CN110773128A - Photo-thermal synergistic modification method of biomass charcoal - Google Patents
Photo-thermal synergistic modification method of biomass charcoal Download PDFInfo
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- CN110773128A CN110773128A CN201911202437.2A CN201911202437A CN110773128A CN 110773128 A CN110773128 A CN 110773128A CN 201911202437 A CN201911202437 A CN 201911202437A CN 110773128 A CN110773128 A CN 110773128A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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Abstract
The invention discloses a photo-thermal synergistic modification method of biomass charcoal, and belongs to the technical field of biomass resource utilization. The invention provides a photo-thermal synergistic modification method of biomass charcoal, which aims to improve the surface functional group and the specific surface area of a biomass charcoal material and improve the modification efficiency, and comprises the following steps: the biochar is irradiated under ultraviolet light, heated at 100-300 ℃ and modified by the cooperation of photo-heat. According to the invention, through photo-thermal correlation modification, the specific surface area and surface acid functional groups of the biomass charcoal can be remarkably increased in a short time, so that the treatment capacity of the biomass charcoal on pollutants in the environment is enhanced. The method has the advantages of simple operation, no secondary pollution, suitability for popularization and application and great economic benefit.
Description
Technical Field
The invention belongs to the technical field of biomass resource utilization, and particularly relates to a method for modifying surface functional groups and specific surface area of a biomass charcoal material.
Background
In recent years, the biochar material has the characteristics of environmental friendliness, wide preparation raw materials, low production cost and the like, can be used as a heavy metal contaminated soil conditioner, a water treatment adsorbent, an air pollution adsorbent and the like, and is the focus of attention in the field of environmental materials at present.
However, unmodified biochar has some drawbacks in its application, due to its low specific surface area or low content of surface acidic functional groups, which makes it limited in its capacity of adsorbing pollutants in the environment. Modification of the biochar is necessary to improve its adsorption properties. The conventional modification methods include acid/alkali modification, chemical modification, heavy metal modification and the like, and although the methods can obviously improve the adsorption capacity of the biochar, the methods often generate secondary pollution and have poor economy.
Currently, CN102921380B discloses a method for modifying biomass charcoal by ultraviolet catalysis, which uses a high-pressure mercury lamp tube with power of 1000W, spectral range of 365-.
The modification method adopts a photo-thermal synergistic modification technology, develops a more economic and environment-friendly modification technology, and can remarkably increase the specific surface area and the surface acidic functional groups of the biomass charcoal in a short time.
Disclosure of Invention
The technical problem to be solved by the invention is how to improve the surface functional group and the specific surface area of the biomass charcoal material and improve the modification efficiency.
The invention provides a photo-thermal synergistic modification method of biomass charcoal, which is used for solving the technical problems and comprises the following steps: and irradiating the biochar under ultraviolet light, heating at 100-300 ℃, and cooling to obtain the modified biochar after the photo-thermal synergistic modification is finished.
In the photo-thermal synergistic modification method of the biomass charcoal, the temperature of the photo-thermal synergistic modification is 300 ℃.
In the photo-thermal synergistic modification method of the biomass charcoal, the photo-thermal synergistic modification time is 0.5-24 h.
Preferably, in the photo-thermal synergistic modification method of the biomass charcoal, the photo-thermal synergistic modification time is 2-16 h.
More preferably, in the photo-thermal synergistic modification method of biomass charcoal, the photo-thermal synergistic modification time is 4-16 h.
In the photo-thermal synergistic modification method of the biomass charcoal, the wavelength of the ultraviolet light is 320-400 nm, and the ultraviolet lamp is placed 1-10 cm above the biomass charcoal.
The invention has the beneficial effects that:
the invention can obviously improve the specific surface area and the surface acidic functional group of the biomass charcoal material, obviously improve the adsorption capacity of the biomass charcoal material to heavy metals or organic pollutants in the environment, can be widely used in the aspects of soil pollution treatment, sewage treatment, organic gas treatment and the like, and ensures that the environment-friendly material has great value.
Detailed Description
Specifically, the photo-thermal synergistic modification method of biomass charcoal comprises the following steps: and irradiating the biochar under ultraviolet light, heating at 100-300 ℃, and cooling to obtain the modified biochar after the photo-thermal synergistic modification is finished.
The inventor finds in experiments that the specific surface area and the surface acidic functional group of the biomass charcoal can not be obviously improved under the condition of only heating the biomass charcoal in the air environment of 100-300 ℃; the specific surface area and the content of acidic functional groups of the biomass charcoal can be remarkably improved through photo-thermal synergistic modification of ultraviolet irradiation and temperature control; the photo-thermal synergistic modification effect is better along with the rise of the temperature, so that the temperature of the photo-thermal synergistic modification is preferably 300 ℃; when the modification external temperature exceeds 300 ℃, the ignition point of the biomass charcoal is close to that of the biomass charcoal, and the biomass charcoal is often combusted in the modification process.
In the method, the modification efficiency can be obviously improved through photo-thermal synergistic modification, and the photo-thermal synergistic modification time is 0.5-24 h. When the biomass charcoal is subjected to photo-thermal synergistic modification for 2 hours by ultraviolet irradiation and temperature control, the total acidic functional groups (relative to unmodified groups) are increased by about 1 time; when the modification time is 4h, the increase of the total acidic functional groups tends to be smooth, and then the total acidic functional groups slightly increase along with the extension of the modification time. Therefore, the optimal time for photo-thermal synergistic modification is 2-16 h; more preferably 4-16 h.
In the method, the wavelength of ultraviolet light is 320-400 nm, and the ultraviolet lamp is arranged 1-10 cm above the biomass charcoal.
The feasibility of the invention is illustrated below in specific examples, which are described in detail below:
the biomass charcoal is prepared by taking coconut shells as a preparation raw material and pyrolyzing the coconut shells for 2 hours at the pyrolysis temperature of 700 ℃, and a sample is marked as B; the main wavelength of the ultraviolet lamp is 365nm, and the power is 250W; the temperature required by the modification of the biochar is controlled by an electric heating plate, the temperature control precision of the electric heating plate is +/-1 ℃, and the specific description is as follows:
example 1
Firstly, the biochar is uniformly spread in a glass culture dish with the diameter of 15cm, and the thickness of the spread biochar is about 2 mm. Then, the sample was irradiated under a 250W lamp with a lamp cover having a main wavelength of 365nm for 10cm, and the irradiation time was set to 16 hours. During the irradiation period, the glass culture dish is placed on an electric heating plate, the temperature required by the modification of the biochar is controlled by the electric heating plate, and the temperature control precision of the electric heating plate is +/-1 ℃. The temperature of the electric heating plate is respectively set to be 100 ℃, 200 ℃ and 300 ℃, after the irradiation time is reached, the glass culture dish is taken out and put into a dryer for cooling, modified biochar is respectively marked as B-100UV, B-200UV and B-300UV, simultaneously, a comparison sample which is heated under the conditions of 100 ℃, 200 ℃ and 300 ℃ and is not subjected to ultraviolet irradiation is prepared and marked as B-100, B-200 and B-300, and a comparison sample which is only irradiated by light and is not heated is prepared, and the specific surface area (measured by a BELSORP-max full-automatic specific surface area and porosity analyzer) and the surface acidic functional group (measured by a Boehm titration method) after modification are respectively measured, and the results are shown in Table 1.
TABLE 1 specific surface area and surface acid functional group changes of photothermal synergistically modified Biomass charcoal
As can be seen from Table 1, the specific surface area and the surface acidic functional groups of the biomass charcoal can not be obviously improved under the condition of only heating the biomass charcoal in the air environment of 100-300 ℃; under the same condition, the specific surface area and the acidic functional group content of the biomass charcoal can be obviously improved without heating by illumination, but the specific surface area and the acidic functional group content of the biomass charcoal can be more obviously improved by the photo-thermal synergistic modification of ultraviolet irradiation and temperature control, and the modification effect is more obvious along with the increase of the modification temperature.
Example 2
The biomass charcoal is uniformly spread in a glass culture dish with the diameter of 15cm, and the spreading thickness is about 2 mm. Then the sample is placed under an air environment with the main wavelength of 365nm and under a 250W ultraviolet lamp for 10cm, and the irradiation time is set to be 2h, 4h, 6h and 16h respectively. During the irradiation period, the temperature required by the modification of the biochar is controlled to be 100 ℃, 200 ℃ and 300 ℃ respectively by using a temperature control electric heating plate. Marking the prepared modified biochar as B100-2h, B100-4h, B100-6h and B100-16h respectively; b200-2h, B200-4h, B200-6h, B200-16h, B300-2h, B300-4h, B300-6h and B300-16h, and determining the modified surface acidic functional group (determined by Boehm titration), the results are shown in Table 2.
TABLE 2 photo-thermal synergistic modification of the change of acidic functional groups on the surface of biomass charcoal under different irradiation times and different heating temperatures
| Physical and chemical characteristics | B | B100-2h | B100-4h | B100-6h | B100-16h |
| Total acidic functional groups (mmol.g) -1) | 0.28 | 0.55 | 0.99 | 1.02 | 1.05 |
| Physical and chemical characteristics | B | B200-2h | B100-4h | B200-6h | B200-16h |
| Total acidic functional groups (mmol.g) -1) | 0.28 | 0.51 | 1.04 | 1.07 | 1.10 |
| Physical and chemical characteristics | B | B300-2h | B300-4h | B300-6h | B300-16h |
| Total acidic functional groups (mmol.g) -1) | 0.28 | 0.42 | 0.81 | 1.02 | 1.40 |
As can be seen from Table 2, when the biomass charcoal is subjected to photo-thermal synergistic modification for 2 hours by ultraviolet irradiation and temperature control, the total acidic functional groups are increased by about 1 time; when the modification time is 4 hours, the increase of the total acidic functional groups tends to be gentle, and then the increase of the total acidic functional groups tends to be further gentle as the modification time is prolonged.
Example 3
To further confirm the effect of improving the adsorption capacity of the modified biomass charcoal, example 3 examined the results of examples 1, wherein B (unmodified), B-100, B-200 and BSaturated adsorption amounts of benzene and toluene for biochar of-300 and B-100UV, B-200UV, B-300 UV. The inlet concentrations of benzene and toluene were 2.79g.m
-3(800ppm) and 3.69g.m
-3(900ppm), the mass of the biochar in each adsorption experiment is 3.18g, and the air inflow is 300mL.min
-1. When the outlet concentration of the adsorption column is equal to the inlet gas concentration, the adsorption is regarded as saturated, and the corresponding adsorption amount is regarded as saturated adsorption amount. From the obtained concentration-time curve, the adsorption amount at the saturation of the adsorption of the biochar can be finally obtained by integrating the obtained concentration-time curve, and the results are shown in table 3.
TABLE 3 comparison of adsorption performance of photo-thermal synergistic modified biomass charcoal under different modification conditions
As can be seen from Table 3, the adsorption performance of the biomass charcoal cannot be significantly changed or improved only by heating in an air environment of 100-300 ℃; and the adsorption performance can be obviously improved under the photo-thermal coordination modification condition, and the photo-thermal coordination modification effect is better along with the rise of the temperature.
It should be understood that the above-mentioned embodiments, objects, technical solutions and advantages of the present invention are described in further detail, and the above-mentioned embodiments are merely examples of the present invention and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit of the present invention should be included in the protection scope of the present invention, and the protection scope of the present invention should be subject to the protection scope defined by the claims.
Claims (6)
1. The photo-thermal synergistic modification method of the biomass charcoal is characterized by comprising the following steps: the method comprises the following steps: and irradiating the biochar under ultraviolet light, heating at 100-300 ℃, and cooling to obtain the modified biochar after the photo-thermal synergistic modification is finished.
2. The photo-thermal synergistic modification method of biomass charcoal according to claim 1, characterized in that: the temperature of the photo-thermal synergistic modification is 300 ℃.
3. The photo-thermal synergistic modification method of biomass charcoal according to claim 2, characterized in that: the photo-thermal synergistic modification time is 0.5-24 h.
4. The photo-thermal synergistic modification method of biomass charcoal according to claim 3, characterized in that: the photo-thermal synergistic modification time is 2-16 h.
5. The photo-thermal synergistic modification method of biomass charcoal as claimed in claim 4, characterized in that: the photo-thermal synergistic modification time is 4-16 h.
6. The photo-thermal synergistic modification method of biomass charcoal according to any one of claims 1 to 5, characterized in that: the wavelength of the ultraviolet light is 320-400 nm, and the ultraviolet light is arranged 1-10 cm above the biomass charcoal.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111807895A (en) * | 2020-07-21 | 2020-10-23 | 武汉美佳源环境工程有限公司 | Preparation process of soil remediation agent with multiple elements |
| CN111821946A (en) * | 2020-07-14 | 2020-10-27 | 江苏省地质工程勘察院 | Preparation method of modified restoration plant biochar for cadmium-polluted soil restoration |
Citations (3)
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| CA2241292A1 (en) * | 1997-07-04 | 1999-01-04 | Henri-Jean Caupin | Process and device for anti-odour treatment of the air |
| CN102921380A (en) * | 2012-11-16 | 2013-02-13 | 重庆大学 | Modification method for improving absorption performance of biomass carbon |
| CN106925222A (en) * | 2017-04-28 | 2017-07-07 | 安徽科技学院 | Hydrogen peroxide cooperates with raising charcoal oxy radical technique with ultraviolet irradiation |
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2019
- 2019-11-29 CN CN201911202437.2A patent/CN110773128A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2241292A1 (en) * | 1997-07-04 | 1999-01-04 | Henri-Jean Caupin | Process and device for anti-odour treatment of the air |
| CN102921380A (en) * | 2012-11-16 | 2013-02-13 | 重庆大学 | Modification method for improving absorption performance of biomass carbon |
| CN106925222A (en) * | 2017-04-28 | 2017-07-07 | 安徽科技学院 | Hydrogen peroxide cooperates with raising charcoal oxy radical technique with ultraviolet irradiation |
Non-Patent Citations (2)
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| 丁文川等: "紫外辐照引入含氧官能团对生物炭吸附气体和水中苯的影响", 《环境科学学报》 * |
| 李桥等: "紫外辐照改性生物炭对VOCs的动态吸附", 《环境科学》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111821946A (en) * | 2020-07-14 | 2020-10-27 | 江苏省地质工程勘察院 | Preparation method of modified restoration plant biochar for cadmium-polluted soil restoration |
| CN111807895A (en) * | 2020-07-21 | 2020-10-23 | 武汉美佳源环境工程有限公司 | Preparation process of soil remediation agent with multiple elements |
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Application publication date: 20200211 |