CN114950362A - Wastewater treatment material and preparation method and application thereof - Google Patents
Wastewater treatment material and preparation method and application thereof Download PDFInfo
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- CN114950362A CN114950362A CN202210498325.1A CN202210498325A CN114950362A CN 114950362 A CN114950362 A CN 114950362A CN 202210498325 A CN202210498325 A CN 202210498325A CN 114950362 A CN114950362 A CN 114950362A
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- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 36
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 36
- 239000002351 wastewater Substances 0.000 claims abstract description 23
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 22
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 22
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 32
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 26
- 150000003751 zinc Chemical class 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000006722 reduction reaction Methods 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 8
- 239000011701 zinc Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 5
- 230000003213 activating effect Effects 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000004043 dyeing Methods 0.000 abstract 1
- 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 description 10
- HJLSLZFTEKNLFI-UHFFFAOYSA-N Tinidazole Chemical compound CCS(=O)(=O)CCN1C(C)=NC=C1[N+]([O-])=O HJLSLZFTEKNLFI-UHFFFAOYSA-N 0.000 description 10
- 229960003376 levofloxacin Drugs 0.000 description 10
- JCCNYMKQOSZNPW-UHFFFAOYSA-N loratadine Chemical compound C1CN(C(=O)OCC)CCC1=C1C2=NC=CC=C2CCC2=CC(Cl)=CC=C21 JCCNYMKQOSZNPW-UHFFFAOYSA-N 0.000 description 10
- 229960003088 loratadine Drugs 0.000 description 10
- 229960005053 tinidazole Drugs 0.000 description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 2
- -1 radionuclides Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000012425 OXONE® Substances 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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
- C02F2103/003—Wastewater from hospitals, laboratories and the like, heavily contaminated by pathogenic microorganisms
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
-
- 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
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention belongs to the field of materials science, and particularly relates to a wastewater treatment material as well as a preparation method and application thereof. The wastewater treatment material provided by the invention comprises carbon nano tubes and zinc sulfide loaded on the carbon nano tubes. The wastewater treatment material provided by the invention is prepared by adding Zn into 2+ Is stably loaded in the form of zinc sulfide in the carbon nano tube, and can effectively prevent Zn 2+ In the process of activating persulfate to treat wastewater, the persulfate is released to a water body in a free state, so that secondary pollution is effectively preventedA dyeing problem occurs. Moreover, the material can realize the synergistic effect of adsorption and catalytic degradation, thereby greatly improving the removal effect of organic pollutants. The wastewater treatment material provided by the invention can safely and efficiently activate persulfate to remove various organic pollutants in wastewater, has a wide application range, and has a wide application prospect in the field of wastewater treatment, particularly in the field of medical wastewater treatment.
Description
Technical Field
The invention belongs to the field of materials science, and particularly relates to a wastewater treatment material as well as a preparation method and application thereof.
Background
Hospitals generally use a variety of chemicals such as medicines, radionuclides, solvents, and disinfectants, which are introduced into water through excretions of patients in medical rooms, radiology departments, and wards after use, resulting in medical wastewater as a complex matrix containing a large amount of chemicals and microorganisms. The advanced oxidation method can utilize free radicals (hydroxyl free radicals, oxygen free radicals and the like) generated in the oxidation reaction to oxidize refractory macromolecules in the water body into low-toxicity or non-toxic micromolecules and even directly degrade the micromolecules into CO 2 、H 2 O and inorganic salts. The persulfate advanced oxidation technology based on the activation of the transition metal ions is an important means for treating wastewater at present, but the introduction of the transition metal ions can easily cause secondary pollution to a water body.
Disclosure of Invention
In view of the above, the present invention provides a wastewater treatment material, and a preparation method and an application thereof, and the wastewater treatment material provided by the present invention can safely and efficiently activate persulfate to remove organic pollutants in wastewater without generating secondary pollution.
The invention provides a wastewater treatment material, which comprises: carbon nanotubes and zinc sulfide supported on the carbon nanotubes.
Preferably, the outer diameter of the carbon nano tube is 10-20 nm; the length of the carbon nano tube is 5-20 mu m.
Preferably, the content of the zinc sulfide in the wastewater treatment material is more than or equal to 10 wt%.
The invention provides a preparation method of a wastewater treatment material, which comprises the following steps:
a) mixing the carbon nano tube with a zinc salt solution, then mixing with a dimethyl imidazole solution, and carrying out solid-liquid separation to obtain a solid substance;
the zinc salt solution contains zinc salt, methanol and water; the dimethyl imidazole solution contains dimethyl imidazole and methanol;
b) mixing the solid substance, sulfur powder and water, and heating for reaction to obtain a solid product;
c) and carrying out reduction reaction on the solid product in a hydrogen-containing atmosphere to obtain the wastewater treatment material loaded with zinc sulfide.
Preferably, in the step a), the mass ratio of the carbon nanotube to the zinc salt to the dimethyl imidazole is 5: (1-3): (2-5).
Preferably, in the step a), the mixing speed of the carbon nano tube and the zinc salt solution is 300-500 rpm; the mixing time of the carbon nano tube and the zinc salt solution is 1-3 h; mixing with the dimethyl imidazole solution under ultrasonic conditions; the mixing time of the dimethyl imidazole solution is 1-2 h.
Preferably, in the step b), the mass ratio of the solid matter to the sulfur powder is (2-5): (5-2).
Preferably, in step b), the mixing is carried out under ultrasonic conditions; the mixing time is 0.5-2 h; the temperature of the heating reaction is 160-180 ℃; the reaction time is 8-15 h.
Preferably, in the step c), the hydrogen content of the hydrogen-containing atmosphere is 3-5%; the temperature of the reduction reaction is 500-700 ℃; the time of the reduction reaction is 1-3 h.
The invention provides a wastewater treatment method, which comprises the following steps:
treating organic wastewater by utilizing persulfate and a wastewater treatment material to obtain treated wastewater;
the wastewater treatment material is the wastewater treatment material in the technical scheme or the wastewater treatment material prepared by the preparation method in the technical scheme.
Compared with the prior art, the invention provides a wastewater treatment material, and a preparation method and application thereof. The inventionThe provided wastewater treatment material comprises carbon nano-tubes and zinc sulfide loaded on the carbon nano-tubes. The wastewater treatment material provided by the invention is prepared by adding Zn into 2+ Is stably loaded in the form of zinc sulfide in the carbon nano tube, and can effectively prevent Zn 2+ In the process of activating persulfate to treat wastewater, the persulfate is released to a water body in a free state, so that the problem of secondary pollution is effectively prevented. Moreover, the material can realize the synergistic effect of adsorption and catalytic degradation, thereby greatly improving the removal effect of organic pollutants. The wastewater treatment material provided by the invention can safely and efficiently activate persulfate to remove various organic pollutants in wastewater, has a wide application range, and has a wide application prospect in the field of wastewater treatment, particularly in the field of medical wastewater treatment.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an X-ray photoelectron spectrum of a wastewater treatment material provided in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a wastewater treatment material, which comprises: carbon nanotubes and zinc sulfide supported on the carbon nanotubes.
In the wastewater treatment material provided by the invention, the carbon nanotubes are preferably multi-walled carbon nanotubes; the outer diameter of the carbon nano tube is preferably 10-20 nm, and specifically can be 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm or 20 nm; the length of the carbon nanotube is preferably 5-20 μm, and specifically may be 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm or 20 μm.
In the wastewater treatment material provided by the invention, the content of the zinc sulfide in the wastewater treatment material is preferably not less than 10 wt%, more preferably 10-20 wt%, and specifically may be 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt% or 20 wt%.
The invention also provides a preparation method of the wastewater treatment material, which comprises the following steps:
a) mixing the carbon nano tube with a zinc salt solution, then mixing with a dimethyl imidazole solution, and carrying out solid-liquid separation to obtain a solid substance;
the zinc salt solution contains zinc salt, methanol and water; the dimethyl imidazole solution contains dimethyl imidazole and methanol;
b) mixing the solid substance, sulfur powder and water, and heating for reaction to obtain a solid product;
c) and carrying out reduction reaction on the solid product in a hydrogen-containing atmosphere to obtain the wastewater treatment material loaded with zinc sulfide.
In the preparation method provided by the invention, in the step a), the zinc salt is preferably zinc nitrate and/or zinc acetate; the preferable dosage ratio of the zinc salt, the methanol and the water in the zinc salt solution is (1-3) g: (10-20) mL: (10-20) mL, more preferably (1-3) g:15mL of: 15mL, specifically 1g:15mL, 1.2g:15mL, 1.5g:15mL, 1.7g:15mL, 2g:15mL, 2.3g:15mL, 2.5g:15mL, 2.7g:15mL, or 3g:15 mL.
In the preparation method provided by the invention, in the step a), the dosage ratio of the dimethyl imidazole and the methanol in the dimethyl imidazole solution is preferably (2-5) g: (20-40) mL, more preferably (2-5) g:30mL, specifically 2 g/30 mL, 2.5 g/30 mL, 3 g/30 mL, 3.5 g/30 mL, 4 g/30 mL, 4.5 g/30 mL or 5 g/30 mL.
In the preparation method provided by the present invention, in step a), the mass ratio of the carbon nanotube, the zinc salt in the zinc salt solution, and the dimethyl imidazole in the dimethyl imidazole solution is preferably 5: (1-3): (2-5); wherein the mass ratio of the carbon nano tube to the zinc salt is 5:1, 5:1.2, 5:1.5, 5:1.7, 5:2, 5:2.3, 5:2.5, 5:2.7 or 5: 3; the mass ratio of the carbon nanotube to the dimethyl imidazole can be 5:2, 5:2.5, 5:3, 5:3.5, 5:4, 5:4.5 or 5: 5.
In the preparation method provided by the invention, in the step a), the rotation speed of the carbon nano tube and the zinc salt solution during mixing is preferably 300-500 rpm, and specifically can be 300rpm, 350rpm, 400rpm, 450rpm or 500 rpm; the mixing temperature of the carbon nano tube and the zinc salt solution is preferably 15-35 ℃, and specifically can be 15 ℃, 20 ℃, 25 ℃ (room temperature), 30 ℃ or 35 ℃; the mixing time of the carbon nano tube and the zinc salt solution is preferably 1-3 h, and specifically can be 1h, 1.5h, 2h, 2.5h or 3 h.
In the preparation method provided by the invention, in the step a), the mixing with the dimethyl imidazole solution is preferably carried out under ultrasonic conditions; the mixing temperature with the dimethyl imidazole solution is preferably 15-35 ℃, and specifically can be 15 ℃, 20 ℃, 25 ℃ (room temperature), 30 ℃ or 35 ℃; the time for mixing with the dimethyl imidazole solution is preferably 1-2 h, and specifically can be 1h, 1.2h, 1.5h, 1.7h or 2 h.
In the preparation method provided by the invention, in the step a), after the mixing is completed, the mixture is preferably kept stand, and the standing time is preferably 0.5-3 hours, and specifically can be 0.5 hour, 1 hour, 1.5 hour, 2 hours, 2.5 hours or 3 hours.
In the preparation method provided by the invention, in the step a), the solid-liquid separation mode is preferably centrifugal separation; the rotation speed of the centrifugal separation is preferably 6000-10000 rpm, and specifically can be 6000rpm, 7000rpm, 8000rpm, 9000rpm or 10000 rpm; the centrifugal separation time is preferably 5-10 min, and specifically can be 5min, 6min, 7min, 8min, 9min or 10 min; preferably, the centrifugation is repeated several times, more preferably 3 times; the collected solids were washed with methanol after each centrifugation.
In the preparation method provided by the invention, in the step a), after the solid-liquid separation is finished, the obtained solid substance is preferably dried; the drying temperature is preferably 60-90 ℃, and specifically can be 60 ℃, 70 ℃, 80 ℃ or 90 ℃; the drying time is preferably 8-16 h, and specifically can be 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h or 16 h.
In the preparation method provided by the invention, in the step b), the mass ratio of the solid matter to the sulfur powder is preferably (2-5): (5-2), specifically 2:5, 2.5:4.5, 3:4, 3.5:3.5, 4:3, 4.5:2.5 or 5: 2; the dosage ratio of the solid matter to the water is preferably (2-5) g: (50-65) mL, more preferably (2-5 g): 60mL, specifically 2 g/60 mL, 2.5 g/60 mL, 3 g/60 mL, 3.5 g/60 mL, 4 g/60 mL, 4.5 g/60 mL or 5 g/60 mL.
In the preparation method provided by the invention, in the step b), the mixing is preferably carried out under ultrasonic conditions; the mixing temperature is preferably 15-35 ℃, and specifically can be 15 ℃, 20 ℃, 25 ℃ (room temperature), 30 ℃ or 35 ℃; the mixing time is preferably 0.5-2 h, and specifically can be 0.5h, 0.7h, 1h, 1.2h, 1.5h, 1.7h or 2 h.
In the preparation method provided by the invention, in the step b), the heating reaction is preferably carried out under a closed condition; the temperature of the heating reaction is preferably 160-180 ℃, and specifically can be 160 ℃, 165 ℃, 170 ℃, 175 ℃ or 180 ℃; the reaction time is preferably 8-15 h, and specifically can be 8h, 9h, 10h, 11h, 12h, 13h, 14h or 15 h.
In the preparation method provided by the invention, in the step b), after the heating reaction is finished, the collected solid product is preferably washed; the washing mode is preferably water washing; the number of washing is preferably 1 to 5, and specifically 3. After the washing, it is preferable to dry the mixture; the drying temperature is preferably 60-100 ℃, and specifically can be 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃; the drying time is preferably 8-16 h, and specifically can be 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h or 16 h.
In the preparation method provided by the invention, in the step c), the hydrogen content of the hydrogen-containing atmosphere is preferably 3-5%, and specifically can be 3%, 3.5%, 4%, 4.5% or 5%; the rest atmosphere in the hydrogen-containing atmosphere is inert gas, preferably argon; the inflow rate of the hydrogen-containing atmosphere is preferably 100-500 mL/min, and specifically may be 100mL/min, 150mL/min, 200mL/min, 250mL/min, 300mL/min, 350mL/min, 400mL/min, 450mL/min or 500 mL/min.
In the preparation method provided by the invention, in the step c), the heating rate of the reduction reaction is preferably 1-5 ℃/min, and specifically can be 1 ℃/min, 1.5 ℃/min, 2 ℃/min, 2.5 ℃/min, 3 ℃/min, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min or 5 ℃/min; the temperature of the reduction reaction is preferably 500-700 ℃, and specifically can be 500 ℃, 520 ℃, 550 ℃, 570 ℃, 600 ℃, 620 ℃, 650 ℃, 670 ℃ or 700 ℃; the time of the reduction reaction is preferably 1-3 h, and specifically may be 1h, 1.2h, 1.5h, 1.7h, 2h, 2.3h, 2.5h, 2.7h or 3h, and the time of the reduction reaction does not include the time consumed before the temperature is raised to the reaction temperature.
The invention also provides a wastewater treatment method, which comprises the following steps:
treating organic wastewater by utilizing persulfate and a wastewater treatment material to obtain treated wastewater; wherein the wastewater treatment material is the wastewater treatment material in the technical scheme or the wastewater treatment material prepared by the preparation method in the technical scheme.
In the wastewater treatment method provided by the invention, the organic wastewater is preferably medical wastewater; the organic pollutants contained in the medical wastewater include, but are not limited to, tinidazole, levofloxacin and loratadine; the content of the tinidazole in the medical wastewater is preferably 5-20 mg/L, and specifically 10 mg/L; the content of the levofloxacin in the medical wastewater is preferably 5-20 mg/L, and specifically 10 mg/L; the content of the loratadine in the medical wastewater is preferably 5-20 mg/L, and specifically 10 mg/L.
In the wastewater treatment method provided by the invention, the persulfate is preferably potassium peroxymonosulfate; the mass ratio of the sulfate to the wastewater treatment material is preferably (1-5): 1, specifically 1:1, 2:1, 3:1, 4:1 or 5: 1; the addition amount of the sulfate in the wastewater is preferably (0.01-0.1) g/100mL, and specifically may be 0.01g/100mL, 0.02g/100mL, 0.03g/100mL, 0.04g/100mL, 0.05g/100mL, 0.06g/100mL, 0.07g/100mL, 0.08g/100mL, 0.09g/100mL, or 0.1g/100 mL.
In the wastewater treatment method provided by the invention, the organic wastewater is preferably treated under the shaking condition of a shaking table, the rotating speed of the shaking table is preferably 100-300 r/min, and specifically can be 100r/min, 120r/min, 150r/min, 180r/min, 200r/min, 230r/min, 250r/min, 270r/min or 300 r/min; the treatment temperature is preferably 15-35 ℃, and specifically can be 15 ℃, 20 ℃, 25 ℃ (room temperature), 30 ℃ or 35 ℃; the treatment time is preferably 5-90 min, and specifically can be 5min, 15min, 30min, 45min, 60min, 75min or 90 min.
The technical scheme provided by the invention is that Zn is added 2+ Is stably loaded in the form of zinc sulfide in the carbon nano tube, and can effectively prevent Zn 2+ In the process of activating persulfate to treat wastewater, the persulfate is released to a water body in a free state, so that the problem of secondary pollution is effectively prevented. Moreover, the scheme can realize the synergistic effect of adsorption and catalytic degradation, thereby greatly improving the removal effect of organic pollutants. The technical scheme provided by the invention can safely and efficiently activate persulfate to remove various organic pollutants in wastewater, has a wide application range, and has a wide application prospect in the field of wastewater treatment, particularly in the field of medical wastewater treatment.
For the sake of clarity, the following examples are given in detail.
Example 1
A waste water treatment material loaded with zinc sulfide is prepared by the following specific steps:
2.0g of zinc nitrate is dissolved in 15mL of methanol and 15mL of deionized water to obtain a zinc nitrate solution; 4.0g of dimethylimidazole was dissolved in 30mL of methanol to obtain a dimethylimidazole solution.
Adding 5.0g of carbon nanotubes (commercial grade, multi-walled carbon nanotubes, the outer diameter of which is 10-20 nm and the length of which is 5-20 mu m) into the zinc nitrate solution, stirring for 2 hours at the rotating speed of 500rpm by using a magnetic stirrer, then adding the dimethyl imidazole solution, carrying out ultrasonic treatment for 1.5 hours, and standing for 1 hour; centrifuging the turbid solution at 8000rpm for 8min, repeating for 3 times, and washing the collected solid with methanol after each centrifugation; and after the centrifugation is finished, drying the solid substance in an oven at 70 ℃ for 12h to obtain a solid substance.
Mixing 5.0g of the solid substance with 2.0g of sulfur powder, adding 60mL of deionized water, and carrying out ultrasonic treatment on the suspension for 1 h; then transferring the suspension into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, heating to 180 ℃, and keeping for 12 hours; after the reaction is finished, naturally cooling the high-pressure reaction kettle to room temperature, collecting a solid product in the kettle body, washing the solid product for 3 times by using deionized water, and drying the solid product in an oven at 80 ℃ for 12 hours.
Putting the dried solid product into a tubular furnace, and heating to 600 ℃ at the speed of 2 ℃/min under the argon atmosphere doped with 3% hydrogen (flow is 200mL/min), and keeping for 2 h; after natural cooling, the obtained solid product is the wastewater treatment material loaded with zinc sulfide, and the loading capacity of the zinc sulfide is about 13 wt%.
The above-obtained wastewater treatment material was observed to have a black appearance.
The obtained wastewater treatment material was subjected to X-ray photoelectron spectroscopy, and the result is shown in FIG. 1, where FIG. 1 is an X-ray photoelectron spectroscopy of the wastewater treatment material provided in example 1 of the present invention.
Example 2
The wastewater treatment material loaded with zinc sulfide prepared in example 1 is used for adsorbing and removing tinidazole, levofloxacin and loratadine, and the specific experimental process is as follows:
100mL of aqueous solution containing tinidazole, levofloxacin and loratadine is prepared in a 250mL conical flask, wherein the concentrations of the tinidazole, the levofloxacin and the loratadine are all 10mg/L, 0.020g of the wastewater treatment material loaded with zinc sulfide prepared in example 1 is added, and the conical flask is placed in a shaking table and shaken at the speed of 180 r/min. The concentrations of tinidazole, levofloxacin and loratadine were measured by liquid chromatography at intervals. The results are shown in Table 1.
Table 1: residual concentration data of organic matter under different adsorption time
Example 3
The wastewater treatment material loaded with zinc sulfide prepared in example 1 is used for activating persulfate to remove tinidazole, levofloxacin and loratadine, and the specific experimental process is as follows:
100mL of aqueous solution containing tinidazole, levofloxacin and loratadine is prepared in a 250mL conical flask, wherein the concentrations of the tinidazole, the levofloxacin and the loratadine are all 10mg/L, 0.040g of potassium hydrogen peroxymonosulfate and 0.020g of the wastewater treatment material loaded with zinc sulfide prepared in the example 1 are added, and the conical flask is placed in a shaking table and vibrated at the rotating speed of 180 r/min. The concentrations of tinidazole, levofloxacin and loratadine were measured by liquid chromatography at intervals. The results are shown in Table 2.
Table 2: residual concentration data of organic matter under different degradation time
Example 4
The stability evaluation was carried out on the wastewater treatment material loaded with zinc sulfide prepared in example 1, specifically as follows:
the aqueous solutions of example 2 and example 3 after 60min treatment were collected and the zinc concentration was determined by inductively coupled plasma mass spectrometry. The results are shown in Table 3.
Table 3: release of zinc in different reaction systems
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A wastewater treatment material comprising: carbon nanotubes and zinc sulfide supported on the carbon nanotubes.
2. The wastewater treatment material according to claim 1, wherein the carbon nanotubes have an outer diameter of 10 to 20 nm; the length of the carbon nano tube is 5-20 mu m.
3. The wastewater treatment material according to claim 1, wherein the content of the zinc sulfide in the wastewater treatment material is not less than 10 wt%.
4. A preparation method of a wastewater treatment material comprises the following steps:
a) mixing the carbon nano tube with a zinc salt solution, then mixing with a dimethyl imidazole solution, and carrying out solid-liquid separation to obtain a solid substance;
the zinc salt solution contains zinc salt, methanol and water; the dimethyl imidazole solution contains dimethyl imidazole and methanol;
b) mixing the solid substance, sulfur powder and water, and heating for reaction to obtain a solid product;
c) and carrying out reduction reaction on the solid product in a hydrogen-containing atmosphere to obtain the wastewater treatment material loaded with zinc sulfide.
5. The preparation method according to claim 4, wherein in the step a), the mass ratio of the carbon nanotubes to the zinc salt to the dimethylimidazole is 5: (1-3): (2-5).
6. The preparation method according to claim 4, wherein in the step a), the mixing speed of the carbon nanotubes and the zinc salt solution is 300-500 rpm; the mixing time of the carbon nano tube and the zinc salt solution is 1-3 h; mixing with the dimethyl imidazole solution under ultrasonic conditions; the mixing time of the dimethyl imidazole solution is 1-2 h.
7. The preparation method according to claim 4, wherein in the step b), the mass ratio of the solid matters to the sulfur powder is (2-5): (5-2).
8. The method of claim 4, wherein in step b), the mixing is performed under ultrasonic conditions; the mixing time is 0.5-2 h; the temperature of the heating reaction is 160-180 ℃; the reaction time is 8-15 h.
9. The method according to claim 4, wherein in step c), the hydrogen content of the hydrogen-containing atmosphere is 3-5%; the temperature of the reduction reaction is 500-700 ℃; the time of the reduction reaction is 1-3 h.
10. A method of wastewater treatment comprising the steps of:
treating organic wastewater by utilizing persulfate and a wastewater treatment material to obtain treated wastewater;
the wastewater treatment material is the wastewater treatment material as defined in any one of claims 1 to 3 or the wastewater treatment material prepared by the preparation method as defined in any one of claims 4 to 9.
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