide, the microorganisms are embedded by using a pH-sensitive gel after being treated by a mercaptoethylamine-sodium carbonate mixed solution, the damage of a strong alkaline and high-concentration heavy metal environment to the microorganisms is reduced, the modified graphene oxide and the microorganisms are combined to treat wastewater, and the wastewater treatment effect is remarkably improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of sewage treatment, in particular to an industrial sewage treatment agent and a preparation method thereof. BACKGROUND

[0002] Industrial wastewater refers to wastewater, sewage and waste liquid generated in industrial production, which contains industrial production materials, intermediate products and products lost with water flow and pollutants generated in the production process. With the rapid development of industry, the types and quantity of wastewater are increasing rapidly, and the pollution of water bodies is becoming more and more widespread and serious, which threatens human health and safety. Therefore, the treatment of industrial wastewater is particularly important.

[0003] At present, the main methods for treating industrial wastewater are physical method, chemical method and biological method. The physical method includes reverse osmosis, distillation and soil irrigation. The chemical method includes ion exchange method, ammonia stripping, chemical precipitation method, breakpoint chlorination, electrodialysis, electrochemical treatment and catalytic cracking. The biological method includes nitrification and algae cultivation. The treatment cycle of the physical method is generally long, and many water storage tanks are needed, and the treatment effect is not ideal. The chemical method has good treatment effect, but has high energy consumption and cost. The biological treatment method is an effective method for treating industrial polluted water bodies, which uses the action of microorganisms to decompose compounds. Since the biological treatment method has lower cost than the physical and chemical methods, and does not cause secondary pollution, and microorganisms have strong variability and adaptability, it becomes an ideal method for treating industrial polluted water bodies. However, since microorganisms have strict requirements for the living environment, if the microorganisms are directly put into the wastewater, the strong alkaline and high-concentration heavy metal environment will damage the microorganisms and cause the death of the microorganisms, resulting in a large consumption of microorganisms and low efficiency of wastewater treatment. Therefore, the microbial treatment method is greatly affected by the environment and has poor impact resistance.

[0004] Therefore, it is urgent to find an industrial sewage treatment agent and a preparation method thereof to solve the problems of large consumption of microorganisms and low efficiency of wastewater treatment caused by the damage of strong alkaline and high-concentration heavy metal environment to microorganisms when the microorganisms are directly put into the wastewater. SUMMARY

[0005] In view of this, the present application provides an industrial sewage treatment agent and a preparation method thereof, which treats industrial wastewater by combining microbial treatment method with adsorption method. The microbial treatment agent used can be directly put into the wastewater environment with strong alkaline or high-concentration heavy metals, solving the problems of great influence of the microbial treatment agent on the environment and low treatment efficiency.

[0006] The present application solves the above technical problems by the following technical means:

[0007] An industrial sewage treatment agent, the treatment agent comprising the following raw materials:

[0008] Graphene oxide 20-30 parts by mass, 30-50 wt% N-methyl pyrrolidone solution 40-60 parts by mass, sodium persulfate 7-10 parts by mass, acrylic acid 8-13 parts by mass, benzene sulfonamide 10-13 parts by mass, ethyl glyoxylate 8-12 parts by mass, microbial bacteria liquid 50-70 parts by mass, mercaptoethylamine 10-20 parts by mass, sodium carbonate 10-20 parts by mass, dimethylaminoethyl methacrylate 30-40 parts by mass, potassium persulfate 3-5 parts by mass, methylene acrylamide 5-8 parts by mass.

[0009] Further, the microbial bacteria liquid includes nitrous acid bacteria liquid, Pseudomonas putida bacteria liquid.

[0010] The application also discloses a preparation method of the industrial wastewater treatment agent.

[0011] (1) After graphene oxide is uniformly mixed in N-methyl pyrrolidone solution, ultrasonic treatment is carried out, after the ultrasonic treatment is completed, sodium persulfate and acrylic acid are added and placed in a stirring machine to carry out stirring reaction, after the reaction is completed, overnight standing at room temperature is carried out, then the filtrate is removed by filtration, and the primary modified graphene oxide is obtained by drying after washing with ethanol;

[0012] (2) After benzene sulfonamide and ethyl glyoxylate are uniformly mixed, 60 wt% ethanol is added, after water bath heating, benzene sulfonamide-ethyl glyoxylate mixed liquid is obtained, then the primary modified graphene oxide is added and placed in a homogenizer to carry out homogenization, after the homogenization is completed, the secondary modified graphene oxide is obtained by drying;

[0013] (3) The secondary modified graphene oxide is uniformly mixed in the microbial bacteria liquid, then placed in an ultrasonic oscillator to carry out ultrasonic oscillation to obtain graphene oxide loaded with microorganisms; mercaptoethylamine and sodium carbonate are added in water to be dissolved by stirring to obtain a mercaptoethylamine-sodium carbonate mixed liquid, which is added to the graphene oxide loaded with microorganisms to continue ultrasonic oscillation for 1-2 h to obtain graphene oxide coating;

[0014] (4) Dimethylaminoethyl methacrylate is prepared into a 25 wt% dimethylaminoethyl methacrylate solution by adding water, then potassium persulfate and methylene acrylamide are added and placed in a reaction kettle to carry out heating reaction to obtain a gel mixture, after cooling to room temperature, the graphene oxide coating is added and uniformly mixed by stirring to obtain the treatment agent.

[0015] The graphene oxide has electrostatic adsorption effect and can effectively adsorb pollutants in sewage, but the industrial sewage contains different kinds of heavy metal ions or organic matters and inorganic matters, if the graphene oxide is directly put into the sewage, the adsorption effect will be significantly reduced, therefore, the graphene oxide is treated by N-methyl pyrrolidone, then sodium persulfate and acrylic acid are used to modify and graft carboxyl groups to the graphene oxide, so that the electrostatic adsorption capacity of the graphene oxide is improved, and the adsorption of pollutants is improved. However, after the graphene oxide is modified by the acrylic acid, the electrostatic adsorption force is improved, which can cause agglomeration in the subsequent reaction, therefore, the graphene oxide with the grafted carboxyl groups is mixed with a benzene sulfonamide-ethyl glyoxylate mixed solution to perform a homogeneous reaction, so that the graphene oxide with a hydrophobic group is obtained, the graphene oxide has hydrophobicity on the surface, the adsorption of the graphene oxide is further improved, and the dispersibility and stability of the graphene oxide are also improved. The modified graphene oxide has strong adsorption, large specific surface area and many pores, so that microorganisms can better adhere to the pores of the graphene oxide, and sufficient space is provided for the microorganisms, but the graphene oxide with improved adsorption force is more likely to adsorb heavy metal ions in the sewage, and the adsorbed heavy metal ions can harm the microorganisms in the pores, therefore, the graphene oxide loaded with the microorganisms is coated by a mercaptoethylamine-sodium carbonate mixed solution, the mercaptoethylamine and sodium carbonate in the mixed solution react with the adsorbed heavy metal ions to generate stable compounds, so that the heavy metal ions in the sewage are reduced, and the toxic effect of the heavy metal ions on the microorganisms is reduced.

[0016] In addition to the high-concentration heavy metal environment, the strong alkaline environment can also affect the microorganisms, inhibit the life activities of the microorganisms and cause the death of the microorganisms, the graphene oxide loaded with the microorganisms is further embedded by a gel mixture prepared from dimethylaminoethyl methacrylate, the gel has pH sensitivity, and shrinks in the strong alkaline environment, so that the strong alkaline environment is isolated, and the damage of the strong alkaline environment to the microorganisms is reduced, after the pH of the sewage is reduced, the gel gradually swells, and the microorganisms enter the sewage to combine with the modified graphene oxide to treat the sewage, the alkaline impact resistance is increased, and the sewage treatment effect is improved.

[0017] Further, the microorganism bacterial liquid preparation method is as follows:

[0018] The nitrite bacteria and the pseudomonas putida are inoculated into the nitrite bacteria culture medium and the pseudomonas putida culture medium respectively, and are cultured at 25-30 DEG C and 120-150 r / min on a shaking table for 20-30 h to obtain the nitrite bacteria liquid and the pseudomonas putida liquid, and the microorganism bacterial liquid is obtained by mixing the two liquids in a weight ratio of 1:1.

[0019] Further, the nitrite bacteria culture medium formula is: ammonium sulfate 0.5g / L, sodium chloride 0.3g / L, ferrous sulfate 0.03g / L, sodium dihydrogen phosphate 1g / L, magnesium sulfate 0.03g / L, calcium chloride 7.5g / L.

[0020] Further, the Pseudomonas putida culture medium formula is: glucose 6g / L, yeast powder 12g / L, magnesium sulfate heptahydrate 3.5g / L, potassium dihydrogen phosphate 2.5g / L, calcium chloride 1.5g / L.

[0021] Further, the ultrasonic treatment condition in step (1) is: the frequency is 25-40KHz, the temperature is 50-60℃, and the time is 40-60min.

[0022] Further, the stirring condition in step (1) is: the speed is 500-700r / min, the temperature is 55-65℃, and the time is 50-70min.

[0023] Further, the water bath heating condition in step (2) is: water bath heating at 40-50℃ water temperature for 15-25min.

[0024] Further, the homogenization condition in step (2) is: the speed is 8000-10000r / min, and the time is 3-6min.

[0025] Further, the ultrasonic oscillation condition in step (3) is: the frequency is 20-30KHz, and the time is 3-5h.

[0026] Further, the reaction condition in the reaction kettle in step (4) is: the temperature is 65-75℃, and the time is 4-6h.

[0027] Beneficial effects:

[0028] 1. The microorganism and modified graphene oxide in the prepared treatment agent are combined, which can remove organic pollutants, heavy metal ions and the like in sewage, and effectively treat the sewage.

[0029] 2. The treatment agent disclosed by the application modifies the graphene oxide raw material twice, increases the adsorption of the graphene oxide, loads the microorganism in the modified graphene oxide, and embeds the microorganism through the pH-sensitive gel after treatment by the mercaptoethylamine-sodium carbonate mixed solution, reduces the toxicity of high-concentration heavy metals and strong alkaline environment to the microorganism, and improves the sewage treatment effect. DETAILED DESCRIPTION

[0030] The application will be described in detail below in combination with specific embodiments:

[0031] The application discloses an industrial wastewater treatment agent and a preparation method thereof.

[0032] Example 1: Preparation of microbial bacteria liquid

[0033] Nitrite bacteria and Pseudomonas putida are inoculated into a nitrite bacteria culture medium and a Pseudomonas putida culture medium respectively, and are cultured at 28 DEG C under the condition of 140 r / min shaking bed vibration for 25 h to obtain a nitrite bacteria liquid and a Pseudomonas putida liquid, wherein the concentration of the nitrite bacteria liquid is 2.6 x 10 8 cfu / ml, the concentration of the Pseudomonas putida liquid is 3.4 x 10 8 cfu / ml, and then the microbial bacteria liquid is obtained by mixing the two liquids in a weight ratio of 1:1.

[0034] The nitrite bacteria culture medium comprises 0.5 g / L of ammonium sulfate, 0.3 g / L of sodium chloride, 0.03 g / L of ferrous sulfate, 1 g / L of sodium dihydrogen phosphate, 0.03 g / L of magnesium sulfate and 7.5 g / L of calcium chloride.

[0035] The Pseudomonas putida culture medium comprises 6 g / L of glucose, 12 g / L of yeast powder, 3.5 g / L of magnesium sulfate heptahydrate, 2.5 g / L of potassium dihydrogen phosphate and 1.5 g / L of calcium chloride.

[0036] Example 2: Preparation of the treatment agent

[0037] The preparation method comprises the following steps: weighing 250 g of graphene oxide, 500 g of 40 wt% N-methyl pyrrolidone solution, 80 g of sodium persulfate, 100 g of acrylic acid, 110 g of benzenesulfonamide, 100 g of ethyl glyoxylate, 600 g of the microbial bacteria liquid, 150 g of mercaptoethylamine, 150 g of sodium carbonate, 350 g of dimethylaminoethyl methacrylate, 40 g of potassium persulfate and 60 g of methylene acrylamide.

[0038] Preparation method

[0039] (1) graphene oxide is added into the N-methyl pyrrolidone solution and uniformly mixed, ultrasonic treatment is carried out at a frequency of 30 KHz and a temperature of 55 DEG C for 50 min, then sodium persulfate and acrylic acid are added and put into a stirring machine, stirring reaction is carried out at a speed of 600 r / min and a temperature of 60 DEG C for 60 min, after the reaction is completed, the mixture is left to stand overnight at room temperature, then the filtrate is removed by filtration, the obtained graphene oxide is washed with ethanol for three times and dried to obtain the primary modified graphene oxide;

[0040] (2)mixing benzene sulfonamide and ethyl glyoxylate, adding 1050g of 60wt% ethanol, heating in water bath at 45℃ for 20min to obtain benzene sulfonamide-ethyl glyoxylate mixture, adding the primary modified graphene oxide into the homogenizer, homogenizing at 9000r / min for 4min, drying after homogenization to obtain the secondary modified graphene oxide;

[0041] (3)mixing the secondary modified graphene oxide with microbial bacteria solution, then putting into ultrasonic oscillator, ultrasonic oscillation at 25KHz for 4h to obtain graphene oxide loaded with microorganisms; adding mercaptoethylamine and sodium carbonate into 600g of water, stirring to dissolve to obtain mercaptoethylamine-sodium carbonate mixture, adding into the graphene oxide loaded with microorganisms and continuing ultrasonic oscillation for 1.5h to obtain graphene oxide coating;

[0042] (4)preparing dimethylaminoethyl methacrylate solution by adding water to obtain 25wt% dimethylaminoethyl methacrylate solution, then adding potassium persulfate and methylene acrylamide into the reaction kettle, heating at 70℃ for 5h to obtain gel mixture, cooling to room temperature, adding graphene oxide coating and stirring to obtain the treating agent.

[0043] Example 3: Preparation of treating agent for preparing graphene oxide

[0044] Taking 200g of graphene oxide, 400g of 30wt% N-methyl pyrrolidone solution, 70g of sodium persulfate, 80g of acrylic acid, 100g of benzene sulfonamide, 80g of ethyl glyoxylate, 500g of microbial bacteria solution, 100g of mercaptoethylamine, 100g of sodium carbonate, 300g of dimethylaminoethyl methacrylate, 30g of potassium persulfate and 50g of methylene acrylamide.

[0045] Preparation method:

[0046] (1) adding graphene oxide into N-methyl pyrrolidone solution, mixing, ultrasonic treatment at 25KHz and 50℃ for 40min, adding sodium persulfate and acrylic acid into the stirring machine after ultrasonic treatment, stirring at 500r / min and 55℃ for 50min, standing overnight after reaction, then filtering to remove filtrate, washing with ethanol for 3 times and drying to obtain the primary modified graphene oxide;

[0047] (2)mixing benzene sulfonamide and ethyl glyoxylate, adding 900g of 60wt% ethanol, heating in water bath at 40℃ for 15min to obtain benzene sulfonamide-ethyl glyoxylate mixture, adding the primary modified graphene oxide into the homogenizer, homogenizing at 8000r / min for 4min, drying after homogenization to obtain the secondary modified graphene oxide;

[0048] (3) Put the secondary modified graphene oxide into the microbial bacteria solution and mix uniformly, then put into the ultrasonic oscillator, ultrasonic oscillation at 20KHz frequency for 3h, to obtain the graphene oxide loaded with microorganisms; Put mercaptoethylamine and sodium carbonate into 400g water, stir to dissolve to obtain mercaptoethylamine-sodium carbonate mixed solution, add to the graphene oxide loaded with microorganisms and continue to ultrasonic oscillation for 1h to obtain graphene oxide coating;

[0049] (4) Prepare dimethylaminoethyl methacrylate into 25wt% dimethylaminoethyl methacrylate solution by adding water, then add potassium persulfate and methylene acrylamide into the reaction kettle, heat at 65℃ for 4h to obtain a gel mixture, cool to room temperature, then add the graphene oxide coating and stir to mix uniformly to obtain the treating agent.

[0050] Example 4: Preparation of treating agent three

[0051] Take graphene oxide 300g, 50wt% N-methyl pyrrolidone solution 600g, sodium persulfate 100g, acrylic acid 130g, benzene sulfonamide 130g, ethyl glyoxylate 120g, microbial bacteria solution 700g, mercaptoethylamine 200g, sodium carbonate 200g, dimethylaminoethyl methacrylate 400g, potassium persulfate 50g, methylene acrylamide 80g.

[0052] Preparation method:

[0053] (1) Put graphene oxide into N-methyl pyrrolidone solution and mix uniformly, ultrasonic treatment at a frequency of 40KHz and a temperature of 60℃ for 60min, after ultrasonic treatment, add sodium persulfate and acrylic acid into the stirring machine and stir at a speed of 700r / min and a temperature of 65℃ for 70min, after reaction, stand overnight at room temperature, then filter to remove the filtrate, wash with ethanol for 3 times and dry to obtain the primary modified graphene oxide;

[0054] (2) Mix benzene sulfonamide and ethyl glyoxylate, then add 1250g 60wt% ethanol, heat in water bath at a water temperature of 50℃ for 25min to obtain benzene sulfonamide-ethyl glyoxylate mixed solution, add the primary modified graphene oxide into the homogenizer and homogenize at a speed of 10000r / min for 6min, after homogenization, dry to obtain the secondary modified graphene oxide;

[0055] (3) Put the secondary modified graphene oxide into the microbial bacteria solution and mix uniformly, then put into the ultrasonic oscillator, ultrasonic oscillation at 30KHz frequency for 5h, to obtain the graphene oxide loaded with microorganisms; Put mercaptoethylamine and sodium carbonate into 800g water, stir to dissolve to obtain mercaptoethylamine-sodium carbonate mixed solution, add to the graphene oxide loaded with microorganisms and continue to ultrasonic oscillation for 2h to obtain graphene oxide coating;

[0056] (4) The dimethylaminoethyl methacrylate was prepared into a 25wt% dimethylaminoethyl methacrylate solution by adding water, then potassium persulfate and methylene methacrylamide were added and placed in a reaction kettle, heated at 75°C for 6h to obtain a gel mixture, and then the graphene oxide coating was added after cooling to room temperature to obtain the treating agent.

[0057] Comparative Example 1: Preparation of treating agent

[0058] In contrast to Example 2, the only difference is that in Comparative Example 1, the graphene oxide is not subjected to the initial modification of step (1) when preparing the treating agent, and is directly subjected to the treatment of step (2) to obtain the modified graphene oxide.

[0059] The graphene oxide was weighed at 250g, the benzene sulfonamide was weighed at 110g, the ethyl glyoxylate was weighed at 100g, the microbial liquid was weighed at 600g, the mercaptoethylamine was weighed at 150g, the sodium carbonate was weighed at 150g, the dimethylaminoethyl methacrylate was weighed at 350g, the potassium persulfate was weighed at 40g, and the methylene methacrylamide was weighed at 60g.

[0060] Preparation method:

[0061] (1) The benzene sulfonamide and the ethyl glyoxylate were mixed and then 1050g of 60wt% ethanol was added, heated in a water bath at 45°C for 20min to obtain a benzene sulfonamide-ethyl glyoxylate mixture, the graphene oxide was added and placed in a homogenizer, homogenized at a speed of 9000r / min for 4min, and then dried after homogenization to obtain the modified graphene oxide;

[0062] (2) The modified graphene oxide was placed in the microbial liquid and mixed uniformly, then placed in an ultrasonic oscillator, ultrasonically vibrated at a frequency of 25KHz for 4h to obtain the graphene oxide loaded with microorganisms; the mercaptoethylamine and the sodium carbonate were added to 600g of water, stirred and dissolved to obtain a mercaptoethylamine-sodium carbonate mixture, and then added to the graphene oxide loaded with microorganisms and ultrasonically vibrated for 1.5h to obtain the graphene oxide coating;

[0063] (3) The dimethylaminoethyl methacrylate was prepared into a 25wt% dimethylaminoethyl methacrylate solution by adding water, then potassium persulfate and methylene methacrylamide were added and placed in a reaction kettle, heated at 70°C for 5h to obtain a gel mixture, and then the graphene oxide coating was added after cooling to room temperature to obtain the treating agent.

[0064] Comparative Example 2: Preparation of treating agent

[0065] In contrast to Example 2, the only difference is that in Comparative Example 2, the graphene oxide is not subjected to the modification of step (2) when preparing the treating agent, and is only subjected to the modification of step (1) to obtain the modified graphene oxide.

[0066] Take the graphene oxide 250g, 40wt% N-methyl pyrrolidone solution 500g, sodium persulfate 80g, acrylic acid 100g, microbial bacteria liquid 600g, mercaptoethylamine 150g, sodium carbonate 150g, methyl methacrylate dimethylaminoethyl ester 350g, potassium persulfate 40g, methylene acrylamide 60g.

[0067] Preparation method:

[0068] (1) In the N-methyl pyrrolidone solution, add graphene oxide and mix well, ultrasonic treatment at a frequency of 30KHz and a temperature of 55℃ for 50min, then add sodium persulfate and acrylic acid and put into a blender, stirring at a speed of 600r / min and a temperature of 60℃ for 60min, then filter the filtrate, wash with ethanol for 3 times and dry to get modified graphene oxide;

[0069] (2) Put the modified graphene oxide into the microbial bacteria liquid and mix well, then put it into an ultrasonic oscillator, ultrasonic oscillation at a frequency of 25KHz for 4h to get the graphene oxide loaded with microorganisms; add mercaptoethylamine and sodium carbonate into 600g water, stir to dissolve to get mercaptoethylamine-sodium carbonate mixed solution, add to the graphene oxide loaded with microorganisms and continue ultrasonic oscillation for 1.5h to get graphene oxide coating;

[0070] (3) Prepare 25wt% methyl methacrylate dimethylaminoethyl ester solution by adding water to methyl methacrylate dimethylaminoethyl ester, then add potassium persulfate and methylene acrylamide into a reaction kettle, heat at 70℃ for 5h to get a gel mixture, cool to room temperature, then add graphene oxide coating and stir to mix well to get the treatment agent.

[0071] Comparative example 3: preparation of treatment agent

[0072] In contrast to example 2, the only difference is that in comparative example 3, the treatment agent is prepared without step (4), directly using steps (1), (2), (3) to prepare the treatment agent.

[0073] Take the graphene oxide 250g, 40wt% N-methyl pyrrolidone solution 500g, sodium persulfate 80g, acrylic acid 100g, benzene sulfonamide 110g, ethyl glyoxylate 100g, microbial bacteria liquid 600g, mercaptoethylamine 150g, sodium carbonate 150g.

[0074] Preparation method:

[0075] (1) adding graphene oxide into N-methyl pyrrolidone solution, mixing, ultrasonic treatment at a frequency of 30 KHz and a temperature of 55°C for 50 min, adding sodium persulfate and acrylic acid after ultrasonic treatment, putting into a stirring machine, stirring at a speed of 600 r / min and a temperature of 60°C for 60 min, standing overnight at room temperature after reaction, then filtering to remove the filtrate, washing with ethanol for 3 times, and drying to obtain primary modified graphene oxide;

[0076] (2) mixing benzenesulfonamide and ethyl glyoxylate, adding 1050 g of 60 wt% ethanol, heating in a water bath at a water temperature of 45°C for 20 min to obtain a benzenesulfonamide-ethyl glyoxylate mixed solution, adding primary modified graphene oxide into a homogenizer, homogenizing at a speed of 9000 r / min for 4 min, and drying after homogenization to obtain secondary modified graphene oxide;

[0077] (3) mixing secondary modified graphene oxide into microbial bacteria liquid, then putting into an ultrasonic oscillator, ultrasonic oscillation at a frequency of 25 KHz for 4 h to obtain graphene oxide loaded with microorganisms; adding mercaptoethylamine and sodium carbonate into 600 g of water, stirring and dissolving to obtain a mercaptoethylamine-sodium carbonate mixed solution, adding into graphene oxide loaded with microorganisms, and continuing ultrasonic oscillation for 1.5 h to obtain a treatment agent.

[0078] Comparative Example 4: Preparation of a treatment agent

[0079] In contrast to Example 2, the only difference is that no mercaptoethylamine is added in the preparation of the treatment agent in Comparative Example 4.

[0080] Graphene oxide 250 g, 40 wt% N-methyl pyrrolidone solution 500 g, sodium persulfate 80 g, acrylic acid 100 g, benzenesulfonamide 110 g, ethyl glyoxylate 100 g, microbial bacteria liquid 600 g, sodium carbonate 150 g, dimethylaminoethyl methacrylate 350 g, potassium persulfate 40 g, and methylene acrylamide 60 g are weighed.

[0081] Preparation method:

[0082] (1) adding graphene oxide into N-methyl pyrrolidone solution, mixing, ultrasonic treatment at a frequency of 30 KHz and a temperature of 55°C for 50 min, adding sodium persulfate and acrylic acid after ultrasonic treatment, putting into a stirring machine, stirring at a speed of 600 r / min and a temperature of 60°C for 60 min, standing overnight at room temperature after reaction, then filtering to remove the filtrate, washing with ethanol for 3 times, and drying to obtain primary modified graphene oxide;

[0083] (2) mixing benzene sulfonamide and ethyl glyoxylate, adding 1050 g of 60 wt% ethanol, heating in water bath at 45 °C for 20 min to obtain benzene sulfonamide-ethyl glyoxylate mixture, adding secondary modified graphene oxide into homogenizer, homogenizing at 9000 r / min for 4 min, drying after homogenization to obtain secondary modified graphene oxide;

[0084] (3) mixing secondary modified graphene oxide and microbial bacteria liquid, then putting into ultrasonic oscillator, ultrasonic oscillation at 25 KHz for 4 h to obtain graphene oxide loaded with microorganisms; adding sodium carbonate into 300 g of water, stirring to dissolve to obtain sodium carbonate solution, adding into graphene oxide loaded with microorganisms, continuing ultrasonic oscillation for 1.5 h to obtain graphene oxide coating;

[0085] (4) preparing dimethylaminoethyl methacrylate solution by adding water to obtain 25 wt% dimethylaminoethyl methacrylate solution, then adding potassium persulfate and methylene acrylamide into reaction kettle, heating at 70 °C for 5 h to obtain gel mixture, cooling to room temperature, adding graphene oxide coating, stirring to mix uniformly to obtain treating agent.

[0086] Comparative Example 5: Treating agent preparation

[0087] Comparative Example 5 is formed in contrast to Example 2, the only difference is that no sodium carbonate is added in the preparation of treating agent in Comparative Example 5.

[0088] Taking 250 g of graphene oxide, 500 g of 40 wt% N-methyl pyrrolidone solution, 80 g of sodium persulfate, 100 g of acrylic acid, 110 g of benzene sulfonamide, 100 g of ethyl glyoxylate, 600 g of microbial bacteria liquid, 150 g of mercaptoethylamine, 350 g of dimethylaminoethyl methacrylate, 40 g of potassium persulfate, and 60 g of methylene acrylamide.

[0089] Preparation method:

[0090] (1) adding graphene oxide into N-methyl pyrrolidone solution, mixing uniformly, ultrasonic treatment at 30 KHz and 55 °C for 50 min, after ultrasonic treatment, adding sodium persulfate and acrylic acid into stirring machine, stirring at 600 r / min and 60 °C for 60 min, after reaction, standing overnight at room temperature, then filtering to remove filtrate, washing with ethanol for 3 times, and drying to obtain primary modified graphene oxide;

[0091] (2) mixing benzene sulfonamide and ethyl glyoxylate, then adding 1050 g of 60 wt% ethanol, heating in water bath at 45°C for 20 min to obtain benzene sulfonamide-ethyl glyoxylate mixture, adding secondary modified graphene oxide into homogenizer, homogenizing at 9000 r / min for 4 min, drying after homogenization to obtain secondary modified graphene oxide;

[0092] (3) mixing secondary modified graphene oxide and microbial bacteria solution, then putting into ultrasonic oscillator, ultrasonic oscillation at 25 KHz for 4 h to obtain graphene oxide loaded with microorganisms; adding mercaptoethylamine into 300 g of water, stirring to dissolve to obtain mercaptoethylamine solution, adding into graphene oxide loaded with microorganisms, continuing ultrasonic oscillation for 1.5 h to obtain graphene oxide coating;

[0093] (4) preparing dimethylaminoethyl methacrylate into 25 wt% dimethylaminoethyl methacrylate solution by adding water, then adding potassium persulfate and methylene acrylamide into reaction kettle, heating at 70°C for 5 h to obtain gel mixture, cooling to room temperature, then adding graphene oxide coating, stirring to mix uniformly to obtain treating agent.

[0094] Experiment: sewage treatment experiment

[0095] (1) carrying out sewage treatment experiment on treating agent prepared in example 2 and comparative examples 1-5, and selecting graphene oxide, microbial bacteria solution, mixture of graphene oxide and microbial bacteria solution as sewage treatment experiment control, in turn as control group 1, control group 2 and control group 3. Taking 45 kg of sewage, measuring that the pH of sewage is 10.4, dividing the sewage into 9 groups averagely, corresponding to example 2, comparative examples 1-5 and control groups 1-3.

[0096] (2) measuring the initial value of cadmium content, ammonia nitrogen content, phosphorus content and COD content of sewage before experiment, then adding treating agent of example 2, comparative examples 1-5 and control groups 1-3 into corresponding group of sewage, wherein the adding amount of treating agent of example 2 and comparative examples 1-5 is 100 g, the adding amount of graphene oxide of control group 3 is 300 g, the adding amount of microbial bacteria solution of control group 2 is 300 g, the adding amount of mixture of graphene oxide and microbial bacteria solution of control group 3 is 200 g, adding hydrochloric acid to adjust the pH of each group of sewage to 7.5 after adding treating agent, measuring the cadmium content, ammonia nitrogen content, phosphorus content and COD content of each group of sewage again after 10 days, obtaining data as shown in table 1:

[0097] Table 1

[0098] Cadmium content (mg / kg) Ammonia nitrogen content (mg / kg) Phosphorus content (mg / kg) COD content (mg / kg) Initial value 1.2 11.21 3.64 117 Example 2 0.3 3.67 0.64 26 Comparative Example 1 0.5 8.42 2.67 86 Comparative Example 2 0.6 8.31 2.51 89 Comparative Example 3 0.5 8.95 2.74 91 Comparative Example 4 0.7 7.47 2.06 68 Comparative Example 5 0.7 7.39 2.14 65 Control Group 1 0.9 9.64 3.04 97 Control Group 2 0.9 9.85 2.97 98 Control Group 3 0.8 8.43 2.83 94

[0099] According to the data analysis of table 1, it can be known that:

[0100] (1) After the treatment agent of example 2, comparative examples 1-5 and control groups 1-3 is treated, the cadmium content, ammonia nitrogen content, phosphorus content and COD content in sewage are obviously decreased, wherein the degree of decrease of example 2 is the highest, and the sewage treatment effect is the best, compared with example 2, the decrease degree of cadmium content, ammonia nitrogen content, phosphorus content and COD content of comparative examples 1-5 is relatively small, and the sewage treatment effect is relatively reduced, wherein the graphene oxide in comparative example 1 is not subjected to the initial modification of step (1), the electrostatic interaction of graphene oxide to pollutants is not enhanced, and the adsorption of pollutants is reduced, so that the treatment effect is reduced; the graphene oxide in comparative example 2 is not subjected to the modification of step (2), the hydrophobic interaction on the surface of graphene oxide is not enhanced, and the adsorption is reduced, so that the treatment effect is reduced; the microorganism in comparative example 3 is not subjected to the treatment of step (4), and the pH sensitive gel prepared by dimethylaminoethyl methacrylate is not embedded, the microorganism in water is damaged by strong alkaline environment, the activity of microorganism is inhibited, the microorganism is killed, and the sewage treatment effect is reduced; comparative example 4 does not add mercaptoethylamine, and comparative example 5 does not add sodium carbonate, so that the combination amount of cadmium ion is reduced, the activity of microorganism is inhibited, and the treatment effect is reduced; control groups 1-3 respectively use graphene oxide, microbial liquid, and mixture of graphene oxide and microbial liquid, but the treatment effect is poor, which shows that the method for preparing the treatment agent of the application can enhance the adsorption of graphene oxide to pollutants in sewage, and reduce the damage of strong alkaline environment and high concentration heavy metal environment to microorganism, the combination of microorganism and graphene oxide improves the sewage treatment effect.

[0101] The above examples are only used to illustrate the technical solutions of the present application, not to limit it. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the purpose and scope of the present application, which should be covered in the scope of the claims of the present application. The technical, shape and structure parts not described in detail in the present application are well-known technologies.

Claims

1. An industrial wastewater treatment agent, characterized by, The processing agent comprises the following raw materials: Graphene oxide 20-30 parts by mass, 30-50 wt% N-methyl pyrrolidone solution 40-60 parts by mass, sodium persulfate 7-10 parts by mass, acrylic acid 8-13 parts by mass, benzene sulfonamide 10-13 parts by mass, ethyl glyoxylate 8-12 parts by mass, microbial bacteria liquid 50-70 parts by mass, mercaptoethylamine 10-20 parts by mass, sodium carbonate 10-20 parts by mass, dimethylaminoethyl methacrylate 30-40 parts by mass, potassium persulfate 3-5 parts by mass and methylene acrylamide 5-8 parts by mass; The preparation method of the processing agent is as follows: Step (1) : After mixing uniformly in the N-methyl pyrrolidone solution, the graphene oxide is ultrasonically treated, then sodium persulfate and acrylic acid are added and put into a stirring machine for stirring reaction, after the reaction is completed, it is left overnight at room temperature, then the filtrate is removed by filtration, washed with ethanol and dried to obtain the primary modified graphene oxide; Step (2) : After mixing uniformly, benzene sulfonamide and ethyl glyoxylate are added into ethanol, heated in water bath to obtain a benzene sulfonamide-ethyl glyoxylate mixed solution, then the primary modified graphene oxide is added and put into a homogenizer for homogenization, after the homogenization is completed, it is dried to obtain the secondary modified graphene oxide; Step (3) : The secondary modified graphene oxide is mixed uniformly in the microbial bacteria liquid, then put into an ultrasonic oscillator for ultrasonic oscillation to obtain the graphene oxide coated with microorganisms; mercaptoethylamine and sodium carbonate are added into water and stirred to dissolve to obtain a mercaptoethylamine-sodium carbonate mixed solution, then added into the graphene oxide coated with microorganisms and ultrasonic oscillated for 1-2 h to obtain the graphene oxide coating; Step (4) : Dimethylaminoethyl methacrylate is added into water to prepare a 25 wt% dimethylaminoethyl methacrylate solution, then potassium persulfate and methylene acrylamide are added and put into a reaction kettle for heating reaction to obtain a gel mixture, after cooling to room temperature, the graphene oxide coating is added and stirred to mix uniformly to obtain the processing agent.

2. The industrial wastewater treatment agent according to claim 1, characterized in that, The microbial bacteria liquid comprises nitrous acid bacteria liquid and Pseudomonas putida bacteria liquid.

3. The industrial wastewater treatment agent according to claim 2, characterized in that, In step (1), the ultrasonic treatment conditions are as follows: the frequency is 25-40 KHz, the temperature is 50-60℃ and the time is 40-60 min.

4. The industrial wastewater treatment agent according to claim 3, characterized in that, In step (1), the stirring machine stirring conditions are as follows: the speed is 500-700 r / min, the temperature is 55-65℃ and the time is 50-70 min.

5. An industrial wastewater treatment agent according to claim 4, characterised in that, In step (2), the water bath heating conditions are as follows: heated in water bath at 40-50℃ for 15-25 min.

6. An industrial wastewater treatment agent according to claim 5, characterised in that, In step (2), the homogenization conditions are as follows: the speed is 8000-10000 r / min and the time is 3-6 min.

7. An industrial wastewater treatment agent according to claim 6, characterised in that, In step (3), the ultrasonic oscillation conditions are as follows: the frequency is 20-30 KHz and the time is 3-5 h.

8. The industrial wastewater treatment agent according to claim 7, characterized in that, In step (4), the reaction conditions in the reaction kettle are as follows: the temperature is 65-75℃ and the time is 4-6 h.