CN107243323B - Magnetic bamboo fiber based activated carbon material and preparation method and application thereof - Google Patents
Magnetic bamboo fiber based activated carbon material and preparation method and application thereof Download PDFInfo
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- CN107243323B CN107243323B CN201710501383.4A CN201710501383A CN107243323B CN 107243323 B CN107243323 B CN 107243323B CN 201710501383 A CN201710501383 A CN 201710501383A CN 107243323 B CN107243323 B CN 107243323B
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- 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
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- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
Abstract
The invention relates to a magnetic bamboo fiber based activated carbon material, a preparation method and application thereof, which are mainly applied to the treatment of dye-containing industrial wastewater and belong to the field of wastewater treatment in environmental management. The material mainly comprises a bamboo fiber raw material and iron oxide adsorbed on the bamboo fiber raw material, wherein the metal content is 20-35% by mass. The material is prepared from ferric salt, bamboo fiber raw materials and secondary distilled water, wherein the weight parts of the raw materials are 0.5-10 parts of ferric salt; 1-10 parts of bamboo fiber raw material; 5-100 parts of secondary distilled water. The invention also discloses a preparation method and application of the material. The material disclosed by the invention has the characteristics of high stability, good treatment effect, low preparation cost, abundant and renewable preparation raw materials, simple and convenient preparation method and capability of being recycled, can effectively adsorb and degrade the dye in the wastewater, and is an effective recyclable green material for treating the dye-containing wastewater.
Description
Technical Field
The invention relates to a magnetic bamboo fiber based activated carbon material, a preparation method and application thereof, which are mainly applied to the treatment of dye-containing industrial wastewater and belong to the field of wastewater treatment in environmental management.
Background
Statistically, more than 100000 dyes have been used in textile, pulp, paper, pharmaceutical, leather and other industrial fields. Dyes used in the textile industry must have high chemical and light stability, and therefore biodegradation or disposal of these dyes is rather time consuming, inefficient and difficult. Up to now, the textile industry has consumed 10000 dyes per year, a mass of more than 7X 105Ton, and discharge a large amount of waste water, causing serious environmental pollution problems. Even if the dye is degraded and treated, the product still has teratogenic and carcinogenic effects on organisms. Meanwhile, the waste water contains various organic compounds and toxic substances, which can be gradually accumulated in organisms, thereby forming a potential threat to the survival of the organisms, especially great harm to fishes and other aquatic organisms. Therefore, the method is significant for treating the sewage containing the dye in view of strong pollution and toxicity of the sewage.
The waste water containing dye has complex components and poor biochemical degradation capability, generally has nausea smell and darker color, so that the treatment of the sewage is difficult. The method for removing the dye in the wastewater at home and abroad mainly comprises the following steps: chemical methods (coagulation method, electrolytic method, advanced oxidation method, etc.), physicochemical methods (adsorption method, reverse osmosis method, ion exchange method, ultrasonic wave technique, etc.), biological methods (enzyme catalysis method, immobilization technique, biological contact oxidation method, etc.).
Coagulation is considered one of the most effective and economical decolorization techniques, and is particularly effective for disperse dyes, vat dyes, and sulfur dyes. Its advantages are low cost and high output. The disadvantages are that the decoloring condition needs to be changed along with the change of the water quality condition, the decoloring effect on hydrophilic dye is low, the dehydration treatment is difficult, and a large amount of sludge is generated.
The electrochemical technology is an effective method for treating dye-containing wastewater. Its advantages are high adaptability, high treating capacity and low cost. But the universality and feasibility of the method need to be further improved.
The chemical oxidation method includes ozone oxidation, hydrogen peroxide oxidation, photocatalytic oxidation and the like. The ozone oxidation method is often used for removing chromaticity of dye-containing wastewater and organic matters which are difficult to degrade, does not generate sludge, does not cause pollution, is easy to control, but has high treatment cost and is not suitable for treating large-flow wastewater; h2O2By using only less oxidising with Fe2+When coexisting, the oxidizing ability was enhanced. The method has good decolorizing effect, but has higher treatment cost; photocatalytic oxidation method mainly uses semiconductor such as TiO2。TiO2Has no toxicity, low cost and high stability and can be excited by ultraviolet part in sunlight. The method has the advantages of high treatment efficiency, small dosage at one time and less residue. However, due to problems such as catalyst recycling, light source and catalyst price, industrialization has not been realized for a while.
The reverse osmosis method is a quite precise membrane method liquid separation technology and is often applied to advanced treatment in a sewage treatment link. However, the membrane surface is easy to be polluted and blocked, and the manufacturing cost is too high, so that the wide application of the membrane in the dye-containing sewage treatment is limited.
The ion exchange method has wide prospect for treating the wastewater, and the progress is fast in recent years. The ion exchange method has the advantages of simple equipment, easy control of operation and high ion removal efficiency in the wastewater. However, the application range is limited by the variety, yield and cost of the ion exchanger, the requirement for wastewater pretreatment is high, and the regeneration of the ion exchanger and the treatment of the regenerated liquid are difficult to solve.
The ultrasonic technology has wide adaptability to various dyes, and can be used independently or combined with other water treatment technologies. As long as the conditions are proper, the organic matters can be thoroughly degraded into carbon dioxide and inorganic ions, so that the method is an environment-friendly water treatment technology and has good development and application prospects. The ultrasonic technology is better applied to the treatment of dye-containing sewage, and needs to improve the speed and degree of the sound decomposition, improve the utilization efficiency of sound energy and avoid the generation of toxic intermediates or products.
In recent times, biological enzymes have also been increasingly used as catalysts for wastewater treatment. The biological enzyme technology has the advantages of high catalytic efficiency, mild reaction conditions, low requirements on equipment, high reaction speed and the like, but the biological enzyme is quite unstable and has relatively high cost, so that the application of the biological enzyme in sewage treatment is greatly limited.
Immobilization is a technique in which free bacteria are immobilized by chemical or physical means so that they are no longer free but still biologically active. When the technology is used for treating dye-containing wastewater, the reaction is started quickly, reaction equipment is miniaturized, and the treatment effect is good. However, this technique is expensive in treating wastewater, which prevents its widespread use.
The biological contact oxidation method is a high-efficiency water treatment process for purifying organic wastewater by mainly using a biological membrane attached to a carrier. The method has the characteristics of high efficiency, energy conservation, small occupied area, small sludge generation amount, impact load resistance, no need of sludge backflow, convenient operation and management and the like, and is widely applied to sewage treatment systems in various industries. Its disadvantages are easy blocking of filler and difficult uniform gas distribution.
Adsorption is one of the most widely used methods for removing dyes from wastewater. Currently, the dyes used as adsorbents to remove wastewater encompass various types of materials and substances, such as activated carbon, red mud, polyaniline nanotubes, and the like. However, commercial activated carbon is not inexpensive and cannot be applied in large quantities to sewage treatment, and other types of materials and substances are either complicated in preparation process, too high in cost, or not ideal in treatment effect.
Therefore, the material for treating the dye-containing wastewater, which has high stability, good treatment effect, low preparation cost and simple and convenient preparation method, is found to have great significance.
Disclosure of Invention
Aiming at the defects of the treatment method and materials, the invention fully exerts the respective unique advantages of agricultural and sideline products and magnetic adsorbents, adopts bamboo and ferric salt as raw materials to prepare the magnetic bamboo fiber-based activated carbon material, has the characteristics of high stability, good treatment effect, low preparation cost, rich and renewable preparation raw materials, simple and convenient preparation method and recycling, can effectively adsorb and degrade dyes in wastewater, and is an effective recyclable green material for treating dye-containing wastewater.
The purpose of the invention is realized by the following technical scheme:
a magnetic bamboo fiber based activated carbon material mainly comprises a bamboo fiber raw material and iron oxide adsorbed on the bamboo fiber raw material, wherein the mass percentage of metal (iron) is 20-35%.
The iron oxide includes Fe3O4、Fe2O3And FeO, etc.; the content of metal (iron) in percentage by mass is preferably 30-35%.
The magnetic bamboo fiber based activated carbon material is mainly prepared from ferric salt, bamboo fiber raw materials and secondary distilled water, and the bamboo fiber raw materials are soaked in a ferric salt aqueous solution to enable the ferric salt solution to be uniformly adsorbed on the bamboo fiber raw materials; the bamboo fiber raw material can be selected from various common commercial products, such as filiform, strip, powder, granular, etc., such as white, black and brownCoffee, etc.; the iron salt can be ferric ammonium oxalate ((NH)4)3Fe(C2O4)3) Iron chloride hydrate (FeCl)3·6H2O), ferric ammonium citrate ((NH)4)3Fe(C6H5O7)2) Potassium oxalate ferrate (K)3Fe(C2O4)3·3H2O) any one of the above; the weight portions of the preparation raw materials are as follows:
iron salt: 0.5-10 parts;
bamboo fiber raw material: 1-10 parts;
secondary distilled water: 5 to 100 parts.
Preferably, the weight ratio of the iron salt to the bamboo fiber raw material is between 1:2 and 1: 1.
Preferably, the magnetic bamboo fiber based activated carbon is prepared from the following raw materials in parts by weight:
iron salt: 1-2 parts;
bamboo fiber raw material: 2 parts of (1);
secondary distilled water: 10-20 parts.
Preferably, the bamboo fiber raw material can be selected from common commercially available white filiform pure bamboo fiber raw materials.
Preferably, the iron salt is selected from ferric ammonium oxalate ((NH)4)3Fe(C2O4)3)。
The preparation method of the magnetic bamboo fiber based activated carbon material comprises the following steps:
(1) according to the proportion of the ferric salt, the bamboo fiber raw material and the secondary distilled water, adding the secondary distilled water into the ferric salt to completely dissolve the ferric salt, and uniformly soaking the bamboo fiber raw material into the completely dissolved ferric salt solution;
(2) sealing the ferric salt solution soaked with the bamboo fiber raw material, and placing for 20-30h in the dark;
(3) vacuum-drying at 55-65 deg.C in a vacuum drying oven, uniformly shearing the obtained material, and heating in a vacuum tube furnace under the protection of nitrogen gas for staged treatment.
In the step (1), the bamboo fiber raw material is uniformly soaked in the completely dissolved iron salt solution, which means that the bamboo fiber raw material is continuously turned (stirred) during soaking so that the iron salt solution can be uniformly adsorbed on the bamboo fiber raw material.
In the step (3), the temperature-raising treatment process in stages is as follows: firstly, heating to 500 ℃ at the heating rate of 5-10 ℃/min, and preserving heat for 1-2 h; then, the temperature is kept at 500 ℃ or is heated up to more than 500 ℃ for the second time (more than 500 ℃), for example, between 550 ℃ and 900 ℃, preferably between 700 ℃ and 900 ℃, and the temperature is kept for 1 to 2 hours, so that the magnetic bamboo fiber based activated carbon material with the treatment temperature of the second heat preservation temperature is obtained.
The optimization technical scheme of the invention is as follows: accurately weighing 1 part by weight of ferric salt (ferric ammonium oxalate) in a small beaker, adding 20 parts by weight of redistilled water to completely dissolve the ferric salt, weighing 2 parts by weight of bamboo fiber raw material and soaking the bamboo fiber raw material in the ferric salt solution beaker which is completely dissolved. After the bamboo fiber raw material is evenly soaked, a sealing film is pasted on a small beaker, and the beaker is placed for 24 hours in a dark place. Then vacuum-pumping and drying at 60 ℃ in a vacuum drying oven, uniformly shearing the obtained material after drying, and carrying out temperature programming treatment in a vacuum tube furnace under the protection of nitrogen. The specific temperature rise process is that the temperature is firstly 5 ℃/min, the temperature is kept for 1h when the temperature is raised to 500 ℃, then the temperature is continuously raised to 700 ℃, and the magnetic bamboo fiber based activated carbon material with the treatment temperature of 700 ℃ can be obtained after the temperature is kept for 1 h.
The invention also provides application of the magnetic bamboo fiber based activated carbon material in wastewater treatment, in particular application in dye-containing industrial wastewater treatment. The magnetic bamboo fiber based activated carbon material has good adsorption and degradation effects on methylene blue, gentian violet and rhodamine 6G dyes in wastewater.
Aiming at the defects of the traditional adsorbing material and method for treating dye-containing wastewater, the invention fully exerts the respective unique advantages of agricultural and sideline products and magnetic adsorbents, and adopts bamboo and ferric salt as raw materials to prepare the magnetic bamboo fiber-based activated carbon material. The material has the characteristics of high stability, good treatment effect, low preparation cost, rich and renewable preparation raw materials, simple and convenient preparation method and recycling, can effectively adsorb and degrade the dye in the wastewater, and is an effective recyclable green material for treating the dye-containing wastewater.
The magnetic bamboo fiber-based activated carbon material provided by the invention has the following advantages:
1) the main material is bamboo fiber which is prepared from bamboo, and the raw material is rich, easy to obtain, cheap and renewable;
2) the preparation method is simple and convenient, and the preparation cost is low;
3) the material has high stability, and can be recycled by utilizing the characteristics of iron salt;
4) the material has excellent adsorption performance and degradation performance on dye in wastewater.
Drawings
FIG. 1 is a Fourier transform infrared (FT-IR) spectrum of a magnetic bamboo fiber-based activated carbon material obtained in example 2 of the present invention;
FIGS. 2(a) -1 and 2(a) -2 are Scanning Electron Microscope (SEM) spectra of the magnetic bamboo fiber-based activated carbon material prepared in example 2 before adsorbing the dye methylene blue (both washed with ethanol);
FIGS. 2(b) -1 and 2(b) -2 are Scanning Electron Microscope (SEM) spectra of the magnetic bamboo fiber-based activated carbon material prepared in example 2 of the present invention after adsorbing the dye methylene blue (both washed with ethanol);
FIGS. 3(a) -1 and 3(a) -2 are scanning electron microscope (TEM) spectra of the magnetic bamboo fiber-based activated carbon material prepared in example 2 before adsorbing the dye methylene blue (after adsorbing, the material is washed with ethanol for multiple times);
fig. 3(b) -1 and 3(b) -2 are scanning electron microscope (TEM) spectra of the magnetic bamboo fiber-based activated carbon material prepared in example 2 of the present invention after adsorbing the dye methylene blue (after adsorbing, the material was washed with ethanol for several times);
fig. 4(a), 4(b), and 4(c) are X-ray powder diffraction (XRD) spectra of the magnetic bamboo fiber-based activated carbon material prepared in example 2 before and after adsorbing and degrading the dye methylene blue; wherein, fig. 4 (a): XRD spectrum without any treatment; fig. 4 (b): XRD spectrogram after adsorbing MB; fig. 4 (c): XRD spectrum after degradation of MB.
Fig. 5(a), 5(b), and 5(c) are uv-vis spectrograms of the magnetic bamboo fiber-based activated carbon material prepared in example 2 of the present invention, which respectively adsorb three dyes of methylene blue, gentian violet, and rhodamine 6G under optimized conditions;
FIG. 6 is a UV-visible spectrum of the magnetic bamboo fiber-based activated carbon material prepared in example 2 of the present invention, in which methylene blue is degraded under optimized conditions;
fig. 7 is a histogram of the adsorption fraction of magnetic bamboo fiber-based activated carbon material prepared in example 2 of the present invention to MB and the number of recycling times.
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following description is further provided with reference to the specific embodiments and the accompanying drawings.
The preparation method of the magnetic bamboo fiber based activated carbon material comprises the following steps: accurately weighing a certain mass of ferric salt (ferric ammonium oxalate) in a small beaker, adding secondary distilled water to completely dissolve the ferric salt, weighing a certain mass of bamboo fiber raw material, and soaking the bamboo fiber raw material in the ferric salt solution beaker which is completely dissolved. After the bamboo fiber raw material is evenly soaked, a sealing film is pasted on a small beaker, and the beaker is placed for 24 hours in a dark place. Then vacuum-pumping and drying at 60 ℃ in a vacuum drying oven, uniformly shearing the obtained material after drying, and carrying out temperature programming treatment in a vacuum tube furnace under the protection of nitrogen. The specific temperature rise process is that the temperature is firstly increased to 500 ℃ for 1h at the rate of 5 ℃/min, then the temperature is continuously increased to a certain temperature (500 ℃, 700 ℃ and 900 ℃) and the magnetic bamboo fiber based activated carbon material with the processing temperature of the temperature to be prepared can be obtained after the temperature is kept for 1 h.
Example 1
A magnetic bamboo fiber based activated carbon material is prepared from 1 part of iron salt, 2 parts of bamboo fiber raw materials and 20 parts of secondary distilled water. The preparation method comprises the following steps: weighing 1 part by weight of iron salt (ferric ammonium oxalate) in a small beaker, adding 20 parts by weight of redistilled water to completely dissolve the iron salt, weighing 2 parts by weight of bamboo fiber raw material (white filaments) and soaking the bamboo fiber raw material in the ferric salt solution beaker which is completely dissolved. After the bamboo fiber raw material is evenly soaked, a sealing film is pasted on a small beaker, and the beaker is placed for 24 hours in a dark place. Then vacuum-pumping and drying at 60 ℃ in a vacuum drying oven, uniformly shearing the obtained material after drying, and carrying out temperature programming treatment in a vacuum tube furnace under the protection of nitrogen. The specific temperature rise process is that the temperature is firstly 5 ℃/min, the temperature is kept for 1h when the temperature is raised to 500 ℃, then the temperature is continuously raised to 900 ℃, and the magnetic bamboo fiber based activated carbon material with the processing temperature of 900 ℃ can be obtained after the temperature is kept for 1 h.
Example 2
A magnetic bamboo fiber based activated carbon material is prepared from 1 part of iron salt, 2 parts of bamboo fiber raw materials and 20 parts of secondary distilled water. The preparation method comprises the following steps: weighing 1 part by weight of iron salt (ferric ammonium oxalate) in a small beaker, adding 20 parts by weight of redistilled water to completely dissolve the iron salt, weighing 2 parts by weight of bamboo fiber raw material (white filaments) and soaking the bamboo fiber raw material in the ferric salt solution beaker which is completely dissolved. After the bamboo fiber raw material is evenly soaked, a sealing film is pasted on a small beaker, and the beaker is placed for 24 hours in a dark place. Then vacuum-pumping and drying at 60 ℃ in a vacuum drying oven, uniformly shearing the obtained material after drying, and carrying out temperature programming treatment in a vacuum tube furnace under the protection of nitrogen. The specific temperature rise process is that the temperature is firstly 5 ℃/min, the temperature is kept for 1h when the temperature is raised to 500 ℃, then the temperature is continuously raised to 700 ℃, and the magnetic bamboo fiber based activated carbon material with the treatment temperature of 700 ℃ can be obtained after the temperature is kept for 1 h.
Example 3
A magnetic bamboo fiber based activated carbon material is prepared from 1 part of iron salt, 2 parts of bamboo fiber raw materials and 20 parts of secondary distilled water. The preparation method comprises the following steps: weighing 1 part by weight of iron salt (ferric ammonium oxalate) in a small beaker, adding 20 parts by weight of redistilled water to completely dissolve the iron salt, weighing 2 parts by weight of bamboo fiber raw material (white filaments) and soaking the bamboo fiber raw material in the ferric salt solution beaker which is completely dissolved. After the bamboo fiber raw material is evenly soaked, a sealing film is pasted on a small beaker, and the beaker is placed for 24 hours in a dark place. Then vacuum-pumping and drying at 60 ℃ in a vacuum drying oven, uniformly shearing the obtained material after drying, and carrying out temperature programming treatment in a vacuum tube furnace under the protection of nitrogen. The specific temperature rise process is that firstly 5 ℃/min, when the temperature rises to 500 ℃, the temperature is kept for 2h, and the magnetic bamboo fiber based activated carbon material with the processing temperature of 500 ℃ to be prepared can be obtained.
Example 4
A magnetic bamboo fiber based activated carbon material is prepared from 1 part of iron salt, 1 part of bamboo fiber raw material and 10 parts of secondary distilled water. The preparation method comprises the following steps: weighing 1 part by weight of iron salt (ferric ammonium oxalate) in a small beaker, adding 10 parts by weight of redistilled water to completely dissolve the iron salt, weighing 1 part by weight of bamboo fiber raw material (white filaments) and soaking the bamboo fiber raw material in the ferric salt solution beaker which is completely dissolved. After the bamboo fiber raw material is evenly soaked, a sealing film is pasted on a small beaker, and the beaker is placed for 24 hours in a dark place. Then vacuum-pumping and drying at 60 ℃ in a vacuum drying oven, uniformly shearing the obtained material after drying, and carrying out temperature programming treatment in a vacuum tube furnace under the protection of nitrogen. The specific temperature rise process is that the temperature is firstly 5 ℃/min, the temperature is kept for 1h when the temperature is raised to 500 ℃, then the temperature is continuously raised to 900 ℃, and the magnetic bamboo fiber based activated carbon material with the processing temperature of 900 ℃ can be obtained after the temperature is kept for 1 h.
Example 5
A magnetic bamboo fiber based activated carbon material is prepared from 1 part of iron salt, 1 part of bamboo fiber raw material and 10 parts of secondary distilled water. The preparation method comprises the following steps: weighing 1 part by weight of iron salt (ferric ammonium oxalate) in a small beaker, adding 10 parts by weight of redistilled water to completely dissolve the iron salt, weighing 1 part by weight of bamboo fiber raw material (white filaments) and soaking the bamboo fiber raw material in the ferric salt solution beaker which is completely dissolved. After the bamboo fiber raw material is evenly soaked, a sealing film is pasted on a small beaker, and the beaker is placed for 24 hours in a dark place. Then vacuum-pumping and drying at 60 ℃ in a vacuum drying oven, uniformly shearing the obtained material after drying, and carrying out temperature programming treatment in a vacuum tube furnace under the protection of nitrogen. The specific temperature rise process is that the temperature is firstly 5 ℃/min, the temperature is kept for 1h when the temperature is raised to 500 ℃, then the temperature is continuously raised to 700 ℃, and the magnetic bamboo fiber based activated carbon material with the treatment temperature of 700 ℃ can be obtained after the temperature is kept for 1 h.
Example 6
A magnetic bamboo fiber based activated carbon material is prepared from 1 part of iron salt, 1 part of bamboo fiber raw material and 10 parts of secondary distilled water. The preparation method comprises the following steps: weighing 1 part by weight of iron salt (ferric ammonium oxalate) in a small beaker, adding 10 parts by weight of redistilled water to completely dissolve the iron salt, weighing 1 part by weight of bamboo fiber raw material (white filaments) and soaking the bamboo fiber raw material in the ferric salt solution beaker which is completely dissolved. After the bamboo fiber raw material is evenly soaked, a sealing film is pasted on a small beaker, and the beaker is placed for 24 hours in a dark place. Then vacuum-pumping and drying at 60 ℃ in a vacuum drying oven, uniformly shearing the obtained material after drying, and carrying out temperature programming treatment in a vacuum tube furnace under the protection of nitrogen. The specific temperature rise process is that firstly 5 ℃/min, when the temperature rises to 500 ℃, the temperature is kept for 2h, and the magnetic bamboo fiber based activated carbon material with the processing temperature of 500 ℃ to be prepared can be obtained.
Example 7
A magnetic bamboo fiber based activated carbon material is prepared from 1 part of iron salt, 10 parts of bamboo fiber raw materials and 100 parts of secondary distilled water. The preparation method comprises the following steps: weighing 1 part by weight of iron salt (ferric ammonium oxalate) in a small beaker, adding 100 parts by weight of redistilled water to completely dissolve the iron salt, weighing 10 parts by weight of bamboo fiber raw material (white filaments) and soaking the bamboo fiber raw material in the completely dissolved iron salt solution beaker. After the bamboo fiber raw material is evenly soaked, a sealing film is pasted on a small beaker, and the beaker is placed for 24 hours in a dark place. Then vacuum-pumping and drying at 60 ℃ in a vacuum drying oven, uniformly shearing the obtained material after drying, and carrying out temperature programming treatment in a vacuum tube furnace under the protection of nitrogen. The specific temperature rise process is that the temperature is firstly 5 ℃/min, the temperature is kept for 1h when the temperature is raised to 500 ℃, then the temperature is continuously raised to 700 ℃, and the magnetic bamboo fiber based activated carbon material with the treatment temperature of 700 ℃ can be obtained after the temperature is kept for 1 h.
Example 8
A magnetic bamboo fiber based activated carbon material is prepared from 10 parts of iron salt, 1 part of bamboo fiber raw material and 20 parts of secondary distilled water. The preparation method comprises the following steps: weighing 10 parts by weight of iron salt (ferric ammonium oxalate) in a small beaker, adding 20 parts by weight of redistilled water to completely dissolve the iron salt, weighing 1 part by weight of bamboo fiber raw material (white filaments) and soaking the bamboo fiber raw material in the ferric salt solution beaker which is completely dissolved. After the bamboo fiber raw material is evenly soaked, a sealing film is pasted on a small beaker, and the beaker is placed for 24 hours in a dark place. Then vacuum-pumping and drying at 60 ℃ in a vacuum drying oven, uniformly shearing the obtained material after drying, and carrying out temperature programming treatment in a vacuum tube furnace under the protection of nitrogen. The specific temperature rise process is that the temperature is firstly 5 ℃/min, the temperature is kept for 1h when the temperature is raised to 500 ℃, then the temperature is continuously raised to 700 ℃, and the magnetic bamboo fiber based activated carbon material with the treatment temperature of 700 ℃ can be obtained after the temperature is kept for 1 h.
Preliminary studies were conducted on the magnetic bamboo fiber-based activated carbon materials prepared in examples 1 to 8:
1) inductively coupled plasma atomic emission spectroscopy (ICP-AES) was used to determine the metal content in the magnetic bamboo fiber-based activated carbon materials prepared in examples 1-8, and the results are shown in table 1.
TABLE 1 content of metal (wt%) in magnetic bamboo fiber-based activated carbon material
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Metal content (%) | 30.51 | 30.08 | 21.67 | 31.68 | 31.35 | 23.49 | 20.02 | 33.26 |
2) After contacting the same mass (1.0mg) of the magnetic bamboo fiber-based activated carbon material prepared in examples 1-8 with the same amount of Methylene Blue (MB) solution (2.50 mL. times.10 mg. multidot.L-1), the average fading time of the methylene blue MB solution was tested several times, see Table 2.
TABLE 2 average fading time of magnetic bamboo fiber-based activated carbon material applied to methylene blue solution of the same amount
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Average fade time(s) | 04.82 | 04.86 | 15.25 | 04.59 | 04.78 | 12.02 | 16.03 | 04.51 |
Preliminary research results show that the magnetic bamboo fiber-based activated carbon materials prepared in the other examples have excellent adsorption performance except that the magnetic bamboo fiber-based activated carbon materials prepared in the examples 3, 6 and 7 have low metal content and weak adsorption performance, and can completely fade a certain amount of methylene blue solution in a short time.
The magnetic bamboo fiber-based activated carbon material prepared in the preferred embodiment 2 is subjected to deep research on characterization, microstructure, adsorption performance, degradation performance and reusability.
Fourier transform infrared spectrometry was performed on the magnetic bamboo fiber-based activated carbon material prepared in example 2 to obtain a spectrogram shown in fig. 1. The figure shows that the material contains hydroxyl, carboxyl, Fe-O and the like; thus further demonstrating: the iron oxide is successfully loaded on the surface of the bamboo fiber material.
Scanning electron microscope analysis was performed on the magnetic bamboo fiber-based activated carbon material prepared in example 2 to obtain SEM images in fig. 2(a) -1 to 2(b) -2. The microscopic surface structures of the magnetic bamboo fiber-based activated carbon can be clearly observed to be tubular fibers, and iron oxide particles are uniformly loaded on the tubular fibers. Therefore, the material has large specific surface area and strong adsorption performance. And the iron salt is relatively uniformly loaded on the surface of the material, so that the applicability of the material is enhanced, and a theoretical basis is provided for the application research of the material. The comparison between fig. 2(a) -1 and fig. 2(a) -2 and fig. 2(b) -1 and fig. 2(b) -2 is not very different, which means that the material has little change before and after adsorption of the dye (washed with ethanol), and this provides a strong basis for high recycling of the material.
The magnetic bamboo fiber-based activated carbon material prepared in example 2 was analyzed by transmission electron microscopy to obtain TEM images in fig. 3(a) -1 to 3(b) -2. It can be clearly observed that the microscopic surface structures of the magnetic bamboo fiber-based activated carbon are tubular structures, and the tubular structures of the adsorbed material are thinner in fig. 3(b) -1 and 3(b) -2 after adsorption as compared with fig. 3(a) -1 and 3(a) -2 before adsorption, which may be caused by repeatedly washing the material with ethanol after adsorbing the dye. The distribution of the iron salt particles loaded on the material is not changed greatly, which proves that the adsorbed material can still adsorb the dye after being desorbed by ethanol and dried.
The magnetic bamboo fiber-based activated carbon material prepared in example 2 was subjected to X-ray powder diffraction analysis to obtain XRD patterns shown in fig. 4(a), 4(b), and 4 (c). Comparing the three spectra, it can be seen that the characteristic absorption peak of iron can be found in the spectra, and the difference is not very large, especially the spectra of fig. 4(a) and fig. 4(b) are very similar. This shows that the magnetic bamboo fiber based activated carbon material has not been changed significantly by itself after adsorbing and degrading MB.
The magnetic bamboo fiber-based activated carbon material prepared in example 2 was subjected to uv-vis spectroscopy analysis for adsorption of three dyes of methylene blue, gentian violet and rhodamine 6G under optimized conditions, and uv-vis spectrograms 5(a), 5(b) and 5(c) were obtained, respectively. Fig. 5 (a): ultraviolet-visible spectrum spectrogram of the adsorbed MB in the range of 550-700 nm; fig. 5 (b): ultraviolet-visible spectrum spectrogram of the material for adsorbing the gentian violet solution; and (c) an ultraviolet-visible spectrum spectrogram of the material adsorbed on the rhodamine 6G solution.
Under the optimized adsorption conditions, namely, at the pH of the MB solution, the temperature of 30 ℃, the material dosage of 1.5mg and the adsorption time of 90s, 10mL of 10mg/LMB solution is adsorbed by the material prepared in the example, and the adsorption fraction is measured. The adsorption fraction under these conditions was (1.830 to 0.128)/(1.830 to 0.024): 94.24%, as determined by the equation for the adsorption fraction. The adsorption fraction is already quite high, and it can be shown that this example can effectively adsorb MB.
As can be seen from fig. 5(a), the spectrographic spectrum changes from an initially higher black curve to a light green curve which is finally close to the baseline as the adsorption time increases. The MB in the adsorbed solution is almost completely adsorbed by the prepared material of the embodiment along with the increase of the adsorption time, and has better linear relation. The adsorption effect of the material prepared by the embodiment is remarkable, the adsorption capacity is superior, the adsorption condition is well controlled, and the dye pollutants such as methylene blue and the like in the wastewater can be completely and effectively removed.
And washing the adsorbed magnetic bamboo fiber-based activated carbon material by using ethanol, wherein the eluent is blue. This demonstrates that the MB adsorbed into the material does not undergo a chemical change and can be gradually eluted from the material, further consolidating the recycling ability of the material.
5mL of 0.001% gentian violet solution was adsorbed by 1.0mg of magnetic bamboo fiber-based activated carbon material, and it can be seen from FIG. 5(b) that the spectrum of the solution changed from the initially higher blue curve to the final pale green curve close to the baseline as the adsorption time increased. The increase of the magnetic bamboo fiber based activated carbon material along with the adsorption time can be clearly obtained from the change condition of the spectrogram, the gentian violet in the adsorbed solution is less and less, and the gentian violet can be completely adsorbed within about 400 seconds. The magnetic bamboo fiber based active carbon material has good adsorption effect on gentian violet.
The magnetic bamboo fiber-based activated carbon material of 1.0mg is used for respectively adsorbing 10mg/L rhodamine 6G solution of 5mL, and the spectrographic spectrogram of the material changes from an initial higher pink curve to a final blue-green curve close to a baseline along with the increase of the adsorption time as shown in the attached figure 5 (c). The change condition of the spectrogram can clearly obtain that the rhodamine 6G in the adsorbed solution is less and less along with the increase of the adsorption time of the magnetic bamboo fiber-based activated carbon material, and the rhodamine can be completely adsorbed within about 300 s. The magnetic bamboo fiber-based activated carbon material has a good adsorption effect on rhodamine 6G.
As can be seen from the above examples, the magnetic bamboo fiber based activated carbon material has good applicability, has good adsorbability for most dyes, and provides a foundation for the wide application of the material.
The magnetic bamboo fiber based activated carbon material prepared in the example 2 is taken as a catalyst, and a certain amount of NaBH is added4And then, carrying out ultraviolet-visible spectrum analysis of a degradation experiment on the methylene blue under the optimized condition to obtain an ultraviolet-visible spectrum diagram in the attached figure 6.
Under the conditions of normal pH and 30 ℃, 10mL of 10mg/L MB solution is degraded by 1.5mg of magnetic bamboo fiber-based activated carbon material, wherein the degradation rate is 92.79% at 60s, 99.84% at 90s and 100% at 120 s. This demonstrates that the material has very good ability to degrade MB.
FIG. 6 is a UV-VIS spectrum of degraded MB in the range of 550-700 nm. As can be seen from FIG. 6, the spectral spectrum changes from the initially higher pink curve to the final blue-green curve approaching the baseline as the degradation time increases. From the change of the spectrogram, it can be clearly seen that when the magnetic bamboo fiber-based activated carbon material is used as a catalyst, the MB of the MB solution after degradation almost disappears completely with the increase of the degradation time, which also proves that the catalytic degradation capability of the magnetic bamboo fiber-based activated carbon material is quite excellent. To demonstrate that the material in this study was primarily degrading rather than adsorbing MB solution, the degraded material was subjected to ethanol desorption, shaking overnight at 30 ℃ and no MB was desorbed. Indicating that MB has been completely degraded. Therefore, the catalytic degradation characteristic of the magnetic bamboo fiber based activated carbon material is utilized, and dye pollutants such as methylene blue and the like in wastewater can be effectively removed.
MB adsorbed on the magnetic bamboo fiber based activated carbon material can be desorbed by ethanol, so that the magnetic bamboo fiber based activated carbon material washed by the ethanol can adsorb dye again, and the reusability of the magnetic bamboo fiber based activated carbon material is researched. The procedure was repeated, after saturating a sufficient amount of MB with the material prepared in example 2, by washing the material with ethanol until the last elution was blue, which confirmed that the MB adsorbed in the material had been substantially eluted. Drying the material, weighing 1.5mg to adsorb 10mL of 10mg/L MB solution, measuring the adsorption fraction after a certain period of time, and repeating the steps for about 10 times to obtain a bar graph of the adsorption fraction of the magnetic bamboo fiber based activated carbon material to MB and the recycling times as shown in figure 7.
As can be seen from the column chart of the recycling of the material adsorption, when the number of times of recycling is 6, the adsorption fraction of the magnetic bamboo fiber-based activated carbon material to MB is quite high, close to 100%, and decreases from 7 th to 10 th, wherein the 9 th is about 90%, the 10 th is about 85%, and in general, the magnetic bamboo fiber-based activated carbon material has good recycling property.
Claims (6)
1. A magnetic bamboo fiber based activated carbon material is characterized in that: the material is mainly prepared from ferric salt, bamboo fiber raw materials and secondary distilled water, wherein the mass percentage content of metal is 20-35%; the ferric salt is any one of ferric ammonium oxalate, ferric chloride hydrate, ferric ammonium citrate and potassium oxalate ferrate; the weight portions of the preparation raw materials are as follows:
iron salt: 0.5-10 parts;
bamboo fiber raw material: 1-10 parts;
secondary distilled water: 5-100 parts;
the weight ratio of the ferric salt to the bamboo fiber raw material is 1:2 to 1: 1;
the preparation method of the magnetic bamboo fiber based activated carbon material comprises the following steps:
(1) according to the proportion of the ferric salt, the bamboo fiber raw material and the secondary distilled water, adding the secondary distilled water into the ferric salt to completely dissolve the ferric salt, and uniformly soaking the bamboo fiber raw material into the completely dissolved ferric salt solution;
(2) sealing the ferric salt solution soaked with the bamboo fiber raw material, and placing for 20-30h in the dark;
(3) vacuum-drying at 55-65 deg.C in a vacuum drying oven, uniformly shearing the obtained material, and heating in a vacuum tube furnace under the protection of nitrogen gas to perform staged treatment; the staged treatment process comprises the following steps: firstly, heating to 500 ℃ at the heating rate of 5 ℃/min, and preserving heat for 1-2 h; then, raising the temperature to 700-900 ℃ for the second time, and preserving the heat for 1-2 hours to obtain the magnetic bamboo fiber based activated carbon material with the treatment temperature of the second heat preservation temperature.
2. The magnetic bamboo fiber-based activated carbon material as claimed in claim 1, wherein: the metal content in the material is 30-35% by mass.
3. The magnetic bamboo fiber-based activated carbon material as claimed in claim 1, wherein: the magnetic bamboo fiber based activated carbon is prepared from the following raw materials in parts by weight:
iron salt: 1-2 parts;
bamboo fiber raw material: 2 parts of (1);
secondary distilled water: 10-20 parts.
4. A preparation method of a magnetic bamboo fiber based activated carbon material comprises the following steps:
(1) the weight portions of the raw materials are as follows: iron salt: 0.5-10 parts of bamboo fiber raw material: 1-10 parts of secondary distilled water: 5-100 parts of iron salt and bamboo fiber raw materials in a weight ratio of 1:2 to 1: 1; the ferric salt is any one of ferric ammonium oxalate, ferric chloride hydrate, ferric ammonium citrate and potassium oxalate ferrate; according to the proportion of the ferric salt, the bamboo fiber raw material and the secondary distilled water, adding the secondary distilled water into the ferric salt to completely dissolve the ferric salt, and uniformly soaking the bamboo fiber raw material into the completely dissolved ferric salt solution;
(2) sealing the ferric salt solution soaked with the bamboo fiber raw material, and placing for 20-30h in the dark;
(3) vacuum-drying at 55-65 deg.C in a vacuum drying oven, uniformly shearing the obtained material, and heating in a vacuum tube furnace under the protection of nitrogen gas to perform staged treatment; the staged treatment process comprises the following steps: firstly, heating to 500 ℃ at the heating rate of 5 ℃/min, and preserving heat for 1-2 h; then, raising the temperature to 700-900 ℃ for the second time, and preserving the heat for 1-2 hours to obtain the magnetic bamboo fiber based activated carbon material with the treatment temperature of the second heat preservation temperature.
5. Use of a magnetic bamboo fibre-based activated carbon material according to any one of claims 1-3 in wastewater treatment.
6. Use of a magnetic bamboo fibre-based activated carbon material according to any one of claims 1-3 in the treatment of dye-containing industrial waste water.
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