CN111359675B - Carboxymethyl chitosan doped polyaniline-MnFe2O4Spinel catalyst and preparation method and application thereof - Google Patents

Carboxymethyl chitosan doped polyaniline-MnFe2O4Spinel catalyst and preparation method and application thereof Download PDF

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CN111359675B
CN111359675B CN202010297553.3A CN202010297553A CN111359675B CN 111359675 B CN111359675 B CN 111359675B CN 202010297553 A CN202010297553 A CN 202010297553A CN 111359675 B CN111359675 B CN 111359675B
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catalyst
carboxymethyl chitosan
mnfe
polyaniline
spinel
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CN111359675A (en
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周诗健
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Taizhou Heyi New Material Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
    • 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
    • B01J23/005—Spinels
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • 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
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Abstract

The invention relates to carboxymethyl chitosan doped polyaniline-MnFe2O4A spinel catalyst, a preparation method and application thereof, belonging to the technical field of advanced oxidation water treatment. According to the invention, chitosan is doped with conductive polymer polyaniline, so that a large number of amino groups, carboxyl groups and hydroxyl groups are grafted on polyaniline, and metal ions are effectively adsorbed, thereby in-situ loading MnFe on a polyaniline carrier2O4Spinel is used for catalyzing advanced oxidation degradation of organic wastewater by PMS. The catalyst prepared by the invention has the degradation rate of 97% to methyl orange in simulated wastewater within 120min, and after 6 times of circulation, the performance of the catalyst is reduced by less than 8%, so that the catalyst has excellent catalytic activity and good stability. The catalyst provided by the invention has the advantages of rich raw materials, low price, simple preparation process and good application prospect.

Description

Carboxymethyl chitosan doped polyaniline-MnFe2O4Spinel catalyst and preparation method and application thereof
Technical Field
The invention relates to carboxymethyl chitosan doped polyaniline-MnFe2O4A spinel catalyst, a preparation method and application thereof, belonging to the technical field of advanced oxidation water treatment.
Background
Advanced oxidation technologies (AOPs) are a technology that has been gradually developed in recent decades to consider replacing the conventional sewage treatment methods for treating refractory organic matters. Generally, under the conditions of a catalyst, ultraviolet, microwave, ultrasound, light, electricity and the like, organic pollutants are oxidized by using high-activity oxidizing radicals, and the organic matters are mineralized or degraded into non-toxic small molecules to reduce secondary pollution to the environment.
In recent years, based on sulfate radicals (SO)4 -H.) has been extensively studied. SO (SO)4 -Because of its high oxidation potential (2.5-3.1V, OH)-2.7V), a wider pH response range and the advantage of not producing sludge during the reaction. Zero-valent transition metal, transition metal oxide, spinel, and g-C3N4Etc. can be used as catalyst to effectively activate PMS or PS to generate SO4 -·。
PMS is a high-efficiency oxidant and is widely applied to the chemical industry. PMS is a ternary complex salt with KHSO as the component5·0.5KHSO4·0.5K2SO4. The decomposition rate of PMS is very slow at normal temperature, and the PMS can be decomposed only at high temperature or under illumination, so that the PMS is superior to H in storage and transportation2O2The characteristics of (1). Because PMS has many activating measures and mild reaction conditions, PMS is considered to be an oxidant with application prospect for treating wastewater by many researches.
As a novel conductive polymer material, polyaniline has the advantages which are not possessed by many metals, especially unique conductivity, catalytic performance and proton exchange performance, and shows wide application prospects in many fields. Polyaniline has loose structure and large specific surface area, and can disperse and stabilize inorganic metal particles, so that the polyaniline and the inorganic material are compounded to improve the catalytic performance of the polyaniline and the inorganic material in cooperation with the advantages of high polymer materials and the special performance of metal nanoparticles. In recent years, composite materials in which conductive polymer materials are organically combined with noble metals, transition metals and oxides thereof are also gradually and successfully applied to the field of environmental catalysis.
Based on the prior art, the invention develops the polyaniline-MnFe doped with carboxymethyl chitosan2O4The spinel catalyst is used for catalyzing PMS to perform advanced oxidative degradation on organic wastewater. The method comprises the steps of doping conductive polymer polyaniline with chitosan, grafting a large number of amino groups, carboxyl groups and hydroxyl groups on the polyaniline, wherein the groups can effectively adsorb metal ions, so that MnFe is loaded on a polyaniline carrier in situ2O4Spinel. The catalyst has high catalytic activity when catalyzing advanced oxidative degradation of organic wastewater by PMS, has rich raw materials, low price, simple operation and good application prospect.
Disclosure of Invention
One of the purposes of the invention is to provide polyaniline-MnFe doped with carboxymethyl chitosan2O4The spinel catalyst takes carboxymethyl chitosan-doped polyaniline as a carrier and carries MnFe in situ2O4Spinel of which MnFe2O4The catalyst accounts for 5-15wt% of the mass of the catalyst.
Further, in the above-mentioned case,the MnFe2O4The mass fraction of the catalyst is preferably 8 to 12 wt.%.
The invention also aims to provide the polyaniline-MnFe doped with the carboxymethyl chitosan2O4The preparation method of the spinel catalyst comprises the following preparation steps:
(1) adding carboxymethyl chitosan into a proper amount of deionized water, and magnetically stirring for 1-3h until the carboxymethyl chitosan is dissolved; adding aniline monomer into a proper amount of deionized water, and magnetically stirring for dissolving; slowly adding the carboxymethyl chitosan solution into an aniline solution, performing ultrasonic treatment for 1-2 hours to uniformly mix the system, placing the system in an ice bath, adding a proper amount of initiator ammonium persulfate, standing for reaction for 8-20 hours to obtain the polyaniline doped with carboxymethyl chitosan, and filtering, washing and drying for later use;
(2) weighing certain mass of FeCl3·6H2O、MnCl2·4H2Dissolving O in deionized water, adding the carboxymethyl chitosan-doped polyaniline prepared in the step (1), magnetically stirring for 1-3h to ensure that metal ions are fully adsorbed on the surface of the carboxymethyl chitosan-doped polyaniline, adding a proper amount of urea, transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 8-10h at the temperature of 150 ℃ plus 200 ℃, naturally cooling to room temperature, filtering, washing with absolute ethyl alcohol and deionized water respectively, and drying to obtain the carboxymethyl chitosan-doped polyaniline-MnFe2O4A spinel catalyst.
Further, the amount of the carboxymethyl chitosan-doped polyaniline added in the step (2) is such that MnFe is contained in the final product2O4The catalyst accounts for 5-15wt% of the mass of the catalyst.
Further, the reaction temperature in the step (2) is preferably 160-180 ℃.
The invention also aims to provide the carboxymethyl chitosan doped polyaniline-MnFe2O4The spinel catalyst is applied to catalyzing PMS advanced oxidation organic wastewater.
Specifically, the catalyst is added into the organic wastewater, PMS is added, the temperature of the system is adjusted to be 25-40 ℃, the system is magnetically stirred, and advanced oxidation reaction is carried out.
Furthermore, the adding amount of the catalyst is 0.1-1g/L, and the adding amount of PMS is 0.5-2 g/L.
In the invention, a large number of amino, carboxyl and hydroxyl groups are grafted after the polyaniline is functionalized by chitosan, and the groups can effectively adsorb metal ions, so that the auxiliary conductive carrier in-situ hydrothermal load MnFe2O4Spinel. The obtained catalyst contains MnFe2O4Can be firmly and firmly fixed on the surface of the carrier in high dispersion, and avoids the secondary pollution of the water body caused by the loss of the active components.
Furthermore, polyaniline has certain adsorption capacity, can adsorb pollutants in a water body on the surfaces of particles, and can synergistically play the degradation role of the catalyst to accelerate the reaction rate; meanwhile, polyaniline is used as a conductive polymer, has excellent electron conduction efficiency, and can accelerate electron transfer of a system in the process of catalyzing PMS, so that an oxidation active component is generated more quickly by the system, and the degradation efficiency of the catalyst is improved.
The prepared carboxymethyl chitosan doped polyaniline-MnFe2O4The degradation rate of the spinel catalyst to methyl orange in simulated wastewater within 120min can reach 97%, and the performance of the spinel catalyst is reduced by less than 8% after 6 times of circulation, which shows that the spinel catalyst has excellent catalytic activity and good stability.
Drawings
FIG. 1 shows carboxymethyl chitosan doped polyaniline-MnFe prepared by the present invention2O4The degradation rate of the spinel catalyst to methyl orange in the simulated wastewater changes along with the time.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Adding carboxymethyl chitosan into a proper amount of deionized water, and magnetically stirring for 1h until the carboxymethyl chitosan is dissolved; adding aniline monomer into a proper amount of deionized water, and magnetically stirring for dissolving; slowly adding the carboxymethyl chitosan solution into an aniline solution, performing ultrasonic treatment for 2 hours to uniformly mix the system, placing the system in an ice bath, adding a proper amount of initiator ammonium persulfate, standing for reaction for 15 hours to obtain the carboxymethyl chitosan-doped polyaniline, filtering, washing and drying for later use;
(2) weighing certain mass of FeCl3·6H2O、MnCl2·4H2Dissolving O in deionized water, adding the carboxymethyl chitosan-doped polyaniline prepared in the step (1), magnetically stirring for 1h, adding a proper amount of urea, transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting at 160 ℃ for 8h, naturally cooling to room temperature, filtering, washing with absolute ethyl alcohol and deionized water respectively, and drying to obtain the catalyst of the embodiment, which is marked as number C-1, wherein MnFe2O4The mass fraction of the catalyst is 10 wt%.
Example 2
(1) Adding carboxymethyl chitosan into a proper amount of deionized water, and magnetically stirring for 3 hours until the carboxymethyl chitosan is dissolved; adding aniline monomer into a proper amount of deionized water, and magnetically stirring for dissolving; slowly adding the carboxymethyl chitosan solution into an aniline solution, performing ultrasonic treatment for 1-2 hours to uniformly mix the system, placing the system in an ice bath, adding a proper amount of initiator ammonium persulfate, standing for reaction for 8-20 hours to obtain the polyaniline doped with carboxymethyl chitosan, and filtering, washing and drying for later use;
(2) weighing certain mass of FeCl3·6H2O、MnCl2·4H2Dissolving O in deionized water, adding the carboxymethyl chitosan-doped polyaniline prepared in the step (1), magnetically stirring for 1 hour, and adding a proper amount of urineTransferring the catalyst into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 10 hours at 180 ℃, naturally cooling to room temperature, filtering, washing with absolute ethyl alcohol and deionized water respectively, and drying to obtain the catalyst of the embodiment, which is marked as the number C-2, wherein MnFe2O4The mass fraction of the catalyst is 8 wt%. .
Example 3
And selecting methyl orange as a target pollutant to test the catalytic degradation performance of the catalyst. Preparing simulated wastewater, wherein the concentration of methyl orange is 50 mg/L. The catalysts C-1 and C-2 prepared in the example 1-2 are weighed and added into simulated wastewater, the adding amount is 0.3g/L, then PMS is added, the adding amount is 1g/L, the catalytic degradation reaction is carried out under the magnetic stirring at the temperature of 35 ℃, the degradation rate of methyl orange along with the time is measured, and the result is shown in figure 1.
As can be seen from FIG. 1, carboxymethyl chitosan-doped polyaniline-MnFe prepared by the present invention2O4The degradation rate of the spinel catalyst to methyl orange in 120min can reach 97%. The catalyst of the invention can efficiently catalyze PMS to generate SO4 -Thereby degrading the organic contaminants.
In order to test the stability of the catalyst prepared by the invention in the catalytic degradation process, 6 times of cyclic degradation experiments are carried out on the catalysts C-1 and C-2, and the results show that the performance of the catalyst is reduced by less than 8% after 6 times of cycles, which indicates that the catalyst has good stability.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (6)

1. Carboxymethyl chitosan doped polyaniline-MnFe2O4The preparation method of the spinel catalyst is characterized by comprising the following preparation steps of:
(1) adding carboxymethyl chitosan into a proper amount of deionized water, and magnetically stirring for 1-3h until the carboxymethyl chitosan is dissolved; adding aniline monomer into a proper amount of deionized water, and magnetically stirring for dissolving; slowly adding the carboxymethyl chitosan solution into an aniline solution, performing ultrasonic treatment for 1-2 hours to uniformly mix the system, placing the system in an ice bath, adding a proper amount of initiator ammonium persulfate, standing for reaction for 8-20 hours to obtain the polyaniline doped with carboxymethyl chitosan, and filtering, washing and drying for later use;
(2) weighing certain mass of FeCl3·6H2O、MnCl2·4H2Dissolving O in deionized water, adding the carboxymethyl chitosan-doped polyaniline prepared in the step (1), magnetically stirring for 1-3h to ensure that metal ions are fully adsorbed on the surface of the carboxymethyl chitosan-doped polyaniline, adding a proper amount of urea, transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting for 8-10h at the temperature of 150 ℃ plus 200 ℃, naturally cooling to room temperature, filtering, washing with absolute ethyl alcohol and deionized water respectively, and drying to obtain the carboxymethyl chitosan-doped polyaniline-MnFe2O4A spinel catalyst;
the catalyst takes carboxymethyl chitosan-doped polyaniline as a carrier and carries MnFe in situ2O4Spinel of which MnFe2O4The catalyst accounts for 5-15wt% of the mass of the catalyst.
2. The method according to claim 1, wherein the MnFe2O4The catalyst accounts for 8-12wt% of the mass fraction of the catalyst.
3. The method as claimed in claim 1, wherein the reaction temperature in the step (2) is 160-180 ℃.
4. Carboxymethyl chitosan-doped polyaniline-MnFe prepared according to the preparation method of claim 12O4Spinel catalyst for catalyzing advanced oxidation of PMS (poly-p-phenylene-methane-styrene)Application in wastewater.
5. The application of the catalyst as claimed in claim 4, wherein the catalyst is added into the organic wastewater, PMS is added, the temperature of the system is adjusted to 25-40 ℃, and the system is magnetically stirred to perform advanced oxidation reaction.
6. The use of claim 5, wherein the catalyst is added in an amount of 0.1-1g/L and PMS is added in an amount of 0.5-2 g/L.
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