CN111470549B - 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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- CN111470549B CN111470549B CN202010135915.9A CN202010135915A CN111470549B CN 111470549 B CN111470549 B CN 111470549B CN 202010135915 A CN202010135915 A CN 202010135915A CN 111470549 B CN111470549 B CN 111470549B
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- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 235000019204 saccharin Nutrition 0.000 title claims abstract description 43
- 229940081974 saccharin Drugs 0.000 title claims abstract description 43
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 title claims abstract description 43
- 239000004384 Neotame Substances 0.000 title claims abstract description 42
- HLIAVLHNDJUHFG-HOTGVXAUSA-N neotame Chemical compound CC(C)(C)CCN[C@@H](CC(O)=O)C(=O)N[C@H](C(=O)OC)CC1=CC=CC=C1 HLIAVLHNDJUHFG-HOTGVXAUSA-N 0.000 title claims abstract description 42
- 235000019412 neotame Nutrition 0.000 title claims abstract description 42
- 108010070257 neotame Proteins 0.000 title claims abstract description 42
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 18
- 230000000593 degrading effect Effects 0.000 title claims abstract description 9
- 238000006731 degradation reaction Methods 0.000 claims abstract description 37
- 230000015556 catabolic process Effects 0.000 claims abstract description 33
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000002336 sorption--desorption measurement Methods 0.000 claims abstract description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 11
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229930024421 Adenine Natural products 0.000 claims description 2
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 claims description 2
- 229960000643 adenine Drugs 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000008122 artificial sweetener Substances 0.000 abstract description 4
- 235000021311 artificial sweeteners Nutrition 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 2
- 230000002085 persistent effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 231100000041 toxicology testing Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- 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
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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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. The method comprises the following steps: s1, preparing bio-MOF-11; s2, preparing a degradation system; s3, adding bio-MOF-11 with the mass concentration of 1g/L into the degradation system of S2 to form a mixture, and enabling the mixture to establish adsorption-desorption balance; s4, adding persulfate with the mass concentration of 10g/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. The bio-MOF-11 metal organic framework nano material has important significance for rapidly degrading saccharin and neotame in a persistent artificial sweetener in a water environment, improving the biodegradability of high-concentration wastewater and the like.
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 not high in the sewage biological treatment process, and sewage and wastewater are discharged into a water environment. The saccharin and the neotame have long application time and large use scale, have the characteristics of wide pollution range, high pollution level, strong durability and the like when distributed 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 1g/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 10g/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:
step 1: firstly, 0.9mmol of cobalt acetate and 2.7mmol of adenine are mixed and dissolved in 72ml of DMMF, and the mixture is vigorously stirred for 30min to be completely dissolved, so that a uniform mixture is obtained;
and 2, step: pouring the obtained uniform mixture into a 100mL polytetrafluoroethylene lining reaction kettle, 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 ℃.
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 advanced oxidation method provided by the invention can realize the rapid and efficient deep degradation of saccharin and neotame, the removal rate of 50mg/L saccharin can reach 61%, NEO is almost completely degraded, the degradation time is short, and the catalyst has cyclic utilizationHas important significance for the practical application of the composite material.
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 is a schematic view of: 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
To a 50mg/L solution of saccharin and neotame was added 1 g/Lbeio-MOF-11 and reacted for 60min to establish an adsorption-desorption equilibrium prior to the addition of sodium persulfate. Subsequently, 10g/L of sodium persulfate was added. The temperature is adjusted to 25 ℃ and the stirring treatment is carried out for 120min under the condition of 120 r/min.
After pretreatment, the concentration of saccharin and neotame in the system is measured by HPLC, so that the degradation rate of saccharin and neotame is 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/Lbeio-MOF-11 into 50mg/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 HPLC after a 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 reaches balance within the last 30min, 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
Adding 10g/L sodium persulfate into 50mg/L saccharin and neotame solution, adjusting the temperature to 25 ℃, and stirring for 120min under the condition of 120 r/min.
3) And (3) after pretreatment, the concentration of saccharin and neotame in the system is measured by HPLC, so that the degradation rate of saccharin and neotame is calculated, and the result shows that saccharin and neotame are hardly degraded only in a sodium persulfate system.
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
To a 50mg/L solution of saccharin and neotame was added 1 g/Lbei-MOF-11 and reacted for 60min to establish an adsorption-desorption equilibrium prior to the addition of sodium persulfate. Subsequently, 10g/L of sodium persulfate was added. The temperature is adjusted to 25 ℃, and the stirring treatment is carried out for 120min under the condition of 120 r/min.
3) The concentration of saccharin and neotame in the system is measured by HPLC after the sample is pretreated, so that the degradation rate of saccharin and neotame is 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. But for the less degradable saccharin the degradation rate dropped from 61% to 27%.
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 (6)
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 1g/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 10g/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 performing catalytic degradation;
the persulfate in the S4 is any one of sodium persulfate, potassium persulfate and ammonium persulfate;
the hydrothermal reaction in S1 includes the steps of,
step 1: firstly, 0.9mmol of cobalt acetate and 2.7mmol of adenine are mixed and dissolved in 72mLN, N-dimethylformamide, and the mixture is vigorously stirred for 30min to be completely dissolved, so that a uniform mixture is obtained;
step 2: pouring the obtained uniform mixture into a 100mL polytetrafluoroethylene lining reaction kettle, 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 3, 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 ℃.
2. 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 mass concentration of saccharin and neotame in the S2 in the solvent is 50 mg/L.
3. 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.
4. The method for the catalytic degradation of saccharin and neotame by the metal-organic framework nano-material bio-MOF-11 according to claim 3, wherein the metal-organic framework nano-material bio-MOF-11 is characterized in that: the stirring rate was 120 rpm.
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: and the time of catalytic degradation in the S4 is 0-120 min.
6. 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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| 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 |
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