CN104549293B - A kind of method based on carbon pipe Yu the compound catalyst preparation alkenes compounds of transition metal - Google Patents
A kind of method based on carbon pipe Yu the compound catalyst preparation alkenes compounds of transition metal Download PDFInfo
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- CN104549293B CN104549293B CN201510026459.3A CN201510026459A CN104549293B CN 104549293 B CN104549293 B CN 104549293B CN 201510026459 A CN201510026459 A CN 201510026459A CN 104549293 B CN104549293 B CN 104549293B
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- catalyst
- transition metal
- ethylbenzene
- nickel
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- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 60
- 150000001875 compounds Chemical class 0.000 title claims abstract description 49
- -1 alkenes compounds Chemical class 0.000 title claims abstract description 32
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 32
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 122
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 239000007789 gas Substances 0.000 claims abstract description 28
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 18
- 230000009471 action Effects 0.000 claims abstract description 6
- 238000009833 condensation Methods 0.000 claims abstract description 5
- 230000005494 condensation Effects 0.000 claims abstract description 5
- 238000009834 vaporization Methods 0.000 claims abstract 3
- 230000008016 vaporization Effects 0.000 claims abstract 3
- 238000001354 calcination Methods 0.000 claims description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 239000012298 atmosphere Substances 0.000 claims description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 19
- 229910052786 argon Inorganic materials 0.000 claims description 12
- XIKYYQJBTPYKSG-UHFFFAOYSA-N nickel Chemical compound [Ni].[Ni] XIKYYQJBTPYKSG-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 6
- 239000006004 Quartz sand Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 150000001720 carbohydrates Chemical class 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 2
- 150000002815 nickel Chemical class 0.000 claims 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 42
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 23
- 239000012159 carrier gas Substances 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 239000000126 substance Substances 0.000 abstract description 14
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 13
- 150000001336 alkenes Chemical class 0.000 abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003925 fat Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 239000010453 quartz Substances 0.000 description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 230000000694 effects Effects 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 229920000877 Melamine resin Polymers 0.000 description 15
- 230000004044 response Effects 0.000 description 14
- CHVZQMAANSUXJU-JJKGCWMISA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanamide;hydrochloride Chemical class Cl.NC(=O)[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO CHVZQMAANSUXJU-JJKGCWMISA-N 0.000 description 13
- 150000007974 melamines Chemical class 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000001514 detection method Methods 0.000 description 11
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 11
- 239000003570 air Substances 0.000 description 8
- 239000002113 nanodiamond Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Chemical group CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 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 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical group CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- QUBBAXISAHIDNM-UHFFFAOYSA-N 1-ethyl-2,3-dimethylbenzene Chemical group CCC1=CC=CC(C)=C1C QUBBAXISAHIDNM-UHFFFAOYSA-N 0.000 description 1
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 1
- 241000234282 Allium Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910002552 Fe K Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WKYAPGVTFGNPSP-UHFFFAOYSA-N benzene;chloroethene Chemical group ClC=C.C1=CC=CC=C1 WKYAPGVTFGNPSP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000001282 iso-butane Chemical group 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical class CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000012899 standard injection Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method based on carbon pipe Yu the compound catalyst preparation alkenes compounds of transition metal, dehydrogenation reaction is carried out in the reactor under catalyst action after alkane derivative preheating vaporization and carrier gas are mixed, and alkenes compounds are collected after condensation；The catalyst contains 5wt%~30wt% transition metal/transition metal oxide and 70wt%~95wt% carbon pipes.The inventive method is used to prepare fats alkene compound and aromatics olefin(e) compound, use based on carbon pipe and transition metal simple substance/compound catalyst of transition metal oxide to water, air and thermostabilization, continuous experiment more than 150 hours, catalytic activity is constant, continuous operation can be achieved, it is convenient without activation, economy.When catalyst prepares styrene applied to ethylbenzene gas phase direct dehydrogenation in the present invention, the conversion ratio of alkane derivative is up to more than 10%, and the selection rate of alkenes compounds is up to more than 97%.
Description
Technical field
The present invention relates to organic synthesis field, more particularly to it is a kind of based on carbon pipe and the compound catalyst preparation of transition metal
The method of alkenes compounds.
Background technology
Alkenes compounds are important industrial chemicals, are divided into fats olefin(e) compound and aromatics olefin(e) compound.
Coproduction or by-product of the propylene/isobutene essentially from steam cracking and refinery factory fluid catalytic cracking process, can be widely used for closing
Into polymer, gasoline additive, rubber and various chemical intermediates.It is traditional as low-carbon alkene demand is growing
Production process is difficult to meet the market demand.Exploitation is by low-carbon alkanes preparing low-carbon olefins process for making full use of low-carbon alkanes to open
It is significant to ward off new alkene source.
Dehydrogenating low-carbon alkane catalytic reaction is carried out under high temperature, lower pressure, and catalyst carbon deposit catches fire seriously, is developed high living
Property, the catalyst of high selectivity and high stability turn into the key of the technology.Application No. 200710025372.X China is specially
Profit application discloses a kind of catalyst, in the preparation side that alumina modified mesoporous molecular sieve is platinum-impregnated tin component on carrier
Method, conversion of propane are only 17%, Propylene Selectivity 93%.The catalyst employs the activearm of alumina load catalyst
Point tin, the easy coking deactivation of catalyst during applied at elevated temperature, the stability of catalyst are poor.
For aromatics olefin(e) compound by taking styrene as an example, styrene is important Organic Chemicals, is mainly used for making
For synthetic rubber and the monomer of plastics, for producing butadiene-styrene rubber, polystyrene, foamed polystyrene；Can also be used for and other
Monomer copolymerization manufactures the engineering plastics of a variety of different purposes.In addition, styrene is also production ion exchange resin and pharmaceuticals
One of raw material, it may also be used for the industry such as pharmacy, dyestuff, agricultural chemicals and ore dressing.
Styrene industrial manufacture process mainly has two kinds of ethylbenzene catalytic dehydrogenation method and ethylbenzene conjugated oxidation in the world.Ethylbenzene takes off
Hydrogen is that a reversible heat absorption increases molecule reaction, and heating decompression is advantageous to reaction and carried out to generation styrene direction.It is industrial to use
Method be that a large amount of high-temperature vapors are mixed in charging, to reduce hydrocarbon partial pressure, and provide reaction needed for partial heat.For
Ethylbenzene catalytic dehydrogenation method, what is used in early days has the magnesium series catalysts of California, USA standard oil company and German method our company
Zinc system catalyst.After World War II, the exploitation of widely used Shell Oil Company of the U.S. using iron oxide as mainly into
Catalyst (the Fe divided2O3:K2O:Cr2O3=87:10:3), styrene yield about 60%, selectivity about 87%.
1978, occur a kind of Fe-series catalyst added with a variety of co-catalysts again, selectivity of styrene up to 95%,
The co-catalyst of addition is mostly alkali metal or alkaline-earth metal, such as potassium, vanadium, molybdenum, tungsten, cerium, chromium.It is catalyzed for the Fe-K of commercialization
Agent, due to the loss of its potassium in catalytic process, Fe3+State is extremely unstable, and clogged with soot active sites easily occur and cause its catalysis
Stability is poor, is only capable of maintaining several hours, in addition, harmful element Cr in the catalyst system and catalyzing be present, for ring
Border, health etc. are all totally unfavorable.In order to overcome these problems, carbon-based material catalyst is used for the oxidative dehydrogenation of ethylbenzene
Become effective substitute technology.
The oxidative dehydrogenation for being used for ethylbenzene with activated carbon of Figueiredo seminars report shows good catalytic activity,
And find activated carbon surface carbonyl/quinonyl ratio be improve catalytic performance key (A ppl.Catal.A:Gen.,184,
153).But in oxidative airstream atmosphere, the stability extreme difference of activated carbon.D.S.Su and R.Schlogl et al. report more
The nano-carbon material of wall carbon pipe and onion shape is used as the oxidative dehydrogenation (Catal.Today 2005,102,110-114) of ethylbenzene, by
In the essence and its microstructure of carbon material its catalytic stability is increased compared with activated carbon, but its catalytic activity is only reported
At 10 hours or so.In addition, carrying out oxidation processes to more wall carbon pipes by early stage, the oxy radical density of carbon pipe surface is improved
Catalytic performance can be effectively improved, and stabilizing it property significantly improves (Carbon, 2004,42,2807-2813), but its
Catalytic cycle is only limitted to several hours.In addition to the above-mentioned use dioxygen oxidation dehydrogenation referred to, it is also possible to effect of the toluene in methanol
Downside chain hydrocarbonylation prepares styrene (Catal.Today 2003,81,425).Although these means of catalysis have compared with commercial catalyst
It is significant to improve, but its selectivity is poor and flammable mixture uses so that operating than relatively hazardous.
Carbon-supported catalysts are used for the gas phase direct dehydrogenation of ethylbenzene as study hotspot in recent years.Wherein most typically
The use strong oxidizing property of Nano diamond, D.S.Su (Angew.Chem.Int.Ed.2010,49,8640-8644) et al. report
The Nano diamond of core shell structure prepared by the method for pickling blast can be used for the direct dehydrogenation of ethylbenzene in argon atmosphere, and logical
Cross and activate catalyst repeatedly in 400 DEG C of air, its catalytic performance can be extended by 120 hours.Then, D.S.Su seminar is again
Two-step method synthesizing nano diamond/CNT-SiC carbon-supported catalysts are reported, select the macropore of high-termal conductivity and mechanical stability
SiC foam wraps up one layer of carbon pipe, then using ultrasound by the method for chemical vapor deposition as carrier on SiC foam surface
The Nano diamond of commercialization is supported in substrate by the method for assistant soakage, although obtained catalyst has higher conversion
Rate, but the preparation process of its catalyst is complicated, and cost is higher, the stability reported in addition is only 20 hours
(Chem.Commun.,2014,50,7810-7812).The and for example Nano diamond of the preparation such as Z.K.Zhao/carbonitride hydridization material
Expect that (J.Mater.Chem.A.2014,2,13442-13451) is to be fired to difference after being mixed by melamine with Nano diamond
Temperature and obtain, although improving its catalytic performance by melamine introducing hetero-atoms N, in the preparation process of Nano diamond
In need acid with strong oxidizing property explosive treatment, be extremely unfriendly for environment, it is small to be also only reported in 20 for its catalytic stability in addition
When.
In view of the problem of above method is present, develops a kind of excellent catalytic effect, low energy consumption, raw material sources are extensive, and catalysis is steady
Characteristic time is grown, and it is heavy to closing that can be used to prepare fats alkene compound and the new catalyst of aromatics olefin(e) compound simultaneously
Want.
The Chinese patent application of Application No. 201410338644.1 and 201410389748.5 discloses a kind of new big
Caliber, overlength CNT catalyst and preparation method thereof, the catalyst are carried by metallic 5wt%~30wt% and carbon pipe
Body 70wt%~95wt% is formed, and the carbon pipe catalyst compound with transition metal can be prepared by one kettle way, by carbohydrate, mould
Calcine and be made after plate agent and transition metal salt mixing, dinectly bruning obtains the catalyst of carbon tube transitions metal composite.The carbon pipe with
The compound catalyst preparation of transition metal is simple, to water, air and thermostabilization.
The content of the invention
The invention provides a kind of method based on carbon pipe Yu the compound catalyst preparation alkenes compounds of transition metal.
The present invention efficiently, is with high selectivity urged using based on carbon pipe with transition metal simple substance/compound catalyst of transition metal oxide
Change the step dehydrogenation of alkane derivative one synthesis alkenes compounds, this method can be used for preparing fats alkene compound and aromatics
Olefin(e) compound.
A kind of method based on carbon pipe Yu the compound catalyst preparation alkenes compounds of transition metal, after preheating is vaporized
Alkane derivative and carrier gas mixing be passed through in reactor under catalyst action and carry out dehydrogenation reaction, collect alkene after condensation
Class compound；
The catalyst contains 5wt%~30wt% (percentage by weight) transition metal simple substance/transition metal oxide
With 70wt%~95wt% carbon pipe, the average grain diameter of transition metal/transition metal oxide is 1-100nm；
Shown in described alkane derivative structural formula such as formula (I)：
R-CH2CH3(I)；
Shown in described alkenes compounds structural formula such as formula (II)：
R-CH=CH2(II)；
Substituent R is hydrogen atom, C in formula (I) and formula (II)1-C4Alkyl, substituted or unsubstituted aryl；If substituent R
For substituted aryl when, the substituent on the aryl is selected from halogen, C1-C4Alkyl or C1-C4Alkoxy.
The principle that the present invention reacts is：The active sites of catalytic reaction are mainly the-C=O and defective bit (carbon of catalyst surface
The tube wall of pipe), alkane derivative absorption is in active sites and-C-H fracture occurs, so as to which dehydrogenation reaction occur.In catalyst
Big caliber is advantageous to mass transport process, promotes the progress of reaction.And transition metal/transition metal oxide in catalyst is significantly
Raising catalyst stability.
Described aryl refers to not comprising heteroatomic aromatic rings, such as phenyl or naphthyl etc.；Preferably, the aryl is
Phenyl, the selection rate and the equal highest of conversion ratio of alkenes compounds is now made.
Preferably, the substituent of the aryl is selected from chlorine, fluorine, methyl or methoxy；Described substituent can be one
It is individual or multiple, can be with identical or different between respective.
As the one kind of further preferred, described alkane derivative in following compound：
Ethylbenzene, 2- methyl-ethyl benzenes, 4- methoxyl groups ethylbenzene, adjacent chloroethene benzene, 2,3- dimethyl ethylbenzene, normal butane, n-propane or
Iso-butane.
Catalyst is filled into reactor after being mixed with quartz sand, the mass ratio 1 of catalyst and quartz sand：10-100, urge
Agent and quartz sand mixing are for dilute catalyst, improve reaction raw materials in the residence time of beds, raising reaction
Efficiency, and catalyst is played a supporting role.
Described carrier gas is at least one of air, oxygen, nitrogen, argon gas and helium.Carrier gas is air or oxygen, alkane
Under catalyst action oxidative dehydrogenation occurs for hydrocarbon compound, and alkenes compounds are made；Carrier gas is nitrogen, argon gas or helium
Gas, alkane derivative itself dehydrogenation under catalyst action prepare alkenes compounds.
Preferably, the carrier gas is air or argon gas, under the conditions of preferable carrier gas, the inventive method is de- using oxidation
Hydrogen or itself dehydrogenation prepare alkenes compounds, and conversion rate is very fast, and yield is higher.
The pre- thermal evaporation rear and carrier gas of alkane derivative is mixed to form mixed gas, is continuously taken off in the reactor
Hydrogen reacts, and volume fraction of the alkane derivative in carrier gas is 1.0%-40.0%, body of the alkane derivative in carrier gas
When fraction is smaller, it is relatively low to prepare the selectivity of alkenes compounds, but yield is higher；Body of the alkane derivative in carrier gas
When fraction is larger, it is relatively low to prepare the yield of alkenes compounds, but selectivity is higher.
Volume fraction of the alkane derivative in carrier gas represents the volume ratio of alkane derivative and carrier gas.
Preferably, volume fraction of the alkane derivative in carrier gas is 1.0~25.0%, within the range,
The conversion ratio that alkenes compounds are made is higher.
Alkane derivative and the flow velocity of carrier gas are 10-40mL/min, the mass space velocity (WHSV) of the alkane compound
For 0.2-20h-1。
Mass space velocity is by the gas flow of unit mass catalyst layer in the unit time；
Mass space velocity=material quality flow (kg.h-1)/catalyst quality (kg).
The dehydrogenation reaction temperature is 300 DEG C -600 DEG C, and the temperature can make reactant gasify, and heat up within the specific limits
The activity of reaction substrate can be increased, accelerate the progress of reaction.
Preferably, reaction temperature be 400 DEG C -600 DEG C, in the temperature range, reaction substrate activity is higher, react compared with
It hurry up.
Described to react the carry out degree reacted by gas-chromatography on-line checking, the stable reaction time is 0.5h-1h, substrate
Difference, stable reaction time slightly have difference.
In the catalyst carbon pipe be N doping CNT, nitrogen content 0.01wt%-20.0wt%.N doping
CNT and the compound catalyst of transition metal, catalytic effect are more preferable.
Described transition metal simple substance/transition metal oxide represents the mixed of transition metal simple substance and transition metal oxide
Compound.
Transition metal simple substance is Ni, Fe or Co in the catalyst；Described transition metal oxide is Ni's, Fe or Co
Oxide.
Catalyst of the present invention can use the patent of Application No. 201410338644.1 and 201410389748.5
Preparation method is made disclosed in application：
(1) carbohydrate, template and transition metal salt physical mixed, obtain solid precursor；
(2) solid precursor prepares carbon pipe and transition metal simple substance/transition in an inert atmosphere through two-part calcination procedure
The compound catalyst of metal oxide；
The transition metal salt is Fe salt, Ni salt or Co salt.
Preferably, the transition metal salt is Ni salt, higher using catalyst activity made from Ni salt.
More preferably, for direct dehydrogenation, reaction condition is：Described alkane derivative is ethylbenzene, and the carrier gas is
Argon gas, volume fraction of the ethylbenzene in carrier gas are 1%~5%, and the mass space velocity of ethylbenzene is 0.2-1.8h-1, reaction temperature 450
DEG C~600 DEG C.The conversion ratio of ethylbenzene is 15~25% under this condition, and selection rate is 95~100%.For oxidative dehydrogenation, instead
The condition is answered to be：Described alkane derivative is ethylbenzene, and the carrier gas is air, and volume fraction of the ethylbenzene in carrier gas is 10%
~25%, the mass space velocity of ethylbenzene is 7-18h-1, reaction temperature is 450 DEG C~600 DEG C.The conversion ratio of ethylbenzene is under this condition
40~65%, selection rate is 50~80%.
The inventive method conveys ethylbenzene through standard injection pump in initial reaction stage, is then gone forward side by side with argon gas one after preheated section
Enter gasification section, superheater is finally entered with the state of mixed gas, enter reactor after reaching reaction temperature, be filled with
Successive reaction on catalyst, collected after the reacted condensed device condensation of olefin product.
The product that the alkane derivative that the inventive method uses is sold for market, to ensure the purity of alkene, alkanes
The purity grade of compound is at least 99wt%, and the purity of carrier gas is at least 99.99wt%, and alkane derivative is noted by standard
Pump conveying is penetrated, the flow velocity of carrier gas has the control of gas mass flow gauge.
Compared with prior art, the invention has the advantages that：
(1) present invention use based on carbon pipe and transition metal simple substance/compound catalyst of transition metal oxide in argon
The conversion ratio of directly catalytic dehydrogenating reaction is high by more than 50% compared with business carbon pipe catalyst during atmosphere is enclosed.
(2) it is by one pot based on carbon pipe and transition metal simple substance/compound catalyst of transition metal oxide in the present invention
Method is directly prepared, and the metallic nanoparticle being formed in situ is firmly combined with carbon pipe, limits the migration and reunion of nano-particle, so as to
Effectively raise the stability of catalyst.
(3) the inventive method using high activity and high selectivity based on carbon pipe and transition metal simple substance/oxo transition metal
The compound catalyst of compound, raw material is cheap and easy to get, energy-conserving and environment-protective, reaction condition are gentle, safe operation.
(4) the inventive method use based on carbon pipe and transition metal simple substance/compound catalyst of transition metal oxide
To water, air and thermostabilization, continuous experiment more than 150 hours, catalytic activity is constant, and continuous operation can be achieved, without activation, warp
Ji is convenient.Catalyst can be used for preparing fats alkene compound and aromatics olefin(e) compound in the present invention, applied to ethylbenzene gas
When phase direct dehydrogenation prepares styrene, the conversion ratio of alkane derivative obtains the choosing of alkenes compounds up to more than 10%
Rate is selected up to more than 97%.
(5) the inventive method use based on carbon pipe and transition metal simple substance/compound catalyst of transition metal oxide
Available for direct dehydrogenation and oxidative dehydrogenation, and there is superpower stability in air and argon atmosphere.
Brief description of the drawings
Fig. 1 is 20wt%~25wt% nickel nickels and the transmission electricity of the compound catalyst of 75wt%~80wt% carbon pipes
Sub- microphotograph.
Fig. 2 is the continuity of 20wt%~25wt% nickel nickels and the compound catalyst of 75wt%~80wt% carbon pipes
Catalytic effect figure.
Embodiment
Embodiment 1
By 1g aminoglucose hydrochlorides, 20g melamines and 0.7g nickel nitrate physical mixeds, by mixed uniformly solid
Powder is placed in crucible and calcined in inert atmosphere, and calcination procedure is to be incubated 0.5-1.5h at 550-650 DEG C, then in 800-1200
DEG C calcining 0.5-1.5h, after calcination procedure terminates, room temperature is cooled in inert atmosphere, obtain 20wt%~25wt% nickel/
Nickel oxide and the compound catalyst of 75wt%~80wt% carbon pipes.Transmission electron microscope picture is as shown in Figure 1.
The quartz tube reactor that internal diameter is 5mm is encased in after obtained 0.08g catalyst is well mixed with 6g quartz sands
In, volume fraction of the ethylbenzene in argon gas is 5%, and the mass space velocity of ethylbenzene is 1.0h-1, flow velocity 10mL/min, reaction temperature
For 450 DEG C, pressure is normal pressure, after question response is stable, is examined through the gas-chromatography equipped with capillary chromatographic column and hydrogen flame detector
Survey.Under the reaction temperature, the conversion ratio of ethylbenzene is 5%, and the selectivity of styrene is 97-98%, and impurity content is less than
0.5%, by 150h operation, catalyst activity does not reduce.
Embodiment 2
By 1g aminoglucose hydrochlorides, 20g melamines and 0.7g nickel nitrate physical mixeds, by mixed uniformly solid
Powder is placed in crucible and calcined in inert atmosphere, and calcination procedure is to be incubated 0.5-1.5h at 550-650 DEG C, then 800~
1200 DEG C calcining 0.5-1.5h, after calcination procedure terminates, room temperature is cooled in inert atmosphere, you can obtain 20wt%~
25wt% nickel nickels and the compound catalyst of 75wt%~80wt% carbon pipes.
The quartz tube reactor that internal diameter is 5mm is encased in after obtained 0.08g catalyst is well mixed with 6g quartz sands
In, volume fraction of the ethylbenzene in argon gas is 1.0%, and the mass space velocity of ethylbenzene is 1.2h-1, flow velocity 10mL/min, reaction temperature
Spend for 500 DEG C, pressure is normal pressure, after question response is stable, through the gas-chromatography equipped with capillary chromatographic column and hydrogen flame detector
Detection.Under the reaction temperature, the conversion ratio of ethylbenzene is 10%, and the selectivity of styrene is 97-98%, and impurity content is less than
0.5%, by 150h operation, catalyst activity does not reduce.
Embodiment 3
By 1g aminoglucose hydrochlorides, 20g melamines and 0.7g nickel nitrate physical mixeds, by mixed uniformly solid
Powder is placed in crucible and calcined in inert atmosphere, and calcination procedure is to be incubated 0.5-1.5h at 550-650 DEG C, is then forged at 1000 DEG C
1h is burnt, after calcination procedure terminates, room temperature is cooled in inert atmosphere, you can obtain 25wt% nickel nickels and 75wt%
The compound catalyst of carbon pipe.
The quartz tube reactor that internal diameter is 5mm is encased in after obtained 0.08g catalyst is well mixed with 6g quartz sands
In, volume fraction of the ethylbenzene in argon gas is 1.0%-5.0%, and flow velocity 10mL/min, the mass space velocity of ethylbenzene is 1.8h-1,
Reaction temperature is 550 DEG C, and pressure is normal pressure, after question response is stable, through the gas equipped with capillary chromatographic column and hydrogen flame detector
Phase chromatogram detects.Under the reaction temperature, the conversion ratio of ethylbenzene is 10-20%, and the selectivity of styrene is 97-98%, impurity
Content is less than 0.5%, and by 150h operation, catalyst activity does not reduce, as shown in Figure 2.
Embodiment 4
By 1g aminoglucose hydrochlorides, 20g melamines and 0.7g nickel nitrate physical mixeds, by mixed uniformly solid
Powder is placed in crucible and calcined in inert atmosphere, and calcination procedure is to be incubated 0.5-1.5h at 550-650 DEG C, then in 800-1200
DEG C calcining 0.5-1.5h, after calcination procedure terminates, room temperature is cooled in inert atmosphere, you can obtain 20wt%~25wt%
Nickel nickel and the compound catalyst of 75wt%~80wt% carbon pipes.
The quartz tube reactor that internal diameter is 5mm is encased in after obtained 0.16g catalyst is well mixed with 6g quartz sands
In, the aerial volume fraction of ethylbenzene is 10.0%, and the mass space velocity of ethylbenzene is 12h-1, flow velocity 20mL/min, reaction temperature
Spend for 300 DEG C, pressure is normal pressure, after question response is stable, through the gas-chromatography equipped with capillary chromatographic column and hydrogen flame detector
Detection.Under the reaction temperature, the yield of ethylbenzene is 5%, and the selectivity of styrene is 75-85%, by 25h operation, is urged
Agent activity does not reduce.
Embodiment 5
By 1g aminoglucose hydrochlorides, 20g melamines and 0.7g nickel nitrate physical mixeds, by mixed uniformly solid
Powder is placed in crucible and calcined in inert atmosphere, and calcination procedure is to be incubated 0.5-1.5h at 550-650 DEG C, then in 80-1200
DEG C calcining 0.5-1.5h, after calcination procedure terminates, room temperature is cooled in inert atmosphere, you can obtain 20wt%~25wt%
Nickel nickel and the compound catalyst of 75wt%~80wt% carbon pipes.
The quartz tube reactor that internal diameter is 5mm is encased in after obtained 0.16g catalyst is well mixed with 6g quartz sands
In, the aerial volume fraction of ethylbenzene is 15%, and the mass space velocity of ethylbenzene is 10h-1, speed is 20mL/min, and reaction temperature is
350 DEG C, pressure is normal pressure, after question response is stable, through the gas chromatographic detection equipped with capillary chromatographic column and hydrogen flame detector.
Under the reaction temperature, the yield of ethylbenzene is 8%, and the selectivity of styrene is 75-85%, and by 25h operation, catalyst is lived
Property does not reduce.
Embodiment 6
By 1g aminoglucose hydrochlorides, 20g melamines and 0.7g nickel nitrate physical mixeds, by mixed uniformly solid
Powder is placed in crucible and calcined in inert atmosphere, and calcination procedure is to be incubated 0.5-1.5h at 550-650 DEG C, then in 800-1200
DEG C calcining 0.5-1.5h, after calcination procedure terminates, room temperature is cooled in inert atmosphere, you can obtain 20wt%~25wt%
Nickel nickel and the compound catalyst of 75wt%~80wt% carbon pipes.
The quartz tube reactor that internal diameter is 5mm is encased in after obtained 0.16g catalyst is well mixed with 6g quartz sands
In, the aerial volume fraction of ethylbenzene is 25.0%, and the mass space velocity of ethylbenzene is 18h-1, flow velocity 20mL/min, reaction temperature
Spend for 400 DEG C, pressure is normal pressure, after question response is stable, through the gas-chromatography equipped with capillary chromatographic column and hydrogen flame detector
Detection.Under the reaction temperature, the yield of ethylbenzene is 18%, and the selectivity of styrene is 75-85%, by 25h operation, is urged
Agent activity does not reduce.
Embodiment 7
By 1g aminoglucose hydrochlorides, 20g melamines and 0.7g nickel nitrate physical mixeds, by mixed uniformly solid
Powder is placed in crucible and calcined in inert atmosphere, and calcination procedure is to be incubated 0.5-1.5h at 550-650 DEG C, then in 800-1200
DEG C calcining 0.5-1.5h, after calcination procedure terminates, room temperature is cooled in inert atmosphere, you can obtain 20wt%~25wt%
Nickel nickel and the compound catalyst of 75wt%~80wt% carbon pipes.
The quartz tube reactor that internal diameter is 5mm is encased in after obtained 0.16g catalyst is well mixed with 6g quartz sands
In, the aerial volume fraction of ethylbenzene is 15.0%, and the mass space velocity of ethylbenzene is 10-18h-1, flow velocity 20mL/min, reaction
Temperature is 450 DEG C, and pressure is normal pressure, after question response is stable, through the gas phase color equipped with capillary chromatographic column and hydrogen flame detector
Spectrum detection.Under the reaction temperature, the yield of ethylbenzene is 20-45%, and the selectivity of styrene is 75-85%, by 25h fortune
OK, catalyst activity does not reduce.
Embodiment 7
By 1g aminoglucose hydrochlorides, 20g melamines and 0.7g nickel nitrate physical mixeds, by mixed uniformly solid
Powder is placed in crucible and calcined in inert atmosphere, and calcination procedure is to be incubated 0.5-1.5h at 550-650 DEG C, then in 800-1200
DEG C calcining 0.5-1.5h, after calcination procedure terminates, room temperature is cooled in inert atmosphere, you can obtain 20wt%~25wt%
Nickel nickel and the compound catalyst of 75wt%~80wt% carbon pipes.
The quartz tube reactor that internal diameter is 5mm is encased in after obtained 0.10g catalyst is well mixed with 6g quartz sands
In, the aerial volume fraction of ethylbenzene is 10.0%, and the mass space velocity of ethylbenzene is 7-10h-1, flow velocity 20mL/min, reaction
Temperature is 500 DEG C, and pressure is normal pressure, after question response is stable, through the gas phase color equipped with capillary chromatographic column and hydrogen flame detector
Spectrum detection.Under the reaction temperature, the yield of ethylbenzene is 30-45%, and the selectivity of styrene is 75-85%, by 50h fortune
OK, catalyst activity does not reduce.
Embodiment 8
By 1g aminoglucose hydrochlorides, 20g melamines and 0.7g cobalt nitrate physical mixeds, by mixed uniformly solid
Powder is placed in crucible and calcined in inert atmosphere, and calcination procedure is to be incubated 0.5-1.5h at 550-650 DEG C, then in 800-1200
DEG C calcining 0.5-1.5h, after calcination procedure terminates, room temperature is cooled in inert atmosphere, you can obtain 20wt%~25wt
Cobalt/cobalt oxide and the compound catalyst of 75wt%~80wt% carbon pipes.
The quartz tube reactor that internal diameter is 5mm is encased in after obtained 0.10g catalyst is well mixed with 6g quartz sands
In, the aerial volume fraction of ethylbenzene is 10.0%-20.0%, and the mass space velocity of ethylbenzene is 10-18h-1, flow velocity 20mL/
Min, reaction temperature are 450 DEG C, and pressure is normal pressure, after question response is stable, through equipped with capillary chromatographic column and hydrogen flame detector
Gas chromatographic detection.Under the reaction temperature, the yield of ethylbenzene is 15-25%, and the selectivity of styrene is 75-85%, warp
25h operation is crossed, catalyst activity does not reduce.
Embodiment 9
By 1g aminoglucose hydrochlorides, 20g melamines and 0.7g ferric nitrate physical mixeds, by mixed uniformly solid
Powder is placed in crucible and calcined in inert atmosphere, and calcination procedure is to be incubated 0.5-1.5h at 550-650 DEG C, then in 800-1200
DEG C calcining 0.5-1.5h, after calcination procedure terminates, room temperature is cooled in inert atmosphere, you can obtain 20wt%~25wt%
Iron/iron oxide and the compound catalyst of 75wt%~80wt% carbon pipes.
The quartz tube reactor that internal diameter is 5mm is encased in after obtained 0.10g catalyst is well mixed with 6g quartz sands
In, the aerial volume fraction of ethylbenzene is 10.0%-25.0%, and the mass space velocity of ethylbenzene is 15-18h-1, flow velocity 20mL/
Min, reaction temperature are 450 DEG C, and pressure is normal pressure, after question response is stable, through equipped with capillary chromatographic column and hydrogen flame detector
Gas chromatographic detection.Under the reaction temperature, the yield of ethylbenzene is 10-25%, and the selectivity of styrene is 75-85%, warp
25h operation is crossed, catalyst activity does not reduce.
Embodiment 10
By 1g aminoglucose hydrochlorides, 20g melamines and 0.7g nickel nitrate physical mixeds, by mixed uniformly solid
Powder is placed in crucible and calcined in inert atmosphere, and calcination procedure is to be incubated 0.5-1.5h at 550-650 DEG C, then in 800-1200
DEG C calcining 0.5-1.5h, after calcination procedure terminates, room temperature is cooled in inert atmosphere, you can obtain 20wt%~25wt%
Nickel nickel and the compound catalyst of 75wt%~80wt% carbon pipes.
The quartz tube reactor that internal diameter is 5mm is encased in after obtained 0.10g catalyst is well mixed with 6g quartz sands
In, the aerial volume fraction of normal butane is 5%, and the mass space velocity of normal butane is 1.5h-1, flow velocity 15mL/min, reaction
Temperature is 400 DEG C, and pressure is normal pressure, after question response is stable, through the gas phase color equipped with capillary chromatographic column and hydrogen flame detector
Spectrum detection.Under the reaction temperature, the yield of n-butene is 20%, and the selectivity of n-butene is 55%, by 50h operation,
Catalyst activity does not reduce.
Embodiment 11
By 1g aminoglucose hydrochlorides, 20g melamines and 0.7g nickel nitrate physical mixeds, by mixed uniformly solid
Powder is placed in crucible and calcined in inert atmosphere, and calcination procedure is to be incubated 0.5-1.5h at 550-650 DEG C, then in 800-1200
DEG C calcining 0.5-1.5h, after calcination procedure terminates, room temperature is cooled in inert atmosphere, you can obtain 20wt%~25wt%
Nickel nickel and the compound catalyst of 75wt%~80wt% carbon pipes.
The quartz tube reactor that internal diameter is 5mm is encased in after obtained 0.10g catalyst is well mixed with 6g quartz sands
In, the aerial volume fraction of n-propane is 10%, and the mass space velocity of n-propane is 2h-1, flow velocity 20mL/min, reaction temperature
Spend for 400 DEG C, pressure is normal pressure, after question response is stable, through the gas-chromatography equipped with capillary chromatographic column and hydrogen flame detector
Detection.Under the reaction temperature, the yield of positive propylene is 10%, and the selectivity of positive propylene is 60%, by 50h operation, is urged
Agent activity does not reduce.
Embodiment 12
The quartzy tube reaction that internal diameter is 5mm is encased in after the 0.10g business carbon pipes bought are well mixed with 6g quartz sands
In device, the aerial volume fraction of n-propane is 5%-10%, and the mass space velocity of n-propane is 0.2-1.8h-1, flow velocity is
20mL/min, reaction temperature are 400 DEG C, and pressure is normal pressure, after question response is stable, through equipped with capillary chromatographic column and hydrogen flame inspection
Survey the gas chromatographic detection of device.Under the reaction temperature, the yield of positive propylene is 5%, and the selectivity of positive propylene is 20-40%,
By 50h operation, catalyst activity does not reduce.
Embodiment 13
By 1g aminoglucose hydrochlorides, 20g melamines and 0.7g nickel nitrate physical mixeds, by mixed uniformly solid
Powder is placed in crucible and calcined in inert atmosphere, and calcination procedure is to be incubated 0.5-1.5h at 550-650 DEG C, then in 800-1200
DEG C calcining 0.5-1.5h, after calcination procedure terminates, room temperature is cooled in inert atmosphere, through dust technology handle i.e. can obtain it is pure
The higher nickel nickel of degree and the compound catalyst of nitrogenous carbon pipe, wherein carbon pipe content are 93wt%~95wt%, nickel/oxidation
Nickel content is 5wt%~7wt%.
The quartz tube reactor that internal diameter is 5mm is encased in after obtained 0.10g catalyst is well mixed with 6g quartz sands
In, volume fraction of the ethylbenzene in argon gas is 1-5.0%, and the mass space velocity of ethylbenzene is 0.2-1.0h-1, flow velocity 10mL/min,
Reaction temperature is 550 DEG C, and pressure is normal pressure, after question response is stable, through the gas equipped with capillary chromatographic column and hydrogen flame detector
Phase chromatogram detects.Under the reaction temperature, the conversion ratio of ethylbenzene is 15%, and the selectivity of styrene is 97-98%, impurity content
Less than 0.5%, by 50h operation, catalyst activity does not reduce.
Claims (3)
- A kind of 1. method based on carbon pipe Yu the compound catalyst preparation alkenes compounds of transition metal, it is characterised in that will Ethylbenzene and argon gas mixing after preheating vaporization are passed through in reactor under catalyst action and carry out dehydrogenation reaction, and benzene is collected after condensation Ethene；The catalyst contains 20wt%~25wt% nickel nickel and the carbon nanometer of 75wt%~80wt% N doping Pipe, nitrogen content is 0.01wt%~20.0wt%；Described catalyst is prepared by following methods：(1) carbohydrate, template and nickel salt physical mixed, obtain solid precursor；(2) for solid precursor in an inert atmosphere through two-part calcination procedure, calcination procedure is to be incubated 0.5- at 550-650 DEG C 1.5h, 0.5-1.5h then is calcined at 800-1200 DEG C, prepares carbon pipe and the compound catalyst of nickel nickel；Volume fraction of the ethylbenzene in argon gas is 1.0%-5.0%, flow velocity 10mL/min, and the mass space velocity of ethylbenzene is 1.8h-1, reaction temperature is 550 DEG C, and pressure is normal pressure.
- A kind of 2. method based on carbon pipe Yu the compound catalyst preparation alkenes compounds of transition metal, it is characterised in that will Ethylbenzene and air mixing after preheating vaporization are passed through in reactor under catalyst action and carry out dehydrogenation reaction, and benzene is collected after condensation Ethene；The catalyst contains 20wt%~25wt% nickel nickel and the carbon nanometer of 75wt%~80wt% N doping Pipe, nitrogen content is 0.01wt%~20.0wt%；Described catalyst is prepared by following methods：(1) carbohydrate, template and nickel salt physical mixed, obtain solid precursor；(2) for solid precursor in an inert atmosphere through two-part calcination procedure, calcination procedure is to be incubated 0.5- at 550-650 DEG C 1.5h, then calcine 0.5-1.5h at 800-1200 DEG C；Prepare carbon pipe and the compound catalyst of nickel nickel；The aerial volume fraction of ethylbenzene is 10.0%, and the mass space velocity of ethylbenzene is 7-10h-1, flow velocity 20mL/min, Reaction temperature is 500 DEG C, and pressure is normal pressure.
- It is 3. according to claim 1 or 2 based on carbon pipe and the compound catalyst preparation alkenes compounds of transition metal Method, it is characterised in that catalyst is filled into reactor after being mixed with quartz sand, the mass ratio 1 of catalyst and quartz sand： 10-100。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510026459.3A CN104549293B (en) | 2015-01-20 | 2015-01-20 | A kind of method based on carbon pipe Yu the compound catalyst preparation alkenes compounds of transition metal |
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