CN112265991B - Preparation method for preparing mesoporous-rich hierarchical porous carbon by using geminal substances - Google Patents
Preparation method for preparing mesoporous-rich hierarchical porous carbon by using geminal substances Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims description 13
- 239000000126 substance Substances 0.000 title claims description 4
- 239000000463 material Substances 0.000 claims abstract description 62
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000001888 Peptone Substances 0.000 claims abstract description 26
- 108010080698 Peptones Proteins 0.000 claims abstract description 26
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 26
- 235000019319 peptone Nutrition 0.000 claims abstract description 26
- 241000283690 Bos taurus Species 0.000 claims abstract description 25
- 238000000227 grinding Methods 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000010000 carbonizing Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 12
- 238000000967 suction filtration Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007833 carbon precursor Substances 0.000 claims abstract description 9
- 239000002028 Biomass Substances 0.000 claims abstract description 8
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 3
- 239000011812 mixed powder Substances 0.000 claims description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 13
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 11
- 238000001994 activation Methods 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 abstract description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 66
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 54
- 238000001179 sorption measurement Methods 0.000 description 52
- 239000011148 porous material Substances 0.000 description 27
- 239000002243 precursor Substances 0.000 description 21
- 239000004570 mortar (masonry) Substances 0.000 description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000012855 volatile organic compound Substances 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 6
- 230000035515 penetration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 239000002699 waste material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002156 adsorbate Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000009270 solid waste treatment Methods 0.000 description 2
- 238000005287 template synthesis Methods 0.000 description 2
- 239000012494 Quartz wool Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for preparing mesoporous-rich hierarchical porous carbon by using gemini biomass, which comprises the following steps: mixing peptone and bovine bone powder according to the mass ratio of 0.8: 1-1.5: 1, fully grinding, uniformly mixing, heating to above 400 ℃ under an inert atmosphere, and carbonizing to obtain a carbon precursor; then mixing the obtained carbon precursor with potassium salt according to the mass ratio of 1: 1.2-1: 0.8, fully grinding, uniformly mixing, heating the mixture to 700-900 ℃ in an inert atmosphere, keeping the temperature for activating for 1.5-2 h, and cooling in the inert atmosphere to obtain an activated material; finally, placing the activated material in sufficient acid with the concentration of 2-3 mol/L for standing for more than 12h, repeatedly washing the material after standing by using sufficient deionized water, and performing suction filtration until the PH value of the filtrate is 7; keeping the filtered material at 100 ℃ for more than 24h, and taking out to obtain the hierarchical porous carbon rich in mesopores. The method has simple process and is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of gas-phase pollutant treatment by solid waste treatment, and particularly relates to a preparation method for preparing mesoporous-rich hierarchical porous carbon by using twins.
Background
Volatile organic compounds are common gas-phase pollutants with the characteristics of high saturated vapor pressure, low boiling point, high reaction activity and the like under normal temperature and normal pressure environments, have wide sources and active properties, and are partially greatly damaged to human bodies. Several volatile organics are typically detected in the tail gas emitted during energy conversion and solid waste treatment.
The adsorption method is one of the most widely used volatile organic compound treatment methods. The adsorption method has been widely paid attention by researchers because of its advantages such as low cost and simple process. The traditional activated carbon adsorbent has the disadvantages of single pore channel structure, slow adsorption rate and the like, and the hierarchical porous carbon can realize quick adsorption on the premise of ensuring higher adsorption capacity due to the advantages of diversified pore channel structures, large pore volume and the like. Therefore, the volatile organic compound treatment technology based on the graded porous carbon is widely applied to the volatile organic compound treatment in recent years.
At present, four main methods for preparing the graded porous carbon material are available: template synthesis; self-templating; microbial targeted degradation methods and co-pyrolysis methods. The method is successfully applied to the preparation of the graded porous carbon with different structures, but the template synthesis method has the problem of overhigh cost and reduces the economical efficiency of the preparation method; the self-templating method has a problem of low material yield; the preparation process of the microbial targeted degradation method is relatively complex, and the preparation period of the material is relatively long; in order to overcome the above problems, the co-pyrolysis method has recently received attention of researchers, and mainly uses a mixture of biomass-based and non-biomass-based waste raw materials as a main raw material, but there are few reports on related researches on the preparation of graded porous carbon prepared from biomass-based waste raw materials.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing the mesoporous-rich hierarchical porous carbon by using double biomass.
The purpose of the invention is realized by the following technical scheme:
a method for preparing mesoporous-rich hierarchical porous carbon by using geminal substances comprises the following steps:
(1) mixing peptone and bovine bone powder according to the mass ratio of 0.8: 1-1.5: 1, fully grinding, uniformly mixing, heating the mixed powder to above 400 ℃ under an inert atmosphere, and carbonizing to obtain a carbon precursor;
(2) mixing the carbon precursor obtained in the step (1) with potassium salt according to the mass ratio of 1: 1.2-1: 0.8, fully grinding, uniformly mixing, heating the mixture to 700-900 ℃ in an inert atmosphere, keeping the temperature condition for activation for 1.5-2 h, and cooling in the inert atmosphere to obtain an activated material;
(3) placing the activated material in the step (2) in sufficient acid with the concentration of 2-3 mol/L for standing for more than 12h, repeatedly washing the material after standing by using sufficient deionized water, and performing suction filtration until the PH value of the filtrate is 7; keeping the filtered material at 100 ℃ for more than 24h, and taking out to obtain the hierarchical porous carbon rich in mesopores.
In order to produce more mesopores during the activation process, potassium carbonate is selected as the potassium salt.
In order to make the distribution of the two raw materials more uniform, the mass setting ratio of peptone to bovine bone powder was 1:1.
In order to ensure that the prepared graded porous carbon has a high specific surface area and a large pore volume at the same time, the mass ratio of the carbon precursor to the potassium salt is set to 1:1.
In order to ensure that the surface property of the precursor is more uniform, a uniform heating rate is ensured, so the heating rates in the steps (1) and (2) are set to be 10 ℃/min.
In order to maintain the temperature of the inert gas atmosphere during the preparation process, the flow rate of the inert gas introduced in steps (1) and (2) was set to 100 mL/min.
In order to ensure sufficient reaction of the activating agent and the carbon precursor, a sufficient reaction time is required, and therefore, the time of the carbonization treatment in step (1) should be 2 hours or more.
The invention has the following beneficial effects:
(1) the carbon material precursor is prepared by a method of physically mixing peptone and cow bones, so that an additional template and other materials are not added, the activation process is simple, and a complicated pretreatment link is not needed.
(2) The total pore volume of the existing grading porous carbon is 1cm3About/g, and the mesoporous volume is smaller, the total pore volume of the graded porous carbon obtained by the preparation method can reach 2.4cm3Is/g, and the mesoporous volume is also higherThe adsorbent is large and has a three-stage continuous micropore-mesopore-macropore structure, and can realize rapid adsorption of adsorbate on the premise of ensuring higher adsorption capacity.
(3) The raw materials of the invention are wastes, the cost of the raw materials is extremely low, the high-quality graded porous carbon is obtained, meanwhile, the treatment of partial organic solid wastes is realized, the cost is low, and the invention is environment-friendly.
Drawings
FIG. 1 is a scheme for the preparation of a graded porous carbon prepared in the examples.
FIG. 2 is a nitrogen adsorption and desorption isotherm graph of the graded porous carbon prepared in examples 1 to 6 under the 77K condition.
FIG. 3 is a graph showing the distribution of pore diameters of the graded porous carbon prepared in examples 1 to 6.
FIG. 4 is a graph showing the dynamic adsorption breakthrough of benzene at 25 ℃ for the graded porous carbons prepared in examples 1, 3 and 5.
FIG. 5 is a graph showing the dynamic adsorption breakthrough of toluene at 25 ℃ for the graded porous carbons prepared in examples 2, 4 and 6.
FIG. 6 is a graph comparing the benzene vapor adsorption performance of the graded porous carbon prepared in example 3 after different regeneration times.
FIG. 7 is a graph comparing the benzene vapor adsorption performance of the graded porous carbon prepared in example 4 after different regeneration times.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and preferred embodiments, and the objects and effects of the present invention will become more apparent, it being understood that the specific embodiments described herein are merely illustrative of the present invention and are not intended to limit the present invention.
The preparation method for preparing the mesoporous-rich graded porous carbon by using the twin biomass takes waste peptone and bovine bones as raw materials, and the prepared graded porous carbon is used as an efficient adsorbent in the adsorption process of low-concentration volatile organic compounds. The hierarchical porous carbon has the advantages of high specific surface area, large pore volume, rich mesoporous structure and three-stage structure of micropore-mesopore-macropore, and can provide adsorption sites and an adsorbate transmission channel simultaneously in the adsorption process of volatile organic compounds. The specific workflow is shown in fig. 1.
The following examples all employ a tube furnace as heating apparatus, N2As a heating atmosphere. Meanwhile, the volatile organic compound model waste gas (benzene or toluene) with fixed concentration is adopted, the concentration is respectively 200ppm and 400ppm, and the steam flow is 200 mL/min. As the peptone, commercially available ones such as those from Shandong Longhui chemical Co., Ltd; the ox bone adopts the rest waste in the market. The precursor of the hierarchical porous carbon prepared in the following examples is denoted as PC/BC, and the hierarchical porous carbon prepared at an activation temperature of X ℃ is denoted as PC/BC-X.
Example 1
(1) Weighing 10g of peptone and 10g of bovine bone, placing the peptone and the bovine bone into a mortar for full grinding and mixing, placing the uniformly mixed powder into a tube furnace, and placing N2Carbonizing at 400 ℃ for 2h under the atmosphere, and controlling the heating rate to be 10 ℃/min to obtain a precursor PC/BC of the graded porous carbon.
(2) 5g of precursor are weighed out with 5g K2CO3Fully grinding and mixing in a mortar, putting the uniformly mixed powder into a tube furnace, and adding N2Raising the temperature to 700 ℃ under the atmosphere, and activating for 1.5 h. Then in N2Cooling to room temperature under the atmosphere.
(3) And (3) placing the obtained material in sufficient nitric acid with the concentration of 2mol/L for standing for 24h, repeatedly washing the material after standing by using sufficient deionized water, and performing suction filtration until the pH value of the filtrate is 7. And (3) placing the filtered material in an oven, keeping the temperature at 105 ℃ for 24h, and taking out the material to obtain the hierarchical porous carbon PC/BC-700 rich in mesopores.
The specific surface area of the graded porous carbon is 1415m2Per g, total pore volume of 0.91cm3Per g, the mesoporous volume is 0.48cm3(ii) in terms of/g. The average pore diameter of the material was 2.98 nm.
0.1g of PC/BC-700 is placed in a self-made adsorption tube, quartz wool is filled in the self-made adsorption tube to fix the self-made adsorption tube, benzene steam with the concentration of 200ppm and the gas flow of 200mL/min is introduced, the benzene concentration in steam at the outlet of the adsorption tube is measured by using gas chromatography, the penetration curve of the PC/BC-700 to the benzene steam is measured, and the adsorption quantity of the PC/BC to the benzene steam is 90.6mg/g at the temperature of 25 ℃.
Example 2
(1) Weighing 10g of peptone and 10g of bovine bone, placing the peptone and the bovine bone into a mortar for full grinding and mixing, placing the uniformly mixed powder into a tube furnace, and placing N2Carbonizing at 400 ℃ for 2h under the atmosphere, and controlling the heating rate to be 10 ℃/min to obtain a precursor PC/BC of the graded porous carbon.
(2) 5g of precursor are weighed out with 5g K2CO3Fully grinding and mixing in a mortar, putting the uniformly mixed powder into a tube furnace, and adding N2Raising the temperature to 700 ℃ under the atmosphere, and activating for 1.5 h. Then in N2Cooling to room temperature under the atmosphere.
(3) And (3) placing the obtained material in sufficient nitric acid with the concentration of 2mol/L for standing for 24h, repeatedly washing the material after standing by using sufficient deionized water, and performing suction filtration until the pH value of the filtrate is 7. And (3) placing the filtered material in an oven, keeping the temperature at 105 ℃ for 24h, and taking out the material to obtain the hierarchical porous carbon PC/BC-700 rich in mesopores.
The specific surface area of the graded porous carbon is 1415m2Per g, total pore volume of 0.91cm3Per g, the mesoporous volume is 0.48cm3(ii) in terms of/g. The average pore diameter of the material was 2.98 nm.
0.1g of PC/BC-700 is placed in a self-made adsorption tube, toluene steam with the concentration of 400ppm and the gas flow rate of 200mL/min is introduced, the benzene concentration in steam at the outlet of the adsorption tube is measured by gas chromatography, the penetration curve of the PC/BC-700 to the toluene steam is measured, and the adsorption quantity of the PC/BC-700 to the toluene steam is 393.2mg/g at the temperature of 25 ℃.
Example 3
(1) Weighing 10g of peptone and 10g of bovine bone, placing the peptone and the bovine bone into a mortar for full grinding and mixing, placing the uniformly mixed powder into a tube furnace, and placing N2Carbonizing at 400 ℃ for 2h under the atmosphere, and controlling the heating rate to be 10 ℃/min to obtain a precursor PC/BC of the graded porous carbon.
(2) 5g of precursor are weighed out with 5g K2CO3Fully grinding and mixing in a mortar, putting the uniformly mixed powder into a tube furnace, and adding N2Raising the temperature to 800 ℃ under the atmosphere, and activating for 1.5 h. Then in N2Cooling to room temperature under the atmosphere.
(3) And (3) placing the obtained material in sufficient nitric acid with the concentration of 2mol/L for standing for 24h, repeatedly washing the material after standing by using sufficient deionized water, and performing suction filtration until the pH value of the filtrate is 7. And (3) placing the filtered material in an oven, keeping the temperature at 105 ℃ for 24h, and taking out the material to obtain the hierarchical porous carbon PC/BC-800 rich in mesopores.
The specific surface area of the graded porous carbon is 2110m2Per g, total pore volume 2.26cm3Per g, the mesoporous volume is 1.38cm3(ii) in terms of/g. The average pore size of the material was 4.28 nm.
Placing 0.1g of PC/BC-800 in a self-made adsorption tube, introducing benzene steam with the concentration of 200ppm and the gas flow of 200mL/min, measuring the benzene concentration in the steam at the outlet of the adsorption tube by using gas chromatography, and measuring the penetration curve of the PC/BC-800 to the benzene steam, wherein the adsorption quantity of the PC/BC-800 to the benzene steam is 139.5mg/g at the temperature of 25 ℃.
And (3) placing the classified porous carbon with saturated adsorption in a tubular furnace, heating for 1h at 300 ℃, taking out, adsorbing again, and repeatedly carrying out three times of adsorption-regeneration cycles, wherein the adsorption capacity of the PC/BC-800 to the benzene vapor is 127.2mg/g, which is 91.2% of the original adsorption capacity.
Example 4
(1) Weighing 10g of peptone and 10g of bovine bone, placing the peptone and the bovine bone into a mortar for full grinding and mixing, placing the uniformly mixed powder into a tube furnace, and placing N2Carbonizing at 400 ℃ for 2h under the atmosphere, and controlling the heating rate to be 10 ℃/min to obtain a precursor PC/BC of the graded porous carbon.
(2) 5g of precursor are weighed out with 5g K2CO3Fully grinding and mixing in a mortar, putting the uniformly mixed powder into a tube furnace, and adding N2Raising the temperature to 800 ℃ under the atmosphere, and activating for 1.5 h. Then in N2Cooling to room temperature under the atmosphere.
(3) And (3) placing the obtained material in sufficient nitric acid with the concentration of 2mol/L for standing for 24h, repeatedly washing the material after standing by using sufficient deionized water, and performing suction filtration until the pH value of the filtrate is 7. And (3) placing the filtered material in an oven, keeping the temperature at 105 ℃ for 24h, and taking out the material to obtain the hierarchical porous carbon PC/BC-800 rich in mesopores.
The specific surface area of the graded porous carbon is 2110m2Per g, total pore volume 2.26cm3Per g, the mesoporous volume is 1.38cm3(ii) in terms of/g. The average pore size of the material was 4.28 nm.
Placing 0.1g of PC/BC-800 in a self-made adsorption tube, introducing toluene steam with the concentration of 400ppm and the gas flow rate of 200mL/min, measuring the toluene concentration in the steam at the outlet of the adsorption tube by using gas chromatography, and measuring the penetration curve of the PC/BC-800 to the toluene steam, wherein the adsorption quantity of the PC/BC to the toluene steam is 440.7mg/g under the condition of 25 ℃.
And (3) placing the classified porous carbon saturated in adsorption into a tubular furnace, heating for 1h at 300 ℃, taking out, adsorbing again, and repeatedly carrying out three times of adsorption-regeneration cycles, wherein the adsorption capacity of the PC/BC-800 to toluene steam is 400.2mg/g and is 90.8% of the original adsorption capacity.
Example 5
(1) Weighing 10g of peptone and 10g of bovine bone, placing the peptone and the bovine bone into a mortar for full grinding and mixing, placing the uniformly mixed powder into a tube furnace, and placing N2Carbonizing at 400 ℃ for 2h under the atmosphere, and controlling the heating rate to be 10 ℃/min to obtain a precursor PC/BC of the graded porous carbon.
(2) 5g of precursor are weighed out with 5g K2CO3Fully grinding and mixing in a mortar, putting the uniformly mixed powder into a tube furnace, and adding N2Raising the temperature to 900 ℃ in the atmosphere and activating for 1.5 h. Then in N2Cooling to room temperature under the atmosphere.
(3) And (3) placing the obtained material in sufficient nitric acid with the concentration of 2mol/L for standing for 24h, repeatedly washing the material after standing by using sufficient deionized water, and performing suction filtration until the pH value of the filtrate is 7. And (3) placing the filtered material in an oven, keeping the temperature at 105 ℃ for 24h, and taking out the material to obtain the hierarchical porous carbon PC/BC-900 rich in mesopores.
The specific surface area of the graded porous carbon is 1954m2(g) total pore volume of 2.45cm3The mesoporous volume is 1.47cm3(ii) in terms of/g. The average pore diameter of the material was 5.02 nm.
Placing 0.1g of PC/BC-900 in a self-made adsorption tube, introducing benzene steam with the concentration of 200ppm and the gas flow rate of 200mL/min, measuring the benzene concentration in the steam at the outlet of the adsorption tube by using gas chromatography, and measuring the penetration curve of the PC/BC-900 to the benzene steam, wherein the adsorption quantity of the PC/BC-900 to the benzene steam is 127.1mg/g at the temperature of 25 ℃.
Example 6
(1) Weighing 10g of peptone and 10g of bovine bone, placing the peptone and the bovine bone into a mortar for full grinding and mixing, placing the uniformly mixed powder into a tube furnace, and placing N2Carbonizing at 400 ℃ for 2h under the atmosphere, and controlling the heating rate to be 10 ℃/min to obtain a precursor PC/BC of the graded porous carbon.
(2) 5g of precursor are weighed out with 5g K2CO3Fully grinding and mixing in a mortar, putting the uniformly mixed powder into a tube furnace, and adding N2Raising the temperature to 900 ℃ in the atmosphere and activating for 1.5 h. Then in N2Cooling to room temperature under the atmosphere.
(3) And (3) placing the obtained material in sufficient nitric acid with the concentration of 2mol/L for standing for 24h, repeatedly washing the material after standing by using sufficient deionized water, and performing suction filtration until the pH value of the filtrate is 7. And (3) placing the filtered material in an oven, keeping the temperature at 105 ℃ for 24h, and taking out the material to obtain the hierarchical porous carbon PC/BC-900 rich in mesopores.
The specific surface area of the material is 1954m2(g) total pore volume of 2.45cm3The mesoporous volume is 1.47cm3(ii) in terms of/g. The average pore diameter of the material was 5.02 nm.
0.1g of PC/BC-900 is placed in a self-made adsorption tube, toluene steam with the concentration of 400ppm and the gas flow rate of 200mL/min is introduced, the toluene concentration in the steam at the outlet of the adsorption tube is measured by gas chromatography, the penetration curve of the PC/BC-900 to the toluene steam is measured, and the adsorption quantity of the PC/BC-900 to the toluene steam is 399.3mg/g under the condition of 25 ℃.
Example 7
(1) Weighing 8g of peptone and 10g of bovine bone, placing the peptone and the bovine bone into a mortar, fully grinding and mixing, placing the uniformly mixed powder into a tube furnace, and placing N2Carbonizing at 400 ℃ for 2h under the atmosphere, and controlling the heating rate to be 10 ℃/min to obtain a precursor PC/BC of the graded porous carbon.
(2) 5g of precursor are weighed out with 5g K2CO3Fully grinding and mixing in a mortar, putting the uniformly mixed powder into a tube furnace, and adding N2Heating to 800 deg.C under atmosphere, activating for 2h. Then in N2Cooling to room temperature under the atmosphere.
(3) And (3) placing the obtained material in sufficient nitric acid with the concentration of 2mol/L for standing for 24h, repeatedly washing the material after standing by using sufficient deionized water, and performing suction filtration until the pH value of the filtrate is 7. And (3) placing the filtered material in an oven, keeping the temperature at 105 ℃ for 24h, and taking out the material to obtain the hierarchical porous carbon PC/BC-800 rich in mesopores.
The specific surface area of the graded porous carbon is 2071m2Per g, total pore volume of 2.28cm3Per g, the mesoporous volume is 1.32cm3(ii) in terms of/g. The average pore size of the material was 4.33 nm.
Example 8
(1) Weighing 15g of peptone and 10g of bovine bone, placing the peptone and the bovine bone into a mortar, fully grinding and mixing, placing the uniformly mixed powder into a tube furnace, and placing N2Carbonizing at 400 ℃ for 2h under the atmosphere, and controlling the heating rate to be 10 ℃/min to obtain a precursor PC/BC of the graded porous carbon.
(2) 5g of precursor are weighed out with 4g K2CO3Fully grinding and mixing in a mortar, putting the uniformly mixed powder into a tube furnace, and adding N2Raising the temperature to 900 ℃ in the atmosphere and activating for 1.5 h. Then in N2Cooling to room temperature under the atmosphere.
(3) And (3) placing the obtained material in sufficient nitric acid with the concentration of 2mol/L for standing for 24h, repeatedly washing the material after standing by using sufficient deionized water, and performing suction filtration until the pH value of the filtrate is 7. And (3) placing the filtered material in an oven, keeping the temperature at 105 ℃ for 24h, and taking out the material to obtain the hierarchical porous carbon PC/BC-900 rich in mesopores.
The specific surface area of the graded porous carbon is 2006m2Per g, total pore volume of 2.16cm3Per g, the mesoporous volume is 1.19cm3(ii) in terms of/g. The average pore diameter of the material was 4.07 nm.
Example 9
(1) Weighing 10g of peptone and 10g of bovine bone, placing the peptone and the bovine bone into a mortar for full grinding and mixing, placing the uniformly mixed powder into a tube furnace, and placing N2Carbonizing at 400 ℃ for 2h under the atmosphere, and controlling the heating rate to be 10 ℃/min to obtain a precursor PC/BC of the graded porous carbon.
(2) 5g of precursor are weighed out, together with 6g K2CO3Fully grinding and mixing in a mortar, putting the uniformly mixed powder into a tube furnace, and adding N2Raising the temperature to 800 ℃ under the atmosphere, and activating for 1.5 h. Then in N2Cooling to room temperature under the atmosphere.
(3) And (3) placing the obtained material in sufficient nitric acid with the concentration of 2mol/L for standing for 12h, repeatedly washing the material after standing by using sufficient deionized water, and performing suction filtration until the pH value of the filtrate is 7. And (3) placing the filtered material in an oven, keeping the temperature at 105 ℃ for 24h, and taking out the material to obtain the hierarchical porous carbon PC/BC-800 rich in mesopores.
The specific surface area of the graded porous carbon is 2216m2Per g, total pore volume of 2.36cm3Per g, the mesoporous volume is 1.34cm3(ii) in terms of/g. The average pore size of the material was 4.31 nm.
FIG. 2 is a nitrogen adsorption and desorption isotherm graph of the graded porous carbon prepared in examples 1 to 6 under a 77K condition, and it can be seen from the graph that the adsorption capacity of the graded porous carbon rapidly rises under a working condition of extremely low relative pressure, which indicates that a large number of micropores exist; with the continuous rise of the relative pressure, the adsorption capacity of the graded porous carbon continuously rises, and when the relative pressure is more than 0.4, hysteresis loops exist among adsorption and desorption curves, which indicates that a large number of mesopores exist in the graded porous carbon; when the relative pressure is more than 0.9, the adsorption capacity still rises rapidly, which indicates that macropores exist in the hierarchical porous carbon, thereby proving that the hierarchical porous carbon has a three-stage continuous micropore-mesopore-macropore structure.
Fig. 3 is a pore size distribution diagram of the graded porous carbon prepared in examples 1 to 6, which also reflects that a large number of mesopores exist in the graded porous carbon.
Fig. 4 is a graph showing the dynamic adsorption breakthrough of the graded porous carbon prepared in examples 1, 3 and 5 to benzene at 25 ℃, and fig. 5 is a graph showing the dynamic adsorption breakthrough of the graded porous carbon prepared in examples 2, 4 and 6 to toluene at 25 ℃, from these two graphs, it can be seen that the graded porous carbon has better adsorption performance to benzene and toluene vapor, and the breakthrough process is very fast, which shows that the graded porous carbon has better mass transfer performance to benzene and toluene vapor, and can realize the rapid adsorption of the two vapors.
Fig. 6 is a comparison of benzene vapor adsorption performance of the graded porous carbon prepared in example 3 after different regeneration times, and fig. 7 is a comparison of toluene vapor adsorption performance of the graded porous carbon prepared in example 4 after different regeneration times.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and although the invention has been described in detail with reference to the foregoing examples, it will be apparent to those skilled in the art that various changes in the form and details of the embodiments may be made and equivalents may be substituted for elements thereof. All modifications, equivalents and the like which come within the spirit and principle of the invention are intended to be included within the scope of the invention.
Claims (7)
1. A preparation method for preparing mesoporous-rich hierarchical porous carbon by using geminal substances is characterized by comprising the following steps:
(1) mixing peptone and bovine bone powder according to the mass ratio of 0.8: 1-1.5: 1, fully grinding, uniformly mixing, heating the mixed powder to above 400 ℃ under an inert atmosphere, and carbonizing to obtain a carbon precursor;
(2) mixing the carbon precursor obtained in the step (1) with potassium salt according to the mass ratio of 1: 1.2-1: 0.8, fully grinding, uniformly mixing, heating the mixture to 700-900 ℃ in an inert atmosphere, keeping the temperature condition for activation for 1.5-2 h, and cooling in the inert atmosphere to obtain an activated material;
(3) placing the activated material in the step (2) in sufficient acid with the concentration of 2-3 mol/L for standing for more than 12h, repeatedly washing the material after standing by using sufficient deionized water, and performing suction filtration until the filtrate p H = 7; keeping the filtered material for more than 24h under the condition of 100 ℃, and then taking out the material to obtain the graded porous carbon with a three-stage continuous micropore-mesopore-macropore structure.
2. The method for preparing mesoporous-rich hierarchical porous carbon according to claim 1, wherein the potassium salt is potassium carbonate.
3. The method for preparing the mesoporous-rich hierarchical porous carbon by using the twin biomass as claimed in claim 1, wherein the mass ratio of the peptone to the bovine bone powder is 1:1.
4. The method for preparing the mesoporous-rich hierarchical porous carbon by using the twin biomass as claimed in claim 1, wherein the mass ratio of the carbon precursor to the potassium salt is 1:1.
5. The method for preparing mesoporous-rich hierarchical porous carbon according to claim 1, wherein the temperature rise rate in steps (1) and (2) is 10 ℃/min.
6. The method for preparing mesoporous-rich hierarchical porous carbon according to claim 1, wherein the inert gas flow rate introduced in the steps (1) and (2) is 100 mL/min.
7. The method for preparing mesoporous-rich hierarchical porous carbon according to claim 1, wherein the carbonization time in step (1) is 2 hours or more.
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