CN112121770A - Sludge ceramsite for heavy metal wastewater treatment and preparation method thereof - Google Patents

Sludge ceramsite for heavy metal wastewater treatment and preparation method thereof Download PDF

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CN112121770A
CN112121770A CN202011008980.1A CN202011008980A CN112121770A CN 112121770 A CN112121770 A CN 112121770A CN 202011008980 A CN202011008980 A CN 202011008980A CN 112121770 A CN112121770 A CN 112121770A
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ceramsite
heavy metal
metal wastewater
humic acid
wastewater treatment
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陈庆
司文彬
白涛
李钧
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Chengdu New Keli Chemical Science Co Ltd
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Abstract

The invention provides sludge ceramsite for treating heavy metal wastewater and a preparation method thereof, wherein the sludge ceramsite is prepared by pelletizing and sintering mixed raw materials of riverway bottom mud, fly ash, vermiculite powder, clay and ammonium bicarbonate to prepare porous ceramsite, mixing humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate, absolute ethyl alcohol and deionized water to prepare a mixed solution, grinding the mixed solution into slurry, and finally repeatedly soaking and drying the porous ceramsite in the slurry. The modified sludge ceramsite provided by the invention is modified by humic acid, has large specific surface area, strong adsorbability on heavy metals such as Pb, Cd and Cu, stable adsorption rate, repeated recycling and no secondary pollution, can be widely used for heavy metal wastewater treatment, realizes the resource utilization of river sediment, and achieves the purpose of treating waste by waste.

Description

Sludge ceramsite for heavy metal wastewater treatment and preparation method thereof
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to sludge ceramsite for heavy metal wastewater treatment and a preparation method thereof.
Background
The rapid development of industry and the inadequately attached environment of human beings cause the serious pollution of water bodies such as rivers, lakes and the like, a large amount of pollutants which are difficult to degrade enter the water bodies through the discharge of waste water and the washing of rainwater, are accumulated and gradually enriched in bottom mud of the water bodies, accumulate day by day and month and block rivers. Common disposal methods for recycling the river sediment comprise land utilization, building materials, filling materials and sewage treatment materials.
The heavy metal wastewater refers to wastewater containing heavy metals discharged in the industrial production process. The heavy metal wastewater cannot be degraded by any method, and can only be removed from the water body by generating various complexes or chelates by the compounds and metal ions or reducing the metal ions into simple substances. At present, methods for treating heavy metals in wastewater include an adsorption method, a chemical precipitation method and an electrolysis method, wherein the adsorption method is most widely applied, and common adsorption materials mainly comprise activated carbon, zeolite, ceramsite and the like. In recent years, the resource utilization of sludge is more and more concerned, if a large amount of bottom mud of a river channel is utilized, waste is changed into valuable, the problems of river channel blockage, secondary pollution of the bottom mud and the like caused by the sludge can be solved, certain economic benefit can be created, and the purpose of treating waste by waste is achieved.
In order to promote the environment-friendly development, the production of the ceramsite is more and more realized by taking solid waste as a raw material, and the cost is low. The ceramsite prepared by the sintering method has higher adsorption performance, and can be used as a sewage treatment material with excellent properties for adsorbing phosphorus and organic pollutants in water. The biological ceramsite carrier is mainly applied to a biological ceramsite carrier in a biological aerated filter, is applied to a filtering material for treating oily wastewater, can replace a filtering material for advanced treatment in the traditional water treatment, is low in price, environment-friendly and high in feasibility, and is widely applied to the field of wastewater treatment.
The Chinese patent application No. 201610712330.2 discloses a preparation method of urban sludge solidified heavy metal high-strength ceramsite, which comprises the following steps: (1) preparing materials: mixing the following raw materials in percentage by weight, 40-80% of urban dewatered sludge, 15-50% of saline soil, 5-10% of plasticizer and 0.2-0.35% of water-material ratio, and uniformly stirring after mixing; (2) and (3) granulation: putting the mixture into a granulator for granulation, wherein the granules are spherical or elliptical; (3) and (3) drying: drying the granulated particles in a drying box; (4) and (3) calcining: and then placing the dried particles into high-temperature calcining equipment to sinter so as to obtain the ceramsite. The invention discloses a preparation method of hydrophobic cellulose organic nano clay composite heavy metal ion adsorption ceramsite, which comprises the steps of firstly carrying out organic treatment on sodium-based montmorillonite to obtain organic montmorillonite, changing the hydrophilicity of the montmorillonite into hydrophobicity, then depositing a titanium dioxide film on the surface of a cellulose acetate film by a surface sol-gel method, pulping, then preparing hydrophobic composite cellulose acetate film pulp by using octadecyl trimethoxy silane toluene solution, putting the hydrophobic composite cellulose acetate film pulp and the organic montmorillonite into a high-speed emulsification homogenizer for intercalation reaction, and finally granulating and calcining.
In order to improve the adsorption capacity of the porous ceramsite to heavy metal pollutants in wastewater treatment application and improve the wastewater treatment effect, a novel modified sludge ceramsite needs to be provided, so that the effective application of the porous ceramsite in heavy metal wastewater treatment is realized.
Disclosure of Invention
Aiming at the defect that the adsorption performance of the common porous ceramsite on heavy metal pollutants in heavy metal wastewater is poor at present, the invention provides the sludge ceramsite for treating the heavy metal wastewater and the preparation method thereof, so that the application effect of the porous ceramsite in the heavy metal wastewater is improved.
In order to solve the problems, the invention adopts the following technical scheme:
a preparation method of sludge ceramsite for heavy metal wastewater treatment is characterized in that the sludge ceramsite is prepared by pelletizing and sintering a mixed raw material of riverway bottom mud, fly ash, vermiculite powder, clay and ammonium bicarbonate to obtain porous ceramsite, mixing nano humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate, absolute ethyl alcohol and deionized water to prepare a mixed solution, and finally repeatedly soaking and drying the porous ceramsite in the mixed solution, wherein the preparation method comprises the following steps:
(1) uniformly mixing river sediment serving as a main raw material with fly ash, vermiculite powder, clay, ammonium bicarbonate and water, pelletizing the raw material, and sintering at a high temperature to obtain porous ceramsite;
(2) uniformly mixing humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate, absolute ethyl alcohol and deionized water, and grinding by using a ball mill to obtain uniformly dispersed humic acid slurry;
(3) and adding the prepared porous ceramsite into the humic acid slurry, soaking for a certain time, taking out, drying, and repeating the soaking-drying process to obtain the modified sludge ceramsite for treating the heavy metal wastewater.
Preferably, the temperature of the high-temperature sintering in the step (1) is 1000-.
Preferably, the particle size of the porous ceramsite is 3-5 mm.
Preferably, in the preparation of the porous ceramsite in the step (1), the mass ratio of the river sediment, the fly ash, the water, the vermiculite powder, the clay and the ammonium bicarbonate is 100:50-70:60-80:20-30:20-25: 1-1.5.
Preferably, in the humic acid slurry in the step (2), the mass ratio of deionized water, humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate and absolute ethyl alcohol is 100:40-50:3-5:1-2:0.5-1: 2-4.
Preferably, the soaking time in the step (3) is 1-2 h.
Preferably, the temperature for drying in step (3) is 100-105 ℃, and the time is 15-20 min.
Preferably, the soaking-drying process is repeated 3 to 4 times in the step (3).
The invention also provides the sludge ceramsite for heavy metal wastewater treatment, which is prepared by the preparation method
The existing porous ceramic particles have poor adsorption performance to heavy metals in wastewater treatment, and limit the application of the porous ceramic particles. In view of the above, the invention provides a sludge ceramsite for heavy metal wastewater treatment and a preparation method thereof, wherein river sediment is used as a main raw material, and is uniformly mixed with fly ash, vermiculite powder, clay and ammonium bicarbonate according to a certain raw material ratio to form raw material balls, and then the raw material balls are sintered to prepare porous ceramsite; uniformly mixing humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate, absolute ethyl alcohol and deionized water according to a certain mass ratio, and grinding into fine humic acid slurry by a ball mill; soaking the prepared porous ceramsite in humic acid slurry, taking out the porous ceramsite, drying the porous ceramsite, and repeating the soaking-drying steps for a plurality of times to obtain the modified sludge ceramsite. The modified sludge ceramsite provided by the invention is modified by adopting the nano humic acid, has large specific surface area, strong adsorbability on heavy metals such as Pb, Cd and Cu, stable adsorption rate, repeated recycling and no secondary pollution, can be widely used for treating heavy metal wastewater, realizes the resource utilization of bottom mud of a river channel, and achieves the purpose of treating waste by waste.
Compared with the prior art, the invention provides the sludge ceramsite for treating the heavy metal wastewater and the preparation method thereof, and the outstanding characteristics and excellent effects are as follows:
1. according to the invention, the river sediment is used as a raw material to prepare the ceramsite, the property that nano humic acid has a strong adsorption effect on heavy metal ions is utilized, and the humic acid is adopted to modify the ceramsite, so that the obtained modified ceramsite has a large specific surface area, has strong adsorbability on heavy metals such as Pb, Cd and Cu, has a stable adsorption rate, and can be used for treating heavy metal wastewater.
2. The sludge ceramsite prepared by the method can be recycled for multiple times, does not cause secondary pollution to the environment, realizes the resource utilization of the bottom mud of the river channel, and achieves the purpose of treating wastes with processes of wastes against one another.
Drawings
FIG. 1: the modified ceramsite slice obtained in example 1 was observed by high power electron microscope to show the internal structure.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Uniformly mixing river sediment serving as a main raw material with fly ash, vermiculite powder, clay, ammonium bicarbonate and water, pelletizing the raw material, and sintering at a high temperature to obtain porous ceramsite; the temperature of high-temperature sintering is 1120 ℃, and the sintering heat preservation time is 13 min; the average grain diameter of the porous ceramsite is 4 mm; in the preparation of the porous ceramsite, the mass ratio of the river sediment, the fly ash, the water, the vermiculite powder, the clay and the ammonium bicarbonate is 100:58:80:24:23: 1.2;
(2) uniformly mixing humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate, absolute ethyl alcohol and deionized water, adding into a ball mill, and carrying out ball milling for 30min at the rotating speed of 50rpm to obtain fine humic acid slurry; in the slurry, the mass ratio of deionized water, nano humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate and absolute ethyl alcohol is 100:50:3:1:0.5: 4.
(3) Adding the prepared porous ceramsite into humic acid slurry, soaking for a certain time, taking out, drying, and repeating the soaking-drying process to obtain modified sludge ceramsite for treating heavy metal wastewater; the soaking time is 1.5 h; the drying temperature is 103 ℃, and the drying time is 18 min; the number of times of repeating the soaking-drying process was 3.
The modified ceramsite slice obtained in example 1 was observed by high power electron microscope to have an internal structure, as shown in FIG. 1, with abundant meshes.
Example 2
(1) Uniformly mixing river sediment serving as a main raw material with fly ash, vermiculite powder, clay, ammonium bicarbonate and water, pelletizing the raw material, and sintering at a high temperature to obtain porous ceramsite; the temperature of high-temperature sintering is 1000 ℃, and the sintering temperature is kept for 15 min; the average grain diameter of the porous ceramsite is 3 mm; in the preparation of the porous ceramsite, the mass ratio of the river sediment, the fly ash, the water, the vermiculite powder, the clay and the ammonium bicarbonate is 100:50:80:20:20: 1;
(2) uniformly mixing humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate, absolute ethyl alcohol and deionized water, adding into a ball mill, and carrying out ball milling for 30min at the rotating speed of 50rpm to obtain fine humic acid slurry; in the slurry, the mass ratio of deionized water, humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate and absolute ethyl alcohol is 100:50:3:1:0.5: 2;
(3) adding the prepared porous ceramsite into the humic acid slurry, soaking for a certain time, taking out, drying, and repeating the soaking-drying process to obtain the modified sludge ceramsite for treating the heavy metal wastewater; the soaking time is 1 h; the drying temperature is 100 ℃, and the drying time is 20 min; the number of times of repeating the soaking-drying process was 4.
Example 3
(1) Uniformly mixing river sediment serving as a main raw material with fly ash, vermiculite powder, clay, ammonium bicarbonate and water, pelletizing the raw material, and sintering at a high temperature to obtain porous ceramsite; the temperature of high-temperature sintering is 1200 ℃, and the sintering heat preservation time is 10 min; the average grain diameter of the porous ceramsite is 5 mm; in the preparation of the porous ceramsite, the mass ratio of the river sediment, the fly ash, the water, the vermiculite powder, the clay and the ammonium bicarbonate is 100: 70: 80: 30: 25: 1.5;
(2) uniformly mixing humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate, absolute ethyl alcohol and deionized water, adding into a ball mill, and carrying out ball milling for 30min at the rotating speed of 50rpm to obtain fine humic acid slurry; in the slurry, the mass ratio of deionized water, nano humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate and absolute ethyl alcohol is 100:40:5:1:0.5: 4.
(3) Adding the prepared porous ceramsite into the humic acid slurry, soaking for a certain time, taking out, drying, and repeating the soaking-drying process to obtain the modified sludge ceramsite for treating the heavy metal wastewater; the soaking time is 2 h; the drying temperature is 105 ℃, and the drying time is 15 min; the number of times of repeating the soaking-drying process was 3.
Example 4
(1) Uniformly mixing river sediment serving as a main raw material with fly ash, vermiculite powder, clay, ammonium bicarbonate and water, pelletizing the raw material, and sintering at a high temperature to obtain porous ceramsite; the temperature of high-temperature sintering is 1100 ℃, and the sintering heat preservation time is 12 min; the average grain diameter of the porous ceramsite is 4 mm; in the preparation of the porous ceramsite, the mass ratio of the river sediment, the fly ash, the water, the vermiculite powder, the clay and the ammonium bicarbonate is 100:60:75:25:22: 1.2;
(2) uniformly mixing humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate, absolute ethyl alcohol and deionized water, adding into a ball mill, and carrying out ball milling for 30min at the rotating speed of 50rpm to obtain fine humic acid slurry; in the slurry, the mass ratio of deionized water, nano humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate and absolute ethyl alcohol is 100:50:3:1:0.5: 3.
(3) Adding the prepared porous ceramsite into the humic acid slurry, soaking for a certain time, taking out, drying, and repeating the soaking-drying process to obtain the modified sludge ceramsite for treating the heavy metal wastewater; the soaking time is 2 h; the drying temperature is 102 ℃, and the drying time is 18 min; the number of times of repeating the soaking-drying process was 4.
Comparative example 1
Comparative example 1 compared to example 1, the ceramsite was not treated with humic acid slurry. The heavy metal removing effect of the obtained sludge ceramsite is obviously reduced.
Comparative example 2
(1) Uniformly mixing river sediment serving as a main raw material with fly ash, vermiculite powder, clay, ammonium bicarbonate and water, pelletizing the raw material, and sintering at a high temperature to obtain porous ceramsite; the temperature of high-temperature sintering is 1120 ℃, and the sintering heat preservation time is 13 min; the average grain diameter of the porous ceramsite is 4 mm; in the preparation of the porous ceramsite, the mass ratio of the river sediment, the fly ash, the water, the vermiculite powder, the clay and the ammonium bicarbonate is 100:58:80:24:23: 1.2;
(2) uniformly mixing humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate, absolute ethyl alcohol and deionized water, adding into a ball mill, and carrying out ball milling for 30min at the rotating speed of 50rpm to obtain fine humic acid slurry; in the slurry, the mass ratio of deionized water, nano humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate and absolute ethyl alcohol is 100:50:3:1:0.5: 4.
(3) Adding the prepared porous ceramsite into humic acid slurry, soaking for a certain time, taking out, and drying to obtain modified sludge ceramsite for treating heavy metal wastewater; the soaking time is 1.5 h; the drying temperature is 103 deg.C, and the drying time is 18 min.
Comparative example 2 compared with example 1, only humic acid slurry was used for 1 time of treatment of ceramsite. The effect of adsorbing heavy metals can be influenced due to the reduction of the amount of the loaded humic acid.
Comparative example 3
(1) Uniformly mixing river sediment serving as a main raw material with fly ash, vermiculite powder, clay and water, pelletizing the raw material, and sintering at high temperature to obtain porous ceramsite; the temperature of high-temperature sintering is 1120 ℃, and the sintering heat preservation time is 13 min; the average grain diameter of the porous ceramsite is 4 mm; in the preparation of the porous ceramsite, the mass ratio of the river sediment, the fly ash, the water, the vermiculite powder and the clay is 100:58:80:24: 23;
(2) uniformly mixing humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate, absolute ethyl alcohol and deionized water, adding into a ball mill, and carrying out ball milling for 30min at the rotating speed of 50rpm to obtain fine humic acid slurry; in the slurry, the mass ratio of deionized water, nano humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate and absolute ethyl alcohol is 100:50:3:1:0.5: 4.
(3) Adding the prepared porous ceramsite into humic acid slurry, soaking for a certain time, taking out, drying, and repeating the soaking-drying process to obtain modified sludge ceramsite for treating heavy metal wastewater; the soaking time is 1.5 h; the drying temperature is 103 ℃, and the drying time is 18 min; the number of times of repeating the soaking-drying process was 3.
Comparative example 3 compared to example 1, no ammonium bicarbonate was added to prepare the porous ceramsite. The ceramsite has fewer gaps, low specific surface area and limited load humic acid, so that the heavy metal adsorption effect is influenced.
The test method comprises the following steps:
the porous ceramsite prepared in the steps (1) of examples 1-4 and comparative examples 1-3 was tested for specific surface area by the BET nitrogen adsorption method. The results obtained are shown in Table 1;
the adsorption performance of the modified sludge ceramsite prepared in examples 1-4 and comparative examples 1-3 on heavy metal was tested, and 1000mL of the modified sludge ceramsite containing Pb was respectively taken2+、Cd2+、Cu2+The concentration of the simulated heavy metal wastewater is about 100mg/L, 0.5g of the sludge ceramsite prepared by the method is respectively added, ultrasonic oscillation is carried out for 2h at the temperature of 25 ℃, then the mixture is kept stand for 8h, supernatant is taken, the supernatant is filtered by a 0.45pm filter membrane, the concentration of heavy metal ions in filtrate is measured by adopting ICP, the adsorption performance of the modified sludge ceramsite on different heavy metals is calculated according to the ratio of the difference value of the concentrations before and after treatment to the initial concentration, and the obtained result is shown in Table 1.
Table 1:
Figure 423565DEST_PATH_IMAGE002

Claims (9)

1. a preparation method of sludge ceramsite for heavy metal wastewater treatment is characterized by comprising the following steps:
(1) uniformly mixing river sediment serving as a main raw material with fly ash, vermiculite powder, clay, ammonium bicarbonate and water, pelletizing the raw material, and sintering at a high temperature to obtain porous ceramsite;
(2) uniformly mixing humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate, absolute ethyl alcohol and deionized water, adding into a ball mill, and grinding into slurry to obtain uniformly dispersed humic acid slurry;
(3) and adding the prepared porous ceramsite into the humic acid slurry, soaking for a certain time, taking out, drying, and repeating the soaking-drying process to obtain the modified sludge ceramsite for treating the heavy metal wastewater.
2. The method for preparing sludge ceramsite for heavy metal wastewater treatment according to claim 1, wherein the temperature of the high-temperature sintering in step (1) is 1000-1200 ℃, and the sintering temperature is kept for 10-15 min.
3. The method for preparing sludge ceramsite for heavy metal wastewater treatment according to claim 1, wherein the particle size of said porous ceramsite is 3-5 mm.
4. The preparation method of the sludge ceramsite for heavy metal wastewater treatment according to claim 1, wherein in the preparation of the porous ceramsite in step (1), the mass ratio of the river sediment, the fly ash, the water, the vermiculite powder, the clay and the ammonium bicarbonate is 100:50-70:60-80:20-30:20-25: 1-1.5.
5. The preparation method of sludge ceramsite for heavy metal wastewater treatment according to claim 1, wherein in the humic acid slurry in the step (2), the mass ratio of deionized water, humic acid, isopropanol, sodium carbonate, sodium dodecyl benzene sulfonate and absolute ethyl alcohol is 100:40-50:3-5:1-2:0.5-1: 2-4.
6. The method for preparing sludge ceramsite for heavy metal wastewater treatment according to claim 1, wherein the soaking time in the step (3) is 1-2 h.
7. The method for preparing sludge ceramsite for heavy metal wastewater treatment according to claim 1, wherein the drying temperature in step (3) is 100-105 ℃ and the drying time is 15-20 min.
8. The method for preparing sludge ceramsite according to claim 1, wherein the soaking-drying process is repeated 3-4 times in step (3).
9. A sludge ceramsite for treating heavy metal wastewater, which is prepared by the preparation method of any one of claims 1-8.
CN202011008980.1A 2020-09-23 2020-09-23 Sludge ceramsite for heavy metal wastewater treatment and preparation method thereof Withdrawn CN112121770A (en)

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CN113952934A (en) * 2021-11-08 2022-01-21 中国环境科学研究院 Internal load control material for water body mud source
CN115608340A (en) * 2022-10-11 2023-01-17 青岛科技大学 Magnetic ceramsite adsorbent for removing heavy metal copper ions in water and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113368819A (en) * 2021-06-01 2021-09-10 河海大学 In-situ covering material aiming at flaky slow-sinking adsorption of floating mud and preparation method
CN113368819B (en) * 2021-06-01 2024-04-12 河海大学 Sheet slow-sedimentation adsorption in-situ covering material for floating mud and preparation method thereof
CN113952934A (en) * 2021-11-08 2022-01-21 中国环境科学研究院 Internal load control material for water body mud source
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