CN117735524A - Preparation method, material and application of nitrogen-doped porous carbon adsorption material - Google Patents
Preparation method, material and application of nitrogen-doped porous carbon adsorption material Download PDFInfo
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- CN117735524A CN117735524A CN202410184037.8A CN202410184037A CN117735524A CN 117735524 A CN117735524 A CN 117735524A CN 202410184037 A CN202410184037 A CN 202410184037A CN 117735524 A CN117735524 A CN 117735524A
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 130
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 95
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 65
- 239000002904 solvent Substances 0.000 claims abstract description 46
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- 239000001257 hydrogen Substances 0.000 claims abstract description 29
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- 238000003756 stirring Methods 0.000 claims abstract description 17
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- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 10
- 235000019743 Choline chloride Nutrition 0.000 claims description 10
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 10
- 229960003178 choline chloride Drugs 0.000 claims description 10
- 239000003463 adsorbent Substances 0.000 claims description 8
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
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- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 4
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 4
- 239000007833 carbon precursor Substances 0.000 description 4
- 235000015165 citric acid Nutrition 0.000 description 4
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- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 3
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- 238000010168 coupling process Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- JTXJZBMXQMTSQN-UHFFFAOYSA-N amino hydrogen carbonate Chemical compound NOC(O)=O JTXJZBMXQMTSQN-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BKRKYEFQSANYGA-UHFFFAOYSA-N bromo-methyl-triphenyl-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(Br)(C=1C=CC=CC=1)(C)C1=CC=CC=C1 BKRKYEFQSANYGA-UHFFFAOYSA-N 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical compound NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 235000004400 serine Nutrition 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
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Classifications
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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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method, a material and application of a nitrogen-doped porous carbon adsorption material, comprising the following steps: s1, dispersing a biomass waste raw material in low-temperature alkali solution, stirring for reaction, and centrifuging to obtain an alkaline hydrolysis solid mixture; s2, dispersing the alkaline hydrolysis solid mixture in deionized water, heating for pre-carbonization, and then filtering to obtain a hydrothermal carbon material; s3, dispersing the hydrothermal carbon material in deionized water, adding a eutectic solvent, heating to 160-220 ℃ for reaction, and washing by using an alkali solution to obtain the amino-functionalized hydrothermal carbon material; eutectic solvent is hydrogenA mixture of bond acceptors and hydrogen bond donors; s4, in the presence of CO 2 Under the inert atmosphere, after reacting the amino functionalized hydrothermal carbon material at room temperature, heating to 650-850 ℃ to perform pore-forming and nitrogen doping reaction, thus obtaining the nitrogen doped porous carbon adsorption material; can overcome the technical difficulty of combining the high specific surface area and the high nitrogen content, and can effectively promote the CO of the nitrogen doped porous carbon material 2 Is used for the adsorption performance of the catalyst.
Description
Technical Field
The invention relates to the technical field of adsorption materials, in particular to a preparation method, a material and application of a nitrogen-doped porous carbon adsorption material.
Background
CO 2 Adsorption is a novel carbon trapping technology, and the technology has the advantages of high adsorption capacity, strong adsorption selectivity, easiness in material preparation, mild operation conditions, potential low energy consumption and the like, and is a solution which is paid attention to in a plurality of carbon emission reduction modes. The carbon material has good stability and biocompatibility and is widely used for CO in air, industrial flue gas and natural gas 2 Adsorption has wide application prospect. However, the carbon material itself is CO 2 Adsorption performance is generally poor.
Since the adsorption capacity of carbon materials is related to the pore structure and surface groups, to increase CO 2 The adsorption performance, the related technology carries out nitrogen doping and pore forming on the carbon material, and the nitrogen doped porous carbon material leads the carbon material to carry out CO treatment due to basic nitrogen atoms and rich pore canal structures on the surface of the carbon material 2 Has better adsorption efficiency.
At present, most of the nitrogen doped porous carbon in the technology takes phenolic resin as raw material and uses NH as raw material 3 Heat treatment or preparation by corrosive activator and expensive template agent, and has low nitrogen content and specific surface area, and is suitable for CO 2 The adsorption capacity is poor. Therefore, a technical scheme for preparing the nitrogen-doped porous carbon material with high nitrogen content and specific surface area is needed.
Disclosure of Invention
In view of the above, the present application provides a method for preparing a nitrogen-doped porous carbon adsorption material, a material and an application thereof, which are used for solving the problem of CO generated by the nitrogen-doped porous carbon adsorption material 2 Poor adsorption effect.
The prior art often requires the preparation of nitrogen-doped porous carbon materials by adding expensive templating agents and corrosive activators to increase the pore volume and specific surface area of the carbon material and by NH 3 Introduction of CO by pyrolysis 2 And introducing an amino functional group into the precursor by in-situ doping or post-treatment, and finally obtaining the nitrogen doped carbon material by high-temperature pyrolysis or activation treatment. The high-temperature pyrolysis or activation function is to realize nitrogen doping on one hand, and on the other hand, in the high-temperature pyrolysis or activation process, volatile small organic molecules are generated by expansion of carbon lattices and destruction of original ordered lattice structures, and the formation of rich pore structures is promoted, so that the specific surface area of the carbon material is improved. In this process, the nitrogen-containing functional groups are also converted into volatile small organic molecules, resulting in a lower final nitrogen content (< 3 wt%) of the carbon material; the pyrolysis or activation is insufficient, so that the effect of increasing the specific surface area of the carbon material is not achieved, namely, the preparation of the carbon material with high specific surface area and N content by pyrolyzing the carbon precursor containing the amine functional groups is not easy to realize, the low-temperature pyrolysis is carried out, the surface area is low, and the nitrogen content is high; high-temperature pyrolysis, high specific surface area and reduced nitrogen content, so that the characteristics of high specific surface area and high nitrogen content are difficult to be achieved, and if the technical difficulty of combining the performances of high specific surface area and high nitrogen content can be overcome, the CO of the nitrogen-doped porous carbon material can be effectively improved 2 Based on this, the present application was created.
In order to achieve the technical purpose, the application adopts the following technical scheme:
in a first aspect, the present application provides a method for preparing a nitrogen-doped porous carbon adsorption material, comprising the steps of:
s1, dispersing a biomass waste raw material in low-temperature alkali solution, stirring for reaction, and centrifuging to obtain an alkaline hydrolysis solid mixture;
s2, dispersing the alkaline hydrolysis solid mixture in deionized water, heating for pre-carbonization, and then filtering to obtain a hydrothermal carbon material;
s3, dispersing the hydrothermal carbon material in deionized water, adding a eutectic solvent, heating to 160-220 ℃ for reaction, and washing with an alkali solution at room temperature to remove soluble organic matters to obtain an amino-functionalized hydrothermal carbon material; the eutectic solvent is a mixture of hydrogen bond acceptors and hydrogen bond donors, wherein the hydrogen bond acceptors are one or more of choline chloride and serine, and the hydrogen bond donors are one or more of urea, citric acid and glycerol;
s4 is in the presence of CO 2 Under the inert atmosphere, the amino functionalized hydrothermal carbon material reacts at room temperature, and then the temperature is raised to 650-850 ℃ to carry out pore-forming and nitrogen doping reaction, thus obtaining the nitrogen doped porous carbon adsorption material.
Preferably, in step S1, the temperature of the stirring reaction is 0-10 ℃.
Preferably, in step S2, the temperature of the heating pre-carbonization is 160-240 ℃.
Preferably, the biomass waste raw material comprises one or more of peanut shells, straws and orange peels.
Preferably, in step S1 and step S3, the alkaline solution comprises urea and/or sodium hydroxide.
Preferably, it contains CO 2 CO in an inert atmosphere 2 The concentration of (2) is 10-100%, and contains CO 2 The flow rate of the inert atmosphere is 50-200mL/min.
Preferably, in step S4, the rate of temperature rise is 5-10deg.C/min.
In a second aspect, the present application provides a nitrogen-doped porous carbon adsorbent material.
In a third aspect, the present application provides a nitrogen-doped porous carbon adsorbent material for adsorbing CO 2 Is used in the field of applications.
The beneficial effects of this application are as follows:
the amino functionalized hydrothermal carbon material firstly adsorbs CO under the condition of room temperature 2 The method is characterized in that carbamic acid (ester) and bicarbonate are formed, amine functional groups on the carbon material are protected, nitrogen element content reduction caused by excessively fast decomposition of the amine functional groups in the pyrolysis process is prevented, and along with carbonization heating, the carbamic acid (ester) and the bicarbonate are slowly decomposed, and the slow-release decomposition mode can improve the content of nitrogen element in the carbon material on one hand, so that the nitrogen element is doped into carbon lattices in the forms of pyridine nitrogen, pyrrole nitrogen, quaternary ammonium salt and the like, and on the other hand, CO formed by slow decomposition of the carbamic acid salt is prevented 2 、H 2 Small molecules such as O serve as physical activating agents, so that the carbon material is further promoted to form a richer pore channel structure; finally realize highThe specific surface area and the high nitrogen content performance are improved simultaneously.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The application provides a preparation method of a nitrogen-doped porous carbon adsorption material, which comprises the following steps:
s1, dispersing a biomass waste raw material in low-temperature alkali solution, stirring for reaction, centrifuging, and washing with water to obtain an alkaline hydrolysis solid mixture;
s2, dispersing the alkaline hydrolysis solid mixture in deionized water, heating for pre-carbonization, and then filtering to obtain a hydrothermal carbon material;
s3, dispersing the hydrothermal carbon material in deionized water, adding a eutectic solvent, heating to 120-220 ℃ for reaction, and washing with an alkaline solution at room temperature to obtain an amino-functionalized hydrothermal carbon material; the eutectic solvent is a mixture of a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond acceptor is one or more of choline chloride, glycine, serine and histidine, and the hydrogen bond donor is one or more of urea, citric acid and glycerol; in the step, the temperature range of the heating reaction is 160-220 ℃, and the temperature lower than the temperature is unfavorable for the embedding of DES (eutectic solvent) in the carbon material and the loading of an amino functional group, and the temperature higher than the temperature range is easy to lead the DES to be directly decomposed into ammonia or other small molecular compounds; preferably, the eutectic solvent is a mixed solution of choline chloride and urea;
s4 is in the presence of CO 2 Under the inert atmosphere, after reacting the amino functionalized hydrothermal carbon material at room temperature, heating to 650-850 ℃ to perform pore-forming and nitrogen doping reaction, thus obtaining the nitrogen doped porous carbon adsorption material; the temperature of pore-forming and nitrogen-doping reaction is 650-850 ℃, below which organic matters in the precursor skeleton cannot be well decomposed, the specific surface area is low, and above which the pore canal is easy to collapse, and the specific surface area of the material is reduced. Furthermore, temperatures above 850℃result in greater process energy consumptionHigh and leads to excessive decomposition of amine functional groups, and reduced nitrogen content of the resulting carbon material.
In the reaction process, the step S1 is an alkali liquor pretreatment process, crystallinity and partial hydrogen bonds of lignocellulose in the biomass waste raw material are destroyed through alkali liquor treatment, the step S2 is a hydrothermal carbonization process, partial cellulose, hemicellulose and lignin are promoted to be carbonized to obtain a hydrothermal carbon material serving as a carbon material precursor, and meanwhile, the hydrothermal carbon material is provided with rich oxygen-containing functional groups through the treatment of the steps S1 and S2.
In the scheme, after solvent thermal carbonization, the eutectic solvent loads amine groups on the surface of a carbon material, and the amine groups are decomposed into small molecules in the pyrolysis process and serve as pore formers, and the specific process is as follows: through the solvothermal reaction of the step S3, the eutectic solvent directly loads the amine groups contained in the eutectic solvent on the surface of the hydrothermal carbon material obtained in the step S2 in one step to obtain the amine-functionalized hydrothermal carbon material, and the hydrothermal carbon material treated in the steps S1 and S2 has rich oxygen-containing functional groups which react with the amine functional groups through hydrogen bonds or electrostatic interaction, so that the content of the amine functional groups on the surface of the carbon material is improved, and the subsequent pyrolysis of the amine functional groups is prevented to inhibit the reduction of the nitrogen content of the final nitrogen-doped porous carbon adsorption material; in step S3, the eutectic solvent has an intercalation effect, which is beneficial to the improvement of the specific surface area of the carbon material.
The eutectic solvent has rich composition forms, can be used as a nitrogen source to prepare an amino functional hydrothermal carbon material, can diversify the introduced amino functional groups, and comprises a compound with the effect of a hydrogen bond acceptor, such as choline chloride and amino acid, wherein the hydrogen bond acceptor is alkyl quaternary ammonium salt, and a compound formed by heating a hydrogen bond donor compound, such as urea, citric acid, glycerol and the like, at a temperature lower than 80 ℃. The carbon precursor is embedded and carbonized by the eutectic solvent to expand the fiber and enrich the surface of the precursor with amine functional groups. The above amine functional group refers to functional group containing primary amine or secondary amine and having strong electron donating ability, and can be combined with CO 2 Directly reacting at room temperature to form carbamate, and reacting the above compound with CO 2 Reacting at room temperature to form carbonic acidA hydrogen salt; therefore, in the step S4, the nitrogen doping and the pore forming are simultaneously carried out, and specifically, the amino-functionalized hydrothermal carbon material of the application firstly adsorbs CO under the room temperature condition 2 The method is characterized in that carbamic acid (ester) and bicarbonate are formed, amine functional groups on the carbon material are protected, nitrogen element content reduction caused by excessively fast decomposition of the amine functional groups in the pyrolysis process is prevented, and along with carbonization heating, the carbamic acid (ester) and the bicarbonate are slowly decomposed, and the slow-release decomposition mode can improve the content of nitrogen element in the carbon material on one hand, so that the nitrogen element is doped into carbon lattices in the forms of pyridine nitrogen, pyrrole nitrogen, quaternary ammonium salt and the like, and on the other hand, CO formed by slow decomposition of the carbamic acid salt is prevented 2 、H 2 Small molecules such as O serve as physical activating agents, so that the carbon material is further promoted to form a richer pore channel structure; and finally, the performance of high specific surface area and high nitrogen content is improved.
The DES has a good embedding effect, the DES promotes the hydrothermal carbon fiber to swell in the solvothermal carbonization process, and nitrogen elements can be enriched on the surface or in pore channels of the hydrothermal carbon. The carbon material is loaded with amino functional groups through Van der Waals force, maillard reaction and other modes after DES solvothermal treatment, and the amino types comprise primary amine, tertiary amine and a little amino oxide, and the amino functional groups and CO 2 The reaction is carried out to form carbamate or carbonate, and after high-temperature pyrolysis, the amino functional group of the prepared carbon material contains pyridine, pyrrole and graphite nitrogen. In addition, the eutectic solvent hydrogen bond donor used is alkyl ammonium salt, and part of alkyl ammonium salt groups enter the carbon material precursor after intercalation and carbonization to form quaternary ammonium salt functional groups. The presence of multiple types of amine functional groups helps the carbon material to CO 2 And the physical and chemical adsorption of the catalyst can improve the adsorption capacity of the catalyst. Whereas most of the traditional activated carbon materials are pressure swing physical adsorption. In addition, NH 3 The temperature for preparing the nitrogen-doped carbon material by activation is higher, and is generally 900-1000 ℃. Whereas the invention uses CO 2 The temperature required by activation is lower than 900 ℃, and the energy consumption is low.
Preferably, in step S1, the temperature of the stirring reaction is 0 to 10 ℃, which is a temperature range that contributes to the destruction of the crystalline structure in the cellulose by the alkaline solution, above which it is disadvantageous to achieve, while below 0 ℃ it is difficult to handle practically; the stirring time in the step S1 is 1-6h, and the concentration of the alkali solution is 5-20 wt%.
Preferably, in step S2, the temperature of the heating pre-carbonization is 160-240 ℃, the reaction time is 6-24 hours, cellulose and hemicellulose in lignocellulose are difficult to carbonize below 160 ℃, and excessive carbonization is caused above 240 ℃, so that the amount of active oxygen-containing functional groups is reduced.
Preferably, the biomass waste raw material comprises one or more of peanut shells, straws and orange peels, and the mass ratio of the biomass waste raw material to the eutectic solvent is 5-20:20-50, wherein the mass ratio of the two is too low, so that the yield of the final carbon material is low, and the ratio is too high, so that the nitrogen doping amount is small; the ratio of hydrogen bond acceptor to donor in the eutectic solvent is 1:2; in the step S3, the mass ratio of the eutectic solvent to the deionized water in the step S3 is 1:1-5, and below the ratio, the eutectic solvent cannot function and is easily damaged by water to damage the hydrogen bond structure, and above the ratio, the viscosity is too high, and the utilization efficiency of the eutectic solvent is low.
Preferably, in step S1 and step S3, the alkaline solution includes urea and/or sodium hydroxide; preferably, the alkaline solution in the step S1 is an equal mass mixture of urea and sodium hydroxide, and in the step S3, the alkaline solution is sodium hydroxide, and the urea and the sodium hydroxide synergistically damage the crystallization and hydrogen bond structure of cellulose in the biomass raw material, so that the efficiency of loading amino functional groups in the later stage of cellulose is promoted.
Preferably, it contains CO 2 CO in an inert atmosphere 2 The concentration of (2) is 10-100%, and contains CO 2 The flow rate of the inert atmosphere is 50-200mL/min. The specific operation of the step S4 is that the amino functionalized hydrothermal carbon material is placed in a tube furnace, and N is introduced first 2 Purging, maintaining inert atmosphere, and switching to CO-containing state 2 After reacting for a period of time at room temperature, slowly heating to the appointed temperature of 650-850 ℃ to obtain the nitrogen-doped porous carbon adsorption material.
Preferably, in step S4, the heating rate is 5-10 ℃/min, and slow heating is beneficial to slow decomposition of carbamic acid (ester) and bicarbonate.
The application provides a nitrogen-doped porous carbon adsorption material.
The application provides a nitrogen-doped porous carbon adsorption material for adsorbing CO 2 Is used in the field of applications.
Compared with the prior art, the carbon material with high specific surface area is obtained by adding an activating agent such as acid, alkali or salt or using a template agent for activation after hydrothermal carbonization. The invention firstly prepares the amino functionalized carbon material by a eutectic solvent assisted hydrothermal method. On one hand, the eutectic solvent has a certain dissolution effect on lignin of biomass, and is helpful for promoting carbonization of lignin; on the other hand, the eutectic solvent also serves as a nitrogen source, the amino group is directly loaded on the surface of the hydrothermal carbon after the hydrothermal treatment, and the amino group hydrothermal carbon is pyrolyzed in a carbon dioxide atmosphere to prepare the nitrogen-doped porous carbon material with high specific surface area.
The present invention will be further described by way of specific embodiments.
Example 1
A preparation method of a nitrogen-doped porous carbon adsorption material comprises the following steps:
s1, dispersing 10g of peanut shells in 50mL of a mixed solution of 20wt% sodium hydroxide and urea (mass ratio is 1:1), stirring for 3 hours at 5 ℃, centrifuging, washing with water, and drying to obtain an alkaline hydrolysis solid mixture;
s2, dispersing the alkaline hydrolysis solid mixture in 50mL of deionized water, stirring for 15min, and uniformly mixing to obtain a suspension; placing the suspension in a stainless steel reactor for reaction at 220 ℃ for 24 hours, naturally cooling, filtering, washing with deionized water and ethanol for 3 times, and drying at 60 ℃ for 12 hours to obtain a hydrothermal carbon material;
s3, dispersing the hydrothermal carbon material in 50mL of deionized water, adding 50g of a eutectic solvent formed by choline chloride and urea in a molar ratio of 1:2, stirring for 30min, uniformly mixing to obtain a suspension, placing the suspension in a stainless steel reactor, reacting at 220 ℃ for 24h, naturally cooling, filtering, washing with deionized water for 3 times, treating with 1mmol/L NaOH at room temperature for 3h, filtering at 60 ℃ and drying for 12h to obtain the amino-functionalized hydrothermal carbon material;
s4, placing the amino functionalized hydrothermal carbon material into a tube furnace, and introducing 100mL/min of N 2 Purged for 0.5h and then switched to 50 vol% CO 2 After purging for 15min, heating to 800 ℃ at the speed of 10 ℃/min, maintaining at 800 ℃ for 2h, and naturally cooling to room temperature to obtain the nitrogen-doped porous carbon adsorption material.
Example 2-example 4
A method for preparing a nitrogen-doped porous carbon adsorption material, which is otherwise the same as in example 1, except that the eutectic solvents are serine and glycerin, choline chloride and citric acid, respectively.
Example 5
The preparation method of the nitrogen-doped porous carbon adsorption material is the same as in example 1, except that in step S4, the temperature rising rate is 5 ℃/min.
Example 6
A preparation method of a nitrogen-doped porous carbon adsorption material comprises the following steps:
s1, dispersing 5.0g of peanut shells in 50mL of a mixed solution of 5wt% sodium hydroxide and urea (mass ratio is 1:1), stirring for 3 hours at 10 ℃, centrifuging, washing with water, and drying to obtain an alkaline hydrolysis solid mixture;
s2, dispersing the alkaline hydrolysis solid mixture in 50mL of deionized water, stirring for 15min, and uniformly mixing to obtain a suspension; placing the suspension in a stainless steel reactor for reaction at 180 ℃ for 24 hours, naturally cooling, filtering, washing with deionized water and ethanol for 3 times, and drying at 60 ℃ for 12 hours to obtain a hydrothermal carbon material;
s3, dispersing the hydrothermal carbon material in 50mL of deionized water, adding 20g of a eutectic solvent formed by choline chloride and urea, stirring for 30min, uniformly mixing to obtain a suspension, placing the suspension in a stainless steel reactor, reacting for 18h at 200 ℃, naturally cooling, filtering, washing with deionized water for 3 times, treating for 3h at 1mmol/L NaOH at room temperature, filtering, drying for 12h at 60 ℃ to obtain the amino-functionalized hydrothermal carbon material;
s4, placing the amino functionalized hydrothermal carbon material in a tube furnace, and introducing 50mL/min of N at room temperature 2 Purging for 0.5h and switching to 100 vol% CO 2 Purging for 15min at a rate of 10deg.C/minHeating to 850 ℃, keeping for 2 hours at 850 ℃, and naturally cooling to room temperature to obtain the nitrogen-doped porous carbon adsorption material.
Example 7
A preparation method of a nitrogen-doped porous carbon adsorption material comprises the following steps:
s1, dispersing 20.0g of peanut shells in 50mL of a mixed solution of 10wt% sodium hydroxide and urea (mass ratio is 1:1), stirring for 3 hours at 0 ℃, centrifuging, washing with water, and drying to obtain an alkaline hydrolysis solid mixture;
s2, dispersing the alkaline hydrolysis solid mixture in 50mL of deionized water, stirring for 15min, and uniformly mixing to obtain a suspension; placing the suspension in a stainless steel reactor for reaction at 240 ℃ for 6 hours, naturally cooling, filtering, washing with deionized water and ethanol for 3 times, and drying at 60 ℃ for 12 hours to obtain a hydrothermal carbon material;
s3, dispersing the hydrothermal carbon material in 50mL of deionized water, adding 30g of a eutectic solvent formed by choline chloride and urea, stirring for 30min, uniformly mixing to obtain a suspension, placing the suspension in a stainless steel reactor, reacting at 220 ℃ for 12h, naturally cooling, filtering, washing with deionized water for 3 times, treating at 1mmol/L NaOH at room temperature for 3h, filtering at 60 ℃ and drying for 12h to obtain the amino-functionalized hydrothermal carbon material;
s4, placing the amino functionalized hydrothermal carbon material in a tube furnace, and introducing 200mL/min of N at room temperature 2 Purging for 0.5h and switching to 100 vol% CO 2 After purging for 15min, the temperature is raised to 650 ℃ at the speed of 7.5 ℃/min, the temperature is kept at 650 ℃ for 2h, and the temperature is naturally lowered to room temperature, so that the nitrogen-doped porous carbon adsorption material is obtained.
Example 8
A method for preparing a nitrogen-doped porous carbon adsorption material, otherwise identical to example 1, except that the mixture of sodium hydroxide and urea in step S1 is replaced with an equal amount of urea.
Comparative example 1
A method for preparing a nitrogen-doped porous carbon adsorption material was the same as in example 1, except that step S1 was not included.
Comparative example 2
A method for preparing a nitrogen-doped porous carbon adsorption material was the same as in example 1, except that step S2 was not included.
Comparative example 3
A method for preparing a nitrogen-doped porous carbon adsorption material was the same as in example 1, except that steps S1 and S2 were not included.
Comparative example 4
A method for preparing a nitrogen-doped porous carbon adsorption material was the same as in example 1, except that an equal amount of urea was used instead of the eutectic solvent.
Comparative example 5
A method for preparing a nitrogen-doped porous carbon adsorption material was the same as in example 1, except that an equal amount of choline chloride was used instead of the eutectic solvent.
Comparative example 6
A method for preparing a nitrogen-doped porous carbon adsorption material was the same as in example 1, except that the eutectic solvent was not used.
Comparative example 7
The preparation method of the nitrogen-doped porous carbon adsorption material is the same as in example 1 except that N is used in the whole process in step S4 2 An atmosphere.
Comparative example 8
A method for preparing a nitrogen-doped porous carbon adsorption material was the same as in example 1, except that in step S4, 50% CO was directly introduced 2 Without prior introduction of nitrogen.
Comparative example 9
A method for preparing a nitrogen-doped porous carbon adsorption material, otherwise the same as in example 1, except that in step S3, the eutectic solvent is exchanged for glucose and urea.
Comparative example 10
A method for preparing a nitrogen-doped porous carbon adsorption material, otherwise the same as in example 1, except that in step S3, the eutectic solvent is replaced with a mixture of N-methyldiethanolamine and methyltriphenylphosphorus bromide.
Evaluation test
The carbon materials obtained in each example and comparative example were tested, the test results are shown in table 1, and the test method is as follows: through N 2 Structural parameters such as specific surface area of the adsorption-desorption test material, and the content of N is tested by CHNS element analysis; simulated smoke (10% CO) was tested by thermogravimetric analyzer of the material pair 2 Adsorption at normal temperature and normal pressure) of CO 2 Is used as a catalyst.
Table 1 test results
It can be seen that the specific surface area and nitrogen content of the material synergistically promote its CO-oxidation 2 Is adsorbed by the adsorbent. Alkali treatment, hydrothermal carbonization and eutectic solvent solvothermal carbonization coupling CO 2 The activation method is an effective method for preparing porous carbon materials with high specific surface area and nitrogen content. The carbon material prepared in example 1 has a high surface area and nitrogen content, which is relative to CO 2 The adsorption capacity of the catalyst is also high, and physical adsorption and chemical adsorption can be realized at the same time. The specific surface area and nitrogen content of the prepared materials were reduced by replacing the hydrogen bond donor and ligand of the eutectic solvent in examples 2-4, indicating that the specific combination of eutectic solvents helps to increase the surface area and nitrogen content of the materials. In example 2, the carbon material prepared has no quaternary ammonium salt functional group, cannot form a eutectic solvent of quaternary ammonium salt, lacks para-CO 2 Is a physical adsorption function of (a). In examples 3 and 4, the hydrogen bond donor in the low co-solvent used cannot provide a nitrogen source, resulting in a material with a low total nitrogen content and few chemisorption sites for pyridine nitrogen, pyrrole nitrogen, etc.
In example 5, the pyrolysis heating rate is 5 ℃/min, and the nitrogen content of the prepared material is improved, which shows that the slow heating is helpful to reduce the decomposition of the amine functional group.
Comparison of example 6 and example 7 shows that the coupling process conditions have a large effect on the properties of the material.
In example 8, the alkaline mixed solution of S1 is replaced by a single component alkaline solution, and the result shows that the nitrogen content and the specific surface area of the prepared material are obviously reduced, because the mixed alkaline solution can effectively destroy cellulose crystals and hydrogen bond structures of biomass precursors under the low-temperature condition, and the mixed alkaline solution is favorable for loading more amine functional groups, so that the nitrogen content and the specific surface area of the material are improved.
In comparative example 1, the nitrogen element content of the prepared carbon material was remarkably reduced without the preliminary low-temperature treatment with an alkali solution. The pretreatment can effectively destroy the crystallization and hydrogen bond structure of cellulose, is favorable for forming more oxygen-containing functional groups in the subsequent hydrothermal carbonization and solvothermal carbonization processes, promotes the combination of materials and amino groups, and improves the nitrogen content of the carbon material. The results of comparative example 2 and comparative example 3 show that the specific surface area and nitrogen content of the carbon material finally obtained without the hydrothermal carbonization treatment are reduced. The hydrothermal process leads cellulose, hemicellulose and lignin to be partially carbonized, rich oxygen-containing functional groups are formed, the oxygen-containing functional groups interact with amine functional groups through hydrogen bonds or electrostatic actions, the amine functional group content on the surface of the carbon material is improved, and the reduction of the nitrogen content of the final carbon material caused by high-temperature decomposition of the amine functional groups is inhibited to a certain extent.
In comparative examples 4 and 5, the eutectic solvent was not added but only a hydrogen bond donor or acceptor was used, and although nitrogen atoms were eventually doped into the carbon material, the surface area was reduced and the nitrogen content was small, indicating that the eutectic solvent acts as a pore-forming agent to some extent. In comparative example 6, the specific surface area and nitrogen content of the carbon material obtained without adding the eutectic solvent were drastically reduced.
In comparative example 7, the amine groups in the amine-based carbon material were not CO 2 The amino carbonate is formed, and is rapidly decomposed in the heating pyrolysis process, and nitrogen can not be used as a physical activator to pore the material, so that the surface area, the nitrogen content and the adsorption capacity of the material are low.
Comparative example 8 where 50% CO was directly introduced in a high temperature environment 2 Resulting in direct decomposition of the amine functional groups without adequate protection, low specific surface area and nitrogen content, and CO 2 The adsorption capacity is also not high.
In comparative example 9, the eutectic solvent was changed to glucose and urea having no intercalation effect, and the prepared material had low surface area and nitrogen content, and the adsorption capacity was also general.
In comparative example 10, the eutectic solvent used was unable to form carbamates, and the eutectic solvent used was carbonized to form tertiary amine groups on the surface of the carbon precursor, which were then dried to CO 2 The adsorption capacity is weak and tertiary amine groups are not well protected during activation, resulting in low nitrogen content and poor adsorption capacity of the final carbon material.
How to increase CO in the flue gas by carbon materials 2 The difficulty of the adsorption effect of the catalyst is how to obtain better balance between the nitrogen content and the pore channel structure of the carbon material, and the existing technology has the disadvantages of complex preparation process, high pollution and environmental protection; or the prepared nitrogen-containing material has rich pore canal structure, large specific surface area or high nitrogen content but small specific surface area. Therefore, the excellent carbon material is prepared by selecting the process, and a balance is achieved between the nitrogen content and the specific surface area, and the CO is improved 2 The adsorption capacity of the carbon material and how to couple the carbon material preparation process to form a specific preparation technical scheme are all the invention points of the application.
The invention is characterized in that amine functional groups are loaded on the surface of a carbon precursor in situ through alkali treatment, eutectic solvent intercalation effect and the like to provide the functional groups and CO 2 Forming nitrogen source of carbamate and bicarbonate by reaction, and adsorbing CO 2 Forming an intermediate with protective amino functional groups, and slowly releasing to finally obtain the N-doped carbon material with high specific surface area to realize CO 2 High adsorption capacity. The material prepared by the invention not only contains alkaline sites such as pyridine nitrogen, pyrrole nitrogen and graphite nitrogen, but also has quaternary ammonium salt functional groups, is favorable for the material to have physical and chemical adsorption effects at the same time, and has low overall adsorption energy consumption. In general, the invention has low cost of raw materials, is green and environment-friendly, realizes high specific surface area, high N content and high CO through multi-technology coupling 2 And (3) preparing the carbon material with adsorption capacity. Compared with pressure swing adsorption, the method has the advantages of lower energy consumption (normal temperature and normal pressure adsorption, no need of providing extra energy) and larger adsorption capacity.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (9)
1. The preparation method of the nitrogen-doped porous carbon adsorption material is characterized by comprising the following steps of:
s1, dispersing a biomass waste raw material in an alkali solution, stirring for reaction, and centrifuging to obtain an alkaline hydrolysis solid mixture;
s2, dispersing the alkaline hydrolysis solid mixture in deionized water, heating for pre-carbonization, and then filtering to obtain a hydrothermal carbon material;
s3, dispersing the hydrothermal carbon material in deionized water, adding a eutectic solvent, heating to 160-220 ℃ for reaction, and washing with an alkaline solution at room temperature to obtain an amino-functionalized hydrothermal carbon material; the eutectic solvent is a mixture of a hydrogen bond acceptor and a hydrogen bond donor, wherein the hydrogen bond acceptor is one or more of choline chloride and serine, and the hydrogen bond donor is one or more of urea, citric acid and glycerol;
s4 is in the presence of CO 2 Under the inert atmosphere, the amino functionalized hydrothermal carbon material is reacted at room temperature, and then the temperature is raised to 650-850 ℃ for pore-forming and nitrogen doping reaction, so that the nitrogen doped porous carbon adsorption material is obtained.
2. The method for producing a nitrogen-doped porous carbon adsorbent material according to claim 1, wherein in step S1, the temperature of the stirring reaction is 0 to 10 ℃.
3. The method for producing a nitrogen-doped porous carbon adsorbent material according to claim 1, wherein in step S2, the temperature of the heating pre-carbonization is 160-240 ℃.
4. The method for preparing a nitrogen-doped porous carbon adsorption material according to claim 1, wherein the biomass waste raw material comprises one or more of peanut shells, straws and orange peels.
5. The method of claim 1, wherein in step S1 and step S3, the alkaline solution comprises urea and/or sodium hydroxide.
6. The method for producing a nitrogen-doped porous carbon adsorbent material according to claim 1, wherein the CO-containing gas is a gas 2 CO in an inert atmosphere 2 The concentration of (2) is 10-100%.
7. The method for preparing a nitrogen-doped porous carbon adsorption material according to claim 1, wherein in step S4, the heating rate is 5-10 ℃/min.
8. A nitrogen-doped porous carbon adsorbent material obtainable by the process of any one of claims 1 to 7.
9. A nitrogen-doped porous carbon adsorbent material as claimed in claim 8 for adsorbing CO 2 Is used in the field of applications.
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| CN110015662A (en) * | 2019-04-25 | 2019-07-16 | 太原理工大学 | A kind of CO absorption2With the preparation method of nitrogen-doped porous carbon material |
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