CN111392846A - Green degradation method for organic pollutants in water - Google Patents
Green degradation method for organic pollutants in water Download PDFInfo
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- CN111392846A CN111392846A CN202010141553.4A CN202010141553A CN111392846A CN 111392846 A CN111392846 A CN 111392846A CN 202010141553 A CN202010141553 A CN 202010141553A CN 111392846 A CN111392846 A CN 111392846A
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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
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- C02F1/722—Oxidation by peroxides
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention discloses a green degradation method of organic pollutants in water, which is different from the degradation method of organic pollutants in water absorbed by conventional biochar and is characterized in that the surface of the hydrothermal carbon contains environment-lasting free radicals with oxidation activity and H2O2And (3) degrading organic pollutants in the water body by heterogeneous catalysis. Under the conditions of normal temperature and normal pressure, the liquid-solid ratio of organic pollutants to powdery particle hydrothermal carbon is 1: 1-1: 4ml/mg, the powdery particle hydrothermal carbon is 1: 1-1: 5g/ml, and H2O2The volume ratio of the powdery particles is hydrothermal carbon and H2O2Adding the mixture into the polluted water to be treated, and fully and uniformly mixing the mixture so as to cooperatively remove the organic pollutants in the water body. The method accelerates the removal rate of pollutants in the organic polluted water body, simultaneously, the reaction system does not have the precipitation of pollutants and the generation of secondary pollution, and does not have the influence on the ecological environment of the water bodyThe environment causes damage. The method has the advantages of simple process, economy, high efficiency, environmental protection and great potential in the field of organic polluted water degradation.
Description
Technical Field
The invention relates to a method for degrading organic pollutants in water, in particular to a green method for degrading organic pollutants difficult to degrade in water, and belongs to the technical field of remediation of the organic pollutants difficult to degrade in water.
Background
There are many degradation technologies for organic pollutants in water, and when a specific degradation technology in water is selected, the proper degradation technology needs to be selected according to the comprehensive comparison of the pollutants and factors such as the property of water, the treatment time, the cost and the like. The existing pyrolytic carbon adsorption technology[1]Fenton-like degradation technology[2-3]And biodegradation[4-5]And the like are organic polluted water degradation technologies with wider application. The pyrolytic carbon adsorption degradation technology is to prepare a biochar material with high aperture ratio by a pyrolytic method, so that organic pollutants which are difficult to degrade in water are adsorbed on the biochar and then are separated, but the adsorption efficiency is not high, and the adsorbed biochar is also dangerous waste and is difficult to treat. The Fenton reaction is used for degrading organic pollutants by catalyzing hydrogen peroxide or persulfate to generate active oxygen substances by using low-valence transition metals, but the Fenton reaction has high requirement on Fenton conditions and is difficult to control in actual environment. Biodegradation is to adsorb or degrade organic pollutants in water by plants or microorganisms, and has low degradation cost, environmental friendliness and long degradation period. Meanwhile, some chemical degradation technologies can also be used for degradation in water, and although the method is simple and low in cost, secondary pollution can be generated and irreversible damage can be caused to the structure and components in water. Therefore, it is necessary to find an economical, practical, simple to operate and environment-friendly green degradation technology for organic polluted water. With the rapid development of science and technology and economy, China can generate a large amount of biomass including agricultural waste, household garbage, forest waste and the like every year, the biomass which is large in quantity, different in quality and easy to generate various hazards can not be effectively treated, and great hazards can be caused to human beings and the environment. The effective treatment and utilization of the waste biomass can meet the requirement of environmental protection, is beneficial to energy development and utilization, and realizes the treatment of waste by waste. Therefore, in recent years, the technology of applying the biochar to degrade the organic polluted water body has come. The biochar can adsorb organic pollutants in water to achieve the purpose of transferring the pollutants due to unique physicochemical properties and rich specific surface area, although the biochar degradation method well overcomes the problems of damage to the ecological environment in water and the like, the method only transfers the pollutants through adsorption and does not achieve the purpose of degradation, and the problems of secondary pollution and the like caused by treatment of the biochar after adsorption and re-precipitation of the pollutants can also exist subsequently.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects of the prior art, provides a green degradation method of organic pollutants in water, is a simple, high-efficiency and environment-friendly green degradation process for organic pollutants in water, and adopts hydrothermal carbon and H2O2Heterogeneous catalysis degrades organic pollutants in a water phase, and H can be catalyzed by utilizing the fact that the surface of hydrothermal carbon contains environment-persistent free radicals with oxidation activity2O2The generated hydroxyl free radicals rapidly degrade organic pollutants in water through oxidation reaction.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
green degradation method of organic pollutants in water by using hydrothermal carbon and H2O2Carrying out heterogeneous catalytic reaction to degrade organic pollutants in a water phase, and specifically comprising the following steps:
a. preparing powdery carbon source particles:
grinding the biomass material into powdery carbon source particles with particle size not larger than 100 meshes by using the crushed biomass material as a raw material;
b. preparation of hydrothermal carbon containing oxidative active environment persistent free radicals:
b, placing the powdery carbon source particles obtained in the step a into a high-pressure reaction kettle, adding metal salt into the reaction kettle according to the mass ratio of the powdery carbon source particles to the soluble metal salt being 20:1, adding water into the reaction kettle according to the solid-to-liquid ratio of the powdery carbon source particles to the water being 1: 5-1: 10g/ml, dissolving the soluble metal salt in the water, uniformly mixing the soluble metal salt with the powdery carbon source particles to form a reactant, wherein the mixed reactant is in a semisolid state, and performing hydrothermal carbonization reaction at the temperature of 180-300 ℃ in an inert atmosphere for 2-10 hours to prepare the hydrothermal carbon containing the persistent free radicals in the oxidative active environment; after the hydrothermal carbonization reaction is finished, washing reaction products in the reaction kettle for at least three times by using methanol and deionized water respectively, and then drying the obtained hydrothermal carbon in a vacuum drying oven at the temperature of not higher than 80 ℃ for at least 24 hours to obtain the hydrothermal carbon containing the oxidative active environment persistent free radicals for later use;
c. preparing powdery granular hydrothermal carbon:
grinding the hydrothermal carbon obtained in the step b into powdery granular hydrothermal carbon with the grain size not larger than 100 meshes;
d. and (3) catalytic degradation of the organic polluted water by oxidation reaction:
hydrothermal carbonization of the powdery particles obtained in step c and H2O2The solid-liquid ratio of 1: 1-1: 5g/ml, adding the hydrothermal carbon degradation solution into organic polluted water to be treated, the organic pollution concentration of which is not lower than 50 mg/L, and controlling the liquid-solid ratio of the organic polluted water to be treated and the powdery granular hydrothermal carbon to be 1: 1-1: 4ml/mg for fully mixing, thereby obtaining the powdery granular hydrothermal carbon and H2O2Adding the organic polluted water to be treated into the organic polluted water to be fully and uniformly mixed to form a mixed liquid reactant system; under the conditions of normal temperature and normal pressure, the reaction time is controlled to be not more than 24 hours, so that the organic pollutants in the organic polluted water to be treated are fully degraded.
In a preferred embodiment of the present invention, in the step b, the atmosphere in which the hydrothermal carbonization reaction is performed is controlled to be N2An atmosphere or an inert gas atmosphere.
As a preferable technical scheme of the invention, in the step b, the hydrothermal carbonization reaction is carried out at the temperature of 240-300 ℃ for 4-10 h.
As a preferable technical scheme of the present invention, in the step b, after the hydrothermal carbonization reaction is finished, the reaction product in the reaction kettle is washed with methanol and deionized water at least three times, then the reaction product in the reaction kettle is poured into a container for suction filtration, then the obtained hydrothermal carbon is dried in a vacuum drying oven at a temperature of not higher than 80 ℃ for at least 24 hours, and then the dried product is taken out, so as to obtain the hydrothermal carbon containing the oxidative active environment persistent free radicals.
In a preferred embodiment of the present invention, in the step b, any one of ferric chloride, aluminum chloride and zinc chloride is used as the soluble metal salt.
In the step d, the powdery granular hydrothermal carbon obtained in the step c and H are mixed2O2The solid-liquid ratio of 1: 1-1: 4g/ml, adding the hydrothermal carbon degradation solution into organic polluted water to be treated, the organic pollution concentration of which is not lower than 50 mg/L, and controlling the liquid-solid ratio of the organic polluted water to be treated and the powdery granular hydrothermal carbon to be 1: 1-1: 2ml/mg for fully mixing, thereby obtaining the powdery granular hydrothermal carbon and H2O2Adding the organic polluted water to be treated into the organic polluted water to be fully and uniformly mixed; forming a mixed solution reactant system; under the conditions of normal temperature and normal pressure, the reaction time is controlled to be not more than 6-23 hours, so that the organic pollutants in the organic polluted water to be treated are fully degraded.
As a preferred technical solution of the present invention, in the step d, the organic pollutant in the organically-polluted water to be treated includes at least one organic pollutant of polycyclic aromatic hydrocarbon, polychlorinated biphenyl, organic dye, methyl orange and bisphenol a.
As a preferable technical scheme of the present invention, in the step a, the biomass material is waste fruit peel or crop straw. The biomass material is preferably waste fruit peel.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the invention has simple reaction process, mild reaction condition, easy control, simple operation and low cost;
2. in the reaction process of the invention, the hot carbon and H are removed2O2No other chemical reagent is required to be introduced, no additional energy is required to be provided, and the hydrothermal process is realizedCarbon and H2O2The materials are environment-friendly materials, and have the advantages of green, high efficiency and low energy consumption;
3. the invention has no secondary pollution in the reaction process, and the unique physicochemical property of the hydrothermal carbon can not cause irreversible damage to the ecological environment in water;
4. the hydrothermal carbon used in the method is prepared from waste biomasses such as waste fruit peels, crop straws and the like, has wide sources and low price, achieves the aim of treating waste by waste, and has simple and easy preparation process, economy and environmental protection.
Drawings
FIG. 1 is a graph showing the effect of hydrothermal charcoal alone for degrading bisphenol A, an organic pollutant in water, according to an embodiment of the present invention.
FIG. 2 is a graph showing the effect of using hydrothermal charcoal of wheat straw to degrade methyl orange as an organic pollutant in water in example two of the present invention and using hydrothermal charcoal alone in comparative example two.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
the first embodiment is as follows:
in this embodiment, a green degradation method of organic pollutants in water utilizes hydrothermal carbon and H2O2Carrying out heterogeneous catalytic reaction to degrade organic pollutants in a water phase, and specifically comprising the following steps:
a. preparing powdery carbon source particles:
the method comprises the following steps of (1) grinding the cleaned shaddock peel into particles by taking the cleaned shaddock peel as a raw material, sieving the particles by a 100-mesh sieve, and collecting 100-mesh shaddock peel powder as powdery carbon source particles;
b. preparation of hydrothermal carbon containing oxidative active environment persistent free radicals:
selecting the part which is sieved in the step a, weighing 10g of the part, placing the part in a high-pressure reaction kettle, and weighing 0.5g of FeCl3Dissolving in 50ml deionized water, and mixing with pericarpium Citri Grandis powderMixing uniformly, pouring into a high-pressure reaction kettle, and adding FeCl3Dissolving in water, mixing with pericarpium Citri Grandis powder to obtain reactant, mixing the reactant in semisolid state, introducing inert gas N into the reaction kettle2Exhausting for 15min, covering the reaction kettle with a cover after ventilation, putting the reaction kettle into an oven, and performing hydrothermal carbonization reaction for 4h at the temperature of 240 ℃ to prepare hydrothermal carbon containing oxidative active environment persistent free radicals; after the hydrothermal carbonization reaction is finished, washing reaction products in the reaction kettle respectively with methanol and deionized water for three times, and then drying the obtained hydrothermal carbon in a vacuum drying oven at 80 ℃ for 24 hours to obtain the hydrothermal carbon containing the oxidative active environment persistent free radicals;
c. preparing powdery granular hydrothermal carbon:
b, taking out the dried product obtained in the step b, grinding the dried product by a porcelain mortar, sieving the ground product by a 100-mesh sieve, and storing the ground product in a vacuum box for later use;
d. and (3) catalytic degradation of the organic polluted water by oxidation reaction:
0.05g of bisphenol A is dissolved in 1 liter of deionized water to prepare 50 mg/L of bisphenol A polluted water, 0.25g of powdery granular hydrothermal carbon obtained in the step c and 1ml of H are adopted as a sample of organic polluted water to be treated2O2Adding 250ml of organic polluted water, and heating powdered granular hydrothermal carbon and H under normal temperature and pressure2O2Adding the bisphenol A polluted water to be treated into the water, and fully and uniformly mixing to form a mixed liquid reactant system; stirring and reacting in a constant-temperature water bath magnetic stirrer, sampling at different moments, filtering by a 0.22 mu m pinhole filter membrane, detecting the concentration change of the bisphenol A by using a high performance liquid phase, and controlling the reaction time to be 6h so as to degrade organic pollutants in a water phase.
Comparative example one:
and (c) melting 0.05g of bisphenol A in 1 liter of deionized water to prepare 50 mg/L of bisphenol A polluted water phase, adding 0.25g of the powdery granular hydrothermal carbon obtained in the step c into 250ml of the organic polluted water phase, fully and uniformly mixing the powdery granular hydrothermal carbon and the organic polluted water phase under the conditions of normal temperature and normal pressure, stirring and reacting in a constant-temperature water bath magnetic stirrer, sampling at different moments, and degrading the organic pollutants in the water phase for 6 hours.
Experimental test analysis:
experimental tests and analyses are carried out on the organic pollutant aqueous phase reactant systems of the first embodiment and the first comparative example, in the step d of the green degradation method of the organic pollutant in water, samples are taken at different moments, after filtration through a 0.22 mu m pinhole filter membrane, the concentration change of the bisphenol A is detected by using a high performance liquid phase, and fig. 1 is a graph showing the effect of degrading the organic pollutant bisphenol A in water by using the shaddock peel hydrothermal carbon in the first embodiment and degrading the organic pollutant bisphenol A in water by using the hydrothermal carbon alone in the first comparative example.
As can be seen by combining the first example and the first comparative example, as shown in FIG. 1, the first comparative example adopts hydrothermal carbon to treat the bisphenol A pollutants in water alone, and the removal rate of the bisphenol A pollutants in the water after 6 hours of reaction is only 10%, which is almost unchanged; EXAMPLE 1 liquid-solid ratio of organic contaminant and powdery granular hydrothermal carbon of 1.0ml/mg, powdery granular hydrothermal carbon of 0.25g/ml and H2O2Volume ratio, using 0.25g of hydrothermal charcoal and 1ml of H2O2Adding into polluted water, adding powdery granular hydrothermal carbon and H2O2The bisphenol A pollutant in the water to be treated is added and fully mixed uniformly, the removal rate of the bisphenol A pollutant in the water is jointly treated after 6 hours can reach 99 percent, the removal effect is obviously superior to that of a hydrothermal carbon system which is adopted independently, the Fenton-like reaction based on the hydrothermal carbon material can effectively degrade the organic pollutant in the water, and the environment-lasting free radicals with oxidation activity on the surface of the hydrothermal carbon are utilized to activate H2O2Generate active oxygen substances such as hydroxyl free radicals and the like, and quickly reduce organic pollutants in water.
Example two:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
in the embodiment, the biomass is wheat straw, the pollutant is methyl orange, and the green degradation method of the organic pollutant in water utilizes hydrothermal carbon and H2O2Carrying out heterogeneous catalytic reaction to degrade organic pollutants in a water phase, and specifically comprising the following steps:
a. preparing powdery carbon source particles:
the method comprises the following steps of (1) crushing and grinding wheat straws serving as raw materials into particles, sieving the particles by a 100-mesh sieve, and collecting wheat straw powder with the particle size of 100 meshes as powdery carbon source particles;
b. preparation of hydrothermal carbon containing oxidative active environment persistent free radicals:
selecting the part which is sieved in the step a, weighing 10g of the part, placing the part in a high-pressure reaction kettle, and weighing 0.5g of FeCl3Dissolving in 50ml deionized water, mixing with wheat straw powder, pouring into high pressure reactor, adding FeCl3Dissolving in water, mixing with wheat straw powder to obtain reactant, making the mixed reactant be in semi-solid state, introducing inert gas N into reaction kettle2Exhausting for 15min, covering the reaction kettle with a cover after ventilation, putting the reaction kettle into an oven, and performing hydrothermal carbonization reaction at the temperature of 300 ℃ for 10h to prepare hydrothermal carbon containing oxidative active environment persistent free radicals; after the hydrothermal carbonization reaction is finished, washing reaction products in the reaction kettle respectively with methanol and deionized water for three times, and then drying the obtained hydrothermal carbon in a vacuum drying oven at 80 ℃ for 24 hours to obtain the hydrothermal carbon containing the oxidative active environment persistent free radicals;
c. preparing powdery granular hydrothermal carbon:
b, taking out the dried product obtained in the step b, grinding the dried product by a porcelain mortar, sieving the ground product by a 100-mesh sieve, and storing the ground product in a vacuum box for later use;
d. and (3) catalytic degradation of the organic polluted water by oxidation reaction:
taking 0.5g of methyl orange polluted water to be treated, mixing the methyl orange polluted water with deionized water to form organic polluted water, taking 0.25g of powdery granular hydrothermal carbon obtained in the step c and 1ml of H as a sample of the organic polluted water to be treated2O2Adding 250ml of organic polluted water, and heating powdered granular hydrothermal carbon and H under normal temperature and pressure2O2Adding the organic polluted water into methyl orange polluted water to be treated, placing the organic polluted water into an oscillation box for continuous oscillation, and fully and uniformly mixing to form a reactant system in the organic polluted water; reacting at normal temperature and pressure, sampling at different times, filtering with 0.22 μm pinhole filter membraneThen, detecting the concentration change of the methyl orange by using a high performance liquid phase; the reaction time is controlled to be 23h, so that the organic pollutants in the water phase are degraded.
Comparative example two:
and (c) mixing 0.05g of methyl orange polluted water phase to be treated with deionized water to form an organic polluted water phase, adding 0.25g of the powdery granular hydrothermal carbon obtained in the step c into the organic polluted water phase, placing the organic polluted water phase into an oscillation box for continuous oscillation, fully and uniformly mixing the organic polluted water phase to form an organic polluted water phase reactant system, and reacting for 23 hours under the conditions of normal temperature and normal pressure to degrade organic pollutants in the water phase.
Experimental test analysis:
and (3) carrying out experimental test analysis on the organic pollution aqueous phase reactant systems of the second embodiment and the second comparative embodiment, sampling at different moments in the degradation process of the organic pollutants in water, filtering through a 0.45-micrometer pinhole filter membrane, measuring absorbance at 464nm by using an ultraviolet-visible spectrophotometer, and calculating the concentration of residual methyl orange in the reaction system. The second example shows the effect curve of using the hydrothermal carbon of the wheat straws to degrade the organic pollutant methyl orange in the water and the second comparative example to separately use the hydrothermal carbon to degrade the organic pollutant methyl orange in the water.
As can be seen from the combination of the above examples and comparative examples, as shown in FIG. 2, the removal rate of methyl orange contaminant in water after 23H reaction is only 9% in the comparative example II in which hydrothermal charcoal is used alone, and the liquid-solid ratio of organic contaminant of 1.0ml/mg and powdery granular hydrothermal charcoal of 0.25g/m L is used as the liquid-solid ratio of powdery granular hydrothermal charcoal and H2O2Volume ratio, using 0.25g of hydrothermal charcoal and 1m L of H2O2Adding into 250ml polluted water, adding powdery granular hydrothermal carbon and H2O2The bisphenol A-containing wastewater is added into the bisphenol A-containing wastewater to be treated and is fully and uniformly mixed to jointly treat methyl orange pollutants in the water, the removal rate after 23 hours can reach 94%, the removal effect is obviously superior to that of a hydrothermal carbon system which is adopted independently, the Fenton-like reaction based on the hydrothermal carbon material can effectively degrade organic pollutants in the water, and the environment that the surface of the hydrothermal carbon has oxidation activity is utilized to maintainActivation of H by persistent free radicals2O2Generate active oxygen substances such as hydroxyl free radicals and the like, and quickly reduce organic pollutants in water.
In conclusion, the method is different from the conventional degradation method for adsorbing organic pollutants in water by using the biological carbon, namely, the surface of the hydrothermal carbon contains the environment-lasting free radicals with oxidation activity and H2O2And degrading organic pollutants in water by heterogeneous catalysis. Mixing an organic polluted water phase and the powdery granular hydrothermal carbon obtained in the step c in a solid-liquid ratio of 1: 1-1: 4, and mixing the mass and the H of the powdery granular hydrothermal carbon obtained in the step c2O2The solid-liquid ratio is 1: 1-1: 5g/ml, and the three are fully and uniformly mixed under the conditions of normal temperature and normal pressure, so that organic pollutants in water are removed in a synergistic manner. The method of the invention accelerates the removal rate of organic pollutants in water, and simultaneously, the reaction system does not have the precipitation of pollutants and the generation of secondary pollution, and can not cause irreversible damage to the structure and components in water. The method has the advantages of simple process, economy, high efficiency, environmental protection and great application potential in the field of organic polluted water degradation.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions, so long as the technical principle and the inventive concept of the method for green degradation of organic pollutants in water according to the present invention are met, and the present invention shall fall within the protection scope of the present invention.
Claims (8)
1. A green degradation method of organic pollutants in water is characterized in that hydrothermal carbon and H are utilized2O2Carrying out heterogeneous catalytic reaction to degrade organic pollutants in a water phase, and specifically comprising the following steps:
a. preparing powdery carbon source particles:
grinding the biomass material into powdery carbon source particles with particle size not larger than 100 meshes by using the crushed biomass material as a raw material;
b. preparation of hydrothermal carbon containing oxidative active environment persistent free radicals:
b, placing the powdery carbon source particles obtained in the step a into a high-pressure reaction kettle, adding metal salt into the reaction kettle according to the mass ratio of the powdery carbon source particles to the soluble metal salt being 20:1, adding water into the reaction kettle according to the solid-to-liquid ratio of the powdery carbon source particles to the water being 1: 5-1: 10g/ml, dissolving the soluble metal salt in the water, uniformly mixing the soluble metal salt with the powdery carbon source particles to form a reactant, wherein the mixed reactant is in a semisolid state, and performing hydrothermal carbonization reaction at the temperature of 180-300 ℃ in an inert atmosphere for 2-10 hours to prepare the hydrothermal carbon containing the persistent free radicals in the oxidative active environment; after the hydrothermal carbonization reaction is finished, washing reaction products in the reaction kettle for at least three times by using methanol and deionized water respectively, and then drying the obtained hydrothermal carbon in a vacuum drying oven at the temperature of not higher than 80 ℃ for at least 24 hours to obtain the hydrothermal carbon containing the oxidative active environment persistent free radicals for later use;
c. preparing powdery granular hydrothermal carbon:
grinding the hydrothermal carbon obtained in the step b into powdery granular hydrothermal carbon with the grain size not larger than 100 meshes;
d. and (3) catalytic degradation of the organic polluted water by oxidation reaction:
hydrothermal carbonization of the powdery particles obtained in step c and H2O2The solid-liquid ratio of 1: 1-1: 5g/ml, adding the hydrothermal carbon degradation solution into organic polluted water to be treated, the organic pollution concentration of which is not lower than 50 mg/L, and controlling the liquid-solid ratio of the organic polluted water to be treated and the powdery granular hydrothermal carbon to be 1: 1-1: 4ml/mg for fully mixing, thereby obtaining the powdery granular hydrothermal carbon and H2O2Adding the organic polluted water to be treated into the organic polluted water to be fully and uniformly mixed to form a mixed liquid reactant system; under the conditions of normal temperature and normal pressure, the reaction time is controlled to be not more than 24 hours, so that the organic pollutants in the organic polluted water to be treated are fully degraded.
2. The method for green degradation of organic pollutants in water according to claim 1, wherein: in the step b, the atmosphere in which the hydrothermal carbonization reaction is carried out is controlled to be N2An atmosphere or an inert gas atmosphere.
3. The method for green degradation of organic pollutants in water according to claim 1, wherein: in the step b, the hydrothermal carbonization reaction is carried out at the temperature of 240-300 ℃ for 4-10 h.
4. The method for green degradation of organic pollutants in water according to claim 1, wherein: in the step b, after the hydrothermal carbonization reaction is finished, washing reaction products in the reaction kettle respectively with methanol and deionized water for at least three times, then pouring the reaction products in the reaction kettle into a container for suction filtration, then drying the obtained hydrothermal carbon in a vacuum drying oven at the temperature of not higher than 80 ℃ for at least 24 hours, and then taking out the dried product, thereby obtaining the hydrothermal carbon containing the oxidative active environment persistent free radicals.
5. The method for green degradation of organic pollutants in water according to claim 1, wherein: in the step b, any one of ferric chloride, aluminum chloride and zinc chloride is used as the soluble metal salt.
6. The method for green degradation of organic pollutants in water according to claim 1, wherein: in step d, the powdery particles obtained in step c are hydrothermally carbonized with H2O2The solid-liquid ratio of 1: 1-1: 4g/ml, adding the hydrothermal carbon degradation solution into organic polluted water to be treated, the organic pollution concentration of which is not lower than 50 mg/L, and controlling the liquid-solid ratio of the organic polluted water to be treated and the powdery granular hydrothermal carbon to be 1: 1-1: 2ml/mg for fully mixing, thereby obtaining the powdery granular hydrothermal carbon and H2O2Adding the organic polluted water to be treated into the organic polluted water to be fully and uniformly mixed; forming a mixed solution reactant system;under the conditions of normal temperature and normal pressure, the reaction time is controlled to be not more than 6-23 hours, so that the organic pollutants in the organic polluted water to be treated are fully degraded.
7. The method for green degradation of organic pollutants in water according to claim 1, wherein: in the step d, the organic pollutants in the organic polluted water to be treated comprise at least one organic pollutant of polycyclic aromatic hydrocarbon, polychlorinated biphenyl, organic dye, methyl orange and bisphenol A.
8. The method for green degradation of organic pollutants in water according to claim 1, wherein: in the step a, the biomass material is waste fruit peel or crop straw.
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|---|---|---|---|---|
| CN107364942A (en) * | 2017-08-24 | 2017-11-21 | 上海大学 | It can be applied to hydro-thermal carbon composite, its preparation method and its application of class Fenton's reaction |
| CN109013693A (en) * | 2018-08-28 | 2018-12-18 | 上海大学 | The green restorative procedure of organic polluted soil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107364942A (en) * | 2017-08-24 | 2017-11-21 | 上海大学 | It can be applied to hydro-thermal carbon composite, its preparation method and its application of class Fenton's reaction |
| CN109013693A (en) * | 2018-08-28 | 2018-12-18 | 上海大学 | The green restorative procedure of organic polluted soil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113134347A (en) * | 2021-03-23 | 2021-07-20 | 西安理工大学 | Preparation method and application of heteroatom porous carbon |
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