CN110723797B - Polysilicate aluminum cerium acrylate flocculant and preparation method and application thereof - Google Patents
Polysilicate aluminum cerium acrylate flocculant and preparation method and application thereof Download PDFInfo
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- C02F1/00—Treatment of water, waste water, or sewage
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- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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Abstract
The invention discloses a polysilicate aluminum cerium acrylate flocculant and a preparation method and application thereof, wherein tuff is ground and sieved to obtain tuff powder; respectively weighing aluminum ash and tuff powder, mixing, and stirring to obtain tuff mixed powder; respectively weighing water and tuff mixed powder, mixing, and stirring to obtain tuff; adding concentrated sulfuric acid into the mortar, uniformly stirring to make the pH of the slurry be 1-2, and aging for 3-6 hours to obtain silicon-aluminum polymerization slurry; adding acrylic acid into the silicon-aluminum polymerization slurry, uniformly stirring, and aging for 1-3 hours to obtain acrylic acid mixed silicon-aluminum polymerization slurry; weighing ammonium ceric nitrate and acrylic acid mixed silicon-aluminum polymer slurry, mixing, uniformly stirring, aging for 6-12 hours at the temperature of 20-80 ℃, drying in vacuum, grinding, and sieving with a 200-400-mesh sieve to obtain the polysilicon aluminum-cerium acrylate flocculant. The flocculant prepared by the invention can efficiently remove various heavy metal pollutants in water, and has the advantages of small dosage and high heavy metal removal rate.
Description
Technical Field
The invention relates to the technical field of resource utilization of nonmetallic ore tuff, and particularly relates to a polysilicate aluminum cerium acrylate flocculant and a preparation method and application thereof.
Background
Tuff is a volcaniclastic rock that contains a large amount of active alumino-silica materials. Compared with aluminosilicate non-metal ores such as bentonite, perlite, zeolite and the like, the tuff has lower market price. At present, the resource utilization way of tuff is narrow, and most tuff is used as coarse and fine aggregates. A few enterprises use the admixture and the cement raw material for producing concrete by using tuff. Generally, tuff has limited effect and low resource utilization rate. Therefore, other purposes of tuff need to be researched and developed, the tuff use path is developed, the tuff resource utilization rate is improved, and the economic benefit is increased.
At present, the problem of the disordered discharge of industrial waste liquid of enterprises of chemical engineering, metallurgy, pharmacy and the like is prominent. Heavy metal pollutants such as arsenic, mercury, chromium, nickel and the like are easily and illegally discharged along with waste liquid, so that surrounding soil, rivers and underground water are polluted, and the change of ecological environment is caused. The removal of heavy metals from waste streams by flocculation-coagulation is one of the most common methods for the disposal of industrial waste streams. Flocculants commonly used in the market include inorganic flocculants and organic flocculants, and specifically include polyaluminium chloride (PAC), polyaluminium sulfate (PAS), polyferric chloride (PFC), polyferric sulfate (polyferric sulfate), Polyacrylamide (PAM), and the like. However, the current flocculant for treating the heavy metal polluted waste liquid has the problems of large flocculant dosage, low heavy metal removal rate, few applicable heavy metal types, low flocculation speed, difficult filtration and the like.
In order to solve the problems, the key point for solving the problems is to develop a novel, efficient and flocculant suitable for removing various heavy metals by utilizing the characteristic of the silicoaluminate of tuff.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of providing a preparation method of a polysilicate aluminum cerium acrylate flocculant.
The invention also aims to solve the technical problem of providing the polysilicate aluminum cerium acrylate flocculant and the application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme: a preparation method of a polysilicate aluminum cerium acrylate flocculant comprises the following steps:
1) grinding tuff, and sieving with a 200-400 mesh sieve to obtain tuff powder;
2) respectively weighing aluminum ash and tuff powder, mixing, and stirring to obtain tuff mixed powder;
3) respectively weighing water and tuff mixed powder, mixing, and stirring to obtain tuff;
4) adding concentrated sulfuric acid into the mortar, uniformly stirring to make the pH of the slurry be 1-2, and aging for 3-6 hours to obtain silicon-aluminum polymerization slurry;
5) adding acrylic acid into the silicon-aluminum polymerization slurry, uniformly stirring, and aging for 1-3 hours to obtain acrylic acid mixed silicon-aluminum polymerization slurry;
6) weighing ammonium ceric nitrate and acrylic acid mixed silicon-aluminum polymer slurry, mixing, uniformly stirring, aging for 6-12 hours at the temperature of 20-80 ℃, drying in vacuum, grinding, and sieving with a 200-400-mesh sieve to obtain the polysilicon aluminum-cerium acrylate flocculant.
Wherein the mass ratio of the aluminum ash and the tuff powder in the step 2) is 1-3: 10.
Wherein the liquid-solid ratio of the mixed powder of water and tuff in the step 3) is 0.6-1: 1 mL/mg.
Wherein, the volume ratio of the acrylic acid and the silicon-aluminum polymer slurry in the step 5) is 10-20%.
Wherein, the mass ratio of the ammonium ceric nitrate and the acrylic acid mixed silicon-aluminum polymer slurry in the step 6) is 5-15: 100.
The invention also discloses the polysilicate aluminum cerium acrylate flocculant prepared by the preparation method.
The invention also discloses the application of the polysilicate aluminum cerium acrylate flocculant in sewage treatment.
Wherein the sewage is a water body containing heavy metal ions.
Wherein the heavy metal ions are one or more of zinc ions, copper ions, lead ions, nickel ions, cadmium ions, hexavalent chromium ions, arsenic ions or mercury ions.
The reaction mechanism is as follows: under the strong acid environment, active silicate in tuff and aluminum-containing substance in aluminum ash are dissolved, hydrolyzed and polymerized, and a three-dimensional silicon-aluminum framework structure built by silicon-oxygen octahedron and aluminum-oxygen tetrahedron is formed through bridge connection and silicon-aluminum interaction. And adding acrylic acid into the silicon-aluminum polymerized slurry, wherein the acrylic acid covers the surface of the silicon-aluminum skeleton structure and is filled in the pores of the silicon-aluminum skeleton structure through the capillary adsorption effect and the hydroxyl connection effect. After the ammonium ceric nitrate is added into the acrylic mixed silicon-aluminum polymer slurry, part of acrylic acid is initiated by the ammonium ceric nitrate to generate free radicals through oxidation and catalytic oxidation, and the ammonium ions in the ammonium ceric nitrate are transferred to the acrylic acid and aminated by the free radicals. The free radical and the aminated acrylic acid are further subjected to oxidative polymerization under the initiation of cerium nitrate salt to generate polyacrylamide. In the process of acrylic acid conversion, cerium in the cerium nitrate salt is gradually converted into nano cerium dioxide. The nano cerium dioxide is distributed on the surface of the polyacrylamide to form the flocculant of the three-dimensional space structure of the polysilicate aluminum cemented by the polyacrylamide and modified by the cerium dioxide.
Has the advantages that: the preparation method is simple and has wide raw material sources. The flocculant prepared by the invention can efficiently remove various heavy metal pollutants in water, and has the advantages of small dosage and high heavy metal removal rate. The flocculant prepared by the method has the advantages of wide pH application range, strong durability, high stability and repeated use. The invention provides a new idea for resource utilization of tuff and aluminum ash.
Drawings
FIG. 1 is a flow chart of the process of the present invention.
Detailed Description
The invention is further described below with reference to the figures and examples.
The 98% concentrated sulfuric acid of the present invention is commercially available (Yangzhou Huafu chemical Co., Ltd.). The tuff in the invention is from Xinyang Si Munda technology of Henan, and the aluminum ash is from Song biological industrial materials of Yangguan region of Shaoguan city, and the results of the element components of each substance are shown in Table 1.
TABLE 1 elemental composition of tuff and aluminum ash
Example 1 influence of the quality ratio of aluminum ash and tuff powder on the removal rate of heavy metals in the adsorption water body of the prepared flocculant
Grinding tuff, and sieving with 200 mesh sieve to obtain tuff powder. Respectively weighing aluminum ash and tuff powder according to the mass ratio of 0.5: 10, 0.7: 10, 0.9: 10, 1: 10, 2: 10, 3:10, 3.2: 10, 3.5: 10 and 4: 10, mixing, and stirring uniformly to obtain nine groups of tuff mixed powder. And respectively weighing the mixed powder of water and tuff according to the liquid-solid ratio of 0.6: 1mL/mg, mixing and uniformly stirring to obtain nine groups of mortar. And (3) adding concentrated sulfuric acid into the nine groups of mortar, stirring uniformly to enable the pH value of the slurry to be 1, and aging for 3 hours to obtain nine groups of silicon-aluminum polymer slurry. And respectively adding acrylic acid into the nine groups of silicon-aluminum polymerization slurries according to the volume ratio of the acrylic acid to the silicon-aluminum polymerization slurries being 10%, uniformly stirring, and aging for 1 hour to obtain nine groups of acrylic acid mixed silicon-aluminum polymerization slurries. Weighing the mixed silicon aluminum polymerization slurry of ammonium cerium nitrate and acrylic acid according to the mass ratio of 5:100 of the ammonium cerium nitrate and the mixed silicon aluminum polymerization slurry of acrylic acid, mixing, uniformly stirring, aging for 6 hours at the temperature of 20 ℃, drying in vacuum, grinding, and sieving with a 200-mesh sieve to obtain nine groups of polysilicon aluminum acrylate cerium flocculants.
Adsorption experiment: putting nine groups of flocculating agents into a water body with initial pH of 3 and containing 10mg/L zinc ions, 10mg/L copper ions, 1mg/L lead ions, 1mg/L nickel ions, 0.5mg/L cadmium ions, 1mg/L chromium ions (hexavalent), 1mg/L arsenic ions and 0.1mg/L mercury ions according to the solid-liquid ratio of the prepared flocculating agents to the water body containing heavy metal ions of 1g to 1L, stirring for 10min at the rotating speed of 120rpm, and carrying out solid-liquid separation.
And (3) determining the concentration of heavy metal ions in the water body: the concentration of five pollutants of zinc, copper, lead, cadmium and nickel in the water body is measured according to an inductively coupled plasma emission spectrometry (HJ 776) 2015 for measuring 32 elements of water quality, the concentration of hexavalent chromium ion pollutants is measured according to a flow injection-dibenzoyl dihydrazide photometry (HJ 908) 2017 for measuring hexavalent chromium of water quality, the concentration of two pollutants of arsenic and mercury is measured according to an atomic fluorescence method (HJ694-2014) for measuring mercury, arsenic, selenium, bismuth and antimony of water quality, and the test results are shown in Table 1.
Calculating the heavy metal removal rate: the removal rate of heavy metals in the water body is calculated according to the following equation, wherein RMIs the removal rate of heavy metal M (heavy metal M represents zinc ion, copper ion, lead ion, nickel ion, cadmium ion, hexavalent chromium ion, arsenic ion or mercury ion), c0And ctThe concentrations of heavy metal M in the solution before and after the adsorption experiment are respectively shown. The test results are shown in Table 1.
Table 1 influence of mass ratio of aluminum ash and tuff powder on removal rate of heavy metals in adsorption water body of prepared flocculant
As can be seen from table 1, when the mass ratio of the aluminum ash to the tuff powder is less than 1: 10 (as shown in table 1, when the mass ratio of the aluminum ash to the tuff powder is 0.9: 10, 0.7: 10, 0.5: 10 and lower ratios not listed in table 1), the aluminum-containing substance is less dissolved, and through subsequent hydrolysis and polymerization, the three-dimensional silicon-aluminum framework structure substance formed by bridge connection and silicon-aluminum interaction is reduced, so that the stability of the generated flocculant is poor, the polyacrylamide cementation and cerium dioxide modification effects are poor, and finally the removal rate of zinc, copper, lead, nickel, cadmium, chromium, arsenic and mercury in water is lower than 85% and is significantly reduced as the mass ratio of the aluminum ash to the tuff powder is reduced; when the mass ratio of the aluminum ash to the tuff powder is 1-3: 10 (as shown in table 1, when the mass ratio of the aluminum ash to the tuff powder is 1: 10, 2: 10 or 3: 10), dissolving, hydrolyzing and polymerizing active silicate in the tuff and an aluminum-containing substance in the aluminum ash under a strong acid environment, forming a three-dimensional silicon-aluminum framework structure built by a silicon-oxygen octahedron and an aluminum-oxygen tetrahedron through bridge connection and silicon-aluminum interaction, wherein the flocculant has good stability, polyacrylamide cementation and cerium dioxide modification are sufficient, and finally the removal rate of zinc, copper, lead, nickel, cadmium, chromium, arsenic and mercury in water is higher than 90%; when the mass ratio of the aluminum ash to the tuff powder is more than 3:10 (as shown in table 1, when the mass ratio of the aluminum ash to the tuff powder is 3.2: 10, 3.5: 10, 4: 10 and higher ratios not listed in table 1), the further increase of the mass ratio of the aluminum ash to the tuff powder has no significant influence on the removal rate of zinc, copper, lead, nickel, cadmium, chromium, arsenic and mercury in water. Therefore, in summary, the benefit and the cost are combined, and when the mass ratio of the aluminum ash to the tuff powder is equal to 1-3: 10, the prepared flocculant is most beneficial to improving the removal of heavy metals in a water body.
Example 2 influence of volume ratio of acrylic acid to silicon-aluminum polymerized slurry on removal rate of heavy metals in water body adsorbed by prepared flocculant
Grinding tuff, and sieving with 300 mesh sieve to obtain tuff powder. Respectively weighing the aluminum ash and the tuff powder according to the mass ratio of 3:10, mixing, uniformly stirring to obtain tuff mixed powder, and weighing nine groups of tuff mixed powder according to the same mass ratio. And weighing the mixed powder of water and tuff according to the liquid-solid ratio of 0.8: 1mL/mg, mixing and uniformly stirring to obtain nine groups of mortar. And adding concentrated sulfuric acid into the nine groups of mortar, stirring uniformly to make the pH value of the slurry be 1.5, and aging for 4.5 hours to obtain nine groups of silicon-aluminum polymer slurry. Respectively adding acrylic acid into the nine groups of silicon-aluminum polymerization slurries according to the volume ratio of the acrylic acid to the silicon-aluminum polymerization slurries of 5%, 7%, 9%, 10%, 15%, 20%, 21%, 23% and 25%, uniformly stirring, and aging for 2 hours to obtain nine groups of acrylic acid mixed silicon-aluminum polymerization slurries. Weighing the ammonium ceric nitrate and the nine groups of acrylic acid mixed silicon aluminum polymer slurries according to the mass ratio of the ammonium ceric nitrate to the nine groups of acrylic acid mixed silicon aluminum polymer slurries of 10: 100, mixing, uniformly stirring, aging for 9 hours at the temperature of 50 ℃, drying in vacuum, grinding, and sieving with a 300-mesh sieve to obtain the nine groups of polysilicon aluminum acrylate cerium flocculants.
The adsorption experiment, the determination of the concentration of heavy metal ions in the water body and the calculation of the removal rate of heavy metal are the same as those in example 1. The test results are shown in Table 2.
Table 2 influence of volume ratio of acrylic acid to silicon-aluminum polymerized slurry on removal rate of heavy metal in water body adsorbed by prepared flocculant
As can be seen from table 2, when the volume ratio of the acrylic acid to the silicon-aluminum polymerized syrup is less than 10% (for example, when the volume ratio of the acrylic acid to the silicon-aluminum polymerized syrup is 9%, 7%, 5% and lower ratios not listed in table 2), the acrylic acid covering the surface of the silicon-aluminum skeleton structure and filling the pores of the silicon-aluminum skeleton structure is less, the amount of polyacrylamide is less, the polyacrylamide cementation effect is poor, and the removal rate of zinc, copper, lead, nickel, cadmium, chromium, arsenic and mercury in water is lower than 84% and is significantly reduced as the volume ratio of the acrylic acid to the silicon-aluminum polymerized syrup is reduced; when the volume ratio of acrylic acid to the silicon-aluminum polymerized syrup is 10% to 20% (as shown in table 2, the volume ratio of acrylic acid to the silicon-aluminum polymerized syrup is 10%, 15%, 20%), the acrylic acid covers the surface of the silicon-aluminum skeleton structure and fills the pores of the silicon-aluminum skeleton structure by capillary adsorption and hydroxyl linking. Ammonium cerium nitrate causes part of acrylic acid to generate free radicals through oxidation and catalytic oxidation, and further uses the free radicals to realize the transfer and amination of ammonium ions in ammonium cerium nitrate to acrylic acid. The free radical and the aminated acrylic acid are further subjected to oxidative polymerization under the initiation of cerium nitrate salt to generate polyacrylamide. The polyacrylamide strengthens the adsorption capacity of the flocculant on heavy metals through electrostatic adsorption and amide cross-linking, and enlarges the adsorption capacity of the flocculant. Meanwhile, polyacrylamide is filled in the cerium dioxide modified polysilicate aluminum three-dimensional space structure in a cross-bonding mode, so that the stability of the flocculant in a water environment is remarkably improved. Finally, the removal rate of zinc, copper, lead, nickel, cadmium, chromium, arsenic and mercury in the water is higher than 92 percent; when the volume ratio of acrylic acid to silicon aluminum polymer paste is more than 20% (as shown in table 2, when the volume ratio of acrylic acid to silicon aluminum polymer paste is 21%, 23%, 25% and higher ratio not listed in table 2), the further increase of the volume ratio of acrylic acid to silicon aluminum polymer paste has no significant effect on the removal rate of zinc, copper, lead, nickel, cadmium, chromium, arsenic and mercury in water. Therefore, in summary, the benefit and the cost are combined, and when the volume ratio of the acrylic acid to the silicon-aluminum polymer slurry is equal to 10-20%, the prepared flocculant is most beneficial to improving the removal of heavy metals in a water body.
Example 3 influence of the quality ratio of cerium ammonium nitrate and acrylic acid mixed silicon-aluminum polymer slurry on the removal rate of heavy metals in the adsorption water body of the flocculant
Grinding tuff, and sieving with 400 mesh sieve to obtain tuff powder. Respectively weighing the aluminum ash and the tuff powder according to the mass ratio of 3:10, mixing and uniformly stirring to obtain tuff mixed powder, and weighing nine groups of tuff mixed powder according to the same mass ratio. And weighing the mixed powder of water and tuff according to the liquid-solid ratio of 1: 1mL/mg, mixing and uniformly stirring to obtain nine groups of mortar. And respectively adding concentrated sulfuric acid into the nine groups of mortar, uniformly stirring to ensure that the pH value of the slurry is 2, and aging for 6 hours to obtain nine groups of silicon-aluminum polymer slurry. Respectively adding acrylic acid into the nine groups of silicon-aluminum polymerization slurries according to the volume ratio of the acrylic acid to the silicon-aluminum polymerization slurries being 20%, uniformly stirring, and aging for 3 hours to obtain nine groups of acrylic acid mixed silicon-aluminum polymerization slurries. And weighing ammonium cerium nitrate and the prepared nine groups of acrylic acid mixed silicon-aluminum polymer pastes according to the mass ratio of the ammonium cerium nitrate to the acrylic acid mixed silicon-aluminum polymer pastes of 2.5: 100, 3.5: 100, 4.5: 100, 5:100, 10: 100, 15:100, 16: 100, 18: 100 and 20: 100 respectively, mixing the ammonium cerium nitrate and the prepared nine groups of acrylic acid mixed silicon-aluminum polymer pastes, uniformly stirring, aging for 12 hours at the temperature of 80 ℃, drying in vacuum, grinding, and sieving by a 400-mesh sieve to obtain nine groups of polysilicon aluminum-cerium acrylate flocculants.
The adsorption experiment, the determination of the concentration of heavy metal ions in the water body and the calculation of the removal rate of heavy metal are the same as those in example 1. The test results are shown in Table 3.
Table 3 influence of mass ratio of ammonium ceric nitrate and acrylic acid mixed silicon-aluminum polymer slurry on removal rate of heavy metals in water body of flocculant prepared
As can be seen from table 3, when the mass ratio of the ammonium ceric nitrate to the acrylic mixed silica-alumina polymer syrup is less than 5:100 (as shown in table 3, when the mass ratio of the ammonium ceric nitrate to the acrylic mixed silica-alumina polymer syrup is 4.5: 100, 3.5: 100, 2.5: 100 and lower ratios not listed in table 3), part of acrylic acid generated by oxidation and catalytic oxidation of the ammonium ceric nitrate is less free radicals, the formation amount of polyacrylamide and nano ceria is reduced, and the removal rate of zinc, copper, lead, nickel, cadmium, chromium, arsenic and mercury in water is lower than 83% and is significantly reduced as the mass ratio of the ammonium ceric nitrate to the acrylic mixed silica-alumina polymer syrup is reduced; when the mass ratio of the ammonium ceric nitrate to the acrylic acid mixed silicon-aluminum polymer syrup is 5-15: 100 (as shown in table 3, the mass ratio of the ammonium ceric nitrate to the acrylic acid mixed silicon-aluminum polymer syrup is 5:100, 10: 100, 15: 100), part of acrylic acid is initiated by the ammonium ceric nitrate through oxidation and catalytic oxidation to generate free radicals, and ammonium ions in the ammonium ceric nitrate are further transferred to acrylic acid and aminated by utilizing the free radicals. The free radical and the aminated acrylic acid are further subjected to oxidative polymerization under the initiation of cerium nitrate salt to generate polyacrylamide. In the process of acrylic acid conversion, cerium in the cerium nitrate salt is gradually converted into nano cerium dioxide. The nano cerium dioxide is distributed on the surface of the polyacrylamide to form the flocculant of the three-dimensional space structure of the polysilicate aluminum cemented by the polyacrylamide and modified by the cerium dioxide. The polyacrylamide strengthens the adsorption capacity of the flocculant on heavy metals through electrostatic adsorption and amide cross-linking, and enlarges the adsorption capacity of the flocculant. Meanwhile, polyacrylamide is filled in the cerium dioxide modified polysilicate aluminum three-dimensional space structure in a cross-bonding mode, so that the stability of the flocculant in a water environment is remarkably improved. The ceria can enable the surface pores of the flocculant to be developed through oxidation, so that the active sites for heavy metal adsorption are increased, and the removal rate of the heavy metal is further improved. Finally, the removal rate of zinc, copper, lead, nickel, cadmium, chromium, arsenic and mercury in the water is higher than 95 percent; when the mass ratio of the ammonium ceric nitrate to the acrylic mixed silicon-aluminum polymer syrup is more than 15:100 (as shown in table 3, when the mass ratio of the ammonium ceric nitrate to the acrylic mixed silicon-aluminum polymer syrup is 16: 100, 18: 100, 20: 100 and higher ratios not listed in table 3), the further increase of the mass ratio of the ammonium ceric nitrate to the acrylic mixed silicon-aluminum polymer syrup has no significant influence on the removal rate of zinc, copper, lead, nickel, cadmium, chromium, arsenic and mercury in water. Therefore, in summary, the benefit and the cost are combined, and when the mass ratio of the ammonium ceric nitrate to the acrylic acid mixed silicon-aluminum polymer slurry is 5-15: 100, the prepared flocculant is most beneficial to improving the removal of heavy metals in a water body.
Comparison of removal rates of heavy metals in adsorbed water bodies of different flocculants
The preparation of the polysilicate aluminum cerium acrylate flocculant of the invention comprises the following steps: grinding tuff, and sieving with 400 mesh sieve to obtain tuff powder. Respectively weighing the aluminum ash and the tuff powder according to the mass ratio of 3:10, mixing, uniformly stirring, and respectively weighing and mixing to obtain tuff mixed powder. And respectively weighing the mixed powder of water and tuff according to the liquid-solid ratio of 1: 1mL/mg, mixing and uniformly stirring to obtain the tuff. And respectively adding concentrated sulfuric acid into the mortar, uniformly stirring to ensure that the pH value of the slurry is 2, and aging for 6 hours to obtain the silicon-aluminum polymerization slurry. And adding acrylic acid into the silicon-aluminum polymerization slurry according to the volume ratio of the acrylic acid to the silicon-aluminum polymerization slurry of 20%, uniformly stirring, and aging for 3 hours to obtain the acrylic acid mixed silicon-aluminum polymerization slurry. And weighing ammonium cerium nitrate according to the mass ratio of 15:100 of ammonium cerium nitrate to acrylic acid mixed silicon-aluminum polymer slurry, mixing the ammonium cerium nitrate with the prepared acrylic acid mixed silicon-aluminum polymer slurry, uniformly stirring, aging at the temperature of 80 ℃ for 12 hours, drying in vacuum, grinding, and sieving with a 400-mesh sieve to obtain the polysilicon aluminum-acrylate cerium flocculant.
Preparation of comparative flocculant 1: grinding tuff, and sieving with 400 mesh sieve to obtain tuff powder. Respectively weighing water and tuff powder according to the liquid-solid ratio of 1: 1mL/mg, mixing, and uniformly stirring to obtain tuff slurry. Adding concentrated sulfuric acid into the tuff slurry, uniformly stirring to ensure that the pH value of the slurry is 2, and aging for 6 hours to obtain the tuff silicon polymer slurry. According to the volume ratio of 20 percent of acrylic acid to the coagulated gray silicon polymer slurry, adding acrylic acid into the coagulated gray silicon polymer slurry, uniformly stirring, and aging for 3 hours to obtain the acrylic acid coagulated gray silicon polymer slurry. And weighing ammonium ceric nitrate and the prepared acrylic acid coagulated lime silicon polymer slurry according to the mass ratio of 15:100 of ammonium ceric nitrate to the acrylic acid coagulated lime silicon polymer slurry, mixing the ammonium ceric nitrate and the prepared acrylic acid coagulated lime silicon polymer slurry, uniformly stirring, aging for 12 hours at the temperature of 80 ℃, drying in vacuum, grinding, and sieving by a 400-mesh sieve to obtain the comparative flocculant 1.
Preparation of comparative flocculant 2: grinding tuff, and sieving with 400 mesh sieve to obtain tuff powder. Respectively weighing the aluminum ash and the tuff powder according to the mass ratio of 3:10, mixing, uniformly stirring, and respectively weighing and mixing to obtain tuff mixed powder. And respectively weighing the mixed powder of water and tuff according to the liquid-solid ratio of 1: 1mL/mg, mixing and uniformly stirring to obtain the tuff. And respectively adding concentrated sulfuric acid into the mortar, uniformly stirring to ensure that the pH value of the slurry is 2, and aging for 6 hours to obtain the silicon-aluminum polymerization slurry. And weighing ammonium ceric nitrate according to the mass ratio of 15:100 of ammonium ceric nitrate to the silicon-aluminum polymer slurry, mixing the ammonium ceric nitrate with the prepared silicon-aluminum polymer slurry, uniformly stirring, aging at the temperature of 80 ℃ for 12 hours, drying in vacuum, grinding, and sieving with a 400-mesh sieve to obtain the comparative flocculant 2.
Preparation of comparative flocculant 3: grinding tuff, and sieving with 400 mesh sieve to obtain tuff powder. Respectively weighing the aluminum ash and the tuff powder according to the mass ratio of 3:10, mixing, uniformly stirring, and respectively weighing and mixing to obtain tuff mixed powder. And respectively weighing the mixed powder of water and tuff according to the liquid-solid ratio of 1: 1mL/mg, mixing and uniformly stirring to obtain the tuff. And respectively adding concentrated sulfuric acid into the mortar, uniformly stirring to ensure that the pH value of the slurry is 2, and aging for 6 hours to obtain the silicon-aluminum polymerization slurry. Adding acrylic acid into the silicon-aluminum polymerization slurry according to the volume ratio of 20% of the acrylic acid to the silicon-aluminum polymerization slurry, uniformly stirring, aging for 3 hours, drying in vacuum, grinding, and sieving with a 400-mesh sieve to obtain a comparative flocculant 3.
Calculating the settling time of the flocculant per unit mass: t is the settling time of the flocculant in unit mass, m is the mass (g) of the flocculant added into the still water, and T is the time(s) from the moment the flocculant is just added into the still water to the moment the flocculant is completely precipitated in the still water.
T＝t/m
The adsorption experiment, the determination of the concentration of heavy metal ions in the water body and the calculation of the removal rate of heavy metal are the same as those in example 1. The test results are shown in Table 4.
TABLE 4 comparison of the removal rate and the sedimentation rate of heavy metals in water adsorbed by different flocculants
The results in table 4 show that the removal rates and the corresponding sedimentation rates of the heavy metal of the comparative flocculant 1, the comparative flocculant 2 and the comparative flocculant 3 which are respectively prepared due to the lack of aluminum ash, acrylic acid and ammonium ceric nitrate in the preparation process of the polysilicate aluminum cerium acrylate flocculant are all significantly lower than those of the polysilicate aluminum cerium acrylate flocculant prepared by the invention, the loss of aluminum ash in the preparation process of the flocculant leads to the failure of forming a three-dimensional silicon-aluminum framework structure built by silicon-oxygen octahedrons and aluminum-oxygen tetrahedrons through bridge connection and interaction of silicon and aluminum, so that the acrylamide cementation effect is weakened, the stability of the comparative flocculant 1 is poor, and the retention time of the comparative flocculant 1 in the water body for adsorbing heavy metal pollutants is short. The lack of acrylic acid in the preparation process of the flocculant makes polyacrylamide unable to generate, the stability of the three-dimensional silicon-aluminum skeleton structure built by the silicon-oxygen octahedron and the aluminum-oxygen tetrahedron is poor, cerium ammonium nitrate can not be converted into cerium dioxide, the stability of the comparative flocculant 2 is poor and the surface active sites are fewer, which results in the poor adsorption effect of the comparative flocculant 2 on heavy metal pollutants in water. The lack of ammonium ceric nitrate in the preparation process of the flocculant prevents acrylic acid from being converted into polyacrylamide, and compared with the flocculant 3, the stability is poor and the surface active sites are few, so that the comparative flocculant 3 has poor adsorption effect on heavy metal pollutants in a water body. The polysilicate aluminum cerium acrylate flocculant prepared by the invention has the advantages of long retention time for adsorbing heavy metal pollutants, high sedimentation rate and high removal rate of heavy metal ions far higher than that of a comparative flocculant 1, a comparative flocculant 2 and a comparative flocculant 3.
Claims (5)
1. The preparation method of the polysilicate aluminum cerium acrylate flocculant is characterized by comprising the following steps of: 1) grinding tuff, and sieving with a 200-400 mesh sieve to obtain tuff powder;
2) respectively weighing aluminum ash and tuff powder, mixing, and stirring to obtain tuff mixed powder;
3) respectively weighing water and tuff mixed powder, mixing, and stirring to obtain tuff;
4) adding concentrated sulfuric acid into the mortar, uniformly stirring to make the pH of the slurry be 1-2, and aging for 3-6 hours to obtain silicon-aluminum polymerization slurry;
5) adding acrylic acid into the silicon-aluminum polymerization slurry, uniformly stirring, and aging for 1-3 hours to obtain acrylic acid mixed silicon-aluminum polymerization slurry;
6) weighing ammonium ceric nitrate and acrylic acid mixed silicon-aluminum polymer slurry, mixing, uniformly stirring, aging at the temperature of 20-80 ℃ for 6-12 hours, drying in vacuum, grinding, and sieving with a 200-400-mesh sieve to obtain a polysilicon aluminum-cerium acrylate flocculant;
the mass ratio of the aluminum ash to the tuff powder in the step 2) is 1-3: 10, and the liquid-solid ratio of the mixed powder of the water and the tuff in the step 3) is 0.6-1: 1mL/mg, the volume ratio of the acrylic acid and the silicon-aluminum polymer slurry in the step 5) is 10-20%, and the mass ratio of the cerium ammonium nitrate and the acrylic acid mixed silicon-aluminum polymer slurry in the step 6) is 5-15: 100.
2. The polyaluminum cerium polysilicate flocculant prepared by the method of claim 1.
3. The use of the aluminum cerium polysilicate flocculant of claim 2 in sewage treatment.
4. The use according to claim 3, wherein the contaminated water is a body of water containing heavy metal ions.
5. The use according to claim 4, wherein the heavy metal ions are one or more of zinc ions, copper ions, lead ions, nickel ions, cadmium ions, hexavalent chromium ions, arsenic ions or mercury ions.
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