CN111533313A - Method for treating antibiotic wastewater by using iron-cobalt layered double metal hydroxide material with ZIF-67 as template - Google Patents
Method for treating antibiotic wastewater by using iron-cobalt layered double metal hydroxide material with ZIF-67 as template Download PDFInfo
- Publication number
- CN111533313A CN111533313A CN202010399133.6A CN202010399133A CN111533313A CN 111533313 A CN111533313 A CN 111533313A CN 202010399133 A CN202010399133 A CN 202010399133A CN 111533313 A CN111533313 A CN 111533313A
- Authority
- CN
- China
- Prior art keywords
- zif
- iron
- template
- layered double
- hydroxide material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 105
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000002351 wastewater Substances 0.000 title claims abstract description 71
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 58
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 50
- 150000004692 metal hydroxides Chemical class 0.000 title abstract description 48
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 49
- 238000001179 sorption measurement Methods 0.000 claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- -1 iron ions Chemical class 0.000 claims abstract description 17
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 10
- 230000003534 oscillatory effect Effects 0.000 claims abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 3
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical group [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims description 35
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 15
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229940088710 antibiotic agent Drugs 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical group [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000003864 humus Substances 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 10
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 description 27
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 24
- 230000000694 effects Effects 0.000 description 20
- 239000004098 Tetracycline Substances 0.000 description 15
- 229960002180 tetracycline Drugs 0.000 description 15
- 229930101283 tetracycline Natural products 0.000 description 15
- 235000019364 tetracycline Nutrition 0.000 description 15
- 150000003522 tetracyclines Chemical class 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000593 degrading effect Effects 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910017061 Fe Co Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for treating antibiotic wastewater by using an iron-cobalt layered double metal hydroxide material taking ZIF-67 as a template, which comprises the following steps: firstly, carrying out oscillatory adsorption on an iron-cobalt layered double-metal hydroxide material taking ZIF-67 as a template and antibiotic wastewater in a dark place, adding PMS to carry out advanced oxidation reaction after the adsorption is saturated, thereby achieving the purpose of treating the antibiotic wastewater; the iron-cobalt layered double metal hydroxide material with the ZIF-67 as the template comprises iron ions and ZIF-67(Co), and the ZIF-67(Co) template is etched by the iron ions. The method for treating the antibiotic wastewater by using the iron-cobalt layered double-metal hydroxide material with the ZIF-67 as the template has the advantages of simple steps, convenience in operation, low equipment requirement, high degradation efficiency, short time consumption, reusability of the material and no secondary pollution. Therefore, the method is an antibiotic treatment method which is comprehensive and efficient, clean, cyclic and low in consumption, and has a good commercial application prospect.
Description
Technical Field
The invention belongs to the field of antibiotic wastewater treatment, relates to a method for treating antibiotic wastewater, and particularly relates to a method for treating antibiotic wastewater by using an iron-cobalt layered double metal hydroxide material with ZIF-67 as a template.
Background
Antibiotics enter human production and life due to the effective bacteriostasis and sterilization effects, and are widely applied to the fields of medicine, animal husbandry and the like. However, antibiotics exist in water environment as a pollutant which is difficult to degrade, have great harm to human health, and seriously pollute the environment. Therefore, the exploration of a method for effectively treating antibiotic wastewater is a worldwide problem which needs to be solved urgently in water pollution treatment, and is also a current research hotspot. The traditional process for treating antibiotic wastewater usually has the defects of long time consumption, easy generation of secondary pollution, high cost, high difficulty in treating low-concentration wastewater and the like, and the advanced oxidative degradation process has the advantages of simple operation, high degradation efficiency, no secondary pollution and great potential in degrading pollutants, thereby being widely concerned.
Layered Double Hydroxides (LDHs) are compounds assembled from host platelets and guest anions, and non-covalent interactions exist between the two. LDHs are receiving wide attention because of their excellent stability and catalytic performance. However, the traditional synthesis method of LDHs has the defects of strict operation conditions, high energy consumption and the like, so that the LDHs is difficult to produce at low cost and on a large scale. Zeolite imidazolate framework material (ZIF-67) with transition metal cobalt as a node is a porous crystal material formed by crosslinking organic imidazolate on cobalt, and has attracted extensive attention due to mild operation conditions, simple and convenient synthesis, structural diversity and controllability, but ZIF-67 still has the problems of poor catalytic performance, easy loss of toxic cobalt and the like. Therefore, the preparation method of the LDHs material, which combines the excellent catalytic performance of the LDHs with the advantage of simple and convenient synthesis of the ZIF-67, has the advantages of good advanced oxidation performance, mild synthesis conditions, simple and convenient operation and few raw material types, and has very important significance for expanding the application of the LDHs material in sewage treatment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for treating antibiotic wastewater by using an iron-cobalt layered double-metal hydroxide material taking ZIF-67 as a template, which is comprehensive, efficient, clean, cyclic and low in consumption.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for treating antibiotic wastewater by using an iron-cobalt layered double hydroxide material with ZIF-67 as a template is characterized by comprising the following steps: firstly, carrying out oscillatory adsorption on an iron-cobalt layered double-metal hydroxide material taking ZIF-67 as a template and antibiotic wastewater in a dark place, adding PMS to carry out advanced oxidation reaction after the adsorption is saturated, thereby achieving the purpose of treating the antibiotic wastewater; the iron-cobalt layered double-metal hydroxide material with the ZIF-67 as the template comprises iron ions and ZIF-67(Co), and the ZIF-67(Co) template is etched by the iron ions.
In a further improvement of the above method, the method for preparing the iron-cobalt layered double metal hydroxide material using ZIF-67 as a template comprises the following steps:
s1, mixing dimethyl imidazole, cobalt nitrate hexahydrate and organic solvent, and stirring to obtain ZIF-67(Co)
S2, mixing the ZIF-67(Co) obtained in the step S1 with an ethanol solution containing ferric nitrate nonahydrate, and stirring to obtain the iron-cobalt layered double hydroxide material taking the ZIF-67 as a template.
In a further improvement of the above process, the molar ratio of dimethylimidazole to cobalt nitrate hexahydrate is 1: 4; the molar ratio of the dimethyl imidazole to the cobalt nitrate hexahydrate to the organic solvent is 1: 4: 786.
in a further improvement of the above process, the organic solvent is methanol.
In a further improvement of the above process, the molar ratio of ZIF-67(Co) to ferric nitrate nonahydrate is 3.57: 0.5 to 2; the molar ratio of ZIF-67(Co), ferric nitrate nonahydrate and ethanol is 3.57: 0.5-2: 1090.
in the above method, further improvement, in step S1, the rotation speed of the stirring is 300r/min to 400 r/min; the stirring time is 24 hours; in step S2, the stirring speed is 200 r/min-300 r/min; the stirring time is 1 h.
In a further improvement of the above method, the steps S1 and S2 are followed by the steps of: centrifuging, washing and drying a reaction product obtained after stirring; the rotating speed of the centrifugation is 3000 r/min-5000 r/min; methanol and ethanol are adopted for washing; the washing times are 3-5 times, and the drying is carried out under the vacuum condition; the drying temperature is 60 ℃; the drying time was 12 h.
In the method, the mass-to-volume ratio of the iron-cobalt layered double metal hydroxide material taking ZIF-67 as the template to the antibiotic wastewater is 0.2 g: 1L of the compound.
In the method, the antibiotic in the antibiotic wastewater is tetracycline hydrochloride; the concentration of the antibiotics in the antibiotic wastewater is 5 mg/L-100 mg/L; the pH value of the antibiotic wastewater is 3-11; the inorganic interference added into the antibiotic wastewater is sulfate ions and chloride ions; organic interference added into the antibiotic wastewater is humus; the concentration of inorganic interference in the antibiotic wastewater is 5 mmol/L-15 mmol/L; the concentration of organic interference in the antibiotic wastewater is 3 mg/L-9 mg/L.
In the method, the rotation speed of the oscillating adsorption in the dark is 200 r/min; the time of oscillating adsorption in the dark is 1 h.
In the method, the method is further improved, and after the oscillating adsorption in the dark is completed, the method further comprises the following steps: adding a certain amount of PMS and oscillating for advanced oxidation reaction; the mass volume ratio of the PMS to the antibiotic wastewater is 0.25 g: 1L; the oscillation speed of the advanced oxidation reaction is 200 r/min; the advanced oxidation reaction time is 0.5 h.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a method for treating antibiotic wastewater by using an iron-cobalt layered double-metal hydroxide material taking ZIF-67 as a template, which comprises the steps of mixing the iron-cobalt layered double-metal hydroxide material taking ZIF-67 as the template with the antibiotic wastewater in a dark place, oscillating and adsorbing the mixture, and deducting the influence of material adsorption; on the basis, a proper amount of PMS is added into the suspension with balanced adsorption, and then advanced oxidation reaction is carried out, so that the aim of efficiently degrading antibiotics is fulfilled. The method has the advantages of simple steps, convenience in operation, low equipment requirement, high degradation efficiency, short time consumption, recyclable materials and no secondary pollution. Therefore, the method is an antibiotic treatment method which is comprehensive and efficient, clean, cyclic and low in consumption, and has a good commercial application prospect.
(2) The iron-cobalt layered double metal hydroxide material adopting the ZIF-67 as the template comprises iron ions and ZIF-67(Co), wherein the iron ions etch the ZIF-67 (Co). In the invention, the iron-cobalt layered double metal hydroxide material which is synthesized by in-situ etching the ZIF-67(Co) material by using iron ions and takes the ZIF-67 as a template inherits the high pore diameter of the ZIF-67(Co) material so that the composite material is more fully in chemical contact with the Peroxymonosulfate (PMS). Because the electronegativity of Co in the ZIF-67(Co) is higher than that of Fe existing in the iron-cobalt layered double metal hydroxide material taking the ZIF-67 as a template, electron cloud can be instantly moved from Fe to Co, therefore, electron-rich Co sites can better activate PMS, and the introduction of iron ions with stronger catalytic performance can further enhance PMS activation, thereby improving the advanced oxidation performance of the ZIF-67(Co) material. Compared with the prior art, the iron-cobalt layered double-metal hydroxide material taking the ZIF-67 as the template has the advantages of larger aperture, good dispersibility, good stability, good advanced oxidation performance and the like, can realize the efficient degradation of antibiotics through a PMS advanced oxidation system, and has better application prospect.
(3) In the preparation method of the iron-cobalt layered double-metal hydroxide material with the ZIF-67 as the template, the molar ratio of the ZIF-67 to the ferric nitrate nonahydrate is optimized, and the addition molar ratio of the ZIF-67 to the ferric nitrate nonahydrate is optimized to be 3.57: 0.5-2, so that the prepared iron-cobalt layered double-metal hydroxide material taking the ZIF-67 as the template contains proper introduced amount of iron ions, and the ZIF-67(Co) material has stronger catalytic performance for activating PMS, namely the iron-cobalt layered double-metal hydroxide material taking the ZIF-67 as the template and having better advanced oxidation effect for activating PMS is obtained. In particular, the molar ratio of the ZIF-67 to the iron nitrate nonahydrate added is 3.57: 1.5, the catalyst has the best effect of activating PMS advanced oxidation. Therefore, the invention optimizes the molar ratio of the ZIF-67 to the ferric nitrate nonahydrate to obtain more appropriate iron ion introduction amount, and has important significance for improving the advanced oxidation performance of the iron-cobalt layered double hydroxide material taking the ZIF-67 as the template.
(4) In the invention, the iron-cobalt layered double-metal hydroxide material with good advanced oxidation performance and high stability and taking ZIF-67 as a template is synthesized for the first time. The synthesis process has the advantages of simple operation, low energy consumption, low cost, high yield and the like, and is suitable for large-scale preparation.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is a scanning electron micrograph of an iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) and ZIF-67(Co) in which (a) is ZIF-67(Co) and (b) is FeCo-LDH-1.5, using ZIF-67 as a template in example 1 of the present invention.
FIG. 2 is an X-ray diffraction pattern of an iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) using ZIF-67 as a template in example 1 of the present invention.
FIG. 3 is a Fourier transform infrared spectrum of an iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) and ZIF-67(Co) using ZIF-67 as a template in example 1 of the present invention.
FIG. 4 is a graph showing the effect of high-level oxidation of tetracycline by Fe-Co layered double metal hydroxide materials (FeCo-LDH-0.5, FeCo-LDH-1.0, FeCo-LDH-1.5, FeCo-LDH-2.0), ZIF-67(Co) and the reaction system containing only PMS using ZIF-67 as a template in example 1 of the present invention.
FIG. 5 is a graph showing the effect of layered iron-cobalt double metal hydroxide materials (FeCo-LDH-1.5) prepared by using ZIF-67 as a template on the advanced oxidation of tetracycline hydrochloride wastewater at different pH values in example 2 of the present invention.
FIG. 6 is a graph showing the effect of a layered iron-cobalt double hydroxide material (FeCo-LDH-1.5) on the advanced oxidation of tetracycline hydrochloride wastewater of different concentrations in example 3 of the present invention using ZIF-67 as a template.
FIG. 7 is a graph showing the effect of an iron-cobalt layered double hydroxide material (FeCo-LDH-1.5) with ZIF-67 as a template on the advanced oxidation of tetracycline hydrochloride wastewater containing different concentrations of inorganic and organic interferences in example 4 of the present invention; sulfate ion influence (a), chloride ion influence (b), and humus influence (c).
FIG. 8 is a cycle chart (a) and Fourier transform infrared spectra (b) before and after the reaction of tetracycline treated with an iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) using ZIF-67 as a template in example 1 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings of the specification and to specific preferred embodiments, without thereby limiting the scope of protection of the invention.
The starting materials and equipment used in the following examples are commercially available. In the following examples, unless otherwise specified, the data obtained are the average of three or more repeated experiments.
Example 1
A method for treating antibiotic wastewater by using an iron-cobalt layered double hydroxide material taking ZIF-67 as a template specifically comprises the following steps of degrading tetracycline hydrochloride in an advanced oxidation system containing PMS by using the iron-cobalt layered double hydroxide material taking ZIF-67 as the template:
weighing iron-cobalt layered double metal hydroxide materials (FeCo-LDH-0.5, FeCo-LDH-1.0, FeCo-LDH-1.5 and FeCo-LDH-2.0) and ZIF-67 with ZIF-67 as a template, respectively adding 20mg of the iron-cobalt layered double metal hydroxide materials and the ZIF-67 into 100mL of hydrochloric acid tetracycline wastewater with the concentration of 30mg/L, stirring for 1h in a dark place at the rotation speed of 200r/min, respectively adding 25mg of PMS after reaching adsorption equilibrium, continuously stirring for 30min at the rotation speed of 200r/min for advanced oxidation reaction, and finishing the treatment of tetracycline.
In this example, the iron-cobalt layered double hydroxide material using ZIF-67 as a template includes iron ions and ZIF-67(Co), where the iron ions etch the ZIF-67 (Co).
In this embodiment, the preparation method of the iron-cobalt layered double hydroxide material (FeCo-LDH-1.5) using ZIF-67 as the template specifically uses cobalt nitrate hexahydrate, dimethyl imidazole, and ferric nitrate nonahydrate as raw materials, and an organic solvent to stir at room temperature for a suitable time to prepare the iron-cobalt layered double hydroxide material using ZIF-67 as the template, which includes the following steps:
(1) according to the molar ratio of dimethyl imidazole to methanol of 4: 393 of the mixed solution, slowly adding the mixed solution into a mixture of cobalt nitrate hexahydrate and methanol, wherein the molar ratio of the cobalt nitrate hexahydrate to the methanol is 1: 393 to the mixed solution. Stirring for 24h at the rotating speed of 300r/min, centrifuging the obtained reaction product, washing the obtained centrifugal product with methanol for three times, and then drying in vacuum for 12h at the temperature of 60 ℃ to obtain the ZIF-67(Co) material.
(2) And (2) taking the ZIF-67(Co) obtained in the step (1) as a template, and dispersing the ZIF-67 template and the ferric nitrate nonahydrate in an ethanol solution according to the molar ratio of the ZIF-67 to the ferric nitrate nonahydrate to the ethanol of 3.57.5:1.5: 1090. Stirring for 1h at the rotating speed of 200r/min, centrifuging the obtained reaction product, washing the obtained centrifugal product with ethanol for three times, and then carrying out vacuum drying for 12h at the temperature of 60 ℃ to obtain the iron-cobalt layered double metal hydroxide material with the ZIF-67 as the template.
In this example, the method for preparing the iron-cobalt layered double metal hydroxide material (FeCo-LDH-0.5) using ZIF-67 as the template is basically the same as the method for preparing the iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) using ZIF-67 as the template, and the difference is only that: in the preparation method of the iron-cobalt layered double metal hydroxide material (FeCo-LDH-0.5) by taking ZIF-67 as the template, the molar ratio of ZIF-67 to ferric nitrate nonahydrate is 3.57: 0.5.
in this example, the method for preparing the iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.0) using ZIF-67 as the template is basically the same as the method for preparing the iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) using ZIF-67 as the template, and the difference is only that: in the preparation method of the iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.0) by taking ZIF-67 as the template, the molar ratio of ZIF-67 to ferric nitrate nonahydrate is 3.57: 1.0.
in this example, the preparation method of the iron-cobalt layered double metal hydroxide material (FeCo-LDH-2.0) using ZIF-67 as the template is basically the same as the preparation method of the iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) using ZIF-67 as the template, and the difference is only that: in the preparation method of the iron-cobalt layered double metal hydroxide material (FeCo-LDH-2.0) by taking ZIF-67 as the template, the molar ratio of ZIF-67 to ferric nitrate nonahydrate is 3.57: 2.0.
in this example, the preparation method of ZIF-67(Co) used is completely the same as the preparation method of step (1) in the preparation method of an iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) using ZIF-67 as a template.
FIG. 1 is a scanning electron micrograph of an iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) and ZIF-67(Co) in which (a) is ZIF-67(Co) and (b) is FeCo-LDH-1.5, using ZIF-67 as a template in example 1 of the present invention. As can be seen from FIG. 1, ZIF-67(Co) exhibits a smooth surfaced regular dodecahedral morphology. The FeCo-LDH-1.5 surface becomes rough due to the presence of a lamellar structure. Therefore, the appearance of ZIF-67(Co) etched by iron ions is closer to a three-dimensional layered double hydroxide structure.
FIG. 2 is an X-ray diffraction pattern of an iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) using ZIF-67 as a template in example 1 of the present invention. As shown in FIG. 2, the characteristic peaks (003), (006) and (012) belonging to the conventional FeCo-LDH can be observed in the graph, indicating that the etching success is more likely. The disorder of the peak patterns indicates that the crystallinity of the sample is low.
FIG. 3 is a Fourier transform infrared spectrum of an iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) and ZIF-67(Co) using ZIF-67 as a template in example 1 of the present invention. As can be seen from FIG. 3, the appearance of characteristic peaks belonging to the covalent bonds of hydroxyl, carbonate, metal and oxygen illustrates that the iron ion-etched ZIF-67(Co) is a layered double hydroxide assembled from host plates containing divalent and trivalent metal ions and interlayer anions of carbonate ions, namely FeCo-LDH-1.5.
And after the reaction in the dark, taking 4mL of sample, filtering the sample, measuring the absorbance of the filtered clear liquid by using an ultraviolet-visible spectrophotometer, determining the adsorption removal rate of the tetracycline, and deducting the rate by taking the rate as a background value. In the advanced oxidation reaction process, 4mL of samples are taken at intervals (the advanced oxidation reaction is carried out for 0min, 1min, 3min, 5min, 10min, 20min and 30 min), the samples are filtered, clear liquid obtained after filtering is taken, the absorbance is measured by an ultraviolet visible spectrophotometer, the advanced oxidation removal rate of the tetracycline is determined, and therefore the photocatalytic effect of different materials on the tetracycline is obtained, and the result is shown in figure 4.
FIG. 4 is a graph showing the effect of high-level oxidation of tetracycline by Fe-Co layered double metal hydroxide materials (FeCo-LDH-0.5, FeCo-LDH-1.0, FeCo-LDH-1.5, FeCo-LDH-2.0), ZIF-67(Co) and a system containing only PMS using ZIF-67 as a template in example 1 of the present invention. As shown in FIG. 4, the removal rate of ZIF-67 monomer was only 39.55%, which was 48.17% lower than that of the PMS-only system of comparative example 2. When the amount of iron ions added as an etching agent is gradually increased, the removal rate of the tetracycline by the obtained product is also improved, and the removal rates of FeCo-LDH-0.5, FeCo-LDH-1.0, FeCo-LDH-1.5 and FeCo-LDH-2.0 are respectively 62%, 73%, 92% and 93%. Wherein the removal of antibiotics by FeCo-LDH-1.5 has reached a higher level.
Example 2
A method for treating antibiotic wastewater by using an iron-cobalt layered double hydroxide material taking ZIF-67 as a template specifically comprises the following steps of degrading tetracycline hydrochloride in an advanced oxidation system containing PMS by using the iron-cobalt layered double hydroxide material taking ZIF-67 as the template:
weighing 6 parts of iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) taking ZIF-67 as a template in example 1, adding 20mg of each part of the iron-cobalt layered double metal hydroxide material into tetracycline hydrochloride wastewater with pH values of 3, 5, 7, 9 and 11, wherein the tetracycline hydrochloride wastewater has a volume of 100mL and a concentration of 30mg/L, stirring for 1h in a dark place at a rotation speed of 200r/min, adding 25mg of PMS after adsorption equilibrium is achieved, and continuously stirring for 30min at a rotation speed of 200r/min to perform advanced oxidation reaction, thereby completing tetracycline treatment.
In the advanced oxidation reaction process, 4mL of samples are taken at intervals (the advanced oxidation reaction is carried out for 0min, 1min, 3min, 5min, 10min, 20min and 30 min), the samples are filtered, clear liquid obtained by filtering is measured by an ultraviolet-visible spectrophotometer to measure absorbance, the advanced oxidation removal rate of tetracycline is determined, and therefore a diagram of the advanced oxidation effect of the iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) with ZIF-67 as a template on tetracycline hydrochloride wastewater with different pH values is obtained, and the result is shown in figure 5.
FIG. 5 is a graph showing the effect of layered iron-cobalt double metal hydroxide materials (FeCo-LDH-1.5) prepared by using ZIF-67 as a template on the advanced oxidation of tetracycline hydrochloride wastewater at different pH values in example 2 of the present invention. As can be seen from fig. 5, when the pH values of the tetracycline hydrochloride wastewater were 3, 5, 7, 9, and 11, respectively, the removal rates of tetracycline hydrochloride by the iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) using ZIF-67 as a template were 88%, 89%, 83%, 76%, and 74%, respectively. Therefore, the iron-cobalt layered double-metal hydroxide material taking the ZIF-67 as the template has a good removal effect on tetracycline hydrochloride wastewater with the pH value of 3-11. However, as the pH value of tetracycline hydrochloride gradually increases, the degradation rate is inhibited because of the partial dominance of SO in the reaction system under an alkaline environment4 ·-Free radicals are converted into HO with poor effect·-Free radicals, making the degradation efficientThere is a break in the way.
Example 3
A method for treating antibiotic wastewater by using an iron-cobalt layered double hydroxide material taking ZIF-67 as a template specifically comprises the following steps of degrading tetracycline hydrochloride in an advanced oxidation system containing PMS by using the iron-cobalt layered double hydroxide material taking ZIF-67 as the template:
6 parts of iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) taking ZIF-67 as a template in example 1 are weighed, 20mg of each part is added into tetracycline hydrochloride wastewater with the concentration of 5mg/L, 10mg/L, 30mg/L, 50mg/L, 70mg/L and 100mg/L respectively, wherein the volume of the tetracycline hydrochloride wastewater is 100mL, the concentration of the tetracycline hydrochloride wastewater is 30mg/L, the tetracycline hydrochloride wastewater is stirred for 1h in a dark place at the rotating speed of 200r/min, after adsorption equilibrium is reached, 25mg of PMS is added respectively, and the stirring is continued for 30min at the rotating speed of 200r/min for advanced oxidation reaction, so that the tetracycline treatment is completed.
In the advanced oxidation reaction process, 4mL of samples are taken at intervals (when the advanced oxidation reaction is carried out for 0min, 1min, 3min, 5min, 10min, 20min and 30 min), the samples are filtered, clear liquid obtained by filtering is measured for absorbance through an ultraviolet-visible spectrophotometer, the advanced oxidation removal rate of tetracycline is determined, and therefore a diagram of the advanced oxidation effect of the iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) with ZIF-67 as a template on tetracycline hydrochloride wastewater with different concentrations is obtained, and the result is shown in FIG. 6.
FIG. 6 is a graph showing the effect of a layered iron-cobalt double hydroxide material (FeCo-LDH-1.5) on the advanced oxidation of tetracycline hydrochloride wastewater of different concentrations in example 3 of the present invention using ZIF-67 as a template. As can be seen from FIG. 6, when the tetracycline hydrochloride wastewater concentrations were 5mg/L, 10mg/L, 30mg/L, 50mg/L, 70mg/L and 100mg/L, respectively, the removal rates of tetracycline hydrochloride by the iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) using ZIF-67 as a template were 99%, 97%, 92%, 87%, 82% and 70%, respectively. Therefore, the iron-cobalt layered double-metal hydroxide material taking the ZIF-67 as the template has a good degradation effect on tetracycline hydrochloride wastewater with different concentrations. Particularly, the effect of nearly completely removing the tetracycline hydrochloride wastewater with lower concentration is achieved, and the increase of the concentration of the tetracycline hydrochloride wastewater relatively reduces the available chemical contact sites on the iron-cobalt layered double metal hydroxide material taking ZIF-67 as a template, so that the degradation efficiency is reduced, but the degradation efficiency is still maintained at a higher level.
Example 4
A method for treating antibiotic wastewater by using an iron-cobalt layered double hydroxide material taking ZIF-67 as a template specifically comprises the following steps of degrading tetracycline hydrochloride in an advanced oxidation system containing PMS by using the iron-cobalt layered double hydroxide material taking ZIF-67 as the template:
weighing 9 parts of iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) taking ZIF-67 as a template in example 1, adding 20mg of each part of the iron-cobalt layered double metal hydroxide material into tetracycline hydrochloride wastewater containing sodium sulfate and sodium chloride at concentrations of 5mmol/L, 10mmol/L and 15mmol/L and humic substances at concentrations of 3mg/L, 6mg/L and 9mg/L respectively, stirring for 1h in a dark place at a rotation speed of 200r/min, adding 25mg of PMS after adsorption equilibrium is reached, and continuously stirring for 30min at a rotation speed of 200r/min to perform a high-level oxidation reaction to complete tetracycline treatment.
In the advanced oxidation reaction process, 4mL of samples are taken at intervals (the advanced oxidation reaction is carried out for 0min, 1min, 3min, 5min, 10min, 20min and 30 min), the samples are filtered, clear liquid obtained by filtering is measured by an ultraviolet-visible spectrophotometer to measure absorbance, and the advanced oxidation removal rate of tetracycline is determined, so that an advanced oxidation effect graph of an iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) with ZIF-67 as a template on tetracycline hydrochloride wastewater containing different concentrations of organic and inorganic interferences is obtained, and the result is shown in FIG. 7.
FIG. 7 is a graph showing the effect of an iron-cobalt layered double hydroxide material (FeCo-LDH-1.5) with ZIF-67 as a template on the advanced oxidation of tetracycline hydrochloride wastewater containing different concentrations of inorganic and organic interferences in example 4 of the present invention; sulfate ion influence (a), chloride ion influence (b), and humus influence (c). As can be seen from FIG. 7, the iron-cobalt layered double hydroxide material using ZIF-67 as a template has a good degradation effect on tetracycline hydrochloride wastewater containing organic and inorganic interferences with different concentrations, which indicates that the iron-cobalt layered double hydroxide material using ZIF-67 as a template has a strong anti-interference capability on inorganic substances and organic substances in the tetracycline hydrochloride wastewater, and is of great significance for the application of the iron-cobalt layered double hydroxide material using ZIF-67 as a template in actual wastewater.
It is noted that, as shown in fig. 8(a), after the iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) using ZIF-67 as a template is centrifugally washed and recovered, the tetracycline hydrochloride still has a good degradation effect after being recycled for three times. Fourier transform infrared spectrum analysis is carried out on the iron-cobalt layered double metal hydroxide material (FeCo-LDH-1.5) which takes ZIF-67 as a template before and after tetracycline hydrochloride treatment, as shown in figure 8(b), the change of the Fourier transform infrared spectrum before and after the reaction of the iron-cobalt layered double metal hydroxide material which takes ZIF-67 as the template is small, and the obvious difference represents that the characteristic peak of carbonate ions is changed greatly, but the stability is good.
Therefore, the method for treating the antibiotic wastewater by using the iron-cobalt layered double-metal hydroxide material with the ZIF-67 as the template has the advantages that the iron-cobalt layered double-metal hydroxide material with the ZIF-67 as the template and the antibiotic wastewater are subjected to oscillation adsorption in a dark place, PMS is added after adsorption saturation is achieved, and oscillation reaction is continued, so that the aim of treating the antibiotic wastewater is fulfilled. Therefore, the method is an antibiotic treatment method which is comprehensive and efficient, clean, cyclic and low in consumption, and has a good commercial application prospect.
The above examples are only preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (12)
1. A method for treating antibiotic wastewater by using an iron-cobalt layered double hydroxide material with ZIF-67 as a template is characterized by comprising the following steps: firstly, carrying out oscillatory adsorption on an iron-cobalt layered double-metal hydroxide material taking ZIF-67 as a template and antibiotic wastewater in a dark place, adding PMS to carry out advanced oxidation reaction after the adsorption is saturated, thereby achieving the purpose of treating the antibiotic wastewater; the iron-cobalt layered double-metal hydroxide material with the ZIF-67 as the template comprises iron ions and ZIF-67(Co), and the ZIF-67(Co) template is etched by the iron ions.
2. The method as claimed in claim 1, wherein the ZIF-67-templated fe-co layered double hydroxide material has a pore size of 3.679 nm.
3. The method for preparing an iron-cobalt layered double hydroxide material using ZIF-67 as a template according to claim 2, comprising the steps of:
s1, mixing dimethyl imidazole, cobalt nitrate hexahydrate and organic solvent, and stirring to obtain ZIF-67(Co)
S2, mixing the ZIF-67(Co) obtained in the step S1 with an ethanol solution containing ferric nitrate nonahydrate, and stirring to obtain the iron-cobalt layered double hydroxide material taking the ZIF-67 as a template.
4. The method according to claim 3, wherein the molar ratio of the dimethylimidazole to the cobalt nitrate hexahydrate is 1: 4: 786; the molar ratio of the dimethyl imidazole to the cobalt nitrate hexahydrate to the organic solvent is 1: 4: 3930.
5. the method according to claim 4, wherein the organic solvent is methanol.
6. The method of claim 3, wherein the molar ratio of ZIF-67(Co) to ferric nitrate nonahydrate is 3.57: 0.5 to 2; the molar ratio of ZIF-67(Co), ferric nitrate nonahydrate and ethanol is 3.57: 0.5-2: 1090.
7. the method according to claim 3, wherein in step S1, the rotation speed of the stirring is 300r/min to 400 r/min; the stirring time is 24 hours; in step S2, the stirring speed is 200 r/min-300 r/min; the stirring time is 1 h.
8. The method of claim 3, wherein the steps S1 and S2 are further followed by the steps of: centrifuging, washing and drying a reaction product obtained after stirring; the rotating speed of the centrifugation is 3000 r/min-5000 r/min; methanol and ethanol are adopted for washing; the washing times are 3-5 times; the drying is carried out under vacuum conditions; the drying temperature is 60 ℃; the drying time was 12 h.
9. The method according to any one of claims 1 to 8, wherein the mass-to-volume ratio of the iron-cobalt layered double hydroxide material using ZIF-67 as a template to the antibiotic wastewater is 0.2 g: 1L of the compound.
10. The method according to any one of claims 1 to 8, wherein the antibiotic in the antibiotic wastewater is tetracycline hydrochloride; the concentration of the antibiotics in the antibiotic wastewater is 5 mg/L-100 mg/L; the pH value of the antibiotic wastewater is 3-11; the inorganic interference added into the antibiotic wastewater is sulfate ions and chloride ions; organic interference added into the antibiotic wastewater is humus; the concentration of inorganic interference in the antibiotic wastewater is 5 mmol/L-15 mmol/L; the concentration of organic interference in the antibiotic wastewater is 3 mg/L-9 mg/L.
11. The method according to any one of claims 1 to 8, wherein the rotation speed of the oscillating adsorption in the dark is 200 r/min; the time of oscillating adsorption in the dark is 1 h.
12. The method according to any one of claims 1 to 8, further comprising the following treatment after the completion of the dark shaking adsorption: adding a certain amount of PMS and oscillating for advanced oxidation reaction; the mass volume ratio of the PMS to the antibiotic wastewater is 0.25 g: 1L; the oscillation speed of the advanced oxidation reaction is 200 r/min; the advanced oxidation reaction time is 0.5 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010399133.6A CN111533313A (en) | 2020-05-12 | 2020-05-12 | Method for treating antibiotic wastewater by using iron-cobalt layered double metal hydroxide material with ZIF-67 as template |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010399133.6A CN111533313A (en) | 2020-05-12 | 2020-05-12 | Method for treating antibiotic wastewater by using iron-cobalt layered double metal hydroxide material with ZIF-67 as template |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111533313A true CN111533313A (en) | 2020-08-14 |
Family
ID=71972037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010399133.6A Pending CN111533313A (en) | 2020-05-12 | 2020-05-12 | Method for treating antibiotic wastewater by using iron-cobalt layered double metal hydroxide material with ZIF-67 as template |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111533313A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112047388A (en) * | 2020-09-08 | 2020-12-08 | 湖南垚恒环境科技有限公司 | Iron-cobalt layered double-metal hydroxide material with ZIF-67 as template and preparation method thereof |
| CN113522317A (en) * | 2021-08-22 | 2021-10-22 | 沈阳药科大学 | Preparation method and application of cobalt-based bimetallic sulfur/carbon catalyst derived from MOFs (metal-organic frameworks) |
| CN114130394A (en) * | 2021-11-26 | 2022-03-04 | 合肥智慧环境研究院 | Cobalt oxide hollow polyhedron type catalyst and preparation method and application thereof |
| CN114653374A (en) * | 2022-04-02 | 2022-06-24 | 北京师范大学 | Double-metal hydroxide and preparation method and application thereof |
| CN115353189A (en) * | 2022-08-19 | 2022-11-18 | 湘潭大学 | Method for treating ciprofloxacin-containing wastewater by regulating and controlling dissolved oxygen |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150110131A (en) * | 2014-03-24 | 2015-10-02 | 한국과학기술원 | Efficient Co-Fe layered double hydroxide photocatalysts for water oxidation under visible light and Method Thereof |
| CN110801839A (en) * | 2019-11-21 | 2020-02-18 | 中国科学技术大学 | Co2FeAl-LDH, preparation method thereof and method for degrading pollutants |
| CN110961159A (en) * | 2019-12-31 | 2020-04-07 | 五邑大学 | Supported Fe-Co/ZIF-67 bimetallic catalyst and preparation method and application thereof |
-
2020
- 2020-05-12 CN CN202010399133.6A patent/CN111533313A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150110131A (en) * | 2014-03-24 | 2015-10-02 | 한국과학기술원 | Efficient Co-Fe layered double hydroxide photocatalysts for water oxidation under visible light and Method Thereof |
| CN110801839A (en) * | 2019-11-21 | 2020-02-18 | 中国科学技术大学 | Co2FeAl-LDH, preparation method thereof and method for degrading pollutants |
| CN110961159A (en) * | 2019-12-31 | 2020-04-07 | 五邑大学 | Supported Fe-Co/ZIF-67 bimetallic catalyst and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| CAO JIAO ET AL: "Efficient charge transfer in aluminum-cobalt layered double hydroxide derived from Co-ZIF for enhanced catalytic degradation of tetracycline through peroxymonosulfate activation", 《CHEMICAL ENGINEERING JOURNAL》 * |
| GONG CHENG ET AL: "Heterogeneous activation of peroxymonosulfate by Fe-Co layered doubled hydroxide for efficient catalytic degradation of Rhoadmine B", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 商梦莉等: "金属有机骨架 ZIF-67材料的合成及微结构调控研究", 《人工晶体学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112047388A (en) * | 2020-09-08 | 2020-12-08 | 湖南垚恒环境科技有限公司 | Iron-cobalt layered double-metal hydroxide material with ZIF-67 as template and preparation method thereof |
| CN113522317A (en) * | 2021-08-22 | 2021-10-22 | 沈阳药科大学 | Preparation method and application of cobalt-based bimetallic sulfur/carbon catalyst derived from MOFs (metal-organic frameworks) |
| CN114130394A (en) * | 2021-11-26 | 2022-03-04 | 合肥智慧环境研究院 | Cobalt oxide hollow polyhedron type catalyst and preparation method and application thereof |
| CN114130394B (en) * | 2021-11-26 | 2024-04-30 | 合肥智慧环境研究院 | Cobalt oxide hollow polyhedral catalyst and preparation method and application thereof |
| CN114653374A (en) * | 2022-04-02 | 2022-06-24 | 北京师范大学 | Double-metal hydroxide and preparation method and application thereof |
| CN115353189A (en) * | 2022-08-19 | 2022-11-18 | 湘潭大学 | Method for treating ciprofloxacin-containing wastewater by regulating and controlling dissolved oxygen |
| CN115353189B (en) * | 2022-08-19 | 2024-01-16 | 湘潭大学 | Method for treating ciprofloxacin-containing wastewater by regulating and controlling dissolved oxygen |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111533313A (en) | Method for treating antibiotic wastewater by using iron-cobalt layered double metal hydroxide material with ZIF-67 as template | |
| CN111204837A (en) | Tetracycline degradation method | |
| CN113908878B (en) | Preparation method and application of bimetallic Prussian blue analogue catalyst | |
| Ye et al. | Synthesis of Ferrocene‐Modified Carbon Nitride Photocatalysts by Surface Amidation Reaction for Phenol Synthesis | |
| Shen et al. | Cobalt–copper oxalate nanofibers mediated Fenton degradation of Congo red in aqueous solutions | |
| CN111346609B (en) | Adsorbing material for heavy metal dye-containing wastewater and preparation method thereof | |
| CN109289772B (en) | Carbon nano tube/hydrotalcite material for removing nitrate nitrogen in water and preparation method thereof | |
| CN111617731A (en) | Method for treating antibiotics in water body by coupling magnetic nano material with persulfate | |
| CN114849748B (en) | CoS/Ti 3 C 2 Preparation and application of MXene composite material | |
| CN111569944A (en) | Manganese ion doped metal organic framework material and preparation method thereof | |
| CN112023882A (en) | Method for treating and adsorbing water antibiotics by using two-dimensional nitrogen-doped nano porous carbon material | |
| CN111533237A (en) | Method for treating antibiotic wastewater by using manganese ion doped metal organic framework material | |
| CN114082432B (en) | Iron-nitrogen co-doped porous carbon prepared by taking ferrate as iron source, and preparation method and application thereof | |
| CN110975846A (en) | Clay mineral/conductive polymer composite adsorbent and preparation method and application thereof | |
| Liu et al. | Structural characterizations of zinc-copper silicate polymer (ZCSP) and its mechanisms of ozonation for removal of p-chloronitrobenzene in aqueous solution | |
| CN111111734B (en) | Preparation and application of ferrous disulfide/carbon nitride composite photocatalyst | |
| CN114768857B (en) | Nanometer zero-valent iron composite material and preparation method and application thereof | |
| CN115041211A (en) | MOFs-derived Fe-N/C catalyst containing defect Fe-Nx and preparation method and application thereof | |
| CN112047388A (en) | Iron-cobalt layered double-metal hydroxide material with ZIF-67 as template and preparation method thereof | |
| Wang et al. | Sulfite activation for ciprofloxacin rapid degradation using an iron-based metal organic framework derivative in heterogeneous processes: Performance and mechanisms investigation | |
| Xie et al. | Synthesis of a stable iron (iii)–organic framework for a visible light induced simultaneous photocatalytic reduction of Cr (vi) and the degradation of organic dyes in water | |
| CN111545245A (en) | Iron ion doped metal organic framework material and preparation method thereof | |
| CN113600133A (en) | Phosphorus removal adsorbent and preparation method and application thereof | |
| CN113318791B (en) | Preparation method and application of amino-modified Fe/Cu-MOF photocatalyst | |
| CN112844475B (en) | Preparation method of Janus type magnetic cyclodextrin-graphite phase carbon nitride and experimental method for removing polychlorinated biphenyl in water by using Janus type magnetic cyclodextrin-graphite phase carbon nitride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200814 |
|
| WD01 | Invention patent application deemed withdrawn after publication |