CN112791700A - Iron-titanium-manganese composite oxide modified carbon nanotube and preparation method and application thereof - Google Patents
Iron-titanium-manganese composite oxide 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 70
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- UWIMQBMUGNMYPA-UHFFFAOYSA-N [Ti].[Mn].[Fe] Chemical compound [Ti].[Mn].[Fe] UWIMQBMUGNMYPA-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 35
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 34
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 16
- 239000011572 manganese Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims abstract description 10
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 229910002090 carbon oxide Inorganic materials 0.000 claims abstract description 8
- 239000002071 nanotube Substances 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 230000032683 aging Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 39
- 239000011259 mixed solution Substances 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 32
- 229910052785 arsenic Inorganic materials 0.000 claims description 20
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 230000002431 foraging effect Effects 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 7
- 150000004706 metal oxides Chemical class 0.000 abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 229910021392 nanocarbon Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 239000003651 drinking water Substances 0.000 description 7
- 235000020188 drinking water Nutrition 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
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- 239000002245 particle Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 206010005003 Bladder cancer Diseases 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 208000007097 Urinary Bladder Neoplasms Diseases 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 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
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- 125000000524 functional group Chemical group 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
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- 201000007270 liver cancer Diseases 0.000 description 1
- 208000014018 liver neoplasm Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000002105 nanoparticle Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 231100001223 noncarcinogenic Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 201000005112 urinary bladder cancer Diseases 0.000 description 1
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- 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
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- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- 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
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Abstract
The invention discloses a ferro-titanium-manganese composite oxide modified carbon nanotube and a preparation method and application thereof. The preparation method of the iron-titanium-manganese composite oxide modified carbon nanotube comprises the following steps: carbon nanotubes, concentrated sulfuric acid, concentrated nitric acid and KMnO4Mixing, reacting, adding water and H2O2Filtering, washing and drying to obtain the carbon oxide nano-tube, mixing with water, adding ferric trichloride hexahydrate, ferrous sulfate heptahydrate and titanium trichloride solution, adding potassium permanganate solution and ammonia water, aging, filtering, washing and drying to obtain the iron-titanium-manganese composite oxide modified nano-carbon tube. The iron-titanium-manganese composite oxide modified carbon nanotube of the invention is made of amorphous carbonThe shaped composite metal oxide is loaded on the surface and pore channels of the porous oxidized carbon nano-tube, and a hydrothermal reaction is adopted, so that the loading rate is high, the use and the storage are convenient, and the effect is durable; the iron-titanium-manganese composite oxide is rich in hydroxyl active sites and has high adsorption rate; has no biological toxicity to human body, safe use and no pollution.
Description
Technical Field
The invention relates to the technical field of environmental protection and chemical separation, in particular to a ferro-titanium-manganese composite oxide modified carbon nanotube and a preparation method and application thereof.
Background
Currently, the problem of arsenic pollution is ubiquitous in the world, the pollution of arsenic to water resources threatens millions of people all over the world seriously, the pollution is reported in many places all over the world, and countries such as China, America, Russia, India, Japan and the like face the problem of arsenic pollution in different degrees. Arsenic is a highly toxic, carcinogenic and mutagenic contaminant, and prolonged exposure to excessive amounts of contaminants in drinking water can lead to skin problems and liver and bladder cancer. In addition, non-carcinogenic effects of arsenic include cardiovascular disease, diabetes, anemia, effects on fertility and the nervous system. The World Health Organization (WHO) and the United States Environmental Protection Agency (USEPA) set the maximum allowable concentration of arsenic in drinking water to 10 ppb. According to the world health organization's guidelines for the contamination of water with arsenic, more than 2 million people in the world are at risk for arsenic at concentrations above the norm, so the problem of disposing of arsenic contamination is imminent. As (III) is more toxic and dangerous than As (V), has higher toxicity than As (V) by tens of times and is more mobile. In addition, it is more difficult to remove as (iii) from water sources by conventional water treatment processes. Thus, oxidation of As (III) to As (V) is a more efficient method of removing As (III) from drinking water to the desired level.
Most chemical oxidants are effective in As (III) oxidation, but they may also produce by-products causing secondary contamination problems. In order to prepare an adsorbent with high efficiency and low cost as arsenite for removing polluted water, the preparation of an efficient adsorption material becomes a hot spot of research and development, and iron oxide and manganese oxide are gradually paid attention and researched as adsorption materials for removing trivalent arsenic in recent years. However, the single metal oxide has a limited processing capability, and thus the double metal oxide is gradually mature in research and application. In addition, the trivalent arsenic can be oxidized by using the nano particles with photocatalytic performance, secondary pollution is not caused in the photocatalytic process, and oxygen can be increasedThe efficiency is improved. TiO commonly used in photocatalytic oxidation process2Exhibit many advantages (e.g., physical and chemical stability, negligible toxicity, photocatalytic properties, ease of preparation and high affinity for arsenic) and have been widely used as effective adsorption and photocatalytic media in environmental remediation due to the use of mild oxidizing agents, the absence of harmful compounds, the ability to combine with other physical and chemical methods, and the option of replacing traditional high energy processing techniques. It has also been shown that manganese oxide, one of the most important oxidants for As (III) oxidation, has been extensively studied due to its cost effectiveness, strong oxidizing power and strong stability. Because two or more metals are used in a combination and each has a synergistic effect on each metal, the bimetallic nano-oxide compound can promote various processes of oxidizing and adsorbing arsenic from an aqueous environment, effectively combine three metal oxides of iron, titanium and manganese together, and improve the oxidizing and adsorbing capacity of trivalent arsenic. In recent years, carbon-based materials (such as activated carbon, carbon nanotubes, and graphene) have attracted research interest of researchers due to their characteristics of large specific surface area, porous property, good thermal stability, high mechanical strength, and the like, and in particular, carbon nanotubes have a large specific surface area and abundant surface functional groups. The carbon-based material and the metal oxide are organically combined to prepare different novel composite materials, so that the adsorption capacity efficiency of the composite materials to pollutants is enhanced. The loading method has various methods, wherein the hydrothermal method can control the formation of material phases, the size and the shape of particle diameters, and finally the product has better dispersibility. Most importantly, the hydrothermal method enables the metal oxide to be loaded on the carbon nano-tube more.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a modified carbon nanotube of iron-titanium-manganese composite oxide.
Another object of the present invention is to provide a fe-ti-mn composite oxide modified carbon nanotube obtained by the above preparation method.
The invention also aims to provide the application of the iron-titanium-manganese composite oxide modified carbon nanotube.
The purpose of the invention is realized by the following technical scheme: a preparation method of a ferrum-titanium-manganese composite oxide modified carbon nanotube comprises the following steps:
(1) mixing Carbon Nanotubes (CNTs), concentrated sulfuric acid and concentrated nitric acid, and adding KMnO4Mixing again, reacting at 50-55 ℃, and stirring at 60-70 ℃ to obtain a mixed solution 1;
(2) diluting the mixed solution 1 obtained in the step (1), and adding H2O2Stirring the solution to obtain a mixed solution 2;
(3) carrying out suction filtration, washing and drying on the mixed solution 2 obtained in the step (2) to obtain an oxidized carbon nanotube;
(4) dispersing the carbon oxide nanotubes obtained in the step (3) in water, adding ferric trichloride hexahydrate, ferrous sulfate heptahydrate and a titanium trichloride solution, and stirring to obtain a mixed solution A; adding a potassium permanganate solution, and stirring to obtain a mixed solution B; dropwise adding ammonia water to keep the pH value of the solution at 8-9;
(5) and (4) aging the solution B after the pH value is adjusted in the step (4), performing suction filtration, washing and drying to obtain the iron-titanium-manganese composite oxide modified carbon nanotube.
The mixing mode in the step (1) is ultrasonic and then stirring.
The ultrasonic time is 10-20 min; preferably for 15 min.
The stirring time is 10-15 min; preferably 10 min.
The mode of remixing in the step (1) is stirring.
The remixing time in the step (1) is 2-3 h; preferably 2 to 2.5 hours.
The amount of the CNTs in the step (1) is 10-12 g/L of the final concentration of the CNTs in concentrated sulfuric acid and concentrated nitric acid.
In the step (1), the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3: 1.
the KMnO in the step (1)4The dosage of the compound is that the final concentration of the compound in a system is 30-45 g/L.
The operation of step (1) is carried out under ice bath conditions.
The reaction time in the step (1) is 3-3.5 h; preferably 3 hours.
The stirring time in the step (1) is 1.5-2 h.
And (2) adopting a constant-temperature water bath to keep the temperature in the step (1).
The stirring in step (1) is preferably magnetic stirring.
And (3) diluting the mixed solution 1 in the step (2) by using deionized water.
The dosage of the deionized water is that the volume ratio of the deionized water to the mixed solution 1 is 2:5, calculating the mixture ratio.
Said H in step (2)2O2The dosage of the solution is that the volume ratio of the solution to the mixed solution 1 is 1-1.2: and 35, calculating the mixture ratio.
Said H in step (2)2O2The concentration of the solution was 30% by volume.
Said H in step (2)2O2The solution was added while stirring.
And (3) stirring for 10-15 min in the step (2).
Washing in the step (3) is washing by respectively adopting deionized water and ethanol in sequence; preferably, deionized water and ethanol are respectively adopted for washing for 2-3 times.
In the step (3), the drying is carried out for 20-24 hours at the temperature of 70-80 ℃.
And (4) grinding the oxidized carbon nano tubes into powder in the step (3).
The water in step (4) is preferably deionized water.
The amount of the water used in the step (4) is that the final concentration of the carbon oxide nanotubes dispersed in the water is 2.5-3 g/L.
The dispersion mode in the step (4) is ultrasonic.
The ultrasonic time is 1-2 h; preferably 1 h.
In the step (4), the dosage of the ferric trichloride hexahydrate is such that the final concentration of the ferric trichloride in the system is 0.03-0.04 mol/L.
In the step (4), the dosage of the ferrous sulfate heptahydrate is such that the final concentration of the ferrous sulfate in the system is 0.01-0.0125 mol/L.
In the step (4), the dosage of the titanium trichloride solution is such that the final concentration of the titanium trichloride in the system is 19-20 g/L.
The concentration of the titanium trichloride solution in the step (4) is 16-18% by mass volume ratio.
The concentration of the potassium permanganate solution in the step (4) is 0.02-0.03 mol/L.
In the step (4), the dosage of the potassium permanganate solution is that the volume ratio of the potassium permanganate solution to the mixed solution A is 1: and 2, calculating the mixture ratio.
The stirring in step (4) is preferably magnetic stirring.
The stirring time in the step (4) is 5-10 min; preferably for 5 min.
The concentration of the ammonia water in the step (4) is 25% by volume.
And (4) adding the potassium permanganate solution and the ammonia water and stirring.
In the step (5), an autoclave is adopted for aging, and no pressurization is carried out.
In the step (5), the aging is carried out for 18-20 h at 130-140 ℃, and the mixture is placed for 5-6 h.
The washing in the step (5) is washing with deionized water; preferably 3 washes.
And (5) drying at 70-80 ℃ for 20-24 h.
A carbon nanotube modified by Fe-Ti-Mn composite oxide is prepared by the preparation method.
The application of the iron-titanium-manganese composite oxide modified carbon nano-tube in absorbing trivalent arsenic.
The application method comprises the following steps: adding the iron-titanium-manganese composite oxide into a water body with over-standard trivalent arsenic content, and adsorbing for 24-36 hours.
The dosage of the iron-titanium-manganese composite oxide is 0.5 g.L-1～3g·L-1。
Compared with the prior art, the invention has the following advantages and effects:
1. the iron-titanium-manganese composite oxide modified carbon nanotube is loaded on the surface and pore channels of the porous oxidized carbon nanotube by amorphous composite metal oxide, and adopts hydrothermal reaction, so that the loading rate is high. The iron-titanium-manganese composite oxide is rich in hydroxyl active sites and high in removal efficiency.
2. The iron-titanium-manganese composite oxide modified carbon nanotube is convenient to use, can be directly applied without adding large-scale equipment and constructing a set of treatment process, is convenient to store, and has a lasting effect.
3. The iron-titanium-manganese composite oxide modified carbon nanotube has no biotoxicity to human body, and is safe and pollution-free to use.
Drawings
Fig. 1 is a scanning electron microscope image of the surface of the fe-ti-mn composite oxide-modified carbon nanotube in example 1.
FIG. 2 is an EDS energy spectrum of a FeTi-Mn composite oxide-modified carbon nanotube in example 1; wherein A is an energy spectrum and B is a corresponding table.
Fig. 3 is an X-ray diffraction pattern of the oxidatively modified carbon nanotubes of example 1.
Fig. 4 is an X-ray diffraction pattern of the fe-ti-mn composite oxide-modified carbon nanotubes of example 1.
Fig. 5 is a statistical chart of the removal rate of as (iii) from the modified carbon nanotubes of fe-ti-mn composite oxide in example 1.
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
(1) Adding CNTs into a beaker containing concentrated sulfuric acid and concentrated nitric acid at a volume ratio of 3:1 according to a final concentration of 10g/L in a system in an ice-water bath (0 ℃), performing ultrasonic treatment for 15min, and continuously stirring for 10 min; then KMnO is added according to the final concentration of 30g/L in the system4Continuously stirring for 2 hours; transferring the obtained mixed solution to a constant-temperature water bath kettle at 50 ℃ for reaction for 3 hours; then, the mixture was magnetically stirred at 65 ℃ for 1.5 hours to obtain a mixed solution 1.
(2) Adding the mixed solution into deionized water according to the proportion of the mixed solution 1 to the deionized water of 2:5 for dilution, and then adding the diluted mixed solution into the deionized water according to the volume ratio of 1:35 for 30 percent in volume ratio under the condition of magnetic stirringH of (A) to (B)2O2Stirring the solution for 10min to obtain a mixed solution 2, filtering the mixed solution 2, and washing the mixed solution 3 times respectively with deionized water and ethanol. Finally, the material is dried for 20h at 80 ℃ to obtain the carbon oxide nano tube and ground into powder,
(3) adding the carbon oxide nano tube into deionized water according to the final concentration of 2.5g/L in the system, carrying out ultrasonic treatment for 1h, adding ferric trichloride hexahydrate to ensure that the concentration of ferric trichloride in the solution is 0.03mol/L, adding ferrous sulfate heptahydrate to ensure that the concentration of ferrous sulfate in the solution is 0.01mol/L, and adding a titanium trichloride solution with the concentration of 16% by mass-volume ratio according to the final concentration of 19.0g/L in the system to obtain a mixed solution A. Stirring the obtained mixed solution A for 5 minutes under magnetic stirring; according to the volume ratio of the potassium permanganate solution to the mixed solution A of 1: 2 adding a potassium permanganate solution with the concentration of 0.02mol/L to obtain a mixed solution B, and stirring the mixed solution B for 5 minutes under magnetic stirring; slowly dropwise adding 25% ammonia water into the mixed solution B to keep the pH of the solution at 8, keeping stirring,
(4) putting the solution B into the lining according to 70-80% of the volume of the lining of the reaction kettle, sealing the high-pressure kettle, keeping the high-pressure kettle at 130 ℃ for 18 hours, and standing for 5 hours for aging; and carrying out suction filtration on the obtained material, washing the material for 3 times by using deionized water, and then drying the material for 20 hours at the temperature of 70-80 ℃ to obtain the iron-titanium-manganese composite oxide modified carbon nanotube.
Fig. 1 is a scanning electron microscope image of the surface of a fe-ti-mn composite oxide modified carbon nanotube. As can be seen from fig. 2, the fe-ti-mn composite oxide modified carbon nanotubes prepared by the above steps are loaded on the carbon nanotubes unevenly, and have a particle size of 50nm to 300nm, because the carbon nanotubes have abundant pores and gaps, the fe-ti-mn composite oxide can be loaded on the carbon nanotubes better, and the average particle size is smaller than that of the fe-ti-mn composite oxide prepared by the conventional hydrothermal method, and the fe-ti-mn composite oxide modified carbon nanotubes are combined with the porous characteristic of the carbon nanotubes, which is beneficial to oxidation and adsorption of more as (iii) on the surface of the material, and more effective oxidation and adsorption of as (iii) in water.
Fig. 2 is an EDS spectrum of the carbon nanotube modified by the fe-ti-mn composite oxide in example 1, and it can be seen from the spectrum and the corresponding table that the atomic ratio of fe, ti, and mn is about 6: 3: 1.
fig. 3 and 4 are X-ray diffraction patterns (XRD) of the carbon oxide nanotubes and the fe-ti-mn composite oxide modified carbon nanotubes, respectively. It can be seen from fig. 3 that the oxidized carbon nanotube before loading the Fe-Ti-Mn composite oxide has a fixed peak, and it can be seen from fig. 4 that the peak strength of the Fe-Ti-Mn composite oxide modified carbon nanotube of example 1 becomes relatively poor, which proves that the Fe-Ti-Mn composite oxide has been loaded on the oxidized carbon nanotube, and a weak peak is observed in the range of about 24 ° to 37 ° indicating that the adsorbent is an amorphous phase, and it can be seen that Fe, Ti and Mn form a complex structure in the adsorbent, which is not a simple mixture, and is beneficial to adsorbing arsenic.
Example 2
As (III) of river water of a river used as raw water of drinking water is about 0.1-0.2 mg.L due to illegal steal and discharge of production enterprises-1The water taking and using safety is seriously threatened, and the pH value of the river water is about 7-7.5 under normal conditions. The method for treating As (III) pollution of the drinking water raw water by using the iron-titanium-manganese composite oxide modified carbon nano-tube prepared in the embodiment 1 comprises the following steps: 2g and L are added after water is taken-1The outlet water of the modified carbon nano-tube of the iron-titanium-manganese composite oxide after detection treatment can meet the drinking water quality standard of less than or equal to 10ppb of As (III). 0.5 g.L-1～1.5g·L-1The effluent after being treated by the iron-titanium-manganese composite oxide meets the drinking water quality standard of less than or equal to 10ppb of As (III).
And (3) testing the processing capacity:
to study the effect of the amount of carbon nanotubes modified by FeTi-Mn composite oxide on the removal rate of As (III), the carbon nanotubes modified by FeTi-Mn composite oxide in example 1 were each added in an amount of 0.5 g.L-1、1g·L-1、1.5g·L-1、2g·L-1、3g·L-1The addition amount of (a) is 200ppb, pH is 7.0, and T is 25 +/-1 ℃, the adsorption reaction time is 24h, and the relationship between the removal rate of (a), (iii) and the addition amount of the iron-titanium-manganese composite oxide modified carbon nano-tubes is shown in figure 5.
As can be seen from FIG. 5, the amount of addition was 0.5 g.L-1～3g·L-1And As: (III) the removal rates are approximately in direct proportion, and the removal rates are all more than 95 percent, so that the residual arsenic concentration is reduced to be less than 10 ppb. The dosage of the iron-titanium-manganese composite oxide modified carbon nano-tube is 0.5 g.L-1、1.0g·L-1The removal rate reaches 97.6 percent and 97.9 percent respectively.
Example 3
The embodiment is different from the embodiment 1 in that the titanium trichloride solution added in the step (2) is the final concentration of 20g/L in the system, the heating and stirring temperature in the step (1) is 60 ℃, and other steps and parameters are the same as the embodiment 1.
The conditions of the removal rate of 10mg/L of As (III) by the Fe-Ti-Mn composite oxide modified carbon nanotube obtained in example 3 were examined, and when the added amount is 3.0 g.L-1In this case, the removal rate reached 97.8%.
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 ferrum-titanium-manganese composite oxide modified carbon nanotube is characterized by comprising the following steps:
(1) mixing carbon nanotube, concentrated sulfuric acid and concentrated nitric acid, and adding KMnO4Mixing again, reacting at 50-55 ℃, and stirring at 60-70 ℃ to obtain a mixed solution 1;
(2) diluting the mixed solution 1 obtained in the step (1), and adding H2O2Stirring the solution to obtain a mixed solution 2;
(3) carrying out suction filtration, washing and drying on the mixed solution 2 obtained in the step (2) to obtain an oxidized carbon nanotube;
(4) dispersing the carbon oxide nanotubes obtained in the step (3) in water, adding ferric trichloride hexahydrate, ferrous sulfate heptahydrate and a titanium trichloride solution, and stirring to obtain a mixed solution A; adding a potassium permanganate solution, and stirring to obtain a mixed solution B; dropwise adding ammonia water to keep the pH value of the solution at 8-9;
(5) and (4) aging the solution B after the pH value is adjusted in the step (4), performing suction filtration, washing and drying to obtain the iron-titanium-manganese composite oxide modified carbon nanotube.
2. The method of claim 1, wherein the carbon nanotubes modified by the iron-titanium-manganese composite oxide,
the amount of the carbon nano-tubes in the step (1) is that the final concentration of the carbon nano-tubes in concentrated sulfuric acid and concentrated nitric acid is 10-12 g/L;
in the step (1), the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 3: 1;
the KMnO in the step (1)4The dosage of the compound is that the final concentration of the compound in a system is 30-45 g/L;
said H in step (2)2O2The dosage of the solution is that the volume ratio of the solution to the mixed solution 1 is 1-1.2: 35, calculating the mixture ratio;
said H in step (2)2O2The concentration of the solution was 30% by volume.
3. The method of claim 1, wherein the carbon nanotubes modified by the iron-titanium-manganese composite oxide,
the amount of the water used in the step (4) is that the final concentration of the carbon oxide nanotubes dispersed in the water is 2.5-3 g/L;
the dosage of the ferric trichloride hexahydrate in the step (4) is such that the final concentration of the ferric trichloride in the system is 0.03-0.04 mol/L;
the dosage of the ferrous sulfate heptahydrate in the step (4) is such that the final concentration of the ferrous sulfate in the system is 0.01-0.0125 mol/L;
the dosage of the titanium trichloride solution in the step (4) is such that the final concentration of the titanium trichloride in the system is 19-20 g/L;
the concentration of the potassium permanganate solution in the step (4) is 0.02-0.03 mol/L;
in the step (4), the dosage of the potassium permanganate solution is that the volume ratio of the potassium permanganate solution to the mixed solution A is 1: and 2, calculating the mixture ratio.
4. The method of claim 1, wherein the carbon nanotubes modified by the iron-titanium-manganese composite oxide,
the mixing mode in the step (1) is ultrasonic and then stirring;
the ultrasonic time is 10-20 min;
the stirring time is 10-15 min;
the re-mixing mode in the step (1) is stirring;
the remixing time in the step (1) is 2-3 h;
the operation of the step (1) is carried out under the ice bath condition;
the reaction time in the step (1) is 3-3.5 h;
the stirring time in the step (1) is 1.5-2 h;
and (2) adopting a constant-temperature water bath to keep the temperature in the step (1).
5. The method of claim 1, wherein the carbon nanotubes modified by the iron-titanium-manganese composite oxide,
diluting the mixed solution 1 in the step (2) by using deionized water;
the dosage of the deionized water is that the volume ratio of the deionized water to the mixed solution 1 is 2:5, calculating the mixture ratio;
said H in step (2)2O2Stirring the solution while adding the solution;
and (3) stirring for 10-15 min in the step (2).
6. The method of claim 1, wherein the carbon nanotubes modified by the iron-titanium-manganese composite oxide,
washing in the step (3) is washing by respectively adopting deionized water and ethanol in sequence;
in the step (3), drying is carried out for 20-24 hours at the temperature of 70-80 ℃;
and (4) grinding the oxidized carbon nano tubes into powder in the step (3).
7. The method of claim 1, wherein the carbon nanotubes modified by the iron-titanium-manganese composite oxide,
the water in the step (4) is deionized water;
the dispersion mode in the step (4) is ultrasonic;
the ultrasonic time is 1-2 h;
the stirring time in the step (4) is 5-10 min;
the concentration of the ammonia water in the step (4) is 25% by volume;
in the step (4), the potassium permanganate solution and the ammonia water are added and stirred simultaneously;
in the step (5), an autoclave is adopted for aging, and no pressurization is carried out;
in the step (5), the aging is carried out for 18-20 h at 130-140 ℃, and the mixture is placed for 5-6 h;
the washing in the step (5) is washing with deionized water;
and (5) drying at 70-80 ℃ for 20-24 h.
8. A carbon nanotube modified by a Fe-Ti-Mn composite oxide, characterized by being prepared by the method of any one of claims 1 to 7.
9. The use of the carbon nanotubes modified by the iron-titanium-manganese composite oxide according to claim 8 in adsorption of trivalent arsenic.
10. Use according to claim 9,
the application method comprises the following steps: adding the iron-titanium-manganese composite oxide into a water body with over-standard trivalent arsenic content, and adsorbing for 24-36 hours;
the dosage of the iron-titanium-manganese composite oxide is 0.5-3 g.L-1。
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