CN112264098A - Iron oxide-loaded attapulgite-chitosan heterogeneous composite catalyst and preparation method thereof - Google Patents
Iron oxide-loaded attapulgite-chitosan heterogeneous composite catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
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- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229960000892 attapulgite Drugs 0.000 claims abstract description 64
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 64
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 239000002351 wastewater Substances 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
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- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
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- 238000001035 drying Methods 0.000 claims description 19
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 239000007863 gel particle Substances 0.000 claims description 14
- 238000007605 air drying Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
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- 238000001816 cooling Methods 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 5
- 238000006731 degradation reaction Methods 0.000 claims description 5
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- 229940031182 nanoparticles iron oxide Drugs 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 3
- 229940010698 activated attapulgite Drugs 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 59
- 239000000047 product Substances 0.000 description 12
- 238000000227 grinding Methods 0.000 description 9
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
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- 229910052742 iron Inorganic materials 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
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- 238000001179 sorption measurement Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
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- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 description 1
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- 239000010802 sludge Substances 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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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
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/61—
-
- 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
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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Abstract
The invention discloses an iron oxide-loaded attapulgite-chitosan heterogeneous composite catalyst and a preparation method thereof. During preparation, the attapulgite is purified and activated, the attapulgite and chitosan are mixed, the mixture is molded by using an injector, and ferric oxide nano particles are loaded on the surface of the attapulgite-chitosan composite carrier after the attapulgite and the chitosan are dried, so that the ferric oxide-loaded attapulgite-chitosan heterogeneous composite catalyst is obtained. The preparation method of the catalyst is simple, does not need special equipment, and has low cost and good repeatability; the prepared catalyst has good catalytic performance, can be repeatedly used, has wide pH range, can be used at the temperature of 20-80 ℃, does not produce secondary pollution, and can be widely applied to the fields of treatment of organic wastewater difficult to degrade and the like.
Description
Technical Field
The invention relates to the field of catalysts, and in particular relates to an iron oxide-loaded attapulgite-chitosan heterogeneous composite catalyst and a preparation method thereof.
Background
Chitosan (CS) is one of the most interesting novel materials at present as a renewable resource existing in a large amount in the nature due to its characteristics such as biocompatibility and degradability, and is widely used in many fields such as functional materials and water treatment. However, in water treatment, the amino group in the macromolecular side group of chitosan as a typical cationic flocculant can only neutralize negatively charged sludge particles in sewage, and the chitosan has the defects of small surface area, poor mechanical strength, low specific gravity, easy caking and the like, thereby greatly limiting the efficient utilization of the chitosan. The chitosan is combined with the nano material, so that the surface area can be effectively improved, the active sites can be enhanced, and the functional groups can be enriched, thereby greatly improving the removal efficiency when removing pollutants in wastewater. For example, Zhao et al under the irradiation of simulated sunlight are catalytically coupled into a material formed by Ag/TiO2The modified chitosan-based photocatalytic film (ATCPF) and the hydrophilic ATCPF film show higher adsorption capacity and photocatalytic activity.But of TiO alone2The nanometer only absorbs photons less than 387.5 nm, and the utilization rate and the quantum efficiency of the solar energy are lower. Wu et al use cross-linking method to synthesize magnetic chitosan nano-composite with sodium tripolyphosphate as cross-linking agent, Ma et al use two-step co-precipitation method to synthesize magnetic chitosan nano-composite (MFe)3O4/CSNPs), but these processes are complicated and require a large number of reagents.
The Fenton method refers to the simultaneous presence of Fe in an acidic solution2+And hydrogen peroxide, can effectively oxidize and degrade organic matters. The Fenton method is an efficient oxidation technology and has more researches in the field of treatment of organic wastewater difficult to degrade. The Fenton method can effectively oxidize and degrade various organic pollutants which are difficult to degrade. Compared with other methods, the method has three main advantages: (1) various organic matters in the wastewater can be degraded without selectivity, toxic intermediate products can not be generated, and secondary pollution is greatly reduced, (2) most of catalysts used in the Fenton reaction are safe and easily obtained catalysts; (3) the Fenton reaction also has the characteristics of mild reaction conditions, high reaction rate, simple equipment and operation, automatic flocculation generation, no secondary pollution, high removal rate of organic matters and the like. However, the homogeneous Fenton reaction has two major disadvantages: firstly, the reaction has strict pH requirement, and secondly, iron mud which is difficult to treat is generated after the reaction. Heterogeneous Fenton catalysis is being widely studied as an advanced oxidation technology for the catalytic degradation of organic pollutants. The heterogeneous Fenton catalyst is easy to separate and recover, has no iron loss or small iron loss, can be repeatedly used, has stable catalytic performance and wide application range, and has better catalytic degradation capability on organic matters which are difficult to degrade in water.
The attapulgite is a water-containing magnesium-rich aluminate mixed mineral material with a two-dimensional layered and rod-shaped structure, and has attracted extensive attention of scientific researchers due to the advantages of low cost, rich reserves, high mechanical strength, good chemical stability, strong practicability, high exchange capacity, environmental protection and the like. In recent years, attapulgite with excellent performance is widely applied to the preparation of attapulgite-based adsorbents and catalysts or used as a doping material for the preparation of composite materials. The chitosan is combined with the attapulgite, so that the surface area can be effectively improved, the active sites can be enhanced, and the functional groups can be enriched, thereby greatly improving the removal efficiency when removing pollutants in wastewater.
Disclosure of Invention
In order to solve the problems, the invention provides an iron oxide-loaded attapulgite-chitosan heterogeneous composite catalyst and a preparation method thereof, and the obtained catalyst has good catalytic performance, can be recycled, has a wide pH range, can be used at 20-80 ℃, does not produce secondary pollution, and can be widely applied to the fields of treatment of refractory organic wastewater and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
an iron oxide-loaded attapulgite-chitosan heterogeneous composite catalyst takes a composite formed by compounding attapulgite and chitosan as a carrier, and iron oxide nano-particles are loaded on the carrier.
Further, the attapulgite is purified activated soil.
The invention also provides a preparation method of the iron oxide-loaded attapulgite-chitosan heterogeneous composite catalyst, which comprises the following steps:
s1, activation and purification of attapulgite
Taking 50g of industrial grade attapulgite clay, placing the industrial grade attapulgite clay in a muffle furnace, drying and roasting at 240 ℃ for 2h, cooling, transferring to a beaker, adding 100mL of 1mol/L hydrochloric acid, reacting for 2h, placing in a centrifuge, centrifuging and filtering, and replacing water until the supernatant is neutral; drying the filtered attapulgite clay in a vacuum drying oven at 90 deg.C for 12h, taking out, and grinding;
s2 preparation of attapulgite-chitosan carrier by blending method
Adding 1-5 mL of acetic acid into 99-95 mL of deionized water to prepare 1-5% acetic acid solution;
adding 1-5 g of purified and activated attapulgite and 1-5 g of chitosan into the prepared acetic acid solution, and magnetically stirring uniformly at room temperature until the attapulgite and the chitosan are fully mixed uniformly;
taking a 500mL beaker, adding 200 mL of 0.2-1 mol/L NaOH, pouring the uniformly mixed attapulgite/chitosan gel solution into a 50mL injector, dropwise adding the attapulgite/chitosan gel solution into the beaker, standing for 30-60 min, adding 5-20 mL of 2-5% wt glutaraldehyde solution, carrying out crosslinking reaction for 0.5-2 h, standing for 30-60 min, and carrying out suction filtration by using deionized water until the filtrate is neutral to obtain gel particles with the diameter of 5mm, namely the attapulgite-chitosan composite carrier.
S3, and loading of iron oxide nanoparticles
Placing the prepared attapulgite-chitosan composite carrier gel particles in a forced air drying oven, carrying out forced air drying at 100-105 ℃ for 1-3 h, introducing nitrogen at the speed of 5-15 mL/min at 300-500 ℃ for roasting for 1-2 h after water in the catalyst is completely volatilized, and obtaining black particles with the diameter of 1 mm;
taking a 50mL beaker, adding 2.5-10 g of Fe (NO)3)3·9H2Preparing 5-20 wt% ferric nitrate solution by using O and 47.5-40 mL of deionized water;
and respectively adding a proper amount of calcined catalyst into ferric nitrate solutions with different concentrations, carrying out ultrasonic impregnation for 10-60 min, taking out, repeatedly washing with deionized water, and then putting into a tubular furnace to be calcined for 1-3 h at the temperature of 200-400 ℃ and the speed of 5-15 mL/min through nitrogen gas, thus obtaining the yellow-black particle type catalyst.
The invention has the following beneficial effects:
the composite prepared by compounding attapulgite and chitosan is used as a carrier, the gel property of the chitosan is utilized to wrap the attapulgite rod crystals, and the composite can be formed by an injector and has higher specific surface area, adsorption performance and more active point sites than attapulgite and chitosan monomers, so that the catalytic performance of the catalyst is improved, the using amount of the carrier is greatly reduced, and the catalytic capacity and the impact resistance of the catalyst are improved.
The attapulgite-chitosan heterogeneous composite catalyst loaded with ferric oxide prepared by the invention can rapidly perform catalytic reaction in a wide pH range (2-12) and temperature range (20-80 ℃), but active components cannot be leached out, secondary pollution is not generated, and the catalyst can be recycled and has the characteristic of environmental friendliness.
Drawings
FIG. 1 is a scanning electron micrograph of the attapulgite-chitosan heterogeneous composite catalyst loaded with iron oxide prepared in example 4 of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
S1, taking 50g of industrial attapulgite clay produced in Jiangsu province, placing the clay in a muffle furnace, drying and roasting the clay for 2h at 240 ℃, cooling the clay, transferring the clay to a beaker, adding 100mL of 1mol/L hydrochloric acid, reacting for 2h, placing the clay in a centrifuge, centrifuging and filtering the clay, and replacing water until the supernatant is neutral; drying the filtered attapulgite clay in a vacuum drying oven at 90 deg.C for 12h, taking out, and grinding for use.
S2, 1mL of acetic acid is added to 99mL of deionized water to prepare a 1% acetic acid solution. Adding 2g of pretreated attapulgite and 2g of chitosan into the prepared acetic acid solution, and magnetically stirring the attapulgite and the chitosan uniformly at room temperature until the attapulgite and the chitosan are fully mixed uniformly. Adding 200 mL and 1mol/L NaOH into a 500mL beaker, pouring the uniformly mixed attapulgite-chitosan gel solution into a 50mL injector, dropwise adding the attapulgite-chitosan gel solution into the beaker, standing for 30min, adding 10mL of 5 wt% glutaraldehyde solution, carrying out crosslinking reaction for 1h, standing for 30min, and carrying out suction filtration by using deionized water until the filtrate is neutral to obtain gel particles with the diameter of 5mm, namely the attapulgite-chitosan composite carrier.
S3, placing the prepared attapulgite-chitosan composite carrier gel particles into a forced air drying oven, carrying out forced air drying at 100 ℃ for 1h, taking out the particles after the moisture in the catalyst is completely volatilized, placing the particles into a crucible, placing the crucible into a tubular furnace, and introducing nitrogen at the speed of 15mL/min at 400 ℃ for roasting for 2h to obtain black particles with the diameter of 1mm, black particles. A100 mL beaker was charged with 2.5g of Fe (NO)3)3·9H2Preparing 5 wt% ferric nitrate solution by using O and 47.5mL of deionized water, respectively adding a proper amount of calcined catalyst into the ferric nitrate solution, and carrying out ultrasonic impregnation for 30 min. After the impregnation is finished, taking out the obtained product, repeatedly washing the obtained product with deionized water, putting the obtained product into a tubular furnace, introducing nitrogen at the temperature of 200 ℃ and the speed of 15mL/min, and roasting the obtained product for 1h to obtain the yellow-black granular iron oxide/attapulgite-chitosan catalyst.
Example 2
S1, taking 50g of industrial attapulgite clay produced in Jiangsu province, placing the clay in a muffle furnace at 240 ℃ for drying and roasting for 2h, cooling, transferring the clay to a beaker, adding 100mL of 1mol/L hydrochloric acid for reaction for 2h, placing the clay in a centrifuge for centrifugal filtration, and replacing water until the supernatant is neutral. Drying the filtered attapulgite clay in a vacuum drying oven at 90 deg.C for 12h, taking out, and grinding for use.
S2, 2mL of acetic acid is added to 98mL of deionized water to prepare a 2% acetic acid solution. Adding 1g of pretreated attapulgite and 2g of chitosan into the prepared acetic acid solution, and magnetically stirring the attapulgite and the chitosan at room temperature until the attapulgite and the chitosan are fully and uniformly mixed. And (2) adding 200 mL and 0.5mol/L NaOH into a 500mL beaker, pouring the uniformly mixed attapulgite/chitosan gel solution into a 50mL injector, dropwise adding into the beaker, standing for 60min, adding 5mL of 2 wt% glutaraldehyde solution, carrying out crosslinking reaction for 1h, standing for 60min, and carrying out suction filtration by using deionized water until the filtrate is neutral to obtain gel particles with the diameter of 5mm, namely the attapulgite-chitosan composite carrier.
S3, placing the prepared attapulgite-chitosan composite carrier gel particles into a forced air drying oven, carrying out forced air drying at 105 ℃ for 2h, taking out the particles after the moisture in the catalyst is completely volatilized, placing the particles into a crucible, placing the crucible into a tubular furnace, and introducing nitrogen at 300 ℃ at a rate of 10mL/min for roasting for 1h to obtain black particles with the diameter of 1 mm. A100 mL beaker was charged with 5g of Fe (NO)3)3·9H2O and 45mL of deionized water to prepare a 10 wt% ferric nitrate solution, and adding a proper amount of calcined catalyst into the ferric nitrate solution respectively, and carrying out ultrasonic impregnation for 40 min. Taking out after the impregnation is finishedRepeatedly washing with deionized water, placing into a tubular furnace, introducing nitrogen at 300 deg.C and 5mL/min, and calcining for 3 hr to obtain yellow-black granular iron oxide/attapulgite-chitosan catalyst.
Example 3
S1, taking 50g of industrial attapulgite clay produced in Jiangsu province, placing the clay in a muffle furnace at 240 ℃ for drying and roasting for 2h, cooling, transferring the clay to a beaker, adding 100mL of 1mol/L hydrochloric acid for reaction for 2h, placing the clay in a centrifuge for centrifugal filtration, and replacing water until the supernatant is neutral. Drying the filtered attapulgite clay in a vacuum drying oven at 90 deg.C for 12h, taking out, and grinding for use.
S2, 5mL of acetic acid is added to 95mL of deionized water to prepare a 5% acetic acid solution. Adding 2g of pretreated attapulgite and 1g of chitosan into the prepared acetic acid solution, and magnetically stirring the attapulgite and the chitosan uniformly at room temperature until the attapulgite and the chitosan are fully mixed uniformly. Adding 200 mL and 1mol/L NaOH into a 500mL beaker, pouring the uniformly mixed attapulgite-chitosan gel solution into a 50mL injector, dropwise adding the attapulgite-chitosan gel solution into the beaker, standing for 30min, adding 15mL of 2 wt% glutaraldehyde solution, carrying out crosslinking reaction for 0.5h, standing for 60min, and carrying out suction filtration by using deionized water until the filtrate is neutral to obtain gel particles with the diameter of 5mm, namely the attapulgite-chitosan composite carrier.
S3, placing the prepared attapulgite-chitosan composite carrier gel particles into a forced air drying oven, carrying out forced air drying at 100 ℃ for 2h, taking out the particles after the moisture in the catalyst is completely volatilized, placing the particles into a crucible, placing the crucible into a tubular furnace, and introducing nitrogen at the speed of 5mL/min at 500 ℃ for roasting for 1h to obtain black particles with the diameter of 1 mm. A100 mL beaker was charged with 7.5g of Fe (NO)3)3·9H2Preparing 15 wt% ferric nitrate solution by using O and 42.5mL of deionized water, respectively adding a proper amount of calcined catalyst into the ferric nitrate solution, and carrying out ultrasonic impregnation for 60 min. After the impregnation is finished, taking out the obtained product, repeatedly washing the obtained product by using deionized water, putting the obtained product into a tubular furnace, introducing nitrogen at the temperature of 400 ℃ and the speed of 10mL/min, and roasting the obtained product for 2 hours to obtain the yellow-black granular iron oxide/attapulgite-chitosan catalyst.
Example 4
S1, taking 50g of industrial attapulgite clay produced in Jiangsu province, placing the clay in a muffle furnace at 240 ℃ for drying and roasting for 2h, cooling, transferring the clay to a beaker, adding 100mL of 1mol/L hydrochloric acid for reaction for 2h, placing the clay in a centrifuge for centrifugal filtration, and replacing water until the supernatant is neutral. Drying the filtered attapulgite clay in a vacuum drying oven at 90 deg.C for 12h, taking out, and grinding for use.
S2, 5mL of acetic acid is added to 95mL of deionized water to prepare a 5% acetic acid solution. Adding 5g of pretreated attapulgite and 5g of chitosan into the prepared acetic acid solution, and magnetically stirring the attapulgite and the chitosan uniformly at room temperature until the attapulgite and the chitosan are fully mixed uniformly. And (2) adding 200 mL and 0.5mol/L NaOH into a 500mL beaker, pouring the uniformly mixed attapulgite/chitosan gel solution into a 50mL injector, dropwise adding into the beaker, standing for 30min, adding 20mL of 2 wt% glutaraldehyde solution, carrying out crosslinking reaction for 1.5h, standing for 30min, and carrying out suction filtration by using deionized water until the filtrate is neutral to obtain gel particles with the diameter of 5mm, namely the attapulgite-chitosan composite carrier.
S3, placing the prepared attapulgite-chitosan composite carrier gel particles into a forced air drying oven, carrying out forced air drying at 105 ℃ for 1.5h, taking out the particles after the moisture in the catalyst is completely volatilized, placing the particles into a crucible, placing the crucible into a tubular furnace, and introducing nitrogen at 350 ℃ at a rate of 15mL/min to roast the particles for 1h to obtain black particles with the diameter of 1 mm. A100 mL beaker was charged with 10g of Fe (NO)3)3·9H2Preparing 20 wt% ferric nitrate solution by using O and 40mL of deionized water, respectively adding a proper amount of calcined catalyst into the ferric nitrate solution, and ultrasonically dipping for 60 min. After the impregnation is finished, taking out the obtained product, repeatedly washing the obtained product by using deionized water, putting the obtained product into a tubular furnace, introducing nitrogen at the temperature of 400 ℃ and the speed of 15mL/min, and roasting the obtained product for 3 hours to obtain the yellow-black granular iron oxide/attapulgite-chitosan catalyst.
Comparative example 1
S1, taking 50g of industrial attapulgite clay produced in Jiangsu province, placing the clay in a muffle furnace at 240 ℃ for drying and roasting for 2h, cooling, transferring the clay to a beaker, adding 100mL of 1mol/L hydrochloric acid for reaction for 2h, placing the clay in a centrifuge for centrifugal filtration, and replacing water until the supernatant is neutral. The filtered attapulgite clay is put into a vacuum drying oven to be dried for 12 hours at the temperature of 90 ℃ and then taken out for grinding. And (3) taking 20g of purified soil, adding 20mL of deionized water, uniformly mixing, forming into 1mm attapulgite particles, aging for 24h, and drying at 105 ℃ for 2h to obtain the attapulgite carrier.
S2, putting the prepared attapulgite carrier into 8 wt% ferric nitrate solution, ultrasonically dipping for 30min, and drying at 105 ℃ to obtain the iron oxide/attapulgite particle catalyst.
Comparative example 2
S1, 2mL of acetic acid is added to 98mL of deionized water to prepare a 2% acetic acid solution. And adding 2g of chitosan into the prepared acetic acid solution, and magnetically stirring the chitosan and the acetic acid solution uniformly at room temperature until the chitosan and the acetic acid solution are fully mixed uniformly. Adding 200 mL of 0.5mol/L NaOH into a 500mL beaker, pouring the chitosan gel solution into a 50mL injector, dropwise adding the chitosan gel solution into the beaker, standing for 60min, adding 10mL of 2% wt glutaraldehyde solution, carrying out crosslinking reaction for 1h, standing for 60min, and carrying out suction filtration by using deionized water until the filtrate is neutral to obtain gel particles with the diameter of 5mm, namely the chitosan carrier.
S2, putting the prepared chitosan carrier into 8 wt% ferric nitrate solution, ultrasonically dipping for 30min, and drying at 105 ℃ to obtain the ferric oxide/chitosan catalyst.
Comparative example 3
S1, taking 50g of industrial attapulgite clay produced in Jiangsu province, placing the clay in a muffle furnace at 240 ℃ for drying and roasting for 2h, cooling, transferring the clay to a beaker, adding 100mL of 1mol/L hydrochloric acid for reaction for 2h, placing the clay in a centrifuge for centrifugal filtration, and replacing water until the supernatant is neutral. Drying the filtered attapulgite clay in a vacuum drying oven at 90 deg.C for 12h, taking out, and grinding for use.
S2, 5mL of acetic acid is added to 95mL of deionized water to prepare a 5% acetic acid solution. Adding 5g of pretreated attapulgite and 5g of chitosan into the prepared acetic acid solution, and magnetically stirring the attapulgite and the chitosan uniformly at room temperature until the attapulgite and the chitosan are fully mixed uniformly. Adding 200 mL and 0.5mol/L NaOH into a 500mL beaker, pouring the uniformly mixed attapulgite-chitosan gel solution into a 50mL injector, dropwise adding the attapulgite-chitosan gel solution into the beaker, standing for 30min, adding 15mL of 2 wt% glutaraldehyde solution, carrying out crosslinking reaction for 1.5h, standing for 30min, and carrying out suction filtration by using deionized water until the filtrate is neutral to obtain gel particles with the diameter of 5mm, namely the attapulgite-chitosan composite carrier.
Comparative example 4
S1, taking 50g of industrial attapulgite clay produced in Jiangsu province, placing the clay in a muffle furnace at 240 ℃ for drying and roasting for 2h, cooling, transferring the clay to a beaker, adding 100mL of 1mol/L hydrochloric acid for reaction for 2h, placing the clay in a centrifuge for centrifugal filtration, and replacing water until the supernatant is neutral. Drying the filtered attapulgite clay in a vacuum drying oven at 90 deg.C for 12h, taking out, and grinding for use.
S2, mixing 10g Fe (NO)3)3Dissolved in 40mL of distilled water to give 20% wt Fe (NO)3)3Putting a certain amount of pretreated attapulgite into the solution, ultrasonically dispersing for 2h under the condition of 50Hz, vacuum drying for 4h at 90 ℃ after suction filtration, roasting for 2h at 400 ℃ in a vacuum tube type high-temperature sintering furnace, taking out, and grinding to obtain Fe2O3ATP powder.
S3, 1g of Fe2O3Dispersing ATP powder into 50mL of acetic acid solution with the volume ratio of 1%, weighing 1g of chitosan, adding the chitosan into the solution, covering a preservative film, and magnetically stirring at the temperature of 55 ℃ until the chitosan and the preservative film are fully and uniformly mixed. After the mixture was cooled to room temperature, the mixture was poured into a syringe and dropped into 1mol/L sodium hydroxide solution at a height of 20cm from the liquid surface. Standing for 30min, adding 2mL of glutaraldehyde, stirring for reaction for 1h, and aging for 2 h. Filtering, replacing with water until neutral, vacuum drying at 90 deg.C for 4 hr, and taking out to obtain Fe2O3a/ATP/CS granular type catalyst.
Testing of catalytic Performance of the catalyst
Preparing a methylene blue solution with the concentration of 100mg/L, adjusting the pH value to 5 by using 0.1mol/L hydrochloric acid, putting a conical flask containing the methylene blue solution into a water bath at 60 ℃, adding 50mg of the prepared catalyst, adding 0.5mL of 30% hydrogen peroxide, reacting for 60min, taking the supernatant of the solution, measuring the absorbance of the solution at the wavelength of 664nm, and calculating the corresponding concentration according to a calibration curve.
Preparing a ciprofloxacin solution with the concentration of 50mg/L, adjusting the pH value to 5 by using 0.1mol/L hydrochloric acid, putting a conical flask containing the ciprofloxacin solution into a water bath at 60 ℃, adding 100mg of the prepared catalyst, adding 0.2mL of 30% hydrogen peroxide, reacting for 60min, taking the supernatant of the solution, measuring the absorbance of the solution at the wavelength of 277nm, and calculating the corresponding concentration according to a calibration curve.
The test results are shown in tables 1 and 2.
TABLE 1 test results of catalytic degradation of Methylene Blue (MB) by catalyst
TABLE 2 test results of the performance of the catalyst in the catalytic degradation of Ciprofloxacin (CIP)
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (5)
1. An iron oxide-loaded attapulgite-chitosan heterogeneous composite catalyst is characterized in that: the catalyst takes a compound formed by compounding attapulgite and chitosan as a carrier, and iron oxide nano-particles are loaded on the carrier.
2. The iron oxide-loaded attapulgite-chitosan heterogeneous composite catalyst according to claim 1, wherein: the attapulgite is purified activated soil and is prepared by the following method:
taking 50g of industrial grade attapulgite clay, placing the industrial grade attapulgite clay in a muffle furnace, drying and roasting at 240 ℃ for 2h, cooling, transferring to a beaker, adding 100mL of 1mol/L hydrochloric acid, reacting for 2h, placing in a centrifuge, centrifuging and filtering, and replacing water until the supernatant is neutral; the filtered attapulgite clay is put into a vacuum drying oven to be dried for 12 hours at the temperature of 90 ℃, and then is taken out to be ground for standby.
3. The iron oxide-loaded attapulgite-chitosan heterogeneous composite catalyst according to claim 1, wherein: the attapulgite-chitosan carrier is prepared by a blending method, and the concrete operation comprises the following steps:
adding 1-5 mL of acetic acid into 99-95 mL of deionized water to prepare 1-5% acetic acid solution;
adding 1-5 g of purified and activated attapulgite and 1-5 g of chitosan into the prepared acetic acid solution, and magnetically stirring uniformly at room temperature until the attapulgite and the chitosan are fully mixed uniformly;
taking a 500mL beaker, adding 200 mL of 0.2-1 mol/L NaOH, pouring the uniformly mixed attapulgite/chitosan gel solution into a 50mL injector, dropwise adding the attapulgite/chitosan gel solution into the beaker, standing for 30-60 min, adding 5-20 mL of 2-5% wt glutaraldehyde solution, carrying out crosslinking reaction for 0.5-2 h, standing for 30-60 min, and carrying out suction filtration by using deionized water until the filtrate is neutral to obtain gel particles with the diameter of 5mm, namely the attapulgite-chitosan composite carrier.
4. The iron oxide-loaded attapulgite-chitosan heterogeneous composite catalyst according to claim 1, wherein: the preparation method comprises the following steps:
placing the prepared attapulgite-chitosan composite carrier gel particles in a forced air drying oven, carrying out forced air drying at 100-105 ℃ for 1-3 h, introducing nitrogen at the speed of 5-15 mL/min at 300-500 ℃ for roasting for 1-2 h after water in the catalyst is completely volatilized, and obtaining black particles with the diameter of 1 mm;
taking a 50mL beaker, adding 2.5-10 g of Fe (NO)3)3·9H2Preparing 5-20 wt% ferric nitrate solution by using O and 47.5-40 mL of deionized water;
and respectively adding a proper amount of calcined catalyst into ferric nitrate solutions with different concentrations, carrying out ultrasonic impregnation for 10-60 min, taking out, repeatedly washing with deionized water, and then putting into a tubular furnace to be calcined for 1-3 h at the temperature of 200-400 ℃ and the speed of 5-15 mL/min through nitrogen gas, thus obtaining the yellow-black particle type catalyst.
5. The iron oxide, attapulgite and chitosan heterogeneous composite catalyst as claimed in claim 1, wherein the iron oxide/attapulgite-chitosan heterogeneous composite catalyst can be used for catalytic degradation treatment of refractory organic wastewater.
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