JPS61234944A - Fine powder catalyst for treating heavy hydrocarbon - Google Patents
Fine powder catalyst for treating heavy hydrocarbonInfo
- Publication number
- JPS61234944A JPS61234944A JP60074366A JP7436685A JPS61234944A JP S61234944 A JPS61234944 A JP S61234944A JP 60074366 A JP60074366 A JP 60074366A JP 7436685 A JP7436685 A JP 7436685A JP S61234944 A JPS61234944 A JP S61234944A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- powder
- metal
- fine powder
- ultrafine powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 15
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 title abstract description 87
- 239000004215 Carbon black (E152) Substances 0.000 title abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 76
- 239000002245 particle Substances 0.000 abstract description 30
- 239000002904 solvent Substances 0.000 abstract description 16
- 229910052723 transition metal Inorganic materials 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 5
- 230000001376 precipitating effect Effects 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 230000016615 flocculation Effects 0.000 abstract 1
- 238000005189 flocculation Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 150000003568 thioethers Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 29
- -1 olefin compounds Chemical class 0.000 description 20
- 238000001556 precipitation Methods 0.000 description 20
- 239000011148 porous material Substances 0.000 description 14
- 229910052976 metal sulfide Inorganic materials 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 239000003921 oil Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- 150000002736 metal compounds Chemical class 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 150000003623 transition metal compounds Chemical class 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000002776 aggregation Effects 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 8
- 235000019241 carbon black Nutrition 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 6
- 239000000571 coke Substances 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000004438 BET method Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000000935 solvent evaporation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 241000208140 Acer Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- LCPUDZUWZDSKMX-UHFFFAOYSA-K azane;hydrogen sulfate;iron(3+);sulfate;dodecahydrate Chemical compound [NH4+].O.O.O.O.O.O.O.O.O.O.O.O.[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCPUDZUWZDSKMX-UHFFFAOYSA-K 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229920000140 heteropolymer Polymers 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000011802 pulverized particle Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、水素の存在下、重質炭化水素類を処理する際
に、ＭＩＩＪ！状態で使用するのに適“した新規な微粉
体触媒に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides MIIJ! The present invention relates to a novel fine powder catalyst suitable for use in a variety of conditions.
重質炭化水素類とは、石油原油、石油原油の常圧蒸留残
渣油および減圧蒸留残渣油のような残油、タール、ター
ルサンドオイル、けつ岩油、石炭液化油などが包含され
る。水素の存在下、】ｋ質炭化水素類を処理する反りと
は、Ｍ’Ｘ炭化水素類に含まれている硫黄化合物、望素
化合物およびバナジウムやニッケルなどの金属を含む１
ヒ合物を低下ま次は除去するための水素化反応、アスフ
ァルテン、コークス先駆物質である残留炭素を低下また
は除去するための水素比反応、芳香に化合物の核水添反
応、オレフィン化合物の水添反応、重質・成分を軽質ｆ
ヒさせる水素化分解反応などが包含される。Heavy hydrocarbons include petroleum crude oil, residual oil such as atmospheric distillation residue oil and vacuum distillation residue oil of petroleum crude oil, tar, tar sand oil, rock oil, coal liquefied oil, and the like. In the presence of hydrogen, the warping that treats K-type hydrocarbons refers to 1 containing sulfur compounds, desired compounds, and metals such as vanadium and nickel contained in M'X hydrocarbons.
Hydrogenation reaction to reduce or remove asphaltene, hydrogen ratio reaction to reduce or remove residual carbon that is a coke precursor, nuclear hydrogenation reaction of aromatic compounds, hydrogenation of olefin compounds Reaction, converting heavy components to light f
This includes hydrogenolysis reactions that cause heat.
（従来の技術）
これらの反応は、それぞれの目的や原料炭化水素類の種
類によシ反応条件が異なるが、反応温度としては、概ね
３５０Ｃ以上の高温反応をであシ、単独の反応として起
こることは少なく、複合的に起こることが多い。(Prior art) The reaction conditions for these reactions differ depending on the purpose and type of raw material hydrocarbons, but the reaction temperature generally requires high temperature reactions of 350C or higher and occurs as a single reaction. This is rare and often occurs in combination.
水素が関与するこれらの反応において、活性金属成分を
触媒として有効利用するためＫは、金属成分の表面積を
増大し、粒径を小さくすることによって、同じ重量当シ
のトータルな活性増大と単位表面積の活性、すなわち、
比活性とを高くする必要かある。このための方法として
、２０〜１００ｍμの超微粒な金属単体を作シ、触媒と
して使用する試みも行なわれているが、超微粒金属ゆえ
の特性でもある易焼結性によって、約２００Ｃ以上の反
応温度条件では、超微粒金属であることによる触媒活性
を期待することができなくなる。In these reactions involving hydrogen, in order to effectively use the active metal component as a catalyst, K increases the surface area of the metal component and reduces the particle size, thereby increasing the total activity and increasing the unit surface area for the same weight. activity, i.e.
Is it necessary to increase the specific activity? As a method for this purpose, attempts have been made to use ultrafine metal particles of 20 to 100 mμ in size as catalysts, but due to the easy sinterability, which is a characteristic of ultrafine metals, reactions over about 200C are not possible. Under temperature conditions, catalytic activity due to the ultrafine metal cannot be expected.
この金属微粒子同士の融着を防ぐために、従来からの多
くの固体触媒製造方法におりては、担体を使用して、金
属粒子を担体上に保持することによって、分散状態の金
属粒子を熱的に安定化することが行なわれているわけで
ある。この際、一般に使用されている担体は、バルクな
無機質物質群、すなわち、粒子径に基づく外表面積がわ
ずか数ｄ／１程度であるが、いわゆる細孔構造を持つこ
とにょシ、数ば／１〜１０００ゴ／１の高表面積を有す
る、いわゆる多孔質物質群である。したがって、触媒活
性金属成分を担体に担持、固定化させて高分散させる場
合も、触媒として使用して効果を期待する場合も、はと
んど細孔構造に由来する、いわゆる内表面に依存するこ
とになる。In order to prevent this fusion between fine metal particles, in many conventional solid catalyst production methods, a carrier is used to hold the metal particles on the carrier, and the dispersed metal particles are thermally heated. In other words, efforts are being made to stabilize the situation. In this case, the carriers commonly used are bulk inorganic substances, that is, the outer surface area based on the particle size is only about a few d/1, but they often have a so-called pore structure. They are a group of so-called porous substances that have a high surface area of ~1000/1. Therefore, whether a catalytically active metal component is supported and immobilized on a carrier to achieve high dispersion, or if it is used as a catalyst and expected to be effective, it depends mostly on the so-called inner surface derived from the pore structure. It turns out.
しかしながら、これらの場合、金属成分にしても、反応
物質にしても、拡散速度が問題になり、細孔の内部と表
面近傍とで濃度勾配ができ、不均一な状態になる。した
がって、有効係数が問題となり、細孔径、細孔分布、粉
砕粒子径分布などの物理構造が金属成分の分散度や触媒
の性能に常に影響してくる結果となる。しかも、重質炭
化水素類を原料に使用する場合、含有されているアスフ
ァルテン様物質、重金属を含むポルフィリン様物質、シ
よび生成してくることが避けられないコークスプレカー
サー、コークスなどの分子量が大きい物質類が、細孔内
部まで入シきれず表面近傍付近の細孔を閉塞させやすく
シ、実質的には、細孔に依存する内表面はわずかじか機
能せず、期待されるほどの効果が得られないことが多い
。このため、細孔径を大きくする試みもなされているが
、細孔径を大きくすると、触媒活性、金属を分散させる
担体表面積そのものが低下するため、やはり期待される
ほどの効果が得られない結果となる。However, in these cases, the diffusion rate of both the metal component and the reactant becomes a problem, and a concentration gradient is created between the inside of the pore and the vicinity of the surface, resulting in a non-uniform state. Therefore, the effective coefficient becomes a problem, and the physical structure such as pore diameter, pore distribution, and pulverized particle size distribution always influences the degree of dispersion of metal components and the performance of the catalyst. Furthermore, when heavy hydrocarbons are used as raw materials, they contain asphaltene-like substances, porphyrin-like substances containing heavy metals, coke precursors that inevitably form, and substances with large molecular weights such as coke. The particles cannot penetrate into the pores and tend to block the pores near the surface, and in reality, the inner surface, which depends on the pores, barely functions and is not as effective as expected. often not obtained. For this reason, attempts have been made to increase the pore size, but as the pore size increases, the catalytic activity and the surface area of the carrier for dispersing the metal decrease, so the expected effect is not obtained. .
（発明が解決しようとする問題点）
これらバルクな担体の持つ問題点を克服して担体に担持
した分散金属を有効に働かせるためには、担体そのもの
を微粒にして、それによって粒子径に依存する表面積、
いわゆる外表面積を大きくし、これに金属成分を高分散
させればよいと考えられる。すなわち、粒径が小さくな
ればなるほど粒径に依存する外表面積は大きくなり、超
微粉体と呼ばれる数〜数百ｍμの粒径のものになると、
バルクな多孔性担体の全比表面積に匹敵するほどの外表
面積が得られるようになシ、担体として好ましめ。(Problems to be Solved by the Invention) In order to overcome these problems with bulk carriers and make the dispersed metal supported on the carrier work effectively, the carrier itself must be made into fine particles, which will depend on the particle size. Surface area,
It is thought that it is sufficient to increase the so-called outer surface area and highly disperse the metal component therein. In other words, the smaller the particle size, the larger the outer surface area that depends on the particle size, and when it comes to particles with a particle size of several to several hundred microns, which is called ultrafine powder,
It is preferred as a carrier because it provides an external surface area comparable to the total specific surface area of a bulk porous carrier.
しかしながら、一方で、超微粉体に通常の固体触媒調装
法、すなわち、担持、焼成、活性化の各処理工程を適用
すると、高温で処理する焼成、活性化の段階で、微粉体
そのものが微粒であることや、微粉体表面およびその近
傍に存在する金属化合物のバインダー的な作用によって
、微粉体同士の凝集や癒着が起こシやすぐなり、また、
金属成分同士も、微粉体表面およびその近傍に存在する
ため、融着しあう傾向になり、バルクな多孔性物質群を
担体として使用する場合と変らないか、むしろ低い触媒
金属活性になってしまう。However, on the other hand, when applying the usual solid catalyst preparation method to ultrafine powder, that is, the processing steps of supporting, calcination, and activation, the fine powder itself is Due to the fineness of the particles and the binder-like action of the metal compounds present on and near the surface of the fine powders, agglomeration and adhesion of the fine powders may occur.
Since the metal components exist on and near the surface of the fine powder, they tend to fuse together, resulting in the same or even lower catalytic metal activity than when bulk porous materials are used as a carrier. .
（問題点を解決するための手段）
本発明者らは、これらの欠点を克服し、重責炭化水素類
を水素の存在下で処理する高温反応型の懸濁状態で使用
するのに適した粉体触媒について鋭意研究を重ねた結果
、遷移金属硫化物は、高温反応条件で使用する触媒組成
として優れていること、および比較的穏やかな温度条件
で容易に形成されることによシ、超微粉体との共存下で
遷移金属化合物を硫化処理したものは、分散金属硫化物
の状態で超微粉体の表面およびその近傍に存在し易く、
シかも、高温での固定化処理や活性化処理を施すことな
く、そのまま触媒として使用できるため、微粉体同士の
凝集や癒着を起こしにくく、高分散金属担持超微粉体と
しての特徴を充分に発揮することを見い出し、本発明を
完成するに至った。(Means for Solving the Problems) The present inventors have overcome these drawbacks and have developed a powder suitable for use in a suspension state in a high temperature reaction type in which heavy hydrocarbons are treated in the presence of hydrogen. As a result of extensive research into catalysts, we have found that transition metal sulfides are excellent as catalyst compositions for use in high-temperature reaction conditions, and that they are easily formed under relatively mild temperature conditions. Transition metal compounds that are sulfurized in coexistence with powder tend to exist on the surface of ultrafine powder and in its vicinity in the form of dispersed metal sulfides.
However, since it can be used as a catalyst as it is without immobilization treatment or activation treatment at high temperatures, it is difficult to cause aggregation or adhesion between fine powders, and the characteristics of a highly dispersed metal-supported ultrafine powder are fully realized. The present inventors have discovered that the present invention is effective and have completed the present invention.
すなわち、本発明は、平均粒子径５００ｍμ以下の超微
粉体の存在下に、少なぐとも１株類の遷移金属化合物を
硫化処理することによって得られる、水素の存在下＠濁
状態で使用する重質炭化水素処理用触媒に関するもので
ある。That is, the present invention is obtained by sulfurizing at least one type of transition metal compound in the presence of ultrafine powder with an average particle diameter of 500 mμ or less, and is used in the presence of hydrogen @ in a turbid state. This invention relates to a catalyst for treating heavy hydrocarbons.
本発明における担体としての役割を果たす微粉体は５０
０ｍμ以下、好ましくは１００ｍμ以下の平均粒径を持
つ、いわゆる超微粉体と呼ばれるもので、粒径が小さく
なればなるほど、触媒金楓成分を担持する有効な外表面
積が大きくなるので好ましくなる。加えて、これら微粉
体は、懸濁状態で使用する場合、反応帯域において高す
分散性と大きい自由運動が確保でき、局在しない均一な
反応の場を与えることができること、さらに１反応帯域
に滞溜することが少なく、付着、堆積した重縮合物、例
えば、アスファルテン、コークスプレカーサー、コーク
ス等を高分散、浮遊させた状態で容易に反応帯域外に排
出し、反応帯域での閉塞現象を起こさせないことなどか
らも優れた効果を示す。The fine powder that serves as a carrier in the present invention is 50%
It is a so-called ultrafine powder having an average particle size of 0 mμ or less, preferably 100 mμ or less, and the smaller the particle size, the larger the effective outer surface area for supporting the catalyst gold maple component, so it is preferable. In addition, when these fine powders are used in a suspended state, they can ensure high dispersion and large free movement in the reaction zone, and can provide a uniform reaction field without localization. There is little stagnation, and attached and deposited polycondensates such as asphaltene, coke precursor, coke, etc. are easily discharged out of the reaction zone in a highly dispersed and suspended state, causing blockage in the reaction zone. It also shows excellent effects in that it does not cause any damage.
これら超微粉体を構造するプロセスとしては、粗粒子粉
体を微粉砕するブレーキングダウンプロセスと分子、イ
オン、原子からの核生成と成長とによって粒子を作るビ
ルドアッププロセスとがあるが、本発明の粒径範囲に適
合する微粉体を効率よく製造するためには、ビルドアッ
ププロセスの方が優れている。The processes for structuring these ultrafine powders include the breaking down process, in which coarse powder is pulverized, and the build-up process, in which particles are created by nucleation and growth from molecules, ions, and atoms. The build-up process is better for efficiently producing fine powders that fit the particle size range of the invention.
適用範囲の平均粒径を有する超微粉体としては、組成的
には大きく分けて、無機質物質と炭素質物質とがある。Ultrafine powder having an average particle size within the applicable range can be roughly divided into inorganic substances and carbonaceous substances in terms of composition.
無機質物質である超微粉体の製造法としては、液相法と
気相法があシ、液相法では、共沈法、均−沈殿法、アル
コキシド化合物からの加水分解法などによる沈殿法や凍
結乾燥法、噴霧乾燥法、噴霧熱分解法などによる溶媒蒸
発法によって、超微粉体が製造でき、大部分は酸化物も
しくは複合酸化物である。また、気相法では、蒸発、凝
縮法、気相化学反応や化学的蒸着法による気相合成法、
気相酸化法、気相熱分解法や気相還元法による気相分解
法によって超微粉体が製造でき、酸化物、複合酸化物や
、炭化物、窒化物、ケイ化物などの非酸化物系が生成で
きる。これら無機質の超微粉ｌｅｔ、 最近、ニューセ
ラミックスやファインセラミックスと呼ばれている材料
における原料微粉末の製造方法が全て適用できるが、こ
れらにおいて要求される高純度性は、本発明において必
要としない。実用的見地からすれば、無機質超微粉体と
しては、シリカ、アルミナ、シリカ−アルζす、チタニ
アを主成分とする平均粒径５００ｍμ以下の酸化物系が
好ましい。There are two methods for producing ultrafine powder, which is an inorganic substance, the liquid phase method and the gas phase method.The liquid phase method includes precipitation methods such as coprecipitation method, homogeneous precipitation method, and hydrolysis method from an alkoxide compound. Ultrafine powders can be produced by solvent evaporation methods such as freeze drying, spray drying, and spray pyrolysis, and most of them are oxides or composite oxides. In addition, gas phase methods include evaporation, condensation methods, gas phase synthesis methods using gas phase chemical reactions and chemical vapor deposition methods,
Ultrafine powders can be produced by vapor phase decomposition methods such as vapor phase oxidation, vapor phase pyrolysis, and vapor phase reduction, and can be used to produce oxides, composite oxides, and non-oxides such as carbides, nitrides, and silicides. can be generated. All methods for producing raw material fine powders for these inorganic ultrafine powders and materials recently called new ceramics and fine ceramics can be applied, but the high purity required in these methods is not required in the present invention. From a practical standpoint, the inorganic ultrafine powder is preferably an oxide system containing silica, alumina, silica-aluminum, or titania as main components and having an average particle size of 500 mμ or less.
一方、炭素質の超微粉体としては、炭化水素類の炭素化
により得られる物質群のうち、気相炭素化によシ形成さ
れる物質群、具体的には、カーボンブラックや熱分解炭
素が含まれる。カーボンブラックは、製造法によシ、オ
イルファーネスブラック、ガスファーネスブラック、チ
ャンネルブラック、サーマルブラックなどく分類され、
非常に多くの樵類のものが、工業的規模で生産されてい
る安価な超微粉体である。また、はとんど全ての徨類の
カーボンブラックの平均粒径は１０〜５００ｍμの範囲
、さらには、１０〜１００ｍμの範囲にあシ、本発明に
おいて使用する超微粉体として特に好ましい。On the other hand, carbonaceous ultrafine powder includes a group of substances formed by gas-phase carbonization among the group of substances obtained by carbonizing hydrocarbons, specifically carbon black and pyrolytic carbon. is included. Carbon black is classified into oil furnace black, gas furnace black, channel black, thermal black, etc. depending on the manufacturing method.
A large number of millstones are inexpensive ultrafine powders that are produced on an industrial scale. In addition, the average particle size of almost all of the carbon blacks is in the range of 10 to 500 mμ, more preferably in the range of 10 to 100 mμ, which is particularly preferable as the ultrafine powder used in the present invention.
加えて、カーボンブラックは酸化反応を施すことにより
、表面粗度、すなわち、粒径依存の外部表面積に対する
全表面積の比を自由に増大させることができるので好ま
しい。カーボンブラック特にファーネス法カーボンブラ
ックは、一般に知られているバルクな多孔性物質に対し
ては、非多孔性物質と位置付けられるものであるが、ミ
クロに見ると、非晶質部分と微品質部分とから構成され
る非常に複雑な構造を有している微粉体である。In addition, carbon black is preferred because the surface roughness, ie, the ratio of the total surface area to the external surface area, which is dependent on the particle size, can be freely increased by subjecting it to an oxidation reaction. Carbon black, especially furnace-processed carbon black, is positioned as a non-porous material compared to the generally known bulk porous materials, but when viewed microscopically, it has an amorphous part and a fine quality part. It is a fine powder with a very complex structure composed of.
酸化を受けることにより、非晶質成分と微品質成分のい
ずれもがさまざまに酸化反応を起こし、通常の細孔の概
念に含まれな＾ミクロ孔などが多数形成されることによ
って、すなわち、表面粗度が増すことによって、表面積
の増大が起こると考えラレる。また、酸化反応により、
カルボキシル基、フェノール性水酸基、エーテル基など
の官能基の導入がもたらされるので、分散さすべき金属
成分と相互作用することも期待できる。By undergoing oxidation, both the amorphous component and the fine quality component undergo various oxidation reactions, and a large number of micropores, etc., which are not included in the normal concept of pores, are formed, in other words, the surface It is thought that an increase in surface area occurs due to an increase in roughness. In addition, due to oxidation reaction,
Since functional groups such as carboxyl groups, phenolic hydroxyl groups, and ether groups are introduced, they can be expected to interact with the metal components to be dispersed.
酸化の方法は、公知の数多くの方法が適用でき、大きく
は、気相における酸化と液相における酸化との二つに分
けられる。すなわち、気相酸化方法は、空気などの分子
状酸素、原子状酸素、オゾン、窒素酸化物、ハロゲンガ
スなどの気相酸化剤を１種または２種以上用いて行なう
方法であり、一方、液相酸化方法は、硝酸、過マンガン
酸カリ、塩素酸、次亜塩素酸ソーダなどの薬剤を１種ま
たは２種以上用いて行なう方法や、酸、アルカリ、塩類
などの各種電解質を用すて、行なう電解酸化の方法があ
る。酸化反応の程度は、実用的見地からして、質量の減
少と、表面積の増大や官能基導入の程度とのバランスを
考えて、適度な条件が選択されるべきであるが、いずれ
にしても、カーボンブラックおよびカーボンブラックを
酸化処理したものの全てが本発明の超微粉体として包含
できる。Many known methods can be applied to the oxidation method, and it can be roughly divided into two types: oxidation in the gas phase and oxidation in the liquid phase. In other words, the gas phase oxidation method is a method that uses one or more gas phase oxidants such as molecular oxygen such as air, atomic oxygen, ozone, nitrogen oxides, and halogen gas; Phase oxidation methods include methods using one or more chemicals such as nitric acid, potassium permanganate, chloric acid, and sodium hypochlorite, and methods using various electrolytes such as acids, alkalis, and salts. There is an electrolytic oxidation method. From a practical standpoint, appropriate conditions should be selected for the degree of oxidation reaction, taking into consideration the balance between mass reduction, surface area increase, and degree of functional group introduction. , carbon black, and oxidized carbon black can all be included as the ultrafine powder of the present invention.
本発明において、これら超微粉体に担持するのに使用す
る金属化合物原料は、硫化物の組成で高温反応量触媒と
しての活性を持つことが知られている遷移金属を少なく
とも１８以上含む化合物から選ぶことができる。すなわ
ち、銅、バナジウム、クロム、モリブデン、タングステ
ン、鉄、コバルト、ニッケルから選ばれる金属を１種以
上含む化合物を、単独または混合物として使用するのが
好ましい。In the present invention, the metal compound raw material used to support these ultrafine powders is selected from compounds containing at least 18 or more transition metals that are known to have sulfide composition and activity as a high-temperature reaction catalyst. You can choose. That is, it is preferable to use a compound containing one or more metals selected from copper, vanadium, chromium, molybdenum, tungsten, iron, cobalt, and nickel, either alone or as a mixture.
化合物組成としては、有機金属化合物、金属錯化合物、
無機金属塩々どから選ばれるものであればよく、具体的
には、アルキル基、アリル基、シクロペンタジェニル基
などを配位子として含む化合物、カルボニル化合物、水
素化物、アルコキシ化合物、アセチルアセトナト錯体な
どのジケト／化合物、有機カルボン酸化合物、有機スル
ホン酸または有機スルフィン酸化合物、有機ジアミン錯
体などのアミン化合物、フタロシアニン化合物、ニトリ
ルまたはイノニトリル化合物、ジチオカーバメート錯体
などのアミン化合物、ホスフィン化合物、ヘテロポリ酸
化合物、炭酸塩、カルボン酸塩、硫酸塩、硝酸塩、水酸
化物、゛ハロゲン化物などがある。Compound compositions include organometallic compounds, metal complex compounds,
It may be selected from inorganic metal salts, and specifically, compounds containing alkyl groups, allyl groups, cyclopentadienyl groups, etc. as ligands, carbonyl compounds, hydrides, alkoxy compounds, acetylacetate, etc. diketo/compounds such as nato complexes, organic carboxylic acid compounds, organic sulfonic acid or organic sulfinic acid compounds, amine compounds such as organic diamine complexes, amine compounds such as phthalocyanine compounds, nitrile or inonitrile compounds, dithiocarbamate complexes, phosphine compounds, heteropolymers. These include acid compounds, carbonates, carboxylates, sulfates, nitrates, hydroxides, and halides.
本発明の触媒活性の高い触媒の製造を行なう場合、超微
粉体の存在下に遷移金属化合物を硫化処理することが必
要である。具体的製造方法としては、遷移金属硫化物を
沈殿法により直接析出させて、超微粉体に担持させる方
法、および遷移金属化合物を含浸法により超微粉体に担
持するか、沈殿法により硫化物以外の化合物組成で析出
させて超微粉体に担持し、その後、硫化処理して、遷移
金属硫化物に変化させて担持させる方法とが代表的であ
る。When producing the catalyst of the present invention with high catalytic activity, it is necessary to sulfurize the transition metal compound in the presence of ultrafine powder. Specific manufacturing methods include directly precipitating transition metal sulfides using a precipitation method and supporting them on ultrafine powder, and supporting transition metal compounds on ultrafine powder using an impregnation method or sulfurization using a precipitation method. A typical method is to precipitate a compound composition other than a transition metal sulfide, support it on an ultrafine powder, and then sulfurize it to change it to a transition metal sulfide and support it.
これらの方法の大部分は、超微粉体を溶剤に懸濁させて
行なう必要があるが、その場合、遷移金属化合物を１種
以上溶解した溶液に懸濁しても、溶剤そのものに懸濁し
た後、遷移金属化合物を１種以上溶解した溶液を加えて
も、いずれでもよいが、要は微粉体を充分に浸漬し、分
散、混合することが必要であり、そのために公知の分散
剤などを使用してもさしつかえない。Most of these methods require suspending ultrafine powder in a solvent, but in that case, even if it is suspended in a solution containing one or more transition metal compounds, After that, a solution containing one or more transition metal compounds dissolved therein may be added, but the important thing is that the fine powder must be thoroughly immersed, dispersed, and mixed, and for this purpose, known dispersants may be used. It is safe to use.
使用する溶剤としては、水溶剤と有機溶剤とに区分でき
るが、超微粉体の凝集を緩和するためには、有機溶剤の
方が好ましい。具体的には、メタノール、エタノール、
グロパノール、フェノール、クレゾール、エチレングリ
コール、プロピレングリコールナトのアルコール類、ジ
エチルエーテル、ジオキサン、テトラヒドロフランなど
のエーテル類、アセトン、メチルエチルケトン、ペンタ
ノンなどのケトン類、ジクロロメタン、クロロホルム、
四塩化炭素、ジクロロエタンなどのハロゲン化炭素類、
ヘキサン、ヘプタン、ベンゼン、トルエン、キシレンな
どの炭化水素類、酢酸、プロピオン酸などの脂肪酸類、
酢酸メチル、酢酸エチルなどのエステル類６、アセトニ
トリル、トリエチルアミン、ブチルアミン、ピリジンな
どの窒素化合物系溶剤、二硫化炭素、チオフェン、ジメ
チルスルホキシドなどの硫黄化合物系溶剤などを用いる
ことができる。The solvent used can be classified into aqueous solvents and organic solvents, but organic solvents are preferred in order to alleviate agglomeration of the ultrafine powder. Specifically, methanol, ethanol,
Alcohols such as glopanol, phenol, cresol, ethylene glycol, and propylene glycol, ethers such as diethyl ether, dioxane, and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, and pentanone, dichloromethane, chloroform,
Halogenated carbons such as carbon tetrachloride and dichloroethane,
Hydrocarbons such as hexane, heptane, benzene, toluene, and xylene; fatty acids such as acetic acid and propionic acid;
Esters 6 such as methyl acetate and ethyl acetate, nitrogen compound solvents such as acetonitrile, triethylamine, butylamine, and pyridine, and sulfur compound solvents such as carbon disulfide, thiophene and dimethyl sulfoxide can be used.
これら有機溶剤は、使用する遷移金属化合物あるいは場
合によっては沈殿剤に対して溶解度の高り溶剤が選択さ
れ、しかも、沈殿法を行なう場合には、沈殿物として生
成させる遷移金属化合物の溶解性の低い溶剤が選択され
、また、製造する触媒に残存することを避けるため、蒸
気圧の高いもの、洲点の低いものが好ましい。These organic solvents are selected to have a high solubility for the transition metal compound to be used or, in some cases, for the precipitant.Moreover, when performing a precipitation method, the solubility of the transition metal compound to be formed as a precipitate is high. A solvent with a low vapor pressure is selected, and in order to avoid remaining in the catalyst to be produced, a solvent with a high vapor pressure and a low point are preferred.
遷移金属化合物を溶解し、超微粉体を分散混合した懸濁
溶液から遷移金属硫化物を直接析出させて、超微粉体に
沈殿担持させる方法は、適当な沈殿剤を加えて反応させ
る必要があり、硫化水素ガス、硫化ナトリウム、硫化ア
ンモニウム等の沈殿剤を使って直接沈殿担持させる方法
や、チオアセトアミド等を加水分解し沈殿剤を発生させ
て沈殿させる、いわゆる均−沈殿法などが採用できる。The method of directly precipitating a transition metal sulfide from a suspension solution in which a transition metal compound is dissolved and dispersing and mixing ultrafine powder and supporting the precipitate on the ultrafine powder requires the addition of an appropriate precipitant and reaction. There are two methods that can be used, such as direct precipitation support using a precipitant such as hydrogen sulfide gas, sodium sulfide, or ammonium sulfide, or the so-called homogeneous precipitation method in which thioacetamide, etc. is hydrolyzed to generate a precipitant and then precipitated. can.
沈殿反応が終了した後は、従来公知の濾過や遠心分離な
どによシ固液分離を行なめ、洗浄、乾燥することによっ
て、遷移金属硫化物を少なくとも１種以上担持した微粉
体を得る。これら得られた微粉体は、そのまま懸濁触媒
として使用できる。After the precipitation reaction is completed, solid-liquid separation is performed by conventionally known filtration, centrifugation, etc., followed by washing and drying to obtain a fine powder supporting at least one transition metal sulfide. The obtained fine powder can be used as it is as a suspended catalyst.
この硫化物沈殿担持法による触媒製造法は、遷移金属硫
化物が沈殿析出した段階では、遷移金属硫化物が結晶質
状態であるか、非晶質状態であるかに関係なく、単位粒
子としては、数百λ〜数λのオーダーの非常に細かい粒
子が析出する方法である沈殿法を、超微粉体の存在下で
行なうため、析出した細かい遷移金属硫化物の粒子がそ
のｉまの状態で、超微粉体の表面やその近傍に捕捉され
ることや、沈殿担持処理後、高温での焼成処理や活性化
処理を施すことなく、そのまま触媒として使用できるた
め、超微粉体同士の凝集や癒着を起こしにくｂことなど
により、高分散金属担持微粉体としての触媒の特徴を充
分に発揮できる好ましい触媒製造法である。In this catalyst production method using the sulfide precipitation support method, at the stage where the transition metal sulfide is precipitated, it does not matter whether the transition metal sulfide is in a crystalline state or an amorphous state, as a unit particle. Since the precipitation method, which is a method in which very fine particles on the order of several hundred λ to several λ are precipitated, is carried out in the presence of ultrafine powder, the precipitated fine transition metal sulfide particles are in their original state. This prevents the particles from being trapped on the surface of the ultrafine powder or its vicinity, and can be used as a catalyst without requiring high-temperature firing or activation after precipitate support treatment. This is a preferable catalyst production method that can fully exhibit the characteristics of the catalyst as a highly dispersed metal-supported fine powder by not causing agglomeration or adhesion.
一方、もう一つの代表的触媒表造方法である含浸法や、
沈殿法によシ超微粉体に担持し、その後、硫化処理する
方法における担持法は、通常、公知のあらゆる方法が適
用できる。沈殿法の場合は、均−沈殿法、有機金属化合
物や金属錯体などの加水分解法、共沈法、還元剤を用い
ての還元状態金属成分の沈殿法、金属化合物分解析出法
をはじめ、金属イオンと沈殿剤イオンとのイオン種同士
の直接反応による一般の沈殿法が適用でき、沈殿析出し
てくる金属成分の化合物組成は、水酸化物、酸化ｇＩＪ
ｂ低級酸化物、ホウ化物、リン化物、還元金属などの単
種、混合種、複合檀である。On the other hand, the impregnation method, which is another typical catalyst surface preparation method,
In the method of supporting ultrafine powder by a precipitation method and then sulfiding treatment, any known method can generally be applied. Precipitation methods include homogeneous precipitation, hydrolysis of organometallic compounds and metal complexes, co-precipitation, precipitation of reduced metal components using reducing agents, and separation of metal compounds. A general precipitation method based on a direct reaction between metal ions and precipitant ions can be applied, and the compound composition of the precipitated metal components is hydroxide, oxidized gIJ
(b) Single, mixed, and composite materials such as lower oxides, borides, phosphides, and reduced metals.
また、含浸法の場合は、イオン交換法を含めての吸着法
、半乾燥担持法、溶媒蒸発法、噴霧法などが適用でき、
担持後の化合物組成は、原料の金属化合物組成のままか
、金属イオンや金属錯イオンであることが多い。ただし
、含浸法を行なう場合、溶剤を蒸発させて担持物を乾固
させることが多く、その際、微粉体が凝集、癒着しやす
くなるため、溶剤として、蒸気圧が高く、沸点の低い有
機溶剤を使用することが％に望ましい。In addition, in the case of impregnation methods, adsorption methods including ion exchange methods, semi-dry support methods, solvent evaporation methods, spray methods, etc. can be applied.
The compound composition after being supported is often the same as the raw metal compound composition, or is a metal ion or metal complex ion. However, when performing the impregnation method, the solvent is often evaporated to dry the supported material, and in this case, the fine powder tends to aggregate and adhere, so organic solvents with high vapor pressure and low boiling point are used as the solvent. It is preferable to use %.
沈殿法や含浸法によって得られる担持物は、焼成などの
固定化処理を施すことなく、硫化処理して触媒とするこ
とが要求される。硫化処理の方法としては、担持物を再
度新たな有機溶剤にＳ濁させて、チオフェンや二硫化炭
素との反応により硫化させる方法もあるが、担持物を硫
化水素を含む気体中で気固反応を行ない金属成分を硫化
させる方法が、微粉体同士や金属成分同士の凝集や癒着
をできる限シ回避する方法として望ましい。The supported material obtained by the precipitation method or the impregnation method is required to be sulfurized and made into a catalyst without being subjected to a fixing treatment such as calcination. As a method for sulfiding, there is a method in which the supported material is sulfurized again in a new organic solvent and then sulfurized by reaction with thiophene or carbon disulfide. A method of sulfurizing the metal components by performing this is desirable as a method of avoiding aggregation and adhesion of fine powders and metal components as much as possible.
・ 以上、超微粉体の存在下に遷移金属化合物を硫化処
理して触媒を得る方法すべてにおいて、操作温度は低い
ことが望ましく、３５００以下、好ましくは２５０Ｃ以
下でおる。このことは、微粉体同士の凝集や癒着を防ぐ
ためのみでなく、分散金属硫化物同士の融着を防ぐため
にも必要である。- In all of the above methods for obtaining a catalyst by sulfurizing a transition metal compound in the presence of ultrafine powder, the operating temperature is desirably low, 3500C or lower, preferably 250C or lower. This is necessary not only to prevent agglomeration and adhesion of fine powders, but also to prevent fusion of dispersed metal sulfides.
本発明において、分散金属硫化物の微粉体担体への担持
状態は、特に規定するものではなく、担体とのさまざま
な相互作用によ）固定化された状態にあろうが、担体と
の相互作用が非常に弱く反応の場に存在する場合、互い
Ｋａ離して挙動しょうが、触媒効果に本質的な差はない
。また、金属硫化物の組成や形態は、原料や西進条件に
よってさまざまであり得るが、本発明の適用範囲として
は、それらの全て、すなわち、金属／硫黄原子比に関し
て単種あるいＶｉ混合種である場合、２種以上の金属を
使用して、それらが複合硫化物組成を形成する場合、ま
た、場合によっては、金属、硫黄以外の他の元素を含め
ての複合化合物組成を形成する場合や、存在する混合種
の全てが硫化物を形成してｈない場合なども包含するも
のである。In the present invention, the state in which the dispersed metal sulfide is supported on the fine powder carrier is not particularly defined, and may be in an immobilized state (due to various interactions with the carrier); If they are very weak and exist in the reaction field, they will behave apart from each other in Ka, but there is no essential difference in the catalytic effect. Furthermore, although the composition and form of the metal sulfide may vary depending on the raw material and westward propagation conditions, the scope of application of the present invention covers all of them, that is, a single type or a mixed type of Vi with respect to the metal/sulfur atomic ratio. In some cases, two or more metals are used to form a composite sulfide composition, and in some cases, a composite compound composition including other elements other than metals and sulfur is formed. This also includes cases where all of the existing mixed species do not form sulfides.
金属硫化物の微粉体への担持量は、金属に換算して、微
粉体重量に基づき５０重量％以下の範囲にあるのが好ま
しい。下限は、本発明の触媒を使用する反応の目的によ
り異なシ、使用する微粉体量と金属硫化物の触媒活性が
充分に得られる量とで決まってくるものであり、触媒製
造の面からは。The amount of metal sulfide supported on the fine powder is preferably in the range of 50% by weight or less based on the weight of the fine powder in terms of metal. The lower limit varies depending on the purpose of the reaction using the catalyst of the present invention, and is determined by the amount of fine powder used and the amount at which sufficient catalytic activity of the metal sulfide can be obtained.From the viewpoint of catalyst production, .
いくら少なくてもかまわない。一方、５０重量慢を超え
る場合は、金属使用量の割には、金属の触媒活性の向上
が認められず、むしろ、触媒製造の段階で微粉体の凝集
や癒着が起こり、結果として、微粉体触媒を使用する特
徴が薄れてくるため望ましくない。It doesn't matter how little it is. On the other hand, if the weight exceeds 50%, no improvement in the catalytic activity of the metal is observed considering the amount of metal used, and rather agglomeration and adhesion of fine powder occur during the catalyst production stage, resulting in fine powder This is undesirable because the characteristics of using a catalyst are diminished.
具体的な金属の種類や組合せ、微粉体の檻類、金属の微
粉体への担持量および触媒としての使用量などは、触媒
の使用目的、処ｆＭ原料の種類、使用条件などに応じて
任意に選択することができる。The specific types and combinations of metals, cages for the fine powder, amount of metal supported on the fine powder, amount used as a catalyst, etc. are arbitrary depending on the purpose of use of the catalyst, the type of raw materials to be processed, the conditions of use, etc. can be selected.
（発明の効果）
後記実施例および比較例かられかるように、本発明に係
る触媒は、水素の存在下、重質炭化水素を処理する反応
において優れた触媒効果を示す。(Effects of the Invention) As can be seen from the Examples and Comparative Examples described below, the catalyst according to the present invention exhibits an excellent catalytic effect in the reaction of treating heavy hydrocarbons in the presence of hydrogen.
（実施例）
次に、実施例によって本発明をさらに詳細に説明するが
、本発明は、これらの実施例によシ限定されるものでは
ない。(Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
実施例１〜６
それぞれの実施例は、金属硫化物を沈殿法により直接析
出させて、超微粉体に担持させる方法により触媒を製造
した。それぞれの実施例で使用した溶剤、超微粉体の種
類と電子顕微鏡（ＪＭ、）Ｋよシ測定した平均粒径と、
ＢＩＴ法で測定した比表面積、および原料の金属化合物
、沈殿剤、沈殿反応によシ析出して超微粉体に担持され
る金属硫１ヒ物の担持量を表１に示す。Examples 1 to 6 In each of the Examples, catalysts were produced by directly depositing metal sulfides by a precipitation method and supporting them on ultrafine powder. The solvent used in each example, the type of ultrafine powder, the average particle size measured using an electron microscope (JM,) K,
Table 1 shows the specific surface area measured by the BIT method, the metal compound as the raw material, the precipitant, and the supported amount of the metal sulfur compound precipitated by the precipitation reaction and supported on the ultrafine powder.
それぞれの触媒製造の方法は、以下に記す方法によって
実施した。金属化合物を多量の溶剤に完全に溶解し、こ
の希薄溶液に、炭素質微粉体または無機質微粉体を充分
に分散させた。この懸濁溶液を充分に攪拌混合した状態
で、液体または固体の沈殿剤の場合は、溶剤に溶解した
溶液を徐々に滴下することによって、気体の沈殿剤の場
合は、懸濁溶液中に吹き込むことによって、金属硫化物
を沈殿させた。この場合、沈殿剤は金属硫化物が充分に
沈殿する量加え、沈殿反応の温度は室温（１５〜５０Ｃ
）で実施した。沈殿反応終了後、濾過を行ない、得られ
た固形物を、使用した溶剤さらにメタノールで充分洗浄
した。その後、１００〜１５０Ｃで減圧乾燥して、分散
金属硫化物担持微粉体触媒を得た。原料微粉体と製造後
の触媒との電子顕微＠！による平均粒子径比較を行なっ
た結果、有意な差は認められなかった。Each catalyst was produced by the method described below. The metal compound was completely dissolved in a large amount of solvent, and the carbonaceous fine powder or inorganic fine powder was sufficiently dispersed in this dilute solution. With this suspended solution thoroughly stirred and mixed, in the case of a liquid or solid precipitant, a solution dissolved in a solvent is gradually added dropwise, or in the case of a gaseous precipitant, it is blown into the suspended solution. This caused the metal sulfides to precipitate. In this case, the precipitant is added in an amount sufficient to precipitate the metal sulfide, and the temperature of the precipitation reaction is room temperature (15-50C).
) was carried out. After the precipitation reaction was completed, filtration was performed, and the obtained solid was thoroughly washed with the solvent used and methanol. Thereafter, it was dried under reduced pressure at 100 to 150 C to obtain a fine powder catalyst supported on a dispersed metal sulfide. Electron microscopy of raw material fine powder and manufactured catalyst @! As a result of comparing the average particle diameters, no significant difference was observed.
実施例７〜１０
それぞれの実施例は、金属化合物を含浸法により超微粉
体に担持し、その後、硫化処理する方法によシ触媒を製
造した。それぞれの実施例で使用した溶剤、超微粉体の
種類とＥ、Ｍ、法により測定した平均粒径とＢＥＴ法で
測定した比表面積、および原料の金属化合物、超微粉体
に担持される金属硫化物の担持量を表２に示す。Examples 7 to 10 In each of the examples, a catalyst was produced by a method in which a metal compound was supported on ultrafine powder by an impregnation method, and then a sulfurization treatment was performed. The solvent used in each example, the type of ultrafine powder, the average particle diameter measured by the E, M, method, the specific surface area measured by the BET method, the metal compound as a raw material, and the amount supported on the ultrafine powder. Table 2 shows the amount of metal sulfide supported.
それぞれの触媒人造の方法は、以下に記す方法によって
実施した。金属化合物を多量の溶剤に完全に溶解し、こ
の希薄溶液に、炭素質微粉体または無機質微粉体を充分
に分散させた。この懸濁溶液を充分に攪拌混合した後、
攪拌しながら溶剤を減圧下に蒸発させる蒸発乾固法によ
り、金属化合物を超微粉体に担持した。操作温度は１５
〜１００Ｃの範四で実施した。得られた金属化合物担持
微粉体は、ボールミルで凝集状態を緩和した後、ロータ
リーキルン方式の電気炉によｊ５．２０％Ｈ，Ｓ−８０
％ Ｎ、気流中、１５０〜２００Ｃ（２）＠度で硫化処
理して、分散金属硫化物担持微粉体触媒を得た。原料微
粉体と製造後の触媒との電子顕微鏡による平均粒子径比
較を行なった結果、有意な差は認められなかった。Each catalyst preparation method was carried out by the method described below. The metal compound was completely dissolved in a large amount of solvent, and the carbonaceous fine powder or inorganic fine powder was sufficiently dispersed in this dilute solution. After stirring and mixing this suspension solution thoroughly,
The metal compound was supported on the ultrafine powder by an evaporation to dryness method in which the solvent was evaporated under reduced pressure while stirring. The operating temperature is 15
It was carried out in the range 4 to 100C. The obtained metal compound-supported fine powder was heated in a ball mill to reduce the agglomeration state, and then heated in a rotary kiln type electric furnace with j5.20% H, S-80.
% N in an air stream at 150 to 200 C(2) degrees to obtain a fine powder catalyst supported on a dispersed metal sulfide. As a result of comparing the average particle diameters of the raw material fine powder and the manufactured catalyst using an electron microscope, no significant difference was observed.
実施例１１〜２０
実施例１〜１０で製造した分散金属硫化物担持微粉体の
水素存在下での重質炭化水素処理に対する触媒効果を見
るため、表３に示す性状を持った重質残渣油を原料油と
して用い、水素化分解反応を実施した。実験方法は、内
容積１００ｏ−の攪拌式オートクレーブに１原料油と触
媒１．５重量修（対原料油）とを仕込み、水素圧ｔｓ１
ｇ／ｍを封入し、回転数１００ Ｏｒｐｍで攪拌しなが
ら、温度４５０Ｃで１時間反応させた。反応時間は、実
際時間とし、上昇シよび冷却に要した時間の補償は加味
しなかった。反応後の生成油は、全量回収して分析に供
した。実施例１１〜２ｏで実施した結果をまとめて表４
に示す。Examples 11 to 20 In order to examine the catalytic effect of the dispersed metal sulfide-supported fine powder produced in Examples 1 to 10 on heavy hydrocarbon treatment in the presence of hydrogen, heavy residual oil having the properties shown in Table 3 was prepared. A hydrocracking reaction was carried out using this as a feedstock oil. The experimental method was to charge 1 feedstock oil and 1.5 weight of catalyst (based on feedstock oil) into a stirred autoclave with an internal volume of 100o-, and hydrogen pressure ts1.
g/m and reacted for 1 hour at a temperature of 450 C while stirring at a rotational speed of 100 Orpm. The reaction time was the actual time and did not take into account compensation for the time required for rising and cooling. The entire amount of the oil produced after the reaction was collected and subjected to analysis. Table 4 summarizes the results of Examples 11 to 2o.
Shown below.
表 ３
比較例１〜５
実施例１１〜２０と同様の実験方法によプ実施したが、
比較例１の場合は、触媒を使用しないで、比較例２の場
合は、ニッケル酸化物として４重量％、タングステン酸
化物として１５重重量上含む比表面積２２０ゴ／ｆ（Ｂ
ＥＴ法）の多孔性ｒ−アルミナ触媒を、約１０〜６０μ
の範囲に粉砕したものを１．５重量％加えて行なった。Table 3 Comparative Examples 1 to 5 The experiments were carried out using the same experimental method as Examples 11 to 20, but
In the case of Comparative Example 1, no catalyst was used, and in the case of Comparative Example 2, the specific surface area was 220 g/f (B
ET method) porous r-alumina catalyst with a thickness of about 10 to 60μ
The test was carried out by adding 1.5% by weight of the powder crushed within the range of .
比較例５の場合は、微粉シリカ〔平均粒子径１６ｍμ（
Ｅ、Ｍ。In the case of Comparative Example 5, fine powder silica [average particle diameter 16 mμ (
E,M.
法）、比表面積１５０ゴ／Ｖ（ＢＥＴ法）〕のみｆｔｔ
、ｓ重量％加えて行なった。比較例４の場合は、鉄ミョ
ウバンの水溶液に硫化水素を吹き込むことによって得た
硫化鉄を、鉄換算で１．５重量％加えて行なった。比較
例５の場合は、コバルトカルボニルをペンタン中で微粉
アルミナ〔平均粒子径２０ ｍｐ （ＥｏＭ、法）、比
表面積９０ゴ／ｐ（ＢＥＴ法）〕に溶媒蒸発法により含
浸漬、乾燥し、６００Ｃで焼成することによって得たＣ
ｏｏ ／ Ａ４０． （Ｃ。method), specific surface area 150g/V (BET method)] only ftt
, s weight % was added. In the case of Comparative Example 4, iron sulfide obtained by blowing hydrogen sulfide into an aqueous solution of iron alum was added in an amount of 1.5% by weight in terms of iron. In the case of Comparative Example 5, cobalt carbonyl was impregnated into fine powder alumina [average particle size 20 mp (EoM method), specific surface area 90 g/p (BET method)] in pentane by solvent evaporation method, dried at 600C. C obtained by firing with
oo/A40. (C.
含有量１０重量％）触媒をボールミルで粉砕後、１．５
重ｉ％加えて行なった。それぞれの実施結果を表５に示
す。Content: 10% by weight) After pulverizing the catalyst with a ball mill, 1.5
The experiment was carried out by adding i% by weight. Table 5 shows the results of each implementation.
実施例１１〜２０と比較例１〜５との結果から明らかな
ように１本発明による触媒が、水素の存在下重質炭化水
素を処理する反応にシいて、すぐれた触媒効果を示すこ
とが明らかである。As is clear from the results of Examples 11 to 20 and Comparative Examples 1 to 5, the catalyst according to the present invention exhibits an excellent catalytic effect in the reaction of treating heavy hydrocarbons in the presence of hydrogen. it is obvious.
表 ５
リ 金属／硫黄原子比は一義的に決まらず、また、混合
種であることが多いため、ＭｅＳｘで示した。Table 5 Since the metal/sulfur atomic ratio is not uniquely determined and is often a mixed species, it is expressed as MeSx.
２）アスファルテンは、ヘキサン不溶、テトラヒドロフ
ラン溶解として定義
３） コークスは、テトラヒドロフラン不溶分のうち、
仕込み触媒量を差し引いたものとして定義り 固形物の
壁面付着がある場合は、連続装置による反応においては
、反応器の閉塞が起こる可能性が高いことを示唆する。2) Asphaltene is defined as hexane-insoluble and tetrahydrofuran-soluble.3) Coke is defined as tetrahydrofuran-insoluble.
Defined as the amount minus the amount of catalyst charged. If solids adhere to the walls, it suggests that there is a high possibility that reactor clogging will occur in a continuous reaction.
Claims (1)
くとも１種類の銅、バナジウム、クロム、モリブデン、
タングステン、鉄、コバルト、ニッケルから選ばれる金
属の化合物を硫化処理することによつて得られる、水素
の存在下懸濁状態で使用する重質炭化水素処理用触媒。At least one type of copper, vanadium, chromium, molybdenum,
A catalyst for treating heavy hydrocarbons that is obtained by sulfurizing a compound of a metal selected from tungsten, iron, cobalt, and nickel and is used in a suspended state in the presence of hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60074366A JPS61234944A (en) | 1985-04-10 | 1985-04-10 | Fine powder catalyst for treating heavy hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60074366A JPS61234944A (en) | 1985-04-10 | 1985-04-10 | Fine powder catalyst for treating heavy hydrocarbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61234944A true JPS61234944A (en) | 1986-10-20 |
Family
ID=13545087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60074366A Pending JPS61234944A (en) | 1985-04-10 | 1985-04-10 | Fine powder catalyst for treating heavy hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61234944A (en) |
-
1985
- 1985-04-10 JP JP60074366A patent/JPS61234944A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5320741A (en) | Combination process for the pretreatment and hydroconversion of heavy residual oils | |
| US4424142A (en) | Catalyst for hydrotreatment of heavy hydrocarbon oils | |
| US4831003A (en) | Catalyst composition and process of making | |
| JPH11256430A (en) | Carbon fibril and catalytic vapor growth for producing the same carbon fibril | |
| JPH08176559A (en) | Method of hydroaromatizing hydrocarbon oil by using metal sulfide catalyst supported by new phosphorated carbon | |
| CN107442147B (en) | Iron carbide catalyst wrapped by high-iron-content graphite layer and synthesis method and application thereof | |
| US5051389A (en) | Catalyst composition prepared by vapor depositing onto a carbon support | |
| JP2014510615A5 (en) | ||
| US7014830B2 (en) | Method for mass-producing carbon nanocoils | |
| US4120780A (en) | Catalysts for hydrodemetallization of hydrocarbons containing metallic compounds as impurities and process for hydro-treating such hydrocarbons using such catalysts | |
| CN107511159B (en) | Preparation method and application of nickel-tungsten bimetallic carbide catalyst prepared by organic-inorganic hybrid route | |
| US4326991A (en) | Process for preparing a catalyst for hydrotreatment of heavy hydrocarbon oils | |
| CN114225932A (en) | Petroleum asphalt-based carbon-supported monatomic molybdenum catalyst and preparation method and application method thereof | |
| Cugini et al. | Development of a dispersed iron catalyst for first stage coal liquefication | |
| US4295995A (en) | Catalysts hydrocarbon treating processes | |
| CN110743595B (en) | Catalyst with carbon-nitrogen-coated cobalt-molybdenum alloy material as active ingredient and application thereof | |
| JPS61234944A (en) | Fine powder catalyst for treating heavy hydrocarbon | |
| KR100251294B1 (en) | Preparation of carbon microfiber by using transition metal particle supported on alkaline earth metal oxide | |
| US5951849A (en) | Resid hydroprocessing method utilizing a metal-impregnated, carbonaceous particle catalyst | |
| CN111922334B (en) | Microwave-based carbon-coated powder and preparation method thereof | |
| JPS61220741A (en) | Fine powdery catalyst for treating hydrocarbon | |
| CN1186152C (en) | Method for preparing carbon-coated metal nano crystal | |
| Ramos-Fernández et al. | Preparation of mesophase pitch doped with TiO2 or TiC particles | |
| AU9357798A (en) | Heat treated fischer-tropsch catalyst particles | |
| JPS60120791A (en) | Conversion of heavy hydrocarbon to light hydrocarbon |