CN115057540A - Phenol sewage treatment method based on nano enzyme UMP-Cu with laccase activity - Google Patents
Phenol sewage treatment method based on nano enzyme UMP-Cu with laccase activity Download PDFInfo
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- CN115057540A CN115057540A CN202210798321.5A CN202210798321A CN115057540A CN 115057540 A CN115057540 A CN 115057540A CN 202210798321 A CN202210798321 A CN 202210798321A CN 115057540 A CN115057540 A CN 115057540A
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/342—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes used
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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Abstract
The invention is suitable for the technical field of sewage phenol removal, and provides a phenol sewage treatment method based on nano enzyme UMP-Cu with laccase activity, which comprises the following steps: adding nano enzyme UMP-Cu with laccase activity into a phenol water body, catalyzing and oxidizing phenol by nano enzyme for polymerization after a certain time to generate precipitate, and removing phenol in the phenol-containing water body by filtering and other modes. The invention utilizes nano enzyme UMP-Cu with laccase activity to catalyze phenol substances to polymerize, thereby realizing the removal of precipitates. Compared with natural laccase, the nano-enzyme UMP-Cu has better environmental stability and wider temperature use range. Therefore, compared with a phenol polymerization removal method based on natural laccase, the method can be used in treatment of more complex wastewater (such as high-temperature wastewater and the like).
Description
Technical Field
The invention belongs to the technical field of phenol removal of sewage, and particularly relates to a phenol sewage treatment method based on UMP-Cu nano enzyme with laccase activity.
Background
Phenolic substances are recognized environmental endocrine interferons and carcinogens in the world, have the characteristics of lasting action, bioaccumulation and the like, and influence the normal reproduction and development of organisms and offspring thereof. The detection and removal of polyphenolic substances in water is of central importance. Laccase is a polyphenol oxidase, which has the dual properties of oxidase and hydroxylase. Under the condition of oxygen, the phenolic compound can be catalyzed and oxidized to generate a high molecular polymer precipitate which is not easy to dissolve, and the high molecular polymer precipitate is removed by a filtration mode and the like. Because laccase can oxidize phenolic substances and most of products are water, the laccase can be widely applied to industries such as food, textile, paper making and the like. However, the natural laccase has poor stability, cannot exist in reaction environments such as high temperature, strong acid and alkali and the like stably, and is difficult to recycle, so that the large-scale industrial application of the laccase is hindered.
Compared with natural laccase, the artificially synthesized nano-enzyme generally has the advantages of low cost, wide applicable pH and salinity range, large use temperature range, easy storage and the like. Meanwhile, the nanoenzyme also has the advantage of strong substrate applicability, so that the nanoenzyme has a good application prospect. At present, laccase nanoenzyme is applied to the fields of agricultural food, wastewater treatment, biotechnology, manufacture of phenolic substance detectors and the like, but no research report on the aspect of wastewater polymerization and phenol removal is provided. Therefore, the laccase activity of the nano-enzyme can be utilized to polymerize phenolic compounds in water, and the problem of application limitation of the traditional natural laccase in the aspect of removing phenol in industrial wastewater under severe conditions such as high temperature, strong alkali and the like is solved.
Disclosure of Invention
The embodiment of the invention aims to provide a phenol sewage treatment method based on a nano enzyme UMP-Cu with laccase activity, and aims to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a phenol sewage treatment method based on nano enzyme UMP-Cu with laccase activity comprises the following steps:
adding nano enzyme UMP-Cu with laccase activity into a phenol water body, catalyzing and oxidizing phenol by nano enzyme for polymerization after a certain time to generate precipitate, and removing phenol in the phenol-containing water body in a filtering mode.
Further, the synthesis of the nano enzyme UMP-Cu is specifically operated as follows: adding Tris-HCl, UMP and CuCl into a 1000 mu L system at room temperature 2 And H 2 And O, centrifugally washing, dispersing the obtained precipitate into water after washing, and refrigerating for later use.
Further, in the specific operation of synthesizing the nano-enzyme UMP-Cu, 100. mu.L of 100mM Tris-HCl, 200. mu.L of 10mM UMP and 100. mu.L of 50mM CuCl are added into a 1000. mu.L system 2 And 600. mu.L of H 2 O。
Further, the blue precipitate obtained after the centrifugal washing was dispersed in 1mL of water and stored under refrigeration at 4 ℃ for further use.
Further, the nano enzyme UMP-Cu has laccase activity, and in the presence of oxygen, the nano enzyme UMP-Cu generates a polymerization product which is not easy to dissolve in a mode of catalyzing and oxidizing a plurality of phenols to generate polymerization reaction.
Further, the mass concentration of the nano enzyme UMP-Cu is 0.01-0.5 mg/ml.
Further, the temperature of the phenol-containing water body is 20-40 ℃.
Compared with the prior art, the invention has the beneficial effects that:
compared with natural laccase, the phenol sewage treatment method based on the nano-enzyme UMP-Cu with laccase activity has the advantages that the nano-enzyme UMP-Cu has better environmental stability and wider temperature application range. Therefore, compared with a phenol polymerization removal method based on natural laccase, the method can be used for treating more complex wastewater (high-temperature wastewater and the like). The nano enzyme has better removing effect on phenolic substances, and is suitable for the field of treatment of the phenolic substances in the environmental sewage.
Drawings
Fig. 1 is a schematic diagram of an embodiment of the invention.
FIG. 2 is a laccase activity diagram of UMP-Cu in the invention example.
FIG. 3 is a schematic diagram of UMP-Cu catalyzed polymerization of hydroquinone and catechol at 40 ℃ in the examples of the present invention.
FIG. 4 is an HPLC chromatogram of UMP-Cu catalyzed catechol polymerization at 20 ℃ in the inventive examples.
FIG. 5 is an HPLC chromatogram of UMP-Cu catalyzed catechol polymerization at 40 ℃ in an example of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Specific implementations of the present invention are described in detail below with reference to specific embodiments.
The phenolic sewage treatment method based on the nano enzyme UMP-Cu with laccase activity provided by the embodiment of the invention comprises the following steps:
adding nano enzyme UMP-Cu with laccase activity into a phenol water body, catalyzing and oxidizing phenol by nano enzyme for polymerization after a certain time to generate precipitate, and removing phenol in the phenol-containing water body in a filtering mode.
As a preferred embodiment of the invention, the synthesis of the nano-enzyme UMP-Cu is specifically operated as follows: adding Tris-HCl, UMP and CuCl into a 1000 mu L system at room temperature 2 And H 2 And O, centrifugally washing, dispersing the obtained precipitate into water after washing, and refrigerating for later use.
As a preferred embodiment of the present invention, in the specific operation of the synthesis of the nanoenzyme UMP-Cu, 100. mu.L of 100mM Tris-HCl, 200. mu.L of 10mM UMP, and 100. mu.L of 50mM CuCl are added to a 1000. mu.L system 2 And 600. mu.L of H 2 O。
In a preferred embodiment of the present invention, the blue precipitate obtained after the centrifugal washing is dispersed in 1mL of water and stored under refrigeration at 4 ℃ for further use.
As a preferred embodiment of the invention, the nano-enzyme UMP-Cu has laccase activity, and in the presence of oxygen, the nano-enzyme UMP-Cu generates a polymerization product which is not easy to dissolve in a mode of catalyzing and oxidizing a plurality of phenols to generate polymerization reaction.
As a preferred embodiment of the invention, the mass concentration of the nano enzyme UMP-Cu is 0.01-0.5 mg/ml.
As a preferred embodiment of the invention, the temperature of the phenol-containing water body is 20-40 ℃.
Examples
The invention provides a method for treating phenolic sewage by using nano enzyme UMP-Cu with laccase activity, which comprises the following steps:
s1: under the condition of room temperature, a synthesis system is constructed: to a 1000. mu.L system, 100. mu.L Tris-HCl (100mM), 200. mu.L UMP (10mM), and CuCl were added 2 (50mM)100μL，H 2 O600. mu.L (final concentration in the system: Tris-HCl 10 mM; UMP 2 mM; CuCl 2 5mM), collecting blue precipitate by centrifugation, washing with ultrapure water to remove unreacted reagents, and dispersing in 1mL of ultrapure water to obtain nano enzyme UMP-Cu with laccase activity;
s2: treating with 2,4-DP as a substrate, 4-AP as an indicator and MES as a buffer solution by using synthesized UMP-Cu, reacting for 0.5h, performing spectral measurement on the supernatant of the reaction system by using an ultraviolet absorption spectrometry, and setting a control group;
s3: treating synthesized UMP-Cu by using catechol and hydroquinone as substrates under the reaction condition of 40 ℃, and observing an experimental phenomenon after reacting for 1 h;
s4: treating with catechol as substrate under different temperature reaction conditions by using synthesized UMP-Cu, setting a control group, measuring the concentration of phenolic substances in the supernatant before and after the reaction by using high performance liquid chromatography to obtain an HPLC chromatogram, and comparing with the control group.
In the embodiment of the present invention, in step S2,the mass concentration of 2,4-DP and 4-AP is 0.1mg/mL, the concentration of MES buffer solution is 50mM, the pH value is 6.8, and the wavelength range of ultraviolet absorption spectrum is 400nm-700 nm; in the step S3, the mass concentration of catechol and hydroquinone is 0.1mg/ml, and the reaction temperature condition is set to 40 ℃; in step S4, the high performance liquid chromatography measures the concentration of the phenols in the supernatant, and the measurement parameters are: the mobile phase is methanol: 0.2% acetic acid ═ 5: 5; the flow rate is 1.0 ml/min; the column temperature was 35 ℃. Referring to fig. 2, in the presence of nanoenzyme, the catalytic reaction system generates a characteristic peak at 510nm, confirming that the synthesized nanoenzyme UMP-Cu has laccase activity; referring to fig. 3, the experimental phenomenon of the catalysis of catechol and catechol by the nanoenzyme at 40 ℃ proves that the nanoenzyme UMP-Cu still maintains the catalytic activity at 40 ℃ and catalyzes the phenol substance to generate the macroscopic polymerization phenomenon, thus proving the catalytic polymerization capability of the nanoenzyme UMP-Cu on the phenol substance; referring to fig. 4 and 5, the left graph in fig. 4 is the HPLC chromatogram of the nano-enzyme catalyzed catechol at 20 ℃, and the right graph is the control group catechol; it can be seen that compared with catechol on the right, a new peak appears on the left, which indicates that the nano enzyme UMP-Cu catalyzes catechol to produce polymers with different molecular weights; in FIG. 5, the left graph is HPLC chromatogram of catechol catalyzed by nano-enzyme at 40 deg.C, and the right graph is control group catechol; compared with FIG. 4, more new peaks appear in the nanoenzyme group under the high-temperature condition, which indicates that the catalytic polymerization capability of the nanoenzyme UMP-Cu under the high-temperature condition is stronger, and more polymers are generated in the system. Therefore, the nano enzyme UMP-Cu has good stability, still keeps activity under a high-temperature condition, and is suitable for the field of treatment of environmental sewage phenolic substances. The invention uses Cu 2+ Is used as an active center and UMP is used as a ligand, so that nano enzyme UMP-Cu with laccase activity is synthesized, catechol is used as a substrate to catalyze the nano enzyme UMP-Cu to carry out polymerization reaction, and then the nano enzyme UMP-Cu is removed. Compared with the existing means for treating the environmental wastewater, the method has lower requirements on equipment, can obtain good removal effect of phenolic substances on the basis of low cost, is suitable for environmental wastewater treatment, and has the advantages of low cost, better removal effect, difficult inactivation, wider application range and the likeConvenient storage and the like.
The working principle of the invention is as follows:
the phenol sewage treatment method based on the nano enzyme UMP-Cu with laccase activity utilizes the nano enzyme UMP-Cu with laccase activity to catalyze phenol substances to polymerize, thereby realizing the removal of precipitates. Compared with natural laccase, the nano-enzyme UMP-Cu has better environmental stability and wider temperature use range. Therefore, compared with a phenol polymerization removal method based on natural laccase, the method can be used in treatment of more complex wastewater (such as high-temperature wastewater and the like).
The above is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, it is possible to make several variations and modifications without departing from the concept of the present invention, and these should be considered as the protection scope of the present invention, which will not affect the effect of the implementation of the present invention and the utility of the patent.
Claims (7)
1. A phenol sewage treatment method based on nano enzyme UMP-Cu with laccase activity is characterized by comprising the following steps:
adding nano enzyme UMP-Cu with laccase activity into a phenol water body, catalyzing and oxidizing phenol by nano enzyme for polymerization after a certain time, generating precipitate, and removing phenol in the phenol-containing water body by a filtering mode.
2. The phenol sewage treatment method based on nano-enzyme UMP-Cu with laccase activity as claimed in claim 1, wherein the synthesis of nano-enzyme UMP-Cu is specifically operated as follows: adding Tris-HCl, UMP and CuCl into a 1000 mu L system at room temperature 2 And H 2 And O, centrifugally washing, dispersing the obtained precipitate into water after washing, and refrigerating for later use.
3. The phenol type sewage treatment method based on nano-enzyme UMP-Cu with laccase activity as claimed in claim 2, wherein in the specific operation of synthesizing nano-enzyme UMP-Cu, 1000 μ L system is added100 μ L of 100mM Tris-HCl, 200 μ L of 10mM UMP, 100 μ L of 50mM CuCl 2 And 600. mu.L of H 2 O。
4. The method for treating phenol-based sewage with laccase activity according to claim 2, wherein the blue precipitate obtained after centrifugal washing is dispersed in 1mL of water and stored under refrigeration at 4 ℃ for further use.
5. The method for treating phenolic wastewater based on UMP-Cu nano-enzyme with laccase activity as claimed in claim 2, wherein the UMP-Cu nano-enzyme has laccase activity, and under the condition of oxygen, UMP-Cu nano-enzyme generates insoluble polymerization products by means of catalytic oxidation of a plurality of phenols to perform polymerization reaction.
6. The phenol-based sewage treatment method with laccase activity based on UMP-Cu as claimed in claim 5, wherein the mass concentration of UMP-Cu is 0.01-0.5 mg/ml.
7. The phenol sewage treatment method based on the nano enzyme UMP-Cu with laccase activity according to claim 1, wherein the temperature of the phenol-containing water body is 20-40 ℃.
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| CN113000069A (en) * | 2021-02-25 | 2021-06-22 | 广西大学 | Preparation method and application of bionic laccase functionalized imine covalent organic framework nanoenzyme |
| CN113295682A (en) * | 2021-05-21 | 2021-08-24 | 吉林大学 | Phenolic compound analysis method based on polyphenol oxidase activity nanoenzyme |
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2022
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0686998A (en) * | 1992-09-07 | 1994-03-29 | Agency Of Ind Science & Technol | Method for removing phenols and anilines in water |
| CN102329008A (en) * | 2011-08-26 | 2012-01-25 | 湖南大学 | Method for removing phenol pollutants in water body by using immobilized laccase based on magnetic mesoporous carbon |
| CN104478068A (en) * | 2014-10-30 | 2015-04-01 | 华中科技大学 | Method for treating antibiotic-contaminated water through immobilized laccase and lignin mediator |
| CN110085877A (en) * | 2019-04-18 | 2019-08-02 | 南京师范大学 | A kind of phenols sewage generating set and its preparation method and application based on single enzyme inorganic composite nano flower |
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| CN113000069A (en) * | 2021-02-25 | 2021-06-22 | 广西大学 | Preparation method and application of bionic laccase functionalized imine covalent organic framework nanoenzyme |
| CN113295682A (en) * | 2021-05-21 | 2021-08-24 | 吉林大学 | Phenolic compound analysis method based on polyphenol oxidase activity nanoenzyme |
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