CN111470549A - Method for catalytically degrading saccharin and neotame by using bio-MOF-11 as metal organic framework nano material - Google Patents
Method for catalytically degrading saccharin and neotame by using bio-MOF-11 as metal organic framework nano material Download PDFInfo
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- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
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Abstract
The invention provides a method for catalytically degrading saccharin and neotame by using a metal organic framework nano material bio-MOF-11, which comprises the following steps of S1, preparing bio-MOF-11, S2, preparing a degradation system, S3, adding bio-MOF-11 with the mass concentration of 1 g/L into the degradation system of S2 to form a mixture, enabling the mixture to establish adsorption-desorption balance, S4, adding persulfate with the mass concentration of 10 g/L into the mixture of S3, enabling the pH of the formed solution to be 3-10, keeping the reaction temperature at 25 ℃, and carrying out catalytic degradation.
Description
Technical Field
The invention relates to the technical field of environmental engineering water treatment, and particularly relates to a method for catalytically degrading saccharin and neotame by using a metal organic framework nano material bio-MOF-11.
Technical Field
Saccharin and neotame are two common artificial sweeteners, widely used in the fields of food, beverages, pharmaceuticals, personal care products and the like, and replace organic compounds of sucrose. Saccharin and neotame are hardly metabolized by human bodies, the degradation efficiency is low in the biological sewage treatment process, and sewage is discharged into a water environment. The saccharin and the neotame have long application time and large application scale, have the characteristics of wide pollution range, high pollution level, strong durability and the like in distribution in a water environment, and are defined as novel pollutants. The detection of artificial sweeteners in water environments at minute concentrations, their ecotoxicity, their transformation during water treatment and their toxicological studies have become one of the hot problems, the presence of which may pose serious threats to the ecosystem and human health.
Saccharin and neotame are easily soluble in water and have high thermal stability, and the removal effects of the traditional water treatment processes such as coagulation, precipitation, filtration, disinfection and the like are very limited. Advanced treatment techniques such as electro-Fenton, ozonation, O3/H2O2，O3/UV-C，H2O2The UV-C combined oxidation technology can remove the artificial sweetener in water, and the advanced oxidation technology is an effective method for realizing the rapid degradation of trace organic pollutants in water environment.
Disclosure of Invention
Catalytic persulfate is one of the important directions for the development of the current advanced oxidation water treatment technology. The persulfate can be activated by heat, ultraviolet light, transition metal, alkali and the like to generate the persulfate with stronger oxidizing capability
(E02.5-3.1eV) and HO · (E)02.7-2.8eV), capable of oxidatively degrading a variety of persistent organic pollutants including chlorinated hydrocarbons, polycyclic aromatic hydrocarbons, benzene-based compounds, and the like.
The invention aims to provide a method for catalytically degrading saccharin and neotame by using a metal organic framework nano material bio-MOF-11, and the system can realize the rapid and efficient degradation of saccharin and neotame.
The technical scheme adopted by the invention is as follows: a method for catalytically degrading saccharin and neotame by using a metal organic framework nano material bio-MOF-11 comprises the following steps:
s1, preparing bio-MOF-11 through a hydrothermal reaction;
s2, preparing a degradation system, wherein the degradation system is formed by combining saccharin, neotame and an aqueous medium;
s3, adding bio-MOF-11 with the mass concentration of 1 g/L into the degradation system of S2 to form a mixture, and establishing adsorption-desorption equilibrium of the mixture;
s4, adding persulfate with the mass concentration of 10 g/L into the mixture in the S3, enabling the pH of the formed solution to be 3-10, keeping the reaction temperature at 25 ℃, and carrying out catalytic degradation.
Preferably, the hydrothermal reaction preparation in S1 includes the following steps:
and step 3: and naturally cooling the obtained reactant to room temperature, stirring, centrifuging to obtain bio-MOF-11, and placing the product in a vacuum drying oven at 60 ℃.
Preferably, the mass concentration of saccharin and neotame in the S2 in the solvent is 50 mg/L.
Preferably, the persulfate in S4 is any one of sodium persulfate, potassium persulfate and ammonium persulfate.
Preferably, the catalytic degradation mode in S4 includes any one of standing and stirring.
Preferably, the rate of agitation is 120 rpm.
Preferably, the time of catalytic degradation in S4 is 0-120 min.
Preferably, the reaction time in S3 is 60 min.
The invention has the beneficial effects that: the metal organic framework nano material bio-MOF-11 provided by the invention catalyzes a persulfate system through Co under the conditions that the pH is 3-10 and the temperature is 25 DEG C2+And Co3+Successive transition of valence states to produce
And HO, finally, the rapid and efficient deep degradation of saccharin and neotame can be realized by adopting the advanced oxidation method provided by the invention, the saccharin removal rate of 50 mg/L can reach 61%, NEO is almost completely degraded, the degradation time is short, and the recycling property of the catalyst has important significance for the practical application of the catalyst.
Drawings
FIG. 1: the removal efficiency figures of saccharin under the conditions of the invention case-bio-MOF-11 catalytic persulfate, the comparison case-single-bio-MOF-11 treatment and the comparison case-single-persulfate treatment are shown;
FIG. 2: the graph of the removal efficiency of neotame under the conditions of the invention case-bio-MOF-11 catalyzed persulfate, the comparison case-bio-MOF-11 alone treatment, and the comparison case-persulfate alone treatment is shown.
FIG. 3: the catalyst bio-MOF-11 is repeatedly used for three times, and the degradation efficiency of saccharin is shown in a graph.
FIG. 4: degradation efficiency chart of Neotame for three times of repeated use of the catalyst bio-MOF-11 of the invention
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples in conjunction with the accompanying drawings.
Embodiments of the present invention will be described in detail below with reference to examples. The following examples are merely illustrative of the present invention and should not be construed as limiting the scope of the invention. The reagents or instruments are not indicated by manufacturers, and are all conventional products which can be purchased through normal channels.
Example one
1) Preparation of bio-MOF-11
The bio-MOF-11 is prepared by hydrothermal reaction.
2) Selection of persulfates
The persulfate salt chosen in this example was sodium persulfate
3) The specific degradation process is carried out according to the following steps
1 g/L bio-MOF-11 was added to 50 mg/L saccharin and neotame solution and reacted for 60min to establish adsorption-desorption equilibrium prior to addition of sodium persulfate, then 10 g/L sodium persulfate was added, the temperature was adjusted to 25 deg.C, and the mixture was stirred at 120r/min for 120 min.
After pretreatment, the concentrations of saccharin and neotame in the system are measured by using HP L C, so that the degradation rates of saccharin and neotame are calculated, and the result shows that the degradation rate of saccharin is 61%, and neotame is almost completely degraded.
Example two
1) Preparation of bio-MOF-11
The bio-MOF-11 is prepared by hydrothermal reaction.
2) The specific degradation process is carried out according to the following steps
Adding 1 g/L bio-MOF-11 into 50 mg/L saccharin and neotame solution, adjusting the temperature to 25 ℃, and stirring for 120min under the condition of 120 r/min.
The concentration of saccharin and neotame in a system is measured by HP L C after the sample is pretreated, so that the removal efficiency rate of saccharin and neotame is calculated, and the result shows that the adsorption of saccharin and neotame by bio-MOF-11 mainly occurs within the first 30min, the desorption occurs within the last 30min to reach balance, and the adsorption effect of saccharin and neotame by bio-MOF-11 is poor.
Example three
1) Selection of persulfates
The persulfate salt chosen in this example was sodium persulfate
2) The specific degradation process is carried out according to the following steps
10 g/L g of sodium persulfate is added into 50 mg/L of saccharin and neotame solution, the temperature is adjusted to 25 ℃, and the mixture is stirred for 120min under the condition of 120 r/min.
3) The concentrations of saccharin and neotame in the system were measured after pretreatment of the samples with HP L C to calculate the degradation rates of saccharin and neotame, which indicated that saccharin and neotame were barely degraded in the sodium persulfate system alone.
Case four
1) Preparation of bio-MOF-11
The bio-MOF-11 is prepared by hydrothermal reaction.
2) Selection of persulfates
The persulfate salt chosen in this example was sodium persulfate
3) Post-use treatment of bio-MOF-11
Filtering the reaction solution, taking out the bio-MOF-11 after catalytic reaction, washing with pure water for 3 times, removing the surface reaction product, vacuum drying at 60 ℃, and inspecting the recycling property
4) The specific degradation process is carried out according to the following steps
1 g/L bio-MOF-11 was added to 50 mg/L saccharin and neotame solution and reacted for 60min to establish adsorption-desorption equilibrium prior to addition of sodium persulfate, then 10 g/L sodium persulfate was added, the temperature was adjusted to 25 deg.C, and the mixture was stirred at 120r/min for 120 min.
3) The concentrations of saccharin and neotame in a system are measured by HP L C after a sample is pretreated, so that the degradation rates of saccharin and neotame are calculated, and the result shows that the neotame can be almost completely degraded within 60min after the catalyst is used for the third time, the degradation kinetics are similar, and the stability of bio-MOF-11 is shown.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (8)
1. A method for catalytically degrading saccharin and neotame by using a metal organic framework nano material bio-MOF-11 is characterized by comprising the following steps:
s1, preparing bio-MOF-11 through a hydrothermal reaction;
s2, preparing a degradation system, wherein the degradation system is formed by combining saccharin, neotame and an aqueous medium;
s3, adding bio-MOF-11 with the mass concentration of 1 g/L into the degradation system of S2 to form a mixture, and establishing adsorption-desorption equilibrium of the mixture;
s4, adding persulfate with the mass concentration of 10 g/L into the mixture in the S3, enabling the pH of the formed solution to be 3-10, keeping the reaction temperature at 25 ℃, and carrying out catalytic degradation.
2. The method for catalyzing the degradation of saccharin and neotame through the metal-organic framework nano-material bio-MOF-11 according to claim 1, wherein the hydrothermal reaction in S1 comprises the following steps,
step 1, mixing 0.9mmol of cobalt acetate and 2.7mmol of adenine, dissolving in 72m of L N, N-dimethylformamide, and vigorously stirring for 30min to completely dissolve to obtain a uniform mixture;
step 2, pouring the obtained uniform mixture into a polytetrafluoroethylene lining reaction kettle of 100m L, sealing the lining reaction kettle in a stainless steel high-pressure kettle, heating the stainless steel high-pressure kettle in a 120 ℃ oven, and keeping the constant temperature to perform hydrothermal reaction for 48 hours to obtain a reactant;
and step 3: and naturally cooling the obtained reactant to room temperature, stirring, centrifuging to obtain bio-MOF-11, and placing the product in a vacuum drying oven at 60 ℃.
3. The method for catalyzing the degradation of saccharin and neotame by using the metal-organic framework nano-material bio-MOF-11 as claimed in claim 1, wherein the mass concentration of saccharin and neotame in a solvent in S2 is 50 mg/L.
4. The method for the catalytic degradation of saccharin and neotame by the metal organic framework nano-material bio-MOF-11 according to claim 1, wherein the metal organic framework nano-material bio-MOF-11 is characterized in that: the persulfate in the S4 is any one of sodium persulfate, potassium persulfate and ammonium persulfate.
5. The method for the catalytic degradation of saccharin and neotame by the metal organic framework nano-material bio-MOF-11 according to claim 1, wherein the metal organic framework nano-material bio-MOF-11 is characterized in that: the catalytic degradation mode in S4 includes any one of standing and stirring.
6. The method for the catalytic degradation of saccharin and neotame by the metal-organic framework nano-material bio-MOF-11 according to claim 5, wherein the metal-organic framework nano-material bio-MOF-11 is characterized in that: the stirring rate was 120 rpm.
7. The method for the catalytic degradation of saccharin and neotame by the metal organic framework nano-material bio-MOF-11 according to claim 1, wherein the metal organic framework nano-material bio-MOF-11 is characterized in that: and the time of catalytic degradation in the S4 is 0-120 min.
8. The method for the catalytic degradation of saccharin and neotame through the metal-organic framework nano-material bio-MOF-11 according to claim 1, wherein the reaction time in S3 is 60 min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105854944A (en) * | 2016-03-31 | 2016-08-17 | 华南理工大学 | Copper doped ferrous metal organic framework material as well as preparation method and method for activating persulfate to treat organic wastewater by using same |
| CN105923738A (en) * | 2016-06-20 | 2016-09-07 | 华南理工大学 | Method for utilizing metal organic skeleton to carry out efficient catalytic activation on persulfate or peroxymonosulfate to process organic wastewater |
| CN108384025A (en) * | 2018-04-08 | 2018-08-10 | 东华大学 | A kind of biological MOF and preparation method thereof based on adenine |
| CN109002685A (en) * | 2018-06-28 | 2018-12-14 | 南京大学 | The degradation prediction technique of artificial sweetener in ultraviolet/sodium peroxydisulfate removal secondary effluent |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105854944A (en) * | 2016-03-31 | 2016-08-17 | 华南理工大学 | Copper doped ferrous metal organic framework material as well as preparation method and method for activating persulfate to treat organic wastewater by using same |
| CN105923738A (en) * | 2016-06-20 | 2016-09-07 | 华南理工大学 | Method for utilizing metal organic skeleton to carry out efficient catalytic activation on persulfate or peroxymonosulfate to process organic wastewater |
| CN108384025A (en) * | 2018-04-08 | 2018-08-10 | 东华大学 | A kind of biological MOF and preparation method thereof based on adenine |
| CN109002685A (en) * | 2018-06-28 | 2018-12-14 | 南京大学 | The degradation prediction technique of artificial sweetener in ultraviolet/sodium peroxydisulfate removal secondary effluent |
Non-Patent Citations (1)
| Title |
|---|
| MUHAMMAD RIZWAN AZHAR等: "Submicron sized water-stable metal organic framework (bio-MOF-11) for catalytic degradation of pharmaceuticals and personal care products", 《CHEMOSPHERE》 * |
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