CN111137988A - Method for decoloring dye wastewater - Google Patents
Method for decoloring dye wastewater Download PDFInfo
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- CN111137988A CN111137988A CN202010056065.3A CN202010056065A CN111137988A CN 111137988 A CN111137988 A CN 111137988A CN 202010056065 A CN202010056065 A CN 202010056065A CN 111137988 A CN111137988 A CN 111137988A
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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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- 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
- C02F3/348—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
- C12N9/0004—Oxidoreductases (1.)
- C12N9/0055—Oxidoreductases (1.) acting on diphenols and related substances as donors (1.10)
- C12N9/0057—Oxidoreductases (1.) acting on diphenols and related substances as donors (1.10) with oxygen as acceptor (1.10.3)
- C12N9/0061—Laccase (1.10.3.2)
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- C12Y—ENZYMES
- C12Y110/00—Oxidoreductases acting on diphenols and related substances as donors (1.10)
- C12Y110/03—Oxidoreductases acting on diphenols and related substances as donors (1.10) with an oxygen as acceptor (1.10.3)
- C12Y110/03002—Laccase (1.10.3.2)
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- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- 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
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
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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
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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
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention provides a method for decoloring dye wastewater, which comprises the step of preparing hydroxyl/carboxyl functionalized magnetic Fe by a hydrothermal method3O4@ C nanoparticles, re-coordinated adsorption of Cu2+Ion preparation of magnetic Cu (II) chelated Fe3O4The @ C nano particle is finally used for preparing magnetic Cu (II) chelated Fe with high stability, high activity and reusability by utilizing the coordination effect between histidine residues of laccase and Cu (II)3O4@ C nanoparticle immobilized laccase. The invention not onlyCan degrade triphenylmethane dye, azo dye and anthraquinone dye, has a removal rate of 75-99% in a concentration range of 5-200mg/L, and can be repeatedly used for more than 10 times.
Description
Technical Field
The invention belongs to the field of dye wastewater decolorization treatment, and particularly relates to a method for treating dye wastewater decolorization by using immobilized laccase.
Background
With the rapid development of the industry, the problem of wastewater treatment is increasingly prominent, and the problem becomes an urgent solution to the development of the industry. Among them, dye wastewater is considered to be one of the most difficult industrial wastewater because of its wide source, large discharge amount, deep chromaticity, high concentration, complex composition, large change of pH value, and poor biodegradability.
The most widely used dyes at present are mainly of three types: azo dyes, anthraquinone dyes, triphenylmethane dyes. In the prior art, methods for treating dye wastewater such as adsorption decoloration, catalytic oxidation, combined process and the like have certain effects, but the traditional methods for treating dye wastewater are not widely applied due to the problems of high cost, generation of a large amount of sludge which is difficult to treat, easy generation of secondary pollution and the like.
How to treat dye wastewater by a biological method with low treatment cost and little pollution has important scientific significance and application value.
Laccase is a polyphenol oxidase containing 4 copper ions, can catalyze oxygen in air, directly oxidize and decompose various dyes, chlorophenol compounds, aromatic amine and other organic matters, and has potential application value in the aspects of dye wastewater treatment, biological bleaching, environmental pollutant detoxification, biosensor construction and the like. As the laccase is a protein consisting of amino acids, the molecular structure of the laccase is very sensitive to the external environment, is volatile in the using process and cannot be recycled from a reaction system.
In order to overcome the defects of the free laccase, the prior art combines the free laccase with an insoluble carrier to form immobilized laccase, so that the stability and the recyclability of the laccase are improved, and the laccase can be recycled. Therefore, the development of an application method of the immobilized laccase in dye wastewater decolorization has important theoretical significance and practical application value.
Disclosure of Invention
The invention aims to provide a method for decoloring dye wastewater, which is simple and mild, can quickly degrade dye wastewater with large concentration, and can repeatedly use triphenylmethane dye, azo dye and anthraquinone dye for more than 10 times.
The specific technical scheme of the invention is as follows:
a method for decoloring dye wastewater specifically comprises the following steps: chelation of Fe by magnetic Cu (II)3O4@ C nano particle immobilized laccase decoloration dye wastewater.
Further, the pH value of the dye wastewater is adjusted to 2.5-6.0, and then magnetic Cu (II) is used for chelating Fe3O4Treating the @ C nano particle immobilized laccase; preferably, the pH is 4.5.
Further, the decoloring condition is that the decoloring is carried out for 1 to 3 hours at a temperature of between 30 and 60 ℃. The preferred temperature is 50 ℃;
further, the decolorization treatment is carried out in a shaking incubator with the shaking frequency of 200 r/min.
Further, the dye wastewater comprises triphenylmethane dye wastewater, azo dye wastewater and anthraquinone dye wastewater.
The concentration of the triphenylmethane dye wastewater is 5-200 mg/L.
The concentration of the azo dye wastewater is 20-50 mg/L.
The concentration of the anthraquinone dye wastewater is 1-100 mg/L.
Specifically, magnetic Cu (II) is used for chelating Fe3O4A method for decoloring triphenylmethane dye wastewater by using @ C nano particle immobilized laccase comprises the following steps:
chelating magnetic Cu (II) to Fe3O4The @ C nano particle immobilized laccase is placed in triphenylmethane dye wastewater and reacts for 2-3h under the oscillation condition at the temperature of 30-60 ℃ to obtain the product.
Preferably, the reaction conditions are preferably 50 ℃ and the reaction time is 2 h.
The triphenylmethane dye is malachite green or brilliant green or crystal violet, the concentration of the malachite green dye wastewater is 200mg/L, the concentration of the brilliant green dye wastewater is 40mg/L, and the concentration of the crystal violet dye wastewater is 5 mg/L; the magnetic Cu (II) chelates Fe3O4The dosage ratio of the @ C nano particle immobilized laccase to the triphenylmethane dye is 1: 1-10; mass/volume, mg/mL.
Further, magnetic Cu (II) is used for chelating Fe3O4@ C nanoparticlesThe method for decolorizing azo dye wastewater by immobilized laccase comprises the following steps:
placing 2, 2-biazonitrogen-di (3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt in azo dye wastewater, and adding magnetic Cu (II) to chelate Fe3O4And (3) carrying out reaction on the @ C nano particle immobilized laccase for 1-1.5h at 50 ℃ under the oscillation condition.
The concentration of 2, 2-dinitrogen-bis (3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt in the azo dye wastewater is 14 mg/L.
The azo dye is azo fluorescent pink or reactive red, wherein the concentration of the azo fluorescent pink is 50mg/L, and the concentration of the reactive red is 20 mg/L; the decoloring and degrading reaction time of the azo fluorescent pink is 1h, and the decoloring and degrading reaction time of the reactive red is 1.5 h; the magnetic Cu (II) chelates Fe3O4The dosage ratio of the @ C nano particle immobilized laccase to the azo dye is 1: 2-10; mass/volume, mg/mL.
Further, magnetic Cu (II) is used for chelating Fe3O4A method for decoloring anthraquinone dye wastewater by using @ C nano particle immobilized laccase comprises the following steps:
placing 2, 2-dinitrogen-di (3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt in anthraquinone dye wastewater, and adding magnetic Cu (II) to chelate Fe3O4And (3) carrying out reaction on the @ C nano particle immobilized laccase at the temperature of 30-60 ℃ for 1-2h under the oscillation condition.
Preferably, the treatment temperature is 50 ℃ and the reaction time is 1 h.
Wherein the concentration of the 2, 2-dinitrogen-bis (3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt in the anthraquinone dye wastewater is 14 mg/L.
The anthraquinone dye is active brilliant blue-19; the magnetic Cu (II) chelates Fe3O4The dosage ratio of the @ C nano particle immobilized laccase to the anthraquinone dye is 1: 2.5-10; mass/volume, mg/mL.
In the invention, 2, 2-biazonitrogen-di (3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt with a molecular formula C18H24N6O6S4ABTS for short.
The magnetic Cu (II) chelates Fe3O4@ C nanoparticlesThe preparation method of the immobilized laccase comprises the following steps:
1) preparation of hydroxy/carboxy functionalized magnetic Fe3O4@ C nanoparticles;
2) adsorption of Cu2+Preparing magnetic copper (II) chelated ferroferric oxide @ carbon nanoparticles by ions;
3) chelating the prepared magnetic Cu (II) to Fe3O4Adding the @ C nano particles into a crude laccase solution to obtain the magnetic Cu (II) chelated Fe3O4@ C nanoparticle immobilized laccase.
Further, step 1) comprises the following steps:
1-1) adding concentrated ammonia water into the iron source solution under the stirring condition and in the nitrogen atmosphere, and heating for reaction to prepare Fe3O4A nanoparticle suspension;
1-2) Fe prepared to step 1-1)3O4Adding a carbon source and sodium hydroxide into the nanoparticle suspension, and heating for reaction to obtain the hydroxyl/carboxyl functionalized magnetic Fe3O4@ C nanoparticles.
Further, the heating reaction in the step 1-1) refers to a reaction at 60-70 ℃ for 1-2 h; then reacting for 1-2h at 90-100 ℃.
Further, in the step 1-1), concentrated ammonia water is added for three times.
More preferably, in the step 1-1), half of the required amount of concentrated ammonia water is added firstly, the mixture reacts for 20min at 60 ℃, then one fourth of the amount of concentrated ammonia water is added after the temperature of 60 ℃ is maintained, the mixture reacts for 20min at 60 ℃, then the remaining one fourth of the amount of concentrated ammonia water is added, the mixture reacts for 20-80min at 60 ℃, and finally the temperature is increased to 90-100 ℃ for reaction for 1-2 h.
The method of the invention can lead Fe3O4The particle size of the nano particles is more uniform and smaller, and the size of the nano particles is 10-100 nm.
The iron source in the step 1-1) is a mixture of an Fe (II) iron source and an Fe (III) iron source, and the molar ratio of the Fe (II) iron source to the Fe (III) iron source is 1: 1-2;
the Fe (II) iron source is ferrous sulfate or ferrous chloride; the Fe (III) iron source is ferric sulfate or ferric chloride.
The mass percentage concentration of the strong ammonia water in the step 1-1) is 28%.
In the step 1-1), the concentration of the iron source solution is 0.012mol/L-0.12 mol/L; the preparation method comprises the following steps: adding 1.2-6mmol of iron source into 50-100mL of water to obtain the iron-based catalyst.
The carbon source in the step 1-2) is glucose or sucrose, and the molar ratio of the iron source to the carbon source is 1: 2-7.5; the molar ratio of the carbon source to the sodium hydroxide is 1: 15-20.
The heating reaction in the step 1-2) is as follows: reacting at 180 ℃ and 260 ℃ for 12-24 h.
After the reaction in the step 1-2), naturally cooling to room temperature, separating and collecting the product, washing and drying to obtain the hydroxyl/carboxyl functionalized magnetic Fe3O4@ C nanoparticles.
The step 2) is specifically as follows: subjecting the hydroxyl/carboxyl functionalized magnetic Fe prepared in step 1)3O4@ C nanoparticle addition with Cu2 +Reacting in the solution to obtain magnetic copper (II) chelated ferroferric oxide @ carbon nano particles, namely magnetic Cu (II) chelated Fe3O4@ C nanoparticles.
Further, the reaction in the step 2) refers to a reaction at a temperature of between 25 and 45 ℃ for 0.5 to 2 hours. High temperature, Cu2+The concentration is high, the adsorption reaction speed is high, the adsorption balance is easier to achieve, but the temperature cannot be too high, otherwise, Cu2+Hydrolysis takes place, Cu2+Excessive concentration and physical adsorption capacity, and the need of removing the physically adsorbed Cu2+。
The Cu content in the step 2)2+The solution is preferably a copper sulfate solution or a copper chloride solution.
Magnetic Fe described in step 2)3O4@ C nanoparticles and Cu2+The mass ratio of solute in the solution is 1: 0.15-0.5; the Cu2+The concentration of the solution is 1-4 mmol/L;
the reaction in the step 3) is carried out for 0.5-2h at the temperature of 25-35 ℃.
The activity of the laccase solution in the step 3) is 20U/mL.
Magnetic Cu (1) described in step 3: (II) chelating Fe3O4The dosage ratio of the @ C nano particles to the laccase solution is 40:2-5 mg/mL.
The magnetic Cu (II) chelate Fe3O4The method for determining the catalytic activity of the @ C nanoparticle immobilized laccase comprises the following steps: dissolving 1mmol of ABTS in 1000mL of water to prepare 1mmol/L ABTS aqueous solution; determination of magnetic Cu (II) chelated Fe by oxidation ABTS method3O4The catalytic activity of the @ C nano-particle immobilized laccase. Wherein the 2, 2-diaza-bis (3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt has a molecular formula C18H24N6O6S4ABTS for short.
Preferably, the preparation method of the magnetic copper (II) chelated ferroferric oxide @ carbon nano particle comprises the following steps:
1) preparation of hydroxy/carboxy functionalized magnetic Fe3O4The operation process of the @ C nanoparticle is as follows:
1-1) dissolving 0.4mmol of ferrous chloride and 0.8mmol of ferric chloride in 50mL of water in a three-neck flask, and adding 4mL of concentrated ammonia water (28 mass percent concentration) and 4mL of concentrated ammonia water for 3 times under the conditions of stirring and nitrogen atmosphere; adding 2mL of concentrated ammonia water, reacting at 60 ℃ for 20min, adding 1mL of concentrated ammonia water at 60 ℃, reacting at 60 ℃ for 20min, adding 1mL of concentrated ammonia water, reacting at 60 ℃ for 20min, heating to 90 ℃ and reacting for 1h to prepare Fe3O4Cooling the nanoparticle suspension to room temperature;
1-2) to the above Fe3O4Adding 9mmol glucose and 180mmol sodium hydroxide into the nanoparticle suspension, transferring into a hot-pressing reaction kettle, screwing the hot-pressing reaction kettle, and reacting at 200 ℃ for 18 h; after the reaction is finished, naturally cooling to room temperature, carrying out magnetic separation to collect a product, washing with water for 2 times, washing with absolute ethyl alcohol for 1 time, and carrying out vacuum drying at 60 ℃ for 0.5h to obtain the hydroxyl/carboxyl functionalized magnetic Fe3O4@ C nanoparticles. The product is characterized by X-ray diffraction, a transmission electron microscope, a superconducting quantum interferometer and a Fourier transform infrared spectrometer, and as shown in figures 1 to 4, the product is proved to be hydroxyl/carboxyl functionalized magneticFe (Fe) property3O4@ C nanoparticles, magnetic Fe prepared3O4The @ C nano particle is smaller, and the number of surface functional groups is large, so that the immobilization of laccase is facilitated.
2) Magnetic Cu (II) chelate Fe3O4The operation process of the @ C nanoparticle immobilized laccase is as follows:
4mg of the hydroxy/carboxy functionalized magnetic Fe prepared by the above method3O4Adding the @ C nano particles into 4mL of 2mmol/L copper sulfate solution, reacting for 1h at 30 ℃, carrying out magnetic separation on the obtained product, washing for 2 times with water, washing for 1 time with absolute ethyl alcohol, and drying for 0.5h at 60 ℃ in vacuum, thus obtaining the magnetic Cu (II) chelated Fe3O4@ C nanoparticles;
3) preparing a crude laccase solution with the activity of 200U/mL, and diluting by 10 times for reuse; prepared 4mg of magnetic Cu (II) chelated Fe3O4Ultrasonically dispersing the @ C nano particles into 1mL of water, adding 0.4mL of diluted crude laccase liquid, reacting for 1h at 30 ℃, and carrying out magnetic separation and water washing on the obtained product for 3 times to obtain magnetic Cu (II) chelated Fe3O4@ C nanoparticle immobilized laccase.
The magnetic Cu (II) chelate Fe3O4The method for determining the catalytic activity of the @ C nanoparticle immobilized laccase comprises the following steps: dissolving 1mmol of ABTS in 1000mL of water to prepare 1mmol/L ABTS aqueous solution; determination of magnetic Cu (II) chelated Fe by oxidation ABTS method3O4The catalytic activity of the @ C nano-particle immobilized laccase. Wherein the 2, 2-diaza-bis (3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt has a molecular formula C18H24N6O6S4ABTS for short.
The prior art is referred to in the art for techniques not mentioned in the present invention.
The glucose or the sucrose is carbonized under the action of sodium hydroxide at high temperature (180-260 ℃), and the glucose or the sucrose is incompletely carbonized in the carbonization process, so that hydroxyl and carboxyl functional groups are remained. High carbonization temperature (or large amount of sodium hydroxide), high carbonization speed, short time, less residual functional groups, Cu adsorption2+Less immobilized laccase, less immobilized laccase amount and low activity; low carbonization temperature (or less sodium hydroxide), slow carbonization speed, long time, more residual functional groups, thin and unstable carbon layer outside the ferroferric oxide, and Cu adsorption caused by the carbon layer2+Less immobilized laccase, less immobilized laccase and low activity. Therefore, the invention designs the conditions of 180-260 ℃ and the molar ratio of the iron source to the carbon source as 1: 2-7.5; the molar ratio of the carbon source to the sodium hydroxide is 1: 15-20.
Firstly, the invention adopts a hydrothermal method to prepare hydroxyl/carboxyl functionalized magnetic Fe3O4@ C nanoparticles, re-coordinated adsorption of Cu2+Ion preparation of magnetic Cu (II) chelated Fe3O4The @ C nano particle is finally used for preparing magnetic Cu (II) chelated Fe with high stability, high activity and reusability by utilizing the coordination effect between histidine residues of laccase and Cu (II)3O4@ C nanoparticle immobilized laccase. Furthermore, the invention prepares magnetic Cu (II) chelated Fe3O4The @ C nano particle immobilized laccase is simple to operate, economic and environment-friendly; magnetic Cu (II) chelate Fe3O4The @ C nano particle has high enzyme carrying amount, high catalytic activity and high stability of the immobilized laccase, can be simply recycled, can effectively reduce the actual production cost, and has wide application prospect.
Compared with the prior art, the invention has the following beneficial effects:
magnetic Cu (II) chelate Fe3O4The application method of the @ C nano particle immobilized laccase in dye wastewater decolorization is simple, economic and environment-friendly, and high in degradation efficiency;
magnetic Fe3O4The surface of the @ C nano particle is rich in hydroxyl and carboxyl functional groups and can chelate a large amount of Cu2+The prepared immobilized laccase has high catalytic activity and good stability, so that the efficiency of degrading dye wastewater is high, the immobilized laccase can be repeated for many times, and the immobilized laccase still can keep high catalytic activity;
magnetic Cu (II) chelate Fe3O4The surface functional group of the @ C nanoparticle can transfer electrons to dye molecules, so that the immobilized laccase can be directly transferred without adding ABTS as a mediumDegrading triphenylmethane dyes;
the application method has wide application range, can degrade triphenylmethane dyes, azo dyes and anthraquinone dyes, and has a removal rate of 75-99% for the three dyes within the concentration range of 5-200 mg/L;
magnetic Cu (II) chelate Fe for use in the present invention3O4The preparation method of the @ C nano particle is simple, high in yield, economic and environment-friendly; the protein structure of the laccase can be stabilized during the immobilization process, so that the magnetic Cu (II) chelate Fe3O4The @ C nano particle immobilized laccase has high activity, and the enzyme activity recovery rate in the immobilization process can reach 75.3-113.4%; can carry a large amount of laccase, and the protein carrying amount is up to 273-515 mg/g; the immobilized laccase has good stability and can be repeatedly used for many times and still maintain higher catalytic activity; the magnetic Cu (II) chelate Fe of the invention3O4The @ C nano particle immobilized laccase has magnetic responsiveness, and can quickly and simply enrich, separate and recover magnetic Cu (II) chelated Fe from a reaction system by means of an external magnetic field3O4The @ C nano particle immobilized laccase can effectively reduce the actual production cost and has wide application prospect.
Drawings
FIG. 1 shows the hydroxyl/carboxyl functionalized magnetic Fe prepared in example 13O4The transmission electron microscope detection map of the @ C nanoparticle; FIG. 1 shows that the hydroxyl/carboxyl functionalized magnetic Fe prepared in example 13O4The @ C nano particle is 15-25 nm;
FIG. 2 is an X-ray powder diffraction pattern of the product prepared in example 1; in fig. 2, the abscissa is the diffraction angle 2 θ (°), and the ordinate is the Intensity (a.u.); by comparison with a standard map (JCPDS:77-1545), the diffraction peaks of the product are positioned at 18.3 degrees, 30.1 degrees, 35.5 degrees, 43.1 degrees, 53.6 degrees, 57.0 degrees, 62.7 degrees, 71.0 degrees, 74.2 degrees and 79.0 degrees, which respectively correspond to the diffraction peaks (111), (220), (311), (400), (422), (511), (440), (620), (533), (444) of the cubic phase ferroferric oxide;
FIG. 3 is an infrared spectrum of the product prepared in example 1, wherein in FIG. 3, the abscissa is the wave number levelength/cm-1The ordinate is the Transmittance% transmission; hydroxyl and carboxyl on the surface of the product are determined by infrared spectrum characterization; 3340cm-1And 896cm-1Two absorption peaks are stretching and bending vibration peaks of hydroxyl, 2922cm-1And 2854cm-1Is assigned as-CH2Peak of telescopic vibration, 1559cm-1And 1402cm-1The absorption peak is C ═ O stretching vibration peak 1085cm in carboxyl-1And 573cm-1The absorption peak is the characteristic absorption peak of the ferroferric oxide;
FIG. 4 is a hysteresis chart of the product prepared in example 1, in FIG. 4, the abscissa is the magnetic field intensity H (Oe), the ordinate is the saturation magnetization M (emu/g), it can be seen from the figure that the saturation magnetization is 73.8emu/g, and the coercive force is 51.5Oe, and it is known that this magnetic carbon material has magnetism;
FIG. 5 shows the magnetic Cu (II) chelated Fe prepared in example 13O4Comparison graph of thermal stability of @ C nanoparticle immobilized laccase and free laccase; in fig. 5, the abscissa is time (time) and the ordinate is relative activity (%); the immobilized laccase and the free laccase are kept in the environment at 60 ℃ for the same time (1-10 h);
FIG. 6 shows the magnetic Cu (II) chelated Fe prepared in example 13O4Comparison graph of organic pollution resistance of the @ C nano particle immobilized laccase and free laccase; in FIG. 6, the Organic solvents are plotted on the abscissa and Relative activity (%) is plotted on the ordinate; the immobilized laccase and the free laccase are stored in an organic solvent for 2 hours at the temperature of 25 ℃;
FIG. 7 shows the magnetic Cu (II) chelated Fe prepared in example 13O4A recycling effect diagram of the @ C nano particle immobilized laccase; in FIG. 7, the Number of cycles is plotted on the abscissa and the relative activity relative (%);
FIG. 8 shows the magnetic Cu (II) chelated Fe in example 13O4The effect diagram of the @ C nano particle immobilized laccase for degrading the triphenylmethane dye is shown; in FIG. 8, the Number of cycles is plotted on the abscissa and the degradation rate is plotted on the ordinate (%); degradation IIIThe phenylmethane dye is reacted for 2 hours at the temperature of 50 ℃;
FIG. 9 shows the magnetic Cu (II) chelated Fe in example 23O4The @ C nano particle immobilized laccase has an effect diagram for degrading azo dyes, and in FIG. 9, the abscissa is cycle Number of cycles, and the ordinate is degradation rate (%); the reaction time for degrading azo fluorescent pink and reactive red is 1h and 1.5h respectively;
FIG. 10 shows the magnetic Cu (II) chelated Fe in example 33O4The effect graph of the @ C nano particle immobilized laccase for degrading anthraquinone dye is shown; in FIG. 10, the Number of cycles is plotted on the abscissa and the degradation rate is plotted on the ordinate (%); the reaction time of the degradation activity brilliant blue-19 is 1 h.
Detailed Description
The present invention will be further understood from the following examples, which are not intended to limit the scope of the present invention.
Example 1
A method for decoloring dye wastewater specifically comprises the following steps: chelation of Fe by magnetic Cu (II)3O4@ C nano particle immobilized laccase decoloration dye wastewater.
The preparation method of the magnetic copper (II) chelated ferroferric oxide @ carbon nano particle comprises the following steps:
1) preparation of hydroxy/carboxy functionalized magnetic Fe3O4The operation process of the @ C nanoparticle is as follows:
1-1) dissolving 0.4mmol of ferrous chloride and 0.8mmol of ferric chloride in 50mL of water in a three-neck flask, and adding 4mL of concentrated ammonia water (28 mass percent concentration) and 4mL of concentrated ammonia water for 3 times under the conditions of stirring and nitrogen atmosphere; adding 2mL of concentrated ammonia water, reacting at 60 ℃ for 20min, adding 1mL of concentrated ammonia water at 60 ℃, reacting at 60 ℃ for 20min, adding 1mL of concentrated ammonia water, reacting at 60 ℃ for 20min, heating to 90 ℃ and reacting for 1h to prepare Fe3O4Cooling the nanoparticle suspension to room temperature;
1-2) to the above Fe3O4After 9mmol glucose and 180mmol sodium hydroxide are added into the nano particle suspensionTransferring the mixture into a hot-pressing reaction kettle, screwing the hot-pressing reaction kettle, and reacting for 18 hours at 200 ℃; after the reaction is finished, naturally cooling to room temperature, carrying out magnetic separation to collect a product, washing with water for 2 times, washing with absolute ethyl alcohol for 1 time, and carrying out vacuum drying at 60 ℃ for 0.5h to obtain the hydroxyl/carboxyl functionalized magnetic Fe3O4@ C nanoparticles. The product is characterized by X-ray diffraction, a transmission electron microscope, a superconducting quantum interferometer and a Fourier transform infrared spectrometer, and as shown in figures 1 to 4, the product is proved to be hydroxyl/carboxyl functionalized magnetic Fe3O4@ C nanoparticles, magnetic Fe prepared3O4The @ C nano particle is smaller, and the number of surface functional groups is large, so that the immobilization of laccase is facilitated.
2) Magnetic Cu (II) chelate Fe3O4The operation process of the @ C nanoparticle immobilized laccase is as follows:
4mg of the hydroxy/carboxy functionalized magnetic Fe prepared by the above method3O4Adding the @ C nano particles into 4mL of 2mmol/L copper sulfate solution, reacting for 1h at 30 ℃, carrying out magnetic separation on the obtained product, washing for 2 times with water, washing for 1 time with absolute ethyl alcohol, and drying for 0.5h at 60 ℃ in vacuum, thus obtaining the magnetic Cu (II) chelated Fe3O4@ C nanoparticles;
3) the fermentation medium of 7L is filled in a full-automatic ventilation fermentation tank of 10L, the trametes fungus is inoculated, the inoculation amount is 10 percent, and the dissolved oxygen is controlled to be about 30 percent by adjusting the rotating speed, the tank pressure and the ventilation quantity. The whole fermentation process is not controlled in pH and is finished at 10d of fermentation. Filtering with 4 layers of gauze after fermentation to remove large solid such as mycelium in the fermentation liquid, centrifuging the filtrate at 4 deg.C and 5000r/min for 30min, collecting supernatant, preparing crude laccase solution with activity of 200U/mL, diluting by 10 times, and using; prepared 4mg of magnetic Cu (II) chelated Fe3O4Ultrasonically dispersing the @ C nano particles into 1mL of water, adding 0.4mL of diluted crude laccase liquid, reacting for 1h at 30 ℃, and carrying out magnetic separation and water washing on the obtained product for 3 times to obtain magnetic Cu (II) chelated Fe3O4@ C nanoparticle immobilized laccase.
Determination of magnetic Cu (II) chelated Fe3O4The operation process of the catalytic activity of the @ C nanoparticle immobilized laccase is as follows:
step 1) weighing 1mmol of ABTS and dissolving the ABTS in 1L of water to prepare 1mmol/L of ABTS aqueous solution, and storing the ABTS aqueous solution in a refrigerator at 4 ℃ for later use;
step 2) determination of magnetic Cu (II) chelated Fe by Bradford method3O4@ C nanoparticles the amount of bovine serum albumin immobilized, and the determination of magnetic Cu (II) chelated Fe by the oxidation ABTS method3O4The catalytic activity of the @ C nano-particle immobilized laccase. Respectively preserving the immobilized laccase (or free laccase) at 60 ℃ for the same time, determining enzyme activity by using an oxidation ABTS method, and researching the thermal stability of the immobilized laccase; respectively placing the immobilized laccase (or free laccase) in different organic solvents for storage for 2h, determining enzyme activity by using an oxidation ABTS method, and researching organic matter pollution resistance of the immobilized laccase; recovering immobilized laccase from reaction liquid, measuring enzyme activity, and researching magnetic Cu (II) chelated Fe3O4And (3) recycling the @ C nano particle immobilized laccase.
Detecting the laccase in magnetic Cu (II) chelated Fe3O4The solid loading amount on the @ C nano particle is 436 mg/g; the enzyme activity of the immobilized laccase is 1646U/g; the recovery rate of the enzyme activity of the immobilized laccase is 82.3 percent; after standing at 60 ℃ for 10h, the activity of the immobilized laccase can still be maintained at 80% which is 1.2 times that of the free enzyme (see FIG. 5); after being placed in methanol or ethanol or acetone or dimethyl sulfoxide or acetonitrile solution for 2 hours, the activity of the immobilized laccase can be maintained at 92.6%, 93.7%, 82.3%, 94.4% and 95.2%, which are 1.1-1.3 times of that of free enzyme (see figure 6); after the immobilized laccase is recycled for 10 times, magnetic Cu (II) chelates Fe3O4The activity of the @ C nanoparticle immobilized laccase was still maintained at 61% (see FIG. 7).
Chelation of Fe by magnetic Cu (II)3O4A method for decoloring triphenylmethane dye wastewater by using @ C nano particle immobilized laccase comprises the following steps:
preparing 0.1mol/L acetic acid buffer solution with pH value of 4.5; dissolving 200mg of malachite green dye in 1000mL of prepared acetic acid buffer solution to prepare 200mg/L of malachite green dye solution serving as malachite green dye wastewater to be treated;
preparing 0.1mol/L acetic acid buffer solution with pH value of 4.5; dissolving 40mg of brilliant green dye in 1000mL of prepared acetic acid buffer solution, and preparing to obtain 40mg/L brilliant green dye solution as brilliant green dye wastewater to be treated;
preparing 0.1mol/L acetic acid buffer solution with pH value of 4.5; dissolving 5mg of crystal violet dye in 1000mL of prepared acetic acid buffer solution, and preparing to obtain 5mg/L of crystal violet dye solution as crystal violet dye wastewater to be treated;
magnetic Cu (II) chelate Fe prepared in example 13O4The @ C nano particle immobilized laccase is dispersed into the three dye solutions, and the dosage is respectively as follows: dispersing 4mg of immobilized laccase into 4mL of malachite green dye solution; 8mg of immobilized laccase is dispersed into 8mL of brilliant green dye solution; dispersing 12mg of immobilized laccase into 12mL of crystal violet dye solution; all react for 2h at 50 ℃ under the condition of oscillation, and the decolorization rate of the triphenylmethane dye is measured by a spectrophotometry method.
Detecting the magnetic Cu (II) chelated Fe3O4The degradation rates of the @ C nano particle immobilized laccase for degrading malachite green, brilliant green and crystal violet are respectively 99%, 93% and 79%; the magnetic Cu (II) chelates Fe3O4When the @ C nano particle immobilized laccase is degraded circularly for 10 times, the degradation rates of the immobilized laccase to the malachite green, the brilliant green and the crystal violet can still reach 94%, 80% and 71% respectively (see figure 8).
Example 2
A method for decoloring dye wastewater specifically comprises the following steps: fe chelation Using magnetic Cu (II) prepared in example 13O4The method for decoloring azo dye wastewater by using the @ C nano particle immobilized laccase comprises the following steps:
preparing 0.1mol/L acetic acid buffer solution with pH value of 4.5; dissolving 14mg of ABTS and 50mg of azo-fluorescent pink in 1000mL of the acetic acid buffer solution, wherein the concentration of the azo-fluorescent pink is 50mg/L, and taking the azo-fluorescent pink as the azo-fluorescent pink dye wastewater to be treated; example 1 preparation of 4mg magnetic Cu (II) chelated Fe3O4The @ C nano particle immobilized laccase is dispersed into the 8mL of azo fluorescent pink dye wastewater,reacting for 1h at 50 ℃ under the condition of oscillation, and measuring the decolorization rate of the azo fluorescent pink dye by a spectrophotometry.
Preparing 0.1mol/L acetic acid buffer solution with pH value of 4.5; dissolving 14mg of ABTS and 20mg of reactive red dye in 1000mL of the acetic acid buffer solution, wherein the concentration of the reactive red dye is 20mg/L, and taking the reactive red dye as reactive red dye wastewater to be treated; 8mg of magnetic Cu (II) prepared in example 1 chelated Fe3O4And dispersing the @ C nano particle immobilized laccase into the 16mL of the active red dye wastewater, reacting for 1.5h at 50 ℃ under an oscillation condition, and measuring the decolorization rate of the azo fluorescent pink dye by a spectrophotometry method.
Detecting the magnetic Cu (II) chelated Fe3O4The degradation rates of the @ C nanoparticle immobilized laccase for degrading azo fluorescent pink and active red are 88% and 75% respectively; the magnetic Cu (II) chelates Fe3O4When the @ C nano particle immobilized laccase is degraded circularly for 10 times, the degradation rates of the immobilized laccase to azo fluorescent pink and active red are respectively 78% and 60% (see figure 9).
Example 3
A method for decoloring dye wastewater specifically comprises the following steps: fe chelation Using magnetic Cu (II) prepared in example 13O4A method for decoloring anthraquinone dye wastewater by using @ C nano particle immobilized laccase comprises the following steps:
preparing 0.1mol/L acetic acid buffer solution with pH value of 4.5; dissolving 14mg of ABTS and 100mg of anthraquinone dye active brilliant blue-19 in 1000mL of the acetic acid buffer solution to prepare 100mg/L anthraquinone dye solution; as anthraquinone dye wastewater to be treated; example 1 preparation of 4mg magnetic Cu (II) chelated Fe3O4And (3) dispersing the @ C nano particle immobilized laccase into the 10ml anthraquinone dye solution, reacting for 1h at 50 ℃ under the oscillation condition, and measuring the decolorization rate of the anthraquinone dye by using a spectrophotometry.
Detecting the magnetic Cu (II) chelated Fe3O4The degradation rate of the @ C nano particle immobilized laccase to the active brilliant blue-19 is 81 percent; the magnetic Cu (II) chelates Fe3O4When the @ C nano-particle immobilized laccase is degraded circularly for 10 times, the degradation rate of the immobilized laccase to the active brilliant blue-19 is 65% (see figure 10)。
Claims (10)
1. The method for decoloring the dye wastewater is characterized in that magnetic Cu (II) is utilized to chelate Fe3O4@ C nano particle immobilized laccase decoloration dye wastewater.
2. The method of claim 1, wherein the pH of the dye wastewater is adjusted to 2.5-6.0, and then magnetic Cu (II) is used to chelate Fe3O4@ C nanoparticle immobilized laccase treatment.
3. The process according to claim 1 or 2, characterized in that the decolorizing conditions are a treatment at 30-60 ℃ for 1-3 h.
4. The method of claim 1, wherein the dye wastewater comprises triphenylmethane dye wastewater, azo dye wastewater and anthraquinone dye wastewater.
5. The method of claim 4, wherein Fe is chelated using magnetic Cu (II)3O4A method for decoloring triphenylmethane dye wastewater by using @ C nano particle immobilized laccase comprises the following steps:
chelating magnetic Cu (II) to Fe3O4The @ C nano particle immobilized laccase is placed in triphenylmethane dye wastewater and reacts for 2-3h under the oscillation condition at the temperature of 30-60 ℃ to obtain the product.
6. The method of claim 4, wherein Fe is chelated using magnetic Cu (II)3O4The method for decoloring azo dye wastewater by using the @ C nano particle immobilized laccase comprises the following steps:
placing 2, 2-biazonitrogen-di (3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt in azo dye wastewater, and adding magnetic Cu (II) to chelate Fe3O4And (3) carrying out reaction on the @ C nano particle immobilized laccase for 1-1.5h at 50 ℃ under the oscillation condition.
7. The method of claim 4, wherein the first and second light sources are selected from the group consisting of,characterized in that magnetic Cu (II) is used for chelating Fe3O4A method for decoloring anthraquinone dye wastewater by using @ C nano particle immobilized laccase comprises the following steps:
placing 2, 2-dinitrogen-di (3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt in anthraquinone dye wastewater, and adding magnetic Cu (II) to chelate Fe3O4And (3) carrying out reaction on the @ C nano particle immobilized laccase at the temperature of 30-60 ℃ for 1-2h under the oscillation condition.
8. The method of claim 1, wherein said magnetic Cu (II) chelates Fe3O4The preparation method of the @ C nano particle immobilized laccase comprises the following steps:
1) preparation of hydroxy/carboxy functionalized magnetic Fe3O4@ C nanoparticles;
2) adsorption of Cu2+Preparing magnetic copper (II) chelated ferroferric oxide @ carbon nanoparticles by ions;
3) chelating the prepared magnetic Cu (II) to Fe3O4Adding the @ C nano particles into a crude laccase solution to obtain the magnetic Cu (II) chelated Fe3O4@ C nanoparticle immobilized laccase.
9. The method according to claim 8, wherein step 1) comprises the steps of:
1-1) adding concentrated ammonia water into the iron source solution under the stirring condition and in the nitrogen atmosphere, and heating for reaction to prepare Fe3O4A nanoparticle suspension;
1-2) Fe prepared to step 1-1)3O4Adding a carbon source and sodium hydroxide into the nanoparticle suspension, and heating for reaction to obtain the hydroxyl/carboxyl functionalized magnetic Fe3O4@ C nanoparticles.
10. The method of claim 8, wherein the hydroxy/carboxy functionalized magnetic Fe prepared in step 1) is3O4@ C nanoparticle addition with Cu2+Reacting in the solution to obtain magnetic copper (II) chelated ferroferric oxide @ carbon nano particles, namely magnetismCu (II) chelate Fe3O4@ C nanoparticles.
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