CN110066013A - The preparation method of magnetic Nano material rich in quinoid structure and its application in anaerobic sludge processing azo dye wastewater - Google Patents

The preparation method of magnetic Nano material rich in quinoid structure and its application in anaerobic sludge processing azo dye wastewater Download PDF

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Publication number
CN110066013A
CN110066013A CN201910365575.6A CN201910365575A CN110066013A CN 110066013 A CN110066013 A CN 110066013A CN 201910365575 A CN201910365575 A CN 201910365575A CN 110066013 A CN110066013 A CN 110066013A
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nano material
magnetic nano
lawsone
preparation
anaerobic sludge
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虞磊
宋宇航
华景秋
汪子阳
常钟月
韩雪
项良锐
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Nanjing Forestry University
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Nanjing Forestry University
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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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • 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
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry

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  • Life Sciences & Earth Sciences (AREA)
  • Microbiology (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The present invention provides a kind of magnetic Nano quinoid composite material, is lawsone, graphene oxide, Fe2+The magnetism that three-component compound system is constituted is rich in the nano material of quinoid structure.And it discloses preparation method and its anaerobic sludge is being promoted to degrade containing the application in azo dye wastewater.On the one hand material of the present invention is rich in quinoid functional group, the extracellular electron transport rate of anaerobe can be significantly increased；Another aspect material particle size is nanoscale, and dispersibility preferably, can come into full contact with microbial flora, improve mass-transfer efficiency in water；The biodegradable efficiency that azo dyes are effectively promoted in such composite material is thus added in waste water treatment system；Simultaneously, the quinoid nanocomposite of synthesis has magnetism, can be efficiently separated this composite material with sewage using externally-applied magnetic field, it can be achieved that the recycling of nano material and recycling, outflowing with water for material is avoided, the cost of such wastewater treatment is controlled.

Description

The preparation method of magnetic Nano material rich in quinoid structure and its in anaerobic sludge Handle the application in azo dye wastewater
Technical field
The present invention relates to a kind of preparation method of magnetic Nano material rich in quinoid structure and its in anaerobic sludge processing Application in azo dye wastewater, belongs to technical field of biological sewage treatment.
Background technique
The main source of China's dyeing waste water is dyeing waste-water (accounting for 80%), complicated component, coloration height, COD and BOD Numerous features such as height, difficult for biological degradation.Since azo dyes is the most commonly used a class of dyes of current dyeing, azo dyes Direct discharging of waste water can inhibit the photosynthesis of water plant into water body, the dissolved oxygen for consuming water body, seriously destroy ecosystem System and threat human health.Therefore, the pollution problem for effectively solving waste water from dyestuff shows particularly important.
Currently, azo dyes processing method mainly includes physical method, chemical method and bioanalysis three categories, though first two method Efficiently, convenient, but that there is processing costs is high, is also easy to produce the disadvantages of secondary pollution；Compared to processing methods such as physics, chemistry, Anaerobic Microbiological Treatment Technology has been widely applied to treatment of dyeing wastewater neck because having the advantages that operating cost is low, environmental-friendly In domain.However, decoloration rate of reduction is lowly still one of main problem existing for current biological method processing dyeing waste water.
A few thing has also been made in dye wastewater treatment field in China environmentalist: for example, Chinese Patent Application No. 201710598541.2, denomination of invention are as follows: a kind of preparation method of magnetic polymer dye sorbent, disclosure of the invention one kind The preparation method of magnetic polymer dye sorbent, the inventive method prepare magnetic material using improvement chemical coprecipitation, so It is copolymerized the magnetic material of preparation and functional monomer to obtain the magnetism of multi-layer cross-linked structure and a variety of adsorption groups afterwards Polymeric dye adsorbent.Since magnetic Nano material is because of its own distinctive bigger serface, active site abundant and high magnetic The advantages that property, can there is huge adsorption capacity to dyestuff, and under the action of external magnetic field, dyestuff and mother liquor may be implemented Quick separating.What the invention proposed is the physical removing method based on absorption method, though dyestuff is realized from water phase to solid phase Transfer, but be not implemented to dyestuff substantial degradation and conversion, inorganic agent higher cost, and the adsorbent waste formed is generally recognized It is set to danger wastes, thus further improves the processing cost of technique itself.
For cost problem existing for physisorphtion removal dyeing waste water, Chinese Patent Application No. 201810916226.4, denomination of invention are as follows: the anaerobic biodegradation method of azo dyes gold orange II and the processing method of waste water, Disclose a kind of processing method using anaerobe degradation azo dyes.The inventive method using methane as electron donor, Azo dyes carries out biodegrade to dyestuff as electron acceptor, using denitrification anaerobic methane oxidation archaeal (DAMO).The hair Bright patent solves economic problems and secondary pollution problems in terms of azo dye wastewater processing, but still has electricity The problems such as sub- delivery rate is low, and dye wastewater degradation rate is slow, and the wastewater degradation period is long is not efficiently solved.
It is retrieved, wears (201610727187.4) for army building etc. and disclose a kind of " utilization iron carbon Fenton pretreatment-UBF-A/O Handle the system and method for waste water from dyestuff ", this method has mainly combined the joint work such as materializing strategy system, biological treatment system Skill handles waste water from dyestuff, and the process is by destroying larger molecular organics structure, reducing waste water to the poison of biochemical sludge Property, improve waste water biodegradability, to improve the treatment effeciency of dyeing waste water；But it needs to add in the disclosure invention big Amount chemical reagent easily causes the process of secondary pollution and technique lengthy and tedious, and management is inconvenient, it is more difficult to realize it in actual dying Extensive use in processing.
It is cumbersome and add for physical absorption higher cost, Biochemical method low efficiency, materialization and bioanalysis process integration Environmental risk problem existing for chemical reagent, this patent use quinonoid compound (Lawsone) and GO, Fe2+Deng synthesis nanometer Material, with bioanalysis associated with processing mode solve the existing above problem during treatment of dyeing wastewater.The magnetic Nano Material is added in the technical process of Biochemical method waste water from dyestuff, can not only accelerate the biography of electronics in biodegradation process It passs, improves the rate of biodegradable waste water from dyestuff, efficiently solve the problems, such as that the wastewater degradation period long；It can also be by outer Add magnetic field to realize effective recycling to magnetic Nano material, so as to avoid quinonoid compound outflows with water and the secondary dirt of bring Dye problem.
Summary of the invention
The object of the present invention is to provide a kind of magnetic Nano materials, can improve anaerobic sludge degrading azoic dye waste water Effect.
The technical solution of the present invention is as follows: a kind of magnetic Nano material, it is characterised in that: be lawsone (Lawsone), oxygen Graphite alkene (GO), Fe2+Three-component compound system.
The invention also discloses the preparation methods of above-mentioned magnetic Nano material, it is characterised in that the following steps are included:
1) a certain amount of Lawsone is weighed, is added in GO solution, stirs evenly；
2) mixed solution of step 1) is placed in autoclave, is heated at high temperature, be prepared into Lawsone@rGO coupling material Material；
3) freeze-drying obtains powdered coupling material；
4) Hybrid Heating in iron salt solutions is added in the powdered coupling material in step 3), after heating, in the temperature Under continue be added dropwise ammonium hydroxide reacted；
5) material obtained in step 4) is separated with magnet with liquid after completion of the reaction, dries, obtains after cleaning material Magnetic Nano material.
Preferably, GO solution concentration is 2g/L in step 1), and the mass ratio of Lawsone:GO is 0.2:1~5:1, stirring temperature Degree is room temperature, and the time of stirring is 6h.
Preferably, it is 180 DEG C, heating time 12h that step 2), which is specially heating temperature, reaction pressure 1.0~ 1.1Mpa。
Preferably, in step 3) first use deionized water cleaning step 2) coupling material Lawsone remained on surface, then into Row freeze-drying, the condition of freeze-drying is -50 DEG C, vacuum degree 100pa or less.
Preferably, Fe in step 4)2+Concentration is 20~25g/L, and heating temperature is 90 DEG C, reaction time 30min, is added dropwise The concentration and volume of ammonium hydroxide are 25%, 10ml respectively.
The invention also discloses application of the above-mentioned magnetic Nano material in anaerobic sludge processing azo dye wastewater.
Using the step of include:
A, a period of time in the medium by anaerobic sludge inoculation, is cultivated in constant temperature oscillator；
B, M9 culture medium is configured, M9 culture medium, azo dye wastewater and magnetic Nano material is dosed in a reservoir, blasts H2、N2Or CO2/H2Mixed gas forms anaerobic system；
C, it will be reacted in the container in cultured anaerobic sludge addition step B.
Preferably, culture medium is RF basal medium in step A, and ingredient is 1.112g/L K2HPO4、2.088g/L KH2PO4、0.94g/L C6H12O6、5.0g/L NaHCO3、0.28g/L NH4Cl、0.1g/L MgSO4·7H2O, 0.1g/L ferment Female cream and microelement；The formula of microelement is 0.3g/L H3BO3、0.2g/L CoCl2·6H2O、0.1g/L ZnSO4· 7H2O、0.03g/L MnCl2·4H2O、0.03g/L Na2MoCl2·6H2O、0.02g/L NiCl2·6H2O、0.01 g/L CuCl2·2H2O；The revolving speed of constant temperature oscillator is 160~170rpm, temperature is 35 DEG C, incubation time is 14 hours.
The ingredient of M9 culture medium is 15.1369g/L Na in step B2HPO4·12H2O、3g/L KH2PO4、1g/L NH4Cl、50g/L NaCl、6g/L C6H12O6、0.246g/L MgSO4·7H2The microelement of O and 2.5%.
Beneficial effects of the present invention are as follows:
1, magnetic Nano material preparation method prepared by the present invention is simple, low in cost, related experimental test procedures, Laboratory apparatus is relatively conventional.
2, magnetic Nano material prepared by the present invention is added in the system of biodegradable waste water from dyestuff, can significantly be mentioned The electron transport rate of high microorganism improves the efficiency of biodegradable azo dyes, considerably reduces the degradation of waste water from dyestuff Period, moreover it is possible to be effectively prevented from Lawsone and outflow with water and bring secondary pollution.
3, Lawsone can be well fixed on redox graphene (rGO) by magnetism Lawsone@rGO, not only It can be avoided quinonoid compound and outflow with water caused secondary pollution, and can be realized by externally-applied magnetic field to magnetic Nano material The recycling of material.
Detailed description of the invention
The electron paramagnetic resonance figure (EPR) of Fig. 1 magnetism Lawsone@rGO-1.
The electron paramagnetic resonance figure (EPR) of Fig. 2 magnetism Lawsone@rGO-5.
The electron paramagnetic resonance figure (EPR) of Fig. 3 magnetism Lawsone@rGO-3.
Fig. 4 dyestuff degradation figure.
Specific embodiment
For a better understanding of the present invention, below with specific example come the technical solution that the present invention will be described in detail, but this Invention is not limited thereto.
Lawsone@rGO-1 prepared by the success of embodiment 1, the specific steps are as follows:
The graphene oxide of sheet is shredded, is put into volumetric flask and adds water ultrasonic dissolution, obtain the graphene oxide of 2g/L Solution measures the graphene oxide solution of 60ml in beaker respectively, according to the mass ratio of Lawsone:GO --- and 0.2:1 claims 0.024g Lawsone is taken, is added in the beaker for filling graphene oxide solution, after 6h is stirred at room temperature, mixed liquor is transferred to In autoclave, reaction pressure control is spent after heating reaction in 1.0~1.1Mpa, the heating reaction 12h at 180 DEG C Ionized water cleans the Lawsone@rGO-0.2 material being prepared into, and is freeze-dried resulting nano material to obtain powder after cleaning The coupled nanosecond material of shape, freeze-drying condition are -50 DEG C, vacuum degree 100pa or less.
Attached drawing 1 is the EPR of Lawsone@rGO-1.We are available from figure, and magnetic Nano material has at 3481G Apparent transition peak, illustrate the experimental procedure successfully by quinoid material (Lawsone) and redox graphene (rGO) it is synthesized together.
Lawsone@rGO-3 prepared by the success of embodiment 2, the specific steps are as follows:
The graphene oxide of sheet is shredded, is put into volumetric flask and adds water ultrasonic dissolution, obtain the graphene oxide of 2g/L Solution measures the graphene oxide solution of 60ml in beaker respectively, according to the mass ratio of Lawsone:GO --- and 3:1 is weighed 0.36 g Lawsone, is added in the beaker for filling graphene oxide solution, after 6h is stirred at room temperature, mixed liquor is shifted supreme Press in reaction kettle, reaction pressure control is in 1.0~1.1Mpa, the heating reaction 12h at 180 DEG C, spent after heating reaction from Sub- water cleans the Lawsone@rGO-5 material being prepared into, and by resulting nano material is freeze-dried to obtain after cleaning powdered Coupled nanosecond material, freeze-drying condition are -50 DEG C, vacuum degree 100pa or less.
Attached drawing 2 is the EPR of Lawsone@rGO-3.We are available from figure, and the magnetic Nano material is at 3481G There is apparent transition peak, illustrates that quinoid material (Lawsone) is successfully fixed on oxygen reduction fossil by the experimental procedure On black alkene (rGO).
Lawsone@rGO-5 prepared by the success of embodiment 3, the specific steps are as follows:
The graphene oxide of strip is shredded, is put into volumetric flask and adds water ultrasonic dissolution, obtain the graphene oxide of 2g/L Solution measures the graphene oxide solution of 60ml in beaker respectively, according to the mass ratio of Lawsone:GO --- and 5:1 is weighed 0.6g Lawsone, is added in the beaker for filling graphene oxide solution, and after 6h is stirred at room temperature, mixed liquor is transferred to high pressure In reaction kettle, reaction pressure control is using deionization after heating reaction in 1.0~1.1Mpa, the heating reaction 12h at 180 DEG C Water cleans the Lawsone@rGO-3 material being prepared into, and is freeze-dried resulting nano material after cleaning to obtain powdered coupling Nano material is closed, freeze-drying condition is -50 DEG C, vacuum degree 100pa or less.
Attached drawing 3 is the EPR of Lawsone@rGO-5.We are available from figure, and the magnetic Nano material is at 3481G There is apparent transition peak, illustrates that the experimental procedure successfully synthesizes Lawsone rGO-5 nano material.
4 magnetic Nano material Lawsone@rGO-1 of embodiment promotes biodegradable waste water from dyestuff, the specific steps are as follows:
First anaerobic sludge is connected in RF basal medium, anaerobic sludge is derived from municipal sewage plant, 35 DEG C, After cultivating 14h under 160rpm, 10min is centrifuged at 8000g with centrifuge and separates bacterium and culture solution, then anaerobic sludge is used Syringe is added in the closed serum bottle for filling 0.2mmol/L methyl orange solution and M9 culture medium, in order to play the role of control, Be respectively set anaerobic sludge+methyl orange, anaerobic sludge+GO+ methyl orange, anaerobic sludge+Lawsone+ methyl orange, anaerobic sludge+ This four groups of serum bottles are placed on the constant temperature oscillator of 35 DEG C, 160rpm by four groups of experiments such as magnetic Lawsone@rGO-1+ methyl orange Middle reaction, and the concentration of methyl orange in serum bottle is measured in certain period of time ultraviolet-uisible spectrophotometer at 464nm.
Attached drawing 4 is the dyestuff degradation figure of four groups of experiments.It can be seen from the figure that individually adding quinoid material (Lawsone) Experimental group, degradation rate be it is most fast, degradation efficiency is also highest；Add magnetism Lawsone@rGO-1 nano material Experimental group, degradation rate do not add the fast of the experimental group of Lawsone individually, but last degradation efficiency and addition The experimental group of Lawsone is essentially identical；And the experimental group of GO is individually added, since GO has very big absorption to methyl orange dye Amount, cause reaction early period dye strength variation it is bigger, but GO can not accelerate bioanalysis degradation of dye waste water Rate can not improve bioanalysis to the degradation efficiency of waste water.It can be seen that the magnetic Lawsone@in the application patent RGO-1 nano material is the extracellular electron transmission that can promote bioanalysis degradation of dye waste water, improves bioanalysis to waste water from dyestuff Degradation efficiency.
It summarizes:
By analyzing above, the present invention is successfully prepared magnetic Lawsone@rGO-X nano material, and the present invention discloses Magnetic Nano material can accelerate the electron transport rate during Biochemical method waste water from dyestuff, promote microorganism to dyestuff Lawsone is fixed on GO by the degradation efficiency of waste water, the magnetic Nano material, quinonoid compound can not only be avoided with water flow Secondary pollution caused by losing, improves bioanalysis to the degradation efficiency of waste water from dyestuff, but also can realize by externally-applied magnetic field Recycling to magnetic Nano material.

Claims (9)

1. a kind of magnetic Nano material, it is characterised in that: be Lawsone, GO, Fe2+Ternary system.
2. a kind of preparation method of magnetic Nano material, it is characterised in that the following steps are included:
1) a certain amount of Lawsone is weighed, is added in GO solution, stirs evenly；
2) mixed solution of step 1) is placed in autoclave, is heated at high temperature, is prepared into Lawsone@rGO coupling material；
3) freeze-drying obtains powdered coupling material；
4) Hybrid Heating in iron salt solutions is added in powdered coupling material in step 3), after heating, at such a temperature after The continuous ammonium hydroxide that is added dropwise is reacted；
5) material obtained in step 4) is separated with magnet with liquid after completion of the reaction, is dried after cleaning material, obtains magnetism Nano material.
3. the preparation method of magnetic Nano material according to claim 2, it is characterised in that: GO solution concentration in step 1) Mass ratio for 1~4g/L, Lawsone:GO is 0.2:1~5:1, and whipping temp is room temperature, and the time of stirring is 6~8h.
4. the preparation method of magnetic Nano material according to claim 2, it is characterised in that: step 2) is specially to heat temperature Degree is 180 DEG C, heating time 12h, and reaction pressure is 1.0~1.1Mpa.
5. the preparation method of magnetic Nano material according to claim 2, it is characterised in that: first use deionization in step 3) Cleaning step 2) coupling material Lawsone remained on surface after, then be freeze-dried, the condition of freeze-drying is -50 DEG C, vacuum Spend 100pa or less.
6. the preparation method of magnetic Nano material according to claim 2, it is characterised in that: Fe in step 4)2+Concentration is 20~25g/L is heated to 90 DEG C, reaction time 30min, and the concentration and volume that ammonium hydroxide is added dropwise are respectively 25%, 10ml.
7. magnetic Nano material made from the preparation method of magnetic Nano material described in any one of claim 3-6 is promoting Application in anaerobic sludge degrading azoic dye waste water.
8. application according to claim 7, step include:
A, a period of time in the medium by anaerobic sludge inoculation, is cultivated in constant temperature oscillator；
B, M9 culture medium is configured, M9 culture medium, azo dye wastewater and magnetic Nano material are dosed in closed container, blasts H2、 N2Or CO2/H2Mixed gas forms anaerobic system；
C, it will be reacted in the container in cultured anaerobic sludge addition step B.
9. application according to claim 8, it is characterised in that: culture medium is RF basal medium in step A, and ingredient is 1.112g/L K2HPO4、2.088g/L KH2PO4、0.94g/L C6H12O6、5.0g/L NaHCO3、0.28g/L NH4Cl、 0.1g/L MgSO4·7H2O, 0.1g/L yeast extract and microelement；The formula of microelement is 0.3g/L H3BO3、0.2g/L CoCl2·6H2O、0.1g/L ZnSO4·7H2O、0.03g/L MnCl2·4H2O、0.03g/L Na2MoCl2·6H2O、0.02g/ L NiCl2·6H2O、0.01g/L CuCl2·2H2O；The revolving speed of constant temperature oscillator is 160~170rpm, temperature is 35 DEG C, training Supporting the time is 14 hours.
CN201910365575.6A 2019-05-01 2019-05-01 The preparation method of magnetic Nano material rich in quinoid structure and its application in anaerobic sludge processing azo dye wastewater Pending CN110066013A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112591741A (en) * 2020-11-17 2021-04-02 同济大学 Preparation method and application of carbon-based composite material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103752281A (en) * 2014-01-21 2014-04-30 南京林业大学 Magnetic humic acid nano material as well as preparation method and application of magnetic humic acid nano material
CN103801395A (en) * 2014-02-26 2014-05-21 大连理工大学 Graphene material modified by water-soluble anthraquinone compound and preparation method of graphene material
US20170152141A1 (en) * 2015-11-27 2017-06-01 Institute Of Process Engineering Chinese Academy Of Sciences Method for preparing heterogeneous metal-free fenton catalyst and application
CN106830311A (en) * 2017-03-01 2017-06-13 大连理工大学 A kind of graphene oxide and naphtoquinone compounds are modified the preparation method of hydroxyl macrocellular foam carrier altogether

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103752281A (en) * 2014-01-21 2014-04-30 南京林业大学 Magnetic humic acid nano material as well as preparation method and application of magnetic humic acid nano material
CN103801395A (en) * 2014-02-26 2014-05-21 大连理工大学 Graphene material modified by water-soluble anthraquinone compound and preparation method of graphene material
US20170152141A1 (en) * 2015-11-27 2017-06-01 Institute Of Process Engineering Chinese Academy Of Sciences Method for preparing heterogeneous metal-free fenton catalyst and application
CN106830311A (en) * 2017-03-01 2017-06-13 大连理工大学 A kind of graphene oxide and naphtoquinone compounds are modified the preparation method of hydroxyl macrocellular foam carrier altogether

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
RUIYING SHI等: "Redox-Active Organic Sodium Anthraquinone-2-Sulfonate(AQS) Anchored on Reduced Graphene Oxide for High-Performance Supercapacitors", 《ADVANCED ENERGY MATERIALS》 *
张海坤: "新型醌介体改性材料的制备及其强化含氮芳香化合物和Cr（Ⅵ）生物还原研究", 《中国博士学位论文全文数据库-工程科技I辑》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112591741A (en) * 2020-11-17 2021-04-02 同济大学 Preparation method and application of carbon-based composite material

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Application publication date: 20190730