CN109110742A - Utilize the mesoporous carbon and preparation method of manganese compound preparation - Google Patents
Utilize the mesoporous carbon and preparation method of manganese compound preparation Download PDFInfo
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- CN109110742A CN109110742A CN201710484481.1A CN201710484481A CN109110742A CN 109110742 A CN109110742 A CN 109110742A CN 201710484481 A CN201710484481 A CN 201710484481A CN 109110742 A CN109110742 A CN 109110742A
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- CN
- China
- Prior art keywords
- manganese
- mesoporous carbon
- mesoporous
- carbon
- preparation
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 150000002697 manganese compounds Chemical class 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000003763 carbonization Methods 0.000 claims abstract description 39
- 239000007833 carbon precursor Substances 0.000 claims abstract description 31
- 239000012298 atmosphere Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 36
- 239000011656 manganese carbonate Substances 0.000 claims description 18
- 235000006748 manganese carbonate Nutrition 0.000 claims description 18
- 229940093474 manganese carbonate Drugs 0.000 claims description 18
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 18
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 12
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 9
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 8
- -1 polyethylene terephthalate Polymers 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- HYFPVPNWNRFTMP-UHFFFAOYSA-N formic acid;manganese Chemical compound [Mn].OC=O HYFPVPNWNRFTMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 239000011564 manganese citrate Substances 0.000 claims description 3
- 235000014872 manganese citrate Nutrition 0.000 claims description 3
- 229940097206 manganese citrate Drugs 0.000 claims description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims description 3
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000011683 manganese gluconate Substances 0.000 claims description 2
- 235000014012 manganese gluconate Nutrition 0.000 claims description 2
- 229940072543 manganese gluconate Drugs 0.000 claims description 2
- OXHQNTSSPHKCPB-IYEMJOQQSA-L manganese(2+);(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Mn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OXHQNTSSPHKCPB-IYEMJOQQSA-L 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 239000010920 waste tyre Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 1
- 239000011295 pitch Substances 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 49
- 239000011148 porous material Substances 0.000 abstract description 27
- 239000011572 manganese Substances 0.000 abstract description 19
- 238000010521 absorption reaction Methods 0.000 abstract description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 8
- 229910052748 manganese Inorganic materials 0.000 abstract description 8
- 239000000843 powder Substances 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 238000000197 pyrolysis Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000006193 liquid solution Substances 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 238000005554 pickling Methods 0.000 description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 36
- 239000003610 charcoal Substances 0.000 description 24
- 238000001179 sorption measurement Methods 0.000 description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 19
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 17
- 229960000907 methylthioninium chloride Drugs 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 230000008569 process Effects 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
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- 238000002156 mixing Methods 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- YCIHPQHVWDULOY-FMZCEJRJSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 description 7
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- 230000009514 concussion Effects 0.000 description 7
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- 239000000126 substance Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
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- 230000008859 change Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 231100001010 corrosive Toxicity 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LGZQSRCLLIPAEE-UHFFFAOYSA-M sodium 1-[(4-sulfonaphthalen-1-yl)diazenyl]naphthalen-2-olate Chemical compound [Na+].C1=CC=C2C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C(S([O-])(=O)=O)C2=C1 LGZQSRCLLIPAEE-UHFFFAOYSA-M 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
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- 229960002477 riboflavin Drugs 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 235000019163 vitamin B12 Nutrition 0.000 description 1
- 239000011715 vitamin B12 Substances 0.000 description 1
- 235000019164 vitamin B2 Nutrition 0.000 description 1
- 239000011716 vitamin B2 Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- ORZHVTYKPFFVMG-UHFFFAOYSA-N xylenol orange Chemical compound OC(=O)CN(CC(O)=O)CC1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(CN(CC(O)=O)CC(O)=O)C(O)=C(C)C=2)=C1 ORZHVTYKPFFVMG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/617—
-
- B01J35/618—
-
- B01J35/638—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- 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
- 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
-
- 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
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The invention discloses a kind of mesoporous carbons and preparation method thereof using manganese compound preparation.This method is that the manganese oxide crystal nano particle being decomposed to form during carbon precursor pyrolysis charring using the compound of manganese has intermediate pore size characteristic, and the compound of manganese has the characteristics that catalysis carbon-forming to carbon precursor, it is specific as follows using the compound of manganese as template agent precursor preparation mesoporous carbon: 1, uniformly to mix thermoplasticity carbon precursor by solid phase powder or liquid solution with the compound of manganese；2, mixture high temperature carbonization is obtained into the carbide of package MnO nano particle in an inert atmosphere；3, carbide is uniformly mixed with dilute acid soln, removes MnO, obtains mesoporous carbon.Mesoporous carbon specific surface area prepared by the present invention is high, mesoporous is high, mesoporous holds greatly, and pore structure, pore-size distribution are easy to regulate and control, and the carbonization temperature of carbon precursor can be greatly reduced, and can be widely applied for the fields such as absorption, catalysis, separation.
Description
Technical field
The invention belongs to a kind of mesoporous carbons and preparation method thereof, specially utilize the mesoporous carbon and its system of manganese compound preparation
Preparation Method, gained mesoporous carbon can be applied to absorption, catalysis, separation and electrochemistry etc..
Background technique
Porous charcoal is a kind of widely used adsorbent, with specific surface area is high, pore volume is big, Surface chemical functional group of wood is rich
The advantages that rich, possesses higher absorption property, flourishes in field of environment protection, can effectively handle water body, more in atmosphere
Kind pollutant.International Union of Pure and Applied Chemistry (IUPAC) carries out porous material internal void according to its pore size
It divides comprising micropore (< 2nm), mesoporous (2~50nm) and macropore (> 50nm).
Conventional porous charcoal is mostly microporous activated carbon, and relative to microporous activated carbon, mesoporous carbon is had the advantages that due to hole ruler
Very little big compared with micropore, i.e., adsorbable larger-size organic pollutant can also be used as the absorption that channel promotes small-molecule substance；It is right
In CO2Deng the gas molecule with higher electric, micropore filling, but also meeting not only occur in micropore for gas molecule
Occur capillary condensation in biggish duct, and CH4Molecule Deng no electric will not then agglomerate in macropore, root
According to this characteristic, the separation that mesoporous carbon realizes heterogeneity gas molecule can use；Mesoporous can promote ion inside duct
Diffusion, mesoporous carbon shows higher energy density in the capacitor, can be used as double layer capacitor in new energy field
In electrode material.
Also, the macromolecule contaminant being described in table 1 below substantially molecular diameter:
Table 1
| Adsorbate | Molecular diameter (nm) | Adsorbate | Molecular diameter (nm) |
| Crystal violet | 1.31 | Vitamin B2 | 1.23 |
| Acid red 88 | 1.23 | Vitamin B12 | 1.84 |
| Erythrosine | 1.90 | Tannic acid | 1.60 |
| Methylene blue | 1.09 | Alpha's cyclodextrine | 1.14 |
| Xylenol orange | 1.44 | Gamma cyclodextrine | 1.31 |
| Acid blue 90 | 2.09 | Directly Huang 11 | 3.47 |
| Alkali blue 90 | 1.41 |
According to adsorption dynamics adsorption kinetics correlation theory, it is easier to realize that its is right when adsorbent channel diameter is 2~3 times of adsorbate
The absorption of adsorbate.In conjunction with 1 data of table, for such organic macromolecule adsorbate, adsorbent aperture need to be in 2~10nm range.
Too small aperture is difficult to realize the diffusion of macromolecular organic pollutant, and excessive hole can then reduce the specific surface of porous charcoal
Product reduces the active site of absorption organic molecule.Therefore, largely the mesoporous carbon with the pore diameter range can be mentioned effectively for orientation production
Absorption of the height to such macromolecule contaminant.
Currently, mesoporous carbon generallys use template preparation, different holes are prepared by the M8003 line of template architectural characteristic
The mesoporous carbon of diameter, hole pattern, mesoporous is high, and application prospect is good.According to the difference of template, template can be divided into hard template and
Two class of soft template method.
Hard template method: be otherwise known as " inorganic template method ", uses the substance of rigid structure for template, first by template
It is compound with carbon precursor, then composite material is carbonized, then inorganic template agent in carbide is removed, obtains mesoporous carbon.The party
Method can regulate and control the pore structure of Carbon Materials from nanometer level, more accurate to pore size control, study the most extensive.Currently, most often
Template is the inorganic silicon oxide with ordered structure, however, the highly corrosives such as hydrogen fluoride will be used by removing silicon template
Chemical reagent, it is very high to device properties and environmental protection requirement, and complex process, it is with high costs, it is difficult to realize that industrialization is answered
With.
Soft template method: generally using the compound that can be crosslinked for carbon precursor, with organic point of the adjustable flexibility of structure
Son, microemulsion etc. are template.By the method for organic-organic self assembly, it is compounded to form soft template with carbon precursor organic
Nanocomposite, carbon precursor is further crosslinked the central hole structure for generating and having fixed form in carbonization process, then takes off
After removing template, ordered mesoporous carbon can be obtained.Soft template method prepare mesoporous carbon need to satisfy two conditions:: at least one kind is needed to have one
The component determined decomposition temperature, serve as pore-creating template；With it is a kind of be able to maintain under template decomposition temperature nanostructure at charcoal
Component.Because template can depolymerization at high temperature in soft template method, it is difficult to realize the accurate control to pore structure, and soft template
Use can not be regenerated after carbonization stage, it is with high costs, constrain the application of soft template method.
Summary of the invention
For the various problems of prior art preparation mesoporous carbon, the present invention provides a kind of manganese compounds to prepare mesoporous carbon
In purposes.Manganese compound has method simplicity, template low to equipment corrosion as the method that template prepares mesoporous carbon
The advantages that easily recycling.The mesoporous carbon specific surface area being prepared is high, mesoporous is high, and the aperture overwhelming majority is in 2~20nm, specific surface
Product is 500~2000m2/ g, mesopore volume is in 1~4cm3/ g, mesoporous >=95%, the mesoporous carbon can perform well in handling
Multiple pollutant in water body, atmosphere.
First technical problem to be solved by this invention is to provide manganese compound in preparing mesoporous carbon as template
Purposes.
Further, the manganese compound is manganese monoxide (MnO), manganous hydroxide (Mn (OH)2) or non-oxidizable two
At least one of valence manganese salt.
Further, the non-oxidizable manganous salt is manganese carbonate, manganese oxalate, formic acid manganese, manganese acetate, gluconic acid
At least one of manganese or manganese citrate.
Second technical problem to be solved by this invention is to provide the side that manganese compound prepares mesoporous carbon as template
Method.Method includes the following steps: carbon precursor and manganese compound are mixed, under an inert atmosphere, mixture is warming up to charcoal
Change temperature to be carbonized, then cool to room temperature, then use dilute acid pretreatment demanganization, is then washed to neutrality and is obtained after drying
Hole charcoal.
Preferably, above-mentioned manganese compound is prepared in the method for mesoporous carbon as template, and the carbon precursor is polyethylene
Alcohol (PVA), polyacrylonitrile (PAN), hydroxypropyl cellulose (HPC), polyethylene terephthalate (PET), polyethylene
(PE), polypropylene (PP), polystyrene (PS), polyamide (PA), acrylonitrile-butadiene-styrene copolymer (ABS),
Polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polycarbonate (PC), polyformaldehyde (POM), polyphenylene oxide (PPO), drip
At least one of green, waste tire or waste old.
Preferably, above-mentioned manganese compound is prepared in the method for mesoporous carbon as template, and the granularity of the carbon precursor is
100~300 mesh.
Preferably, above-mentioned manganese compound is prepared in the method for mesoporous carbon as template, and the granularity of the manganese compound is removed
The granularity of other compounds is 100~500 mesh outside manganese monoxide, and manganese monoxide granularity is 10~50nm.
Preferably, above-mentioned manganese compound is prepared in the method for mesoporous carbon as template, it is described be mixed into carbon precursor and
The directly solid mixing of manganese compound；Or first dissolved carbon precursor with water, manganese compound is added, is mixed, re-dry water removal.
Preferably, above-mentioned manganese compound is prepared in the method for mesoporous carbon as template, and the carbon precursor and manganese are closed
Object (in terms of MnO) mass ratio is 5 ︰, 1~1 ︰ 5.
Preferably, above-mentioned manganese compound is prepared in the method for mesoporous carbon as template, before being warming up to carbonization temperature,
It further include that mixture is first warming up to 150~350 DEG C of Pre oxidation under an inert atmosphere, then keeping in air atmosphere should
0.5~4h of Pre oxidation, then it is warming up to carbonization temperature under an inert atmosphere.
Preferably, above-mentioned manganese compound is prepared in the method for mesoporous carbon as template, and the heating rate is 5~20
℃/min。
Preferably, above-mentioned manganese compound is prepared in the method for mesoporous carbon as template, the carbonization temperature be 600~
1000℃.The carbonization time is 0.5~4h.
Preferably, above-mentioned manganese compound is prepared in the method for mesoporous carbon as template, and the diluted acid is that concentration is 0.1
Any one in~3 mol/L hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid.
Preferably, above-mentioned manganese compound is prepared in the method for mesoporous carbon as template, and the treatment temperature is 0~50
DEG C, the time is 0.5~2h.
The present invention also provides the mesoporous that the method for preparing mesoporous carbon as template by above-mentioned manganese compound is prepared
Charcoal.
Preferably, in above-mentioned mesoporous carbon, the mesoporous carbon specific surface area is 500~2000m2/ g, mesopore volume 1~
4cm3/ g range, mesoporous >=95%.
The method of the present invention prepares mesoporous carbon as template using manganese compound, and raw material sources are extensive, at low cost, prepare
Journey is simple, a step carbonizes, and post-processing does not use the strong corrosive materials such as hydrogen fluoride, has many advantages, such as environmentally friendly, safe.And
It selects manganese compound to can be effectively reduced charing and the graphitization temperature of carbon precursor, reduces energy consumption.Gained mesoporous of the invention
Charcoal specific surface area is high, mesoporous is high, and the mesoporous carbon aperture overwhelming majority is 500~2000m in 2~20nm, specific surface area2/ g, in
Kong Kongrong is in 1~4cm3/ g range, mesoporous >=95%；To organic macromolecule pollutant large amount of adsorption, and to CO2And CH4Separation
It has excellent performance；Can supported catalyst, to Zero-valent Iron load capacity up to 20%；Mn in recyclable pickling solution2+, realize template
Recycle, preparation cost is greatly reduced.
Detailed description of the invention
Fig. 1 manganese compound template prepares the process flow chart of mesoporous carbon.
The thermogravimetric curve of 1 process of Fig. 2 PVA, manganese carbonate and embodiment and the PVA+ manganese carbonate thermogravimetric curve of fitting.By Fig. 2
It is found that decomposition takes place in PVA in 200~300 DEG C, in this stage, the DTG peak value of aggregate sample goes out earlier than matched curve
It is existing, show that the introducing of manganese carbonate can promote the degradation of PVA.
Fig. 3 embodiment 2 (manganese carbonate mesoporous carbon), embodiment 10 (the manganese carbonate mesoporous carbon of load Zero-valent Iron) are to hydrochloric acid Fourth Ring
Catalytic degradation performance of the plain absorption property and embodiment 10 to quadracycline.Fig. 3 shows the mesoporous carbon to quadracycline
With stronger absorption property and catalytic degradation performance, eliminating rate of absorption about 80%, catalytic elimination rate is up to 95%.
The distribution of (manganese oxalate mesoporous carbon) mesopore pore size of Fig. 4 embodiment 5.The result shows that 5 sample aperture of embodiment is mainly concentrated
In 4~5nm, which is conducive to the absorption of larger molecular organics.
Absorption property curve of Fig. 5 embodiment 5 (manganese oxalate mesoporous carbon) to methylene blue and acid red 88.The result shows that should
Mesoporous carbon has higher adsorption capacity (respectively up to 1100mg/g and 1200mg/g) two kinds of dyestuffs.In addition, a large amount of mesoporous
In the presence of can significantly reduce diffusional resistance of the adsorption molecule inside adsorbent duct, so as to significantly improve the rate of adsorption.This
In test, two groups of adsorption processes reach adsorption equilibrium within 1min, and rate is much higher than other similar adsorbents.
The XRD diffracting spectrum of Fig. 6 embodiment 9 (PAN mesoporous carbon) and pure PAN pyrolysis sample.The result shows that in two kinds of samples
Nearby there is the diffraction maximum in graphite charcoal (002) face in 2 θ=26 °, and the sample diffraction maximum is more sharp in embodiment 9, table
The bright sample has higher degree of graphitization, and therefore, the introducing of manganese compound can be catalyzed the graphited process of carbon precursor,
Graphitization temperature is effectively reduced, significantly improves the stability of carbon structure.
Specific embodiment
For conventional method prepare mesoporous carbon method exist pollution, not environmentally, difficult operation, raw material is not easily recycled and mesoporous
Charcoal cannot be applied to the defects of processing organic macromolecule pollutant well, and the present inventor have passed through a large amount of test to a large amount of
Substance is found after being researched and analysed:
Partial results are as follows: as the template for preparing mesoporous carbon, at 800 DEG C, calcium carbonate can decompose generation titanium dioxide
The carbon dioxide of carbon and calcium oxide, generation can react with charcoal, to change the hole of active carbon, cannot achieve pore structure
Orientation regulation.Ferric nitrate, ferric sulfate can decompose generation di-iron trioxide at high temperature again, at a high temperature of 700 DEG C or more, three
Redox reaction can be occurred with fixed carbon by aoxidizing two iron, release carbon dioxide, and the carbon dioxide of generation can further same charcoal
It reacts, changes pore structure, destroy the homogeneous structural that template generates.In addition, ferric nitrate, ferric sulfate are in thermal decomposition process
In can generate the strong oxidizing properties gas such as nitrogen oxides, sulfur dioxide, the gas of generation can equally be reacted with charcoal, to influence to control
As a result orientation regulation.In addition, sulfur dioxide can be restored by charcoal generates sulfide, the sulfide of generation can be same in acid cleaning process
H+In conjunction with releasing highly corrosive, highly toxic hydrogen sulfide gas, endanger environment and human health.Nano ferriferrous oxide is same
Sample can be reacted with charcoal at high temperature generates fe and carbon dioxide, thus is difficult to realize the regulation of pore structure.
Finally, selecting manganese compound as template by a large amount of test discovery, mesoporous of good performance can be obtained
Charcoal, and do not generate to human body and the harmful intermediate product of environment.Manganese under the conditions of high temperature inert have good thermal stability and
Chemical stability, 1000 DEG C of whens, also do not react with carbon and hydrogen, at high temperature without the change of structure and composition, and easily remove.
Also, the presence of carbon precursor can hinder the undue growth and reunion of MnO nanocrystal, thus generate crystallite dimension 2~
MnO nano particle within the scope of 20nm.The even particle distribution of generation, and crystallite dimension can be by changing carbon precursor and mould
The modes such as type, relative scale, hybrid mode, carbonization temperature, the carbonization time of plate agent are adjusted.In addition, MnO is to carbon precursor
Pyrolytic process has certain catalytic action, can promote its carbonization process, can be effectively reduced the carbonization temperature of carbon precursor.So
And not every manganese compound can be as the template for preparing mesoporous carbon, since manganese nitrate, manganese sulfate etc. can be anti-
NOx and SO should be generated in the process2Etc. the oxidizing gas that can be reacted with charcoal, the central hole structure of template generation is influenced, so, this
The manganese compound of invention is manganese monoxide (MnO), manganous hydroxide (Mn (OH)2) or non-oxidizable manganous salt at least one
Kind.The non-oxidizable manganous salt is in manganese carbonate, manganese oxalate, formic acid manganese, manganese acetate, manganese gluconate or manganese citrate
It is at least one.
The method of the present invention using different manganese compounds as template or template presoma, using high-molecular compound as charcoal before
It drives body and prepares mesoporous carbon.In carbonization process, under lower temperature conditions (300~400 DEG C), one side manganese compound, which decomposes, to be generated
Nano-scale (2~20nm) particle forms template；On the other hand, carbon precursor melts, and wraps template.Then, after
High-temperature (500 DEG C of >) of continuing rising, carbon precursor carbonizes, and manganese oxide does not react always with charcoal, to guarantee to be formed steady
Fixed carbon structure is conducive to the orientation regulation of pore structure.After carbonization process, the MnO nano particle in sample is carbonized with dilute
Pickling solution reacts, and forms Mn2+, removed from sample, to form hole in layer of charcoal.
The present invention provides the methods that manganese compound prepares mesoporous carbon as template, comprising the following steps: by charcoal forerunner
Body and manganese compound mixing, under an inert atmosphere, are warming up to carbonization temperature for mixture and carbonize, then cool to room temperature,
Dilute acid pretreatment demanganization is used again, is then washed to neutrality and is dried to obtain mesoporous carbon.
It has been observed that will lead to mesoporous carbon porosity and specific surface area that preparation generates if manganese compound additive amount is too low
It is too low；If manganese compound adding too much, excessive manganese compound is difficult to be wrapped up by carbon precursor, and can not generate more
Hole causes the waste of raw material.It is preferred, therefore, that carbon precursor and manganese compound (in terms of MnO) mass ratio are 5 ︰, 1~1 ︰ 5.
It has been observed that pre-oxidizing a period of time under air atmosphere before charing, the yield of charcoal can be increased and improve charcoal
The intensity of material.It is preferred that Pre oxidation is 150~350 DEG C, the time is 0.5~4h.It is warming up to before carbonization temperature, also wraps
It includes and mixture is first warming up to 150~350 DEG C of Pre oxidation under an inert atmosphere, the pre- oxygen is then kept in air atmosphere
Change 0.5~4h of temperature, then is warming up to carbonization temperature under an inert atmosphere.
It has been observed that the heating rate of charing is too low, it will cause the waste of the energy and increase technique duration；Heating rate mistake
Height, and will lead to sample pyrolysis not exclusively, so that stable carbon structure can not be formed.It is preferred, therefore, that heating rate is 5~20
℃/min。
Manganese compound is as template precursor preparation mesoporous carbon, and in carbonization process, the presence of carbon precursor can hinder
The undue growth and reunion of manganese oxide nanocrystal, to generate the oxidation having in different crystallite dimensions (2~20nm) range
Manganese nano particle.After pickling, gained mesoporous can inherit the size and shape of template manganese oxide particle, pore-size distribution well
It is narrow.The intermediate pore size and volume of gained mesoporous carbon can be by changing carbon precursor and the type of template, relative scale, mixing
The modes such as mode, carbonization temperature, carbonization time are adjusted.
The present invention is further explained combined with specific embodiments below, but the present invention is not limited to following embodiments.Institute
State method is conventional method unless otherwise instructed.The material can obtain unless otherwise instructed from public commercial source.
Embodiment 1
PVA solid particle is ground to 200 mesh.By gained PVA powder with manganese carbonate according to 1 ︰ 1 (mass ratio of PVA and MnO)
Ratio mechanical uniform mixing.Certain mass aggregate sample is weighed in quartz tube furnace, in N2Sample is carbonized in atmosphere.Heating speed
Rate be 5 DEG C/min, 900 DEG C of carbonization temperature, carbonization time 1h.Then, continue to keep N2Atmosphere waits sample to be cooled to room temperature.
Sample after cooling is poured into mechanical concussion 30min in 1.8mol/L sulfuric acid solution, is then stood, filtering, and molten with fresh sulfuric acid
Liquid pickling sample again.Pickling is repeated for several times, until Mn in pickling solution2+Concentration Testing does not go out.Pickling sample is extremely wash with distilled water
Neutrality, it is finally that sample is dry in 105 DEG C of air dry ovens, it can be obtained mesoporous carbon of the present invention.
PVA, manganese carbonate, the pyrolysis curve for mixing sample and the calculated fitting of pyrolysis according to PVA and manganese carbonate
Curve is as shown in Figure 2.As shown in Figure 2, in 200-300 DEG C of temperature range, decomposition takes place in PVA, in this stage, mixing
The DTG peak value of sample occurs earlier than matched curve, shows that the introducing of manganese carbonate can promote the degradation of PVA.
The pore structure parameter and methylene blue (MB) adsorbance of mesoporous carbon obtained by the present embodiment are as shown in table 2.
Embodiment 2
PVA solid particle is ground to 200 mesh.By gained PVA powder with manganese carbonate according to 1 ︰ 3 (mass ratio of PVA and MnO)
Ratio mechanical uniform mixing.Certain mass aggregate sample is weighed in quartz tube furnace, in N2Sample is carbonized in atmosphere.Heating speed
Rate be 5 DEG C/min, 900 DEG C of carbonization temperature, carbonization time 1h.Then, continue to keep N2Atmosphere waits sample to be cooled to room temperature.
Sample after cooling is poured into mechanical concussion 30min in 1.8mol/L sulfuric acid solution, is then stood, filtering, and molten with fresh sulfuric acid
Liquid pickling sample again.Pickling is repeated for several times, until Mn in pickling solution2+Concentration Testing does not go out.Pickling sample is extremely wash with distilled water
Neutrality, it is finally that sample is dry in 105 DEG C of air dry ovens, it can be obtained mesoporous carbon of the present invention.
Fig. 3 is absorption property of the embodiment 2 to quadracycline.Fig. 3 show the mesoporous carbon to quadracycline have compared with
Strong absorption property, removal rate about 80%.
The pore structure parameter and methylene blue adsorption number amount of mesoporous carbon obtained by the present embodiment are as shown in table 2.
Embodiment 3
PVA solid particle is added in 80 DEG C of hot water, is stirred continuously (revolving speed=600r/min), it is molten to obtain 20wt.%PVA
Liquid.Manganese carbonate is added according to the ratio of 1 ︰ 3 (mass ratio of PVA and MnO), continues to stir, keeps manganese carbonate and PVA solution sufficiently mixed
It closes.The solution mixed is fallen in silica crucible, is dried overnight in 105 DEG C of air dry ovens.Sample after drying is placed in
In quartz tube furnace, in N2Sample is carbonized in atmosphere.Heating rate be 5 DEG C/min, 900 DEG C of carbonization temperature, carbonization time 1h.With
Afterwards, continue to keep N2Atmosphere waits sample to be cooled to room temperature.Sample after cooling is poured into mechanical shake in 1.8mol/L sulfuric acid solution
30min is swung, is then stood, filtering, and with fresh sulfuric acid solution pickling sample again.Pickling is repeated for several times, until in pickling solution
Mn2+Concentration Testing does not go out.Pickling sample finally does sample to neutrality overnight in 105 DEG C of air dry ovens wash with distilled water
It is dry, it can be obtained mesoporous carbon of the present invention.
The pore structure parameter and methylene blue adsorption number amount of mesoporous carbon obtained by the present embodiment are as shown in table 2.
Embodiment 4
PVA solid particle is ground to 200 mesh.By gained PVA powder with manganese oxalate according to 1 ︰ 3 (mass ratio of PVA and MnO)
Ratio mechanical uniform mixing.Certain mass aggregate sample is weighed in quartz tube furnace, in N2Sample is carbonized in atmosphere.Heating speed
Rate be 5 DEG C/min, 900 DEG C of carbonization temperature, carbonization time 1h.Then, continue to keep N2Atmosphere waits sample to be cooled to room temperature.
Sample after cooling is poured into mechanical concussion 30min in 2.0mol/L sulfuric acid solution, is then stood, filtering, and molten with fresh sulfuric acid
Liquid pickling sample again.Pickling is repeated for several times, until Mn in pickling solution2+Concentration Testing does not go out.Pickling sample is extremely wash with distilled water
Sample is finally dried overnight in 105 DEG C of air dry ovens, can be obtained mesoporous carbon of the present invention by neutrality.
The pore structure parameter and methylene blue adsorption number amount of mesoporous carbon obtained by the present embodiment are as shown in table 2.
Embodiment 5
PVA solid particle is added in 80 DEG C of hot water, is stirred continuously (revolving speed=600r/min), it is molten to obtain 20wt.%PVA
Liquid.Manganese oxalate is poured into solution according to the ratio of 1 ︰ 3 (mass ratio of PVA and MnO), continues to stir, keeps manganese oxalate molten with PVA
Liquid is sufficiently mixed.The solution mixed is fallen in silica crucible, is dried overnight in 105 DEG C of air dry ovens.After dry
Sample is placed in quartz tube furnace, in N2Sample is carbonized in atmosphere.Heating rate is 5 DEG C/min, 900 DEG C of carbonization temperature, is carbonized
Time 1h.Then, continue to keep N2Atmosphere waits sample to be cooled to room temperature.It is molten that sample after cooling is poured into 2.0mol/L sulfuric acid
Mechanical concussion 30min, then stands, filtering in liquid, and with fresh sulfuric acid solution pickling sample again.Repeat pickling for several times, directly
The Mn into pickling solution2+Concentration Testing does not go out.Pickling sample is to neutrality wash with distilled water, finally by sample in 105 DEG C of forced air dryings
It is dried overnight in case, can be obtained mesoporous carbon of the present invention.
Fig. 4 is the distribution of 5 mesoporous carbon mesopore pore size of embodiment.The result shows that 5 sample aperture of embodiment focus primarily upon 4~
5nm, the pore diameter range sample are conducive to the absorption of larger molecular organics.
Fig. 5 is absorption property curve of the embodiment 5 to methylene blue and acid red 88.The result shows that the mesoporous carbon is to two kinds
Dyestuff has higher adsorption capacity (respectively up to 1100mg/g and 1200mg/g).In addition, the presence of a large amount of mesoporous can significantly drop
Diffusional resistance of the low adsorption matter molecule inside adsorbent duct, so as to significantly improve the rate of adsorption.In this test, two groups of suctions
Attached process reaches adsorption equilibrium within 1min, and rate is much higher than other similar adsorbents.
The pore structure parameter and methylene blue adsorption number amount of mesoporous carbon obtained by the present embodiment are as shown in table 2.
Embodiment 6
PVA solid particle is ground to 200 mesh.By gained PVA powder with manganese carbonate according to 1 ︰ 2 (mass ratio of PVA and MnO)
Ratio mechanical mixture.Certain mass aggregate sample is weighed in quartz tube furnace, in N2Sample is carbonized in atmosphere.Heating rate is
10 DEG C/min, 800 DEG C of carbonization temperature, carbonization time 2h.Then, continue to keep N2Atmosphere waits sample to be cooled to room temperature.It will be cold
But sample pours into mechanical concussion 30min in 2.0mol/L sulfuric acid solution after, then stands, filtering, and again with fresh sulfuric acid solution
Secondary pickling sample.Pickling is repeated for several times, until Mn in pickling solution2+Concentration Testing does not go out.Pickling sample is to neutrality wash with distilled water,
Sample is dried overnight in 105 DEG C of air dry ovens finally, can be obtained mesoporous carbon of the present invention.
The pore structure parameter and methylene blue adsorption number amount of mesoporous carbon obtained by the present embodiment are as shown in table 2.
Embodiment 7
PVA solid particle is ground to 200 mesh.By gained PVA powder with manganese carbonate according to 1 ︰ 3 (mass ratio of PVA and MnO)
Ratio mechanical uniform mixing.Certain mass aggregate sample is weighed in quartz tube furnace, in N2Sample is carbonized in atmosphere.Heating speed
Rate be 10 DEG C/min, 700 DEG C of carbonization temperature, carbonization time 2h.Then, continue to keep N2Atmosphere waits sample to be cooled to room temperature.
Sample after cooling is poured into mechanical concussion 30min in 3.0mol/L sulfuric acid solution, is then stood, filtering, and molten with fresh sulfuric acid
Liquid pickling sample again.Pickling is repeated for several times, until Mn in pickling solution2+Concentration Testing does not go out.Pickling sample is extremely wash with distilled water
Sample is finally dried overnight in 105 DEG C of air dry ovens, can be obtained mesoporous carbon of the present invention by neutrality.
The pore structure parameter and methylene blue adsorption number amount of mesoporous carbon obtained by the present embodiment are as shown in table 2.
Embodiment 8
PVA solid particle is ground to 200 mesh.By gained PVA powder with manganese carbonate reagent according to 1 ︰, the 3 (matter of PVA and MnO
Measure ratio) ratio mechanical mixture.Certain mass aggregate sample is weighed in quartz tube furnace, in N2Sample is carbonized in atmosphere.Heating
Rate be 20 DEG C/min, 600 DEG C of carbonization temperature, carbonization time 3h.Then, continue to keep N2Atmosphere waits sample to be cooled to room
Temperature.Sample after cooling is poured into mechanical concussion 30min in 1.8mol/L sulfuric acid solution, is then stood, filtering, and use fresh sulfuric acid
Solution pickling sample again.Pickling is repeated for several times, until Mn in pickling solution2+Concentration Testing does not go out.Pickling sample wash with distilled water
To neutrality, sample is dried overnight in 105 DEG C of air dry ovens finally, can be obtained mesoporous carbon of the present invention.
The pore structure parameter and methylene blue adsorption number amount of mesoporous carbon obtained by the present embodiment are as shown in table 2.
Embodiment 9
PAN solid particle is ground to 400 mesh.By gained PAN powder with MnO solid according to 1 ︰, the 5 (quality of PAN and MnO
Than) ratio mechanical uniform mixing.It weighs certain mass aggregate sample to be transferred in high temperature process furnances, in a nitrogen atmosphere with 10
DEG C/heating rate of min rises to 200 DEG C, it is subsequently converted to air, in air atmosphere stable 1h.Then, in N2Under atmosphere with
The heating rate of 5 DEG C/min rises to 900 DEG C, and is cooled to room temperature after holding 1h at such a temperature.It is molten with the sulfuric acid of 3mol/L
Liquid pickling carbonizes sample, removes MnO.When the Concentration Testing of Mn ion in pickling solution does not go out, sample is washed till using distilled water
It is dry after neutrality, it can be obtained mesoporous carbon of the present invention.
The pore structure parameter and methylene blue adsorption number amount of mesoporous carbon obtained by the present embodiment are as shown in table 2.
Fig. 6 is the XRD diffracting spectrum that 9 mesoporous carbon of embodiment and pure PAN are pyrolyzed sample.The result shows that existing in two kinds of samples
Nearby there is the diffraction maximum in graphite charcoal (002) face in 2 θ=26 °, and the sample diffraction maximum is more sharp in embodiment 9, shows this
Sample has higher degree of graphitization, and therefore, the introducing of manganese compound can be catalyzed the graphited process of carbon precursor, effectively
Graphitization temperature is reduced, the stability of carbon structure is significantly improved.
Embodiment 10
It measures 100mL deoxidation ethanol/water (30%v/v) solution and in three-necked flask, is passed through N to its kind2, and keep
30min is to exclude air.Weigh 1g FeSO4·7H2The three-necked flask after emptying is added in O, under nitrogen atmosphere stirring and dissolving.
Add 0.3g polyethylene glycol, stirring and dissolving.In the mesoporous carbon addition system for weighing the preparation of 1g embodiment 2, it is mixed
30min.Then, by 5mL 2.1mol/L NaBH4Solution is added in reaction system with 1 drop/sec of speed, lasting to stir,
Up to no gas generates.Products obtained therefrom is washed 3 times or so with a large amount of deoxidation ethanol/water (50%v/v) solution, then anhydrous with deoxygenating
Ethyl alcohol is washed three times, and after filtering, 12h is dried in vacuo at 100 DEG C, obtains the mesoporous carbon of load nano zero valence iron.Fig. 3 is negative for gained
Carry absorption and catalytic degradation performance of the nano zero valence iron mesoporous carbon to quadracycline.Fig. 3 embodiment 10 is to quadracycline
Absorption property and catalytic degradation performance.Fig. 3 shows that the mesoporous carbon of the load Zero-valent Iron has stronger catalysis to quadracycline
Removal rate is up to 95%.
Pore structure and methylene blue adsorption number amount in obtained by 2 embodiment 1-9 of table
SBET(Specific surface area): BET specific surface area；Vmicro(Micropore volume): micropore volume
Vmeso(Mesopore volume): mesoporous holds；MB (Methylene blue): methylene blue.
Claims (10)
1. manganese compound is in preparing mesoporous carbon as the purposes of template.
2. manganese compound according to claim 1 is in preparing mesoporous carbon as the purposes of template, the manganese compound
For at least one of manganese monoxide, manganous hydroxide or non-oxidizable manganous salt；Preferably, the non-oxidizable manganous salt
For at least one of manganese carbonate, manganese oxalate, formic acid manganese, manganese acetate, manganese gluconate or manganese citrate.
3. the preparation method of mesoporous carbon, it is characterised in that: the following steps are included: carbon precursor and manganese compound are mixed, lazy
Property atmosphere under, mixture, which is warming up to carbonization temperature, to be carbonized, then cool to room temperature, then use dilute acid pretreatment demanganization, so
After be washed to neutrality and obtain mesoporous carbon after drying.
4. the preparation method of mesoporous carbon according to claim 3, it is characterised in that: the carbon precursor be polyvinyl alcohol,
Polyacrylonitrile, hydroxypropyl cellulose, polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polyamide,
Acrylonitrile-butadiene-styrene copolymer, polymethyl methacrylate, polyvinyl chloride, polycarbonate, polyformaldehyde, polyphenylene oxide,
At least one of pitch, waste tire or waste old.
5. the preparation method of mesoporous carbon according to claim 3, it is characterised in that: the granularity of the carbon precursor is 100
~300 mesh；The granularity of the granularity of the manganese compound other compounds in addition to manganese monoxide is 100~500 mesh, manganese monoxide grain
Degree is 10~50nm.
6. the preparation method of mesoporous carbon according to claim 3, it is characterised in that: the carbon precursor and manganese compound matter
Amount is than being 5 ︰, 1~1 ︰ 5；The manganese compound is in terms of MnO.
7. the preparation method of mesoporous carbon according to claim 3, it is characterised in that: before being warming up to carbonization temperature, also
Including mixture to be first warming up to 150~350 DEG C of Pre oxidation under an inert atmosphere, then keep this pre- in air atmosphere
0.5~4h of oxidizing temperature, then it is warming up to carbonization temperature under an inert atmosphere.
8. the preparation method of mesoporous carbon according to claim 3 or 7, it is characterised in that: the heating rate is 5~20
℃/min。
9. the preparation method of mesoporous carbon according to claim 3, it is characterised in that: the carbonization temperature is 600~1000
℃。
10. the mesoporous carbon being prepared by the preparation method of the described in any item mesoporous carbons of claim 3~9.
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