CN111905814A - Preparation method of biocatalyst - Google Patents
Preparation method of biocatalyst Download PDFInfo
- Publication number
- CN111905814A CN111905814A CN202010622819.7A CN202010622819A CN111905814A CN 111905814 A CN111905814 A CN 111905814A CN 202010622819 A CN202010622819 A CN 202010622819A CN 111905814 A CN111905814 A CN 111905814A
- Authority
- CN
- China
- Prior art keywords
- chitosan
- biocatalyst
- copper complex
- sodium hydroxide
- gelatin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 40
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 40
- 239000011942 biocatalyst Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 60
- 229920001661 Chitosan Polymers 0.000 claims abstract description 54
- 108010010803 Gelatin Proteins 0.000 claims abstract description 38
- 229920000159 gelatin Polymers 0.000 claims abstract description 35
- 239000008273 gelatin Substances 0.000 claims abstract description 35
- 235000019322 gelatine Nutrition 0.000 claims abstract description 35
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 35
- 150000004699 copper complex Chemical class 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000012065 filter cake Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 42
- 239000003054 catalyst Substances 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 25
- 239000002351 wastewater Substances 0.000 abstract description 22
- 239000002245 particle Substances 0.000 abstract description 10
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 58
- 238000004042 decolorization Methods 0.000 description 24
- 238000004043 dyeing Methods 0.000 description 13
- 238000007639 printing Methods 0.000 description 13
- 239000002699 waste material Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 229920001222 biopolymer Polymers 0.000 description 3
- -1 copper metal complex Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 241000238557 Decapoda Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 210000003746 feather Anatomy 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000009897 hydrogen peroxide bleaching Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- YYYARFHFWYKNLF-UHFFFAOYSA-N 4-[(2,4-dimethylphenyl)diazenyl]-3-hydroxynaphthalene-2,7-disulfonic acid Chemical compound CC1=CC(C)=CC=C1N=NC1=C(O)C(S(O)(=O)=O)=CC2=CC(S(O)(=O)=O)=CC=C12 YYYARFHFWYKNLF-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000010796 biological waste Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003256 environmental substance Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- QTTDXDAWQMDLOF-UHFFFAOYSA-J tetrasodium 3-[[4-[[4-[(6-amino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-6-sulfonatonaphthalen-1-yl]diazenyl]naphthalen-1-yl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].Nc1ccc2c(O)c(N=Nc3ccc(N=Nc4ccc(N=Nc5cc(c6cccc(c6c5)S([O-])(=O)=O)S([O-])(=O)=O)c5ccccc45)c4ccc(cc34)S([O-])(=O)=O)c(cc2c1)S([O-])(=O)=O QTTDXDAWQMDLOF-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B01J35/60—
-
- B01J35/61—
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention discloses a preparation method of a biocatalyst, which specifically comprises the following steps: step 1, preparing a chitosan colloidal solution; step 2, dripping a gelatin copper complex into the chitosan colloidal solution obtained in the step 1, keeping the temperature and stirring for a period of time to obtain a chitosan gelatin composite macromolecular copper complex, and step 3, preparing a sodium hydroxide solution with a certain concentration; step 4, adding the chitosan gelatin composite polymer copper complex obtained in the step 2 into the sodium hydroxide solution obtained in the step 3 at the temperature of 20-30 ℃, and precipitating to separate out the chitosan gelatin composite polymer copper complex; and 5, filtering the chitosan gelatin composite polymer copper complex obtained in the step 4, washing a filter cake with water, and drying to obtain the biocatalyst. The catalyst prepared by the invention has the characteristic of catalyzing hydrogen peroxide to decompose high-activity particles with strong oxidizing property, and can effectively catalyze and degrade organic pollutants in wastewater.
Description
Technical Field
The invention belongs to the technical field of environmental chemical engineering, and particularly relates to a preparation method of a biocatalyst.
Background
The production and the life inevitably generate waste water, for example, a large amount of waste water is generated in the process of producing various textiles loved by people, and the discharge of a large amount of waste water not only causes water resource waste, but also pollutes the living environment of people. The textile printing and dyeing industry is an industrial wastewater discharge large household, 3 tons to 5 tons of wastewater can be generated when a printing and dyeing mill processes 100m of fabrics, and the research on the purification of the wastewater such as printing and dyeing and the like is highly valued by people along with the enhancement of the environmental protection consciousness of people.
The printing and dyeing wastewater has the characteristics of large water quantity, complex components, high organic pollutant content, deep chromaticity, large alkalinity, large water quality change and the like, the COD of the printing and dyeing wastewater is much higher than the BOD, the printing and dyeing wastewater belongs to industrial wastewater which is difficult to biodegrade, particularly, the removal of the chromaticity is a great problem in the treatment of the printing and dyeing wastewater, and the harm of the printing and dyeing wastewater to the living environment of human beings is always a key point of attention of people.
The printing and dyeing wastewater treatment method mainly comprises the following steps: flocculation, precipitation (air flotation), electrolysis, oxidation, adsorption, biological methods, or a combination of several treatment methods. For years, the homogeneous Fenton technology has attracted much attention in dye wastewater treatment due to simple reaction and low material cost, but the homogeneous Fenton technology has the defects that the pH value of a reaction system needs to be controlled between 2 and 4, and Fe in a homogeneous catalyst3+Difficult to separate from the reaction medium, resulting in a large amount of iron sludge being produced, causing secondary pollution. Therefore, in recent years, heterogeneous Fenton technology has become a research hotspot, which can be applied in a wider pH range, and the heterogeneous catalytic material is easy to recycle and reuse, and does not cause secondary pollution.
Disclosure of Invention
The invention aims to provide a preparation method of a biocatalyst, which has the characteristic of catalyzing hydrogen peroxide to decompose high-activity oxide particles, and the high-activity particles can effectively degrade organic pollutants such as dye in wastewater.
The technical scheme adopted by the invention is as follows: a preparation method of a biocatalyst specifically comprises the following steps:
step 1, preparing a chitosan colloidal solution;
step 2, dripping a gelatin copper complex into the chitosan colloidal solution obtained in the step 1, and stirring for a period of time while keeping the temperature to obtain a chitosan gelatin composite polymer copper complex;
step 3, preparing a sodium hydroxide solution with a certain concentration;
step 4, adding the chitosan gelatin composite polymer copper complex obtained in the step 2 into the sodium hydroxide solution obtained in the step 3 at the temperature of 20-30 ℃, and precipitating to separate out the chitosan gelatin composite polymer copper complex;
and 5, filtering the chitosan gelatin composite polymer copper complex obtained in the step 4, washing a filter cake with water, and drying to obtain the biocatalyst.
The technical scheme adopted by the invention is also characterized in that the specific steps of the step 1 are as follows: weighing chitosan, adding the chitosan into 1-2% acetic acid aqueous solution by volume ratio, stirring for 30-60 min at 40-60 ℃, and dissolving to obtain chitosan colloidal solution.
The ratio of the chitosan to the water is 1: 40-60.
In the step 2, the content of copper in the gelatin copper complex is 10% -20% of that of solid chitosan, the dropping speed is 2-5 drops/s, the temperature of the chitosan solution is kept at 40-60 ℃ during reaction, and the stirring time is 40-80 min.
The specific steps in step 3 are as follows: weighing sodium hydroxide, dissolving the sodium hydroxide into water to obtain a sodium hydroxide solution, wherein the concentration of the sodium hydroxide is 3-6 g/L, and the volume ratio of the sodium oxide solution to the chitosan gelatin composite polymer copper complex obtained in the step 2 is 2-4: 1.
And 5, washing the filter cake to be neutral by using water, wherein the drying temperature is 90-105 ℃, and the drying time is 1-2 h.
The invention has the beneficial effects that: the invention relates to a preparation method of a biocatalyst, the selected raw materials are biodegradable biological chitosan and gelatin protein which have rich sources and low price; the macromolecular biocatalyst has the advantages of porosity, large surface area and structure containing a plurality of groups capable of being combined with the dye, so that a large acting force is generated between the macromolecular biocatalyst and the dye, the dye is favorably and rapidly adsorbed on the surface of the macromolecular biocatalyst, and the dye is concentrated; in addition, the chitosan and gelatin protein structure contains coordination atoms capable of complexing with metal ions, and can form a high-molecular metal complex with the metal ions, so that the prepared biopolymer chitosan and gelatin protein metal complex has high catalytic activity; therefore, the biological catalyst prepared by the invention has high adsorptivity and catalytic performance on colored organic matters. And has the characteristics of small dosage and repeated use.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention relates to a preparation method of a biocatalyst, which specifically comprises the following steps:
step 1, weighing chitosan, adding the chitosan into an acetic acid aqueous solution with the volume fraction of 1% -2%, stirring for 30-60 min at the temperature of 40-60 ℃, and dissolving to obtain a chitosan colloidal solution, wherein the mass ratio of the chitosan to water is 1: 40-60.
And 2, weighing a gelatin copper complex, slowly adding the gelatin copper complex into the chitosan colloidal solution obtained in the step 1 at a dropping speed of 2-5 drops/s, keeping the chitosan colloidal solution at 40-60 ℃ during dropping, and continuing to keep the temperature and stir for 40-80 min after dropping is finished to obtain the chitosan gelatin composite polymer copper complex.
The copper content in the gelatin copper complex is 10-20% of that of solid chitosan, and the gelatin copper complex is a hydrogen peroxide bleaching catalyst prepared in a hydrogen peroxide bleaching catalyst (application number: 201510018299.8, patent number: ZL 201510018299.8) in Chinese patent.
And 3, weighing sodium hydroxide, adding the sodium hydroxide into water, and dissolving to obtain a sodium hydroxide solution, wherein the concentration of the sodium hydroxide solution is 3-6 g/L, and the volume ratio of the sodium hydroxide solution to the chitosan gelatin composite polymer copper complex in the step 2 is 2-4: 1.
And 4, dripping the chitosan gelatin composite polymer copper complex obtained in the step 2 into the sodium hydroxide solution obtained in the step 3 at the temperature of 20-30 ℃, and precipitating to separate out the chitosan gelatin composite polymer copper complex.
And 5, filtering the precipitate separated out in the step 4, washing a filter cake to be neutral by using water, and drying the filter cake for 1-2 hours at the temperature of 90-105 ℃ to obtain the biocatalyst.
Based on the structural characteristics of chitosan, the chitosan and the dye have high affinity, and the chitosan can adsorb the dye in the wastewater and has a certain decolorizing effect. The invention compounds the macromolecule chitosan and the macromolecule gelatin copper metal complex for the first time to prepare the biopolymer chitosan and gelatin copper metal complex, and the biopolymer chitosan and gelatin copper metal complex is used as a catalyst to catalyze hydrogen peroxide to decompose high-activity particles, thereby effectively destroying organic pollutants in wastewater, such as: the dye can further achieve the purposes of high-efficiency decolorization and water quality purification. Based on the structural characteristics of the catalyst, the catalyst belongs to a composite polymer complex, contains a plurality of polar groups on the structure, has strong binding force with dye, can quickly adsorb the dye and concentrate the dye, and can effectively destroy the dye structure, and the polymer catalyst is different from a gelatin copper complex and is insoluble in water. Therefore, the biocatalyst of the invention is different from other catalysts, has special structural characteristics, and has the excellent characteristics of high efficiency, small dosage, repeated use and the like.
The invention discloses a method for verifying the decoloring effect of a biocatalyst:
experimental groups: the solid biocatalyst prepared by the invention and 30% hydrogen peroxide are put into a simulated waste dye solution containing 0.1g/L of active red K2BP dye, so that the concentration of the catalyst in the dye solution is kept at 0.4g/L, and the concentration of the 30% hydrogen peroxide is kept at 3 ml/L;
control group 1: adding 30% hydrogen peroxide into a simulated waste dye solution containing 0.1g/L of reactive red K2BP dye, so that the concentration of the 30% hydrogen peroxide in the dye solution is kept at 3 ml/L;
control group 2: putting the solid biocatalyst prepared by the invention into a simulated waste dye solution containing 0.1g/L of active red K2BP dye, so that the concentration of the catalyst in the dye solution is kept at 0.4 g/L; all three decolorized solutions are decolorized for 20min at 50 ℃, and the decolorization effect is shown in table 1.
TABLE 1 Effect of catalysts on the decolorization ratio of different kinds of dyes
As can be seen from Table 1: the contrast group 1 only adds hydrogen peroxide in the simulated waste dye solution, and the decolorization rate is very low and is less than 25%; only a biocatalyst is added into the simulated dye solution in the control group 2, so that the decolorization rate is low and is less than 25%; in the experimental group of the invention, hydrogen peroxide and the biocatalyst are added into the simulated dye solution at the same time, so that the decolorization rate is remarkably improved and is more than 90 percent, which shows that the biocatalyst disclosed by the invention can effectively catalyze the hydrogen peroxide to decompose high-activity oxide particles, efficiently destroy the structure of the dye in the wastewater, and achieve the effect of effectively decolorizing the printing and dyeing.
The biological catalyst of the invention is used for verifying the decoloring effect of different dyes:
the solid biocatalyst prepared by the invention is put into simulated waste dye liquor containing 0.1g/L of different dyes, so that the concentration of the catalyst in the dye liquor is kept at 0.4g/L, and then a proper amount of hydrogen peroxide is added into the dye liquor, so that the dye liquor contains 30% of hydrogen peroxide by 3ml/L and is decolorized for 40min at 50 ℃. The different types of dyes are respectively: reactive red K2BP, acid scarlet GR, direct fast blue BR, and cationic Red 2GL, with decolorizing effects shown in Table 2.
TABLE 2 Effect of biocatalysts on the decolorization rates of different kinds of dyes
As seen from table 2: the invention selects four dyes of reactive dye, acid dye, direct dye and cationic dye, the decolorization rate is above 80%, which shows that the biological catalyst of the invention is a catalyst with excellent performance, which can catalyze hydrogen peroxide to decompose high-activity oxidation particles, and the high-activity particles have good destructive effect on different dyes, thereby leading the printing and dyeing to obtain good decolorization effect.
The effect of the biocatalyst prepared by the invention in the dye wastewater decolorization is verified as follows:
putting the prepared solid biocatalyst into a simulated waste dye solution containing 0.1g/L of active red K2BP dye to keep the concentration of the catalyst in the dye solution at 0.4g/L, adding a proper amount of hydrogen peroxide into the dye solution to enable the dye solution to contain 30% of hydrogen peroxide at 3ml/L, and decoloring at 50 ℃ for 25min, wherein the operation is primary decoloring, and after decoloring, filtering the decolored dye solution to determine the primary decoloring rate of the dye solution; collecting the filtered solid biocatalyst, naturally airing, and then applying to the decolorization of the simulated waste dye liquor of 0.1g/L active red K2BP dye again, wherein the decolorization condition is the same as the first decolorization, namely the second decolorization, and after the second decolorization, filtering the decolorized dye liquor, and measuring the second decolorization rate of the dye liquor; and (3) collecting the filtered solid biocatalyst, naturally airing, carrying out third decolorization, repeating the above steps, carrying out fourth decolorization, and measuring the decolorization rate after each decolorization, wherein the decolorization effect is shown in table 3.
TABLE 3 influence of different bleaching times on the bleaching effect of reactive Red K2BP dye
As can be seen from the data in Table 3: the solid biocatalyst of the invention can be repeatedly used for 4 times, the decolorization rate is more than 95%, which shows that the biocatalyst can catalyze hydrogen peroxide to decompose high-activity particles, effectively destroy the dye structure in wastewater, and achieve the effect of high-efficiency decolorization, and the biocatalyst can be repeatedly used for at least 4 times, and the decolorization effect is not reduced.
Based on the fact that a large amount of biological wastes such as waste shrimp shells and shells, waste leather, animal hair, feathers and the like are generated in life of people, chitosan can be prepared from the shrimp shells and the shells, and protein can be extracted from the leather, the animal hair and the feathers. The invention takes chitosan and protein metal copper complex as raw materials to prepare a biocatalyst, the catalyst has the characteristic of catalyzing hydrogen peroxide to decompose strong-oxidability high-activity particles, the catalyst is combined with the hydrogen peroxide to construct a hydrogen peroxide catalytic system, the hydrogen peroxide catalytic system is applied to the treatment process of organic wastewater such as dye, and the like, and proper conditions are selected, the catalyst can effectively catalyze and degrade organic pollutants in the wastewater, including the dye and the like, so that the purpose of purifying the water quality is achieved; in addition, under proper conditions, the catalytic system can destroy floating dyes on dyed fabrics, and enables the floating dyes falling off in water to decolor, thereby not only reducing the chroma pollution of printing and dyeing wastewater, but also greatly reducing the staining of the falling dyes on the fabrics, improving the color fastness of dyed products and improving the quality of the dyed products; meanwhile, the catalyst has the advantages of small using amount, repeated use, rich raw material sources, low price, biodegradability and the like.
The catalyst of the invention is characterized in that: although the gelatin copper complex can be used as a catalyst to catalyze hydrogen peroxide to decompose high-activity particles, destroy dye structures in wastewater and have a decoloring effect, the decoloring performance is inferior to that of the biocatalyst, the gelatin copper complex is easy to dissolve in water, the gelatin copper complex can remain in the water after the printing and dyeing wastewater is decolored to generate secondary pollution, the gelatin copper complex is not easy to recycle and reuse, the biocatalyst is a water-insoluble macromolecular complex, the secondary pollution is not generated after the decoloration, and the catalyst can be recycled and reused, so that the catalyst can be reused for multiple times, and the decoloring cost is reduced.
Claims (6)
1. The preparation method of the biocatalyst is characterized by comprising the following steps:
step 1, preparing a chitosan colloidal solution;
step 2, dripping a gelatin copper complex into the chitosan colloidal solution obtained in the step 1, and stirring for a period of time while keeping the temperature to obtain a chitosan gelatin composite polymer copper complex;
step 3, preparing a sodium hydroxide solution with a certain concentration;
step 4, adding the chitosan gelatin composite polymer copper complex obtained in the step 2 into the sodium hydroxide solution obtained in the step 3 at the temperature of 20-30 ℃, and precipitating to separate out the chitosan gelatin composite polymer copper complex;
and 5, filtering the chitosan gelatin composite polymer copper complex obtained in the step 4, washing a filter cake with water, and drying to obtain the biocatalyst.
2. The preparation method of the biocatalyst as claimed in claim 1, wherein the specific steps of step 1 are: weighing chitosan, adding the chitosan into 1-2% acetic acid aqueous solution by volume ratio, stirring for 30-60 min at 40-60 ℃, and dissolving to obtain the chitosan colloidal solution.
3. The preparation method of the biocatalyst as claimed in claim 2, wherein the mass ratio of the chitosan to the water is 1: 40-60.
4. The preparation method of the biocatalyst as claimed in claim 3, wherein in the step 2, the content of copper in the gelatin copper complex is 10% -20% of that of the solid chitosan, the dropping speed is 2-5 drops/s, the chitosan solution is kept at 40-60 ℃ during the reaction, and the stirring time is 40-80 min.
5. The preparation method of the biocatalyst as claimed in claim 1, wherein the specific steps in the step 3 are: weighing sodium hydroxide, dissolving the sodium hydroxide into water to obtain a sodium hydroxide solution, wherein the concentration of the sodium hydroxide is 3-6 g/L, and the volume ratio of the sodium oxide solution to the chitosan gelatin composite polymer copper complex obtained in the step 2 is 2-4: 1.
6. The preparation method of the biocatalyst as claimed in claim 1, wherein the filter cake in the step 5 is washed to neutral with water, the drying temperature is 90-05 ℃, and the drying time is 1-2 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010622819.7A CN111905814A (en) | 2020-07-01 | 2020-07-01 | Preparation method of biocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010622819.7A CN111905814A (en) | 2020-07-01 | 2020-07-01 | Preparation method of biocatalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111905814A true CN111905814A (en) | 2020-11-10 |
Family
ID=73226755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010622819.7A Pending CN111905814A (en) | 2020-07-01 | 2020-07-01 | Preparation method of biocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111905814A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4383022A (en) * | 1981-06-26 | 1983-05-10 | Polaroid Corporation | Diffusion transfer film unit with protective layer of water soluble copper salt, chitosan and gelatin |
| CN1685831A (en) * | 2005-04-30 | 2005-10-26 | 武汉大学 | Preparation method of chitin/metal copper composite antibactericidal agent |
| CN101781374A (en) * | 2010-02-04 | 2010-07-21 | 聊城大学 | Preparation method and application of copper compound with chitosan and/or derivatives thereof |
| CN104611906A (en) * | 2015-01-14 | 2015-05-13 | 西安工程大学 | Hydrogen peroxide bleaching catalyst and preparation method thereof |
| CN104689315A (en) * | 2015-03-19 | 2015-06-10 | 吉林大学 | Chitosan loading copper complex type nano-composite photo-thermal agent and preparation method thereof |
| CN108569754A (en) * | 2018-05-07 | 2018-09-25 | 北京化工大学 | A kind of environmentally friendly sewage-treating agent and its application method and application |
| CN109569725A (en) * | 2018-11-22 | 2019-04-05 | 东华大学 | A kind of method of one-step method preparation magnetism Cu (I) microspherical catalyst |
-
2020
- 2020-07-01 CN CN202010622819.7A patent/CN111905814A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4383022A (en) * | 1981-06-26 | 1983-05-10 | Polaroid Corporation | Diffusion transfer film unit with protective layer of water soluble copper salt, chitosan and gelatin |
| CN1685831A (en) * | 2005-04-30 | 2005-10-26 | 武汉大学 | Preparation method of chitin/metal copper composite antibactericidal agent |
| CN101781374A (en) * | 2010-02-04 | 2010-07-21 | 聊城大学 | Preparation method and application of copper compound with chitosan and/or derivatives thereof |
| CN104611906A (en) * | 2015-01-14 | 2015-05-13 | 西安工程大学 | Hydrogen peroxide bleaching catalyst and preparation method thereof |
| CN104689315A (en) * | 2015-03-19 | 2015-06-10 | 吉林大学 | Chitosan loading copper complex type nano-composite photo-thermal agent and preparation method thereof |
| CN108569754A (en) * | 2018-05-07 | 2018-09-25 | 北京化工大学 | A kind of environmentally friendly sewage-treating agent and its application method and application |
| CN109569725A (en) * | 2018-11-22 | 2019-04-05 | 东华大学 | A kind of method of one-step method preparation magnetism Cu (I) microspherical catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 孙宏等: ""壳聚糖铜（Ⅱ）配合物催化氧化水中的罗丹明B"", 《印染助剂》 * |
| 张利军等: ""活性红3BSN 的H2O2/明胶铜配合物催化脱色"", 《印染》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pang et al. | Current status of textile industry wastewater management and research progress in Malaysia: a review | |
| Carmen et al. | Textile organic dyes-characteristics, polluting effects and separation/elimination procedures from industrial effluents-a critical overview | |
| Suresh | Treatment of textile dye containing effluents | |
| CN107758789A (en) | The preparation and its application of a kind of printing and dyeing wastewater treatment agent | |
| CN109265611A (en) | A kind of functional fiber element based porous materials and the preparation method and application thereof | |
| Rajhans et al. | Degradation of dyes by fungi: an insight into mycoremediation | |
| CN115196739A (en) | Method for improving catalytic degradation rate of methylene blue in dye wastewater | |
| CN113318790B (en) | Phthalocyanine catalyst for treating dye wastewater and preparation method thereof | |
| CN109092264B (en) | Preparation method of solid decolorizing agent | |
| CN107043729B (en) | Microbial inoculum for treating printing and dyeing sewage and preparation method thereof | |
| CN111905814A (en) | Preparation method of biocatalyst | |
| CN108069558B (en) | Method for decoloring biochemical effluent of catalytic ozone treatment cellulosic ethanol wastewater | |
| CN108218040B (en) | Treatment process for degrading printing and dyeing wastewater by catalytic ozone | |
| AU2020103640A4 (en) | Porous Biomass Adsorbing Material, And Application Thereof | |
| CN108658148A (en) | A kind of imvite modified Sodium Polyacrylate printing and dyeing wastewater treatment agent and preparation method thereof | |
| CN108314174B (en) | Treatment process for degrading dye wastewater by catalyzing ozone | |
| CN107973366A (en) | One kind utilizes persulfuric acid hydrogen salt and photochemical catalyst BiVO4The method of purifying dyestuff waste water | |
| CN112076730A (en) | Dye wastewater decolorizer and preparation method and application thereof | |
| CN112934191A (en) | Dye adsorbent and preparation method and application thereof | |
| CN108203184B (en) | Treatment process for catalytic degradation of printing and dyeing wastewater by ozone | |
| CN111039416A (en) | Novel biological method for removing chromaticity in printing and dyeing wastewater | |
| CN113578253A (en) | Self-floating adsorbent based on hollow glass beads and preparation method and application thereof | |
| CN102463108A (en) | Catalyst for processing azo dyes in printing and dyeing waste water and preparation method | |
| CN111559833A (en) | Method for treating pulping wastewater by using enzyme membrane reactor | |
| CN107162342B (en) | Method for repairing printing and dyeing wastewater by using biochemical technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201110 |
|
| RJ01 | Rejection of invention patent application after publication |