CN111470696A - Treatment method of emulsified oil-containing industrial wastewater - Google Patents

Treatment method of emulsified oil-containing industrial wastewater Download PDF

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CN111470696A
CN111470696A CN202010370967.4A CN202010370967A CN111470696A CN 111470696 A CN111470696 A CN 111470696A CN 202010370967 A CN202010370967 A CN 202010370967A CN 111470696 A CN111470696 A CN 111470696A
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wastewater
industrial wastewater
emulsified oil
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oil
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李荣竹
马红霞
刘冬
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Dongyang Yan'an Construction Engineering Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • 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
    • C02F1/24—Treatment of water, waste water, or sewage by flotation
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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    • 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
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention relates to the field of environmental protection, in particular to a method for treating industrial wastewater containing emulsified oil; the invention provides a method for treating industrial wastewater containing emulsified oil, which comprises the steps of forming small oil drops by using a chemical demulsification method, hydrolyzing an oleophilic modified polymeric flocculant to generate oleophilic colloid to adsorb the oil drops, achieving the purpose of flocculating the oil drops by utilizing the bridging action of added substances through physical and chemical actions, and removing the oil by air flotation and sedimentation.

Description

Treatment method of emulsified oil-containing industrial wastewater
Technical Field
The invention relates to the field of environmental protection, in particular to a method for treating industrial wastewater containing emulsified oil.
Background
While oil is an important life necessity for human beings, the pollution of oil leakage and emission to the environment during the processes of exploitation, storage, transportation, processing and application is also becoming serious. The oil concentration of discharged wastewater is regulated and limited in many countries around the world. The problem of treating oily wastewater has been of great concern.
CN103359846B relates to a system for treating oily wastewater and a process for treating oily wastewater by using the system, wherein a diversion trench is communicated with a first oil separation tank through a water inlet provided with a flashboard, the first oil separation tank is communicated with a second oil separation tank, the second oil separation tank is communicated with a third oil separation tank, the third oil separation tank is communicated with a fourth oil separation tank, the fourth oil separation tank is communicated with a fifth oil separation tank, the fifth oil separation tank is communicated with a sixth oil separation tank, a turnover tank is communicated with a balance tank, the balance tank is communicated with a filter tank, the filter tank is communicated with a clean water tank, the clean water tank is communicated with the outside, the waste oil in the oily wastewater is purified by utilizing the difference of the specific gravity of water and oil in the oily wastewater, the whole system has low investment cost and obvious purification effect, the purified water resource meets the requirements of national wastewater discharge standard, the water resource is energy-saving and environment-friendly, the process is simple, the purification capacity is strong, and the pollution is prevented, the water resource is purified, and the environment is protected.
CN107792972A relates to a treatment process and a treatment system for oily wastewater, comprising the following steps: A. the oily wastewater passes through a grid well and then is discharged into an oil separation tank; B. sending the wastewater separated from the oil separation tank into an electric floating device; C. sending the oily wastewater treated in the electric floating device into an ozone pool to obtain oxidation decomposition water; D. adding sodium persulfate and iron powder into the oxidative decomposition water; E. adding a demulsifier and a flocculant into the oily wastewater; F. filtering the oily wastewater by a microfiltration membrane filtering device, and discharging the filtered oily wastewater into a collecting tank; the wastewater treatment process provided by the invention can effectively separate oil and water in the oily wastewater, effectively degrade organic matters, achieve an oil-water separation effect of over 90 percent, and achieve a COD removal rate of 60-80%.
CN1129674A relates to a process for treating scum generated after oil-containing wastewater is treated by aluminum salt series inorganic coagulants, which is characterized in that sulfuric acid or hydrochloric acid is used for acidizing the scum containing oil, the layered upper layer of the scum is used as floating oil and the layered lower layer of turbid aluminum salt solution is respectively recycled after reaction, and the obtained regenerated aluminum salt solution is used as a coagulant for deoiling treatment of the oil-containing wastewater again. The method has the advantages of simple process, low cost and little environmental pollution, and can realize the ideal purpose of treating industrial waste and simultaneously realizing resource utilization of waste pollutants.
Due to the fact that amphoteric substances exist in a lot of waste water, the substances can enable grease and water to form emulsified oil, the emulsified oil is difficult to process and highly harmful, water bodies can be deteriorated, aquatic resources are damaged, human health is damaged, and symptoms such as headache, nausea, vomiting and dyspnea are caused.
Disclosure of Invention
In order to solve the problems, the invention provides a method for treating industrial wastewater containing emulsified oil.
A treatment method of industrial wastewater containing emulsified oil comprises the following specific preparation scheme:
heating industrial wastewater containing emulsified oil to 60-80 deg.C, standing for 60-90min, and removing small amount of floating oil; then adding sulfuric acid to adjust the pH value to 2.3-4.5, stirring uniformly, and adding 20-60g/m330-80 g/m of ethyl cellulose318-60g/m of adsorbent3Nano magnesium hydroxide and 10-35g/m3The polyoxyethylene fatty acid ester is subjected to chemical demulsification, then the wastewater is cooled to 30-50 ℃, and 18-45g/m is added3Stirring and uniformly mixing the flocculating agent, standing for 30-90min, promoting oil in the wastewater to flocculate to form suspended matters by an air floatation machine, and enabling the flocculated wastewater to be 20-50m3The filtering speed of/h is passed through the filter filled with the double-layer filtering material, and the precipitate is removed; the purified wastewater is filtered by an ultrafiltration membrane at the temperature of 20-35 ℃ and the pressure of 3-20kPa to obtain the treated wastewater.
The ultrafiltration membrane adopts an immersed ultrafiltration system.
The adsorbent is attapulgite, active carbon or diatomite.
The filter with double-layer filter materials adopts an anthracite-pottery sand double-layer filter material system.
The polyoxyethylene fatty acid ester is polyoxyethylene stearate or polyoxyethylene sorbitan stearate or polyoxyethylene lauryl ether.
The flocculant adopts chlorinated carboxymethyl chitosan as a raw material, and the preparation method comprises the following steps:
adding 50-80 parts by mass of carboxymethyl chitosan into 5-15 parts by mass of zinc chloride and 300 parts by mass of hydrochloric acid with the mass percentage concentration of 10-20%, stirring for 5-10h, filtering, washing with water until the pH =7, filtering, mixing and stirring uniformly, standing for 10-30h, filtering, and drying to obtain the carboxymethyl chitosan chloride.
The reaction equation is as follows:
Figure DEST_PATH_IMAGE002
the flocculant is an oleophylic modified polymeric flocculant and the preparation method comprises the following steps:
according to the mass portion, 100 portions of carboxymethyl chitosan chloride and 0.02 to 0.07 portion of 1-aminoethyl-3-methylimidazole tetrafluoroborate, 5 to 20 portions of methyl silanetriol and 300 portions of hydrochloric acid with the mass percentage concentration of 10 to 20 are mixed evenly, the temperature is controlled to be 50 to 80 ℃, the stirring is carried out for 5 to 10 hours, the filtration is carried out, the mixture is washed by water until the PH =7, the filtration is carried out, the stirring is carried out for 0.5 to 2 hours at the temperature of 50 to 80 ℃, the filtration is carried out, then the drying is carried out at the temperature of 120 ℃ and 160 ℃, the drying and the grinding are carried out to obtain powder with the mesh of 50 to 100, and the obtained product is called as lipophilic modified.
The partial reaction equation is schematically shown as follows:
Figure 1
the invention provides a method for treating industrial wastewater containing emulsified oil, which comprises the steps of forming small oil drops by using a chemical demulsification method, hydrolyzing an oleophilic modified polymeric flocculant to generate oleophilic colloid to adsorb the oil drops, achieving the purpose of flocculating the oil drops by utilizing the bridging action of added substances through physical and chemical actions, and removing the oil by air flotation and sedimentation.
Drawings
FIG. 1 is a Fourier infrared spectrum of a sample of oleophilic modified polymeric flocculant prepared in example 2.
At 767cm-1The absorption peak of the carbon-chlorine bond in the vicinity of the peak is 3352cm-1The absorption peak of the amino group is 1129cm-1An antisymmetric telescopic absorption peak of ether exists nearby and is at 1728cm-1A stretching absorption peak of ester carbonyl exists nearby, which indicates that the chlorinated carboxymethyl chitosan participates in the reaction; at 1080/815cm-1The antisymmetric stretching/symmetric stretching absorption peak of the silicon oxygen exists nearby, and is 1410cm-1An in-plane bending absorption peak of hydroxyl exists nearby, which indicates that methylsilanetriol participates in the reaction; at 1636cm-1The absorption peak of carbon-nitrogen double bond is 1045cm-1An absorption peak of boron-fluorine bond exists nearby, and the 1-aminoethyl-3-methylimidazole tetrafluoroborate participates in the reaction.
Detailed Description
The invention is further illustrated by the following specific examples:
in the experiment, various indexes of sample wastewater are detected according to the third edition of Water and wastewater monitoring and analyzing method, wherein the oil is detected at the wavelength of 254nm by adopting an ultraviolet spectrophotometry; CODCrThe oil content in the raw wastewater of the experiment is 224 mg/L by adopting a potassium dichromate methodCrThe content was 367 mg/L.
Example 1
A treatment method of industrial wastewater containing emulsified oil comprises the following specific preparation scheme:
heating industrial wastewater containing emulsified oil to 60 ℃, standing for 60min, and removing a small amount of floating oil; then adding sulfuric acid to adjust the pH value to 2.3, stirring uniformly and adding 20g/m3Ethyl cellulose, 30g/m3Adsorbent of (2), 18g/m3Nano magnesium hydroxide and 10g/m3The polyoxyethylene fatty acid ester is subjected to chemical demulsification, then the wastewater is cooled to 30 ℃, and 18g/m of the polyoxyethylene fatty acid ester is added3Stirring and uniformly mixing the flocculating agent, standing for 30min, promoting oil in the wastewater to flocculate to form suspended matters by an air flotation machine, and enabling the flocculated wastewater to be 20m3The filtering speed of/h is passed through the filter filled with the double-layer filtering material, and the precipitate is removed; the purified wastewater is filtered by an ultrafiltration membrane at 20 ℃ and 3kPa to obtain the treated wastewater.
The ultrafiltration membrane adopts an immersed ultrafiltration system.
The adsorbent is attapulgite.
The filter with double-layer filter materials adopts an anthracite-pottery sand double-layer filter material system.
The polyoxyethylene fatty acid ester is polyoxyethylene stearate.
The flocculant adopts chlorinated carboxymethyl chitosan as a raw material, and the preparation method comprises the following steps:
adding 50g of carboxymethyl chitosan into 5g of zinc chloride and 100g of hydrochloric acid with the mass percent concentration of 10%, stirring for 5h, filtering, washing with water until the pH =7, filtering, mixing and stirring uniformly, standing for 10h, filtering, and drying to obtain the carboxymethyl chitosan chloride.
The flocculant is an oleophylic modified polymeric flocculant and the preparation method comprises the following steps:
100g of carboxymethyl chitosan chloride, 0.02g of 1-aminoethyl-3-methylimidazole tetrafluoroborate, 5g of methylsilanetriol and 100g of hydrochloric acid with the mass percentage concentration of 10 are uniformly mixed, the temperature is controlled at 50 ℃, the mixture is stirred for 5 hours, filtered, washed by water until the pH value is =7, filtered, stirred for 0.5 hour at 50 ℃, filtered, dried at 120 ℃, dried and ground into powder of 50 meshes, and the obtained product is called lipophilic modified polymeric flocculant.
The oil content in the wastewater treated by the experiment is 28 mg/LCrThe content was 61 mg/L.
Example 2
A treatment method of industrial wastewater containing emulsified oil comprises the following specific preparation scheme:
heating industrial wastewater containing emulsified oil to 70 ℃, standing for 80min, and removing a small amount of floating oil; then adding sulfuric acid to adjust the pH value to 3.2, stirring uniformly and adding 40g/m3Ethyl cellulose, 50 g/m3Adsorbent of 41g/m3Nano magnesium hydroxide and 21g/m3The polyoxyethylene fatty acid ester is subjected to chemical demulsification, then the wastewater is cooled to 40 ℃, and 32g/m of the polyoxyethylene fatty acid ester is added3Stirring and uniformly mixing the flocculating agent, standing for 60min, promoting oil in the wastewater to flocculate to form suspended matters by an air flotation machine, and enabling the flocculated wastewater to be 30m3The filtering speed of/h is passed through the filter filled with the double-layer filtering material, and the precipitate is removed; purificationThe wastewater is filtered by an ultrafiltration membrane at 25 ℃ and 10kPa pressure, and the treated wastewater can be obtained.
The ultrafiltration membrane adopts an immersed ultrafiltration system.
The adsorbent is activated carbon.
The filter with double-layer filter materials adopts an anthracite-pottery sand double-layer filter material system.
The polyoxyethylene fatty acid ester is polyoxyethylene sorbitan stearate.
The flocculant adopts chlorinated carboxymethyl chitosan as a raw material, and the preparation method comprises the following steps:
adding 72g of carboxymethyl chitosan into 12g of zinc chloride and 165g of hydrochloric acid with the mass percent concentration of 14%, stirring for 6h, filtering, washing with water until the pH =7, filtering, mixing and stirring uniformly, standing for 15h, filtering, and drying to obtain the carboxymethyl chitosan chloride.
The reaction equation is as follows:
the flocculant is an oleophylic modified polymeric flocculant and the preparation method comprises the following steps:
100g of carboxymethyl chitosan chloride, 0.03g of 1-aminoethyl-3-methylimidazole tetrafluoroborate, 11g of methylsilanetriol and 160g of hydrochloric acid with the mass percent concentration of 17 are uniformly mixed, the temperature is controlled to be 75 ℃, the mixture is stirred for 6 hours, filtered, washed by water until the pH value is =7, filtered, stirred for 0.9 hour at the temperature of 65 ℃, filtered, dried at the temperature of 140 ℃, dried and ground into powder of 50-100 meshes, and the obtained product is called lipophilic modified polymeric flocculant.
The oil content in the wastewater treated by the experiment is 24 mg/LCrThe content was 57 mg/L.
Example 3
A treatment method of industrial wastewater containing emulsified oil comprises the following specific preparation scheme:
heating industrial wastewater containing emulsified oil to 80 ℃, standing for 90min, and removing a small amount of floating oil; then adding sulfuric acid to adjust the pH value to 4.5, stirring uniformly and adding 60g/m3Ethyl cellulose of (5), 80 g/m360g/m of adsorbent3Nano magnesium hydroxide and 35g/m3Is polymerized byCarrying out chemical demulsification on the ethylene oxide fatty acid ester, then cooling the wastewater to 50 ℃, and adding 45g/m3Stirring and uniformly mixing the flocculating agent, standing for 90min, promoting oil in the wastewater to flocculate to form suspended matters by an air flotation machine, and enabling the flocculated wastewater to be 50m3The filtering speed of/h is passed through the filter filled with the double-layer filtering material, and the precipitate is removed; the purified wastewater is filtered by an ultrafiltration membrane at the temperature of 35 ℃ and the pressure of 20kPa to obtain the treated wastewater.
The ultrafiltration membrane adopts an immersed ultrafiltration system.
The adsorbent is diatomite.
The filter with double-layer filter materials adopts an anthracite-pottery sand double-layer filter material system.
The polyoxyethylene fatty acid ester is polyoxyethylene lauryl ether.
The flocculant adopts chlorinated carboxymethyl chitosan as a raw material, and the preparation method comprises the following steps:
adding 80g of carboxymethyl chitosan into 15g of zinc chloride and 300g of hydrochloric acid with the mass percent concentration of 20%, stirring for 10h, filtering, washing with water until the pH =7, filtering, mixing and stirring uniformly, standing for 30h, filtering, and drying to obtain the carboxymethyl chitosan chloride.
The flocculant is an oleophylic modified polymeric flocculant and the preparation method comprises the following steps:
100g of carboxymethyl chitosan chloride, 0.07g of 1-aminoethyl-3-methylimidazole tetrafluoroborate, 20g of methylsilanetriol and 300g of hydrochloric acid with the mass percentage concentration of 20 are uniformly mixed, the temperature is controlled at 80 ℃, the mixture is stirred for 10 hours, filtered, washed by water until the pH value is =7, filtered, stirred for 2 hours at 80 ℃, filtered, dried at 160 ℃, dried and ground into powder of 100 meshes, and the obtained product is called lipophilic modified polymeric flocculant.
The oil content in the wastewater treated by the experiment is 21 mg/LCrThe content was 54 mg/L.
Comparative example 1
A treatment method of industrial wastewater containing emulsified oil comprises the following specific preparation scheme:
industrial waste containing emulsified oilHeating water to 60 deg.C, standing for 60min, and removing small amount of floating oil; then adding sulfuric acid to adjust the pH value to 2.3, stirring uniformly and adding 20g/m3Ethyl cellulose, 30g/m3Adsorbent of (2), 18g/m3Nano magnesium hydroxide and 10g/m3The polyoxyethylene fatty acid ester is subjected to chemical demulsification, then the wastewater is cooled to 30 ℃, and 18g/m of the polyoxyethylene fatty acid ester is added3Stirring and uniformly mixing the flocculating agent, standing for 30min, promoting oil in the wastewater to flocculate to form suspended matters by an air flotation machine, and enabling the flocculated wastewater to be 20m3The filtering speed of/h is passed through the filter filled with the double-layer filtering material, and the precipitate is removed; the purified wastewater is filtered by an ultrafiltration membrane at 20 ℃ and 3kPa to obtain the treated wastewater.
The ultrafiltration membrane adopts an immersed ultrafiltration system.
The adsorbent is attapulgite.
The filter with double-layer filter materials adopts an anthracite-pottery sand double-layer filter material system.
The polyoxyethylene fatty acid ester is polyoxyethylene stearate.
The flocculant is polyferric chloride.
The oil content in the wastewater treated by the experiment is 157 mg/LCrThe content was 248 mg/L.
Comparative example 2
A treatment method of industrial wastewater containing emulsified oil comprises the following specific preparation scheme:
the flocculant is an oleophylic modified polymeric flocculant and the preparation method comprises the following steps:
100g of carboxymethyl chitosan, 0.02g of 1-aminoethyl-3-methylimidazolium tetrafluoroborate, 5g of methylsilanetriol and 100g of hydrochloric acid with the mass percentage concentration of 10 are uniformly mixed, the temperature is controlled at 50 ℃, the mixture is stirred for 5h, filtered, washed by water until the pH value is =7, filtered, stirred for 0.5h at 50 ℃, filtered, dried at 120 ℃, dried and ground into powder of 50 meshes, and the obtained product is called lipophilic modified polymeric flocculant.
Otherwise, the same as example 1
The oil content in the wastewater treated by the experiment is 112mgL，CODCrThe content was 189 mg/L.
Comparative example 3
The flocculant adopts chlorinated carboxymethyl chitosan as a raw material, and the preparation method comprises the following steps:
adding 50g of carboxymethyl chitosan into 5g of zinc chloride and 100g of hydrochloric acid with the mass percent concentration of 10%, stirring for 5h, filtering, washing with water until the pH =7, filtering, mixing and stirring uniformly, standing for 10h, filtering, and drying to obtain the carboxymethyl chitosan chloride.
The flocculant is an oleophylic modified polymeric flocculant and the preparation method comprises the following steps:
uniformly mixing 100g of carboxymethyl chitosan chloride, 5g of methyl silanetriol and 100g of hydrochloric acid with the mass percentage concentration of 10, controlling the temperature to be 50 ℃, stirring for 5h, filtering, washing with water to the pH =7, filtering, stirring for 0.5h at 50 ℃, filtering, drying at 120 ℃, drying, and grinding into powder of 50 meshes to obtain the product called lipophilic modified polymeric flocculant.
Otherwise, the same as example 1
The oil content in the wastewater treated by the experiment is 55 mg/LCrThe content was 94 mg/L.
Comparative example 4
The flocculant adopts chlorinated carboxymethyl chitosan as a raw material, and the preparation method comprises the following steps:
adding 50g of carboxymethyl chitosan into 5g of zinc chloride and 100g of hydrochloric acid with the mass percent concentration of 10%, stirring for 5h, filtering, washing with water until the pH =7, filtering, mixing and stirring uniformly, standing for 10h, filtering, and drying to obtain the carboxymethyl chitosan chloride.
The flocculant is an oleophylic modified polymeric flocculant and the preparation method comprises the following steps:
100g of carboxymethyl chitosan chloride, 0.02g of 1-aminoethyl-3-methylimidazole tetrafluoroborate, 5g of methylsilanetriol and 100g of hydrochloric acid with the mass percentage concentration of 10 are uniformly mixed, the temperature is controlled at 50 ℃, the mixture is stirred for 5 hours, filtered, washed by water until the pH value is =7, filtered, stirred for 0.5 hour at 50 ℃, filtered, dried at 120 ℃, dried and ground into powder of 50 meshes, and the obtained product is called lipophilic modified polymeric flocculant.
The oil content in the wastewater treated by the experiment is 70 mg/LCrThe content was 147 mg/L.

Claims (7)

1. A treatment method of industrial wastewater containing emulsified oil comprises the following specific preparation scheme:
heating industrial wastewater containing emulsified oil to 60-80 deg.C, standing for 60-90min, and removing small amount of floating oil; then adding sulfuric acid to adjust the pH value to 2.3-4.5, stirring uniformly, and adding 20-60g/m330-80 g/m of ethyl cellulose318-60g/m of adsorbent3Nano magnesium hydroxide and 10-35g/m3The polyoxyethylene fatty acid ester is subjected to chemical demulsification, then the wastewater is cooled to 30-50 ℃, and 18-45g/m is added3Stirring and uniformly mixing the flocculating agent, standing for 30-90min, promoting oil in the wastewater to flocculate to form suspended matters by an air floatation machine, and enabling the flocculated wastewater to be 20-50m3The filtering speed of/h is passed through the filter filled with the double-layer filtering material, and the precipitate is removed; the purified wastewater is filtered by an ultrafiltration membrane at the temperature of 20-35 ℃ and the pressure of 3-20kPa to obtain the treated wastewater.
2. The method for treating emulsified oil containing industrial wastewater according to claim 1, wherein the method comprises the following steps: the ultrafiltration membrane adopts an immersed ultrafiltration system.
3. The method for treating emulsified oil containing industrial wastewater according to claim 1, wherein the method comprises the following steps: the adsorbent is attapulgite, active carbon or diatomite.
4. The method for treating emulsified oil containing industrial wastewater according to claim 1, wherein the method comprises the following steps: the filter with double-layer filter materials adopts an anthracite-pottery sand double-layer filter material system.
5. The method for treating emulsified oil containing industrial wastewater according to claim 1, wherein the method comprises the following steps: the polyoxyethylene fatty acid ester is polyoxyethylene stearate or polyoxyethylene sorbitan stearate or polyoxyethylene lauryl ether.
6. The method for treating emulsified oil containing industrial wastewater according to claim 1, wherein the method comprises the following steps: the flocculant adopts chlorinated carboxymethyl chitosan as a raw material, and the preparation method comprises the following steps:
adding 50-80 parts by mass of carboxymethyl chitosan into 5-15 parts by mass of zinc chloride and 300 parts by mass of hydrochloric acid with the mass percentage concentration of 10-20%, stirring for 5-10h, filtering, washing with water until the pH =7, filtering, mixing and stirring uniformly, standing for 10-30h, filtering, and drying to obtain the carboxymethyl chitosan chloride.
7. The method for treating emulsified oil containing industrial wastewater as claimed in claim 6, wherein the method comprises the following steps: the flocculant is an oleophylic modified polymeric flocculant and the preparation method comprises the following steps:
according to the mass portion, 100 portions of carboxymethyl chitosan chloride and 0.02 to 0.07 portion of 1-aminoethyl-3-methylimidazole tetrafluoroborate, 5 to 20 portions of methyl silanetriol and 300 portions of hydrochloric acid with the mass percentage concentration of 10 to 20 are mixed evenly, the temperature is controlled to be 50 to 80 ℃, the stirring is carried out for 5 to 10 hours, the filtration is carried out, the mixture is washed by water until the PH =7, the filtration is carried out, the stirring is carried out for 0.5 to 2 hours at the temperature of 50 to 80 ℃, the filtration is carried out, then the drying is carried out at the temperature of 120 ℃ and 160 ℃, the drying and the grinding are carried out to obtain powder with the mesh of 50 to 100, and the obtained product is called as lipophilic modified.
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