CN111573817B - Method for removing paracetamol in water based on in-situ Fenton reaction - Google Patents
Method for removing paracetamol in water based on in-situ Fenton reaction Download PDFInfo
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- CN111573817B CN111573817B CN202010445347.2A CN202010445347A CN111573817B CN 111573817 B CN111573817 B CN 111573817B CN 202010445347 A CN202010445347 A CN 202010445347A CN 111573817 B CN111573817 B CN 111573817B
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a method for removing acetaminophen in water based on an in-situ Fenton reaction, and belongs to the field of treatment of pollutants in water. The method comprises the following steps: A. synthesizing iron-doped graphite-phase carbon nitride: calcining a mixture of ferric ions and melamine at high temperature, washing and drying; B. ultrasonic activation to remove acetaminophen: adding iron-doped graphite-phase carbon nitride into polluted water containing acetaminophen, performing ultrasonic activation to generate hydrogen peroxide and hydroxyl radicals, and oxidizing and degrading acetaminophen. The method is simple to operate, high in removal efficiency and wide in application condition, and does not need to introduce ultraviolet light or additionally add hydrogen peroxide or other oxidants.
Description
Technical Field
The invention belongs to the technical field of water environment pollutant removal.
Background
Acetaminophen, also known as paracetamol, is one of the most commonly used over-the-counter analgesics and antipyretics in the world and is toxic when used in doses exceeding the recommended safe use. In recent years, acetaminophen-induced liver and kidney damage has received much attention. Researches show that the acetaminophen is one of medicines and personal care products with the highest detection frequency in the effluent of natural surface water and sewage treatment plants, and the detection concentration is 0.003-30 mu g/L, which indicates that the acetaminophen cannot be effectively removed by the traditional domestic sewage treatment method. Treatment of acetaminophen in tap water with sodium hypochlorite produces a semi-quinoid intermediate that is more toxic than acetaminophen. Therefore, the establishment of the method for efficiently removing the acetaminophen in the water has important research significance and practical value.
Currently, there are a variety of physicochemical methods available to effectively remove acetaminophen from water. However, these methods have the following disadvantages and limitations: first, the physical method merely transfers the acetaminophen from the water to the adsorption phase and does not effect the oxidative decomposition of acetaminophen. Second, the efficiency of catalysts such as titanium dioxide and zinc oxide is limited by factors such as the crystal form and the intensity of the light. Finally, in order to improve the chemical removal efficiency, oxidizing substances such as hydrogen peroxide and ozone need to be additionally added, but the addition of the oxidizing agent not only increases the process complexity and the removal cost, but also causes secondary pollution to the water body due to the excessive oxidizing agent. Therefore, a new catalyst is needed to be synthesized, and a more efficient and environment-friendly method for removing acetaminophen in water is established.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for efficiently removing paracetamol in water based on an in-situ heterogeneous Fenton reaction.
The purpose of the invention is realized by the following technical scheme:
a method for efficiently removing acetaminophen in water based on in-situ heterogeneous Fenton reaction comprises the following steps:
(1) adding iron-doped graphite-phase carbon nitride into a water sample containing acetaminophen to obtain an iron-doped graphite-phase carbon nitride solution with the mass volume concentration of 0.2-1.0g/L, placing the iron-doped graphite-phase carbon nitride solution in an ultrasonic field for reaction, controlling the concentration of dissolved oxygen in the solution according to the proportion of oxygen, nitrogen and air, and sampling at different reaction times;
(2) centrifuging the sample in the step (1), and taking the supernatant for analysis;
(3) measuring the solution centrifuged in the step (2) by adopting high performance liquid chromatography, measuring the concentration of acetaminophen through a standard curve, and calculating the removal rate of acetaminophen in different reaction times through concentration change before and after reaction;
as a preferred option: the iron-doped graphite-phase carbon nitride (Fe/g-C) in the step (1) 3 N 4 ) The preparation method comprises the following steps:
to a 250mL round bottom flask was added 3g of melamine (C) 3 H 6 N 6 ) Powders to which different amounts of ferric chloride hexahydrate (FeCl) were added respectively 3 ·6H 2 O), 100mL of H were added 2 O and 5mL of concentrated hydrochloric acid are stirred and evaporated to dryness at the temperature of 100 ℃ to obtain a precursor, the precursor is heated to 550 ℃ at the speed of 5 ℃/min in a muffle furnace and then is insulated for 3 hours, and the precursor is cooled to room temperature to obtain Fe/g-C with different iron contents 3 N 4 Ultrasonically washing the obtained product with deionized water and ethanol respectively, drying the product in an oven, and grinding to obtain the final Fe/g-C 3 N 4 And (5) producing the product.
As the preferred items: the iron-doped graphite-phase carbon nitride (Fe/g-C) 3 N 4 ) FeCl in the preparation method step 3 ·6H 2 The final iron contents of the products obtained were 0.0%, 0.05%, 0.1%, 0.2%, 0.5%, 0.7%, and 1.0% by adding 0.0, 3.2, 6.4, 12.8, 32, 44.8, and 64mg of O, respectively, and whether or not the iron ions were successfully supported on the graphite-phase carbon nitride was judged by X-ray photoelectron spectroscopy (XPS) (fig. 1).
As the preferred items: the iron-doped graphite-phase carbon nitride (Fe/g-C) 3 N 4 ) The washing conditions of the product in the preparation method steps are 100mL of deionized water and 100mL of ethanol, and the washing times are respectively 3 times.
As the preferred items: the iron-doped graphite-phase carbon nitride (Fe/g-C) 3 N 4 ) The drying conditions in the preparation method steps are drying at 80 ℃ for 12 hours.
As the preferred items: the ultrasonic power in the step (1) is 300W, and the volume of the reaction solution is 100 mL.
As a preferred option: the centrifugation condition in the step (2) is 3000rpm, and the centrifugation time is 10 min.
As the preferred items: the determination conditions of the high performance liquid chromatography in the step (3) are as follows: the wavelength of the ultraviolet detector is 250 nm; column COSMOSIL 5C18-MS-II column (250X 4.6mm,5 μm); a mixed solution of 30% methanol and 70% water (containing 1% formic acid) as a mobile phase; the flow rate of the mobile phase is 0.8 mL/min; the injection volume was 20. mu.L.
The invention adopts iron-doped graphite phase carbon nitride (Fe/g-C) 3 N 4 ) The basic principle of removing acetaminophen from water is that graphite-phase carbon nitride in a catalyst activates water molecules and dissolved oxygen to generate hydrogen peroxide (figure 2), supported Fe and generated hydrogen peroxide generate hydroxyl radicals through heterogeneous Fenton reaction (figure 3), and the hydroxyl radicals and oxidized cavities generated by the graphite-phase carbon nitride under the ultrasonic condition jointly act to generate acetaminophen oxygenAnd (5) decomposing.
Compared with the prior art, the invention has the following advantages and effects:
the invention provides a method for doping graphite-phase carbon nitride (Fe/g-C) by using iron 3 N 4 ) The method does not need to use ultraviolet light as excitation energy, eliminates the damage of the ultraviolet light to operating personnel, does not need to additionally add hydrogen peroxide or ozone, and avoids secondary chemical pollution.
Drawings
FIG. 1 shows the obtained carbon nitride (Fe/g-C) containing 0.7% of iron-doped graphite phase 3 N 4 ) And graphite phase carbon nitride (g-C) containing no iron 3 N 4 ) The X photoelectron spectrum (1a) and the Fe2p spectrum (1 b).
As can be seen from FIG. 1, Fe/g-C doped with iron ions 3 N 4 The energy spectrum of Fe2p is significant, but the graphite-phase carbon nitride containing no iron element does not contain the energy spectrum of Fe2 p.
FIG. 2 shows ultrasonically driven g-C in different gas (air and argon Ar) environments 3 N 4 And g-C containing 0.7% Fe 3 N 4 (g-C 3 N 4 0.7% Fe) produced H 2 O 2 Amount of the compound (A).
FIG. 3 shows the g-C under Ultrasound (US) 3 N 4 And g-C 3 N 4 0.7% Fe and no catalyst (H) 2 O) amount of hydroxyl radical generated in the solution at different reaction times (3a), 3b is concentration of hydroxyl radical generated in the solution after 5 minutes of reaction.
FIG. 4 is a graph showing the ratio (4a) of the concentration and initial concentration (50mM) of acetaminophen in the presence of Ultrasound (US) under different reaction conditions (4b) in a graphite-phase carbon nitride solution without catalyst (only US), without iron (C3N4) and with different iron-doping concentrations.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
1. Iron-doped graphite-phase carbon nitride (Fe/g-C) 3 N 4 ) Preparation of
To a 250mL round bottom flask was added 3g of melamine (C) 3 H 6 N 6 ) Powders to which were added 3.2, 6.4, 12.8, 32, 44.8, 64mg ferric chloride hexahydrate (FeCl) respectively 3 ·6H 2 O), 100mL of H were added 2 O and 5mL of concentrated hydrochloric acid are stirred and evaporated to dryness at the temperature of 100 ℃ to obtain a precursor, the precursor is heated to 550 ℃ at the speed of 5 ℃/min in a muffle furnace and then is insulated for 3 hours, and the precursor is cooled to room temperature to obtain Fe/g-C with different iron contents of 0.05%, 0.1%, 0.2%, 0.5%, 0.7% and 1.0% 3 N 4 The resulting product was ultrasonically washed three times with 100mL of deionized water and 100mL of ethanol, respectively, and the product was placed in an oven to be dried at 80 ℃ for 12 hours.
2. Removal experiment of Paracetamol
Into a 250mL three-necked flask, 100mL of an aqueous solution containing 50. mu.M of acetaminophen was placed, and 100mg (1.0g/L) of the above-prepared g-C solution containing 0.7% Fe was added 3 N 4 Subsequently, the reaction was started with ultrasound (300W) at an oxygen content of 7.8mg/L, samples were taken every 15min, the samples were centrifuged at 3000rpm for 10min, and the concentration of acetaminophen in the supernatant was determined under optimized conditions. The result shows that after the reaction is carried out for 30 minutes, the removal rate of the acetaminophen can reach 90 percent; after the reaction is carried out for 60 minutes, the removal rate of the acetaminophen is more than 99 percent, and the removal reaction kinetic constant of the acetaminophen is 0.081min -1 。
Example 2
Into a 250mL three-necked flask, 100mL of an aqueous solution containing 50. mu.M of acetaminophen was added, and 100mg (1.0g/L) of g-C having different Fe contents prepared in example 1 was added 3 N 4 Subsequently, the reaction was started with the ultrasound (300W) turned on at an oxygen content of 7.8mg/L, samples were taken every 15min, the samples were centrifuged at 3000rpm for 10 minutes, and the concentration of acetaminophen in the supernatant was determined under optimized conditions. After reacting for 60 minutes, isThe iron-doped proportion of the acetaminophen is 0.0%, 0.05%, 0.1%, 0.2%, 0.5% and 1% of Fe/g-C 3 N 4 The degradation rate in (3) is as follows in sequence: 48%, 58%, 71%, 88%, 92% and 92% (FIG. 4).
It should be understood that parts of the specification not set forth in detail are well within the prior art.
It should be understood that the above description of the preferred embodiments is given for clarity and not for any purpose of limitation, and that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. A method for removing paracetamol in water based on in-situ Fenton reaction is characterized by comprising the following steps: the method comprises the following steps:
(1) iron-doped graphite phase carbon nitride Fe/g-C 3 N 4 Adding into a water sample containing paracetamol to obtain Fe/g-C with the mass volume concentration of 0.2-1.0g/L 3 N 4 The solution is placed in an ultrasonic field for reaction, the concentration of dissolved oxygen in the solution is controlled by the proportion of conditioned oxygen, nitrogen and air, and sampling is carried out at different reaction times; wherein Fe/g-C 3 N 4 The preparation method comprises the following steps: to a 250mL round bottom flask was added 3g of melamine C 3 H 6 N 6 Powder to which FeCl, iron chloride hexahydrate is added 3 ·6H 2 O, adding 100mL of water and 5mL of concentrated hydrochloric acid, stirring and evaporating at 100 ℃ to obtain a precursor, heating to 550 ℃ at a speed of 5 ℃/min in a muffle furnace, preserving heat for 3 hours, and cooling to room temperature to obtain Fe/g-C 3 N 4 Ultrasonically washing the obtained product with deionized water and ethanol respectively, putting the product into an oven, drying for 12 hours at 80 ℃, and grinding to obtain Fe/g-C 3 N 4 Producing a product; the FeCl 3 ·6H 2 The addition amount of O meets the requirement of Fe/g-C 3 N 4 The iron content in the product is 0.05%-1.0％；
(2) Centrifuging the sample in the step (1), and taking the supernatant for analysis;
(3) and (3) measuring the solution centrifuged in the step (2) by adopting high performance liquid chromatography, measuring the concentration of the acetaminophen through a standard curve, and calculating the removal rate of the acetaminophen in different reaction times through the concentration change before and after the reaction.
2. The method for removing acetaminophen from water based on in-situ Fenton's reaction according to claim 1, wherein: the optimal doping amount of iron in the iron-doped graphite-phase carbon nitride in the step (1) is 0.7%.
3. The method for removing acetaminophen in water based on in-situ Fenton's reaction according to claim 1, wherein: and (3) the centrifugation condition in the step (2) is that the rotating speed is more than or equal to 3000rpm, and the centrifugation time is more than or equal to 10 minutes.
4. The method for removing acetaminophen from water based on in-situ Fenton's reaction according to claim 1, wherein: the detection method of the high performance liquid chromatography in the step (3) is as follows: the wavelength of the ultraviolet detector is 250 nm; column COSMOSIL 5C18-MS-II column (250X 4.6mm,5 μm); a mixed solution of mobile phase 30% methanol and 70% aqueous solution containing 1% formic acid; the flow rate of the mobile phase is 0.8 mL/min; the injection volume is 20. mu.L.
5. The method for removing acetaminophen from water based on in situ fenton reaction of claim 4, wherein: the Fe/g-C 3 N 4 The washing conditions in the preparation method of (1) are 100mL of deionized water and 100mL of ethanol, and the washing times are respectively 3 times.
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