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CN117088486B - Sewage treatment method and preparation method of polymeric ferric sulfate composite polymeric flocculant - Google Patents

Sewage treatment method and preparation method of polymeric ferric sulfate composite polymeric flocculant Download PDF

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Publication number
CN117088486B
CN117088486B CN202311259783.0A CN202311259783A CN117088486B CN 117088486 B CN117088486 B CN 117088486B CN 202311259783 A CN202311259783 A CN 202311259783A CN 117088486 B CN117088486 B CN 117088486B
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flocculant
ferric sulfate
polymeric
polymeric ferric
silicon dioxide
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CN117088486A (en
Inventor
孟庆杰
宋伽奥
覃文达
李宇霞
钟鑫
戚莎莎
郑怀礼
霍国友
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Shenzhen Jiayao Ecological Environmental Protection Technology Co ltd
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Shenzhen Jiayao Ecological Environmental Protection Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/40Devices for separating or removing fatty or oily substances or similar floating material
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The invention relates to the technical field of sewage treatment, in particular to a sewage treatment method and a preparation method of a polymeric ferric sulfate composite polymeric flocculant, wherein the polymeric ferric sulfate composite polymeric flocculant is added into sewage according to the adding amount of 10-100mg/L, and is stirred for 1-3min at the rotating speed of 200-300r/min and then for 3-8min at the rotating speed of 20-60r/min, and then is kept stand for 10-40min after the stirring is finished, so that flocculation sedimentation is completed; wherein the polymeric ferric sulfate composite polymeric flocculant is a composite flocculant composed of polymeric ferric sulfate and double modified silica hollow microspheres; the outer surface of the double modified silica hollow microsphere is grafted with polyacrylamide; the inner surface is grafted with the poly octadecyl methacrylate. The treatment method has good flocculation sedimentation effect on lipophilic and hydrophilic impurities in sewage, so that the treatment method can be used for treating various industrial wastewater and has wide application prospect.

Description

Sewage treatment method and preparation method of polymeric ferric sulfate composite polymeric flocculant
Technical Field
The invention relates to the technical field of flocculant preparation, in particular to a sewage treatment method and a preparation method of a polymeric ferric sulfate composite polymeric flocculant.
Background
Along with the continuous development of industrialization, the sewage discharge amount is gradually increased year by year, such as domestic sewage, petrochemical sewage, dyeing chemical sewage and the like. The control and management of water environmental pollution is becoming more important and progress is being made, most of which require the removal of most suspended substances from sewage by flocculants. The flocculant commonly used at present comprises two major types of inorganic flocculant and organic flocculant, and aiming at different sewage, inorganic-organic composite flocculant is developed gradually to improve flocculation effect.
Most of the sewage contains a plurality of impurities, and mainly contains organic pollutants, inorganic pollutants, nutrient elements such as nitrogen and phosphorus, microorganisms and the like. For example, oilfield produced water contains high suspended matters such as grease organic matters, silicon dioxide, insoluble salts and the like, and the components are complex, so that the treatment difficulty is increased. In order to remove impurities with different properties to the greatest extent, the flocculant needs to be subjected to composite modification.
Patent CN202010998550.2 discloses an oily sewage treatment flocculant, a preparation method and application thereof. Adding small molecular olefine acid, diallylamine, methacrylamide, cosolvent and buffer solution into water, and uniformly mixing to obtain emulsion; respectively preparing aqueous solutions of an initiator and a reducing agent; dividing the emulsion into two parts according to mass ratio, simultaneously dripping the second part of emulsion and the aqueous solution of the initiator into the first part of emulsion under stirring for polymerization reaction, and obtaining a primary product after the reaction; and (3) dropwise adding the aqueous solution of the reducing agent into the primary product to remove residual initiator, thereby obtaining the flocculant. The flocculant has a removal rate of suspended matters in oily sewage of more than 95%. However, the flocculant has a good flocculation effect only on negatively charged suspended matters, and has poor removal effect on neutral oil and fat organic matters. Therefore, there is a need to provide an improved sewage treatment method and a preparation method of polymeric ferric sulfate composite polymeric flocculant to solve the above problems.
Disclosure of Invention
The invention aims to provide a sewage treatment method and a preparation method of a polymeric ferric sulfate composite polymeric flocculant, which can obviously improve flocculation effects on lipophilic and hydrophilic impurities in sewage by adding a flocculant with a specific structure and a flocculation method which is cooperatively adapted.
In order to achieve the above purpose, the invention provides a sewage treatment method, which is characterized in that polymeric ferric sulfate composite polymeric flocculant is added into sewage according to the adding amount of 10-100mg/L, stirring is carried out for 1-3min at the rotating speed of 200-300r/min, stirring is carried out for 3-8min at the rotating speed of 20-60r/min, and the solution is kept stand for 10-40min after the stirring is finished, so that flocculation sedimentation is completed;
Wherein the polymeric ferric sulfate composite polymeric flocculant is a composite flocculant composed of polymeric ferric sulfate and double modified silica hollow microspheres; the outer surface of the double modified silicon dioxide hollow microsphere is grafted with polyacrylamide; the inner surface is grafted with the poly octadecyl methacrylate.
Further, the polymeric ferric sulfate composite polymeric flocculant is obtained by in-situ oxidation of ferrous sulfate in the double modified silica hollow microspheres;
and/or the oil removal rate of the sewage is more than or equal to 68%, and the particulate matter removal rate is more than or equal to 98%.
Further, the polymeric ferric sulfate composite polymeric flocculant is prepared by the following steps:
s1, preparing a silica hollow microsphere modified by acrylamide and a vinyl silane coupling agent;
S2, polymerizing the silicon dioxide hollow microspheres and octadecyl methacrylate under the action of an initiator to obtain double modified silicon dioxide hollow microspheres;
S3, adding ferrous sulfate and sulfuric acid into the solution of the double modified silica hollow microspheres, dropwise adding hydrogen peroxide when the temperature is raised to 30-60 ℃, and oxidizing in situ to obtain the polymeric ferric sulfate/double modified silica hollow microsphere composite flocculant.
In the step S1, tetraethoxysilane and vinyltriethoxysilane are used as raw materials, a template method is used for preparing the silicon dioxide microsphere, then acrylamide and an initiator are added, and after the reaction is completed, the template is removed, so that the silicon dioxide hollow microsphere is obtained.
Further, step S1 includes: dispersing polystyrene microsphere into mixed solution of isopropanol and water, adding tetraethoxysilane and vinyltriethoxysilane, heating to 60-80 ℃, regulating pH value to 10-11 with ammonia water for reaction, adding acrylamide and initiator after 2-10h of reaction, reacting for 2-6h, collecting product, and removing polystyrene microsphere with toluene to obtain silica hollow microsphere.
Further, the mass ratio of the tetraethoxysilane to the vinyltriethoxysilane is (1-10): 1;
and/or the polystyrene microsphere has a diameter of 200-450nm; the addition amount of the acrylamide is 5-20% of the mass of the ethyl orthosilicate.
Further, in the step S2, the addition amount of the octadecyl methacrylate is 1-15% of the mass of the tetraethoxysilane.
Further, step S2 includes: dispersing the silicon dioxide hollow microspheres into acetone, then adding the octadecyl methacrylate and an initiator, heating to 60-80 ℃ for reaction for 3-8 hours, and obtaining double modified silicon dioxide hollow microspheres;
and/or the initiator comprises one or more of ammonium persulfate, potassium persulfate or potassium sulfite.
Further, step S3 includes: dispersing the double modified silicon dioxide hollow microspheres into a mixed solution of glycerol and water, and then adding ferrous sulfate and sulfuric acid to enable the pH value of the solution to be 1-3; heating to 30-60 ℃, dropwise adding hydrogen peroxide solution, and reacting for 1-5h; and adding sodium hydroxide to adjust the pH value to 6.5-7.5, continuing to react for 1-5h, collecting a solid product, and drying to obtain the polymeric ferric sulfate/double modified silica hollow microsphere composite flocculant.
Further, the addition amount of the ferrous sulfate is 15-35% of the mass of the double modified silica hollow microspheres;
and/or, the volume ratio of the glycerol to the water is 4:6-6:4.
The invention also provides a polymeric ferric sulfate composite polymeric flocculant which is prepared by adopting any one of the preparation methods.
The beneficial effects of the invention are as follows:
1. According to the sewage treatment method provided by the invention, the flocculation method of stirring at a high speed, stirring at a low speed and then standing is adopted by adopting the polymeric ferric sulfate composite type polymeric flocculant with dual properties, so that the flocculation effect can be obviously improved, the oil removal rate in sewage is more than or equal to 68%, and the particulate matter removal rate is more than or equal to 98%.
2. The internal and external surfaces of the silicon dioxide hollow microspheres are respectively modified by octadecyl methacrylate and propionamide, and the hydrophilicity and hydrophobicity of the silicon dioxide hollow microspheres are regulated and controlled, so that the flocculant can not only effectively settle particulate matters, but also effectively adsorb and remove lipid organic matters, thereby obviously improving flocculation effect; meanwhile, the polymeric ferric sulfate is doped on the inner surface and the outer surface in situ, so that the flocculation effect is further improved, and the hollow structure of the silicon dioxide hollow microspheres is also beneficial to improving the flocculation adsorption effect.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of the structure of a polymeric ferric sulfate/dual modified silica hollow microsphere composite flocculant provided by the invention;
FIG. 2 is a plot of residual turbidity as a function of dosage for the composite flocculant prepared in example 1;
FIG. 3 is a graph showing the oil removal rate of the composite flocculant prepared in example 1 according to the amount of the additive.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a sewage treatment method which is characterized in that polymeric ferric sulfate composite polymeric flocculant is added into sewage according to the adding amount of 10-100mg/L, stirring is carried out for 1-3min at the rotating speed of 200-300r/min, stirring is carried out for 3-8min at the rotating speed of 20-60r/min, and the solution is kept stand for 10-40min after the stirring is finished, so that flocculation sedimentation is completed;
Wherein the polymeric ferric sulfate composite polymeric flocculant is a composite flocculant composed of polymeric ferric sulfate and double modified silica hollow microspheres; the outer surface of the double modified silicon dioxide hollow microsphere is grafted with polyacrylamide; the inner surface is grafted with the poly octadecyl methacrylate.
The preparation method of the polymeric ferric sulfate composite polymeric flocculant comprises the following steps:
s1, preparing a silica hollow microsphere modified by acrylamide and a vinyl silane coupling agent;
S2, polymerizing the silicon dioxide hollow microspheres and octadecyl methacrylate under the action of an initiator to obtain double modified silicon dioxide hollow microspheres;
S3, adding ferrous sulfate and sulfuric acid into the solution of the double modified silica hollow microspheres, dropwise adding hydrogen peroxide when the temperature is raised to 30-60 ℃, and oxidizing in situ to obtain the polymeric ferric sulfate/double modified silica hollow microsphere composite flocculant. As shown in fig. 1.
Firstly, preparing the hollow silica microspheres modified by the acrylamide and the vinyl silane coupling agent, so that the acrylamide is mainly grafted and polymerized on the outer surfaces of the hollow silica microspheres; then removing the template, and reacting with octadecyl methacrylate, wherein the octadecyl methacrylate is mainly grafted and polymerized on the inner surface, so that the silicon dioxide hollow microsphere has the property similar to a janus structure. And then in-situ oxidizing to prepare polymeric ferric sulfate, wherein the polymeric ferric sulfate is doped on the inner and outer surfaces of the microsphere. Through the hydrophilic and hydrophobic regulation and control of the inner surface and the outer surface of the silicon dioxide hollow microsphere, the flocculant can not only effectively settle particulate matters, but also effectively adsorb and remove lipid organic matters, thereby obviously improving flocculation effect and expanding application range.
In the step S1, tetraethoxysilane and vinyltriethoxysilane are used as raw materials, a template method is used for preparing silicon dioxide microspheres, then acrylamide and an initiator are added, and after the reaction is completed, the template is removed, so that the silicon dioxide hollow microspheres are obtained.
The step S1 comprises the following steps: dispersing polystyrene microsphere into mixed solution of isopropanol and water, adding tetraethoxysilane and vinyltriethoxysilane, heating to 60-80 ℃, regulating pH value to 10-11 with ammonia water for reaction, adding acrylamide and initiator after 2-10h of reaction, reacting for 2-6h, collecting product, and removing polystyrene microsphere with toluene to obtain silica hollow microsphere.
The mass ratio of the tetraethoxysilane to the vinyltriethoxysilane is (1-10) 1; for example, 1:1,2:1,5:1,6:1,8:1, 10:1, etc. The main function of vinyltriethoxysilane is to provide an active site for grafting of acrylamide and octadecyl methacrylate.
The diameter of the polystyrene microsphere is 200-450nm; the addition amount of the acrylamide is 5-20% of the mass of the tetraethoxysilane, for example, 5%, 8%, 10%, 15%, 18%, 20% and the like.
In step S2, the amount of octadecyl methacrylate added is 1 to 15% by mass, for example, 1%, 3%, 5%, 8%, 10%, 12%, 15% by mass, etc., of the ethyl orthosilicate.
The step S2 comprises the following steps: dispersing the silicon dioxide hollow microspheres into acetone, then adding the octadecyl methacrylate and an initiator, heating to 60-80 ℃ for reaction for 3-8 hours, and obtaining the double modified silicon dioxide hollow microspheres.
The initiator comprises one or more of ammonium persulfate, potassium persulfate or potassium sulfite.
The step S3 comprises the following steps: dispersing the double modified silicon dioxide hollow microspheres into a mixed solution of glycerol and water, and then adding ferrous sulfate and sulfuric acid to enable the pH value of the solution to be 1-3; heating to 30-60 ℃, dropwise adding hydrogen peroxide solution, and reacting for 1-5h; and adding sodium hydroxide to adjust the pH value to 6.5-7.5, continuing to react for 1-5h, collecting a solid product, and drying to obtain the polymeric ferric sulfate/double modified silica hollow microsphere composite flocculant.
The volume ratio of the glycerol to the water is 4:6-6:4. the addition amount of the ferrous sulfate is 15-35% of the mass of the double modified silica hollow microsphere, for example, 15%, 18%, 20%, 25%, 28%, 30% and the like.
The flocculant is prepared according to the following examples, and then a certain flocculation process is cooperated to realize mine sewage treatment.
Example 1
The preparation method of the polymeric ferric sulfate composite polymeric flocculant comprises the following steps:
S1, dispersing polystyrene microspheres into a mixed solution of isopropanol and water (volume ratio is 2:1), adding tetraethoxysilane and vinyltriethoxysilane (mass ratio is 5:1), heating to 70 ℃, adjusting pH value to 10.5 with ammonia water for reaction, adding acrylamide (the addition amount is 12% of the mass of the tetraethoxysilane) and potassium persulfate after reaction for 5 hours, reacting for 3 hours, collecting a product, and removing the polystyrene microspheres with toluene to obtain the silica hollow microspheres;
S2, dispersing the silicon dioxide hollow microspheres into acetone, then adding octadecyl methacrylate (the addition amount is 10% of the mass of the tetraethoxysilane) and an initiator, heating to 70 ℃ and reacting for 5 hours to obtain double modified silicon dioxide hollow microspheres;
S3, dispersing the double modified silica hollow microspheres into a mixed solution of glycerol and water (volume ratio is 1:1), and then adding ferrous sulfate (the addition amount is 25% of the mass of the double modified silica hollow microspheres) and sulfuric acid to enable the pH value of the solution to be 2; heating to 40 ℃, dropwise adding hydrogen peroxide solution, and reacting for 3h; and adding sodium hydroxide to adjust the pH value to 7.0, continuing to react for 2 hours, collecting a solid product, and drying to obtain the polymeric ferric sulfate/double modified silicon dioxide hollow microsphere composite flocculant.
Example 2
A preparation method of a polymeric ferric sulfate composite polymeric flocculant is different from example 1 in that the addition amount of acrylamide is 5% of the mass of tetraethoxysilane. The other components are the same as those in embodiment 1, and will not be described in detail here.
Example 3
A preparation method of a polymeric ferric sulfate composite polymeric flocculant is different from example 1 in that the addition amount of acrylamide is 20% of the mass of tetraethoxysilane. The other components are the same as those in embodiment 1, and will not be described in detail here.
Example 4
A preparation method of a polymeric ferric sulfate composite polymeric flocculant is different from example 1 in that the addition amount of octadecyl methacrylate is 1% of the mass of tetraethoxysilane. The other components are the same as those in embodiment 1, and will not be described in detail here.
Example 5
A preparation method of a polymeric ferric sulfate composite polymeric flocculant is different from example 1 in that the addition amount of octadecyl methacrylate is 15% of the mass of tetraethoxysilane. The other components are the same as those in embodiment 1, and will not be described in detail here.
Example 6
The preparation method of the polymeric ferric sulfate composite polymeric flocculant is different from the embodiment 1 in that the addition amount of ferrous sulfate is 15% of the mass of the double modified silica hollow microspheres. The other components are the same as those in embodiment 1, and will not be described in detail here.
Example 7
The preparation method of the polymeric ferric sulfate composite polymeric flocculant is different from the embodiment 1 in that the addition amount of ferrous sulfate is 35% of the mass of the double modified silica hollow microspheres. The other components are the same as those in embodiment 1, and will not be described in detail here.
Comparative example 1
The preparation method of the polymeric ferric sulfate composite polymeric flocculant comprises the following steps:
S1, dispersing polystyrene microspheres into a mixed solution of isopropanol and water (volume ratio is 2:1), adding tetraethoxysilane and vinyltriethoxysilane (mass ratio is 5:1), heating to 70 ℃, adjusting pH value to 10.5 by ammonia water for reaction, collecting a product after reaction for 5 hours, and removing the polystyrene microspheres by toluene to obtain silica hollow microspheres;
S2, dispersing the silicon dioxide hollow microspheres into acetone, then adding acrylamide (the addition amount is 12% of the mass of the ethyl orthosilicate), octadecyl methacrylate (the addition amount is 10% of the mass of the ethyl orthosilicate) and an initiator, and heating to 70 ℃ for reacting for 5 hours to obtain double modified silicon dioxide hollow microspheres;
S3, dispersing the double modified silica hollow microspheres into a mixed solution of glycerol and water (volume ratio is 1:1), and then adding ferrous sulfate (the addition amount is 25% of the mass of the double modified silica hollow microspheres) and sulfuric acid to enable the pH value of the solution to be 2; heating to 40 ℃, dropwise adding hydrogen peroxide solution, and reacting for 3h; and adding sodium hydroxide to adjust the pH value to 7.0, continuing to react for 2 hours, collecting a solid product, and drying to obtain the polymeric ferric sulfate/double modified silicon dioxide hollow microsphere composite flocculant.
Comparative example 2
A process for the preparation of a flocculant differs from example 1 in that step S3, i.e. uncomplexed polymeric ferric sulphate, is not included. The other components are the same as those in embodiment 1, and will not be described in detail here.
Comparative example 3
A method of preparing a flocculant, differing from example 1 in that it comprises the steps of:
Mixing acrylamide, octadecyl methacrylate (the mass ratio of the acrylamide to the octadecyl methacrylate is 12 percent to 10 percent) and an initiator, and heating to 70 ℃ for reacting for 5 hours to obtain an acrylamide-octadecyl methacrylate copolymer;
Adding an acrylamide-octadecyl methacrylate copolymer into a mixed solution of glycerol and water (volume ratio is 1:1), and then adding ferrous sulfate (the addition amount is 25% of the mass of the double modified silica hollow microspheres) and sulfuric acid to enable the pH value of the solution to be 2; heating to 40 ℃, dropwise adding hydrogen peroxide solution, and reacting for 3h; and adding sodium hydroxide to adjust the pH value to 7.0, continuing to react for 2 hours, collecting a solid product, and drying to obtain the polymeric ferric sulfate/double modified silicon dioxide hollow microsphere composite flocculant.
Sewage treatment method
The mine produced water samples are respectively placed in 20 coagulating sedimentation cups (one cup for one liter), and are divided into 5 groups, 4 coagulating sedimentation cups are arranged in each group, all coagulating sedimentation cups are placed on a six-link stirrer platform, and the 5 groups of coagulating sedimentation cups are respectively subjected to comparative analysis of the effects of turbidity reduction and oil removal by adding 10mg/L, 20mg/L, 30mg/L, 40mg/L and 50mg/L of flocculating agents (prepared in the embodiment 1). After adding flocculant into the coagulating sedimentation cup, stirring at a stirring speed of 250r/min for 1min at a high speed, stirring at a stirring speed of 40r/min for 5min at a low speed, standing the solution for 20min after stirring, taking the supernatant at a position of 2cm below the liquid level for water sample analysis, and testing turbidity and oil content.
And flocculating the mine produced water with the following parameters, and detecting the removal rate of particulate matters and the removal rate of oil.
Table 1 mine produced water parameters
Project Oil content (mg/L) Turbidity (NTU) PH value of
Mine produced water 22.5 1210 7.5
As shown in fig. 2 and 3, it can be seen that as the amount of flocculant increases, the turbidity gradually decreases and the oil removal rate gradually increases. When the amount of the flocculant is more than 30mg/L, the oil removal rate does not change much. Thus, flocculation effects were tested in examples 2 to 7 and comparative examples 1 to 3, respectively, at an addition level of 30 mg/L. The test results are shown in Table 2.
Table 2 flocculation test results for examples and comparative examples
Sample preparation Oil removal Rate (%) Residual turbidity (NTU) Particulate removal rate (%)
Example 1 75.6 42 99.2
Example 2 74.5 55 98.6
Example 3 73.8 38 99.5
Example 4 58.1 41 99.1
Example 5 76.1 48 98.9
Example 6 75.1 56 98.4
Example 7 74.2 40 99.4
Comparative example 1 68.9 68 97.8
Comparative example 2 72.4 67 98.1
Comparative example 3 55.6 74 97.3
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (4)

1. A sewage treatment method is characterized in that polymeric ferric sulfate composite polymeric flocculant is added into sewage according to the adding amount of 10-100mg/L, stirring is carried out for 1-3min at the rotating speed of 200-300r/min, stirring is carried out for 3-8min at the rotating speed of 20-60r/min, and the solution is kept stand for 10-40min after the stirring is finished, so that flocculation sedimentation is completed;
Wherein the polymeric ferric sulfate composite polymeric flocculant is a composite flocculant composed of polymeric ferric sulfate and double modified silica hollow microspheres; the outer surface of the double modified silicon dioxide hollow microsphere is grafted with polyacrylamide; the inner surface is grafted with the poly (octadecyl methacrylate);
the polymeric ferric sulfate composite polymeric flocculant is prepared by the following steps:
s1, dispersing polystyrene microspheres into a mixed solution of isopropanol and water, adding tetraethoxysilane and vinyltriethoxysilane, heating to 60-80 ℃, adjusting the pH value to 10-11 with ammonia water for reaction, adding acrylamide and an initiator after 2-10h of reaction, reacting for 2-6h, collecting a product, and removing the polystyrene microspheres with toluene to obtain the silica hollow microspheres;
s2, dispersing the silicon dioxide hollow microspheres into acetone, then adding the octadecyl methacrylate and an initiator, and heating to 60-80 ℃ for reaction for 3-8 hours to obtain double modified silicon dioxide hollow microspheres; the initiator comprises one or more of ammonium persulfate, potassium persulfate or potassium sulfite;
S3, dispersing the double modified silicon dioxide hollow microspheres into a mixed solution of glycerol and water, and then adding ferrous sulfate and sulfuric acid to enable the pH value of the solution to be 1-3; heating to 30-60 ℃, dropwise adding hydrogen peroxide solution, and reacting for 1-5h; adding sodium hydroxide to adjust the pH value to 6.5-7.5, continuing to react for 1-5h, collecting a solid product, and drying to obtain the polymeric ferric sulfate/double modified silicon dioxide hollow microsphere composite flocculant;
The addition amount of the ferrous sulfate is 15-35% of the mass of the double modified silica hollow microspheres; the addition amount of the acrylamide is 5-20% of the mass of the tetraethoxysilane; the addition amount of the octadecyl methacrylate is 1-15% of the mass of the tetraethoxysilane.
2. The method for treating sewage according to claim 1, wherein the oil removal rate of the sewage is not less than 68% and the particulate removal rate is not less than 98%.
3. The method for treating sewage according to claim 1, wherein the mass ratio of the tetraethoxysilane to the vinyltriethoxysilane is (1-10): 1;
And/or the polystyrene microsphere has a diameter of 200-450nm.
4. The wastewater treatment method according to claim 1, wherein the volume ratio of glycerol to water is 4:6-6:4.
CN202311259783.0A 2023-09-26 2023-09-26 Sewage treatment method and preparation method of polymeric ferric sulfate composite polymeric flocculant Active CN117088486B (en)

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