CN113603197A - Preparation method and application of flocculating agent for water body treatment - Google Patents
Preparation method and application of flocculating agent for water body treatment Download PDFInfo
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- CN113603197A CN113603197A CN202110829832.4A CN202110829832A CN113603197A CN 113603197 A CN113603197 A CN 113603197A CN 202110829832 A CN202110829832 A CN 202110829832A CN 113603197 A CN113603197 A CN 113603197A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910001868 water Inorganic materials 0.000 title claims abstract description 66
- 239000008394 flocculating agent Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 28
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 28
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 239000004113 Sepiolite Substances 0.000 claims description 24
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- 239000000243 solution Substances 0.000 claims description 22
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229960000892 attapulgite Drugs 0.000 claims description 7
- 229910052625 palygorskite Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000440 bentonite Substances 0.000 claims description 5
- 229910000278 bentonite Inorganic materials 0.000 claims description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 5
- 239000010865 sewage Substances 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000005067 remediation Methods 0.000 claims 6
- 238000005189 flocculation Methods 0.000 abstract description 14
- 230000016615 flocculation Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 230000015271 coagulation Effects 0.000 abstract description 3
- 238000005345 coagulation Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000008400 supply water Substances 0.000 abstract description 2
- 230000001687 destabilization Effects 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 7
- 239000004927 clay Substances 0.000 description 6
- 150000003608 titanium Chemical class 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000004021 humic acid Substances 0.000 description 3
- 239000000413 hydrolysate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
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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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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a preparation method and application of a flocculating agent for water treatment. And dropwise adding the obtained mixed solution B into the mixed solution A at the dropping speed of 1mL/min, and stirring at the speed of 500rpm/min to obtain a mixed solution C. And drying the mixed liquor C until the weight of the mixed liquor C is not changed, thus obtaining the composite flocculant. The flocculant has good effects of removing turbidity and reducing pollutants in flocculation treatment of water, can realize rapid destabilization and coagulation of suspended matters in the water, and improves the transparency of the water. The flocculant can be widely applied to turbidity removal and pollutant removal in water supply and wastewater, is simple and rapid to prepare, has good repeatability, is easy for quantitative production, and has excellent coagulation performance, low residual metal and good precipitation performance.
Description
Technical Field
The invention relates to a preparation method and application of a flocculating agent for water treatment, and belongs to the technical field of water treatment.
Background
With the rapid development of economy in China, the urbanization development rate is continuously accelerated, so that the production and domestic water is greatly increased, and the discharge amount of industrial wastewater and domestic sewage is increasingly increased. Due to the imperfect sewage treatment facilities, a large amount of untreated sewage is discharged into the surrounding water body, which causes the deterioration of the water quality of rivers and lakes, and a large amount of water environment problems occur, such as: the generation of black and odorous water, the outbreak of blue algae bloom and the like. The flocculation is a common technology in water treatment and restoration, and is to put a flocculating agent into water to remove solid matters and suspended matters in the water by utilizing the colloid chemical property of the flocculating agent, wherein the common flocculating agent comprises polyaluminium chloride (PAC), ferric chloride (FeCl3), Polyacrylamide (PAM) and the like.
The flocculating agent is one of the important factors influencing the flocculating effect, and at present, according to the components of the flocculating agent, the flocculating agent is divided into three categories, namely: inorganic flocculants, organic flocculants, and biological flocculants. Aluminum salt and iron salt flocculants have been studied extensively in the past decades, but have had major problems in their use. As early as 1937, Upton and busswell first used titanium salts as flocculants for treating wastewater containing fluorine in water treatment processes, which found that titanium salts had excellent decolorizing capacity. Research shows that titanium salt, aluminum salt and iron salt have good flocculation effect, and the sludge after titanium salt flocculation is calcined to produce photocatalyst titanium dioxide (TiO 2).
Clay minerals are a class of natural silicate materials consisting of aluminum-silicon layered structures, such as kaolin, sepiolite, montmorillonite, and the like; due to its layered structure, clay has a large specific surface area and a large amount of negative charges on the surface. The clay flocculation method has the advantages of low cost and high removal rate, and in addition, the clay minerals are widely applied to the water pollution treatment, such as the removal of heavy metals in water, the adsorption of organic pollutants and the like, and are a potential effective method applied to water treatment. In the flocculation process, the addition of the sepiolite can increase the volume of the floc and accelerate the sedimentation rate. Therefore, the method provides a new idea for preparing the clay modified flocculant.
At present, the titanium salt flocculant has high manufacturing cost and cannot be applied to production and life in large quantity, so that a manufacturing method which is high in efficiency and can ensure cost reduction is of great importance.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the existing problems and defects, the invention aims to provide a preparation method and application of a flocculant for water body treatment.
The technical scheme is as follows: in order to realize the purpose, the invention adopts the following technical scheme:
a flocculating agent for water body treatment is characterized in that: the raw material formula a comprises titanium tetrachloride/polymeric titanium tetrachloride, ethanol/isopropanol/n-propanol and acetylacetone, and the weight ratio of each component is 1: (0-15): (0-1) in the ratio.
Further, the weight ratio of the titanium tetrachloride/polymeric titanium tetrachloride, ethanol/isopropanol/n-propanol and acetylacetone is 1: 1.6: 0.09.
further, the volume ratio of the solution of titanium tetrachloride is 99%, and the volume ratio of the solution of ethanol is 95%.
Further, the polymerized titanium tetrachloride had an OH/Ti molar ratio of 3 and a solution volume ratio of isopropanol or n-propanol of 99%.
Further, the raw material formula b comprises ethanol/isopropanol/n-propanol, sepiolite/attapulgite/bentonite, deionized water and acetic acid/hydrochloric acid, wherein the components are in a weight ratio (0-10): (0-5): (0-10): (0-1) mixing.
Further, the weight ratio of each component of ethanol/isopropanol/n-propanol, sepiolite, deionized water and acetic acid/hydrochloric acid is 1: 0.1: 0.5: 0.2.
further, the volume ratio of the ethanol solution is 95%, the volume ratio of the isopropanol or n-propanol solution is 99%, the resistivity of the deionized water is 18.25M omega, the volume ratio of the acetic acid solution is 99.5%, and the volume ratio of the hydrochloric acid solution is 36% -38%.
A preparation method of a flocculating agent for water body treatment comprises the following steps:
step 1: stirring and mixing the raw material formula a according to claims 1 to 4 at a speed of 500rpm/min at 20-30 ℃, with the increase of alkalization degree, taking ethanol/isopropanol/n-propanol as a solvent, carrying out polymerization reaction on titanium tetrachloride/polymerized titanium tetrachloride, then decomposing, slowing down hydrolysis reaction by acetylacetone in the reaction process, generating a plurality of functional groups, providing binding sites, and obtaining a mixed solution A;
step 2: mixing the raw materials according to the formula B of claims 5 to 7, and adding sepiolite/attapulgite/bentonite for coating to obtain a mixed solution B;
and step 3: dropwise adding the mixed solution B obtained in the step 2 into the mixed solution A obtained in the step 1 at the dropping speed of 1mL/min, stirring at the speed of 500rpm/min, and obtaining a mixed solution C by a sol-gel method;
and 4, step 4: and drying the mixed liquor C until the weight of the mixed liquor C is not changed, thus obtaining the composite flocculant.
Further, the drying in the step 4 is natural drying or drying in a vacuum environment at 70-80 ℃.
Use of a flocculant for water treatment obtained according to any one of the methods of claims 1 to 9 in sewage treatment.
Has the advantages that: compared with the prior art, the invention has the following advantages: the method is a novel method for preparing the flocculating agent for water treatment, can be widely applied to turbidity removal and pollutant removal in water supply and wastewater, and has the advantages of simple and rapid preparation, good repeatability, easy quantitative production, excellent coagulation performance, low residual metal and good precipitation performance.
Drawings
FIG. 1 is a scanning electron micrograph of example 1 of the present invention;
in the figure: when the flocculant is not modified, the flocculant is modified,
FIG. 2 is a diagram of an energy spectrum analyzer according to embodiment 1 of the present invention;
FIG. 3 is a graph showing the turbidity removal rate in example 2 of the present invention;
FIG. 4 is the present inventionUV of Bright example 2254A removal rate diagram;
FIG. 5 is a schematic diagram of the pH of example 2 of the present invention in an experiment;
FIG. 6 is a schematic of turbidity as a function of time in a water sample according to example 3 of the present invention;
figure 7 is a schematic representation of the SRP over time in a water sample according to example 3 of the present invention.
Detailed Description
The present invention is further illustrated by the following figures and specific examples, which are to be understood as illustrative only and not as limiting the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalent modifications thereof which may occur to those skilled in the art upon reading the present specification.
As shown in fig. 1, a method for preparing a flocculant for water body treatment is verified by the following examples:
example 1
Preparing a composite flocculant: firstly, preparing a titanium tetrachloride solution, ethanol and acetylacetone mixed solution, taking 1kg of titanium tetrachloride with the solution volume ratio of 99%, and 1.6kg of ethanol with the solution volume ratio of 95%; 0.09kg of acetic acid having a solution volume ratio of 99.5% was stirred at 500rpm/min for 30min to obtain a mixed solution A. 1kg of ethanol with the solution volume ratio of 95%, 0.1kg of sepiolite, 0.5kg of deionized water with the resistivity of 18.25M omega and 0.2kg of acetic acid with the solution volume ratio of 99.5% or hydrochloric acid with the solution volume ratio of 36% -38% are taken and evenly mixed to obtain mixed liquid B. The mixed solution B was dropped into the mixed solution A, followed by stirring at a rate of 500rpm/min for 90min to obtain a mixed solution C. And drying the mixed solution C at 70-80 ℃ to constant weight to obtain the natural clay composite flocculant, namely TXC-SE.
The titanium tetrachloride is rich in products during the hydrolysis process and is summarized as [ TixOy (OH) zCln (H2O) m ] (4x-2y-z-n) +. In the preparation process of the polymerized titanium tetrachloride, titanium tetrachloride is used as a raw material, and under the alkalinity, the titanium tetrachloride is hydrolyzed, polymerized and then decomposed. Compared with a titanium hydrolysate produced by prehydrolysis of titanium tetrachloride, the polymerized titanium tetrachloride solution is stable, the raw material cost is low, but both the titanium hydrolysate and the titanium hydrolysate have over-fast hydrolysis phenomena in different degrees, and acetylacetone plays a role in relieving the over-fast hydrolysis, forms a multifunctional group, is beneficial to controllable hydrolysis and provides a plurality of binding sites for pollutants. In addition, in consideration of practical application, the price of the titanium salt is higher, and a physical modification mode is adopted, so that a higher flocculation effect is ensured, and the reduction of the pollutant content can be promoted to a certain degree. Dispersing or dissolving easily hydrolysable substances such as titanium tetrachloride or polymeric titanium tetrachloride and polymers such as acetylacetone in solvents such as ethanol and the like to serve as a matrix of the polymer composite material, adding inorganic filler dispersed phases such as clay and the like, and acting for a period of time under certain conditions to obtain the inorganic-organic composite material. The inorganic filler in the embodiment is mainly a natural phyllosilicate clay mineral, such as attapulgite, bentonite, sepiolite and the like. The method can directly realize the coating of the polymer and the sepiolite, and the sepiolite after organic treatment can improve the affinity of the sepiolite and the polymer and improve the performance of the polymer. In the use of the flocculant, the raw material cost is reduced, the adsorption effect is increased, and the flocculant is effective for a long time.
The TXC-SE is observed through a scanning electron microscope and an energy spectrum analyzer (EVO18) to obtain a sample characterization of the generated composite flocculant, and the scanning electron microscope result is shown in figure 1, wherein in figure 1(a), due to the three-dimensional steric bond structure and Si-O-Si bonds of the sepiolite, most of the chemical compositions and structures of the sepiolite are illustrated, the mineral has enough cations and can basically fill 8 (7.74-8.14) octahedral positions. Therefore, most of the cations in the octahedral sites of sepiolite are large cations and the smaller Al ions are relatively small, unlike other minerals such as attapulgite, in which half of the octahedral sites are typically filled with Al ions. Because the forming environment of sepiolite is more alkaline than attapulgite, in such an environment, Si and Mg are highly enriched, while the content of Al is low. As shown in fig. 1(b), the TXC is in a block shape, and the surface of the TXC is wrapped by a large amount of granular substances and is uneven. The flocculant is prepared by adopting a sol-gel method, and sepiolite is attached to the surface of the Ti complex to form the special structure. As is obvious from a scanning electron microscope picture 1(c) of TXC-SE, a large amount of sepiolite rod-shaped fiber structures are attached to the surfaces of the particles, which shows that in the ethanol evaporation process, sepiolite is attached to the flocculated surfaces to form a special natural clay-titanium-based flocculant composite structure. The sepiolite has the characteristics of pure nature, no toxicity, no odor, no asbestos, no radioactivity and the like, can adsorb pollutants in a water body when being loaded on the surface of the flocculating agent, and plays a role in reducing the cost.
The results of the energy spectrum analyzer are shown in fig. 2, and the TXC-SE energy spectrum line scanning graph shows that the percentage content of silicon (Si) and magnesium (Mg) elements in the whole material is obviously increased at the area A, and the sepiolite is aqueous magnesium-rich silicate mineral with a layer chain structure, and when the sepiolite is loaded on the flocculating agent, the content of Mg and Si is further increased. The energy spectrum linear scanning further verifies that the sepiolite can be loaded on the surface of the flocculant by adopting a sol-gel method to form the natural clay composite flocculant.
Example 2
(1) Preparing a simulation experiment water sample: the humic acid-kaolin mixed water sample is used as an experimental simulation water sample and is prepared according to the following method: firstly, weighing 1g of humic acid, fixing the volume to 1L, and preparing a humic acid stock solution with the concentration of 1 g/L. Accurately weighing 5g of kaolin, sequentially adding a proper amount of deionized water and 50ml of humic acid stock solution, and fixing the volume to 1L to obtain a humic acid-kaolin simulated water sample. The initial water quality indexes of the simulated water sample are as follows: turbidity is 40 ± 0.5NTU, UV254 is 0.2 ± 0.01cm-1, pH is 7.85-8.24.
(2) Flocculation experiment steps: placing six beakers containing 1L of experimental water sample on a stirrer, adding a known amount of flocculant, and quickly stirring at the rotating speed of 250rpm/min for 5 min; then, the stirring speed was changed to 50rpm/min, and after stirring was continued for 15min, the mixture was allowed to stand for 30 min. Sampling at 2cm below water surface, and measuring related water quality index.
The turbidity removal rate calculation formula is as follows:
turbidity removal rate (%) - (initial turbidity-residual turbidity)/initial turbidity 100
The UV254 removal rate calculation formula is as follows:
UV254 removal (%) (initial UV 254-residual UV 254)/initial UV254 x 100
Experimental example 2 analysis of results:
various indexes of the water sample treated by adding different flocculants in the embodiment 2 are detected by adopting a turbidity meter, an ultraviolet spectrophotometer and a portable handheld pH meter, and the flocculation effect is shown in figure 3, figure 4 and figure 5.
As can be seen from fig. 3, 4 and 5, the composite flocculant prepared by the method of the present application has the best effect of removing turbidity and reducing organic matters and has stable effluent pH value under the condition of the same flocculant adding amount. The turbidity removal rate is up to 98.52%, and the UV254 removal rate is up to 100%.
Example 3
The black and odorous water sample collected in a certain black and odorous river channel in Nanjing is treated by the prepared composite flocculant, and the water quality parameters are shown in Table 1
TABLE 1 Black odorous Water sample Water quality parameters
Flocculation experiment steps: the sampling is respectively collected to cover water and bottom mud in the river channel, the collected bottom mud is sieved to remove large particles and benthonic animals and then is fully and uniformly mixed, then the mixture is arranged in 6 organic glass columns of 8 x 70cm, the height of the bottom mud is 15cm, the collected cover water is added from the upper end of the organic glass columns, and the experiment is carried out after the mixture is stabilized for two weeks. One group was the experimental group, treated with flocculant, and one group was the control group without any treatment. After the column sample was stabilized, samples were taken from 2cm below the water surface (surface layer). Before the experiment, the corresponding blank water quality index is measured, and then the same amount of flocculant (100m/l) is added into the experimental group. After a series of flocculation processes, within 30 days, the corresponding index change of the overlying water is measured, the flocculation effect of the composite flocculant is evaluated, the change of the water quality index along with the time is observed, and the stability of the water sample after flocculation treatment is evaluated.
Experimental example 3 analysis of results:
in this example 3, a flocculating agent is added into a water sample to observe the change of turbidity and SRP in the water sample with time, and the results are shown in fig. 6 and 7. The turbidity decreased gradually in both the experimental and control groups. After standing for one day, the turbidity of the control group water sample is 18NTU, the turbidity reduction is not obvious, the turbidity removal rate is 0%, the turbidity of the experimental group water sample is 3NTU, the turbidity is rapidly reduced, and the removal rate reaches 53.54%.
The SRP at different depths in both experimental and control groups decreased with time. After the control surface water sample SRP is flocculated and stirred, the SRP is released due to the disturbance of surface sediment, the concentration is increased to 0.72mg/l, the concentration is 0.35mg/l at the end of the experiment, and the maximum removal rate is 52.88%. When the experiment is started, the concentration of the SRP of the surface water sample of the experimental group reaches 0.71mg/l, the concentration of the SRP is gradually reduced to reach 0.04mg/l through a series of flocculation processes, and the maximum removal rate reaches 95.06%. Therefore, the method can finally achieve the characteristics of cost reduction, high adsorbability, raw material cost reduction and long-term effectiveness.
Claims (10)
1. A flocculating agent for water body treatment is characterized in that: the raw material formula a comprises titanium tetrachloride/polymeric titanium tetrachloride, ethanol/isopropanol/n-propanol and acetylacetone, and the weight ratio of each component is 1: (0-15): (0-1) in the ratio.
2. The flocculant for water body remediation according to claim 1, wherein: the weight ratio of the titanium tetrachloride to the polymeric titanium tetrachloride to the ethanol to the isopropanol to the n-propanol to the acetylacetone is 1: 1.6: 0.09.
3. the flocculant for water body remediation according to claim 1, wherein: wherein the volume ratio of the titanium tetrachloride solution is 99 percent, and the volume ratio of the ethanol solution is 95 percent.
4. The flocculant for water body remediation according to claim 1, wherein: the molar ratio of OH/Ti of the polymerized titanium tetrachloride was 3 and the volume ratio of the solution of isopropanol or n-propanol was 99%.
5. The flocculant for water body remediation according to claim 1, wherein: the raw material formula b comprises ethanol/isopropanol/n-propanol, sepiolite/attapulgite/bentonite, deionized water and acetic acid/hydrochloric acid, wherein the components are in a weight ratio of (0-10): (0-5): (0-10): (0-1) mixing.
6. The flocculant for water body remediation according to claim 5, wherein: the weight ratio of the ethanol/isopropanol/n-propanol, sepiolite, deionized water and acetic acid/hydrochloric acid is 1: 0.1: 0.5: 0.2.
7. the flocculant for water body remediation according to claim 5, wherein: wherein the volume ratio of the ethanol solution is 95 percent, the volume ratio of the isopropanol or n-propanol solution is 99 percent, the resistivity of the deionized water is 18.25M omega, the volume ratio of the acetic acid solution is 99.5 percent, and the volume ratio of the hydrochloric acid solution is 36 to 38 percent.
8. A preparation method of a flocculating agent for water body treatment is characterized by comprising the following steps: the method comprises the following steps:
step 1: stirring and mixing the raw material formula a according to claims 1 to 4 at a speed of 500rpm/min at 20-30 ℃, with the increase of alkalization degree, taking ethanol/isopropanol/n-propanol as a solvent, carrying out polymerization reaction on titanium tetrachloride/polymerized titanium tetrachloride, then decomposing, slowing down hydrolysis reaction by acetylacetone in the reaction process, generating a plurality of functional groups, providing binding sites, and obtaining a mixed solution A;
step 2: mixing the raw materials according to the formula B of claims 5 to 7, and adding sepiolite/attapulgite/bentonite for coating to obtain a mixed solution B;
and step 3: dropwise adding the mixed solution B obtained in the step 2 into the mixed solution A obtained in the step 1 at the dropping speed of 1mL/min, stirring at the speed of 500rpm/min, and obtaining a mixed solution C by a sol-gel method;
and 4, step 4: and drying the mixed liquor C until the weight of the mixed liquor C is not changed, thus obtaining the composite flocculant.
9. The method for preparing the flocculant for water body treatment according to claim 8, wherein: and the drying in the step 4 is natural drying or drying in a vacuum environment at 70-80 ℃.
10. Use of a flocculant for water treatment obtained according to any one of the methods of claims 1 to 9 in sewage treatment.
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