CN114130417A - Preparation method of three-dimensional composite material for oily wastewater treatment - Google Patents
Preparation method of three-dimensional composite material for oily wastewater treatment Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 56
- 239000011165 3D composite Substances 0.000 title claims abstract description 22
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000000243 solution Substances 0.000 claims abstract description 87
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- 150000003839 salts Chemical class 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 229920000767 polyaniline Polymers 0.000 claims abstract description 27
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 230000008021 deposition Effects 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 230000010355 oscillation Effects 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 239000011159 matrix material Substances 0.000 claims description 22
- 239000004814 polyurethane Substances 0.000 claims description 22
- 229920002635 polyurethane Polymers 0.000 claims description 22
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 19
- 239000004202 carbamide Substances 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 229920000877 Melamine resin Polymers 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 17
- 239000002351 wastewater Substances 0.000 abstract description 8
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 230000001360 synchronised effect Effects 0.000 abstract description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 39
- 239000002657 fibrous material Substances 0.000 description 33
- -1 hydroxide modified activated carbon Chemical class 0.000 description 27
- 238000000926 separation method Methods 0.000 description 22
- 238000006731 degradation reaction Methods 0.000 description 19
- 230000015556 catabolic process Effects 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 18
- 238000000151 deposition Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 10
- 239000003344 environmental pollutant Substances 0.000 description 9
- 231100000719 pollutant Toxicity 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000356 contaminant Substances 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
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- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000013172 zeolitic imidazolate framework-7 Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 230000036541 health Effects 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002569 water oil cream Substances 0.000 description 1
- 238000009736 wetting Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B01J35/58—
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
Abstract
The invention discloses a preparation method of a layered double hydroxide modified three-dimensional composite material for oily wastewater treatment, which comprises the following steps: (1) immersing a substrate material into an aniline polymerization solution, and performing oscillation deposition to obtain a polyaniline modified substrate; (2) placing the modified substrate in a tubular furnace, heating and calcining to obtain a composite material with a nitrogen-doped carbon layer on the surface; (3) and (2) immersing the composite material into an aqueous solution containing divalent metal salt, trivalent metal salt and alkaline substances, and transferring the mixed solution into a reaction kettle for hydrothermal reaction to obtain the layered double hydroxide modified three-dimensional composite material. The three-dimensional composite material prepared by the invention can realize good synchronous removal effect on emulsified oil drops and organic pollutants in oily wastewater, has excellent mechanical properties and can be recycled repeatedly. The method is simple and easy to implement, strong in controllability and low in cost.
Description
Technical Field
The invention relates to the field of inorganic material preparation, in particular to a preparation method of a layered double hydroxide modified three-dimensional composite material for oily wastewater treatment.
Background
The frequent occurrence of oil leakage events and the oily wastewater discharged in industrial production cause the pollution of water body oil to become a great environmental problem of global concern. Super wetting materials are considered one of the most desirable oil-water separation materials because they take advantage of the distinct affinity of surfaces for oil and water to selectively wet one of the phases of an oil-water mixture and prevent the other phase from passing through. Many researchers have carried out productive work in the field, but due to the defects of small pore diameter, low porosity, short permeation channel and the like of the separation membrane, the separation material is easy to adsorb oil drops and surfactants in the operation process, so that the channel blockage is caused, and the separation flux is greatly reduced. In addition, various harmful water-soluble organic substances (dyes, antibiotics, pesticides and the like) are generally present in the oily wastewater, and also pose a great threat to the ecological environment and human health. The patent with the application number of 201911376354.5 discloses a preparation method of a super-durable hydrophobic three-dimensional porous oil-water separation sponge material, which comprises the following steps: the sponge material is endowed with high hydrophobicity and mechanical durability by soaking and curing treatment, and the continuous oil-water separation capability of the sponge material is improved. The patent with the application number of 202110365853.5 discloses a preparation method of a superhydrophobic ZIF-7 composite polysulfone three-dimensional porous oil-water separation material, which comprises the following steps: the three-dimensional oil-water separation material is obtained by using the polysulfone chloride, the ZIF-7 particles, the pore-forming agent and a freeze-drying process, and has the capability of treating oil-water mixtures. The oil-water separation materials have no obvious improvement on the treatment flux of oil-water mixtures and can be used for treating oily wastewaterWater soluble organic substanceThere is substantially no removal effect. Therefore, aiming at the problem that the insoluble oil stain and the soluble organic pollutant in the oily wastewater are difficult to treat, a novel oil-water separation material is needed to be developed to treat the oil stain in the water,and (3) carrying out catalytic degradation on organic pollutants dissolved in water.
Layered Double Hydroxides (LDH) are hydrotalcite compounds having exchangeable anions between layers, and the composition can be represented by the following general formula: [ M ] A2+ 1-xM3+ x(OH)2](An-)x/n·mH2O, wherein M2+、M3+Respectively divalent and trivalent metal cations, A, located in the octahedral voids of the host laminan-Is an anion which can be stably present between layers. LDH shows hydrophilicity, and chemical components on LDH main body laminates can be reasonably regulated and controlled, so that the LDH has great potential in the fields of catalysis and the like. Therefore, uniform, dense and stable LDH growth on the surface of the matrix by a specific method is essential in the fields of oil-water separation, catalytic degradation and other frontiers.
Disclosure of Invention
Aiming at the defects of the existing oily wastewater treatment method, the invention provides a preparation method of a layered double hydroxide modified three-dimensional composite material for oily wastewater treatment. The method is simple and feasible and is suitable for industrial production; when the prepared composite material is used for treating oily wastewater, the composite material has the functions of oil-water separation and catalytic degradation, and has the advantages of large oil-water separation treatment capacity, high efficiency, high catalytic degradation speed, good effect and reusability.
A preparation method of a layered double hydroxide modified three-dimensional composite material for oily wastewater treatment comprises the following steps:
(1) immersing a proper matrix material into an aniline polymerization solution, and performing oscillation deposition to obtain a polyaniline modified matrix;
(2) placing the modified substrate obtained in the step (1) in a tubular furnace, heating and calcining to obtain a composite material with a nitrogen-doped carbon layer on the surface;
(3) and (3) immersing the composite material obtained in the step (2) into an aqueous solution containing divalent metal salt, trivalent metal salt and alkaline substances, and transferring the mixed solution into a reaction kettle for hydrothermal reaction to obtain the three-dimensional composite material modified by the layered double hydroxide.
Preferably, the matrix material in step (1) is one of melamine sponge, polyurethane sponge, or activated carbon fiber.
Preferably, the concentration of the dilute hydrochloric acid in the aniline solution in the step (1) is 0.1-2mol/L, and more preferably 0.5-1 mol/L; the volume ratio of the aniline to the dilute hydrochloric acid is 1:10-50, and the preferred volume ratio is 1: 10-30; the concentration of the ammonium persulfate solution is 1-10mol/L, and more preferably 3-7 mol/L.
Preferably, the modified substrate in the step (2) is placed in a tubular furnace for heating and calcining, the heating rate is adjustable and is 3-10 ℃/min, the calcining temperature is 200-800 ℃, and the calcining time is 2-8 h; further preferably, the heating rate is 5 ℃/min, the calcination temperature is 400-.
Preferably, the divalent metal ion in the divalent metal salt in the step (3) is Co2+、Cu2+、Fe2+、Ni2+、Mg2+One or two kinds of metal ions, and more preferably, the divalent metal ion in the divalent metal salt is Co2+、Fe2+、Ni2+、Mg2+One or two of metal ions; the trivalent metal ion in the trivalent metal salt is A13+、Fe3+One or two of them; the anions of the divalent metal salt and the trivalent metal salt are Cl-、NO3 -、SO4 2-、CO3 2-Wherein the anion of the divalent metal salt or the trivalent metal salt is Cl-、NO3 -、SO4 2-One or two of them.
Preferably, the alkaline substance is urea, ammonia water or sodium hydroxide. Further preferred is urea or aqueous ammonia. The urea or ammonia water can slowly release hydroxide radicals in the reaction process, provide necessary alkaline environment for the precipitation of metal ions, ensure that LDH growth elements have sufficient time to interact with the surface of the matrix, and further continuously nucleate and grow. The alkaline material cannot be a strongly alkaline material such as sodium hydroxide, since sodium hydroxide is more basic and reacts rapidly with the metal salt to nucleate. The LDH lamella size is smaller due to the larger number of the cores; too fast nucleation results in the nuclei not producing good interaction with the matrix surface, hindering LDH growth on its surface.
Preferably, in the step (3), the total concentration of the divalent metal salt and the trivalent metal salt is 0.01-0.5 mol/L; in the mixed solution of the divalent metal salt and the trivalent metal salt, the molar ratio of the divalent metal salt to the trivalent metal salt is 1: 0.5 to 4; the molar mass ratio of the total amount of the divalent metal salt and the trivalent metal salt to the alkaline substance is 1: 1-10. Further preferably, the total concentration of the divalent metal salt and the trivalent metal salt is 0.05-0.25 mol/L; the molar ratio of the divalent metal salt to the trivalent metal salt is 1: 1-3; the molar mass ratio of the total amount of the divalent metal salt and the trivalent metal salt to the alkaline substance is 1: 2-6.
Preferably, the hydrothermal reaction in step (3) is carried out at a temperature of 90-110 ℃ for a period of 3-24 hours. Further preferably, the temperature of the hydrothermal reaction is 90-110 ℃, and the time duration is 6-18 h. The preferred hydrothermal reaction conditions favor the formation of regular and densely distributed LDH micron sheets on the surface of a three-dimensional matrix: the decomposition of alkaline substances is not facilitated due to too low temperature, and the excessive decomposition of the alkaline substances is caused due to too high temperature; meanwhile, the hydrothermal time needs to be controlled within a proper range, the hydrothermal time is short, the content of trivalent metal in the LDH laminate is high, the LDH is seriously agglomerated if the hydrothermal time is long, and the LDH is easy to fall off from the surface of the matrix.
Preferably, the time of the oscillating deposition in the step (1) is 1 to 12 hours. Further preferably, the time of the oscillating deposition is 3-9 h. Through oscillation deposition, a layer of polyaniline is formed on the surface of the substrate, and a nitrogen-doped carbon layer generated after calcination is beneficial to anchoring of LDH growth elements, so that dense LDH micron sheets are synthesized on the surface of the substrate.
When the layered double hydroxide modified three-dimensional composite material obtained by the preparation method provided by the invention is used for oil-water separation, the oil-water separation treatment capacity is large, the separation efficiency is high, and the treatment capacity of the oil-water emulsion can reach 4.16 multiplied by 10 for the oil-water separation oil-in-water emulsion which is stable to the surfactant difficult to treat6L m-2h-1bar-1Is divided intoThe separation efficiency can reach 98.71 percent. When the catalyst is used for catalytic degradation, different types of organic pollutants (drugs, phenols or dyes) can be well removed. The oil-water separation process and the catalytic degradation process are synchronously carried out by combining a peristaltic pump, and the three-dimensional composite material prepared by the method can achieve excellent synchronous treatment effect on oil drops and water-soluble pollutants in the oily wastewater.
Compared with the prior art, the invention has the following advantages:
1. the three-dimensional matrix material is optimized, the surface of the three-dimensional matrix material is modified, the roughness and the super-hydrophilicity are endowed, the defects of high energy consumption and low efficiency in the traditional oily wastewater treatment process are overcome, and the problems of oil drop blockage and easy pollution of the hydrophilic surface in the oil-water separation process are also reduced.
2. The method utilizes the nitrogen-doped carbon layer deposited on the surface of the substrate to induce the LDH to perform nucleation growth on the surface of the modified substrate, thereby overcoming the problem of heterogeneity of the LDH growth on the surface of the substrate. The method is simple and convenient to operate and is widely applicable.
3. The uniform and mild growth environment provided by the invention is beneficial to synthesizing LDH with regular and dense appearance on the surface of the matrix, and the hydrophilicity and roughness of LDH laminates and transition metal catalytic active sites between the laminates are fully utilized, so that the three-dimensional material has the functions of oil-water separation and catalytic degradation, and can achieve excellent synchronous treatment effect on oil drops and water-soluble pollutants in oily wastewater.
Drawings
FIG. 1 is an XRD pattern of LDH-modified activated carbon fibers prepared in example 1;
FIG. 2 is an SEM photograph of LDH-modified activated carbon fibers prepared in example 1;
FIG. 3 is a photograph showing the water contact angle and the underwater oil contact angle of the material prepared in example 1;
FIG. 4 is a graph showing the degradation effect of the material prepared in example 1 on bisphenol A, a soluble contaminant;
FIG. 5 is an SEM image of LDH-modified activated carbon fibers prepared in example 2;
FIG. 6 is an SEM photograph of LDH-modified activated carbon fibers prepared in example 3;
FIG. 7 is an SEM photograph of LDH-modified activated carbon fibers prepared in example 4;
FIG. 8 is an SEM photograph of LDH-modified activated carbon fibers prepared in example 10;
FIG. 9 is an SEM photograph of LDH-modified activated carbon fibers prepared in example 11;
FIG. 10 is an SEM image of LDH-modified activated carbon fibers prepared in example 12;
fig. 11 is an SEM image of the LDH-modified activated carbon fiber prepared in comparative example 1.
Detailed Description
The invention is further described below with reference to the figures and examples.
Example 1:
2.3mL of aniline was added to 50mL of a 1mol/L dilute hydrochloric acid solution, and 5.8g of ammonium persulfate was added to another dilute hydrochloric acid solution of the same concentration, and the two solutions were mixed to form an aniline polymer solution. And (2) immersing the activated carbon fiber into an aniline polymerization solution, oscillating and depositing for 6 hours to obtain polyaniline modified activated carbon fiber, then placing the polyaniline modified activated carbon fiber in a tubular furnace, heating to 400 ℃, and calcining for 4 hours to obtain the activated carbon fiber with a nitrogen-doped carbon layer on the surface.
To 50mL of deionized water, 0.2249g of CoSO was added4、0.6901gMgSO4、0.4gAl2(SO4)3And 2.592g of urea are stirred and dissolved, the surface modified activated carbon fiber is soaked into the solution, the system is transferred to a reaction kettle, and the reaction kettle is placed into a vacuum oven to be crystallized for 12 hours at the temperature of 100 ℃, so that the activated carbon fiber material modified by the layered double hydroxide is obtained.
The XRD spectrum of the layered double hydroxide modified activated carbon fiber material prepared in this example is shown in fig. 1. As can be seen, the positions of the diffraction peaks of the product are consistent with the typical hydrotalcite-like crystal phase (JCPDS PDF #51-0045), which indicates that the double metal hydroxide is indeed synthesized on the surface of the matrix and has higher crystallinity.
An SEM photograph of the layered double hydroxide-modified activated carbon fiber material prepared in this example is shown in fig. 2. It can be seen that LDH micron sheets uniformly and densely grow on the surface of the activated carbon fiber.
The test photographs of the contact angle of the layered double hydroxide modified activated carbon fiber material prepared in this example to water and the contact angle to oil under water are shown in fig. 3. As can be seen, the three-dimensional composite material has super-hydrophilicity and underwater super-lipophobicity.
The degradation effect of the layered double hydroxide modified activated carbon fiber material prepared by the embodiment on the soluble pollutant bisphenol A is shown in FIG. 4, and 100% of pollutants can be removed within 16 min. It can be seen that the three-dimensional composite material has excellent catalytic degradation effect on pollutants.
Example 2:
2.3mL of aniline was added to 50mL of a 1mol/L dilute hydrochloric acid solution, and 5.8g of ammonium persulfate was added to another dilute hydrochloric acid solution of the same concentration, and the two solutions were mixed to form an aniline polymer solution. And (2) immersing the activated carbon fiber into an aniline polymerization solution, oscillating and depositing for 6 hours to obtain polyaniline modified activated carbon fiber, then placing the polyaniline modified activated carbon fiber in a tubular furnace, heating to 400 ℃, and calcining for 4 hours to obtain the activated carbon fiber with a nitrogen-doped carbon layer on the surface.
To 50mL of deionized water, 0.1125g of CoSO was added4、0.3451gMgSO4、0.2gAl2(SO4)3And 1.296g of urea are stirred and dissolved, the activated carbon fiber with modified surface is immersed into the solution, the system is moved to a reaction kettle and is put into a vacuum oven to be crystallized for 12 hours at the temperature of 100 ℃, and the activated carbon fiber material modified by the layered double hydroxide is obtained.
The XRD spectrum of the layered double hydroxide modified activated carbon fiber material prepared in this example is similar to that of fig. 1. The SEM photograph of the layered double hydroxide modified activated carbon fiber material prepared in this example is shown in fig. 5, and it can be seen that LDH micrometer pieces are uniformly and densely grown on the surface of the activated carbon fiber. The super-hydrophilicity and underwater super-lipophobicity of the layered double hydroxide modified activated carbon fiber material prepared in the embodiment are similar to those of fig. 3. The catalytic degradation effect of the layered double hydroxide modified activated carbon fiber material prepared in this example on the contaminant bisphenol a is similar to that in fig. 4.
Example 3:
2.3mL of aniline was added to 50mL of a 1mol/L dilute hydrochloric acid solution, and 5.8g of ammonium persulfate was added to another dilute hydrochloric acid solution of the same concentration, and the two solutions were mixed to form an aniline polymer solution. And (2) immersing the activated carbon fiber into an aniline polymerization solution, oscillating and depositing for 6 hours to obtain polyaniline modified activated carbon fiber, then placing the polyaniline modified activated carbon fiber in a tubular furnace, heating to 400 ℃, and calcining for 4 hours to obtain the activated carbon fiber with a nitrogen-doped carbon layer on the surface.
To 50mL of deionized water, 0.2249g of CoSO was added4、0.6901gMgSO4、0.4gAl2(SO4)3And 1.944g of urea are stirred and dissolved, the surface modified activated carbon fiber is immersed into the solution, the system is moved to a reaction kettle, and the system is put into a vacuum oven to be crystallized for 12 hours at 100 ℃, so that the activated carbon fiber material modified by the layered double hydroxide is obtained.
The XRD spectrum of the layered double hydroxide modified activated carbon fiber material prepared in this example is similar to that of fig. 1. The SEM photograph of the layered double hydroxide modified activated carbon fiber material prepared in this example is shown in fig. 6, and it can be seen that LDH micrometer pieces are uniformly and densely grown on the surface of the activated carbon fiber. The super-hydrophilicity and underwater super-lipophobicity of the layered double hydroxide modified activated carbon fiber material prepared in the embodiment are similar to those of fig. 3. The catalytic degradation effect of the layered double hydroxide modified activated carbon fiber material prepared in this example on the contaminant bisphenol a is similar to that in fig. 4.
Example 4:
2.3mL of aniline was added to 50mL of a 1mol/L dilute hydrochloric acid solution, and 5.8g of ammonium persulfate was added to another dilute hydrochloric acid solution of the same concentration, and the two solutions were mixed to form an aniline polymer solution. And (2) immersing the activated carbon fiber into an aniline polymerization solution, oscillating and depositing for 6 hours to obtain polyaniline modified activated carbon fiber, then placing the polyaniline modified activated carbon fiber in a tubular furnace, heating to 400 ℃, and calcining for 4 hours to obtain the activated carbon fiber with a nitrogen-doped carbon layer on the surface.
To 50mL of deionized water, 0.2249g of CoSO was added4、0.6901gMgSO4、0.4gAl2(SO4)3And 2.592g of urea are stirred and dissolved, the surface modified activated carbon fiber is soaked into the solution, the system is transferred to a reaction kettle, and the reaction kettle is placed into a vacuum oven to be crystallized for 6 hours at the temperature of 100 ℃, so that the activated carbon fiber material modified by the layered double hydroxide is obtained.
The XRD spectrum of the layered double hydroxide modified activated carbon fiber material prepared in this example is similar to that of fig. 1. The SEM photograph of the layered double hydroxide modified activated carbon fiber material prepared in this example is shown in fig. 7, and it can be seen that LDH micrometer pieces are uniformly and densely grown on the surface of the activated carbon fiber. The super-hydrophilicity and underwater super-lipophobicity of the layered double hydroxide modified activated carbon fiber material prepared in the embodiment are similar to those of fig. 3. The catalytic degradation effect of the layered double hydroxide modified activated carbon fiber material prepared in this example on the contaminant bisphenol a is similar to that in fig. 4.
Example 5:
2.8mL of aniline was added to 50mL of 0.5mol/L dilute hydrochloric acid solution, and 6.2g of ammonium persulfate was added to another dilute hydrochloric acid solution of the same concentration, and the two solutions were mixed to form an aniline polymer solution. And (2) immersing the activated carbon fiber into an aniline polymerization solution, oscillating and depositing for 12h to obtain polyaniline modified activated carbon fiber, then placing the polyaniline modified activated carbon fiber in a tubular furnace, heating to 400 ℃, and calcining for 3h to obtain the activated carbon fiber with a nitrogen-doped carbon layer on the surface.
To 50mL of deionized water, 0.45g of FeSO was added4、0.44gMgSO4、0.8gAl2(SO4)3And 2.592g of urea are stirred and dissolved, the surface modified activated carbon fiber is soaked in the solution, the system is transferred to a reaction kettle, and the system is placed into a vacuum oven to be crystallized for 6 hours at the temperature of 110 ℃, so that the activated carbon fiber material modified by the layered double hydroxide is obtained.
The XRD spectrum of the layered double hydroxide modified activated carbon fiber material prepared in this example is similar to that of fig. 1. The SEM photograph of the layered double hydroxide modified activated carbon fiber material prepared in this example is similar to that of fig. 2. The super-hydrophilicity and underwater super-lipophobicity of the layered double hydroxide modified activated carbon fiber material prepared in the embodiment are similar to those of fig. 3. The catalytic degradation effect of the layered double hydroxide modified activated carbon fiber material prepared in this example on the contaminant bisphenol a is similar to that in fig. 4.
Example 6:
2.3mL of aniline was added to 50mL of a 1mol/L dilute hydrochloric acid solution, and 5.8g of ammonium persulfate was added to another dilute hydrochloric acid solution of the same concentration, and the two solutions were mixed to form an aniline polymer solution. And (3) immersing the polyurethane sponge into an aniline polymerization solution, vibrating and depositing for 9h to obtain polyaniline modified polyurethane sponge, then placing the polyaniline modified polyurethane sponge in a tubular furnace, heating to 400 ℃, and calcining for 6h to obtain the polyurethane sponge with the nitrogen-doped carbon layer on the surface.
To 50mL of deionized water, 0.2249g of CoSO was added4、0.6901gMgSO4、0.4gAl2(SO4)3And 2.592g of urea are stirred and dissolved, the polyurethane sponge with the modified surface is soaked into the solution, the system is transferred to a reaction kettle, and the reaction kettle is placed into a vacuum oven to be crystallized for 12 hours at the temperature of 100 ℃, so that the polyurethane sponge material modified by the layered double hydroxide is obtained.
The XRD spectrum of the layered double hydroxide modified polyurethane sponge material prepared in this example is similar to that of fig. 1. The SEM photograph of the layered double hydroxide modified polyurethane sponge material prepared in this example is similar to that of fig. 2. The super-hydrophilicity and underwater super-lipophobicity of the layered double hydroxide modified polyurethane sponge prepared in the embodiment are similar to those of FIG. 3. The catalytic degradation effect of the layered double hydroxide modified polyurethane sponge material prepared in this example on the pollutant bisphenol a is similar to that in fig. 4.
Example 7:
2.8mL of aniline was added to 50mL of 0.8mol/L dilute hydrochloric acid solution, and 6.5g of ammonium persulfate was added to another dilute hydrochloric acid solution of the same concentration, and the two solutions were mixed to form an aniline polymer solution. And (3) immersing the polyurethane sponge into an aniline polymerization solution, vibrating and depositing for 6 hours to obtain polyaniline modified polyurethane sponge, then placing the polyaniline modified polyurethane sponge in a tubular furnace, heating to 400 ℃, and calcining for 4 hours to obtain the polyurethane sponge with the nitrogen-doped carbon layer on the surface.
To 50mL of deionized water, 0.302g of Cu (NO) was added3)2、0.321gMg(NO3)2、0.505gFe(NO3)3And 5mL of ammonia water (the concentration is 20 percent), stirring and dissolving, soaking the surface modified polyurethane sponge into the solution, transferring the system to a reaction kettle, and placing the reaction kettle into a vacuum oven to crystallize for 12 hours at 100 ℃ to obtain the layered double hydroxide modified polyurethane sponge material.
The XRD spectrum of the layered double hydroxide modified polyurethane sponge material prepared in this example is similar to that of fig. 1. The SEM photograph of the layered double hydroxide modified polyurethane sponge material prepared in this example is similar to that of fig. 2. The super-hydrophilicity and underwater super-lipophobicity of the layered double hydroxide modified polyurethane sponge prepared in the embodiment are similar to those of FIG. 3. The catalytic degradation effect of the layered double hydroxide modified polyurethane sponge material prepared in this example on the pollutant bisphenol a is similar to that in fig. 4.
Example 8:
2.3mL of aniline was added to 50mL of a 1mol/L dilute hydrochloric acid solution, and 5.8g of ammonium persulfate was added to another dilute hydrochloric acid solution of the same concentration, and the two solutions were mixed to form an aniline polymer solution. And immersing the melamine sponge into an aniline polymerization solution, oscillating and depositing for 6 hours to obtain polyaniline modified melamine sponge, then placing the melamine sponge in a tubular furnace, heating to 400 ℃, and calcining for 4 hours to obtain the melamine sponge material with the nitrogen-doped carbon layer on the surface.
To 50mL of deionized water, 0.695g of FeSO was added4、1.23gMgSO4、0.96gFe2(SO4)3And 2.592g of urea are stirred and dissolved, the melamine sponge with the modified surface is soaked into the solution, the system is transferred to a reaction kettle, and the reaction kettle is placed into a vacuum oven to be crystallized for 8 hours at the temperature of 95 ℃, so that the melamine sponge material modified by the layered double hydroxide is obtained.
The XRD spectrum of the layered double hydroxide modified melamine sponge material prepared in this example is similar to that of fig. 1. The SEM photograph of the layered double hydroxide modified melamine sponge material prepared in this example is similar to that of fig. 2. The super-hydrophilicity and underwater super-lipophobicity of the layered double hydroxide modified melamine sponge prepared in the embodiment are similar to those of FIG. 3. The catalytic degradation effect of the layered double hydroxide modified melamine sponge material prepared in the embodiment on the pollutant bisphenol a is similar to that of fig. 4.
Example 9:
2.6mL of aniline was added to 50mL of 0.8mol/L dilute hydrochloric acid solution, and 4.5g of ammonium persulfate was added to another dilute hydrochloric acid solution of the same concentration, and the two solutions were mixed to form an aniline polymer solution. And immersing the melamine sponge into an aniline polymerization solution, vibrating and depositing for 9h to obtain polyaniline modified melamine sponge, then placing the melamine sponge in a tubular furnace, heating to 600 ℃, and calcining for 3h to obtain the melamine sponge material with the nitrogen-doped carbon layer on the surface.
To 50mL of deionized water, 0.578g of FeSO was added4、1.68gMgSO4、1.24gFe2(SO4)3And 5mL of ammonia water (the concentration is 20 percent) are stirred and dissolved, the melamine sponge with the modified surface is immersed into the solution, the system is moved to a reaction kettle, and the reaction kettle is placed into a vacuum oven to be crystallized for 12 hours at the temperature of 100 ℃, so that the melamine sponge material modified by the layered double hydroxide is obtained.
The XRD spectrum of the layered double hydroxide modified melamine sponge material prepared in this example is similar to that of fig. 1. The SEM photograph of the layered double hydroxide modified melamine sponge material prepared in this example is similar to that of fig. 2. The super-hydrophilicity and underwater super-lipophobicity of the layered double hydroxide modified melamine sponge prepared in the embodiment are similar to those of FIG. 3. The catalytic degradation effect of the layered double hydroxide modified melamine sponge material prepared in the embodiment on the pollutant bisphenol a is similar to that of fig. 4.
Example 10:
2.3mL of aniline was added to 50mL of a 1mol/L dilute hydrochloric acid solution, and 5.8g of ammonium persulfate was added to another dilute hydrochloric acid solution of the same concentration, and the two solutions were mixed to form an aniline polymer solution. And (2) immersing the activated carbon fiber into an aniline polymerization solution, oscillating and depositing for 6 hours to obtain polyaniline modified activated carbon fiber, then placing the polyaniline modified activated carbon fiber in a tubular furnace, heating to 400 ℃, and calcining for 4 hours to obtain the activated carbon fiber with a nitrogen-doped carbon layer on the surface.
To 50mL of deionized water, 0.0562g of CoSO was added4、0.1725gMgSO4、0.1gAl2(SO4)3And 2.592g of urea are stirred and dissolved, the surface modified activated carbon fiber is soaked into the solution, the system is transferred to a reaction kettle, and the reaction kettle is placed into a vacuum oven to be crystallized for 12 hours at the temperature of 100 ℃, so that the activated carbon fiber material modified by the layered double hydroxide is obtained.
An SEM photograph of the layered double hydroxide-modified activated carbon fiber material prepared in this example is shown in fig. 8. It can be seen that the scattered LDH is packed on the surface of the substrate, which indicates that the low concentration of metal ions is not favorable for uniform and dense LDH micron sheets growth on the surface of the substrate.
Example 11:
2.3mL of aniline was added to 50mL of a 1mol/L dilute hydrochloric acid solution, and 5.8g of ammonium persulfate was added to another dilute hydrochloric acid solution of the same concentration, and the two solutions were mixed to form an aniline polymer solution. And (2) immersing the activated carbon fiber into an aniline polymerization solution, oscillating and depositing for 6 hours to obtain polyaniline modified activated carbon fiber, then placing the polyaniline modified activated carbon fiber in a tubular furnace, heating to 400 ℃, and calcining for 4 hours to obtain the activated carbon fiber with a nitrogen-doped carbon layer on the surface.
To 50mL of deionized water, 0.2249g of CoSO was added4、0.6901gMgSO4、0.4gAl2(SO4)3And 1.296g of urea are stirred and dissolved, the activated carbon fiber with modified surface is immersed into the solution, the system is moved to a reaction kettle and is put into a vacuum oven to be crystallized for 12 hours at the temperature of 100 ℃, and the activated carbon fiber material modified by the layered double hydroxide is obtained.
An SEM photograph of the layered double hydroxide-modified activated carbon fiber material prepared in this example is shown in fig. 9. It can be seen that the LDH, which is sparse and insufficiently grown, is distributed on the surface of the matrix, which indicates that the number of nucleation on the surface of the matrix is small and the LDH micron sheets are insufficiently grown at a low concentration of the alkali substance.
Example 12:
2.3mL of aniline was added to 50mL of a 1mol/L dilute hydrochloric acid solution, and 5.8g of ammonium persulfate was added to another dilute hydrochloric acid solution of the same concentration, and the two solutions were mixed to form an aniline polymer solution. And (2) immersing the activated carbon fiber into an aniline polymerization solution, oscillating and depositing for 6 hours to obtain polyaniline modified activated carbon fiber, then placing the polyaniline modified activated carbon fiber in a tubular furnace, heating to 400 ℃, and calcining for 4 hours to obtain the activated carbon fiber with a nitrogen-doped carbon layer on the surface.
To 50mL of deionized water, 0.2249g of CoSO was added4、0.6901gMgSO4、0.4gAl2(SO4)3And 2.592g of urea are stirred and dissolved, the surface modified activated carbon fiber is soaked into the solution, the system is transferred to a reaction kettle, and the reaction kettle is placed into a vacuum oven to be crystallized for 3 hours at the temperature of 100 ℃, so that the activated carbon fiber material modified by the layered double hydroxide is obtained.
An SEM photograph of the layered double hydroxide-modified activated carbon fiber material prepared in this example is shown in fig. 10. It can be seen that the LDH with insufficient growth is sparsely distributed on the surface of the matrix, which indicates that when the hydrothermal time is too short, the metal ions and the alkaline substances cannot be effectively nucleated on the surface of the matrix, and the LDH micron sheets are insufficiently grown.
Comparative example 1:
to 50mL of deionized water, 0.2249g of CoSO was added4、0.6901gMgSO4、0.4gAl2(SO4)3And 2.592g of urea are stirred and dissolved, the activated carbon fiber is immersed into the solution, the system is transferred to a reaction kettle, and the reaction kettle is placed into a vacuum oven to be crystallized for 12 hours at the temperature of 100 ℃, so that the activated carbon fiber material modified by the layered double hydroxide is obtained.
An SEM photograph of the layered double hydroxide-modified activated carbon fiber material prepared in this comparative example is shown in fig. 11. It can be seen that the tiny LDH sheets are randomly and sparsely stacked on the surface of the matrix, which indicates that the nitrogen-doped carbon layer formed by calcining polyaniline deposited on the surface of the matrix can well induce LDH to grow on the surface of the fiber, and also helps to successfully prepare the three-dimensional composite material with a stable surface.
Comparative example 2:
to 50mL of deionized water, 0.2249g of CoSO was added4、0.6901gMgSO4、0.4gAl2(SO4)3And 2.592g of urea are stirred and dissolved, the mixed solution is transferred to a reaction kettle and is put into a vacuum oven to be crystallized for 12 hours at the temperature of 100 ℃, and the layered double hydroxide is obtained.
The XRD spectrum of the layered double hydroxide prepared in this comparative example is similar to that of fig. 1. The SEM photograph of the layered double hydroxide prepared in this comparative example is similar to fig. 2. The effect of the layered double hydroxide prepared in this comparative example on the catalytic degradation of contaminant bisphenol a is similar to that of fig. 4. The powder sample prepared in this comparative example, even if having super-hydrophilicity, was difficult to achieve effective oil-water separation due to lack of a growing matrix.
Claims (9)
1. A preparation method of a three-dimensional composite material for oily wastewater treatment is characterized by comprising the following steps:
(1) immersing a proper matrix material into an aniline polymerization solution, and performing oscillation deposition to obtain a polyaniline modified matrix; the matrix material is one of melamine sponge, polyurethane sponge or activated carbon fiber; the aniline polymerization solution is a uniform solution formed by mixing an aniline solution and an ammonium persulfate solution;
(2) placing the modified substrate obtained in the step (1) in a tubular furnace, heating and calcining to obtain a composite material with a nitrogen-doped carbon layer on the surface;
(3) and (3) immersing the composite material obtained in the step (2) into an aqueous solution containing divalent metal salt, trivalent metal salt and alkaline substances, and transferring the mixed solution into a reaction kettle for hydrothermal reaction to obtain the layered double hydroxide modified three-dimensional composite material.
2. The method for preparing the three-dimensional composite material for oily wastewater treatment according to claim 1, wherein the aniline solution is a solution formed by mixing aniline and dilute hydrochloric acid; the ammonium persulfate solution is formed by dissolving ammonium persulfate in dilute hydrochloric acid; the concentration of the dilute hydrochloric acid is 0.1-2mol/L, the volume ratio of the aniline to the dilute hydrochloric acid is 1:10-50, and the concentration of ammonium persulfate in the ammonium persulfate solution is 1-10 mol/L. The time of the oscillating deposition is 1-12 h.
3. The method for preparing the three-dimensional composite material for oily wastewater treatment according to claim 1, wherein the concentration of the dilute hydrochloric acid is 0.5-1 mol/L; the volume ratio of the aniline to the dilute hydrochloric acid is 1: 10-30; the concentration of the ammonium persulfate solution is 3-7 mol/L.
4. The method as claimed in claim 1, wherein the modified substrate in step (2) is calcined in a tubular furnace at an adjustable temperature of 3-10 ℃/min at 200-800 ℃ for 2-8 h.
5. The method as claimed in claim 4, wherein the modified substrate in step (2) is placed in a tubular furnace for temperature rise and calcination at a temperature of 400 ℃ and 600 ℃ for 2-6h, wherein the temperature rise rate is 5 ℃/min.
6. The method for preparing the three-dimensional composite material for oily wastewater treatment according to claim 1, wherein the divalent metal ion in the divalent metal salt in the step (3) is Co2+、Cu2+、Fe2+、Ni2+、Mg2+One or two of metal ions; the trivalent metal ion in the trivalent metal salt is A13+、Fe3+One or two of them; the anions of the divalent metal salt and the trivalent metal salt are CO3 2-、Cl-、NO3 -、SO4 2-One or two of them; the alkaline substance is urea, ammonia water or sodium hydroxide.
7. The method for preparing the three-dimensional composite material for oily wastewater treatment according to claim 1, wherein the total concentration of the divalent metal salt and the trivalent metal salt is 0.01-0.5 mol/L; in the mixed solution of the divalent metal salt and the trivalent metal salt, the molar ratio of the divalent metal salt to the trivalent metal salt is 1: 0.5 to 4; the molar mass ratio of the total amount of the divalent metal salt and the trivalent metal salt to the alkaline substance is 1: 1-10.
8. The method for preparing the three-dimensional composite material for oily wastewater treatment according to claim 7, wherein the total concentration of the divalent metal salt and the trivalent metal salt is 0.05 to 0.25 mol/L; in the mixed solution of the divalent metal salt and the trivalent metal salt, the molar ratio of the divalent metal salt to the trivalent metal salt is 1: 1-3; the molar mass ratio of the total amount of the divalent metal salt and the trivalent metal salt to the alkaline substance is 1: 2-6.
9. The method for preparing the three-dimensional composite material for oily wastewater treatment according to claim 1, wherein the temperature of the hydrothermal reaction in the step (3) is 90-110 ℃ and the time period is 3-24 h.
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