CN112723512B - Preparation method and application of composite flocculant - Google Patents
Preparation method and application of composite flocculant Download PDFInfo
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- CN112723512B CN112723512B CN202011599803.5A CN202011599803A CN112723512B CN 112723512 B CN112723512 B CN 112723512B CN 202011599803 A CN202011599803 A CN 202011599803A CN 112723512 B CN112723512 B CN 112723512B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
Abstract
The invention discloses a preparation method of a composite flocculant, which comprises the following steps: carrying out homogeneous phase compounding on polymeric ferric sulfate and an organic flocculant to obtain the composite flocculant; the polymeric ferric sulfate is prepared by hydrothermal synthesis of ferrous sulfate, and the organic flocculant is a polymer polymerized by acrylamide, dimethyl diallyl ammonium chloride and octadecyl methacrylate. The composite flocculant prepared by the preparation method of the composite flocculant provided by the application has good turbidity reducing and oil removing effects in pretreatment of high-turbidity oil-containing mine water, can realize destabilization and coagulation of suspended particles and emulsified oil drops in the high-turbidity oil-containing mine water, and promotes recycling of the high-turbidity oil-containing mine water.
Description
Technical Field
The invention relates to the field of environmental protection, and particularly relates to a preparation method and application of a composite flocculant.
Background
In the coal mining and production process, the water consumption is huge, and in addition, underground water burst events often occur in the deep well excavation process, so that a large amount of mine wastewater is generated. According to statistics of relevant data, the annual discharge of mine water in China reaches about 71.7 hundred million m3In recent years, along with the improvement of water treatment technology and stricter treatment requirements of mine water, the treatment and recycling of the mine water are forced to become a necessary approach for green coal mining. The most common domestic treatment process for high-turbidity mine water consists of the links of coagulation, precipitation, filtration and disinfection, and the coagulation is the most important.
With the technical popularization of mechanized and intensive engineering mining, the phenomena of emulsified oil running, overflowing, dripping, leaking and the like often occur in the operation process of excavating equipment, so that the oil content of mine water is far higher than the limit value (1mg/L) of petroleum content specified in the Integrated wastewater discharge Standard (GB8978-2016), and further higher requirements are provided for the green purification treatment of the mine water. Conventional deoiling equipment investment cost is high, the utilization efficiency is low, and be difficult to realize the downhole application, so deoiling link generally does not set up alone, but thoughtlessly congeals with polluting impurities such as suspended particles, colloid and gets rid of jointly.
At present, the chemicals for flocculation treatment of mine water mainly adopt the application and research and development of iron/aluminum inorganic flocculants. However, the inorganic flocculant has poor oil removal effect, so that a preparation method of the flocculant which can reduce the turbidity of high-turbidity oil-containing mine water and has good oil removal effect is needed.
Disclosure of Invention
The invention discloses a preparation method and application of a composite flocculant, and aims to solve the technical problem that the flocculant in the prior art has poor oil removal effect on high-turbidity oil-containing mine water.
In order to solve the problems, the invention adopts the following technical scheme:
according to one aspect of the present application, there is provided a method for preparing a composite flocculant, comprising: carrying out homogeneous phase compounding on polymeric ferric sulfate and an organic flocculant to obtain the composite flocculant; the polymeric ferric sulfate is prepared by hydrothermal synthesis of ferrous sulfate, and the organic flocculant is a polymer polymerized by acrylamide, dimethyl diallyl ammonium chloride and octadecyl methacrylate.
Optionally, the step of homogeneously compounding polymeric ferric sulfate with the organic flocculant comprises: preparing a homogeneous solution containing the ferric polysulfate and the organic flocculant to homogeneously complex the ferric polysulfate with the organic flocculant; wherein the mass ratio of the polymeric ferric sulfate to the organic flocculant is 7-9: 1; the homogeneous phase composite has the following composite conditions: the compounding temperature is 60-80 ℃; the compounding time is 30-60 minutes.
Optionally, the preparation method of the polymeric ferric sulfate comprises the following steps: adding an oxidant into an acidic solution containing ferrous sulfate for oxidation reaction, then adding strong base to adjust the pH of a reaction system to 6.8-7.2, then carrying out a first reaction, and then transferring the reaction solution to a hydrothermal reaction kettle for hydrothermal reaction to obtain the polymeric ferric sulfate.
Alternatively, the method for preparing the acidic solution containing ferrous sulfate comprises: adding a glycerol solution into a ferrous sulfate monomer, and then adding concentrated sulfuric acid to obtain an acidic solution containing ferrous sulfate and having a pH value of 1.0-1.5; the oxidant comprises H2O2The reaction temperature of the oxidation reaction is 50-70 ℃; the strong base is sodium hydroxide or potassium hydroxide; the reaction temperature of the first reaction is 55-65 ℃, and the reaction time of the first reaction is 110-130 minutes; the reaction temperature of the hydrothermal reaction is 110-130 ℃, and the reaction time of the hydrothermal reaction is 15-17 hours.
Optionally, after the hydrothermal reaction, filtering, separating, drying and grinding a reaction product of the hydrothermal reaction to obtain the nano polymeric ferric sulfate with the particle size of 10-80 nm.
Optionally, the preparation method of the organic flocculant comprises the following steps: and (2) carrying out polymerization reaction on a solution containing acrylamide, dimethyl diallyl ammonium chloride, octadecyl methacrylate and an initiator to obtain the organic flocculant.
Optionally, in the solution containing acrylamide, dimethyl diallyl ammonium chloride, octadecyl methacrylate and an initiator, the mass ratio of the acrylamide to the dimethyl diallyl ammonium chloride to the octadecyl methacrylate is 10-12: 12-14: 4-6; the initiator is selected from at least one of ammonium persulfate, potassium persulfate or potassium sulfite;
the polymerization reaction is carried out under the protection of nitrogen or inert gas; the reaction temperature of the polymerization reaction is 68-72 ℃; the reaction time of the polymerization reaction is 5-7 hours.
Optionally, the polymeric ferric sulfate has a molecular formula of [ Fe [ ]2(OH)s(SO4)3－0.5s]tWherein s is 2, and t is 150-200; the structural formula of the organic flocculant is as follows:
wherein x, y and z are (1-3): (1-2): (1-2); the intrinsic viscosity of the organic flocculant is 590-610 mL/g; the molecular formula of the composite flocculant is C32nH(64n+4m)O(3n+8m)N2nClnSmFe2mWherein n is 18000-20000; and n, m is 11: 200.
According to a second aspect of the present application, there is provided a composite flocculant produced by the production method according to the first aspect of the present application.
According to a third aspect of the application, the composite flocculant prepared according to the preparation method of the first aspect of the application or the composite flocculant according to the second aspect of the application is applied to flocculation pretreatment of mine water.
The technical scheme adopted by the invention can achieve the following beneficial effects:
1) the composite flocculant prepared by the preparation method of the composite flocculant provided by the application has good turbidity reducing and oil removing effects in pretreatment of high-turbidity oil-containing mine water, can realize destabilization and coagulation of suspended particles and emulsified oil drops in the high-turbidity oil-containing mine water, and promotes recycling of the high-turbidity oil-containing mine water. Compared with the conventional inorganic and organic flocculating agents, the flocculating agent provided by the invention has the advantages that the flocculating performance is obviously improved, and the flocculating agent is suitable for the water quality treatment process of high-turbidity and oil-containing well water.
2) The composite flocculant prepared by the preparation method of the composite flocculant provided by the application has the advantages of inorganic and organic flocculants, for example, the inorganic flocculant nano Polymeric Ferric Sulfate (PFS) in the composite flocculant contains both single-core complex and multi-core complex, which is beneficial to carrying out net capture and rolling sweeping on particles; the cationic monomer dimethyl diallyl ammonium chloride in the organic flocculant improves the density of positive charges, and is beneficial to the adsorption and electric neutralization between colloids, particles and the flocculant; the octadecyl methacrylate containing hydrophobic groups has the demulsification effect, and the adsorption treatment capacity of the emulsified oil is improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a FT-IR spectrum of polymeric ferric sulfate according to example 1 of the present application;
FIG. 2 is a FT-IR spectrum of an organic flocculant (AM-DMDAAC-ODMA) according to example 1 of the present application;
FIG. 3 is an FT-IR spectrum of a composite flocculant prepared in example 1 of the present application;
FIG. 4 is an SEM photograph of the polymeric ferric sulfate prepared in example 1 of the present application;
FIG. 5 is an SEM image of a composite flocculant prepared in example 1 of the present application;
FIG. 6 graphically illustrates the effect of different dosing amounts of different flocculants on turbidity; and
figure 7 shows in a bar graph the effect of different dosing of different flocculants on oil removal rate.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the specific embodiments of the present invention and the accompanying drawings. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The technical solutions disclosed in the embodiments of the present invention are described in detail below with reference to the accompanying drawings.
According to an embodiment of the present invention, there is provided a method for preparing a composite flocculant, including:
carrying out homogeneous phase compounding on polymeric ferric sulfate and an organic flocculant to obtain a composite flocculant; wherein, the polyferric sulfate is prepared by ferrous sulfate through hydrothermal synthesis, and the organic flocculant is a polymer polymerized by acrylamide, dimethyl diallyl ammonium chloride and octadecyl methacrylate.
Further, the preparation method of the polymeric ferric sulfate comprises the following steps: adding an oxidant into an acidic solution containing ferrous sulfate for oxidation reaction, then adding strong base to adjust the pH of a reaction system to 6.8-7.2, then stirring for reaction, and then transferring the reaction solution into a hydrothermal reaction kettle for hydrothermal reaction to obtain polymeric ferric sulfate.
Further, the preparation method of the organic flocculant comprises the following steps: and (2) carrying out polymerization reaction on the solution containing the acrylamide, the dimethyl diallyl ammonium chloride, the octadecyl methacrylate and the initiator to obtain the organic flocculant.
In this embodiment, the polymeric ferric sulfate has the formula [ Fe ]2(OH)s(SO4)3－0.5s]tWherein s is 2, and t is 150-200;
the structural formula of the organic flocculant is as follows:
wherein x, y and z are (1-3): (1-2): (1-2); the intrinsic viscosity of the organic flocculant is 590-610 mL/g; the molecular formula of the composite flocculant is C32nH(64n+4m)O(3n+8m)N2nClnSmFe2mWherein n is 18000-20000; and n, m is 11: 200.
The invention is described below with reference to specific embodiments.
Example 1
1) Preparation of nano Polymeric Ferric Sulfate (PFS):
firstly, 27.8 g of FeSO is weighed4·7H2Dissolving O solid particles in 300mL of glycerol solution with the mass fraction of 50% (glycerol and water are mixed according to the proportion of 1: 1), adding 10-12 mL of concentrated sulfuric acid for acidification, and controlling Fe2+：SO4 2-The molar ratio is 1.1-1.2, the pH value of the solution is 1.5, and then 30% H by mass is dripped under the condition of constant temperature of 60 ℃ in a water bath2O2The amount of the solution added was 51mL (excess H was added)2O2To ensure Fe in the solution2+Is completely oxidized), H is added2O2And quickly oxidizing the solution into reddish brown, continuously and slowly dropwise adding 0.1mol/L sodium hydroxide solution under the stirring condition, adjusting the pH value of the solution to 7.0, continuously stirring and reacting in a 60-DEG C constant-temperature heating magnetic stirrer for 120min, putting the reaction solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 15h at the hydrothermal reaction temperature of 120 ℃, filtering, collecting solid particles, drying and grinding to obtain the nano Polymeric Ferric Sulfate (PFS) powder with the particle size of 10-80 nm.
2) Preparation of organic flocculant (AM-DMDAAC-ODMA):
11.7 g of Acrylamide (AM), 13.3 g of dimethyldiallylammonium chloride (DMDAAC) and 5.0 g of octadecyl methacrylate (ODMA) were weighed and charged with a constant pressure funnel, thermometer and stirrer5-6 mL of initiator ammonium persulfate ((NH) is stored in a three-mouth reaction flask of a stirrer and a nitrogen introducing device and a constant-pressure funnel4)2S2O8) The method comprises the steps of preparing a solution (the mass fraction is 0.2%), screwing a cock, preventing a constant-pressure funnel from dripping, adding a small amount of EDTA (ethylene diamine tetraacetic acid) to complex heavy metal ion impurities, shielding the polymerization inhibition effect of the heavy metal ions, adding a proper amount of nitrogen-introducing distilled water into a three-neck flask, starting stirring, opening a nitrogen valve to introduce nitrogen into the solution, removing oxygen in the solution, introducing nitrogen for 30min, opening the cock of the constant-pressure funnel, controlling the initiator solution to drip off within 30min, continuously introducing nitrogen, closing the nitrogen valve after about 10min, sealing the three-neck flask, adjusting the temperature of a water bath kettle to 70 ℃, keeping constant temperature, and obtaining a colloid of a polymerization reactant after 6h of polymerization reaction. Leaching the colloid with mixed solution of ethanol and acetone to obtain white precipitate, drying and grinding the white precipitate to obtain final product organic flocculant (AM-DMDAAC-ODMA).
3) Preparing a composite flocculant:
dissolving the polymeric sulfuric acid (PFS) prepared in the step 1) and the organic flocculant prepared in the step 2) in a beaker according to a mass fraction ratio of 9:1 and a proper amount of distilled water, heating and stirring for about 45 minutes under a water bath condition at 60 ℃ until a stable homogeneous solution is formed, stopping heating and stirring, adding a mixed solution (1:2) of ethanol and acetone into the solution after the solution is recovered to room temperature, leaching the mixed solution to obtain a white precipitate, and finally drying and grinding the white precipitate to obtain a composite flocculant product.
Example 2
1) Preparation of nano Polymeric Ferric Sulfate (PFS):
firstly, 27.8 g of FeSO is weighed4·7H2Dissolving O solid particles in 300mL of glycerol solution with the mass fraction of 50% (glycerol and water are mixed according to the proportion of 1: 1), adding 10-12 mL of concentrated sulfuric acid for acidification, and controlling Fe2+：SO4 2-The molar ratio is 1.1-1.2, the pH value of the solution is 1.3, and then 30% H by mass fraction is dripped under the condition of constant temperature of 50 ℃ in a water bath2O2The amount of the solution added was 51mL (excess H was added)2O2To ensure Fe in the solution2+Is completely oxidized), is addedH2O2And quickly oxidizing the solution into reddish brown, continuously and slowly dropwise adding 0.1mol/L sodium hydroxide solution under the stirring condition, adjusting the pH value of the solution to 6.8, continuously stirring and reacting in a magnetic stirrer at the constant temperature of 55 ℃ for 130min, putting the reaction solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at the hydrothermal reaction temperature of 110 ℃ for 17h, filtering, collecting solid particles, drying and grinding to obtain the nano Polymeric Ferric Sulfate (PFS) powder with the particle size of 10-80 nm.
2) Preparation of organic flocculant (AM-DMDAAC-ODMA):
weighing 10.0 g of Acrylamide (AM), 12.0 g of dimethyldiallylammonium chloride (DMDAAC) and 4.0 g of octadecyl methacrylate (ODMA), feeding into a three-neck reaction flask with a constant-pressure funnel, a thermometer, a stirrer and a nitrogen introducing device, and storing 5-6 mL of initiator potassium persulfate (K) in the constant-pressure funnel2S2O8) The method comprises the steps of preparing a solution (the mass fraction is 0.2%), screwing a cock, preventing a constant-pressure funnel from dripping, adding a small amount of EDTA (ethylene diamine tetraacetic acid) to complex heavy metal ion impurities, shielding the polymerization inhibition effect of the heavy metal ions, adding a proper amount of nitrogen-introducing distilled water into a three-neck flask, starting stirring, opening a nitrogen valve to introduce nitrogen into the solution, removing oxygen in the solution, introducing nitrogen for 30min, opening the cock of the constant-pressure funnel, controlling the initiator solution to drip off within 30min, continuously introducing nitrogen, closing the nitrogen valve after about 10min, sealing the three-neck flask, adjusting the temperature of a water bath kettle to 72 ℃, keeping constant temperature, and obtaining a colloid of a polymerization reactant after 5h of polymerization reaction. Leaching the colloid with mixed solution of ethanol and acetone to obtain white precipitate, drying and grinding the white precipitate to obtain final product organic flocculant (AM-DMDAAC-ODMA).
3) Preparing a composite flocculant:
dissolving the polymeric sulfuric acid (PFS) prepared in the step 1) and the organic flocculant prepared in the step 2) in a beaker according to a mass fraction ratio of 8:1 and a proper amount of distilled water, heating and stirring the mixture for about 30 minutes under a water bath condition at 80 ℃ until a stable homogeneous solution is formed, stopping heating and stirring the mixture, adding a mixed solution (1:2) of ethanol and acetone into the mixture after the mixture is recovered to room temperature, leaching the mixture to obtain a white precipitate, and finally drying and grinding the white precipitate to obtain a composite flocculant product.
Example 3
1) Preparation of nano Polymeric Ferric Sulfate (PFS):
firstly, 27.8 g of FeSO is weighed4·7H2Dissolving O solid particles in 300mL of glycerol solution with the mass fraction of 50% (glycerol and water are mixed according to the proportion of 1: 1), adding 10-12 mL of concentrated sulfuric acid for acidification, and controlling Fe2+：SO4 2-The molar ratio is 1.1-1.2, the pH value of the solution is 1.0, and then 30% H by mass fraction is dripped under the condition of constant temperature of 70 ℃ in a water bath2O2The amount of the solution added was 51mL (excess H was added)2O2To ensure Fe in the solution2+Is completely oxidized), H is added2O2And quickly oxidizing the solution into reddish brown, continuously and slowly dropwise adding 0.1mol/L potassium hydroxide solution under the stirring condition, adjusting the pH value of the solution to 7.2, continuously stirring and reacting in a magnetic stirrer at the constant temperature of 65 ℃ for 110min, putting the reaction solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at the hydrothermal reaction temperature of 130 ℃ for 16h, filtering, collecting solid particles, drying and grinding to obtain the nano Polymeric Ferric Sulfate (PFS) powder with the particle size of 10-80 nm.
2) Preparation of organic flocculant (AM-DMDAAC-ODMA):
weighing 12.0 g of Acrylamide (AM), 14.0 g of dimethyldiallylammonium chloride (DMDAAC) and 6.0 g of octadecyl methacrylate (ODMA), feeding into a three-mouth reaction flask with a constant pressure funnel, a thermometer, a stirrer and a nitrogen introducing device, storing 4-5 mL of initiator potassium sulfite solution (the mass fraction is 0.3%) in the constant pressure funnel, screwing a cock to prevent the constant pressure funnel from dripping, adding a small amount of EDTA (ethylene diamine tetraacetic acid) to complex heavy metal ion impurities, shielding the polymerization inhibition effect of the heavy metal ions, adding a proper amount of nitrogen introducing distilled water into the three-mouth flask, starting stirring, opening a nitrogen valve to introduce nitrogen into the solution, removing oxygen in the solution, introducing nitrogen for 30min, opening the cock of the constant pressure funnel, controlling the initiator solution to drip off in 30min, continuing to introduce nitrogen, closing the nitrogen valve after about 10min, sealing the three-mouth flask, adjusting the temperature of a water bath to 68 ℃, keeping constant temperature, and obtaining the colloid of the polymerization reactant after polymerization reaction for 7 hours. Leaching the colloid with mixed solution of ethanol and acetone to obtain white precipitate, drying and grinding the white precipitate to obtain final product organic flocculant (AM-DMDAAC-ODMA).
3) Preparing a composite flocculant:
dissolving the polymeric sulfuric acid (PFS) prepared in the step 1) and the organic flocculant prepared in the step 2) in a beaker according to a mass fraction ratio of 7:1 and a proper amount of distilled water, heating and stirring for about 60 minutes under a water bath condition at 70 ℃ until a stable homogeneous solution is formed, stopping heating and stirring, adding a mixed solution (1:2) of ethanol and acetone into the solution after the solution is recovered to room temperature, leaching the mixed solution to obtain a white precipitate, and finally drying and grinding the white precipitate to obtain a composite flocculant product.
Example 4
The mine water raw water pumped to the ground under a certain coal mine in Yulin City of Shaanxi province is treated by adopting the prepared coagulant, and the water quality parameters are shown in Table 1.
TABLE 1 mine water quality characteristic parameters
And (3) respectively placing 20L of water sample in 20 coagulating sedimentation cups (one cup and one liter) which are divided into 5 groups, wherein each group comprises 4 coagulating sedimentation cups, placing all the coagulating sedimentation cups on a six-joint stirrer platform, and performing comparative analysis on turbidity reduction and oil removal effects on the 5 groups of coagulating sedimentation cups under the conditions of 15mg/L, 30mg/L, 45mg/L, 60mg/L and 75mg/L of flocculant use amount according to the principle that the adding amount of different types of flocculants is the same. After the flocculating agent is added into the coagulating sedimentation cup, firstly stirring at high speed to quickly dissolve the flocculating agent, wherein the stirring speed is 250r/min, continuously stirring for 1min, then stirring at low speed, the stirring speed is 40r/min, stirring for 5min, standing the solution for 30min after the stirring is finished, taking supernatant liquid 2cm below the liquid surface to perform water sample analysis, and testing the turbidity and the oil content of the supernatant liquid.
The nano polyferric sulfate (PFS) prepared in example 1, the organic flocculant P (AM-DMDAAC-ODMA), the composite flocculant of the two and the mixture of polyaluminium chloride and polyacrylamide (PAC + PAM, the mass ratio of PAC to PAM is 100:3) are selected to carry out a beaker experiment on mine water, and the experimental conditions are set as follows: the addition amounts of the four flocculants are changed at room temperature (20 ℃), so that the treatment effect on the turbidity and the emulsified oil is obtained, as shown in fig. 6 and 7, and the addition modes of the flocculants are shown in table 2.
TABLE 2 addition of flocculating agent
Note: PFS is the nano polymeric ferric sulfate prepared in example 1; p (AM-DMDAAC-ODMA) is the organic flocculant prepared in example 1; PFS-P (AM-DMDAAC-ODMA) is the composite flocculant prepared in example 1.
Example 1 analysis of the product:
1) a fourier transform infrared spectrometer (instrument model: united states PE company Spectrum400) the Polymeric Ferric Sulfate (PFS), the organic flocculant (AM-DMDAAC-ODMA) and the prepared composite flocculant of example 1 were respectively subjected to a Spectrum test, as shown in fig. 1 to 3, and it can be seen by comparing fig. 1 to 3: the FT-IR spectrum of the composite flocculant has a characteristic peak of polymeric ferric sulfate, for example, 3404.1cm-1The antisymmetric vibration peak of the hydroxyl group of the Fe (III) polymer and-NH of acrylamide2SO in the PFS, the part of the radicals where the stretching vibration peaks overlap4 2-The absorption peak is 1250-1000 cm-1In addition, the characteristic peak of the organic flocculant (AM-DMDAAC-ODMA) is masked, for example, 1453.54cm-1The disappearance of the stretching vibration peak related to the five-membered nitrogen heterocycle is covered by the absorption peak in PFS after displacement, 1641.8cm-1The absorption peak is the stretching vibration peak of C ═ O and quaternary ammonium ion N+The deformation vibration peak of the flocculant is subjected to blue shift, and in conclusion, the characteristic functional group of the composite flocculant indicates that the polymeric ferric sulfate and the organic flocculant (AM-DMDAAC-ODMA) are successfully compounded.
2) The Polymeric Ferric Sulfate (PFS) prepared in example 1 and the composite flocculant were pretreated by gold spraying, and SEM images thereof were obtained by a scanning electron microscope, as shown in fig. 4 to 5.
As shown in FIG. 4, the PFS is a block-shaped particle formed by aggregating a plurality of spherical particles with different sizes, and has a smooth and flat surface and a loose structure. As can be seen from FIG. 5, the structural morphology of the composite flocculant is similar to a net shape, branches appear and are staggered with each other, and dispersed Polymeric Ferric Sulfate (PFS) particles are agglomerated together to form a net-like complex with a relatively compact structure, so that the surface area of the composite flocculant particles is effectively increased, and the effects of adsorption bridging, rolling, sweeping and net-catching are enhanced. It is also proved that the Polymeric Ferric Sulfate (PFS) and the organic flocculant (AM-DMDAAC-ODMA) in the composite flocculant are mutually blended and act together to promote the improvement of flocculation capability.
Example 4 analysis of results:
the turbidity of the mine water treated with different flocculants in example 4 was measured by a photoelectric turbidimeter method using a U.S. hash turbidimeter (model number: 2100N), and the results are shown in fig. 6.
The oil content of the mine water treated by different flocculants in example 4 was detected by an ultraviolet spectrophotometer (instrument model: Shimadzu UV-2550 in Japan) by using an oil content measuring method in determination of oil contents in boiler water and cooling water (GB/T12152-2007), and the oil removal rate was calculated, and the result is shown in FIG. 7.
As can be seen from fig. 6 and 7, under the condition of the same flocculant adding amount, the composite flocculant prepared by the method has the best turbidity reduction and oil removal effects, the removal rate of colloid and particulate matters can reach 99.3% at most, and the removal rate of emulsified oil is more than 70%. In addition, the removal rate of the composite flocculant and the organic flocculant prepared by the method provided by the application to the oil content of the mine water is obviously higher than that of the situation that PFS is independently added and polyaluminium chloride (PAC) is combined with Polyacrylamide (PAM) for use, which shows that the hydrophobic monomer ODMA in the composite flocculant plays a positive role in the adsorption effect of the oil.
In the above embodiments of the present invention, the difference between the embodiments is mainly described, and different optimization features between the embodiments can be combined to form a better embodiment as long as they are not contradictory, and further description is omitted here in view of brevity of the text.
The above description is only an example of the present invention, and is not intended to limit the present invention. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (8)
1. The preparation method of the composite flocculant is characterized by comprising the following steps: carrying out homogeneous phase compounding on polymeric ferric sulfate and an organic flocculant to obtain the composite flocculant;
the polymeric ferric sulfate is prepared by hydrothermal synthesis of ferrous sulfate, and the organic flocculant is a polymer polymerized by acrylamide, dimethyl diallyl ammonium chloride and octadecyl methacrylate;
the method for homogeneously compounding the polymeric ferric sulfate and the organic flocculant comprises the following steps: preparing a homogeneous solution containing the ferric polysulfate and the organic flocculant to homogeneously complex the ferric polysulfate with the organic flocculant;
wherein the mass ratio of the polymeric ferric sulfate to the organic flocculant is 7-9: 1;
the homogeneous phase composite has the following composite conditions:
the compounding temperature is 60-80 ℃;
the compounding time is 30-60 minutes;
the molecular formula of the polymeric ferric sulfate is [ Fe ]2(OH)s(SO4)3－0.5s]tWherein s is 2, and t is 150-200;
the structural formula of the organic flocculant is as follows:
wherein x, y and z are (1-3): (1-2): (1-2);
the intrinsic viscosity of the organic flocculant is 590-610 mL/g;
the molecular formula of the composite flocculant is C32nH(64n+4m)O(3n+8m)N2nClnSmFe2mWherein n is 18000-20000; and n, m is 11: 200.
2. The preparation method of the composite flocculant according to claim 1, wherein the preparation method of the polymeric ferric sulfate comprises the following steps:
adding an oxidant into an acidic solution containing ferrous sulfate for oxidation reaction, then adding strong base to adjust the pH of a reaction system to 6.8-7.2, then carrying out a first reaction, and then transferring the reaction solution to a hydrothermal reaction kettle for hydrothermal reaction to obtain the polymeric ferric sulfate.
3. The method for preparing the composite flocculant according to claim 2, wherein the method for preparing the acidic solution containing ferrous sulfate comprises: adding a glycerol solution into a ferrous sulfate monomer, and then adding concentrated sulfuric acid to obtain an acidic solution containing ferrous sulfate and having a pH value of 1.0-1.5;
the oxidant comprises H2O2The reaction temperature of the oxidation reaction is 50-70 ℃;
the strong base is sodium hydroxide or potassium hydroxide;
the reaction temperature of the first reaction is 55-65 ℃, and the reaction time of the first reaction is 110-130 minutes;
the reaction temperature of the hydrothermal reaction is 110-130 ℃, and the reaction time of the hydrothermal reaction is 15-17 hours.
4. The preparation method of the composite flocculant according to claim 2, characterized by further comprising the step of separating, drying and grinding reaction products of the hydrothermal reaction after the hydrothermal reaction to obtain nano polymeric ferric sulfate with the particle size ranging from 10 nm to 80 nm.
5. The method for preparing a composite flocculant according to claim 1, wherein the method for preparing an organic flocculant comprises:
and (2) carrying out polymerization reaction on a solution containing acrylamide, dimethyl diallyl ammonium chloride, octadecyl methacrylate and an initiator to obtain the organic flocculant.
6. The preparation method of the composite flocculant according to claim 5, wherein in the solution containing acrylamide, dimethyldiallylammonium chloride, octadecyl methacrylate and an initiator, the mass ratio of the acrylamide to the dimethyldiallylammonium chloride to the octadecyl methacrylate is 10-12: 12-14: 4-6;
the initiator is selected from at least one of ammonium persulfate, potassium persulfate or potassium sulfite;
the polymerization reaction is carried out under the protection of nitrogen or inert gas;
the reaction temperature of the polymerization reaction is 68-72 ℃;
the reaction time of the polymerization reaction is 5-7 hours.
7. A composite flocculant prepared by the preparation method of any one of claims 1 to 6.
8. The composite flocculant prepared by the preparation method according to any one of claims 1 to 6 or the application of the composite flocculant according to claim 7 in flocculation pretreatment of mine water.
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