CN113120903B - Activated carbon and preparation method and application thereof - Google Patents
Activated carbon and preparation method and application thereof Download PDFInfo
- Publication number
- CN113120903B CN113120903B CN201911423780.XA CN201911423780A CN113120903B CN 113120903 B CN113120903 B CN 113120903B CN 201911423780 A CN201911423780 A CN 201911423780A CN 113120903 B CN113120903 B CN 113120903B
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- China
- Prior art keywords
- activated carbon
- gas
- temperature
- carbon
- atmosphere
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 203
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 109
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000011148 porous material Substances 0.000 claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 31
- 239000002006 petroleum coke Substances 0.000 claims abstract description 28
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 21
- 230000003213 activating effect Effects 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000003860 storage Methods 0.000 claims abstract description 10
- 230000004913 activation Effects 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- 239000012298 atmosphere Substances 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 22
- 239000012159 carrier gas Substances 0.000 claims description 20
- 239000004215 Carbon black (E152) Substances 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 239000001307 helium Substances 0.000 claims description 16
- 229910052734 helium Inorganic materials 0.000 claims description 16
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 16
- 229930195733 hydrocarbon Natural products 0.000 claims description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims description 16
- 239000011261 inert gas Substances 0.000 claims description 16
- 238000004321 preservation Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 230000001186 cumulative effect Effects 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 229910052754 neon Inorganic materials 0.000 claims description 8
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 238000003775 Density Functional Theory Methods 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 238000004939 coking Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims 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 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000002717 carbon nanostructure Substances 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- -1 transition metal salt Chemical class 0.000 claims description 3
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000005750 Copper hydroxide Substances 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 239000005955 Ferric phosphate Substances 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 claims description 2
- QDAYJHVWIRGGJM-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QDAYJHVWIRGGJM-UHFFFAOYSA-B 0.000 claims description 2
- YPGLWPWPVJBCEM-UHFFFAOYSA-K [Pt+3].[O-]P([O-])([O-])=O Chemical compound [Pt+3].[O-]P([O-])([O-])=O YPGLWPWPVJBCEM-UHFFFAOYSA-K 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- CTUFHBVSYAEMLM-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O.CC(O)=O CTUFHBVSYAEMLM-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 2
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 2
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000005336 cracking Methods 0.000 claims description 2
- 229960004887 ferric hydroxide Drugs 0.000 claims description 2
- 229940032958 ferric phosphate Drugs 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 2
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 claims description 2
- TXCOQXKFOPSCPZ-UHFFFAOYSA-J molybdenum(4+);tetraacetate Chemical compound [Mo+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O TXCOQXKFOPSCPZ-UHFFFAOYSA-J 0.000 claims description 2
- GDXTWKJNMJAERW-UHFFFAOYSA-J molybdenum(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mo+4] GDXTWKJNMJAERW-UHFFFAOYSA-J 0.000 claims description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- 229910000159 nickel phosphate Inorganic materials 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 2
- NFOHLBHARAZXFQ-UHFFFAOYSA-L platinum(2+);dihydroxide Chemical compound O[Pt]O NFOHLBHARAZXFQ-UHFFFAOYSA-L 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- PQTLYDQECILMMB-UHFFFAOYSA-L platinum(2+);sulfate Chemical compound [Pt+2].[O-]S([O-])(=O)=O PQTLYDQECILMMB-UHFFFAOYSA-L 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims 1
- 230000000274 adsorptive effect Effects 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 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 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 238000009826 distribution Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000003345 natural gas Substances 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 11
- 239000003463 adsorbent Substances 0.000 description 7
- 238000001994 activation Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000003949 liquefied natural gas Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- YHGPYBQVSJBGHH-UHFFFAOYSA-H iron(3+);trisulfate;pentahydrate Chemical compound O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YHGPYBQVSJBGHH-UHFFFAOYSA-H 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The invention discloses an activated carbon and a preparation method and application thereof, wherein the accessibility A of the activated carbon is 1.4-2.2; wherein the accessibility A is a parameter for characterizing the methane adsorption and storage performance of the activated carbon. The preparation method of the activated carbon comprises the steps of firstly, uniformly mixing petroleum coke, an activating agent and a transition metal compound, and then carrying out an activation reaction; and then washing and drying the obtained activated product to obtain the activated carbon. The active carbon obtained by the method has reasonable pore distribution, proper specific surface area, micropores capable of adsorbing a large amount of methane, mesopores capable of accelerating mass transfer, good methane storage effect, simple preparation method and the like.
Description
Technical Field
The invention belongs to the technical field of carbon material preparation, and particularly relates to activated carbon and a preparation method and application thereof.
Background
Among the traditional fossil energy sources, natural gas is expected to be the preferred energy source for replacing coal and petroleum due to the advantages of abundant reserves, high calorific value, no pollution and the like. Compared with the conventional liquid fuel, the main disadvantage of natural gas is that the volumetric energy density is lower, which is only 0.11% of that of gasoline, so how to realize high-capacity storage of natural gas and improve the volumetric energy density of natural gas become the key to limit the wide-range application of natural gas, especially for the large-scale popularization of the rapidly developed Natural Gas Vehicles (NGV) in recent years.
At present, natural gas storage technologies mainly comprise four types: compressed Natural Gas (CNG), liquefied Natural Gas (LNG), natural gas hydrates (NHG), and Adsorbed Natural Gas (ANG) storage technologies. Compared with other technologies, the CNG technology is mature and has been commercially applied to natural gas automobiles, the volume energy density is 9.2MJ/L and is about 29 percent of that of gasoline, but the CNG storage pressure is as high as 20MPa, the requirement on equipment materials is very high, and the cost is also high. The LNG technology is to store natural gas in a liquid form under the pressure of 112K and 0.1MPa, the energy density can reach 22.2MJ/L which is about 72 percent of that of gasoline, but the LNG technology has high cost and complex design of a storage tank, and has safety risks of leakage and the like. NGH technology, which stores natural gas and water as clathrate hydrates, is currently immature. The ANG technology is that a storage tank is filled with a porous adsorbent, and natural gas is adsorbed and stored at normal temperature and medium and low pressure (3-4 MPa) by utilizing the huge specific surface area and rich pore channel structure of the adsorbent. Because of the low operation pressure, the high energy storage density, the relatively low cost and the more convenient and safer use of the ANG technology, the ANG technology is expected to replace CNG and LNG technologies to realize large-scale application, and the most important thing is to prepare the adsorbent with high methane adsorption capacity.
Among a plurality of adsorbent materials, the activated carbon has strong adsorption capacity due to the characteristics of large specific surface area, rich pore channel structures and the like, and can be used as an adsorbent for adsorbing and storing methane. The activated carbon used as a methane adsorbent is required to have a large specific surface area, the activated carbon with an ultrahigh specific surface area is generally prepared by a KOH chemical activation method, the prepared activated carbon contains a plurality of micropores with the pore diameter less than 0.8nm, the pore diameter of the part of micropores is too small, methane is difficult to adsorb, and the part of micropores are wasted; meanwhile, the activated carbon suitable for adsorbing and storing methane also has a certain mesopore as a gas channel, so that the development and preparation of the activated carbon with high surface area and reasonable pore structure distribution have very important significance in improving the methane adsorption quantity.
CN1091073C discloses a method for preparing activated carbon for adsorbing and storing methane, and the prepared activated carbon has the surface area of 1916-2700 m 2 The adsorption amount of the formed activated carbon to methane at 3.5MPa was 170v/v.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the activated carbon and the preparation method and the application thereof, and the activated carbon with reasonable pore structure distribution and high specific surface area is prepared by comprehensively regulating and controlling a process route and reaction conditions, so that high-capacity adsorption of methane is realized.
The invention provides an activated carbon, wherein the accessibility A of the activated carbon is 1.4-2.2; wherein the accessibility A is a parameter for representing the performance of adsorbing and storing methane by the activated carbon, and the accessibility A is calculated by the following formula:
wherein V mic Is the micropore volume, V, of the activated carbon measured by the t-plot method 0 Is the total pore volume (cm) of the activated carbon 3 /g)，V′ 0 Is the cumulative total pore volume (cm) of micropores smaller than 2nm calculated by DFT method 3 /g)，V i Is the cumulative pore volume (cm) of 0.8-2.0 nm pores calculated by DFT method 3 (g), S is the specific surface area (m) of the activated carbon 2 /g)。
The second aspect of the present invention provides a method for preparing activated carbon, comprising the following steps:
(1) Uniformly mixing petroleum coke, an activating agent and a transition metal compound, and then carrying out an activation reaction;
(2) Washing and drying the activated product obtained in the step (1) to obtain activated carbon;
the specific process of the activation reaction in the step (1) is as follows: heating the uniformly mixed petroleum coke, activating agent and transition metal compound to a temperature A in an atmosphere A, preserving heat for a certain time A, then adjusting the temperature to a temperature B, stopping introducing the atmosphere A, introducing the atmosphere B, preserving heat for a certain time B under the condition of the temperature B, and cooling to obtain an activated product;
when the atmosphere A is a mixed gas of a carbon-containing gas and a carrier gas, the atmosphere B is nitrogen and/or an inert gas; wherein, the carbon-containing gas is one or more of hydrocarbon gas and carbon monoxide; the hydrocarbon gas is one or more of acetylene and methane; the carrier is one or more of nitrogen, helium and argon; the volume ratio of the carbon-containing gas to the carrier gas is 1.1-20; the inert gas is one or more of helium, argon, neon and the like; the temperature A is 400-850 ℃; the heat preservation time A is 5-200 min; the temperature B is 600-1100 ℃, and the heat preservation time B is 5-500 min;
when the atmosphere A is nitrogen and/or inert gas, the atmosphere B is a mixed gas of carbon-containing gas and carrier gas, wherein the inert gas is one or more of helium, argon and neon; the carbon-containing gas is one or more of hydrocarbon gas and carbon monoxide; the hydrocarbon gas is one or more of acetylene and methane; the carrier is one or more of nitrogen, helium and argon; the volume ratio of the carbon-containing gas to the carrier gas is 1.1-20; the temperature A is 600-1100 ℃, and the heat preservation time A is 5-500 min; the temperature B is 400-850 ℃; the heat preservation time B is 5-200 min.
In the preparation method of the activated carbon, the petroleum coke in the step (1) is solid coke generated by cracking and coking vacuum residue by a coking device.
In the preparation method of the activated carbon, the activating agent in the step (1) is one or more of potassium hydroxide, sodium hydroxide, calcium hydroxide, potassium carbonate and potassium bicarbonate.
In the preparation method of the activated carbon, the activating agent in the step (1) is potassium hydroxide.
In the preparation method of the activated carbon, the transition metal compound in the step (1) is one or more of transition metal salt, transition metal oxide and transition metal hydroxide, and the transition metal can be one or more of Fe, co, ni, cu, cr, mo and Pt; the transition metal compound may be one or more of ferric nitrate, ferric sulfate, ferric chloride, ferric phosphate, ferric acetate, ferric oxide, ferric hydroxide, nickel nitrate, nickel sulfate, nickel chloride, nickel phosphate, nickel acetate, nickel oxide, nickel hydroxide, cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt phosphate, cobalt acetate, cobalt oxide, cobalt hydroxide, copper nitrate, copper sulfate, copper chloride, copper phosphate, copper acetate, copper oxide, copper hydroxide, chromium nitrate, chromium sulfate, chromium chloride, chromium phosphate, chromium acetate, chromium oxide, chromium hydroxide, molybdenum nitrate, molybdenum sulfate, molybdenum chloride, molybdenum phosphate, molybdenum acetate, molybdenum oxide, molybdenum hydroxide, platinum nitrate, platinum sulfate, platinum chloride, platinum phosphate, platinum acetate, platinum oxide, and platinum hydroxide.
In the preparation method of the activated carbon, the transition metal compound in the step (1) is one or more of ferric oxide, nickel nitrate and cobalt nitrate.
In the above method for producing activated carbon, the mass ratio of the petroleum coke, the activating agent and the transition metal compound in the step (1) is 1.
In the above method for producing activated carbon, the mass ratio of the petroleum coke, the activating agent and the transition metal compound in step (1) is 1.
In the preparation method of the activated carbon, the specific process of the activation reaction in the step (1) is as follows: heating the uniformly mixed petroleum coke, activating agent and transition metal compound to a temperature A in an atmosphere A, preserving heat for a certain time A, then adjusting the temperature to a temperature B, stopping introducing the atmosphere A, introducing the atmosphere B, preserving heat for a certain time B under the condition of the temperature B, and cooling to obtain an activated product.
When the atmosphere A is a mixed gas of a carbon-containing gas and a carrier gas, the atmosphere B is nitrogen and/or an inert gas; wherein, the carbon-containing gas is one or more of hydrocarbon gas and carbon monoxide; the hydrocarbon gas is one or more of acetylene and methane; the carrier is one or more of nitrogen, helium and argon; the volume ratio of the carbon-containing gas to the carrier gas is 1. The inert gas is one or more of helium, argon and neon. The temperature A is 500-800 ℃; the heat preservation time A is 20-120 min; the temperature B is 700-950 ℃, and the heat preservation time B is 15-300 min.
When the atmosphere A is nitrogen and/or inert gas, the atmosphere B is a mixed gas of carbon-containing gas and carrier gas, wherein the inert gas is one or more of helium, argon and neon. The carbon-containing gas is one or more of hydrocarbon gas and carbon monoxide; the hydrocarbon gas is one or more of acetylene and methane; the carrier is one or more of nitrogen, helium and argon. The volume ratio of the carbon-containing gas to the carrier gas is 1.2-10. The temperature A is 700-950 ℃, and the heat preservation time A is 15-300 min. The temperature B is 500-800 ℃; the heat preservation time B is 20-120 min.
In the preparation method of the activated carbon, the washing in the step (2) is performed by acid washing and then water washing; preferably, water washing is further performed before acid washing, wherein water washing refers to washing with water until the pH value of the filtrate is neutral. The acid washing is carried out by using inorganic acid solution, wherein the inorganic acid can be one or more of hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, and hydrochloric acid is preferred.
In the preparation method of the activated carbon, the concentration of the acid solution is 5-50 wt%, and the acid washing time is 5-600 min. The pickling temperature is 20-100 ℃.
In the preparation method of the activated carbon, the concentration of the acid solution is 10-40 wt%. The pickling time is 30-400 min. The pickling temperature is 40-80 ℃.
In the above method for preparing activated carbon, the drying process in step (2) may be normal pressure drying or vacuum drying; the drying temperature is 50-250 ℃; the drying time is 2-16 h.
In the preparation method of the activated carbon, the drying temperature in the step (2) is 60-150 ℃; the drying time is 5-12 h.
The third aspect of the present invention provides an activated carbon prepared by the above method, wherein the accessibility a of the activated carbon is 1.4 to 2.2, wherein the accessibility a of the activated carbon is calculated by the following formula:
wherein V mic Is the micropore volume, V, of the activated carbon measured by the t-plot method 0 Is total pore volume (cm) of activated carbon 3 /g)，V′ 0 Is the cumulative total pore volume (cm) of micropores smaller than 2nm calculated by DFT method 3 /g)，V i Is the cumulative pore volume (cm) of 0.8-2.0 nm pores calculated by DFT method 3 (g), S is the specific surface area (m) of the activated carbon 2 /g)。
The invention also provides a method for preparing the activated carbon.
Compared with the prior art, the active carbon and the preparation method thereof have the following advantages:
1. the preparation method of the activated carbon has the advantages of reasonable pore distribution of the activated carbon, proper specific surface area, good methane storage effect, simple preparation method and the like, and has micropores capable of adsorbing a large amount of methane and mesopores capable of accelerating mass transfer by optimizing process conditions.
2. The preparation method of the activated carbon for adsorbing and storing methane comprises the steps of introducing a transition metal compound in the petroleum coke activation process, forming a diffusion path formed by leading the transition metal compound into a petroleum coke bulk phase by using an activating agent, and leading the transition metal compound to enter a petroleum coke-based activated carbon pore channel along with the activating agent in a molten state to form a high-dispersion structure; meanwhile, carbon-containing gas is subjected to vapor deposition under the catalytic action of the transition metal to grow a carbon nano structure on the surface of the active carbon pore canal. Thus, on the basis that the alkali-activated petroleum coke mainly forms tiny micropores, hole expansion is further realized, and a channel for adsorbing and storing methane is provided; meanwhile, the carbon nanostructure has high graphitization degree, high aromatic atom capacity of accommodating high-density pi electrons, stronger methane adsorption performance, and capability of preparing activated carbon with reasonable pore distribution, appropriate specific surface area and high methane adsorption capacity.
3. In the preparation method of the activated carbon for adsorbing and storing methane, petroleum coke is used as a raw material for preparing the activated carbon, so that a novel utilization method for the petroleum coke is provided, and the resource utilization of the petroleum coke is realized.
Detailed Description
The technical content and technical effects of the present invention will be further described with reference to the following specific examples, but the present invention is not limited thereto.
In the examples and comparative examples of the present invention, the pore structure of activated carbon was characterized and tested by ASAP 2460 physical adsorption apparatus of Micromeritics, USA, and by N 2 And measuring the specific surface area, the pore volume and the pore size distribution of the activated carbon by a physical adsorption method. The analysis conditions are as follows: before testing, the samples were first treated under vacuum at 300 ℃ to>4h, the test was carried out at liquid nitrogen temperature (77.35K). The adsorption-desorption isotherm is obtained by measurement according to a static method, the specific surface area S of the activated carbon is calculated according to the BET (Brunauer-Emmett-Teller) equation,<cumulative pore volume V 'of 2nm micropores' 0 And a cumulative pore volume V of 0.8 to 2.0nm pores i Calculated by DFT method, total pore volume V 0 Is the total pore volume of single-point desorption of pores, the pore volume of micropores V mic Calculated by the t-plot method. The adsorption capacity of the activated carbon to methane is measured by adopting an ASAP2050 high-pressure physical adsorption instrument of Micromeritics company in America, and the test conditions are as follows: 25 ℃,3.5MPa, and the unit of adsorption capacity is mL/(g, STP), wherein STP is the standard condition, i.e. 1 standard atmosphere and 0 ℃.
Example 1
Uniformly mixing petroleum coke, potassium hydroxide and nickel nitrate which are ground to have the granularity of 20-300 meshes according to the mass ratio of 1. The accessibility A of AC-1 is 2.0, scale tableArea 1937m 2/ g,3.5MPa, and the methane adsorption capacity at 25 ℃ is 236 ml/(g, STP).
Example 2
Uniformly mixing petroleum coke, potassium hydroxide and cobalt nitrate which are ground to 20-300 meshes according to the mass ratio of 1. Cooling to room temperature, filtering and washing the activated product with water until the pH value of the filtrate is neutral, then adding 20wt% dilute sulfuric acid into the filter cake, washing at 50 ℃ for 240min, continuously washing the product after filtering and separation with water until the pH value of the filtrate is neutral, and drying the solid product at 100 ℃ for 12h to obtain the active carbon AC-2. The accessibility degree A of the AC-2 is 1.9, and the specific surface area is 1843m 2/ g,3.5MPa, and the adsorption capacity of methane at 25 ℃ is 215 mL/(g, STP).
Example 3
Uniformly mixing petroleum coke, potassium hydroxide and ferric oxide which are ground to have the granularity of 20-300 meshes according to the mass ratio of 1 to 0.2, activating for 60min at 950 ℃ in a nitrogen atmosphere, cooling to 800 ℃ in the nitrogen atmosphere, stopping introducing nitrogen, introducing a methane/nitrogen mixed gas (the volume ratio of methane to nitrogen is 1. The accessibility degree A of AC-3 is 1.7, the specific surface area is 1521m 2/ g, the adsorption capacity of the adsorbent to methane at 25 ℃ under 3.5MPa is 201 mL/(g, STP).
Example 4
Uniformly mixing petroleum coke ground to 20-300 meshes, potassium hydroxide and copper nitrate according to the mass ratio of 1Washing with water until the pH value of the filtrate is neutral, and drying the solid product at 120 ℃ for 12h to obtain the active carbon AC-4. The accessibility A of AC-4 is 1.8, the specific surface area is 1764m 2/ g,3.5MPa, and the adsorption capacity of methane at 25 ℃ is 195 mL/(g, STP).
Example 5
Uniformly mixing petroleum coke, potassium hydroxide and chromium nitrate which are ground to be 20-300 meshes according to the mass ratio of 1. Cooling to room temperature, filtering and washing the activated product with water until the pH value of the filtrate is neutral, then adding 20wt% of dilute hydrochloric acid into the filter cake, washing for 250min at 60 ℃, continuously washing the product with water after filtering and separating until the pH value of the filtrate is neutral, and drying the solid product at 150 ℃ for 10h to obtain the active carbon AC-5. The accessibility degree A of AC-5 is 1.8, the specific surface area is 1895m 2/ g,3.5MPa, and the adsorption capacity of methane at 25 ℃ is 203 mL/(g, STP).
Comparative example 1
Evenly mixing petroleum coke ground to the granularity of 20-300 meshes and potassium hydroxide according to the mass ratio of 1 to 3, activating for 60min at 900 ℃ in a nitrogen atmosphere, cooling to 600 ℃ in the nitrogen atmosphere, stopping introducing nitrogen, introducing a methane/nitrogen mixed gas (the volume ratio of methane to nitrogen is 2. The accessibility A of AC-4 is 1.1, the specific surface area is 723m 2/ g,3.5MPa, and the adsorption capacity of methane at 25 ℃ is 73 mL/(g, STP). .
Comparative example 2
Uniformly mixing petroleum coke ground to the granularity of 20-300 meshes, potassium hydroxide and nickel nitrate according to the mass ratio of 1And (3) neutralizing, adding 10wt% of dilute hydrochloric acid into a filter cake, washing for 180min at 60 ℃, continuously washing the product after filtration and separation with water until the pH value of the filtrate is neutral, and drying the solid product at 120 ℃ for 5h to obtain the activated carbon AC-5. The accessibility degree A of AC-5 is 2.3, the specific surface area is 2845m 2/ g,3.5MPa, and the adsorption capacity of methane at 25 ℃ is 150 mL/(g, STP).
Claims (19)
1.A preparation method of activated carbon comprises the following steps:
(1) Uniformly mixing petroleum coke, an activating agent and a transition metal compound, and then carrying out an activation reaction;
(2) Washing and drying the activated product obtained in the step (1) to obtain activated carbon;
the specific process of the activation reaction in the step (1) is as follows: heating the uniformly mixed petroleum coke, activating agent and transition metal compound to a temperature A in an atmosphere A, preserving heat for a certain time A, then adjusting the temperature to a temperature B, stopping introducing the atmosphere A, introducing the atmosphere B, preserving heat for a certain time B under the condition of the temperature B, and cooling to obtain an activated product;
when the atmosphere A is a mixed gas of a carbon-containing gas and a carrier gas, the atmosphere B is nitrogen and/or an inert gas; wherein, the carbon-containing gas is one or more of hydrocarbon gas and carbon monoxide; the hydrocarbon gas is one or more of acetylene and methane; the carrier gas is one or more of nitrogen, helium and argon; the volume ratio of the carbon-containing gas to the carrier gas is 1.1-20; the inert gas is one or more of helium, argon and neon; the temperature A is 400-850 ℃; the heat preservation time A is 5-200 min; the temperature B is 600-1100 ℃, and the heat preservation time B is 5-500 min;
when the atmosphere A is nitrogen and/or inert gas, the atmosphere B is a mixed gas of carbon-containing gas and carrier gas, wherein the inert gas is one or more of helium, argon and neon; the carbon-containing gas is one or more of hydrocarbon gas and carbon monoxide; the hydrocarbon gas is one or more of acetylene and methane; the carrier gas is one or more of nitrogen, helium and argon; the volume ratio of the carbon-containing gas to the carrier gas is 1.1-20; the temperature A is 600-1100 ℃, and the heat preservation time A is 5-500 min; the temperature B is 400-850 ℃; the heat preservation time B is 5-200 min;
the activated carbon has micropores and mesopores; the transition metal compound enters a petroleum coke-based active carbon pore channel along with a molten activator, and simultaneously, the carbon-containing gas generates gas phase deposition to grow a carbon nano structure, so that the hole expansion is realized.
2. The process for producing activated carbon according to claim 1, wherein: the petroleum coke in the step (1) is solid coke generated by cracking and coking vacuum residue by a coking device.
3. The process for producing activated carbon according to claim 1, wherein: the activating agent in the step (1) is one or more of potassium hydroxide, sodium hydroxide, calcium hydroxide, potassium carbonate and potassium bicarbonate.
4. The process for producing activated carbon according to claim 3, wherein: the activating agent in the step (1) is potassium hydroxide.
5. The process for producing activated carbon according to claim 1, wherein: the transition metal compound in the step (1) is one or more of transition metal salt, transition metal oxide and transition metal hydroxide.
6. The process for producing activated carbon according to claim 1, wherein: the transition metal is one or more of Fe, co, ni, cu, cr, mo and Pt.
7. The process for producing activated carbon according to claim 1, wherein: in the step (1), the transition metal compound is one or more of ferric nitrate, ferric sulfate, ferric chloride, ferric phosphate, ferric acetate, ferric oxide, ferric hydroxide, nickel nitrate, nickel sulfate, nickel chloride, nickel phosphate, nickel acetate, nickel oxide, nickel hydroxide, cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt phosphate, cobalt acetate, cobalt oxide, cobalt hydroxide, copper nitrate, copper sulfate, copper chloride, copper phosphate, copper acetate, copper oxide, copper hydroxide, chromium nitrate, chromium sulfate, chromium chloride, chromium phosphate, chromium acetate, chromium oxide, chromium hydroxide, molybdenum nitrate, molybdenum sulfate, molybdenum chloride, molybdenum phosphate, molybdenum acetate, molybdenum oxide, molybdenum hydroxide, platinum nitrate, platinum sulfate, platinum chloride, platinum phosphate, platinum acetate, platinum oxide and platinum hydroxide.
8. The process for producing activated carbon according to claim 7, wherein: in the step (1), the transition metal compound is one or more of ferric oxide, nickel nitrate and cobalt nitrate.
9. The process for producing activated carbon according to claim 1, wherein: the mass ratio of the petroleum coke, the activating agent and the transition metal compound in the step (1) is 1.
10. The process for producing activated carbon according to claim 9, wherein: the mass ratio of the petroleum coke, the activating agent and the transition metal compound in the step (1) is 1.
11. The process for producing activated carbon according to claim 1, wherein: the specific process of the activation reaction in the step (1) is as follows: heating the uniformly mixed petroleum coke, activating agent and transition metal compound to a temperature A in an atmosphere A, preserving heat for a certain time A, then adjusting the temperature to a temperature B, stopping introducing the atmosphere A, introducing the atmosphere B, preserving heat for a certain time B at the temperature B, and cooling to obtain an activated product;
when the atmosphere A is a mixed gas of a carbon-containing gas and a carrier gas, the atmosphere B is nitrogen and/or an inert gas; wherein the carbon-containing gas is one or more of hydrocarbon gas and carbon monoxide; the hydrocarbon gas is one or more of acetylene and methane; the carrier gas is one or more of nitrogen, helium and argon; the volume ratio of the carbon-containing gas to the carrier gas is 1; the inert gas is one or more of helium, argon and neon; the temperature A is 500-800 ℃; the heat preservation time A is 20-120 min; the temperature B is 700-950 ℃, and the heat preservation time B is 15-300 min;
when the atmosphere A is nitrogen and/or inert gas, the atmosphere B is a mixed gas of carbon-containing gas and carrier gas, wherein the inert gas is one or more of helium, argon and neon; the carbon-containing gas is one or more of hydrocarbon gas and carbon monoxide; the hydrocarbon gas is one or more of acetylene and methane; the carrier gas is one or more of nitrogen, helium and argon; the volume ratio of the carbon-containing gas to the carrier gas is 1.2-10; the temperature A is 700-950 ℃, and the heat preservation time A is 15-300 min; the temperature B is 500-800 ℃; the heat preservation time B is 20-120 min.
12. The process for producing activated carbon according to claim 1, wherein: and (3) washing in the step (2) is carried out by using acid washing and then washing with water.
13. The process for producing activated carbon according to claim 12, wherein: the washing in the step (2) is carried out by acid washing and then water washing; washing with water before acid washing, wherein the water washing refers to washing with water until the pH value of the filtrate is neutral; the acid washing is carried out by adopting inorganic acid solution, and the inorganic acid is hydrochloric acid.
14. The process for producing activated carbon according to claim 13, wherein: the concentration of the acid solution is 5-50 wt%; the pickling temperature is 20-100 ℃.
15. The process for producing activated carbon according to claim 14, wherein: the concentration of the acid solution is 10-40 wt%; the pickling temperature is 40-80 ℃.
16. The process for producing activated carbon according to claim 1, wherein: the drying temperature in the step (2) is 50-250 ℃; the drying time is 2-16 h.
17. The process for producing an activated carbon as claimed in claim 16, wherein: the drying temperature in the step (2) is 60-150 ℃; the drying time is 5-12 h.
18. An activated carbon prepared by the method of any one of claims 1-17, said activated carbon having an accessibility a of 1.4 to 2.2, wherein the accessibility a of the activated carbon is calculated by the formula:
；
wherein V mic Is the micropore volume, V, of the activated carbon measured by the t-plot method 0 Is the total pore volume of the activated carbon, the unit of which is cm 3 /g，
Is the cumulative total pore volume of micropores smaller than 2nm calculated by a DFT method, and the unit of the cumulative total pore volume is cm 3 /g，V i Is the cumulative pore volume of 0.8-2.0 nm pores calculated by DFT method, and the unit is cm 3 S is the specific surface area of the activated carbon in m 2 /g。
19. Use of the activated carbon of claim 18 for the adsorptive storage of methane.
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| CN1303732A (en) * | 2000-05-11 | 2001-07-18 | 中国科学院山西煤炭化学研究所 | Method for preparing active carbon for storing methane |
| CN1411903A (en) * | 2001-10-19 | 2003-04-23 | 石油大学(北京) | Micropore carbon adsorbent for storing natural gas and its preparation method |
| CN101329924A (en) * | 2008-07-30 | 2008-12-24 | 中国科学院山西煤炭化学研究所 | Method for preparing high performance electrode material |
| CN109179415A (en) * | 2018-09-12 | 2019-01-11 | 中国地质科学院郑州矿产综合利用研究所 | Preparation method of coal-based carbon molecular sieve |
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| CN1303732A (en) * | 2000-05-11 | 2001-07-18 | 中国科学院山西煤炭化学研究所 | Method for preparing active carbon for storing methane |
| CN1411903A (en) * | 2001-10-19 | 2003-04-23 | 石油大学(北京) | Micropore carbon adsorbent for storing natural gas and its preparation method |
| CN101329924A (en) * | 2008-07-30 | 2008-12-24 | 中国科学院山西煤炭化学研究所 | Method for preparing high performance electrode material |
| CN109179415A (en) * | 2018-09-12 | 2019-01-11 | 中国地质科学院郑州矿产综合利用研究所 | Preparation method of coal-based carbon molecular sieve |
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