CN114229967A - Three-dimensional electrode material, preparation method thereof and electrochemical oxidation method for treating high-concentration phosphorus-containing organic wastewater - Google Patents
Three-dimensional electrode material, preparation method thereof and electrochemical oxidation method for treating high-concentration phosphorus-containing organic wastewater Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 72
- 239000011574 phosphorus Substances 0.000 title claims abstract description 72
- 239000002351 wastewater Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000007772 electrode material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006056 electrooxidation reaction Methods 0.000 title claims abstract description 16
- 239000010802 sludge Substances 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000003703 phosphorus containing inorganic group Chemical group 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
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- 239000012425 OXONE® Substances 0.000 claims description 2
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
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- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
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- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 description 1
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- 229950001327 dichlorvos Drugs 0.000 description 1
- JXSJBGJIGXNWCI-UHFFFAOYSA-N diethyl 2-[(dimethoxyphosphorothioyl)thio]succinate Chemical compound CCOC(=O)CC(SP(=S)(OC)OC)C(=O)OCC JXSJBGJIGXNWCI-UHFFFAOYSA-N 0.000 description 1
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- PZXOQEXFMJCDPG-UHFFFAOYSA-N omethoate Chemical compound CNC(=O)CSP(=O)(OC)OC PZXOQEXFMJCDPG-UHFFFAOYSA-N 0.000 description 1
- 239000003987 organophosphate pesticide Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 description 1
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- 239000002686 phosphate fertilizer Substances 0.000 description 1
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- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
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- 238000002604 ultrasonography Methods 0.000 description 1
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Classifications
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- 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
- C02F2101/105—Phosphorus compounds
Abstract
The invention relates to a three-dimensional electrode material, a preparation method thereof and an electrochemical oxidation method for treating high-concentration phosphorus-containing organic wastewater. The preparation method of the three-dimensional electrode material comprises the steps of preparing biochar, preparing modified biochar, calcining and the like. When the electrode material is used as a microelectrode in an electrochemical oxidation method of phosphorus-containing wastewater, the electrolysis efficiency can be improved, organic phosphorus is efficiently oxidized into phosphate ions, and the phosphate ions are efficiently precipitated and recovered, so that the method is suitable for the phosphorus-containing wastewater under various water quality conditions; and the waste utilization of sludge and slag is realized.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a three-dimensional electrode material, a preparation method thereof and an electrochemical oxidation method for treating high-concentration phosphorus-containing organic wastewater.
Background
The wastewater with high phosphorus content mainly comprises domestic sewage, phosphate fertilizer production wastewater, organophosphorus pesticide wastewater, phosphorite mining wastewater, breeding wastewater, meat food processing wastewater and the like. The COD of the wastewater is usually more than 10000, and the phosphorus content is usually more than 3000 mg/L. The phosphorus-containing wastewater has the characteristics of high COD, high phosphorus content, great harm, difficult biodegradation, great toxicity and the like. If the waste water is directly discharged into natural water without being treated, the waste water can cause potential threats to the environment and human bodies such as: causing eutrophication of water bodies, indirectly or directly causing death of animals and plants and harming human health.
The commonly used phosphorus-containing wastewater treatment methods at present mainly comprise chemical methods and biological methods (Sichuan et al, advanced research on high-salt wastewater phosphorus removal technology [ J ] China Academic Journal Electronic Publishing House, 1994-2021). The chemical method efficiently deposits inorganic phosphorus by generating chemical sludge, but organic phosphorus substances in the wastewater cannot be effectively removed, and the sludge generates secondary pollution, so that the treatment cost is increased; biological processes enrich the phosphorus in water by functional microorganisms or algae, but their phosphorus removal efficiency is limited by the composition of the wastewater and the nitrate nitrogen concentration.
The patent of the invention discloses a preparation method of biochar for removing phosphorus, which utilizes sludge and egg shells to obtain biochar through heat treatment, and can realize the removal of phosphorus in sewage and wastewater. But the method mainly utilizes physical adsorption of phosphorus in the sewage, has limited removal effect and can not realize the treatment of phosphorus-containing wastewater under various water quality conditions.
Therefore, it is necessary to develop a method for efficiently treating phosphorus-containing wastewater under various water quality conditions.
Disclosure of Invention
The invention aims to overcome the defects or shortcomings of the existing treatment method of phosphorus-containing wastewater and provides a preparation method of a three-dimensional electrode material. When the electrode material is used as a microelectrode in an electrochemical oxidation method of phosphorus-containing wastewater, the electrolysis efficiency can be improved, organic phosphorus is efficiently oxidized into phosphate ions, and the phosphate ions are efficiently precipitated and recovered, so that the method is suitable for the phosphorus-containing wastewater under various water quality conditions; and the waste utilization of sludge and slag is realized.
Another object of the present invention is to provide a three-dimensional electrode material.
The invention also aims to provide an electrochemical oxidation method for treating high-concentration phosphorus-containing organic wastewater.
The invention also aims to provide a method for treating the high-concentration phosphorus-containing inorganic wastewater.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a three-dimensional electrode material comprises the following steps:
s11: drying, grinding and calcining the sludge to obtain biochar;
s12: mixing biochar, metal salt and water to obtain a suspension, adding an alkaline agent and a pore-forming agent into the suspension to adjust the pH to 11-11.5, ultrasonically stirring, standing, centrifuging, washing and drying to obtain modified biochar;
s13: grinding the modified biochar, and calcining at 700-800 ℃ to obtain the three-dimensional electrode material.
In the preparation method, the sludge is calcined in the step S1 to obtain the biochar, and the biochar has the advantages of large specific surface area and small particle size.
In the step S2, the metal salt is subjected to uniform precipitation (or coprecipitation) reaction under alkaline and ultrasonic agitation to obtain metal hydroxide, and the metal hydroxide is uniformly loaded on the biochar to realize the preparation of the modified biochar.
In the step S3, the modified biochar is subjected to high-temperature calcination treatment, and in addition, a pore-forming agent is used for forming pores in the calcination process, so that the biochar forms a porous structure and the specific surface area can be further improved; calcining the metal hydroxide to obtain metal oxide uniformly loaded on the biochar; the metal oxide can be absorbed and combined with phosphate ions in the phosphorus-containing wastewater treatment process, so that the precipitation and recovery of the phosphate ions are realized.
In addition, the three-dimensional electrode material prepared by the specific method has excellent conductivity, rich and uniformly distributed active groups, and can accelerate electron transfer and particle movement in a solution when being used as a microelectrode in an electrochemical oxidation method of phosphorus-containing wastewater, so that the electrolysis efficiency is improved, and the efficient oxidation of organic phosphorus into phosphate ions is promoted; meanwhile, the phosphate ions can be combined with metal ions on the surface of the three-dimensional electrode material and attached to the three-dimensional electrode material, so that the efficient precipitation and recovery of the phosphate ions are realized, and the method is suitable for phosphorus-containing wastewater under various water quality conditions; and realizes the waste utilization of the sludge and the slag.
Research shows that in the step S4, the calcining temperature has a very critical influence on the performance of the obtained three-dimensional electrode material, such as the calcining temperature is too low (e.g. 600 ℃), and the obtained three-dimensional electrode material has a poor treatment effect on phosphorus-containing wastewater, which may be because the calcining temperature has a very large influence on the amount of oxygen-containing functional groups on the surface of the biochar, at a higher calcining temperature, more oxygen-containing functional groups can be formed on the surface of the biochar, and a richer pore structure can be generated, so that the specific surface area is larger, and under the condition of the same pollutant concentration, more adsorption sites can be provided, so that the adsorption capacity of the biochar can be improved; on the other hand, if the calcination temperature is low, the formed oxygen-containing functional groups and pore structures are fewer, the specific surface area is small, and the adsorption capacity is weak.
The three-dimensional electrode material can also be directly used for removing phosphorus-containing inorganic wastewater. Similar to the electrochemical oxidation method, phosphate ions in the phosphorus-containing wastewater can be combined with metal ions on the surface of the three-dimensional electrode material and attached to the three-dimensional electrode material, so that efficient precipitation and recovery of the phosphate ions are realized.
Preferably, the sludge drying process in S11 is: drying the sludge at the temperature of 50-70 ℃ for 20-24 h.
Preferably, the sludge drying process further comprises a ball milling and crushing process.
Preferably, the calcination temperature of the dry sludge in S11 is 500-600 ℃, and the calcination time is 2-4 h.
Preferably, S11 is calcined under an inert atmosphere (e.g., nitrogen atmosphere, argon atmosphere).
Preferably, S11 is heated to the calcination temperature at a heating rate of 5 deg.C/min.
Preferably, the mass ratio of the biochar to the metal salt is 1: 1-3.
Preferably, the metal salt in S12 is one or more of iron salt, aluminum salt, manganese salt, magnesium salt or calcium salt. The anion in the metal salt can be a conventional anion such as nitrate, chloride, sulfate, etc.
The alkaline agent which is conventional in the field can be used in the invention, and the pH can be adjusted to 11-11.5.
Preferably, the alkaline agent in S13 is one or both of sodium hydroxide and potassium hydroxide.
Pore formers conventional in the art may be used in the present invention.
Preferably, the pore-forming agent in S13 is one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium carbonate.
Preferably, the calcining time in S13 is 2-4 h.
Preferably, the temperature is raised to the calcination temperature at a temperature raising rate of 5 ℃/min in S13.
The invention also claims a three-dimensional electrode material prepared by the preparation method.
An electrochemical oxidation method for treating high-concentration phosphorus-containing organic wastewater comprises the following steps:
s21: taking high-concentration phosphorus-containing wastewater as electrolyte; inert electrodes are used as an anode and a cathode, and the anode and the cathode are separated by a diaphragm;
s22: adding persulfate and the three-dimensional electrode material into electrolyte, aerating, and electrifying for electrochemical treatment;
the mass concentration of the three-dimensional electrode material is 5-10 g/L; the mass concentration of the persulfate is 2-8 g/L.
Electrocatalytic oxidation has recently emerged as an advanced wastewater treatment technology, and is commonly used in the treatment of refractory substances under study. However, in the conventional two-dimensional electrode method (i.e., only the anode and the cathode), the treatment effect has an upper limit and the reaction speed is slow.
The three-dimensional electrode is used as a novel electrolytic reactor, a microelectrode is added on the basis of the traditional electrolytic cell, the electron transfer and the particle movement in the solution can be accelerated, so that the electrolytic efficiency is improved, and the three-dimensional electrode is small in occupied area, simple in equipment and convenient to operate. The persulfate advanced oxidation is also a research hotspot for treating organic wastewater in recent years, and the process can efficiently degrade organic pollutants by generating sulfate radicals with strong oxidation effect to achieve the purpose of reducing COD (chemical oxygen demand) of the wastewater.
The invention combines a persulfate advanced oxidation method and a three-dimensional electrode system, and simultaneously uses the three-dimensional electrode material with large area, more pores and small particles prepared by a specific method as a microelectrode (three-dimensional electrode), which can greatly improve the conductivity of the solution, thereby accelerating the electron transfer and the particle movement, obviously improving the electrolysis efficiency, further promoting persulfate to generate sulfate radicals more and more quickly and efficiently oxidizing the organic phosphorus in the phosphorus-containing wastewater into phosphate ions; meanwhile, phosphate ions can be combined with metal ions on the surface of the three-dimensional electrode to form precipitates and attach to the surface of the three-dimensional electrode, so that the effective recovery of phosphorus in phosphorus-containing wastewater under various water quality conditions can be realized.
Preferably, the phosphorus in the high-concentration phosphorus-containing wastewater is organic phosphorus (such as omethoate, malathion, phoxim, trichlorphon, dichlorvos, chlorpyrifos, glyphosate, glufosinate and the like) or inorganic phosphorus (such as PO)4 3-、 PO3 3Etc.).
Preferably, the anode is a carbon electrode, a titanium electrode or a stainless steel electrode.
Preferably, the cathode is a doped carbon electrode, a modified carbon electrode or a graphite electrode.
Preferably, the electrochemical treatment is a galvanostatic method.
More preferably, the current is 2-3A.
More preferably, the current density is 40-60 mA/cm2。
Preferably, the persulfate is one or more of potassium persulfate, sodium persulfate, ammonium persulfate, potassium monopersulfate, sodium monopersulfate and ammonium monopersulfate.
The invention also provides a method for treating the high-concentration phosphorus-containing inorganic wastewater, which comprises the following steps: and adding the three-dimensional electrode material into the phosphorus-containing inorganic wastewater, and stirring.
Compared with the prior art, the invention has the following beneficial effects:
when the electrode material is used as a microelectrode in an electrochemical oxidation method of phosphorus-containing wastewater, the electrolysis efficiency can be improved, organic phosphorus is efficiently oxidized into phosphate ions, the phosphate ions are efficiently precipitated and recovered, the COD and phosphorus content in the wastewater are greatly reduced, and the method is suitable for the phosphorus-containing wastewater under various water quality conditions; and the waste utilization of sludge and slag is realized.
Drawings
FIG. 1 is a scanning electron micrograph of a three-dimensional electrode provided in example 5;
fig. 2 is an electrochemical oxidation treatment apparatus, in which 1: a constant current power supply; 2: a cathode; 3: aerating stones; 4: an anode; 5: a three-dimensional electrode;
fig. 3 shows the time-dependent change in the effluent Tp removal rate.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Preparation of three-dimensional electrodes of examples 1 to 6 and comparative examples 1 to 4
The present examples and comparative examples 1-3 provide a series of three-dimensional electrodes prepared as follows:
s1: and (3) putting the municipal sludge with the water content of 80% into a 60 ℃ oven for 24 hours to obtain dewatered sludge, and grinding the dewatered sludge by using a grinder to pass through a 100-mesh sieve to obtain dried sludge.
S2: spreading the dry sludge in a quartz dish, and then putting the quartz dish into a tube furnace. Raising the temperature to 600 ℃ at the temperature raising speed of 5 ℃/min under the condition of filling nitrogen, preserving the heat for 2 hours, and then automatically cooling to the room temperature. Putting the pyrolyzed biochar into a ball mill, wherein the mass ratio of the biochar to balls is 1:200, and then operating the ball mill at the speed of 250rpm for 6 hours to obtain the ball-milled biochar.
S3: adding ferric sulfate and ball-milling biochar with specific mass (shown in table 1) into 50mL of deionized water to obtain suspension a; 1g of NaOH and 10g of Na2CO3Adding the mixture into 50mL of deionized water, and uniformly mixing to obtain a solution b;
s4: putting a pH meter into the suspension a, then slowly adding the solution b into the suspension a, controlling the pH value to be within the range of 11-11.5, and ultrasonically stirring; after stirring with ultrasound for 30 minutes, the resulting slurry was allowed to stand for 6 hours. After standing, the mixture was centrifuged at 2000rpm for 30 minutes. Washing with deionized water, placing in a 30 ℃ oven, and drying to constant weight to obtain loaded ball-milled biochar;
s5: grinding the loaded ball-milling biochar into powder by a grinder, and putting the powder into a tube furnace. Under the condition of filling nitrogen, the initial temperature is 25 ℃, the temperature is increased to a specific temperature (shown in table 1) at the temperature increasing speed of 5 ℃/min, and the temperature is automatically reduced to the room temperature after 2 hours of heat preservation.
Comparative example 4 provides a ball-milled biochar as the three-dimensional electrode material # 10, which is prepared through steps S1-S2.
Specific conditions in each example and comparative example are shown in table 1.
TABLE 1 Condition control of examples and comparative examples
FIG. 1 is a scanning electron micrograph of a three-dimensional electrode 8# obtained in example 5. As can be seen from FIG. 1, the three-dimensional electrode has a very rich pore structure, so that the three-dimensional electrode has a large specific surface area, and is beneficial to improving the adsorption capacity and the electrocatalytic efficiency of the electrode. The three-dimensional electrodes obtained in the other examples were similar to those of example 5, and had a relatively rich pore structure. The three-dimensional electrodes obtained in the comparative examples 1 to 3 have relatively few pore structures and small specific surface area due to low calcination temperature.
Firstly, the three-dimensional electrodes prepared in each example and comparative example are utilized to treat high-concentration phosphorus-containing inorganic wastewater
The treatment process is as follows: adding 13gKH into 1L of deionized water2PO4And use of H in combination2SO4The pH of the solution was adjusted to 5 to prepare a simulated wastewater with a total phosphorus content of 3000 mg/L. 10g of three-dimensional electrodes 1# to 10# are respectively added into the simulated wastewater, the temperature of the solution is controlled to be kept at 35 ℃, and the solution is stirred for 24 hours at 200 rpm.
And (3) filtering the treated simulated wastewater by using filter paper, extracting 0.1mL of sample, diluting and metering to 50mL of colorimetric tube, and measuring the total phosphorus content in the treated simulated wastewater by adopting the total phosphorus measuring method of GB 11893-89, wherein the total phosphorus content is shown in tables 2 and 3.
TABLE 2 treatment results of three-dimensional electrodes 1# to 10# for high-concentration phosphorus-containing inorganic wastewater
As can be seen from Table 2, the three-dimensional electrode prepared in this example can realize efficient treatment of high-concentration phosphorus-containing inorganic wastewater. From comparative example 2, example 2 and example 5, it can be seen that the calcination temperature has a large influence on the performance of the three-dimensional electrode, and the calcination temperature is too low, so that more oxygen-containing functional groups cannot be formed on the surface of the biochar, and a richer pore structure cannot be generated, so that the biochar has a larger specific surface area, and under the condition of the same pollutant concentration, more adsorption sites can be provided, so that the adsorption capacity of the biochar can be improved. The treatment effect on the high-concentration phosphorus-containing inorganic wastewater is poor. From the comparison of examples 4 to 6, the amount of the sludge and the slag has a certain influence on the performance of the three-dimensional electrode, and when the amount of the sludge and the slag is controlled to be 1: 1-3, the treatment effect on the high-concentration phosphorus-containing inorganic wastewater is better, and the effect is better by 1: 2-3. Comparative example 4 no modification and pore-forming treatment were performed on the ball-milled biochar, and adsorption of phosphate ions was limited; and phosphorus (phosphorus remained in microbial cells contained in the sludge) remained in the ball-milling biochar obtained after the sludge is calcined is released to high-concentration phosphorus-containing inorganic wastewater, so that the phosphorus content is increased.
And secondly, treating the high-concentration phosphorus-containing organic wastewater by using the three-dimensional electrodes prepared in example 5 and comparative example 4 and combining an electrochemical oxidation method.
The treatment process is as follows:
(1) a simulated wastewater was prepared by adding 16g glyphosate to 1L of deionized water and adjusting the pH of the solution to 5 with KOH, having a total phosphorus content of 3064mg/L and a COD of 11259 mg/L.
(2) The simulated wastewater of step (1) was fed into the apparatus shown in FIG. 2, the current of the constant current source (see tables 4 and 5) was set, and a certain amount of three-dimensional electrodes (see tables 4 and 5) and aeration stones were added to the apparatus. Open the aeration valve at 10m3Aeration is carried out at the aeration rate per hour. The whole treatment process was maintained for 6 hours.
Specifically, the device is designed as follows: graphite is used as an anode and is connected with the anode of a constant current power supply, and the effective area of the anode is 50cm2The graphite electrode is used as a cathode and is connected with the negative electrode of a constant current power supply, and the effective area of the cathode is 50cm2And the cathode and the anode are separated by a diaphragm.
TABLE 4 Process conditions during the treatment of high-concentration phosphorus-containing organic wastewater
TABLE 6 treatment results of high concentration phosphorus-containing organic wastewater under different parameters
FIG. 3 shows that the Tp removal rate of the effluent varies with time when treating high-concentration phosphorus-containing organic wastewater under the condition of parameter No. 6, and after 6 hours of treatment, the phosphorus removal rate is as high as 98.03%, and the COD removal rate is as high as 97.02%.
As can be seen from Table 6, the current (current density) was increased, the phosphorus removal rate and the COD removal rate were also increased, and the current density was 50 to 60mA/cm2The treatment effect is better; the addition amount of the three-dimensional electrode is increased, and the phosphorus removal rate and the COD removal rate are also increased. When the ball-milled biochar (three-dimensional electrode # 10, parameter 7) provided in comparative example 4 is directly used for treatment, the effect is not good, because the electrocatalytic efficiency cannot be improved and the adsorption of phosphate ions is limited because the biochar is not modified and pore-formed; in addition, phosphorus (phosphorus remaining in microbial cells contained in the sludge) remaining in the ball-milled biochar obtained after the sludge calcination is released to high-concentration phosphorus-containing organic wastewater, so that the phosphorus content is increased on the contrary.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a three-dimensional electrode material is characterized by comprising the following steps:
s11: drying, grinding and calcining the sludge to obtain biochar;
s12: mixing biochar, metal salt and water to obtain a suspension, adding an alkaline agent and a pore-forming agent into the suspension to adjust the pH to 11-11.5, ultrasonically stirring, standing, centrifuging, washing and drying to obtain modified biochar;
s13: grinding the modified biochar, and calcining at 700-800 ℃ to obtain the three-dimensional electrode material.
2. The method according to claim 1, wherein the sludge drying process in S11 is: drying the sludge at the temperature of 50-70 ℃ for 20-24 h; and in the S2, the calcination temperature of the dry sludge is 500-600 ℃, and the calcination time is 2-4 h.
3. The preparation method according to claim 1, wherein the mass ratio of the biochar to the metal salt is 1: 1-3; the metal salt in S12 is one or more of iron salt, aluminum salt, manganese salt, magnesium salt or calcium salt.
4. The preparation method according to claim 1, wherein the alkaline agent in S12 is one or both of sodium hydroxide and potassium hydroxide; the pore-forming agent is one or more of sodium carbonate, potassium carbonate, sodium bicarbonate or potassium carbonate.
5. The preparation method of claim 1, wherein the calcination time in S13 is 2-4 h.
6. A three-dimensional electrode material prepared by the preparation method of any one of claims 1 to 5.
7. An electrochemical oxidation method for treating high-concentration phosphorus-containing organic wastewater is characterized by comprising the following steps:
s21: taking high-concentration phosphorus-containing wastewater as electrolyte; inert electrodes are used as an anode and a cathode, and the anode and the cathode are separated by a diaphragm;
s22: adding persulfate and the three-dimensional electrode material as claimed in claim 6 into the electrolyte, aerating, and electrifying for electrochemical treatment;
the mass concentration of the three-dimensional electrode material is 5-10 g/L; the mass concentration of the persulfate is 2-8 g/L.
8. The electrochemical oxidation method of claim 7, wherein the phosphorus in the high-concentration phosphorus-containing wastewater is one or more of organic phosphorus or inorganic phosphorus.
9. The electrochemical oxidation process of claim 7, wherein the anode is a carbon electrode, a titanium electrode, a stainless steel electrode, or a graphite electrode; the cathode is a doped carbon electrode, a modified carbon electrode or a graphite electrode; the electrochemical treatment is a constant current method; the persulfate is one or more of potassium persulfate, sodium persulfate, ammonium persulfate, potassium peroxymonosulfate, sodium peroxymonosulfate or ammonium peroxymonosulfate.
10. A method for treating high-concentration phosphorus-containing inorganic wastewater is characterized by comprising the following steps: adding the three-dimensional electrode material of claim 6 into phosphorus-containing inorganic wastewater, and stirring.
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| CN117305854A (en) * | 2023-11-30 | 2023-12-29 | 常熟理工学院 | Method for recycling elemental phosphorus from organophosphorus pesticide-containing soil by utilizing waste incineration fly ash |
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