US20050020446A1 - Desulfurization and novel process for same - Google Patents
Desulfurization and novel process for same Download PDFInfo
- Publication number
- US20050020446A1 US20050020446A1 US10/914,798 US91479804A US2005020446A1 US 20050020446 A1 US20050020446 A1 US 20050020446A1 US 91479804 A US91479804 A US 91479804A US 2005020446 A1 US2005020446 A1 US 2005020446A1
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- United States
- Prior art keywords
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- sulfur
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- Prior art date
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- Abandoned
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- 238000000034 method Methods 0.000 title claims abstract description 130
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 46
- 230000023556 desulfurization Effects 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 341
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 114
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 112
- 239000011593 sulfur Substances 0.000 claims abstract description 112
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 85
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 84
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 76
- 230000002829 reductive effect Effects 0.000 claims abstract description 53
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 21
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims description 86
- 239000002184 metal Substances 0.000 claims description 86
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 67
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 63
- 239000003502 gasoline Substances 0.000 claims description 57
- 150000001875 compounds Chemical class 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- 239000002283 diesel fuel Substances 0.000 claims description 34
- 239000011363 dried mixture Substances 0.000 claims description 31
- 239000000377 silicon dioxide Substances 0.000 claims description 31
- 230000009467 reduction Effects 0.000 claims description 29
- 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 claims description 28
- 230000000694 effects Effects 0.000 claims description 28
- 239000010451 perlite Substances 0.000 claims description 28
- 235000019362 perlite Nutrition 0.000 claims description 28
- 230000008929 regeneration Effects 0.000 claims description 26
- 238000011069 regeneration method Methods 0.000 claims description 26
- -1 atapulgite Chemical compound 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000004005 microsphere Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 150000004645 aluminates Chemical class 0.000 claims description 8
- 239000000446 fuel Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000000440 bentonite Substances 0.000 claims description 7
- 229910000278 bentonite Inorganic materials 0.000 claims description 7
- 229940092782 bentonite Drugs 0.000 claims description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 5
- 239000008188 pellet Substances 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012702 metal oxide precursor Substances 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 claims description 3
- 230000002708 enhancing effect Effects 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229940080314 sodium bentonite Drugs 0.000 claims description 3
- 229910000280 sodium bentonite Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052621 halloysite Inorganic materials 0.000 claims description 2
- 229910052900 illite Inorganic materials 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical group [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims description 2
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical group [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims 1
- 229910000271 hectorite Inorganic materials 0.000 claims 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 33
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000002253 acid Substances 0.000 description 12
- 239000011787 zinc oxide Substances 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
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- 238000005470 impregnation Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
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- 239000007789 gas Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 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 6
- 239000007921 spray Substances 0.000 description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
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- 239000005995 Aluminium silicate Substances 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
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- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
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- 125000003118 aryl group Chemical group 0.000 description 3
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- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
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- 238000009472 formulation Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- SMAMDWMLHWVJQM-UHFFFAOYSA-L nickel(2+);diformate;dihydrate Chemical compound O.O.[Ni+2].[O-]C=O.[O-]C=O SMAMDWMLHWVJQM-UHFFFAOYSA-L 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000012255 powdered metal Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
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- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
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- 239000008119 colloidal silica Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 238000000921 elemental analysis Methods 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical class O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011412 natural cement Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000008427 organic disulfides Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 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
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
-
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/104—Alumina
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
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- B01D2257/30—Sulfur compounds
- B01D2257/308—Carbonoxysulfide COS
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/703—Activation
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Definitions
- This invention relates to the removal of sulfur from hydrocarbon streams.
- this invention relates to compositions suitable for use in the desulfurization of fluid streams of cracked gasolines and diesel fuels.
- a further aspect of this invention relates to processes for the production of compositions for use in the removal of sulfur bodies from fluid streams of cracked gasolines and diesel fuels.
- Thermally processed gasolines such as, for example, thermally cracked gasoline, visbreaker gasoline, coker gasoline and catalytically cracked gasoline (hereinafter collectively referred to as “cracked gasoline”) contains, in part, olefins, aromatics, sulfur, and sulfur containing compounds. Since most gasolines, such as, automobile gasolines, racing gasolines, aviation gasolines, boat gasolines, and the like contain a blend of, at least in part, cracked gasoline, reduction of sulfur in cracked gasoline will inherently serve to reduce the sulfur levels in most gasolines, such as, for example, automobile gasolines, racing gasolines, aviation gasolines, boat gasolines, and the like.
- Such adverse effect on the olefin content is generally due to the severe conditions normally employed, such as during hydrodesulfurization, to remove thiophenic compounds (such as, for example, thiophenes, benzothiophenes, alkyl thiophenes, alkylbenzothiophenes, alkyl dibenzothiophenes and the like) which are some of the most difficult sulfur containing compounds to remove from cracked gasoline.
- thiophenic compounds such as, for example, thiophenes, benzothiophenes, alkyl thiophenes, alkylbenzothiophenes, alkyl dibenzothiophenes and the like
- thiophenic compounds such as, for example, thiophenes, benzothiophenes, alkyl thiophenes, alkylbenzothiophenes, alkyl dibenzothiophenes and the like
- the conditions are such that the aromatic content of the cracked
- Fluidized bed reactors have advantages over fixed bed reactors, such as, for example, better heat transfer and better pressure drop. Fluidized bed reactors generally use reactants that are particulate. The size of these particulates is generally in the range of from about 1 micron to about 1000 microns. However, the reactants used generally do not have sufficient attrition resistance for all applications.
- an object of the present invention is to provide novel methods for the production of compositions, which are usable in the desulfurization of hydrocarbon streams.
- Another object of the present invention is to provide a process for the removal of sulfur from hydrocarbon streams, which minimizes the consumption of hydrogen and the saturation of olefins and aromatics contained in such streams.
- a still further object of the present invention is to provide an increased content of a promoter component in compositions, which facilitate the removal of sulfur from diesel fuel.
- a still further object of the present invention is to provide a desulfurized cracked gasoline that contains less than about 100 ppm, preferably less than 50 ppm, of sulfur based on the weight of the desulfurized cracked gasoline, and which contains essentially the same amount of olefins and aromatics as are in the cracked gasoline from which such desulfurized cracked gasoline was made.
- Another further object is to provide a desulfurized diesel fuel.
- the third embodiment of this invention is a method comprising, consisting or, or consisting essentially of:
- the fourth embodiment of this invention is a method comprising, consisting of, or consisting essentially of:
- gasoline denotes a mixture of hydrocarbons boiling in the range of from about 37.8° C. to about 260° C., or any fraction thereof.
- suitable gasoline include, but are not limited to, hydrocarbon streams in refineries such as naphtha, straight run naphtha, coker naphtha, catalytic gasoline, visbreaker naphtha, alkylate, isomerate, reformate, and the like and combinations thereof.
- cracked gasoline denotes a mixture of hydrocarbons boiling in the range of from about 37.8° C. to about 260° C., or any fraction thereof, that are products from either thermal or catalytic processes that crack larger hydrocarbon molecules into smaller molecules.
- suitable thermal processes include, but are not limited to, coking, thermal cracking, visbreaking, and the like and combinations thereof.
- suitable catalytic cracking processes include, but are not limited to, fluid catalytic cracking, heavy oil cracking, and the like and combinations thereof.
- suitable cracked gasoline include, but are not limited to, coker gasoline, thermally cracked gasoline, visbreaker gasoline, fluid catalytically cracked gasoline, heavy oil cracked gasoline, and the like and combinations thereof.
- the cracked gasoline may be fractionated and/or hydrotreated prior to desulfurization when used as a hydrocarbon stream in the process of the present invention.
- diesel fuel denotes a mixture of hydrocarbons boiling in the range of from about 148.9° C. to about 398.9° C., or any fraction thereof.
- suitable diesel fuels include, but are not limited to, light cycle oil, kerosene, jet fuel, straight-run diesel, hydrotreated diesel, and the like and combinations thereof.
- sulfur denotes sulfur in any form such as elemental sulfur or a sulfur compound normally present in a hydrocarbon-containing fluid such as cracked gasoline or diesel fuel.
- sulfur which can be present during a process of the present invention usually contained in a hydrocarbon stream, include, but are not limited to, hydrogen sulfide, carbonyl sulfide (COS), carbon disulfide (CS 2 ), mercaptans (RSH), organic sulfides (R—S—R), organic disulfides (R—S—S—R), thiophenes, substituted thiophenes, organic trisulfides, organic tetrasulfides, benzothiophenes, alkyl thiophenes, alkyl benzothiophenes, alkyl dibenzothiophenes, and the like and combinations thereof as well as the heavier molecular weights of same which are normally present in a diesel fuel of the types contemplated for use in a process of the present
- fluid denotes gas, liquid, vapor, and combinations thereof.
- gaseous denotes that state in which the hydrocarbon-containing fluid, such as cracked-gasoline or diesel fuel, is primarily in a gas or vapor phase.
- Attrition resistance denotes the attrition resistance of a composition produced by the inventive method(s).
- DI Davisson Index
- the term “Davison Index” (“DI”) refers to a measure of a composition's resistance to particle size reduction under controlled conditions of turbulent motion. The higher the value of the measured DI, the lower the attrition resistance of the composition.
- Attrition-resistance-enhancing component denotes any component, which can be added to a composition made by the methods of the present invention to enhance the attrition resistance of such composition compared to a composition, which does not contain such attrition-resistance-enhancing component.
- suitable attrition-resistance-enhancing component include, but are not limited to, clays, high alumina cements, natural cements, portland cement, calcium aluminate, calcium silicate, talc, and the like and combinations thereof.
- clay denotes any clay, which can be used as an attrition-resistance-enhancing component of a composition of the present invention.
- a suitable clay examples include, but are not limited to, bentonite, sodium bentonite, acid-washed bentonite, atapulgite, china clay, kaolinite, montmorillonite, illite, halloysite, hectonite, sepiolite, and the like and combinations thereof.
- attrition-resistance-enhancing component comprises clay. More preferably, such attrition-resistance-enhancing component is selected from the group consisting of bentonite, sodium bentonite, acid-washed bentonite, and the like and combinations thereof. Most preferably, such attrition-resistance-enhancing component is bentonite.
- metal denotes metal in any form such as elemental metal or a metal-containing compound.
- the metal-containing compound which is a separate component from the promoter component in the composition(s) produced from the inventive methods can have a metal selected from the group consisting of zinc, manganese, silver, copper, cadmium, tin, lanthanum, scandium, cerium, tungsten, molybdenum, iron, niobium, tantalum, gallium, indium, and combinations of any two or more thereof.
- a zinc-containing compound is used, producing a composition containing a zinc oxide.
- metal formate denotes a compound formed by at least one metal ion and at least one formate ion.
- a formate ion is a carbon atom with bonds to a hydrogen atom and two oxygen atoms with one of the oxygen atoms having a double bond to the carbon atom.
- the metal oxide will preferably be present in the composition produced by the inventive method in an amount in the range of from about 10 to about 90 weight percent metal oxide based on the total weight of the inventive composition, more preferably in an amount in the range of from about 30 to about 80 weight percent metal oxide, and most preferably in an amount in the range of from about 40 to about 70 weight percent metal oxide.
- promoter denotes any component, which when added to the composition of the present invention, helps promote the desulfurization of hydrocarbon streams.
- Such promoters can be at least one metal, metal oxide, precursor for the metal oxide, solid solution of more than one metal, or alloy of more than one metal wherein the metal component is selected from the group consisting of nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony, vanadium, gold, platinum, ruthenium, iridium, chromium, palladium, titanium, zirconium, rhodium, rhenium, and combinations of any two or more thereof.
- the promoter is added to the composition in the form of a second metal formate.
- promoter metal containing compounds include metal acetates, metal carbonates, metal nitrates, metal sulfates, metal thiocyanates, and the like and combinations thereof.
- the metal of the promoter is nickel.
- the promoter selected from the group consisting of metals, metal oxides, and the like, and combinations thereof may initially be in the form of a metal-containing compound and/or a metal oxide precursor. It should be understood that when the promoter is initially a metal-containing compound and/or a metal oxide precursor, a portion of, or all of, such compound and/or precursor may be converted to the corresponding metal or metal oxide of such compound and/or precursor during the inventive process disclosed herein.
- the common oxidation state of the promoter is combined with the metal oxide portion of the inventive composition produced by the inventive methods.
- the number of oxygen atoms associated with the promoter must be reduced to form a reduced valence promoter. Consequently, at least a portion of the promoter present in the inventive composition must be present as a reduced valence promoter. While not wishing to be bound by theory, it is believed that the reduced valence promoter can chemisorb, cleave, or remove sulfur. Thus, either the number of oxygen atoms associated with the promoter is reduced or the oxidation state of the promoter is a zero-valent metal.
- nickel is the promoter metal
- nickel oxide (NiO) can be used and the reduced valence nickel (promoter metal) can be either nickel metal (Ni 0 ) or a non-stoichiometric nickel oxide having a formula of NiO( 1-x ) wherein 0 ⁇ x ⁇ 1.
- tungsten oxide (WO 3 ) can be used and the reduced valence tungsten (promoter metal) can be either tungsten oxide (WO 3 ), tungsten metal (W 0 ), or a non-stoichiometric tungsten oxide having a formula of WO( 3-y ) wherein 0 ⁇ y ⁇ 3.
- the promoter is present in an amount, which will effect the removal of sulfur from the hydrocarbon stream when contacted with the composition under desulfurization conditions.
- the total quantity of the promoter present in the inventive composition it is preferred for at least about 10 weight percent of the promoter to be present in the form of a reduced valence promoter, more preferably at least about 40 weight percent of the promoter is a reduced valence promoter, and most preferably at least 80 weight percent of the promoter is a reduced valence promoter for best activity in sulfur removal.
- the silica-containing material used in the preparation of, and present in the compositions produced by the inventive methods may be either in the form of silica or in the form of one or more silica-containing materials.
- silica-containing material may be employed in the composition such as, for example, diatomite, expanded perlite, colloidal silica, silica gel, precipitated silica, and the like, and combinations thereof.
- silicon compounds that are convertible to silica such as silicic acid, ammonium silicate, and the like, and combinations thereof can also be employed.
- the silica-containing material is in the form of crushed expanded perlite.
- perlite as used herein is the petrographic term for a siliceous volcanic rock, which naturally occurs in certain regions throughout the world. The distinguishing feature, which sets it apart from other volcanic minerals, is its ability to expand four to twenty times its original volume when heated to certain temperatures. When heated above 871.1° C., crushed perlite expands due to the presence of combined water within the crude perlite rock. The combined water vaporizes during the heating process and creates countless tiny bubbles in the heat softened glassy particles. The glass sealed bubbles account for its light weight. Expanded perlite can be crushed to produce a porosity enhancing powder with a weight as little as 2.5 lbs per cubic foot.
- Typical physical properties of expanded perlite are: softening point 1600-2000° F., fusion point 2300-2450° F., pH 6.6-6.8, and specific gravity 2.2-2.4.
- crushed expanded perlite or “milled expanded perlite” as used herein denotes that form of expanded perlite which has first been subjected to milling so as to yield a particle size of about 20 microns to about 500 microns, and then heated with a flame at a temperature of about 871.1° C., and finally subjected to crushing in a hammer mill. While not wishing to be bound to any particular theory, it is believed that the shape of the crushed expanded perlite impacts the activity of the final composition produced by the inventive methods.
- the preferred alumina is hydrated alumina such as, for example, bohemite or pseudobohemite for best activity and sulfur removal.
- a composition is exposed to high temperatures (e.g., during calcinations) at least a portion, preferably a substantial portion of the alumina can be converted to an aluminate, preferably a zinc aluminate spinel.
- the aluminum-containing material will preferably be present in a composition produced by the inventive methods in an amount in the range of from about 1.0 to about 30 weight percent, preferably in an amount in the range of from about 5 to about 25 weight percent, and most preferably, in the range of from 10 to 22 weight percent, based on the total weight of the composition.
- the composition can generally be prepared by admixing a liquid, a zinc-containing compound, a silica-containing material, alumina, and a promoter in appropriate proportions by any suitable method or manner which provides for the intimate mixing of such components to thereby provide a substantially homogenous mixture thereof comprising a liquid, a zinc-containing compound, a silica-containing material, alumina, and a promoter.
- an attrition-resistance-enhancing component can also be added to the mixture.
- admixing denotes mixing components in any order and/or any combination or sub-combination.
- a dispersant component can optionally be utilized and can be any suitable compound that helps to promote the spray drying ability of the mix, which is preferably in the form of a slurry.
- these components are useful in preventing deposition, precipitation, settling, agglomerating, adhering, and caking of solid particles in a fluid medium.
- Suitable dispersants include, but are not limited to, condensed phosphates, sulfonated polymers, and combinations thereof.
- condensed phosphates refers to any dehydrated phosphate containing more than one phosphorus atom and having a phosphorus-oxygen-phosphorus bond.
- an acid component can be used.
- the acid in the acid component can be an organic acid or a mineral acid such as nitric acid. If the acid component is an organic acid, it is preferred to be a carboxylic acid. If the acid component is a mineral acid, it is preferred to be a nitric acid or a phosphoric acid. Mixtures of these acids can also be used.
- the acid is used with water to form a dilute aqueous acid solution.
- the amount of acid in the acid component is generally in the range of from about 0.01 volume percent based on the total volume of the acid component to about 20 volume percent.
- the spray-dried material has a mean particle size in the range of from about 10 micrometers to about 1000 micrometers, preferably in the range of from about 20 micrometers to from about 150 micrometers.
- mean particle size refers to the size of the particulate material as determined by using a RO-TAP® Testing Sieve Shaker, manufactured by W. S. Tyler Inc., of Mentor, Ohio, or other comparable sieves.
- the material to be measured is placed in the top of a nest of standard 8-inch diameter stainless steel framed sieves with a pan on the bottom. The material undergoes sifting for a period of about 10 minutes; thereafter, the material retained on each sieve is weighed. The percent retained on each sieve is calculated by dividing the weight of the material retained on a particular sieve by the weight of the original sample. This information is used to compute the mean particle size.
- the calcined mixture is thereafter subjected to reduction with a suitable reducing agent, preferably hydrogen, so as to produce a composition having a substantially reduced valence promoter content therein, preferably a substantially zero-valent promoter content therein, with such zero-valent promoter being present in an amount sufficient to permit the removal of sulfur from a hydrocarbon stream such as cracked gasoline or diesel fuel, according to the process disclosed herein.
- a suitable reducing agent preferably hydrogen
- the reduction conditions can include a temperature in the range of from about 37.8° C. to about 815.5° C., a pressure in the range of from about 15 psia to about 1500 psia and for a time sufficient to permit the formation of a reduced valence promoter.
- composition can also be produced by the following inventive method;
- the composition can generally be prepared by admixing a liquid, a metal-containing compound, a silica-containing material, alumina, and a first promoter in appropriate proportions by any suitable methods or manner which provides for the intimate mixing of such components to thereby provide a substantially homogenous mixture comprising a liquid (as described above), a metal-containing compound, a silica-containing material, alumina, and a promoter. Any suitable means for admixing these components, as described above, can be used to achieve the desired dispersant of such components.
- the metal-containing compound used in the preparation of a composition of the present inventive method can either be in the form of a metal oxide or in the form of one or more metal compounds that are convertible to a metal oxide under the conditions of preparation described herein.
- suitable metal-containing compounds include, but are not limited to, a metal sulfide, metal sulfate, metal hydroxide, metal carbonate, metal acetate, metal nitrate, and the like and combinations thereof.
- the metal-containing compound is in the form of a powdered metal oxide.
- the components are mixed to provide a mixture which can be in the form selected from the group consisting of a wet mix, dough, paste, slurry, and the like.
- the mixture is in the form of a slurry.
- Such mixture can then optionally be shaped by densifying, extruding, or spray drying to form a particulate selected from the group consisting of a granule, an extrudate, a tablet, a sphere, a pellet, or a microsphere, as described above.
- the mixture is then dried to form a dried mixture, according to the drying conditions described above.
- the dried mixture comprising a metal-containing compound, a silica-containing material, and alumina (or an aluminate), is then incorporated with a second promoter.
- the dried mixture can be calcined before the incorporation of the second promoter, according to the calcining conditions described above.
- first promoter and second promoter distinguish between promoter components that are added to the mixture at different times. Both components can be comprised of the same element (i.e., nickel) or each can be comprised of different elements (i.e., the first promoter can comprise nickel and the second promoter can comprise cobalt). Together, the first promoter and the second promoter comprise the promoter component present in the recovered composition of the second embodiment.
- the second promoter can be incorporated into or onto the dried mixture by any suitable means or method known in the art for incorporating a promoter into or onto a substrate material.
- a preferred method of incorporating is to impregnate using any conventional wetness impregnation technique (i.e. essentially completely or partially filling the pores of a substrate material with a solution of the incorporating elements) for impregnating a substrate.
- This preferred method uses an impregnating solution comprising the desirable concentration of a promoter to ultimately provide an incorporated mixture that can then be subjected to drying and calcining (which can convert at least a portion of the alumina to an aluminate) followed by reduction with a reducing agent such as hydrogen.
- a preferred impregnating solution comprises a solution formed by dissolving a metal containing compound, preferably such metal containing compound is in the form of a metal salt such as a metal chloride, a metal nitrate, a metal sulfate, and the like and combinations thereof, in a solvent such as water, alcohols, esters, ethers, ketones, and combinations thereof.
- a metal salt such as a metal chloride, a metal nitrate, a metal sulfate, and the like and combinations thereof
- a solvent such as water, alcohols, esters, ethers, ketones, and combinations thereof.
- the weight ratio of metal promoter to the solvent of such solution can be in the range of from about 1:1 to about 4:1 but, more preferably it is in the range of from 1.5:1 to 3:1. It is preferred for the particulates to be impregnated with a nickel component by use of a solution containing nickel nitrate hexahydrate dissolved in water.
- the resulting incorporated mixture is then subjected to drying under drying conditions, as described above, to form a dried incorporated mixture, and calcined under calcining conditions, as described above, to form a calcined incorporated mixture.
- the calcined incorporated mixture can then be subjected to reduction with a reducing agent, as described above, to thereby provide the composition.
- the composition can then be recovered.
- the third embodiment of this invention is a method comprising, consisting or, or consisting essentially of:
- alumina can then be added to the mixture, to form an alumina-containing mixture.
- the fifth embodiment of this invention includes a novel process for the removal of sulfur from a hydrocarbon stream. This process comprises:
- the desulfurization zone of step a) includes the following conditions: total pressure, temperature, weight hourly space velocity, and hydrogen flow. These conditions are such that the inventive composition can desulfurize the hydrocarbon stream to produce a desulfurized hydrocarbon stream and a sulfurized composition.
- the total pressure can be in the range of from about 15 pounds per square inch absolute (psia) to about 1500 psia. However, it is presently referred that the total pressure be in a range of from about 50 psia to about 500 psia.
- Weight hourly space velocity is defined as the numerical ratio of the rate at which a hydrocarbon stream is charged to the desulfurization zone in pounds per hour at standard conditions of temperature and pressure (STP) divided by the pounds of composition contained in the desulfurization zone to which the hydrocarbon stream is charged.
- STP temperature and pressure
- WHSV should be in the range of from about 0.5 hr. ⁇ 1 to about 50 hrs. ⁇ 1 , preferably in the range of from about 1 hr. ⁇ 1 to about 50 hrs. ⁇ 1 .
- the amount of sulfur in the hydrocarbon stream can be in the range of from about less than 10-ppm sulfur by weight of the hydrocarbon stream to about 50,000 ppm.
- the amount of sulfur can be in the range of from about less than 10 ppm sulfur by weight of the cracked gasoline to about 10,000 ppm sulfur by weight of the cracked gasoline.
- the hydrocarbon stream is diesel fuel, the amount of sulfur can be in the range of from about less than 10 ppm sulfur by weight of the diesel fuel to about 50,000 ppm sulfur by weight of the diesel fuel.
- the amount of olefins in cracked gasoline is generally in the range of from about 10 to about 3 5 weight percent olefins based on the total weight of the cracked gasoline. For diesel fuel there is essentially no olefin content.
- the amount of aromatics in cracked gasoline is generally in the range of from about 20 to about 40 weight percent aromatics based on the total weight of the cracked gasoline.
- the amount of aromatics in diesel fuel is generally in the range of from about 10 to about 90 weight percent aromatics based on the total weight of the diesel fuel.
- the desulfurized hydrocarbon stream can be separated from the sulfurized composition by any appropriate separation method known in the art thereby forming a separated desulfurized hydrocarbon stream and a separated sulfurized composition.
- the amount of sulfur in the desulfurized hydrocarbon stream, following treatment in accordance with a desulfurization process of the present invention is less than about 500 ppm sulfur by weight of hydrocarbon stream, preferably less than about 150 ppm sulfur by weight of hydrocarbon stream, and more preferably less than about 50 ppm sulfur by weight of hydrocarbon stream.
- a stripper unit can be inserted before and/or after the regeneration of the sulfurized composition.
- Such stripper will serve to remove a portion, preferably all, of any hydrocarbon from the sulfurized composition.
- Such stripper can also serve to remove oxygen and sulfur dioxide from the system prior to the introduction of the regenerated composition into the reduction zone.
- the stripping comprises a set of conditions that include total pressure, temperature, and a stripping agent partial pressure.
- Temperature for such stripping can be in the range of from about 7.8° C. to about 537.8° C.
- the regeneration zone employs a set of conditions that includes total pressure and sulfur removing agent partial pressure.
- the total pressure is generally in the range of from about 25 psia to about 50 psia.
- the sulfur removing agent partial pressure is generally in the range of from about 1% to about 25% of the total pressure.
- the sulfur-removing agent is a composition that helps to generate gaseous sulfur containing compounds and oxygen containing compounds such as sulfur dioxide, as well as to burn off any remaining hydrocarbon deposits that might be present.
- the preferred sulfur removing agent suitable for use in the regeneration zone is selected from oxygen containing gases such as, but not limited to, air.
- the temperature in the regeneration zone is generally in the range of from about 37.8° C. to about 815.5° C., preferably in the range of from about 426.7° C. to about 648.9° C.
- the regeneration zone can be any vessel wherein the desulfurizing or regeneration of the sulfurized composition can take place.
- the regenerated composition is then reduced in a reduction zone with a reducing agent including, but not limited to, hydrogen, so that at least a portion of the promoter content of the composition is reduced to produce a reduced composition having a reduced valence promoter content to permit the removal of sulfur from the hydrocarbon stream according to the inventive process disclosed herein.
- a reducing agent including, but not limited to, hydrogen
- reduction of the desulfurized composition is carried out at a temperature in the range of from about 37.8° C. to about 815.5° C. and at a pressure in the range of from about 15 psia to about 1500 psia.
- Such reduction is carried out for a time sufficient to achieve the desired level of promoter reduction of the promoter, which is preferably contained in the skin of the composition.
- Such reduction can generally be achieved in a time period in the range of from about 0.01 hour to about 20 hours.
- At least a portion of the resulting reduced composition can be returned to the desulfurization zone.
- the steps of desulfurization, regeneration, reduction, and optionally stripping before and/or after such regeneration can be accomplished in the single zone or vessel or in multiple zones or vessels.
- the desulfurized cracked gasoline can be used in the formulation of gasoline blends to provide gasoline products suitable for commercial consumption and can also be used where a cracked gasoline containing low levels of sulfur is desired.
- the desulfurized diesel fuel can be used in the formulation of diesel fuel blends to provide diesel fuel products.
- a zinc oxide/alumina/perlite composition promoted with nickel was prepared.
- a 56-gram quantity of Vista Dispal alumina was added to 118.43 grams of deionized water and was mixed for 20 minutes.
- a 43.6-gram quantity of a base (prepared by treating perlite with nitric acid, and then adding alumina, zinc oxide and kaolin clay) was added to the mixture of water and alumina over a 5-minute period and was mixed for five additional minutes. This mixture will be referred to hereinafter as Mixture #1.
- Mixture #2 was then poured into Mixture #1 and was then mixed for 10 minutes. Then, a 204.8-gram quantity of zinc oxide was added to the mixture over a five minute period and was then mixed for an additional 15 minutes. The zinc oxide mixture was spray dried, and then dried in an oven.
- a 100-gram quantity of the zinc oxide mixture was impregnated via an ultra-sonic nozzle with a combination of 87.5 grams of nickel nitrate hexahydrate plus 13.75 grams of deionized water.
- the impregnated mixture was dried at 150° C. for 1 hour and calcined at 635° C. for 1 hour.
- the Davison Index (DI) value for this composition was 10.3.
- Example I The composition as prepared in Example I was tested for its desulfurization activity as follows. 10 grams of the material as prepared was placed in a 1 ⁇ 2 inch diameter quartz tube having a length of about 12 inches and having a glass frit positioned above the lower one-third so as to provide an inert support for the bed of the composition.
- reaction conditions During each reaction cycle, the reactor was maintained at a temperature of 398.9° C. and a pressure of 15 pounds per square inch absolute (psia). Hydrogen flow was at 130 standard cubic centimeters per minute (sccm) diluted with 130 sccm of nitrogen. A model diesel feed was pumped upwardly through the reactor at a rate of 13.4 ml per hour. Such conditions are hereinafter referred to as “reaction conditions.”
- Cycle 2 began, like Cycle 1 under reducing conditions; i.e., with treatment at 398.9° C. of the composition in hydrogen at a flow rate 300 sccm for one hour.
- a 70-gram quantity of a base (prepared by treating perlite with 15 nitric acid, and then adding alumina, zinc oxide, and kaolin clay) was impregnated with nickel in two steps using the conventional wet impregnation method. Each impregnation was with 74.3 grams of nickel nitrate hexahydrate in 7 grams of deionized water. After the first impregnation, the composition was dried at a temperature of 150° C. for 1 hour. After the second impregnation the composition was dried at 150° C. for 1 hour and calcined at 635° C. for 1 hour. The DI value for this composition was 12.2.
- Example III 10 grams of the composition as prepared in Example III were tested for desulfurization activity as described in Example II. The composition was tested over two reaction cycle with the results in Table II given in parts per million by weight of sulfur in the product after the first hour, second hour, third hour, and fourth hour of treatment, respectively. TABLE II Feed - 135 ppm Sulfur Time Cycle 1 (ppm S) Cycle 2 (ppm S) First Hour 80 72 Second Hour 90 95 Third Hour 91 101 Fourth Hour 97 106
- composition prepared by the inventive method in Example I removes sulfur just as well, if not better, than the compositions prepared in Examples III and V.
- a zinc oxide/alumina/perlite composition promoted with nickel was prepared.
- a 685-gram quantity of distilled water was mixed with 1007.5 grams of nickel nitrate hexahydrate.
- a 146-gram quantity of Condea Disperal alumina was then added to the mixture.
- 150 grams of perlite Silbrico Sil-Kleer #27-M was mixed with 575 grams of zinc oxide. This mixture was then added to the alumina mixture.
- the composition was then dried and calcined as disclosed in the previous examples.
- a 30-gram quantity of nickel diformate dihydrate was dissolved in 200 mL of concentrated ammonium hydroxide.
- a 45-gram quantity of zinc diformate dihydrate was then added to the above solution.
- 20 grams of alumina was then slowly stirred in. This solution was heated on a stirred hot plate until the ammonia left the solution.
- a 10-gram quantity of expanded crushed perlite was then added. This composition was filtered and washed and was then dried at 110° C. and was reduced at 300° C. for 1 hour.
- a composition as prepared in Example VIII was tested for its desulfurization activity as follows. 10 grams of the material as prepared were placed in a 1 ⁇ 2 inch diameter quartz tube having the length of about 12 inches and having a glass frit positioned above the lower 1 ⁇ 3 so as to provide an inner support for the bed of the composition.
- the composition was reduced at a temperature of 398° C. with a 300 cc/min flow of hydrogen. These conditions are hereinafter referred to as “reducing conditions”.
- reaction Conditions During each reaction cycle, the reactor is maintained at a temperature of 398° C. and a pressure of 15 psia. Hydrogen flow was at 80 cc/min. Nitrogen flow was 120 cc/min. A model diesel feed was pumped upwardly through the reactor at a rate of 72. cc/min. Such conditions are hereinafter referred to as “Reaction Conditions”.
- the diesel feed had a sulfur content of 135 parts per million (ppm) sulfur.
- Sulfur was in the form a 4,6-dimethyl dibenzothiophene. This compound is the most difficult sulfur-containing compound to remove due to steric hindrance.
- Each reaction cycle consisted of 4 hours with the product sulfur (ppm) for each cycle measured after 1, 2, 3 and 4 hours exposure to the feed.
- Cycle 2 began like cycle 1 under reducing conditions; i.e., with treatment at 398° C. of the composition in hydrogen at a flow rate of 300 cc/min for 1 hour.
- Example VIII was tested over 3 reaction cycles with regeneration occurring after cycles 1 and 2.
- Table IV were obtained where the values given are the parts per million by weight of sulfur for the product after the 1 st hour, 2 nd hour, 3 rd hour, and 4 th hour of treatment, respectively.
- a 300-gram quantity of nickel diformate dihydrate was dissolved in 2000 mL of a concentrated ammonium hydroxide solution.
- a 450 gram quantity of zinc diformate dihydrate was then added to the above solution.
- a 200-gram quantity of alumina was slowly stirred into the solution.
- the solution was then heated on a stirred hot plate until the ammonia was no longer in the solution.
- an 80-gram quantity of expanded crushed perlite was added to the solution.
- the solution was then filtered and washed and was then spray dried. The composition was reduced at 360° C. for 1 hour under a flow of hydrogen.
- Example X 10 grams of the composition as prepared in Example X were tested for desulfurization activity as described in Example IX. The composition was tested over 3 reaction cycles with the results in Table V given in parts per million by weight of sulfur in the product after the 1 st hour, 2 nd hour, 3 rd hour, and 4 th hour of treatment, respectively. TABLE V Spray-dried Composition Feed - 135 pm Sulfur Time Cycle 2 (ppm S) Cycle 3 (ppm S) First Hour 39 38 Second Hour 24 34 Third Hour 38 43 Fourth Hour 54 63
- microspheres A slurry containing alumina, perlite, zinc oxide, and water was spray dried to form microspheres. These microspheres were then impregnated with a nickel nitrate salt solution to give a nominal nickel loading of 17 weight percent. The impregnated microspheres were dried at 150° C. and calcined at 635° C.
- Example XII 10 grams of the composition as prepared in Example XII were tested for desulfurization activity as described in Example IX.
- the composition was tested over 3 reaction cycles with the results in Table VI given in parts per million by weight of sulfur in the product after the 1 st hour, 2 nd hour, 3 rd hour, and 4 th hour of treatment, respectively.
- TABLE VI Spray-dried Composition Feed - 135 pm Sulfur Time Cycle 2 (ppm S) Cycle 3 (ppm S) First Hour 54 44 Second Hour 65 71 Third Hour 81 89 Fourth Hour 88 99
- a 0.025-gram quantity of nitric acid was added to 440 mL of deionized water and was mixed for 5 minutes. Then, a 55.6-gram quantity of perlite was added to the nitric acid solution and was mixed for 20 minutes. Then, a 125-gram quantity of nickel hydroxide was added to the above solution and was mixed for 15 minutes. Then, a 43.6-gram quantity of kaolin clay was added to the solution and mixed for 5 minutes. After that, over 5 minutes, a 204.8-gram quantity of zinc oxide was added to the above solution and was mixed for 15 minutes. In a separate container, over a 5-minute time, a 56-gram quantity of alumina was added to 118.43 mL of water and was mixed for 20 minutes. Then, the alumina solution was poured into the zinc/nickel solution and was mixed for 15 minutes. The slurry was then spray dried. The composition was then dried at 150° C. for 1 hour and calcined at 635° C. for 1 hour.
- Example XIV 10 grams of the composition as prepared in Example XIV were tested for desulfurization activity as described in Example IX.
- the composition was tested over 3 reaction cycles with the results for the 2 nd and 3 rd cycles in Table VII given in parts per million by weight of sulfur in the product after the 1 st hour, 2 nd hours, 3 rd hour, and 4 th hour of treatment, respectively.
- TABLE VII Feed - 135 pm Sulfur Time Cycle 2 (ppm S) Cycle 3 (ppm S) First Hour 64 72 Second Hour 68 84 Third Hour 89 94 Fourth Hour 94 108
- a 0.026-gram quantity of nitric acid was added to 413.05 mL of water and was mixed for 5 minutes. Then, over a 5-minute period, a 74.01-gram quantity of perlite was added to the nitric acid solution and was mixed for 15 minutes. Then, over a 5-minute period, a 273.94-gram quantity of zinc oxide was added to the perlite solution and was mixed for 15 minutes. Then, over a 5-minute period, a 74.49-gram quantity of alumina was added to a 137.68 mL quantity of water and was mixed for 20 minutes. Then, over a 5-minute period, a 58.15-gram quantity of kaolin clay was added to the alumina solution and was mixed for 5 minutes.
- the perlite solution was poured into the alumina solution while mixing the alumina solution.
- the combined solution was then mixed for 15 minutes and was then spray dried.
- a 25-gram quantity of water was then added to the slurry.
- a 113-gram quantity of nickel nitrate hexahydrate with 10 grams of deionized water to dissolve was heated. This was then incorporated onto 120 grams of the alumina composition.
- the final composition was then dried at 150° C. for 1 hour and calcined at 635° C. for 1 hour.
- Example XVI 10 grams of the composition as prepared in Example XVI were tested for desulfurization activity as described in Example IX. The composition was tested over 3 reaction cycles with the results given in Table VIII in parts per million by weight of sulfur in the product after the 1 st hour, 2 nd hour, 3 rd hour, and 4 th hour of treatment, respectively.
- Table VIII in parts per million by weight of sulfur in the product after the 1 st hour, 2 nd hour, 3 rd hour, and 4 th hour of treatment, respectively.
- TABLE VII Feed - 135 pm Sulfur Time Cycle 2 (ppm S) Cycle 3 (ppm S) First Hour 61 74 Second Hour 80 99 Third Hour 94 108 Fourth Hour 97 114
Abstract
Description
- This application is a Continuation-in-Part of pending Application Ser. No. 10/625,366, filed Jul. 23, 2003.
- This invention relates to the removal of sulfur from hydrocarbon streams. In another aspect, this invention relates to compositions suitable for use in the desulfurization of fluid streams of cracked gasolines and diesel fuels. A further aspect of this invention relates to processes for the production of compositions for use in the removal of sulfur bodies from fluid streams of cracked gasolines and diesel fuels.
- The need for cleaner burning fuels has resulted in a continuing worldwide effort to reduce sulfur levels in hydrocarbon streams such as gasoline and diesel fuels. The reduction of sulfur in such hydrocarbon streams is considered to be a means for improving air quality because of the negative impact the sulfur has on performance of sulfur sensitive items such as automotive catalytic converters. The presence of oxides of sulfur in automotive engine exhaust inhibits and may irreversibly poison noble metal catalysts contained in the converter. Emissions from an inefficient or poisoned converter contain levels of non-combusted, non-methane hydrocarbons, oxides of nitrogen, and carbon monoxide. Such emissions are catalyzed by sunlight to form ground level ozone, more commonly referred to as smog.
- Thermally processed gasolines such as, for example, thermally cracked gasoline, visbreaker gasoline, coker gasoline and catalytically cracked gasoline (hereinafter collectively referred to as “cracked gasoline”) contains, in part, olefins, aromatics, sulfur, and sulfur containing compounds. Since most gasolines, such as, automobile gasolines, racing gasolines, aviation gasolines, boat gasolines, and the like contain a blend of, at least in part, cracked gasoline, reduction of sulfur in cracked gasoline will inherently serve to reduce the sulfur levels in most gasolines, such as, for example, automobile gasolines, racing gasolines, aviation gasolines, boat gasolines, and the like.
- The public discussion about gasoline sulfur has not centered on whether or not sulfur levels should be reduced. A consensus has emerged that lower sulfur gasoline reduces automotive emissions and improves air quality. Thus, the rules to date have focused on the required level of reduction, the geographical areas in need of lower sulfur gasoline, and the time frame for implementation.
- As the concern over the impact of automotive air pollution continues, it is clear that further effort to reduce the sulfur level in automotive fuels will be required. While the current gasoline products contain about 330 parts per million (ppm) sulfur, the US Environmental Protection Agency recently issued regulations requiring the average sulfur content in gasoline to be less than 30-ppm average with an 80-ppm cap. By 2008, the standards will effectively require every blend of gasoline sold in the United States to meet the 30-ppm level.
- In addition to the need to be able to produce low sulfur content automotive fuels, there is also a need for a process, which will have a minimal effect on the olefin content of such fuels so as to maintain the octane number (both research and motor octane number). Such a process would be desirable since saturation of olefins greatly affects the octane number. Such adverse effect on the olefin content is generally due to the severe conditions normally employed, such as during hydrodesulfurization, to remove thiophenic compounds (such as, for example, thiophenes, benzothiophenes, alkyl thiophenes, alkylbenzothiophenes, alkyl dibenzothiophenes and the like) which are some of the most difficult sulfur containing compounds to remove from cracked gasoline. In addition, there is a need to avoid a system wherein the conditions are such that the aromatic content of the cracked gasoline is lost through saturation. Thus, there is a need for a process, which achieves desulfurization and maintains the octane number.
- In addition to the need for removal of sulfur from cracked gasolines, there is a need for the petroleum industry to reduce the sulfur content in diesel fuels. In general, it is much harder to remove sulfur from diesel as compared to gasoline. In removing sulfur from diesel fuels by hydrodesulfurization, the cetane is improved but there is a large cost in hydrogen consumption. Such hydrogen is consumed by both hydrodesulfurization and aromatic hydrogenation reaction.
- Thus, there is a need for a desulfurization process without a significant consumption of hydrogen so as to provide a more economical process for the treatment of cracked gasolines and diesel fuels.
- As a result of the lack of success in providing a successful and economically feasible process for the reduction of sulfur levels in cracked gasolines and diesel fuels, it is apparent that there is a need for a better process for the desulfurization of such hydrocarbon streams which has minimal effect on octane levels while achieving high levels of sulfur removal.
- Traditionally, compositions used in processes for the removal of sulfur from hydrocarbon streams have been agglomerates used in fixed bed applications. Because of the various process advantages of fluidized beds, hydrocarbon streams are sometimes processed in fluidized bed reactors. Fluidized bed reactors have advantages over fixed bed reactors, such as, for example, better heat transfer and better pressure drop. Fluidized bed reactors generally use reactants that are particulate. The size of these particulates is generally in the range of from about 1 micron to about 1000 microns. However, the reactants used generally do not have sufficient attrition resistance for all applications. Consequently, finding a composition with sufficient attrition resistance that removes sulfur from these hydrocarbon streams and that can be used in fluidized, transport, moving, or fixed bed reactors and producing that composition in an economical manner is desirable and would be a significant contribution to the art and to the economy.
- It is thus an object of the present invention is to provide novel methods for the production of compositions, which are usable in the desulfurization of hydrocarbon streams.
- Another object of the present invention is to provide a process for the removal of sulfur from hydrocarbon streams, which minimizes the consumption of hydrogen and the saturation of olefins and aromatics contained in such streams.
- A still further object of the present invention is to provide an increased content of a promoter component in compositions, which facilitate the removal of sulfur from diesel fuel.
- A still further object of the present invention is to provide a desulfurized cracked gasoline that contains less than about 100 ppm, preferably less than 50 ppm, of sulfur based on the weight of the desulfurized cracked gasoline, and which contains essentially the same amount of olefins and aromatics as are in the cracked gasoline from which such desulfurized cracked gasoline was made. Another further object is to provide a desulfurized diesel fuel.
- The first embodiment of this invention includes a novel method for the production of a composition comprising:
- a) admixing: 1) a liquid, 2) a zinc-containing compound, 3) a silica-containing material, 4) alumina, and 5) a promoter so as to form a mixture thereof;
- b) drying the mixture so as to form a dried mixture;
- c) calcining the dried mixture so as to form a calcined mixture;
- d) reducing the calcined mixture with a suitable reducing agent under suitable conditions to produce a composition having a reduced valence promoter content therein, and e) recovering the composition.
- The second embodiment of this invention includes another novel method for the production of a composition comprising:
- a) admixing: 1) a liquid, 2) a metal-containing compound, 3) a silica-containing material, 4) alumina, and 5) a first promoter so as to form a mixture thereof;
- b) drying the mixture so as to form a dried mixture;
- c) incorporating a second promoter onto or into the dried mixture to form an incorporated mixture;
- d) drying the incorporated mixture to form a dried incorporated mixture;
- e) calcining the dried incorporated mixture to form a calcined promoted mixture;
- f) reducing the calcined promoted mixture with a suitable reducing agent under suitable conditions to produce a composition having a reduced valence promoter content therein; and
- g) recovering the composition.
- The third embodiment of this invention is a method comprising, consisting or, or consisting essentially of:
- (a) admixing: 1) a liquid, 2) a metal-containing compound, 3) a silica-containing material, and 4) a promoter so as to form a mixture thereof;
- (b) adding alumina to the mixture to form an alumina-containing mixture;
- (c) drying the alumina-containing mixture to form a dried mixture;
- (d) calcining the dried mixture to form a calcined mixture;
- (e) reducing the calcined mixture with a suitable reducing agent under suitable conditions to produce a composition having a reduced valence promoter content therein, and
- (f) recovering the composition.
- The fourth embodiment of this invention is a method comprising, consisting of, or consisting essentially of:
- (a) admixing: 1) a liquid, 2) a first metal formate, 3) a silica-containing material, 4) alumina, and 5) a second metal formate so as to form a mixture thereof;
- (b) drying the mixture to form a dried mixture;
- (c) calcining the dried mixture so as to form a calcined mixture; and
- (d) reducing the calcined mixture with a reducing agent under reducing conditions to provide a composition having a reduced valence promoter content therein, and
- (e) recovering said composition.
- The fifth embodiment of this invention includes a process for the removal of sulfur from a hydrocarbon stream comprising:
- a) contacting the hydrocarbon stream with a composition from the first or second, third or fourth embodiments in a desulfurization zone under conditions such that there is formed a desulfurized hydrocarbon stream and a sulfurized composition;
- b) separating the desulfurized hydrocarbon stream from the sulfurized composition thereby forming a separated desulfurized hydrocarbon stream and a separated sulfurized composition;
- c) regenerating at least a portion of the separated sulfurized composition in a regeneration zone to remove at least a portion of the sulfur contained therein and/or thereon thereby forming a regenerated composition;
- d) reducing the regenerated composition in a reduction zone so as to provide a reduced composition having a reduced valence promoter content therein which will effect the removal of sulfur from a hydrocarbon stream when contacted with same; and thereafter
- e) returning at least a portion of the reduced composition to the desulfurization zone.
- Other aspects, objectives, and advantages of the present invention will be apparent from the detailed description of the invention and the appended claims.
- The term “gasoline” denotes a mixture of hydrocarbons boiling in the range of from about 37.8° C. to about 260° C., or any fraction thereof. Examples of suitable gasoline include, but are not limited to, hydrocarbon streams in refineries such as naphtha, straight run naphtha, coker naphtha, catalytic gasoline, visbreaker naphtha, alkylate, isomerate, reformate, and the like and combinations thereof.
- The term “cracked gasoline” denotes a mixture of hydrocarbons boiling in the range of from about 37.8° C. to about 260° C., or any fraction thereof, that are products from either thermal or catalytic processes that crack larger hydrocarbon molecules into smaller molecules. Examples of suitable thermal processes include, but are not limited to, coking, thermal cracking, visbreaking, and the like and combinations thereof. Examples of suitable catalytic cracking processes include, but are not limited to, fluid catalytic cracking, heavy oil cracking, and the like and combinations thereof. Thus, examples of suitable cracked gasoline include, but are not limited to, coker gasoline, thermally cracked gasoline, visbreaker gasoline, fluid catalytically cracked gasoline, heavy oil cracked gasoline, and the like and combinations thereof. In some instances, the cracked gasoline may be fractionated and/or hydrotreated prior to desulfurization when used as a hydrocarbon stream in the process of the present invention.
- The term “diesel fuel” denotes a mixture of hydrocarbons boiling in the range of from about 148.9° C. to about 398.9° C., or any fraction thereof. Examples of suitable diesel fuels include, but are not limited to, light cycle oil, kerosene, jet fuel, straight-run diesel, hydrotreated diesel, and the like and combinations thereof.
- The term “sulfur” denotes sulfur in any form such as elemental sulfur or a sulfur compound normally present in a hydrocarbon-containing fluid such as cracked gasoline or diesel fuel. Examples of sulfur which can be present during a process of the present invention usually contained in a hydrocarbon stream, include, but are not limited to, hydrogen sulfide, carbonyl sulfide (COS), carbon disulfide (CS2), mercaptans (RSH), organic sulfides (R—S—R), organic disulfides (R—S—S—R), thiophenes, substituted thiophenes, organic trisulfides, organic tetrasulfides, benzothiophenes, alkyl thiophenes, alkyl benzothiophenes, alkyl dibenzothiophenes, and the like and combinations thereof as well as the heavier molecular weights of same which are normally present in a diesel fuel of the types contemplated for use in a process of the present invention, wherein each R can be an alkyl or cycloalkyl or aryl group containing one carbon atom to ten carbon atoms.
- The term “fluid” denotes gas, liquid, vapor, and combinations thereof.
- The term “gaseous” denotes that state in which the hydrocarbon-containing fluid, such as cracked-gasoline or diesel fuel, is primarily in a gas or vapor phase.
- The term “attrition resistance” denotes the attrition resistance of a composition produced by the inventive method(s). The term “Davison Index” (“DI”) refers to a measure of a composition's resistance to particle size reduction under controlled conditions of turbulent motion. The higher the value of the measured DI, the lower the attrition resistance of the composition.
- The term “attrition-resistance-enhancing component” denotes any component, which can be added to a composition made by the methods of the present invention to enhance the attrition resistance of such composition compared to a composition, which does not contain such attrition-resistance-enhancing component. Examples of a suitable attrition-resistance-enhancing component include, but are not limited to, clays, high alumina cements, natural cements, portland cement, calcium aluminate, calcium silicate, talc, and the like and combinations thereof. The term “clay” denotes any clay, which can be used as an attrition-resistance-enhancing component of a composition of the present invention. Examples of a suitable clay include, but are not limited to, bentonite, sodium bentonite, acid-washed bentonite, atapulgite, china clay, kaolinite, montmorillonite, illite, halloysite, hectonite, sepiolite, and the like and combinations thereof. Preferably, such attrition-resistance-enhancing component comprises clay. More preferably, such attrition-resistance-enhancing component is selected from the group consisting of bentonite, sodium bentonite, acid-washed bentonite, and the like and combinations thereof. Most preferably, such attrition-resistance-enhancing component is bentonite.
- The term “metal” denotes metal in any form such as elemental metal or a metal-containing compound. The metal-containing compound, which is a separate component from the promoter component in the composition(s) produced from the inventive methods can have a metal selected from the group consisting of zinc, manganese, silver, copper, cadmium, tin, lanthanum, scandium, cerium, tungsten, molybdenum, iron, niobium, tantalum, gallium, indium, and combinations of any two or more thereof. In the method of the first embodiment, preferably a zinc-containing compound is used, producing a composition containing a zinc oxide.
- The term “metal formate”, as used herein, denotes a compound formed by at least one metal ion and at least one formate ion. A formate ion is a carbon atom with bonds to a hydrogen atom and two oxygen atoms with one of the oxygen atoms having a double bond to the carbon atom.
- The term “metal oxide”, as used herein, denotes any oxide of a metal.
- The term “metal oxide” also denotes metal oxide in any form such as a metal oxide or a metal oxide precursor.
- The metal oxide will preferably be present in the composition produced by the inventive method in an amount in the range of from about 10 to about 90 weight percent metal oxide based on the total weight of the inventive composition, more preferably in an amount in the range of from about 30 to about 80 weight percent metal oxide, and most preferably in an amount in the range of from about 40 to about 70 weight percent metal oxide.
- The term “promoter” denotes any component, which when added to the composition of the present invention, helps promote the desulfurization of hydrocarbon streams. Such promoters can be at least one metal, metal oxide, precursor for the metal oxide, solid solution of more than one metal, or alloy of more than one metal wherein the metal component is selected from the group consisting of nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony, vanadium, gold, platinum, ruthenium, iridium, chromium, palladium, titanium, zirconium, rhodium, rhenium, and combinations of any two or more thereof. In the fourth embodiment, the promoter is added to the composition in the form of a second metal formate.
- Some examples of promoter metal containing compounds include metal acetates, metal carbonates, metal nitrates, metal sulfates, metal thiocyanates, and the like and combinations thereof. Preferably, the metal of the promoter is nickel.
- The composition having a reduced valence promoter content is a composition that has the ability to react chemically and/or physically with sulfur. It is also preferable that the composition removes diolefins and other gum forming compounds from cracked gasoline.
- During the preparation of a composition of the present invention, the promoter, selected from the group consisting of metals, metal oxides, and the like, and combinations thereof may initially be in the form of a metal-containing compound and/or a metal oxide precursor. It should be understood that when the promoter is initially a metal-containing compound and/or a metal oxide precursor, a portion of, or all of, such compound and/or precursor may be converted to the corresponding metal or metal oxide of such compound and/or precursor during the inventive process disclosed herein.
- Typically, the common oxidation state of the promoter is combined with the metal oxide portion of the inventive composition produced by the inventive methods. The number of oxygen atoms associated with the promoter must be reduced to form a reduced valence promoter. Consequently, at least a portion of the promoter present in the inventive composition must be present as a reduced valence promoter. While not wishing to be bound by theory, it is believed that the reduced valence promoter can chemisorb, cleave, or remove sulfur. Thus, either the number of oxygen atoms associated with the promoter is reduced or the oxidation state of the promoter is a zero-valent metal. For example, if nickel is the promoter metal, nickel oxide (NiO) can be used and the reduced valence nickel (promoter metal) can be either nickel metal (Ni0) or a non-stoichiometric nickel oxide having a formula of NiO(1-x) wherein 0<x<1. If tungsten is the promoter, tungsten oxide (WO3) can be used and the reduced valence tungsten (promoter metal) can be either tungsten oxide (WO3), tungsten metal (W0), or a non-stoichiometric tungsten oxide having a formula of WO(3-y) wherein 0<y<3.
- Preferably, the promoter is present in an amount, which will effect the removal of sulfur from the hydrocarbon stream when contacted with the composition under desulfurization conditions. Of the total quantity of the promoter present in the inventive composition, it is preferred for at least about 10 weight percent of the promoter to be present in the form of a reduced valence promoter, more preferably at least about 40 weight percent of the promoter is a reduced valence promoter, and most preferably at least 80 weight percent of the promoter is a reduced valence promoter for best activity in sulfur removal. The reduced valence promoter will generally be present in the inventive composition in an amount in the range of from about 1 to about 60 weight percent reduced valence promoter based on the total weight of the inventive composition, preferably in an amount in the range of from about 5 to about 40 weight percent reduced valence promoter, and most preferably in an amount in the range of from 8 to 20 weight percent reduced valence promoter for best activity in sulfur removal. When the promoter comprises a bimetallic promoter, the bimetallic promoter should comprise a ratio of the two metals forming such bimetallic promoter in the range of from about 20:1 to about 1:20.
- The silica-containing material used in the preparation of, and present in the compositions produced by the inventive methods may be either in the form of silica or in the form of one or more silica-containing materials.
- Any suitable silica-containing material may be employed in the composition such as, for example, diatomite, expanded perlite, colloidal silica, silica gel, precipitated silica, and the like, and combinations thereof. In addition, silicon compounds that are convertible to silica such as silicic acid, ammonium silicate, and the like, and combinations thereof can also be employed.
- More preferably the silica-containing material is in the form of crushed expanded perlite. The term “perlite” as used herein is the petrographic term for a siliceous volcanic rock, which naturally occurs in certain regions throughout the world. The distinguishing feature, which sets it apart from other volcanic minerals, is its ability to expand four to twenty times its original volume when heated to certain temperatures. When heated above 871.1° C., crushed perlite expands due to the presence of combined water within the crude perlite rock. The combined water vaporizes during the heating process and creates countless tiny bubbles in the heat softened glassy particles. The glass sealed bubbles account for its light weight. Expanded perlite can be crushed to produce a porosity enhancing powder with a weight as little as 2.5 lbs per cubic foot.
- The typical elemental analysis of expanded perlite is: silicon 33.8%, aluminum 7%, potassium 3.5%, sodium 3.4%, calcium 0.6%, magnesium 0.2%, iron 0.6%, trace elements 0.2%, oxygen (by difference) 47.5%, and bound water 3%.
- Typical physical properties of expanded perlite are: softening point 1600-2000° F., fusion point 2300-2450° F., pH 6.6-6.8, and specific gravity 2.2-2.4.
- The term “crushed expanded perlite” or “milled expanded perlite” as used herein denotes that form of expanded perlite which has first been subjected to milling so as to yield a particle size of about 20 microns to about 500 microns, and then heated with a flame at a temperature of about 871.1° C., and finally subjected to crushing in a hammer mill. While not wishing to be bound to any particular theory, it is believed that the shape of the crushed expanded perlite impacts the activity of the final composition produced by the inventive methods.
- The compositions produced by the inventive methods contain an aluminum-containing material selected from the group consisting of alumina, aluminate, and combinations thereof. Alumina can be used to produce the compositions. The alumina employed in the preparation of the compositions can be any suitable commercially available aluminum-containing substance of which at least a portion can be converted to an aluminate upon calcinations. Examples include, but are not limited to, aluminum chlorides, aluminum nitrates, colloidal alumina solutions, hydrated aluminas, peptized aluminas, and, generally, those alumina compounds produced by the dehydration of alumina hydrates. The preferred alumina is hydrated alumina such as, for example, bohemite or pseudobohemite for best activity and sulfur removal. When a composition is exposed to high temperatures (e.g., during calcinations) at least a portion, preferably a substantial portion of the alumina can be converted to an aluminate, preferably a zinc aluminate spinel.
- The aluminum-containing material will preferably be present in a composition produced by the inventive methods in an amount in the range of from about 1.0 to about 30 weight percent, preferably in an amount in the range of from about 5 to about 25 weight percent, and most preferably, in the range of from 10 to 22 weight percent, based on the total weight of the composition.
- The silica-containing material will preferably be present in a composition produced by the inventive methods in an amount in the range of from about 10 to about 40 weight percent silica-containing material based on the total weight of the composition, more preferably in an amount in the range of from about 12 to about 35 weight percent, and most preferably in the range of from 15 to 30 weight percent.
- The composition can be a particulate in the form of one of granules, extrudates, tablets, spheres, pellets, or microspheres. Preferably, the particulate is a fluidizable microsphere.
- In accordance with the first embodiment of the present invention, a composition can be produced by the following inventive method.
- a) admixing: 1) a liquid, 2) a zinc-containing compound, 3) a silica-containing material, 4) alumina, and 5) a promoter so as to form a mixture thereof;
- b) drying the mixture to form a dried mixture;
- c) calcining the dried mixture to form a calcined mixture;
- d) reducing the calcined mixture with a suitable reducing agent under suitable conditions to produce a composition having a reduced valence promoter content therein, and
- e) recovering the composition.
- In the inventive production method of the first embodiment, the composition can generally be prepared by admixing a liquid, a zinc-containing compound, a silica-containing material, alumina, and a promoter in appropriate proportions by any suitable method or manner which provides for the intimate mixing of such components to thereby provide a substantially homogenous mixture thereof comprising a liquid, a zinc-containing compound, a silica-containing material, alumina, and a promoter. Optionally, an attrition-resistance-enhancing component can also be added to the mixture. The term “admixing,” as used herein, denotes mixing components in any order and/or any combination or sub-combination. However, in the embodiment in which a liquid, a metal-containing compound, a silica-containing material, and a promoter are admixed, alumina is added to the mixture after all the other components. Any suitable means for admixing the components of the composition can be used to achieve the desired dispersion of such components. Examples of suitable admixing include, but are not limited to, mixing tumblers, stationary shelves or troughs, Eurostar mixers, which are of the batch or continuous type, impact mixers, and the like. It is presently preferred to use a Eurostar mixer in the admixing of the components of the inventive composition.
- The liquid can be any solvent capable of dispersing a metal-containing compound, a silica-containing material, alumina, and a promoter, and, preferably, the liquid can be selected from the group consisting of water, ethanol, acetone and combinations of any two or more thereof. Most preferably, the liquid is water.
- The metal-containing compound (preferably a zinc-containing compound) used in the preparation of a composition in the first, second, and third embodiments of the present inventive method can either be in the form of a metal oxide or in the form of one or more metal compounds that are convertible to a metal oxide under the conditions of preparation described herein. Examples of suitable metal compounds include, but are not limited to, a metal sulfide, a metal sulfate, a metal hydroxide, a metal nitrate, a metal formate and the like and combinations thereof. Preferably, the metal-containing compound is in the form of a powdered metal oxide.
- When the particulation is achieved, preferably by spray drying, a dispersant component can optionally be utilized and can be any suitable compound that helps to promote the spray drying ability of the mix, which is preferably in the form of a slurry. In particular, these components are useful in preventing deposition, precipitation, settling, agglomerating, adhering, and caking of solid particles in a fluid medium. Suitable dispersants include, but are not limited to, condensed phosphates, sulfonated polymers, and combinations thereof. The term “condensed phosphates” refers to any dehydrated phosphate containing more than one phosphorus atom and having a phosphorus-oxygen-phosphorus bond. Specific examples of suitable dispersants include sodium pyrophosphate, sodium metaphosphate, sulfonated styrene maleic anhydride polymer, and combinations thereof. The amount of dispersant component used is generally in the range of from about 0.01 weight percent based on the total weight of the components to about 10 weight percent. Preferably, the amount of the dispersant component used is generally in the range of from about 0.1 weight percent to about 8 weight percent.
- In preparing the preferred spray dried composition, an acid component can be used. In general, the acid in the acid component can be an organic acid or a mineral acid such as nitric acid. If the acid component is an organic acid, it is preferred to be a carboxylic acid. If the acid component is a mineral acid, it is preferred to be a nitric acid or a phosphoric acid. Mixtures of these acids can also be used. Generally, the acid is used with water to form a dilute aqueous acid solution. The amount of acid in the acid component is generally in the range of from about 0.01 volume percent based on the total volume of the acid component to about 20 volume percent.
- Generally, the spray-dried material has a mean particle size in the range of from about 10 micrometers to about 1000 micrometers, preferably in the range of from about 20 micrometers to from about 150 micrometers.
- The term “mean particle size” refers to the size of the particulate material as determined by using a RO-TAP® Testing Sieve Shaker, manufactured by W. S. Tyler Inc., of Mentor, Ohio, or other comparable sieves. The material to be measured is placed in the top of a nest of standard 8-inch diameter stainless steel framed sieves with a pan on the bottom. The material undergoes sifting for a period of about 10 minutes; thereafter, the material retained on each sieve is weighed. The percent retained on each sieve is calculated by dividing the weight of the material retained on a particular sieve by the weight of the original sample. This information is used to compute the mean particle size.
- The mixture is then dried to form a dried mixture. The drying conditions, as referred to herein, can include a temperature in the range of from about 65.5° C. to about 550° C., preferably in the range of from about 87.8° C. to about 210° C. and, most preferably, in the range of from 93.3° C. to 176.7° C. Such drying conditions can also include a time period generally in the range of from about 0.5 hour to about 60 hours, preferably in the range of from about 1 hour to about 40 hours, and most preferably, in the range of from 1.5 hours to 20 hours. Such drying conditions can also include a pressure generally in the range of from about atmospheric (i.e., about 14.7 pounds per square inch absolute) to about 150 pounds per square inch absolute (psia), preferably in the range of from about atmospheric to about 100 psia and, most preferably about atmospheric, so long as the desired temperature can be maintained. Any drying method(s) known to one skilled in the art such as, for example, air drying, heat drying, and the like and combinations thereof can be used. Preferably, heat drying is used.
- The dried mixture is then calcined to form a calcined mixture. Preferably, the dried mixture is calcined in an oxidizing atmosphere such as in the presence of oxygen or air. The calcining conditions, as referred to herein, can include a temperature in the range of from about 204.4° C. to about 815.5° C., preferably in the range of from about 426.7° C. to about 815.5° C. and, more preferably, in the range of from 482.2° C. to 760° C. Such calcining conditions can also include a pressure, generally in the range of from about 7 psia to about 750 psia, preferably in the range of from about 7 psia to about 450 psia and, most preferably, in the range of from 7 psia to 150 psia, and a time period in the range of from about 1 hour to about 60 hours, preferably for a time period in the range of from about 1 hour to about 20 hours and, most preferably, for a time period in the range of from 1 hour to 15 hours. In the process of this invention, the calcination can convert at least a portion of the alumina to an aluminate.
- The calcined mixture is thereafter subjected to reduction with a suitable reducing agent, preferably hydrogen, so as to produce a composition having a substantially reduced valence promoter content therein, preferably a substantially zero-valent promoter content therein, with such zero-valent promoter being present in an amount sufficient to permit the removal of sulfur from a hydrocarbon stream such as cracked gasoline or diesel fuel, according to the process disclosed herein.
- The reduction conditions can include a temperature in the range of from about 37.8° C. to about 815.5° C., a pressure in the range of from about 15 psia to about 1500 psia and for a time sufficient to permit the formation of a reduced valence promoter.
- The composition is then recovered.
- In accordance with the second embodiment of the present invention, the composition can also be produced by the following inventive method;
- a) admixing: 1) a liquid, 2) a metal-containing compound, 3) a silica-containing material, 4) alumina, and 5) a first promoter so as to form a mixture thereof;
- b) drying the mixture to form a dried mixture;
- c) incorporating a second promoter onto or into the dried mixture to form an incorporated mixture;
- d) drying the incorporated mixture to form a dried incorporated mixture;
- e) calcining the dried incorporated mixture to form a calcined promoted mixture;
- f) reducing the calcined promoted mixture with a suitable reducing agent under suitable conditions to produce a composition having a reduced valence promoter content therein; and
- g) recovering the composition.
- In the production of a composition of the present invention, the composition can generally be prepared by admixing a liquid, a metal-containing compound, a silica-containing material, alumina, and a first promoter in appropriate proportions by any suitable methods or manner which provides for the intimate mixing of such components to thereby provide a substantially homogenous mixture comprising a liquid (as described above), a metal-containing compound, a silica-containing material, alumina, and a promoter. Any suitable means for admixing these components, as described above, can be used to achieve the desired dispersant of such components.
- The metal in the metal-containing compound is selected from the group consisting of zinc, manganese, silver, copper, cadmium, tin, lanthanum, scandium, cerium, tungsten, molybdenum, iron, niobium, tantalum, gallium, indium, and combinations of any two or more thereof. Preferably, the metal is zinc.
- The metal-containing compound used in the preparation of a composition of the present inventive method can either be in the form of a metal oxide or in the form of one or more metal compounds that are convertible to a metal oxide under the conditions of preparation described herein. Examples of suitable metal-containing compounds include, but are not limited to, a metal sulfide, metal sulfate, metal hydroxide, metal carbonate, metal acetate, metal nitrate, and the like and combinations thereof. -Preferably, the metal-containing compound is in the form of a powdered metal oxide.
- The components are mixed to provide a mixture which can be in the form selected from the group consisting of a wet mix, dough, paste, slurry, and the like. Preferably, the mixture is in the form of a slurry. Such mixture can then optionally be shaped by densifying, extruding, or spray drying to form a particulate selected from the group consisting of a granule, an extrudate, a tablet, a sphere, a pellet, or a microsphere, as described above.
- The mixture is then dried to form a dried mixture, according to the drying conditions described above.
- The dried mixture comprising a metal-containing compound, a silica-containing material, and alumina (or an aluminate), is then incorporated with a second promoter. Optionally, the dried mixture can be calcined before the incorporation of the second promoter, according to the calcining conditions described above.
- The terms “first promoter” and “second promoter” distinguish between promoter components that are added to the mixture at different times. Both components can be comprised of the same element (i.e., nickel) or each can be comprised of different elements (i.e., the first promoter can comprise nickel and the second promoter can comprise cobalt). Together, the first promoter and the second promoter comprise the promoter component present in the recovered composition of the second embodiment.
- The second promoter can be incorporated into or onto the dried mixture by any suitable means or method known in the art for incorporating a promoter into or onto a substrate material.
- A preferred method of incorporating is to impregnate using any conventional wetness impregnation technique (i.e. essentially completely or partially filling the pores of a substrate material with a solution of the incorporating elements) for impregnating a substrate. This preferred method uses an impregnating solution comprising the desirable concentration of a promoter to ultimately provide an incorporated mixture that can then be subjected to drying and calcining (which can convert at least a portion of the alumina to an aluminate) followed by reduction with a reducing agent such as hydrogen.
- A preferred impregnating solution comprises a solution formed by dissolving a metal containing compound, preferably such metal containing compound is in the form of a metal salt such as a metal chloride, a metal nitrate, a metal sulfate, and the like and combinations thereof, in a solvent such as water, alcohols, esters, ethers, ketones, and combinations thereof. Preferably, the weight ratio of metal promoter to the solvent of such solution can be in the range of from about 1:1 to about 4:1 but, more preferably it is in the range of from 1.5:1 to 3:1. It is preferred for the particulates to be impregnated with a nickel component by use of a solution containing nickel nitrate hexahydrate dissolved in water.
- Following the incorporating of the dried mixture, preferably by impregnation, with a second promoter, the resulting incorporated mixture is then subjected to drying under drying conditions, as described above, to form a dried incorporated mixture, and calcined under calcining conditions, as described above, to form a calcined incorporated mixture. The calcined incorporated mixture can then be subjected to reduction with a reducing agent, as described above, to thereby provide the composition. The composition can then be recovered.
- The third embodiment of this invention is a method comprising, consisting or, or consisting essentially of:
- (a) admixing: 1) a liquid, 2) a metal-containing compound, 3) a silica-containing material, and 4) a promoter so as to form a mixture thereof;
- (b) adding alumina to the mixture to form an alumina-containing mixture;
- (c) drying the alumina-containing mixture to form a dried mixture;
- (d) calcining the dried mixture to form a calcined mixture;
- (e) reducing the calcined mixture with a suitable reducing agent under suitable conditions to produce a composition having a reduced valence promoter content therein, and
- (f) recovering the composition.
- In the production of a composition in the third embodiment, the composition can generally be prepared by admixing a liquid, a metal-containing compound, a silica-containing materials, and a promoter. The components can generally be admixed in the manner described above. The metal-containing compound used is the same as described for the second embodiment above.
- The mixture can be in the form selected from the group consisting of a wet mix, dough, paste, slurry, and the like.
- Once the components described above are mixed together, alumina can then be added to the mixture, to form an alumina-containing mixture.
- The alumina-containing mixture is then dried and calcined, as described above.
- In accordance with the fourth embodiment of the present invention, the composition can also be produced by the following inventive method:
- (a) admixing: 1) a liquid, 2) a first metal formate, 3) a silica-containing material, 4) alumina, and 5) a second metal formate so as to form a mixture thereof;
- (b) drying the mixture to form a dried mixture;
- (c) calcining the dried mixture so as to form a calcined mixture; and
- (d) recovering said composition.
- The composition can generally be prepared by admixing (in the manner described above) a liquid, a first metal formate, a silica-containing material, alumina, and a second metal formate to form a mixture thereof.
- The metals in the first and second metal formates can be different or they can be the same. Preferably, the first metal format is a zinc formate and the second metal formate is a nickel formate.
- In the fourth embodiment, the promoter is in the form of a metal formate. Also in the fourth embodiment, the above-listed components of the composition are mixed to provide a mixture which can be in the form selected from the group consisting of a wet mix, dough, paste, slurry and the like. Preferably, the mixture is in the form of a slurry. Such mixture can then be shaped to form a particulate selected from the group consisting of a granule, an extrudate, a tablet, a sphere, a pellet, or a microsphere.
- Preferably, the liquid is ammonium hydroxide or ammonia.
- After mixing, the mixture is dried and calcined, as described above.
- The fifth embodiment of this invention includes a novel process for the removal of sulfur from a hydrocarbon stream. This process comprises:
- a) contacting the hydrocarbon stream with a composition of the first or second embodiments of the present invention in a desulfurization zone under conditions such that there is formed a desulfurized hydrocarbon stream and a sulfurized composition;
- b) separating the desulfurized hydrocarbon stream from the sulfurized composition thereby forming a separated desulfurized hydrocarbon stream and a separated sulfurized composition;
- c) regenerating at least a portion of the separated sulfurized composition in a regeneration zone so as to remove at least a portion of the sulfur contained therein and/or thereon thereby forming a regenerated composition;
- d) reducing the regenerated composition in a reduction zone so as to provide a reduced composition having a reduced valence promoter content therein which will effect the removal of sulfur from a hydrocarbon stream when contacted with same; and thereafter
- e) returning at least a portion of the reduced composition to the desulfurization zone.
- The contacting, in step a), of the hydrocarbon stream with the composition prepared by the methods of the first or second embodiments in the desulfurization zone can be by any method known to those skilled in the art.
- The desulfurization zone can be any zone wherein desulfurization of a hydrocarbon stream can take place. Examples of suitable zones are fixed bed reactors, moving bed reactors, fluidized bed reactors, transport reactors, and the like. Presently a fluidized bed reactor or a fixed bed reactor is preferred.
- The desulfurization zone of step a) includes the following conditions: total pressure, temperature, weight hourly space velocity, and hydrogen flow. These conditions are such that the inventive composition can desulfurize the hydrocarbon stream to produce a desulfurized hydrocarbon stream and a sulfurized composition.
- The total pressure can be in the range of from about 15 pounds per square inch absolute (psia) to about 1500 psia. However, it is presently referred that the total pressure be in a range of from about 50 psia to about 500 psia.
- In general, the temperature should be sufficient to keep the hydrocarbon stream in essentially a vapor or gas phase. While such temperatures can be in the range of from about 37.8° C. to about 537.8° C., it is presently preferred that the temperature be in the range of from about 204.4° C. to about 426.7° C. when treating a cracked-gasoline, and in the range of from about 260° C. to about 482.2° C. when treating a diesel fuel.
- Weight hourly space velocity (“WHSV”) is defined as the numerical ratio of the rate at which a hydrocarbon stream is charged to the desulfurization zone in pounds per hour at standard conditions of temperature and pressure (STP) divided by the pounds of composition contained in the desulfurization zone to which the hydrocarbon stream is charged. In the practice of the present invention, such WHSV should be in the range of from about 0.5 hr.−1 to about 50 hrs.−1, preferably in the range of from about 1 hr.−1 to about 50 hrs.−1.
- Any suitable hydrocarbon stream, which comprises, consists of, or consists essentially of sulfur containing hydrocarbons can be used as the feed to be contacted with the inventive composition. The hydrocarbon stream preferably comprises, consists of, or consists essentially of a fuel selected from the group consisting of a cracked gasoline, diesel fuel, and combinations thereof.
- The amount of sulfur in the hydrocarbon stream can be in the range of from about less than 10-ppm sulfur by weight of the hydrocarbon stream to about 50,000 ppm. When the hydrocarbon stream is cracked gasoline, the amount of sulfur can be in the range of from about less than 10 ppm sulfur by weight of the cracked gasoline to about 10,000 ppm sulfur by weight of the cracked gasoline. When the hydrocarbon stream is diesel fuel, the amount of sulfur can be in the range of from about less than 10 ppm sulfur by weight of the diesel fuel to about 50,000 ppm sulfur by weight of the diesel fuel.
- As used herein, the terms “sulfur” or “ppmw sulfur” denotes the amount of atomic sulfur (about 32 atomic mass units) contained in the sulfur-containing hydrocarbons of the hydrocarbon stream, based on the total weight of the hydrocarbon stream, not the atomic mass, or weight, of a sulfur compound, such as an organo-sulfur compound.
- The cracked gasoline or diesel fuel, suitable as a feed in a process of the present invention, is a composition that contains, in part, olefins, aromatics, sulfur, paraffins and naphthenes.
- The amount of olefins in cracked gasoline is generally in the range of from about 10 to about 3 5 weight percent olefins based on the total weight of the cracked gasoline. For diesel fuel there is essentially no olefin content.
- The amount of aromatics in cracked gasoline is generally in the range of from about 20 to about 40 weight percent aromatics based on the total weight of the cracked gasoline. The amount of aromatics in diesel fuel is generally in the range of from about 10 to about 90 weight percent aromatics based on the total weight of the diesel fuel.
- In carrying out the desulfurization step of a process of the present invention, it is preferred that the hydrocarbon stream be in a gas or vapor phase. However, in the practice of the present invention, it is not essential that such hydrocarbon stream be totally in a gas or vapor phase.
- In carrying out the desulfurizing step, it is presently preferred that an agent be employed which interferes with any possible chemical or physical reacting of the olefinic or aromatic compounds in the hydrocarbon stream which is being treated with the inventive composition. Preferably such agent is hydrogen.
- Hydrogen flow in the desulfurization zone is generally such that the mole ratio of hydrogen to the hydrocarbon stream is the range of from about 0.1 to about 10, preferably in the range of from about 0.2 to about 3.
- If desired, during the desulfurization of the cracked gasoline or diesel fuel, diluents such as methane, carbon dioxide, flue gas, nitrogen, and the like and combinations thereof can be used. Thus, it is not essential to the practice of the present invention that a high purity hydrogen be employed in achieving the desired desulfurization of the hydrocarbon stream such as, but not limited to, cracked gasoline or diesel fuel.
- It is presently preferred when utilizing a fluidized bed reactor system that a composition be used having a particle size in the range of from about 10 micrometers to about 1000 micrometers. Preferably, such composition should have a particle size in the range of from about 20 micrometers to about 500 micrometers, and, more preferably, in the range of from 30 micrometers to 400 micrometers. When a fixed bed reactor system is employed for the practice of a desulfurization process of the present invention, the composition should generally have a particle size in the range of about {fraction (1/32)} inch to about ½ inch diameter, preferably in the range of from about {fraction (1/32)} inch to about ¼ inch diameter.
- It is further presently preferred to use a composition having a surface area in the range of about 1 square meter per gram (m2/g) to about 1000 square meters per gram of composition, preferably in the range of from about 1 m2/g to about 800 m2/g.
- The desulfurized hydrocarbon stream can be separated from the sulfurized composition by any appropriate separation method known in the art thereby forming a separated desulfurized hydrocarbon stream and a separated sulfurized composition.
- Examples of such means are cyclonic devices, settling chambers, impingement devices for separating solids and gases, and the like and combinations thereof. Separation can include, but is not limited to, allowing the hydrocarbon stream to flow out of the desulfurization zone. The desulfurized gaseous cracked gasoline or desulfurized gaseous diesel fuel, can then be recovered and preferably liquefied. Liquification of such desulfurized hydrocarbon streams can be accomplished by any manner known in the art.
- The amount of sulfur in the desulfurized hydrocarbon stream, following treatment in accordance with a desulfurization process of the present invention, is less than about 500 ppm sulfur by weight of hydrocarbon stream, preferably less than about 150 ppm sulfur by weight of hydrocarbon stream, and more preferably less than about 50 ppm sulfur by weight of hydrocarbon stream.
- In carrying out the process of the present invention, if desired, a stripper unit can be inserted before and/or after the regeneration of the sulfurized composition. Such stripper will serve to remove a portion, preferably all, of any hydrocarbon from the sulfurized composition. Such stripper can also serve to remove oxygen and sulfur dioxide from the system prior to the introduction of the regenerated composition into the reduction zone. The stripping comprises a set of conditions that include total pressure, temperature, and a stripping agent partial pressure.
- Preferably, the total pressure in the stripper when employed is in the range of from about 25 psia to about 500 psia.
- Temperature for such stripping can be in the range of from about 7.8° C. to about 537.8° C.
- The stripping agent is a composition that helps to remove hydrocarbon from the sulfurized composition. Preferably, the stripping agent is nitrogen. The sulfurized composition can have sulfur contained therein (for example, within the pores of the composition) or thereon (for example, located on the surface of the composition).
- The regeneration zone employs a set of conditions that includes total pressure and sulfur removing agent partial pressure. The total pressure is generally in the range of from about 25 psia to about 50 psia.
- The sulfur removing agent partial pressure is generally in the range of from about 1% to about 25% of the total pressure.
- The sulfur-removing agent is a composition that helps to generate gaseous sulfur containing compounds and oxygen containing compounds such as sulfur dioxide, as well as to burn off any remaining hydrocarbon deposits that might be present. The preferred sulfur removing agent suitable for use in the regeneration zone is selected from oxygen containing gases such as, but not limited to, air.
- The temperature in the regeneration zone is generally in the range of from about 37.8° C. to about 815.5° C., preferably in the range of from about 426.7° C. to about 648.9° C.
- The regeneration zone can be any vessel wherein the desulfurizing or regeneration of the sulfurized composition can take place.
- The regenerated composition is then reduced in a reduction zone with a reducing agent including, but not limited to, hydrogen, so that at least a portion of the promoter content of the composition is reduced to produce a reduced composition having a reduced valence promoter content to permit the removal of sulfur from the hydrocarbon stream according to the inventive process disclosed herein.
- In general, when practicing the present invention, reduction of the desulfurized composition is carried out at a temperature in the range of from about 37.8° C. to about 815.5° C. and at a pressure in the range of from about 15 psia to about 1500 psia. Such reduction is carried out for a time sufficient to achieve the desired level of promoter reduction of the promoter, which is preferably contained in the skin of the composition. Such reduction can generally be achieved in a time period in the range of from about 0.01 hour to about 20 hours.
- Following the reduction of the regenerated composition, at least a portion of the resulting reduced composition can be returned to the desulfurization zone.
- In carrying out the process of the present invention, the steps of desulfurization, regeneration, reduction, and optionally stripping before and/or after such regeneration can be accomplished in the single zone or vessel or in multiple zones or vessels.
- When carrying out the process of the present invention in a fixed bed reactor system, the steps of desulfurization, regeneration, reduction, and optionally stripping before and/or after such regeneration are accomplished in a single zone or vessel.
- The desulfurized cracked gasoline can be used in the formulation of gasoline blends to provide gasoline products suitable for commercial consumption and can also be used where a cracked gasoline containing low levels of sulfur is desired.
- The desulfurized diesel fuel can be used in the formulation of diesel fuel blends to provide diesel fuel products.
- A zinc oxide/alumina/perlite composition promoted with nickel was prepared. A 56-gram quantity of Vista Dispal alumina was added to 118.43 grams of deionized water and was mixed for 20 minutes. Then, a 43.6-gram quantity of a base (prepared by treating perlite with nitric acid, and then adding alumina, zinc oxide and kaolin clay) was added to the mixture of water and alumina over a 5-minute period and was mixed for five additional minutes. This mixture will be referred to hereinafter as Mixture #1.
- Meanwhile, a 0.03-gram quantity of nitric acid was added to 473.73 grams of deionized water and was mixed for five minutes. Then, over a Five-minute period, a 55.6-gram quantity of perlite (Silbrico Sil-Kleer #27-M) was added to the nitric acid solution and was mixed for 20 minutes. Then, over a 5-minute period, a 198-gram quantity of nickel nitrate was added to the perlite solution and was mixed for 15 minutes. This mixture will be referred to hereinafter as Mixture #2.
- Mixture #2 was then poured into Mixture #1 and was then mixed for 10 minutes. Then, a 204.8-gram quantity of zinc oxide was added to the mixture over a five minute period and was then mixed for an additional 15 minutes. The zinc oxide mixture was spray dried, and then dried in an oven.
- A 100-gram quantity of the zinc oxide mixture was impregnated via an ultra-sonic nozzle with a combination of 87.5 grams of nickel nitrate hexahydrate plus 13.75 grams of deionized water. The impregnated mixture was dried at 150° C. for 1 hour and calcined at 635° C. for 1 hour. The Davison Index (DI) value for this composition was 10.3.
- The composition as prepared in Example I was tested for its desulfurization activity as follows. 10 grams of the material as prepared was placed in a ½ inch diameter quartz tube having a length of about 12 inches and having a glass frit positioned above the lower one-third so as to provide an inert support for the bed of the composition.
- During each reaction cycle, the reactor was maintained at a temperature of 398.9° C. and a pressure of 15 pounds per square inch absolute (psia). Hydrogen flow was at 130 standard cubic centimeters per minute (sccm) diluted with 130 sccm of nitrogen. A model diesel feed was pumped upwardly through the reactor at a rate of 13.4 ml per hour. Such conditions are hereinafter referred to as “reaction conditions.”
- The diesel feed had a sulfur content of 135 parts per million (ppm) sulfur. The sulfur was in the form of 4,6-dimethyl dibenzothiophene. This compound is the most difficult sulfur-containing compound to remove due to steric hindrance.
- Before Cycle 1 was initiated, the composition was reduced with hydrogen flowing at a rate of 300 sccm at a temperature of 398.9° C. for a period of one hour. Such conditions are hereinafter referred to as “reducing conditions.” Each reaction cycle consisted of four hours with the product sulfur (ppm) for each cycle measured after one, two, three, and four hours of exposure to the feed.
- After completion of the reaction cycle, the composition was flushed with 180-sccm nitrogen at 398.9° C. for fifteen minutes. The temperature was then raised to 537.8° C. where the composition was regenerated under 120-sccm air and 180-sccm nitrogen for two hours. The temperature was then decreased to 398.9° C. and the sample purged with nitrogen for 15 minutes. Such conditions are hereinafter referred to as “regeneration conditions.” Cycle 2 began, like Cycle 1 under reducing conditions; i.e., with treatment at 398.9° C. of the composition in hydrogen at a flow rate 300 sccm for one hour.
- The composition of Example I was tested over two reaction cycles with regeneration occurring after Cycle 1. The results in Table I were obtained where the values given are the parts per million by weight of sulfur in the product after the first hour, second hour, third hour, and fourth hour of treatment, respectively.
TABLE I Feed: 135 ppm Sulfur Time Cycle 1 (ppm S) Cycle 2 (ppm S) First Hour 65 47 Second Hour 82 76 Third Hour 86 90 Fourth Hour 91 98 - A 70-gram quantity of a base (prepared by treating perlite with 15 nitric acid, and then adding alumina, zinc oxide, and kaolin clay) was impregnated with nickel in two steps using the conventional wet impregnation method. Each impregnation was with 74.3 grams of nickel nitrate hexahydrate in 7 grams of deionized water. After the first impregnation, the composition was dried at a temperature of 150° C. for 1 hour. After the second impregnation the composition was dried at 150° C. for 1 hour and calcined at 635° C. for 1 hour. The DI value for this composition was 12.2.
- 10 grams of the composition as prepared in Example III were tested for desulfurization activity as described in Example II. The composition was tested over two reaction cycle with the results in Table II given in parts per million by weight of sulfur in the product after the first hour, second hour, third hour, and fourth hour of treatment, respectively.
TABLE II Feed - 135 ppm Sulfur Time Cycle 1 (ppm S) Cycle 2 (ppm S) First Hour 80 72 Second Hour 90 95 Third Hour 91 101 Fourth Hour 97 106 - An 85-gram quantity of a base (as described in Examples I and III) was impregnated with nickel in one step using the conventional wet impregnation method. The impregnation was with 74.3 grams of nickel nitrate hexahydrate in 7 grams deionized water. The composition was dried at 150° C. for 1 hour and calcined at 635° C. for 1 hour. The DI value for this composition was 14.7.
- 10 grams of the composition as prepared in Example V were tested for desulfurization activity as described in Example II. The composition was tested over two reaction cycles with the results in Table III given in parts per million by weight of sulfur in the product after the first hour, second hour, third hour, and fourth hour of treatment, respectively.
TABLE III Feed - 135 ppm Sulfur Time Cycle 1 (ppm S) Cycle 2 (ppm S) First Hour 67 63 Second Hour 76 94 Third Hour 81 105 Fourth Hour 89 108 - Based upon the results, the composition prepared by the inventive method in Example I removes sulfur just as well, if not better, than the compositions prepared in Examples III and V.
- A zinc oxide/alumina/perlite composition promoted with nickel was prepared. A 685-gram quantity of distilled water was mixed with 1007.5 grams of nickel nitrate hexahydrate. A 146-gram quantity of Condea Disperal alumina was then added to the mixture. Meanwhile, 150 grams of perlite (Silbrico Sil-Kleer #27-M) was mixed with 575 grams of zinc oxide. This mixture was then added to the alumina mixture. The composition was then dried and calcined as disclosed in the previous examples.
- A 30-gram quantity of nickel diformate dihydrate was dissolved in 200 mL of concentrated ammonium hydroxide. A 45-gram quantity of zinc diformate dihydrate was then added to the above solution. 20 grams of alumina was then slowly stirred in. This solution was heated on a stirred hot plate until the ammonia left the solution. A 10-gram quantity of expanded crushed perlite was then added. This composition was filtered and washed and was then dried at 110° C. and was reduced at 300° C. for 1 hour.
- A composition as prepared in Example VIII was tested for its desulfurization activity as follows. 10 grams of the material as prepared were placed in a ½ inch diameter quartz tube having the length of about 12 inches and having a glass frit positioned above the lower ⅓ so as to provide an inner support for the bed of the composition.
- The composition was reduced at a temperature of 398° C. with a 300 cc/min flow of hydrogen. These conditions are hereinafter referred to as “reducing conditions”.
- During each reaction cycle, the reactor is maintained at a temperature of 398° C. and a pressure of 15 psia. Hydrogen flow was at 80 cc/min. Nitrogen flow was 120 cc/min. A model diesel feed was pumped upwardly through the reactor at a rate of 72. cc/min. Such conditions are hereinafter referred to as “Reaction Conditions”.
- The diesel feed had a sulfur content of 135 parts per million (ppm) sulfur. Sulfur was in the form a 4,6-dimethyl dibenzothiophene. This compound is the most difficult sulfur-containing compound to remove due to steric hindrance.
- Each reaction cycle consisted of 4 hours with the product sulfur (ppm) for each cycle measured after 1, 2, 3 and 4 hours exposure to the feed.
- After completion of the reaction cycle, the composition was flushed with 180-cc/min nitrogen at 398° C. for 15 minutes. The temperature was then raised to 549° C. where the composition was regenerated under a flow of air at 50 cc/min and nitrogen at 180 cc/min for 2 hours. The temperature was then decreased to 398° C. and the sample purged with nitrogen for 15 minutes. Such conditions are hereinafter referred to as “Regeneration Conditions”. Cycle 2 began like cycle 1 under reducing conditions; i.e., with treatment at 398° C. of the composition in hydrogen at a flow rate of 300 cc/min for 1 hour.
- The composition of Example VIII was tested over 3 reaction cycles with regeneration occurring after cycles 1 and 2. The results in Table IV were obtained where the values given are the parts per million by weight of sulfur for the product after the 1st hour, 2nd hour, 3rd hour, and 4th hour of treatment, respectively.
TABLE IV Granulated Composition Feed - 135 pm Sulfur Time Cycle 2 (ppm S) Cycle 3 (ppm S) First Hour 7 8 Second Hour 4 8 Third Hour 8 17 Fourth Hour 33 46 - A 300-gram quantity of nickel diformate dihydrate was dissolved in 2000 mL of a concentrated ammonium hydroxide solution. A 450 gram quantity of zinc diformate dihydrate was then added to the above solution. A 200-gram quantity of alumina was slowly stirred into the solution. The solution was then heated on a stirred hot plate until the ammonia was no longer in the solution. Then, an 80-gram quantity of expanded crushed perlite was added to the solution. The solution was then filtered and washed and was then spray dried. The composition was reduced at 360° C. for 1 hour under a flow of hydrogen.
- 10 grams of the composition as prepared in Example X were tested for desulfurization activity as described in Example IX. The composition was tested over 3 reaction cycles with the results in Table V given in parts per million by weight of sulfur in the product after the 1st hour, 2nd hour, 3rd hour, and 4th hour of treatment, respectively.
TABLE V Spray-dried Composition Feed - 135 pm Sulfur Time Cycle 2 (ppm S) Cycle 3 (ppm S) First Hour 39 38 Second Hour 24 34 Third Hour 38 43 Fourth Hour 54 63 - A slurry containing alumina, perlite, zinc oxide, and water was spray dried to form microspheres. These microspheres were then impregnated with a nickel nitrate salt solution to give a nominal nickel loading of 17 weight percent. The impregnated microspheres were dried at 150° C. and calcined at 635° C.
- 10 grams of the composition as prepared in Example XII were tested for desulfurization activity as described in Example IX. The composition was tested over 3 reaction cycles with the results in Table VI given in parts per million by weight of sulfur in the product after the 1st hour, 2nd hour, 3rd hour, and 4th hour of treatment, respectively.
TABLE VI Spray-dried Composition Feed - 135 pm Sulfur Time Cycle 2 (ppm S) Cycle 3 (ppm S) First Hour 54 44 Second Hour 65 71 Third Hour 81 89 Fourth Hour 88 99 - A 0.025-gram quantity of nitric acid was added to 440 mL of deionized water and was mixed for 5 minutes. Then, a 55.6-gram quantity of perlite was added to the nitric acid solution and was mixed for 20 minutes. Then, a 125-gram quantity of nickel hydroxide was added to the above solution and was mixed for 15 minutes. Then, a 43.6-gram quantity of kaolin clay was added to the solution and mixed for 5 minutes. After that, over 5 minutes, a 204.8-gram quantity of zinc oxide was added to the above solution and was mixed for 15 minutes. In a separate container, over a 5-minute time, a 56-gram quantity of alumina was added to 118.43 mL of water and was mixed for 20 minutes. Then, the alumina solution was poured into the zinc/nickel solution and was mixed for 15 minutes. The slurry was then spray dried. The composition was then dried at 150° C. for 1 hour and calcined at 635° C. for 1 hour.
- 10 grams of the composition as prepared in Example XIV were tested for desulfurization activity as described in Example IX. The composition was tested over 3 reaction cycles with the results for the 2nd and 3rd cycles in Table VII given in parts per million by weight of sulfur in the product after the 1st hour, 2nd hours, 3rd hour, and 4th hour of treatment, respectively.
TABLE VII Feed - 135 pm Sulfur Time Cycle 2 (ppm S) Cycle 3 (ppm S) First Hour 64 72 Second Hour 68 84 Third Hour 89 94 Fourth Hour 94 108 - A 0.026-gram quantity of nitric acid was added to 413.05 mL of water and was mixed for 5 minutes. Then, over a 5-minute period, a 74.01-gram quantity of perlite was added to the nitric acid solution and was mixed for 15 minutes. Then, over a 5-minute period, a 273.94-gram quantity of zinc oxide was added to the perlite solution and was mixed for 15 minutes. Then, over a 5-minute period, a 74.49-gram quantity of alumina was added to a 137.68 mL quantity of water and was mixed for 20 minutes. Then, over a 5-minute period, a 58.15-gram quantity of kaolin clay was added to the alumina solution and was mixed for 5 minutes. Then, over a 5-minute period, the perlite solution was poured into the alumina solution while mixing the alumina solution. The combined solution was then mixed for 15 minutes and was then spray dried. A 25-gram quantity of water was then added to the slurry. A 113-gram quantity of nickel nitrate hexahydrate with 10 grams of deionized water to dissolve was heated. This was then incorporated onto 120 grams of the alumina composition. The final composition was then dried at 150° C. for 1 hour and calcined at 635° C. for 1 hour.
- 10 grams of the composition as prepared in Example XVI were tested for desulfurization activity as described in Example IX. The composition was tested over 3 reaction cycles with the results given in Table VIII in parts per million by weight of sulfur in the product after the 1st hour, 2nd hour, 3rd hour, and 4th hour of treatment, respectively.
TABLE VII Feed - 135 pm Sulfur Time Cycle 2 (ppm S) Cycle 3 (ppm S) First Hour 61 74 Second Hour 80 99 Third Hour 94 108 Fourth Hour 97 114 - While this invention has been described in detail for the purpose of illustration, it should not be construed as limited thereby but intended to cover all changes and modifications within the spirit and scope thereof.
Claims (62)
Priority Applications (7)
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US10/914,798 US20050020446A1 (en) | 2003-07-23 | 2004-08-10 | Desulfurization and novel process for same |
JP2007525741A JP2008510035A (en) | 2004-08-10 | 2005-08-09 | Desulfurization and novel process for it |
EP05784424A EP1799794A4 (en) | 2004-08-10 | 2005-08-09 | Desulfurization and novel process for same |
PCT/US2005/028277 WO2006020642A2 (en) | 2004-08-10 | 2005-08-09 | Desulfurization and novel process for same |
RU2007108545/04A RU2393919C2 (en) | 2004-08-10 | 2005-08-09 | Desulphuration and novel desulphuration method |
CN2005800342008A CN101432398B (en) | 2004-08-10 | 2005-08-09 | Desulfurization and novel process for same |
BRPI0514299A BRPI0514299B1 (en) | 2004-08-10 | 2005-08-09 | methods for producing compositions and processes for removing sulfur from a hydrocarbon stream |
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US10/625,366 US7351328B2 (en) | 2003-07-23 | 2003-07-23 | Desulfurization and novel process for same |
US10/914,798 US20050020446A1 (en) | 2003-07-23 | 2004-08-10 | Desulfurization and novel process for same |
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US10/625,366 Continuation-In-Part US7351328B2 (en) | 2003-07-23 | 2003-07-23 | Desulfurization and novel process for same |
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EP (1) | EP1799794A4 (en) |
JP (1) | JP2008510035A (en) |
CN (1) | CN101432398B (en) |
BR (1) | BRPI0514299B1 (en) |
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EP1799794A4 (en) | 2010-06-09 |
CN101432398B (en) | 2012-03-28 |
EP1799794A2 (en) | 2007-06-27 |
BRPI0514299B1 (en) | 2016-03-29 |
RU2393919C2 (en) | 2010-07-10 |
BRPI0514299A (en) | 2008-06-10 |
JP2008510035A (en) | 2008-04-03 |
WO2006020642A3 (en) | 2009-06-04 |
CN101432398A (en) | 2009-05-13 |
WO2006020642A2 (en) | 2006-02-23 |
RU2007108545A (en) | 2008-09-20 |
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