A process for the treatment of wastewater from abamectin

Abstract

The application relates to the technical field of abamectin wastewater treatment, and particularly discloses a wastewater treatment process for abamectin. The wastewater treatment process comprises the following steps: S1, collecting, precipitating, filtering and adjusting the pH of abamectin wastewater generated after anaerobic biochemical treatment; S2, introducing the abamectin wastewater treated in step S1 and mixed gas containing ozone into a fixed bed reactor for ozone oxidation; S3, introducing the abamectin wastewater treated in step S2 into a reverse osmosis equipment for membrane concentration to obtain product water and membrane concentrated water; and S4, evaporating and concentrating the membrane concentrated water. The wastewater treatment process has a COD removal rate of greater than 97%, that is, the COD value of the product water is less than 30 ppm, the wastewater treatment effect is enhanced, and the discharge standard is met.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of abamectin wastewater treatment, and more particularly to an abamectin wastewater treatment process. BACKGROUND

[0002] Abamectin is a sixteen-membered macrocyclic lactone compound, mainly produced by fermentation of Streptomyces avermitilis, and can prevent and control agricultural pests, so it is often used as a pesticide. In the production process of abamectin, wastewater is inevitably produced, and the main components of the wastewater are soluble protein, residual sugar, amino acid, inorganic salt, trace abamectin, etc. At present, the abamectin wastewater is often treated by aerobic biochemical treatment and anaerobic biochemical treatment, and after anaerobic biochemical treatment, the COD value of the effluent is >500 ppm, which cannot meet the discharge standard. SUMMARY

[0003] In order to enhance the wastewater treatment effect and make the COD value of the produced water <30 ppm, the present application provides an abamectin wastewater treatment process.

[0004] In a first aspect, the present application provides an abamectin wastewater treatment process, which adopts the following technical scheme:

[0005] An abamectin wastewater treatment process, comprising the following steps:

[0006] S1, collecting abamectin wastewater produced after anaerobic biochemical treatment, the COD value of the abamectin wastewater being 500-1000 ppm, and then performing sedimentation, filtration, and adjusting the pH value to 8-10;

[0007] S2, synchronously feeding the abamectin wastewater treated in step S1 and a mixed gas containing ozone into a fixed bed reactor filled with fillers for ozone oxidation;

[0008] S3, feeding the abamectin wastewater treated in step S2 into a reverse osmosis equipment filled with reverse osmosis membranes for membrane concentration to obtain produced water and membrane concentrated water;

[0009] S4, evaporating and concentrating the membrane concentrated water;

[0010] The reverse osmosis membrane comprises a non-woven fabric layer, a polymer porous layer, and a polyamide functional layer arranged in sequence, and the raw material of the polyamide functional layer comprises a water phase solution, an oil phase solution, and a modified solution, the water phase solution is made of the following raw materials in weight percentage: m-phenylenediamine 3-5%, 4-aminobenzoic acid methyl ester hydrochloride 1-3%, triethylamine 0.5-1.5%, camphor sulfonic acid 2-4%, and the balance being water;

[0011] The oil phase solution is an organic solution containing acyl chloride monomers;

[0012] The modified solution is made of raw materials in the following weight percentages: hydrochloric acid 4-6%, trifluoromethyl sulfonic acid 0.3-0.7%, ethanolamine 1-3%, fatty alcohol polyoxyethylene ether 0.1-0.3%, and the rest is water.

[0013] The wastewater treatment process of the abamectin of the present application first pretreats the abamectin wastewater after anaerobic biochemical treatment, then degrades the pollutants in the abamectin wastewater by ozone, then concentrates by reverse osmosis membrane, and then evaporates the membrane concentrated water. In step S1, adjusting the pH value can make the ozone produce more hydroxyl radicals, enhancing the ozone degradation effect. In step S2, the fixed bed reactor filled with fillers is used for ozone oxidation, which can greatly increase the contact area of ozone and pollutants, further enhance the ozone oxidation effect, and reduce the COD value of the produced water. In step S3, the reverse osmosis membrane is used for membrane concentration, which can effectively remove the salt in the abamectin wastewater, and further reduce the COD value of the produced water, enhance the wastewater treatment effect, and make the COD removal rate > 97%, that is, the COD value of the produced water < 30 ppm, meeting the discharge standard.

[0014] The reverse osmosis membrane of the present application includes a non-woven fabric layer, a polymer porous layer, and a polyamide functional layer. Through the mutual cooperation of the polyamide functional layer raw materials, the reverse osmosis membrane has excellent flux and desalination rate and boron removal rate, flux > 26 GFD, desalination rate > 99%, and boron removal rate > 95%. Moreover, after pollution, the desalination rate of the reverse osmosis membrane decreases by < 5%, and the boron removal rate decreases by < 8%, showing higher anti-pollution ability and enhancing the use effect and service life of the reverse osmosis membrane.

[0015] The reverse osmosis membrane of the present application first forms a polymer porous layer on the surface of the non-woven fabric layer, and then is immersed in an aqueous phase solution, an oil phase solution, and a modified solution in sequence, thereby obtaining the reverse osmosis membrane. In the raw materials of the aqueous phase solution, m-phenylenediamine and 4-amino benzoic acid methyl ester hydrochloride are added, which contain phenyl, amine groups. In the raw materials of the oil phase solution, acyl chloride monomers are added, which contain acyl chloride groups and can react with amine groups to form polyamide. At this time, the polyamide contains a large number of phenyl, amide, and ester groups. In the raw materials of the modified solution, hydrochloric acid, trifluoromethyl sulfonic acid, and ethanolamine are added. Hydrochloric acid can promote the hydrolysis of ester groups in polyamide to form carboxyl groups, trifluoromethyl sulfonic acid can enhance the activity of carboxyl groups, and the amine groups in ethanolamine can react with carboxyl groups and introduce hydroxyl groups into polyamide, thereby improving the hydrophilicity of the polyamide functional layer and making the reverse osmosis membrane show higher desalination rate, boron removal rate, and anti-pollution ability, and enhancing the use effect of the reverse osmosis membrane.

[0016] Optionally, the fatty alcohol polyoxyethylene ether is one or more of fatty alcohol polyoxyethylene ether AEO-7, fatty alcohol polyoxyethylene ether AEO-15, and fatty alcohol polyoxyethylene ether AEO-25.

[0017] By adopting the above technical solution, the fatty alcohol polyoxyethylene ether is optimized, and the fatty alcohol polyoxyethylene ether AEO-7, the fatty alcohol polyoxyethylene ether AEO-15, and the fatty alcohol polyoxyethylene ether AEO-25 have better surface activity and emulsification, which reduces the interfacial tension between the modified solution and the polymer porous layer and improves the use effect of the modified solution.

[0018] Optionally, the oil phase solution is made of the following raw materials by weight percentage: 1,3,5-trimesyl chloride 0.1-0.3%, chloroethylenediamine 0.1-0.3%, and the rest is an organic solvent.

[0019] By adopting the above technical solution, the raw materials and the raw material ratio of the oil phase solution are optimized, the 1,3,5-trimesyl chloride and the chloroethylenediamine are both acyl chloride monomers, can occur interfacial polymerization reaction with the amine monomer in the water phase solution, and form a polyamide, which is convenient for the preparation of the polyamide functional layer.

[0020] Optionally, the organic solvent is one or more of cyclohexane, n-heptane, and toluene.

[0021] By adopting the above technical solution, the organic solvent is optimized, which is convenient for the selection of the organic solvent, and the cyclohexane, the n-heptane, and the toluene have excellent solubility and stability, which increases the uniformity of the oil phase solution.

[0022] Optionally, the non-woven fabric layer is one of a polyethylene non-woven fabric, a polypropylene non-woven fabric, and a polyester non-woven fabric.

[0023] By adopting the above technical solution, the non-woven fabric is optimized, which is convenient for the selection of the non-woven fabric, and the polyethylene non-woven fabric, the polypropylene non-woven fabric, and the polyester non-woven fabric are abundant in sources and easy to obtain raw materials.

[0024] Optionally, the polymer porous layer is one of a polysulfone layer, a polyether sulfone layer, a polyethyleneimine layer, and a polyacrylonitrile layer. Preferably, the polymer porous layer is a polysulfone layer.

[0025] By adopting the above technical solution, the polymer porous layer plays a supporting role, increases the strength and stability of the reverse osmosis membrane, and also plays a filtering role to realize the separation and filtration of the solution. Moreover, the preferred polysulfone layer is abundant in raw materials, has excellent mechanical strength and pressure resistance, can withstand high operating pressure, has higher chemical resistance, oxidation resistance, and temperature resistance, can be stably used in a wider pH and temperature range, and enhances the use stability and range of the reverse osmosis membrane.

[0026] Further, the polysulfone layer is made of the following raw materials in weight percentage: polysulfone 15-25%, and the balance of N,N-dimethylacetamide.

[0027] Optionally, the reverse osmosis membrane is prepared by the following method:

[0028] T1, forming a polymer porous layer on the surface of the non-woven fabric layer to obtain a preliminary product;

[0029] T2, immersing the preliminary product in an aqueous solution for 10-20s, taking it out, blowing dry, then immersing it in an oil phase solution for 20-30s, taking it out, blowing dry, to obtain a semi-finished product;

[0030] T3, immersing the semi-finished product in a modification solution for 1-3h, taking it out, blowing dry, washing with water, and drying to obtain a reverse osmosis membrane.

[0031] By adopting the above technical scheme, the preparation of the reverse osmosis membrane is facilitated.

[0032] In multiple embodiments, the COD value of the abamectin wastewater is 900 ppm, and the COD value can also be adjusted to 500 ppm, 600 ppm, 700 ppm, 800 ppm, 1000 ppm, etc. as needed.

[0033] Optionally, in step S2, the filling volume of the filler in the fixed bed reactor is 70-90%, the average particle size of the filler is 10-50mm, and the diameter to height ratio of the fixed bed reactor is 1:(2-5).

[0034] By adopting the above technical scheme, the diameter to height ratio of the fixed bed reactor is optimized, and the mixing of the mixed gas and the abamectin is facilitated. The filler increases the contact area of the abamectin wastewater and the mixed gas, and if the amount of the filler added is too small or the particle size is too large, the area of the pollutants and the ozone is reduced, and if the amount of the filler added is too large or the particle size is too small, the pressure of the fixed bed reactor is increased. The amount of the filler added and the particle size are optimized, which improves the degradation effect of the ozone on the basis of ensuring the normal operation of the fixed bed reactor.

[0035] Further, the filler is one or several of activated carbon particles, gravel, and pebbles. Preferably, the filler is activated carbon particles.

[0036] Further, the abamectin wastewater treated in step S1 is introduced from the bottom side wall of the fixed bed reactor and discharged from the top side wall of the fixed bed reactor, and the mixed gas is introduced from the bottom end bottom wall of the fixed bed reactor and discharged from the top end top wall of the fixed bed reactor.

[0037] Optionally, in step S2, the hydraulic retention time of the abamectin wastewater in the filler is 1-2h; the mixed gas dosage per 1L of the abamectin wastewater is 1L, and the mass percentage concentration of ozone in the mixed gas is 5-15mg / L.

[0038] By adopting the above technical solution, the hydraulic retention time of the abamectin wastewater and the mixed gas dosage are optimized, the degradation effect caused by too little ozone dosage is reduced, the cost caused by too much ozone dosage is reduced, the pollutants and ozone can be fully contacted, the degradation effect is enhanced, and the COD value of the produced water is reduced.

[0039] Optionally, in step S3, the working pressure of the reverse osmosis equipment is 1-3MPa, and the working temperature is 5-35℃.

[0040] By adopting the above technical solution, the working pressure and the working temperature of the reverse osmosis equipment are optimized, the working pressure is increased, and the water production is increased on the basis of keeping the normal operation of the reverse osmosis equipment.

[0041] Further, in step S4, the condensate water and the crystalline substance are obtained after evaporation and concentration, the condensate water is recycled, and the crystalline substance is recycled.

[0042] In summary, the present application has at least the following beneficial effects:

[0043] 1. The abamectin wastewater treatment process of the present application first pretreats the abamectin wastewater after anaerobic biochemical treatment, then degrades the pollutants in the abamectin wastewater by using ozone, then concentrates by using a reverse osmosis membrane, and then evaporates the membrane concentrated water. Through the mutual cooperation of each step, the COD removal rate is >97%, that is, the COD value of the produced water is <30ppm, the wastewater treatment effect is enhanced, and the discharge standard is met.

[0044] 2. The reverse osmosis membrane of the present application comprises a non-woven fabric layer, a polymer porous layer, and a polyamide functional layer, and a large number of phenyl groups, amide groups, and hydroxyl groups are introduced on the surface of the polyamide functional layer through the mutual cooperation of the polyamide functional layer raw materials, the hydrophilicity of the polyamide functional layer is improved, and the reverse osmosis membrane exhibits higher desalination rate, deboronization rate, and anti-pollution ability, the desalination rate is >99%, the deboronization rate is >95%, the desalination rate decreases by <5% after being polluted, the deboronization rate decreases by <8%, the use effect and the service life of the reverse osmosis membrane are enhanced. DETAILED DESCRIPTION

[0045] In order to make the present application easier to understand, the present application will be further described in detail below in combination with embodiments, which only serve an illustrative purpose and are not limited to the application range of the present application. The raw materials or components used in the present application can be prepared by commercial channels or conventional methods if not specifically stated.

[0046] Preparation Example

[0047] Preparation Example 1

[0048] A reverse osmosis membrane comprising a non-woven fabric layer, a polymer porous layer, and a polyamide functional layer arranged in sequence, wherein the non-woven fabric layer is a polyethylene non-woven fabric, and the polymer porous layer is a polysulfone layer.

[0049] A method for preparing a reverse osmosis membrane, comprising the following steps:

[0050] T0, preparing a polysulfone solution, an aqueous phase solution, an oil phase solution, and a modification solution.

[0051] The polysulfone solution is prepared by the following method: the polysulfone solution is prepared from the following raw materials by weight percentage: 20% of polysulfone, and the balance of N,N-dimethylacetamide. N,N-dimethylacetamide is heated to 80℃, then polysulfone is added, the polysulfone is polysulfone S3010, stirring is performed for 8h, and the temperature is lowered to 23℃ to obtain the polysulfone solution.

[0052] The aqueous phase solution is prepared by the following method: the aqueous phase solution is prepared from the following raw materials by weight percentage: 4% of m-phenylenediamine, 2% of methyl 4-aminobenzoate hydrochloride, 1% of triethylamine, and 3% of camphor sulfonic acid, and the balance of water. Water is heated to 80℃, then camphor sulfonic acid is added, stirring is performed for 3min, then m-phenylenediamine, methyl 4-aminobenzoate hydrochloride, and triethylamine are added, stirring is performed for 10min, and the temperature is lowered to 23℃ to obtain the aqueous phase solution.

[0053] The oil phase solution is prepared by the following method: the oil phase solution is prepared from the following raw materials by weight percentage: 0.2% of 1,3,5-trimesyl chloride and 0.2% of chloroformic acetyl, and the balance of cyclohexane. 1,3,5-trimesyl chloride and chloroformic acetyl are added in cyclohexane, stirring is performed for 10min to obtain the oil phase solution.

[0054] The modification solution is prepared by the following method: the modification solution is prepared from the following raw materials by weight percentage: 5% of hydrochloric acid, 0.5% of trifluoromethyl sulfonic acid, 2% of ethanolamine, and 0.2% of fatty alcohol polyoxyethylene ether, and the balance of water. Hydrochloric acid is added in water, stirring is performed for 2min, then trifluoromethyl sulfonic acid, ethanolamine, and fatty alcohol polyoxyethylene ether are added, the fatty alcohol polyoxyethylene ether is fatty alcohol polyoxyethylene ether AEO-25, stirring is performed for 5min to obtain the modification solution.

[0055] T1, the polysulfone solution is coated on the surface of the polyethylene non-woven fabric, then immersed in water at a temperature of 8℃ for 40s, taken out, and blown dry, the polysulfone solution forms a polymer porous layer to obtain a preliminary product.

[0056] T2, immerse the primary product in the water phase solution for 15 seconds, take out and dry, then immerse in the oil phase solution for 25 seconds, take out and dry, to obtain a semi-product.

[0057] T3, immerse the semi-product in the modification solution for 2 hours, take out and dry, wash with water for 3 times, then dry at 35°C to obtain a reverse osmosis membrane.

[0058] Preparation Example 2

[0059] A reverse osmosis membrane, which is different from Preparation Example 1 in that the raw material ratio of the polysulfone solution, the water phase solution, the oil phase solution and the modification solution in step T0 is different.

[0060] The polysulfone solution is made of the following raw materials in weight percentage: polysulfone 15%, the rest is N,N-dimethylacetamide.

[0061] The water phase solution is made of the following raw materials in weight percentage: m-phenylenediamine 3%, methyl 4-aminobenzoate hydrochloride 3%, triethylamine 0.5%, camphor sulfonic acid 4%, the rest is water.

[0062] The oil phase solution is made of the following raw materials in weight percentage: 1,3,5-trimesyl chloride 0.1%, chloroformic dichoride 0.3%, the rest is cyclohexane.

[0063] The modification solution is made of the following raw materials in weight percentage: hydrochloric acid 4%, trifluoromethyl sulfonic acid 0.7%, ethanol amine 1%, fatty alcohol polyoxyethylene ether 0.1%, the rest is water.

[0064] Preparation Example 3

[0065] A reverse osmosis membrane, which is different from Preparation Example 1 in that the raw material ratio of the polysulfone solution, the water phase solution, the oil phase solution and the modification solution in step T0 is different.

[0066] The polysulfone solution is made of the following raw materials in weight percentage: polysulfone 25%, the rest is N,N-dimethylacetamide.

[0067] The water phase solution is made of the following raw materials in weight percentage: m-phenylenediamine 5%, methyl 4-aminobenzoate hydrochloride 1%, triethylamine 1.5%, camphor sulfonic acid 2%, the rest is water.

[0068] The oil phase solution is made of the following raw materials in weight percentage: 1,3,5-trimesyl chloride 0.3%, chloroformic dichoride 0.1%, the rest is cyclohexane.

[0069] The modification solution is made of the following raw materials in weight percentage: hydrochloric acid 6%, trifluoromethyl sulfonic acid 0.3%, ethanol amine 3%, fatty alcohol polyoxyethylene ether 0.3%, the rest is water.

[0070] Comparative Example

[0071] Comparative Example 1

[0072] A reverse osmosis membrane, which differs from Preparation Example 1 in that an equivalent amount of m-toluidine is substituted for 4-aminobenzoic acid methyl ester hydrochloride in the aqueous solution of step T0.

[0073] Comparative Example 2

[0074] A reverse osmosis membrane, which differs from Preparation Example 1 in that an equivalent amount of 4-aminobenzoic acid methyl ester hydrochloride is substituted for m-toluidine in the aqueous solution of step T0.

[0075] Comparative Example 3

[0076] A reverse osmosis membrane, which differs from Preparation Example 1 in that an equivalent amount of 3-ethylaniline is substituted for 4-aminobenzoic acid methyl ester hydrochloride in the aqueous solution of step T0.

[0077] Comparative Example 4

[0078] A reverse osmosis membrane, which differs from Preparation Example 1 in that an equivalent amount of water is substituted for ethanolamine in the modified solution of step T0.

[0079] Comparative Example 5

[0080] A reverse osmosis membrane, which differs from Preparation Example 1 in that an equivalent amount of 3-ethylaniline is substituted for ethanolamine in the modified solution of step T0.

[0081] Example

[0082] Example 1

[0083] A wastewater treatment process for abamectin, comprising the following steps:

[0084] S1, collecting abamectin wastewater generated after anaerobic biochemical treatment, the COD value of the abamectin wastewater after anaerobic biochemical treatment being 900 ppm. Then, performing sedimentation and filtration. Subsequently, adjusting the pH value to 9 by using saturated sodium hydroxide solution.

[0085] S2, synchronously introducing the abamectin wastewater after step S1 treatment and a mixed gas containing ozone into a fixed bed reactor filled with fillers to perform ozone oxidation. The abamectin wastewater after step S1 treatment is introduced from the bottom side wall of the fixed bed reactor and discharged from the top side wall of the fixed bed reactor, and the mixed gas is introduced from the bottom end bottom wall of the fixed bed reactor and discharged from the top end top wall of the fixed bed reactor.

[0086] The cross section of the fixed bed reactor is a hollow cylindrical type, and the diameter is 0.5 m and the height is 2 m, at this time the ratio of the diameter and the height is 1:4. The filler in the fixed bed reactor is activated carbon particles, the average particle size of the activated carbon particles is 30 mm, the activated carbon particles are coal activated carbon particles, and are selected from Shijiazhuang Hongsen Activated Carbon Co., Ltd., and the filling volume of the activated carbon particles in the fixed bed reactor is 80%. The hydraulic retention time of the abamectin wastewater in the filler is 1.5 h, the mixed gas addition amount of each 1 L of the abamectin wastewater is 1 L, the mass percentage concentration of ozone in the mixed gas is 10 mg / L, and the mixed gas is obtained by treating air with an ozone generator.

[0087] S3, the abamectin wastewater treated in step S2 is introduced into a reverse osmosis equipment filled with a reverse osmosis membrane for membrane concentration to obtain product water and membrane concentrated water. The working pressure of the reverse osmosis equipment is 2 MPa, and the working temperature is 23℃. The reverse osmosis membrane is prepared by the method of Preparation Example 1.

[0088] S4, the membrane concentrated water is evaporated and concentrated, and after evaporation and concentration, condensate water and crystalline substances are obtained, the condensate water is recycled, and the crystalline substances are recycled.

[0089] Example 2-3

[0090] A wastewater treatment process of abamectin, which is different from Example 1 in that the reverse osmosis membrane in step S3 is different, and the reverse osmosis membranes of Example 2-3 are prepared by the methods of Preparation Examples 2-3, respectively.

[0091] Comparative Example

[0092] Comparative Example 1-5

[0093] A wastewater treatment process of abamectin, which is different from Example 1 in that the reverse osmosis membrane in step S3 is different, and the reverse osmosis membranes of Comparative Example 1-5 are prepared by the methods of Comparative Examples 1-5, respectively.

[0094] Performance detection

[0095] (1) The reverse osmosis membranes obtained from Comparative Examples 1-3 and Comparative Examples 1-5 are taken as samples, respectively, and are installed on a membrane detection platform for testing. The flux, desalination rate and boron removal rate of the samples are detected under the conditions that the temperature of the feed liquid is 25℃, the pH value is 6.8, and the pressure is 2 MPa. The detection results are shown in Table 1.

[0096] The feed liquid is a mixed aqueous solution of sodium chloride and boric acid, and the concentration of sodium chloride in the feed liquid is 30000 ppm and the concentration of boric acid is 10 ppm.

[0097] Desalination rate / (%)=(concentration of sodium chloride in feed liquid-concentration of sodium chloride in product water) / concentration of sodium chloride in feed liquid x 100%; boron removal rate / (%)=(concentration of boric acid in feed liquid-concentration of boric acid in product water) / concentration of boric acid in feed liquid x 100%.

[0098] (2) The treatment processes of Examples 1-3 and Comparative Examples 1-5 were respectively used to treat avermectin wastewater, and the treatment was continuously operated for 7 days, and the COD value of the product water after treatment was detected, and the COD removal rate was calculated.

[0099] Wherein, the COD removal rate / (%)=(COD value of avermectin wastewater-COD value of product water) / COD value of avermectin wastewater x 100%.

[0100] (3) The reverse osmosis membranes continuously operated for 7 days in detection method (2) were respectively taken as samples, at this time, the reverse osmosis membranes were contaminated reverse osmosis membranes, and then were installed on the membrane detection table for testing, and the desalination rate and the boron removal rate of the samples were detected under the conditions that the temperature of the feed liquid was 25℃, the pH value was 6.8, and the pressure was 2 MPa. Since the reverse osmosis membrane used in detection method (1) was a non-contaminated reverse osmosis membrane, the desalination rate and the boron removal rate in detection method (1) were combined to calculate the desalination rate drop and the boron removal rate drop, and the detection results are shown in Table 1.

[0101] Wherein, the feed liquid was the same as that used in detection method (1).

[0102] Desalination rate drop / (%)=desalination rate of non-contaminated reverse osmosis membrane-desalination rate of contaminated reverse osmosis membrane; boron removal rate drop / (%)=boron removal rate of non-contaminated reverse osmosis membrane-boron removal rate of contaminated reverse osmosis membrane.

[0103] Table 1 detection results

[0104]

[0105]

[0106] As can be seen from Table 1, the reverse osmosis membrane of the present application has excellent flux and desalination rate and boron removal rate, the flux is 26.32-28.89 GFD, the desalination rate is 99.62-99.86%, and the boron removal rate is 95.41-95.66%. Moreover, the reverse osmosis membrane also has better anti-pollution ability, after pollution, the desalination rate drop is 4.46-5.15%, and the boron removal rate drop is 6.55-7.96%, so that the reverse osmosis membrane maintains high removal rate and use stability. At the same time, by using the wastewater treatment process of the present application in combination with the reverse osmosis membrane, the COD removal rate is 97.56-98.78%, i.e. the COD value of the product water is <30 ppm, which shows better wastewater treatment effect.

[0107] Comparing Preparation Example 1 with Comparative Examples 1-2, Comparative Example 1 uses m-phenylenediamine as the raw material of the aqueous solution; Comparative Example 2 uses methyl 4-aminobenzoate hydrochloride as the raw material of the aqueous solution; and Preparation Example 1 uses m-phenylenediamine and methyl 4-aminobenzoate hydrochloride as the raw materials of the aqueous solution. It can be seen that, by adding m-phenylenediamine and methyl 4-aminobenzoate hydrochloride as the raw materials of the aqueous solution and through the synergistic effect therebetween, the desalination rate and the desalination rate of the reverse osmosis membrane can be increased, and the anti-pollution ability of the reverse osmosis membrane can be significantly increased. In combination with Comparative Example 3, if methyl 4-aminobenzoate hydrochloride in the aqueous solution is replaced by 3-ethylaniline, the desalination rate and the desalination rate decrease, which is not conducive to the use of the reverse osmosis membrane.

[0108] Comparing Comparative Examples 4-5, Comparative Example 4 does not add ethanolamine as the raw material of the modified solution; and Comparative Example 5 adds 3-ethylaniline as the raw material of the modified solution. It can be seen that, by adding 3-ethylaniline as the raw material of the modified solution, the anti-pollution ability of the reverse osmosis membrane is reduced. In combination with Preparation Example 1, Preparation Example 1 adds ethanolamine as the raw material of the modified solution. It can be seen that, by adding ethanolamine as the raw material of the modified solution, the desalination rate and the desalination rate decrease, the anti-pollution ability of the reverse osmosis membrane is increased, and the use effect and the service life of the reverse osmosis membrane are improved.

[0109] It should be noted that the above-described embodiments are only used to explain the present application and do not constitute any limitation on the present application. The present application is described by referring to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than limiting words. The present application can be modified within the scope of the claims of the present application, and the present application can be revised within the scope and spirit of the present application. Although the present application described therein relates to specific methods, materials and embodiments, it does not mean that the present application is limited to the specific examples disclosed therein, but rather, the present application can be extended to all other methods and applications having the same function.

Claims

1. A process for the treatment of wastewater of avermectins, characterized by: It comprises the following steps: S1, collecting the abamectin wastewater generated after anaerobic biochemical treatment, the COD value of the abamectin wastewater being 500-1000 ppm, then performing precipitation, filtration, and adjusting the pH value to 8-10; S2, synchronously feeding the abamectin wastewater treated in step S1 and the mixed gas containing ozone into a fixed bed reactor filled with fillers to perform ozone oxidation; S3, feeding the abamectin wastewater treated in step S2 into a reverse osmosis equipment filled with reverse osmosis membranes to perform membrane concentration, and obtaining product water and membrane concentrated water; S4, performing evaporation concentration on the membrane concentrated water; The reverse osmosis membrane comprises, in sequence, a non-woven fabric layer, a polymer porous layer, and a polyamide functional layer, and the raw material of the polyamide functional layer comprises an aqueous solution, an oil phase solution, and a modified solution. The aqueous solution is made of the following raw materials in percentage by weight: m-phenylenediamine 3-5%, 4-aminobenzoic acid methyl ester hydrochloride 1-3%, triethylamine 0.5-1.5%, camphor sulfonic acid 2-4%, and the balance being water. The oil phase solution is an organic solution containing acyl chloride monomers, and is made of the following raw materials in percentage by weight: 1,3,5-trimesyl chloride 0.1-0.3%, chloroformic dicarboxylic acid 0.1-0.3%, and the balance being an organic solvent. The modified solution is made of the following raw materials in percentage by weight: hydrochloric acid 4-6%, trifluoromethyl sulfonic acid 0.3-0.7%, ethanolamine 1-3%, fatty alcohol polyoxyethylene ether 0.1-0.3%, and the balance being water. The reverse osmosis membrane is prepared by the following method: T1, forming a polymer porous layer on the surface of the non-woven fabric layer to obtain a preliminary product; T2, immersing the preliminary product in the aqueous solution for 10-20 s, taking it out, blowing it dry, then immersing it in the oil phase solution for 20-30 s, taking it out, blowing it dry, and obtaining a semi-finished product; T3, immersing the semi-finished product in the modified solution for 1-3 h, taking it out, blowing it dry, washing it with water, and drying it to obtain the reverse osmosis membrane.

2. The process for the treatment of wastewater of avermectins according to claim 1, characterized in that: The fatty alcohol polyoxyethylene ether is one or more of fatty alcohol polyoxyethylene ether AEO-7, fatty alcohol polyoxyethylene ether AEO-15, and fatty alcohol polyoxyethylene ether AEO-25.

3. The process for the treatment of wastewater of avermectins according to claim 1, characterized in that: The organic solvent is one or more of cyclohexane, n-heptane, and toluene.

4. The process for the treatment of wastewater of avermectins according to claim 1, characterized in that: The non-woven fabric layer is one of polyethylene non-woven fabric, polypropylene non-woven fabric, and polyester non-woven fabric.

5. The process for the treatment of wastewater of avermectins according to claim 1, characterized in that: The polymer porous layer is one of a polysulfone layer, a polyether sulfone layer, a polyethylene imine layer, and a polyacrylonitrile layer.

6. The process for the treatment of wastewater of avermectins according to claim 1, characterized in that: In step S2, the filling volume of the fillers in the fixed bed reactor is 70-90%, the average particle size of the fillers is 10-50 mm, and the ratio of the diameter to the height of the fixed bed reactor is 1:(2-5).

7. The process for the treatment of wastewater of avermectins according to claim 1, characterized in that: In step S2, the hydraulic retention time of the abamectin wastewater in the fillers is 1-2 h, and the dosage of the mixed gas per 1 L of the abamectin wastewater is 1 L, and the mass percentage concentration of ozone in the mixed gas is 5-15 mg / L.

8. The process for the treatment of wastewater of avermectins according to claim 1, characterized in that: In step S3, the working pressure of the reverse osmosis equipment is 1-3 MPa, and the working temperature is 5-35℃.

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