CN118062828A - Nitrogen-doped hierarchical porous carbon material and preparation method and application thereof - Google Patents
Nitrogen-doped hierarchical porous carbon material and preparation method and application thereof Download PDFInfo
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- CN118062828A CN118062828A CN202410347519.0A CN202410347519A CN118062828A CN 118062828 A CN118062828 A CN 118062828A CN 202410347519 A CN202410347519 A CN 202410347519A CN 118062828 A CN118062828 A CN 118062828A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims abstract description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 230000003213 activating effect Effects 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000012190 activator Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 229920001661 Chitosan Polymers 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims 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 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- 235000011148 calcium chloride Nutrition 0.000 claims description 2
- 239000004281 calcium formate Substances 0.000 claims description 2
- 229940044172 calcium formate Drugs 0.000 claims description 2
- 235000019255 calcium formate Nutrition 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 235000013904 zinc acetate Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- 230000007935 neutral effect Effects 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 41
- 239000007789 gas Substances 0.000 abstract description 26
- 239000011148 porous material Substances 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 8
- 238000003795 desorption Methods 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 5
- 230000008929 regeneration Effects 0.000 abstract description 5
- 238000011069 regeneration method Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 4
- 150000004706 metal oxides Chemical class 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000002808 molecular sieve Substances 0.000 abstract 1
- 238000005457 optimization Methods 0.000 abstract 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 20
- 238000012360 testing method Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000003068 static effect Effects 0.000 description 8
- 238000003860 storage Methods 0.000 description 7
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- -1 and forms acid rain Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003463 sulfur Chemical class 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000002316 fumigant Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010920 waste tyre Substances 0.000 description 1
- 229910006364 δ-MnO2 Inorganic materials 0.000 description 1
Classifications
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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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biomedical Technology (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a synthesis method of a nitrogen-doped hierarchical porous carbon material and application of the nitrogen-doped hierarchical porous carbon material in SO 2 renewable adsorption, and belongs to the technical fields of material preparation and environmental catalysis. The adsorption alkaline site content of the catalyst is improved by further carrying out nitrogen doping after the unordered hierarchical porous carbon material is synthesized. The synthesis method has simple and feasible synthesis steps, realizes the regulation and optimization of the electronic structure and the surface property of the catalyst in the nitrogen-doped hierarchical porous carbon by utilizing the action of the activating agent, and the prepared catalyst has high specific surface area and pore volume, shows high catalytic activity and selectivity in the reproducible adsorption and desorption of acid gases such as SO 2, can realize the efficient adsorption and removal of SO 2, achieves the effect of enriching SO 2, further realizes the utilization of sulfur resources, has higher regeneration efficiency, wider use environment, simple preparation process and environment-friendly and cheap raw materials, and has huge industrial application prospect compared with the traditional catalysts such as metal oxides, molecular sieves and the like.
Description
Technical Field
The invention belongs to the technical field of material preparation and environmental catalysis, and particularly relates to a preparation method of a nitrogen-doped hierarchical porous carbon catalyst and application of the nitrogen-doped hierarchical porous carbon catalyst in SO 2 renewable adsorption.
Background
Sulfur dioxide (SO 2) is a common industrial toxic gas which is usually discharged along with the combustion of sulfur-containing fossil fuel, and forms acid rain, acid mist and other bad weather in the atmosphere, SO that the sulfur dioxide is not only severely corroded on land, buildings and the like, but also is harmless to people. How to effectively treat the emissions of SO 2 has been an extremely important issue in the last decades. The most commonly used technology for treating SO 2 at present is wet flue gas desulfurization, but the water consumption is high, the occupied area is large, the ecological is destroyed by exploiting a large amount of limestone, the byproduct of inferior gypsum is large and single, and meanwhile, a large amount of sulfur compounds are required to be imported every year in China, SO 2 serious pollution and sulfur resource shortage form sharp contrast, and the resource utilization faces a bottleneck. Therefore, there is an urgent need to develop a renewable catalyst that can efficiently adsorb SO 2 and realize desorption for resource recycling.
Physical adsorption is carried out by utilizing the high specific surface area of the porous material and the action of the surface active site, and desorption is carried out by heating so as to enrich the porous material, thereby realizing the removal of acid gas and the recycling of resources. SO 2 can be used for producing sulfur-containing compounds, fumigants, preservatives, disinfectants, reducing agents, pesticides and the like, is widely used in industrial departments of pesticides, artificial fibers, dyes and the like, and can recycle resources, protect the environment and increase the sulfur resources in China, SO that the method has a huge application prospect. Compared with the wet adsorption method for generating single low-value byproduct gypsum, the method has the advantages that SO 2 is used for resource utilization more reasonably, and the renewable SO 2 adsorption and desorption catalyst is designed.
Conventionally, SO 2 that can be used is adsorbed with a metal oxide (CaO, mgO, hydrotalcite NiAl composite oxide, etc.), a zeolite (NaX, clinoptilolite, etc.), a MOF (MFM-601, ctf-CSU41, etc.) material, a carbon material, etc., and the above materials have disadvantages. For example, the regeneration temperature of the metal oxide is high, SO 2 absorbed in the regeneration process can form sulfite with the metal oxide, and O 2 can further generate sulfate which is difficult to remove, SO that the performance is reduced; the zeolite can produce a large amount of alkaline substances and trace heavy metals harmful to the environment in the preparation process, and besides the preparation cost is high, the water resistance of the catalyst is poor; MOF materials are also used as adsorbents only in the laboratory stage, and the cost of synthesis is high, limiting their industrial application. The traditional carbon material has low cost, but has low adsorption sulfur capacity and is not easy to regenerate, so that the use amount is large, and more wastes are generated, thereby affecting the economy. Therefore, the search for a new green adsorption catalyst with high adsorption sulfur capacity, multiple regeneration and relatively simple synthesis path is an important link for developing low-solubility SO 2 removal and resource utilization.
It is noted that natural biomass is a renewable energy source that can be used as a carbon source, wherein nitrogen-free materials are used, because doping of nitrogen elements can change the locally unbalanced charged region of the whole carbon structure, and can be divided into chemical nitrogen and structural nitrogen according to the environment in which the nitrogen atoms are located. Chemical nitrogen mainly exists on the surface of the material in the form of a surface functional group, SO that the B-alkalinity of porous carbon can be improved, namely, a proton (H +) is accepted, such as amino, nitrosyl and other surface nitrogen-containing functional groups, while structural nitrogen refers to a molecule which is formed by leading nitrogen atoms into a framework structure of the carbon material to be directly bonded with carbon atoms, and can enhance the L-alkalinity of the material, namely, electron pair providing molecules, ions or atomic groups, such as pyridine nitrogen and other nitrogen atoms can provide lone electron pairs, and the lone electron pairs are combined with the 3 center 4 electrons of SO 2 to form a stable structure, SO that gas adsorption is carried out. Pyridine nitrogen species have a higher basicity than pyridine nitrogen species due to their containing lone electron pairs, and are more active in capturing such gases through strong acid-base interactions between the pyridine nitrogen and the acid gas. Based on the method, the invention creatively designs and develops a green, mild and simple method for preparing the nitrogen-doped hierarchical porous carbon catalyst, and the nitrogen-doped hierarchical porous carbon catalyst is applied to the reproducible adsorption-desorption reaction of SO 2.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a synthesis method and application of a disordered nitrogen-doped porous carbon material, and the catalyst solves the problems of high water consumption, poor byproducts, low availability and the like in an SO 2 adsorption mode in the prior art, can realize SO 2 adsorption and desorption at normal temperature, consumes no water, enriches sulfur resources and efficiently recovers the resources.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a disordered nitrogen-doped hierarchical porous carbon material is prepared by taking a relatively cheap carbon raw material as a precursor, taking a nitrogen-containing raw material as a pore-forming agent and a doping nitrogen source, and modifying by using a certain activating agent; the preparation method comprises the following steps:
(1) Grinding and mixing a carbon raw material and a nitrogen-containing raw material in a certain proportion, and then adding a proper amount of activating agent to continuously grind and mix uniformly to obtain a mixture A;
(2) Placing the mixture A in a certain solvent, stirring until the mixture A is completely dispersed, and then placing the mixture A in a vacuum drying oven for drying to obtain a mixture B;
(3) Further grinding and mixing the mixture B uniformly at room temperature;
(4) Transferring the powder obtained in the step (3) into a tube furnace, and roasting in corresponding roasting gas to obtain an activator doped nitrogen doped carbon catalyst C;
(5) Adding the catalyst C obtained in the step (4) into deionized water, stirring and cleaning, and then drying to obtain a catalyst D;
(6) And (3) adding a small amount of hydrochloric acid into the catalyst D for cleaning, then cleaning to neutrality by deionized water, and drying to obtain the SO 2 adsorption removal catalyst.
Further, the carbon raw material in the step (1) is one or more than two of glucose, cellulose acetate, fructose, chitosan and carboxymethyl cellulose, and the mass ratio of the carbon raw material to the nitrogen-containing raw material is 1:1 to 4;
Further, the nitrogenous raw material in the step (1) is one or more than two of ammonium carbonate, melamine, dinitrile diamine, urea, cyanamide, ammonium nitrate and ammonium chloride;
Further, the activator in the step (1) is one or more than two of zinc chloride, calcium carbonate, zinc acetate, calcium formate, calcium chloride, magnesium carbonate and ammonium carbonate as pore-forming agents, and the mass ratio of the activator to the carbon raw material is 1:1 to 8.
Further, the solvent in the step (2) is one or more than two of deionized water, ethanol, acetone, deionized water, ammonia water and acetic acid, and the amount of the added solvent is 10-400 times of the mass of the raw materials.
Further, in the step (2), the drying temperature is 50 ℃, and the drying time is 10-24 hours.
Further, in the step (4), the roasting temperature is 600-900 ℃, the heat preservation time is 1-3 hours, and the heating rate is 1-5 ℃/min.
Further, the roasting atmosphere in the step (4) is one of helium, nitrogen, ammonia and argon.
Further, the deionized water in the step (5) is in an amount of 100-400ml.
Further, the drying temperature in the step (5) is 50-100 ℃.
Further, the concentration of the hydrochloric acid in the step (6) is 0.5-2 mol/L.
Further, the drying temperature in the step (6) is 50-80 ℃.
Further, the specific surface area of the catalyst is 300-1000m 2/g.
Further, the application conditions of the SO 2 adsorption are as follows: the reaction temperature is 25-100 ℃, the reaction pressure is normal pressure to 2.0MPa, the heating rate is 1 ℃/min, the flow rate of the raw material gas is 10-50ml/min, and the concentration of SO 2 in the raw material gas is 35100-1755000mg/m 3.
The invention has the beneficial effects that:
(1) The disordered nitrogen doped hierarchical porous carbon catalyst provided by the invention has high specific surface area and pore volume, is favorable for adhesion of reactive sites and diffusion adsorption of SO 2 gas, has simple synthesis method conditions, is simple and feasible in steps, is easy to realize industrial production, and has a huge application prospect.
(2) The disordered nitrogen doped hierarchical porous carbon catalyst provided by the invention can effectively improve the specific surface area and pore volume of the catalyst by adding the activating agent, effectively improve the geometric structure, electronic structure and surface chemical property of a carbon material, maintain the morphology of a precursor, improve the yield and have higher performance in the aspect of SO 2 gas adsorption.
(3) The disordered nitrogen doped hierarchical porous carbon catalyst provided by the invention is not easy to cause pore blocking, has no obvious change in performance before and after reaction, can be recycled, can reduce consumable materials, and has the current performance superior to that of traditional desulfurizing agents such as NiAlO, znAl 2O4,δ-MnO2,Fe3O4, cuO modified SBA-15, cuO-CeO 2 modified KIT-6, naX, NH 4 Y,13X, ZX-WS, fly ash, cork dust, sludge, semi-coke, coconut shell, waste tires, mesoporous carbon materials, carbon material modified adsorbents such as commercial activated carbon and the like.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of CSN-Ca600, CSN-Ca700, CSN-Ca800, CSN-Ca900 prepared in examples 1 to 4 of the present invention;
FIG. 2 shows the physical adsorption and desorption curves of the CSN-Ca600, the CSN-Ca700, the CSN-Ca800 and the N 2 of the CSN-Ca900 prepared in examples 1 to 4 of the present invention;
FIG. 3 is an SEM image of CSN-Ca600, CSN-Ca700, CSN-Ca800, CSN-Ca900 prepared in examples 1 to 4 of the present invention;
FIG. 4 shows XPS diagrams of CSN-Ca600, CSN-Ca700, CSN-Ca800 and CSN-Ca900 prepared in examples 1 to 4 of the present invention, wherein A is a total spectrum diagram, B is a C1s spectrum diagram, and C is an N1s spectrum diagram;
FIG. 5 is a dynamic adsorption drawing of CSN-Ca600, CSN-Ca700, CSN-Ca800, CSN-Ca900 in adsorbing SO 2 prepared in examples 1-4 of the present invention;
FIG. 6 is a diagram showing a static adsorption apparatus for CSN-Ca600, CSN-Ca700, CSN-Ca800, and CSN-Ca900 prepared in examples 1 to 4 of the present invention;
FIG. 7 shows the static adsorption patterns of the CSN-Ca600, the CSN-Ca700, the CSN-Ca800 and the CSN-Ca900 on SO 2 and the static adsorption patterns of the CSN-Ca800 at different temperatures, which are prepared in examples 1 to 4 of the present invention;
FIG. 8 is a cyclic adsorption drawing of CSN-Ca800 prepared in example 3 of the present invention at normal temperature.
Detailed Description
The objects, technical solutions and advantages of the present invention will become more apparent by the following detailed description of the present invention with reference to the accompanying examples and drawings, which illustrate the present invention further, but not by way of limitation.
Example 1
Firstly, weighing chitosan, urea and calcium chloride (1:2:1), mixing and grinding uniformly, then adding the mixture into absolute ethyl alcohol, stirring and dispersing uniformly on a magnetic stirrer, and then drying for 24 hours at 40 ℃ in a vacuum drying oven until the ethyl alcohol is completely dried. The mixture taken out is then ground continuously, and then the mixture is placed in a tube furnace, carbonized by high-temperature activation under nitrogen atmosphere, heated to 600 ℃ from room temperature at a rate of 3 ℃/min, kept for 1h and naturally cooled to room temperature. The activated porous carbon was stirred in 400ml of deionized water at room temperature for 8 hours to remove soluble impurities in the water, then filtered using vacuum, and washed 2 to 3 times with deionized water, and then dried in a vacuum dryer at 70 ℃ for 12 hours. The dried porous carbon was added to 100ml of 1M hydrochloric acid to wash out the residual activator therein, stirred for 1h, then vacuum filtered, and repeatedly washed with deionized water until ph=7, further cooled naturally to room temperature in a vacuum dryer at 70 ℃ for 12h, and then the synthesized sample was collected, and the disordered nitrogen doped hierarchical porous carbon catalyst was named CSN-Ca600.
Example 2
Firstly, weighing chitosan, urea and calcium chloride (1:2:1), mixing and grinding uniformly, then adding the mixture into absolute ethyl alcohol, stirring and dispersing uniformly on a magnetic stirrer, and then drying for 24 hours at 40 ℃ in a vacuum drying oven until the ethyl alcohol is completely dried. The mixture taken out is continuously grinded, then the mixture is placed in a tube furnace, high-temperature activated carbonization is carried out under the nitrogen atmosphere, the temperature is increased to 700 ℃ from the room temperature at the speed of 3 ℃/min, the temperature is kept for 1h, and the mixture is naturally cooled to the room temperature. The activated porous carbon was stirred in 400ml of deionized water at room temperature for 8 hours to remove soluble impurities in the water, then filtered using vacuum, and washed 2 to 3 times with deionized water, and then dried in a vacuum dryer at 70 ℃ for 12 hours. The dried porous carbon was added to 100ml of 1M hydrochloric acid to wash out the residual activator therein, stirred for 1h, then vacuum filtered, and repeatedly washed with deionized water until ph=7, further cooled naturally to room temperature in a vacuum dryer at 70 ℃ for 12h, and then the synthesized sample was collected, and the disordered nitrogen doped hierarchical porous carbon catalyst was named CSN-Ca700.
Example 3
Firstly, weighing chitosan, urea and calcium chloride (1:2:1), mixing and grinding uniformly, then adding the mixture into absolute ethyl alcohol, stirring and dispersing uniformly on a magnetic stirrer, and then drying for 24 hours at 40 ℃ in a vacuum drying oven until the ethyl alcohol is completely dried. The mixture taken out is continuously grinded, then the mixture is placed in a tube furnace, high-temperature activated carbonization is carried out under the nitrogen atmosphere, the temperature is increased to 800 ℃ from the room temperature at the speed of 3 ℃/min, the temperature is kept for 1h, and the mixture is naturally cooled to the room temperature. The activated porous carbon was stirred in 400ml of deionized water at room temperature for 8 hours to remove soluble impurities in the water, then filtered using vacuum, and washed 2 to 3 times with deionized water, and then dried in a vacuum dryer at 70 ℃ for 12 hours. The dried porous carbon was added to 100ml of 1M hydrochloric acid to wash out the residual activator therein, stirred for 1h, then vacuum filtered, and repeatedly washed with deionized water until ph=7, further cooled naturally to room temperature in a vacuum dryer at 70 ℃ for 12h, and then the synthesized sample was collected, and the disordered nitrogen doped hierarchical porous carbon catalyst was named CSN-Ca800.
Example 4
Firstly, weighing chitosan, urea and calcium chloride (1:2:1), mixing and grinding uniformly, then adding the mixture into absolute ethyl alcohol, stirring and dispersing uniformly on a magnetic stirrer, and then drying for 24 hours at 40 ℃ in a vacuum drying oven until the ethyl alcohol is completely dried. The mixture taken out is continuously grinded, then the mixture is placed in a tube furnace, high-temperature activated carbonization is carried out under the nitrogen atmosphere, the temperature is increased to 900 ℃ from the room temperature at the speed of 3 ℃/min, the temperature is kept for 1h, and the mixture is naturally cooled to the room temperature. The activated porous carbon was stirred in 400ml of deionized water at room temperature for 8 hours to remove soluble impurities in the water, then filtered using vacuum, and washed 2 to 3 times with deionized water, and then dried in a vacuum dryer at 70 ℃ for 12 hours. The dried porous carbon was added to 100ml of 1M hydrochloric acid to wash out the residual activator therein, stirred for 1h, then vacuum filtered, and repeatedly washed with deionized water until ph=7, further cooled naturally to room temperature in a vacuum dryer at 70 ℃ for 12h, and then the synthesized sample was collected, and the disordered nitrogen doped hierarchical porous carbon catalyst was named CSN-Ca900.
Characterization analysis:
1. Instrument and equipment
X-ray powder diffraction (XRD): the XRD pattern of the catalyst was measured on a Bruker D8 Advance type X-ray diffraction, a copper target (Cu kα, λ=0.154 nm) X-ray tube, a Ni filter, operating voltage 45kV, current 40mA, and scan range 2θ=10 to 60 °.
Determination of specific surface area and pore size distribution (low temperature N 2 physisorption): the specific surface area and pore size distribution of the catalyst were determined by analysis in an ASAP2020 type other adsorption pore size meter (Micrometrics, USA). The vacuum degree P/P 0 of the sample chamber is in the range of 0-1, and is measured by a liquid nitrogen static adsorption method. Before the test, the catalyst is firstly placed under vacuum and deaerated for 8 hours at a temperature of 473K, then the adsorption-desorption isotherm is measured according to a static method, the specific surface area is calculated by a multipoint Barrett-Emmett-Teller (BET) method, and the pore volume and pore size distribution are calculated by using a Barrett-Joyner-Halanda (BJH) model.
Field emission Scanning Electron Microscope (SEM): SEM images of the samples were observed on a scanning electron microscope model S-4800, with test currents and voltages of 7. Mu.A and 5kV, respectively.
The elemental chemistry of the sample surface was tested using an X-ray photoelectron spectrometer (ESCACAB xi). A monochromatic Alkalpha excitation source (1486.6 eV,15kV,10.8 mA) was used. The sample is fixed on the ultra-high vacuum insulating adhesive tape after being pressed into a tablet, and the adhesive tape is stuck on the sample holder. And after the sample introduction chamber and the sample preparation chamber are respectively pumped to the designated vacuum degree step by step, the sample is introduced into the analysis chamber for testing. Analysis chamber vacuum <10 -8 bar. Charge calibration was performed with c1s=284.8ev as an internal standard.
FIG. 1 shows the X-ray powder diffraction patterns of CSN-Ca600, CSN-Ca700, CSN-Ca800 and CSN-Ca900 prepared in examples 1 to 4 of the present invention. As can be seen from fig. 1, all catalysts have a broad diffraction peak at about 27.4 ° in 2θ, attributable to the (002) crystal plane, representing the interlayer spacing of graphitic carbon, and a weak peak at about 44.2 ° in 2θ, which corresponds to the (100) in-plane spacing of carbon material, with very low intensities representing the typical amorphous carbon material structure of the synthesized catalyst, with broad and weak diffraction peaks indicating the presence of a rich defect structure. As the temperature increases, the diffraction angle shifts to a low angle, which indicates that the graphitization degree is reduced, the peak width is widened and the intensity is reduced, which indicates that the internal defects of the crystal are increased, and the material performance is further improved.
FIG. 2 shows the physical adsorption and desorption curves of CSN-Ca600, CSN-Ca700, CSN-Ca800 and N 2 of CSN-Ca900 prepared in examples 1 to 4 of the present invention. From the graph, all catalysts belong to an IV-type curve isothermal adsorption curve and an H3-type hysteresis loop appears. The pore size distribution diagram shows that the catalyst has a structure of combining micropores and mesopores, and the pore size distribution is between 2.78 and 3.31nm, and belongs to the range of mesopores. The specific surface areas of CSN-Ca600, CSN-Ca700, CSN-Ca800 and CSN-Ca900 were 380.0, 614.9, 1040.1 and 603.2m 2/g, respectively, as calculated by the BET method. Wherein CSN-Ca800 has the largest BET specific surface area and total pore volume. And the total pore volume of CSN-Ca800 (0.502 cm 3/g) was about 2 times that of CSN-Ca600 (0.215 cm 3/g). This is because NH 3 and CO 2 released from the material during calcination will release more as the temperature increases, acting as a soft template for pore formation during pyrolysis, thus expanding the BET surface area of the catalyst. The high specific surface area is beneficial to contact of reactants and a catalyst, and is more beneficial to combination of SO 2 and N alkaline sites. Whereas the specific surface area and pore volume of CSN-Ca900 is smaller relative to CSN-Ca800 because the temperature is too high, and the excessive activation results in partial pore collapse of the material.
FIG. 3 is an SEM image of CSN-Ca600 (a-c), CSN-Ca700 (d-f), CSN-Ca800 (g-i), CSN-Ca900 (j-l) prepared in examples 1 to 4 of the present invention. As can be seen from fig. 3, the use of the calcium chloride activator better maintained the shape of the sample, a large number of fine pores were seen under the high power mirror, while a large portion of the pores were seen as planar structures under the low power mirror, and the pores of the surface were more apparent as the temperature increased.
FIG. 4 shows XPS patterns of CSN-Ca600, CSN-Ca700, CSN-Ca800 and CSN-Ca900 prepared in examples 1 to 4 of the present invention, wherein A is a total spectrum, B is a C1s spectrum, and C is an N1s spectrum. From the results, the surfaces of the four catalysts only contain three elements of C, N and O and do not contain other elements after the hydrochloric acid is used for cleaning the activator, and the positions of the binding energy of the C1s energy level, the N1s energy level and the O1s energy level are respectively corresponding to 284.5eV,399.5eV and 530.0 eV. As can be seen in FIG. 4B, the C1s curve can be divided into three peaks centered at 284.9, 286.7, 289eV, which are related to the C-C, C-N and C-O bonds, and the C-O bond content is smaller, probably because the O element in the sample is consumed as the temperature increases. Four peaks of N1s can be seen in fig. 4C, corresponding to pyridine nitrogen, pyrrole nitrogen, graphite nitrogen and oxynitride species at 398.1, 399.2, 400.5 and 403.5eV, respectively, which have higher base intensities due to their single electron pair compared to other nitrogen structural sites, which are the most active sites for the porous carbon to capture acid gases, with the highest content in CSN-Ca 800.
Reaction test of SO 2 adsorption: the CSN-Ca600, CSN-Ca700, CSN-Ca800, CSN-Ca900 prepared in examples 1 to 4 were ground and weighed and then applied to the activity test. The test conditions were as follows: the catalyst was used in an amount of 100mg, the feed gas consisted of 1000ppm SO 2 and balanced nitrogen, the feed gas flow rate was 50mL min -1, and the reaction temperature was 25 ℃.
FIG. 5 shows dynamic adsorption test curves of CSN-Ca600, CSN-Ca700, CSN-Ca800 and CSN-Ca900 prepared in examples 1 to 4 of the present invention, wherein the penetration times of CSN-Ca600, CSN-Ca700, CSN-Ca800 and CSN-Ca900 are 53, 34, 52 and 14min, and the saturation times are 93, 162, 104 and 150min, respectively, and the saturated sulfur capacities are 86, 91, 114 and 60mg/g, respectively, so that the best sample performance at 800 ℃ can be seen.
FIG. 6 is a static adsorption test device consisting essentially of a feed gas, a supply system, a detection system, a temperature control system, a vacuum system, and a reaction system (including storage tanks and adsorption tanks). The main sources of errors are that the equipment respectively sources are: the gas is supplied by Dalianda gas cable company, the reactor system is supplied by Feiyu oil technology development Co., nannong, china, the pressure measuring system is supplied by Nanjing from electric Co., ltd, and the temperature control system is supplied by ya Ma Ta, japan.
The testing process comprises the following steps: the sample is placed in a vacuum at 150 ℃ for drying for more than 12 hours before testing, so as to remove substances adsorbed on the surface of the sample, such as water, oxygen and the like. And (3) taking about 0.1g of the treated sample, placing the sample into an adsorption tank of the device for sealing, transferring the storage tank and the adsorption tank into a constant-temperature water bath kettle together, vacuumizing the two tanks by using a vacuum pump, closing a pipeline between the two tanks, and preventing gas on two sides from flowing. In order to measure the free volume of the adsorption tank, a certain amount of He is filled into the storage tank, after the pressure indication is stable, the gas in the storage tank is led into the adsorption tank, then the needle valve is closed, and the free volume value in the adsorption tank can be obtained after the indication is stable. And then pumping the storage tank and the adsorption tank to vacuum again, introducing enough needed measurement gas SO 2 into the storage tank, controlling the pressure of the gas discharged from the storage tank to the adsorption tank, recording the value of the gas which is stable for 10 minutes, obtaining the balanced adsorption quantity under the current pressure, controlling the pressure to about 1bar, and finishing a test after balancing. The adsorption capacity of the sample can be calculated according to the following equation:
Wherein m G is the adsorption amount (mmol/g) of SO 2, Is the density (mol/L) of SO 2 under P i pressure. V j (j=1, 2) is the free volume (mL) of the cavity, W s is the mass (g) of solid adsorbent added to the cavity,/>Is the density of SO 2 available from NIST chemical website. The value of V j was determined using helium as the probe gas. The amount of SO 2 adsorbed at high pressure was determined by adding more SO 2 to the adsorption chamber. After the measurement is completed, the SO 2 gas in the reaction chamber is introduced into sodium hydroxide solution to prevent the SO 2 gas from escaping.
Fitting the adsorption curve to the data by using a double-point Langmuir-Freundlich (DSLF) equation, and drawing an adsorption isotherm, wherein the equation is shown as a formula (2-2):
In formula 2-2, P is the bulk gas pressure (Pa) at equilibrium with the adsorption phase, q is the adsorption amount (mol/kg) of the adsorbent, q m.1 and q m.2 are the saturation capacities (mol/kg) of sites 1,2, and b 1,b2 is the affinity coefficient at sites 1,2 (Pa -1),n1,n2 represents the deviation from the ideal homogeneous surface.
FIG. 7A shows the static adsorption curves of CSN-Ca600, CSN-Ca700, CSN-Ca800 and CSN-Ca900 prepared in examples 1 to 4 of the present invention. As can be seen, the adsorption saturated sulfur capacities of CSN-Ca600, CSN-Ca700, CSN-Ca800 and CSN-Ca900 were 6.2,7.1,9.0 and 6.8mmol/g, respectively, and it was found that the adsorption capacities at 800℃were maximized, which was indistinguishable from their higher pyridine nitrogen contents and specific surface densities. On this basis, CSN-Ca800 was subjected to static adsorption at various temperatures, and it can be seen in FIG. 7B that the adsorption amount at 25℃was 9.0mmol/g, and that at 50℃was 6.3mmol/g, and that even at 75℃5.6mmol/g was adsorbed, whereby the application temperature window of the catalyst was higher than normal temperature.
FIG. 8 is a cyclic adsorption drawing of CSN-Ca800 prepared in example 3 of the present invention at normal temperature. It can be seen that after saturation of the first catalyst adsorption, the amount of adsorption can reach 9.0mmol/g, and then the temperature of the reaction apparatus is raised, and at the same time, SO 2 gas is extracted, and thermal regeneration is performed to restore the catalyst activity. The adsorption process for the first time was repeated for 5 times, and the adsorption amount was recorded, and it was found that the adsorption amounts for the subsequent several cycles were 8.8,8.9,8.7,8.6mmol/g, respectively, and the adsorption capacity remained at 95% or more, demonstrating that the recyclability of this material was good.
In summary, the nitrogen doped disordered graded porous carbon with different activation temperatures prepared by the invention has good adsorption performance on the reverse side of SO 2 adsorption application, wherein the performance of CSN-Ca800 is the best. The prepared nitrogen doped disordered hierarchical porous carbon material has higher yield, pore volume and higher specific surface area, the preparation method is simple, the raw materials are green and cheap, and the recycling property is good, so that the method has a great industrial application prospect.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A preparation method of a nitrogen-doped hierarchical porous carbon material is characterized by comprising the following steps of: the method comprises the following steps:
(1) Grinding and mixing a carbon raw material and a nitrogen-containing raw material, adding an activating agent, and continuously grinding and mixing uniformly to obtain a mixture A;
(2) Dissolving the mixture A in a solvent, stirring until the mixture A is completely dispersed, and drying the mixture A in vacuum to obtain a mixture B;
(3) Continuously grinding and uniformly mixing the mixture B at room temperature, and roasting to obtain a nitrogen-doped carbon material C;
(4) Adding the nitrogen-doped carbon material C into deionized water, stirring, cleaning and drying to obtain a nitrogen-doped carbon material D;
(5) And adding the nitrogen-doped carbon material D into hydrochloric acid for cleaning, and then cleaning with deionized water to be neutral and drying to obtain the nitrogen-doped hierarchical porous carbon material.
2. The method of manufacturing according to claim 1, characterized in that: the carbon raw material in the step (1) is at least one of glucose, cellulose acetate, fructose, chitosan and carboxymethyl cellulose, and the nitrogen-containing raw material is at least one of ammonium carbonate, melamine, dinitrile diamine, urea, cyanamide, ammonium nitrate and ammonium chloride; the mass ratio of the carbon raw material to the nitrogen-containing raw material is 1:1-4.
3. The method of manufacturing according to claim 1, characterized in that: the activating agent in the step (1) is at least one of zinc chloride, calcium carbonate, zinc acetate, calcium formate, calcium chloride, magnesium carbonate and ammonium carbonate; the mass ratio of the activator to the carbon raw material is 1: 1-8.
4. The method of manufacturing according to claim 1, characterized in that: the solvent in the step (2) is at least one of deionized water, ethanol, acetone, ammonia water and acetic acid, and the mass ratio of the solvent to the mixture A is 10-400: 1.
5. The method of manufacturing according to claim 1, characterized in that: the drying temperature in the step (2) is 50 ℃, and the drying time is 10-24 h.
6. The method of manufacturing according to claim 1, characterized in that: the roasting temperature in the step (3) is 600-900 ℃, and the heat preservation time is 1-3 h; the temperature rising rate is 1-5 ℃/min; the roasting atmosphere is one of helium, nitrogen, ammonia and argon.
7. The method of manufacturing according to claim 1, characterized in that: the drying temperature in the step (4) is 50-100 ℃.
8. The method of manufacturing according to claim 1, characterized in that: in the step (5), the concentration of hydrochloric acid is 0.5-2 mol/L; the drying temperature is 50-80 ℃.
9. A nitrogen-doped graded porous carbon material made by the method of any one of claims 1-8, wherein: the specific surface area of the carbon material is 300-1000 m 2/g.
10. Use of a nitrogen-doped graded porous carbon material prepared by the method of any one of claims 1-8 in SO 2 regenerable adsorption.
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