CN114984912A - Method for preparing biomass charcoal material from pericarp of citrus - Google Patents
Method for preparing biomass charcoal material from pericarp of citrus Download PDFInfo
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- CN114984912A CN114984912A CN202210695094.3A CN202210695094A CN114984912A CN 114984912 A CN114984912 A CN 114984912A CN 202210695094 A CN202210695094 A CN 202210695094A CN 114984912 A CN114984912 A CN 114984912A
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- biomass charcoal
- pyrolysis
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Images
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
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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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present disclosure provides a method for preparing biomass charcoal material from citrus peel, comprising: pretreating pericarp of citrus; carrying out anaerobic pyrolysis on the pretreated fruit peel in the atmosphere of inert gas, so that biomass in the pretreated fruit peel is heated and decomposed to form hot steam, and obtaining a pyrolysis product; and cleaning and drying the pyrolysis product to obtain the biomass charcoal material. The prepared biomass charcoal material contains huge specific surface area and porous structure, and simultaneously has more oxygen-containing functional groups on the surface of the biochar, when the biomass charcoal material is used as an adsorbing material to remove persistent organic pollutants in water, the pollutants can be intercepted through the complicated gully shapes on the surface of the biomass charcoal material, and meanwhile, the oxygen-containing functional groups on the surface of the biomass charcoal material can also enhance the binding force with the organic pollutants, so that the biomass charcoal material can firmly adsorb the organic pollutants on the surface of the biochar when water quality purification is carried out, and has a better water quality purification effect.
Description
Technical Field
The disclosure relates to the technical field of biomass, in particular to a method for preparing a biomass charcoal material from citrus peels.
Background
Biochar is a carbon-rich material produced by pyrolysis (generally < 700 ℃) under anoxic or hypoxic conditions, based on biomass resources widely existing in nature. The research level of purifying water quality by using the biochar material still stays in the experimental exploration or demonstration engineering stage at present, and the application of water treatment is influenced by various factors. The adsorption mechanism and the application conditions are not clear, and the regulation and control rule of the adsorption performance of the biochar material still needs to be further researched. As a green water purification technology with low energy consumption and no pollution, the biochar technology continuously improves the process conditions and the actual application level. However, the existing preparation method of the biomass material is complex, high in cost, limited in adsorption capacity and rarely applied to actual water, so that a preparation method of the biochar, which is simple in process, low in cost and capable of being produced in a large scale, is needed to realize popularization and application of the biochar material for water purification.
Disclosure of Invention
To at least partially address at least one of the above-mentioned technical deficiencies, embodiments of the present disclosure provide a method for preparing biomass charcoal material from citrus peel using anaerobic pyrolysis to prepare biomass-derived charcoal from citrus peel for use as an adsorbent material to remove persistent organic contaminants in water.
To achieve the above object, as an embodiment of one aspect of the present disclosure, there is provided a method of preparing a biomass char material from citrus peel, comprising: pretreating pericarp of citrus; carrying out anaerobic pyrolysis on the pretreated pericarp in an inert gas atmosphere, so that biomass in the pretreated pericarp is heated and decomposed to form hot steam, and obtaining a pyrolysis product; and cleaning and drying the pyrolysis product to obtain the biomass charcoal material.
According to an embodiment of the present disclosure, the anaerobic pyrolysis includes: partially decomposing cellulose and hemicellulose in the pretreated pericarp through a preheating process; and completely decomposing the residual cellulose and hemicellulose in the pretreated pericarp through a pyrolysis process, and growing a carbon skeleton hierarchical porous structure.
According to the embodiment of the disclosure, the preheating process is executed under the conditions that the heating rate comprises 10-30 ℃/min, the temperature comprises 90-110 ℃ and the time comprises 10-30 min.
According to the embodiment of the disclosure, the pyrolysis process is performed under the conditions that the heating rate comprises 10 ℃/min to 30 ℃/min, the temperature comprises 600 ℃ to 800 ℃, and the time comprises 2h to 3 h.
According to an embodiment of the present disclosure, the temperature increase rate of the preheating process and the pyrolysis process is the same.
According to an embodiment of the present disclosure, the citrus may include any one of orange, mandarin orange, kumquat, pomelo, and poncirus trifoliata; the pretreatment process is carried out under the conditions that the temperature is 60-150 ℃ and the time is 1-24 h; the inert gas is selected from argon or nitrogen with the purity of more than 99.999 percent, wherein the flow rate of the inert gas comprises 60mL/min to 80 mL/min.
According to the embodiment of the present disclosure, the pH of the washing solution obtained at the end of the above washing process is 7; the drying step is carried out under the conditions that the temperature is 70-80 ℃ and the time is 10-12 h.
As an embodiment of another aspect of the disclosure, an application of the biomass charcoal material obtained by the preparation method in the aspect of removing persistent organic pollutants in water by adsorption is provided.
According to an embodiment of the present disclosure, the persistent organic contaminant includes a phthalate-based contaminant.
The method for preparing the biomass charcoal material from the citrus peel provided by the embodiment of the disclosure uses the anaerobic pyrolysis method to prepare the citrus peel into the biomass-derived charcoal. In the pyrolysis process, biomass in the peels of the citrus is heated and decomposed to form hot steam, and the hot steam can enable the biomass charcoal material to form a large amount of pore structures; hemicellulose, cellulose and the like in the citrus peel are decomposed, and a large amount of oxygen-containing functional groups are generated on the surface of the biomass charcoal material; aromatic compounds in citrus peel react to form persistent radical species in the presence of metal oxides within the biomass in the citrus peel. The prepared biomass charcoal material has huge specific surface area and porous structure, and can be used as an adsorbing material for removing persistent organic pollutants in water.
Drawings
Fig. 1 is a macroscopic view of a biomass char material produced by example 5 of a method of producing a biomass char material from citrus peel according to an exemplary embodiment of the present disclosure;
fig. 2A is a Scanning Electron Microscope (SEM) image at 100000 magnifications of a biochar material prepared by example 1 of a method of preparing a biochar material from citrus peel according to an exemplary embodiment of the disclosure;
fig. 2B is a Scanning Electron Microscope (SEM) image at 100000 magnifications of a biochar material prepared by example 3 of a method of preparing a biochar material from citrus peel according to an exemplary embodiment of the disclosure;
fig. 2C is a Scanning Electron Microscope (SEM) image at 100000 magnifications of a biochar material prepared by example 5 of a method of preparing a biochar material from citrus peel according to an exemplary embodiment of the disclosure;
fig. 3A is a Scanning Electron Microscope (SEM) image at 5000 magnification of a biomass char material produced according to example 5 of a method of producing a biomass char material from citrus peel, according to an exemplary embodiment of the present disclosure;
fig. 3B is an EDS (X-ray energy spectroscopy) plot of element C corresponding to a Scanning Electron Microscope (SEM) plot at 5000 magnification for a biomass char material of a peel of an orange prepared according to example 5 of a method of preparing a biomass char material from a peel of a citrus according to an exemplary embodiment of the present disclosure;
fig. 3C is an EDS plot of X-ray energy spectrum analysis of O element at 5000 magnification for the biomass char material of the peel of citrus prepared according to example 5 of the method of preparing biomass char material from the peel of citrus according to an exemplary embodiment of the present disclosure;
fig. 3D is an EDS diagram of X-ray energy spectrum analysis of Fe element at 5000 magnification for the biomass char material of the peel of oranges prepared according to example 5 of the method of preparing biomass char material from the peel of citrus according to an exemplary embodiment of the present disclosure;
fig. 3E is an EDS diagram of X-ray energy spectrum analysis of Cu element at 5000 magnification for the biomass char material of the peel of oranges prepared according to example 5 of the method of preparing biomass char material from the peel of citrus according to an exemplary embodiment of the present disclosure;
FIG. 4 is a graph of an infrared spectrum (FT-IR) characterization of biochar material from peel of oranges prepared by example 5 of a method of preparing biochar material from peel of citrus according to an exemplary embodiment of the disclosure;
FIG. 5 is a graph of surface persistent free radical characterization of biochar material from citrus peel, prepared according to example 5 of a method of preparing biochar material from citrus peel according to an exemplary embodiment of the disclosure; and
fig. 6 is a graph showing the effect of removing dimethyl phthalate from water using biomass charcoal material of pericarp of orange prepared under different conditions as an adsorbing material in examples 7 to 12 of the method for preparing biomass charcoal material from pericarp of citrus according to the present disclosure.
Detailed Description
For the purpose of promoting a better understanding of the objects, aspects and advantages of the present disclosure, reference is made to the following detailed description taken in conjunction with the accompanying drawings.
The biochar not only has a rich pore structure and a larger specific surface area, but also has high aromatizing, physical thermal stability and biochemical anti-decomposition performance. These characteristics make the biological carbon as excellent adsorbing material for repairing polluted water environment. The mechanism related to the water purification function realized by the biological carbon adsorption mainly comprises the actions of micropore and gap capture, pi-pi bond, surface functional group action, phosphorus-containing organic matter complexation and the like. At present, researches on the use of biochar in removing polycyclic aromatic hydrocarbon, tylosin, sulfadiazine, heavy metals, environmental nano materials and the like in water have been carried out, and the biochar shows equivalent adsorption removal performance. The biomass charcoal material also has high plasticity, and can be used for doping heteroatoms into a charcoal network and introducing metal ions into the surface of the charcoal so as to improve the expected adsorption performance of the charcoal material on persistent pollutants in water.
According to a general inventive concept of an aspect of the present disclosure, there is provided a method of preparing a biomass charcoal material from citrus peel, including: pretreating pericarp of citrus; carrying out anaerobic pyrolysis on the pretreated pericarp in an inert gas atmosphere, so that biomass in the pretreated pericarp is heated and decomposed to form hot steam, and obtaining a pyrolysis product; and cleaning and drying the pyrolysis product to obtain the biomass charcoal material.
The method for preparing biomass charcoal material from citrus peel provided by the embodiment of the disclosure uses an anaerobic pyrolysis method to prepare biomass-derived charcoal from citrus peel. In the pyrolysis process, biomass in the peel of the citrus is heated and decomposed to form hot steam, and the hot steam can enable the biomass charcoal material to form a large number of pore structures, so that the specific surface area is improved; hemicellulose, cellulose, and the like inside the citrus peel are decomposed, and a large amount of oxygen-containing functional groups are generated on the surface of the biomass charcoal material. In addition, during pyrolysis, aromatic compounds in citrus peel react to form persistent radical species in the presence of metal oxides within the biomass in the citrus peel. In addition, the precursor for preparing the biomass charcoal material in the embodiment of the disclosure is citrus peel, and has the characteristics of wide source and low cost; the method disclosed by the embodiment of the disclosure has the advantages of simple preparation steps, no special equipment requirement and environmental friendliness.
In some embodiments of the present disclosure, the oxygen-free pyrolysis process includes a preheating process and a pyrolysis process. The preheating process can not only primarily decompose hemicellulose and cellulose in the peels of the citrus, but also facilitate the carbonization process in the pyrolysis process; meanwhile, the furnace tube can be preheated, so that the cracking caused by the rapid temperature rise of the furnace tube of the tube furnace is prevented. The citrus peel is sintered in the pyrolysis process, so that on one hand, pyrolysis steam is generated to enable the citrus peel to generate an internal pore structure and surface micropores, and the improvement of the specific surface area is facilitated; on the other hand, the method is beneficial to the reaction of biomass such as aromatic compounds, cellulose, lignin and the like of the citrus peels to generate surface oxygen-containing functional groups.
In some disclosed embodiments, the method for preparing biomass charcoal material from citrus peel comprises the following specific steps:
(1) performing a pretreatment process on the peel of citrus under the conditions that the temperature is 60-150 ℃ and the time is 1-24 h, for example, the temperature is 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, preferably 150 ℃, and the time is 3h, 10h, 15h, 18h, 22 h, preferably 24 h;
(2) performing anaerobic pyrolysis on the pretreated pericarp in an inert gas atmosphere selected from argon or nitrogen with purity of more than 99.999% to obtain a pyrolysis product; the flow rate of the inert gas is, for example, 60mL/min to 80mL/min, for example, 65mL/min, 70mL/min or 78mL/min, preferably 60 mL/min. The inert gas is used as the protective gas, so that the situation that the peels of the citrus are not fully combusted or the carbonization degree is low in the anaerobic pyrolysis process can be prevented. In addition, the economic cost of high purity nitrogen is more economical than argon. The nitrogen flow rate is suitable for ensuring the anoxic atmosphere and preventing the citrus peel powder from being blown away by the nitrogen flow, which causes the blockage of the air holes of the reactor (such as a tube furnace) and the quality loss of the biomass charcoal material.
The specific process of anaerobic pyrolysis is as follows: firstly, the preheating process is executed under the conditions that the heating rate comprises 10 ℃/min-30 ℃/min, the temperature comprises 90-110 ℃ and the time comprises 10 min-30 min; for example, the temperature rise rate in the preheating process is 16 ℃/min, 18 ℃/min, 26 ℃/min, preferably 10 ℃/min; the temperature is 95 deg.C, 98 deg.C, 105 deg.C, 108 deg.C, preferably 100 deg.C; the time is 12min, 15min, 18min, 26min, preferably 20 min; then, the pyrolysis process is carried out under the conditions that the heating rate comprises 10 ℃/min to 30 ℃/min, the temperature comprises 600 ℃ to 800 ℃, and the time comprises 1h to 3h, for example, the heating rate is 13 ℃/min, 17 ℃/min, 23 ℃/min, 28 ℃/min, preferably 10 ℃/min; the temperature is 650 deg.C, 680 deg.C, 700 deg.C, 750 deg.C, 780 deg.C, preferably 800 deg.C; the time is 1.2h, 1.5h, 2.2h, 2.5h, 2.8h, preferably 2 h. Among them, the preheating process and the pyrolysis process have the same temperature rise rate, and the reasons for the specific explanation include the following two aspects: on one hand, the preheating process ensures that the reactor (such as a tube furnace) cannot be cracked due to large-scale change of temperature in a short time; on the other hand, in the process from preheating to pyrolysis, the constant and slow heating rate is favorable for gradual generation of a hierarchical porous structure and a precise pore structure of the biomass charcoal material, and can also enhance the physicochemical characteristics of biomass such as lignocellulose and the like, and is favorable for retention of oxygen elements in the biomass charcoal material, so that the adsorption capacity of the biomass charcoal material to pollutants is enhanced.
(3) Washing the obtained pyrolysis product until the pH value of the washing liquid is 7, and drying the solid obtained after washing under the conditions of 70-80 ℃ and 10-12 h, wherein the temperature is 72 ℃, 74 ℃, 76 ℃, 78 ℃, and 70 ℃ is preferred; the time is 10.5h, 10.6h, 11h, 11.2h, 11.5h, preferably 12 h. Wherein, the obtained pyrolysis product is washed for a plurality of times by using a solvent (such as ultrapure water) until the washing solvent (such as ultrapure water) is neutral, and impurities on the surface of the biomass charcoal material can be washed away so as to eliminate the influence of the existence of the impurities on the pollutant adsorption performance of the biomass charcoal material in the water purification process of the biomass charcoal material; the obtained pyrolysis product is dried to remove moisture in the biomass charcoal material and slow down natural oxidation of the biomass charcoal material caused by the presence of moisture in the long-term storage process.
In some embodiments of the present disclosure, citrus includes any of mandarin, orange, kumquat, pomelo, and poncirus trifoliata.
According to another general inventive concept of the present disclosure, there is provided an application of the biomass charcoal material obtained by the above preparation method in removing persistent organic pollutants in water by adsorption.
When the biomass charcoal material obtained by the preparation method of the biomass charcoal material provided by the embodiment of the disclosure is used as an adsorbing material for removing persistent organic pollutants in water, the pollutants can be intercepted through the complicated gully shapes on the surface of the biomass charcoal material, meanwhile, the oxygen-containing functional groups on the surface of the biomass charcoal material can also enhance the binding force with the organic pollutants, so that the organic pollutants can be firmly adsorbed on the surface of the biomass charcoal material during water purification, and a good water purification effect is achieved.
In some embodiments of the present disclosure, the persistent organic contaminant comprises a phthalate-based contaminant.
In some embodiments of the present disclosure, the phthalate-based contaminants include at least one of dimethyl phthalate, dibutyl phthalate, and diesters of phthalic acid.
The disclosure is further illustrated by the following comparative examples and examples. In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough explanation of the embodiments of the disclosure. It may be evident, however, that one or more embodiments may be practiced without these specific details. Moreover, the details of the following embodiments may be combined arbitrarily into other possible embodiments, without conflict.
Example 1
Method for preparing biomass charcoal material from pericarp of citrus
S1: pretreating fresh pericarpium Citri Tangerinae
The method comprises the following specific steps: firstly, crushing peel of fresh oranges into small pieces with different sizes by using scissors, and cleaning the peel of the oranges by using ultrapure water; then, drying the cleaned orange peel in an oven at 150 ℃ for 24 hours; then, the dried orange peel was ground into powder using a mortar and sieved through a 80-mesh sieve to obtain an orange peel powder.
S2: performing anaerobic pyrolysis on the pretreated pericarp in inert gas atmosphere to obtain pyrolysis product
The method comprises the following specific steps: firstly, placing orange peel powder obtained in S1 in a quartz boat, and placing the whole in a tubular graphite furnace; secondly, a preheating process is executed: raising the temperature to 100 ℃ at a heating rate of 10 ℃/min, and maintaining the temperature at 100 ℃ for 20 min; next, a pyrolysis process is performed: raising the temperature to 600 ℃ at a heating rate of 10 ℃/min and maintaining the temperature at 600 ℃ for 2 h; and finally, naturally cooling to room temperature, and taking out the pyrolysis product.
S3: and cleaning and drying the pyrolysis product to obtain the biomass charcoal material.
The method comprises the following specific steps: firstly, repeatedly cleaning a pyrolysis product by using ultrapure water until the pH value of a washing water solution is 7.0; and then, putting the biomass charcoal obtained after washing in an oven at 60 ℃, and drying for 12h to obtain the biomass charcoal material of the pericarp of the orange.
S4: and (5) characterizing the specific surface area and a Scanning Electron Microscope (SEM) image of the biomass charcoal material obtained in S3.
The specific surface area of the biomass charcoal material of the pericarp of the orange prepared by the method that the anaerobic pyrolysis condition is 'the heating rate is 10 ℃/min and the pyrolysis temperature is 600 ℃' measured by a specific surface determinator is 0.0397m 2 /g。
FIG. 2A is a Scanning Electron Microscope (SEM) image of biomass charcoal material of pericarp of orange prepared under anaerobic pyrolysis condition of "temperature rise rate of 10 deg.C/min and pyrolysis temperature of 600 deg.C" under 100000 magnification.
Example 2
The procedure of example 1 was repeated except that "the temperature rising rate in the preheating process and the pyrolysis process in the step S2 was 20 ℃/min".
The specific surface area of the biomass charcoal material of the pericarp of the orange prepared by the method that the anaerobic pyrolysis condition is 'the heating rate is 20 ℃/min and the pyrolysis temperature is 600 ℃' measured by a specific surface determinator is 0.0688 m 2 /g。
Example 3
The procedure of example 1 was repeated, except that "the temperature of the pyrolysis process in the step S2 was 700 ℃.
The oxygen-free pyrolysis conditions measured by a specific surface analyzer are that the heating rate is 10 ℃/min, the pyrolysis temperatureSpecific surface area of biomass charcoal material of pericarp of orange prepared at 700 ℃ "was 3.8369 m 2 /g。
FIG. 2B is a Scanning Electron Microscope (SEM) image of biomass charcoal material of orange peel prepared under anaerobic pyrolysis conditions of "temperature rise rate of 10 deg.C/min and pyrolysis temperature of 700 deg.C" at 100000 magnifications.
Example 4
The procedure was as in example 1 except that "the temperature rising rate in the preheating process and the pyrolysis process in the step S2 was 20 ℃/min, and the temperature in the pyrolysis process was 700 ℃.
The specific surface area of the biomass charcoal material of the pericarp of the orange prepared by the anaerobic pyrolysis condition of' the heating rate is 20 ℃/min and the pyrolysis temperature is 700 ℃ measured by a specific surface determinator is 5.01m 2 /g。
Example 5
The procedure of example 1 was repeated, except that "the temperature of the pyrolysis process in the step S2 was 800 ℃.
The specific surface area of the biomass charcoal material of the peel of the orange prepared by the method is 324.5886m when the anaerobic pyrolysis condition measured by a specific surface determinator is that the temperature rise rate is 10 ℃/min and the pyrolysis temperature is 800 ℃ 2 /g。
FIG. 1 is a macroscopic view of biomass charcoal material of pericarp of orange prepared under anaerobic pyrolysis condition of "temperature rise rate of 10 deg.C/min and pyrolysis temperature of 800 deg.C".
As shown in fig. 1, the obtained biomass charcoal material is in a fine black powder form.
FIG. 2C is a Scanning Electron Microscope (SEM) image of the biomass charcoal material of pericarp of orange prepared under the anaerobic pyrolysis condition of "temperature rise rate of 10 deg.C/min and pyrolysis temperature of 800 deg.C" at a magnification of 100000.
As shown in fig. 2A to 2C, from the SEM results of examples 1, 3 and 5 of the present disclosure, it can be seen that, when the "anaerobic pyrolysis condition is a temperature rise rate of 10 ℃/min and a pyrolysis temperature of 800 ℃", a large amount of irregularly shaped particles are attached to the surface of the biomass charcoal material of the pericarp of the citrus fruit prepared, forming a complex concave or convex structure, which facilitates the biomass charcoal material to fix the pollutants on the surface thereof by entanglement and interception, and to remove the pollutants from the water. In addition, the oxygen-free pyrolysis condition is that the surface of the biomass charcoal material of the peel of the orange prepared when the heating rate is 10 ℃/min and the pyrolysis temperature is 800 ℃, has an unevenly distributed pore structure, and the opening degree of the pores is good. Under the magnification of 100000 times, the SEM pictures of 600 ℃ and 700 ℃ biochar can not observe the pore structure, and the SEM picture of 800 ℃ biochar still shows the existence of a fine pore structure, which is beneficial to the improvement of the specific surface area of 800 ℃ biochar and increases the adsorption performance of the biochar to pollutants.
FIG. 3A is a Scanning Electron Microscope (SEM) image at 5000 magnification of biomass charcoal material of pericarp of orange prepared under anaerobic pyrolysis condition of "temperature rise rate of 10 deg.C/min and pyrolysis temperature of 800 deg.C".
Fig. 3B, fig. 3C, fig. 3D, and fig. 3E are respectively an EDS (electron emission spectroscopy) diagram of C element, an EDS (electron emission spectroscopy) diagram of O element, an EDS (electron emission spectroscopy) diagram of Fe element, and an EDS (electron emission spectroscopy) diagram of Cu element corresponding to a Scanning Electron Microscope (SEM) diagram of the biomass charcoal material of the pericarp of the citrus fruit prepared under the anaerobic pyrolysis condition "temperature rise rate of 10 ℃/min and pyrolysis temperature of 800 ℃" of fig. 3A under 5000 magnification.
As shown in fig. 3A to 3E, the main constituent elements of the biomass charcoal material of the pericarp of orange prepared under the anaerobic pyrolysis condition "when the temperature rise rate is 10 ℃/min and the pyrolysis temperature is 800 ℃" are carbon and oxygen elements. The carbon skeleton structure of the biomass charcoal material is sporadically dispersed with trace metal elements such as copper, iron and the like, and the positions of the metal elements are overlapped with oxygen elements, so that the mineral elements are firmly present in the form of metal oxides or carbonates mainly in the biomass charcoal. The metal elements existing in the cells of the peel of the orange are beneficial to generating pyrolysis steam in the anaerobic pyrolysis process, provide secondary heat for biomass carbonization, and simultaneously are beneficial to forming an internal pore structure, so that the material transmission in the biochar is enhanced, and the adsorption rate of the biochar to persistent organic pollutants in water is improved.
FIG. 4 is an infrared spectrum characterization diagram of biomass charcoal material of pericarp of orange prepared under anaerobic pyrolysis conditions of "temperature rise rate of 10 ℃/min and pyrolysis temperature of 800 ℃".
As shown in fig. 4, the material composition and surface functional groups of biomass charcoal material of the pericarp of orange were analyzed by infrared spectroscopy test to find: the anaerobic pyrolysis condition is that C ═ N group and-CH-/CH in aromatic compound exist in biomass charcoal material of peel of orange prepared when the temperature rise rate is 10 ℃/min and the pyrolysis temperature is 800 ℃ 2 -structure, and a plurality of-OH structures in the biopolymer produced by the breakdown of cellulose. Thus, it is demonstrated that the surface of the biomass charcoal material prepared from citrus peel according to the embodiment of the present disclosure contains a certain amount of oxygen-containing functional groups, and the functional groups on the surface of the biomass charcoal material can form chemical bonds with pollutants, thereby enhancing the adsorption performance of the biomass charcoal material.
FIG. 5 is a graph showing the result of persistent radical characterization on the surface of biomass charcoal material of pericarp of orange prepared under anaerobic pyrolysis conditions of "temperature rise rate of 10 ℃/min and pyrolysis temperature of 800 ℃".
Persistent free radicals are generally classified into three classes according to the g-factor of the ESR test: oxygen-centered persistent radicals (g >2.0040, e.g., semiquinone radicals), carbon-centered persistent radicals (2.0040> g >2.0030), and carbon-centered radical species adjacent to an oxygen atom. As shown in FIG. 5, the persistent free radical signal with a g-factor of 2.00305 was detected on the surface of biomass charcoal material of pericarp of orange prepared under the anaerobic pyrolysis condition of "temperature rise rate of 10 ℃/min and pyrolysis temperature of 800 ℃", which proves that the pericarp of orange, which is the precursor of biomass, generates a large amount of persistent free radicals centered on charcoal during pyrolysis.
Furthermore, from the EDS characterization results of fig. 3B to 3E, it can be concluded that: the peel of fructus Citri Tangerinae contains transition metal elements (such as Cu and Fe) and aromatic compounds. At high temperature, aromatic compounds are adsorbed on the surface of transition metal particles by physical adsorption, electrons are transferred to the transition metal, and a large number of persistent radical species (P) centered on carbon and adjacent to an oxygen atom are generatedFR· ﹣ ). The persistent radical species on the surface of the biochar has the capability of providing and receiving electrons, and is beneficial to enhancing the binding force between the biochar and pollutants in water.
Example 6
The procedure was as in example 1 except that "the temperature rising rate in the preheating process and the pyrolysis process in the step S2 was 20 ℃/min, and the temperature in the pyrolysis process was 800 ℃.
The specific surface area of the biomass charcoal material of the peel of the orange prepared by the method is 319.2668m under the anaerobic pyrolysis condition of 'the heating rate is 20 ℃/min and the pyrolysis temperature is 800℃' measured by a specific surface determinator 2 /g
Example 7
An adsorption removal experiment was performed using the biomass charcoal material of the pericarp of orange prepared in the method of example 1 as an adsorbing material
S001: when the anaerobic pyrolysis condition in the method of example 1 is that the temperature rise rate is 10 ℃/min and the pyrolysis temperature is 600 ℃, the prepared biomass charcoal material of the peel of the orange is prepared into biomass charcoal material mother liquor with the concentration of 0.5 g/L;
s002: the biomass charcoal material mother liquor obtained in S001 was put into self-prepared water having a dimethyl phthalate concentration of 10mg/L to perform an adsorption removal experiment.
S003: the effect of using biomass charcoal as an adsorbent to remove dimethyl phthalate from water is shown in fig. 6.
Example 8
The procedure of example 7 was repeated except that "the concentration of the biomass char material in the S001 step was 1 g/L".
Example 9
An adsorption removal experiment was performed using the biomass charcoal material of the pericarp of orange prepared in the method of example 3 as an adsorbing material
S001: when the anaerobic pyrolysis condition in the method of example 3 is that the heating rate is 10 ℃/min and the pyrolysis temperature is 700 ℃, the prepared biomass charcoal material of the peel of the orange is prepared into biomass charcoal material mother liquor with the concentration of 0.5 g/L;
s002: the biomass charcoal material mother liquor obtained in the S001 was put into self-prepared water having a dimethyl phthalate concentration of 10mg/L to perform an adsorption removal experiment.
S003: the effect of using biomass charcoal as an adsorbent to remove dimethyl phthalate from water is shown in fig. 6.
Example 10
The procedure of example 9 was repeated except that "the concentration of the biomass char material in the S001 step was 1 g/L".
Example 11
An adsorption removal experiment was performed using the biomass charcoal material of the pericarp of orange prepared by the method in example 5 as an adsorbing material
S001: when the anaerobic pyrolysis condition in the method of example 5 is that the heating rate is 10 ℃/min and the pyrolysis temperature is 800 ℃, the prepared biomass charcoal material of the peel of the orange is prepared into biomass charcoal material mother liquor with the concentration of 0.5 g/L;
s002: the biomass charcoal material mother liquor obtained in S001 was put into self-prepared water having a dimethyl phthalate concentration of 10mg/L to perform an adsorption removal experiment.
S003: the effect of using biomass charcoal as an adsorbent to remove dimethyl phthalate from water is shown in fig. 6.
Example 12
The procedure of example 11 was repeated except that "the concentration of the biomass char material in the S001 step was 1 g/L".
Fig. 6 is a graph showing the effect of dimethyl phthalate removal from water in examples 7 to 12 using biomass charcoal material of pericarp of citrus prepared under different conditions according to the examples of the present disclosure as an adsorbing material.
As shown in FIG. 6, the removal effect of three different biomass charcoal materials with the initial concentration of 10mg/L dimethyl phthalate within 2h was measured, wherein the concentrations were 0.5g/L and 1g/L, respectively. From fig. 6, the following results can be obtained: in 2h, under the conditions of two concentrations of 0.5g/L and 1g/L, (1) the biomass charcoal material of the peel of the orange prepared by the method of example 1 when the temperature rise rate of the anaerobic pyrolysis condition is 10 ℃/min and the pyrolysis temperature is 600 ℃ has almost no adsorption effect on dimethyl phthalate. (2) In the method of example 3, the adsorption removal performance of the biomass charcoal material of the peel of orange prepared under the conditions of the temperature rise rate of 10 ℃/min and the pyrolysis temperature of 700 ℃ under the anaerobic pyrolysis condition on dimethyl phthalate is improved to about 18 percent and 27 percent respectively under the two biomass charcoal concentration conditions. (3) The biomass charcoal material of pericarp of citrus fruit prepared in the method of example 5 under "anaerobic pyrolysis condition with temperature rise rate of 10 ℃/min and pyrolysis temperature of 800 ℃" exhibited the optimum adsorption effect on dimethyl phthalate, reaching about 82% at a concentration of 0.5g/L and about 93% at a concentration of 1 g/L.
From the above analysis results, the following conclusions can be drawn: in the preparation method of the biomass charcoal material according to the embodiment of the disclosure, when the pyrolysis temperature is controlled to be a single variable, the adsorption performance of the biomass charcoal material of the pericarp of the prepared orange to dimethyl phthalate is far better than the adsorption performance of the biomass charcoal material of the pericarp of the orange to dimethyl phthalate when the pyrolysis temperature under the anaerobic pyrolysis condition is 800 ℃. The specific reasons are explained below: first, according to analysis of material characterization results such as BET, SEM, FTIR and the like of the biomass charcoal material of the pericarp of mandarin orange prepared in the method of example 5, in which "the temperature rise rate under the anaerobic pyrolysis condition is 10 ℃/min and the pyrolysis temperature is 800 ℃", the rugged surface structure of the biomass charcoal material of the pericarp of mandarin orange prepared in the method of example 5, in which "the temperature rise rate under the anaerobic pyrolysis condition is 10 ℃/min and the pyrolysis temperature is 800 ℃, can effectively bind dimethyl phthalate on the surface thereof through physical actions of entanglement and interception. Meanwhile, in the method of example 5, the specific surface area (324.5886 m) of biomass charcoal material of pericarp of orange prepared at the time of "temperature rise rate under oxygen-free pyrolysis condition of 10 ℃/min and pyrolysis temperature of 800 ℃" was set 2 /g) is far larger than the specific surface area (0.0397 m) of the biomass charcoal material of the peel of the orange prepared by the method of example 1 when the temperature rise rate of the anaerobic pyrolysis condition is 10 ℃/min and the pyrolysis temperature is 600 ℃ 2 /g) and "anaerobic pyrolysis conditions in the Process of example 3 temperature ramp rate of 10 deg.C/min, pyrolysis temperature of 700 deg.C"specific surface area of biomass charcoal material of pericarp of prepared orange (3.829 m) 2 And/g), which can provide a large number of attachment sites for dimethyl phthalate, accelerate the mass transfer of dimethyl phthalate in the internal pores of the biochar, and is beneficial to improving the adsorption performance of the biomass charcoal material of the pericarp of the orange prepared by the method of example 5 when the temperature rise rate under the anaerobic pyrolysis condition is 10 ℃/min and the pyrolysis temperature is 800 ℃. In addition, in the method of example 5, the oxygen-containing functional group and the persistent radical species on the surface of the biomass charcoal material of the pericarp of the orange prepared under the anaerobic pyrolysis condition with the temperature rise rate of 10 ℃/min and the pyrolysis temperature of 800 ℃ can enhance the direct bonding force between the biomass charcoal material and the pollutants with dimethyl phthalate, and fix the biomass charcoal material and the pollutants on the surface of the biochar, thereby achieving the purpose of purifying water quality. In summary, the above is provided. In the preparation method of the biomass charcoal material according to the embodiment of the disclosure, when the pyrolysis temperature is controlled to be a single variable, the adsorption performance of the biomass charcoal material of the pericarp of the prepared orange to dimethyl phthalate is far better than that of the biomass charcoal material of the pericarp of the orange prepared when the pyrolysis temperature under the anaerobic pyrolysis condition is 600 ℃ and the pyrolysis temperature under the anaerobic pyrolysis condition is 700 ℃.
The above-mentioned embodiments are intended to illustrate the objects, aspects and advantages of the present disclosure in further detail, and it should be understood that the above-mentioned embodiments are only illustrative of the present disclosure and are not intended to limit the present disclosure, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present disclosure should be included in the scope of the present disclosure.
Claims (10)
1. A method for preparing biomass charcoal material from pericarp of citrus comprises:
pretreating pericarp of citrus;
carrying out anaerobic pyrolysis on the pretreated fruit peel in the atmosphere of inert gas, so that biomass in the pretreated fruit peel is heated and decomposed to form hot steam, and obtaining a pyrolysis product;
and cleaning and drying the pyrolysis product to obtain the biomass charcoal material.
2. The method of claim 1, wherein the step of anaerobic pyrolysis comprises:
partially decomposing cellulose and hemicellulose in the pretreated pericarp by a preheating process;
and completely decomposing the residual cellulose and hemicellulose in the pretreated pericarp through a pyrolysis process, and growing a carbon skeleton hierarchical porous structure.
3. The method of claim 2,
the preheating process is executed under the conditions that the heating rate comprises 10-30 ℃/min, the temperature comprises 90-110 ℃ and the time comprises 10-30 min.
4. The method of claim 2,
the pyrolysis process is carried out under the conditions that the heating rate comprises 10 ℃/min to 30 ℃/min, the temperature comprises 600 ℃ to 800 ℃, and the time comprises 2h to 3 h.
5. The method of claim 2,
the temperature rise rate of the preheating process and the pyrolysis process is the same.
6. The method of claim 1,
the citrus comprises any one of fructus Citri Tangerinae, mandarin orange, fructus Citri Junoris, fructus Citri Grandis, and fructus Aurantii Immaturus;
the pretreatment process is carried out under the conditions that the temperature is 60-150 ℃ and the time is 1-24 h;
the inert gas is selected from argon or nitrogen with the purity of more than 99.999 percent, wherein the flow rate of the inert gas comprises 60mL/min to 80 mL/min.
7. The method of claim 1,
the pH of the final wash solution from the washing process was 7;
the drying step is carried out under the conditions that the temperature is 70-80 ℃ and the time is 10-12 h.
8. Application of the biomass charcoal material obtained by the preparation method of any one of claims 1-7 in adsorption removal of persistent organic pollutants in water.
9. The use according to claim 8,
the persistent organic contaminants include phthalate-based contaminants.
10. The use according to claim 8,
the phthalate ester pollutant comprises at least one of dimethyl phthalate, dibutyl phthalate and diester phthalate.
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