CN112441659A - Method for degrading and treating organic pollutants by activating persulfate through multi-stage mesoporous biochar material - Google Patents
Method for degrading and treating organic pollutants by activating persulfate through multi-stage mesoporous biochar material Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 59
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- 230000003213 activating effect Effects 0.000 title claims abstract description 26
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Images
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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
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- B01J35/638—
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- B01J35/647—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- 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
Abstract
The invention discloses a method for degrading and treating organic pollutants by activating persulfate through a multilevel mesoporous biochar material. The method for degrading organic pollutants by activating persulfate through the multi-stage mesoporous biochar material can effectively remove organic pollutants, has the advantages of simple operation, short period, low cost, high degradation efficiency, good removal effect, strong anti-interference capability, wide application range, easy recycling and the like, and has good application prospect in the actual treatment of organic pollutant wastewater, natural water bodies and soil polluted by organic pollutants.
Description
Technical Field
The invention belongs to the field of advanced oxidation treatment of organic pollutants, and relates to a method for degrading organic pollutants by activating persulfate through a biomass material, in particular to a method for degrading organic pollutants by activating persulfate through a multi-stage mesoporous biochar material.
Background
The problem of water and soil environmental pollution caused by organic pollutants is becoming serious, and the organic pollutants attract extensive attention of researchers and society. Organic pollutants represented by phenol as a fixed form are inevitably discharged into water and soil environments in the industrial application process, and the phenol-containing wastewater has high toxicity; and the intermediate product generated in the phenol degradation process has high toxicity, has carcinogenic, mutagenic and teratogenic properties, and poses great threat to water plants and organisms. Based on the above hazards, the phenol-containing wastewater is a difficult problem facing the current water treatment technology which needs to be treated and solved urgently. Common treatment methods include adsorption, membrane separation, common oxidation, biological methods and the like, but the methods have the defects of complex process flow, high equipment requirement, high cost, damage to microenvironment, relatively low treatment efficiency and the like, and even need additional energy and excessive chemical agents as assistance. The advanced oxidation technology based on the carbon material as the catalyst can effectively degrade phenol in the presence of persulfate, and meanwhile, the persulfate is superior in chemical stability and price; and the carbon-based material can be conveniently recycled, and can not remain in the wastewater to cause secondary pollution to the environment, so that the water treatment method has the advantages of high treatment efficiency, thorough removal, low cost, convenience in operation and wide application range. In the system, persulfate is used as an oxidant and is activated under the catalytic action of a catalyst to generate high-activity oxidation free radicals or intermediate active substances, so that target pollutants are further attacked and degraded. However, conventional advanced oxidation techniques like fenton's reaction and widely used reactions based on metal and oxide catalysts suffer from a number of drawbacks (large amount of precipitation, metal leaching and too narrow pH range, etc.). The persulfate activation technology developed in recent years by utilizing carbon materials (reduced graphene oxide, carbon nano tubes, activated carbon, nano diamond and mesoporous carbon) can solve the problems existing in the traditional technology; however, many carbon materials suffer from poor catalytic performance, poor catalytic efficiency, and excessive preparation cost, and are not ideal in material cycle performance. Therefore, how to overcome the problems in the prior art, the novel carbon catalytic material for activating the persulfate, which is simple to prepare, low in cost, strong in catalytic performance, strong in anti-interference capability, good in dispersibility, strong in stability, easy to recycle and reuse, is obtained, and has very important significance for improving the treatment effect of the persulfate advanced oxidation system on treating organic pollutants.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide the method for degrading and treating the organic pollutants by activating the persulfate through the multi-stage mesoporous charcoal material, which has the advantages of simple operation, short period, low cost, high degradation efficiency and wide application range.
In order to solve the technical problems, the invention adopts the technical scheme that:
a method for activating persulfate to degrade and treat organic pollutants by utilizing a multi-stage mesoporous biochar material comprises the steps of treating the organic pollutants by utilizing the multi-stage mesoporous biochar material and persulfate; the multilevel mesoporous biochar material is prepared by mixing bagasse as a raw material with calcium chloride and potassium hydroxide and then calcining.
In the method, the multilevel mesoporous charcoal material is further improved and mainly comprises a mesoporous structure; the pore size distribution range of mesopores in the multilevel mesoporous biochar material is 2 nm-50 nm; the pore volume of the multilevel mesoporous biochar material is 0.318cm3/g～1.329cm3(ii)/g; the specific surface area of the multilevel mesoporous biochar material is 431.7m2/g～1642m2/g。
In the method, the preparation method of the multilevel mesoporous biochar material is further improved and comprises the following steps:
s1, mixing calcium chloride and bagasse in water, drying, adding potassium hydroxide with the same mass as the calcium chloride, and uniformly mixing to obtain a calcium chloride/potassium hydroxide/bagasse mixture;
s2, calcining the calcium chloride/potassium hydroxide/bagasse mixture obtained in the step S1 to obtain bagasse porous biochar;
s3, mixing the bagasse biochar obtained in the step S2 with water, performing ultrasonic treatment, stirring, filtering, washing and drying to obtain the multilevel mesoporous biochar.
In the step S1, the mass ratio of the calcium chloride to the bagasse is 1-3: 1; the drying temperature is 60-80 ℃; the drying time is 10 hours; the bagasse also comprises the steps of washing, drying and crushing the bagasse before use, and sieving the bagasse by a 100-200-mesh sieve.
In a further improvement of the above method, in step S2, the calcining is performed under an inert gas atmosphere; the heating rate is 5-10 ℃/min in the calcining process; the calcining temperature is 600-800 ℃; the calcining time is 1-3 h.
In the step S3, the ratio of the bagasse biochar to water is 1 g: 10 mL-40 mL; the ultrasonic time is 20-40 min; the stirring speed is 200 r/min-1000 r/min; the stirring temperature is 20-30 ℃; the stirring time is 0.5-4 h; the washing is to wash the product obtained by stirring with hydrochloric acid, ethanol and ultrapure water in sequence; the drying temperature is 60-80 ℃.
The method is further improved, and organic pollutants in water are treated by adopting the multi-stage mesoporous biochar material and persulfate, and the method comprises the following steps: the multi-stage mesoporous biochar material, persulfate and the organic pollutant water body are mixed for degradation treatment, and the degradation of the organic pollutant in the water body is completed.
In the method, the mass concentration ratio of the multilevel mesoporous biochar material to organic pollutants in an organic pollutant water body is further improved to be 1.65-5: 1; the mass concentration ratio of the persulfate to the organic pollutants in the organic pollutant water body is 25-100: 1.
In the method, further improvement is that the organic pollutant in the organic pollutant water body is at least one of tetracycline hydrochloride, 2, 4-dichlorophenol, rhodamine B, phenol and bisphenol A; the persulfate is sodium persulfate.
In the method, the degradation treatment is carried out at the oscillation speed of 100 rpm-300 rpm; the temperature of the degradation treatment is 15-35 ℃; the time of the degradation treatment is 60-180 min.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a method for degrading and treating organic pollutants by activating persulfate through a multi-stage mesoporous biochar material, and particularly relates to a method for treating organic pollutants by activating persulfate through the multi-stage mesoporous biochar material, wherein the multi-stage mesoporous biochar material is prepared by mixing bagasse as a raw material with calcium chloride and potassium hydroxide and then calcining. In the invention, the used multi-stage mesoporous biochar material is prepared by leading bagasse biomass to pass through KOH and CaCl2Co-processed and calcined, due to KOH and CaCl2On one hand, oxygen from KOH can enter a C net through a doping mode to form a functional group and a hydrogen bond through a high-temperature reaction, so that adsorption is facilitated, and more catalytic sites are provided (as shown in a formula (1)); on the other hand, Ca2+The introduction of the organic carbon composite material also accelerates and promotes the electron transfer between carbon networks to a certain extent, active sites formed in the process can effectively activate persulfate, the oxidative degradation rate of the whole system is accelerated, and the rapid degradation of organic pollutants (such as phenol) is realized. Because the multilevel mesoporous biochar material used by the invention has high graphitization degree, rich oxygen doping content, rough surface with more mesopores and small amount of calcium is introduced, which is beneficial to forming oxygen-containing functional groups,the defect sites and the accelerated electron transfer substantially improve the adsorption and catalytic performance of the material. The biochar material rich in the mesoporous structure can quickly and efficiently adsorb organic pollutants, for example, the adsorption balance of phenol can be realized within 10 min; meanwhile, the abundant mesoporous structure can accelerate the mass transfer rate of the whole system and provide more catalytic sites, thereby increasing the contact with pollutants and promoting the degradation. Compared with most biochar materials mainly made of sp 3-hybridized amorphous carbon, the mesoporous-rich biochar disclosed by the invention is high in graphitization degree, and the carbon framework mainly comprises sp 2-hybridized graphite carbon, so that the multilevel mesoporous biochar disclosed by the invention has the advantages of higher speed, higher efficiency in electron transfer performance and higher stability. The method for degrading organic pollutants by activating persulfate through the multi-stage mesoporous biochar material has the advantages of simplicity in operation, high degradation efficiency, short period and the like, is convenient to recover, is low in cost, and has a good application prospect in actual treatment of organic pollutant (such as phenol) wastewater, polluted natural water and soil.
6KOH+2C→2K+3H2+2K2CO3 (1)
(2) According to the invention, the multi-stage mesoporous biochar material realizes efficient degradation of organic pollutants through a new free radical and non-free radical path (which is a new degradation path and is a reaction path with non-free radical singlet oxygen as a leading part and free radical as an auxiliary part), wherein the degradation effect of the non-free radical leading reaction is little influenced by the environment, the reaction is attached to the surface of a carbon material for a long time, the carbon material is beneficial to fully contacting with the pollutants, and a better degradation effect is achieved, namely, the proportion of non-free radical components is more beneficial to catalytic degradation. Taking phenol as an example, the non-radical-dominated reaction pathway of the multi-stage mesoporous biochar material is a direct two-electron transfer degradation pathway and a singlet oxygen degradation pathway (as shown in formula (2) to formula (3)). According to the invention, rich mesoporous structures of the multilevel mesoporous biochar (Ca/BS-KOH) can quickly and efficiently adsorb phenol in a solution, after Persulfate (PDS) is added into the system, the persulfate can also be adsorbed to the surface of the biochar material, under the interaction of the ternary system, the phenol rich in electrons is used as an electron donor, electrons are transferred to the persulfate (electron acceptor) through the mediation effect and the electron bridge assistance of the multilevel mesoporous biochar, and the activated persulfate further attacks and oxidizes a target pollutant and completes mineralization degradation. The non-free radical path has the advantages of high degradation rate, small influence by the pH value of the solution, small interference by anions and natural organic matters in water and the like, and solves the problem that most catalyst materials are greatly interfered by the environment in a persulfate advanced oxidation system.
(3) In the invention, the used multi-stage mesoporous biochar material adopts biological waste bagasse as a raw material and is prepared by KOH and CaCl2The processing and simple calcination one-step pyrolysis method is simple and convenient, and the preparation method is low in cost. In the invention, the multi-stage mesoporous biochar material can be well dispersed in the solution and cannot float on the surface of a water body, so that the full contact with the reaction solution is relatively ensured; meanwhile, the multi-stage mesoporous biochar material is used as a heterogeneous solid catalyst, can be separated from a reaction solution through a simple centrifugal process or a suction filtration process, is convenient to recycle, and the overall performance of the catalytic material can be greatly improved after the recycled catalytic material (the multi-stage mesoporous biochar material) is subjected to heat treatment. The multistage mesoporous biochar mainly contains C, O and other elements, does not contain harmful metal elements, and does not have the risks of secondary pollution such as metal dissolution and the like. The multistage mesoporous biochar has the advantages of simple preparation, low cost, strong catalytic performance, strong anti-interference capability, good dispersibility, strong stability and easy recycling, and is an environment-friendly catalytic material for activating persulfate, which can be widely applied and has excellent catalytic performance.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is a drawing showing the nitrogen desorption and the pore size distribution of the multi-stage mesoporous biochar material (Ca/BS-KOH) prepared in example 1 of the present invention.
FIG. 2 is an XPS graph of the multi-stage mesoporous biochar material (Ca/BS-KOH) prepared in example 1 of the present invention.
FIG. 3 is a graph showing the effect of the multi-stage mesoporous biochar material (Ca/BS-KOH), the potassium hydroxide modified bagasse biochar material (BS-KOH) and the bagasse biochar material (BS) on the removal of phenol under different time conditions in example 1 of the present invention.
FIG. 4 is a graph showing the effect of removing the multi-stage mesoporous biochar material (Ca/BS-KOH), activated carbon and coconut shell biochar on the phenol solution in example 1 of the present invention.
FIG. 5 is a diagram illustrating the effect of the recovered multi-stage mesoporous biochar material (Ca/BS-KOH) in removing phenol solution in example 1 of the present invention after treatment in different ways.
Fig. 6 is a graph showing the effect of the multilevel mesoporous biochar material (Ca/BS-KOH) on removing phenol at different temperatures and different amounts of the multilevel mesoporous biochar material in example 2 of the present invention.
FIG. 7 is a graph showing the effect of the multi-stage mesoporous biochar material (Ca/BS-KOH) on removing phenol under natural water and soil conditions in example 3 of the present invention.
FIG. 8 is a graph showing the effect of the multi-stage mesoporous biochar material (Ca/BS-KOH) on removing different organic pollutants in example 4 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and instruments used in the following examples are commercially available and the starting materials were analytically pure. In the following examples, unless otherwise specified, the data obtained are the average of three or more replicates.
Example 1
A method for degrading organic pollutants by activating persulfate through a multi-stage mesoporous biochar material specifically comprises the following steps: the method for degrading phenol in water by activating sodium persulfate through the multistage mesoporous biochar material comprises the following steps:
adding a multistage mesoporous biochar material (Ca/BS-KOH) and sodium persulfate into a phenol solution (the temperature of the solution is 25 ℃) containing 0.6mg according to the mass concentration ratio of the multistage mesoporous biochar material to phenol in the phenol solution being 3.3: 1 (namely the mass concentration ratio of the multistage mesoporous biochar material to phenol in the reaction system, if the initial mass concentration of the multistage mesoporous biochar material in the reaction system is 3.3mg/L, the initial mass concentration of phenol in the system is 1mg/L) and the mass concentration ratio of the sodium persulfate to phenol in the phenol solution is 50: 1 (namely the mass concentration ratio of the sodium persulfate to phenol in the reaction system, if the initial mass concentration of the sodium persulfate in the reaction system is 50mg/L, the initial mass concentration of phenol in the system is 1mg/L), uniformly mixing, and degrading for 180min under the conditions of 200rpm and 25 ℃, in the treatment process, adsorption and oxidative degradation are performed simultaneously to complete the degradation of phenol, and the degradation effect corresponds to the "Ca/BS-KOH degradation" in FIG. 3. And after the treatment is finished, recovering the multilevel mesoporous biochar material.
Meanwhile, in the embodiment, the adsorption effect of the multilevel mesoporous biochar material (Ca/BS-KOH) on the phenol solution is also considered, and the method specifically comprises the following steps: adding the multilevel mesoporous biochar material (Ca/BS-KOH) into a phenol solution containing 0.6mg (the temperature of the solution is 25 ℃) according to the mass concentration ratio of the multilevel mesoporous biochar material to phenol in the phenol solution being 3.3: 1, uniformly mixing, and carrying out adsorption treatment for 180min at 200rpm and 25 ℃, wherein the adsorption effect corresponds to 'Ca/BS-KOH adsorption' in figure 3.
In this example, the following comparative tests were also considered:
(a) the potassium hydroxide modified bagasse biochar material (BS-KOH) is used for replacing the multilevel mesoporous biochar (Ca/BS-KOH), the influence of the potassium hydroxide modified bagasse biochar material (BS-KOH) on the adsorption effect (the adsorption effect corresponds to 'BS-KOH adsorption' in figure 3) and the degradation effect (the degradation effect corresponds to 'BS-KOH degradation' in figure 3) of a phenol solution containing 0.6mg (the temperature of the solution is 25 ℃) is examined, and other conditions are the same.
(b) The bagasse biochar material (BS) was used to replace the multilevel mesoporous biochar material (Ca/BS-KOH), and the effects of the bagasse biochar material (BS) on the adsorption effect (the adsorption effect corresponds to "BS adsorption" in fig. 3) and the degradation effect (the degradation effect corresponds to "BS degradation" in fig. 3) of a phenol solution containing 0.6mg (the temperature of the solution is 25 ℃) were examined, and the other conditions were the same.
(c) Without any addition of biochar material, the other conditions were the same, i.e. Persulfate (PS) alone, the removal effect corresponding to "PS" in fig. 3.
In this embodiment, the preparation method of the multilevel mesoporous biochar material (Ca/BS-KOH) includes the following steps:
(1) washing bagasse with deionized water, and drying in an oven at 80 deg.C (for 12 hr); putting a proper amount of dried bagasse into a grinder for grinding treatment, and screening the bagasse with a 100-200 mesh screen to obtain bagasse powder; placing a certain amount of bagasse powder into a beaker, adding a proper amount of ultrapure water, and then taking a proper amount of CaCl2(the mass ratio of calcium chloride to bagasse is 3: 1) is dissolved in a beaker, is stirred to be fully contacted with bagasse powder, and is placed in an oven for drying at 80 ℃ for 10h (in the drying process, calcium ions enter bagasse biomass in a doped and complexed mode and play a role in electron transfer for subsequent catalytic degradation); and then taking out the beaker, uniformly mixing the mixture in the beaker with KOH (the mass of the mixture is the same as that of calcium chloride), putting the mixture into a quartz boat, heating the mixture to 800 ℃ at the heating rate of 5 ℃/min under the protective atmosphere of flowing nitrogen gas, and calcining the mixture at the constant temperature for 2 hours to obtain the bagasse porous biochar.
(2) Adding 2.5g of bagasse porous biochar prepared in the step (1) into ultrapure water, uniformly mixing, placing the obtained mixed solution into an ultrasonic cleaning instrument for ultrasonic treatment for 40min, placing the mixed solution after ultrasonic treatment on a magnetic stirrer, adding a magnetic stirrer, adjusting the rotating speed to 600rpm, adjusting the treatment temperature to 30 ℃, and performing magnetic stirring treatment for 2 h; carrying out suction filtration on the mixed solution after the magnetic stirring treatment to obtain a solid material; and repeatedly washing the obtained solid material with hydrochloric acid (the concentration is 1M), ethanol and deionized water, and drying the washed solid material in an oven at 80 ℃ to obtain the multilevel mesoporous biochar material, which is recorded as Ca/BS-KOH.
In this example, the multi-stage mesoporous biochar material (Ca/BS-KOH) has a rough surface and a large specific surface area (1209 m)2The graphitization degree is high, and the graphite material mainly comprises a mesoporous structure, wherein the pore diameter of the contained mesoporous structure is distributed between 2nm and 35 nm. The pore volume of the multilevel mesoporous biochar is 0.318-1.231 cm3/g。
In the implementation, the preparation method of the potassium hydroxide modified bagasse biochar material (BS-KOH) comprises the following steps:
(1) washing bagasse with deionized water, and drying in an oven at 80 deg.C (for 12 hr); putting a proper amount of dried bagasse into a grinder for grinding treatment, and screening the bagasse with a 100-200 mesh screen to obtain bagasse powder; uniformly mixing the bagasse powder and KOH (the mass ratio of the KOH to the bagasse powder is 3: 1), putting the mixture into a quartz boat, heating to 800 ℃ at the heating rate of 5 ℃/min under the protective atmosphere of flowing nitrogen gas, and calcining at constant temperature for 2h to obtain the potassium hydroxide modified bagasse biochar.
(2) Adding 2.5g of the potassium hydroxide modified bagasse biochar prepared in the step (1) into ultrapure water, uniformly mixing, placing the obtained mixed solution into an ultrasonic cleaning instrument for ultrasonic treatment for 40min, placing the mixed solution after ultrasonic treatment on a magnetic stirrer, adding a magnetic stirrer, adjusting the rotating speed to 600rpm, the treatment temperature to 30 ℃, and performing magnetic stirring treatment for 2 h; carrying out suction filtration on the mixed solution after the magnetic stirring treatment to obtain a solid material; and repeatedly washing the obtained solid material with hydrochloric acid (1M), ethanol and deionized water, and drying the washed solid material in an oven at 80 ℃ to obtain the potassium hydroxide modified bagasse biochar material, which is recorded as BS-KOH.
In the implementation, the preparation method of the bagasse biochar material (BS) comprises the following steps:
(1) washing bagasse with deionized water, and drying in an oven at 80 deg.C (for 12 hr); putting a proper amount of dried bagasse into a grinder for grinding treatment, and screening the bagasse with a 100-200 mesh screen to obtain bagasse powder; placing the bagasse powder into a quartz boat, heating to 800 ℃ at a heating rate of 5 ℃/min under the protective atmosphere of flowing nitrogen gas, and calcining for 2h at constant temperature to obtain the bagasse biochar.
(2) Adding 2.5g of bagasse biochar prepared in the step (1) into ultrapure water, uniformly mixing, placing the obtained mixed solution into an ultrasonic cleaning instrument for ultrasonic treatment for 40min, placing the mixed solution after ultrasonic treatment on a magnetic stirrer, adding a magnetic stirrer, adjusting the rotating speed to 600rpm, adjusting the treatment temperature to 30 ℃, and performing magnetic stirring treatment for 2 h; carrying out suction filtration on the mixed solution after the magnetic stirring treatment to obtain a solid material; and repeatedly washing the obtained solid material with hydrochloric acid (1M), ethanol and deionized water in sequence, and drying the washed solid material in an oven at 80 ℃ to obtain the bagasse biochar material, which is marked as BS.
FIG. 1 is a drawing showing the nitrogen desorption and the pore size distribution of the multi-stage mesoporous biochar material (Ca/BS-KOH) prepared in example 1 of the present invention. As can be seen from FIG. 1, the multilevel mesoporous biochar material prepared by the invention contains abundant mesopores, wherein the pore diameter range of the mesopores is concentrated at 2 nm-35 nm, and the hierarchical pore structure is proved. In addition, as can be seen from the inner diagram in fig. 1, the multi-level mesoporous biochar material prepared by the invention has more mesoporous pores within the pore diameter range of 2nm to 50nm, that is, has multi-level mesopores within the pore diameter range of 2nm to 50nm, and the more such structures, the more beneficial the adsorption and adhesion of pollutants and the catalytic degradation on the surface of the multi-level mesoporous biochar material.
FIG. 2 is an XPS graph of the multi-stage mesoporous biochar material (Ca/BS-KOH) prepared in example 1 of the present invention. As can be seen from fig. 2, the multilevel mesoporous biochar material prepared by the invention mainly contains C, O elements, which proves the rich oxygen content thereof, and simultaneously indicates that Ca element is introduced, wherein the atomic percentage of C, O, Ca is respectively 88.5%, 10.36% and 0.6%. The multi-stage mesoporous biochar material is doped with calcium ions and oxygen, and provides more oxygen-containing functional groups and active sites for electron transfer for modified mesoporous carbon.
In this example, the phenol concentration was sampled and measured at 0min, 10min, 20min, 30min, 40min, 50min, 60min, 70min, 90min, 120min, 150min, and 180min of the treatment, and the influence of different materials on the phenol removal effect at different times was calculated, as shown in fig. 3.
FIG. 3 is a graph showing the effect of the multi-stage mesoporous biochar material (Ca/BS-KOH), the potassium hydroxide modified bagasse biochar material (BS-KOH) and the bagasse biochar material (BS) on the removal of phenol under different time conditions in example 1 of the present invention. In fig. 3, the ordinate represents the ratio of the phenol concentration to the initial concentration at a certain time, i.e., the removal effect includes the adsorption effect and the degradation effect. As can be seen from fig. 3, the phenol solution is treated by the multi-stage mesoporous biochar material (Ca/BS-KOH) and sodium Persulfate (PS), so that the phenol solution not only has a good adsorption effect on phenol, but also can efficiently catalyze and activate persulfate and complete degradation removal of phenol, wherein the removal rate of phenol after 180 minutes of adsorption treatment is 18% (as the corresponding "Ca/BS-KOH adsorption" curve in fig. 3), and the removal rate of phenol after 90 minutes of oxidative degradation is 100% (as the corresponding "Ca/BS-KOH degradation" curve in fig. 3), which is mainly due to the rough surface (sheet shape), the mesoporous biochar material (Ca/BS-KOH) containing a large number of mesoporous structures and doped oxygen-containing functional groups. Meanwhile, as can be seen from fig. 3, the removal effect of the multilevel mesoporous biochar material (Ca/BS-KOH) on phenol is obviously better than that of the potassium hydroxide modified bagasse biochar material (BS-KOH). The bagasse biochar material (BS) and sodium Persulfate (PDS) are adopted to treat the phenol solution, the removal rate of phenol after adsorption treatment for 180 minutes is 21% (shown as a corresponding 'BS adsorption' curve in figure 3), and the removal rate of phenol after oxidative degradation for 180 minutes is 26% (shown as a corresponding 'BS degradation' curve in figure 3), because the bagasse biochar material (BS) has a smooth surface and a small amount of mesoporous structures, and has a low specific surface area, the capacity of activating persulfate to degrade phenol is remarkably reduced, so that persulfate cannot be effectively activated, and the phenol cannot be effectively removed. The removal rate of phenol is respectively 18% and 7% by simple multistage mesoporous biochar (Ca/BS-KOH) adsorption and simple sodium Persulfate (PS) degradation. The comparison shows that the composite system of the multilevel mesoporous biochar material (Ca/BS-KOH) and persulfate is more beneficial to the efficient removal of phenol in water, which shows that the multilevel mesoporous biochar material (Ca/BS-KOH) has excellent catalytic performance for activating persulfate and can be used for degrading organic pollutants.
In addition, the phenol removal effect of activated carbon (normal activated carbon) and coconut shell biochar (prepared by calcining coconut shell as a raw material) was examined (except for the material, the conditions were the same as in example 1), and the results are shown in fig. 4. FIG. 4 is a graph showing the effect of removing the multi-stage mesoporous biochar material (Ca/BS-KOH), activated carbon and coconut shell biochar on the phenol solution in example 1 of the present invention. In fig. 4, the adsorption effect and the degradation effect of activated carbon on the phenol solution are respectively shown as the corresponding "activated carbon adsorption" curve and "activated carbon degradation" curve in fig. 4; the adsorption effect and degradation effect of coconut shell biochar on phenol solution are respectively shown as the corresponding "coconut shell biochar adsorption" curve and "coconut shell biochar degradation" curve in fig. 4. As shown in FIG. 4, the removal effect of the multilevel mesoporous biochar material (Ca/BS-KOH) on phenol is obviously superior to that of activated carbon and coconut shell biochar, which shows that the multilevel mesoporous biochar material (Ca/BS-KOH) has stronger catalytic performance and can rapidly, efficiently and thoroughly remove organic pollutants (such as phenol) in water under the combined action of persulfate.
In addition, the multi-stage mesoporous biochar material recovered in example 1 was treated in the following manner:
the first method is as follows: the multi-stage mesoporous biochar material recovered in example 1 was cleaned with ultrapure water.
The second method comprises the following steps: the multilevel mesoporous biochar material recovered in example 1 was washed with ethanol.
The third method comprises the following steps: the multilevel mesoporous biochar material recovered in example 1 was calcined (conventional calcination).
The method is as follows: the multi-stage mesoporous biochar material recovered in example 1 was washed with ethanol and then calcined (conventional calcination).
The multi-stage mesoporous biochar material obtained by the treatment in the first to fourth modes is continuously used for treating a phenol solution containing 0.6mg (the temperature of the solution is 25 ℃), and the other conditions are the same as those in example 1, and the result is shown in fig. 5. FIG. 5 is a diagram illustrating the effect of the recovered multi-stage mesoporous biochar material (Ca/BS-KOH) in removing phenol solution in example 1 of the present invention after treatment in different ways. As can be seen from fig. 5, after the treatment by different treatment methods, the obtained multi-stage mesoporous biochar material can still effectively remove phenol in the water, wherein the removal rate of phenol by the multi-stage mesoporous biochar material obtained by the four-way treatment is still higher than 90%, which indicates that the multi-stage mesoporous biochar material (Ca/BS-KOH) of the present invention has faster and more efficient electron transfer performance and relatively higher stability, and can be repeatedly used for treating organic pollutants (such as phenol) in the water under the combined action of persulfate.
Example 2
A method for degrading organic pollutants by activating persulfate through a multi-stage mesoporous biochar material specifically comprises the following steps: the method for degrading phenol in water by activating sodium persulfate through the multistage mesoporous biochar material comprises the following steps:
the multi-stage mesoporous biochar material (Ca/BS-KOH) and sodium persulfate prepared in example 1 were added to a phenol solution (containing 0.6mg of phenol) at 25 ℃, 30 ℃, 35 ℃ (25 ℃, 30 ℃, 35 ℃ in turn corresponding to T1, T2, T3) at a temperature of 25 ℃, 30 ℃, 35 ℃ (25 ℃, 30 ℃, 35 ℃) according to a mass concentration ratio of the multi-stage mesoporous biochar material to phenol in the phenol solution of 3.3: 1 and a mass concentration ratio of the sodium persulfate to phenol in the phenol solution of 50: 1, and were subjected to degradation treatment at 200rpm for 180min, wherein adsorption and oxidative degradation were simultaneously performed during the treatment, thereby completing degradation of phenol. The degradation effects at 25 deg.C, 30 deg.C, and 35 deg.C are shown as "T1 degradation", "3.3: 1 and T2 degradation", and "T3 degradation" in FIG. 6, respectively.
Meanwhile, in the embodiment, the adsorption effect of the multilevel mesoporous biochar material (Ca/BS-KOH) on the phenol solution at different temperatures is also considered, and the method specifically comprises the following steps: adding the multilevel mesoporous biochar material (Ca/BS-KOH) into a phenol solution (containing 0.6mg of phenol) at the temperature of 25 ℃, 30 ℃ and 35 ℃ (25 ℃, 30 ℃ and 35 ℃) which sequentially corresponds to T1, T2 and T3 according to the mass concentration ratio of the multilevel mesoporous biochar material to the phenol in the phenol solution being 3.3: 1, uniformly mixing, and carrying out adsorption treatment at 200rpm for 180 min. The adsorption effects at 25 deg.C, 30 deg.C and 35 deg.C are shown as "T1 adsorption", "3.3: 1 and T2 adsorption" and "T3 adsorption", respectively, in FIG. 6.
Meanwhile, the influence of the mass concentration ratio of the multi-stage mesoporous biochar material to phenol in the phenol solution of 1.65: 1 and 5: 1 on the adsorption effect and the degradation effect of the phenol solution containing 0.6mg (at the temperature of 25 ℃) is respectively considered, and other conditions are the same. Wherein the adsorption effect and the degradation effect corresponding to the mass concentration ratio of 1.65: 1 are respectively shown as '1.65: 1 adsorption' and '1.65: 1 degradation' in figure 6; the adsorption effect and degradation effect corresponding to a mass concentration ratio of 5: 1 are respectively shown as "5: 1 adsorption" and "5: 1 degradation" in FIG. 6.
In this embodiment, the phenol concentration is sampled and measured at 0min, 10min, 20min, 30min, 40min, 50min, 60min, 70min, 90min, 120min, 150min, and 180min during the treatment, and the influence of different temperatures on the phenol removal effect, the reaction activation energy, and the influence of different amounts of added multi-stage mesoporous biochar on the phenol removal effect are calculated. The results are shown in FIG. 6.
Fig. 6 is a graph showing the effect of the multilevel mesoporous biochar material (Ca/BS-KOH) on removing phenol at different temperatures and different amounts of the multilevel mesoporous biochar material in example 2 of the present invention. As can be seen from FIG. 6, the method for degrading organic pollutants by activating persulfate through multi-stage mesoporous biochar has a promoting effect on adsorption and catalytic oxidation of phenol at a higher temperature, which implies that the reaction is an endothermic reaction, and the reaction for degrading phenol through multi-stage mesoporous biochar (Ca/BS-KOH) serving as a catalyst has relatively low activation energy, which indicates that phenol is easily catalytically degraded in the presence of multi-stage mesoporous biochar (Ca/BS-KOH). Meanwhile, as can be seen from fig. 6, the adsorption effect and the degradation effect of phenol are better as the addition amount of the multi-stage mesoporous biochar is increased. When the mass concentration ratio of the multi-stage mesoporous biochar material to phenol in the phenol solution is 5: 1, the adsorption removal rate can reach 20%, and 100% phenol removal and degradation removal can be realized within 60minThe speed is up to 0.0609min-1The result shows that the multistage mesoporous biochar can efficiently and thoroughly remove phenol.
Example 3
The method for investigating the anti-interference capability of the multilevel mesoporous biochar material in the process of activating sodium persulfate to degrade phenol in water comprises the following steps:
the multi-stage mesoporous biochar material (Ca/BS-KOH) prepared in example 1 and sodium persulfate were added to a natural water body containing a variety of organic substances (xiangjiang water body four sampling points, the degradation effects of these four water samples are shown in "water sample 1", "water sample 2", "water sample 3", "water sample 4" curves in fig. 7) and a soil sample (xiangjiang wetland soil, total 3 soil samples, the degradation effects of these three samples are shown in "m (water: soil) ═ 2: 1", "m (water: soil): 2: 1", "m (water: sand): 2: 1" curves in fig. 7) according to the concentration ratio of the multi-stage mesoporous biochar material to phenol in a phenol solution of 3.3: 1 and according to the concentration ratio of persulfate to phenol in a phenol solution of 50: 1, and a phenol solution was prepared in the above water sample and soil sample (water sample contains 0.6mg, 0.45mg of phenol in a soil sample) is subjected to oxidative degradation at 25 ℃ for 180min at 200r/min, solid-liquid separation is performed after the reaction is finished, the degradation of the phenol is finished, and the multi-stage mesoporous biochar is recovered.
In this embodiment, the phenol concentration is sampled and measured when the treatment time is 0min, 10min, 20min, 30min, 40min, 50min, 60min, 70min, 90min, 120min, 150min, and 180min, and the influence of the multistage mesoporous biochar on the phenol removal effect under the conditions of natural water and soil is calculated, and the result is shown in fig. 7.
FIG. 7 is a graph showing the effect of the multi-stage mesoporous biochar material (Ca/BS-KOH) on removing phenol under natural water and soil conditions in example 3 of the present invention. As can be seen from FIG. 7, although the degradation rate in Hunan river water is slightly lower than the reaction rate in the classical experiment (0.0398 min)-1) But also completely degraded phenol in the four river water samples. The multi-stage mesoporous biochar material (Ca/BS-KOH) still has the advantage of completely degrading phenol under the complex system of coexistence of various organic matters. Simultaneously the soil sample is pollutedThe product also shows unusual phenol degradation capability under the condition of insufficient contact with the multilevel mesoporous biochar material. The degradation removal rate of phenol is not obviously changed when the multistage mesoporous biochar is used for activating the sodium persulfate to degrade phenol in river water and soil, and the method for activating the persulfate to degrade organic pollutants by using the multistage mesoporous biochar material has high efficiency and good environmental application potential.
Example 4
The method for investigating the capability of activating persulfate to degrade common organic pollutants in water by using the multi-stage mesoporous biochar material (each reaction solution contains 1.2mg of 2.4-dichlorophenol, 0.6mg of bisphenol A, 1.2mg of tetracycline hydrochloride and 1.2mg of rhodamine B respectively) comprises the following steps:
according to the concentration ratio of the multi-stage mesoporous biochar material to common organic pollutants in a common pollutant solution (bisphenol A, 3.3: 1; tetracycline hydrochloride, rhodamine B and 2.4-dichlorophenol are all 1.65: 1) and the concentration ratio of persulfate to phenol in a phenol solution is 50: 1, the multi-stage mesoporous biochar material (Ca/BS-KOH) prepared in the example 1 and sodium persulfate are respectively added into the common pollutant aqueous solution, oxidative degradation is carried out for 180min under the conditions of 200r/min and 25 ℃, solid-liquid separation is carried out after the reaction is finished, the degradation of phenol is finished, and the multi-stage mesoporous biochar material is recovered.
In this embodiment, after the treatment is completed, samples are taken to determine the concentration of the corresponding pollutant, and the influence of the multi-stage mesoporous biochar material on the removal effect of various organic pollutants in a water body is calculated, and the result of the removal efficiency is shown in fig. 8.
FIG. 8 is a graph showing the effect of the multi-stage mesoporous biochar material (Ca/BS-KOH) on removing different organic pollutants in example 4 of the present invention. As can be seen from FIG. 8, the removal rates of the multilevel mesoporous biochar material (Ca/BS-KOH) to tetracycline hydrochloride, 2, 4-dichlorophenol, rhodamine B, phenol and bisphenol A are 95%, 100% and 98% in sequence, and the removal rate to most organic pollutants in water is very good (all higher than 95%), which indicates that the multilevel mesoporous biochar material (Ca/BS-KOH) has very good development potential for treatment and reuse of polluted water.
In conclusion, the multistage mesoporous biochar has the advantages of simple preparation, low cost, strong catalytic performance, strong anti-interference capability, good dispersibility, strong stability and easy recycling, and when the multistage mesoporous biochar is used for activating sodium persulfate to degrade organic pollutants (such as phenol) in a water body, the multistage mesoporous biochar can efficiently and thoroughly remove the organic pollutants (such as phenol) in the water body, so that the multistage mesoporous biochar has high use value and good application prospect.
The foregoing is merely a preferred embodiment of the invention, which is not to be construed as limiting the invention. Many possible variations and modifications of the present invention may be made by one of ordinary skill in the art using the above disclosure. Therefore, any simple modification of the above embodiments according to the technical essence of the present invention is within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method for degrading and treating organic pollutants by activating persulfate through a multi-stage mesoporous biochar material is characterized in that the organic pollutants are treated by the multi-stage mesoporous biochar material and persulfate; the multilevel mesoporous biochar material is prepared by mixing bagasse as a raw material with calcium chloride and potassium hydroxide and then calcining.
2. The method of claim 1, wherein the multilevel mesoporous biochar material comprises predominantly a mesoporous structure; the pore size distribution range of mesopores in the multilevel mesoporous biochar material is 2 nm-50 nm; the pore volume of the multilevel mesoporous biochar material is 0.318cm3/g～1.329cm3(ii)/g; the specific surface area of the multilevel mesoporous biochar material is 431.7m2/g～1642m2/g。
3. The method according to claim 2, wherein the preparation method of the multilevel mesoporous biochar material comprises the following steps:
s1, mixing calcium chloride and bagasse in water, drying, adding potassium hydroxide with the same mass as the calcium chloride, and uniformly mixing to obtain a calcium chloride/potassium hydroxide/bagasse mixture;
s2, calcining the calcium chloride/potassium hydroxide/bagasse mixture obtained in the step S1 to obtain bagasse porous biochar;
s3, mixing the bagasse biochar obtained in the step S2 with water, performing ultrasonic treatment, stirring, filtering, washing and drying to obtain the multilevel mesoporous biochar.
4. The method according to claim 3, wherein in the step S1, the mass ratio of the calcium chloride to the bagasse is 1-3: 1; the drying temperature is 60-80 ℃; the drying time is 10 hours; the bagasse also comprises the steps of washing, drying and crushing the bagasse before use, and sieving the bagasse by a 100-200-mesh sieve.
5. The method according to claim 4, wherein in the step S2, the calcining is performed under an inert gas protective atmosphere; the heating rate is 5-10 ℃/min in the calcining process; the calcining temperature is 600-800 ℃; the calcining time is 1-3 h.
6. The method according to claim 5, wherein in the step S3, the ratio of the bagasse biochar to water is 1 g: 10 mL-40 mL; the ultrasonic time is 20-40 min; the stirring speed is 200 r/min-1000 r/min; the stirring temperature is 20-30 ℃; the stirring time is 0.5-4 h; the washing is to wash the product obtained by stirring with hydrochloric acid, ethanol and ultrapure water in sequence; the drying temperature is 60-80 ℃.
7. The method according to claims 1-6, wherein the organic pollutants in the water body are treated by the multi-stage mesoporous biochar material and persulfate, and the method comprises the following steps: the multi-stage mesoporous biochar material, persulfate and the organic pollutant water body are mixed for degradation treatment, and the degradation of the organic pollutant in the water body is completed.
8. The method according to claim 7, wherein the mass concentration ratio of the multilevel mesoporous biochar material to the organic pollutants in the organic pollutant water body is 1.65-5: 1; the mass concentration ratio of the persulfate to the organic pollutants in the organic pollutant water body is 25-100: 1.
9. The method of claim 8, wherein the organic contaminant in the body of water of organic contaminants is at least one of tetracycline hydrochloride, 2, 4-dichlorophenol, rhodamine B, phenol, and bisphenol a; the persulfate is sodium persulfate.
10. The method according to claim 7, wherein the degradation treatment is performed at an oscillation speed of 100rpm to 300 rpm; the temperature of the degradation treatment is 15-35 ℃; the time of the degradation treatment is 60-180 min.
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| CN113371813A (en) * | 2021-06-11 | 2021-09-10 | 常州大学 | Method for degrading tetracycline by using cerium-manganese modified charcoal activated persulfate |
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| CN114275761A (en) * | 2021-12-22 | 2022-04-05 | 中国科学院江西稀土研究院 | Carbon material for producing singlet oxygen and preparation method and application thereof |
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