CN115057540B - Phenolic sewage treatment method based on nano enzyme UMP-Cu with laccase activity - Google Patents
Phenolic sewage treatment method based on nano enzyme UMP-Cu with laccase activity Download PDFInfo
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- CN115057540B CN115057540B CN202210798321.5A CN202210798321A CN115057540B CN 115057540 B CN115057540 B CN 115057540B CN 202210798321 A CN202210798321 A CN 202210798321A CN 115057540 B CN115057540 B CN 115057540B
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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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- Microbiology (AREA)
- Biodiversity & Conservation Biology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention is applicable to the technical field of wastewater dephenolization, and provides a phenolic wastewater 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, and after a certain time, polymerizing phenol by catalytic oxidation of nano enzyme to generate precipitate, and removing phenol in the phenol-containing water body by means of filtration and the like. According to the invention, nano enzyme UMP-Cu with laccase activity is utilized to catalyze phenolic substances to polymerize, so that sediment removal is realized. Compared with natural laccase, the nano enzyme UMP-Cu has better environmental stability and wider temperature application range. Therefore, compared with the phenol polymerization removal method based on the natural laccase, the method can be used in the treatment of more complex wastewater (such as high-temperature wastewater and the like).
Description
Technical Field
The invention belongs to the technical field of sewage dephenolization, and particularly relates to a phenolic sewage treatment method based on nano enzyme UMP-Cu with laccase activity.
Background
Phenolic substances are world-recognized environmental endocrine disruptors and carcinogens, have the characteristics of durable action, bioaccumulation and the like, and can influence normal reproduction and development of organisms and offspring thereof. Therefore, the detection and removal of polyphenol substances in the water body is of great importance. Laccase is a polyphenol oxidase, having both oxidase and hydroxylase properties. Under the aerobic condition, the phenolic compound can be catalyzed and oxidized to generate a polymer precipitate which is not easy to dissolve, and the polymer precipitate is removed by a filtration mode and the like. Laccase is widely used in the industries of food, textile, paper-making, etc. because it can oxidize phenols and most of its products are water. However, the natural laccase has poor stability, cannot be stably present in high-temperature, strong acid and alkali reaction environments, and is difficult to recycle, thus preventing the laccase from being applied to the industry on a large scale.
Compared with natural laccase, the artificially synthesized nano-enzyme has the advantages of low cost, wide applicable pH and salinity range, large use temperature range, easy storage and the like. Meanwhile, the nano-enzyme has the advantage of strong substrate applicability, so that the nano-enzyme has good application prospect. At present, laccase nanoenzymes are applied to the fields of agricultural foods, wastewater treatment, biotechnology, manufacturing of phenolic substance detectors and the like, but no research and report on wastewater polymerization dephenolization are available. 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 from 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 phenolic sewage treatment method based on nano enzyme UMP-Cu with laccase activity, which aims to solve the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a phenolic 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 phenolic water body, and after a certain time, polymerizing phenol by catalytic oxidation of nano enzyme to generate precipitate, and removing phenol in the phenolic water body by a filtering mode.
Further, the specific operation of the synthesis of the nano enzyme UMP-Cu is as follows: tris-HCl, UMP, cuCl is added into 1000 mu L system at room temperature 2 And H 2 And O, centrifugally washing, dispersing the obtained precipitate into water, and refrigerating for later use.
Further, in the specific operation of the nanoenzyme UMP-Cu synthesis, 100. Mu.L of 100mM Tris-HCl, 200. Mu.L of 10mM UMP, 100. Mu.L of 50mM CuCl were added to 1000. Mu.L of the system 2 And 600. Mu.L of H 2 O。
Further, the blue precipitate obtained after centrifugal washing is dispersed into 1mL of water, and is refrigerated at 4 ℃ for standby.
Furthermore, 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 various phenols to generate polymerization reaction.
Further, the mass concentration of the nano enzyme UMP-Cu is 0.01-0.5mg/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 the natural laccase, the phenolic wastewater treatment method based on the nano enzyme UMP-Cu with laccase activity has better environmental stability and wider temperature application range. Therefore, compared with the phenol polymerization removal method based on natural laccase, the method can be used in the treatment of more complex wastewater (high-temperature wastewater and the like). The nano enzyme has better removal effect on phenolic substances and is suitable for the field of environmental sewage phenolic substance treatment.
Drawings
Fig. 1 is a schematic diagram of an embodiment of the invention.
FIG. 2 is a graph showing the laccase activity of UMP-Cu in an inventive example.
FIG. 3 is a schematic illustration of polymerization of hydroquinone and catechol catalyzed by UMP-Cu at 40℃in an example of the invention.
FIG. 4 is a HPLC chromatogram of UMP-Cu catalyzed catechol polymerization at 20℃in an inventive example.
FIG. 5 is a HPLC chromatogram of UMP-Cu catalyzed catechol polymerization at 40℃in an inventive example.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Specific implementations of the invention are described in detail below in connection with specific embodiments.
The phenolic sewage treatment method based on nano enzyme UMP-Cu with laccase activity provided by one embodiment of the invention comprises the following steps:
adding nano enzyme UMP-Cu with laccase activity into a phenolic water body, and after a certain time, polymerizing phenol by catalytic oxidation of nano enzyme to generate precipitate, and removing phenol in the phenolic water body by a filtering mode.
As a preferred embodiment of the invention, the specific operation of the synthesis of the nanoenzyme UMP-Cu is as follows: tris-HCl, UMP, cuCl is added into 1000 mu L system at room temperature 2 And H 2 And O, centrifugally washing, dispersing the obtained precipitate into water, 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, 100. Mu.L of 50mM CuCl are added to 1000. Mu.L of the system 2 And 600. Mu.L of H 2 O。
As a preferred embodiment of the invention, the blue precipitate obtained after centrifugal washing is dispersed in 1mL of water and is refrigerated at 4 ℃ for later use.
As a preferred embodiment of the invention, the nano-enzyme UMP-Cu has laccase activity, and the nano-enzyme UMP-Cu generates a polymerization product which is not easy to dissolve by catalyzing and oxidizing various phenols to generate polymerization reaction in the presence of oxygen.
As a preferred embodiment of the invention, the mass concentration of the nano-enzyme UMP-Cu is 0.01-0.5mg/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: room temperature stripUnder the piece, a synthesis system is constructed: 100. Mu.L Tris-HCl (100 mM), 200. Mu.L UMP (10 mM), cuCl were added to 1000. Mu.L system 2 (50mM)100μL，H 2 O600. Mu.L (final concentration in the system: tris-HCl 10mM; UMP 2mM; cuCl) 2 5 mM), removing unreacted reagent by collecting blue precipitate through centrifugation and washing with ultrapure water, and dispersing in 1mL of ultrapure water to obtain nano enzyme UMP-Cu with laccase activity;
s2: 2,4-DP is used as a substrate, 4-AP is used as an indicator, MES is used as a buffer solution, the synthesized UMP-Cu is used for processing, after 0.5h of reaction, the ultraviolet absorption spectrometry is used for spectrometry of the supernatant of the reaction system, and a control group is arranged;
s3: using catechol and hydroquinone as substrates, using synthesized UMP-Cu for treatment under the reaction condition of 40 ℃, and observing experimental phenomena after reacting for 1 h;
s4: catechol is used as a substrate, synthetic UMP-Cu is used for treatment under the reaction conditions of different temperatures, a control group is arranged, the concentration of phenolic substances in supernatant liquid before and after the reaction is measured by using a high performance liquid chromatography, and an HPLC chromatogram is obtained and is compared with the control group.
In the embodiment of the invention, in the step S2, the mass concentration of the 2,4-DP and 4-AP is 0.1mg/mL, the concentration of the MES buffer solution is 50mM, the pH=6.8, and the wavelength range of the ultraviolet absorption spectrum is 400nm-700nm; 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 concentration of the supernatant phenolic substance is measured by high performance liquid chromatography, and the measurement parameters are as follows: the mobile phase is methanol: 0.2% acetic acid = 5:5, a step of; the flow rate is 1.0ml/min; column temperature was 35 ℃. Referring to FIG. 2, in the presence of the nano-enzyme, the catalytic reaction system generates a characteristic peak at 510nm, confirming that the synthesized nano-enzyme UMP-Cu has laccase activity; referring to FIG. 3, for the experimental phenomenon of nano enzyme catalysis catechol and catechol at 40 ℃, it is proved that nano enzyme UMP-Cu still maintains catalytic activity at 40 ℃, and visible polymerization phenomenon is generated by catalyzing phenolic substances, thus proving the catalytic polymerization capability of nano enzyme UMP-Cu to phenolic substances; see fig. 4 andFIG. 5, left panel of FIG. 4 shows HPLC chromatogram of nanoenzyme-catalyzed catechol at 20deg.C, right panel shows control group of catechol; it can be seen that the left plot shows a new peak compared to the right plot catechol, which illustrates that the nanoenzyme UMP-Cu catalyzes catechol to produce polymers of different molecular weights; the left graph in FIG. 5 shows the HPLC chromatogram of the nano-enzyme catalyzed catechol at 40℃and the right graph shows the catechol of the control group; it can be seen that more new peaks appear in the nanoenzyme group at high temperature compared with fig. 4, which indicates that the nanoenzyme UMP-Cu has stronger catalytic polymerization capability at high temperature and generates more polymer in the system. Therefore, the nano enzyme UMP-Cu has good stability, still keeps activity under high temperature, and is suitable for the field of treatment of environmental sewage phenolic substances. The invention uses Cu 2+ The active center and UMP are used as ligands, so that nano enzyme UMP-Cu with laccase activity is synthesized, catechol is used as a substrate to catalyze the polymerization reaction, and then the nano enzyme UMP-Cu is removed. Compared with the existing means for treating environmental wastewater, the method has lower requirements on equipment, can obtain good phenolic substance removal effect on the basis of low cost, is suitable for environmental sewage treatment, and has the advantages of low cost, better removal effect, difficult inactivation, wider application range, convenience in storage and the like.
The working principle of the invention is as follows:
according to the phenolic wastewater treatment method based on the nano enzyme UMP-Cu with laccase activity, the nano enzyme UMP-Cu with laccase activity is utilized to catalyze phenolic substances to polymerize, and then sediment removal is achieved. Compared with natural laccase, the nano enzyme UMP-Cu has better environmental stability and wider temperature application range. Therefore, compared with the phenol polymerization removal method based on the natural laccase, the method can be used in the treatment of more complex wastewater (such as high-temperature wastewater and the like).
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the present invention, and these should also be considered as the scope of the present invention, which does not affect the effect of the implementation of the present invention and the utility of the patent.
Claims (2)
1. A phenolic 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 phenolic water body, and after a certain time, polymerizing phenol by catalytic oxidation of nano enzyme to generate precipitate, and removing phenol in the phenolic water body by a filtering mode;
the specific operation of the synthesis of the nano enzyme UMP-Cu is as follows: at room temperature, 100. Mu.L of 100mM Tris-HCl, 200. Mu.L of 10mM UMP, 100. Mu.L of 50mM CuCl were added to 1000. Mu.L of the system 2 And 600. Mu.L of H 2 O, centrifugally washing, dispersing the obtained precipitate into water, and refrigerating and preserving for later use;
the mass concentration of the nano enzyme UMP-Cu is 0.01-0.5mg/ml;
the temperature of the phenol-containing water body is 20-40 ℃;
the nano enzyme UMP-Cu has laccase activity, and generates a polymerization product which is not easy to dissolve by catalyzing and oxidizing various phenols to generate polymerization reaction in the presence of oxygen.
2. The phenolic wastewater treatment method based on nano enzyme UMP-Cu with laccase activity according to claim 1, wherein blue precipitate obtained after centrifugal washing is dispersed into 1mL of water, and the blue precipitate is refrigerated at 4 ℃ for later use.
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Citations (9)
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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 |
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| CN111889140A (en) * | 2019-05-05 | 2020-11-06 | 天津大学 | Preparation method and application of nano-enzyme based on cysteine-histidine dipeptide and copper ion compound |
| 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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Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111889140A (en) * | 2019-05-05 | 2020-11-06 | 天津大学 | Preparation method and application of nano-enzyme based on cysteine-histidine dipeptide and copper ion compound |
| CN110240292A (en) * | 2019-07-26 | 2019-09-17 | 江西省水利科学研究院 | A method of antibiotic in industrialization laccase and syringaldehyde combined degradation aquiculture sewerage |
| CN111686815A (en) * | 2020-06-22 | 2020-09-22 | 北京化工大学 | Self-assembly nano material and preparation method and application thereof |
| 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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