CN117699933A - Flocculant and preparation method thereof - Google Patents
Flocculant and preparation method thereof Download PDFInfo
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- CN117699933A CN117699933A CN202410166799.5A CN202410166799A CN117699933A CN 117699933 A CN117699933 A CN 117699933A CN 202410166799 A CN202410166799 A CN 202410166799A CN 117699933 A CN117699933 A CN 117699933A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 46
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- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 25
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
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- 238000003756 stirring Methods 0.000 claims description 18
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- 239000002202 Polyethylene glycol Substances 0.000 claims description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 15
- -1 4-fluoro-phenyl ammonium tetrafluoroborate Chemical compound 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 claims description 9
- 239000002918 waste heat Substances 0.000 claims description 9
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- 230000016615 flocculation Effects 0.000 abstract description 14
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- 238000009776 industrial production Methods 0.000 abstract description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000012043 crude product Substances 0.000 description 21
- 239000002351 wastewater Substances 0.000 description 19
- 150000002500 ions Chemical class 0.000 description 18
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- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
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- 229910052751 metal Inorganic materials 0.000 description 4
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- 230000005591 charge neutralization Effects 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
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- 238000011068 loading method Methods 0.000 description 3
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- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
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- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical class OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 2
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- 230000000977 initiatory effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
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- 239000002184 metal Substances 0.000 description 2
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- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Abstract
The invention belongs to the field of sewage treatment, and particularly relates to a flocculant and a preparation method thereof. The method comprises the following steps: 1) Taking metal oxide, adding water and a stabilizer, heating, adding the mixture, and performing heat treatment to obtain a composite material; 2) Mixing the composite material, the monomer and water, heating and reacting in a protective atmosphere until the monomer is dispersed, adding an initiator, reacting, standing and forming to obtain a modified polymer; 3) Adding the modified high polymer into an organic solvent, heating and refluxing, adding grafted organic matters, heating and refluxing, adding a coupling agent, cooling, washing a product with the organic solvent, and performing suction filtration and drying to obtain the flocculant. The preparation method disclosed by the invention is simple in flow, strong in operability and strong in controllability, is suitable for industrial production, and the prepared flocculant is good in water solubility, can quickly settle pollutant, can neutralize charges in polluted water and has a good flocculation effect.
Description
Technical Field
The invention belongs to the field of sewage treatment, and particularly relates to a flocculant and a preparation method thereof.
Background
In the water injection process, flocculant is a very common and commonly used agent. Compared with the traditional inorganic flocculant, the organic flocculant has the advantages of more functional groups, strong adsorption bridging capability, wide application range, high use efficiency, good flocculation effect and good filterability, and the polyacrylamide flocculant is a common organic flocculant. As a water-soluble polymer, it can play an important role in sewage treatment. When the method is applied, the restriction on the pH value of the solution and the coexisting salts is low, and the polyacrylamide flocculant can quickly settle and remove negatively charged particles and other pollutants through the ion adsorption and bridging effects, has the functions of good decolorization and the like, and is suitable for the aspects of wastewater with high colloid substance content, sludge dehydration, treatment of colored wastewater and the like. It is widely recognized by those skilled in the art that the development of novel high performance, inexpensive flocculants is an important approach to improving wastewater treatment efficiency.
For example, patent CN104861950a discloses a supermolecule linear polyacrylamide oil displacement agent, which consists of the following components: adamantane terminated polyacrylamide, beta-cyclodextrin dimer, additive, oxygen scavenger, water; the preparation method of the supermolecule linear polyacrylamide oil displacement agent comprises the following steps: a. preparing adamantane terminated polyacrylamide; b. adding an additive and an deoxidizer into water, uniformly stirring, adding adamantane terminated polyacrylamide, stirring, standing for reaction, adding beta-cyclodextrin dimer, stirring, standing for reaction, and obtaining a solution which is the supermolecule linear polyacrylamide oil displacement agent. The supermolecule linear polyacrylamide oil displacement agent prepared by the method has linear molecular chains and good solubility, and has better ageing resistance, so that the recovery ratio of the oil displacement agent is obviously improved.
However, most of the currently commercialized polyacrylamide flocculants have the problems of high viscosity, low charge utilization rate, easy pipeline blockage caused by chain entanglement and the like, and cannot meet the current wastewater treatment requirements. Therefore, there is a need to develop a flocculant with better flocculation effect.
Disclosure of Invention
The invention provides a flocculant and a preparation method thereof, aiming at solving the problems that most of the existing polyacrylamide flocculants have high viscosity, low charge utilization rate, weak actual use effect, low actual load rate and the like caused by easy entanglement.
The main purpose of the invention is that: 1. can be effectively used for water injection flocculation treatment.
2. Overcomes the defects of the linear flocculant, reduces the occurrence of entanglement phenomenon, and leads to the problems of blockage or low loading rate.
3. The preparation method is simple and controllable.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
A method of preparing a flocculant, the method comprising: 1) And (3) taking metal oxide, adding water and a stabilizer, heating, adding a mixture, wherein the mixture is composed of ethyl silicate and 4-fluoro-phenyl ammonium tetrafluoroborate, and performing heat treatment to obtain the composite material.
2) And mixing the composite material, the monomer and water, heating and reacting in a protective atmosphere until the monomer is dispersed, adding an initiator, reacting, standing and forming to obtain the modified polymer.
3) Adding the modified high polymer into an organic solvent, heating and refluxing, adding grafted organic matters, heating and refluxing, adding a coupling agent, cooling, washing a product with the organic solvent, and performing suction filtration and drying to obtain the flocculant.
Preferably, the metal oxide of step 1) is Fe 3 O 4 The method comprises the steps of carrying out a first treatment on the surface of the The stabilizer in the step 1) is ammonium tartrate; the dosage ratio of the metal oxide, the water and the stabilizer in the step 1) is 1g: (8-13) mL: (0.1-0.2) g; the heating temperature is controlled to be 65-75 ℃ in the heating process of the step 1), the heating time is 1-2 h, and stirring is continuously carried out in the heating process.
Preferably, step 1) the mixture is prepared from ethyl silicate and 4-fluoro-phenyl ammonium tetrafluoroborate according to (5-10) mL: mixing the materials according to the dosage ratio of 1g, and then performing constant temperature treatment at the temperature of 90-100 ℃ until the materials are dried to obtain a mixture; the dosage of the mixture in the step 1) is 0.2 to 0.5g/g of metal oxide; the heat treatment process in the step 1) is carried out in a protective atmosphere, and the heat treatment is carried out for 1 to 2 hours at the temperature of 780 to 820 ℃.
Preferably, the monomer in the step 2) is a mixture of acrylamide and dimethyl diallyl ammonium chloride, and the mass ratio of the acrylamide to the dimethyl diallyl ammonium chloride is (4-5): 1, a step of; the dosage ratio of the composite material, the monomer and the water in the step 2) is 1g: (0.8-1.2) g: (4-18) mL; and 2) controlling the reaction temperature to be 30-40 ℃ and the reaction time to be 0.5-1.0 h in the heating reaction process.
Preferably, the initiator in the step 2) is ammonium persulfate, and the dosage of the ammonium persulfate is 0.1-0.4 g/g of monomer; and 2) controlling the temperature of the reaction process after the initiator is added in the step 2) to be 50-70 ℃ and the reaction time to be 4-6 h.
Preferably, the organic solvent in the step 3) is dimethylbenzene, and the dosage of the organic solvent is 1-10 mL/g modified high polymer; and 3) controlling the reaction temperature to be 80-90 ℃ and the reaction time to be 1-2 h in the heating reflux process.
Preferably, the grafted organic matter in the step 3) is polyethylene glycol, and the dosage of the grafted organic matter is 1.1-1.3 g/g modified high polymer; and 3) controlling the reaction temperature to be 110-120 ℃ and the reaction time to be 1-2 h in the heating reflux process.
Preferably, the coupling agent in the step 3) is a silane coupling agent, the dosage of the coupling agent is 0.1-0.3 g/g modified high polymer, and the coupling agent is added and then reacted by means of waste heat.
A flocculant capable of neutralizing charge and flocculating treatment contaminants.
In the technical scheme of the invention, fe is prepared 3 O 4 /SiO 2 Composite material, fe 3 O 4 As a metal core, siO 2 Is a shell. Firstly, ammonium tartrate has good hydrophilicity, and ionized tartrate ions and Fe 3 O 4 Form monomolecular adsorption to enrich negative charge on the surface of the nano-particle and promote Fe 3 O 4 Stable dispersion and improved utilization rate. Secondly, ethyl silicate is used as a silicon source, using BF 4 - The hydrogen bonding between ions and Si-OH promotes BF 4 - The ions are orderly arranged, pi-pi accumulation is formed under the action of the coulomb force between the ions, and finally Fe with a core-shell structure is obtained by regulation and control 3 O 4 /SiO 2 A composite material. Characterized by Fe 3 O 4 /SiO 2 The composite material is spherical and Fe 3 O 4 No change in crystal form due to SiO 2 Coating Fe 3 O 4 The agglomeration of particles is inhibited, so that the material has good dispersibility. In addition, the composite material is not only SiO 2 Mesoporous channels of the particles, also Fe 3 O 4 /SiO 2 The stacking pores among the particles are rich in adsorption active sites and have a large amount of negative charges.
Due to single Fe 3 O 4 /SiO 2 The composite material has insufficient flocculation effect, and in the copolymerization system of inorganic components and organic monomers, two monomers of acrylamide and dimethyl diallyl ammonium chloride are initiated to form a long chain and grafted on a core-shell structure to prepare the copolymer containing active branched chains. Ammonium persulfate can be dissolved in water, can be reduced to form sulfate radical and ionized to form hydroxyl radical, efficiently initiates monomers to generate free radical, and is easy to control. Flexible amide-ammonium branching in Fe 3 O 4 /SiO 2 The particles form adsorption bridging, and the material is dissolved and swelled in water to formThe long straight chain and the long straight chain are connected to construct a three-dimensional spherical network structure, so that the three-dimensional spherical network structure has excellent complexing effect and dispersing effect on pollutant molecules. Two monomers construct an amide-ammonium long chain, and the amide-ammonium long chain is linked with Fe 3 O 4 /SiO 2 On the particles, the structure branching characteristics are obvious, the branching chain is long, and the asymmetric branching structure shows the characteristics of low viscosity, high water solubility, high reactivity and the like. The branched chain end has a large number of active sites, and can combine with components such as aromatic compounds, sulfur, phenol and the like, so that the flocculation effect can be well exerted in the environment of high temperature, strong acid and strong alkali. The formed modified high polymer can be adsorbed on the surface of pollutant molecules, and the metal core with enriched negative charges neutralizes the positive charges carried by pollutant ions, so that the electric double layer of the modified high polymer is compressed, and the electrostatic repulsive force is reduced. When the electrostatic repulsive force between pollutant particles tends to zero under the action of charge neutralization, the pollutant particles realize destabilization and spontaneously aggregate to form a flocculating body with strong stability after collision.
In terms of the initiation conditions, the reaction temperature has an influence on the rate of decomposition of the initiator, the free radical number. The high temperature promotes the decomposition of the initiator, the more free radicals are generated, the small particle size and low long-chain molecular weight are achieved, the water solubility is improved, and meanwhile, the material is rich in holes and adsorption active sites. However, the reaction temperature is too high, so that the polymerization speed is too high, the polymerization degree is too high, long chain entanglement is caused, a plurality of side reactions are caused, the polymerization structure is difficult to singly control, the molecular weight is too high, the long chain is unevenly distributed, and the intermolecular bridging effect is weakened, so that flocculant sedimentation pollutant molecules are influenced. In addition, the conversion rate of polymerization reaction monomers is small in a short time, the reaction is incomplete, and the too long polymerization time leads to too small pore diameter of the polymer, so that the permeability of the composite material is influenced, and the adsorption performance is influenced.
The polyethylene glycol can further improve the water solubility of the material and avoid excessive addition of other demulsifiers and coagulant aids. The flocculant has high dissolution speed and good compatibility, namely, can stabilize the settled pollutant molecules after dilution, has high density of settled substances, and has tight and clustered floccules in the water body and high settling speed. The flocculant overcomes the problems of poor adsorption effect, large usage amount and flocculant residue of a single flocculant, can realize performance complementation and improves the sedimentation capacity of materials. Meanwhile, the flocculant can prolong the nucleation induction time of crystals and cause lattice distortion to pollutants, a metal center attracts pollutant ions through a charge neutralization effect, a branched chain structure can destroy the intermolecular acting force of the pollutants, the branched chain structure is adsorbed on the pollutant molecules, and active sites of the lattices of the branched chain structure are occupied to prevent the growth of the crystals. In addition, the flocculant is directly added into the water body without adjusting the pH value, and the operation is simple and convenient.
The beneficial effects of the invention are as follows: (1) The preparation method provided by the invention has the advantages of simple flow, strong operability and strong controllability, and is suitable for industrial production.
(2) The flocculant prepared by the invention has good water solubility and can quickly settle pollutants.
(3) The flocculant prepared by the invention has rich charge, namely, has high charge density, can neutralize the charge in polluted water and has good flocculation effect.
Detailed Description
The present invention will be described in further detail with reference to specific examples. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. In addition, the embodiments of the present invention referred to in the following description are typically only some, but not all, embodiments of the present invention. Therefore, all other embodiments, which can be made by one of ordinary skill in the art without undue burden, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
The raw materials used in the examples of the present invention are all commercially available or available to those skilled in the art unless specifically stated otherwise; the methods used in the examples of the present invention are those known to those skilled in the art unless specifically stated otherwise.
Example 1: a method of preparing a flocculant, the method comprising: 1) According to 1g:10mL:0.1g of Fe 3 O 4 Mixing with water and ammonium tartrate, stirring at 65deg.C for 2 hr to disperse the particles thoroughly to obtain mixed solution,according to 5mL: mixing ethyl silicate and 4-fluoro-phenyl ammonium tetrafluoroborate at a ratio of 1g, and drying at 100deg.C to obtain a mixture per gram of Fe 3 O 4 The mixture was added to the mixed solution at a ratio of 0.35g of the mixture, and the temperature was kept constant at 800℃for 1.5 hours under nitrogen protection to obtain a composite material.
2) According to 10g:9g:2g:100mL of the composite material prepared in the step 1), acrylamide, dimethyl diallyl ammonium chloride and deionized water are respectively weighed and mixed, nitrogen is introduced and continuously stirred, air is removed and the temperature is kept constant for 1h at 30 ℃ until the monomer is dispersed to obtain a dispersion liquid, ammonium persulfate is added into the dispersion liquid according to the proportion of adding 2g of the total mass of each 10g of acrylamide and dimethyl diallyl ammonium chloride, the temperature is kept constant for 6h at 50 ℃, and the mixture is kept still for molding, so that the modified polymer is obtained.
3) 2g:15mL:2.4g: and (3) respectively weighing a modified polymer, dimethylbenzene, polyethylene glycol and a silane coupling agent SiSiSiB@PC1130 in a proportion of 0.3g as raw materials, adding the modified polymer into dimethylbenzene, refluxing for 2 hours at a constant temperature of 80 ℃, adding polyethylene glycol, keeping the temperature at a constant temperature of 110 ℃ for 2 hours, adding the silane coupling agent SiSiSiB@PC1130 after finishing the constant temperature, reacting until the mixture is naturally cooled by using waste heat, removing a solvent by suction filtration, obtaining a flocculant crude product, weighing a proper amount of dimethylbenzene as a cleaning agent, immersing the flocculant crude product, performing ultrasonic immersion washing on the flocculant crude product, and drying to obtain the flocculant.
The flocculant obtained in the example is subjected to performance detection, wherein the detection comprises a decolorizing performance experiment, an oil stain and suspended matter removal performance experiment, a heavy metal ion removal performance experiment and a limit decontamination load rate experiment, and the specific process of the performance characterization experiment is as follows.
1. And (3) simulating wastewater flocculation and decoloration experiments: preparing active brilliant blue KN-R mother liquor with the concentration of 5g/L, diluting the mother liquor by 700 times, measuring absorbance at 593nm, adjusting the absorbance of the solution to 0.06, adding a proper amount of SDS, uniformly stirring, standing overnight, adding 10mg of flocculant into 50mL of active brilliant blue KN-R simulated dye wastewater, and stirring and settling for 3h. Centrifuging the supernatant for 10min, and measuring absorbance at 593nmThe decoloring rate is calculated by the formula: />The method comprises the steps of carrying out a first treatment on the surface of the Wherein: />For decolorizing rate, jatropha curcas L>For the absorbance after treatment, +.>The absorbance before treatment.
2. Oil stain and suspended matter removal performance experiment: the experimental water is wastewater provided by a Xinjiang sewage treatment plant. 10L of slaughter wastewater to be treated is taken, 2g of flocculating agent is added, stirring is carried out for 15min, standing is carried out, the water quality change and the flocculating body formation process are observed, and the flocculating body is sucked by a magnet, so that treated sewage is obtained. According to SY/T5329-94 and GB11902-89, the content of sewage oil and suspended matter before and after treatment is measured, and the removal rate of greasy dirt and suspended matter is calculated.
3. Heavy metal ion removal rate experiment: the experimental water is wastewater provided by a Xinjiang sewage treatment plant. And adding 2g of flocculant into 10L of waste water of a metallurgical plant to be treated, stirring for 15min, absorbing and removing the floccules by using a magnet, measuring the content of heavy metal ions in the waste water before and after treatment by using a Pride ion detector, and calculating the removal rate of the heavy metal ions.
4. Limit decontamination load factor experiment: the experimental water is wastewater provided by a Xinjiang sewage treatment plant. Mixing 10L of slaughter wastewater to be treated and 10L of metallurgical plant wastewater to be treated as excessive water to be treated, adding 0.2g of flocculant, stirring for 15min, sucking the floccule by using a magnet, weighing and recovering the weight of the dry flocculant containing sewage, and calculating the pollution removal limit load rate of the flocculant, wherein the calculation formula of the pollution removal limit load rate is as follows:the method comprises the steps of carrying out a first treatment on the surface of the Wherein: />For decontamination limit load rate->For the weight of the dry soil-containing flocculant after recovery +.>The weight of flocculant used (0.2 g).
The above characterization results are shown in the following table:
according to the results in the table, the flocculant prepared by the invention can be rapidly dissolved in wastewater, has an obvious dispersion process, can effectively decolorize dye liquor, and can remove oil from wastewater with high mineralization degree. When the wastewater containing a large amount of greasy dirt and suspended pollutant such as slaughter wastewater is treated, the flocculant forms stable and large-volume floccules in the wastewater, no particle residue exists, and the oil removal rate is over 99.5 percent. When heavy metal ions and suspended matters coexist in the wastewater, the flocculant adsorbs the heavy metal ions through various mechanisms such as chelation, ion exchange, electrostatic attraction and the like, and the organic matter molecules are agglomerated through adsorption bridging action of molecular chains to form flocculating bodies with larger volumes, so that the organic matter molecules are effectively precipitated. The flocculant prepared by the invention has good flocculation effect.
Meanwhile, in the pollution removal limit load rate experiment, the flocculant of the invention shows extremely high load limit and contains Fe 3 O 4 /SiO 2 The reason for the core-shell structure is that the density is higher, but the ultimate load rate is still extremely high and is close to the ultimate load rate of about 410-430% of the commercially available high-quality polyacrylamide, mainly because the molecular chains are more uniformly dispersed and are not easy to be entangled under the action of the organic-inorganic composite system, and the utilization rate of the actual flocculant is higher, if the mixture of the polyacrylamide and the ferroferric oxide with equal quality is recorded, the commercially available high-quality polyacrylamide is actually soldThe ultimate loading rate of the quality polyacrylamide flocculant is even about 205-215% in theory, and the actual performance is probably lower. Unlike conventional polyacrylamide flocculant, which produces molecular entanglement and agglomeration during use and sometimes produces oversized flocculent mass with the particle size close to 6-10 mm during use, so that pipeline blockage and the like occur during subsequent treatment, the flocculant of the invention keeps the particle size of the produced flocculent mass to 2-3 mm generally even under the action of limited flocculation, and can be separated and removed effectively in a simple and efficient magnetic attraction manner, thereby having extremely high convenience and showing very excellent use effect.
Example 2: a method of preparing a flocculant, the method comprising: 1) According to 1g:10mL:0.1g of Fe 3 O 4 Mixing water and ammonium tartrate, stirring at 65 ℃ for 2 hours to fully disperse the particles to obtain a mixed solution, and mixing according to 5mL: mixing ethyl silicate and 4-fluoro-phenyl ammonium tetrafluoroborate at a ratio of 1g, and drying at 100deg.C to obtain a mixture per gram of Fe 3 O 4 The mixture was added to the mixed solution at a ratio of 0.35g of the mixture, and the temperature was kept constant at 800℃for 1.5 hours under nitrogen protection to obtain a composite material.
2) According to 10g:9g:2g:100mL of the composite material prepared in the step 1), acrylamide, dimethyl diallyl ammonium chloride and deionized water are respectively weighed and mixed, nitrogen is introduced and continuously stirred, air is removed and the temperature is kept constant for 1h at 30 ℃ until the monomer is dispersed to obtain a dispersion liquid, ammonium persulfate is added into the dispersion liquid according to the proportion of adding 2g of the total mass of each 10g of acrylamide and dimethyl diallyl ammonium chloride, the temperature is kept constant for 5h at 60 ℃, and the mixture is kept still for molding, so that the modified polymer is obtained.
3) 2g:15mL:2.4g: and (3) respectively weighing a modified polymer, dimethylbenzene, polyethylene glycol and a silane coupling agent SiSiSiB@PC1130 in a proportion of 0.3g as raw materials, adding the modified polymer into dimethylbenzene, refluxing for 2 hours at a constant temperature of 80 ℃, adding polyethylene glycol, keeping the temperature at a constant temperature of 110 ℃ for 2 hours, adding the silane coupling agent SiSiSiB@PC1130 after finishing the constant temperature, reacting until the mixture is naturally cooled by using waste heat, removing a solvent by suction filtration, obtaining a flocculant crude product, weighing a proper amount of dimethylbenzene as a cleaning agent, immersing the flocculant crude product, performing ultrasonic immersion washing on the flocculant crude product, and drying to obtain the flocculant.
The flocculant obtained in this example was subjected to performance detection and the characterization results are shown in the following table:
according to the results in the table, the high temperature in this example promotes the decomposition of the initiator, more free radicals are generated, particles with smaller size and low molecular weight are obtained, the water solubility is improved, and meanwhile, the material has rich holes and rich adsorption active sites. Therefore, the flocculant is quickly dissolved, so that the floccules in the water body are tightly clustered and quickly settled, and furthermore, the characterization shows that the flocculant prepared by the method shows higher decolorizing rate and better settling property, and the flocculant further shows higher dirt removal limit load rate due to more uniform molecular chain dispersion, so that the flocculation effect is improved.
Example 3: a method of preparing a flocculant, the method comprising: 1) According to 1g:10mL:0.1g of Fe 3 O 4 Mixing water and ammonium tartrate, stirring at 65 ℃ for 2 hours to fully disperse the particles to obtain a mixed solution, and mixing according to 5mL: mixing ethyl silicate and 4-fluoro-phenyl ammonium tetrafluoroborate at a ratio of 1g, and drying at 100deg.C to obtain a mixture per gram of Fe 3 O 4 The mixture was added to the mixed solution at a ratio of 0.35g of the mixture, and the temperature was kept constant at 800℃for 1.5 hours under nitrogen protection to obtain a composite material.
2) According to 10g:9g:2g:100mL of the composite material prepared in the step 1), acrylamide, dimethyl diallyl ammonium chloride and deionized water are respectively weighed and mixed, nitrogen is introduced and continuously stirred, air is removed and the temperature is kept constant for 1h at 30 ℃ until the monomer is dispersed to obtain a dispersion liquid, ammonium persulfate is added into the dispersion liquid according to the proportion of adding 2g of the total mass of each 10g of acrylamide and dimethyl diallyl ammonium chloride, the temperature is kept constant for 4h at 70 ℃, and the mixture is kept still for molding, so that the modified polymer is obtained.
3) 2g:15mL:2.4g: and (3) respectively weighing a modified polymer, dimethylbenzene, polyethylene glycol and a silane coupling agent SiSiSiB@PC1130 in a proportion of 0.3g as raw materials, adding the modified polymer into dimethylbenzene, refluxing for 2 hours at a constant temperature of 80 ℃, adding polyethylene glycol, keeping the temperature at a constant temperature of 110 ℃ for 2 hours, adding the silane coupling agent SiSiSiB@PC1130 after finishing the constant temperature, reacting until the mixture is naturally cooled by using waste heat, removing a solvent by suction filtration, obtaining a flocculant crude product, weighing a proper amount of dimethylbenzene as a cleaning agent, immersing the flocculant crude product, performing ultrasonic immersion washing on the flocculant crude product, and drying to obtain the flocculant.
The flocculant obtained in this example was subjected to performance detection and the characterization results are shown in the following table:
according to the results in the above table, this example further increases the initiation reaction temperature, and at this time, the polymerization rate of the two monomers is too high, which not only causes side reactions, but also causes excessive polymerization degree, which causes long chain entanglement, and not only makes it difficult to control the polymerization structure, but also causes uneven distribution of long chains, and the intermolecular bridging effect is weakened, thereby affecting the sedimentation of the contaminant molecules by the flocculant. Although the flocculant of the example has reduced sedimentation performance on pollutant molecules, the flocculant can still exert good flocculation effect in a short time, and the flocculant has good prospect in the field of sewage treatment.
From examples 1 to 3, it is understood that the reaction temperature has a certain influence on the decomposition rate and the radical number of the initiator, and thus, attention should be paid to control the reaction temperature during the preparation.
In addition, a 20-group water sample test group is arranged to represent the ion concentration in the solution system before and after the flocculant treatment and the average particle diameter of filter residues so as to represent the average particle diameter of agglomerated particles in the sample liquid, and the average particle diameter of the agglomerated particles is found to be in a micron level and is increased by 60-80%. The flocculant can prolong the nucleation induction time of the crystal and cause lattice distortion to pollutants, a metal center attracts pollutant ions through a charge neutralization effect, and a branched chain structure can destroy the intermolecular acting force of the pollutants, is adsorbed on the pollutant molecules, occupies the active sites of the crystal lattice and prevents the crystal from growing. The complexing agent has better complexing capability on pollutant molecules.
Comparative example 1: a method of preparing a flocculant, the method comprising: 1) According to 1g:10mL:0.1g of Fe 3 O 4 Mixing water and ammonium tartrate, stirring at 65 ℃ for 2 hours to fully disperse the particles to obtain a mixed solution, and mixing according to 5mL: mixing ethyl silicate and 4-fluoro-phenyl ammonium tetrafluoroborate at a ratio of 1g, and drying at 100deg.C to obtain a mixture per gram of Fe 3 O 4 The mixture was added to the mixed solution at a ratio of 0.35g of the mixture, and the temperature was kept constant at 800℃for 1.5 hours under nitrogen protection to obtain a composite material.
2) 2g:15mL:2.4g: the preparation method comprises the steps of respectively weighing a composite material, dimethylbenzene, polyethylene glycol and a silane coupling agent SiSiSiB@PC1130 in a proportion of 0.3g, adding the modified polymer into the dimethylbenzene, refluxing for 2 hours at a constant temperature of 80 ℃, adding the polyethylene glycol, keeping the temperature at a constant temperature of 110 ℃ for 2 hours, adding the silane coupling agent SiSiB@PC1130 after the constant temperature is finished, reacting the mixture until the mixture is naturally cooled by waste heat, filtering to remove a solvent, obtaining a flocculant crude product, weighing a proper amount of dimethylbenzene as a cleaning agent, immersing the flocculant crude product, performing ultrasonic immersion washing on the flocculant crude product, and drying the flocculant to obtain the flocculant.
The flocculant obtained in this example was subjected to performance detection and the characterization results are shown in the following table:
according to the results in the above table, this example is for Fe only 3 O 4 /SiO 2 The composite material is modified, and the flocculant obtained by modifying the composite material has rich adsorption active sites, but the flocculantThe complexing effect of the flocculant on pollutant molecules is poor, the dispersibility of the flocculant in wastewater is poor, the adsorption capacity of the flocculant on pollutant small molecules is poor, and the pollution removal limit load rate is greatly reduced. If a good flocculation effect is to be achieved, more flocculant is required to be added, the bonding strength of the agglomerates is poor, and a large amount of agglomerates and flocculant still remain in the water body after filtration. In addition, from the viewpoint of the pollution-removing limit load rate, the pollution-removing limit load rate of the inorganic system flocculant is very low, and the pollution-removing limit load rate is about 260% and far less than the flocculant compositely constructed by the invention, wherein the pollution-removing limit load rate is mixed with the commercial high-quality polyacrylamide flocculant according to the mass ratio. The method shows that the organic and inorganic systems are coordinated and matched after the preparation in a specific mode, and the inorganic system part regulates and controls the organic molecular chains while realizing pollutant load, so that the load rate of the organic molecular chains is further improved.
Comparative example 2: a method of preparing a flocculant, the method comprising: 1) According to 9g:2g:100mL of acrylamide, dimethyl diallyl ammonium chloride and deionized water are respectively weighed and mixed, nitrogen is introduced and stirring is continuously carried out, air is removed, the temperature is kept at 30 ℃ for 1h until monomer is dispersed to obtain a dispersion liquid, ammonium persulfate is added into the dispersion liquid according to the proportion of adding 2g of the total mass of each 10g of acrylamide and dimethyl diallyl ammonium chloride, the temperature is kept at 60 ℃ for 5h, and the modified high polymer is obtained after standing and molding.
2) 2g:15mL:2.4g: and (3) respectively weighing a modified polymer, dimethylbenzene, polyethylene glycol and a silane coupling agent SiSiSiB@PC1130 in a proportion of 0.3g as raw materials, adding the modified polymer into dimethylbenzene, refluxing for 2 hours at a constant temperature of 80 ℃, adding polyethylene glycol, keeping the temperature at a constant temperature of 110 ℃ for 2 hours, adding the silane coupling agent SiSiSiB@PC1130 after finishing the constant temperature, reacting until the mixture is naturally cooled by using waste heat, removing a solvent by suction filtration, obtaining a flocculant crude product, weighing a proper amount of dimethylbenzene as a cleaning agent, immersing the flocculant crude product, performing ultrasonic immersion washing on the flocculant crude product, and drying to obtain the flocculant.
The flocculant obtained in this example was subjected to performance detection and the characterization results are shown in the following table:
according to the results in the table, the polyacrylamide-polydimethyl diallyl ammonium chloride carrier is only modified, and the flocculant can remove greasy dirt, but on one hand, the flocculant adsorption sites are insufficient, long chains are easy to tangle, so that the viscosity of a water body is overlarge, on the other hand, the attraction capability of heavy metal ions is insufficient, sufficient negative charge is not available for neutralizing positive charges carried by pollutant ions, electrostatic repulsive force between pollutant molecules is large, pollutant particles exist stably, and effective adsorption sedimentation cannot be performed. The effect is significantly reduced in terms of suspended matter removal. It can also be seen that the soil release limit loading of the polyacrylamide system exhibits excellent performance, which is relatively higher than the flocculant system claimed in the present invention, as expected.
Comparative example 3: a method of preparing a flocculant, the method comprising: 1) According to 1g:10mL:0.1g of Fe 3 O 4 Mixing water and ammonium tartrate, stirring at 65 ℃ for 2 hours to fully disperse the particles to obtain a mixed solution, and mixing according to 5mL: mixing ethyl silicate and 4-fluoro-phenyl ammonium tetrafluoroborate at a ratio of 1g, and drying at 100deg.C to obtain a mixture per gram of Fe 3 O 4 The mixture was added to the mixed solution at a ratio of 0.35g of the mixture, and the temperature was kept constant at 800℃for 1.5 hours under nitrogen protection to obtain a composite material.
2) According to 10g:9g:100mL of the composite material prepared in the step 1), acrylamide and deionized water are respectively weighed and mixed, nitrogen is introduced and stirring is continuously carried out, air is removed and the temperature is kept at 30 ℃ for 1h until the monomer is dispersed to obtain a dispersion liquid, ammonium persulfate is added into the dispersion liquid according to the proportion of adding 2g of the ammonium persulfate into every 10g of acrylamide, the temperature is kept at 60 ℃ for 5h, and the modified high polymer is obtained after standing and molding.
3) 2g:15mL:2.4g: and (3) respectively weighing a modified polymer, dimethylbenzene, polyethylene glycol and a silane coupling agent SiSiSiB@PC1130 in a proportion of 0.3g as raw materials, adding the modified polymer into dimethylbenzene, refluxing for 2 hours at a constant temperature of 80 ℃, adding polyethylene glycol, keeping the temperature at a constant temperature of 110 ℃ for 2 hours, adding the silane coupling agent SiSiSiB@PC1130 after finishing the constant temperature, reacting until the mixture is naturally cooled by using waste heat, removing a solvent by suction filtration, obtaining a flocculant crude product, weighing a proper amount of dimethylbenzene as a cleaning agent, immersing the flocculant crude product, performing ultrasonic immersion washing on the flocculant crude product, and drying to obtain the flocculant.
The flocculant obtained in this example was subjected to performance detection and the characterization results are shown in the following table:
according to the results in the above table, fe in this example 3 O 4 /SiO 2 The particles are only grafted with amide chains, but not formed into amide-ammonium long chains, so that the structural branching characteristics are not obvious enough, the chain entanglement phenomenon is obvious, active groups are difficult to play a role, the complexation effect on pollutant molecules is weakened, and components such as aromatic compounds, sulfur, phenol and the like still exist in a large quantity. After the flocculant is put into a water body, the increase of the viscosity of the water body can be obviously measured, the dispersibility of the floccule is poor, the floccule is quickly agglomerated and sunk, and the poor flocculation effect is caused. In addition, the actual dirt removal limit load rate is lower due to the viscosity increase and rapid precipitation. The pollution-removing limit load rate depends on the adsorbable load limit of the material, and depends on the effective dispersivity of the material in a sewage system, and the two are complementary to each other.
Comparative example 4: a method of preparing a flocculant, the method comprising: 1) According to 1g:10mL:0.1g of Fe 3 O 4 Mixing water and ammonium tartrate, stirring at 65 ℃ for 2 hours to fully disperse the particles to obtain a mixed solution, and mixing according to 5mL: mixing ethyl silicate and 4-fluoro-phenyl ammonium tetrafluoroborate at a ratio of 1g, and heating to 100deg.CDrying under mild conditions to obtain a mixture, wherein the mixture is prepared according to each gram of Fe 3 O 4 The mixture was added to the mixed solution at a ratio of 0.35g of the mixture, and the temperature was kept constant at 800℃for 1.5 hours under nitrogen protection to obtain a composite material.
2) According to 10g:9g:2g:100mL of the composite material prepared in the step 1), acrylamide, dimethyl diallyl ammonium chloride and deionized water are respectively weighed and mixed, nitrogen is introduced and continuously stirred, air is removed and the temperature is kept constant for 1h at 30 ℃ until the monomer is dispersed to obtain a dispersion liquid, ammonium persulfate is added into the dispersion liquid according to the proportion of adding 2g of the total mass of each 10g of acrylamide and dimethyl diallyl ammonium chloride, the temperature is kept constant for 2h at 60 ℃, and the mixture is kept still for molding, so that the modified polymer is obtained.
3) 2g:15mL:2.4g: and (3) respectively weighing a modified polymer, dimethylbenzene, polyethylene glycol and a silane coupling agent SiSiSiB@PC1130 in a proportion of 0.3g as raw materials, adding the modified polymer into dimethylbenzene, refluxing for 2 hours at a constant temperature of 80 ℃, adding polyethylene glycol, keeping the temperature at a constant temperature of 110 ℃ for 2 hours, adding the silane coupling agent SiSiSiB@PC1130 after finishing the constant temperature, reacting until the mixture is naturally cooled by using waste heat, removing a solvent by suction filtration, obtaining a flocculant crude product, weighing a proper amount of dimethylbenzene as a cleaning agent, immersing the flocculant crude product, performing ultrasonic immersion washing on the flocculant crude product, and drying to obtain the flocculant.
The flocculant obtained in this example was subjected to performance detection and the characterization results are shown in the following table:
from the results in the above table, it can be seen that the flocculant prepared in this example has significantly reduced decolorization rate, because too short a time would result in a small conversion of the monomers in the polymerization reaction, incomplete reaction, insufficient chain length, and poor complexation with contaminant molecules. The ion concentration and the average particle diameter of filter residues in the solution system before and after the flocculant treatment are characterized, and the average particle diameter of agglomerated particles is only increased by 10-20%, so that the sedimentation effect of the flocculant is poor.
In addition, the inventor experiments find that too long polymerization time causes too small pore diameter of the polymer, and products which continue to polymerize block a part of pores to influence the permeability of the composite material, thereby influencing the adsorption performance.
Claims (9)
1. A method of preparing a flocculant, the method comprising: 1) Taking metal oxide, adding water and a stabilizer, heating, adding a mixture, wherein the mixture consists of ethyl silicate and 4-fluoro-phenyl ammonium tetrafluoroborate, and performing heat treatment to obtain a composite material; 2) Mixing the composite material, the monomer and water, heating and reacting in a protective atmosphere until the monomer is dispersed, adding an initiator, reacting, standing and forming to obtain a modified polymer; 3) Adding the modified high polymer into an organic solvent, heating and refluxing, adding grafted organic matters, heating and refluxing, adding a coupling agent, cooling, washing a product with the organic solvent, and performing suction filtration and drying to obtain the flocculant.
2. The method for preparing a flocculant according to claim 1, wherein in step 1) the metal oxide is Fe 3 O 4 The method comprises the steps of carrying out a first treatment on the surface of the The stabilizer in the step 1) is ammonium tartrate; the dosage ratio of the metal oxide, the water and the stabilizer in the step 1) is 1g: (8-13) mL: (0.1-0.2) g; the heating temperature is controlled to be 65-75 ℃ in the heating process of the step 1), the heating time is 1-2 h, and stirring is continuously carried out in the heating process.
3. A method of preparing a flocculant according to claim 1 or 2, wherein in step 1) the mixture is prepared from ethyl silicate and 4-fluoro-phenyl ammonium tetrafluoroborate in the following (5-10) mL: mixing the materials according to the dosage ratio of 1g, and then performing constant temperature treatment at the temperature of 90-100 ℃ until the materials are dried to obtain a mixture; the dosage of the mixture in the step 1) is 0.2 to 0.5g/g of metal oxide; the heat treatment process in the step 1) is carried out in a protective atmosphere, and the heat treatment is carried out for 1 to 2 hours at the temperature of 780 to 820 ℃.
4. The method for preparing a flocculant according to claim 1, wherein the monomer in the step 2) is a mixture of acrylamide and dimethyldiallylammonium chloride, and the mass ratio of the acrylamide to the dimethyldiallylammonium chloride is (4-5): 1, a step of; the dosage ratio of the composite material, the monomer and the water in the step 2) is 1g: (0.8-1.2) g: (4-18) mL; and 2) controlling the reaction temperature to be 30-40 ℃ and the reaction time to be 0.5-1.0 h in the heating reaction process.
5. The method for preparing a flocculant according to claim 1 or 4, wherein the initiator in the step 2) is ammonium persulfate, and the ammonium persulfate dosage is 0.1-0.4 g/g monomer; and 2) controlling the temperature of the reaction process after the initiator is added in the step 2) to be 50-70 ℃ and the reaction time to be 4-6 h.
6. The method for preparing a flocculant according to claim 1, wherein the organic solvent in the step 3) is xylene, and the dosage of the xylene is 1-10 mL/g modified polymer; and 3) controlling the reaction temperature to be 80-90 ℃ and the reaction time to be 1-2 h in the heating reflux process.
7. The method for preparing a flocculant according to claim 1 or 6, wherein the grafted organic matter in step 3) is polyethylene glycol, and the dosage is 1.1-1.3 g/g modified polymer; and 3) controlling the reaction temperature to be 110-120 ℃ and the reaction time to be 1-2 h in the heating reflux process.
8. The method for preparing a flocculant according to claim 1, wherein the coupling agent in the step 3) is a silane coupling agent, and the amount of the silane coupling agent is 0.1-0.3 g/g modified polymer, and the silane coupling agent is added and reacted by means of waste heat.
9. A flocculant produced by the method of any one of claims 1 to 8.
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