CN110404504B - Cu-doped walnut shell activated carbon for treating printing and dyeing sewage and preparation method and application thereof - Google Patents
Cu-doped walnut shell activated carbon for treating printing and dyeing sewage and preparation method and application thereof Download PDFInfo
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- CN110404504B CN110404504B CN201810387224.0A CN201810387224A CN110404504B CN 110404504 B CN110404504 B CN 110404504B CN 201810387224 A CN201810387224 A CN 201810387224A CN 110404504 B CN110404504 B CN 110404504B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses Cu-doped walnut shell activated carbon for treating printing and dyeing sewage, and a preparation method and application thereof. The preparation method of the Cu-doped walnut shell activated carbon for treating printing and dyeing sewage comprises the following steps: sequentially carrying out copper salt treatment, carbonization treatment, activation treatment and high-temperature heat treatment on walnut shells to obtain the Cu-doped walnut shell activated carbon. The preparation method and the preparation process flow of the Cu-doped walnut shell activated carbon for treating printing and dyeing sewage provided by the invention are simple, the prepared Cu-doped walnut shell activated carbon is easy to regenerate, the adsorption efficiency is still stable, the adsorption capacity is large and the speed is high after repeated cyclic utilization, and the walnut shell is used as a raw material, so that the Cu-doped walnut shell activated carbon has the advantages of low cost, good biocompatibility, environmental friendliness and the like, and has a good application prospect.
Description
Technical Field
The invention particularly relates to Cu-doped walnut shell activated carbon for treating printing and dyeing sewage, and a preparation method and application thereof, belonging to the technical field of sewage treatment.
Background
With the continuous acceleration of industrialization and urbanization, a large amount of industrial sewage and domestic sewage are directly discharged without being treated, and according to data statistics, about 700000 tons of dye wastewater are discharged in the world every year, wherein the industrial textile dye is used by more than 10000 tons every year, more than 90% of textile dye is directly used in the printing and dyeing industry, and more than 1000 tons of dye wastewater are directly discharged in the water body (Bouaziz F, Koubaa M, Kallel F, et al. These industrial waste water and domestic sewage contain a large amount of organic matters, heavy metal particles and the like harmful to human bodies, which leads to the aggravation of water environment pollution. The sewage discharged by the printing and dyeing industry has complex components, high concentration, high toxicity, difficult biochemical degradation, large discharge amount and the like, is one of main sources of water pollution in China, and the dye sewage enters natural water to cause the light transmittance of the water to be reduced, slow down photosynthesis, further influence the growth of aquatic animals and plants and influence the chelation of dyes discharged to the natural water and metal ions to cause toxicity to the aquatic animals, even cause toxicity, mutation and distortion to human beings (Zhang X, LinQ, Luo S, et al. Researches show that triphenylmethane dyes have carcinogenic properties, wherein Malachite Green (MG) is a toxic triphenylmethane compound, has the harmfulness of large residual quantity, high toxicity, carcinogenicity, teratogenesis and the like, the high toxicity causes that the malachite green is difficult to be degraded by microorganisms in wastewater treatment, the metabolite in aquatic organisms is colorless malachite green, the colorless malachite green is insoluble in water, and the residual toxicity is stronger than that of the malachite green. The method is an important method for treating dye wastewater because of its simplicity, feasibility, small investment and high efficiency (Ghaedi M, shojaeibour E, Ghaedi A M, et al, Isotherm and dynamics study of fatty green absorption on copper nano-loaded on activated carbon: organic neural network model and genetic algorithm optimization. [ J ]. Spectrochim Acta A Mol Biospectrum, 2015,142:135-149.Wang D, Liu L, Jiang X, et al, addition and regression of fatty green concrete absorption synthesis [ J ]. P-cyclic-epoxy synthesis ] ingredients J & S & S.A & S. No. 2,S.G & S. 2,S.G.G.: A.S.: 2, P.S.: A.S.: D, P.S.: A.S.: 2, P.S.: A. & S. 2. sub.S.: yellow & S. 2. sub.S.: 2. sub.S. A.,S. 2. sub.S. 2. A. Activated carbon is a porous carbonaceous material, has a developed pore structure, a large specific surface area and excellent adsorption properties, and is widely used in the fields of environmental protection, Chemical Engineering and the like (Yu M, Li J, Wang l.koh-activated carbon enzymes derived from sodium carbonate units and carbon nanoparticles for high-performance catalysis and force adsorption [ J ]. Chemical Engineering Journal,2016,310).
With the increasing water environment pollution, the processing and treatment of sewage are paid attention by researchers in various countries and make certain progress. In the prior art, crushed wheat husks or pecan husks-corn straws are used as raw materials to prepare the adsorbing material to deal with malachite green and the like in wastewater, but the prior art has the defects of complex process, harsh treatment conditions and the like, is not favorable for large-scale industrial production and application, and the obtained adsorbing material has low adsorbing capacity on pollution components containing the malachite green and the like. Therefore, it is still an urgent need to solve the problem of providing a rapid and efficient adsorbent for dealing with pollution treatment of Malachite Green (MG).
Disclosure of Invention
The invention mainly aims to provide Cu-doped walnut shell activated carbon for treating printing and dyeing sewage, and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of Cu-doped walnut shell activated carbon for treating printing and dyeing sewage, which comprises the following steps:
(1) mixing walnut shells withContaining Cu2+Uniformly mixing the inorganic salt aqueous solution, and then drying to obtain an inorganic salt-walnut shell mixture;
(2) carbonizing the inorganic salt-walnut shell mixture in a protective atmosphere at 400-600 ℃ for 0.5-2 h to obtain a Cu-doped walnut shell carbide;
(3) uniformly mixing the Cu-doped walnut shell carbide with an alkaline solution, and then drying to obtain a Cu-doped walnut shell active product;
(4) and carrying out heat treatment on the Cu-doped walnut shell active compound in a protective atmosphere at 700-900 ℃ for 1-3 h, and carrying out post-treatment to obtain the Cu-doped walnut shell active carbon.
The embodiment of the invention also provides the Cu-doped walnut shell activated carbon prepared by the preparation method.
The embodiment of the invention also provides application of the Cu-doped walnut shell activated carbon in the field of printing and dyeing sewage treatment.
The embodiment of the invention also provides a method for treating printing and dyeing sewage, which comprises the following steps:
providing the Cu-doped walnut shell activated carbon;
adding the Cu-doped walnut shell activated carbon into printing and dyeing sewage and fully mixing;
wherein the printing and dyeing wastewater contains any one or the combination of more than two of malachite green, methyl red and methylene blue.
Compared with the prior art, the invention has the advantages that: the invention provides Cu-doped walnut shell activated carbon for treating printing and dyeing sewage, and a preparation method and application thereof. The preparation method of the Cu-doped walnut shell activated carbon for treating printing and dyeing sewage comprises the following steps: sequentially carrying out inorganic salt treatment, carbonization treatment, activation treatment and high-temperature heat treatment on walnut shells to obtain the Cu-doped walnut shell activated carbon. The preparation method and the preparation process flow of the Cu-doped walnut shell activated carbon for treating printing and dyeing sewage provided by the invention are simple, the Cu-doped walnut shell activated carbon is easy to regenerate, the adsorption efficiency is still stable, the adsorption capacity is large and the speed is high after repeated cyclic utilization, and the walnut shell is used as a raw material, so that the Cu-doped walnut shell activated carbon has the advantages of low cost, good biocompatibility, environmental friendliness and the like, and has a good application prospect.
Drawings
FIG. 1 is an elemental analysis chart of Cu-doped walnut shell activated carbon in example 1 of the present invention;
FIG. 2 is a microscopic morphology of Cu-doped walnut shell activated carbon in example 1 of the present invention;
FIG. 3 is a microscopic morphology of Cu-doped walnut shell activated carbon in comparative example 1 of the present invention;
FIG. 4 is a graph showing the adsorption amount of Cu-doped walnut shell activated carbon in example 1 and comparative example 1 according to the present invention;
FIG. 5 shows N of Cu-doped walnut shell activated carbon in example 1 of the present invention2Adsorption-desorption curve chart;
FIG. 6X-ray powder diffraction patterns of Cu-doped walnut shell activated carbon in inventive example 1 and comparative example 1.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
The embodiment of the invention provides a preparation method of Cu-doped walnut shell activated carbon for treating printing and dyeing sewage, which comprises the following steps:
(1) mixing walnut shell with Cu2+Uniformly mixing the inorganic salt aqueous solution, and then drying to obtain an inorganic salt-walnut shell mixture;
(2) carbonizing the inorganic salt-walnut shell mixture in a protective atmosphere at 400-600 ℃ for 0.5-2 h to obtain a Cu-doped walnut shell carbide;
(3) uniformly mixing the Cu-doped walnut shell carbide with an alkaline solution, and then drying to obtain a Cu-doped walnut shell active product;
(4) and carrying out heat treatment on the Cu-doped walnut shell active compound in a protective atmosphere at the temperature of 600-800 ℃ for 2-4 h, and carrying out post-treatment to obtain the Cu-doped walnut shell active carbon.
Furthermore, the particle size of the walnut shells in the step (1) is 100-200 meshes.
Furthermore, the walnut shells are dried at the temperature of 100-120 ℃ for 12-36 hours.
Further, the Cu is contained2+The concentration of the inorganic salt aqueous solution is 5-15 mmol-1。
Further, the walnut shell and the Cu-containing material2+The mass-volume ratio of the inorganic salt water solution is 1-3 g: 100 to 300 ml.
Further, Cu in the inorganic salt aqueous solution2+The source of (b) includes any one or a combination of two or more of copper nitrate, copper sulfate and copper chloride, but is not limited thereto.
In some more specific embodiments, step (1) specifically comprises: adding walnut shells into Cu-containing materials at the temperature of 20-40 DEG C2+In the inorganic salt aqueous solution, and the reaction is carried out for 200 to 400r min-1The stirring speed of (3) is kept for 12-24 h, and then the obtained mixture is dried at the temperature of 60-100 ℃, and the drying time is 0.5-1 h.
In some more specific embodiments, the step (2) comprises: placing the inorganic salt-walnut shell mixture in a protective atmosphere at 2-10 ℃ for min-1The temperature is increased to 500-700 ℃ at the temperature increasing rate for carbonization treatment, and the carbonization treatment time is 0.5-1 h.
Preferably, the protective atmosphere includes a nitrogen atmosphere, but is not limited thereto. .
Preferably, the nitrogen flow rate for forming the protective atmosphere is 100-200 mL min-1。
In some more specific embodiments, the mass ratio of the Cu-doped walnut shell carbide to the alkaline solution in step (3) is 1: (1-3).
Further, the concentration of the alkaline solution is 5-10 mmol L-1。
Further, the alkaline solution includes any one or a combination of two or more of a sodium hydroxide solution, a potassium hydroxide solution, and an ammonia solution, but is not limited thereto.
In some more specific embodiments, the step (3) specifically comprises: adding the Cu-doped walnut shell carbide into an alkaline solution at the temperature of 20-40 ℃, and performing reaction for 200-400 r min-1The stirring speed is kept for 2-4 h, and then the obtained mixture is dried at 60-100 ℃, wherein the drying time is 2-4 h.
In some more specific embodiments, the step (4) specifically includes: placing the Cu-doped walnut shell active substance into a protective atmosphere, and heating for 2-10 ℃ for min-1The temperature is raised to 700-900 ℃ at the temperature raising rate for heat treatment, and the heat treatment time is 1-3 h.
Preferably, the protective atmosphere includes a nitrogen atmosphere, but is not limited thereto.
Preferably, the nitrogen flow rate for forming the protective atmosphere is 100-200 mL min-1。
In some more specific embodiments, the step (4) further comprises: and after the heat treatment is finished, washing the obtained product to be neutral, and drying at 100-140 ℃ for 4-6 h to obtain the Cu-doped walnut shell activated carbon.
The embodiment of the invention also provides the Cu-doped walnut shell activated carbon prepared by the method.
Furthermore, mesoporous structures are distributed in the Cu-doped walnut shell activated carbon and on the surface of the Cu-doped walnut shell activated carbon, and the total pore volume is 0.5-1.0 cm3g-1The specific surface area is 1000 to 2000m2g-1The pore diameter of the mesoporous structure is 1-3 nm, and the content of Cu element is 5-10 wt%.
The embodiment of the invention also provides application of the Cu-doped walnut shell activated carbon in the field of printing and dyeing sewage treatment.
The embodiment of the invention also provides a method for treating printing and dyeing sewage, which comprises the following steps:
providing the Cu-doped walnut shell activated carbon;
adding the Cu-doped walnut shell activated carbon into printing and dyeing sewage and fully mixing;
the printing and dyeing wastewater contains any one or a combination of more than two of malachite green, methyl red and methylene blue, but is not limited to the above.
Preferably, the concentration of the printing and dyeing wastewater is 500-2000 mg L-1。
Preferably, the dosage ratio of the Cu-doped walnut shell activated carbon to the printing and dyeing wastewater is 1 g: (1000-2000) ml.
Preferably, the mixing reaction time of the Cu-doped walnut shell activated carbon added into the printing and dyeing wastewater is 10-360 min.
Preferably, the printing and dyeing wastewater treatment method further comprises the following steps: carrying out cyclic regeneration treatment on the Cu-doped walnut shell activated carbon subjected to adsorption treatment on the printing and dyeing wastewater; the cyclic regeneration treatment comprises: cleaning Cu-doped walnut shell activated carbon subjected to adsorption treatment on printing and dyeing sewage, drying at 100-140 ℃ for 4-6 h, and then performing room temperature treatment at 2-10 ℃ for min in protective atmosphere-1Heating to 400-600 ℃ at the heating rate, carrying out heat treatment for 1-3 h, and cooling to room temperature to obtain the regenerated Cu-doped walnut shell carbide;
preferably, the protective atmosphere comprises a nitrogen atmosphere; preferably, the nitrogen flow rate for forming the protective atmosphere is 50-200 mL min-1。
Preferably, the method comprises: and (3) carrying out 4-6 times of cyclic regeneration treatment on the Cu-doped walnut shell activated carbon subjected to the adsorption treatment on the printing and dyeing sewage.
The technical solution, the implementation process and the principle thereof will be further explained with reference to the specific embodiments as follows.
Example 1
(1) Dipping treatment: taking 100-200 meshes of walnut shells as a raw material, and drying the walnut shells in a drying oven at 110 ℃ for 24 hours to remove water; 200mL of 10mmol L is prepared-1CuCl of2Weighing 2.0g of the walnut shell, adding CuCl into the walnut shell2In solution, afterAt 25 ℃ for 300r min-1Magnetic stirring at constant speed for 12h to ensure that the walnut shells and the CuCl2Fully mixing the solution, and then carrying out rotary evaporation on the prepared mixture to form powder by a rotary evaporator;
(2) and (3) carbonization treatment: weighing the walnut shell-inorganic salt mixture, adding the walnut shell-inorganic salt mixture into a quartz tube, and placing the mixture in a fixed bed reactor for 100mL min-1The flow of (2) is continuously introduced into N2From room temperature at 5 ℃ for min-1Heating to 600 ℃ at the heating rate, keeping the temperature for 0.5h, and cooling to room temperature to obtain the Cu-doped walnut shell carbide;
(3) activation treatment, namely preparing the active agent with the concentration of 6mol L-1KOH solution, mixing the obtained Cu-doped walnut shell carbide with 6mol L-1The KOH solution (2) was mixed at a mass ratio of 1:1 and the mixture was heated at 25 ℃ for 300r min-1Magnetically stirring at constant speed for 2h, and drying at 60 ℃ for 12h to obtain a Cu-doped walnut shell active product;
(4) adding the obtained Cu-doped walnut shell active product into a quartz tube, and placing the product in a fixed bed reactor for 100mL min-1The flow of (2) is continuously introduced into N2，And at 5 ℃ for min-1The temperature is raised to 800 ℃ at the heating rate, the temperature is kept for 2 hours, and then the temperature is cooled to the room temperature; and washing the obtained activated carbon material with deionized water for several times until the activated carbon material is neutral, drying the activated carbon material in a drying oven at 120 ℃ for 5 hours, and then cooling the dried activated carbon material to room temperature to obtain the Cu-doped walnut shell activated carbon.
The Cu-doped walnut shell activated carbon material prepared in this example was named Cu-AC, wherein the element content of the Cu-doped walnut shell activated carbon is shown in table 1.
In the embodiment 1 of the invention, the treatment of the malachite green sewage by using the Cu-doped walnut shell activated carbon catalyst comprises the following steps:
0.0150g of Cu-doped walnut shell activated carbon in example 1 was taken and 15ml of an initial concentration of 1000mg L was added-1Putting the malachite green solution into a small test tube of 50ml, putting the small test tube into a magnetic stirring water bath kettle for 300r min-1Stirring was carried out while keeping the bath temperature at 25 ℃. Then taking it at 5min, 10min, 15min, 20min, 30min, 60min, 120min, 180min, 240min, 360min, etcAnd (4) carrying out centrifugal separation on the supernatant liquid, and then determining the concentration of the malachite green solution.
It can be seen from fig. 4 that the Cu-doped walnut shell activated carbon provided in example 1 has a strong adsorption effect on malachite green, and the initial concentration of the malachite green solution is 1000mg L-1In the case of (1), the amount of adsorbed water reached 997.37mg g in 5min-1The removal rate reaches 99.74 percent, and the adsorption saturation is reached within 10 min.
The Cu-doped walnut shell activated carbon in the example 1 is adopted to adsorb malachite green and then regenerated: collecting the adsorbed Cu-doped walnut shell activated carbon, centrifugally washing with ethanol, drying at 105 deg.C for 5h, placing into a fixed bed reactor, and continuously introducing 100mL min-1N of (A)2From room temperature at 5 ℃ for min-1The temperature is raised to 500 ℃ at the heating rate, the temperature is kept for 2 hours and then the temperature is cooled to room temperature, the regenerated Cu-doped walnut shell carbide is obtained, and five times of cyclic regeneration are carried out.
The results show that the treatment conditions of adsorbing malachite green by using the regenerated Cu-doped walnut shell carbide are the same as the treatment process and conditions of adsorbing malachite green by using the Cu-doped walnut shell carbide:
during the first circulation regeneration, the adsorption capacity reaches 997.37mg g within 5min-1The removal rate reaches 99.74 percent, and the adsorption saturation is reached within 10 min.
During the second cycle regeneration, the solution is basically clear within 5min, the adsorption saturation is reached within 30min, and the adsorption capacity reaches 997.25mgg-1The removal rate reaches 99.73%.
During the third cycle regeneration, the solution is basically clear within 5min, the adsorption saturation is achieved within 30min, and the adsorption capacity reaches 996.45mgg-1The removal rate reaches 99.65%.
During the fourth cycle regeneration, the solution is basically clear within 5min, the adsorption saturation is reached within 30min, and the adsorption capacity reaches 997.31mgg-1The removal rate reaches 99.73%.
During the fifth cycle regeneration, the solution is basically clear within 5min, the adsorption saturation is reached within 30min, and the adsorption capacity reaches 997.31mgg-1The removal rate reaches 99.73%.
Table 1 is an elemental analysis table of Cu-doped walnut shell activated carbon in example 1 of the present invention
Example 2
The preparation process and conditions were substantially the same as in example 1, except that 200mL of 5mmol L was prepared in step (1)-1CuCl of2The solution is subjected to an impregnation treatment.
The Cu-doped walnut shell activated carbon prepared in the example 2 is added to the initial concentration of 500-1500 mg L according to the same conditions as the example 1-1Adsorbing with malachite green solution. The results showed that the maximum adsorption amount of the Cu-doped walnut shell activated carbon in example 2 to the malachite green solution was 884.19mg g-1。
Example 3
The preparation process and conditions were substantially the same as in example 1, except that 200mL of 15mmol L was prepared in step (1)-1CuCl of2The solution is subjected to an impregnation treatment.
The Cu-doped walnut shell activated carbon prepared in the example 3 is added to the initial concentration of 500-1500 mg L according to the same conditions as the example 1-1Adsorbing with malachite green solution. The results showed that the maximum adsorption amount of the Cu-doped walnut shell activated carbon in example 3 to the malachite green solution was 891.99mg g-1。
Example 4
The preparation process and conditions were substantially the same as in example 1, except that 200mL of 10mmol L was prepared in step (1)-1Cu (NO) of3)2The solution is subjected to an impregnation treatment.
The Cu-doped walnut shell activated carbon prepared in the example 4 is added to the initial concentration of 500-1500 mg L according to the same conditions as the example 1-1Adsorbing with malachite green solution. The results showed that the maximum adsorption amount of the Cu-doped walnut shell activated carbon in example 4 to the malachite green solution was 889.76mg g-1。
Example 5
The preparation process and conditions were substantially the same as in example 1, except that 200mL of 10mmol L was prepared in step (3)-1CuSO (C)4The solution is subjected to an impregnation treatment.
The Cu-doped walnut shell activated carbon prepared in the example 5 is added to the initial concentration of 500-1500 mg L according to the same conditions as the example 1-1Adsorbing with malachite green solution. The results showed that the maximum adsorption amount of the Cu-doped walnut shell activated carbon in example 5 to the malachite green solution was 907.57mg g-1。
Example 6
The preparation process and conditions were substantially the same as in example 1, except that in step (3), the Cu-doped walnut shell carbide was mixed with 6mol L of the mixture-1The KOH solution (2) was mixed at a mass ratio of 1: 2.
The Cu-doped walnut shell activated carbon prepared in the example 6 is added to the initial concentration of 500-1500 mg L according to the same conditions as the example 1-1Adsorbing with malachite green solution. The results showed that the maximum adsorption amount of the Cu-doped walnut shell activated carbon in example 6 to the malachite green solution was 933.18mg g-1。
Example 7
The preparation process and conditions were substantially the same as in example 1, except that in step (3), the Cu-doped walnut shell carbide was mixed with 6mol L of the mixture-1The KOH solution (2) was mixed at a mass ratio of 1: 3.
The Cu-doped walnut shell activated carbon prepared in the example 7 is added to the initial concentration of 500-1500 mg L according to the same conditions as the example 1-1Adsorbing with malachite green solution. The results showed that the maximum adsorption amount of Cu-doped walnut shell activated carbon in example 7 to the malachite green solution was 893.10mg g-1。
Comparative example 1:
this comparative example 1 was substantially identical to the procedure of example 1, except that CuCl in step (2) was not present2The solution is dipped and treated, and the obtained activated carbon material is named as AC.
The Cu-doped walnut shell activated carbon prepared in comparative example 1 was added to the initial concentration under the same conditions as in example 1500-1500 mg L-1Adsorbing with malachite green solution. The results showed that the maximum adsorption amount of the undoped Cu walnut shell activated carbon in comparative example 1 to the malachite green solution was 783.32mg g-1。
Comparative example 2
CN105664849A (CN 105664849A) is adopted to prepare mixed matrix biomass activated carbon by taking pecan shells and corn straws as raw materials, 0.0150g of mixed matrix biomass activated carbon is obtained and added into 15ml of malachite green solution with the initial concentration of 1000mg L < -1 >, the adsorption rate is slow, and the adsorption capacity is extremely low; tests show that the mixed-base biomass activated carbon provided in comparative example 2 has 65-93% of effect on the adsorption rate of malachite green, but aims at the malachite green solution with the initial concentration of 300mg L at most-1And the adsorption time is longer.
As shown in fig. 1 and 6, the Cu-doped walnut shell activated carbon of example 1 contains Cu and has a significant adsorption effect. Fig. 2 and 3 are scanning electron micrographs of the Cu-doped walnut shell activated carbon of example 1 and the walnut shell activated carbon of comparative example 1. As can be seen from fig. 2 and 3, in example 1 of the present invention, the surface of the Cu-doped walnut shell activated carbon is activated by NaOH, and then the surface channels are increased, so that the Cu-doped walnut shell activated carbon has rich channel structures, the channels become main adsorption sites for adsorbing the malachite green solution, and the more the channels are, the more the adsorption is facilitated. Referring to FIG. 5 (Cu-doped walnut shell activated carbon catalyst N in example 1 of the present invention)2Adsorption-desorption attached figure) shows that the mass fraction of Cu in the Cu-doped walnut shell activated carbon is 5.50 wt%, the interior and the surface of the Cu-doped walnut shell activated carbon contain rich mesoporous structures, and the specific surface area reaches 1015.3924m2g-1Total pore volume up to 0.55cm3g-1The average pore volume reaches 2.16nm, and sufficient sites are provided for adsorbing malachite green. As can be seen from fig. 3, the walnut shell activated carbon catalyst not doped with Cu has less pores on the surface, more protrusions on the surface, and smaller specific surface area, which does not provide sufficient active sites for adsorbing malachite green.
Fig. 4 is a graph showing the adsorption amount of Cu-doped walnut shell activated carbon in example 1 and comparative example 1 of the present invention. It can be seen from the figure that the Cu-doped walnut shell activated carbon has no pore in the peacock in example 1The malachite green has strong adsorption effect, and the initial concentration of the malachite green solution is 1000mg L-1In the case of (1), the amount of adsorbed water reached 997.37mg g in 5min-1The removal rate reaches 97.74 percent, and the adsorption saturation is reached within 10 min. The maximum adsorption amount of the un-doped Cu walnut shell activated carbon in comparative example 1 is 783.32mg g-1The removal rate was 78.33%. Comparison shows that the Cu-doped walnut shell activated carbon in example 1 has a strong adsorption effect on malachite green.
When the Cu-doped walnut shell activated carbon is used for adsorbing malachite green, the adsorption effect is more remarkable, the adsorption rate is higher, and the initial concentration of a malachite green solution is 1000mg L-1In the case of (2), the maximum adsorption amount of malachite green reached 997.37mg g-1The adsorption time is only 5min, the removal rate reaches 99.74%, and the adsorption saturation is reached within 10 min. On one hand, the adsorption is facilitated due to rich pore channels and larger specific surface area; on one hand, copper plays an important catalytic role in the adsorption process, is distributed in the interior and on the surface of the activated carbon, changes the polarity of the activated carbon, increases oxygen-containing functional groups, shows strong coordination binding force on malachite green macromolecules, and improves the adsorption capacity; in addition, because malachite green is a cationic dye, copper atoms on the surface show strong electron accepting tendency due to discretization of electronic unsaturated energy level, have strong activity and are unstable, and are easy to adsorb malachite green molecules or form a complex with the malachite green molecules to tend to be stable.
In addition, it was found through similar experiments that the products obtained in the other examples of the present invention also had excellent adsorption rate and adsorption capacity for malachite green in printing and dyeing wastewater.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (11)
1. A method for treating printing and dyeing sewage is characterized by comprising the following steps:
providing Cu-doped walnut shell activated carbon, wherein mesoporous structures are distributed in the Cu-doped walnut shell activated carbon and on the surface of the Cu-doped walnut shell activated carbon, and the total pore volume is 0.5-1.0 cm3·g-1The specific surface area is 1000 to 2000m2·g-1The pore diameter of the mesoporous structure is 1-3 nm, the content of Cu element is 5-10 wt%, and the Cu-doped walnut shell activated carbon is prepared by the following method:
(1) adding walnut shells into Cu-containing materials at the temperature of 20-40 DEG C2+In the aqueous solution of inorganic salt at 200 to 400 r.min-1The stirring speed of the inorganic salt-walnut shell stirring device is kept for stirring for 12-24 hours, then the obtained mixture is dried at the temperature of 60-100 ℃, and the drying time is 0.5-1 hour, so that the inorganic salt-walnut shell mixture is obtained, wherein the walnut shell and the mixture containing Cu2+The mass-volume ratio of the inorganic salt water solution is 1-3 g: 100 to 300mL of the Cu-containing2+The concentration of the inorganic salt aqueous solution is 5 to 15 mmol.L-1 ；
(2) Placing the inorganic salt-walnut shell mixture in a protective atmosphere at 2-10 ℃ per minute-1The temperature is increased to 400-600 ℃ at the temperature increasing rate, and carbonization is carried out for 0.5-2 h, so that the Cu-doped walnut shell carbide is obtained;
(3) mixing the Cu-doped walnut shell carbide with an alkaline solution at the temperature of 20-40 ℃ to form a mixture, and performing reaction for 200-400 r.min-1Continuously stirring for 2-4 h, drying the obtained mixture at 60-100 ℃ for 2-4 h to obtain a Cu-doped walnut shell active product, wherein the mass ratio of the Cu-doped walnut shell carbide to the alkaline solution is 1: (1-3) the concentration of the alkaline solution is 5-10 mmol.L-1；
(4) Placing the Cu-doped walnut shell active product into a protective atmosphere at 2-10 ℃ per minute-1Heating to 600-800 ℃ at a heating rate, carrying out heat treatment for 2-4 h, washing the obtained product to be neutral after the heat treatment is finished, and then carrying out heat treatment at 100-14 DEG CDrying for 4-6 h at 0 ℃ to obtain Cu-doped walnut shell activated carbon;
adding the Cu-doped walnut shell activated carbon into printing and dyeing sewage, and fully mixing, wherein the dosage ratio of the Cu-doped walnut shell activated carbon to the printing and dyeing sewage is 1 g: (1000-2000) mL, and the concentration of the printing and dyeing wastewater is 500-2000 mg.L-1；
Wherein the printing and dyeing wastewater contains any one or the combination of two of malachite green, methyl red and methylene blue.
2. The method of claim 1, wherein: the mixing reaction time of the Cu-doped walnut shell activated carbon added into the printing and dyeing sewage is 10-360 min.
3. The method of claim 1, wherein: the printing and dyeing sewage treatment method also comprises the following steps: carrying out cyclic regeneration treatment on the Cu-doped walnut shell activated carbon subjected to adsorption treatment on the printing and dyeing sewage; the cyclic regeneration treatment comprises: cleaning Cu-doped walnut shell activated carbon subjected to adsorption treatment on printing and dyeing sewage, drying at 100-140 ℃ for 4-6 h, and then drying at 2-10 ℃ per minute from room temperature in protective atmosphere-1Heating to 400-600 ℃ at the heating rate, carrying out heat treatment for 1-3 h, and cooling to room temperature to obtain the regenerated Cu-doped walnut shell carbide.
4. The method of claim 3, wherein: the protective atmosphere comprises a nitrogen atmosphere, and the nitrogen flow for forming the protective atmosphere is 50-200 mL/min-1。
5. The method of claim 3, wherein the method comprises: and (3) carrying out cyclic regeneration treatment for 4-6 times on the Cu-doped walnut shell activated carbon subjected to adsorption treatment on the printing and dyeing sewage.
6. The method of claim 1, wherein: the particle size of the walnut shells in the step (1) is 100-200 meshes.
7. The method of claim 1, wherein: the walnut shells are dried at the temperature of 100-120 ℃ for 12-36 hours.
8. The method of claim 1, wherein: cu in the aqueous solution of the inorganic salt2+The source of (B) comprises any one or the combination of more than two of copper nitrate, copper sulfate and copper chloride.
9. The method of claim 1, wherein: the protective atmosphere comprises a nitrogen atmosphere.
10. The method of claim 9, wherein: the flow rate of nitrogen for forming the protective atmosphere is 100-200 mL/min-1。
11. The method of claim 1, wherein: the alkaline solution comprises any one or the combination of more than two of sodium hydroxide solution, potassium hydroxide solution and ammonia water solution.
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| CN111530424B (en) * | 2020-06-17 | 2022-07-08 | 福州大学 | Copper-loaded modified carbon material adsorbent for efficiently removing gaseous benzene series and preparation method and application thereof |
| CN113559824B (en) * | 2021-08-27 | 2023-12-19 | 西北大学 | Nitrogen-doped porous carbon material adsorbent for treating dye wastewater and preparation method and application thereof |
| CN114917871A (en) * | 2022-06-21 | 2022-08-19 | 徐靖才 | Photocatalytic regenerated active carbon and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1876232A (en) * | 2006-07-04 | 2006-12-13 | 北京交通大学 | Activated charcoal carried copper oxide catalyst and process for preparing same |
| CN101613096A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of preparation method of transient metal doped meso-porous carbon material |
| CN102240576A (en) * | 2011-05-24 | 2011-11-16 | 北京航空航天大学 | Method for preparing transitional metal/active carbon catalyst |
| CN103011129A (en) * | 2012-12-13 | 2013-04-03 | 黑龙江大学 | Method for preparing high-specific-surface-area porous graphitic nanocarbon plate with coconut shells serving as raw materials |
| CN103803545A (en) * | 2014-01-18 | 2014-05-21 | 复旦大学 | Method for preparing copper-doped activated carbon by utilizing complexing process |
| CN104525116A (en) * | 2014-12-31 | 2015-04-22 | 上海克硫环保科技股份有限公司 | Desulfurization and denitrification modified active coke and preparation method thereof |
| CN105664896A (en) * | 2016-02-02 | 2016-06-15 | 西北大学 | Fe-doped walnut shell activated carbon for treating dye wastewater as well as preparation method and application of activated carbon |
| CN105776181A (en) * | 2016-04-29 | 2016-07-20 | 大连理工大学 | Preparation method of flaky nanoholes carbon and carbon nanotube composite |
| CN106076344A (en) * | 2016-06-06 | 2016-11-09 | 浙江工业大学 | Activated carbon supported type copper metal oxide catalyst and its preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN2013DE02463A (en) * | 2013-08-20 | 2015-06-26 | Indian Inst Technology Kanpur |
-
2018
- 2018-04-26 CN CN201810387224.0A patent/CN110404504B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1876232A (en) * | 2006-07-04 | 2006-12-13 | 北京交通大学 | Activated charcoal carried copper oxide catalyst and process for preparing same |
| CN101613096A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of preparation method of transient metal doped meso-porous carbon material |
| CN102240576A (en) * | 2011-05-24 | 2011-11-16 | 北京航空航天大学 | Method for preparing transitional metal/active carbon catalyst |
| CN103011129A (en) * | 2012-12-13 | 2013-04-03 | 黑龙江大学 | Method for preparing high-specific-surface-area porous graphitic nanocarbon plate with coconut shells serving as raw materials |
| CN103803545A (en) * | 2014-01-18 | 2014-05-21 | 复旦大学 | Method for preparing copper-doped activated carbon by utilizing complexing process |
| CN104525116A (en) * | 2014-12-31 | 2015-04-22 | 上海克硫环保科技股份有限公司 | Desulfurization and denitrification modified active coke and preparation method thereof |
| CN105664896A (en) * | 2016-02-02 | 2016-06-15 | 西北大学 | Fe-doped walnut shell activated carbon for treating dye wastewater as well as preparation method and application of activated carbon |
| CN105776181A (en) * | 2016-04-29 | 2016-07-20 | 大连理工大学 | Preparation method of flaky nanoholes carbon and carbon nanotube composite |
| CN106076344A (en) * | 2016-06-06 | 2016-11-09 | 浙江工业大学 | Activated carbon supported type copper metal oxide catalyst and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| Copper loaded on activated carbon as an efficient adsorbent for removal of methylene blue;Jianhua Shu et al.;《RSC Adv.》;20170303;第7卷;第14395-14405页 * |
| Thermodynamics of Adsorption of Methyl Formate on Metal Dopant/Active Carbon Systems;Muhammad Afzal et al.;《Collect. Czech. Chem. Commun.》;19931231;第58卷(第3期);第474页 * |
| 过渡金属共混制备核桃壳活性炭的脱硫性能研究;何浩东等;《环境科学与技术》;20130831;第36卷(第8期);第103-106页 * |
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