CN112958157B - Bimetallic organic framework material catalyst, preparation method and application - Google Patents
Bimetallic organic framework material catalyst, preparation method and application Download PDFInfo
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- CN112958157B CN112958157B CN202110172332.8A CN202110172332A CN112958157B CN 112958157 B CN112958157 B CN 112958157B CN 202110172332 A CN202110172332 A CN 202110172332A CN 112958157 B CN112958157 B CN 112958157B
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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Abstract
The invention discloses a bimetallic organic framework material catalyst, a preparation method and application. The invention adopts a direct solvent thermal synthesis method to prepare the effective bimetallic organic framework material catalyst, and comprises the steps of synthesis, washing, drying and activation; and the catalyst is applied to the field of water treatment and is used for catalytically reducing the ozonization of a precursor to generate a nitrogen-containing byproduct. The raw materials needed by the synthetic design catalyst are cheap and easy to obtain, and the reaction operation is simple and convenient and easy to control; the reaction condition is mild, and the reduction rate of the nitrogen-containing by-products can be obviously realized.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a bimetallic organic framework material catalyst, a preparation method and application thereof, which are used for catalytically reducing nitrogen-containing byproducts generated by ozonization of precursors.
Background
Dimethyl Nitrosamine (NDMA) is a nitrogenous disinfection by-product (N-DBPs) found in chlorine/chloramine disinfection that is highly carcinogenic, teratogenic, mutagenic, and 0.7ng/L NDMA in drinking water poses one part per million of cancer risk. NDMA with different concentrations is detected in effluent of many water sources or water plants in China and other countries, and frequent detection of NDMA is a great hidden danger of drinking water safety in China, and needs to be solved urgently.
Once NDMA is formed, it is difficult to blow it off in water and easily seeps into ground water from the soil, and it is also difficult to directly remove it by conventional water treatment processes. Therefore, studies have been conducted to reduce the generation of NDMA from the viewpoint of removing precursors. The existing methods for directly or indirectly reducing NDMA mainly comprise advanced oxidation, adsorption, biodegradation, reverse osmosis, direct photolysis of ultraviolet rays and the like. The treatment cost of the reverse osmosis membrane and the ultraviolet direct photolysis method is high, and the defects of poor treatment effect and overlong treatment time can exist in the biodegradation and adsorption process. Preoxidation is a common water treatment mode, ozone has strong oxidizing capacity, and the ozone is widely applied to the aspects of disinfection, decoloration, odor removal, coagulation aiding and the like; the subsequent chlorine/chloramine disinfection of the precursor to NDMA may also be reduced. However, in recent years, it has been found that ozone can also react with actual water and some precursors (such as butyrhydrazide) to directly generate NDMA.
Butyryl hydrazine is a plant inhibitor widely used at home and abroad, has a bactericidal effect, can be used as a dwarfing agent, a fruit setting agent, a rooting agent, a preservative and the like, is often detected on plants and fruits, and is also often detected in surface water polluted by agricultural wastewater. As early as the 20 th century, butyrhydrazide was identified as a carcinogen, and it and its metabolites were also recognized as precursors with high molar conversion of NDMA, which is much higher than other amine-based compounds. Research shows that the butyryl hydrazine can directly generate NDMA in the ozonization process, and the molar yield reaches 55-100%. There is still no research on how to control the generation of NDMA in the ozonation process of butyrohydrazide, and it is highly desirable to find a method to reduce the generation.
The metal organic framework materials, namely MOFs, are novel materials with porous network structure frameworks, which are mainly formed by self-assembling organic ligands containing oxygen and nitrogen elements and metal ions and belong to microporous or mesoporous materials. In recent years, the use of MOFs and their composites for catalyzing the degradation of organic compounds has been studied extensively, but studies on the catalytic ozonation reduction of precursors to nitrogen-containing by-products have not been reported, and the characteristics and synthesis methods of MOFs catalysts for this purpose are not clear.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a bimetallic organic framework material catalyst, a preparation method and application thereof, and solves the problems in the background technology.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: the preparation method of the bimetallic organic framework material catalyst is provided, the catalyst is prepared by a direct solvent thermal synthesis method, and the preparation method comprises the following steps:
(1) synthesizing: placing nanoscale zero-valent iron, manganese nitrate solution, ligand trimesic acid, hydrofluoric acid and pure water in a reaction kettle with a tetrafluoroethylene liner, stirring and mixing uniformly, and moving to an oven for heating; wherein the molar ratio of the iron element to the manganese element is 2:1-1: 2;
(2) washing: after the temperature in the oven is reduced to room temperature, taking out a product in the reaction kettle, filtering by suction filtration, stirring and soaking the obtained solid in absolute ethyl alcohol, and washing the solid for a plurality of times by using the absolute ethyl alcohol after soaking;
(3) and (3) drying: drying the powder sample separated after washing in a constant-temperature drying oven;
(4) and (3) activation: and placing the dried powdery sample in a constant-temperature vacuum drying oven for activation to finally obtain the bimetallic organic framework material catalyst, namely MOFs (MIL-100 (Fe-Mn)).
In a preferred embodiment of the present invention, the stirring manner in step (1) is manual or mechanical stirring.
In a preferred embodiment of the present invention, the heating in step (1) adopts a temperature programmed heating: after heating at 100-120 ℃ for 2-4 hours, the temperature is programmed to 150-180 ℃ and then heating is continued for 4-6 hours.
In a preferred embodiment of the present invention, in the step (2), the obtained solid is stirred and soaked in absolute ethyl alcohol for 6-12 hours.
In a preferred embodiment of the present invention, in the step (3), the powdered sample is dried at 60-80 ℃ for 6-12 hours.
In a preferred embodiment of the present invention, in the step (4), the activation condition is a vacuum environment and the activation temperature is 100-300 ℃.
The invention also provides a bimetallic organic framework material catalyst prepared by the method.
The invention also provides application of the bimetallic organic framework material catalyst, which is used as a catalyst in ozone oxidation water treatment and used for reducing typical precursors and nitrogen-containing by-products NDMA generated by actual water body ozonization.
The second technical scheme adopted by the invention for solving the technical problems is as follows: the method for reducing the generation of nitrogen-containing byproduct NDMA in the water treatment process is provided, wherein 10-200mg/L of the bimetallic organic framework material catalyst is added into a water sample containing a precursor, and catalytic oxidation is carried out under the conditions that the pH is 5-9 and the ozone adding amount is 0.5-4 mg/L.
In a preferred embodiment of the present invention, the precursor comprises butyrhydrazide.
Compared with the background technology, the technical scheme has the following advantages:
1. the invention adopts the direct solvent thermal synthesis method to prepare the effective bimetallic organic framework material catalyst, firstly uses the MOFs catalyst in the aspect of reducing the generation of the nitrogen-containing byproducts, explores the efficiency of the MOFs catalyst in the aspect of reducing the byproducts, has distinctive characteristics and innovation, is beneficial to exploring the effect of reducing the generation of the nitrogen-containing byproducts in the process of ozonizing the precursor by the MOFs catalyst, promotes the development of the catalytic ozonization based on the MOFs material, provides basic data and scientific basis for the practical application of the technology, and simultaneously provides more possibilities for expanding the application range of ozone in the practical water body;
2. the method has excellent effect of reducing the generation of nitrogen-containing byproducts in the process of ozonization of the precursor, and the reduction rate is as high as 97.5 percent.
Drawings
FIG. 1 is an SEM photograph of a bimetallic organic framework material catalyst of example 1 taken before (a) and after (b);
FIG. 2 is a XPS plot of the bimetallic organic framework catalyst of example 1 before and after use;
FIG. 3 is a comparison of the different catalyst dosages of example 1 to catalytically ozonize and reduce the nitrogen-containing by-product NDMA produced by the exemplary precursor, butyrhydrazide;
FIG. 4 is a comparison of NDMA, a nitrogen-containing by-product, produced by catalytic ozonation of butyrhydrazide, a typical precursor, in example 2, at different ozone concentrations;
FIG. 5 is a comparison of NDMA, a nitrogen-containing by-product, produced by a bimetallic organic framework material at different pH's in example 3 to catalyze the ozonation of a typical precursor, butyrhydrazide;
FIG. 6 is a comparison of NDMA, a nitrogen-containing byproduct, produced by catalytic ozonation of a real water body by a bi-metal organic framework material in comparative example 1 and example 1.
Detailed Description
Example 1
A preparation method of a bimetallic organic framework material catalyst comprises the following steps:
(1) synthesis: 0.3350g of zero-valent iron, 2.1470g of Mn (NO) 3 ) 2 Solution (50 wt%), 2.5220g H 3 BTC, 600. mu.L hydrofluoric acid (100%) and 75ml H 2 And (3) placing the O into a 100mL reaction kettle with a tetrafluoroethylene inner liner, stirring and mixing the O and the O uniformly by using a tetrafluoroethylene stirring rod, heating the mixture for 2 hours at the temperature of 120 ℃, and then heating the mixture for 4 hours continuously after the temperature is programmed to be 150 ℃.
(2) Washing: taking out the product, filtering, soaking the obtained product in absolute ethyl alcohol for 12h, and washing with fresh absolute ethyl alcohol for 5 times;
(3) and (3) drying: and (4) performing suction filtration and separation to obtain an orange product, and drying the product at the constant temperature of 70 ℃ for 12 hours.
(4) Vacuum activation: and (3) carrying out vacuum activation on the dried powder product at the constant temperature of 200 ℃ for 12h to finally obtain the required catalyst.
Subsequently, the method for reducing the generation of the nitrogen-containing byproduct NDMA in the water treatment process by using the catalyst comprises the following steps of:
(5) the catalyst was added to a sample containing 20. mu.M butyrhydrazide at 0, 10, 20, 30, 40, 50, 100, 200mg/L, and the reaction was terminated by catalytic oxidation at pH 7 and an ozone concentration of 2mg/L for 1 hour, and quenching was performed with an 80g/L sodium thiosulfate solution, and the formation of NDMA after the reaction was detected.
The results are shown in FIG. 3. It is obvious that compared with single ozonization, the production of NDMA is greatly reduced, and when the catalyst addition is 200mg/L, the NDMA reduction rate is about 96%.
Example 2
The preparation method of the catalyst of steps (1) to (4) of example 2 is the same as that of example 1, and differs from example 1 in that: the NDMA generation of butyryl hydrazine by ozone oxidation catalysis with different ozone concentrations comprises the following steps:
respectively adding 0, 0.5, 1, 2 and 4mg/L ozone concentration into a sample containing 20 mu M of butyrylhydrazine, carrying out catalytic oxidation for 1h under the conditions that the pH is 7 and the adding amount of a catalyst is 200mg/L, quenching by using 80g/L sodium thiosulfate solution to terminate the reaction, and respectively detecting the generation of NDMA after the reaction.
As a result, as shown in fig. 4, it can be seen that the generation of NDMA increases with the increase of the ozone concentration in both the catalytic ozonation and the ozone-alone oxidation, but it is apparent that the catalytic ozonation significantly reduces the generation amount of NDMA at different ozone concentrations.
Example 3
The preparation method of the catalyst of steps (1) to (4) of example 3 is the same as that of example 1, and differs from example 1 in that: the NDMA production by catalytic ozonation of butyrhydrazide at different pH's comprises the following steps:
a series of samples containing 20 μ M of butyrhydrazide were adjusted to 5, 6, 7, 8, and 9, respectively, and catalytic oxidation was carried out for 1 hour under the conditions that the amount of ozone added was 2mg/L and the amount of catalyst added was 200mg/L, and quenching was carried out with 80g/L of sodium thiosulfate solution to terminate the reaction, and the formation of NDMA after the reaction was detected, respectively.
As a result, as shown in FIG. 5, it can be seen that when ozone alone oxidizes butyrhydrazide, the generation of NDMA increases and then decreases with increasing pH, reaching a maximum at pH 8; when the bimetallic organic framework material catalyzes ozone, the generation of NDMA is reduced firstly and then slowly increased along with the increase of pH, and the generation amount is the lowest when the pH is 6.
Comparative example 1
Comparative example 1 provides a scheme for carrying out a water treatment process by using ozone alone, and the difference from the step (5) in example 1 is that a bimetallic organic framework material catalyst is not added.
Comparing the influence of single ozone and catalytic ozone on the amount of NDMA generated by the actual water body: the adding amount of ozone is 2mg/L, the catalyst bimetallic organic framework material catalyst is not added in the comparative example 1, the catalytic oxidation is carried out for 1h under the condition that the adding amount in the example 1 is 200mg/L, the quenching is carried out by using 80g/L sodium thiosulfate solution to terminate the reaction, and the generation of NDMA after the reaction is respectively detected.
As a result, as shown in FIG. 6, it can be seen that the generation of NDMA is much lower than that of ozone alone in catalytic ozonation, and the reduction rate is as high as 97.5%.
The above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. A method for reducing nitrogen-containing byproducts generated in a water treatment process is characterized by comprising the following steps: adding 10-200mg/L of bimetallic organic framework material catalyst into a water sample containing the precursor, and carrying out catalytic oxidation under the conditions that the pH is 5-9 and the adding amount of ozone is 0.5-4 mg/L; the bimetallic organic framework material catalyst is prepared by adopting a direct solvent thermal synthesis method, and comprises the following steps:
(1) synthesizing: placing nanoscale zero-valent iron, a manganese nitrate solution, ligand trimesic acid, hydrofluoric acid and pure water in a reaction kettle with a tetrafluoroethylene liner, stirring and mixing uniformly, and moving the reaction kettle into an oven to heat; wherein the molar ratio of the iron element to the manganese element is 2:1-1: 2; the heating adopts temperature programming heating: after heating at the temperature of 100 ℃ and 120 ℃ for 2-4 hours, heating to the temperature of 150 ℃ and 180 ℃ for 4-6 hours;
(2) washing: after the temperature in the oven is reduced to room temperature, taking out a product in the reaction kettle, filtering by suction filtration, stirring and soaking the obtained solid in absolute ethyl alcohol, and washing the solid for a plurality of times by using the absolute ethyl alcohol after soaking;
(3) and (3) drying: drying the powder sample separated after washing in a constant-temperature drying oven;
(4) and (3) activation: placing the dried powdery sample in a constant-temperature vacuum drying oven for activation to finally obtain the bimetallic organic framework material catalyst; the activation condition is a vacuum environment and the activation temperature is 100-300 ℃.
2. The method for reducing the formation of nitrogen-containing byproducts in a water treatment process according to claim 1, wherein: the stirring mode in the step (1) is manual or mechanical stirring.
3. The method for reducing nitrogen-containing byproducts generated in a water treatment process according to claim 1, wherein the method comprises the following steps: in the step (2), the obtained solid is stirred and soaked in absolute ethyl alcohol for 6-12 hours.
4. The method for reducing nitrogen-containing byproducts generated in a water treatment process according to claim 1, wherein the method comprises the following steps: in the step (3), the powdery sample is dried at 60-80 ℃ for 6-12 hours.
5. The method for reducing nitrogen-containing byproducts generated in a water treatment process according to claim 1, wherein the method comprises the following steps: the precursor comprises butyryl hydrazine and an actual water body.
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| CN108358298A (en) * | 2018-01-12 | 2018-08-03 | 河南师范大学 | A method of it is generated using ozone control nitrosamines substance |
| CN109603884A (en) * | 2019-01-03 | 2019-04-12 | 同济大学 | A kind of preparation method and applications of visible light catalyst material |
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| CN105149006B (en) * | 2015-07-24 | 2017-09-29 | 浙江工业大学 | Ligand aminated metal-organic framework supported catalyst and preparation method and application thereof |
| US20180274013A1 (en) * | 2015-09-23 | 2018-09-27 | Nanyang Technological University | Metal-organic framework nanosheet |
| CN105237586A (en) * | 2015-10-15 | 2016-01-13 | 大连理工大学 | Preparation and application of novel dual-core organic skeleton material MIL-100(Fe-Mn) |
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| CN108358298A (en) * | 2018-01-12 | 2018-08-03 | 河南师范大学 | A method of it is generated using ozone control nitrosamines substance |
| CN109603884A (en) * | 2019-01-03 | 2019-04-12 | 同济大学 | A kind of preparation method and applications of visible light catalyst material |
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