CN101466654A - Hydrogenation of polynuclear aromatic compounds - Google Patents
Hydrogenation of polynuclear aromatic compounds Download PDFInfo
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- CN101466654A CN101466654A CN200780022240.XA CN200780022240A CN101466654A CN 101466654 A CN101466654 A CN 101466654A CN 200780022240 A CN200780022240 A CN 200780022240A CN 101466654 A CN101466654 A CN 101466654A
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- 150000001491 aromatic compounds Chemical class 0.000 title claims description 12
- 238000005984 hydrogenation reaction Methods 0.000 title description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000011593 sulfur Substances 0.000 claims abstract description 81
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 81
- 238000000034 method Methods 0.000 claims abstract description 77
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 67
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 66
- 239000000203 mixture Substances 0.000 claims abstract description 57
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 claims abstract description 53
- 239000002184 metal Substances 0.000 claims abstract description 53
- 230000008569 process Effects 0.000 claims abstract description 29
- 239000011787 zinc oxide Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims description 84
- 239000005864 Sulphur Substances 0.000 claims description 76
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- 239000002283 diesel fuel Substances 0.000 claims description 28
- 239000000446 fuel Substances 0.000 claims description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 239000011701 zinc Substances 0.000 claims description 21
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- 230000002779 inactivation Effects 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 239000010451 perlite Substances 0.000 claims description 12
- 235000019362 perlite Nutrition 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 230000005484 gravity Effects 0.000 claims description 8
- 239000005083 Zinc sulfide Substances 0.000 claims description 7
- 150000004645 aluminates Chemical class 0.000 claims description 7
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- 239000002594 sorbent Substances 0.000 claims description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 4
- 230000009183 running Effects 0.000 claims description 4
- 229940095064 tartrate Drugs 0.000 claims description 4
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-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
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000005243 fluidization Methods 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 7
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 43
- 150000001875 compounds Chemical class 0.000 description 20
- 238000001035 drying Methods 0.000 description 19
- 239000002253 acid Substances 0.000 description 16
- 239000002585 base Substances 0.000 description 15
- 238000010306 acid treatment Methods 0.000 description 14
- 238000001354 calcination Methods 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 11
- SHFGJEQAOUMGJM-UHFFFAOYSA-N dialuminum dipotassium disodium dioxosilane iron(3+) oxocalcium oxomagnesium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Na+].[Na+].[Al+3].[Al+3].[K+].[K+].[Fe+3].[Fe+3].O=[Mg].O=[Ca].O=[Si]=O SHFGJEQAOUMGJM-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000006477 desulfuration reaction Methods 0.000 description 9
- 230000023556 desulfurization Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 150000003752 zinc compounds Chemical class 0.000 description 7
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000006104 solid solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- -1 aromatic hydroxy compound Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 238000010606 normalization Methods 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000006187 pill Substances 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005547 polycyclic aromatic hydrocarbon Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CCEKAJIANROZEO-UHFFFAOYSA-N sulfluramid Chemical group CCNS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CCEKAJIANROZEO-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 229940043825 zinc carbonate Drugs 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/52—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing platinum group metals or compounds thereof
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
A process for reducing the polynuclear aromatics (PNA) content of a sulfur-containing hydrocarbon stream. The process includes contacting the sulfur-containing hydrocarbon stream with a dearomatization composition comprising a promoter metal component and zinc oxide. The dearomatization composition has enhanced resistance to sulfur poisoning and is also effective to remove sulfur from the hydrocarbon stream.
Description
Background
Relate generally to of the present invention carries out hydrogenation to the multi-nucleus aromatic compound in low-sulfur flow containing hydrocarbons such as the diesel oil fuel (PNA).On the other hand, the present invention relates to be suitable for use in the composition that increases the cetane value of this fuel in desulfurization of diesel fuel and the dearomatization (dearomatization) simultaneously.
Diesel oil fuel itself comprises a certain amount of aromatic hydroxy compound (hydrocarbon compound that promptly contains one or more " benzene class " ring structure).Commercial diesel fuel makes by mixing " straight run " diesel oil (making by simple distillation crude oil) and catalytic cracking material (being generally through the cracked Residual oil) usually.A lot of aromatic contents in the Medium diesel oil fuel come from the cracking material, because catalytic cracking has increased aromatic content.
The spontaneous ignition character of aromatic hydrocarbons is poor, and the diesel oil fuel that consequently contains a large amount of aromatic substance often has low cetane value.The typical cetane value of straight-run diesel oil is 50-55, and the cetane value of the Medium diesel oil fuel of high aromatic substance is generally 40-45.These low cetane value can cause engine cold starting more difficult, and can increase combustion noise.The ignition delay that low-cetane diesel oil fuel met with can also cause hydrocarbon to disengage thing to be increased and NO
xDisengaging thing increases.
Multi-nucleus aromatic compound (PNA) is also referred to as polycyclic aromatic hydrocarbon (PAH), is that a class does not wish that especially it is present in the aromatic substance in the diesel oil fuel.PNA is the aromatic substance that has more than an aromatic ring.Some tests have shown that some PNA compound can influence animal health unfriendly.Therefore, expectation disengages thing to the PNA of motor vehicle and limits, and is special in the city densely populated, that traffic is heavy.Scientist has found that there are linear relationship in fuel PNA input and PNA between disengaging.Therefore, be purchased fuel PNA content in the diesel oil fuel by reduction, the PNA that is discharged in the environment will reduce.
There are many be used to the reduce total aromatic substance of diesel oil fuel and the commercial technologies of PNA content.The catalyzer that most popular dearomatization method is included in periodic table of elements group VIII exists down the aromatic substance hydrogenation.But conventional group VIII catalyzer is very easy to be poisoned by the sulphur of the sulfocompound in the diesel oil fuel, even the diesel oil of process Hydrodearomatization is that sulphur content is lower than the low-sulfur diesel-oil of per by weight 30/1000000ths (ppmw).
Goal of the invention and content
Therefore, the purpose of this invention is to provide improving one's methods of multi-nucleus aromatic compound (PNA) content that is used to reduce flow containing hydrocarbons, wherein use the catalyzer that sulphur is had height endurability.
Therefore, one aspect of the present invention relates to and is used for removing the method that sulphur content is lower than the multi-nucleus aromatic compound of the low-sulfur flow containing hydrocarbons of making an appointment with per by weight 500/1000000ths (ppmw).This method is included in to be enough to make under the dearomatization condition of PNA content reduction at least about 25 weight % of low-sulfur materials flow, described low-sulfur materials flow is contacted with the theadearomatizationacompriseson that contains promoter metal component and zinc oxide, obtain the materials flow that PNA reduces thus, the sulphur content of the materials flow that wherein said PNA reduces is lower at least about 5 weight % than the sulphur content of described low-sulfur materials flow.
Another aspect of the present invention relates to and is used to handle sulphur content and is at least the method that about 500ppmw and PNA content are at least the initial flow containing hydrocarbons of about 5 weight %, this method comprises: (a) be enough to make under the desulfurization condition of sulphur content reduction at least about 25 weight % of described initial materials flow, described initial materials flow is contacted in first district with catalyzer and/or adsorbent composition, obtain sulphur content thus and be lower than the materials flow that sulphur that about 500ppmw and PNA content is at least about 5 weight % reduces; And (b) sulphur of near small part reduces materials flow and contacts in second district with the theadearomatizationacompriseson of zinc oxide with nickeliferous, obtains its PNA content thus and hangs down materials flow at least about the PNA minimizing of 25 weight % than the PNA content of described sulphur minimizing materials flow.
The accompanying drawing summary
Fig. 1 has drawn the function of the PNA hydrogenation activity of three kinds of different compositions as the amount of the sulphur on the catalyst bed.
Fig. 2 has drawn the funtcional relationship of the amount of the amount of contained sulphur in the incoming flow and the sulphur on the catalyst bed, thereby relatively two kinds of different compositions are to the tolerance of inactivation.
Detailed description of the preferred embodiments
A kind of embodiment of the present invention relates to the theadearomatizationacompriseson that sulfur poisoning is had the enhancing tolerance.This theadearomatizationacompriseson generally comprises promoter metal component and zinc oxide.
Promoter metal component used in the theadearomatizationacompriseson comprises promoter metal, or is formed or be made up of it substantially by it.Promoter metal is can catalytic hydrogenation reaction, for example metal of the hydrogenation of multi-nucleus aromatic compound (PNA).Preferably, promoter metal is selected from nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony, vanadium, gold, platinum, ruthenium, iridium, chromium, palladium, titanium, zirconium, rhodium, rhenium and combination thereof.Most preferably, promoter metal is a nickel.
In one embodiment of the present invention, all promoter metal component are present in the theadearomatizationacompriseson to go back ortho states substantially.As used herein, " go back ortho states " and refer to the state of composition/component that the number with its bonded Sauerstoffatom reduced.Preferably, all promoter metal component exist with 0 valence state substantially, promptly do not have Sauerstoffatom to combine with it.Therefore, with discussed in detail, preferably in the preparation process of theadearomatizationacompriseson, it is carried out reduction step as hereinafter.In addition, preferably in the preparation process of theadearomatizationacompriseson, it is carried out acid treatment step, preferably use tartrate and/or citric acid pre-treatment, most preferably use the citric acid pre-treatment.
In one embodiment of the present invention, the promoter metal component of theadearomatizationacompriseson comprises the substituted metal sosoloid of the sosoloid form of promoter metal and another metal, or is formed or be made up of it substantially by it.This substituted metal sosoloid is preferably used formula M
AZn
BCharacterize, wherein M is a promoter metal, and Zn is a zinc, respectively the do for oneself numerical value of 0.01-0.99 of A and B.In above substituted metal sosoloid formula, the preferably about 0.70-of A is about 0.97, and most preferably from about 0.85-about 0.95.In addition, the preferably about 0.03-of B is about 0.30, most preferably from about 0.05-0.15.Preferably, B equals (1-A).
Subtractional solid solution has for the chemical feature of theadearomatizationacompriseson described herein important unique physical and chemical property.Subtractional solid solution is the subclass of the alloy that forms by the solvent metal atom in the direct substitution crystalline structure of solute metal.For example, we think the substituted metal sosoloid (M in this theadearomatizationacompriseson
AZn
B) replace the formation of solvent promoter metal component by the solute zinc metal atom.Have 3 primary standards for helping for subtractional solid solution forms: (1) these two kinds of atoms of elements radiuses are each other in 15%; (2) crystalline structure of these two kinds of pure phases is identical; And the electronegativity of (3) these two kinds of components is close.Used promoter metal (as metal element or metal oxide) and zinc oxide preferably satisfy in above-mentioned 3 standards at least 2 in the theadearomatizationacompriseson described herein.For example, when promoter metal is nickel, satisfy the 1st and 3 standard, but the 2nd is not satisfied.Nickel and zinc metallic atomic radius are each other in 10%, and electronegativity is close.But nickel oxide (NiO) preferentially forms the cubes crystalline structure, and zinc oxide (ZnO) preferentially forms the hexahedron crystalline structure.Nickel-zinc sosoloid has kept the cube structure of nickel oxide.Force zinc oxide to keep cube structure to increase the energy of phase, and this increase has limited the amount that can be dissolved in the zinc in the nickel oxide structure.On this stoichiometry control microcosmic as nickel oxide-formed 92:8 nickel zinc sosoloid (Ni when zinc oxide sosoloid is reduced
0.92Zn
0.08) in reflect.
Except zinc oxide and going back the ortho states promoter metal component, this theadearomatizationacompriseson can also comprise porosity dose and promoter metal-zinc aluminate subtractional solid solution.Promoter metal-zinc aluminate subtractional solid solution can be used formula M
zZn
(1-z)Al
2O
4Characterize, wherein Z is the numerical value of 0.01-0.99.
The porosity dose when using, can be the compound of the open grain of any final this theadearomatizationacompriseson of increase.Preferably, the porosity dose is a perlite.As used herein, term " perlite " is the petrography term that is used for the siliceous volcanic that some regional nature forms in the world.The distinctive feature of itself and other volcano mineral is, when being heated some temperature, the 4-20 that it can be expanded to its original volume doubly.When being heated to 1600 ℉ when above, the perlite of pulverizing expands because of the existence of thick perlitic combination water.This combination water is evaporated in heat-processed, and forms countless micro-bubbles in the remollescent glassiness particle that is heated.Be that these small glass capsulation bubbles cause its light weight.It is low to 2.5lbs/ft that pearlstone can be made weight
3The typical chemical analysis character of pearlstone is: silicon-dioxide 73%, aluminum oxide 17%, potassium oxide 5%, sodium oxide 3%, calcium oxide 1% and trace elements.The representative physical properties of pearlstone is: softening temperature 1,600-2,000 ℉, fusing point 2,300 ℉-2,450 ℉, pH6.6-6.8 and proportion 2.2-2.4.As used herein, term " pearlstone " refers to by the perlite siliceous volcanic being heated to temperature more than 1600 ℉ and expansible Uniones rock.As used herein, term " grain expansion perlite " or " milled perlite " refer to the pearlstone that forms the particulate matter form through broken, and wherein the material of this granularity comprises at least 97% size less than 2 microns particle.Term " grinds pearlstone " and is intended to represent expanded perlite granule is milled or the broken product that obtains.
This theadearomatizationacompriseson preferably comprises zinc oxide, goes back ortho states promoter metal component (M
AZn
B), porosity dose (PE) and promoter metal-zinc aluminate (M
zZn
(1-z)Al
2O
4), their amount is listed in the following table 1.
Table 1
This theadearomatizationacompriseson preferably is and is adapted at the solid particulate form used in fixed bed or the moving-burden bed reactor.This theadearomatizationacompriseson can be following one or more forms: particle, squeeze-up, sheet, spherical, pill or microballoon.Preferably, this theadearomatizationacompriseson is its average smallest particles diameter and is at least about 0.0625 inch, more preferably at least about 0.125 inch particle, squeeze-up, sheet, spherical or pill form.
Above-mentioned theadearomatizationacompriseson preferably makes by the method that comprises following step:
(a) liquid, zinc compound, porosity dose and aluminum contained compound are mixed the formation wet mixture;
(b), form the moulding base particle with the wet mixture moulding;
(c), form the base particle of drying with moulding base particle drying;
(d) base particle of calcining drying forms through the incinerating base particle;
(e) promoter metal is sneaked in the incinerating base particle and/or on it, form the promotor particle;
(f) the promotor particle is contacted with acid, form through acid-treated particle;
(g) dry through acid-treated particle, form the acid treatment particle of drying;
(h) the acid treatment particle of calcining drying forms through incinerating acid treatment particle;
(i) will form the theadearomatizationacompriseson of going back ortho states through the reduction of incinerating acid treatment particle;
(j) theadearomatizationacompriseson that will go back ortho states contact with acid, and formation is through the acid-treated ortho states theadearomatizationacompriseson of going back; And
(k) dry through the acid-treated ortho states theadearomatizationacompriseson of going back, form the final theadearomatizationacompriseson that the method that is adapted at being used for reducing the PNA content of flow containing hydrocarbons such as diesel oil fuel is used.
Be described in more detail below step (a)-(k).
In order to carry out step (a), liquid, zinc compound, porosity dose and the aluminum contained compound of proper ratio mixed for these components provide deep layer blended appropriate method or mode by any, obtain its basic mixture uniformly thus.As used herein, term " mixing " refers in any order and/or arbitrary combination or sub-portfolio blending ingredients.The device of the component of any suitable this composition of mixing can be used for making these components to reach desired dispersion.The example of suitable mixing device includes but not limited to mix rotating cylinder, anchor or groove, Eurostar mixing machine (intermittent type or continous way), impact mixer etc.
Used liquid can be any liquid that can disperse zinc compound, porosity dose and aluminum contained compound in the step (a).Preferably, this liquid is selected from water, ethanol, acetone and combination thereof.Most preferably, this liquid is water.Used zinc compound can be that zinc oxide or one or more can be converted into the zn cpds of zinc oxide under preparation condition as herein described in the step (a).The example of suitable zinc compound includes but not limited to zinc sulphide, zinc sulfate, zinc hydroxide, zinc carbonate, zinc acetate, zinc nitrate etc. and their combination.Preferably, zinc compound is a powder zinc oxide.
Used porosity dose can be any porosity that increases final theadearomatizationacompriseson and/or compound that reduces its density of being applicable in the step (a).Preferably, the porosity dose is to contain earth silicon material, for example perlite, diatomite, colloid silica, silica gel and/or the precipitated silica that expands and pulverize.In addition, can be converted into the silicon compound of silicon-dioxide, for example silicic acid, ammonium silicate etc. also can use.Most preferably, the porosity dose is a crushed expanded perlite.
Used aluminum contained compound can be the aluminiferous compound of any bag, for example aluminum oxide or aluminate in the step (a).Preferably, aluminum contained compound is the aluminum oxide that can be converted into aluminate (for example Zinc aluminate) in calcining up to small part.The example of suitable aluminum contained compound comprises aluminum chloride, aluminum nitrate, colloidal alumina solution, hydrated aluminum oxide, peptization aluminum oxide and usually, those alumina cpds that make by the hydrated alumina dehydration.Most preferably, aluminum contained compound is a hydrated aluminum oxide, for example boehmite or pseudobochmite.
The preferable amount of these dried components (being zinc compound, porosity dose and aluminum contained compound) is listed in following table 2.Listed amount is based on total per-cent of doing component (not comprising liquid).
Table 2
The amount that adds the liquid in these dried components is to form the required any amount of wet mixture with desired denseness.The gained wet mixture preferably is the form of wet compound, dough, paste or slurry.
According to step (b),, form the moulding base particle that is selected from particle, squeeze-up, lamellar body, ball, pill or microballoon with the wet mixture moulding of step (a) gained.Preferably, the wet mixture of gained is the form of dough or paste, and can form the smallest particles diameter by extrusion moulding and be at least about 0.0625 inch, and more preferably the smallest particles diameter is the about 0.5 inch particle of about 0.125-.
According to step (c), then dry under the drying conditions that the gained base particle is about to describe below, form butt plinth particle.Drying conditions as described herein can comprise about 450 ℉ of about 150-, preferably about 410 ℉ of about 190-, the temperature of 200-350 ℉ most preferably.This drying conditions can also comprise and is generally about 0.5-about 60 hours, preferably about 40 hours of about 1-, time of 1.5-20 hour most preferably.This drying conditions can also comprise and be generally about normal atmosphere (i.e. 14.7 pounds/square inch absolute)-Yue 150 pounds/square inch absolute (psia), preferably about normal atmosphere-Yue 100psia, atmospheric pressure most preferably from about that condition is the temperature that can keep desired.Any drying means well known by persons skilled in the art, for example dry air and/or heat drying can use.The preferred heat drying that adopts.
According to step (d), then calcine the base particle of drying, form through the incinerating base particle.Preferably, calcining is carried out in the oxidation atmosphere, for example carries out in the presence of oxygen or air.Calcination condition as described herein can comprise about 1500 ℉ of about 400-, preferably about 1450 ℉ of about 750-, the temperature of 750-1400 ℉ most preferably.This calcination condition can also comprise and be generally the about 750psia of about 7-, the preferably about 450psia of about 7psia-, the pressure of the about 150psia of 7psia-most preferably from about, and about 1 hour-Yue 60 hours, preferred about 1 hour-Yue 20 hours, time of 1-15 hour most preferably.In the technology of this embodiment, calcine preferred near small part aluminum contained compound (as aluminum oxide) and be converted into aluminate (as Zinc aluminate).
According to step (e), promoter metal is sneaked in the incinerating base particle and/or on it, form the promotor particle.The preferred method that promoter metal is sneaked into is to utilize incipient wetness pickling process dipping through incinerating base particle (promptly with the solution that contains promoter metal almost the hole of wadding warp incinerating base particle).Be used to make promoter metal component to sneak in the incinerating base particle and/or the preferred dipping solution on it comprises the aqueous solution of the compound that contains promoter metal.Preferably, this compound that contains promoter metal is a metal-salt, for example metal chloride, metal nitrate or metal sulfate.The concentration of promoter metal in this solution can be in the required any OK range of the promoter metal of sneaking into desired amount.Preferably contain the hexahydrated solution of the nickelous nitrate that is dissolved in the water, make through the incinerating base particle and be soaked with the nickel component, thereby make final theadearomatizationacompriseson comprise at least 10 weight % nickel by use.
According to step (f), the promotor particle is contacted with acid, form through acid-treated particle.The acid that contacts with the promotor particle is preferably selected from citric acid, tartrate and combination thereof.Preferably, acid treatment is by carrying out as above-mentioned dipping method.As promotor, acid is dissolved in solvent, in the preferably water, form dipping solution.
According to step (g), then, form the acid treatment particle of drying thus as above-mentioned dry through acid-treated particle under drying conditions.
According to step (h), then, form thus through incinerating acid treatment particle as the above-mentioned acid treatment particle of under calcination condition, calcining drying.Preferably, calcining makes at least partial oxidation zinc and forms subtractional solid solution to the small part promoter metal.
According to step (i), then will form the theadearomatizationacompriseson of going back ortho states thus through the reduction of incinerating acid treatment particle.Appropriate reductant comprises any causing and the reductive agent that reduces through incinerating acid treatment particle bonded oxygen atomicity.Preferably, hydrogen is as reductive agent.Reductive condition can comprise the temperature of about 1500 ℉ of about 100-, the pressure of the about 1500psia of about 15-, and enough form the time of going back the ortho states promoter metal component.
According to step (j), then, obtain through the acid-treated ortho states theadearomatizationacompriseson of going back with the acid treatment theadearomatizationacompriseson of ortho states also.With go back the acid that the ortho states theadearomatizationacompriseson contacts and be preferably selected from citric acid, tartrate and combination thereof.Most preferably, this acid is citric acid.Preferably, acid treatment is by carrying out as above-mentioned dipping method.
According to step (k), preferably, obtain final theadearomatizationacompriseson thus as above-mentioned dry through the acid-treated ortho states theadearomatizationacompriseson of going back under drying conditions.
In replaceable embodiment of the present invention, before step (i)-(k) is carried out, step (e)-(h) is repeated one or many.In some cases, when repeating step (e)-(h), may need a plurality of promoter metals to sneak into step to sneak into high-load promoter metal.In another embodiment, do not carry out step (j) and (k), so that do not have last acid treatment step, going back the ortho states theadearomatizationacompriseson becomes final theadearomatizationacompriseson.In another embodiment of the present invention, this theadearomatizationacompriseson is according to U.S. Patent application No.10/443, and the method described in 380 makes, and the full content of the document is incorporated herein by reference.
According to a kind of embodiment of the present invention, above-mentioned theadearomatizationacompriseson is used in the method for amount of the multi-nucleus aromatic compound (PNA) that is used for reducing the low-sulfur flow containing hydrocarbons.Preferably, this method is included in and is enough to make in the low-sulfur flow containing hydrocarbons existing to the dearomatization condition of small part PNA hydrogenation, and described low-sulfur flow containing hydrocarbons is contacted with this theadearomatizationacompriseson.
The used preferred boiling range of low-sulfur flow containing hydrocarbons (ASTM D86-00) is about 300 ℉-Yue 750 ℉, the mixture of the hydrocarbon of 350 ℉-Yue 725 ℉ most preferably from about in the dearomatization method.This low-sulfur flow containing hydrocarbons preferably have be higher than about 350 ℉, more preferably be higher than about 400 ℉, most preferably be higher than the mid-boiling point (ASTM D86-00) of about 450 ℉.This low-sulfur flow containing hydrocarbons preferably has about 50, the api gravity of 25-about 45 (ASTM D287-92) more preferably from about of about 20-.This low-sulfur flow containing hydrocarbons preferably has at least about 80 ℉, most preferably at least about the minimum flash point (ASTM D93-99) of 90 ℉.
Preferably, this low-sulfur flow containing hydrocarbons is the middle runnings materials flow, for example diesel oil fuel, jet fuel, kerosene and/or light cycle.Most preferably, this low-sulfur flow containing hydrocarbons is that 375 ℉-700 ℉, mid-boiling point are higher than 500 ℉, api gravity is that 30-38 and the diesel oil fuel of minimum flash point more than 100 ℉ are formed by boiling range substantially.
The step that described low-sulfur flow containing hydrocarbons is contacted with this theadearomatizationacompriseson disclosed herein can be by continuous processing, or is preferably undertaken by batch technology.Preferably, the dearomatization district is arranged in fixed bed or the moving-burden bed reactor.Most preferably, use fixed-bed reactor.
Described low-sulfur flow containing hydrocarbons carries out under the dearomatization condition that promotes PNA compound hydrogenation with contacting preferably of this theadearomatizationacompriseson.Usually, this dearomatization condition comprises about 800 ℉ of about 350-, the temperature of 550-650 ℉ most preferably.This dearomatization condition also comprises the about 2000psia of about 200-, the pressure of 500-1000psia most preferably.This dearomatization condition also comprises the speed of low-sulfur flow containing hydrocarbons and hydrogen being sent into the dearomatization district.The flow velocity of low-sulfur flow containing hydrocarbons can quantize its normalization method (normalize) by the amount based on catalyzer in the dearomatization district.This normalization method tachograph of low-sulfur flow containing hydrocarbons is shown weight hourly space velocity (" WHSV ").WHSV is by the speed of the low-sulfur flow containing hydrocarbons being sent into the dearomatization district of following Pounds Per Hour of standard temperature and pressure (STP) (STP) the numerical value ratio divided by the poundage of contained theadearomatizationacompriseson in the dearomatization district.Preferably, at the about 5hr of about 0.1-
-1, the about 3hr of 0.5-most preferably from about
-1WHSV under the low-sulfur flow containing hydrocarbons is sent into the dearomatization district.Hydrogen is sent into the low-sulfur flow containing hydrocarbons (scf/bbl) of hydrogen/bucket that the flow velocity in dearomatization district can be by being shown the hydrogen tachograph standard cubic foot and is sent into the speed normalization method in dearomatization district based on the low-sulfur flow containing hydrocarbons.Preferably, with hydrogen with the about 5000scf/bbl of about 1000-, most preferably from about the speed of the about 3500scf/bbl of 2500-is introduced the dearomatization district.
The low-sulfur flow containing hydrocarbons contacts in the dearomatization district with this theadearomatizationacompriseson, the materials flow that the PNA lower than the PNA content of the low-sulfur flow containing hydrocarbons of sending into the dearomatization district that obtain PNA content reduces.The PNA content of low-sulfur flow containing hydrocarbons of sending into the dearomatization district is preferably at least about 5 weight %, more preferably from about the about 70 weight % of 10-, most preferably from about 15-55 weight %.The PNA content of the materials flow that PNA reduces is preferably lower at least about 25 weight % than the PNA content of low-sulfur flow containing hydrocarbons, and is more preferably low at least about 50 weight %, most preferably low at least 75 weight %.For example, if the PNA content of the materials flow that the PNA content of low-sulfur flow containing hydrocarbons is 20 weight % and PNA to be reduced is 10 weight %, then the PNA content of the materials flow of PNA minimizing is than the low 50 weight % of PNA content of low-sulfur flow containing hydrocarbons.Preferably, the PNA content of the materials flow that PNA reduces is lower than about 10 weight %, more preferably less than about 7.5 weight %, most preferably is lower than 5 weight %.
Low-sulfur flow containing hydrocarbons and this theadearomatizationacompriseson contact the theatotal aromaticsacontent that has also preferably reduced this materials flow in the dearomatization district.The about 90 weight % of the preferably about 10-of the theatotal aromaticsacontent of low-sulfur flow containing hydrocarbons, most preferably 20-80 weight %.Preferably, the theatotal aromaticsacontent of the materials flow that PNA reduces is lower at least about 10 weight % than the theatotal aromaticsacontent of low-sulfur flow containing hydrocarbons, and is more preferably low at least about 25 weight %, most preferably low at least 50 weight %.
In addition, the sulphur content that has preferably reduced this materials flow that contacts of low-sulfur flow containing hydrocarbons and this theadearomatizationacompriseson.The sulphur content of low-sulfur flow containing hydrocarbons preferably is lower than about 500ppmw, more preferably from about the about 400ppmw of 5-, most preferably 10-250ppmw.Preferably, the sulphur content of the materials flow that PNA reduces is lower at least about 5 weight % than the sulphur content of low-sulfur flow containing hydrocarbons, and is more preferably low at least about 25 weight %, most preferably low at least 50 weight %.Preferably, the sulphur content of the materials flow that PNA reduces is lower than about 10ppmw, most preferably is lower than 5ppmw.As used herein, term " sulphur " refers to the common any type of sulphur that exists, for example elementary sulfur or sulphur compound in the flow containing hydrocarbons.
In addition, the cetane value that has preferably increased this materials flow that contacts of low-sulfur flow containing hydrocarbons and this theadearomatizationacompriseson.The cetane value of low-sulfur flow containing hydrocarbons is preferably at least about 20, most preferably 20-40.Preferably, the cetane value of the materials flow that PNA reduces than the cetane value of low-sulfur flow containing hydrocarbons greatly at least about 5%, more preferably greatly at least about 10%, most preferably greatly at least 25%.Preferably, the cetane value of the materials flow that PNA reduces is greater than about 30, most preferably 35-60.
Contacting also preferably the influence of alkene total content, mid-boiling point, api gravity and the flash-point of this materials flow of low-sulfur flow containing hydrocarbons and this theadearomatizationacompriseson is very little.Preferably, alkene total content, mid-boiling point, api gravity and the flash-point of the materials flow that PNA reduces is in about 10% scope of alkene total content, mid-boiling point, api gravity and the flash-point of low-sulfur flow containing hydrocarbons, more preferably in about 5%, most preferably in 2%.
As mentioned above, this theadearomatizationacompriseson is compared with the conventional catalyst that is used for PNA compound hydrogenation, and sulfur poisoning is had the enhanced tolerance.Therefore, the dearomatization activity of this theadearomatizationacompriseson keeps for a long time, and need not to change and/or regeneration.This enhanced tolerance can quantize by the active hold-time.As used herein, term " active hold-time " refers to that PNA dearomatization activity remains on more than the certain level, and need not to change or the theadearomatizationacompriseson and need not to change time of dearomatization condition of regenerating.Preferably, this theadearomatizationacompriseson activity be enough to obtain PNA content than active hold-time of the low materials flow that reduces at least about the PNA of 25 weight % of the PNA content of low-sulfur flow containing hydrocarbons at least about 12 hours, more preferably at least about 36 hours, most preferably at least about 72 hours.In addition, this theadearomatizationacompriseson activity is enough to obtain the active hold-time of the materials flow that PNA content reduces than the PNA of the low 50 weight % of PNA content of low-sulfur flow containing hydrocarbons at least preferably at least about 6 hours, more preferably at least about 12 hours, and most preferably at least 36 hours.
In the process of low-sulfur flow containing hydrocarbons dearomatization in the dearomatization district, a part of zinc oxide of this theadearomatizationacompriseson can be converted into zinc sulphide.This zinc oxide is converted into zinc sulphide can cause dearomatization compound inactivation.In this theadearomatizationacompriseson (promptly after the active hold-time) after the inactivation, can by with the theadearomatizationacompriseson of inactivation with containing that the oxygen regeneration stream contacts with its regeneration.With the dearomatization compound regeneration of inactivation, preferably basic all zinc sulphide can be transformed back zinc oxide.Then can be used in once more in the dearomatization district, to reduce the PNA content of low-sulfur flow containing hydrocarbons through the regenerated theadearomatizationacompriseson.
Before this theadearomatizationacompriseson contacts in the dearomatization district, the preferred process desulfurization in suitable desulphurization system of low-sulfur flow containing hydrocarbons.Initial low-sulfur flow containing hydrocarbons in the desulphurization system of introducing upstream, dearomatization district preferably has the sulphur at least about 500ppmw, the most preferably sulphur content of 600-5000ppmw sulphur.The desulfurization that takes place in desulphurization system preferably obtains the sulphur content low at least 25 weight %s of sulphur content than initial flow containing hydrocarbons, and is more preferably low at least about 50 weight %, most preferably the low-sulfur flow containing hydrocarbons of low at least 75 weight %.Except sulphur content, all other character (as boiling range, cetane value, api gravity, minimum flash point, PNA content, theatotal aromaticsacontent and alkene total content) of initial flow containing hydrocarbons are basic identical with the flow containing hydrocarbons that above-mentioned sulphur reduces.
The desulfurization of initial flow containing hydrocarbons can be undertaken by the method for any reduction flow containing hydrocarbons sulphur content known in the art.Preferred sulfur method is included under the existence of hydrogenation catalyst hydrogenating desulfurization and/or adsorbs sulphur in the presence of sulfur absorbent.Suitable hydrodesulfurization is in U.S. Patent No. 5,011, description arranged in 593, and its whole disclosures are incorporated herein by reference.Suitable sulphur absorbing process has description in U.S. Patent application No.2003/0111389, its whole disclosures are incorporated herein by reference.Most preferably, utilize to comprise the regenerable sorbent of going back ortho states promoter metal component and zinc oxide, by sulphur absorption carrying out desulfurization.In one embodiment, used regenerable sorbent has and above-mentioned the essentially identical composition of theadearomatizationacompriseson in the desulphurization system.Desulfurization is preferably carried out in the desulfurization zone of fluidized-bed reactor.
The following examples are intended to illustrate the present invention and instruct those skilled in the art to implement and utilize the present invention.These embodiment are intended to limit the present invention absolutely not.
Embodiment
Example I-preparation of compositions
Composition A (contrast)
Composition A is by obtaining with nickelous nitrate hexahydrate aqueous solution incipient wetness impregnation of silica-alumina supporter.Gained is calcined down 100 ℃ of following dryings and at 400 ℃ through impregnated compositions.The about 9.4 weight % nickel of the nickel metal concentration of final composition A.
Composition B (the present invention)
Composition B makes by utilizing the basic extrudate of pulverizing perlite, zinc oxide and aluminum oxide that expands.Should basis extrudate material with nickelous nitrate hexahydrate solution impregnation.After initial dipping, utilize the dropping liquid pickling process to contact with citric acid immediately through the extrudate of dipping.Then will be through acid-treated composition 100 ℃ of dry down and calcinings under 400 ℃.Then for the second time flood said composition, subsequently 100 ℃ of dry down and calcinings under 400 ℃ with nickel nitrate solution.The about 18.1 weight % nickel of the nickel metal concentration of final composition B.
Composition C (contrast)
Composition C makes by the thickener of extruding perlite, zinc oxide and aluminum oxide.In the retort furnace of temperature program(me) control, that the gained extrudate is dry down and 400 ℃ of calcinings down at 100 ℃.Then the nickelous nitrate hexahydrate aqueous solution is sprayed on the incinerating extrudate, thereby floods this extrudate by the use ultrasonic nozzle.Gained is calcined down 100 ℃ of following dryings and at 635 ℃ through impregnated compositions.The about 13.6 weight % nickel of the nickel metal concentration of final composition C.
The mensuration of example II-multi-nucleus aromatic compound transformation efficiency
The composition A, the B that make of test implementation example I and multi-nucleus aromatic compound (PNA) transformation efficiency of C respectively.
In the fixed-bed reactor of laboratory-scale, estimate these compositions.Reaction conditions comprises the temperature of about 600 ℉, the pressure of about 500psig, about 2h
-1Weight hourly space velocity and the H of about 3500scf/bbl
2/ hydrocarbon ratio.
The charging of reactor is the low sulphur diesel fuel that is mixed with 100ppmw sulphur in addition.The sulphur of this diesel oil fuel of being used to mix is 50 weight % as the sulphur of dibenzothiophene and 50 weight % as 4, the sulphur of 6-dimethyl Dibenzothiophene.Have the sulphur that total content is 118.6ppmw through adulterated diesel feed, content is that PNA and the total content of 25 weight % is the aromatic substance of 48.4 weight %.
With this before adulterated diesel feed contacts, under the temperature of 750 ℉ with hydrogen with composition A, B and C reduction 3 hours.
For the activity of test composition A, B and C, make reaction tubes load the fixed bed of test composition, will under above-mentioned dearomatization condition, pass through fixed bed through adulterated diesel oil.Composition A, B and C with this in the process that adulterated diesel feed contacts, based on the amount of the sulphur that accumulates on the theadearomatizationacompriseson, the PNA conversion percentage of the every gram nickel of periodic measurement.
The PNA hydrogenation activity of composition A, B and C relatively is shown among Fig. 1.Fig. 1 shows the present composition, and composition B is than the PNA hydrogenation activity of composition A and C excellence.In addition, with respect to composition A, composition B can tolerate inactivation better.
EXAMPLE III-composition tolerance inactivation relatively
By measuring the amount of the sulphur in the super low sulfur incoming flow that is mixed with 100ppm sulphur in the certain hour, composition A that test implementation example I makes and B are to the tolerance of inactivation.
In the fixed-bed reactor of laboratory-scale, estimate these compositions.Reaction conditions comprises the temperature of about 600 ℉, the pressure of about 500psig, about 2h
-1Weight hourly space velocity and the H of about 3500scf/bbl
2/ hydrocarbon ratio.
The charging of reactor is the low sulphur diesel fuel that is mixed with 100ppmw sulphur in addition.The sulphur of this diesel oil fuel of being used to mix is 50 weight % as the sulphur of dibenzothiophene and 50 weight % as 4, the sulphur of 6-dimethyl Dibenzothiophene.Have the sulphur that total content is 118.6ppmw through adulterated diesel feed, content is that PNA and the total content of 25 weight % is the aromatic substance of 48.4 weight %.
With this before adulterated diesel feed contacts, under the temperature of 750 ℉ with hydrogen with composition A and B reduction 3 hours.
For the activity of test composition A and B, make reaction tubes load the fixed bed of test composition, will under above-mentioned dearomatization condition, pass through fixed bed through adulterated diesel oil.Composition A and B with this in the process that adulterated diesel feed contacts, the amount of residual sulphur in the periodic measurement incoming flow.
Composition A and B relatively are shown among Fig. 2 the tolerance of inactivation.Fig. 2 shows the present composition, and composition B has more excellent tolerance than composition A to inactivation.
Claims (47)
1. method that is used for removing the multi-nucleus aromatic compound (PNA) that contains the low-sulfur flow containing hydrocarbons that is less than about 500ppmw sulphur, described method comprises: be enough to make under the dearomatization condition of PNA content reduction at least about 25 weight % of described low-sulfur materials flow, described low-sulfur materials flow is contacted with the theadearomatizationacompriseson that contains promoter metal component and zinc oxide, obtain the materials flow that PNA reduces thus, the sulphur content of the materials flow that wherein said PNA reduces is lower at least about 5 weight % than the sulphur content of described low-sulfur materials flow.
2. the method for claim 1 also comprises and uses desulphurization system to remove the sulphur in the initial flow containing hydrocarbons, obtains described low-sulfur materials flow thus, and the sulphur content of wherein said low-sulfur materials flow is lower at least about 50 weight % than the sulphur content of described initial flow containing hydrocarbons.
3. the method for claim 2, wherein said desulphurization system use comprise go back ortho states promoter metal component and zinc oxide regenerable sorbent to remove the sulphur in the described initial flow containing hydrocarbons.
4. the method for claim 3, wherein said desulphurization system comprise and are used for the fluidized-bed reactor that described initial flow containing hydrocarbons contacts with described regenerable sorbent.
5. the process of claim 1 wherein with described contact of described low-sulfur materials flow before, with citric acid and/or the described theadearomatizationacompriseson of tartrate pre-treatment.
6. the process of claim 1 wherein with described contact of described low-sulfur materials flow before, the reduction of described theadearomatizationacompriseson experience.
7. the process of claim 1 wherein that described promoter metal component comprises the promoter metal of the group that is selected from nickel, cobalt, iron, manganese, tungsten, silver, gold, copper, platinum, zinc, ruthenium, molybdenum, antimony, vanadium, iridium, chromium, palladium and combination composition thereof.
8. the method for claim 7, wherein said theadearomatizationacompriseson comprises the described zinc oxide at least about 20 weight %.
9. the method for claim 8 wherein is converted into zinc sulphide with the described described zinc oxide of near small part that contacts of described low-sulfur materials flow.
10. the method for claim 9, wherein said theadearomatizationacompriseson comprises the nickel at least about 10 weight %.
11. the process of claim 1 wherein that described promoter metal component is formula Ni
AZn
BSubstituted metal sosoloid, wherein A and B are respectively 0.01-0.99.
12. the method for claim 11, wherein A is about 0.97 for about 0.70-, and B is about 0.03-about 0.30.
13. the process of claim 1 wherein that described theadearomatizationacompriseson comprises aluminate.
14. the method for claim 13, wherein said aluminate comprises nickel and/or zinc.
15. the method for claim 13, wherein said aluminate are the aluminates of nickel-zinc.
16. the process of claim 1 wherein that described theadearomatizationacompriseson comprises perlite.
17. the process of claim 1 wherein the cetane value of the materials flow that described PNA reduces than the cetane value of described low-sulfur materials flow greatly at least about 5%.
18. the method for claim 1, the PNA content of the materials flow that wherein said PNA reduces is lower at least about 50 weight % than the PNA content of described low-sulfur materials flow, the sulphur content of the materials flow that described PNA reduces is lower at least about 25 weight % than the sulphur content of described low-sulfur materials flow, the cetane value of the materials flow that described PNA reduces than the cetane value of described low-sulfur materials flow greatly at least about 10%.
19. the process of claim 1 wherein that described low-sulfur materials flow has the cetane value at least about 20.
20. the process of claim 1 wherein that described low-sulfur materials flow has the cetane value of about 20-about 40, the materials flow that described PNA reduces has the cetane value of about 35-about 60.
21. the process of claim 1 wherein that described low-sulfur materials flow has the PNA content at least about 5 weight %.
22. the process of claim 1 wherein that described low-sulfur materials flow has the PNA content of the about 70 weight % of about 10-, the materials flow that described PNA reduces has the PNA content that is less than about 7.5 weight %.
23. the process of claim 1 wherein that described low-sulfur materials flow comprises the sulphur of the about 400ppmw of about 5-, the materials flow that described PNA reduces comprises the sulphur that is less than about 10ppmw.
24. the process of claim 1 wherein that described low-sulfur materials flow is the middle runnings materials flow of mid-boiling point at least about 350 ℉.
25. the method for claim 24, wherein said middle runnings materials flow has the boiling range of about 750 ℉ of about 300-, the api gravity of about 20-about 50, and at least about the minimum flash point of 80 ℉.
26. the process of claim 1 wherein that described low-sulfur materials flow is selected from the group that diesel oil fuel, jet fuel, kerosene, light cycle or its mixture are formed.
27. the process of claim 1 wherein that described low-sulfur materials flow is made up of the diesel oil fuel of the minimum flash point of the api gravity of the mid-boiling point of the boiling range with 375-700 ℉, 500 ℉, about 30-about 38 and 100 ℉ substantially at least at least.
Described theadearomatizationacompriseson is not regenerated 28. the process of claim 1 wherein described contact to carry out at least 12 hours active hold-time, the PNA content reduction of described low-sulfur materials flow remains on 25 weight % or more in the described active hold-time.
29. the method for claim 28, wherein in the described active hold-time, the sulphur content reduction of described low-sulfur materials flow remains on 50 weight % or more.
30. the method for claim 28, wherein said active at least 36 hours hold-times.
31. the method for claim 28, wherein after the described active hold-time, described theadearomatizationacompriseson inactivation, described method also comprise by with the theadearomatizationacompriseson of inactivation with contain the oxygen regeneration stream and contact the theadearomatizationacompriseson that makes inactivation and regenerate.
32. the method for claim 31, the theadearomatizationacompriseson of wherein said inactivation comprises zinc sulphide, and the described zinc sulphide of the near small part of described regeneration is converted into zinc oxide.
33. the process of claim 1 wherein that described contact carries out in fixed-bed reactor and/or moving-burden bed reactor.
34. the process of claim 1 wherein that described theadearomatizationacompriseson is average minimum diameter at least about 0.0625 inch solid particulate.
35. the process of claim 1 wherein that described dearomatization condition comprises the temperature of about 800 ℉ of about 500-, the pressure of the about 2000psia of about 200-, the about 5hr of about 0.1-
-1Weight hourly space velocity, the hydrogen flow velocity of the about 5000scf/bbl of about 1000-.
36. one kind is used for handling and contains at least about 500ppmw sulphur with at least about the method for the initial flow containing hydrocarbons of 5 weight % multi-nucleus aromatic compounds (PNA), described method comprises:
(a) be enough to make under the dearomatization condition of sulphur content reduction at least about 25 weight % of described initial materials flow, described initial materials flow is contacted in first district with catalyzer and/or adsorbent composition, obtain sulphur content thus and be lower than the materials flow that about 500ppmw and PNA content reduce at least about the sulphur of 5 weight %; And
(b) materials flow that reduces of the described sulphur of near small part contact in second district with the theadearomatizationacompriseson that comprises nickel and zinc oxide, obtains its PNA content thus and hangs down materials flow at least about the PNA minimizing of 25 weight % than the PNA content of the materials flow of described sulphur minimizing.
37. the method for claim 36, wherein step (a) is carried out in fluidized-bed reactor, and step (b) is carried out in fluidisation and/or moving-burden bed reactor.
38. the method for claim 36, wherein said catalyzer and/or sorbent material are to comprise the regenerable sorbent of going back ortho states promoter metal component and zinc oxide.
39. the method for claim 36, wherein said theadearomatizationacompriseson comprise at least about 10 weight % nickel with at least about 20 weight % zinc oxide.
40. the method for claim 36, wherein before the described contact of step (b), described theadearomatizationacompriseson has been used sour pre-treatment.
41. the method for claim 36, wherein said initial materials flow are the middle runnings materials flow of mid-boiling point at least about 350 ℉.
42. the method for claim 36, wherein said initial materials flow is a diesel oil fuel.
43. the method for claim 36, the sulphur content of the materials flow that wherein said PNA reduces is lower at least about 5 weight % than the sulphur content of the materials flow that described sulphur reduces.
44. the method for claim 36, the PNA content of the materials flow that wherein said PNA reduces is lower than about 10 weight %.
45. the method for claim 36, the sulphur content of the materials flow that wherein said sulphur reduces is lower at least about 50 weight % than the sulphur content of described initial materials flow.
46. the method for claim 45, the PNA content of the materials flow that wherein said PNA reduces is lower at least about 50 weight % than the PNA content of the materials flow that described sulphur reduces.
47. the method for claim 46, the PNA content of the materials flow that wherein said PNA reduces is lower than about 7.5 weight %, and the PNA content of the materials flow that described sulphur reduces is the about 60 weight % of about 10-.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/424,010 US20070289900A1 (en) | 2006-06-14 | 2006-06-14 | Hydrogenation of polynuclear aromatic compounds |
| US11/424,010 | 2006-06-14 | ||
| US11/424010 | 2006-06-14 | ||
| PCT/US2007/070026 WO2007146597A1 (en) | 2006-06-14 | 2007-05-31 | Hydrogenation of polynuclear aromatic compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101466654A true CN101466654A (en) | 2009-06-24 |
| CN101466654B CN101466654B (en) | 2014-02-12 |
Family
ID=38832095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200780022240.XA Active CN101466654B (en) | 2006-06-14 | 2007-05-31 | Hydrogenation of polynuclear aromatic compounds |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20070289900A1 (en) |
| CN (1) | CN101466654B (en) |
| WO (1) | WO2007146597A1 (en) |
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- 2007-05-31 CN CN200780022240.XA patent/CN101466654B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| US20070289900A1 (en) | 2007-12-20 |
| CN101466654B (en) | 2014-02-12 |
| WO2007146597A1 (en) | 2007-12-21 |
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