CN112958036A - Zero-valent iron-manganese composite modified carbon nanotube and preparation method and application thereof - Google Patents
Zero-valent iron-manganese composite modified carbon nanotube and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 52
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 34
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 34
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002791 soaking Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229940107700 pyruvic acid Drugs 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims abstract description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 5
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 4
- 239000003651 drinking water Substances 0.000 claims description 20
- 235000020188 drinking water Nutrition 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910002551 Fe-Mn Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000010842 industrial wastewater Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000010802 sludge Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 16
- 238000011282 treatment Methods 0.000 abstract description 4
- 229910017135 Fe—O Inorganic materials 0.000 abstract description 3
- 229910018663 Mn O Inorganic materials 0.000 abstract description 3
- 229910003176 Mn-O Inorganic materials 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 229910000616 Ferromanganese Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
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- 230000015271 coagulation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 108010061951 Methemoglobin Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 208000007475 hemolytic anemia Diseases 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
Images
Classifications
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- 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
- B01J20/0222—Compounds of Mn, Re
-
- 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
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
Abstract
The invention discloses a zero-valent iron-manganese composite modified carbon nanotube and a preparation method and application thereof. The preparation method of the zero-valent iron-manganese composite modified carbon nanotube comprises the following steps: soaking a carbon nanotube in HCL solution, cleaning, adding ammonia water for reaction, cleaning and drying to obtain a carbon nanotube A; carbon nanotubes A, FeCl3And MnSO4Adding the mixture into a reaction solvent to obtain a solution 1; adding NaBH4And (3) solution, reaction, washing, drying and dropwise adding an pyruvic acid solution to prepare the zero-valent iron-manganese composite modified carbon nanotube. The surface of the zero-valent iron-manganese composite modified carbon nanotube consists of loose and porous zero-valent iron and manganese, has large surface area, is rich in hydroxyl (Fe-O, Mn-O) active sites, can be formed by oxidation reaction with nitrate, has strong adaptability and can be used in various water body treatments; the adsorption is fast, and the removal efficiency is high; the material has no toxicity, no pollution and low by-product.
Description
Technical Field
The invention relates to the technical field of environmental protection and chemical separation, in particular to a zero-valent iron-manganese composite modified carbon nanotube and a preparation method and application thereof.
Background
Nitrate is one of main existing forms of nitrogen elements in water environment and is also an important control index of water quality of drinking water. High concentrations of nitrate in drinking water can increase kidney burden and induce diabetes and hemolytic anemia, and long-term drinking can also increase the risk of human beings suffering from methemoglobin and the blue infant syndrome. Part of nitrate can also generate intermediate product nitrite or nitrosamine with greater harmfulness under the action of the reducing environment of the water transmission and distribution pipeline system and the water storage system and the action of nitric acid reducing bacteria in the stomach of a human body, and the two are both confirmed to be carcinogenic, teratogenic and mutagenic substances. The standards for drinking water quality of European Union (80-778EEC) and the standards for drinking water quality of the world health organization stipulate that the nitrate limit is 50mg/L, the Japanese drinking water standards "Water quality of the Water course Standard について" and the standards for Drinking Water quality of the United states (NPDWRs, USEPA) "stipulate that the limit is 10mg/L, and it is stated that the conditions should be allowed to be reduced as much as possible below the limit. The nitrate concentration is less than 10mg/L when surface water is used as a water source and is less than 20mg/L when underground water is used as a water source according to the sanitary standard of domestic drinking water (GB5749-2006) in China.
Nitrate pollution in water bodies can be divided into non-point source pollution and point source pollution according to sources, the non-point source pollution mainly comes from the use of nitrogen fertilizers and sewage irrigation, and the point source pollution mainly comes from domestic sewage discharge, industrial sewage discharge and filtrate leakage of refuse landfill. Nitrate exceeding is caused in more than 400 centralized water supply points in California in the United states, and serious nitrate exceeding is caused in central America, Indian constant river basin, Turkey plain, Italy Romba plain and hilly land. The nitrate pollution of drinking water in China is mainly concentrated in underground water, for example, the average concentration of nitrate in shallow underground water monitoring wells in the urban areas of Jilin city is 76.5mg/L, the average exceeding rate of the nitrate content in 3672 rural water supply projects in Qingdao city is up to 31.3%, the exceeding rate of underground water in Tianjin city is 12.06-18.23%, the average value of the nitrate content in underground water in rural areas of Shandong province is 10.43mg/L, and the proportion of the exceeding samples is 14.15%. With the increasing agricultural and industrial activities, the nitrate pollution in the water environment is continuously increased, and the annual average content of nitrate in groundwater in Hebei province in 2006 + 2014 is increased by 8.42 percent.
At present, research based on nano-iron materials becomes a research hotspot (CN201710896949.8 is a method for removing tap water ions by loading nano-iron on activated carbon, and a preparation method of CN201510130775.5 cellulose modified nano-iron particles). However, the prior art can generate more byproducts such as nitrite nitrogen, ammonia nitrogen and the like, has limited capability of treating nitrate pollution, and has no good response scheme in the face of the increase of the nitrate concentration of the prior underground drinking water.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a zero-valent iron-manganese composite modified carbon nanotube.
The invention also aims to provide the zero-valent iron-manganese composite modified carbon nano-tube obtained by the preparation method.
The invention also aims to provide the application of the zero-valent iron-manganese composite modified carbon nano-tube.
The purpose of the invention is realized by the following technical scheme: a preparation method of a zero-valent iron-manganese composite modified carbon nanotube comprises the following steps:
(1) soaking a carbon nanotube in HCL solution, cleaning, adding ammonia water for reaction, cleaning and drying to obtain a carbon nanotube A;
preferably, the carbon nanotubes in step (1) are crushed and ground to 400 mesh before use, and are soaked in distilled water before use.
Preferably, the concentration of the HCL solution in the step (1) is 0.8-1.0 mol.L-1。
Preferably, the soaking in the step (1) is carried out at 50-60 ℃ for 10-15 min.
Preferably, the soaking of carbon nanotubes in the HCL solution in step (1) is performed under sealed conditions.
Preferably, deionized water is adopted for cleaning in the step (1), and the time is 3-5 min; filtering with 50nm hydrophilic filter membrane before and after washing.
Preferably, the concentration of the ammonia water in the step (1) is 18-20% by volume.
Preferably, the amount of the ammonia water used in the step (1) is a proper amount.
Preferably, the reaction in step (1) is carried out on a shaker at a speed of 60-120r/min for 15 min.
Preferably, the drying in the step (1) is drying for 1-2 hours at 50-60 ℃.
(2) Soaking the carbon nanotube A prepared in the step (1), and soaking the carbon nanotube A, FeCl3And MnSO4Adding the mixture into a reaction solvent to obtain a solution 1; adding NaBH4And (3) solution, reaction, washing, drying and dropwise adding an pyruvic acid solution to prepare the zero-valent iron-manganese composite modified carbon nanotube.
Preferably, the soaking in the step (2) is performed by rinsing and soaking with deionized water for 3-5 min.
Preferably, the amount of the carbon nanotubes A used in the step (2) is 2.0 to 2.4 g.L according to the final concentration of the carbon nanotubes in the system-1And (5) calculating the mixture ratio.
Preferably, the FeCl in step (2)3The amount of the compound is 0.3-0.4 mol.L according to the final concentration of the compound in the system-1And (5) calculating the mixture ratio.
Preferably, step (2)The MnSO4The amount of the compound is 0.1 mol.L according to the final concentration in the system-1And (5) calculating the mixture ratio.
Preferably, the reaction solvent in the step (2) is ethanol solution with a concentration of 30% by volume.
Preferably, the NaBH used in step (2)4The dosage of the solution is calculated according to the proportion of the molar ratio of the solution to iron and manganese in the system being 4-5: 1.
Preferably, the NaBH used in step (2)4The solution is added in N2Dropwise adding under the conditions of protective atmosphere and 60r/min rotating speed, wherein the dropping speed is 5-10 s per 1 mL.
Preferably, the NaBH used in step (2)4The concentration of the solution is 1.2-2.5 mol.L-1。
Preferably, the reaction time in the step (2) is 10-30 min.
Preferably, the washing in the step (2) is washing by sequentially adopting absolute ethyl alcohol and deionized water, and filtering before washing; preferably, the washing is performed 3 times with absolute ethanol and 2 times with deionized water.
Preferably, the filtration is filtration using a 50nm hydrophilic filter membrane.
Preferably, the drying in the step (2) is vacuum drying at-30 to-40 ℃ for 4 to 6 hours.
Preferably, the dosage of the pyruvic acid solution in the step (2) is 2-3 drops of the pyruvic acid solution per 50g of the product.
Preferably, the concentration of the pyruvic acid solution in the step (2) is 98% by volume.
A zero-valent iron-manganese composite modified carbon nanotube is prepared by the preparation method.
The mass ratio of iron to manganese of the zero-valent iron-manganese composite modified carbon nano-tube is 2-4: 1.
the zero-valent iron-manganese composite modified carbon nanotube is applied to adsorbing nitrate.
Preferably, the zero-valent iron-manganese composite modified carbon nanotube is used for treating nitrate-containing drinking water or nitrate industrial wastewater.
Preferably, the nitrate in the nitrate industrial wastewaterThe acid salt is less than or equal to 300 mg.L-1。
Preferably, the concentration of the nitrate in the drinking water containing the nitrate is less than or equal to 100 mg.L-1。
Preferably, the application comprises the following steps: adjusting the pH value of industrial wastewater or drinking water containing nitrate to 6.5-7, adding zero-valent iron-manganese composite modified carbon nano-tubes, adsorbing, adding polyferric sulfate (PFS) into the adsorbed water for precipitation, discharging supernatant, and conventionally treating sludge.
Preferably, the adding amount of the zero-valent iron-manganese composite modified carbon nano-tube is 0.5-5 g.L-1。
Preferably, the adsorption time is 3-6 h.
Preferably, the adding amount of the polymeric ferric sulfate is 30-60 mg.L-1。
Preferably, the precipitation time is 0.3-0.5 h.
Preferably, the adsorption is carried out in a Plug Flow (PFR) or batch (SBR) reactor.
Compared with the prior art, the invention has the following advantages and effects:
1. the surface of the zero-valent iron-manganese composite modified carbon nanotube consists of loose and porous zero-valent iron and manganese, has large surface area, is rich in hydroxyl (Fe-O, Mn-O) active sites, can be formed by oxidation reaction with nitrate, has strong adaptability and can be used in various water body treatments; the adsorption rate is high, and the removal efficiency is high; the material has no toxicity, no pollution and low by-product.
2. The zero-valent iron-manganese composite modified carbon nanotube has simple preparation process, low cost and convenient use.
Drawings
FIG. 1 is a surface scanning electron micrograph of zero-valent ferromanganese.
FIG. 2 is a scanning electron microscope image of the surface of the zero-valent Fe-Mn composite modified carbon nanotube.
FIG. 3 is an energy spectrum and a corresponding table of zero-valent Fe-Mn composite modified carbon nanotubes; wherein A is an energy spectrum and B is a corresponding table.
FIG. 4 is an X-ray diffraction pattern of a zero-valent Fe-Mn composite modified carbon nanotube; wherein A is zero-valent ferro-manganese, and B is zero-valent ferro-manganese composite modified carbon nano-tube.
Fig. 5 is a statistical graph of the nitrate removal rate of the zero-valent iron-manganese composite modified carbon nanotube for drinking water raw water with different nitrate concentrations.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
A preparation method of a zero-valent iron-manganese composite modified carbon nanotube comprises the following steps:
(1) soaking carbon nanotube (available from Youkouu) in distilled water, heating in water bath at 50 deg.C under sealed condition, and adding 0.8 mol/L-1Soaking in HCL solution for 10min, and filtering with 50nm hydrophilic filter membrane; washing with deionized water for 3-5 min, filtering with 50nm hydrophilic filter membrane, adding 18% ammonia water, reacting in a shaker at 60-120r/min for 15min, and filtering again; then washing with deionized water for 3-5 min, and drying to obtain a carbon nanotube A;
(2) washing and soaking the carbon nanotube A prepared in the step (1) with deionized water for 3 min to 5min, and then carrying out carbon nanotube A, FeCl3And MnSO4Adding into 30% ethanol solution (the final concentration of carbon nanotube A in the system is 2.0 g.L)-1，FeCl3The final concentration in the system was 0.3 mol. L-1，MnSO4The final concentration in the system was 0.1 mol. L-1In (1). In N2Adding NaBH in the condition of protective atmosphere and stirring at the rotating speed of 60r/min4Solution (FeCl)3、MnSO4、NaBH4The molar ratio in the system is 4:1), and fully reacting for 30min after completely dropwise adding; filtering the carbon nano-tube by adopting a 50nm hydrophilic filter membrane, washing the carbon nano-tube by absolute ethyl alcohol for three times, washing the carbon nano-tube by deionized water for two times, filtering the carbon nano-tube by using a 50nm hydrophilic filter membrane, drying the carbon nano-tube at the temperature of minus 30 ℃ in vacuum for constant weight, and dripping 2 to 3 drops of pyruvic acid solution (purchased from Michelin company) with the concentration of 98 percent by volume on the surface of every 50g of the pyruvic acid solution to prepare the zero-valent iron-manganese composite modified carbon nano-tube.
Fig. 1 is a scanning electron microscope image of the surface of zero-valent ferro-manganese, and fig. 2 is a scanning electron microscope image of the surface of the zero-valent ferro-manganese composite modified carbon nanotube. As can be seen from fig. 1 and 2, the particle size of the simple substance of iron and manganese in fig. 1 is about 20nm to 150nm, the particle size of the zero-valent iron and manganese composite modified carbon nanotube in fig. 2 is about 20nm to 60nm, the surface is clean after modification, and no impurities exist; the composite modified carbon nanotube is favorable to changing the magnetic aggregation of iron and manganese grains. The zero-valent iron-manganese composite modified carbon nanotubes shown in fig. 2 are integrally distributed in a flocculent shape, and compared with simple substance iron-manganese loose, the carbon nanotubes can obtain larger specific surface area and more gaps, can lock more pollutants, and are more favorable for adsorption reaction.
Fig. 3 is an energy spectrum and a corresponding table of the zero-valent fe-mn composite modified carbon nanotube in example 1. As can be seen from the energy spectrum and the corresponding table, the atomic ratio of carbon, iron and manganese is about 3:1:1, the combination is good, and the ratio is uniform.
Fig. 4 is an X-ray diffraction pattern of a zero-valent iron-manganese and zero-valent iron-manganese composite modified carbon nanotube, wherein a is an X-ray diffraction pattern of zero-valent iron-manganese, the carbon nanotube a is omitted from the step (2), and B is an X-ray diffraction pattern of the zero-valent iron-manganese composite modified carbon nanotube prepared in example 1. The zero-valent iron-manganese composite modified carbon nanotube has Mn-O diffraction peak at 65.8 deg, Fe-O diffraction peak at 46.2 deg, deviated peak value and amorphous shape, and thus has relatively small grain size.
Example 2
The nitrate concentration of underground water and surface water as the raw water of drinking water in the north is up to 100-150 mg.L due to industrial production and agricultural chemical fertilizer abuse-1And threatens water taking and using safety for a long time. Meanwhile, the pH value of the river water is about 7-7.5. The zero-valent iron-manganese composite modified carbon nanotube electrode electrolysis method of example 1 is adopted to treat the nitrate pollution of the raw drinking water, and the specific process is as follows: after water is taken, the water is led to a neutralization pond, and the pH value is adjusted to 6.5. 2 g.L is added into an adsorption tank-1The zero-valent iron-manganese composite modified carbon nanotube is fully mixed and subjected to adsorption reaction for 6 hours by adopting an intermittent reactor. Then adding 50 mg.L-1The PFS coagulant enters a subsequent coagulation sedimentation link of a water plant for sedimentation for 0.5h, and the zero-valent iron-manganese composite modified carbon nano-tube adsorbed with the nitrate is subjected to sedimentationAnd (4) separating. The effluent after detection treatment can meet the nitrate concentration less than or equal to 20 mg.L-1The water quality standard of the drinking water is that the pH can be stabilized at 7.5-8. In the range of
To investigate the influence of nitrate concentration on the removal rate, the nitrate concentration in the raw water to be treated was controlled to 80 mg.L-1、100mg·L-1、120mg·L-1、140mg·L-1、160mg·L-1(ii) a The pH value is 7.0, the T is 25 +/-1 ℃, and the adsorption reaction time is 3 h. The method comprises the following specific steps: adjusting the pH value of drinking water with different nitrate concentrations to 7.0, and then mixing the zero-valent iron-manganese composite modified carbon nano-tube according to the proportion of 1.2 g.L-1The adding amount of the flocculant is added into water to be treated in a dry adding mode, the water is subjected to adsorption reaction for 3 hours, the water after the adsorption reaction enters a sedimentation tank, simultaneously, a PFS coagulant of 20 mg.L < -1 > is added for sedimentation for 40 hours, and the concentration of nitrate in the supernatant is detected. The relationship between the nitrate removal rate and the raw water nitrate concentration is shown in fig. 5. Nitrate concentration is less than or equal to 140.0 mg.L-1The concentration of the nitrate in the treated effluent is less than or equal to 20.0 mg.L < -1 >, and the concentration of the nitrate is more than 140 mg.L-1(＝160mg·L-1) In time, the concentration of the nitrate in the treated effluent can not reach the water quality standard of drinking water. Nitrate concentration 160 mg.L-1The treatment time needs to be prolonged to 6 hours, so that the concentration of the nitrate in the treated effluent is less than or equal to 20 mg.L-1However, the carbon nanotube particles may be dissolved and dispersed in the reaction time, the solution is highly turbid in appearance, and the load of subsequent processes such as coagulation precipitation and filtration is increased, so that the dosage of the poly-coagulated ferric sulfate is increased to 50-60 mg.L-1More preferably. In addition, as shown in fig. 5, the zero-valent iron-manganese composite modified carbon nanotube obtained after the carbon nanotube is added has higher removal rate.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a zero-valent iron-manganese composite modified carbon nanotube is characterized by comprising the following steps:
(1) soaking a carbon nanotube in HCL solution, cleaning, adding ammonia water, reacting, cleaning and drying to obtain a carbon nanotube A;
(2) soaking the carbon nanotube A prepared in the step (1), and soaking the carbon nanotube A, FeCl3And MnSO4Adding the mixture into a reaction solvent to obtain a solution 1; adding NaBH4And (3) solution, reaction, washing, drying and dropwise adding an pyruvic acid solution to prepare the zero-valent iron-manganese composite modified carbon nanotube.
2. The method of claim 1, wherein the zero-valent Fe-Mn composite modified carbon nanotube is prepared by the following steps,
the concentration of the HCL solution in the step (1) is 0.8-1.0 mol.L-1；
The soaking in the step (1) is carried out for 10-15 min at the temperature of 50-60 ℃;
in the step (1), deionized water is adopted for cleaning for 3-5 min; filtering with 50nm hydrophilic filter membrane before and after cleaning;
the reaction in the step (1) is carried out on a shaking table for 15min at the rotating speed of 60-120 r/min.
3. The method of claim 1, wherein the zero-valent Fe-Mn composite modified carbon nanotube is prepared by the following steps,
the carbon nano-tubes in the step (1) are crushed and ground to 400 meshes before use, and are soaked in distilled water before use;
the carbon nanotubes soaked in the HCL solution in the step (1) are soaked under a sealed condition;
the concentration of the ammonia water in the step (1) is 18-20% by volume ratio;
the carbon nanotubes soaked in the HCL solution in the step (1) are soaked under a sealed condition;
the drying in the step (1) is drying, and drying is carried out for 1-2 hours at 50-60 ℃.
4. The method of claim 1, wherein the zero-valent Fe-Mn composite modified carbon nanotube is prepared by the following steps,
the amount of the carbon nanotube A in the step (2) is 2.0-2.4 g.L according to the final concentration of the carbon nanotube A in a system-1Calculating the mixture ratio;
the FeCl in the step (2)3The amount of the compound is 0.3-0.4 mol.L according to the final concentration of the compound in the system-1Calculating the mixture ratio;
MnSO in the step (2)4The amount of the compound is 0.1 mol.L according to the final concentration in the system-1Calculating the mixture ratio;
the NaBH in the step (2)4The dosage of the solution is 0.2-0.5 mol.L according to the final concentration of the solution in the system-1Calculating the mixture ratio;
in the step (2), the dosage of the pyruvic acid solution is 2-3 drops of the pyruvic acid solution per 50g of the product.
5. The method of claim 1, wherein the zero-valent Fe-Mn composite modified carbon nanotube is prepared by the following steps,
soaking in the step (2) by using deionized water for washing and soaking for 3-5 min;
the reaction solvent in the step (2) is an ethanol solution with the concentration of 30% by volume;
the NaBH in the step (2)4The solution is added in N2Dropwise adding under the conditions of protective atmosphere and 60r/min rotating speed, wherein the dropping speed is 5-10 s per 1 mL;
the NaBH in the step (2)4The concentration of the solution is 0.2-0.5 mol.L-1；
The reaction time in the step (2) is 10-30 min;
washing in the step (2) is washing by sequentially adopting absolute ethyl alcohol and deionized water, and filtering before washing;
the filtration is carried out by adopting a 50nm hydrophilic filter membrane;
the drying in the step (2) is vacuum drying at-30 to-40 ℃ for 4 to 6 hours;
the concentration of the pyruvic acid solution in the step (2) is 98% by volume.
6. A zero-valent iron-manganese composite modified carbon nanotube, characterized by being prepared by the preparation method of any one of claims 1 to 5.
7. The zero-valent iron-manganese composite modified carbon nanotube according to claim 6, wherein the iron-to-manganese mass ratio of the zero-valent iron-manganese composite modified carbon nanotube is 2 to 4: 1.
8. the use of the zero-valent iron-manganese composite modified carbon nanotube of claim 6 or 7 in adsorbing nitrate.
9. The application of claim 8, wherein the application is to use the zero-valent iron-manganese composite modified carbon nanotubes for treating nitrate-containing drinking water or nitrate industrial wastewater.
10. The use according to claim 8,
nitrate in the nitrate industrial wastewater is less than or equal to 300 mg.L-1；
The concentration of nitrate in the drinking water containing nitrate is less than or equal to 100 mg.L-1；
The application comprises the following steps: adjusting the pH value of industrial wastewater or drinking water containing nitrate to 6.5-7, adding zero-valent iron-manganese composite modified carbon nano-tubes, adsorbing, adding polyferric sulfate into the adsorbed water for precipitation, discharging supernatant, and conventionally treating sludge;
the dosage of the zero-valent iron-manganese composite modified carbon nano-tube is 0.5-5 g.L-1；
The adsorption time is 3-6 h;
the adding amount of the polymeric ferric sulfate is 30-60 mg.L-1；
The precipitation time is 0.3-0.5 h;
the adsorption is carried out in a plug flow or batch reactor.
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