CN110498471B - Sewage treatment agent and preparation method thereof - Google Patents
Sewage treatment agent and preparation method thereof Download PDFInfo
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- CN110498471B CN110498471B CN201910803144.3A CN201910803144A CN110498471B CN 110498471 B CN110498471 B CN 110498471B CN 201910803144 A CN201910803144 A CN 201910803144A CN 110498471 B CN110498471 B CN 110498471B
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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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Abstract
The invention relates to the technical field of sewage treatment, and provides a sewage treatment agent and a preparation method thereof. The sewage treatment agentThe preparation method comprises the following steps: and (2) mixing the following components in a mass ratio of 2.13-2.35: 1, uniformly mixing magnesium hydroxide powder and aluminum hydroxide powder to prepare a magnesium-aluminum mixture; and (3) mixing the components in a volume ratio of 4-5: 1, mixing deionized water and ethanol to prepare a mixed solvent, and dissolving sodium stearate in the mixed solvent to prepare a clear solution with the concentration of 0.03-0.05 mol/L; adding the magnesium-aluminum mixture into the clear solution under the stirring state to prepare suspension; the suspension is processed by primary hydrothermal treatment, freezing treatment, secondary hydrothermal treatment, centrifugation and drying to obtain the sodium stearate intercalation Mg3Al-OH LDHs. The sodium stearate intercalation Mg prepared by the method3Al-OH LDHs improves Mg3Adsorption of the Al-OH LDHs material to hydrophobic organic pollutants.
Description
Technical Field
The invention relates to the technical field of sewage treatment, and particularly relates to a sewage treatment agent and a preparation method thereof.
Background
Water is an important component of the earth and is the life line of all things on the earth. In recent years, with the rapid development of social economy, the phenomenon of water pollution in China is becoming more serious, and the water pollution has attracted great attention in mission. Contaminants in water include inorganic contaminants and organic contaminants. Wherein, the inorganic pollutants mainly comprise heavy metal ions such as lead, cadmium, mercury, copper and the like. The heavy metal elements have the characteristics of difficult degradation, easy accumulation, non-reversibility, high toxicity, slow metabolism and easy biological enrichment in the environment. If people drink water polluted by heavy metal for a long time, people can suffer from acute and chronic poisoning or canceration of organisms, and the harm is serious. Organic pollutants are various, and with the rapid development of the petrochemical industry, many artificially synthesized organic pollutants, such as organochlorine pesticides, high molecular polymers, dyes, food additives, and the like, are generated. Wherein the harmful organic pollutants are teratogenicity, mutagenicity and carcinogen.
At present, a plurality of sewage treatment agents exist, and an adsorbent is a commonly used reagent. Wherein, the layered double hydroxide (LDHs for short), also called hydrotalcite-like compound, is a novel adsorbent, which is hydroxide with hydrotalcite layered crystal structure composed of two or more technical elements, and the chemical general formula is: [ M ] AII 1-xMIII x(OH)2]x+An- x/n·mH2O, wherein Mg3Al-OH LDHs (chemical structural formula is [ Mg ]3/4Al1/4(OH)2](OH)1/4Quasi water skiStone) is one of the better adsorption effects. There are studies that have shown that it can effectively remove some hydrophilic contaminants, but it is not ideal for hydrophobic organic contaminants. How to modify the LDHs to enhance the removal effect of the LDHs on hydrophobic organic matters needs to be researched.
Disclosure of Invention
The invention aims to provide a preparation method of a sewage treatment agent, which adopts a process of twice hydrothermal and freezing treatments to ensure that sodium stearate reacts with Mg3The Al-OH LDHs material is modified to prepare sodium stearate intercalation Mg3The Al-OH LDHs has good adsorption effect on hydrophobic organic pollutants.
Another object of the present invention is to provide a sewage treatment agent using sodium stearate to Mg3Al-OH LDHs material is modified to improve Mg3The adsorption of the Al-OH LDHs material to hydrophobic organic pollutants, and the prepared sodium stearate intercalated Mg3The Al-OH LDHs has good adsorption effect on hydrophobic organic pollutants.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a preparation method of a sewage treatment agent, which comprises the following steps:
and step S1: and (2) mixing the following components in a mass ratio of 2.13-2.35: 1, uniformly mixing magnesium hydroxide powder and aluminum hydroxide powder to prepare a magnesium-aluminum mixture;
and step S2: and (3) mixing the components in a volume ratio of 4-5: 1, mixing deionized water and ethanol to prepare a mixed solvent, and dissolving sodium stearate in the mixed solvent to prepare a clear solution with the concentration of 0.03-0.05 mol/L;
and step S3: adding the magnesium-aluminum mixture into the clear solution under the stirring state to prepare suspension;
and step S4: the suspension is processed by primary hydrothermal treatment, freezing treatment, secondary hydrothermal treatment, centrifugation and drying to obtain the sodium stearate intercalation Mg3Al-OH LDHs。
Preferably, in the step S4, the first hydrothermal treatment and the second hydrothermal treatment are performed under stirring, and the stirring speed is 120 to 240 r/min.
Preferably, in the step S4, the first hydrothermal process is: heating to 90-100 ℃ at a heating rate of 1-3 ℃/min, and then preserving heat for 24-36 h.
Preferably, in step S4, the freezing process is: the suspension obtained after the first hydrothermal treatment was kept at-15 ℃ for 30 min.
Preferably, in the step S4, the secondary hydrothermal process is: heating to 100-120 ℃ at a heating rate of 1-3 ℃/min, then preserving heat for 2-4 h, and then cooling to 30 ℃ at a cooling rate of 2-4 ℃/min.
Preferably, in the step S1, the magnesium hydroxide powder and the aluminum hydroxide powder are mechanically ball-milled for 1-3 hours at a rotating speed of 100-300 r/min.
Preferably, in the step S3, the dosage ratio of the magnesium-aluminum mixture to the clear solution is 8-12 g: 150 mL.
A sewage treatment agent, which is prepared by the preparation method of the sewage treatment agent.
The sewage treatment agent and the preparation method thereof have the beneficial effects that: a process for preparing sewage treating agent features use of sodium stearate and the primary, freezing and secondary hydrothermal treatments3And modifying the Al-OH LDHs. Traditional sewage treatment agent Mg3Al-OH LDHs have good adsorption effect on hydrophilic organic pollutants, but have poor adsorption effect on hydrophobic organic pollutants. The hydrophobic group of the sodium stearate is a hydrocarbyl group, and the hydrophilic group is a carboxyl group. Under the hydrothermal reaction, sulfonic acid groups can be inserted into Mg through electrostatic attraction and hydrogen bond action3Between the Al-OH LDHs layers, a hydrophobic area is formed between the Al-OH LDHs layers, and the adsorption capacity to hydrophobic organic pollutants is greatly improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Layered double hydroxides (LDHs for short), also called hydrotalcite-like compounds, are novel adsorbents, and the hydroxides with hydrotalcite layered crystal structures are composed of two or more technical elements, and have the chemical general formula: [ M ] AII 1-xMIII x(OH)2]x+An- x/n·mH2O, wherein Mg3Al-OH LDHs (chemical structural formula is [ Mg ]3/4Al1/4(OH)2](OH)1/4Hydrotalcite-like compound of (a) is one having a good adsorption effect. Research shows that LDHs can effectively remove some hydrophilic organic pollutants, but the effect of removing hydrophobic organic pollutants is not ideal.
Sodium stearate, also known as sodium stearate, is made by the interaction of octadecanoic acid and sodium hydroxide and is readily soluble in hot water or hot alcohol. The aqueous solution is alkaline due to hydrolysis, and the alcoholic solution is neutral. Sodium stearate has a hydrophobic group and a hydrophilic group, and the hydrophobic group is a hydrocarbon group and the hydrophilic group is a carboxyl group.
The sewage treatment agent and the preparation method thereof according to the embodiment of the present invention will be specifically described below.
The preparation method of the sewage treatment agent provided by the embodiment of the invention comprises the following steps:
and step S1: and (2) mixing the following components in a mass ratio of 2.13-2.35: 1, uniformly mixing magnesium hydroxide powder and aluminum hydroxide powder to prepare a magnesium-aluminum mixture; intercalation of Mg with sodium stearate according to the product formed3The molar ratio of magnesium to aluminum in the Al-OH LDHs is 3: 1, the optimal mass ratio of the corresponding magnesium hydroxide powder to the aluminum hydroxide powder is 2.24: 1. when the proportion is within 5% of the floating range during compounding, the effect on the result of the final product is small.
Further, the magnesium hydroxide powder and the aluminum hydroxide powder are mechanically ball-milled for 1-3 hours at a rotating speed of 100-300 r/min. The magnesium hydroxide powder and the aluminum hydroxide powder are insoluble in water and ethanol, and can be effectively ground into fine powder in a mechanical ball milling state. And long-time mechanical ball milling can fully mix magnesium atoms and aluminum atoms at the atomic level, thereby providing a powerful guarantee for fully carrying out later hydrothermal reaction.
And step S2: and (3) mixing the components in a volume ratio of 4-5: 1, mixing deionized water and ethanol to prepare a mixed solvent, and dissolving sodium stearate in the mixed solvent to prepare a clear solution with the concentration of 0.03-0.05 mol/L;
it should be noted that the mixed solvent prepared by using deionized water and ethanol as raw materials has more special properties compared with the traditional deionized water solvent, and often enables the crystal nucleus to grow especially, and the prepared material is loose. The resulting sodium stearate intercalated Mg3The Al-OH LDHs has a loose structure, can have a plurality of channels for sewage to enter, improves the overall utilization rate of the material and improves the adsorption effect.
And step S3: adding the magnesium-aluminum mixture into the clear solution under the stirring state to prepare suspension; the magnesium hydroxide powder and the aluminum hydroxide powder are insoluble in water and ethanol, and are added under stirring, so that the magnesium-aluminum mixture and the clear solution can be well mixed.
Further, the dosage ratio of the magnesium-aluminum mixture to the clear solution is 8-12 g: 150 mL.
And step S4: the suspension is processed by primary hydrothermal treatment, freezing treatment, secondary hydrothermal treatment, centrifugation and drying to obtain the sodium stearate intercalation Mg3Al-OH LDHs。
Further, the primary hydrothermal treatment and the secondary hydrothermal treatment are carried out under stirring, and the stirring speed is 120-240 r/min. The magnesium hydroxide powder and the aluminum hydroxide powder are not dissolved in water and ethanol, and the hydrothermal process is carried out under the stirring state, so that the magnesium-aluminum mixture and the clear solution can be well mixed, and the sodium stearate can be conveniently and fully intercalated into Mg3Al-OH LDHs。
Further, the primary hydrothermal process comprises: heating to 90-100 ℃ at a heating rate of 1-3 ℃/min, and then preserving heat for 24-36 h. The mixed solvent is prepared by deionized water and ethanol, and the obtained solvent has a boiling point higher than that of a pure deionized water solution, so that the hydrothermal temperature required in the same reaction is relatively low. The slow rate of temperature increase allows the slow insertion of sodium stearate into the Mg3Interlayer of Al-OH LDHs. Long time guaranteeWarm working can make sodium stearate and Mg3The force and bond between Al-OH LDHs are more stable.
Further, the freezing treatment is as follows: the suspension obtained after the first hydrothermal treatment was kept at-15 ℃ for 30 min. The freezing treatment makes the suspension obtained after the primary hydrothermal treatment quickly cooled to subzero temperature, and the process makes sodium stearate and Mg3The combination of Al-OH LDHs is more stable.
Further, the secondary hydrothermal process comprises: heating to 100-120 ℃ at a heating rate of 1-3 ℃/min, then preserving heat for 2-4 h, and then cooling to 30 ℃ at a cooling rate of 2-4 ℃/min. In the secondary hydrothermal process, Mg3Al-OH LDHs can be inserted into sodium stearate layer more, further increase Mg3A hydrophobic region of Al-OH LDHs.
The invention also provides a sewage treatment agent, and the sewage treatment agent is prepared by the preparation method of the sewage treatment agent.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The preparation method of the sewage treatment agent provided by the embodiment comprises the following steps:
and step S1: weighing 17.50g of magnesium hydroxide powder and 7.80g of aluminum hydroxide powder, placing the magnesium hydroxide powder and the aluminum hydroxide powder in a ball milling tank, keeping the ball-material ratio at 40, and carrying out ball milling for 2 hours by using a ball mill at the rotating speed of 200r/min to obtain a magnesium-aluminum mixture;
and step S2: mixing 450mL of deionized water and 100mL of ethanol to prepare a mixed solvent, heating to 50 ℃ and preserving heat for later use, weighing 6.12g of sodium stearate, dissolving the sodium stearate by adopting the mixed dissolution, and fixing the volume to 500mL in a 500mL volumetric flask to prepare a clear solution with the concentration of the sodium stearate of 0.04 mol/L;
and step S3: weighing 379mL of clear solution in the step S2, and adding the magnesium-aluminum mixture uniformly mixed in the step S1 into the 379mL of clear solution under the stirring state to prepare suspension;
and step S4: putting the suspension prepared in the step S3 into a hydrothermal kettle with the volume of 1L for primary hydrothermal, wherein the specific hydrothermal process comprises the following steps: heating to 95 ℃ at the heating rate of 2 ℃/min, then preserving heat for 30h, and continuously stirring in the hydrothermal process, wherein the stirring speed is set to 180 r/min.
After the primary hydrothermal treatment is finished, the suspension is quickly put into a low-temperature refrigerator for freezing treatment for 30min, and the temperature of the low-temperature refrigerator is set to be minus 15 ℃.
After the freezing treatment is finished, putting the suspension into a 1L hydrothermal kettle for secondary hydrothermal, wherein the specific hydrothermal process comprises the following steps: heating to 110 ℃ at the heating rate of 2 ℃/min, then preserving heat for 3h, and then cooling to 30 ℃ at the cooling rate of 3 ℃/min. Stirring is continuously carried out in the primary hydrothermal process, and the stirring speed is set to be 180 r/min.
Performing liquid-solid separation on the suspension subjected to secondary hydrothermal treatment by a centrifugal machine, and drying the obtained precipitate in a vacuum drying oven at 120 ℃ for 10h to obtain the sodium stearate intercalated Mg3Al-OH LDHs。
A sewage treatment agent is prepared by adopting the method.
Example 2
The preparation method of the sewage treatment agent provided by the embodiment comprises the following steps:
and step S1: weighing 18.33g of magnesium hydroxide powder and 7.80g of aluminum hydroxide powder, placing the magnesium hydroxide powder and the aluminum hydroxide powder in a ball milling tank, keeping the ball-material ratio at 40, and carrying out ball milling for 3 hours by using a ball mill at the rotating speed of 100r/min to obtain a magnesium-aluminum mixture;
and step S2: mixing 500mL of deionized water and 100mL of ethanol to prepare a mixed solvent, heating to 50 ℃ and preserving heat for later use, weighing 7.65g of sodium stearate, dissolving the sodium stearate by adopting the mixed dissolution, and fixing the volume in a 500mL volumetric flask to prepare a clear solution with the concentration of the sodium stearate of 0.05 mol/L;
and step S3: measuring 344mL of clear solution in the step S2, and adding the magnesium-aluminum mixture uniformly mixed in the step S1 into 344mL of clear solution under the stirring state to prepare suspension;
and step S4: putting the suspension prepared in the step S3 into a hydrothermal kettle with the volume of 1L for primary hydrothermal, wherein the specific hydrothermal process comprises the following steps: heating to 100 ℃ at the heating rate of 1 ℃/min, then preserving heat for 24h, and continuously stirring in the primary hydrothermal process, wherein the stirring speed is set to 120 r/min.
After the primary hydrothermal treatment is finished, the suspension is quickly put into a low-temperature refrigerator for freezing treatment for 30min, and the temperature of the low-temperature refrigerator is set to be minus 15 ℃.
After the freezing treatment is finished, putting the suspension into a 1L hydrothermal kettle for secondary hydrothermal, wherein the specific hydrothermal process comprises the following steps: heating to 100 ℃ at a heating rate of 3 ℃/min, then preserving heat for 4h, and then cooling to 30 ℃ at a cooling rate of 2 ℃/min. Stirring is continuously carried out in the secondary hydrothermal process, and the stirring speed is set to be 120 r/min.
Performing liquid-solid separation on the suspension subjected to secondary hydrothermal treatment by a centrifugal machine, and drying the obtained precipitate in a vacuum drying oven at 120 ℃ for 10h to obtain the sodium stearate intercalated Mg3Al-OH LDHs。
A sewage treatment agent is prepared by adopting the method.
Example 3
The preparation method of the sewage treatment agent provided by the embodiment comprises the following steps:
and step S1: weighing 16.61g of magnesium hydroxide powder and 7.80g of aluminum hydroxide powder, placing the powder in a ball milling tank, keeping the ball-material ratio at 40, and performing ball milling for 1 hour by using a ball mill at the rotating speed of 300r/min to obtain a magnesium-aluminum mixture;
and step S2: mixing 400mL of deionized water and 100mL of ethanol to prepare a mixed solvent, heating to 50 ℃ and preserving heat for later use, weighing 2.30g of sodium stearate, dissolving the sodium stearate by adopting the mixed dissolution, and fixing the volume in a 250mL volumetric flask to prepare a clear solution with the concentration of the sodium stearate of 0.03 mol/L;
and step S3: measuring 207mL of clear solution in the step S2, and adding the magnesium-aluminum mixture uniformly mixed in the step S1 into 207mL of clear solution under the stirring state to prepare suspension;
and step S4: putting the suspension prepared in the step S3 into a hydrothermal kettle with the volume of 0.5L for primary hydrothermal, wherein the specific hydrothermal process comprises the following steps: heating to 90 ℃ at the heating rate of 3 ℃/min, then preserving the heat for 36h, and continuously stirring in the primary hydrothermal process, wherein the stirring speed is set to 240 r/min.
After the primary hydrothermal treatment is finished, the suspension is quickly put into a low-temperature refrigerator for freezing treatment for 30min, and the temperature of the low-temperature refrigerator is set to be minus 15 ℃.
After the freezing treatment is finished, putting the suspension into a 0.5L hydrothermal kettle for secondary hydrothermal, wherein the specific hydrothermal process comprises the following steps: heating to 120 ℃ at a heating rate of 1 ℃/min, then preserving heat for 2h, and then cooling to 30 ℃ at a cooling rate of 4 ℃/min. Stirring is continuously carried out in the secondary hydrothermal process, and the stirring speed is set to be 240 r/min.
Performing liquid-solid separation on the suspension subjected to secondary hydrothermal treatment by a centrifugal machine, and drying the obtained precipitate in a vacuum drying oven at 120 ℃ for 10h to obtain the sodium stearate intercalated Mg3Al-OH LDHs。
A sewage treatment agent is prepared by adopting the method.
Example 4
The preparation method of the sewage treatment agent provided by the embodiment comprises the following steps:
and step S1: weighing 17.47g of magnesium hydroxide powder and 7.80g of aluminum hydroxide powder, placing the magnesium hydroxide powder and the aluminum hydroxide powder in a ball milling tank, keeping the ball-material ratio at 40, and carrying out ball milling for 1 hour by a ball mill at the rotating speed of 100r/min to obtain a magnesium-aluminum mixture;
and step S2: mixing 450mL of deionized water and 100mL of ethanol to prepare a mixed solvent, heating to 50 ℃ and preserving heat for later use, weighing 6.12g of sodium stearate, dissolving the sodium stearate by adopting the mixed dissolution, and fixing the volume in a 500mL volumetric flask to prepare a clear solution with the concentration of the sodium stearate of 0.04 mol/L;
and step S3: weighing 474mL of clear solution in the step S2, and adding the magnesium-aluminum mixture uniformly mixed in the step S1 into the 474mL of clear solution under the stirring state to prepare suspension;
and step S4: putting the suspension prepared in the step S3 into a hydrothermal kettle with the volume of 1L for primary hydrothermal, wherein the specific hydrothermal process comprises the following steps: heating to 100 ℃ at the heating rate of 2 ℃/min, then preserving the heat for 36h, and continuously stirring in the primary hydrothermal process, wherein the stirring speed is set to 120 r/min.
After the primary hydrothermal treatment is finished, the suspension is quickly put into a low-temperature refrigerator for freezing treatment for 30min, and the temperature of the low-temperature refrigerator is set to be minus 15 ℃.
After the freezing treatment is finished, putting the suspension into a 1L hydrothermal kettle for secondary hydrothermal, wherein the specific hydrothermal process comprises the following steps: heating to 100 ℃ at a heating rate of 3 ℃/min, then preserving heat for 4h, and then cooling to 30 ℃ at a cooling rate of 3 ℃/min. Stirring is continuously carried out in the secondary hydrothermal process, and the stirring speed is set to be 180 r/min.
Performing liquid-solid separation on the suspension subjected to secondary hydrothermal treatment by a centrifugal machine, and drying the obtained precipitate in a vacuum drying oven at 120 ℃ for 10h to obtain the sodium stearate intercalated Mg3Al-OH LDHs。
A sewage treatment agent is prepared by adopting the method.
Example 5
The preparation method of the sewage treatment agent provided by the embodiment comprises the following steps:
and step S1: weighing 17.47g of magnesium hydroxide powder and 7.80g of aluminum hydroxide powder, placing the magnesium hydroxide powder and the aluminum hydroxide powder in a ball milling tank, keeping the ball-to-material ratio at 40, and carrying out ball milling for 3 hours by using a ball mill at the rotating speed of 300r/min to obtain a magnesium-aluminum mixture;
and step S2: mixing 400mL of deionized water and 100mL of ethanol to prepare a mixed solvent, heating to 50 ℃ and preserving heat for later use, weighing 4.60g of sodium stearate, dissolving the sodium stearate by adopting the mixed dissolution, and fixing the volume in a 500mL volumetric flask to prepare a clear solution with the concentration of the sodium stearate of 0.03 mol/L;
and step S3: measuring 316mL of clear solution in the step S2, and adding the magnesium-aluminum mixture uniformly mixed in the step S1 into 316mL of clear solution under the stirring state to prepare suspension;
and step S4: putting the suspension prepared in the step S3 into a hydrothermal kettle with the volume of 1L for primary hydrothermal, wherein the specific hydrothermal process comprises the following steps: heating to 95 ℃ at a heating rate of 3 ℃/min, then preserving heat for 30h, and continuously stirring in a primary hydrothermal process, wherein the stirring speed is set to 240 r/min.
After the primary hydrothermal treatment is finished, the suspension is quickly put into a low-temperature refrigerator for freezing treatment for 30min, and the temperature of the low-temperature refrigerator is set to be minus 15 ℃.
After the freezing treatment is finished, putting the suspension into a 1L hydrothermal kettle for secondary hydrothermal, wherein the specific hydrothermal process comprises the following steps: heating to 110 ℃ at the heating rate of 2 ℃/min, then preserving heat for 3h, and then cooling to 30 ℃ at the cooling rate of 2 ℃/min. Stirring is continuously carried out in the secondary hydrothermal process, and the stirring speed is set to be 120 r/min.
Performing liquid-solid separation on the suspension subjected to secondary hydrothermal treatment by a centrifugal machine, and drying the obtained precipitate in a vacuum drying oven at 120 ℃ for 10h to obtain the sodium stearate intercalated Mg3Al-OH LDHs。
A sewage treatment agent is prepared by adopting the method.
Comparative example 1
The main difference between this comparative example 1 and example 1 is that:
in the preparation method of the sewage treatment agent, after primary hydrothermal treatment, the temperature is reduced to 30 ℃ at the cooling rate of 3 ℃/min. Then carrying out secondary hydrothermal, heating to 110 ℃ at the heating rate of 2 ℃/min, then preserving heat for 3h, and then cooling to 30 ℃ at the cooling rate of 3 ℃/min. Stirring is continuously carried out in the primary hydrothermal process, and the stirring speed is set to be 180 r/min. Performing liquid-solid separation on the suspension obtained after the secondary hydrothermal treatment by using a centrifugal machine, and drying the obtained precipitate in a vacuum drying oven at 120 ℃ for 10h to obtain the sodium stearate intercalated Mg3Al-OH LDHs。
Comparative example 2
The main difference between this comparative example 2 and example 1 is that:
in the preparation method of the sewage treatment agent, after primary hydrothermal treatment, the temperature is reduced to 30 ℃ at the cooling rate of 3 ℃/min. Directly subjecting the obtained suspension to liquid-solid separation by a centrifuge, and drying the obtained precipitate in a vacuum drying oven at 120 deg.C for 10h to obtain sodium stearate intercalation Mg3Al-OH LDHs。
Comparative example 3
The main difference between this comparative example 3 and example 1 is that:
in step S2, sodium stearate is not dissolved in the clear solution, which has the same composition as the mixed solvent.
Test example 1
Sodium stearate intercalated Mg prepared in examples 1 to 5 and comparative examples 1 to 3 was used3The Al-OH LDHs sewage treatment agent is used for treating a sewage sample, and the amount of nitrobenzene compounds in the sewage before and after treatment is measured by using a gas chromatography. Using an instrument: agilent 6890 gas chromatograph, matching with split-flow/no-flow capillary injection port and microcell electronic capture detector.
The method comprises the following specific steps:
(1) drawing a standard curve
Preparing standard series solutions with the use concentration of 5-1000 mug/L by adopting standard stock solutions of nitrobenzene compounds. 1 μ L of each of the above standard series solutions was taken for analysis, and gas chromatography was performed using a DB-5 quartz capillary column (30. mu. m.times.0.25. mu. m.times.250 μm) under the following conditions: the initial temperature of the chromatographic column is 60 ℃, the temperature is increased to 220 ℃ at the speed of 10 ℃/min and is kept for 12min, and the flow rate of the chromatographic column is 1.6 mL/min; the temperature of a sample inlet is 220 ℃, and the non-split sample injection speed is 20 mL/min; the time from the sample introduction to the opening of the shunt valve is 0.75 min; the detector temperature was 310 ℃ and tail gas was blown at 60 mL/min. The above concentration was measured in duplicate and a standard curve was drawn using the average of the two.
(2) Sample preparation and determination by distillation-toluene extraction
Shaking the water sample, accurately measuring 200mL, placing in a separating funnel, adding 10mL of toluene, shaking for 3min, standing for 10min, allowing the two phases to separate, and discarding the water phase. Passing the extract through an anhydrous sodium sulfate drying column, collecting the extract in a 250mL flat-bottom flask, extracting the extract once with 5mL of toluene, and combining the extracts; after the extract was concentrated to 2mL by evaporation, toluene was added to the concentrate to a volume of 250 mL.
The quantitative analysis of the nitrobenzene compounds can be calculated by adopting an external standard method according to the following formula: c ═ Ai-Ao/As)×Cs×V1/V2，
In the formula, C: the concentration of each component of the nitrobenzene compounds in the water sample is mg/L;
Ai: response values of detected components in the water sample;
Ao: blank sampleThe response value of the detected component;
As: response values of the detected components in the standard sample;
Cs: the concentration of the detected component in the standard sample is mg/L;
V1: the volume of the sample is determined to be mL;
V2: and (5) fixing the volume of the water sample to be mL.
And summing the measured concentrations of the components of the nitrobenzene compounds in the water sample.
Test example 2
Sodium stearate intercalated Mg prepared in examples 1 to 5 and comparative examples 1 to 3 was used3The Al-OH LDHs sewage treatment agent is used for treating a sewage sample, and the amount of polycyclic aromatic hydrocarbon compounds in the sewage before and after treatment is determined by gas chromatography. Using an instrument: agilent 6890 gas chromatograph, matching with split-flow/no-flow capillary injection port and microcell electronic capture detector, extraction oscillator, rotary evaporator, silica gel column 1000mg/6.0 mL.
The method comprises the following specific steps:
(1) drawing a standard curve
A polycyclic aromatic hydrocarbon standard stock solution is adopted, and normal hexane is used for preparing a standard series solution with the use concentration of 1-1000 mug/mL. 1 μ L of each of the above standard series solutions was taken for analysis, and gas chromatography was performed using a DB-5 quartz capillary column (30. mu. m.times.0.25. mu. m.times.320 μm) under the following conditions: the initial temperature of the chromatographic column is 60 ℃, the temperature is increased to 300 ℃ at the rate of 12 ℃/min and is kept for 12min, and the flow rate of the chromatographic column is 1.0 mL/min; the flow rate of carrier gas hydrogen is 1.8 mL/min; keeping the temperature of a sample inlet at 300 ℃ for 5min, and controlling the sample introduction speed without flow splitting to be 20 mL/min; hydrogen flame ionization 200 detector (FID) temperature 310 deg.C, hydrogen flow rate 40mL/min, air 350 mL/min. The above concentration was measured in duplicate and a standard curve was drawn using the average of the two.
(2) Sample preparation and assay
Putting 1000mL of water sample to be detected into a separating funnel, adding 50mL of dichloromethane, adding 30g of sodium chloride, oscillating, discharging gas, placing the solution on an extraction oscillator for oscillation extraction for 20min after the sodium chloride is dissolved, standing for layering, collecting the extract in a 250mL flat-bottomed flask through an anhydrous sodium sulfate drying column, extracting once with 50mL of dichloromethane, and combining the extracts; after the extract was evaporated and concentrated to 2mL, n-hexane was added to the concentrate to a constant volume of 5 mL.
The quantitative analysis of the polycyclic aromatic hydrocarbon compound can be calculated by adopting an external standard method according to the following formula: c ═ Ai-Ao/As)×Cs×V1/V2，
In the formula, C: the concentration of each component of the polycyclic aromatic hydrocarbon in the water sample is mg/L;
Ai: response values of detected components in the water sample;
Ao: response values of the detected components in the blank sample;
As: response values of the detected components in the standard sample;
Cs: the concentration of the detected component in the standard sample is mg/L;
V1: the volume of the sample is determined to be mL;
V2: and (5) fixing the volume of the water sample to be mL.
And summing the concentrations of the components of the polycyclic aromatic hydrocarbon compound in the water sample.
The total concentrations of the individual components of the nitrobenzene compound measured in test example 1 and the total concentrations of the individual components of the polycyclic aromatic hydrocarbon compound measured in test example 2 are reported in table 1.
Table 1 shows the total concentration of each component of the nitrobenzene compounds and the total concentration of each component of the polycyclic aromatic hydrocarbon compounds in the raw sewage, the sewage treated by the sewage treatment agents of examples 1 to 5 and comparative examples 1 to 3
From the experimental results of table 1, it can be seen that: (1) in 8 sewage treatment agents prepared in examples 1 to 5 and comparative examples 1 to 3, the sewage treatment agent prepared in example 1, namely sodium stearate intercalated Mg, was used3The Al-OH LDHs has optimal organic pollutant treatment adsorption capacity, can effectively adsorb organic pollutants in sewage and achieves the aim of purifyingThe purpose of sewage disposal is achieved. (2) Comparative example 3 the procedure of sewage treatment agent preparation was identical to that of example 1 except that sodium stearate was not added, but the sewage treatment agent prepared had very low adsorption capacity to the above two hydrophobic organic pollutants (nitrobenzene-based compound and polycyclic aromatic hydrocarbon compound), but example 1 with sodium stearate added was very effective on the above two hydrophobic organic pollutants, indicating that sodium stearate modification had very significant effects. (3) The sewage treatment agent prepared in comparative example 1 has a very good adsorption effect on organic pollutants, but the effect is much worse than that of the sewage treatment agent prepared in example 1. The reason is that comparative example 1 has no freezing process compared to example 1, indicating that freezing process is better for inserting Mg into sodium stearate3Al-OH LDHs are advantageous between layers. (4) Comparative example 2 compared with comparative example 3, the sewage treatment agent prepared in comparative example 2, which has less secondary hydrothermal step, has a weak treatment effect on the hydrophobic organic pollutants, which shows that the secondary hydrothermal treatment has Mg insertion into sodium stearate3The Al-OH LDHs layers are helpful.
In summary, in the sewage treatment agent and the preparation method of the sewage treatment agent of the embodiments of the present invention, the conventional sewage treatment agent Mg is treated by using sodium stearate and adopting the methods of the primary hydrothermal treatment, the freezing treatment and the secondary hydrothermal treatment3And modifying the Al-OH LDHs. Traditional sewage treatment agent Mg3Al-OH LDHs have good adsorption effect on hydrophilic organic pollutants, but have poor adsorption effect on hydrophobic organic pollutants. The hydrophobic group of the sodium stearate is a hydrocarbyl group, and the hydrophilic group is a carboxyl group. Under the hydrothermal reaction, sulfonic acid groups can be inserted into Mg through electrostatic attraction and hydrogen bond action3Between the Al-OH LDHs layers, a hydrophobic area is formed between the Al-OH LDHs layers, and the adsorption capacity to hydrophobic organic pollutants is greatly improved.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (7)
1. A preparation method of a sewage treatment agent is characterized by comprising the following steps:
and step S1: and (2) mixing the following components in a mass ratio of 2.13-2.35: 1, uniformly mixing magnesium hydroxide powder and aluminum hydroxide powder to prepare a magnesium-aluminum mixture;
and step S2: and (3) mixing the components in a volume ratio of 4-5: 1, mixing deionized water and ethanol to prepare a mixed solvent, and dissolving sodium stearate in the mixed solvent to prepare a clear solution with the concentration of 0.03-0.05 mol/L;
and step S3: adding the magnesium-aluminum mixture into the clear solution under the stirring state to prepare a suspension;
and step S4: carrying out primary hydrothermal treatment, freezing treatment, secondary hydrothermal treatment, centrifugation and drying on the suspension to obtain the sodium stearate intercalated Mg3Al-OH LDHs; the freezing treatment comprises the following steps: the suspension obtained after the first hydrothermal treatment was kept at-15 ℃ for 30 min.
2. The method according to claim 1, wherein the first hydrothermal treatment and the second hydrothermal treatment are performed under stirring at a stirring speed of 120 to 240r/min in the step S4.
3. The method according to claim 1, wherein in the step S4, the primary water heat is: heating to 90-100 ℃ at a heating rate of 1-3 ℃/min, and then preserving heat for 24-36 h.
4. The method for preparing a sewage treatment agent according to claim 1, wherein in the step S4, the secondary hydrothermal process comprises: heating to 100-120 ℃ at a heating rate of 1-3 ℃/min, then preserving heat for 2-4 h, and then cooling to 30 ℃ at a cooling rate of 2-4 ℃/min.
5. The method of claim 1, wherein in the step of S1, the magnesium hydroxide powder and the aluminum hydroxide powder are mechanically ball milled at a rotation speed of 100 to 300r/min for 1 to 3 hours.
6. The preparation method of the sewage treatment agent according to claim 1, wherein in the step S3, the ratio of the magnesium-aluminum mixture to the clear solution is 8-12 g: 150 mL.
7. A sewage treatment agent, which is prepared by the preparation method of the sewage treatment agent as claimed in any one of claims 1 to 6.
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