CN114604955B - Method for degrading levofloxacin by utilizing ultrasonic to cooperate with sludge carbon activation periodate - Google Patents
Method for degrading levofloxacin by utilizing ultrasonic to cooperate with sludge carbon activation periodate Download PDFInfo
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- CN114604955B CN114604955B CN202210082861.3A CN202210082861A CN114604955B CN 114604955 B CN114604955 B CN 114604955B CN 202210082861 A CN202210082861 A CN 202210082861A CN 114604955 B CN114604955 B CN 114604955B
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- levofloxacin
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- GSDSWSVVBLHKDQ-JTQLQIEISA-N Levofloxacin Chemical compound C([C@@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-JTQLQIEISA-N 0.000 title claims abstract description 73
- 229960003376 levofloxacin Drugs 0.000 title claims abstract description 73
- 239000010802 sludge Substances 0.000 title claims abstract description 37
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 title claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000000593 degrading effect Effects 0.000 title claims abstract description 9
- 230000004913 activation Effects 0.000 title abstract description 6
- 238000006731 degradation reaction Methods 0.000 claims abstract description 27
- 230000015556 catabolic process Effects 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000003415 peat Substances 0.000 claims abstract description 15
- 239000010865 sewage Substances 0.000 claims abstract description 11
- 230000002195 synergetic effect Effects 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 22
- 238000000197 pyrolysis Methods 0.000 claims description 8
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- URGYLQKORWLZAQ-UHFFFAOYSA-N azanium;periodate Chemical compound [NH4+].[O-]I(=O)(=O)=O URGYLQKORWLZAQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 239000012459 cleaning agent Substances 0.000 claims 1
- 238000004506 ultrasonic cleaning Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 229940088710 antibiotic agent Drugs 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 238000002306 biochemical method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 101710097943 Viral-enhancing factor Proteins 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229940124350 antibacterial drug Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009916 joint effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 periodate salts Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical class S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000003306 quinoline derived antiinfective agent Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
- Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention belongs to the technical field of environmental engineering, and discloses a method for degrading levofloxacin by ultrasonic synergistic sludge carbon activation periodate, which specifically comprises the following steps: adding peat and periodate into a reaction system containing levofloxacin, and carrying out catalytic degradation of the levofloxacin under ultrasonic conditions. The advanced oxidation method provided by the invention can realize rapid and efficient deep degradation of the levofloxacin, has low dosage of the sewage and the oxidant, effectively reduces the pollution of the levofloxacin to the environment, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of environmental engineering, and particularly relates to a method for degrading levofloxacin by utilizing ultrasonic to cooperate with activated periodate of sludge carbon.
Background
Since the discovery of antibiotics, they have been widely used by people for the treatment of bacterial diseases in humans and animals due to their remarkable efficacy. However, the presence of antibiotics in the environment can lead to bacterial resistance, and the selective pressure resulting from prolonged exposure to antibiotics has prompted a broad distribution of antibiotic resistance genes that are of increasing concern for adverse effects on human health and aquatic ecosystems. Levofloxacin is a third-generation fluoroquinolone antibiotic, has broad-spectrum antibacterial effect, and is an antibacterial drug commonly used in human medical and veterinary clinical application. Research shows that levofloxacin can not be completely absorbed in human and animal bodies, and the traditional biochemical method adopted by a sewage treatment plant has limited effect of removing antibiotics, so that part of medicines are discharged into the environment to cause pollution.
The levofloxacin is difficult to degrade under natural conditions, and the removal of the levofloxacin in the water body at present mainly comprises a physical chemical method, a chemical method and a biochemical method. Because levofloxacin has bacteriostasis and biotoxicity, the water treatment process by a physicochemical and biochemical method has poor removal effect. Therefore, the development of a novel and efficient levofloxacin removal technology has great practical significance.
In recent years, a novel advanced oxidation technology based on the fact that an oxidant is periodate is gradually attracting attention and research due to the characteristics of high efficiency, stability, simplicity and convenience in operation and the like. In this process, periodate (IO 4 - ) The strong oxidizing ability (reduction potential of +1.60V) is discovered by researchers and is applied to degrading organic pollutants in water.
Disclosure of Invention
In view of the above, the invention provides a method for degrading levofloxacin by utilizing ultrasonic to cooperate with activated periodate of sludge carbon, which can realize rapid and efficient degradation of levofloxacin in the environment.
The technical scheme of the invention is as follows:
a method for degrading levofloxacin by ultrasonic synergistic sludge carbon activation periodate specifically comprises the following steps: adding peat and periodate into a reaction system containing levofloxacin, and carrying out catalytic degradation of the levofloxacin under ultrasonic conditions.
Preferably, the periodate is one or more of sodium periodate, potassium periodate and ammonium periodate.
More preferably, the periodate is sodium periodate.
Preferably, the preparation method of the sewage peat comprises the following steps: obtaining surplus sludge from a living sewage treatment plant, removing impurities from the sludge, and drying the sludge; pyrolyzing the sludge in nitrogen atmosphere, grinding and sieving to obtain the sludge peat.
More preferably, the pyrolysis time is 2-3 h, the pyrolysis temperature is 500-700 ℃, and the heating rate during pyrolysis is 8-12 ℃/min.
Preferably, the grain diameter of the sludge carbon is 0.01-0.15 mm.
Preferably, in the reaction system, the molar ratio of the levofloxacin to the periodate is 1 (18-180).
Preferably, the sludge carbon dosage in the reaction system is 0.1-1.0 g/L.
Preferably, the pH of the reaction system is 3 to 9.
More preferably, the treatment mode during the catalytic degradation is stirring, and the stirring speed is 100-120 rpm.
Compared with the prior art, the invention has the beneficial effects that:
the invention is based on advanced oxidation of periodate, the ultrasonic activation and carbon activation effects can be better through the synergistic effect of ultrasonic waves and sludge carbon, the sludge carbon prepared by taking dehydrated sludge as a substrate is combined with ultrasonic waves, the synergistic effect of adsorption and advanced oxidative degradation is realized in a reaction system, the rapid and efficient deep degradation of levofloxacin is realized, for example, for 10mg/L of levofloxacin waste water, the degradation rate can reach 99% in a short time, the levofloxacin removal effect is obvious and stable, the application pH is wide, the sludge carbon consumption is low, and the application prospect is wide.
Drawings
For a brief and clear description of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described as follows:
FIG. 1 is a schematic structural view of a reaction apparatus used in an embodiment of the present invention;
FIG. 2 is a graph of the degradation rate of levofloxacin under the ultrasound-assisted activated periodate of peat in example 1;
FIG. 3 is a graph of the degradation rate of levofloxacin under ultrasound alone and sludge char alone activated periodate in comparative example 1;
FIG. 4 is a plot of the degradation rate of levofloxacin in comparative example 2 under ultrasound alone and peat alone.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples. The following examples are only illustrative of the present invention and should not be construed as limiting the scope of the invention.
It should be noted that all reagents or instruments in the following examples were purchased through normal channels without reference to manufacturers.
Example 1
1) Preparation of peat
Taking a plurality of sludge from a wastewater treatment plant of a Tangshan lake in Wuhan, and cleaning the obtained sludge with ultrapure water in an ultrasonic cleaner for 3 times, removing impurities, and drying in a blast drying oven at 105 ℃ to constant weight; transferring the dried sludge into a tube furnace filled with nitrogen (0.5L/min) for pyrolysis for 2h (600 ℃ C., heating rate of 10 ℃ C./min); grinding sludge carbon (SBC) prepared by pyrolysis through a screen, and storing in a sealing manner for standby. The present example selects a peat with a particle size of less than or equal to 0.15mm.
2) Selection of periodate salts
The periodate salt selected in this example was sodium periodate.
3) The specific degradation process is implemented according to the following steps
Adding peat and sodium periodate into waste water containing 10mg/L levofloxacin (preparing a standard solution of levofloxacin and simulating the waste water of levofloxacin), and starting an ultrasonic generator. Wherein: the power of the ultrasonic generator is 260W, the adding amount of sludge carbon is 0.5g/L, the mol ratio between levofloxacin and sodium periodate is 1:36, the total reaction volume is 100ml under the condition of natural pH, and the stirring treatment is carried out at 150rpm and normal temperature.
Taking a water sample every 10min for testing, and measuring the concentration of the levofloxacin in the system by using a high performance liquid chromatograph after the sample is pretreated, so as to calculate the degradation rate of the levofloxacin, wherein the result is shown in figure 2, and the degradation rate of the levofloxacin after 60min is 95%.
And (3) joint effect analysis:
the cofactor kinetics was calculated using the quasi-first order kinetic equation (eq.1) with the cofactor (SI) calculated as eq.2:
ln(C t /C 0 )＝-k obs t(Eq.1)；
SI＝k(SBC+US+PI)/(k(SBC+PI)+k(US+PI))(Eq.2)；
wherein k is a kinetic constant, k (SBC+US+PI) represents the kinetic constant of Ultrasonic (US) synergistic sewage peat (SBC) activated Periodate (PI), and k (SBC+PI) and k (US+PI) are the kinetic constants of independent activated persulfate; the synergistic factor SI <1 indicates that the synergistic processing efficiency is lower than the superposition of the two, si=1 indicates that the synergistic processing efficiency is equal to the superposition of the two, and SI >1 indicates that the synergistic efficiency of the two is higher than the superposition of the two, and the synergistic efficiency is high.
The current relevant reaction kinetics are well fitted by using a quasi-first-order kinetic equation (eq.1), the kinetic constants of each reaction in the examples can be calculated, and si=1.40 of example 1 is obtained from the calculation equation of eq.2 cofactor. The result shows that the ultrasonic synergistic sewage peat activated periodate system has excellent performance.
Example 2
Unlike example 1, the following is: in the reaction system, the adding amount of the sludge carbon is 1.0g/L.
After the sample is pretreated, the concentration of the levofloxacin in the system is measured by a high performance liquid chromatograph, so that the degradation rate of the levofloxacin is calculated, and the result shows that the degradation rate of the levofloxacin is 99% after 60 minutes.
Example 3
Unlike example 1, the following is: in the reaction system, the molar ratio of the levofloxacin to the potassium periodate is 1:18.
After the sample is pretreated, the concentration of the levofloxacin in the system is measured by a high performance liquid chromatograph, so that the degradation rate of the levofloxacin is calculated, and the result shows that the degradation rate of the levofloxacin is 87% after 60 minutes.
Example 4
Unlike example 1, the following is: in the reaction system, the molar ratio of the levofloxacin to the potassium periodate is 1:72.
After the sample is pretreated, the concentration of the levofloxacin in the system is measured by a high performance liquid chromatograph, so that the degradation rate of the levofloxacin is calculated, and the result shows that the degradation rate of the levofloxacin is 95% after 60 minutes.
Example 5
Unlike example 1, the amount of sludge charcoal added in the reaction system was 0.5g/L, and the molar ratio of levofloxacin to sodium periodate was 1:180.
After the sample is pretreated, the concentration of the levofloxacin in the system is measured by a high performance liquid chromatograph, so that the degradation rate of the levofloxacin is calculated, and the result shows that the degradation rate of the levofloxacin is 99%.
Comparative example 1
(1) In wastewater containing 10mg/L of levofloxacin (preparing a standard solution of levofloxacin and simulating the levofloxacin wastewater), no sewage sludge dust (SBC) is added, wherein: the power of the ultrasonic generator is 260W, the molar ratio of the levofloxacin to the sodium periodate is 1:36, the total volume is 100ml under the condition of natural pH, and the stirring treatment is carried out at 150rpm and normal temperature.
(2) 1.0g/L of calcined and ground sludge charcoal (SBC, same as in example 1) was added to 10mg/L of waste water containing levofloxacin (a standard solution of levofloxacin was prepared, which was simulated to the waste water of levofloxacin), ultrasonic waves were emitted without an additional ultrasonic generator, the molar ratio of levofloxacin to sodium periodate was 1:36 (the concentration of levofloxacin was written in the mating material, please note the check), the total volume was 100ml under the natural pH condition, and the mixture was stirred at 150rpm at room temperature.
Taking a water sample every 10min for testing, and measuring the concentration of the levofloxacin in the system by using a high performance liquid chromatograph after the sample is pretreated, so as to calculate the degradation rate of the levofloxacin, wherein the result shows that the degradation rate is 42% in (1) at 60min and 80% in (2) at 60 min.
Comparative example 2
(1) The method is characterized in that only an ultrasonic generator is additionally arranged in wastewater containing 10mg/L of levofloxacin (a standard levofloxacin solution is prepared and the levofloxacin wastewater is simulated) to emit ultrasonic waves, no sewage peat or sodium periodate is added, the total volume is 100ml under the condition of natural pH, and the stirring treatment is carried out at 150rpm and at normal temperature.
(2) In the wastewater containing 10mg/L of levofloxacin (preparing a standard solution of levofloxacin and simulating the levofloxacin wastewater), only the sewage is added (the specific method is the same as that of example 1), sodium periodate is not added, an ultrasonic generator is not added to emit ultrasonic waves, the total volume is 100ml under the condition of natural pH, and the stirring treatment is carried out at 150rpm and normal temperature.
Taking a water sample every 10min for testing, and measuring the concentration of the levofloxacin in the system by using a high performance liquid chromatograph after the sample is pretreated, so that the degradation rate of the levofloxacin is calculated, and the results show that the degradation rate is 9% in (1) at 60min and 31% in (2) at 60 min.
In addition, although the ultrasonic generator power used in examples and comparative examples was 260W, experiments demonstrated that: in the present invention, the ultrasonic power has no decisive influence on the degradation effect. In practical applications, the power of the ultrasonic generator can be selected by those skilled in the art according to specific requirements.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (2)
1. A method for degrading levofloxacin by utilizing ultrasonic synergistic sludge carbon activated periodate is characterized in that sewage peat and periodate are added into a reaction system containing the levofloxacin, and the catalytic degradation of the levofloxacin is carried out under the ultrasonic condition;
the preparation method of the sewage peat comprises the following steps: obtaining sludge from a sewage treatment plant, removing impurities from the sludge, and drying the sludge; pyrolyzing the sludge in nitrogen atmosphere, grinding and sieving to obtain sludge peat;
the pyrolysis time is 2-3 h, the pyrolysis temperature is 500-700 ℃, and the pyrolysis heating rate is 8-12 ℃/min;
the method for removing impurities from the sludge comprises the following steps: the sludge is cleaned by ultra-pure water in an ultrasonic cleaning agent;
the periodate is at least one of sodium periodate, potassium periodate and ammonium periodate;
the grain diameter of the sludge carbon is 0.01-0.15 mm;
in the reaction system, the molar ratio of the levofloxacin to the periodate is 1 (18-180), the sludge carbon dosage is 0.1-1.0 g/L, and the pH value of the reaction system is 3-9.
2. The method for degrading levofloxacin by utilizing ultrasonic and sludge carbon activated periodate according to claim 1, wherein the reaction system is an aqueous system containing levofloxacin.
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|---|---|---|---|---|
| CN110227416A (en) * | 2019-06-24 | 2019-09-13 | 武汉理工大学 | A kind of preparation and its application in fluoroquinolone antibiotics removal in water of iron zinc and phosphoric acid modification sludge organism charcoal |
| CN111018084A (en) * | 2019-12-23 | 2020-04-17 | 大连理工大学 | Biochar-goethite heterogeneous Fenton oxidation method applied to ofloxacin wastewater treatment |
| CN113559839A (en) * | 2021-08-06 | 2021-10-29 | 哈尔滨工业大学 | Preparation method of paper mill coagulated solid waste-based catalyst, product and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110227416A (en) * | 2019-06-24 | 2019-09-13 | 武汉理工大学 | A kind of preparation and its application in fluoroquinolone antibiotics removal in water of iron zinc and phosphoric acid modification sludge organism charcoal |
| CN111018084A (en) * | 2019-12-23 | 2020-04-17 | 大连理工大学 | Biochar-goethite heterogeneous Fenton oxidation method applied to ofloxacin wastewater treatment |
| CN113559839A (en) * | 2021-08-06 | 2021-10-29 | 哈尔滨工业大学 | Preparation method of paper mill coagulated solid waste-based catalyst, product and application thereof |
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| Title |
|---|
| 炭质材料在活化过硫酸盐高级氧化技术中的应用进展;肖鹏飞等;《化工进展》;20201231(第08期);第3293-3306页 * |
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