CN112811546A - Method for treating heavy metal ions in wastewater - Google Patents
Method for treating heavy metal ions in wastewater Download PDFInfo
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- CN112811546A CN112811546A CN202110070893.7A CN202110070893A CN112811546A CN 112811546 A CN112811546 A CN 112811546A CN 202110070893 A CN202110070893 A CN 202110070893A CN 112811546 A CN112811546 A CN 112811546A
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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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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/158—Purification; Drying; Dehydrating
- C01B33/1585—Dehydration into aerogels
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- 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
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/206—Manganese or manganese 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
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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Abstract
The invention discloses a method for treating heavy metal ions in wastewater, which comprises the following steps: preparation of SiO2‑(NH2)n(ii) a Using the obtained SiO2‑(NH2)nPreparing a heavy metal trapping agent; and (3) putting the heavy metal capture agent into the solution containing the heavy metal ions to perform the heavy metal precipitation process in the solution. The invention provides a method for treating heavy metal ions in wastewater, which can react with Mn in water by preparing2+、Hg2+、Ni2+、Cu2+、Pb2+、Cd2+、Cr3+、Zn2+、Fe2+/Fe3+The heavy metal ions react rapidly to combine into a large precipitated heavy metal trapping agent, and the heavy metal ions are separated from the wastewater. The heavy metal trapping agent has simple synthesis method, can be directly put into water, has small dosage, and can treat large particle precipitates generated by reaction to achieve the treatment effect on high and low concentrations, wherein the discharge standard can be reached by one-time treatment on wastewater containing high concentration.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a method for treating heavy metal ions in wastewater.
Background
In recent years, national environmental protection policies and regulations are tightened correspondingly, and the wastewater discharge standard is gradually improved. With the rapid development of modern industry and urbanization process, the generation amount of heavy metal wastewater is increasing day by day, environmental protection institutions and scientific research units polluted by heavy metals invest a lot of time and money to research how effective treatment can be carried out, the most effective and lowest-cost treatment method which reaches consensus is a chemical precipitation method, and a recapture agent related to the chemical precipitation method is one of the main means for treating the heavy metal wastewater due to simple equipment requirements. However, this conventional method has the following drawbacks:
(1) when the method for removing heavy metals by adjusting alkali is used, the pH value is generally controlled to be more than 10, and the value is higher than the discharge standard, so that the filtrate can be discharged only by adjusting the pH value of the filtrate to 6-9 after separation and precipitation;
(2) when amphoteric metal exists in the wastewater, the precipitate generated under the condition of over-high pH has the tendency of re-dissolution, and the discharge standard cannot be met after the precipitate is too low;
(3) certain components in the wastewater form very stable complexes with heavy metal ions, and the stability of the complexes is also higher than that of hydroxide of the heavy metal, and the stable heavy metal complexes cannot be removed by the alkali regulation method;
(4) the hydroxide of the heavy metal ions can be dissolved back along with the reduction of the pH value, so that the secondary pollution of the water body is caused.
(5) At present, the heavy metal capture agent in the market has wide application range, has poor effect on low-concentration heavy metal, and can not reach the standard for high-concentration wastewater by one-time treatment and can reach the emission standard by circular treatment. Meanwhile, the existing recapture agent on the market has the condition of large unit dosage during treatment.
Disclosure of Invention
The present invention is directed to the above problemsThe method for treating heavy metal ions in wastewater comprises the following steps: preparation of SiO2-(NH2)n(ii) a Using the obtained SiO2-(NH2)nPreparing a heavy metal trapping agent; and (3) putting the heavy metal capture agent into the solution containing the heavy metal ions to perform the heavy metal precipitation process in the solution.
Further, the preparation of SiO2-(NH2)nThe method comprises the following substeps:
s1, uniformly mixing water glass and water ion water, adding acid to adjust the pH value of the solution to 3-4, fully hydrolyzing sodium silicate in the solution, adding ethanol, drying and controlling chemical additives, and stirring to obtain a uniformly mixed solution;
s2, adding ammonia water into the obtained uniform mixed solution, and adjusting the pH value to 7-8 to carry out a gelation reaction to obtain silicon dioxide gel;
s3, washing the prepared silica gel by using deionized water to remove impurities in the silica gel;
s4, soaking the silicon dioxide gel after the impurities are removed into a mixed solution of silicon alkoxide and absolute ethyl alcohol for aging treatment;
s5, washing the aged silica gel by using absolute ethyl alcohol, and preparing the silica aerogel under the normal pressure drying condition;
s6, mixing the prepared silica aerogel and 3-aminopropyltrimethoxysilane, adding toluene, stirring for 30 minutes to form a homogeneous solution, and purging the homogeneous solution with nitrogen for 30-40 minutes;
s7, reacting the glass flask filled with the homogeneous solution obtained in the step S6 in an oil bath at the temperature of 80 ℃ for 6.5-8.5 hours, and cooling to room temperature;
s8, carrying out suction filtration on the solution obtained by the reaction in the step S7, washing the solution with toluene and ethanol to obtain a filter cake, and carrying out vacuum drying on the filter cake at 75 ℃ for 5-12 hours to obtain amino functionalized SiO2-(NH2)n。
Further, the acid of the regulating solution is oxalic acid.
Further, the drying control chemical additive is one of formamide, ethylene glycol, glycerol and dimethylformamide.
Further, in the step S1, the volume ratio of the four solutions of water glass, deionized water, ethanol and the drying control chemical additive is 1: (4-7): (0.45-0.65): (0.7-1.2).
Further, the silicon alkoxide comprises one or two of methyl orthosilicate and ethyl orthosilicate.
Further, in the step S4, the volume ratio of the silica gel to the silicon alkoxide to the ethanol solution in the aging treatment is 1: (0.15-0.32): (0.45-0.67).
Further, the aging treatment time is 24-48 hours.
Further, the drying in step S5 is performed by drying at 35 ℃ for 5-8 hours, and then drying at 60 ℃ for 4-12 hours.
Further, the mass ratio of the silicon dioxide aerogel, the 3-aminopropyl trimethoxy silane and the toluene is 1: (10-35): (17-20).
Further, the preparation method of the heavy metal capture agent comprises the following steps: mixing SiO2-(NH2)nPreparing a methanol solution with the mass solubility of 20-35%, cooling to 4-10 ℃, and dropwise adding a carbon disulfide methanol solution with the mass solubility of 40-50% under a stirring state; heating to 25-30 ℃, stirring for reaction for 2-3.5 h, performing suction filtration, washing for 1-2 times with anhydrous alcohol, and drying to obtain an insoluble white solid recapture agent; mixing the dried insoluble white solid recapture agent with an alkali solution with the mass concentration of 20-30%, heating to 50-60 ℃, and reacting for 2 hours to obtain a light yellow liquid recapture agent.
Further, the dropping speed of the carbon disulfide methanol solution is 2-7 drops/second.
Further, the absolute alcohol is absolute ethyl alcohol or methanol.
Further, the process of putting the heavy metal trapping agent into the solution containing the heavy metal ions to precipitate the heavy metal in the solution comprises the following steps:
collecting heavy metal ion solution: collecting the heavy metal ion solution, and calculating the input amount of the heavy metal capture agent according to the content of the heavy metal ions in the solution;
heavy metal trapping agent input: continuously or in batches, adding the heavy metal capture agent into the heavy metal ion solution, and fully stirring for 25 minutes;
adding coagulant aids and flocculants: polyaluminum chloride (PAC) and high molecular weight Polyacrylamide (PAM) were added to the well-stirred solution, and the precipitate was separated by filtration.
Further, the method also comprises a step of adjusting the pH value of the heavy metal ion solution, wherein the pH value of the heavy metal ion solution is adjusted to be neutral or weakly alkaline, and the pH value is 6-9.
The invention has the beneficial effects that: the invention provides a method for treating heavy metal ions in wastewater, which can react with Mn in water by preparing2+、Hg2+、Ni2+、Cu2+、Pb2+、Cd2+、Cr3+、Zn2+、Fe2+/Fe3+The heavy metal ions react rapidly and are combined into a large precipitated heavy metal trapping agent, and the heavy metal ions are separated from the wastewater. The heavy metal trapping agent has simple synthesis method, can be directly put into water, has small dosage, and can treat large particle precipitates generated by reaction to achieve the treatment effect on high and low concentrations, wherein the discharge standard can be reached by one-time treatment on wastewater containing high concentration.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, embodiments of the present invention will now be described.
SiO2-(NH2)nPreparation:
(1) the preparation method of the silica aerogel comprises the following steps:
the preparation method of the silicon dioxide aerogel amination graft comprises the following steps:
s1, uniformly mixing water glass and water ion water, adding acid to adjust the pH value of the solution to 3-4, fully hydrolyzing sodium silicate in the solution, adding ethanol, drying and controlling chemical additives, and stirring to obtain a uniformly mixed solution;
s2, adding ammonia water into the obtained uniform mixed solution, and adjusting the pH value to 7-8 to carry out a gelation reaction to obtain silicon dioxide gel;
s3, washing the prepared silica gel by using deionized water to remove impurities in the silica gel;
s4, soaking the silicon dioxide gel after the impurities are removed into a mixed solution of silicon alkoxide and absolute ethyl alcohol for aging treatment;
s5, washing the aged silica gel by using absolute ethyl alcohol, and preparing the silica aerogel under the normal pressure drying condition;
(2) silicon dioxide amination step:
s6, mixing the prepared silica aerogel and 3-aminopropyltrimethoxysilane, adding toluene, stirring for 30 minutes to form a homogeneous solution, and purging the homogeneous solution with nitrogen for 30-40 minutes;
s7, reacting the glass flask filled with the homogeneous solution obtained in the step S6 in an oil bath at the temperature of 80 ℃ for 6.5-8.5 hours, and cooling to room temperature;
s8, carrying out suction filtration on the solution obtained by the reaction in the step S7, washing the solution with toluene and ethanol to obtain a filter cake, and carrying out vacuum drying on the filter cake at 75 ℃ for 5-12 hours to obtain amino functionalized SiO2-(NH2)n。
It is to be noted that the acid of the conditioning solution is oxalic acid; the drying control chemical additive is one of formamide, glycol, glycerol and dimethylformamide; in the step S1, the volume ratio of the four solutions of water glass, deionized water, ethanol and the drying control chemical additive is 1: (4-7): (0.45-0.65): (0.7 to 1.2); the silicon alkoxide comprises one or two of methyl orthosilicate or ethyl orthosilicate; the volume ratio of the silica gel to the silanol salt to the ethanol solution in the aging treatment in the step S4 is 1: (0.15-0.32): (0.45-0.67); the aging treatment time is 24-48 hours; the drying in the step S5 is to carry out drying treatment at 35 ℃ for 5 to 8 hours and then drying at 60 ℃ for 4 to 12 hours; the mass ratio of the silicon dioxide aerogel, the 3-aminopropyl trimethoxy silane and the toluene is 1: (10-35): (17-20).
Based on the preparation method, the silicon dioxide aerogel amination graft is prepared from water glass, deionized water, ethanol, a drying control chemical additive, silicon alkoxide, 3-aminopropyl trimethoxy silane and toluene.
Preparing a heavy metal catching agent:
the preparation method of the heavy metal trapping agent comprises the following steps: mixing SiO2-(NH2)nPreparing a methanol solution with the mass solubility of 20-35%, cooling to 4-10 ℃, and dropwise adding a carbon disulfide methanol solution with the mass concentration of 25-50% under a stirring state; heating to 25-30 ℃, stirring for reaction for 2-3.5 h, performing suction filtration, washing for 1-2 times with anhydrous alcohol, and drying to obtain an insoluble white solid recapture agent; mixing the dried insoluble white solid recapture agent with an alkali solution with the mass concentration of 20-30%, heating to 50-60 ℃, and reacting for 1-2 hours to obtain a light yellow liquid recapture agent.
The dropping speed of the carbon disulfide methanol solution is 2-7 drops/second; the absolute alcohol is absolute ethyl alcohol or methanol.
Based on the preparation method, the heavy metal trapping agent is prepared from SiO2-(NH2)nCarbon disulfide, hydroxide, alcohol and water. Wherein the weight ratio of each component is as follows: SiO 22-(NH2)n: 2.5 to 4; carbon disulfide: 27-30; hydroxide: 7-9; alcohols: 38-47; water: 24-30; the SiO2-(NH2)nThe modified silica aerogel is a silica aerogel amination graft, wherein the value of n in the silica aerogel amination graft is a natural number of 10-30, and the particle size of the silica aerogel particles is 10-60 microns; the alcohol is one or a mixture of more than two of methanol, ethanol, n-butanol, isobutanol, propanol and isopropanol; the hydroxide adopts sodium hydroxide and oxyhydrogenOne or a mixture of two potassium compounds in any proportion.
Heavy metal precipitation:
the heavy metal trapping agent feeding method comprises the following steps:
before actual use, a one-liter small test can be made according to the process.
Secondly, the pH value is adjusted to 6-9 when the wastewater is treated, and the treatment effect is better.
And thirdly, detecting the content of heavy metal ions in the wastewater, and determining the drug input amount through a wastewater simulation drug adding experiment.
Fourthly, the medicament can be continuously or batchwise added into the waste water and fully stirred for about 25 minutes.
Fifthly, after the reagents react fully, adding a proper amount of polyaluminium chloride (PAC) and Polyacrylamide (PAM) with high molecular weight to obtain better precipitation effect.
Sixthly, filtering and separating out precipitate, and obtaining the water reaching the standard after filtering.
Specifically, several embodiments are now provided to illustrate the implementation of the present invention.
The first embodiment is as follows:
selecting the following raw materials by weight:
SiO2-(NH2)n：2.8g；
methanol solution of carbon disulfide: 80.4 g;
potassium hydroxide solution: 40 g.
The preparation process specifically comprises the following steps: using a 500g small closed reaction vessel with temperature control, 2.8g of SiO were placed2-(NH2)18Preparing a methanol solution with the mass concentration of 20 percent and putting the methanol solution into a reaction kettle; reducing the temperature to 10 ℃, dropwise adding 80.4g of methanol solution of carbon disulfide with the mass concentration of 27% into the reaction kettle at the speed of 2 drops per second under the stirring state, heating to the room temperature of 25 ℃ after dropwise adding, and continuously stirring for reaction for 2 hours; after two hours, filtering, and washing for 3 times by using absolute ethyl alcohol to obtain white powder; putting the white powder and 40g of potassium hydroxide solution with the mass concentration of 20% into a reaction kettle, and stirring and reacting for 1.5 hours at the temperature of 50 ℃ to obtain the light yellow liquid recapture agent.
The effect of the heavy metal scavenger in the first embodiment: preparing copper, zinc, lead, cadmium and manganese ion solutions, and respectively measuring the initial concentration and the ion concentration after primary treatment by using an atomic absorption spectrophotometer, wherein the details are shown in the following table.
| Ion species | Initial concentration (mg/L) | Concentration after one treatment (mg/L) | Emission standard (mg/L) |
| Cu2+ | 338.35 | 0.3683 | 2 |
| Zn2+ | 465.45 | 0.1931 | 5 |
| Pb2+ | 210.7 | 0.043 | 0.5 |
| Cd2+ | 470.6 | 0.014 | 0.05 |
| Mn2+ | 428.15 | 0.2365 | 2 |
Example two:
selecting the following raw materials by weight:
SiO2-(NH2)n：1.7g；
methanol solution of carbon disulfide: 100g of the total weight of the mixture;
potassium hydroxide solution: 65 g.
The preparation process specifically comprises the following steps: using a 500g small closed reaction vessel with temperature control, 1.7g of SiO were placed2-(NH2)30Preparing a methanol solution with the mass concentration of 20 percent and putting the methanol solution into a reaction kettle; reducing the temperature to 10 ℃, dropwise adding 100g of methanol solution of carbon disulfide with the mass concentration of 20% into the reaction kettle at the speed of 2 drops per second under the stirring state, heating to the room temperature of 25 ℃ after dropwise adding, and continuously stirring and reacting for 2 hours; after two hours, filtering, and washing for 3 times by using absolute ethyl alcohol to obtain white powder; and putting the white powder and 65g of potassium hydroxide solution with the mass concentration of 20% into a reaction kettle, and stirring and reacting for 2 hours at the temperature of 55 ℃ to obtain the light yellow liquid recapture agent.
The effect of the heavy metal scavenger used in example two: preparing copper, zinc, lead, cadmium and manganese ion solutions, and respectively measuring the initial concentration and the ion concentration after primary treatment by using an atomic absorption spectrophotometer, wherein the details are shown in the following table.
| Ion species | Initial concentration (mg/L) | Concentration after one treatment (mg/L) | Emission standard (mg/L) |
| Cu2+ | 338.35 | 0.0651 | 2 |
| Zn2+ | 465.45 | 0.6901 | 5 |
| Pb2+ | 210.7 | 0.203 | 0.5 |
| Cd2+ | 470.6 | 0.02 | 0.05 |
| Mn2+ | 428.15 | 0.1302 | 2 |
Example three:
selecting the following raw materials by weight:
SiO2-(NH2)n：2.4g；
40% carbon disulfide in methanol: 49 g;
20% sodium hydroxide solution: 29 g.
The preparation process specifically comprises the following steps: using a 500g small closed reaction vessel with temperature control, 2.4g of SiO were placed2-(NH2)22Preparing a methanol solution with the mass concentration of 25 percent and putting the methanol solution into a reaction kettle; reducing the temperature to 10 ℃, dropwise adding 49g of methanol solution of carbon disulfide with the mass concentration of 40% into the reaction kettle at the speed of 2 drops per second under the stirring state, heating to the room temperature of 25 ℃ after dropwise adding, and continuously stirring and reacting for 2 hours; after two hours, filtering, and washing for 3 times by using absolute ethyl alcohol to obtain white powder; and putting the white powder and 29g of sodium hydroxide solution with the mass concentration of 20% into a reaction kettle, and stirring and reacting for 1.5 hours at the temperature of 52 ℃ to obtain the light yellow liquid recapture agent.
The effect of the heavy metal scavenger in the third example: preparing copper, zinc, lead, cadmium and manganese ion solutions, and respectively measuring the initial concentration and the ion concentration after primary treatment by using an atomic absorption spectrophotometer, wherein the details are shown in the following table.
| Ion species | Initial concentration (mg/L) | Concentration after one treatment (mg/L) | Emission standard (mg/L) |
| Cu2+ | 338.35 | 0.1001 | 2 |
| Zn2+ | 465.45 | 0.318 | 5 |
| Pb2+ | 210.7 | 0.11 | 0.5 |
| Cd2+ | 470.6 | 0.05 | 0.05 |
| Mn2+ | 428.15 | 0.414 | 2 |
Example four:
selecting the following raw materials by weight:
SiO2-(NH2)n：4.2g；
45% carbon disulfide in methanol: 68g of a mixture;
25% sodium hydroxide solution: 33 g.
The preparation process specifically comprises the following steps: using a 500g small closed reaction vessel with temperature control, 4.2g of SiO were placed2-(NH2)12Preparing a methanol solution with the mass concentration of 20 percent and putting the methanol solution into a reaction kettle; reducing the temperature to 10 ℃, dropwise adding 68g of methanol solution of carbon disulfide with the mass concentration of 45% into the reaction kettle at the speed of 2 drops per second under the stirring state, after the dropwise adding is finished, heating to the room temperature of 25 ℃, and continuously stirring and reacting for 1.5 hours; after two hours, filtering, and washing for 3 times by using absolute ethyl alcohol to obtain white powder; the white powder was put into a reaction vessel together with 33g of a 25% strength by mass sodium hydroxide solutionStirring and reacting for 2 hours in a kettle at the temperature of 60 ℃ to obtain the light yellow liquid recapture agent.
The effect of the heavy metal scavenger in the fourth example: preparing copper, zinc, lead, cadmium and manganese ion solutions, and respectively measuring the initial concentration and the ion concentration after primary treatment by using an atomic absorption spectrophotometer, wherein the details are shown in the following table.
| Ion species | Initial concentration (mg/L) | Concentration after one treatment (mg/L) | Emission standard (mg/L) |
| Cu2+ | 338.35 | 0.41 | 2 |
| Zn2+ | 465.45 | 0.53 | 5 |
| Pb2+ | 210.7 | 0.05 | 0.5 |
| Cd2+ | 470.6 | 0.05 | 0.05 |
| Mn2+ | 428.15 | 0.614 | 2 |
Example five:
selecting the following raw materials by weight:
SiO2-(NH2)n：5.6g；
50% carbon disulfide in methanol: 78g of a mixture;
20% sodium hydroxide solution: 52 g.
The preparation process specifically comprises the following steps: using a 500g small closed reaction vessel with temperature control, 5.6g of SiO were placed2-(NH2)10Preparing a methanol solution with the mass concentration of 25 percent and putting the methanol solution into a reaction kettle; reducing the temperature to 10 ℃, dropwise adding 78g of methanol solution of carbon disulfide with the mass concentration of 50% into the reaction kettle at the speed of 3 drops per second under the stirring state, heating to the room temperature of 25 ℃ after dropwise adding, and continuously stirring and reacting for 2 hours; after two hours, filtering, and washing for 3 times by using absolute ethyl alcohol to obtain white powder; and putting the white powder and 52g of sodium hydroxide solution with the mass concentration of 20% into a reaction kettle, and stirring and reacting for 2 hours at the temperature of 50 ℃ to obtain the light yellow liquid recapture agent.
The use effect of the heavy metal scavenger in the fifth embodiment: preparing copper, zinc, lead, cadmium and manganese ion solutions, and respectively measuring the initial concentration and the ion concentration after primary treatment by using an atomic absorption spectrophotometer, wherein the details are shown in the following table.
| Ion species | Initial concentration (mg/L) | Concentration after one treatment (mg/L) | Emission standard (mg/L) |
| Cu2+ | 338.35 | 0.011 | 2 |
| Zn2+ | 465.45 | 0.4506 | 5 |
| Pb2+ | 210.7 | 0.008 | 0.5 |
| Cd2+ | 470.6 | 0.001 | 0.05 |
| Mn2+ | 428.15 | 0.114 | 2 |
Example six:
selecting the following raw materials by weight:
SiO2-(NH2)n：5.6g；
50% carbon disulfide in methanol: 78g of a mixture;
20% potassium hydroxide solution: 72 g.
The preparation process specifically comprises the following steps: using a 500g small closed reaction vessel with temperature control, 5.6g of SiO were placed2-(NH2)10Preparing a methanol solution with the mass concentration of 25 percent and putting the methanol solution into a reaction kettle; reducing the temperature to 10 ℃, dropwise adding 78g of methanol solution of carbon disulfide with the mass concentration of 50% into the reaction kettle at the speed of 3 drops per second under the stirring state, heating to the room temperature of 25 ℃ after dropwise adding, and continuously stirring and reacting for 2 hours; after two hours, filtering, and washing for 3 times by using absolute ethyl alcohol to obtain white powder; and putting the white powder and 72g of potassium hydroxide solution with the mass concentration of 20% into a reaction kettle, and stirring and reacting for 2 hours at the temperature of 50 ℃ to obtain the light yellow liquid recapture agent.
The use effect of the heavy metal scavenger in the sixth embodiment: preparing copper, zinc, lead, cadmium and manganese ion solutions, and respectively measuring the initial concentration and the ion concentration after primary treatment by using an atomic absorption spectrophotometer, wherein the details are shown in the following table.
| Ion species | Initial concentration (mg/L) | Concentration after one treatment (mg/L) | Emission standard (mg/L) |
| Cu2+ | 338.35 | 0.147 | 2 |
| Zn2+ | 465.45 | 0.2686 | 5 |
| Pb2+ | 210.7 | 0.005 | 0.5 |
| Cd2+ | 470.6 | 0.001 | 0.05 |
| Mn2+ | 428.15 | 0.617 | 2 |
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A method for treating heavy metal ions in wastewater is characterized by comprising the following steps: preparation of SiO2-(NH2)n(ii) a Using the obtained SiO2-(NH2)nPreparing a heavy metal trapping agent; catching heavy metalsThe catcher is put into the solution containing heavy metal ions to carry out the heavy metal precipitation process in the solution.
2. The method for treating heavy metal ions in wastewater according to claim 1, wherein the SiO is prepared2-(NH2)nThe method comprises the following substeps:
s1, uniformly mixing water glass and water ion water, adding acid to adjust the pH value of the solution to 3-4, fully hydrolyzing sodium silicate in the solution, adding ethanol and a drying control chemical additive, and stirring to obtain a uniformly mixed solution;
s2, adding ammonia water into the obtained uniform mixed solution, and adjusting the pH value to 7-8 to carry out a gelation reaction to obtain silicon dioxide gel;
s3, washing the prepared silica gel by using deionized water to remove impurities in the silica gel;
s4, soaking the silicon dioxide gel after the impurities are removed into a mixed solution of silicon alkoxide and absolute ethyl alcohol for aging treatment;
s5, washing the aged silica gel by using absolute ethyl alcohol, and preparing the silica aerogel under the normal pressure drying condition;
s6, mixing the prepared silica aerogel and 3-aminopropyltrimethoxysilane, adding toluene, stirring for 30 minutes to form a homogeneous solution, and purging the homogeneous solution with nitrogen for 30-40 minutes;
s7, reacting the glass flask filled with the homogeneous solution obtained in the step S6 in an oil bath at the temperature of 80 ℃ for 6.5-8.5 hours, and cooling to room temperature;
s8, carrying out suction filtration on the solution obtained by the reaction in the step S7, washing the solution with toluene and ethanol to obtain a filter cake, and carrying out vacuum drying on the filter cake at 75 ℃ for 5-12 hours to obtain amino functionalized SiO2-(NH2)n。
3. The method of claim 2, wherein the acid of the conditioning solution is oxalic acid; the drying control chemical additive is one of formamide, glycol, glycerol and dimethylformamide; the silicon alkoxide comprises one or two of methyl orthosilicate and ethyl orthosilicate.
4. The method as claimed in claim 2, wherein the volume ratio of the four solutions of water glass, deionized water, ethanol and drying control chemical additive in step S1 is 1: (4-7): (0.45-0.65): (0.7-1.2).
5. The method of claim 2, wherein the aging treatment of step S4 is performed in a volume ratio of silica gel, silicon alkoxide, and ethanol solution of 1: (0.15-0.32): (0.45-0.67); the aging treatment time is 24-48 hours.
6. The method of claim 2, wherein the drying in step S5 is performed by drying at 35 ℃ for 5-8 hours and then at 60 ℃ for 4-12 hours.
7. The method for treating heavy metal ions in wastewater according to claim 2, wherein the amount ratio of the silica aerogel, the 3-aminopropyltrimethoxysilane and the toluene substance is 1: (10-35): (17-20).
8. The method for treating heavy metal ions in wastewater according to claim 1, wherein the preparation method of the heavy metal capture agent comprises the following steps: mixing SiO2-(NH2)nPreparing a methanol solution with the mass solubility of 20-35%, cooling to 4-10 ℃, and dropwise adding a carbon disulfide methanol solution with the mass solubility of 40-50% under a stirring state; heating to 25-30 ℃, stirring for reaction for 2-3.5 h, performing suction filtration, washing for 1-2 times with anhydrous alcohol, and drying to obtain an insoluble white solid recapture agent; drying insoluble white solid recapture agent and qualityAnd (3) mixing alkali solution with the concentration of 20-30%, heating to 50-60 ℃, and reacting for 2 hours to obtain the light yellow liquid recapture agent.
9. The method for preparing a heavy metal scavenger according to claim 8, wherein the dropping speed of the carbon disulfide methanol solution is 2 to 7 drops/second; the absolute alcohol is absolute ethyl alcohol or methanol.
10. The method for treating heavy metal ions in wastewater as claimed in claim 1, wherein the step of putting the heavy metal trapping agent into the solution containing the heavy metal ions to precipitate the heavy metal in the solution comprises the following steps:
collecting heavy metal ion solution: collecting the heavy metal ion solution, and calculating the input amount of the heavy metal capture agent according to the content of the heavy metal ions in the solution;
adjusting the pH value of the heavy metal ion solution to be neutral or alkalescent, wherein the pH value is 6-9;
heavy metal trapping agent input: continuously or in batches, adding the heavy metal capture agent into the heavy metal ion solution, and fully stirring for 25 minutes;
adding coagulant aids and flocculants: polyaluminum chloride (PAC) and high molecular weight Polyacrylamide (PAM) were added to the well-stirred solution, and the precipitate was separated by filtration.
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