CN112875848A - Alkali pretreatment activated sludge adsorbent and preparation method and application thereof - Google Patents
Alkali pretreatment activated sludge adsorbent and preparation method and application thereof Download PDFInfo
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- CN112875848A CN112875848A CN202110051210.3A CN202110051210A CN112875848A CN 112875848 A CN112875848 A CN 112875848A CN 202110051210 A CN202110051210 A CN 202110051210A CN 112875848 A CN112875848 A CN 112875848A
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1205—Particular type of activated sludge processes
- C02F3/1226—Particular type of activated sludge processes comprising an absorbent material suspended in the mixed liquor
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention discloses an alkali pretreatment activated sludge adsorbent and a preparation method and application thereof. The method comprises the following steps: taking wet sludge of oxidation ditch activated sludge of a sewage plant as a raw material, and adding NaOH solution for pretreatment; and standing for precipitation, pouring out supernatant, and filtering bottom sludge by using filter paper to obtain the alkali pretreatment activated sludge adsorbent. The application of the alkali pretreatment activated sludge adsorbent comprises the following steps: mixing alkali pretreatment activated sludge adsorbent and antimony-containing wastewater (the concentration of antimony element is 0.19-50mg/L), performing adsorption treatment under a stirring state, and standing to obtain the wastewater after adsorption. The invention carries out alkali pretreatment on the activated sludge of the sewage plant to treat the antimony-containing wastewater, and treats the wastewater with the waste, and the result shows that compared with the untreated activated sludge adsorbent, the activated sludge pretreated by NaOH can improve the removal rate of antimony in the sewage, and provides a new way for treating the antimony in the printing and dyeing wastewater.
Description
Technical Field
The invention belongs to the field of sewage treatment and treatment, and particularly relates to an alkali pretreatment activated sludge adsorbent and a preparation method and application thereof.
Background
Antimony is used as an important mineral resource, and is widely applied in industry, and a large amount of antimony-containing waste water is generated every year. Antimony is discharged into wastewater as a catalyst in textile industry, an auxiliary agent in printing and dyeing industry, a flame retardant and the like. Antimony and compounds thereof have certain toxicity, and can cause pollution to the environment and threaten human health. Therefore, it is important to remove antimony from the printing and dyeing wastewater having a large total amount.
At present, methods for removing heavy metal antimony in water mainly comprise an adsorption method and a coagulating sedimentation method, but the methods have the problems of high treatment cost, large sludge amount and the like. In recent years, the biological adsorbent has good affinity to heavy metal ions in water due to low cost and abundant sources compared with other materials, and is a promising technology for removing heavy metals in an aqueous solution. Commonly used biomaterials are: algae, chitosan, cellulose, and cell organisms, among others. However, some biological adsorbents often have the problems of inconvenient transportation or need of separate culture, and are difficult to popularize in practical application. In contrast, the excess activated sludge generated in the sewage treatment process is used as a biological adsorbent, the defects of transportation, culture and the like are overcome, the excess activated sludge is used for adsorbing heavy metal wastewater, the waste is treated by the waste, the sludge is recycled, and the treatment cost is reduced.
Activated sludge is a flocculent comprised of microbiological organisms, organic polymers, inorganic matter and some minerals. Among them, microbial metabolism can produce EPS (extracellular polymeric substance) -containing substances whose main components are polysaccharides, nucleic acids, proteins, and the like. On the one hand, these materials contain a large number of negatively charged groups, such as amino groups, carboxyl groups, hydroxyl groups, etc., and metal cations in water can combine with these negatively charged active groups to undergo precipitation, complexation, ion exchange, adsorption, etc. On the other hand, the activated sludge zoogloea has large surface area and negative charges on the surface, and can adsorb metal ions through charge neutralization. The method for treating heavy metal ions by utilizing the adsorption effect of the activated sludge is a good way for recycling the sludge, treats waste by waste and can reduce the treatment cost.
The activated sludge as the adsorbent generally has two using ways, one is drying and grinding the sludge into powder, the other is directly using wet sludge, considering the industrial application, the preparation time of the dry sludge is longer, the operation is complicated, and the wet sludge is uniformly dispersed in water, so the wet sludge is used as the raw material in the experiment.
In the basic research on the application of activated sludge biosorbent to lead-containing wastewater, Xiaona of Kunming theory of technology university in 2005, activated sludge wet bacteria is used as a raw material, and activated sludge is treated by pretreatment modes such as NaOH, HCl, ethanol, deionized water and the like to prepare the biosorbent for treating the lead-containing wastewater. The results show that the pretreatment by acid, ethanol and deionized water can increase the effective binding sites of activated sludge thallus cells, thereby increasing the binding sites of activated sludge and metal ions and improving the removal rate of lead ions. However, the research is limited to simulating the treatment of the lead-containing wastewater, is not applied to the actual wastewater, and does not deeply discuss the lead removal mechanism.
The existing researches on removing heavy metals by using the activated sludge adsorbent are mostly directed at lead ions and cadmium ions, and the removal of antimony ions in water is not researched yet.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide an alkali pretreatment activated sludge adsorbent and a preparation method and application thereof.
The invention provides a method for treating antimony-containing wastewater by using NaOH to pretreat activated sludge, and the raw material of an adsorbent is activated sludge in an oxidation ditch of a sewage treatment plant, so that the waste is treated by the waste, the cost is low, and the antimony removal effect is good.
Compared with untreated activated sludge adsorbent, the alkali pretreatment activated sludge biological adsorbent prepared by the invention can not only improve the removal of antimony ions in simulated wastewater, but also effectively remove the antimony ions in actual printing and dyeing wastewater, so that the treatment of the wastewater by waste is realized, the treatment cost is reduced, and a new idea is provided for the removal of antimony in the actual printing and dyeing wastewater; and the antimony removal mechanism of the activated sludge is explored through SEM and FTIR analysis and test.
The purpose of the invention is realized by at least one of the following technical solutions.
The preparation method of the alkali pretreatment activated sludge adsorbent provided by the invention comprises the following steps:
(1) adding the oxidation ditch activated sludge of the sewage treatment plant into NaOH solution, and stirring for reaction to obtain a reacted mixture;
(2) and (2) standing the mixture obtained after the reaction in the step (1), separating supernatant and bottom sludge, removing the supernatant, filtering the bottom sludge with filter paper to remove liquid, and taking precipitate to obtain the alkali pretreatment activated sludge adsorbent.
Further, the water content of the oxidation ditch activated sludge of the sewage treatment plant in the step (1) is 85% -95%, the pH value of the oxidation ditch activated sludge of the sewage treatment plant is 6-7, preferably, the water content of the oxidation ditch activated sludge of the sewage treatment plant in the step (1) is 93.3%, and the pH value of the oxidation ditch activated sludge of the sewage treatment plant is 6.36. Further, the concentration of the NaOH solution in the step (1) is 0.5-2mol/L, and preferably, the concentration of the NaOH solution in the step (1) is 1 mol/L.
Further, the mass ratio of the oxidation ditch activated sludge of the sewage treatment plant in the step (1) to the NaOH solution is 100-300:500g/mL, and preferably, the mass volume ratio of the oxidation ditch activated sludge of the sewage treatment plant in the step (1) to the NaOH solution is 200:500 g/mL.
Further, the speed of the stirring reaction in the step (1) is 150-300r/min, and the time of the stirring reaction is 0.5-2h, preferably, the speed of the stirring reaction in the step (1) is 200r/min, and the time of the stirring reaction is 1 h.
Further, the standing time of the step (2) is 1-3h, and preferably, the standing time of the step (2) is 2 h.
The invention provides an alkali pretreatment activated sludge adsorbent prepared by the preparation method.
The invention provides an application of an alkali pretreatment activated sludge adsorbent in treating antimony-containing wastewater.
The application of the alkali pretreatment activated sludge adsorbent in treating the antimony-containing wastewater comprises the following steps:
mixing the alkali pretreatment activated sludge adsorbent with the antimony-containing wastewater, and performing adsorption treatment to obtain the wastewater subjected to adsorption.
The water content of the sludge is 85 to 95 percent, the pH value is 6 to 7, and the concentration of NaOH is 0.5 to 2 mol/L.
Furthermore, in the antimony-containing wastewater, the concentration of antimony element is 0.19-50mg/L, and the mass-volume ratio of the alkali pretreatment activated sludge adsorbent to the antimony-containing wastewater is 20-120 g/L; the adsorption treatment time is 0.5-2h, and the standing time is 1-3 h.
Preferably, the time of the adsorption treatment is 1 h.
Preferably, the antimony-containing wastewater is actual printing and dyeing wastewater.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the method utilizes the activated sludge pretreated by NaOH to treat the antimony-containing wastewater, uses the activated sludge of a sewage treatment plant as the raw material, and has low cost and good antimony removal effect. Compared with untreated activated sludge adsorbent, the removal rate of antimony in the simulated antimony-containing wastewater can be improved from 59.7% to 80.5% after the activated sludge adsorbent is added for 1 h.
(2) The activated sludge adsorbent prepared by the invention is used for treating actual antimony-containing printing and dyeing wastewater, and after the activated sludge adsorbent is added for 1h, the removal rate of total antimony in the actual printing and dyeing wastewater can reach 70.48%; compared with the traditional coagulation method, the method reduces the treatment cost and provides an application prospect for the antimony removal of the actual printing and dyeing wastewater.
(3) The method for treating the antimony-containing wastewater by using the activated sludge of the sewage treatment plant provides a new way for resource utilization of the sludge of the sewage treatment plant, treats waste by using waste, has good effect, is economic and environment-friendly, and has good social value and economic value.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) micrograph (1000 magnification) of untreated sewage treatment plant oxidation ditch activated sludge of example 1.
Fig. 2 is a Scanning Electron Microscope (SEM) microscopic morphology (800 x magnification) of the alkaline pretreated activated sludge adsorbent of example 1.
FIG. 3 is a graph of IR spectroscopy analysis of untreated activated sludge and alkaline pretreatment activated sludge adsorbent in the examples.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
A preparation method of an alkali pretreatment activated sludge adsorbent comprises the following steps:
1) taking oxidation ditch activated sludge of a sewage treatment plant as a raw material, wherein the water content of the oxidation ditch activated sludge of the sewage treatment plant is 93.3%, the pH value of the oxidation ditch activated sludge of the sewage treatment plant is 6.36, preparing 500mL of 1mol/L NaOH solution, pouring the NaOH solution into a six-joint stirring cup, weighing 200g of oxidation ditch activated sludge of the sewage treatment plant, adding the oxidation ditch activated sludge into the NaOH solution, adjusting the rotating speed to be 200r/min, and reacting for 1h to obtain a reacted mixture;
2) standing and precipitating the mixture obtained after the reaction in the step 1) for 2 hours, separating supernatant and bottom sludge, pouring the supernatant, filtering the bottom sludge with filter paper to remove liquid, and taking the precipitate to obtain the alkali pretreatment activated sludge adsorbent.
Effect verification
And respectively placing the untreated sewage treatment plant oxidation ditch activated sludge and the alkali pretreatment activated sludge adsorbent under a scanning electron microscope for observation. The results are shown in FIGS. 1 and 2. FIG. 1 is a scanning electron microscope analysis chart of untreated sewage treatment plant oxidation ditch activated sludge, as shown in FIG. 1, flocs have larger gaps and a loose structure; FIG. 2 shows that compared with untreated sludge, oxidation ditch sludge pretreated with NaOH has a compact floc structure with more and smaller pores, which is more beneficial to the adsorption of antimony ions.
Respectively activating the oxidation ditch of the untreated sewage treatment plantThe infrared spectroscopic analysis of the sludge and the alkali pretreated activated sludge adsorbent was performed, and the results are shown in fig. 3. The spectral analysis showed that curve 0 is the infrared spectrum analysis curve of untreated activated sludge, which is shown at 3421.72cm-1Has obvious absorption peak related to the stretching vibration of-OH; at 2928.91cm-1Absorption peak and-CH in alkane organic matter and macromolecular polysaccharide2-stretching vibration related; at 1650.10, 1540.16cm-1The absorption peak is related to the special vibration of the-CONH-functional group of the amide I band and the amide II band in the protein; at 1248.91cm-1The absorption peak is related to the stretching vibration of carboxyl C ═ O; 1065cm-1The peak at (a) is from stretching vibration of the saccharide-OH. The polysaccharide, protein and the like in the activated sludge contain active groups such as hydroxyl, carboxyl, amino and the like, and the groups can be combined with metal cations to remove antimony in water. Curve 1 is the infrared spectroscopic analysis curve of alkali pretreated activated sludge at 1420cm-1The absorption peak is stronger and is related to carboxyl C ═ O, alcohol and phenolic hydroxyl, which shows that the increase of the adsorption performance after the alkali pretreatment is mainly to increase the quantity of carboxyl and hydroxyl.
As shown in FIGS. 1-3, after the activated sludge is pretreated by NaOH, the sludge floc structure becomes compact, more and smaller pore canals appear, and the specific surface area of the sludge can be increased as the pores become smaller; infrared spectroscopic analysis shows that the amount of carboxyl and hydroxyl in the activated sludge pretreated by NaOH is increased, so that the adsorption of metal cations is facilitated.
And adding the alkali pretreatment activated sludge adsorbent into the antimony-containing wastewater to verify the adsorption effect. The experiment included:
pouring 1L of a solution with the concentration of Sb (V) being 5mg/L into a six-joint stirring cup, wherein the solution is used as simulated antimony-containing wastewater, then adding 50g of the alkali pretreatment activated sludge adsorbent in the embodiment 1, adjusting the stirring speed to be 200r/min, reacting for 1h, standing for 1h, taking supernatant, performing suction filtration by using a 0.45-micron filter membrane, taking filtrate, measuring total antimony by using an atomic fluorescence spectrometry, and calculating the removal rate of the total antimony to be 71%.
Comparative example 1
The comparative example uses untreated activated sludge to treat simulated antimony-containing wastewater, and differs from example 1 in that: the untreated activated sludge is untreated oxidation ditch activated sludge of a sewage treatment plant.
The experiment comprises the following steps:
pouring 1L of a solution with the concentration of Sb (V) being 5mg/L into a six-joint stirring cup, taking the solution as simulated antimony-containing wastewater, adding 50g of untreated activated sludge, adjusting the stirring speed to be 200r/min, reacting for 1h, standing for 1h, taking a supernatant, filtering through a 0.45-micron filter membrane, measuring total antimony by using an atomic fluorescence spectrometry, and calculating the removal rate of the total antimony to be 41.6%.
Comparative example 2
The difference of the practical antimony-containing wastewater treated by the NaOH pretreatment activated sludge in the comparative example from the example 1 is as follows: the antimony-containing wastewater is actual printing and dyeing wastewater and is taken from raw water of a large regulating reservoir of a sewage treatment plant, the total antimony concentration is 0.19-0.21mg/L, and the adding amount of the alkali pretreatment activated sludge adsorbent is 20-120 g/L.
The experiment comprises the following steps:
1L of printing and dyeing wastewater (large regulating pond water) is poured into a six-joint stirring cup, the total antimony content in the water is 0.21mg/L, 120g of alkali pretreatment activated sludge adsorbent is added, the stirring speed is regulated to be 200r/min, the reaction time is 1h, after standing for 1h, the supernatant is taken, filtered through a 0.45 mu m filter membrane for suction filtration, the total antimony is measured by an atomic fluorescence spectrometry, and the removal rate of the total antimony is calculated to be 70.48%.
Comparative example 3
The comparative example uses untreated activated sludge to treat actual antimony-containing wastewater, and is different from the example 1 in that: the activated sludge is untreated oxidation ditch activated sludge of a sewage treatment plant, the antimony-containing wastewater is actual printing and dyeing wastewater and is taken from raw water of a large regulating reservoir of the sewage treatment plant, the total antimony concentration is 0.19-0.21mg/L, and the adding amount of the sludge is 20-120 g/L.
The experiment comprises the following steps:
1L of printing and dyeing wastewater (large regulating tank water) is poured into a six-joint stirring cup, the total antimony content in the water is 0.21mg/L, 120g of untreated oxidation ditch activated sludge of a sewage treatment plant is added, the stirring speed is regulated to be 200r/min, the reaction time is 1h, the mixture is kept stand for 1h, then supernatant is taken, the supernatant is filtered by a 0.45 mu m filter membrane for suction filtration, the total antimony is measured by an atomic fluorescence spectrometry, and the removal rate of the total antimony is calculated to be 64.29%.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of an alkali pretreatment activated sludge adsorbent is characterized by comprising the following steps:
(1) adding the oxidation ditch activated sludge of the sewage treatment plant into NaOH solution, and stirring for reaction to obtain a reacted mixture;
(2) and (2) standing the mixture obtained after the reaction in the step (1), separating supernatant and bottom sludge, removing the supernatant, filtering the bottom sludge, and taking precipitate to obtain the alkali pretreatment activated sludge adsorbent.
2. The method for preparing the alkali pretreatment activated sludge adsorbent according to claim 1, wherein the water content of the activated sludge of the oxidation ditch of the sewage treatment plant in the step (1) is 85% -95%, and the pH value of the sludge of the oxidation ditch of the sewage treatment plant is 6.0-7.0.
3. The method of preparing an alkali pretreatment activated sludge adsorbent according to claim 1, wherein the concentration of the NaOH solution in the step (1) is 0.5 to 2 mol/L.
4. The method for preparing the alkali pretreatment activated sludge adsorbent according to claim 1, wherein the mass-to-volume ratio of the activated sludge of the oxidation ditch of the sewage treatment plant in the step (1) to the NaOH solution is 100: 300:500 g/mL.
5. The method as claimed in claim 1, wherein the stirring reaction rate in step (1) is 150-300r/min, and the stirring time is 0.5-2 h.
6. The method according to claim 1, wherein the standing time in the step (2) is 1 to 3 hours.
7. An alkali-pretreated activated sludge adsorbent produced by the production method according to any one of claims 1 to 6.
8. Use of the alkaline pretreatment activated sludge adsorbent of claim 7 for treating antimony-containing wastewater.
9. The use of an alkaline pretreatment activated sludge adsorbent according to claim 8 for the treatment of antimony-containing wastewater, comprising the steps of:
mixing the alkali pretreatment activated sludge adsorbent with the antimony-containing wastewater, performing adsorption treatment under a stirring state, and standing to obtain the wastewater after adsorption.
10. The use of the alkaline pretreatment activated sludge adsorbent of claim 9 in the treatment of antimony-containing wastewater, wherein the concentration of antimony element in the antimony-containing wastewater is 0.19-50mg/L, and the mass-to-volume ratio of the alkaline pretreatment activated sludge adsorbent to the antimony-containing wastewater is 20-120:1 g/L; the time of the adsorption treatment is 0.5-2 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113893854A (en) * | 2021-10-18 | 2022-01-07 | 肇庆市鹏凯环保装备有限公司 | Supported binary metal oxide catalyst and preparation method and application thereof |
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Application publication date: 20210601 |