CN115722227A - Iron slag-doped wine-making sludge biochar material and preparation method and application thereof - Google Patents
Iron slag-doped wine-making sludge biochar material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of sewage treatment, and particularly relates to an iron slag doped wine-making sludge biochar material, and a preparation method and application thereof. The preparation method of the iron slag-doped wine-making sludge biochar material comprises the following steps: s1: pretreatment of brewing sludge: drying and crushing the dehydrated brewing sludge, sieving the crushed dehydrated brewing sludge with a 100-mesh sieve, and collecting brewing sludge powder for later use; s2: pretreatment of waste iron slag: washing the waste iron slag, drying in vacuum, grinding, sieving with a 200-mesh sieve, and collecting iron slag powder for later use; s3: the iron slag doped wine-making sludge biochar material comprises the following steps: dissolving the obtained iron slag powder in water, performing ultrasonic treatment, adding brewing sludge powder, uniformly stirring, drying, grinding, calcining the obtained powder at high temperature under oxygen deficiency, cooling to room temperature, washing, and drying in vacuum to obtain the iron slag-doped brewing sludge biochar material. The material provided by the invention can efficiently activate sodium persulfate to deeply treat norfloxacin polluted wastewater.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to an iron slag-doped wine-making sludge biochar material as well as a preparation method and application thereof.
Background
With the rapid development of economy and society, the production quantity and the use quantity of antibiotic drugs are continuously increased, and the problem of antibiotic pollution in water bodies is getting worse. Antibiotics entering natural water can induce the appearance of drug-resistant bacteria and drug-resistant genes, and threaten human health and ecological environment. Wherein Norfloxacin (Norfloxacin, NOR) is widely used as a 3 rd generation fluoroquinolone antibiotic drug with strong broad-spectrum antibacterial property for treating diseases such as dysentery, enteritis and the like. However, the absorption rate of the human body or the animal body to NOR is very limited, and NOR accounting for about 40% -90% of the dosage can be discharged out of the body and enter the environment. The average detected mass concentration of NOR in the effluent of wastewater treatment plants worldwide is 2.0 to 580 mg/L, and the surface water body reaches 5.0 to 1300 ng/L. Residual norfloxacin in the environment has poor degradation performance, and serious threat to the water ecological environment is formed through food chain enrichment. Therefore, how to efficiently remove antibiotics in the water body becomes one of the key problems to be solved urgently in the water environment.
At present, persulfate has attracted much attention in treating organic pollutants due to its strong oxidizing property and stability. With the common oxidant H for wastewater treatment 2 O 2 Compared with the prior art, the persulfate has high stability and convenient transportationAnd the like, and is beneficial to popularization and application in practical engineering. Persulfate is a compound having a high oxidation-reduction potential (E) 0 Oxidizing agent of = 2.01V) under certain reaction conditions to generate free radicals with higher oxidation-reduction potential, such as SO 4 •− And • OH, is widely used in water treatment process. Compared with the other ones • For AOPs with OH as the main active species, persulfate technology has the characteristics of stronger oxidizing ability, better selectivity and longer half-life period. Meanwhile, in terms of the characteristics of the oxidant, the persulfate has low price, low requirements on transportation and storage, simple and convenient reaction process operation and high safety, and has very wide application space in pharmaceutical wastewater treatment.
Biochar is a carbon-fixing material with excellent specific surface area and defect structure, and is easy to prepare and synthesize in a laboratory. Although the biochar can activate persulfate to remove organic pollutants which are difficult to degrade in water, the problems of complex material preparation, poor stability, low activation performance, difficult recovery in water and the like become bottleneck problems which restrict the wide application of biochar in actual wastewater treatment. At present, co-pyrolysis and iron doping are used as common biochar modification means, and have been proved to be capable of remarkably improving the activation activity of biochar materials, so that the biochar material has important application potential. In view of the above, the invention develops the heterogeneous activating agent which is easy to recover and can be recycled for many times by carrying out iron doping on the brewing sludge, namely carrying out co-pyrolysis on the wastewater sludge in the liquor brewing industry and the iron slag discarded by the factory, and establishes the oxidation system for efficiently removing the norfloxacin by activating persulfate, thereby providing technical guidance for advanced treatment of the norfloxacin pharmaceutical wastewater, enhancing the application value of the brewing sludge and the discarded iron slag, and achieving the important purpose of treating wastes with processes of wastes against one another.
Disclosure of Invention
Aiming at the defects and problems of large material consumption, high cost, low norfloxacin removal efficiency and the like in the prior art. The invention provides an iron slag-doped wine-making sludge biochar material as well as a preparation method and application thereof. The material disclosed by the invention is simple to prepare, high in reaction activity, strong in stability and good in recycling effect, and can be used for activating persulfate within a wider pH range to efficiently remove norfloxacin antibiotics in wastewater.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme.
One aspect of the invention provides a preparation method of an iron slag-doped wine-making sludge biochar material, which is characterized by comprising the following steps:
s1: pretreatment of brewing sludge: drying, crushing and screening the sludge generated by the brewery sewage treatment by a 100-mesh sieve after dehydration treatment, and collecting brewing sludge powder for later use;
s2: pretreatment of waste iron slag: washing the waste iron slag, drying in vacuum, grinding, sieving with a 200-mesh sieve, and collecting iron slag powder for later use;
s3: the iron slag doped wine-making sludge biochar material comprises the following steps: dissolving the obtained iron slag powder in water, performing ultrasonic treatment, adding brewing sludge powder, uniformly stirring, drying, grinding, calcining the obtained powder at high temperature under oxygen deficiency, cooling to room temperature, washing, and drying in vacuum to obtain the iron slag-doped brewing sludge biochar material.
Preferably, the drying conditions in step S1 are: the temperature is 100-110 ℃, and the time is 72-74h.
Preferably, the grain size of the brewing sludge powder in the step S1 is less than or equal to 0.150 mm.
Preferably, the washing manner in step S2 is: repeatedly washing with tap water, and washing with pure water and anhydrous ethanol for three times respectively after the washing water is clear.
Preferably, the vacuum drying conditions in step S2 are: the temperature is 50-60 ℃, and the time is 12-13h.
Preferably, the grain size of the iron slag powder in the step S2 is less than or equal to 0.075mm.
Preferably, the ultrasonic treatment conditions in step S3 are: the power is 500W, the frequency is 40KHz, and the time is 30 to 45min.
Preferably, the mass ratio of the iron slag powder to the brewing sludge powder in the step S3 is 0-5.
Preferably, the high-temperature anoxic calcination conditions in step S3 are: the temperature is 800 ℃ and the time is 2h.
Preferably, the vacuum drying conditions in step S3 are: the temperature is 50-55 ℃, and the time is 12-13h.
By the technical scheme, the invention at least has the following advantages:
(1) The preparation method of the iron slag doped wine sludge biochar material is simple, and the iron slag doped wine sludge biochar material can be separated and recovered by a magnet and recycled for multiple times.
(2) The iron slag-doped wine sludge biochar material prepared by the invention can activate sodium persulfate to remove norfloxacin in water within a wide pH and wide water temperature range, and has strong adaptability and good application value.
(3) The iron slag-doped wine-making sludge biochar material prepared by the invention can effectively activate sodium persulfate to treat norfloxacin pollution in different water bodies, and has a wide application prospect.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Drawings
FIG. 1a is an SEM picture of a brewing sludge biochar material prepared according to example 5 of the invention;
FIG. 1b is an SEM image of an iron slag-doped wine sludge biochar material prepared according to example 1 of the invention;
FIG. 1c is an X-ray crystal diffraction pattern of materials made according to examples 1-6 of the present invention;
FIG. 2 is a graph comparing the effect of materials prepared according to examples 1, 5 and 6 of the present invention on activating sodium persulfate to remove norfloxacin;
FIG. 3 is a comparison graph of the effect of removing norfloxacin by activating sodium persulfate through the iron slag-doped wine sludge biochar material prepared in examples 1 to 4 of the present invention;
FIG. 4 is a graph comparing the norfloxacin concentration at different concentrations with the effect of activating sodium persulfate to remove norfloxacin from the iron slag-doped wine-making sludge biochar material prepared in example 1;
FIG. 5 is a graph comparing the effect of reaction temperature on the removal of norfloxacin by activating sodium persulfate through the iron slag-doped wine sludge biochar material prepared in example 1;
FIG. 6 is a graph comparing the effect of pH on the removal of norfloxacin by activating sodium persulfate through the iron slag-doped wine sludge biochar material prepared in example 1;
FIG. 7 is a comparison graph of reusability of iron slag doped wine sludge biochar material prepared according to example 1 of the present invention to activate sodium persulfate to remove norfloxacin;
FIG. 8 is a comparison graph of the effect of removing norfloxacin from different water bodies by activating sodium persulfate through the iron slag-doped wine-making sludge biochar material prepared in example 1 of the present invention.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A: pretreatment of brewing sludge: drying the dewatered brewing sludge at 108 ℃ for 72 h, crushing by a crusher, sieving by a 100-mesh sieve, and collecting sludge powder (the particle size is less than or equal to 0.150 mm) for later use.
B: pretreatment of waste iron slag: repeatedly washing the waste iron slag with tap water, separating by using a magnet to wash away silt in the waste iron slag, washing for three times by using pure water and absolute ethyl alcohol respectively after water is clear, putting into a vacuum drying machine at 50 ℃ for 12 hours, grinding, sieving by using a 200-mesh sieve, collecting iron slag powder (the particle size is less than or equal to 0.075 mm), vacuumizing, sealing and storing for later use.
C: preparing an iron slag-doped wine-making sludge biochar material: weighing 1.0 g of iron slag powder (the particle size is less than or equal to 0.075 mm), putting the iron slag powder into a 250 mL beaker, adding 25 mL of water, and then performing ultrasonic treatment for 30min at 500W and 40KHz by using an ultrasonic cleaning instrument to fully release iron ions in the iron slag powder. After the ultrasonic treatment, 1.0 g of sludge powder (the particle size is less than or equal to 0.150 mm) is weighed and placed into a beaker, stirred for 30min by a mechanical stirrer and then placed into a blast drying oven for drying at 80 ℃. Collecting the dried solid, grinding uniformly by using a mortar, putting the uniformly mixed powder into a corundum crucible, and calcining at high temperature in a tube furnace in an oxygen-deficient manner. The basic working parameters of the tube furnace are 800 ℃, the holding time is 2h, and the heating rate is 5 ℃/min. And after the calcination is finished, cooling the sludge biochar to room temperature by using a tube furnace, taking out the sludge biochar, washing the sludge biochar to be neutral by using oxygen-free water, washing the sludge biochar for three times by using absolute ethyl alcohol, putting the sludge biochar into a vacuum drying oven at 50 ℃, drying the sludge biochar for 12 hours, collecting the dried iron slag doped with the brewing sludge biochar material, grinding the materials uniformly by using a mortar, and vacuumizing and sealing the materials for later use.
Example 2
A: pretreatment of brewing sludge: drying the dewatered brewing sludge at 108 ℃ for 72 h, crushing by a crusher, sieving by a 100-mesh sieve, and collecting brewing sludge powder (the particle size is less than or equal to 0.150 mm) for later use.
B: pretreatment of waste iron slag: repeatedly washing the waste iron slag with tap water, separating by using a magnet to wash away silt in the waste iron slag, washing for three times by using pure water and absolute ethyl alcohol respectively after water is clear, putting the waste iron slag into a 50 ℃ vacuum drier for 12 hours, grinding, sieving by using a 200-mesh sieve, collecting iron slag powder (the particle size is less than or equal to 0.075 mm), vacuumizing, sealing and storing for later use.
C: preparing an iron slag-doped wine-making sludge biochar material: weighing 5.0 g of iron slag powder (the particle size is less than or equal to 0.075 mm), putting the iron slag powder into a 250 mL beaker, adding 25 mL of water, and then performing ultrasonic treatment for 30min at 500W and 40KHz by using an ultrasonic cleaning instrument to fully release iron ions in the iron slag powder. And (3) after the ultrasonic treatment is finished, weighing 1.0 g of brewing sludge powder (the particle size is less than or equal to 0.150 mm) into a beaker, stirring for 30min by using a mechanical stirrer, and then drying in a forced air drying oven at 80 ℃. Collecting the dried solid, grinding uniformly by using a mortar, putting the uniformly mixed powder into a corundum crucible, and calcining at high temperature in a tube furnace in an oxygen-deficient manner. The basic working parameters of the tube furnace are 800 ℃, the heat preservation time is 2h, and the heating rate is 5 ℃/min. After the calcination is finished, cooling the tubular furnace to room temperature, taking out the sludge biochar, washing the sludge biochar to be neutral by using oxygen-free water, washing the sludge biochar for three times by using absolute ethyl alcohol, putting the sludge biochar into a vacuum drying oven at 50 ℃, drying the sludge biochar for 12 hours, collecting the dried iron slag doped with the brewing sludge biochar material, grinding the materials uniformly by using a mortar, and vacuumizing and sealing the materials for later use.
Example 3
A: pretreatment of brewing sludge: drying the dewatered brewing sludge at 108 ℃ for 72 h, crushing by a crusher, sieving by a 100-mesh sieve, and collecting brewing sludge powder (the particle size is less than or equal to 0.150 mm) for later use.
B: pretreatment of waste iron slag: repeatedly washing the waste iron slag with tap water, separating by using a magnet to wash away silt in the waste iron slag, washing for three times by using pure water and absolute ethyl alcohol respectively after water is clear, putting the waste iron slag into a 50 ℃ vacuum drier for 12 hours, grinding, sieving by using a 200-mesh sieve, collecting iron slag powder (the particle size is less than or equal to 0.075 mm), vacuumizing, sealing and storing for later use.
C: preparing an iron slag-doped wine-making sludge biochar material: 2.0 g of iron slag powder (the particle size is less than or equal to 0.075 mm) is weighed, the iron slag powder is put into a 250 mL beaker, 25 mL of water is added, and then an ultrasonic cleaner is used for ultrasonic treatment for 30min at 500W and 40KHz, so that iron ions in the iron slag powder are fully released. And (3) after the ultrasonic treatment, weighing 1.0 g of brewing sludge powder (the particle size is less than or equal to 0.150 mm) into a beaker, stirring for 30min by using a mechanical stirrer, and then drying in a forced air drying oven at 80 ℃. Collecting the dried solid, grinding uniformly by using a mortar, putting the uniformly mixed powder into a corundum crucible, and calcining at high temperature in a tube furnace in an oxygen-deficient manner. The basic working parameters of the tube furnace are 800 ℃, the heat preservation time is 2h, and the heating rate is 5 ℃/min. After the calcination is finished, cooling the tubular furnace to room temperature, taking out the sludge biochar, washing the sludge biochar to be neutral by using oxygen-free water, washing the sludge biochar for three times by using absolute ethyl alcohol, putting the sludge biochar into a vacuum drying oven at 50 ℃, drying the sludge biochar for 12 hours, collecting the dried iron slag doped with the brewing sludge biochar material, grinding the materials uniformly by using a mortar, and vacuumizing and sealing the materials for later use.
Example 4
A: pretreatment of brewing sludge: drying the dewatered brewing sludge at 108 ℃ for 72 h, crushing by a crusher, sieving by a 100-mesh sieve, and collecting brewing sludge powder (the particle size is less than or equal to 0.150 mm) for later use.
B: pretreatment of waste iron slag: repeatedly washing the waste iron slag with tap water, separating by using a magnet to wash away silt in the waste iron slag, washing for three times by using pure water and absolute ethyl alcohol respectively after water is clear, putting into a vacuum drying machine at 50 ℃ for 12 hours, grinding, sieving by using a 200-mesh sieve, collecting iron slag powder (the particle size is less than or equal to 0.075 mm), vacuumizing, sealing and storing for later use.
C: preparing an iron slag-doped wine-making sludge biochar material: weighing 1.0 g of iron slag powder (the particle size is less than or equal to 0.075 mm), putting the iron slag powder into a 250 mL beaker, adding 25 mL of water, and then performing ultrasonic treatment for 30min at 500W and 40KHz by using an ultrasonic cleaning instrument to fully release iron ions in the iron slag powder. And (3) after the ultrasonic treatment, weighing 2.0 g of brewing sludge powder (the particle size is less than or equal to 0.150 mm) and putting into a beaker, stirring for 30min by using a mechanical stirrer, and then putting into a forced air drying oven for drying at 80 ℃. Collecting the dried solid, grinding uniformly by using a mortar, putting the uniformly mixed powder into a corundum crucible, and calcining at high temperature in a tube furnace in an oxygen-deficient manner. The basic working parameters of the tube furnace are 800 ℃, the heat preservation time is 2h, and the heating rate is 5 ℃/min. And after the calcination is finished, cooling the sludge biochar to room temperature by using a tube furnace, taking out the sludge biochar, washing the sludge biochar to be neutral by using oxygen-free water, washing the sludge biochar for three times by using absolute ethyl alcohol, putting the sludge biochar into a vacuum drying oven at 50 ℃, drying the sludge biochar for 12 hours, collecting the dried iron slag doped with the brewing sludge biochar material, grinding the materials uniformly by using a mortar, and vacuumizing and sealing the materials for later use.
Example 5
A: pretreatment of waste iron slag: repeatedly washing the waste iron slag with tap water, separating by using a magnet to wash away silt in the waste iron slag, washing for three times by using pure water and absolute ethyl alcohol respectively after water is clear, putting into a vacuum drying machine at 50 ℃ for 12 hours, grinding, sieving by using a 200-mesh sieve, collecting iron slag powder (the particle size is less than or equal to 0.075 mm), vacuumizing, sealing and storing for later use.
B: preparing an iron slag material: weighing 1.0 g of iron slag powder (the particle size is less than or equal to 0.075 mm), putting the iron slag powder into a 250 mL beaker, adding 25 mL of water, and then performing ultrasonic treatment for 30min at 500W and 40KHz by using an ultrasonic cleaning instrument to fully release iron ions in the iron slag powder. And after the ultrasonic treatment is finished, the mixture is placed into a blast drying oven to be dried at the temperature of 80 ℃. Collecting the dried solid, grinding uniformly by a mortar, putting into a corundum crucible, and calcining at high temperature in a tube furnace under oxygen deficiency. The basic working parameters of the tube furnace are 800 ℃, the heat preservation time is 2h, and the heating rate is 5 ℃/min. And after the calcination is finished, cooling the product to room temperature in a tube furnace, taking out the product, washing the product to be neutral by using oxygen-free water, washing the product for three times by using absolute ethyl alcohol, putting the product into a vacuum drying oven at 50 ℃, drying the product for 12 hours, collecting the dried iron slag material, grinding the iron slag material uniformly by using a mortar, and vacuumizing and sealing the ground iron slag material for later use.
Example 6
A: pretreatment of brewing sludge: drying the dewatered brewing sludge at 108 ℃ for 72 h, crushing by a crusher, sieving by a 100-mesh sieve, and collecting sludge powder (the particle size is less than or equal to 0.150 mm) for later use.
B: preparing a brewing sludge biochar material: weighing 1.0 g of sludge powder (the particle size is less than or equal to 0.150 mm) and putting the sludge powder into a beaker, stirring the sludge powder for 30min by using a mechanical stirrer, and then putting the beaker into an air-blast drying oven to dry the sludge powder at the temperature of 80 ℃. Collecting the dried solid, grinding uniformly by a mortar, putting into a corundum crucible, and calcining at high temperature in a tube furnace under oxygen deficiency. The basic working parameters of the tube furnace are 800 ℃, the heat preservation time is 2h, and the heating rate is 5 ℃/min. And after the calcination is finished, cooling the sludge biochar to room temperature by using a tube furnace, taking out the sludge biochar, washing the sludge biochar to be neutral by using oxygen-free water, washing the sludge biochar for three times by using absolute ethyl alcohol, putting the sludge biochar into a vacuum drying oven at 50 ℃, drying the sludge biochar for 12 hours, collecting the dried wine brewing sludge biochar material, grinding the dried wine brewing sludge biochar material uniformly by using a mortar, and vacuumizing and sealing the dried wine brewing sludge biochar material for later use.
FIG. 1a is an SEM picture of a brewing sludge biochar material prepared according to embodiment 5 of the invention; FIG. 1b is an SEM image of an iron slag-doped wine sludge biochar material prepared according to example 1 of the invention; FIG. 1c is an X-ray crystal diffraction pattern of materials prepared according to examples 1-6 of the present invention. As can be seen from FIG. 1a, the surface texture of the synthesized brewery sludge biochar material is rough, and small clusters of non-uniform particles are formed. As can be seen from fig. 1b, a large number of sheet-like structures are present on the surface of the synthesized material. As shown in FIG. 1c, the synthetic ferrophosphorus phase (Fe) is mainly present on the surface of the material obtained in example 6 3 P, JCPDS: 19-0617), a ferrous phosphate phase (Fe) 3 (PO 4 ) 2 JCPDS: 39-0341) and a carbon phase (C, JCPDS: 26-1080). The surface of the material of example 5 had a magnetite phase (Fe) mainly present 3 O 4 JCPDS: 19-0629), a ferrous oxide phase (FeO, JCPDS: 06-0615) and a graphite phase (C, JCPDS: 26-1079). The surfaces of the materials of examples 3, 1 and 4 were mainly found to have a cobalt-iron phase (CoFe, JCPDS: 48-1816), a ferrous phosphate phase (Fe) 3 (PO 4 ) 2 JCPDS: 39-0341), ferrous sulfate phase (FeSO) 4 And JCPDS: 33-0682), a hardened ferrocarbon phase (c0.09fe1.91, JCPDS: 44-1292) and a graphitic phase (C, JCPDS: 26-1079). In addition, a new diffraction peak was detected on the surface of the material of example 3, corresponding to the ferrous oxide phase (FeO, JCPDS: 06-0615). The material surface of example 2 was detected mainly as a ferrous oxide phase (FeO, JCPDS: 06-0615), a magnetite phase (Fe) 3 O 4 JCPDS: 19-0629), a graphite phase (C, JCPDS: 26-1079) and a cobalt-iron phase (CoFe, JCPDS: 48-1816). These results show that: the biochar material prepared by doping the iron slag into the wine-making sludge can cause the generation of a cobalt-iron phase, a ferrous oxide phase and a hardened carbon-iron phase, and along with the increase of the quality of the iron slag doped in the preparation process, the ferrophosphorus phase and the cobalt-iron phase are gradually reduced, and the ferrous oxide phase and the magnetite phase are gradually increased. The introduction of the ferrous oxide and the magnetite phase into the wine sludge biochar material can not only improve the catalytic activity of the biochar as a persulfate catalyst, but also improve the ferromagnetism of the biochar, so that the biochar can be quickly separated and recovered by using an external magnet, and the popularization of the application of the biochar in wastewater treatment is facilitated.
Experimental example 1 Effect of different materials activating sodium sulfate to remove norfloxacin
Experimental materials: materials from examples 1, 5 and 6
The experimental method comprises the following steps: 50 mL of 10 mg/L norfloxacin solution was added to the brown glass bottle, and the pH was adjusted to 7.0. 5 mg of the material of example 1 was added to the solution, and after mixing for 30 minutes, 0.1 ml of 100 mmol/L sodium persulfate solution was added to initiate the degradation reaction. Sampling 0.5 mL at 1 min, 3 min, 5min, 7 min, 10 min, 15 min, 20min and 30min, adding into equal volume of anhydrous ethanol, and filtering with 0.22 μm PTFE filter head. And finally, detecting the norfloxacin content in the sample by using a high performance liquid chromatography analyzer.
The materials were changed to those of examples 5 and 6 in the same manner as described above to compare the effects. The results are shown in FIG. 2.
As shown in fig. 2, the material of example 1 had a weak adsorption effect on norfloxacin. After the sodium persulfate oxidizer is added, the removal rate of norfloxacin by activating sodium persulfate through the material of example 1 is 99.8% within 20min, and the removal effects of norfloxacin by activating sodium persulfate through the material of example 6 and the material of example 5 are respectively 30.9% and 48.3%. The result shows that the material activated sodium persulfate oxidation system in the embodiment 1 can efficiently restore norfloxacin pollution in a water body, and the waste iron slag doped modified brewing sludge is used for preparing the composite biochar material, so that the performance of the brewing sludge biochar and the performance of the waste iron slag activated sodium persulfate can be obviously improved, and the application values of the brewing sludge and the waste iron slag are improved.
Test example 2 iron slag to sludge mass ratio effect on removal of norfloxacin by activated sodium sulfate
Experimental materials: materials obtained in examples 1 to 4
The experimental method comprises the following steps: 50 mL of 10 mg/L norfloxacin solution was added to the brown glass bottle, and the pH was adjusted to 7.0. 5 mg of the material from example 2 were weighed into the solution, mixed for 30min and then 0.1 mL of 100 mmol/L sodium persulfate solution was added to start the degradation reaction. 0.5 mL of the sample was taken at 1 min, 3 min, 5min, 7 min, 10 min, 15 min, 20min and 30min, respectively, and added to an equal volume of absolute ethanol, followed by filtration through a 0.22. Mu. MPTE filter. And detecting the norfloxacin content in the sample by using a high performance liquid chromatography analyzer.
In the same manner as described above, the materials were changed to those of examples 3, 1 and 4, and the effect of the mass ratio of iron slag to sludge on activating the sodium persulfate system to degrade norfloxacin was compared. The results are shown in FIG. 3.
FIG. 3 is a comparison graph of the effect of removing norfloxacin by activating sodium persulfate through the iron slag-doped wine sludge biochar material prepared in examples 1-4 of the present invention. As shown in fig. 3: the removal rates of norfloxacin by adsorption in examples 1, 2, 3 and 4 were 19.8%,10.6%,14.2% and 18.9%, respectively. After the addition of sodium persulfate oxidizer, the removal rates of norfloxacin by the sodium persulfate systems activated in examples 1, 2, 3 and 4 were 99.8%, 93.8%, 98.7% and 86.8%, respectively, within 20 min. The result shows that the mass ratio of the iron slag to the sludge has influence on the effect of removing norfloxacin from an activated sodium persulfate system, the performance of activating sodium persulfate by the wine-making sludge biochar and the waste iron slag can be obviously improved by regulating the mass ratio of the iron slag to the sludge in the biochar preparation process, and the application value of the wine-making sludge and the waste iron slag is improved.
Experimental example 3 influence of norfloxacin concentrations with different concentrations on effect of removing norfloxacin by activating sodium persulfate through iron slag-doped brewing sludge biochar material
Experimental materials: example 1 iron slag-doped wine sludge biochar material
The experimental method comprises the following steps: a50 ml10 mg/L norfloxacin solution was added to the brown glass bottle to adjust the pH to 7.0. Then 5 mg of the material of example 1 was added and mixed for 30min, and then 0.1 ml of 100 mmol/L sodium persulfate solution was added to initiate the degradation reaction. Then 0.5 mL of the sample was taken at 1 min, 3 min, 5min, 7 min, 10 min, 15 min, 20min, 30min and other time points, added to an equal volume of anhydrous ethanol, and filtered through a 0.22 μm PTFE filter. And finally, detecting the norfloxacin content in the sample by using a high performance liquid chromatography analyzer. In the same manner, norfloxacin solution concentrations were exchanged for 5, 20, and 50 mg/L to compare the effect of norfloxacin solution concentrations on the material of example 1 to activate the sodium persulfate system for norfloxacin removal. The results are shown in FIG. 4.
FIG. 4 is a graph comparing the norfloxacin removal effect of different norfloxacin concentrations on activation of sodium persulfate by the iron slag-doped wine sludge biochar material prepared in example 1. As shown in FIG. 4, the removal rates of 5, 10, 20 and 50 mg/L norfloxacin by adsorption were 31.1%, 19.7%, 8.4% and 3.5% for the material of example 1, respectively. After the addition of the sodium persulfate oxidizer, the removal rates of 5, 10, 20 and 50 mg/L norfloxacin by the sodium persulfate system activated by the material of example 1 are 100%, 99.7%, 83.6% and 50.9% respectively within 20 min. The result shows that the sodium persulfate system activated by the material in the embodiment 1 still has a good removal effect on the high-concentration norfloxacin polluted water body, and is beneficial to practical application.
Experimental example 4 influence of reaction temperature on effect of iron slag doped brewing sludge biochar material activating sodium persulfate to remove norfloxacin
Experimental materials: example 1 iron slag-doped wine sludge biochar material
The experimental method comprises the following steps: separately, 100mL of 10 mg/L norfloxacin solution was added to the beaker, the pH was adjusted to 7.0, and the reaction temperature was controlled to 10 ℃ with a water bath. 5 mg of iron slag doped brewing sludge biochar (1) is added into the solution, and after the mixture is uniformly mixed for 30min, 0.1 mL of 100 mmol/L sodium persulfate solution is added to start degradation reaction. Sampling 0.5 mL at 1 min, 3 min, 5min, 7 min, 10 min, 15 min, 20min and 30min, adding into equal volume of anhydrous ethanol, and filtering with 0.22 μm PTFE filter head. And finally, detecting the norfloxacin content in the sample by using a high performance liquid chromatography analyzer. In the same manner, the reaction temperature was changed to 25 ℃ and 40 ℃ to compare the effect of the reaction temperature on the activation of sodium persulfate by the iron slag sludge biochar (1). The results are shown in FIG. 5.
FIG. 5 is a graph comparing the effect of reaction temperature on the removal of norfloxacin by activating sodium persulfate through the iron slag-doped wine making sludge biochar material prepared according to example 1. As shown in fig. 5, the removal rates of norfloxacin by adsorption at different temperatures of 10 ℃, 25 ℃ and 40 ℃ for the material of example 1 were 7.8%,19.7% and 27.2%, respectively. After the sodium persulfate oxidizer was added, the removal rates of norfloxacin from the material of example 1 were 81.1%,99.7% and 100% by activating sodium persulfate at different temperatures of 10 ℃, 25 ℃ and 40 ℃ within 20 min. The results show that the ambient water temperature affects the removal rate of norfloxacin by activating sodium persulfate through the material of example 1. Although the removal rate of norfloxacin is reduced at low temperature, 81.1 percent of norfloxacin can be removed, and the removal efficiency of norfloxacin is obviously improved at high temperature. Therefore, the norfloxacin pollution of water bodies at different temperatures can be repaired by activating sodium persulfate through the iron slag sludge biochar.
Experimental example 5 influence of pH on effect of iron slag doped brewing sludge biochar material on activation of sodium persulfate to remove norfloxacin
Experimental materials: example 1 iron slag-doped wine sludge biochar material
The experimental method comprises the following steps: a50 ml10 mg/L norfloxacin solution was added to the brown glass bottle to adjust the pH to 7.0. 5 mg of the material of example 1 was added to the solution, and after mixing for 30 minutes, 0.1 ml of 100 mmol/L sodium persulfate solution was added to initiate the degradation reaction. Sampling 0.5 mL at 1 min, 3 min, 5min, 7 min, 10 min, 15 min, 20min and 30min, adding into equal volume of anhydrous ethanol, and filtering with 0.22 μm PTFE filter head. And finally, detecting the norfloxacin content in the sample by using a high performance liquid chromatography analyzer. In the same manner, the solutions were adjusted to pH 4.0, 6.0, 7.0, 9.0 and 10.0, respectively, and the effect of the reaction pH on the removal of norfloxacin by the sodium persulfate system activated by the material of example 1 was compared. The results are shown in FIG. 6.
FIG. 6 is a graph comparing the effect of pH on the removal of norfloxacin by activating sodium persulfate through the iron slag-doped wine sludge biochar material prepared in example 1. As shown in fig. 6, the adsorption of norfloxacin by adsorption at pH 4.0, 6.0, 7.0, 9.0 and 10.0 was 23.4%,19.7%,18.8%, 13.7% and 11.8% for the material of example 1, respectively. After addition of sodium persulfate oxidizer, the removal of norfloxacin by the sodium persulfate system activated by the material of example 1 at pH 4.0, 6.0, 7.0, 9.0 and 10.0 was 100%,99.5%,99.2%,82.2% and 72.1% within 20min, respectively. The result shows that the material in example 1 has a good norfloxacin removing effect under acidic and weakly alkaline conditions, has a wide pH application range, and is beneficial to practical application.
Test example 6 reusability of iron slag doped brewing sludge biochar material for activating sodium persulfate to remove norfloxacin
Experimental materials: example 1 iron slag-doped wine sludge biochar material
The experimental method comprises the following steps: a50 ml10 mg/L norfloxacin solution was added to the brown glass bottle and the pH was adjusted to 7.0. 5 mg of the material of example 1 was added to the solution, and after mixing for 30 minutes, 0.1 ml of 100 mmol/L sodium persulfate solution was added to initiate the degradation reaction. Sampling 0.5 mL at 1 min, 3 min, 5min, 7 min, 10 min, 15 min, 20min and 30min, adding into equal volume of anhydrous ethanol, and filtering with 0.22 μm PTFE filter head. And finally, detecting the norfloxacin content in the sample by using a high performance liquid chromatography analyzer. After the reaction, the reacted material of example 1 was collected by a magnet, and the norfloxacin degradation experiment was repeated five times under the same reaction conditions. The results are shown in FIG. 7.
FIG. 7 is a comparison graph of reusability of iron slag doped wine sludge biochar material prepared according to example 1 of the present invention to activate sodium persulfate to remove norfloxacin. The results are shown in fig. 7, in which the removal rate of norfloxacin by adsorption of the material of example 1 was 19.7%,15.8%, 9.3%, 6.4% and 1.8% in five repeated experiments (first to fifth). After the sodium persulfate oxidizing agent is added, the norfloxacin removal rates of the material activated sodium persulfate system in the example 1 are respectively 99.7%, 99.4%, 98.5%, 96.2% and 89.9% within 20min, which shows that the material in the example 1 has good performance of repeatedly activating sodium persulfate, is easy to recycle for multiple times and reduces the use cost. The good reusability of the material is helpful for improving the application value of the material activation persulfate system in example 1 in norfloxacin pharmaceutical wastewater treatment.
Experimental example 7 influence of effect of iron slag doped with brewing sludge biochar material to activate sodium persulfate to remove norfloxacin in different water bodies
Experimental materials: the iron slag-doped wine sludge biochar material of example 1
The experimental method comprises the following steps: a norfloxacin solution (50 ml, 10 mg/L) prepared with ultrapure water was added to the brown glass bottle, and the pH was adjusted to 7.0. 5 mg of the material obtained in example 1 was added to the solution, and after mixing for 30 minutes, 0.1 ml of 100 mmol/L sodium persulfate solution was added to start the degradation reaction. Sampling 0.5 mL at 1 min, 3 min, 5min, 7 min, 10 min, 15 min, 20min and 30min, adding into equal volume of anhydrous ethanol, and filtering with 0.22 μm PTFE filter head. And finally, detecting the norfloxacin content in the sample by using a high performance liquid chromatography analyzer. In the same manner, tap water, yangtze river water and Wutai sluice water were used to prepare 50 mL of norfloxacin solution at 10 mg/L, and the effect of different water bodies on the removal of norfloxacin by the material activated sodium persulfate system of example 1 was compared. The results are shown in FIG. 8.
FIG. 8 is a comparison graph of the effects of the iron slag doped wine making sludge biochar material prepared according to the invention in activating sodium persulfate to remove norfloxacin in different water bodies. As shown in FIG. 8, the removal rates of norfloxacin by adsorption of the material of example 1 under different water conditions were 8.5% (tap water), 17% (Yangtze river water), 14.2% (Wutai sluice water) and 19.7% (ultrapure water), respectively. After the sodium persulfate oxidizer is added, the removal rates of norfloxacin by activating a sodium persulfate system by using the material of example 1 under different water body conditions are respectively 62.1 percent (tap water), 71.4 percent (Yangtze river water), 73.6 percent (Wutai sluice water) and 99.7 percent (ultrapure water) within 20 min. The result shows that the material activated sodium persulfate system in the embodiment 1 can be used for treating norfloxacin pharmaceutical wastewater in various water bodies, and has a good application value.
Although the present invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the present invention.
Claims (10)
1. The preparation method of the iron slag-doped wine-making sludge biochar material is characterized by comprising the following steps:
s1: pretreatment of brewing sludge: drying, crushing and screening the sludge generated by the brewery sewage treatment by a 100-mesh sieve after dehydration treatment, and collecting brewing sludge powder for later use;
s2: pretreatment of waste iron slag: washing the waste iron slag, drying in vacuum, grinding, sieving with a 200-mesh sieve, and collecting iron slag powder for later use;
s3: the iron slag doped wine-making sludge biochar material comprises the following steps: dissolving the obtained iron slag powder in water, performing ultrasonic treatment, adding brewing sludge powder, uniformly stirring, drying, grinding, calcining the obtained powder at high temperature under oxygen deficiency, cooling to room temperature, washing, and performing vacuum drying to obtain the iron slag-doped brewing sludge biochar material.
2. The preparation method of the iron slag-doped wine-making sludge biochar material according to claim 1, wherein the drying conditions in the step S1 are as follows: the temperature is 100-110 ℃, and the time is 72-74h.
3. The method for preparing the iron slag-doped wine sludge biochar material according to claim 1, wherein the grain size of the wine sludge powder in the step S1 is less than or equal to 0.150 mm.
4. The preparation method of the iron slag-doped wine-making sludge biochar material according to claim 1, wherein the washing mode in the step S2 is as follows: the method comprises the steps of washing the raw materials repeatedly with tap water, and washing the raw materials with pure water and absolute ethyl alcohol respectively for three times after washing water is clear.
5. The preparation method of the iron slag-doped wine-making sludge biochar material according to claim 1, wherein the vacuum drying conditions in the step S2 are as follows: the temperature is 50-60 ℃, and the time is 12-13h.
6. The preparation method of the iron slag-doped wine-making sludge biochar material according to claim 1, wherein the particle size of the iron slag powder in the step S2 is less than or equal to 0.075mm.
7. The preparation method of the iron slag-doped wine-brewing sludge biochar material according to claim 1, wherein the ultrasonic treatment conditions in the step S3 are as follows: the power is 500W, the frequency is 40KHz, and the time is 30 to 45min.
8. The method for preparing the iron slag-doped wine sludge biochar material according to claim 1, wherein the mass ratio of the iron slag powder to the wine sludge powder in step S3 is 0-5.
9. The preparation method of the iron slag-doped wine-making sludge biochar material according to claim 1, wherein the high-temperature anoxic calcination conditions in the step S3 are as follows: the temperature is 800 ℃, and the time is 2h; the vacuum drying conditions are as follows: the temperature is 50-55 ℃, and the time is 12-13h.
10. The application of the iron slag-doped wine brewing sludge biochar material in sewage treatment is characterized in that the iron slag-doped wine brewing sludge biochar material is prepared by the preparation method according to any one of claims 1-9, and the treatment process comprises the step of removing norfloxacin in wastewater through the synergistic effect of the iron slag-doped wine brewing sludge biochar material and sodium persulfate.
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