CN113845115B - Preparation method and application of heteroatom self-doped biomass porous carbon - Google Patents
Preparation method and application of heteroatom self-doped biomass porous carbon Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 86
- 239000002028 Biomass Substances 0.000 title claims abstract description 52
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 64
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 52
- 244000207740 Lemna minor Species 0.000 claims abstract description 33
- 235000006439 Lemna minor Nutrition 0.000 claims abstract description 33
- 235000001855 Portulaca oleracea Nutrition 0.000 claims abstract description 33
- 238000003763 carbonization Methods 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000009656 pre-carbonization Methods 0.000 claims abstract description 19
- 238000002791 soaking Methods 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012043 crude product Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000007873 sieving Methods 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 11
- 125000002091 cationic group Chemical group 0.000 claims abstract description 9
- 125000000129 anionic group Chemical group 0.000 claims abstract description 8
- 230000003213 activating effect Effects 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 230000003313 weakening effect Effects 0.000 claims abstract description 7
- 239000000975 dye Substances 0.000 claims description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 4
- 239000010865 sewage Substances 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 13
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 9
- 229940012189 methyl orange Drugs 0.000 description 9
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 7
- 229960000907 methylthioninium chloride Drugs 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001045 blue dye Substances 0.000 description 3
- 239000001048 orange dye Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
Classifications
-
- 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
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
-
- 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
- B01J2220/4843—Algae, aquatic plants or sea vegetals, e.g. seeweeds, eelgrass
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a preparation method and application of heteroatom self-doped biomass porous carbon, which specifically comprises the following steps: firstly, placing duckweed in absolute ethyl alcohol for ultrasonic treatment, drying, ball milling, sieving, placing in a hydrothermal reaction kettle for pre-carbonization, washing and drying to obtain hydrothermal carbon; then mixing the hydrothermal carbon with solid KOH, soaking in water, and drying to obtain a hydrothermal carbon/KOH mixture; carbonizing the hydrothermal carbon/KOH mixture under the protection of nitrogen, weakening the introducing rate of nitrogen after carbonization, and simultaneously introducing CO 2 Activating and naturally cooling to obtain a crude product; and finally, adding the crude product into hydrochloric acid solution for soaking, washing and drying to obtain the heteroatom self-doped biomass porous carbon. The heteroatom self-doped biomass porous carbon prepared by the method has good removal capacity for both anionic dye and cationic dye, and has good application prospect in the field of sewage purification.
Description
Technical Field
The invention belongs to the technical field of carbon material preparation, and particularly relates to a preparation method of heteroatom self-doped biomass porous carbon and application of the heteroatom self-doped biomass porous carbon.
Background
Water has long been one of the most important resources for human survival and development. With the discharge of various organic pollutants, water pollution is more serious, so that the water pollution problem is increasingly concerned. The synthetic dye is a main component of sewage, has strong stability, carcinogenicity and teratogenicity, and has great threat to ecological environment and human health.
Biomass-derived carbon is one of the most potential materials for repairing polluted groundwater and industrial wastewater because of the advantages of large surface area, developed porous structure, good chemical stability, easy regeneration, wide sources and the like. Therefore, directly preparing porous carbon with heteroatom self-doping without using any other reagent by taking renewable biomass as a precursor is a promising method.
Disclosure of Invention
The invention aims to provide a preparation method of heteroatom self-doped biomass porous carbon, which improves the adsorption capacity of the heteroatom self-doped biomass porous carbon on organic pollutants.
It is another object of the present invention to provide the use of the above-described heteroatom self-doped biomass porous carbon for the removal of wastewater anionic and cationic dyes.
The technical scheme adopted by the invention is that the preparation method of the heteroatom self-doped biomass porous carbon is implemented according to the following steps:
step 1, placing duckweed in absolute ethyl alcohol for ultrasonic treatment, and cleaning soluble impurities;
step 2, drying, ball-milling and sieving the duckweed obtained in the step 1 to obtain duckweed powder;
step 3, placing the duckweed powder obtained in the step 2 into a hydrothermal reaction kettle for pre-carbonization, washing and drying to obtain hydrothermal carbon;
step 4, mixing the hydrothermal carbon obtained in the step 3 with solid KOH, soaking the obtained mixture in water, and drying to obtain a hydrothermal carbon/KOH mixture;
step 5, carbonizing the hydrothermal carbon/KOH mixture obtained in the step 4 under the protection of nitrogen, preserving heat for a period of time, weakening the introducing rate of nitrogen after carbonization, and introducing CO at the same time 2 Activating, and naturally cooling under the protection of nitrogen to obtain a crude product;
and step 6, adding the crude product obtained in the step 5 into hydrochloric acid solution for soaking, washing with deionized water until filtrate is neutral, and drying to obtain the heteroatom self-doped biomass porous carbon.
The present invention is also characterized in that,
in the step 1, the mass ratio of the sophorae duckweed to the absolute ethyl alcohol is 1:8, 8; the ultrasonic treatment time is 30 min-50 min.
In the step 2, the ball milling rotating speed is 500-700 rpm, the ball milling time is 6-12 h, the drying temperature is 60-80 ℃ and the drying time is 12-24 h; a100-mesh screen is adopted during sieving.
In the step 3, the pre-carbonization temperature is 180-230 ℃, and the pre-carbonization time is 10-14 h; the drying temperature is 100-120 ℃, and the drying time is 12-24 hours.
In the step 4, the mass ratio of the hydrothermal carbon, the solid KOH and the water is 5:2:50.
in the step 5, the carbonization temperature is 600-800 ℃, the carbonization time is 2 hours, and the heat preservation time is 2 hours; the activation time is 30min; the nitrogen gas inlet rate is 60mL/min, the reduced nitrogen gas inlet rate is 20mL/min, and the carbon dioxide inlet rate is 60mL/min.
In the step 6, the soaking time is 24 hours, the drying temperature is 60-80 ℃, and the drying time is 12-14 hours.
The invention adopts another technical scheme that the heteroatom self-doped biomass porous carbon can be applied to removing anionic and cationic dyes in wastewater.
The beneficial effects of the invention are as follows:
(1) The invention relates to a preparation method of heteroatom self-doped biomass porous carbon, which takes duckweed as a carbon precursor and adopts a hydrothermal carbonization method and a high-temperature carbonization activation method to prepare heteroatom self-doped biomass porous carbon. The technology has the advantages of wide raw material sources, low cost and simple preparation process, and has great application potential in treating dye wastewater;
(2) According to the preparation method of the heteroatom self-doped biomass porous carbon, the prepared heteroatom self-doped biomass porous carbon has good removal capacity for both anionic dye and cationic dye, and has good application prospect in the field of sewage purification.
Drawings
FIG. 1 is a graph of absorbance of heteroatom self-doped biomass porous carbon prepared by the method of the invention before and after adsorption of methylene blue dye;
FIG. 2 is a graph showing absorbance curves before and after adsorption of methyl orange dye by the porous carbon of the heteroatom-doped biomass prepared by the method of the invention.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The invention relates to a preparation method of heteroatom self-doped biomass porous carbon, which is implemented according to the following steps:
step 1, placing duckweed in absolute ethyl alcohol for ultrasonic treatment, and cleaning soluble impurities;
the mass ratio of the sophorae duckweed to the absolute ethyl alcohol is 1:8, 8; the ultrasonic treatment time is 30 min-50 min;
step 2, drying the duckweed in the step 1, ball-milling for 6-12 hours at a rotating speed of 500-700 rpm, and sieving to obtain duckweed powder;
the drying temperature is 60-80 ℃ and the drying time is 12-24 hours; a 100-mesh screen is adopted during sieving;
step 3, placing the duckweed powder obtained in the step 2 into a hydrothermal reaction kettle for pre-carbonization, washing and drying to obtain hydrothermal carbon;
the pre-carbonization temperature is 180-230 ℃, and the pre-carbonization time is 10-14 h; the drying temperature is 100-120 ℃, and the drying time is 12-24 hours;
step 4, mixing the hydrothermal carbon obtained in the step 3 with solid KOH, soaking the obtained mixture in water, and drying to obtain a hydrothermal carbon/KOH mixture;
the mass ratio of the hydrothermal carbon to the solid KOH to the water is 5:2:50;
step 5, carbonizing the hydrothermal carbon/KOH mixture obtained in the step 4 under the protection of nitrogen, preserving heat for a period of time, weakening the introducing rate of nitrogen after carbonization, and introducing CO at the same time 2 Activating for 30min, stopping heating, cutting off the introduction of carbon dioxide, and naturally cooling to room temperature under the protection of nitrogen to obtain a crude product;
the carbonization temperature is 600-800 ℃, the carbonization time is 2 hours, and the heat preservation time is 2 hours;
the nitrogen gas introducing rate is 60mL/min, the reduced nitrogen gas introducing rate is 20mL/min, and the carbon dioxide introducing rate is 60mL/min;
step 6, adding the crude product obtained in the step 5 into hydrochloric acid solution, soaking for 24 hours, washing with deionized water until filtrate is neutral, and drying to obtain the heteroatom self-doped biomass porous carbon;
the drying temperature is 60-80 ℃ and the drying time is 12-14 h;
the heteroatom self-doped biomass porous carbon prepared by the method can be applied to removal of organic pollutants in dye wastewater, and the specific method comprises the following steps: the heteroatom self-doped biomass porous carbon is used for adsorbing anions and cationic dyes such as methyl orange, methylene blue and the like in wastewater.
Example 1
The invention relates to a preparation method of heteroatom self-doped biomass porous carbon, which is implemented according to the following steps:
step 1, placing duckweed in absolute ethyl alcohol for ultrasonic treatment, and cleaning soluble impurities;
the mass ratio of the sophorae duckweed to the absolute ethyl alcohol is 1:8, 8; the ultrasonic treatment time is 30min;
step 2, drying the duckweed in the step 1, ball-milling for 6 hours at a rotating speed of 500, and sieving to obtain duckweed powder;
the drying temperature is 60 ℃ and the drying time is 24 hours; a 100-mesh screen is adopted during sieving;
step 3, placing the duckweed powder obtained in the step 2 into a hydrothermal reaction kettle for pre-carbonization, washing and drying to obtain hydrothermal carbon;
the pre-carbonization temperature is 180 ℃, and the pre-carbonization time is 14h; the drying temperature is 100 ℃, and the drying time is 24 hours;
step 4, mixing the hydrothermal carbon obtained in the step 3 with solid KOH, soaking the obtained mixture in water, and drying to obtain a hydrothermal carbon/KOH mixture;
the mass ratio of the hydrothermal carbon to the solid KOH to the water is 5:2:50;
step (a)5. Carbonizing the hydrothermal carbon/KOH mixture obtained in the step 4 under the protection of nitrogen, preserving the heat for a period of time, weakening the nitrogen inlet amount in the later stage of carbonization, and simultaneously introducing CO 2 Activating for 30min, stopping heating, cutting off the introduction of carbon dioxide, and naturally cooling to room temperature under the protection of nitrogen to obtain a crude product;
the carbonization temperature is 600 ℃, the carbonization time is 2 hours, and the heat preservation time is 2 hours;
the nitrogen gas introducing rate is 60mL/min, the reduced nitrogen gas introducing rate is 20mL/min, and the carbon dioxide introducing rate is 60mL/min;
step 6, adding the crude product obtained in the step 5 into hydrochloric acid solution, soaking for 24 hours, washing with deionized water until filtrate is neutral, and drying to obtain the heteroatom self-doped biomass porous carbon;
the drying temperature was 60℃and the drying time was 14h.
Fig. 1 is an absorbance curve of the heteroatom-doped biomass porous carbon prepared in example 1 before and after adsorption of methylene blue dye, and it can be seen that the absorbance curve is approximately a horizontal straight line after adsorption of the methyl blue dye by the biomass porous carbon.
Fig. 2 is an absorbance curve of the heteroatom-doped biomass porous carbon prepared in example 1 before and after adsorption of methyl orange dye, and it can be seen that the absorbance curve is almost a horizontal straight line after adsorption of methyl orange dye by the heteroatom-doped biomass porous carbon. Figure 2 shows that the material has higher adsorption properties for both a cationic dye and an anionic dye.
The heteroatom-doped biomass porous carbon prepared in example 1 was used to desorb methylene blue, methyl orange and a mixed solution of methylene and methyl orange, and the removal rate of the sample on methyl orange was found to be 99.55% and the removal rate on methylene blue was found to be 99.75%. The removal rates of the methylene blue and the methyl orange in the mixed solution of the methylene blue and the methyl orange respectively reach 99.56 percent and 99.35 percent. The heteroatom self-doped biomass porous carbon has higher adsorption capacity to both anionic dye and cationic dye. The reason for the high removal rate is that the KOH activation enables the heteroatom self-doped biomass porous carbon to have highly developed porosity and partial mesopores, so that rich adsorption sites are provided for anchoring dyes; on the other hand, because of the hierarchical porous structure of three-dimensional interconnection of the heteroatom self-doped biomass porous carbon, the specific surface area is large, the pore size distribution is proper, and the diffusion of dye molecules is promoted; in addition, the porous carbon material also contains rich functional groups, pi-pi interaction can occur between the porous carbon material and dye molecules, electrostatic interaction, hydrogen bonds and the like, and the adsorption capacity of the heteroatom self-doped biomass porous carbon to organic dyes is enhanced.
Example 2
The invention relates to a preparation method of heteroatom self-doped biomass porous carbon, which is implemented according to the following steps:
step 1, placing duckweed in absolute ethyl alcohol for ultrasonic treatment, and cleaning soluble impurities;
the mass ratio of the sophorae duckweed to the absolute ethyl alcohol is 1:8, 8; the ultrasonic treatment time is 40min;
step 2, drying the duckweed in the step 1, ball-milling for 10 hours at a rotating speed of 700rpm, and sieving to obtain duckweed powder;
the drying temperature is 70 ℃ and the drying time is 13h; a 100-mesh screen is adopted during sieving;
step 3, placing the duckweed powder obtained in the step 2 into a hydrothermal reaction kettle for pre-carbonization, washing and drying to obtain hydrothermal carbon;
the pre-carbonization temperature is 200 ℃, and the pre-carbonization time is 13h; the drying temperature is 110 ℃, and the drying time is 13h;
step 4, mixing the hydrothermal carbon obtained in the step 3 with solid KOH, soaking the obtained mixture in water, and drying to obtain a hydrothermal carbon/KOH mixture;
the mass ratio of the hydrothermal carbon to the solid KOH to the water is 5:2:50;
step 5, carbonizing the hydrothermal carbon/KOH mixture obtained in the step 4 under the protection of nitrogen, preserving heat for a period of time, weakening the inlet amount of nitrogen in the later stage of carbonization, and simultaneously introducing CO 2 Activating for 30min, stopping heating, cutting off the introduction of carbon dioxide, and naturally cooling to room temperature under the protection of nitrogen to obtain a crude product;
the carbonization temperature is 700 ℃, the carbonization time is 2 hours, and the heat preservation time is 2 hours;
the nitrogen gas introducing rate is 60mL/min, the reduced nitrogen gas introducing rate is 20mL/min, and the carbon dioxide introducing rate is 60mL/min;
step 6, adding the crude product obtained in the step 5 into hydrochloric acid solution, soaking for 24 hours, washing with deionized water until filtrate is neutral, and drying to obtain the heteroatom self-doped biomass porous carbon;
the drying temperature was 70℃and the drying time was 13h.
Example 3
The invention relates to a preparation method of heteroatom self-doped biomass porous carbon, which is implemented according to the following steps:
step 1, placing duckweed in absolute ethyl alcohol for ultrasonic treatment, and cleaning soluble impurities;
the mass ratio of the sophorae duckweed to the absolute ethyl alcohol is 1:8, 8; the ultrasonic treatment time is 50min;
step 2, drying the duckweed in the step 1, ball-milling for 6-12 hours at a rotating speed of 500-700 rpm, and sieving to obtain duckweed powder;
the drying temperature is 80 ℃ and the drying time is 24 hours; a 100-mesh screen is adopted during sieving;
step 3, placing the duckweed powder obtained in the step 2 into a hydrothermal reaction kettle for pre-carbonization, washing and drying to obtain hydrothermal carbon;
the pre-carbonization temperature is 220 ℃, and the pre-carbonization time is 14h; the drying temperature is 120 ℃, and the drying time is 12 hours;
step 4, mixing the hydrothermal carbon obtained in the step 3 with solid KOH, soaking the obtained mixture in water, and drying to obtain a hydrothermal carbon/KOH mixture;
the mass ratio of the hydrothermal carbon to the solid KOH to the water is 5:2:50;
step 5, carbonizing the hydrothermal carbon/KOH mixture obtained in the step 4 under the protection of nitrogen, preserving heat for a period of time, weakening the introducing rate of nitrogen after carbonization, and introducing CO at the same time 2 Activating for 30min, stopping heating and cutting offIntroducing carbon dioxide, naturally cooling to room temperature under the protection of nitrogen to obtain a crude product;
the carbonization temperature is 800 ℃, the carbonization time is 2 hours, and the heat preservation time is 2 hours; the nitrogen gas introducing rate is 60mL/min, the reduced nitrogen gas introducing rate is 20mL/min, and the carbon dioxide introducing rate is 60mL/min;
step 6, adding the crude product obtained in the step 5 into hydrochloric acid solution, soaking for 24 hours, washing with deionized water until filtrate is neutral, and drying to obtain the heteroatom self-doped biomass porous carbon;
the drying temperature was 80℃and the drying time was 12 hours.
In the preparation method of the heteroatom self-doped biomass porous carbon, the adsorption mechanism of the heteroatom self-doped biomass porous carbon to the anionic dye and the cationic dye is as follows: (1) The carbon material and the dye may have pi-pi interaction with the surface of the biochar, which is beneficial to the adsorption of the dye; (2) The heteroatom self-doped biomass porous carbon and dye can have hydrogen bonds with the surface of biochar; (3) There may be electrostatic interactions between the heteroatom self-doped biomass porous carbon and the dye surface.
According to the invention, sophorae duckweed is used as a precursor, and hydrothermal carbonization and high-temperature carbonization are adopted to prepare the heteroatom self-doped biomass porous carbon which is used as an adsorbent of dye. The technology has the advantages of wide raw material sources, low cost, simple preparation process and great application potential in the aspect of dye removal.
Claims (5)
1. The preparation method of the heteroatom self-doped biomass porous carbon is characterized by comprising the following steps of:
step 1, placing duckweed in absolute ethyl alcohol for ultrasonic treatment, and cleaning soluble impurities; the mass ratio of the sophorae duckweed to the absolute ethyl alcohol is 1:8, 8; the ultrasonic treatment time is 30 min-50 min;
step 2, drying, ball-milling and sieving the duckweed obtained in the step 1 to obtain duckweed powder;
step 3, placing the duckweed powder obtained in the step 2 into a hydrothermal reaction kettle for pre-carbonization, washing and drying to obtain hydrothermal carbon;
the pre-carbonization temperature is 180-230 ℃, and the pre-carbonization time is 10-14 h; the drying temperature is 100-120 ℃, and the drying time is 12-24 hours;
step 4, mixing the hydrothermal carbon obtained in the step 3 with solid KOH, soaking the obtained mixture in water, and drying to obtain a hydrothermal carbon/KOH mixture;
step 5, carbonizing the hydrothermal carbon/KOH mixture obtained in the step 4 under the protection of nitrogen, preserving heat for a period of time, weakening the introducing rate of nitrogen after carbonization, and introducing CO at the same time 2 Activating, and naturally cooling under the protection of nitrogen to obtain a crude product;
the carbonization temperature is 600-800 ℃, the carbonization time is 2 hours, and the heat preservation time is 2 hours; the activation time is 30min; the nitrogen gas introducing rate is 60mL/min, the reduced nitrogen gas introducing rate is 20mL/min, and the carbon dioxide introducing rate is 60mL/min;
and step 6, adding the crude product obtained in the step 5 into hydrochloric acid solution for soaking, washing with deionized water until filtrate is neutral, and drying to obtain the heteroatom self-doped biomass porous carbon.
2. The method for preparing the heteroatom self-doped biomass porous carbon according to claim 1, wherein in the step 2, the ball milling speed is 500-700 rpm, the ball milling time is 6-12 h, the drying temperature is 60-80 ℃, and the drying time is 12-24 h; a100-mesh screen is adopted during sieving.
3. The method for preparing porous biomass carbon doped with hetero atoms according to claim 1, wherein in said step 4, the mass ratio of hydrothermal carbon, solid KOH and water is 5:2:50.
4. the method for preparing the heteroatom self-doped biomass porous carbon according to claim 1, wherein in the step 6, the soaking time is 24 hours, the drying temperature is 60-80 ℃, and the drying time is 12-14 hours.
5. A method of preparing a heteroatom-self-doped biomass porous carbon as set forth in any one of claims 1-4 wherein the heteroatom-self-doped biomass porous carbon is useful in the removal of anionic and cationic dyes from wastewater.
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