CN109225325B - Fe-PANI/zeolite catalyst and preparation method thereof - Google Patents
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Abstract
The invention discloses a Fe-PANI/zeolite catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: soaking zeolite in aniline-water solution, and passing through FeCl at high temperature3The oxidation of (A) causes the aniline to polymerize while simultaneously reducing the Fe (III), Fe (II) and FeCl in solution3H produced by hydrolysis+Doped in PANI to prepare Fe-PANI/zeolite catalyst. The present invention uses zeolite, aniline and FeCl3Using FeCl as raw material and water as solvent3The oxidation at high temperature promotes aniline polymerization and is simultaneously doped with Fe (III), Fe (II) and H+In PANI, the two processes of loading and doping are completed synchronously, and the solution after reaction is an acidic solution containing iron and aniline oligomers, so that the method has small harm to the environment and is easy to treat. PANI has good electron transmission performance, can improve the conversion efficiency of Fe (II) and Fe (III), and promotes the Fenton-like degradation process of organic matters. In addition, Fe-PANI/zeolite has high activity under the condition that the pH value is 6, and the repeatability and the utilization rate are high, so that the Fe-PANI/zeolite is a good Fenton-like catalyst.
Description
Technical Field
The invention belongs to the field of chemistry and water treatment, and relates to a Fe-PANI/zeolite catalyst and a preparation method thereof.
Background
The essence of the Fenton process is divalent iron ions (Fe)2+) And hydrogen peroxideThe intermediate chain reaction catalyzes to generate hydroxyl free radical, has stronger oxidizing capability, and the oxidation potential of the intermediate chain reaction is second to that of fluorine and is as high as 2.80V. In addition, the hydroxyl free radical has high electronegativity or electrophilicity, and the electron affinity of the hydroxyl free radical is as high as 569.3kJ, so that the Fenton reagent has strong addition reaction characteristics, can indiscriminately oxidize most organic matters in water, and is particularly suitable for the oxidation treatment of organic wastewater which is difficult to biodegrade or to perform effective chemical oxidation generally.
The traditional Fenton technology has wide application in the treatment of organic polluted wastewater difficult to degrade, but has the defects of narrow pH application range (about 3), difficult recovery of catalyst, generation of iron-containing sludge and the like. Research on Fenton-like catalysts can improve the activity of the catalysts under neutral conditions, and simultaneously solve the problems of generating iron-containing sludge and realizing the recycling of the catalysts.
Disclosure of Invention
The invention aims to provide a Fe-PANI/zeolite catalyst and a preparation method thereof, and aims to solve the problems that Fenton technology has no activity under a neutral condition, the catalyst cannot be recycled and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of making a Fe-PANI/zeolite catalyst comprising: soaking zeolite in aniline-water solution, and adding oxidant and hydrothermal process to make aniline polymerize in situ on the zeolite surface to prepare Fe-PANI/zeolite catalyst.
Further, the Fe-PANI/zeolite catalyst can realize synchronous load of PANI and Fe; the specifications of the zeolite are: the particle size is 0.01 to 2 mm.
Further, the method specifically comprises the following steps:
1) mixing water and aniline and performing ultrasonic treatment to ensure that the aniline is uniformly dispersed in an aqueous solution;
2) placing aniline-water solution and zeolite in a hydrothermal reaction kettle for oscillation; placing in a hydrothermal reaction kettle and ensuring that the zeolite is completely immersed in the solution;
3) after oscillation is finished, adding an oxidant into the reaction kettle;
4) placing the reaction kettle in an oven for heat preservation;
5) and after the heat preservation is finished and the reaction solution is cooled to room temperature, taking out the zeolite from the reaction solution, soaking and washing the zeolite, and drying the zeolite to obtain the Fe-PANI/zeolite catalyst.
Further, the oxidant is FeCl3。
Further, the volume ratio of water to aniline in the step 1) is less than 1000, and the ultrasonic time is 1-120 min.
Further, the oscillation time in the step 2) is 1-300 min.
Further, the quantity ratio of the oxidant to the aniline in the step 3) is 0.5-4.
Further, in the step 4), the heat preservation temperature is 60-200 ℃, and the heat preservation time is 3-18 h.
Further, the soaking time in the step 5) is more than 1h, and the soaking solution is neutral.
Further, in the Fe-PANI/zeolite catalyst, the PANI is doped with Fe (II/III).
Further, every 5.0g of zeolite was soaked in 2-20m L aniline-water solution.
The Fe-PANI/zeolite catalyst prepared by the preparation method.
Compared with the prior Fenton-like catalyst, the method has the following beneficial technical effects:
the method takes zeolite, aniline and ferric chloride hexahydrate as raw materials, water as a solvent, the oxidation of the ferric chloride and the principle of hydrolysis reaction at high temperature are directly utilized to generate the PANI doped with Fe (II/III), the whole reaction does not need to adjust the reaction condition to the acidic condition or add any other reactant, and the solution after the reaction is solution containing iron and aniline oligomers, so that the method is low in harm to the environment and easy to treat. Therefore, the whole preparation process is an environment-friendly chemical synthesis process. The Fe-PANI/zeolite catalyst prepared by the method has strong Fenton-like catalytic activity, and researches show that the Fe-PANI/zeolite catalyst has good stability after being combined with a carrier, high repeatable utilization rate and strong catalytic degradation effect on refractory organic pollutants in sewage.
The zeolite is a natural aluminosilicate ore and has good chemical inertness and physical strength, so that the zeolite can be used as a carrier of a Fenton-like catalyst and applied to the field of water treatment. The catalyst has low cost, easily obtained raw materials and easy separation in water, and can greatly reduce the cost and realize the recovery of the catalyst by taking the catalyst as a carrier.
According to the invention, PANI is firmly loaded on the surface of the carbon cloth, and the preparation method is different from PANI prepared by a conventional method, the pH of aniline-water solution is not required to be adjusted, and Fe and PANI can be organically combined. The prepared Fe-PANI/zeolite catalyst not only has the capability of decomposing hydrogen peroxide to generate OH, but also can greatly improve the electron transmission efficiency in the catalysis process due to the conductivity of PANI. The method is simple to operate, and the prepared Fe-PANI/zeolite catalyst still has high catalytic activity under a neutral condition, has high activity for treating organic wastewater difficult to degrade, and has good application prospect. The activity of the Fe-PANI/zeolite catalyst prepared by the invention under the condition of pH 6 is close to that under the condition of pH 3, and the Fe-PANI/zeolite catalyst has good stability, and the catalytic activity can be kept above 80% after 8 times of reaction.
Drawings
FIG. 1 is a schematic representation of Fe-PANI/zeolite catalyst before loading;
FIG. 2 is a schematic representation of Fe-PANI/zeolite catalyst after loading.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The preparation method of Fe-PANI/zeolite catalyst uses zeolite, aniline and ferric chloride hexahydrate as raw material, firstly makes aniline monomer be adsorbed on the surface of zeolite by means of oscillation, then utilizes the oxidability of ferric chloride to make aniline monomer be progressively polymerized on the surface of zeolite at high temperature, at the same time the ferric chloride is hydrolyzed to produce Fe (OH)3，Fe(OH)3Dehydration to produce Fe2O3Doping into polyaniline. The reaction equations mainly involved are as follows:
(1)n C6H5–NH2+FeCl3→[C6H5–NH]n+FeCl2+HCl
(2)FeCl3+3H2O→Fe(OH)3+3HCl
(3)2Fe(OH)3→Fe2O3+3H2O
example 1 (mass ratio of oxidant to aniline 0.05:1)
Adding 1.9m L deionized water and 0.093g (1mmol) aniline into a hydrothermal reaction kettle, respectively, ultrasonically oscillating for 25min, adding 5.00g zeolite into aniline-water solution, oscillating for 1min in a shaking table, adding 0.0135g (0.05mmol) FeCl3·6H2And O, sealing, placing in a 60 ℃ blast drying oven, preserving heat for 24 hours, taking out, placing at room temperature, and cooling. And then taking out the zeolite, washing the zeolite by using deionized water and ethanol, soaking the zeolite until the soaking solution is neutral, draining the water, and drying the zeolite in an oven at 60 ℃ to obtain the Fe-PANI/zeolite catalyst.
Example 2 (mass ratio of oxidant to aniline 3:1)
Adding deionized water 19.9m L and aniline 0.1m L into a hydrothermal reaction kettle, respectively, ultrasonically oscillating for 5min, adding zeolite 5.00g into aniline-water solution, oscillating for 30min in a shaking table, adding FeCl 0.81g (3mmol)3·6H2And O, sealing, placing in a 130 ℃ blast drying oven, preserving the heat for 12 hours, taking out, placing at room temperature, and cooling. And then taking out the zeolite, washing the zeolite by using deionized water and ethanol, soaking the zeolite until the soaking solution is neutral, draining the water, and drying the zeolite in an oven at 60 ℃ to obtain the Fe-PANI/zeolite catalyst. And infrared spectrum and X-ray photoelectron spectrum analysis prove that the surface of the zeolite is successfully loaded with polyaniline and Fe (II/III).
Example 3 (mass ratio of oxidant to aniline 1:1)
Adding 49.9m L deionized water and 0.1m L aniline into a hydrothermal reaction kettle respectively, ultrasonically oscillating for 60min, adding 25.00g zeolite into an aniline-water solution, oscillating for 300min in a shaking table, adding 0.27g (1mmol) FeCl3·6H2And O, sealing, placing in a 200 ℃ blast drying oven, preserving heat for 3h, taking out, placing at room temperature, and cooling. Then taking out zeolite, washing with deionized water and ethanol, soaking until the soaking solution is neutral, and drainingDrying the dried catalyst in an oven at 60 ℃ to obtain the Fe-PANI/zeolite catalyst.
Example 4 (mass ratio of oxidant to aniline 6:1)
Adding 99.9m L deionized water and 0.1m L aniline into a hydrothermal reaction kettle respectively, adding 100.00g zeolite into an aniline-water solution after ultrasonic oscillation for 120min, oscillating in a shaking table for 120min, adding 1.62g (6mmol) FeCl3·6H2And O, sealing, placing in a 180 ℃ blast drying oven, preserving heat for 18h, taking out, placing at room temperature, and cooling. And then taking out the zeolite, washing the zeolite by using deionized water and ethanol, soaking the zeolite until the soaking solution is neutral, draining the water, and drying the zeolite in an oven at 60 ℃ to obtain the Fe-PANI/zeolite catalyst.
Simulation of wastewater treatment case:
in order to verify the treatment effect of the Fe-PANI/zeolite catalyst prepared by the method on refractory organic wastewater, the Fe-PANI/zeolite prepared in example 1 is used as the catalyst, the prepared acid red G dye wastewater is used as a treatment object, Fenton-like degradation research is respectively carried out under the conditions of pH 3 and pH 6, the dye solution after degradation is clear and transparent, and no precipitate is generated after the pH value is adjusted to be neutral, so that the catalyst prepared by the method has good activity under the neutral condition and can effectively avoid the generation of iron-containing sludge.
Claims (6)
1. A preparation method of Fe-PANI/zeolite catalyst for Fenton-like degradation of acid red G dye wastewater is characterized by comprising the following steps: soaking zeolite in aniline-water solution, and adding oxidant and hydrothermal process to make aniline polymerize in situ on the zeolite surface to prepare Fe-PANI/zeolite catalyst;
the preparation method specifically comprises the following steps:
1) mixing water and aniline, and uniformly dispersing the mixture in an aqueous solution by ultrasonic waves to obtain an aniline-aqueous solution;
2) placing aniline-water solution and zeolite in a hydrothermal reaction kettle for oscillation; wherein the zeolite is completely immersed in the solution;
3) after oscillation is finished, adding an oxidant into the reaction kettle; the oxidant is ferric chloride;
4) placing the reaction kettle in an oven for heat preservation;
5) after the heat preservation is finished and the reaction solution is cooled to room temperature, taking out the zeolite from the reaction solution, soaking and washing the zeolite, and drying the zeolite to obtain the Fe-PANI/zeolite catalyst;
the PANI is doped with Fe II/III;
step 4), keeping the heat preservation temperature at 60-200 ℃ and keeping the heat preservation time at 3-24 h;
the oscillation time in the step 2) is 1-300 min; the quantity ratio of the oxidant to the aniline in the step 3) is 0.05-6.
2. The preparation method of claim 1, wherein the Fe-PANI/zeolite catalyst obtained by the preparation method can realize the synchronous loading of PANI and Fe; the specifications of the zeolite are: the particle size is 0.01-2 mm.
3. The preparation method according to claim 1, wherein the volume ratio of water to aniline in step 1) is less than or equal to 1000, and the ultrasonic time is 1-120 min.
4. The preparation method of claim 1, wherein the soaking time in the step 5) is more than 1h, and the soaking solution is neutral.
5. The method of claim 1, wherein the zeolite is soaked in 2-20m L aniline-water solution for every 5.0g zeolite.
6. A Fe-PANI/zeolite catalyst prepared by the method of any one of claims 1 to 5.
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| CN111151147B (en) * | 2020-02-12 | 2021-09-03 | 泰州九润环保科技有限公司 | Polyaniline modified aluminosilicate molecular sieve doped polyamide composite membrane |
| CN111151146B (en) * | 2020-02-12 | 2021-09-03 | 泰州九润环保科技有限公司 | Polyaniline-modified all-silicon molecular sieve-doped polyamide composite membrane |
| CN112387257A (en) * | 2020-11-05 | 2021-02-23 | 西安工程大学 | Preparation method of high-molecular polyaniline porous filler water treatment adsorbent |
| CN114558617B (en) * | 2022-03-03 | 2023-04-28 | 西安交通大学 | Application of Fe-PANI serving as heterogeneous Fenton catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05239482A (en) * | 1992-02-28 | 1993-09-17 | Noriyuki Kuramoto | Electroviscous fluid |
| CN101649111A (en) * | 2009-09-07 | 2010-02-17 | 吉林大学 | Molecular sieve polyaniline compound wave-absorbing material and preparation method thereof |
| CN108299641A (en) * | 2018-02-11 | 2018-07-20 | 黑龙江大学 | A kind of preparation method of polyaniline/ferric oxide composite material |
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- 2018-09-11 CN CN201811057023.0A patent/CN109225325B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05239482A (en) * | 1992-02-28 | 1993-09-17 | Noriyuki Kuramoto | Electroviscous fluid |
| CN101649111A (en) * | 2009-09-07 | 2010-02-17 | 吉林大学 | Molecular sieve polyaniline compound wave-absorbing material and preparation method thereof |
| CN108299641A (en) * | 2018-02-11 | 2018-07-20 | 黑龙江大学 | A kind of preparation method of polyaniline/ferric oxide composite material |
Non-Patent Citations (3)
| Title |
|---|
| "Polyaniline/FeZSM-5 composites – Synthesis, characterization and their high catalytic activity for the oxidative degradation of herbicide glyphosate";Maja Milojević-Rakić等;《Microporous and Mesoporous Materials》;20180315;第267卷;第68-79页 * |
| "水热法制备聚苯胺及其铁氧化物纳米复合材料";刘红缨等;《高等学校化学学报》;20130531;第34卷(第5期);第1303-1308页 * |
| "聚苯胺/凹凸棒石复合材料对染料去除性能研究";唐进;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20170215;B027-2068 * |
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