CN110813240A - Preparation method and application of ultrahigh-performance biomass-based banana peel oriented activated carbon VOCs adsorbent - Google Patents
Preparation method and application of ultrahigh-performance biomass-based banana peel oriented activated carbon VOCs adsorbent Download PDFInfo
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Abstract
The invention relates to a preparation method and application of an ultrahigh-performance biomass-based banana peel oriented activated carbon VOCs adsorbent, wherein banana peel is cut into pieces, washed clean, and subjected to high-temperature carbonization to prepare biochar; then mixing the banana peel biochar with KOH according to a ratio, and then carrying out high-temperature activation to obtain the final banana peel biochar. The invention has the advantages that: the banana peel biochar prepared by taking banana peel as a carbon source and KOH as a dehydrating agent has ultrahigh specific surface area and pore volume and ultrahigh adsorption capacity on VOCs gas; the raw materials adopted by the invention have sufficient sources, low production cost, simple material preparation process, easy operation, good reproducibility and good adsorption performance; the method realizes the high-efficiency utilization of the waste banana peel, solves the problem of processing the waste banana peel, improves the utilization efficiency of the biochar resources, and expands the application of the biochar in the field of environmental protection.
Description
Technical Field
The invention belongs to the technical field of adsorption materials, and particularly relates to a preparation method and application of an ultrahigh-performance biomass-based banana peel oriented activated carbon VOCs adsorbent.
Background
Bananas are one of the four most important fruits in the world, and China is one of the countries in the world where the bananas are produced in the largest quantity. In the development of the banana processing industry, a large amount of waste such as banana peel is also generated. Since the banana peel accounts for 40% of the total weight of the banana, it is necessary to utilize it. The biochar is an adsorbent with application potential, and waste biological resources are comprehensively utilized, so that the aim of changing waste into valuable is fulfilled.
Nowadays, the development of industrialization greatly improves the lives of people and promotes the development of society. But at the same time it also causes a series of serious environmental pollution problems. Volatile Organic Compounds (VOCs) are the main cause of urban photochemical pollution. They can also lead to human cancer and respiratory diseases. Because of the double harm to the environment and human health, the traditional Chinese medicine composition has become a global environmental protection problem and is more and more valued by governments of various countries. In order to effectively solve the problem of air pollution caused by VOCs (volatile organic Compounds)The Goldeberg protocol was co-established and emission limits for VOCs were strictly regulated. Therefore, the development of effective techniques for removing VOCs has become an important research focus. The biochar material has attracted social attention due to the easily available carbon source, simple preparation process and excellent performance, and is widely applied to the fields of supercapacitors, wastewater treatment and the like in recent years, for example, patent CN 109126714A discloses TiO2/SiO2-a preparation method of a banana peel biochar composite adsorbing material and the prepared adsorbing material, which comprises the following steps: cleaning banana peel, drying, crushing, sieving to obtain a powdery material, mixing with a phosphoric acid solution, oscillating, filtering, and drying to obtain phosphoric acid modified banana peel powder; TiO is treated by sol-gel method2And SiO2Loading on the modified banana peel biochar surface to prepare TiO2/SiO2The method has the advantages of simple process and low cost, the prepared composite adsorbing material has obvious adsorbing effect on the herbicide quinclorac, and TiO with photodegradable organic pollutants in the composite material2The adsorption capacity is solved, and the synergy of the adsorption and photocatalytic degradation of the quinclorac by the composite adsorption material can be utilized.
Disclosure of Invention
The invention aims to provide a preparation method and application of an ultrahigh-performance biomass-based banana peel oriented activated carbon VOCs adsorbent, which is simple in synthesis method, does not harm the environment and is high in repeatability.
In order to solve the technical problems, the technical scheme of the invention is as follows: a preparation method of an ultrahigh-performance biomass-based banana peel oriented activated carbon VOCs adsorbent is characterized by comprising the following steps: the preparation method comprises the following steps:
step 1: cutting banana peel, cleaning with distilled water, putting into an oven at 100-120 ℃ after cleaning, and drying overnight;
step 2: putting the dried banana peels in the step 1 into a tube furnace for high-temperature carbonization;
and step 3: grinding the banana peel carbonized at high temperature into powder of 20-100 meshes to obtain the banana peel biochar;
and 4, step 4: uniformly mixing the banana peel biochar with KOH according to different alkali-carbon mass ratios;
and 5: putting the mixed alkali-carbon mixture into a tubular furnace, activating at high temperature, taking out after the activation, and washing and filtering to obtain filtrate and filter residue;
step 6: and (5) putting the filter residue obtained in the step (5) into an oven at 100-120 ℃, and drying overnight to obtain the biochar VOCs adsorbent.
Further, the carbonization condition temperature of the high-temperature carbonization in the step 2 is 300-500 ℃, and the carbonization time is 1-3 h.
Further, the mass ratio of KOH to the banana peel biochar in the step 4 is 1: 1-4: 1.
Further, in the step 4, the banana peel biochar and KOH are uniformly mixed according to different alkali-carbon mass ratios, and the specific steps are as follows:
s1: putting KOH into deionized water, stirring and dissolving, pouring banana skin biochar, stirring for 1-3 hours to form a mixture, wherein the ratio of the banana skin biochar to the deionized water is 1g to 10ml of deionized water;
s2: and (3) placing the mixture in a vacuum drying oven at 110-120 ℃, and drying for 8-12 h to obtain the alkali-carbon mixture.
Further, the activation temperature of the high-temperature activation in the step 5 is 700-850 ℃, and the activation time is 1-3 h.
The application of the biochar VOCs adsorbent is characterized in that: the biochar VOCs adsorbent is applied to adsorption of VOCs gas.
Further, the VOCs gas is benzene or toluene.
The invention has the advantages that:
(1) preparation method of ultrahigh-performance biomass-based banana peel oriented activated carbon VOCs adsorbent and adsorbent prepared by methodThe application and the preparation process are simple, the reproducibility is good, no additional harm is caused to the environment, the utilization of the banana peel waste is realized, the problem of treatment of the banana peel waste is solved, and the obtained biochar has ultrahigh adsorption capacity of 20-30 mmol g of VOCs gas-1The adsorbent is the highest reported in the literature at present, has great social benefit and economic benefit, and is particularly suitable for the selective adsorption of toluene and benzene under the water vapor condition.
(2) The invention relates to a preparation method and application of an ultrahigh-performance biomass-based banana peel oriented activated carbon VOCs adsorbent, wherein banana peel is cleaned and dried overnight, moisture contained in banana peel is fully dried as much as possible, then a two-step high-temperature carbonization method is adopted, the first high-temperature carbonization aims at obtaining basic coke used for subsequent high-temperature activation, and in the process, three types of substances are mainly generated: coke, tar, gas; wherein tar and gas flow out along with flowing nitrogen, and the interior of the primary coke can generate some initial pores due to the loss of the tar and the gas generated by pyrolysis, the generation of the pores is more beneficial to the next step of mixing with KOH, and a part of KOH can enter the pores of the coke; so that more sufficient activation reaction is carried out during activation, the porosity is improved, and the specific surface area and the pore volume of the material are further improved; finally, the product is dried overnight again, and the washed and filtered product contains a large amount of moisture, wherein some moisture is located in the pore passages and is not easy to evaporate, so that the drying is carried out overnight, the drying time is prolonged, and the moisture which is difficult to remove can be dried.
(3) Aiming at the scheme of alkali-carbon mixing, the method adopts a method of mixing and stirring biochar and KOH solution, compared with the conventional common KOH solution impregnation method, the method adopts the stirring and mixing method for shorter time, the conventional impregnation method usually needs to be impregnated for 12-24 hours, only 1-3 hours, and compared with the conventional method of directly grinding and mixing KOH and biochar, the method adopts a method of mixing aqueous solution, so that KOH can enter pores in the biochar, and the method has the advantages that the pores generated originally can be shrunk along with the extension of the activation time in the later-stage activation; at the moment, KOH left in the pore channel after pore-forming reaction can play a role in preventing pore diameter shrinkage, and after the activation reaction is finished and filtered and washed, KOH in the pore channel is washed away, so that pores are left.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a powder X-ray diffraction pattern of the ultra-high performance biomass-based banana peel oriented activated carbon VOCs adsorbent of examples 4-6.
Fig. 2 is an SEM image of the ultra-high performance biomass-based banana peel oriented activated carbon VOCs adsorbent of example 5.
FIG. 3 is an adsorption isotherm of the ultra-high performance biomass-based banana peel oriented activated carbon VOCs adsorbent of examples 4-6 for toluene at 25 ℃.
FIG. 4 is an adsorption isotherm of the ultra-high performance biomass-based banana peel oriented activated carbon VOCs adsorbent of examples 4-6 on benzene at 25 ℃.
Fig. 5 shows the results of 5 adsorption-desorption cycles of the ultrahigh-performance biomass-based banana peel oriented activated carbon VOCs adsorbent on toluene in example 5, wherein the desorption condition is constant temperature of 150 ℃ for 3 hours.
Detailed Description
The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the scope of the embodiments described herein.
The invention discloses a preparation method of an ultrahigh-performance biomass-based banana peel oriented activated carbon VOCs adsorbent, which comprises the following steps:
step 1: cutting banana peel, cleaning with distilled water, putting into an oven at 100-120 ℃ after cleaning, and drying overnight;
step 2: putting the dried banana peels in the step 1 into a tube furnace for high-temperature carbonization;
and step 3: grinding the banana peel carbonized at high temperature into powder of 20-100 meshes to obtain the banana peel biochar;
and 4, step 4: uniformly mixing the banana peel biochar and KOH according to different alkali-carbon mass ratios, specifically, firstly placing KOH in deionized water, stirring and dissolving, then pouring the banana peel biochar into the deionized water, stirring the mixture together (the ratio of the biochar to the water is 1g to 10ml of deionized water), stirring the mixture for 1 to 3 hours, then placing the mixture in a vacuum drying oven at the temperature of between 110 and 120 ℃, and drying the mixture for 8 to 12 hours to obtain an alkali-carbon mixture;
and 5: putting the mixed alkali-carbon mixture into a tubular furnace, activating at high temperature, taking out after the activation, and washing and filtering to obtain filtrate and filter residue;
step 6: and (5) putting the filter residue obtained in the step (5) into an oven at 100-120 ℃, and drying overnight to obtain the biochar VOCs adsorbent.
As an example, the most specific implementation mode is that the carbonization temperature of the high-temperature carbonization in the step 2 is 300-500 ℃, and the carbonization time is 1-3 h; the mass ratio of KOH to the banana peel biochar in the step 4 is 1: 1-4: 1, the activation temperature of high-temperature activation in the step 5 is 700-850 ℃, and the activation time is 1-3 h.
The banana peel biochar prepared by the invention is para-benzene (27.55 mmol g)-1) And toluene (23.82 mmol g)-1) The highest adsorption capacity of the steam is the highest in the same type of adsorbent.
The preparation method of the ultrahigh-performance biomass-based banana peel oriented activated carbon VOCs adsorbent is described in detail by the following specific examples:
example 1
Cutting banana peel, cleaning, putting into an oven at 100-120 ℃ for drying, putting the dried banana peel into a tube furnace for high-temperature carbonization at 300 ℃ for 1-3 h, then naturally cooling to room temperature, grinding and crushing carbonized banana peel biochar, mixing with KOH aqueous solution according to the mass ratio of 1:1 of alkali to carbon, stirring for 1 h, then putting the mixture into a vacuum drying oven at 110-120 ℃, and drying for 8-12 h to obtain an alkali-carbon mixture; and then activating at 700 ℃ for 1-3 h, naturally cooling to room temperature, taking out, washing, filtering, and putting into a 100-120 ℃ oven for overnight drying to obtain the biochar VOCs adsorbent.
Example 2
Cutting banana peel, cleaning, putting into an oven at 100-120 ℃ for drying, putting the dried banana peel into a tube furnace for high-temperature carbonization at 400 ℃ for 1-3 h, then naturally cooling to room temperature, grinding and crushing carbonized banana peel biochar, mixing with KOH aqueous solution according to the mass ratio of 2:1 of alkali to carbon, stirring for 1 h, then putting the mixture into a vacuum drying oven at 110-120 ℃, and drying for 8-12 h to obtain an alkali-carbon mixture; and then activating at 800 ℃ for 1-3 h, naturally cooling to room temperature, taking out, washing, filtering, and putting into a 100-120 ℃ oven for overnight drying to obtain the biochar VOCs adsorbent.
Example 3
Cutting banana peel, cleaning, putting into an oven at 100-120 ℃ for drying, putting the dried banana peel into a tube furnace for high-temperature carbonization at 500 ℃ for 1-3 h, then naturally cooling to room temperature, grinding and crushing carbonized banana peel biochar, mixing with KOH aqueous solution according to the mass ratio of 3:1 of alkali to carbon, stirring for 2h, then putting the mixture into a vacuum drying oven at 110-120 ℃, and drying for 8-12 h to obtain an alkali-carbon mixture; and then activating at 900 ℃ for 1-3 h, naturally cooling to room temperature, taking out, washing, filtering, and putting into a 100-120 ℃ oven for overnight drying to obtain the biochar VOCs adsorbent.
Example 4
Cutting banana peel, cleaning, putting into an oven at 100-120 ℃ for drying, putting the dried banana peel into a tube furnace for high-temperature carbonization at 300 ℃ for 1-3 h, then naturally cooling to room temperature, grinding and crushing the carbonized banana peel biochar, mixing with KOH aqueous solution according to the mass ratio of 2:1 of alkali to carbon, stirring for 2h, then putting the mixture into a vacuum drying oven at 110-120 ℃, and drying for 8-12 h to obtain an alkali-carbon mixture; and then activating at 800 ℃ for 1-3 h, naturally cooling to room temperature, taking out, washing, filtering, and putting into a 100-120 ℃ oven for overnight drying to obtain the biochar VOCs adsorbent.
Example 5
Cutting banana peel, cleaning, putting into an oven at 100-120 ℃ for drying, putting the dried banana peel into a tube furnace for high-temperature carbonization at 500 ℃ for 1-3 h, then naturally cooling to room temperature, grinding and crushing carbonized banana peel biochar, mixing with KOH aqueous solution according to the mass ratio of 3.5:1 of alkali to carbon, stirring for 2h, then putting the mixture into a vacuum drying oven at 110-120 ℃, and drying for 8-12 h to obtain an alkali-carbon mixture; and then activating at 800 ℃ for 1-3 h, naturally cooling to room temperature, taking out, washing, filtering, and drying in an oven at 100-120 ℃ overnight to obtain the biochar VOCs adsorbent.
Example 6
Cutting banana peel, cleaning, putting into an oven at 100-120 ℃ for drying, putting the dried banana peel into a tube furnace for high-temperature carbonization at 400 ℃ for 1-3 h, then naturally cooling to room temperature, grinding and crushing carbonized banana peel biochar, mixing with KOH aqueous solution according to the mass ratio of 4:1 of alkali to carbon, stirring for 3h, then putting the mixture into a vacuum drying oven at 110-120 ℃, and drying for 8-12 h to obtain an alkali-carbon mixture; and then activating at 800 ℃ for 1-3 h, naturally cooling to room temperature, taking out, washing, filtering, and putting into a 100-120 ℃ oven for overnight drying to obtain the biochar VOCs adsorbent.
The biochar obtained in examples 4-6 (named BC for this biochar, followed by the corresponding alkali carbon ratio and activation temperature) was subjected to powder X-ray diffraction characterization, powder X-ray diffraction data collection was performed on a Shimadzu XRD6000 diffractometer, Japan, with a tube voltage of 40 KV, a tube current of 30 mA, using Cu K α radiation monochromatized with graphite, data collection was performed using a theta/2 theta scanning mode with continuous scanning in the range of 10 DEG to 60 DEGCompleted with a scanning speed of 3 deg. min-1. The powder diffraction results are shown in fig. 1, which is the XRD pattern of a typical amorphous carbon material, but the presence of two broad peaks suggests the presence of a small amount of crystalline carbon.
Fig. 2 is an SEM image of the biochar obtained in example 5, and the morphology and structure of the sample were observed by scanning electron microscopy (SEM, ZEISS merlin compact), and the morphology of the carbon material was in an amorphous state, which is consistent with the conclusion of XRD.
FIG. 3 is an adsorption isotherm of the biochar obtained in examples 4-6 for toluene at 25 ℃ and it can be seen that the maximum adsorption amount of the material for toluene can reach 2000 mg g-1The above are outstanding among similar materials. The biological carbon is very suitable for adsorbing toluene steam and has great potential application value.
FIG. 4 is an adsorption isotherm of benzene at 25 ℃ for the biochar obtained in examples 4-6. Similarly, the adsorption capacity of the benzene gas can reach the striking 2000 mg g-1The above. Such performance is also highest in class. This indicates that the material is well suited for treating VOCs gases.
Fig. 5 is the results of 5 adsorption-desorption cycles of toluene on the charcoal adsorbent in example 5. The desorption condition is constant temperature of 150 ℃ for 3 hours, the stability of the material is very good, and the performance of the material is still very stable under continuous work, which indicates that the service life of the material is good, and the material is suggested to have potential application value.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A preparation method of an ultrahigh-performance biomass-based banana peel oriented activated carbon VOCs adsorbent is characterized by comprising the following steps: the preparation method comprises the following steps:
step 1: cutting banana peel, cleaning with distilled water, putting into an oven at 100-120 ℃ after cleaning, and drying overnight;
step 2: putting the dried banana peels in the step 1 into a tube furnace for high-temperature carbonization;
and step 3: grinding the banana peel carbonized at high temperature into powder of 20-100 meshes to obtain the banana peel biochar;
and 4, step 4: uniformly mixing the banana peel biochar with KOH according to different alkali-carbon mass ratios;
and 5: putting the mixed alkali-carbon mixture into a tubular furnace, activating at high temperature, taking out after the activation, and washing and filtering to obtain filtrate and filter residue;
step 6: and (5) putting the filter residue obtained in the step (5) into an oven at 100-120 ℃, and drying overnight to obtain the biochar VOCs adsorbent.
2. The method for preparing the ultra-high performance biomass-based banana peel oriented activated carbon VOCs adsorbent according to claim 1, wherein the method comprises the following steps: and 2, carbonizing at the high temperature in the step 2 at the temperature of 300-500 ℃ for 1-3 h.
3. The method for preparing the ultra-high performance biomass-based banana peel oriented activated carbon VOCs adsorbent according to claim 1, wherein the method comprises the following steps: the mass ratio of the KOH to the banana peel biochar in the step 4 is 1: 1-4: 1.
4. The method for preparing the ultra-high performance biomass-based banana peel oriented activated carbon VOCs adsorbent according to claim 1, wherein the method comprises the following steps: in the step 4, the banana peel biochar and KOH are uniformly mixed according to different alkali-carbon mass ratios, and the specific steps are as follows:
s1: putting KOH into deionized water, stirring and dissolving, pouring banana skin biochar, stirring for 1-3 hours to form a mixture, wherein the ratio of the banana skin biochar to the deionized water is 1g to 10ml of deionized water;
s2: and (3) placing the mixture in a vacuum drying oven at 110-120 ℃, and drying for 8-12 h to obtain the alkali-carbon mixture.
5. The method for preparing the ultra-high performance biomass-based banana peel oriented activated carbon VOCs adsorbent according to claim 1, wherein the method comprises the following steps: the activation temperature of the high-temperature activation in the step 5 is 700-850 ℃, and the activation time is 1-3 h.
6. The use of the ultra-high performance biomass-based banana peel oriented activated carbon VOCs adsorbent of claim 1, wherein: the biochar VOCs adsorbent is applied to adsorption of VOCs gas.
7. The use of the ultra-high performance biomass-based banana peel oriented activated carbon VOCs adsorbent as claimed in claim 6, wherein: the VOCs gas is benzene or toluene.
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