CN113120998B - Covalent bond type silicon-titanium flocculating agent, preparation method and application - Google Patents
Covalent bond type silicon-titanium flocculating agent, preparation method and application Download PDFInfo
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- CN113120998B CN113120998B CN202110560161.6A CN202110560161A CN113120998B CN 113120998 B CN113120998 B CN 113120998B CN 202110560161 A CN202110560161 A CN 202110560161A CN 113120998 B CN113120998 B CN 113120998B
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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
- C02F1/545—Silicon 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
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
Abstract
The invention relates to a covalent bond type silicon-titanium flocculating agent, a preparation method and application thereof. The hybrid flocculant of the invention is prepared by silane coupling agent Y-R-Si- (R')n(OR”)(3‑n)Mixing the titanium salt solution and the solvent, slowly dripping the alkali solution into the mixed solution for copolymerization by high-speed stirring at room temperature, and aging at room temperature to obtain a colorless transparent product, wherein R, R 'and R' are respectively alkyl with carbon number of 1-20, and Y is a functional group. The invention has the advantages that: simple operation method, good product generation reproducibility, high coagulation sedimentation rate and small dosage, and can be used for treating natural organic pollutants, NO and nitrogen and phosphorus simulated wastewater containing humic acid and municipal sewage3The flocculation performance of the-N, TP is excellent, the nitrogen and phosphorus content of the effluent is reduced, and the method has good popularization and application values.
Description
Technical Field
The invention belongs to the technical field of flocculants for urban sewage treatment, and particularly relates to a covalent bond type silicon-titanium flocculant, a preparation method and application thereof.
Background
Along with the improvement of living standard of people, the health of water quality gets more and more extensive attention of people. Some pollutants in municipal sewage, such as nitrogen, phosphorus, natural organic pollutants, etc., cannot be completely removed in the sewage treatment process. The nitrogen-containing pollutant is mainly NH4 +、NO3 -In the form of a phosphorus-containing contaminant, predominantly PO4 3-The pollutants are discharged into the water body, and then eutrophication of the water body can be caused, so that the water body is polluted.
The flocculation sedimentation method is widely applied to the pretreatment and advanced treatment processes of urban sewage due to simple process, convenient operation, economy and high efficiency. The flocculating agent is the core of the flocculation and sedimentation method, and the type, performance and selection of the flocculating agent directly influence the flocculation effect and the operation cost. At present, metal coagulants commonly used in the water treatment process are mainly classified into aluminum coagulants and iron coagulants, and the metal coagulants have the defects of large use amount, low removal rate of nitrogen, phosphorus and DOC, unobvious synergistic effect, easy influence of temperature and water quality fluctuation and the like in urban sewage coagulation treatment, and the effect is unsatisfactory. Compared with the conventional aluminum-iron coagulant, the titanium coagulant has rich reserves, is harmless to human bodies, has little residual quantity in water, and is used as a novel water treatment flocculant due to excellent turbidity removal and decoloration effects. The modified covalent bond type organic silicon-titanium composite flocculant is a novel flocculant developed on the basis of a silicon-titanium composite flocculant, and is prepared by copolymerizing sodium silicate and inorganic titanium salt with a silane coupling agent instead of the sodium silicate. The inorganic and organic components of the polymeric flocculant are bonded together by covalent bonds through the silane coupling agent, so that the respective advantages of the inorganic and organic flocculants are better integrated, and compared with the conventional inorganic silicon-titanium flocculant, the inorganic silicon-titanium flocculant has higher electric neutralization capacity, higher stability and stronger adsorption bridging capacity, and has stronger removal capacity on nitrogen, phosphorus and organic pollutants in water.
Disclosure of Invention
Aiming at the problems, the invention provides a covalent bond type silicon-titanium flocculating agent, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a covalent bond type silicon-titanium flocculating agent is prepared by the following steps:
step 1, silane coupling agent Y-R-Si- (R')n(OR”)(3-n)Mixing the titanium salt and a solvent, wherein R, R 'and R' are respectively alkyl with carbon number of 1-20, and Y is a functional group;
step 2, rapidly stirring at room temperature and slowly dripping alkaline solution to form a mixed solution;
and 3, standing and curing the mixed solution to obtain the covalent bond type hybrid silicon-titanium flocculant.
Further, the silane coupling agent Y-R-Si- (R')n(OR”)(3-n)Is trimethyl [3- (triethoxysilyl) propyl ] methyl]One of ammonium chloride, gamma-aminopropyltriethoxysilane or phenyltriethoxysilane; the titanium salt is titanium tetrachloride and sulfurOne of titanium acid or titanium isopropoxide; the solvent is deionized water; the alkali solution is NaOH solution or Na solution2CO3Solution, NaHCO3One of the solutions.
Further, the molar ratio of Si to Ti in the mixed solution is 0.01-1.0; the alkalization degree of the alkali solution, namely the molar ratio of hydroxide radicals to titanium ions, is 0-2.0.
Further, the curing time in the step 3 is 12-48 h.
Further, the total titanium concentration of the covalent bond type hybrid silicon titanium flocculant is 0.2mol/L, and the pH value is 2.0-5.0.
A preparation method of covalent bond type silicon-titanium flocculant comprises the following steps:
step 1, silane coupling agent Y-R-Si- (R')n(OR”)(3-n)Mixing the titanium salt and a solvent, wherein R, R 'and R' are respectively alkyl with carbon number of 1-20, and Y is a functional group;
step 2, rapidly stirring at room temperature and slowly dripping alkaline solution to form a mixed solution;
and 3, standing and curing the mixed solution to obtain the covalent bond type hybrid silicon-titanium flocculant.
Further, the silane coupling agent Y-R-Si- (R')n(OR”)(3-n)Is trimethyl [3- (triethoxysilyl) propyl ] methyl]One of ammonium chloride, gamma-aminopropyltriethoxysilane or phenyltriethoxysilane; the titanium salt is one of titanium tetrachloride, titanium sulfate or titanium isopropoxide; the solvent is deionized water; the alkali solution is NaOH solution or Na solution2CO3Solution, NaHCO3One of the solutions.
Further, the molar ratio of Si to Ti in the mixed solution is 0.01-1.0; the alkalization degree of the alkali solution, namely the molar ratio of hydroxide radicals to titanium ions, is 0-2.0.
Further, the curing time in the step 3 is 12-48 h; the total titanium concentration of the covalent bond type hybrid silicon titanium flocculating agent is 0.2mol/L, and the pH value is 2.0-5.0.
An application of covalent bond type silicon-titanium flocculant in the process of purifying waste water containing humic acid and nitrogen and phosphorus and treating urban sewage.
Compared with the prior art, the invention has the following advantages:
(1) the process method is carried out at room temperature, and is simple to operate; (2) the organic component silane coupling agent and the inorganic component titanium salt of the covalent bond hybrid silicon-titanium flocculating agent are connected through hydrolysis and polycondensation through Si-O-Ti, so that the organic component and the inorganic component are compounded in a covalent bond form; (3) silicon and titanium metal ions in covalent bond hybrid silicon-titanium flocculant molecules are distributed more uniformly, and the product reproducibility is good; (4) the covalent bond hybrid silicon-titanium flocculant has good effects of removing turbidity, humic acid and pollutants in municipal sewage, particularly nitrogen, phosphorus and organic pollutants.
Drawings
FIG. 1 is a Fourier infrared spectrum of covalent bond hybrid silicon titanium flocculant prepared in example 4
Detailed Description
Preparation of example 1
100.0mL of Ti (SO) at a concentration of 0.25mol/L was taken at a Si/Ti molar ratio of 0.054)2Solution, 0.00125mol of trimethyl ([3- (triethoxysilyl) propyl) acetate]Ammonium chloride), 12.5mL deionized water into a three-neck flask, and stirring and mixing uniformly at room temperature. Then stirring for 4h at room temperature at 500r/min, slowly dropping 12.5mL NaHCO with concentration of 1mol/L3The solution was brought to a degree of basification B of 0.5. Standing and curing the obtained solution for 48 hours until the reaction is completed, and obtaining the flocculant with the total titanium concentration of 0.2 mol/L.
Preparation of example 2
According to a Si/Ti molar ratio of 0.1, 25.0mL of 1.0mol/L TiCl was taken4The solution, 0.0025mol of gamma-aminopropyltriethoxysilane and 75.0mL of deionized water are put into a three-neck flask, and stirred and mixed uniformly at room temperature. Then rapidly stirring at room temperature, and slowly dropwise adding 25.0mL of 0.5mol/L NaOH solution until the alkalization degree B is 0.5. Standing and curing the obtained solution for 24 hours until the reaction is completed, and obtaining the flocculant with the total titanium concentration of 0.2 mol/L.
Preparation example 3:
50.0mL of Ti (SO) with a concentration of 0.5mol/L was taken at a Si/Ti molar ratio of 0.24)2Solution, solution,0.005mol of trimethyl ([3- (triethoxysilyl) propyl) group]Ammonium chloride) and 75.0mL of deionized water are put into a three-neck flask, stirred and mixed uniformly at room temperature, and the obtained solution is kept stand and cured for 24 hours to obtain the flocculating agent with the alkalization degree B of 0 and the total titanium concentration of 0.2mol/L after complete reaction.
Preparation example 4:
according to a Si/Ti molar ratio of 0.4, 25.0mL of 1.5mol/L TiCl was taken4Solution, 0.015mol of trimethyl ([3- (triethoxysilyl) propyl) ester]Ammonium chloride), 125.0mL deionized water into a three-neck flask, and stirring and mixing uniformly at room temperature. Then rapidly stirring at room temperature, slowly and dropwise adding 37.5mL of Na with the concentration of 0.75mol/L2CO3The solution was brought to a degree of basification B of 1.5. Standing and curing the obtained solution for 36h until the reaction is completed, thus obtaining the flocculant with the total titanium concentration of 0.2 mol/L.
Preparation example 5:
according to a Si/Ti molar ratio of 0.8, 25.0mL of TiCl with a concentration of 2.0mol/L4The solution, 0.025mol gamma-aminopropyl triethoxysilane and 175.0mL deionized water are put into a three-neck flask and stirred and mixed evenly at room temperature. Then rapidly stirring at room temperature, and slowly dropwise adding 50mL of 2.0mol/L NaOH solution until the alkalization degree B is 2. Standing and curing the obtained solution for 48 hours until the reaction is completed, and obtaining the flocculant with the total titanium concentration of 0.2 mol/L.
Application example 1:
the covalent bond hybrid silicon-titanium flocculant obtained in the preparation example 3 is applied to flocculation treatment of kaolin-humic acid-nitrogen phosphorus mixed solution for turbidity and UV254、DOC、NO3The removal rate of-N, TP was 99.4%, 99.1%, 87.8%, 24.9%, 98.2%. The covalent bond hybrid silicon-titanium flocculant obtained in the preparation example 2 is applied to flocculation treatment of biochemical effluent of municipal sewage for turbidity and UV254、DOC、NO3The removal rate of-N, TP reaches 91%, 82%, 64%, 21% and 87%. The flocculant can be stably stored for more than 1 month.
Application example 2:
the covalent bond hybrid silicon-titanium flocculant obtained in the preparation example 4 is applied to the flocculation treatment of kaolin-humic acid-nitrogen phosphorus mixed solution, and the turbidity removal rate is pairTurbidity, UV254、DOC、NO3The removal rate of-N, TP was 99.5%, 99.3%, 88.3%, 29.2%, 99.1%. The covalent bond hybrid silicon-titanium flocculant obtained in the preparation example 4 is applied to flocculation treatment of biochemical effluent of coking wastewater to turbidity and UV254、DOC、NO3The removal rate of-N, TP was 93.5%, 60.3%, 39.3%, 22.2%, 87.1%.
Those skilled in the art will appreciate that the invention may be practiced without these specific details. Although illustrative embodiments of the present invention have been described above to facilitate the understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, and various changes may be made apparent to those skilled in the art as long as they are within the spirit and scope of the present invention as defined and defined by the appended claims, and all matters of the invention which utilize the inventive concepts are protected.
Claims (10)
1. A covalent bond type silicon-titanium flocculant is characterized in that: the preparation method comprises the following steps:
step 1, silane coupling agent Y-R-Si- (R')n(OR”)(3-n)Mixing the titanium salt and a solvent, wherein R, R 'and R' are respectively alkyl with carbon number of 1-20, and Y is a functional group;
step 2, rapidly stirring at room temperature and slowly dripping alkaline solution to form a mixed solution;
step 3, standing and curing the mixed solution to obtain a covalent bond type hybrid silicon-titanium flocculant;
the silane coupling agent Y-R-Si- (R')n(OR”)(3-n)Is trimethyl [3- (triethoxysilyl) propyl ] methyl]One of ammonium chloride, gamma-aminopropyltriethoxysilane or phenyltriethoxysilane; the titanium salt is one of titanium tetrachloride, titanium sulfate or titanium isopropoxide.
2. The covalently bonded silicon-titanium flocculant of claim 1, wherein: the solvent is deionized water; the alkali solutionAs NaOH solution, Na2CO3Solution, NaHCO3One of the solutions.
3. The covalently bonded silicon-titanium flocculant of claim 2, wherein: the molar ratio of Si to Ti in the mixed solution is 0.01-1.0; the alkalization degree of the alkali solution, namely the molar ratio of hydroxide radicals to titanium ions, is 0-2.0.
4. The covalently bonded silico-titanium flocculant of claim 3, wherein: the curing time in the step 3 is 12-48 h.
5. The covalently bonded silico-titanium flocculant of claim 4, wherein: the total titanium concentration of the covalent bond type hybrid silicon titanium flocculating agent is 0.2mol/L, and the pH value is 2.0-5.0.
6. A method for preparing a covalently bonded silicon-titanium flocculant according to any one of claims 1 to 5, wherein: the method comprises the following steps:
step 1, silane coupling agent Y-R-Si- (R')n(OR”)(3-n)Mixing the titanium salt and a solvent, wherein R, R 'and R' are respectively alkyl with carbon number of 1-20, and Y is a functional group;
step 2, rapidly stirring at room temperature and slowly dripping alkaline solution to form a mixed solution;
and 3, standing and curing the mixed solution to obtain the covalent bond type hybrid silicon-titanium flocculant.
7. The method for preparing the covalent bond type silicon-titanium flocculating agent according to claim 6, wherein the covalent bond type silicon-titanium flocculating agent comprises the following steps: the silane coupling agent Y-R-Si- (R')n(OR”)(3-n)Is trimethyl [3- (triethoxysilyl) propyl ] methyl]One of ammonium chloride, gamma-aminopropyltriethoxysilane or phenyltriethoxysilane; the titanium salt is one of titanium tetrachloride, titanium sulfate or titanium isopropoxide; the solvent is deionized water; the alkali solution is NaOH solution or Na solution2CO3Solution, NaHCO3One of the solutions.
8. The method for preparing covalent bond type silicon titanium flocculant according to claim 7, wherein the covalent bond type silicon titanium flocculant comprises the following steps: the molar ratio of Si to Ti in the mixed solution is 0.01-1.0; the alkalization degree of the alkali solution, namely the molar ratio of hydroxide radicals to titanium ions, is 0-2.0.
9. The method for preparing covalent bond type silicon titanium flocculant according to claim 8, wherein the method comprises the following steps: the curing time in the step 3 is 12-48 h; the total titanium concentration of the covalent bond type hybrid silicon titanium flocculating agent is 0.2mol/L, and the pH value is 2.0-5.0.
10. The use of a covalently bonded silicon titanium flocculant according to claim 1, wherein: is used for the purification of waste water containing humic acid and nitrogen and phosphorus and the treatment process of urban sewage.
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