CN114797945A - Bonded phase Fenton-like catalyst and preparation method thereof - Google Patents

Bonded phase Fenton-like catalyst and preparation method thereof Download PDF

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CN114797945A
CN114797945A CN202210370971.XA CN202210370971A CN114797945A CN 114797945 A CN114797945 A CN 114797945A CN 202210370971 A CN202210370971 A CN 202210370971A CN 114797945 A CN114797945 A CN 114797945A
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刘文静
梁燕燕
刘叶
张媛媛
张海涛
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Shengli College China University of Petroleum
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    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
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    • B01J2229/37—Acid treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

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Abstract

The invention belongs to the technical field of Fenton-like catalysts, and relates to a bonded phase Fenton-like catalyst and a preparation method thereof. The modification improves the activity of the catalyst, can reduce the loss of iron ions, ensures the high stability of the catalyst, and further obtains the bonded phase Fenton-like catalyst with high activity and high stability.

Description

Bonded phase Fenton-like catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of Fenton-like catalysts, and particularly relates to a bonded phase Fenton-like catalyst and a preparation method thereof.
Background
In recent years, as the demand for resources, particularly petroleum and petrochemical products, has increased, the discharge amount of waste water containing alkylphenol compounds has increased year by year, and the harm of alkylphenol environmental hormones represented by bisphenol a has attracted much attention. Bisphenol A (BPA) with the scientific name of 2, 2-bis (hydroxyphenyl) propane is one of industrial raw materials widely used in the world, is used for producing epoxy resin, polycarbonate plastics, flame retardants, antioxidants, pesticides and the like, and has data that residues in different water bodies are different from microgram to milligram, the precipitation concentration is obviously increased when the temperature is close to the temperature of a human body, and various diseases can be induced when extremely low concentration enters the human body.
The environmental hormone is a chemical substance which is exogenously interfered by organisms and normal endocrine functions of human bodies, is mainly released into the environment by human activities, exerts influence on normal hormone functions of the human bodies and the organisms, has the function similar to hormone, and can cause the reproductive capacity reduction, genital tumor and immunity reduction of the organisms and cause various physiological abnormalities. In order to relieve the threat to the health of organisms and human beings caused by environmental hormone pollution, a catalyst for stably degrading organic pollutants with high efficiency is urgently needed.
Disclosure of Invention
In order to solve the problems, the invention provides a bonded phase Fenton catalyst and a preparation method thereof, wherein the activity of the catalyst is improved through acid modification, and meanwhile, the loss of iron ions is reduced and the high stability of the catalyst is ensured by coordinating the active component iron ions on the modified MCM-41 mesoporous molecular sieve, so that the bonded phase Fenton catalyst with high activity and high stability is obtained.
A bonded phase Fenton-like catalyst is obtained by carrying out coordination on a modified MCM-41 mesoporous molecular sieve and divalent iron ions as an active component, wherein the modified MCM-41 mesoporous molecular sieve has the following structural general formula:
Figure 926355DEST_PATH_IMAGE001
；
wherein Y is selected from aldehyde group or carboxyl group.
Further, the structure of the modified MCM-41 mesoporous molecular sieve is as follows:
Figure 14922DEST_PATH_IMAGE002
。
further, the modified MCM-41 mesoporous molecular sieve is obtained by the reaction of methyl formate and the silanized MCM-41 mesoporous molecular sieve, and the reaction equation is as follows:
Figure 194230DEST_PATH_IMAGE003
。
further, the source of the ferrous ions of the active component is selected from ferrous sulfate, ferrous nitrate or ferrous chloride.
Another object of the present invention is to provide a method for preparing the above bonded phase fenton-like catalyst, comprising the steps of:
s1 acid modification: mixing and heating MCM-41 mesoporous molecular sieve, alumina and water, and soaking an obtained intermediate product 1 with acid to obtain an intermediate product 2;
s2, carrying out coupling reaction on the intermediate product 2 and a silanization reagent to obtain a silanized MCM-41 mesoporous molecular sieve, and reacting the silanized MCM-41 mesoporous molecular sieve with methyl formate to obtain a modified MCM-41 mesoporous molecular sieve;
s3, coordinating the modified MCM-41 mesoporous molecular sieve with ferrous ions under the action of a reducing agent to obtain a product.
Further, the silylation agent is at least one of octadecyltrichlorosilane, octadecyltrimethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, N- [3- (trimethoxysilyl) propyl ] ethylenediamine, and the like.
Further, the source of the ferrous ions is ferrous sulfate solution, and the molar concentration of the ferrous sulfate solution is 0.02-0.08 mol/L.
Further, the reducing agent is selected from potassium iodide, sodium iodide, potassium bromide or sodium bromide.
Further, the concentration of the reducing agent is 0.02-0.08 mol/L.
Further, the acid is selected from sulfuric acid, nitric acid or hydrochloric acid.
The invention has the following beneficial effects:
1. through acid modification of the MCM-41 mesoporous molecular sieve, the acid center and the acid strength of the mesoporous molecular sieve are improved, the activity of the catalyst is improved, and meanwhile, the condition that a medium is acidic is not required to be adjusted when wastewater is degraded, so that the wastewater treatment cost is greatly reduced, and the environmental pollution is also reduced.
2. A more stable Si-O-C chemical bond is formed through a silanization reaction, a specific organic functional group is grafted into a pore channel or between layers of the MCM-41 mesoporous molecular sieve to prepare a series of organic functionalized modified MCM-41 mesoporous molecular sieves, and an active component iron ion is immobilized on the modified MCM-41 mesoporous molecular sieves through coordination, so that the loss of the iron ion is reduced, and the high stability of the catalyst is ensured.
3. By the preparation method, the bonded phase Fenton-like catalyst with high activity and high stability can be safely obtained, the loss amount of ferrous ions as active components can be greatly reduced, secondary pollution is reduced, and the activity and the reutilization rate of the catalyst are ensured.
Drawings
FIG. 1 is an XRD spectrum of the modified MCM-41 mesoporous molecular sieve and the unmodified silanized MCM-41 mesoporous molecular sieve in example 1.
FIG. 2 is the XRD spectrum of the modified MCM-41 mesoporous molecular sieve in example 1 and the obtained product bonded phase Fenton-like catalyst.
FIG. 3 is a graph showing the effect of the catalysts obtained in example 1 and comparative example 1 on phenol degradation.
FIG. 4 is a graph showing the effect of bonded phase Fenton-like catalysts on phenol degradation obtained at different concentrations of ferrous sulfate solution in example 1.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the following examples are listed. The starting materials, reactions and work-up procedures which are given in the examples are, unless otherwise stated, those which are customary on the market and are known to the person skilled in the art.
Example 1
Weighing 2g of MCM-41 mesoporous molecular sieve, activating for 2 h in a forced air drying oven at 220 ℃, adding 0.1g of alumina and deionized water, heating in a water bath at 80 ℃, refluxing for 5 h, carrying out suction filtration and washing on a refluxing product, drying for 2 h at 110 ℃ to obtain an intermediate product 1, and soaking in 6g/L sulfuric acid to obtain an intermediate product 2.
1g of intermediate 2 was taken and activated for 2 h at 250 ℃ in a drying cabinet. Adding the activated intermediate product 2 into 100 mL of toluene, uniformly stirring, then adding a mixture of 20 mL of N- [3- (trimethoxysilyl) propyl ] ethylenediamine and 25 mL of absolute ethyl alcohol, continuously stirring, heating to 120V, and refluxing for 12 h; and (4) performing suction filtration, washing with absolute ethyl alcohol for multiple times, and then placing in a vacuum drying oven for vacuum drying to obtain the silanized MCM-41 mesoporous molecular sieve for later use.
The chemical equation for the silylation reaction is as follows:
Figure 407037DEST_PATH_IMAGE004
adding 1g of silanized MCM-41 mesoporous molecular sieve into 100 mL of ethanol, adding excessive methyl formate, stirring and mixing uniformly, and refluxing for 12 h; and (3) performing suction filtration, washing with absolute ethyl alcohol for multiple times, and then placing in a vacuum drying oven for vacuum drying to respectively obtain the modified MCM-41 mesoporous molecular sieve for later use.
Wherein, the methyl formate is coupled with the silanized MCM-41 mesoporous molecular sieve for reaction, and aldehyde group (-CHO) is grafted on the silanized MCM-41 mesoporous molecular sieve, and the reaction equation is as follows:
Figure 988191DEST_PATH_IMAGE005
preparing a ferrous sulfate solution with the concentration of 0.045 mol/L and a potassium iodide solution with the concentration of 0.045 mol/L; adding 0.5 g of pretreated modified MCM-41 mesoporous molecular sieve and 50 mL of ferrous sulfate solution into a 100 mL conical flask with a plug, and adding a rotor; and (2) putting the mixture into a water bath, stirring the mixture for 30 min under magnetic force at the water temperature of 60 ℃, slowly dripping the potassium iodide solution, controlling the dripping speed to be 2 s/drop, stirring the mixture while dripping, continuing stirring the mixture for 30 min, performing suction filtration, washing the mixture by using distilled water, and drying the mixture in a constant-temperature vacuum drying oven to obtain the product bonded phase Fenton-like catalyst.
XRD characterization comparison was performed on the modified MCM-41 mesoporous molecular sieve and the unmodified silanized MCM-41 mesoporous molecular sieve, as shown in FIG. 1. The diffraction peak of the MCM-41 mesoporous molecular sieve is obvious near 2 degrees, which shows that no collapse of the mesoporous structure is caused before and after grafting.
XRD characterization comparison was performed on the product bonded phase Fenton-like catalyst and the modified MCM-41 mesoporous molecular sieve, as shown in FIG. 2. Fe exists at 17.5 degrees, 35.4 degrees and 52.5 degrees 2 O 3 The characteristic peak of (1) is that Fe exists at 36.4 degrees, 37.4 degrees and 44.7 degrees 3 O 4 The characteristic peak shows that iron ions are successfully coordinated on the modified MCM-41 mesoporous molecular sieve.
Example 2
Weighing 2g of MCM-41 mesoporous molecular sieve, activating for 2 h in a forced air drying oven at 220 ℃, adding 0.1 of alumina and deionized water, heating in a water bath at 80 ℃, refluxing for 4 h, carrying out suction filtration and washing on a refluxing product, drying for 2 h at 110 ℃ to obtain an intermediate product 1, and soaking in 6g/L sulfuric acid to obtain an intermediate product 2.
1g of intermediate 2 was taken and activated for 1.5 h at 250 ℃ in a drying oven. Adding the activated intermediate product 2 into 100 mL of toluene, uniformly stirring, then adding a mixture of 20 mL of N- [3- (trimethoxysilyl) propyl ] ethylenediamine and 25 mL of absolute ethyl alcohol, continuously stirring, heating at 120V, and refluxing for 11 h; and (4) performing suction filtration, washing with absolute ethyl alcohol for multiple times, and then placing in a vacuum drying oven for vacuum drying to obtain the silanized MCM-41 mesoporous molecular sieve for later use.
Adding a proper amount of silanized MCM-41 mesoporous molecular sieve into 100 mL of ethanol, adding excessive methyl formate, stirring and mixing uniformly, and refluxing for 11 h; and (3) performing suction filtration, washing with absolute ethyl alcohol for multiple times, and then placing in a vacuum drying oven for vacuum drying to respectively obtain the modified MCM-41 mesoporous molecular sieve for later use.
Preparing a ferrous sulfate solution with the concentration of 0.030 mol/L and a potassium iodide solution with the concentration of 0.045 mol/L; adding 0.5 g of pretreated modified MCM-41 mesoporous molecular sieve and 50 mL of ferrous sulfate solution into a 100 mL conical flask with a plug, and adding a rotor; and (2) putting the mixture into a water bath, stirring the mixture for 30 min under magnetic force at the water temperature of 60 ℃, slowly dripping the potassium iodide solution, controlling the dripping speed to be 3 s/drop, stirring the mixture while dripping, continuing stirring the mixture for 30 min, performing suction filtration, washing the mixture by using distilled water, and drying the mixture in a constant-temperature vacuum drying oven to obtain the product bonded phase Fenton-like catalyst.
Example 3
Weighing 2g of MCM-41 mesoporous molecular sieve, activating for 2 h in a forced air drying oven at 220 ℃, adding 0.1g of alumina and deionized water, heating in a water bath at 80 ℃, refluxing for 4 h, carrying out suction filtration and washing on a refluxing product, drying for 2 h at 110 ℃ to obtain an intermediate product 1, and soaking in 6g/L sulfuric acid to obtain an intermediate product 2.
1g of intermediate 2 was taken and activated for 2.5 h at 250 ℃ in a drying oven. Adding the activated intermediate product 2 into 100 mL of toluene, uniformly stirring, then adding a mixture of 20 mL of N- [3- (trimethoxysilyl) propyl ] ethylenediamine and 25 mL of absolute ethyl alcohol, continuously stirring, heating at 120V, and refluxing for 10 h; and (3) performing suction filtration, washing with absolute ethyl alcohol for multiple times, and then placing in a vacuum drying oven for vacuum drying to obtain the silanized MCM-41 mesoporous molecular sieve for later use.
Adding a proper amount of silanized MCM-41 mesoporous molecular sieve into 100 mL of ethanol, adding excessive methyl formate, stirring and mixing uniformly, and refluxing for 10 h; and (3) performing suction filtration, washing with absolute ethyl alcohol for multiple times, and then placing in a vacuum drying oven for vacuum drying to respectively obtain the modified MCM-41 mesoporous molecular sieve for later use.
Preparing a ferrous sulfate solution with the concentration of 0.060 mol/L and a potassium iodide solution with the concentration of 0.045 mol/L; adding 0.5 g of pretreated modified MCM-41 mesoporous molecular sieve and 50 mL of ferrous sulfate solution into a 100 mL conical flask with a plug, and adding a rotor; and (2) putting the mixture into a water bath, stirring the mixture for 30 min under magnetic force at the water temperature of 60 ℃, slowly dripping the potassium iodide solution, controlling the dripping speed to be 1 second/drop, stirring the mixture while dripping, continuing stirring the mixture for 30 min, performing suction filtration, washing the mixture by using distilled water, and drying the mixture in a constant-temperature vacuum drying oven to obtain the product bonded phase Fenton-like catalyst.
Comparative example 1
Comparative example 1 was identical to example 1 in terms of the ingredients used, the amounts and concentrations of the ingredients used, and the preparation procedure, with the only difference that comparative example 1 was an Fe-MCM-41 catalyst prepared without the step S2 and prepared as follows:
a. acid modification: mixing and heating MCM-41 mesoporous molecular sieve, alumina and water, and soaking an obtained intermediate product 1 with acid to obtain an intermediate product 2;
b. and (3) coordinating the intermediate product 2 with a ferrous sulfate solution under the action of a potassium iodide solution to obtain a comparative example 1.
Test example 1
Selecting a phenol aqueous solution as a test object, wherein the reaction conditions are as follows: the initial concentration of phenol is 100 mg/L at normal pressure and 50 ℃, the liquid-solid ratio is 500:1, and the pH value is not adjusted. The degradation effect of the catalysts obtained in example 1 and comparative example 1 is shown in fig. 3, and the phenol degradation rate data is shown in table 1, which shows that the degradation effect of the catalyst modified in step S2 is better, and the grafting of the organic functional group improves the activity of the catalyst.
TABLE 1 catalyst degradation rate to phenol
Sample numbering Degradation ratio of p-phenol (%)
Example 1 88.2
Comparative example 1 66.1
Test example 2
The phenol degradation effect of the catalyst obtained in example 1 is shown in fig. 4, and the phenol degradation rate data is shown in table 2; wherein, the degradation reaction rates of the catalyst obtained when the concentration of the ferrous sulfate solution is 0.045 mol/L and 0.060 mol/L are very close, and the activity of the catalyst is enhanced along with the increase of the concentration of the solution; however, as the reaction proceeds, the catalyst obtained by using a ferrous sulfate solution with a concentration of 0.045 mol/L for coordination has a better degradation effect.
TABLE 2 evaluation results of catalyst degradation Properties
Concentration of ferrous sulfate solution (mol/L) Phenol degradation Rate after 240 min (%)
0.045 78.0
0.030 72.9
0.060 73.0
Test example 3
After 240 min of reaction, the iron ion concentration in the solution after the reaction of the two catalyst systems of example 1 and comparative example 1 is measured by adopting an atomic absorption method, and the stability of the two catalyst systems is compared; the test data is shown in table 3, the dissolution concentration of iron ions in the catalyst obtained by the method of the present invention is lower than 2 ppm of the european union standard, and heavy metal pollution to subsequent biological treatment or environmental ecology is not caused, and meanwhile, the bonded phase fenton-like catalyst prepared by the present invention is also shown in the specification that iron ions are better immobilized on the modified MCM-41 mesoporous molecular sieve, and have better stability. And (3) performing a repeated use experiment of the catalyst, namely centrifugally separating the reacted catalyst, recovering the catalyst for the second experiment, repeating the operation for 10 times, wherein after the catalyst is repeatedly used for 10 times, the phenol degradation efficiency of the catalyst is still 87.5%, which indicates that the prepared catalyst has excellent reusability.
TABLE 3 evaluation results of catalyst stability
Sample numbering Iron ion elution concentration (ppm)
Comparative example 1 4.350
Example 1 0.087
Therefore, the activity of the catalyst can be improved through acid modification, and the loss of iron ions is reduced and the high stability of the catalyst is ensured by coordinating the active component iron ions on the modified MCM-41 mesoporous molecular sieve, so that the bonded phase Fenton-like catalyst with high activity and high stability is obtained.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the description is made in terms of embodiments, not every embodiment includes only a single embodiment, and such description is for clarity only, and those skilled in the art will recognize that the embodiments described herein as a whole may be combined to form other embodiments as well, as will be apparent to those skilled in the art.

Claims (10)

1. The bonded phase Fenton-like catalyst is characterized by being obtained by carrying out coordination on a modified MCM-41 mesoporous molecular sieve and an active component ferrous ion, wherein the modified MCM-41 mesoporous molecular sieve has the following structural general formula:
Figure 390664DEST_PATH_IMAGE001
；
wherein Y is selected from aldehyde group or carboxyl group.
2. The bonded phase fenton-like catalyst according to claim 1, wherein the modified MCM-41 mesoporous molecular sieve has the structure:
Figure 322848DEST_PATH_IMAGE002
。
3. the bonded phase fenton-like catalyst according to claim 2, wherein the modified MCM-41 mesoporous molecular sieve is obtained by reacting methyl formate with a silanized MCM-41 mesoporous molecular sieve, the reaction equation being as follows:
Figure 667241DEST_PATH_IMAGE003
。
4. the bonded-phase fenton-like catalyst according to claim 1, wherein the source of ferrous ions as the active component is selected from ferrous sulfate, ferrous nitrate or ferrous chloride.
5. The method for preparing a bonded-phase fenton-like catalyst according to any one of claims 1 to 4, comprising the steps of:
s1 acid modification: mixing and heating MCM-41 mesoporous molecular sieve, alumina and water, and soaking an obtained intermediate product 1 with acid to obtain an intermediate product 2;
s2, carrying out coupling reaction on the intermediate product 2 and a silanization reagent to obtain a silanized MCM-41 mesoporous molecular sieve, and reacting the silanized MCM-41 mesoporous molecular sieve with methyl formate to obtain a modified MCM-41 mesoporous molecular sieve;
s3, coordinating the modified MCM-41 mesoporous molecular sieve with ferrous ions under the action of a reducing agent to obtain a product.
6. The method of claim 5, wherein the silylation agent is at least one of octadecyltrichlorosilane, octadecyltrimethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, N- [3- (trimethoxysilyl) propyl ] ethylenediamine, etc.
7. The method according to claim 5, wherein the source of the ferrous ions is ferrous sulfate solution, and the molar concentration of the ferrous sulfate solution is 0.02-0.08 mol/L.
8. The method of preparing a bonded-phase fenton-like catalyst according to claim 5, wherein the reducing agent is selected from potassium iodide, sodium iodide, potassium bromide or sodium bromide.
9. The method of preparing a bonded-phase Fenton-like catalyst according to claim 8, wherein the concentration of said reducing agent is 0.02 to 0.08 mol/L.
10. A method of preparing a bonded-phase Fenton-like catalyst according to claim 5, wherein said acid is selected from the group consisting of sulfuric acid, nitric acid and hydrochloric acid.
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