CN115155556A - Preparation method and application of activated persulfate sludge-based biochar catalyst - Google Patents
Preparation method and application of activated persulfate sludge-based biochar catalyst Download PDFInfo
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- 239000010802 sludge Substances 0.000 title claims abstract description 107
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical class S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 43
- 239000003054 catalyst Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000000694 effects Effects 0.000 claims abstract description 15
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical group OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 15
- 230000003213 activating effect Effects 0.000 abstract description 11
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000003610 charcoal Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 20
- 238000012360 testing method Methods 0.000 description 16
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 9
- 238000005070 sampling Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 7
- 238000010791 quenching Methods 0.000 description 7
- 230000000171 quenching effect Effects 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 5
- 239000004695 Polyether sulfone Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229920006393 polyether sulfone Polymers 0.000 description 5
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 238000002329 infrared spectrum Methods 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/36—Organic compounds containing halogen
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Treatment Of Sludge (AREA)
Abstract
A preparation method and application of an activated persulfate sludge-based charcoal catalyst relate to a preparation method and application of an activated persulfate catalyst. The invention aims to solve the problems that the preparation of the existing biochar catalyst for activating persulfate is complex and sludge in a water treatment plant is difficult to treat. According to the invention, the sludge in the biochemical tank of the sewage treatment plant is taken as a raw material, and the biochar is prepared through high-temperature pyrolysis, so that the prepared high-temperature modified sludge biochar is low in production cost and simple in preparation process; meanwhile, the high-activity sludge biochar can be used for effectively activating persulfate to degrade phenolic organic pollutants in water by increasing the pyrolysis temperature, the sludge biochar prepared by high-temperature modification not only improves the performance of activating persulfate, but also effectively degrades and removes organic pollutants in water, and more importantly, the technical problem of excessively complicated preparation of a catalyst is solved, and a feasible scheme and a possible approach of resource recycling are provided for the treatment of sludge.
Description
Technical Field
The invention relates to a preparation method and application of an activated persulfate catalyst.
Background
With resource shortage and environmental problems becoming more serious, waste utilization has become a hot topic of concern. With the social development and the improvement of environmental awareness, the harmless treatment and resource utilization of sludge waste become an important trend. Sludge treatment methods vary widely around the world due to differences in environmental conditions, economic levels and transportation means in countries and regions. Therefore, the recycling of sludge is an environmental problem to be solved.
Persulfate oxidation technology is a novel advanced oxidation technology developed in recent years, and has attracted much attention in recent years. The Advanced Oxidation Process (AOPs) reactions generate highly reactive hydroxyl radicals (OH.), convert a wide range of organic contaminants into smaller molecular weight organics, are more readily biodegradable, and in some cases complete CO by activating stable precursors 2 Mineralization of (1). Sulfate radical (SO) in persulfate advanced oxidation process 4 ·- ) Is the main oxidizing species for activating persulfate formation and has become H 2 O 2 Based on conventional processesThe feasible alternative technology has the main technical advantages that 1 persulfate is compared with H 2 O 2 Stable and easier to store and transport; 2. the oxidation performance of persulfate is less sensitive to pH and background components; 3. it is possible to obtain an ideal radical having a higher oxidizing power. Most of the current researches are biased to develop too complicated catalysts and lack of practical consideration, and the persulfate-based advanced oxidation technology should be accelerated to replace the traditional advanced oxidation technology to treat the wastewater more effectively. In addition, the high-temperature carbonization can change the physical properties of the sludge to stabilize the sludge. Researches show that the sludge biochar can be used as an adsorbent for removing pollutants, can also activate persulfate, hydrogen peroxide and the like to generate hydroxyl radicals with strong oxidizing property, realizes the efficient degradation of organic matters, and further realizes the resource utilization of sludge. The persulfate and the hydrogen peroxide have similar structures and contain O-O bonds, and various carbon materials have activation effects on both the persulfate and the hydrogen peroxide, so that the optimized sludge-based biochar can effectively activate the persulfate to remove organic pollutants in water.
Disclosure of Invention
The invention provides a preparation method and application of an activated persulfate sludge-based biochar catalyst, aiming at solving the technical problems that the existing biochar catalyst for activating persulfate is complex to prepare and sludge in a water treatment plant is difficult to treat.
The preparation method of the activated persulfate sludge-based biochar catalyst is carried out according to the following steps:
1. naturally airing sludge in a biochemical pool process of a water treatment plant for 24-25 h, and then sieving the sludge through a 100-mesh polyethylene sieve to retain the sieved sludge to obtain aired sludge;
2. placing the dried sludge in the step one in a constant-temperature drying oven at 105-110 ℃ for drying for 2-2.5 h to obtain pretreated sludge;
3. and D, grinding the pretreated sludge obtained in the step two, pyrolyzing the ground sludge at the high temperature of 400-1000 ℃ for 2-2.5 h under protective gas, and cooling to room temperature to obtain the high-activity sludge biochar.
The high-activity sludge biochar prepared by the invention is applied to activating persulfate to degrade phenolic organic pollutants in water.
The beneficial effects of the invention are as follows:
according to the invention, the biochar is prepared from the sludge in the biochemical pool of the sewage treatment plant through high-temperature pyrolysis, and the prepared high-temperature modified sludge biochar is low in production cost and simple in preparation process; meanwhile, the high-activity sludge biochar is realized by increasing the pyrolysis temperature to effectively activate persulfate to degrade the typical phenol organic pollution, namely 4-chlorophenol, in the water, and the heavy metal contained in the sludge in the biochemical pool is also solidified in the sludge biochar in the pyrolysis process, so that the heavy metal secondary pollution of the biochemical sludge is avoided. The sludge biochar prepared by high-temperature modification not only improves the performance of activating persulfate, effectively degrades and removes organic pollutants in water, but also solves the technical problem of excessively complicated preparation of the catalyst, and more importantly provides a feasible scheme and a possible resource recycling way for sludge treatment.
Drawings
FIG. 1 is a Fourier infrared spectrum analysis chart of high-activity sludge biochar SBC-900 prepared in the first test;
FIG. 2 is a graph showing the comparison of the removal rates of 4-chlorophenol by the biochar of carbonized modified biochemical sludge at different pyrolysis temperatures in test II;
FIG. 3 is a graph showing the comparison of the removal rate of carbonized modified biochemical sludge biochar in the third experiment for removing 4-chlorophenol in water with different pH values:
FIG. 4 is a graph showing the comparison of the removal rate of 4-chlorophenol in test four.
Detailed Description
The first embodiment is as follows: the embodiment is a preparation method of an activated persulfate sludge-based biochar catalyst, which specifically comprises the following steps:
1. naturally airing sludge in a biochemical pool process of a water treatment plant for 24-25 h, then sieving the sludge by a 100-mesh polyethylene sieve, and retaining the sieved sludge to obtain the aired sludge;
2. placing the dried sludge in the step one in a constant-temperature drying oven at 105-110 ℃ for drying for 2-2.5 h to obtain pretreated sludge;
3. and D, grinding the pretreated sludge obtained in the step two, performing high-temperature pyrolysis on the ground sludge for 2-2.5 h under protective gas, wherein the pyrolysis temperature is 400-1000 ℃, and then naturally cooling to room temperature to obtain the high-activity sludge biochar.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: and naturally airing the sludge in the biochemical pool process of the water treatment plant for 24 hours in the first step. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: and in the second step, the dried sludge in the first step is placed in a constant-temperature drying oven at 105 ℃ for drying for 2 hours to obtain pretreated sludge. The other embodiments are the same as the first or second embodiments.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the protective gas in the third step is nitrogen, and the flow rate is 150mL/min. The rest is the same as one of the first to third embodiments.
The fifth concrete implementation mode: the fourth difference between this embodiment and the specific embodiment is that: raising the temperature from the room temperature to 400-1000 ℃ at the temperature raising rate of 5 ℃/min in the third step, and then naturally cooling to the room temperature. The rest is the same as the fourth embodiment.
The sixth specific implementation mode: the embodiment is the application of the high-activity sludge biochar prepared in the first embodiment, and the high-activity sludge biochar is applied to activating persulfate to degrade phenolic organic pollutants in water.
The seventh embodiment: the sixth embodiment is different from the sixth embodiment in that: the phenolic organic pollutant is 4-chlorophenol. The rest is the same as the sixth embodiment.
The invention was verified with the following tests:
test one: the test is a preparation method of an activated persulfate sludge-based biochar catalyst, which is specifically carried out according to the following steps:
1. naturally airing sludge in a biochemical pool process of a water treatment plant for 24 hours, then sieving the sludge by a 100-mesh polyethylene sieve, and reserving the sieved sludge to obtain aired sludge;
2. drying the dried sludge in the step one in a constant-temperature drying oven at 105 ℃ for 2h to obtain pretreated sludge;
3. grinding the pretreated sludge obtained in the second step, carrying out high-temperature pyrolysis on the ground sludge for 2 hours under protective gas, wherein the pyrolysis temperatures are 400 ℃, 600 ℃, 800 ℃, 900 ℃ and 1000 ℃, respectively, and then naturally cooling to room temperature to obtain sludge biochar SBC-400, SBC-600, SBC-800, SBC-900 and SBC-1000 with high activity in sequence; increasing the temperature from room temperature to pyrolysis temperature at a heating rate of 5 ℃/min; the protective gas is nitrogen, and the flow rate of the protective gas is 150mL/min;
fourier infrared spectroscopy was performed on the high activity sludge biochar SBC-900 prepared in test one, as shown in FIG. 1, which is seen at 485cm -1 、574cm -1 、664cm -1 、720cm -1 And 815cm -1 The absorption peaks generated are generated by the skeleton vibration of alkane C-C bonds; at 1032cm -1 The absorption peak generated at the position is the stretching vibration peak of the C-O bond, and the prepared sample can be presumed to contain carbonyl functional groups; at 1467cm -1 The externally generated absorption peak is the deformation vibration peak of the alkane C-H bond; at 1608cm -1 The absorption peak generated at (b) is generated by stretching vibration of the aromatic hydrocarbon C = C bond, which indicates that the surface of the prepared biochar sample contains benzene ring functional groups; at 3317cm -1 ~3535cm -1 The absorption peak has a broad peak shape and is generated by stretching vibration of a hydroxyl group O-H bond in the form of an intermolecular hydrogen bond. According to FTIR spectra, the sludge-based biochar sample contains abundant oxygen-containing functional groups, and the functional groups are beneficial to the activation of persulfate.
And (2) test II: the test is an application of the biochar in the biochemical pond sludge in removing 4-chlorophenol in water, and compares the removing effects of the biochar in the carbonized and modified biochemical sludge at different pyrolysis temperatures on 4-chlorophenol:
adding sodium persulfate and 4-chlorophenol into 60mL of deionized water to ensure that the concentration of 4-chlorophenol and the concentration of sodium persulfate in the solution are 0.05mM and 0.5mM respectively, fully mixing at 700rpm under magnetic stirring to prepare 5 parts of the same solution, then adding 3mg of biochemical sludge biochar SBC-400, SBC-600, SBC-800, SBC-900 and SBC-1000 prepared in the first test respectively, starting timing after sampling at different sampling time (0, 2.5min, 5min, 10min, 15min, 20min, 30min, 40min and 60 min), filtering by using a 0.22 mu m PES polyether sulfone membrane, placing 1mL of filtered sample into a liquid phase vial, adding 0.5mL of methanol respectively, quenching, and storing the sample at low temperature (4 ℃); the concentration of 4-chlorophenol in the sample was analyzed by High Performance Liquid Chromatography (HPLC). The concentration of 4-chlorophenol in different sampling times is measured by high performance liquid chromatography, and the average value is taken after parallel experiments are carried out, the removal rate of 4-chlorophenol degraded by sodium peroxodisulfate activated by various biochemical sludge biochar is shown in figure 2, the pyrolysis temperature from top to bottom in the figure is 400 ℃, 600 ℃, 800 ℃, 1000 ℃ and 900 ℃, the removal capacity can be obviously improved from the figure, the pyrolysis temperature of the biochemical sludge-based biochar is increased from 400 ℃ to 900 ℃, and the removal rate is slightly reduced from continuously increasing to 1000 ℃. The removal rate of SBC-400 to 4-chlorophenol is 3.99%, the removal rate of SBC-600 to 4-chlorophenol is 9.92%, the removal rate of SBC-800 to 4-chlorophenol is 61.65%, the removal rate of SBC-900 to 4-chlorophenol is 70.75%, and the removal rate of SBC-1000 to 4-chlorophenol is 66.23%. From the viewpoint of removal rate, the optimum pyrolysis temperature of the sludge-based biochar activated persulfate is 900 ℃.
And (3) testing three: the experiment shows the application of activating persulfate to remove 4-chlorophenol in water with different pH values for biochemical sludge-based biochar, and the removal effect of the high-temperature carbonized modified biochemical sludge biochar on 4-chlorophenol is examined by adjusting different pH values in water:
adding sodium peroxodisulfate and 4-chlorophenol into 60mL of deionized water, so that the concentration of 4-chlorophenol and the concentration of sodium peroxodisulfate in the solution are respectively 0.05mM and 0.5mM, preparing 3 parts of the same solution, adjusting the pH to 3, 7 and 12 by using hydrochloric acid and sodium hydroxide respectively, beginning timing after adding 3mg of biochemical sludge organism SBC-900 prepared in the test I respectively, sampling at different sampling times (0, 2.5min, 5min, 10min, 15min, 20min, 30min, 40min and 60 min), placing 1mL of filtered sample into a liquid phase bottle after passing through a 0.22 mu m PES (polyether sulfone) membrane, adding 0.5mL of methanol respectively for quenching, and storing the sample at low temperature (4 ℃); the concentration of 4-chlorophenol in the sample was analyzed by High Performance Liquid Chromatography (HPLC). The concentration of 4-chlorophenol in different sampling times is measured by high performance liquid chromatography, and the average value is taken after parallel experiments are carried out, the removal rate of 4-chlorophenol degraded by various biochemical sludge biochar activated PDS is shown in figure 3, the pH values from top to bottom in the figure are 12, 7 and 3 in sequence, and the difference of the adsorption removal rate of three different pH values is 2.18% at most, so that the removal rate of 4-chlorophenol by biochemical sludge-based biochar-SBC 900 activated persulfate prepared in the first experiment is quite good no matter under acidic, neutral or alkaline conditions, namely that the removal rate of 4-chlorophenol by biochemical sludge-based biochar-900 + persulfate is not influenced by pH basically under different pH conditions, and the method can be used in wastewater with a wide pH range SBC.
And (4) testing: in order to explore the oxidation mechanism of the biochemical sludge-based biochar activated persulfate prepared in the first test for removing 4-chlorophenol, the active species in the process of removing the 4-chlorophenol by the high-temperature carbonized modified biochemical sludge biochar activated persulfate are investigated through a quenching test:
sodium persulfate and 4-chlorophenol were added to 60mL of deionized water so that the concentration of 4-chlorophenol and the concentration of sodium persulfate in the solutions were 0.05mM and 0.5mM, respectively, 4 parts of the same solutions were prepared, 100mM methanol, 100mM t-butanol, 10mM 2, 6-tetramethylpiperidine, and one group as a control group were added thereto, and thoroughly mixed at 700rpm in a magnetic stirrer, 3mg of biochemical sludge biochar-900 prepared in test one was added to each of the four groups, and then sampling was carried out at different sampling times (0, 2.5min, 5min, 10min, 15min, 20min, 30min, 40min, 60 min), and then a 0.22 μm PES membrane was applied, and 1mL of the filtered sample was placed in a liquid phase vial, and the sample was divided into 0.5 min, 10min, 15min, 20min, 30min, 40min, and 60minAdding 0.5mL of methanol for quenching, and storing the sample at low temperature (4 ℃); the concentration of 4-chlorophenol in the sample was analyzed by High Performance Liquid Chromatography (HPLC). The concentration of 4-chlorophenol in different sampling times is measured by high performance liquid chromatography, and the average value is taken after parallel experiments are carried out, the removal rate of 4-chlorophenol degraded by sodium peroxodisulfate activated by various biochemical sludge-based biochar is shown in figure 4, a curve 1 corresponds to 2, 6-tetramethylpiperidine, a curve 2 is methanol, a curve 3 is tert-butanol, and a curve 4 is a control group, and it can be seen from the figure that methanol, tert-butanol and 2, 6-tetramethylpiperidine are selected as quenchers to be respectively carried out with an active species quenching experiment to further identify the composition of active species in a reaction system. As shown in FIG. 4, when methanol was added to the SBC-900/sodium peroxodisulfate system, the degradation rate of 4-chlorophenol was 33.49% within 60min, which was decreased by 37.26% compared to the control without quencher (control), indicating that the free radicals generated by activating sodium peroxodisulfate with sludge-based biochar act to promote the degradation of 4-chlorophenol; when tert-butyl alcohol is added into an SBC-900/sodium peroxodisulfate system, the removal rate of 4-chlorophenol in 60min is 49.62%, and is reduced by 21.13% compared with that of a control group without a quenching agent; the change in the removal rate of 4-chlorophenol after adding methanol in the system was compared, and OH and SO were considered to be 4 ·- Are present in the SBC-900/sodium peroxodisulfate system, with OH as the main radical. When 2, 6-tetramethylpiperidine is added into the reaction system, the removal rate of 4-chlorophenol in 60min is 20.29 percent, which is reduced by 50.46 percent compared with that of the reaction system without adding a quenching agent (control group), which indicates that in the process of degrading 4-chlorophenol by using a sludge-based biochar activated sodium persulfate system, 1 O 2 also plays an important role.
Claims (7)
1. A preparation method of an activated persulfate sludge-based biochar catalyst is characterized by comprising the following steps:
1. naturally airing sludge in a biochemical pool process of a water treatment plant for 24-25 h, then sieving the sludge by a 100-mesh polyethylene sieve, and reserving the sieved sludge to obtain aired sludge;
2. placing the dried sludge in the step one in a constant-temperature drying oven at 105-110 ℃ for drying for 2-2.5 h to obtain pretreated sludge;
3. and D, grinding the pretreated sludge obtained in the step two, pyrolyzing the ground sludge at the high temperature of 400-1000 ℃ for 2-2.5 h under protective gas, and naturally cooling to room temperature to obtain the high-activity sludge biochar.
2. The method for preparing the activated persulfate sludge-based biochar catalyst according to claim 1, wherein in the first step, the sludge in the biochemical pond process of the water treatment plant is naturally dried for 24 hours.
3. The method for preparing the activated persulfate sludge-based biochar catalyst according to claim 1, wherein in the second step, the dried sludge in the first step is dried in a constant-temperature drying oven at 105 ℃ for 2 hours to obtain pretreated sludge.
4. The method for preparing the activated persulfate sludge-based biochar catalyst according to claim 1, wherein the shielding gas in the third step is nitrogen, and the flow rate is 150mL/min.
5. The method for preparing the activated persulfate sludge-based biochar catalyst according to claim 1, wherein the temperature is raised from room temperature to 400-1000 ℃ at a heating rate of 5 ℃/min in the third step, and then the activated persulfate sludge-based biochar catalyst is naturally cooled to room temperature.
6. The application of the activated persulfate sludge-based biochar catalyst prepared by the preparation method according to claim 1, wherein the high-activity sludge biochar is applied to activated persulfate so as to degrade phenolic organic pollutants in water.
7. The use of the activated persulfate sludge-based biochar catalyst as claimed in claim 6, wherein the phenolic organic contaminant is 4-chlorophenol.
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