CN116726977B - Bimetallic layered silicate catalyst based on natural zeolite and its application - Google Patents
Bimetallic layered silicate catalyst based on natural zeolite and its applicationInfo
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- CN116726977B CN116726977B CN202310509574.0A CN202310509574A CN116726977B CN 116726977 B CN116726977 B CN 116726977B CN 202310509574 A CN202310509574 A CN 202310509574A CN 116726977 B CN116726977 B CN 116726977B
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Abstract
The invention provides a bimetallic phyllosilicate catalyst based on natural zeolite, which is prepared by calcining natural zeolite, reacting with bimetallic salt and alkaline substance at a certain temperature, and adopting urea or hexamethylenetetramine or sodium hydroxide as pH regulator, which can react with zeolite to provide silicate radical and promote the formation of phyllosilicate. In the preparation method of the natural zeolite-based bimetallic phyllosilicate catalyst, the natural zeolite-based bimetallic phyllosilicate catalyst has high-grade oxidation catalytic degradation effect on organic pollutants in sewage.
Description
Technical Field
The invention provides a natural zeolite-based bimetallic phyllosilicate catalyst and a preparation method and application thereof, belongs to the field of catalyst materials, and particularly relates to a natural zeolite-based bimetallic phyllosilicate catalyst, a preparation method and application thereof in the technical field of advanced oxidation.
Background
In recent years, a transition metal-based catalyst using a single metal or multiple metals of Co, ni or Fe as an active center is one of important development directions of a high-grade oxidation catalyst, and particularly, the catalytic activity of the transition metal-based catalyst can be synergistically improved by utilizing the polyvalent state of a bimetal and the electron conduction among different metal ions.
Layered silicates (such as layered nickel silicate, layered cobalt silicate, and layered iron silicate), also called phyllosilicates, are layered silicate clay compounds composed of polyhedrons composed of metal elements and silicate tetrahedra. The layered silicate has high stability and unique layered structure, has characteristics of metal-based compounds, and is used as a catalyst to exhibit excellent catalytic ability in chemical, environmental and energy conversion related fields. At present, most of the synthesis of the layered silicate is to directly adopt chemical reagents (such as tetraethoxysilane, sodium silicate and the like) for synthesis and preparation, the cost is high, and the preparation of the layered silicate with the special shape of nano tube is relatively difficult, so that the preparation of the layered silicate is unfavorable for large-scale production and preparation.
The natural zeolite is an aluminosilicate mineral with a water-containing frame-shaped structure, has the characteristics of larger specific surface area, exchangeable cations, adsorbable organic pollutants and the like, has the advantages of abundant reserves, low price, wide sources and the like, and is an ideal pollutant adsorption and catalyst carrier material. The natural zeolite is used as raw material and carrier, and the bimetallic phyllosilicate is synthesized on the surface of zeolite, so that the coupling synergistic effect of zeolite, bimetal and phyllosilicate can be simultaneously exerted, at the same time, the synthesis method of the phyllosilicate composite material can be improved, the application of the natural zeolite in the aspect of environmental functional materials can be further improved, and the high-valued utilization value of the natural zeolite can be fully improved.
Disclosure of Invention
The purpose of the present invention is to prepare a catalyst which simultaneously exerts the coupling synergistic effect of zeolite, bimetal and layered silicate.
The technical scheme adopted is as follows:
in a first aspect, the present invention provides a natural zeolite-based bimetallic phyllosilicate catalyst prepared by the method of:
(1) Calcining natural zeolite powder with the particle size of 0.2-200 μm at 300-700 ℃ for 2-4 h (preferably 600 ℃ for 2 h) to obtain calcined zeolite;
(2) Uniformly dispersing the calcined zeolite obtained in the step (1) in deionized water, adding a soluble cobalt salt and a soluble metal salt, uniformly dispersing, adding an alkaline substance, uniformly dispersing, and obtaining a mixed suspension, wherein the soluble metal salt is one of ferric salt and nickel salt, and the mass ratio of the soluble cobalt salt, the soluble metal salt and the alkaline substance to the calcined zeolite is 1.07-1.6:0.25-2.1:0.5-3.6:1 (preferably 1.455-1.6:1.01-2.02:0.5-3.6:1, particularly preferably 1.455:1.455:3.6:1);
(3) And (3) reacting the mixed suspension obtained in the step (2) at 75-95 ℃ for 6-8 hours (preferably 7-8 hours, particularly preferably 8 hours), and carrying out post-treatment on the obtained reaction solution to obtain the natural zeolite-based bimetallic phyllosilicate catalyst.
In one embodiment of the present invention, the particle size of the natural zeolite powder in the step (1) is 0.5-100 μm.
Preferably, the volume of deionized water in step (1) is 30 to 50mL/g (preferably 30 to 40mL/g, particularly preferably 30 mL/g) based on the mass of the calcined zeolite.
Preferably, the soluble metal salt in step (2) is a nickel salt.
In one embodiment of the invention, the soluble cobalt salt is Co (NO 3)2 6H 2 O, the nickel salt is Ni (NO 3)2 6H 2 O, the iron salt is Fe (NO 3)3 9H2O。
Preferably, the alkaline substance in the step (2) is one or a mixture of more than two of urea, hexamethylenetetramine and sodium hydroxide, and particularly preferably urea.
And (3) cooling the reaction liquid to room temperature, carrying out suction filtration, washing the obtained filter cake by sequentially carrying out suction filtration with deionized water and ethanol, and drying to obtain the natural zeolite-based bimetallic phyllosilicate catalyst.
The invention also provides the natural zeolite-based bimetallic phyllosilicate catalyst obtained by the preparation method of the natural zeolite-based bimetallic phyllosilicate catalyst, which can fully utilize the high specific surface area of zeolite powder particles to form a phyllosilicate coating layer on the surfaces of the zeolite powder particles, and the phyllosilicate has a nano tubular morphology structure. A representative reaction process is as follows:
CO(NH2)2 + 3H2O CO2 + 2(NH3·H2O)(>70°C)
NH3·H2O NH4 ++OH-
SiO 2 (from zeolite decomposition) +2OH - SiO3 2-+H2O
3Co2++2SiO3 2-+ 2OH-+H2O Co3Si2O5(OH)4
The bimetallic phyllosilicate catalyst based on natural zeolite can be used for treating organic pollutants in water by an adsorption method or by an advanced oxidation method represented by activated persulfate when treating organic wastewater.
In a second aspect, the invention also provides the use of the natural zeolite-based bimetallic phyllosilicate catalyst in the treatment of wastewater containing organic pollutants.
Further, the organic pollutant in the organic pollutant wastewater is at least one of norfloxacin, tetracycline, sulfamethoxazole, bisphenol A, perfluorinated compounds, pesticide compounds and polycyclic aromatic hydrocarbons.
The application is that the natural zeolite-based bimetallic phyllosilicate catalyst is uniformly dispersed into organic pollutant wastewater for degradation for 30-60min.
Further, the concentration of the organic pollutants in the organic pollutant wastewater is 5-100mg/L, and the mass volume ratio of the bimetallic phyllosilicate catalyst based on natural zeolite to the organic pollutant wastewater is 0.5-20 g/1L.
Compared with the prior art, the invention has the following advantages:
(1) The natural zeolite used in the invention has the advantages of large natural reserve, low price, low equipment requirement, simple and convenient synthesis process, low energy consumption and convenient mass production due to normal pressure operation.
(2) In the natural zeolite-based bimetallic phyllosilicate catalyst provided by the invention, the bimetallic phyllosilicate is uniformly coated on the surface of zeolite in a nano tubular structure, and zeolite particles provide a dispersion carrier for the nano tubular structure bimetallic phyllosilicate.
(3) In the natural zeolite-based bimetallic phyllosilicate catalysts provided by the present invention, the zeolite provides the silicon source required to synthesize the bimetallic phyllosilicate.
(4) According to the preparation method of the natural zeolite-based bimetallic phyllosilicate catalyst, the natural zeolite is calcined, so that the catalytic performance of the prepared natural zeolite-based bimetallic phyllosilicate catalyst can be remarkably improved.
(5) In the preparation method of the natural zeolite-based bimetallic phyllosilicate catalyst, the bimetallic material can be cobalt-nickel (Co/Ni) bimetallic material or cobalt-iron (Co/Fe) bimetallic material.
(6) In the preparation method of the bimetallic phyllosilicate catalyst based on natural zeolite, urea or hexamethylenetetramine or sodium hydroxide is adopted as a pH regulator, so that silicate radicals can be provided by reaction with zeolite, and the formation of phyllosilicate can be promoted.
(7) In the preparation method of the natural zeolite-based bimetallic phyllosilicate catalyst, the natural zeolite-based bimetallic phyllosilicate catalyst has high-grade oxidation catalytic degradation effect on organic pollutants in sewage.
Drawings
Fig. 1 is an XRD pattern of the natural zeolite-based bimetallic phyllosilicate catalyst of example 1.
Fig. 2 is a TEM image of the natural zeolite based bimetallic phyllosilicate catalyst of example 1.
Fig. 3 is a TEM image at high magnification of the natural zeolite-based bimetallic phyllosilicate catalyst of example 1.
Fig. 4 is an XRD pattern of the sample prepared in comparative example 4.
Detailed Description
Example 1
(1) And weighing 10g of natural zeolite powder (natural zeolite is produced from Guangxi Zhuang nationality, powder with the particle size distribution of 0.5-100 mu m is obtained after grinding), calcining in a tube furnace at 600 ℃, preserving the heat for 2h, and heating at the temperature rising rate of 5 ℃ per minute to obtain calcined natural zeolite.
(2) Taking 2g of calcined zeolite calcined at 600 ℃, placing the calcined zeolite in 60mL of deionized water, and stirring by ultrasonic to uniformly disperse to obtain suspension A.
(3) Adding 2.91g Ni (NO) to the mixture 3)2 6H 2 O and 2.91g Co (NO 3)2 And (3) carrying out ultrasonic stirring on the mixture for 10min by using 6H 2 O to obtain a mixed suspension B.
(4) And (3) weighing 7.2g of urea to be dissolved in the mixed suspension B in the step (3), and stirring the mixture for 10min by ultrasonic to obtain a mixed suspension C.
(5) Transferring the mixed suspension into an atmospheric water bath kettle, magnetically stirring and reacting for 8 hours at the temperature of 90 ℃, cooling to room temperature, carrying out suction filtration, washing and suction filtration on the obtained filter cake with deionized water and ethanol for three times, and carrying out vacuum drying for 6 hours at the temperature of 60 ℃ to obtain the nickel-cobalt bimetallic phyllosilicate catalyst based on natural zeolite.
The XRD patterns of the natural zeolite-based nickel-cobalt bimetallic phyllosilicate catalyst are shown in fig. 1, and the results of fig. 1 show that the crystalline phase components of the sample are those of nickel phyllosilicate (Ni 3Si2O5(OH)4), cobalt phyllosilicate (Co 3Si2O5(OH)4) and quartz (SiO 2).
TEM images of the natural zeolite-based bimetallic phyllosilicate catalyst are shown in fig. 2 and 3, and fig. 2 shows that the zeolite surface has obvious nickel-cobalt bimetallic phyllosilicate coating, and the zeolite surface is uniformly distributed, and the coating is uniform in whole. Figure 3 shows that the nickel cobalt bimetallic phyllosilicate catalyst formed on the zeolite surface has a tubular nanostructure.
Example 2
(1.) 10G of natural zeolite powder (natural zeolite is produced from Guangxi Zhuang autonomous region, powder with the particle size distribution of 0.5-100 μm is obtained after grinding) is weighed and calcined in a tube furnace at 600 ℃ for 2h at a temperature rising rate of 5 ℃ per minute, so as to obtain calcined natural zeolite.
(2.) 2G of calcined zeolite calcined at 600℃was placed in 60mL of deionized water, and stirred with ultrasound to uniformly disperse, thereby obtaining suspension A.
(3.) To the mixture was added 2.91.G Co (NO) 3)2 6H2O、4.04 g Fe(NO3)3 9H 2 O is stirred for 10min under magnetic force to obtain a mixed suspension B.
(4.) 7.2G of urea was weighed and dissolved in the mixed suspension B of step (3), and the mixture was stirred with ultrasound for 10 minutes to obtain a mixed suspension C.
And magnetically stirring the mixture in an atmospheric water bath kettle, and reacting for 8 hours at 90 ℃. And then carrying out suction filtration, washing the obtained filter cake by using deionized water and ethanol, and carrying out vacuum drying at 60 ℃ to obtain the natural zeolite-based bimetallic phyllosilicate catalyst.
Example 3
(1) 10G of natural zeolite powder (natural zeolite is produced from Guangxi Zhuang autonomous region, powder with the particle size distribution of 0.5-100 μm is obtained after grinding) is weighed and calcined in a tube furnace at 650 ℃, the heat preservation time is 2h, and the heating rate is 5 ℃ per min, so that the calcined natural zeolite is obtained.
(2) 2G of calcined zeolite calcined at 650 ℃ is taken and placed in 60mL of deionized water, and the mixture is stirred by ultrasonic to be uniformly dispersed, so as to obtain suspension A.
(3) Then 2.91g Co (NO) is added into the mixed solution at the same time 3)2 6H2O、1.01 g Fe(NO3)3 9H 2 O is stirred for 10min under magnetic force to obtain a mixed suspension B.
(4) 6.5G of urea is weighed and dissolved in the mixed suspension B in the step (3), and the mixed suspension C is obtained after ultrasonic stirring for 10min.
And magnetically stirring the mixture in an atmospheric water bath kettle, and reacting for 6 hours at the temperature of 95 ℃. And then carrying out suction filtration, washing the obtained filter cake by using deionized water and ethanol, and carrying out vacuum drying at 60 ℃ to obtain the natural zeolite-based bimetallic phyllosilicate catalyst.
Example 4
(1) And weighing 10g of natural zeolite powder (natural zeolite is produced from Guangxi Zhuang nationality, powder with the particle size distribution of 0.5-100 mu m is obtained after grinding), calcining in a tube furnace at 700 ℃, preserving the heat for 3h, and heating at the temperature rising rate of 5 ℃ per minute to obtain calcined natural zeolite.
(2) Taking 2g of calcined zeolite calcined at 700 ℃, placing the calcined zeolite in 80mL of deionized water, and stirring by ultrasonic to uniformly disperse to obtain suspension A.
(3) Then 2.318g Co (NO) is added into the mixed solution 3)2 6H 2 O and 1.455g Ni (NO 3)2 And (3) carrying out ultrasonic stirring on the mixture for 10min by using 6H 2 O to obtain a mixed suspension B.
(4) And (3) weighing 1g of sodium hydroxide (NaOH) to dissolve in the mixed suspension B in the step (3), and stirring for 10min by ultrasonic to obtain a mixed suspension C.
(5) Transferring the mixed suspension C into an atmospheric water bath kettle, magnetically stirring and reacting for 6 hours at 80 ℃, cooling to room temperature, carrying out suction filtration, washing and suction filtering the obtained filter cake with deionized water and ethanol for three times, and carrying out vacuum drying for 6 hours at 60 ℃ to obtain the natural zeolite-based bimetallic phyllosilicate catalyst.
Example 5
(1) And weighing 10g of natural zeolite powder (natural zeolite is produced from Guangxi Zhuang nationality, powder with the particle size distribution of 0.5-100 mu m is obtained after grinding), calcining in a tube furnace at 600 ℃, preserving the heat for 4h, and heating at a temperature rising rate of 5 ℃ per minute to obtain calcined natural zeolite.
(2) Taking 2g of calcined zeolite calcined at 600 ℃, placing the calcined zeolite into 100mL of deionized water, and stirring by ultrasonic to uniformly disperse to obtain suspension A.
(3) Then 3.201g Co (NO) is added into the mixed solution 3)2 6H 2 O and 2.02g Fe (NO) 3)3 9H 2 O is ultrasonically stirred for 10min, and a mixed suspension B is obtained.
(4) Weighing 8g of hexamethylenetetramine, dissolving in the mixed suspension B in the step (3), and stirring for 10min by ultrasonic to obtain a mixed suspension C.
(5) Transferring the mixed suspension into an atmospheric water bath kettle, magnetically stirring and reacting for 7 hours at the temperature of 95 ℃, cooling to room temperature, carrying out suction filtration, washing and suction filtration on the obtained filter cake with deionized water and ethanol for three times, and carrying out vacuum drying for 6 hours at the temperature of 60 ℃ to obtain the natural zeolite-based bimetallic phyllosilicate catalyst.
Example 6
(1) And weighing 10g of natural zeolite powder (natural zeolite is produced from Guangxi Zhuang nationality, powder with the particle size distribution of 0.5-100 mu m is obtained after grinding), calcining in a tube furnace at 700 ℃, preserving the heat for 3h, and heating at the temperature rising rate of 5 ℃ per minute to obtain calcined natural zeolite.
(2) Taking 2g of calcined zeolite calcined at 700 ℃, placing the calcined zeolite in 70mL of deionized water, and stirring by ultrasonic to uniformly disperse to obtain suspension A.
(3) Adding 2.91g Co (NO) to the mixture 3)2 6H 2 O and 0.582g Ni (NO 3)2 And (3) carrying out ultrasonic stirring on the mixture for 10min by using 6H 2 O to obtain a mixed suspension B.
(4) And (3) weighing 1g of sodium hydroxide (NaOH) to dissolve in the mixed suspension B in the step (3), and stirring for 10min by ultrasonic to obtain a mixed suspension C.
(5) Transferring the mixed suspension into an atmospheric water bath kettle, magnetically stirring and reacting for 8 hours at the temperature of 90 ℃, cooling to room temperature, carrying out suction filtration, washing and suction filtration on the obtained filter cake with deionized water and ethanol for three times, and carrying out vacuum drying for 6 hours at the temperature of 60 ℃ to obtain the natural zeolite-based bimetallic phyllosilicate catalyst.
Comparative example 1
(1) And weighing a proper amount of natural zeolite powder (natural zeolite is produced from Guangxi Zhuang nationality, powder with the particle size distribution of 0.5-100 mu m is obtained after grinding), calcining in a tube furnace at 600 ℃, preserving the heat for 2h, and obtaining the calcined zeolite at the temperature rising rate of 5 ℃ per minute.
(2) Taking 2g of zeolite calcined at 600 ℃, placing the zeolite in 60ml of deionized water, and stirring by ultrasonic to uniformly disperse to obtain suspension A.
(3) 2.91G Ni (NO) was added to the suspension A 3)2 And (3) carrying out ultrasonic stirring on the mixture for 10min by using 6H 2 O to obtain a mixed suspension B.
(4) And (3) weighing 7.2g of urea to be dissolved in the mixed suspension B in the step (3), and stirring the mixture for 10min by ultrasonic to obtain a mixed suspension C.
(5) Transferring the mixed suspension C into an atmospheric water bath kettle, magnetically stirring and reacting for 8 hours at the temperature of 90 ℃, cooling to room temperature, carrying out suction filtration, washing and suction filtering the obtained filter cake with deionized water and ethanol for three times, and carrying out vacuum drying for 6 hours at the temperature of 60 ℃ to obtain a sample of comparative example 1.
Comparative example 1 As compared with example 1, only Ni (NO 3)2 6H 2 O soluble metal salts.
Comparative example 2
(1) Taking 2g of natural zeolite powder (natural zeolite is produced from Guangxi Zhuang autonomous region, grinding to obtain powder with particle size distribution of 0.5-100 μm), placing into 60mL of deionized water, and stirring by ultrasonic to uniformly disperse to obtain suspension A.
(2) Adding 2.91g Ni (NO) to the mixture 3)2 6H 2 O and 2.91.G Co (NO 3)2 And (3) carrying out ultrasonic stirring on the mixture for 10min by using 6H 2 O to obtain a mixed suspension B.
(3) And (3) weighing 7.2g of urea to be dissolved in the solution in the step (2), and stirring the solution for 10min by ultrasonic to obtain a mixed suspension C.
(4) Transferring the mixed suspension C into an atmospheric water bath kettle, magnetically stirring and reacting for 8 hours at the temperature of 90 ℃, cooling to room temperature, carrying out suction filtration, washing and suction filtering the obtained filter cake with deionized water and ethanol for three times, and carrying out vacuum drying for 6 hours at the temperature of 60 ℃ to obtain a sample of comparative example 2.
Comparative example 2 in comparison with example 1, the natural zeolite of comparative example 2 was not subjected to the calcination step.
Comparative example 3
(1) And weighing a proper amount of natural zeolite powder (natural zeolite is produced from Guangxi Zhuang nationality, powder with the particle size distribution of 0.5-100 mu m is obtained after grinding), calcining in a tube furnace at 600 ℃, preserving the heat for 2h, and obtaining the calcined natural zeolite at the temperature rising rate of 5 ℃ per minute.
(2) Taking 3g of natural zeolite calcined at 600 ℃, placing the natural zeolite in 30ml of HCl solution with the concentration of 3mol/L, magnetically stirring the mixture for 8 hours in an 80 ℃ water bath to obtain mixed liquor containing the acid leached natural zeolite, cooling the mixed liquor to room temperature, washing and filtering the mixed liquor with deionized water and ethanol for three times, and vacuum drying the mixed liquor at 60 ℃ for 6 hours to obtain the acid leached calcined zeolite.
(3) Taking 2g of acid-leached calcined zeolite powder, placing the powder in 60mL of deionized water, and stirring by ultrasonic to uniformly disperse the powder to obtain suspension A.
(4) Adding 2.91g Ni (NO) to the mixture 3)2 6H 2 O and 2.91.G Co (NO 3)2 And (3) carrying out ultrasonic stirring on the mixture for 10min by using 6H 2 O to obtain a mixed suspension B.
(5) And (3) weighing 7.2g of urea to be dissolved in the solution obtained in the step (2), and stirring the solution for 10min by ultrasonic to obtain a mixed suspension C.
(5) And transferring the mixed suspension C into a water bath kettle to react for 8 hours at the temperature of 90 ℃, cooling to room temperature, carrying out suction filtration, washing and suction filtering the obtained filter cake with deionized water and ethanol for three times, and carrying out vacuum drying for 6 hours at the temperature of 60 ℃ to obtain a sample of comparative example 3.
Comparative example 3 in comparison with example 1, the calcined zeolite of comparative example 3 was acid leached.
Comparative example 4
(1) And weighing 10g of natural zeolite powder (natural zeolite is produced from Guangxi Zhuang nationality, powder with the particle size distribution of 0.5-100 mu m is obtained after grinding), calcining in a tube furnace at 600 ℃, preserving the heat for 2h, and heating at the temperature rising rate of 5 ℃ per minute to obtain calcined natural zeolite.
(2) Taking 2g of calcined zeolite calcined at 600 ℃, placing the calcined zeolite in 60mL of deionized water, and stirring by ultrasonic to uniformly disperse to obtain suspension A.
(3) Adding 2.91g Ni (NO) to the mixture 3)2 6H 2 O and 2.91.G Co (NO 3)2 And (3) carrying out ultrasonic stirring on the mixture for 10min by using 6H 2 O to obtain a mixed suspension B.
(4) And (3) weighing 7.2g of urea to be dissolved in the mixed suspension B in the step (3), and stirring the mixture for 10min by ultrasonic to obtain a mixed suspension C.
(5) Transferring the mixed suspension C into a hydrothermal reaction kettle, reacting for 8 hours at 140 ℃, cooling to room temperature, performing suction filtration, washing and suction-filtering the obtained filter cake with deionized water and ethanol for three times, and performing vacuum drying for 6 hours at 60 ℃ to obtain a sample of comparative example 4.
Comparative example 4 the reaction temperature in comparative example 4 was 140 deg.c compared to example 1. Fig. 4 is an XRD pattern of comparative example 4 for the prepared sample. The results in FIG. 4 show that the sample has nickel basic carbonate, cobalt carbonate and quartz as crystal phase components, and no obvious nickel-cobalt bimetallic phyllosilicate is generated, which shows that the reaction temperature has an effect on the nickel-cobalt bimetallic phyllosilicate.
Comparative example 5
0.5G of example 1 was weighed and calcined in a tube furnace at 500℃for 2 hours at a temperature rise rate of 5℃/min, to obtain a sample of comparative example 5.
Comparative example 6
0.5 Example 1 was taken and placed in 100mL of 3mol/L sodium hydroxide (NaOH) solution to react, the reaction was kept under stirring at 90℃for 3 hours, and the mixture was left to stand, centrifuged, washed with water to neutrality and dried in vacuo to give a sample of comparative example 6.
Comparative example 7
(1) And weighing a proper amount of natural zeolite powder (natural zeolite is produced from Guangxi Zhuang nationality, powder with the particle size distribution of 0.5-100 mu m is obtained after grinding), calcining in a tube furnace at 600 ℃, preserving the heat for 2h, and obtaining the calcined zeolite at the temperature rising rate of 5 ℃ per minute.
(2) Taking 2g of zeolite calcined at 600 ℃, placing the zeolite in 60ml of deionized water, and stirring by ultrasonic to uniformly disperse to obtain suspension A.
(3) 4.04G Fe (NO) was further added to the suspension A 3)3 9H 2 O is ultrasonically stirred for 10min, and a mixed suspension B is obtained.
(4) And (3) weighing 7.2g of urea to be dissolved in the mixed suspension B in the step (3), and stirring the mixture for 10min by ultrasonic to obtain a mixed suspension C.
(5) Transferring the mixed suspension C into an atmospheric water bath kettle, magnetically stirring and reacting for 8 hours at the temperature of 90 ℃, cooling to room temperature, carrying out suction filtration, washing and suction filtering the obtained filter cake with deionized water and ethanol for three times, and carrying out vacuum drying for 6 hours at the temperature of 60 ℃ to obtain a sample of comparative example 7.
Comparative example 7 in comparison with example 1, only Fe (NO 3)3 9H 2 O soluble metal salts.
Application of comparative experiments
50ML of Norfloxacin (NFA) aqueous solution with initial concentration of 20mg/L is prepared to simulate organic pollutant wastewater, 25mg of samples prepared in examples 1-6 and comparative examples 1-5 are respectively weighed and added into the NFA solution, ultrasonic stirring is carried out, 25mg of potassium hydrogen Persulfate (PMS) is added for reaction for a period of time, 3mL of solution is taken for solid-liquid separation, then the concentration of residual NFA is tested, and the adsorption rate and degradation rate of the samples on the NFA are calculated. The experimental results are shown in table 1.
TABLE 1 catalytic degradation effects of adsorption of organic pollutants on samples of examples and comparative examples
1. Examples 1-3 show that the bimetallic phyllosilicate catalyst based on natural zeolite has a degradation rate of more than 93% for 60min on norfloxacin solution, and the bimetallic phyllosilicate catalyst prepared by the method has excellent catalytic performance.
2. As demonstrated by examples 1-6, the bimetallic phyllosilicate catalysts based on natural zeolite prepared by using urea, hexamethylenetetramine and NaOH as alkaline substances in the above examples all have good catalytic properties for norfloxacin solutions, with urea being the preferred alkaline substance for the preparation of samples having better catalytic properties.
3. Examples 1-6 illustrate that the natural zeolite-based bimetallic phyllosilicate catalyst prepared by changing the types, proportions, reaction temperatures and time of raw materials in the above examples has different catalytic properties, and the degradation rate of the norfloxacin solution in 60min of the sample prepared in example 1 is 95.70%.
4. The degradation rate of the cobalt-nickel bimetallic phyllosilicate catalyst on the norfloxacin solution is improved by the addition of the nickel and cobalt bimetallic salts as demonstrated in example 1 and comparative example 1.
5. The degradation rate of the cobalt-nickel bimetallic phyllosilicate catalyst on norfloxacin solution can be improved by calcining the natural zeolite as demonstrated by the degradation rates of example 1 and comparative example 2.
6. The degradation rate of the cobalt-nickel bimetallic phyllosilicate catalyst in the norfloxacin solution is reduced by acid leaching of the calcined zeolite as demonstrated by the degradation rates of example 1 and comparative example 3.
7. As demonstrated by the degradation rates of example 1 and comparative example 4, increasing the reaction temperature reduced the degradation rate of the cobalt-nickel bimetallic phyllosilicate catalyst to norfloxacin solution.
8. The degradation rate of the sample norfloxacin solution is reduced by the degradation rate of example 1, comparative example 5 and comparative example 6, which shows that the prepared cobalt-nickel bimetallic phyllosilicate catalyst is calcined at high temperature or is reacted in NaOH solution.
9. The degradation rate of the norfloxacin solution by the iron-cobalt bimetallic phyllosilicate catalyst is improved by adding the iron-cobalt bimetallic salt as demonstrated by the degradation rate of example 2 and comparative example 7.
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