US20040140244A1 - Desulfurization and sorbents for same - Google Patents
Desulfurization and sorbents for same Download PDFInfo
- Publication number
- US20040140244A1 US20040140244A1 US10/738,141 US73814103A US2004140244A1 US 20040140244 A1 US20040140244 A1 US 20040140244A1 US 73814103 A US73814103 A US 73814103A US 2004140244 A1 US2004140244 A1 US 2004140244A1
- Authority
- US
- United States
- Prior art keywords
- sulfur
- range
- diesel fuel
- sorbent composition
- weight percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000002594 sorbent Substances 0.000 title claims abstract description 233
- 238000006477 desulfuration reaction Methods 0.000 title claims description 97
- 230000023556 desulfurization Effects 0.000 title claims description 97
- 239000000203 mixture Substances 0.000 claims abstract description 201
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 137
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 112
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 103
- 239000002283 diesel fuel Substances 0.000 claims abstract description 91
- 229910052751 metal Inorganic materials 0.000 claims abstract description 87
- 239000002184 metal Substances 0.000 claims abstract description 87
- 239000011787 zinc oxide Substances 0.000 claims abstract description 54
- 239000010451 perlite Substances 0.000 claims abstract description 52
- 235000019362 perlite Nutrition 0.000 claims abstract description 52
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 51
- 229910052717 sulfur Inorganic materials 0.000 claims description 161
- 239000011593 sulfur Substances 0.000 claims description 161
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 111
- 238000000034 method Methods 0.000 claims description 97
- 230000008569 process Effects 0.000 claims description 87
- 229930195733 hydrocarbon Natural products 0.000 claims description 64
- 150000002430 hydrocarbons Chemical class 0.000 claims description 63
- 230000002829 reductive effect Effects 0.000 claims description 60
- 239000004215 Carbon black (E152) Substances 0.000 claims description 59
- 229910052757 nitrogen Inorganic materials 0.000 claims description 56
- 239000011701 zinc Substances 0.000 claims description 41
- 239000001257 hydrogen Substances 0.000 claims description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 36
- 230000008929 regeneration Effects 0.000 claims description 23
- 238000011069 regeneration method Methods 0.000 claims description 23
- 229910052725 zinc Inorganic materials 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 230000005484 gravity Effects 0.000 claims description 14
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 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
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 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 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
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 5
- 239000003502 gasoline Substances 0.000 abstract description 78
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 42
- 230000009467 reduction Effects 0.000 abstract description 23
- 238000005470 impregnation Methods 0.000 abstract description 8
- 229910000480 nickel oxide Inorganic materials 0.000 abstract description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 2
- 150000004763 sulfides Chemical class 0.000 abstract description 2
- 150000003464 sulfur compounds Chemical class 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 description 43
- 238000001035 drying Methods 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 25
- 238000001354 calcination Methods 0.000 description 23
- 239000002245 particle Substances 0.000 description 23
- -1 methane hydrocarbons Chemical class 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- 239000007787 solid Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000009835 boiling Methods 0.000 description 17
- 229910001868 water Inorganic materials 0.000 description 16
- 229910044991 metal oxide Inorganic materials 0.000 description 14
- 150000004706 metal oxides Chemical class 0.000 description 14
- 239000006104 solid solution Substances 0.000 description 13
- 239000007921 spray Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000000446 fuel Substances 0.000 description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 9
- 230000004913 activation Effects 0.000 description 8
- 238000001994 activation Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000001694 spray drying Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 239000004005 microsphere Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 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
- 238000002360 preparation method Methods 0.000 description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000003009 desulfurizing effect Effects 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229930192474 thiophene Natural products 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000012702 metal oxide precursor Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 3
- WUCBICXOWNTEAT-UHFFFAOYSA-N [O--].[O--].[Ni++].[Zn++] Chemical compound [O--].[O--].[Ni++].[Zn++] WUCBICXOWNTEAT-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 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 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 241000640882 Condea Species 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
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 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
- 238000010926 purge Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 108010083687 Ion Pumps Proteins 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 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
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 230000008859 change Effects 0.000 description 1
- 238000004939 coking Methods 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
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 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
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 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
- 150000002576 ketones Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910001510 metal chloride 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
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-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
- 150000008427 organic disulfides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 235000020030 perry Nutrition 0.000 description 1
- 239000003208 petroleum Substances 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
- 229920000058 polyacrylate Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012956 testing procedure Methods 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
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
Definitions
- This invention relates to the removal of sulfur from fluid streams of cracked-gasolines and diesel fuels.
- this invention relates to sorbent compositions suitable for use in the desulfurization of fluid streams of cracked-gasolines and diesel fuels.
- a further aspect of this invention relates to a process for the production of sulfur sorbents 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.
- Such adverse effect on olefin content is generally due to the severe condition 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 be removed from cracked-gasoline.
- thiophenic compounds such as, for example, thiophenes, benzothiophenes, alkyl thiophenes, alkylbenzothiophenes, alkyl dibenzothiophenes and the like
- sorbent compositions used in processes for the removal of sulfur from hydrocarbon-containing fluids have been agglomerates utilized in fixed bed applications. Because of the various process advantages of fluidized beds, hydrocarbon-containing fluids are sometimes used in fluidized bed reactors. Fluidized bed reactors have advantages over fixed bed reactors such as better heat transfer and better pressure drop. Fluidized bed reactors generally use reactants that are particulates. The size of these particulates is generally in the range of about 1 micron to about 1000 microns. However, the reactants used generally do not have sufficient attrition resistance for all applications. Consequently, finding a sorbent with sufficient attrition resistance that removes sulfur from these hydrocarbon-containing fluids and that can be used in fluidized, transport, moving, or fixed bed reactors is desirable and would be of significant contribution to the art and to the economy.
- Another object of the present invention is to provide a process for the production of novel sorbent compositions which are useful in the desulfurization of cracked-gasolines and diesel fuels.
- Another object of the present invention is to provide a process for the removal of sulfur from cracked-gasolines and diesel fuels which minimizes the consumption of hydrogen and minimizes the saturation of olefins and aromatics contained in such streams.
- a still further object of the present invention is to provide a desulfurized cracked-gasoline that contains less than about 100 parts per million, preferably less than 50 parts per million, 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.
- the present invention is based upon my discovery that through the utilization of expanded perlite to form a sorbent base composition comprising zinc oxide, expanded perlite and alumina, there is provided a novel base composition for the formation of a sorbent system by the addition of a promoter metal thereto which permits both the control of the attrition value of the resulting sorbent system and the control of the sorbent system activity.
- a novel sorbent composition suitable for the desulfurization of cracked-gasolines and diesel fuels which comprises a base support component consisting essentially of zinc oxide, expanded perlite, alumina, and a promoter component wherein the valence of such promoter component is substantially reduced and such reduced-valence promoter component is present in an amount which is effective in the removal of sulfur from cracked-gasolines or diesel fuels.
- a process for the preparation of a novel sorbent system which comprises contacting a base support consisting essentially of zinc oxide, expanded perlite, and alumina so as to form a mixture thereof selected from the group consisting of a wet mix, a dough, a paste, or a slurry; particulating such mixture so as to form a particulate selected from the group consisting of a granule, an extrudate, a tablet, a sphere, a pellet, or a microsphere; drying such particulate to form a dried particulate; calcining such dried particulate to form a calcined particulate; distributing a promoter component upon such dried and calcined particulate to form a promoted particulate; drying such promoted particulate to form a dried promoted particulate; calcining such dried promoted particulate to form a calcined promoted particulate; and reducing such calcined promoted part
- the attrition resistance of the sorbent composition can be enhanced by varying the concentration of the alumina component in the base support.
- the life of the sorbent system for the desulfurization of cracked-gasolines or diesel fuels is controlled through the control of the zinc oxide content of the base support component of the sorbent system.
- an oxidized (i.e., unreduced) sorbent composition which can be made by the sorbent preparation process summarized above, absent the steps after calcination of the promoted particulate.
- the oxidized sorbent composition can comprise all or part of the following components: zinc oxide; expanded perlite; a substitutional solid metal oxide solution characterized by the formula M X Zn Y O wherein M is a promoter metal and X and Y are each numerical values in the range of from 0.01 to 0.99; and a promoter metal-zinc aluminate substitutional solid solution characterized by the formula M Z Zn (1-Z) Al 2 O 4 wherein M is the promoter metal and Z is a numerical value in the range of from 0.01 to 0.99.
- a reduced sorbent composition which can be made by the sorbent preparation process summarized above.
- the reduced sorbent composition can comprise all or part of the following components: zinc oxide; expanded perlite; a substitutional solid metal solution characterized by the formula M A Zn B wherein M is a promoter metal and A and B are each numerical values in the range of from 0.01 to 0.99; and a promoter metal-zinc aluminate substitutional solid solution characterized by the formula M Z Zn (1-Z) Al 2 O 4 wherein M is the promoter metal and Z is a numerical value in the range of from 0.01 to 0.99.
- a process for the desulfurization of cracked-gasolines and diesel fuels which comprises desulfurizing in a desulfurization zone such a hydrocarbon-containing fluid with a sorbent composition, separating the desulfurized hydrocarbon-containing fluid from the sulfurized sorbent composition, regenerating at least a portion of the sulfurized sorbent composition to produce a regenerated, desulfurized sorbent composition; activating at least a portion of the regenerated, desulfurized sorbent composition to produce an activated, regenerated, desulfurized sorbent composition; and thereafter returning at least a portion of the activated, regenerated, desulfurized sorbent composition to the desulfurization zone.
- a low-sulfur diesel fuel composition comprising less than about 50 ppmw sulfur and at least about 20 ppmw nitrogen, wherein the low-sulfur diesel fuel has been produced via a desulfurization process comprising the step of contacting a diesel feed containing sulfur and nitrogen with a sorbent composition under desulfurization conditions sufficient to remove sulfur from the diesel feed, wherein the sorbent composition comprises zinc oxide and a promoter metal component.
- a desulfurization process for removing sulfur from a hydrocarbon-containing feed comprising sulfur and nitrogen.
- the desulfurization process comprises the step of contacting the hydrocarbon-containing feed with a sorbent composition in a desulfurization zone under desulfurization conditions sufficient to remove at least about 80 weight percent of the sulfur and less than about 50 weight percent of the nitrogen from the hydrocarbon-containing feed, thereby providing a desulfurized hydrocarbon-containing product and a sulfurized sorbent composition.
- a desulfurization process for removing sulfur from a diesel feed comprising at least about 100 ppmw sulfur and at least about 25 ppmw nitrogen.
- the desulfurization process comprises the steps of: (a) contacting the diesel feed with a reduced sorbent composition in a desulfurization zone under desulfurization conditions sufficient to remove at least about 90 weight percent of the sulfur and less than about 40 weight percent of the nitrogen from the diesel feed, thereby providing a desulfurized diesel fuel and a sulfurized sorbent composition; (b) contacting at least a portion of the sulfurized sorbent composition with an oxygen-containing regeneration stream in a regeneration zone under regeneration conditions sufficient to remove sulfur from the sulfurized sorbent composition, thereby providing an oxidized sorbent composition; (c) contacting at least a portion of the oxidized sorbent composition with a hydrogen-containing reducing stream in a reducing zone under reducing conditions sufficient to reduce the oxidized sorbent composition, thereby
- the present invention is based upon the discovery by applicant that through the use of milled expanded perlite in the formation of a sorbent support comprising zinc oxide, milled expanded perlite, and a binder there was produced a base support in which the zinc oxide content and binder content could be adjusted so as to provide an attrition resistance sorbent as well as the extension of the useful life of the sorbent system.
- gasoline denotes a mixture of hydrocarbons boiling in the range of from about 100° F. to about 400° F., 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 100° F. to about 400° F., 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-containing fluid in a process of the present invention.
- diesel fuel denotes a mixture of hydrocarbons boiling in the range of from about 300° F. to about 750° F., 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-containing fluid, 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), thiophene, substituted thiophenes, organic trisulfides, organic tetrasulfides, benzothiophene, alkyl thiophenes, alkyl benzothiophenes, alkydibenzothiophenes, 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
- 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.
- the term “attrition resistance” denotes the attrition resistance of a sorbent composition of the present invention measured as the Davison Index.
- the term “Davison Index” (“DI”) refers to a measure of a sorbent's resistance to particle size reduction under controlled conditions of turbulent motion.
- the Davison Index represents the weight percent of the over 20 micrometer particle size fraction which is reduced to particle sizes of less than 20 micrometers under test conditions.
- the Davison Index is measured using a Jet cup attrition determination method.
- the Jet cup attrition determination method involves screening a 5 gram sample of sorbent to remove particles in the 0 to 20 micrometer size range.
- DI Davison Index
- Correction factor (presently 0.3) is determined by using a known calibration standard to adjust for differences in jet cup dimensions and wear.
- support component denotes any component or combination of such components which can be used as a support for a sorbent composition of the present invention to help promote the desulfurization process disclosed herein.
- suitable support component include, but are not limited to, zinc oxide in association with a suitable binder such as alumina and expanded perlite.
- a presently preferred support component is that comprising zinc oxide, expanded perlite, and alumina.
- promoter component denotes any component which can be added to the sorbent composition of the present invention to help promote the desulfurization of cracked-gasolines or diesel fuels.
- promoter components are at least one metal, metal oxide, or precursor for the metal oxide wherein the metal component is selected from the group consisting essentially of nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony, and vanadium.
- promoter metal-containing compounds include metal acetates, metal carbonates, metal nitrates, metal sulfates, metal thiocyanates, and the like and combinations thereof.
- the metal of such promoter component is nickel.
- the sorbent composition is promoted with a precursor of a nickel oxide such as nickel nitrate, more preferably nickel nitrate hexahydrate.
- metal denotes metal in any form such as elemental metal or a metal-containing compound.
- metal oxide denotes metal oxide in any form such as a metal oxide or a metal oxide precursor.
- the promoter component 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 component 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.
- 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.
- crushed perlite expands due to the presence of combined water with the crude perlite rock. The combined water vaporizes during the heating process and creates countless tiny bubbles in the heat softened glassy particles. It is these diminutive glass sealed bubbles which account for its light weight.
- Expanded perlite can be manufactured to weigh as little as 2.5 lbs per cubic foot.
- Typical chemical analysis 1 properties of expanded perlite are: silicon dioxide 73%, aluminum oxide 17%, potassium oxide 5%, sodium oxide 3%, calcium oxide 1%, plus trace elements.
- Typical physical properties of expanded perlite are: softening point 1600-2000° F., fusion point 2300° F.-2450° F., pH 6.6-6.8, and specific gravity 2.2-2.4.
- expanded perlite refers to the spherical form of perlite which has been expanded by heating the perlite siliceous volcanic rock to a temperature above 1600° F.
- particle expanded perlite or “milled perlite” as used herein denotes that form of expanded perlite which has been subjected to crushing so as to form a particulate mass wherein the particle size of such mass is comprised of at least 97% of particles having a size of less than 2 microns.
- milled expanded perlite is intended to mean the product resulting from subjecting expanded perlite particles to milling or crushing.
- the zinc oxide will generally be present in the sorbent support composition in an amount in the range of from about 10 to about 90 weight percent zinc oxide based on the total weight of the sorbent composition, preferably in an amount in the range of from about 40 to about 80 weight percent zinc oxide.
- the zinc oxide used in the preparation of a sorbent support composition of the present invention can either be in the form of zinc oxide or in the form of one or more zinc compounds that are convertible to zinc oxide under the conditions of preparation described herein.
- suitable zinc compounds include, but are not limited to, zinc sulfide, zinc sulfate, zinc hydroxide, zinc carbonate, zinc acetate, zinc nitrate, and the like and combinations thereof.
- the zinc oxide is in the form of powdered zinc oxide.
- the alumina used in preparing a sorbent support composition of the present invention can be any suitable commercially available alumina material including, but not limited to, colloidal alumina solutions and generally those alumina compounds produced by the dehydration of alumina hydrates.
- alumina in the range of about 1.0 to about 20 weight percent, preferably an amount in the range of about 5 to about 15 weight percent, based on the total weight of the sorbent support component.
- the expanded perlite will generally be present in the sorbent support composition in an amount in the range of from about 10 to about 40 weight percent perlite based on the weight of the sorbent support composition, preferably in an amount in the range of from about 15 to about 30 weight percent.
- the promoter component will generally be present in the sorbent composition in an amount in the range of from about 1.0 to about 60 weight percent promoter component based on the total weight of the sorbent composition, preferably in an amount in the range of from about 10 to about 30 weight percent promoter component.
- the bimetallic promoter component should comprise a ratio of the two metals forming such bimetallic promoter component in the range of from about 20:1 to about 1:20.
- the promoter component is a bimetallic promoter component comprising nickel and cobalt in a weight ratio of about 1:1.
- the support component is generally prepared by combining the components of the support component, zinc oxide, expanded perlite, and alumina in appropriate proportions by any suitable method or manner which provides for the intimate mixing of such components to thereby provide a substantially homogeneous mixture comprising zinc oxide, expanded perlite, and alumina.
- Any suitable means for mixing the components of the support component can be used to achieve the desired dispersion of such components.
- suitable mixing means include, but are not limited to, mixing tumblers, stationary shells or troughs, Muller mixers, which are of the batch or continuous type, impact mixers, and the like. It is presently preferred to use a Muller mixer in the mixing of the components of the support component.
- the components of the support component are mixed to provide a resulting mixture which can be in a form selected from the group consisting of wet mix, dough, paste, slurry, and the like. Such resulting 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.
- the wet mix can be densified, dried under a drying condition as disclosed herein, calcined under a calcining condition as disclosed herein, and thereafter shaped, or particulated, through the granulation of the densified, dried, calcined mix to form granulates.
- such mixture when the mixture of the components of the support component results in a form of a mixture which is either in a dough state or paste state, such mixture can then be shaped, preferably extruded, to form a particulate, preferably cylindrical extrudates having a diameter in the range of from about ⁇ fraction (1/32) ⁇ inch to 1 ⁇ 2 inch and any suitable length, preferably a length in the range of from about 1 ⁇ 8 inch to about 1 inch.
- the resulting particulates, preferably cylindrical extrudates are then dried under a drying condition as disclosed herein and then calcined under a calcining condition as disclosed herein.
- the particulation of such slurry is achieved by spray drying the slurry to form microspheres thereof having a size in the range of from about 20 to about 500 microns.
- Such microspheres are then subjected to drying under a drying condition as disclosed herein and calcining under a calcining condition as disclosed herein.
- a dispersant component may 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 condensed phosphates, sulfonated polymers, and combinations thereof.
- condensed phosphates refers to any dehydrated phosphate where the H 2 O:P 2 O 5 is less than about 3:1.
- Suitable dispersants include sodium pyrophosphate, sodium metaphosphate, sulfonated styrene maleic anhydride polymer, and combinations thereof.
- the amount of a 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.
- the amount of a dispersant component used is generally in the range of from about 0.1 weight percent to about 8 weight percent.
- the alumina component of the base support can be any suitable compound of alumina that has cement-like properties which can help to bind the particulate composition together.
- alumina preferably peptized alumina.
- the sorbent composition be formed through spray drying.
- an acid component can be used.
- the acid component can be an organic acid or a mineral 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.
- a base support component comprising zinc oxide, expanded perlite, and alumina can be contacted together in any manner known in the art that will form a mixture that is a liquid solution, a slurry, or a paste that is capable of being dispersed in a fluid-like spray.
- a base support component is a solid, then it should be contacted in a liquid medium to form a mixture that is a liquid solution, a slurry, or a paste that is capable of being dispersed in a fluid-like spray.
- Suitable means for contacting these components are known in the art such as, for example, tumblers, stationary shells, troughs, Muller mixers, impact mixers, and the like.
- these components after contacting to form a mixture, are contacted with an acid component as described hereinabove.
- the dry components and the acid component can be contacted together simultaneously or separately.
- sorbent material having particles, preferably in the form of micro-spheres, that have a mean particle size in the ranges as disclosed herein.
- Spray drying is known in the art and is discussed in Perry's Chemical Engineers' Handbook , Sixth Edition, published by McGraw-Hill, Inc., at pages 20-54 through 20-58, which pages are incorporated herein by reference. Additional information can be obtained from the Handbook of Industrial Drying , published by Marcel Dekker Inc., at pages 243 through 293.
- the spray-dried sorbent material can then be dried under a drying condition as disclosed herein and then calcined, preferably in an oxidizing atmosphere such as in the presence of oxygen or air, under a calcining condition as disclosed herein to form a calcined, spray-dried sorbent material.
- the calcination can be conducted under any suitable condition that removes residual water and oxidizes any combustibles.
- the spray-dried base sorbent material is calcined in an oxygen-containing atmosphere.
- the particulate support component comprising zinc oxide, perlite, and alumina is calcined, at least a portion of the zinc oxide and at least a portion of the alumina combine to form zinc aluminate (ZnAl 2 O 4 ).
- the resulting calcined support component preferably comprises zinc aluminate in an amount in the range of from about 2 to about 50 weight percent, more preferably in the range of from about 5 to about 30 weight percent, and most preferably in the range of from 10 to 20 weight percent.
- the calcined support component preferably comprises zinc oxide in an amount in the range of from about 20 to about 95 weight percent, more preferably in the range of from about 40 to about 90 weight percent, and most preferably in the range of from about 60 to about 80 weight percent.
- the calcined support component preferably comprises perlite in an amount in the range of from about 2 to about 50 weight percent, more preferably in the range of from about 5 to about 30 weight percent, and most preferably in the range of from 10 to 20 weight percent.
- the spray-dried sorbent 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 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 eight inch diameter stainless steel frame 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 resulting particulate (preferably spray-dried) calcined support component comprising zinc aluminate, zinc oxide, crushed expanded perlite, and optionally a binder, preferably alumina (if not all converted to zinc aluminate), is then incorporated with a promoter component.
- the promoter component which is useful in the practice of the present invention is promoter derived from one or more metals, metal oxides, or metal oxide precursors wherein the metal is selected from the group consisting of cobalt, nickel, iron, manganese, zinc, copper, molybdenum, silver, tin, vanadium, and antimony.
- a promoter component of nickel or cobalt or a mixture of cobalt and nickel is particularly preferred.
- the resulting promoted particulates are then subjected to drying under a drying condition as disclosed herein and calcined under a calcining condition as disclosed herein prior to the subjecting of such dried, calcined, promoted particulates to reduction with a reducing agent, preferably hydrogen.
- a reducing agent preferably hydrogen
- the promoter component(s) may be incorporated onto, or with, the particulated (preferably spray-dried), calcined support component by any suitable means or method(s) for incorporating the promoter component(s) onto, or with, a substrate material, such as the dried and calcined particulates, which results in the formation of a promoted sorbent composition which can then be dried under a drying condition as disclosed herein and calcined under a calcining condition as disclosed herein to thereby provide dried, calcined, promoted particulates.
- the dried, calcined, promoted particulates can then be subjected to reduction with a reducing agent, preferably hydrogen, to thereby provide a sorbent composition of the present invention.
- a reducing agent preferably hydrogen
- a preferred method of incorporating is impregnating using any standard incipient wetness impregnation technique (i.e., essentially completely filling the pores of a substrate material with a solution of the incorporating elements) for impregnating a substrate.
- a preferred method uses an impregnating solution comprising the desirable concentration of a promoter component so as to ultimately provide a promoted particulate which can then be subjected to drying and calcining followed by reduction with a reducing agent such as hydrogen.
- the impregnating solution can be any aqueous solution and amounts of such solution which suitably provides for the impregnation of the particulates of support component to give an amount of promoter component that provides, after reduction with a reducing agent, a reduced promoter component content sufficient to permit the removal of sulfur from cracked-gasoline or diesel fuel when such fluid is treated in accordance with a desulfurization process of the present invention.
- a preferred impregnating solution comprises an aqueous 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 concentration of the metal promoter component in the aqueous solution can be in the range of from about 0.1 gram of metal promoter component per gram of aqueous solution to about 5 grams of metal promoter component per gram of aqueous solution.
- the weight ratio of metal promoter component to the aqueous medium of such aqueous 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.
- a promoter component can be added to the spray-dried sorbent material as a component of the original mixture, or they can be added after the original mixture has been spray dried and calcined. If a promoter component is added to the spray-dried sorbent material after it has been spray dried and calcined, the spray-dried sorbent material should be dried and calcined a second time.
- the spray-dried sorbent material is preferably dried a second time at a temperature generally in the range of from about 100° F. to about 650° F.
- the spray-dried sorbent material can be dried a second time at a temperature generally in the range of from about 150° F.
- the time period for conducting the drying a second time is generally in the range of from about 0.5 hour to about 8 hours, preferably in the range of from about 1 hour to about 6 hours and, more preferably, in the range of from 1.5 hours to 4 hours.
- Such drying a second time is generally carried out at a pressure in the range of from about atmospheric (i.e., about 14.7 pounds per square inch absolute) to about 100 pounds per square inch absolute (psia), preferably about atmospheric.
- This spray-dried sorbent material is then calcined, preferably in an oxidizing atmosphere such as in the presence of oxygen or air, under a calcining condition as disclosed herein.
- a preferred impregnating solution is formed by dissolving a metal-containing compound (such as nickel nitrate hexahydrate) in water. It is acceptable to use somewhat of an acidic solution to aid in the dissolution of the metal-containing compound. 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.
- a metal-containing compound such as nickel nitrate hexahydrate
- a drying condition can include a temperature in the range of from about 180° F. to about 290° F., preferably in the range of from about 190° F. to about 280° F. and, most preferably, in the range of from 200° F. to 270° F.
- Such drying condition 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 condition 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, most preferably about atmospheric, so long as the desired temperature can be maintained.
- 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, most preferably about atmospheric, so long as the desired temperature can be maintained.
- Any drying methods(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.
- a calcining condition can include a temperature in the range of from about 700° F. to about 1600° F., preferably in the range of from about 800° F. to about 1500° F. and, more preferably, in the range of from 900° F. to about 1400° F.
- Such calcining condition can also include a pressure, generally in the range of from about 7 pounds per square inch absolute (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 2 hours to about 20 hours and, most preferably, for a time period in the range of from 3 hours to 15 hours.
- psia pounds per square inch absolute
- promoter metal-zinc aluminate substitutional solid solution characterized by the formula: M Z Zn (1-Z) Al 2 O 4 , wherein M is the promoter metal and Z is a numerical value in the range of from 0.01 to 0.99.
- a substitutional solid metal oxide solution characterized by the formula: M X Zn Y O, wherein M is the promoter metal, X is a numerical value in the range of from 0.01 to 0.99, and Y is a numerical value in the range of from 0.01 to 0.99.
- X is in the range of from about 0.50 to about 0.90, more preferably from about 0.60 to about 0.80, and most preferably from 0.65 to 0.75.
- Y is in the range of from about 0.10 to about 0.50, more preferably from about 0.20 to about 0.40, and most preferably from 0.25 to 0.35.
- Y is equal to (1-X).
- Substitutional solid solutions have unique physical and chemical properties that are important to the chemistry of the inventive sorbent composition described herein.
- Substitutional solid solutions are a subset of alloys that are formed by the direct substitution of the solute metal for the solvent metal atoms in the crystal structure.
- the promoter metal-zinc oxide substitutional solid metal oxide solution found in the oxidized (i.e., unreduced), calcined sorbent composition of the present invention is formed by the solute zinc metal atoms substituting for the solvent promoter metal atoms.
- the promoter metal (as the elemental metal or metal oxide) and zinc oxide employed in the inventive sorbent composition preferably meet at least two of the three criteria set forth above. For example, when the promoter metal is nickel, the first and third criteria, are met, but the second is not.
- the nickel and zinc metal atomic radii are within 10 percent of each other and the electronegativities are similar. However, nickel oxide (NiO) preferentially forms a cubic crystal structure, while zinc oxide (ZnO) prefers a hexagonal crystal structure.
- a nickel zinc oxide solid solution retains the cubic structure of the nickel oxide. Forcing the zinc oxide to reside in the cubic structure increases the energy of the phase, which limits the amount of zinc that can be dissolved in the nickel oxide structure.
- This stoichiometry control manifests itself microscopically in a 70:30 nickel zinc oxide solid solution (Ni 0.7 Zn 0.3 O) that is formed during oxidation (i.e., calcination or regeneration) and microscopically in the repeated regenerability of the sorbent.
- the calcined (i.e., oxidized or regenerated), promoted sorbent particulates preferably comprise the substitutional solid metal oxide solution (M X Zn Y O) in an amount in the range of from about 5 to about 70 weight percent, more preferably in the range of from about 10 to about 60 weight percent, still more preferably in the range of from about 20 to about 40 weight percent, and most preferably in the range of 25 to 35 weight percent.
- M X Zn Y O substitutional solid metal oxide solution
- the calcined, promoted sorbent particulates preferably comprise the promoter metal-zinc aluminate substitutional solid solution (M Z Zn (1-Z) Al 2 O 4 ) in an amount in the range of from about 2 to about 50 weight percent, more preferably in the range of from about 5 to about 30 weight percent, and most preferably in the range of from 10 to 20 weight percent.
- the calcined, promoted sorbent particulates preferably comprise zinc oxide in an amount in the range of from about 10 to about 90 weight percent, more preferably in the range of from about 20 to about 70 weight percent, still more preferably in the range of from about 30 to about 50 weight percent, and most preferably in the range of from 35 to 45 weight percent.
- the calcined, promoted sorbent particulates preferably comprise perlite in an amount in the range of from about 2 to about 50 weight percent, more preferably in the range of from about 5 to about 30 weight percent, and most preferably in the range of from 10 to 20 weight percent.
- the desired reduced-valence promoter component sorbent is prepared by drying the resulting composition under a drying condition as disclosed herein followed by calcining under a calcining condition as disclosed herein to thereby provide dried, calcined, promoted particulates.
- the dried, calcined, promoted particulates are thereafter subjected to reduction with a suitable reducing agent, preferably hydrogen or an appropriate hydrocarbon so as to produce a composition having a substantially reduced-valence promoter component content therein, preferably a substantially zero content therein, with such zero valence promoter component being present in an amount sufficient to permit the removal of sulfur from a hydrocarbon-containing fluid such as cracked-gasoline or diesel fuel, according to the process disclosed herein.
- a suitable reducing agent preferably hydrogen or an appropriate hydrocarbon
- a sorbent composition having a reduced-valence promoter component of the present invention is a composition that has the ability to react chemically and/or physically with sulfur. It is also preferable that the sorbent composition removes diolefins and other gum-forming compounds from cracked-gasoline.
- a sorbent composition having a reduced-valence promoter component of the present invention comprises a promoter component that is in a substantially reduced valence state, preferably a zero valence state.
- the reduced-valence promoter component is reduced nickel.
- the amount of reduced-valence promoter component, preferably reduced nickel, in a sorbent composition of the present invention is an amount which will permit the removal of sulfur from cracked-gasoline or diesel fuel.
- Such amounts of reduced-valence promoter component, preferably reduced nickel or cobalt or a mixture of nickel and cobalt are generally in the range of from about 1.0 to about 60 weight percent of the total weight of the sorbent composition (support composition plus promoter).
- the reduced nickel is present in an amount in the range of from about 15 to about 30 weight percent based on the total weight of the nickel and the reduced nickel has been substantially reduced to zero valence.
- zinc oxide is present in an amount in the range of from about 40 to about 80 weight percent zinc oxide based on the total weight of the sorbent support
- expanded perlite is present in an amount in the range of from about 10 to about 30 weight percent expanded perlite based on the total weight of the sorbent support
- alumina is present in an amount in the range of from about 1.0 to about 20 weight percent based on the total weight of the sorbent support
- promoter metal is present prior to reduction in an amount in the range of from about 10 to about 30 weight percent promoter metal based on the total weight of the composition.
- substitutional solid metal oxide solution found in the oxidized sorbent particulates to be reduced to form a substitutional solid metal solution characterized by the formula: M A Zn B , wherein M is the promoter metal, A is a numerical value in the range of from 0.01 to 0.99, and B is a numerical value in the range of from 0.01 to 0.99.
- A is preferred for A to be in the range of from about 0.50 to about 0.97, more preferably in the range of from about 0.80 to about 0.95, and most preferably in the range of from 0.90 to 0.94.
- B is further preferred for B to be in the range of from about 0.03 to about 0.50, more preferably in the range of from about 0.05 to about 0.20, and most preferably in the range of 0.06 to 0.10.
- B is equal to (1-A).
- the reduced sorbent particulates preferably comprise the substitutional solid metal solution (M A Zn B ) in an amount in the range of from about 5 to about 80 weight percent, more preferably in the range of from about 10 to about 60 weight percent, still more preferably in the range of from about 20 to about 50 weight percent, and most preferably in the range of from 30 to 40 weight percent.
- the reduced sorbent particulates preferably comprise the promoter metal-zinc aluminate (M Z Zn (1-Z) Al 2 O 4 ), described above with reference to the oxidized (i.e., unreduced) sorbent particulates, in an amount in the range of from about 2 to about 50 weight percent, more preferably in the range of from about 5 to about 30 weight percent, and most preferably in the range of from 10 to 20 weight percent.
- the reduced sorbent particulates preferably comprise zinc oxide in an amount in the range of from about 10 to about 90 weight percent, more preferably in the range of from about 20 to about 60 weight percent, and most preferably in the range of from 30 to 40 weight percent.
- the reduced sorbent particulates preferably comprise perlite in an amount in the range of from about 2 to about 50 weight percent, more preferably in the range of from about 5 to about 30 weight percent, and most preferably in the range of from 10 to 20 weight percent.
- compositions of the present invention which are useful in the desulfurization process of the present invention, can be prepared by a process comprising:
- particulating preferably spray-drying, the mixture to form particulates selected from the group consisting of granules, extrudates, tablets, pellets, spheres, micro-spheres, and the like and combinations thereof, preferably micro-spheres;
- a process of using a novel sorbent composition(s) of the present invention to desulfurize a hydrocarbon-containing fluid, such as cracked-gasoline or diesel fuel, to provide a desulfurized cracked-gasoline or diesel fuel comprises:
- the desulfurizing step (a) of the present invention is carried out under a set of conditions that includes total pressure, temperature, weight hourly space velocity, and hydrogen flow. These conditions are such that the sorbent composition can desulfurize the hydrocarbon-containing fluid to produce a desulfurized hydrocarbon-containing fluid and a sulfurized sorbent composition.
- the cracked-gasoline or diesel fuel be in a gas or vapor phase.
- 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 preferred that the total pressure be in a range of from about 50 psia to about 500 psia.
- the temperature should be sufficient to keep the hydrocarbon-containing fluid in essentially a vapor or gas phase. While such temperatures can be in the range of from about 100° F. to about 1000° F., it is presently preferred that the temperature be in the range of from about 400° F. to about 800° F. when treating a cracked-gasoline, and in the range of from about 500° F. to about 900° F. when treating a diesel fuel.
- Weight hourly space velocity is defined as the numerical ratio of the rate at which a hydrocarbon-containing fluid is charged to the desulfurization zone in pounds per hour at standard condition of temperature and pressure (“STP”) divided by the pounds of sorbent composition contained in the desulfurization zone to which the hydrocarbon-containing fluid is charged.
- STP temperature and pressure
- WHSV should be in the range of from about 0.5 hr ⁇ 1 to about 50 hr ⁇ 1 , preferably in the range of from about 1 hr ⁇ 1 to about 20 hr ⁇ 1 .
- an agent be employed which interferes with any possible chemical or physical reacting of the olefinic and aromatic compounds in the hydrocarbon-containing fluid which is being treated with the solid reduced metal containing sorbent composition.
- agent is hydrogen.
- Hydrogen flow in the desulfurization zone is generally such that the mole ratio of hydrogen to hydrocarbon-containing fluid is the range of from about 0.1 to about 10, preferably in the range of from about 0.2 to about 3.
- the desulfurization zone can be any zone wherein desulfurization of cracked-gasoline or diesel fuel can take place.
- 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.
- diluents such as methane, carbon dioxide, flue gas, nitrogen, and the like and combinations thereof can be used.
- a high purity hydrogen be employed in achieving the desired desulfurization of a hydrocarbon-containing fluid such as cracked-gasoline or diesel fuel.
- a sorbent composition be used having a particle size in the range of from about 10 micrometers to about 1000 micrometers.
- such sorbent 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.
- the sorbent composition should generally have a particle size in the range of from about ⁇ fraction (1/32) ⁇ inch to about 1 ⁇ 2 inch diameter, preferably in the range of from about ⁇ fraction (1/32) ⁇ inch to about 1 ⁇ 4 inch diameter.
- a sorbent composition having a surface area in the range of from about 1 square meter per gram (m 2 /g) to about 1000 square meters per gram of sorbent composition, preferably in the range of from about 1 m 2 /g to about 800 m 2 /g.
- the separation of the desulfurized hydrocarbon-containing fluid can be accomplished by any manner known in the art that can separate a solid from a gas. Examples of such means are cyclonic devices, settling chambers, impingement devices for separating solids and gases, and the like and combinations thereof.
- the desulfurized gaseous cracked-gasoline or desulfurized gaseous diesel fuel can then be recovered and preferably liquefied. Liquification of such desulfurized hydrocarbon-containing fluid can be accomplished by any manner known in the art.
- the gaseous cracked-gasoline or gaseous diesel fuel, suitable as a feed in a process(es) of the present invention is a composition that contains, in part, olefins, aromatics, sulfur, as well as paraffins and naphthenes.
- the amount of olefins in gaseous cracked-gasoline is generally in the range of from about 10 to about 35 weight percent olefins based on the total weight of the gaseous cracked-gasoline. For diesel fuel there is essentially no olefin content.
- the amount of aromatics in gaseous cracked-gasoline is generally in the range of from about 20 to about 40 weight percent aromatics based on the total weight of the gaseous cracked-gasoline.
- the amount of aromatics in gaseous diesel fuel is generally in the range of from about 10 to about 90 weight percent aromatics based on the total weight of the gaseous diesel fuel.
- the amount of sulfur in the hydrocarbon-containing fluid, i.e. cracked-gasoline or diesel fuel, suitable for use in a process of the present invention can be in the range of from about 100 parts per million sulfur by weight of the cracked-gasoline to about 10,000 parts per million sulfur by weight of the cracked-gasoline and from about 100 parts per million sulfur by weight of the diesel fuel to about 50,000 parts per million sulfur by weight of the diesel fuel prior to the treatment of such hydrocarbon-containing fluid with a desulfurization process(es) of the present invention.
- the amount of sulfur in the desulfurized cracked-gasoline or desulfurized diesel fuel, following treatment in accordance with a desulfurization process of the present invention is less than about 100 parts per million (ppm) sulfur by weight of hydrocarbon-containing fluid, preferably less than about 50 ppm sulfur by weight of hydrocarbon-containing fluid, and more preferably less than about 5 ppm sulfur by weight of hydrocarbon-containing fluid.
- ppm parts per million
- a stripper unit can be inserted before and/or after the regeneration of the sulfurized sorbent composition.
- Such stripper will serve to remove a portion, preferably all, of any hydrocarbon from the sulfurized sorbent composition.
- Such stripper can also serve to remove oxygen and sulfur dioxide from the system prior to introduction of the regenerated sorbent composition into the sorbent activation zone (i.e., sorbent reduction zone).
- the stripping comprises a set of conditions that includes total pressure, temperature, and stripping agent partial pressure.
- the total pressure in a stripper when employed, is in the range of from about 25 pounds per square inch absolute (psia) to about 500 psia.
- the temperature for such stripping can be in the range of from about 100° F to about 1000° F.
- the stripping agent is a composition that helps to remove a hydrocarbon(s) from the sulfurized sorbent composition.
- the stripping agent is nitrogen.
- the sorbent regeneration zone employs a set of conditions that includes total pressure and sulfur removing agent partial pressure.
- Total pressure is generally in the range of from about 25 pounds per square inch absolute (psia) to about 500 psia.
- the sulfur removing agent partial pressure is generally in the range of from about 1 percent to about 25 percent 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 bum off any remaining hydrocarbon deposits that might be present.
- the preferred sulfur removing agent suitable for use in the sorbent regeneration zone is selected from oxygen-containing gases such as air.
- the temperature in the sorbent regeneration zone is generally in the range of from about 100° F. to about 1500° F., preferably in the range of from about 800° F. to about 1200° F.
- the sorbent regeneration zone can be any vessel wherein the desulfurizing or regeneration of the sulfurized sorbent composition can take place.
- the desulfurized sorbent composition is then reduced in an activation zone with a reducing agent so that at least a portion of the promoter component content of the sorbent composition is reduced to produce a solid reduced-valence promoter component to permit the removal of sulfur from a cracked-gasoline or diesel fuel according to the inventive process disclosed herein.
- the activation, i.e., reduction, of the desulfurized sorbent composition is carried out at a temperature in the range of from about 100° F. to about 1500° F. and at a pressure in the range of from about 15 pounds per square inch absolute (psia) to about 1500 psia.
- Such reduction is carried out for a time sufficient to achieve the desired level of promoter component reduction contained in the skin of the sorbent 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 activated (i.e., reduced) sorbent composition can be returned to the desulfurization zone.
- the steps of desulfurization, regeneration, activation (i.e., reduction), and optionally stripping before and/or after such regeneration can be accomplished in a 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.
- inventive sorbent composition and inventive desulfurization process provide unique advantages when employed to remove sulfur from middle distillates, such as diesel fuel, jet fuel, and kerosene.
- middle distillates such as diesel fuel, jet fuel, and kerosene.
- One advantage of using the inventive system to remove sulfur from middle distillates is its ability to greatly reduced the amount of sulfur in the middle distillates without significantly reducing the amount of nitrogen in the middle distillates.
- the presence of nitrogen in a middle distillate, particularly diesel fuel can advantageously improve the lubricity properties of the middle distillate.
- Conventional hydrotreating processes for removing sulfur from middle distillates remove significant amounts of nitrogen from the middle distillates.
- low-sulfur high-nitrogen middle distillates produced by the present invention have advantages (e.g., improved lubricity) over low-sulfur low-nitrogen middle distillates produced by conventional desulfurization processes.
- the middle distillate feed employed in the process of the present invention is preferably a mixture of hydrocarbons having a boiling range (ASTM D86-00) of from about 200° F. to about 800° F., more preferably from about 225° F. to about 775° F.
- the middle distillate feed preferably has a mid-boiling point (ASTM D86-00) of more than about 400° F., more preferably more than about 450° F., and still more preferably more than about 500° F.
- the middle distillate feed preferably has an API gravity (ASTM D287-92) in the range of from about 20 to about 50, more preferably from about 25 to about 45.
- the middle distillate feed preferably has a minimum flash point (ASTM D93-99) of at least about 80° F., more preferably at least about 90° F.
- suitable middle distillates include, but are not limited to, diesel fuel, jet fuel, kerosene, light cycle oil, and the like, and mixtures thereof.
- the middle distillate feed employed in the desulfurization process of the present invention consists essentially of diesel fuel boiling in the range of from 300° F. to 750° F., having a mid-boiling point of more than 510° F., having an API gravity in the range of from 30 to 38, and having a minimum flash point above 100° F.
- the properties described in this paragraph encompass preferred applications and uses for middle distillates, but are in no way to be construed as a limiting definition for middle distillates.
- the middle distillate feed will have a sulfur content (ASTM D2622-82) of at least of about 100 ppmw and a nitrogen content (ASTM D4629-86) of at least about 25 ppmw. More typically, the middle distillate feed will have a sulfur content of at least 200 ppmw and a nitrogen content of at least 50 ppmw.
- ASTM D2622-82 sulfur content
- ASTM D4629-86 nitrogen content
- the middle distillate feed will have a sulfur content of at least 200 ppmw and a nitrogen content of at least 50 ppmw.
- desulfurization of the middle distillate feed in accordance with the inventive process/sorbent taught herein includes a sulfur conversion (i.e., weight percent reduction in total sulfur content of the feed) of at least about 80 weight percent, more preferably at least about 90 weight percent, still more preferably at least about 95 weight percent, even more preferably at least about 98 weight percent, and most preferably 99 weight percent.
- a sulfur conversion i.e., weight percent reduction in total sulfur content of the feed
- desulfurization of the middle distillate feed includes a nitrogen conversion (i.e., weight percent reduction in total nitrogen content of the feed) of less than about 50 weight percent, more preferably less than about 40 weight percent, still more preferably less than about 30 weight percent, even more preferably in the range of from about 5 to about 30 weight percent, and most preferably in the range of from 10 to 25 weight percent.
- the resulting desulfurized middle distillate preferably has a total sulfur content (ASTM D2622-82) of less than about 50 ppmw, more preferably less than about 30 ppmw, still more preferably less than about 20 ppmw, and most preferably less than about 10 ppmw.
- the desulfurized middle distillate preferably has a total nitrogen content (ASTM D4629-86) of at least about 20 ppmw, more preferably at least about 40 ppmw, still more preferably at least about 60 ppmw, most preferably in the range of from 60 to 200 ppmw.
- the nitrogen to sulfur weight ratio of the desulfurized middle distillate is preferably in the range of from about 1 about to 100, more preferably about 2 to about 50, still more preferably about 4 to about 30, and most preferably 5 to 20.
- the cetane number (ASTM D613-84) of the desulfurized product is nearly the same as the cetane number of the middle distillate feed.
- the cetane number of the desulfurized product is within about 5 percent of the cetane number of the middle distillate feed, more preferably within 2 percent, and most preferably within 1 percent.
- the initial boiling point, mid-boiling point, final boiling point, minimum flash point, API gravity and hydrogen content of the desulfurized product are substantially the same as the initial boiling point, mid-boiling point, final boiling point, minimum flash point, API gravity, and hydrogen content of the middle distillate feed.
- the values of each of these properties for the desulfurized middle distillate product is within about 10 percent of the values for the middle distillates feed, more preferably within about 5 percent, still more preferably within about 2 percent, and most preferably within 1 percent.
- the inventive desulfurization process is highly sulfur selective, and provides only minor changes, if any, in other properties of the middle distillate feed.
- a solid reduced nickel sorbent system was produced by mixing 10% alumina (Vista Dispal), 40% diatomaceous earth (World Chemical), and 50% zinc oxide with water at 42% solids using tetra sodium pyrophosphate (TSPP) as the dispersing agent.
- the resulting slip was spray dried using a Niro Mobil Minor Spray Drier fitted with a 0.035 inch air cap and a 0.35 inch fountain head nozzle.
- the inlet temperature was 320° C. and the outlet temperature was 150° C. Air flow through the nozzle was 70 liters per minute.
- the slip was delivered at approximately 43 cc/min H 2 O.
- the spray dried product was dried in air using a muffle furnace at a temperature of 150° C. for 1 hour and then calcined at a temperature of 635° C. for a period of 1 hour.
- the resulting calcined composition was screened to remove fines ⁇ 40 microns and oversized particles of >250 microns.
- the screened sorbent was impregnated with 12% nickel (as the metal) using melted nickel nitrate hexahydrate in 5% water to get it to melt/dissolve. The resulting solution was then sprayed onto the sorbent using a Sono-Tec sprayer while the sorbent particles were rotated in a baffled cement mixer type drum. The nickel impregnated sorbent was again calcined at a temperature of 635° C. for 1 hour.
- the resulting 27% nickel impregnated sorbent was then calcined at a temperature of 635° C. for a period of 1 hour to provide a 30% (by weight) of a nickel impregnated sorbent system.
- the resulting impregnated sorbent system has a Davison attrition resistance value of 19.26.
- gaseous cracked-gasoline was pumped upwardly through the reactor at a rate of 13.6 ml per hour.
- the gaseous cracked-gasoline had a motor octane number of 80.6 (MON) or a research octane number of 92.1 (RON), an olefin content of 21.2 weight percent, 340 parts per million sulfur by weight sulfur-containing compounds based on the total weight of the gaseous cracked-gasoline and about 0.03 weight percent thiophenic compounds based on the weight of sulfur-containing compounds in the gaseous cracked-gasoline.
- the sorbent was reduced with hydrogen flowing at a rate of 300 sccm at a temperature of 700° F. for a period of one hour. Each cycle consisted of four hours with the product sulfur (ppm) for each cycle measured at one hour intervals over each four-hour cycle period. After each cycle, the sorbent was regenerated at 900° F. for two hours with a mixture of oxygen and nitrogen containing four volume percent oxygen, then purged with nitrogen (regeneration), and then reduced in hydrogen flowing at a rate of 300 cc for one hour at 700° F. (activation).
- the sorbent compositions were each tested over 2 cycles. Each cycle utilized a mixture of 150 sccm hydrogen and 150 sccm nitrogen and 350 sccm/hydrocarbon.
- a solid reduced nickel sorbent system was produced by mixing 13.75% alumina (nitric acid peptized Condea Disperal), 17.25% milled expanded perlite (RIF 27M), and 69% zinc oxide with water at 42% solids using ammonium polyacrylate as the dispersing agent.
- the resulting slip was spray dried using a Niro Mobil Minor Spray Drier fitted with a 0.035 inch air cap and a 0.35 inch fountain head nozzle.
- the inlet temperature was 320° C. and the outlet temperature was 150° C. Air flow through the nozzle was 70 liters per minute.
- the slip was delivered at approximately 43 cc/min H 2 O.
- the spray dried product was dried in air using a muffle furnace at a temperature of 150° C. for 1 hour and then calcined at a temperature of 635° C. for a period of 1 hour.
- the resulting calcined composition was screened to remove fines ⁇ 40 microns and oversized particles of >250 microns.
- the screened sorbent was impregnated with 15% nickel (as the metal) using melted nickel nitrate hexahydrate in 5% water to get it to melt/dissolve.
- the resulting solution was then sprayed onto the sorbent using a Sono-Tec sprayer while the sorbent particles were rotated in a baffled cement mixer type drum.
- the nickel impregnated sorbent was again calcined at a temperature of 635° C. for 1 hour.
- the resulting 30% nickel impregnated sorbent was then calcined at a temperature of 635° C. for a period of 1 hour to provide a 30% (by weight) of a nickel impregnated sorbent system.
- the resulting impregnated sorbent system has a Davison attrition resistance value of 10.
- gaseous cracked-gasoline was pumped upwardly through the reactor at a rate of 13.6 ml per HR.
- the gaseous cracked-gasoline had a motor octane number of 80.6 (MON) or a research octane number of 92.4 (RON), an olefin content of 21.2 weight percent, 340 parts per million sulfur by weight sulfur containing compound based on the total weight of the gaseous cracked-gasoline and about 0.03 weight percent thiophenic compounds based on the weight of sulfur-containing compounds in the gaseous cracked-gasoline.
- the sorbent was reduced with hydrogen flowing at a rate of 300 sccm at a temperature of 700° F. for a period of one hour. Each cycle consisted of four hours with the product sulfur (ppm) for each cycle measured at one hour intervals over each four-hour cycle period. After each cycle, the sorbent was regenerated at 900° F. for two hours with a mixture of oxygen and nitrogen containing four volume percent oxygen, then purged with nitrogen (regeneration) and then reduced in hydrogen flowing at a rate of 300 cc for one hour at 700° F. (activation).
- a solid reduced nickel sorbent system was produced by combining 175.9 pounds of deionized water and 28.3 pounds of alumina (Vista DispalTM) in a mixer. The water/alumina slurry was mixed until the alumina was peptized. In a separate mixer, 27.4 pounds of milled expanded perlite (R/F 27M) was dry-blended with 104.8 pounds of powdered zinc oxide. The perlite/ZnO dry mixture was slowly added to the water/alumina slurry while mixing was continued. The resulting support mixture was mixed until homogeneous.
- the support mixture was then spray dried in a 33 foot spray drier having a wheel atomizer which spun at 9,000 RPM.
- the air charged to the spray drier during drying had an inlet temperature of about 500° F. and an outlet temperature of about 280° F.
- the microspherical support particulates produced by spray drying were then dried at about 250° F. for about 3 hours and calcined on a belt calciner at a temperature of about 635° C. for about 1.5 hours.
- the calcined support particulates were then sieved to remove oversized particles (larger than 100 mesh) and fine particles (smaller than 635 mesh).
- the sieved support particulates were then placed in a baffled cement mixer-type mixer and impregnated with nickel by spraying an aqueous solution of nickel nitrate hexahydrate on the support particulates while the mixer was rotated.
- the material was then discharged from the mixer and dried at 250° F. for about 8 hours, then calcined on a belt calciner at 635° C. for 1.5 hours.
- the calcined (i.e., oxidized) promoted sorbent particulates were then sieved to remove oversized particles (larger than 100 mesh) and fine particles (smaller than 635 mesh).
- a portion of the resulting calcined (i.e., oxidized) promoted sorbent was charged to a fixed fluidized bed 1 inch I.D. quartz reactor.
- the sorbent in the reactor was then reduced in hydrogen flowing at 300 sccm at 750° F. for 1 hour.
- the reduced promoted sorbent was then cooled with nitrogen and removed from the reactor.
- Kevex PSI Peltier cooled silicon detector All X-ray diffraction measurements were taken using a Philips XRG 3100 generator equipped with a long fine focus copper X-ray source powered at 40 kV & 30 mA; Philips 3020 digital goniometer & Philips 3710 MPD control computer; and a Kevex PSI Peltier cooled silicon detector.
- the Kevex detector was operated with a Kevex 4601 ion pump controller, Kevex 4608 Peltier current supply, Kevex 4621 detector bias, Kevex 4561A pulse processor, and Kevex 4911-A single channel analyzer.
- Zinc Oxide (ZnO) 70.3 wt. %
- Zinc Aluminate (ZnAl 2 O 4 ): 14.9 wt. %
- Zinc Oxide (ZnO) 40.0 wt. %
- Nickel Zinc Oxide Substitutional Solid Solution (Ni 0.7 Zn 0.3 O): 31.2 wt. %.
- Nickel Zinc Aluminate Substitutional Solid Solution Ni Z Zn (1-Z) Al 2 O 4 : 15.9 wt. %
- Nickel Zinc Metal Substitutional Solid Solution (Ni 0.92 Zno 0.08 ): 34.1 wt. %.
- Desulfurization tests were preformed on two different diesel feeds by contacting the feeds with a sorbent composition in a fixed bed reactor.
- the reactor was a standard steel reactor having a 3 ⁇ 4 inch inner diameter and a 1 ⁇ 4 thermowell.
- the sorbent used in the reactor was prepared by mixing 2,281.3 grams of aluminum hydroxide powder (DISPALTM Alumina Powder, available from CONDEA Vista Company, Houston, Tex.) and 4,562.7 grams of distilled water to form an alumina mixture.
- DISPALTM Alumina Powder available from CONDEA Vista Company, Houston, Tex.
- distilled water 1,4-butanediol
- 2,737.6 grams of expanded perlite HARBORLITETM 205, available from Harborlite Corporation, Antonito, Colo.
- 115.0 grams of 5% nitric acid and 2,185.0 grams of distilled water were combined.
- the resulting perlite-containing mixture was then mixed for about 5 minutes. Thereafter, 8,601.0 grams of zinc oxide powder (available from Zinc Corporation, Monaca, Pa.) were added to the perlite-containing mixture.
- the resulting zinc oxide-containing mixture was then mixed for about 10 minutes and allowed to set at ambient conditions for about 1 hour.
- the alumina mixture, described above, was then added to the zinc oxide-containing mixture over a period of about 12 minutes, and thereafter mixed for an additional 3 minutes.
- the consistency of the resulting mixture was a sticky paste.
- the paste was extruded into 1 ⁇ 8 inch thick and ⁇ fraction (1/16) ⁇ inch diameter extrudate.
- the resulting extrudate was placed in a muffle furnace and dried by ramping the temperature in the furnace at 3° C./min to 150° C. and holding at 150° C. for 1 hour.
- the dried extrudate was then calcined by ramping the temperature in the furnace at 5° C./min to 635° C. and holding at 635° C.
- a 100 gram quantity of the calcined extrudate was then impregnated with nickel by spraying 50 grams of a 15 weight percent nickel solution onto the extrudate with an ultrasonic nozzle, in accordance with standard incipient wetness impregnation techniques.
- the resulting once-impregnating extrudate was placed in a muffle furnace and dried by ramping the temperature in the furnace at 3° C./min to 150° C. and holding at 150° C. for 1 hour.
- the dried impregnated extrudate was then calcined by ramping the temperature in the furnace at 5° C./min to 635° C. and holding at 635° C. for 1 hour.
- the calcined, once-impregnated extrudate was then impregnated again with nickel by spraying 42 grams of a 15 weight percent nickel solution onto the once-impregnated extrudate with an ultrasonic nozzle, in accordance with standard incipient wetness impregnation techniques.
- the resulting twice-impregnating extrudate was placed in a muffle furnace and dried by ramping the temperature in the furnace at 3° C./min to 150° C. and holding at 150° C. for 1 hour.
- the dried twice-impregnated extrudate was then calcined by ramping the temperature in the furnace at 5° C./min to 635° C. and holding at 635° C. for 1 hour.
- the resulting nickel-impregnating sorbent (in the form of ⁇ fraction (1/16) ⁇ inch diameter extrudate) was the sorbent composition employed in the desulfurization tests described in this example.
- the sorbent was reduced with hydrogen prior to testing.
- the testing procedure consisted of a fixed-bed, downflow feed/hydrogen adsorption, followed by a nitrogen purge, a nitrogen/air regeneration, another nitrogen purge, and a hydrogen reduction.
- the reaction conditions under which the diesel fuel was contacted with the sorbent composition in the reactor included a temperature of about 750° F., a pressure of about 500 psig, and a diesel flow rate of about 2 LHSV. Hydrogen was co-fed with the diesel feed to the reactor at a rate of about 4,000 SCFB.
- API Gravity calculated based on density and API Gravity definition.
- Boiling Points either ASTM D2887-01 or ASTM D86-01, depending on sample. TABLE 3 Desulfurization of Diesel Feed #1 (750° F., 500 psig, 2 WHSV, 4000 SCFB H 2 ) Diesel Prod. Prod. Prod. Prod. Prod. Property Feed #1 Run #1 Run #2 Run #3 Run #4 Run #5 Sulfur (ppmw) 485 5.1 7.9 5.3 6.0 10.9 S Conv. — 98.9 98.4 98.9 98.8 97.8 (% by wt) Nitrogen 161 106.0 114.0 108.2 113.8 116.6 (ppmw) N Conv.
- Table 4 describes the properties of a second diesel feed, and summarizes various properties of the desulfurized products for 4 individual runs.
- TABLE 4 Desulfurization of Diesel Feed #2 (750° F., 500 psig, 2 WHSV, 4000 SCFB H 2 ) Feed #2 Prod. Prod. Prod. Prod. Prod. Property Property Run #1 Run #2 Run #3 Run #4 Sulfur (ppmw) 420.0 11.3 14.9 7.9 5.4 S Conv. (% by wt) — 97.3 96.4 98.1 98.7 Nitrogen (ppmw) 99.0 86.0 89.0 82.0 76.0 N Conv.
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Abstract
Attrition resistant, sorbent compositions for the removal of elemental sulfur and sulfur compounds, such as hydrogen sulfide and organic sulfides, from cracked-gasoline and diesel fuels are prepared by the impregnation of a sorbent support comprising zinc oxide, expanded perlite, and alumina with a promoter such as nickel, nickel oxide or a precursor of nickel oxide followed by reduction of the valence of the promoter metal in the resulting promoter metal sorbent support composition.
Description
- This application is a continuation-in-part of application Ser. No. 10/072,209 filed Feb. 6, 2003 still pending, which is a continuation-in-part of application Ser. No. 09/580,611, filed May 30, 2000, pending.
- This invention relates to the removal of sulfur from fluid streams of cracked-gasolines and diesel fuels. In another aspect, this invention relates to sorbent compositions suitable for use in the desulfurization of fluid streams of cracked-gasolines and diesel fuels. A further aspect of this invention relates to a process for the production of sulfur sorbents 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 world-wide effort to reduce sulfur levels in hydrocarbon-containing fluids such as gasoline and diesel fuels. The reduction of sulfur in such hydrocarbon-containing fluids is considered to be a means for improving air quality because of the negative impact the sulfur has on the 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 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.
- Most of the sulfur in a hydrocarbon-containing fluid such as gasoline comes from thermally processed gasolines. 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 for example 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 real debate has 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 efforts to reduce the sulfur levels in automotive fuels will be required. While the current gasoline products contain about 330 parts per million (ppm), the U.S. 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 2006, 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 olefin content is generally due to the severe condition 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 be removed 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 also lost through saturation. Thus, there is a need for a process wherein desulfurization is achieved and the octane number is maintained.
- In addition to the need for removal of sulfur from cracked-gasolines, there is also presented to the petroleum industry a need to reduce the sulfur content in diesel fuels. 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 reactions.
- Thus, there is a need for a process of desulfurization 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 still a need for a better process for the desulfurization of such hydrocarbon-containing fluids which has minimal effect on octane levels while achieving high levels of sulfur removal.
- Traditionally, sorbent compositions used in processes for the removal of sulfur from hydrocarbon-containing fluids have been agglomerates utilized in fixed bed applications. Because of the various process advantages of fluidized beds, hydrocarbon-containing fluids are sometimes used in fluidized bed reactors. Fluidized bed reactors have advantages over fixed bed reactors such as better heat transfer and better pressure drop. Fluidized bed reactors generally use reactants that are particulates. The size of these particulates is generally in the range of about 1 micron to about 1000 microns. However, the reactants used generally do not have sufficient attrition resistance for all applications. Consequently, finding a sorbent with sufficient attrition resistance that removes sulfur from these hydrocarbon-containing fluids and that can be used in fluidized, transport, moving, or fixed bed reactors is desirable and would be of significant contribution to the art and to the economy.
- It is thus an object of the present invention to provide a novel sorbent composition that can be used for the removal of sulfur from cracked-gasolines and diesel fuels.
- Another object of the present invention is to provide a process for the production of novel sorbent compositions which are useful in the desulfurization of cracked-gasolines and diesel fuels.
- Another object of the present invention is to provide a process for the removal of sulfur from cracked-gasolines and diesel fuels which minimizes the consumption of hydrogen and minimizes the saturation of olefins and aromatics contained in such streams.
- A still further object of the present invention is to provide a desulfurized cracked-gasoline that contains less than about 100 parts per million, preferably less than 50 parts per million, 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.
- Other aspects, objectives, and advantages of the present invention will be apparent from the detailed description of the invention and the appended claims.
- The present invention is based upon my discovery that through the utilization of expanded perlite to form a sorbent base composition comprising zinc oxide, expanded perlite and alumina, there is provided a novel base composition for the formation of a sorbent system by the addition of a promoter metal thereto which permits both the control of the attrition value of the resulting sorbent system and the control of the sorbent system activity.
- More specifically, in accordance with the present invention, I have discovered that use of expanded perlite as the silica source in a system comprising zinc oxide, silica, alumina, and a promoter metal resulted in a sorbent composition which permitted variance of the zinc oxide content and the alumina content of the based support composition thereby permitted the variance of the sorbent life when used in the desulfurization of cracked-gasolines or diesel fuels as well as achieving a variance on the attrition value of the sorbent system through the altering of the alumina content of the base support.
- Thus, in one aspect of the present invention, there is provided a novel sorbent composition suitable for the desulfurization of cracked-gasolines and diesel fuels which comprises a base support component consisting essentially of zinc oxide, expanded perlite, alumina, and a promoter component wherein the valence of such promoter component is substantially reduced and such reduced-valence promoter component is present in an amount which is effective in the removal of sulfur from cracked-gasolines or diesel fuels.
- In accordance with another aspect of the present invention, there is provided a process for the preparation of a novel sorbent system which comprises contacting a base support consisting essentially of zinc oxide, expanded perlite, and alumina so as to form a mixture thereof selected from the group consisting of a wet mix, a dough, a paste, or a slurry; particulating such mixture so as to form a particulate selected from the group consisting of a granule, an extrudate, a tablet, a sphere, a pellet, or a microsphere; drying such particulate to form a dried particulate; calcining such dried particulate to form a calcined particulate; distributing a promoter component upon such dried and calcined particulate to form a promoted particulate; drying such promoted particulate to form a dried promoted particulate; calcining such dried promoted particulate to form a calcined promoted particulate; and reducing such calcined promoted particulate with a suitable reducing agent, such as hydrogen, so as to produce a sorbent composition having a substantially reduced, preferably zero-valence promoter component distributed on such based sorbent composition in an amount which is effective in removing sulfur from a cracked-gasoline or diesel fuel stream. The attrition resistance of the sorbent composition can be enhanced by varying the concentration of the alumina component in the base support. The life of the sorbent system for the desulfurization of cracked-gasolines or diesel fuels is controlled through the control of the zinc oxide content of the base support component of the sorbent system.
- In accordance with still another aspect of the present invention, there is provided an oxidized (i.e., unreduced) sorbent composition which can be made by the sorbent preparation process summarized above, absent the steps after calcination of the promoted particulate. The oxidized sorbent composition can comprise all or part of the following components: zinc oxide; expanded perlite; a substitutional solid metal oxide solution characterized by the formula MXZnYO wherein M is a promoter metal and X and Y are each numerical values in the range of from 0.01 to 0.99; and a promoter metal-zinc aluminate substitutional solid solution characterized by the formula MZZn(1-Z)Al2O4 wherein M is the promoter metal and Z is a numerical value in the range of from 0.01 to 0.99.
- In accordance with yet another aspect of the present invention, there is provided a reduced sorbent composition which can be made by the sorbent preparation process summarized above. The reduced sorbent composition can comprise all or part of the following components: zinc oxide; expanded perlite; a substitutional solid metal solution characterized by the formula MAZnB wherein M is a promoter metal and A and B are each numerical values in the range of from 0.01 to 0.99; and a promoter metal-zinc aluminate substitutional solid solution characterized by the formula MZZn(1-Z)Al2O4 wherein M is the promoter metal and Z is a numerical value in the range of from 0.01 to 0.99.
- In accordance with a further aspect of the present invention, there is provided a process for the desulfurization of cracked-gasolines and diesel fuels, which comprises desulfurizing in a desulfurization zone such a hydrocarbon-containing fluid with a sorbent composition, separating the desulfurized hydrocarbon-containing fluid from the sulfurized sorbent composition, regenerating at least a portion of the sulfurized sorbent composition to produce a regenerated, desulfurized sorbent composition; activating at least a portion of the regenerated, desulfurized sorbent composition to produce an activated, regenerated, desulfurized sorbent composition; and thereafter returning at least a portion of the activated, regenerated, desulfurized sorbent composition to the desulfurization zone.
- In accordance with a still further aspect of the present invention, there is provided a low-sulfur diesel fuel composition comprising less than about 50 ppmw sulfur and at least about 20 ppmw nitrogen, wherein the low-sulfur diesel fuel has been produced via a desulfurization process comprising the step of contacting a diesel feed containing sulfur and nitrogen with a sorbent composition under desulfurization conditions sufficient to remove sulfur from the diesel feed, wherein the sorbent composition comprises zinc oxide and a promoter metal component.
- In accordance with a yet further aspect of the present invention, there is provided a desulfurization process for removing sulfur from a hydrocarbon-containing feed comprising sulfur and nitrogen. The desulfurization process comprises the step of contacting the hydrocarbon-containing feed with a sorbent composition in a desulfurization zone under desulfurization conditions sufficient to remove at least about 80 weight percent of the sulfur and less than about 50 weight percent of the nitrogen from the hydrocarbon-containing feed, thereby providing a desulfurized hydrocarbon-containing product and a sulfurized sorbent composition.
- In accordance with still another aspect of present invention, there is provided a desulfurization process for removing sulfur from a diesel feed comprising at least about 100 ppmw sulfur and at least about 25 ppmw nitrogen. The desulfurization process comprises the steps of: (a) contacting the diesel feed with a reduced sorbent composition in a desulfurization zone under desulfurization conditions sufficient to remove at least about 90 weight percent of the sulfur and less than about 40 weight percent of the nitrogen from the diesel feed, thereby providing a desulfurized diesel fuel and a sulfurized sorbent composition; (b) contacting at least a portion of the sulfurized sorbent composition with an oxygen-containing regeneration stream in a regeneration zone under regeneration conditions sufficient to remove sulfur from the sulfurized sorbent composition, thereby providing an oxidized sorbent composition; (c) contacting at least a portion of the oxidized sorbent composition with a hydrogen-containing reducing stream in a reducing zone under reducing conditions sufficient to reduce the oxidized sorbent composition, thereby providing a reduced sorbent composition; and (d) returning at least a portion of the reduced sorbent composition to the desulfurization zone.
- The present invention is based upon the discovery by applicant that through the use of milled expanded perlite in the formation of a sorbent support comprising zinc oxide, milled expanded perlite, and a binder there was produced a base support in which the zinc oxide content and binder content could be adjusted so as to provide an attrition resistance sorbent as well as the extension of the useful life of the sorbent system.
- More specifically, it was discovered that through the use of milled expanded perlite in the formation of a zinc oxide, crushed expanded perlite, and a binder such as alumina there was achieved a base support composition which permitted the variation of the zinc oxide and binder content therein such that following impregnation of the base support with a promoter metal the resulting system exhibited attrition resistance as well as extended life when following the reduction of same with hydrogen. The resulting sorbent composition was employed in the desulfurization of a cracked-gasoline and/or diesel fuel.
- The term “gasoline” denotes a mixture of hydrocarbons boiling in the range of from about 100° F. to about 400° F., 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 100° F. to about 400° F., 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-containing fluid in a process of the present invention.
- The term “diesel fuel” denotes a mixture of hydrocarbons boiling in the range of from about 300° F. to about 750° F., 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-containing fluid, 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), thiophene, substituted thiophenes, organic trisulfides, organic tetrasulfides, benzothiophene, alkyl thiophenes, alkyl benzothiophenes, alkydibenzothiophenes, 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 sorbent composition of the present invention measured as the Davison Index. The term “Davison Index” (“DI”) refers to a measure of a sorbent's resistance to particle size reduction under controlled conditions of turbulent motion. The Davison Index represents the weight percent of the over 20 micrometer particle size fraction which is reduced to particle sizes of less than 20 micrometers under test conditions. The Davison Index is measured using a Jet cup attrition determination method. The Jet cup attrition determination method involves screening a 5 gram sample of sorbent to remove particles in the 0 to 20 micrometer size range. The particles above 20 micrometers are then subjected to a tangential jet of air at a rate of 21 liters per minute introduced through a 0.0625 inch orifice fixed at the bottom of a specially designed Jet cup (1″ I.D. X 2″ height) for a period of 1 hour. The Davison Index (“DI”) is calculated as follows:
- Correction factor (presently 0.3) is determined by using a known calibration standard to adjust for differences in jet cup dimensions and wear.
- The term “support component” denotes any component or combination of such components which can be used as a support for a sorbent composition of the present invention to help promote the desulfurization process disclosed herein. Examples of a suitable support component include, but are not limited to, zinc oxide in association with a suitable binder such as alumina and expanded perlite. A presently preferred support component is that comprising zinc oxide, expanded perlite, and alumina.
- The term “promoter component” denotes any component which can be added to the sorbent composition of the present invention to help promote the desulfurization of cracked-gasolines or diesel fuels. Such promoter components are at least one metal, metal oxide, or precursor for the metal oxide wherein the metal component is selected from the group consisting essentially of nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony, and vanadium.
- 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 such promoter component is nickel. In a preferred embodiment of the present invention, the sorbent composition is promoted with a precursor of a nickel oxide such as nickel nitrate, more preferably nickel nitrate hexahydrate.
- The term “metal” denotes metal in any form such as elemental metal or a metal-containing compound.
- The term “metal oxide” denotes metal oxide in any form such as a metal oxide or a metal oxide precursor.
- During the preparation of a sorbent composition of the present invention, the promoter component 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 component 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 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 1600° F., crushed perlite expands due to the presence of combined water with the crude perlite rock. The combined water vaporizes during the heating process and creates countless tiny bubbles in the heat softened glassy particles. It is these diminutive glass sealed bubbles which account for its light weight. Expanded perlite can be manufactured to weigh as little as 2.5 lbs per cubic foot.
- Typical chemical analysis 1 properties of expanded perlite are: silicon dioxide 73%, aluminum oxide 17%, potassium oxide 5%, sodium oxide 3%, calcium oxide 1%, plus trace elements.
- Typical physical properties of expanded perlite are: softening point 1600-2000° F., fusion point 2300° F.-2450° F., pH 6.6-6.8, and specific gravity 2.2-2.4.
- The term “expanded perlite” as used herein refers to the spherical form of perlite which has been expanded by heating the perlite siliceous volcanic rock to a temperature above 1600° F.
- The term “particulate expanded perlite” or “milled perlite” as used herein denotes that form of expanded perlite which has been subjected to crushing so as to form a particulate mass wherein the particle size of such mass is comprised of at least 97% of particles having a size of less than 2 microns.
- The term “milled expanded perlite” is intended to mean the product resulting from subjecting expanded perlite particles to milling or crushing.
- The zinc oxide will generally be present in the sorbent support composition in an amount in the range of from about 10 to about 90 weight percent zinc oxide based on the total weight of the sorbent composition, preferably in an amount in the range of from about 40 to about 80 weight percent zinc oxide.
- The zinc oxide used in the preparation of a sorbent support composition of the present invention can either be in the form of zinc oxide or in the form of one or more zinc compounds that are convertible to zinc oxide under the conditions of preparation described herein. Examples of suitable zinc compounds include, but are not limited to, zinc sulfide, zinc sulfate, zinc hydroxide, zinc carbonate, zinc acetate, zinc nitrate, and the like and combinations thereof. Preferably, the zinc oxide is in the form of powdered zinc oxide.
- The alumina used in preparing a sorbent support composition of the present invention can be any suitable commercially available alumina material including, but not limited to, colloidal alumina solutions and generally those alumina compounds produced by the dehydration of alumina hydrates.
- In preparing the sorbent support component of the subject invention, there is generally employed an amount of alumina in the range of about 1.0 to about 20 weight percent, preferably an amount in the range of about 5 to about 15 weight percent, based on the total weight of the sorbent support component.
- The expanded perlite will generally be present in the sorbent support composition in an amount in the range of from about 10 to about 40 weight percent perlite based on the weight of the sorbent support composition, preferably in an amount in the range of from about 15 to about 30 weight percent.
- The promoter component will generally be present in the sorbent composition in an amount in the range of from about 1.0 to about 60 weight percent promoter component based on the total weight of the sorbent composition, preferably in an amount in the range of from about 10 to about 30 weight percent promoter component. When the promoter component comprises a bimetallic promoter component, the bimetallic promoter component should comprise a ratio of the two metals forming such bimetallic promoter component in the range of from about 20:1 to about 1:20. In a presently preferred embodiment of the present invention, the promoter component is a bimetallic promoter component comprising nickel and cobalt in a weight ratio of about 1:1.
- In the manufacture of a sorbent composition of the present invention, the support component is generally prepared by combining the components of the support component, zinc oxide, expanded perlite, and alumina in appropriate proportions by any suitable method or manner which provides for the intimate mixing of such components to thereby provide a substantially homogeneous mixture comprising zinc oxide, expanded perlite, and alumina. Any suitable means for mixing the components of the support component can be used to achieve the desired dispersion of such components. Examples of suitable mixing means include, but are not limited to, mixing tumblers, stationary shells or troughs, Muller mixers, which are of the batch or continuous type, impact mixers, and the like. It is presently preferred to use a Muller mixer in the mixing of the components of the support component.
- The components of the support component are mixed to provide a resulting mixture which can be in a form selected from the group consisting of wet mix, dough, paste, slurry, and the like. Such resulting 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. For example, if the resulting mixture is in the form of a wet mix, the wet mix can be densified, dried under a drying condition as disclosed herein, calcined under a calcining condition as disclosed herein, and thereafter shaped, or particulated, through the granulation of the densified, dried, calcined mix to form granulates. Also for example, when the mixture of the components of the support component results in a form of a mixture which is either in a dough state or paste state, such mixture can then be shaped, preferably extruded, to form a particulate, preferably cylindrical extrudates having a diameter in the range of from about {fraction (1/32)} inch to ½ inch and any suitable length, preferably a length in the range of from about ⅛ inch to about 1 inch. The resulting particulates, preferably cylindrical extrudates, are then dried under a drying condition as disclosed herein and then calcined under a calcining condition as disclosed herein. More preferably, when the mix is in the form of a slurry, the particulation of such slurry is achieved by spray drying the slurry to form microspheres thereof having a size in the range of from about 20 to about 500 microns. Such microspheres are then subjected to drying under a drying condition as disclosed herein and calcining under a calcining condition as disclosed herein.
- When the particulation is achieved by preferably spray drying, a dispersant component may 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 condensed phosphates, sulfonated polymers, and combinations thereof. The term condensed phosphates refers to any dehydrated phosphate where the H2O:P2O5 is less than about 3:1. Specific examples of suitable dispersants include sodium pyrophosphate, sodium metaphosphate, sulfonated styrene maleic anhydride polymer, and combinations thereof. The amount of a 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 a dispersant component used is generally in the range of from about 0.1 weight percent to about 8 weight percent.
- The alumina component of the base support can be any suitable compound of alumina that has cement-like properties which can help to bind the particulate composition together. Presently preferred is alumina, preferably peptized alumina.
- In the practice of the present invention, it is presently preferred that the sorbent composition be formed through spray drying. In preparing the preferred spray-dried sorbent composition, an acid component can be used. In general, the acid component can be an organic acid or a mineral 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.
- In preparing the preferred spray-dried sorbent composition a base support component, comprising zinc oxide, expanded perlite, and alumina can be contacted together in any manner known in the art that will form a mixture that is a liquid solution, a slurry, or a paste that is capable of being dispersed in a fluid-like spray. When a base support component is a solid, then it should be contacted in a liquid medium to form a mixture that is a liquid solution, a slurry, or a paste that is capable of being dispersed in a fluid-like spray. Suitable means for contacting these components are known in the art such as, for example, tumblers, stationary shells, troughs, Muller mixers, impact mixers, and the like.
- Generally, these components, after contacting to form a mixture, are contacted with an acid component as described hereinabove. However, the dry components and the acid component can be contacted together simultaneously or separately.
- After the components are contacted together to form a mixture, they are subjected to spray drying to form a spray-dried sorbent material having particles, preferably in the form of micro-spheres, that have a mean particle size in the ranges as disclosed herein. Spray drying is known in the art and is discussed inPerry's Chemical Engineers' Handbook, Sixth Edition, published by McGraw-Hill, Inc., at pages 20-54 through 20-58, which pages are incorporated herein by reference. Additional information can be obtained from the Handbook of Industrial Drying, published by Marcel Dekker Inc., at pages 243 through 293.
- The spray-dried sorbent material can then be dried under a drying condition as disclosed herein and then calcined, preferably in an oxidizing atmosphere such as in the presence of oxygen or air, under a calcining condition as disclosed herein to form a calcined, spray-dried sorbent material. The calcination can be conducted under any suitable condition that removes residual water and oxidizes any combustibles. Usually, the spray-dried base sorbent material is calcined in an oxygen-containing atmosphere.
- When the particulate support component comprising zinc oxide, perlite, and alumina is calcined, at least a portion of the zinc oxide and at least a portion of the alumina combine to form zinc aluminate (ZnAl2O4). The resulting calcined support component preferably comprises zinc aluminate in an amount in the range of from about 2 to about 50 weight percent, more preferably in the range of from about 5 to about 30 weight percent, and most preferably in the range of from 10 to 20 weight percent. The calcined support component preferably comprises zinc oxide in an amount in the range of from about 20 to about 95 weight percent, more preferably in the range of from about 40 to about 90 weight percent, and most preferably in the range of from about 60 to about 80 weight percent. The calcined support component, preferably comprises perlite in an amount in the range of from about 2 to about 50 weight percent, more preferably in the range of from about 5 to about 30 weight percent, and most preferably in the range of from 10 to 20 weight percent.
- Generally, the spray-dried sorbent 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 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 eight inch diameter stainless steel frame 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 resulting particulate (preferably spray-dried) calcined support component comprising zinc aluminate, zinc oxide, crushed expanded perlite, and optionally a binder, preferably alumina (if not all converted to zinc aluminate), is then incorporated with a promoter component.
- The promoter component which is useful in the practice of the present invention is promoter derived from one or more metals, metal oxides, or metal oxide precursors wherein the metal is selected from the group consisting of cobalt, nickel, iron, manganese, zinc, copper, molybdenum, silver, tin, vanadium, and antimony. Presently preferred is a promoter component of nickel or cobalt or a mixture of cobalt and nickel.
- Following the incorporating of the particulated, calcined support component, preferably by impregnation, with a promoter component, the resulting promoted particulates are then subjected to drying under a drying condition as disclosed herein and calcined under a calcining condition as disclosed herein prior to the subjecting of such dried, calcined, promoted particulates to reduction with a reducing agent, preferably hydrogen.
- The promoter component(s) may be incorporated onto, or with, the particulated (preferably spray-dried), calcined support component by any suitable means or method(s) for incorporating the promoter component(s) onto, or with, a substrate material, such as the dried and calcined particulates, which results in the formation of a promoted sorbent composition which can then be dried under a drying condition as disclosed herein and calcined under a calcining condition as disclosed herein to thereby provide dried, calcined, promoted particulates. The dried, calcined, promoted particulates can then be subjected to reduction with a reducing agent, preferably hydrogen, to thereby provide a sorbent composition of the present invention. Examples of means for incorporating the promoter component include impregnating, soaking or spraying, and combinations thereof.
- A preferred method of incorporating is impregnating using any standard incipient wetness impregnation technique (i.e., essentially completely filling the pores of a substrate material with a solution of the incorporating elements) for impregnating a substrate. A preferred method uses an impregnating solution comprising the desirable concentration of a promoter component so as to ultimately provide a promoted particulate which can then be subjected to drying and calcining followed by reduction with a reducing agent such as hydrogen. The impregnating solution can be any aqueous solution and amounts of such solution which suitably provides for the impregnation of the particulates of support component to give an amount of promoter component that provides, after reduction with a reducing agent, a reduced promoter component content sufficient to permit the removal of sulfur from cracked-gasoline or diesel fuel when such fluid is treated in accordance with a desulfurization process of the present invention.
- It can be desirable to use an aqueous solution of a promoter component for the impregnation of the particulates. A preferred impregnating solution comprises an aqueous 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.
- The concentration of the metal promoter component in the aqueous solution can be in the range of from about 0.1 gram of metal promoter component per gram of aqueous solution to about 5 grams of metal promoter component per gram of aqueous solution. Preferably, the weight ratio of metal promoter component to the aqueous medium of such aqueous 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.
- In preparing the spray-dried sorbent material, a promoter component can be added to the spray-dried sorbent material as a component of the original mixture, or they can be added after the original mixture has been spray dried and calcined. If a promoter component is added to the spray-dried sorbent material after it has been spray dried and calcined, the spray-dried sorbent material should be dried and calcined a second time. The spray-dried sorbent material is preferably dried a second time at a temperature generally in the range of from about 100° F. to about 650° F. Preferably, the spray-dried sorbent material can be dried a second time at a temperature generally in the range of from about 150° F. to about 600° F. and, more preferably, in the range of from 200° F. to 550° F. The time period for conducting the drying a second time is generally in the range of from about 0.5 hour to about 8 hours, preferably in the range of from about 1 hour to about 6 hours and, more preferably, in the range of from 1.5 hours to 4 hours. Such drying a second time is generally carried out at a pressure in the range of from about atmospheric (i.e., about 14.7 pounds per square inch absolute) to about 100 pounds per square inch absolute (psia), preferably about atmospheric. This spray-dried sorbent material is then calcined, preferably in an oxidizing atmosphere such as in the presence of oxygen or air, under a calcining condition as disclosed herein.
- A preferred impregnating solution is formed by dissolving a metal-containing compound (such as nickel nitrate hexahydrate) in water. It is acceptable to use somewhat of an acidic solution to aid in the dissolution of the metal-containing compound. 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.
- Generally, a drying condition, as referred to herein, can include a temperature in the range of from about 180° F. to about 290° F., preferably in the range of from about 190° F. to about 280° F. and, most preferably, in the range of from 200° F. to 270° F. Such drying condition 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 condition 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, most preferably about atmospheric, so long as the desired temperature can be maintained. Any drying methods(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.
- Generally, a calcining condition, as referred to herein, can include a temperature in the range of from about 700° F. to about 1600° F., preferably in the range of from about 800° F. to about 1500° F. and, more preferably, in the range of from 900° F. to about 1400° F. Such calcining condition can also include a pressure, generally in the range of from about 7 pounds per square inch absolute (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 2 hours to about 20 hours and, most preferably, for a time period in the range of from 3 hours to 15 hours.
- When the promoted particulates are calcined, at least a portion of the promoter metal and at least a portion of the zinc aluminate combine to form a promoter metal-zinc aluminate substitutional solid solution characterized by the formula: MZZn(1-Z)Al2O4, wherein M is the promoter metal and Z is a numerical value in the range of from 0.01 to 0.99. Further, upon calcination, at least a portion of the promoter metal and at least a portion of the zinc oxide combine to form a substitutional solid metal oxide solution characterized by the formula: MXZnYO, wherein M is the promoter metal, X is a numerical value in the range of from 0.01 to 0.99, and Y is a numerical value in the range of from 0.01 to 0.99. In the above formula, it is preferred for X to be in the range of from about 0.50 to about 0.90, more preferably from about 0.60 to about 0.80, and most preferably from 0.65 to 0.75. It is further preferred for Y to be in the range of from about 0.10 to about 0.50, more preferably from about 0.20 to about 0.40, and most preferably from 0.25 to 0.35. Preferably, Y is equal to (1-X).
- Substitutional solid solutions have unique physical and chemical properties that are important to the chemistry of the inventive sorbent composition described herein. Substitutional solid solutions are a subset of alloys that are formed by the direct substitution of the solute metal for the solvent metal atoms in the crystal structure. For example, it is believed that the promoter metal-zinc oxide substitutional solid metal oxide solution found in the oxidized (i.e., unreduced), calcined sorbent composition of the present invention is formed by the solute zinc metal atoms substituting for the solvent promoter metal atoms. There are three basic criteria that favor the formation of substitutional solid solutions: (1) the atomic radii of the two elements are within 15 percent of each other; (2) the crystal structures of the two pure phases are the same; and (3) the electronegativities of the two components are similar. The promoter metal (as the elemental metal or metal oxide) and zinc oxide employed in the inventive sorbent composition preferably meet at least two of the three criteria set forth above. For example, when the promoter metal is nickel, the first and third criteria, are met, but the second is not. The nickel and zinc metal atomic radii are within 10 percent of each other and the electronegativities are similar. However, nickel oxide (NiO) preferentially forms a cubic crystal structure, while zinc oxide (ZnO) prefers a hexagonal crystal structure. A nickel zinc oxide solid solution retains the cubic structure of the nickel oxide. Forcing the zinc oxide to reside in the cubic structure increases the energy of the phase, which limits the amount of zinc that can be dissolved in the nickel oxide structure. This stoichiometry control manifests itself microscopically in a 70:30 nickel zinc oxide solid solution (Ni0.7Zn0.3O) that is formed during oxidation (i.e., calcination or regeneration) and microscopically in the repeated regenerability of the sorbent.
- The calcined (i.e., oxidized or regenerated), promoted sorbent particulates preferably comprise the substitutional solid metal oxide solution (MXZnYO) in an amount in the range of from about 5 to about 70 weight percent, more preferably in the range of from about 10 to about 60 weight percent, still more preferably in the range of from about 20 to about 40 weight percent, and most preferably in the range of 25 to 35 weight percent. The calcined, promoted sorbent particulates preferably comprise the promoter metal-zinc aluminate substitutional solid solution (MZZn(1-Z)Al2O4) in an amount in the range of from about 2 to about 50 weight percent, more preferably in the range of from about 5 to about 30 weight percent, and most preferably in the range of from 10 to 20 weight percent. The calcined, promoted sorbent particulates preferably comprise zinc oxide in an amount in the range of from about 10 to about 90 weight percent, more preferably in the range of from about 20 to about 70 weight percent, still more preferably in the range of from about 30 to about 50 weight percent, and most preferably in the range of from 35 to 45 weight percent. The calcined, promoted sorbent particulates preferably comprise perlite in an amount in the range of from about 2 to about 50 weight percent, more preferably in the range of from about 5 to about 30 weight percent, and most preferably in the range of from 10 to 20 weight percent.
- Once the promoter component has been distributed on, or with, the particulated, calcined base support component, the desired reduced-valence promoter component sorbent is prepared by drying the resulting composition under a drying condition as disclosed herein followed by calcining under a calcining condition as disclosed herein to thereby provide dried, calcined, promoted particulates. The dried, calcined, promoted particulates are thereafter subjected to reduction with a suitable reducing agent, preferably hydrogen or an appropriate hydrocarbon so as to produce a composition having a substantially reduced-valence promoter component content therein, preferably a substantially zero content therein, with such zero valence promoter component being present in an amount sufficient to permit the removal of sulfur from a hydrocarbon-containing fluid such as cracked-gasoline or diesel fuel, according to the process disclosed herein.
- A sorbent composition having a reduced-valence promoter component of the present invention is a composition that has the ability to react chemically and/or physically with sulfur. It is also preferable that the sorbent composition removes diolefins and other gum-forming compounds from cracked-gasoline.
- A sorbent composition having a reduced-valence promoter component of the present invention comprises a promoter component that is in a substantially reduced valence state, preferably a zero valence state. Preferably, the reduced-valence promoter component is reduced nickel. The amount of reduced-valence promoter component, preferably reduced nickel, in a sorbent composition of the present invention is an amount which will permit the removal of sulfur from cracked-gasoline or diesel fuel. Such amounts of reduced-valence promoter component, preferably reduced nickel or cobalt or a mixture of nickel and cobalt are generally in the range of from about 1.0 to about 60 weight percent of the total weight of the sorbent composition (support composition plus promoter).
- In one presently preferred embodiment of the present invention, the reduced nickel is present in an amount in the range of from about 15 to about 30 weight percent based on the total weight of the nickel and the reduced nickel has been substantially reduced to zero valence.
- In another presently preferred embodiment of the present invention, zinc oxide is present in an amount in the range of from about 40 to about 80 weight percent zinc oxide based on the total weight of the sorbent support, expanded perlite is present in an amount in the range of from about 10 to about 30 weight percent expanded perlite based on the total weight of the sorbent support, and alumina is present in an amount in the range of from about 1.0 to about 20 weight percent based on the total weight of the sorbent support, and promoter metal is present prior to reduction in an amount in the range of from about 10 to about 30 weight percent promoter metal based on the total weight of the composition.
- During reduction of the oxidized sorbent particulates, it is preferred for at least a portion of the substitutional solid metal oxide solution (MXZnYO) found in the oxidized sorbent particulates to be reduced to form a substitutional solid metal solution characterized by the formula: MAZnB, wherein M is the promoter metal, A is a numerical value in the range of from 0.01 to 0.99, and B is a numerical value in the range of from 0.01 to 0.99. In the above formula for the substitutional solid metal solution, it is preferred for A to be in the range of from about 0.50 to about 0.97, more preferably in the range of from about 0.80 to about 0.95, and most preferably in the range of from 0.90 to 0.94. It is further preferred for B to be in the range of from about 0.03 to about 0.50, more preferably in the range of from about 0.05 to about 0.20, and most preferably in the range of 0.06 to 0.10. Preferably, B is equal to (1-A).
- The reduced sorbent particulates preferably comprise the substitutional solid metal solution (MAZnB) in an amount in the range of from about 5 to about 80 weight percent, more preferably in the range of from about 10 to about 60 weight percent, still more preferably in the range of from about 20 to about 50 weight percent, and most preferably in the range of from 30 to 40 weight percent. The reduced sorbent particulates preferably comprise the promoter metal-zinc aluminate (MZZn(1-Z)Al2O4), described above with reference to the oxidized (i.e., unreduced) sorbent particulates, in an amount in the range of from about 2 to about 50 weight percent, more preferably in the range of from about 5 to about 30 weight percent, and most preferably in the range of from 10 to 20 weight percent. The reduced sorbent particulates preferably comprise zinc oxide in an amount in the range of from about 10 to about 90 weight percent, more preferably in the range of from about 20 to about 60 weight percent, and most preferably in the range of from 30 to 40 weight percent. The reduced sorbent particulates preferably comprise perlite in an amount in the range of from about 2 to about 50 weight percent, more preferably in the range of from about 5 to about 30 weight percent, and most preferably in the range of from 10 to 20 weight percent.
- The sorbent compositions of the present invention, which are useful in the desulfurization process of the present invention, can be prepared by a process comprising:
- (a) mixing a support component preferably comprising zinc oxide, expanded perlite, and alumina, so as to form a mixture selected from the group consisting of a wet mix, a dough, a paste, a slurry, and the like and combinations thereof;
- (b) particulating, preferably spray-drying, the mixture to form particulates selected from the group consisting of granules, extrudates, tablets, pellets, spheres, micro-spheres, and the like and combinations thereof, preferably micro-spheres;
- (c) drying the particulate under a drying condition as disclosed herein to form a dried particulate;
- (d) calcining the dried particulate under a calcining condition as disclosed herein to form a calcined particulate;
- (e) incorporating, preferably impregnating, the calcined particulate with a promoter component thereof to form a promoted particulate;
- (f) drying the promoted particulate under a drying condition as disclosed herein to form a dried, promoted particulate;
- (g) calcining the dried, promoted particulate under a calcining condition as disclosed herein to form a calcined, promoted particulate; and
- (h) reducing the calcined, promoted particulate with a suitable reducing agent so as to produce a sorbent composition having a reduced-valence promoter component content therein, preferably a reduced-valence nickel content therein, and wherein the reduced-valence promoter component content is present in an amount effective for the removal of sulfur from a hydrocarbon-containing fluid such as cracked-gasoline or diesel fuel when such hydrocarbon-containing fluid is contacted with a sorbent composition(s) of the present invention according to a process(es) of the present invention.
- A process of using a novel sorbent composition(s) of the present invention to desulfurize a hydrocarbon-containing fluid, such as cracked-gasoline or diesel fuel, to provide a desulfurized cracked-gasoline or diesel fuel comprises:
- (a) desulfurizing, in a desulfurization zone, a hydrocarbon-containing fluid selected from the group consisting of cracked-gasoline, diesel fuel, with a sorbent composition of the present invention;
- (b) separating the desulfurized hydrocarbon-containing fluid from the resulting sulfurized sorbent composition;
- (c) regenerating at least a portion of the sulfurized sorbent composition to produce a regenerated, desulfurized, sorbent composition;
- (d) reducing at least a portion of the regenerated, desulfurized, sorbent composition to produce a reduced, regenerated, desulfurized sorbent composition; and
- (e) returning at least a portion of the reduced, regenerated, desulfurized sorbent composition to the desulfurization zone.
- The desulfurizing step (a) of the present invention is carried out under a set of conditions that includes total pressure, temperature, weight hourly space velocity, and hydrogen flow. These conditions are such that the sorbent composition can desulfurize the hydrocarbon-containing fluid to produce a desulfurized hydrocarbon-containing fluid and a sulfurized sorbent composition.
- In carrying out the desulfurization step of a process of the present invention, it is preferred that the cracked-gasoline or diesel fuel be in a gas or vapor phase. However, in the practice of the present invention, it is not essential that such hydrocarbon-containing fluid be totally in a gas or vapor phase.
- 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 preferred 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-containing fluid in essentially a vapor or gas phase. While such temperatures can be in the range of from about 100° F. to about 1000° F., it is presently preferred that the temperature be in the range of from about 400° F. to about 800° F. when treating a cracked-gasoline, and in the range of from about 500° F. to about 900° F. when treating a diesel fuel.
- Weight hourly space velocity (“WHSV”) is defined as the numerical ratio of the rate at which a hydrocarbon-containing fluid is charged to the desulfurization zone in pounds per hour at standard condition of temperature and pressure (“STP”) divided by the pounds of sorbent composition contained in the desulfurization zone to which the hydrocarbon-containing fluid 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 hr−1, preferably in the range of from about 1 hr−1 to about 20 hr−1.
- 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 and aromatic compounds in the hydrocarbon-containing fluid which is being treated with the solid reduced metal containing sorbent composition. Preferably, such agent is hydrogen.
- Hydrogen flow in the desulfurization zone is generally such that the mole ratio of hydrogen to hydrocarbon-containing fluid is the range of from about 0.1 to about 10, preferably in the range of from about 0.2 to about 3.
- The desulfurization zone can be any zone wherein desulfurization of cracked-gasoline or diesel fuel 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.
- 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 a hydrocarbon-containing fluid such as cracked-gasoline or diesel fuel.
- It is presently preferred when utilizing a fluidized bed reactor system that a sorbent composition be used having a particle size in the range of from about 10 micrometers to about 1000 micrometers. Preferably, such sorbent 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(s) of the present invention, the sorbent composition should generally have a particle size in the range of from 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 sorbent composition having a surface area in the range of from about 1 square meter per gram (m2/g) to about 1000 square meters per gram of sorbent composition, preferably in the range of from about 1 m2/g to about 800 m2/g.
- The separation of the desulfurized hydrocarbon-containing fluid, preferably gaseous or vaporized desulfurized cracked gasoline or diesel fuel and sulfurized sorbent composition, can be accomplished by any manner known in the art that can separate a solid from a gas. Examples of such means are cyclonic devices, settling chambers, impingement devices for separating solids and gases, and the like and combinations thereof. The desulfurized gaseous cracked-gasoline or desulfurized gaseous diesel fuel, can then be recovered and preferably liquefied. Liquification of such desulfurized hydrocarbon-containing fluid can be accomplished by any manner known in the art.
- The gaseous cracked-gasoline or gaseous diesel fuel, suitable as a feed in a process(es) of the present invention is a composition that contains, in part, olefins, aromatics, sulfur, as well as paraffins and naphthenes.
- The amount of olefins in gaseous cracked-gasoline is generally in the range of from about 10 to about 35 weight percent olefins based on the total weight of the gaseous cracked-gasoline. For diesel fuel there is essentially no olefin content.
- The amount of aromatics in gaseous cracked-gasoline is generally in the range of from about 20 to about 40 weight percent aromatics based on the total weight of the gaseous cracked-gasoline. The amount of aromatics in gaseous diesel fuel is generally in the range of from about 10 to about 90 weight percent aromatics based on the total weight of the gaseous diesel fuel.
- The amount of sulfur in the hydrocarbon-containing fluid, i.e. cracked-gasoline or diesel fuel, suitable for use in a process of the present invention can be in the range of from about 100 parts per million sulfur by weight of the cracked-gasoline to about 10,000 parts per million sulfur by weight of the cracked-gasoline and from about 100 parts per million sulfur by weight of the diesel fuel to about 50,000 parts per million sulfur by weight of the diesel fuel prior to the treatment of such hydrocarbon-containing fluid with a desulfurization process(es) of the present invention.
- The amount of sulfur in the desulfurized cracked-gasoline or desulfurized diesel fuel, following treatment in accordance with a desulfurization process of the present invention, is less than about 100 parts per million (ppm) sulfur by weight of hydrocarbon-containing fluid, preferably less than about 50 ppm sulfur by weight of hydrocarbon-containing fluid, and more preferably less than about 5 ppm sulfur by weight of hydrocarbon-containing fluid.
- In carrying out a process of the present invention, if desired, a stripper unit can be inserted before and/or after the regeneration of the sulfurized sorbent composition. Such stripper will serve to remove a portion, preferably all, of any hydrocarbon from the sulfurized sorbent composition. Such stripper can also serve to remove oxygen and sulfur dioxide from the system prior to introduction of the regenerated sorbent composition into the sorbent activation zone (i.e., sorbent reduction zone). The stripping comprises a set of conditions that includes total pressure, temperature, and stripping agent partial pressure.
- Preferably, the total pressure in a stripper, when employed, is in the range of from about 25 pounds per square inch absolute (psia) to about 500 psia.
- The temperature for such stripping can be in the range of from about 100° F to about 1000° F.
- The stripping agent is a composition that helps to remove a hydrocarbon(s) from the sulfurized sorbent composition. Preferably, the stripping agent is nitrogen.
- The sorbent regeneration zone employs a set of conditions that includes total pressure and sulfur removing agent partial pressure. Total pressure is generally in the range of from about 25 pounds per square inch absolute (psia) to about 500 psia.
- The sulfur removing agent partial pressure is generally in the range of from about 1 percent to about 25 percent 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 bum off any remaining hydrocarbon deposits that might be present. The preferred sulfur removing agent suitable for use in the sorbent regeneration zone is selected from oxygen-containing gases such as air.
- The temperature in the sorbent regeneration zone is generally in the range of from about 100° F. to about 1500° F., preferably in the range of from about 800° F. to about 1200° F.
- The sorbent regeneration zone can be any vessel wherein the desulfurizing or regeneration of the sulfurized sorbent composition can take place.
- The desulfurized sorbent composition is then reduced in an activation zone with a reducing agent so that at least a portion of the promoter component content of the sorbent composition is reduced to produce a solid reduced-valence promoter component to permit the removal of sulfur from a cracked-gasoline or diesel fuel according to the inventive process disclosed herein.
- In general, when practicing the present invention, the activation, i.e., reduction, of the desulfurized sorbent composition is carried out at a temperature in the range of from about 100° F. to about 1500° F. and at a pressure in the range of from about 15 pounds per square inch absolute (psia) to about 1500 psia. Such reduction is carried out for a time sufficient to achieve the desired level of promoter component reduction contained in the skin of the sorbent 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 activation, i.e., reduction, of the regenerated sorbent composition, at least a portion of the resulting activated (i.e., reduced) sorbent composition can be returned to the desulfurization zone.
- When carrying out the process of the present invention, the steps of desulfurization, regeneration, activation (i.e., reduction), and optionally stripping before and/or after such regeneration can be accomplished in a 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, activation, 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.
- It has been discovered that the inventive sorbent composition and inventive desulfurization process, described above, provide unique advantages when employed to remove sulfur from middle distillates, such as diesel fuel, jet fuel, and kerosene. One advantage of using the inventive system to remove sulfur from middle distillates is its ability to greatly reduced the amount of sulfur in the middle distillates without significantly reducing the amount of nitrogen in the middle distillates. The presence of nitrogen in a middle distillate, particularly diesel fuel, can advantageously improve the lubricity properties of the middle distillate. Conventional hydrotreating processes for removing sulfur from middle distillates remove significant amounts of nitrogen from the middle distillates. Thus, low-sulfur high-nitrogen middle distillates produced by the present invention have advantages (e.g., improved lubricity) over low-sulfur low-nitrogen middle distillates produced by conventional desulfurization processes.
- The middle distillate feed employed in the process of the present invention is preferably a mixture of hydrocarbons having a boiling range (ASTM D86-00) of from about 200° F. to about 800° F., more preferably from about 225° F. to about 775° F. The middle distillate feed preferably has a mid-boiling point (ASTM D86-00) of more than about 400° F., more preferably more than about 450° F., and still more preferably more than about 500° F. The middle distillate feed preferably has an API gravity (ASTM D287-92) in the range of from about 20 to about 50, more preferably from about 25 to about 45. The middle distillate feed preferably has a minimum flash point (ASTM D93-99) of at least about 80° F., more preferably at least about 90° F. Examples of suitable middle distillates include, but are not limited to, diesel fuel, jet fuel, kerosene, light cycle oil, and the like, and mixtures thereof. Most preferably, the middle distillate feed employed in the desulfurization process of the present invention consists essentially of diesel fuel boiling in the range of from 300° F. to 750° F., having a mid-boiling point of more than 510° F., having an API gravity in the range of from 30 to 38, and having a minimum flash point above 100° F. The properties described in this paragraph encompass preferred applications and uses for middle distillates, but are in no way to be construed as a limiting definition for middle distillates.
- Typically the middle distillate feed will have a sulfur content (ASTM D2622-82) of at least of about 100 ppmw and a nitrogen content (ASTM D4629-86) of at least about 25 ppmw. More typically, the middle distillate feed will have a sulfur content of at least 200 ppmw and a nitrogen content of at least 50 ppmw. When the middle distillate feed is desulfurized via the inventive desulfurization process described above, a substantial amount of the feed sulfur is removed without removing a substantial amount of the feed nitrogen. Preferably, desulfurization of the middle distillate feed in accordance with the inventive process/sorbent taught herein includes a sulfur conversion (i.e., weight percent reduction in total sulfur content of the feed) of at least about 80 weight percent, more preferably at least about 90 weight percent, still more preferably at least about 95 weight percent, even more preferably at least about 98 weight percent, and most preferably 99 weight percent. Preferably, desulfurization of the middle distillate feed includes a nitrogen conversion (i.e., weight percent reduction in total nitrogen content of the feed) of less than about 50 weight percent, more preferably less than about 40 weight percent, still more preferably less than about 30 weight percent, even more preferably in the range of from about 5 to about 30 weight percent, and most preferably in the range of from 10 to 25 weight percent. The resulting desulfurized middle distillate preferably has a total sulfur content (ASTM D2622-82) of less than about 50 ppmw, more preferably less than about 30 ppmw, still more preferably less than about 20 ppmw, and most preferably less than about 10 ppmw. The desulfurized middle distillate preferably has a total nitrogen content (ASTM D4629-86) of at least about 20 ppmw, more preferably at least about 40 ppmw, still more preferably at least about 60 ppmw, most preferably in the range of from 60 to 200 ppmw. The nitrogen to sulfur weight ratio of the desulfurized middle distillate is preferably in the range of from about 1 about to 100, more preferably about 2 to about 50, still more preferably about 4 to about 30, and most preferably 5 to 20.
- Another advantage of the inventive desulfurization process, is that the cetane number (ASTM D613-84) of the desulfurized product is nearly the same as the cetane number of the middle distillate feed. Preferably, the cetane number of the desulfurized product is within about 5 percent of the cetane number of the middle distillate feed, more preferably within 2 percent, and most preferably within 1 percent. Also, the initial boiling point, mid-boiling point, final boiling point, minimum flash point, API gravity and hydrogen content of the desulfurized product are substantially the same as the initial boiling point, mid-boiling point, final boiling point, minimum flash point, API gravity, and hydrogen content of the middle distillate feed. Preferably, the values of each of these properties (i.e., initial boiling point, mid-boiling point, final boiling point, minimum flash point, API gravity, and hydrogen content) for the desulfurized middle distillate product is within about 10 percent of the values for the middle distillates feed, more preferably within about 5 percent, still more preferably within about 2 percent, and most preferably within 1 percent. Thus, the inventive desulfurization process is highly sulfur selective, and provides only minor changes, if any, in other properties of the middle distillate feed.
- The following examples are intended to be illustrative of the present invention and to teach one of ordinary skill in the art to make and use the invention. These examples are not intended to limit the invention in any way.
- A solid reduced nickel sorbent system was produced by mixing 10% alumina (Vista Dispal), 40% diatomaceous earth (World Chemical), and 50% zinc oxide with water at 42% solids using tetra sodium pyrophosphate (TSPP) as the dispersing agent.
- The resulting slip was spray dried using a Niro Mobil Minor Spray Drier fitted with a 0.035 inch air cap and a 0.35 inch fountain head nozzle. The inlet temperature was 320° C. and the outlet temperature was 150° C. Air flow through the nozzle was 70 liters per minute. The slip was delivered at approximately 43 cc/min H2O.
- The spray dried product was dried in air using a muffle furnace at a temperature of 150° C. for 1 hour and then calcined at a temperature of 635° C. for a period of 1 hour.
- The resulting calcined composition was screened to remove fines <40 microns and oversized particles of >250 microns.
- The screened sorbent was impregnated with 12% nickel (as the metal) using melted nickel nitrate hexahydrate in 5% water to get it to melt/dissolve. The resulting solution was then sprayed onto the sorbent using a Sono-Tec sprayer while the sorbent particles were rotated in a baffled cement mixer type drum. The nickel impregnated sorbent was again calcined at a temperature of 635° C. for 1 hour.
- The calcined 12% nickel sorbent composition was again impregnated with 15% nickel as carried out supra.
- The resulting 27% nickel impregnated sorbent was then calcined at a temperature of 635° C. for a period of 1 hour to provide a 30% (by weight) of a nickel impregnated sorbent system.
- The resulting impregnated sorbent system has a Davison attrition resistance value of 19.26.
- 10 grams of the sorbent as prepared in Example I were placed in a 12 inch diameter quartz tube having a length of about 12 inches and having a glass frit positioned above the lower ⅓ thereof so as to provide an inert support for the bed of sorbent which was placed thereon.
- During each cycle, gaseous cracked-gasoline was pumped upwardly through the reactor at a rate of 13.6 ml per hour. The gaseous cracked-gasoline had a motor octane number of 80.6 (MON) or a research octane number of 92.1 (RON), an olefin content of 21.2 weight percent, 340 parts per million sulfur by weight sulfur-containing compounds based on the total weight of the gaseous cracked-gasoline and about 0.03 weight percent thiophenic compounds based on the weight of sulfur-containing compounds in the gaseous cracked-gasoline.
- During each cycle, the reactor was maintained at a temperature of 700° F. and a pressure of 15 pounds per square inch absolute (psia). Hydrogen flow was at 150 standard cubic centimeters per minute (sccm) diluted with 150 sccum of nitrogen.
- Before cycle 1 was initiated, the sorbent was reduced with hydrogen flowing at a rate of 300 sccm at a temperature of 700° F. for a period of one hour. Each cycle consisted of four hours with the product sulfur (ppm) for each cycle measured at one hour intervals over each four-hour cycle period. After each cycle, the sorbent was regenerated at 900° F. for two hours with a mixture of oxygen and nitrogen containing four volume percent oxygen, then purged with nitrogen (regeneration), and then reduced in hydrogen flowing at a rate of 300 cc for one hour at 700° F. (activation).
- The sorbent compositions were each tested over 2 cycles. Each cycle utilized a mixture of 150 sccm hydrogen and 150 sccm nitrogen and 350 sccm/hydrocarbon.
- The following results were obtained:
Cycle 1 2 PPM Sulfur 10 5 PPM Sulfur 20 20 PPM Sulfur 25 15 PPM Sulfur 20 15 - A solid reduced nickel sorbent system was produced by mixing 13.75% alumina (nitric acid peptized Condea Disperal), 17.25% milled expanded perlite (RIF 27M), and 69% zinc oxide with water at 42% solids using ammonium polyacrylate as the dispersing agent.
- The resulting slip was spray dried using a Niro Mobil Minor Spray Drier fitted with a 0.035 inch air cap and a 0.35 inch fountain head nozzle. The inlet temperature was 320° C. and the outlet temperature was 150° C. Air flow through the nozzle was 70 liters per minute. The slip was delivered at approximately 43 cc/min H2O.
- The spray dried product was dried in air using a muffle furnace at a temperature of 150° C. for 1 hour and then calcined at a temperature of 635° C. for a period of 1 hour.
- The resulting calcined composition was screened to remove fines <40 microns and oversized particles of >250 microns.
- The screened sorbent was impregnated with 15% nickel (as the metal) using melted nickel nitrate hexahydrate in 5% water to get it to melt/dissolve. The resulting solution was then sprayed onto the sorbent using a Sono-Tec sprayer while the sorbent particles were rotated in a baffled cement mixer type drum. The nickel impregnated sorbent was again calcined at a temperature of 635° C. for 1 hour.
- One half of the resulting calcined 15% nickel sorbent composition was again impregnated with 15% nickel as carried out supra.
- The resulting 30% nickel impregnated sorbent was then calcined at a temperature of 635° C. for a period of 1 hour to provide a 30% (by weight) of a nickel impregnated sorbent system.
- The resulting impregnated sorbent system has a Davison attrition resistance value of 10.
- 10 grams of each of the sorbents as prepared in Example III (15% and 30% nickel) were separately placed in ½ inch diameter quartz tubes having a length of about 12 inches and having a glass frit positioned above the lower ⅓ thereof so as to provide an inert support for the bed of sorbent which was placed thereon in each of the quartz tubes.
- During each cycle, gaseous cracked-gasoline was pumped upwardly through the reactor at a rate of 13.6 ml per HR. The gaseous cracked-gasoline had a motor octane number of 80.6 (MON) or a research octane number of 92.4 (RON), an olefin content of 21.2 weight percent, 340 parts per million sulfur by weight sulfur containing compound based on the total weight of the gaseous cracked-gasoline and about 0.03 weight percent thiophenic compounds based on the weight of sulfur-containing compounds in the gaseous cracked-gasoline.
- During each cycle, the reactor was maintained at a temperature of 700° F. and a pressure of 15 pounds per square inch absolute (psia). Hydrogen flow was at 150 standard cubic centimeters per minute (sccm) diluted with 150 sccm of nitrogen.
- Before cycle 1 was initiated, the sorbent was reduced with hydrogen flowing at a rate of 300 sccm at a temperature of 700° F. for a period of one hour. Each cycle consisted of four hours with the product sulfur (ppm) for each cycle measured at one hour intervals over each four-hour cycle period. After each cycle, the sorbent was regenerated at 900° F. for two hours with a mixture of oxygen and nitrogen containing four volume percent oxygen, then purged with nitrogen (regeneration) and then reduced in hydrogen flowing at a rate of 300 cc for one hour at 700° F. (activation).
- The following results were obtained:
TABLE 1 PPM Sulfur in Cracked-Gasoline Using 15% Ni Sorbent System Cycle 1 2 3 4 5 ppm sulfur 5 5 10 <5 5 ppm sulfur 5 5 5 <5 <5 ppm sulfur 5 5 10 10 <5 ppm sulfur <5 <5 -
TABLE 2 PPM Sulfur in Cracked-Gasoline Using 30% Ni Sorbent System Sorption Cycle 1 2 3 4 5 ppm sulfur <5 <5 <5 5 <5 ppm sulfur <5 <5 10 5 5 ppm sulfur <5 5 <5 <5 5 - The above data clearly demonstrate that the sorbent system of the present invention provides a system for the ready removal of sulfur from a hydrocarbon containing fluid such as cracked-gasoline.
- In addition, due to the low Davison attrition value of the sorbent systems of Example III, there is provided an operable sorbent system which is attrition resistant and thus capable of extended use prior to the need for replacement of same.
- Use of the milled expanded perlite in the formation of the sorbent systems of Example III provided a sorbent composition which has only two thirds the packing density of the sorbent system of Example I, and thus takes only two thirds the weight to fill the same volume. Moreover, the majority of the pore volume of the resulting composition was as macropores which in turn provided a system most suitable for the removing of gasoline sulfur.
- A solid reduced nickel sorbent system was produced by combining 175.9 pounds of deionized water and 28.3 pounds of alumina (Vista Dispal™) in a mixer. The water/alumina slurry was mixed until the alumina was peptized. In a separate mixer, 27.4 pounds of milled expanded perlite (R/F 27M) was dry-blended with 104.8 pounds of powdered zinc oxide. The perlite/ZnO dry mixture was slowly added to the water/alumina slurry while mixing was continued. The resulting support mixture was mixed until homogeneous.
- The support mixture was then spray dried in a 33 foot spray drier having a wheel atomizer which spun at 9,000 RPM. The air charged to the spray drier during drying had an inlet temperature of about 500° F. and an outlet temperature of about 280° F. The microspherical support particulates produced by spray drying were then dried at about 250° F. for about 3 hours and calcined on a belt calciner at a temperature of about 635° C. for about 1.5 hours.
- The calcined support particulates were then sieved to remove oversized particles (larger than 100 mesh) and fine particles (smaller than 635 mesh). The sieved support particulates were then placed in a baffled cement mixer-type mixer and impregnated with nickel by spraying an aqueous solution of nickel nitrate hexahydrate on the support particulates while the mixer was rotated. The material was then discharged from the mixer and dried at 250° F. for about 8 hours, then calcined on a belt calciner at 635° C. for 1.5 hours. The calcined (i.e., oxidized) promoted sorbent particulates were then sieved to remove oversized particles (larger than 100 mesh) and fine particles (smaller than 635 mesh).
- A portion of the resulting calcined (i.e., oxidized) promoted sorbent was charged to a fixed fluidized bed 1 inch I.D. quartz reactor. The sorbent in the reactor was then reduced in hydrogen flowing at 300 sccm at 750° F. for 1 hour. The reduced promoted sorbent was then cooled with nitrogen and removed from the reactor.
- Samples of the calcined unpromoted support, oxidized promoted sorbent, and reduced promoted sorbent, prepared in Example V, were analyzed using X-ray diffraction and Phase Filtering (R. V. Siriwardane, J. A. Poston, G. Evans, Jr.Ind. Eng. Chem. Res. 33 (1994) 2810-2818), an adapted form of Rietveld modeling (RIQAS rietveld analysis, Operators Manual, Material Data, Inc., Berkley, Calif. (1999)). All X-ray diffraction measurements were taken using a Philips XRG 3100 generator equipped with a long fine focus copper X-ray source powered at 40 kV & 30 mA; Philips 3020 digital goniometer & Philips 3710 MPD control computer; and a Kevex PSI Peltier cooled silicon detector. The Kevex detector was operated with a Kevex 4601 ion pump controller, Kevex 4608 Peltier current supply, Kevex 4621 detector bias, Kevex 4561A pulse processor, and Kevex 4911-A single channel analyzer.
- Diffraction patterns were acquired using Philips APD version 4.1 c software. All Rietveld calculations were performed using Material Data, Inc. Riqas version 3.1c software (Outokumpu HSC Chemistry for Windows: Users Guide, Outokumpo Research Oy, Pori, Finland (1999)). The programs were run under the MS Windows® 95 operating system using an Intel Pentium® III 300 MHz class personal computer equipped with 128 MB of RAM.
- The X-ray diffraction analysis of the calcined unpromoted support indicated that it contained the following components in the following amounts:
- Zinc Oxide (ZnO): 70.3 wt. %
- Zinc Aluminate (ZnAl2O4): 14.9 wt. %
- Perlite: 14.8 wt. %.
- The X-ray diffraction analysis of the oxidized promoted sorbent indicated that it contained the following components in the following amounts:
- Zinc Oxide (ZnO): 40.0 wt. %
- Perlite: 13.5 wt. %
- Zinc Aluminate Substitutional Solid Solution (NiZZn(1-Z)Al2O4): 15.2 wt. %
- Nickel Zinc Oxide Substitutional Solid Solution (Ni0.7Zn0.3O): 31.2 wt. %.
- The X-ray diffraction analysis of the reduced promoted sorbent indicated that it contained the following components in the following amounts:
- Zinc Oxide (ZnO): 36.9 wt. %
- Perlite: 13.1 wt. %
- Nickel Zinc Aluminate Substitutional Solid Solution (NiZZn(1-Z)Al2O4): 15.9 wt. %
- Nickel Zinc Metal Substitutional Solid Solution (Ni0.92Zno0.08): 34.1 wt. %.
- This example demonstrates that the inventive desulfurization process is highly effective for removing sulfur from middle distillates, such as diesel fuel, without significantly reducing nitrogen levels or significantly altering other important fuel properties, such as API gravity, density, and hydrogen content.
- Desulfurization tests were preformed on two different diesel feeds by contacting the feeds with a sorbent composition in a fixed bed reactor. The reactor was a standard steel reactor having a ¾ inch inner diameter and a ¼ thermowell.
- The sorbent used in the reactor was prepared by mixing 2,281.3 grams of aluminum hydroxide powder (DISPAL™ Alumina Powder, available from CONDEA Vista Company, Houston, Tex.) and 4,562.7 grams of distilled water to form an alumina mixture. In a large mix muller, 2,737.6 grams of expanded perlite (HARBORLITE™ 205, available from Harborlite Corporation, Antonito, Colo.), 115.0 grams of 5% nitric acid, and 2,185.0 grams of distilled water were combined. The resulting perlite-containing mixture was then mixed for about 5 minutes. Thereafter, 8,601.0 grams of zinc oxide powder (available from Zinc Corporation, Monaca, Pa.) were added to the perlite-containing mixture. The resulting zinc oxide-containing mixture was then mixed for about 10 minutes and allowed to set at ambient conditions for about 1 hour. The alumina mixture, described above, was then added to the zinc oxide-containing mixture over a period of about 12 minutes, and thereafter mixed for an additional 3 minutes. The consistency of the resulting mixture was a sticky paste. The paste was extruded into ⅛ inch thick and {fraction (1/16)} inch diameter extrudate. The resulting extrudate was placed in a muffle furnace and dried by ramping the temperature in the furnace at 3° C./min to 150° C. and holding at 150° C. for 1 hour. The dried extrudate was then calcined by ramping the temperature in the furnace at 5° C./min to 635° C. and holding at 635° C. for 1 hour. A 100 gram quantity of the calcined extrudate was then impregnated with nickel by spraying 50 grams of a 15 weight percent nickel solution onto the extrudate with an ultrasonic nozzle, in accordance with standard incipient wetness impregnation techniques. The resulting once-impregnating extrudate was placed in a muffle furnace and dried by ramping the temperature in the furnace at 3° C./min to 150° C. and holding at 150° C. for 1 hour. The dried impregnated extrudate was then calcined by ramping the temperature in the furnace at 5° C./min to 635° C. and holding at 635° C. for 1 hour. The calcined, once-impregnated extrudate was then impregnated again with nickel by spraying 42 grams of a 15 weight percent nickel solution onto the once-impregnated extrudate with an ultrasonic nozzle, in accordance with standard incipient wetness impregnation techniques. The resulting twice-impregnating extrudate was placed in a muffle furnace and dried by ramping the temperature in the furnace at 3° C./min to 150° C. and holding at 150° C. for 1 hour. The dried twice-impregnated extrudate was then calcined by ramping the temperature in the furnace at 5° C./min to 635° C. and holding at 635° C. for 1 hour. The resulting nickel-impregnating sorbent (in the form of {fraction (1/16)} inch diameter extrudate) was the sorbent composition employed in the desulfurization tests described in this example.
- The nickel-impregnated sorbent was loaded in the reactor as follows:
- (1) 5 inches of R268 support alundum (bottom);
- (2) 39 grams of 36 grit alundum;
- (3) Dry packed bed of diluted sorbent—30.5 grams of the sorbent mixed with grit alundum; and
- (4) 26 grams if 36 grit alundum (top pre-heat section).
- The sorbent was reduced with hydrogen prior to testing. The testing procedure consisted of a fixed-bed, downflow feed/hydrogen adsorption, followed by a nitrogen purge, a nitrogen/air regeneration, another nitrogen purge, and a hydrogen reduction. The reaction conditions under which the diesel fuel was contacted with the sorbent composition in the reactor included a temperature of about 750° F., a pressure of about 500 psig, and a diesel flow rate of about 2 LHSV. Hydrogen was co-fed with the diesel feed to the reactor at a rate of about 4,000 SCFB.
- Several 60 hour runs were preformed for each diesel feed tested. Table 3, below, describes the properties of a first diesel feed, and summarizes various properties of the desulfurized products for 5 individual runs. The following teat procedures were used:
- Density (g/ml): ASTM D4052-96.
- API Gravity: calculated based on density and API Gravity definition.
- Hydrogen: Hydrogen NMR.
- Boiling Points: either ASTM D2887-01 or ASTM D86-01, depending on sample.
TABLE 3 Desulfurization of Diesel Feed #1 (750° F., 500 psig, 2 WHSV, 4000 SCFB H2) Diesel Prod. Prod. Prod. Prod. Prod. Property Feed #1 Run #1 Run #2 Run #3 Run #4 Run #5 Sulfur (ppmw) 485 5.1 7.9 5.3 6.0 10.9 S Conv. — 98.9 98.4 98.9 98.8 97.8 (% by wt) Nitrogen 161 106.0 114.0 108.2 113.8 116.6 (ppmw) N Conv. — 22.6 16.8 21.0 16.9 14.9 (% by wt) API Gravity 31.99 32.05 32.06 32.05 32.00 31.97 Density (g/ml) 0.8485 0.8481 0.8481 0.8481 0.8646 0.8485 Hydrogen (wt %) 12.82 12.83 12.82 12.79 12.77 12.78 IBP (° F.) 294 — — — — — Mid-BP (° F.) 540 — — — — — FBP (° F.) 728 — — — — — - Table 4, below, describes the properties of a second diesel feed, and summarizes various properties of the desulfurized products for 4 individual runs.
TABLE 4 Desulfurization of Diesel Feed #2 (750° F., 500 psig, 2 WHSV, 4000 SCFB H2) Feed #2 Prod. Prod. Prod. Prod. Property Property Run #1 Run #2 Run #3 Run #4 Sulfur (ppmw) 420.0 11.3 14.9 7.9 5.4 S Conv. (% by wt) — 97.3 96.4 98.1 98.7 Nitrogen (ppmw) 99.0 86.0 89.0 82.0 76.0 N Conv. (% by wt) — 13.1 10.1 17.2 23.2 API Gravity 33.18 33.02 33.02 33.16 32.98 Density (g/ml) 0.8422 0.8430 0.8430 0.8423 0.8432 Hydrogen (wt %) 12.64 13.15 12.94 12.60 12.49 IBP (° F.) 221.3 — — — — Mid-BP (° F.) 520.1 — — — — FBP (° F.) 757.5 — — — — - The test results summarized in Tables 3 and 4 show that the inventive desulfurization process provides high sulfur conversion rates with low nitrogen conversion rates. Further, the test results show that the inventive desulfurization process causes very little change in other fuel properties, such as API gravity, density, and hydrogen content.
- Reasonable variations, modifications, and adaptations can be made within the scope of this disclosure and the appended claims without departing from the scope of this invention.
Claims (50)
1. A low-sulfur diesel fuel composition comprising less than about 50 ppmw sulfur and at least about 20 ppmw nitrogen, wherein said low-sulfur diesel fuel has been produced via a desulfurization process comprising the step of contacting a diesel feed containing sulfur and nitrogen with a sorbent composition under desulfurization conditions sufficient to remove sulfur from said diesel feed, wherein said sorbent composition comprises zinc oxide and a promoter metal component.
2. The low-sulfur diesel fuel of claim 1 , wherein said promoter metal component was reduced prior to said contacting step.
3. The low-sulfur diesel fuel of claim 1 , wherein said contacting step includes removing at least about 80 weight percent of the sulfur and less than about 50 weight percent of the nitrogen from said diesel feed.
4. The low-sulfur diesel fuel of claim 1 , wherein said sorbent composition comprises said zinc oxide in an amount in the range of from about 10 to about 90 weight percent and said promoter metal component in an amount in the range from about 5 to about 80 weight percent.
5. The low-sulfur diesel fuel of claim 1 having a nitrogen to sulfur weight ratio in the range of from about 2 to about 50.
6. The low-sulfur diesel fuel of claim 1 comprising less than about 30 ppmw sulfur and at least about 40 ppmw nitrogen.
7. The low-sulfur diesel fuel of claim 6 , wherein said contacting step includes removing at least about 95 weight percent of the sulfur and less than about 30 weight percent of the nitrogen from said diesel feed.
8. The low-sulfur diesel fuel of claim 7 having a nitrogen to sulfur weight ratio in the range of from about 4 to about 30.
9. The low-sulfur diesel fuel of claim 8 , wherein said sorbent composition comprises said zinc oxide in an amount in the range from about 20 to about 60 weight percent and said promoter metal component in an amount in a range of from about 10 to about 60 weight percent.
10. The low-sulfur diesel fuel of claim 9 , wherein said promoter metal component is in a substantially reduced valence state.
11. The low-sulfur diesel fuel of claim 10 , wherein said promoter metal component comprises a promoter metal selected from the group consisting of nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, antimony, and vanadium.
12. The low-sulfur diesel fuel of claim 11 , wherein said promoter metal is nickel.
13. The low-sulfur diesel fuel of claim 12 , wherein a substantial portion of said promoter metal component is in a zero valence state.
14. The low-sulfur diesel fuel of claim 1 , wherein said promoter metal component is characterized by the formula MAZnB, wherein M is a promoter metal and A and B are each numerical values in the range from of 0.01 to 0.99.
15. The low-sulfur diesel fuel of claim 14 , wherein said promoter metal is selected from the group consisting of nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, antimony, and vanadium and wherein A is in the range of from about 0.50 to about 0.97 and B is in the range of from about 0.03 to about 0.50.
16. The low-sulfur diesel fuel of claim 14 , wherein said promoter metal is nickel, A is in the range of from 0.80 to 0.95, and B is in the range of from 0.05 to 0.20.
17. The low-sulfur diesel fuel of claim 1 comprising less than about 20 ppmw sulfur and at least about 60 ppmw nitrogen.
18. The low-sulfur diesel fuel of claim 1 having a nitrogen to sulfur weight ratio in the range of from 5 to 20.
19. A desulfurization process for removing sulfur from a hydrocarbon-containing feed comprising sulfur and nitrogen, said desulfurization process comprising the steps of:
(a) contacting said hydrocarbon-containing feed with a sorbent composition in a desulfurization zone under desulfurization conditions sufficient to remove at least about 80 weight percent of the sulfur and less than about 50 weight percent of the nitrogen from said hydrocarbon-containing feed, thereby providing a desulfurized hydrocarbon-containing product and a sulfurized sorbent composition.
20. The desulfurization process of claim 19 , wherein said hydrocarbon-containing feed comprises at least about 100 ppmw sulfur and at least about 25 ppmw nitrogen and wherein said desulfurized hydrocarbon-containing product comprises less than about 50 ppmw sulfur and at least about 20 ppmw nitrogen.
21. The desulfurization process of claim 20 , wherein said desulfurized hydrocarbon-containing product has a nitrogen to sulfur weight ratio in the range from about 2 to about 50.
22. The desulfurization process of claim 19 , wherein said contacting step includes removing at least about 90 weight percent of the sulfur and less than about 40 weight percent of the nitrogen from said hydrocarbon-containing feed.
23. The desulfurization process of claim 22 , wherein said desulfurized hydrocarbon-containing product has a nitrogen to sulfur weight ratio in the range from about 4 to about 30.
24. The desulfurization process of claim 23 , wherein said contacting step includes removing at least about 95 weight percent of the sulfur and less than about 30 weight percent of the nitrogen from said hydrocarbon-containing feed.
25. The desulfurization process of claim 19 , wherein said hydrocarbon-containing feed is diesel fuel.
26. The desulfurization process of claim 19 , wherein said sorbent composition comprises zinc oxide and reduced valence promoter metal.
27. The desulfurization process of claim 26 , wherein said sorbent composition comprises said zinc oxide in an amount in the range of from about 10 to about 90 weight percent and said reduced valence promoter metal in amount in the range of from about 1.0 to about 60 weight percent.
28. The desulfurization process of claim 27 , wherein said reduced valence promoter metal is selected from the group consisting nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, antimony, and vanadium.
29. The desulfurization process of claim 28 , wherein said reduced valence promoter is nickel.
30. The desulfurization process of claim 26 , wherein a substantial portion of said reduced valence promoter metal is in a zero valence state.
31. The desulfurization process of claim 26 , wherein said sorbent composition further comprises perlite.
32. The desulfurization process of claim 19 , further comprising the step of:
(b) contacting at least of portion of said sulfurized sorbent composition with an oxygen-containing regeneration stream in a regeneration zone under regeneration conditions sufficient to remove sulfur from said sulfurized sorbent composition, thereby providing an oxidized sorbent composition.
33. The desulfurization process of claim 32 , further comprising the step of:
(c) contacting at least a portion of said oxidized sorbent composition with a hydrogen-containing reducing stream in a reducing zone under reducing conditions sufficient to reduce said oxidized sorbent composition, thereby providing a reduced sorbent composition.
34. The desulfurization process of claim 33 , further comprising the step of:
(d) transporting at least of portion of said reduced sorbent composition from said reducing zone to said desulfurization zone.
35. The desulfurization process of claim 34 , wherein steps (a), (b), (c), and (d) are performed simultaneously.
36. A desulfurized hydrocarbon-containing product produced by the process of claim 19 .
37. A desulfurization process for removing sulfur from a diesel feed comprising at least about 100 ppmw sulfur and at least about 25 ppmw nitrogen, said desulfurization process comprising the steps of:
(a) contacting said diesel feed with a reduced sorbent composition in a desulfurization zone under desulfurization conditions sufficient to remove at least about 90 weight percent of the sulfur and less than about 40 weight percent of the nitrogen from said diesel feed, thereby providing a desulfurized diesel fuel and a sulfurized sorbent composition;
(b) contacting at least a portion of said sulfurized sorbent composition with an oxygen-containing regeneration stream in a regeneration zone under regeneration conditions sufficient to remove sulfur from said sulfurized sorbent composition, thereby providing an oxidized sorbent composition;
(c) contacting at least a portion of said oxidized sorbent composition with a hydrogen-containing reducing stream in a reducing zone under reducing conditions sufficient to reduce said oxidized sorbent composition, thereby providing said reduced sorbent composition; and
(d) returning at least a portion of said reduced sorbent composition to said desulfurization zone.
38. The desulfurization process of claim 37 , wherein said desulfurized diesel fuel comprises less than about 50 ppmw sulfur and at least about 20 ppmw nitrogen and wherein said desulfurized diesel fuel has a nitrogen to sulfur weight ratio in the range of from about 2 to about 50.
39. The desulfurization process of claim 37 , wherein said desulfurized diesel fuel has a cetane number and an API gravity within about 5 percent of said diesel feed.
40. The desulfurization process of claim 37 , wherein said desulfurized diesel fuel comprises less than about 20 ppmw sulfur and at least about 60 ppmw nitrogen and wherein said desulfurized diesel fuel has a nitrogen to sulfur weight ratio in the range of from about 4 to about 30.
41. The desulfurization process of claim 40 , wherein said desulfurized diesel fuel has a cetane number and an API gravity within about 2 percent of said diesel feed.
42. The desulfurization process of claim 37 , wherein said reduced sorbent composition comprises zinc oxide and reduced valence promoter metal.
43. The desulfurization process of claim 42 , wherein said sorbent composition comprises said zinc oxide in an amount in the range of from about 10 to about 90 weight percent and said reduced valence promoter metal in amount in the range of from about 1.0 to about 60 weight percent.
44. The desulfurization process of claim 43 , wherein said reduced valence promoter metal is selected from the group consisting nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, antimony, and vanadium.
45. The desulfurization process of claim 44 , wherein said reduced valence promoter metal is nickel.
46. The low-sulfur diesel fuel of claim 37 , wherein said reduced sorbent composition comprises zinc oxide and a reduced valence promoter metal component characterized by the formula MAZnB, wherein M is a promoter metal and A and B are each numerical values in the range of from 0.01 to 0.99.
47. The low-sulfur diesel fuel of claim 46 , wherein said promoter metal is selected from the group consisting of nickel, cobalt, iron, manganese, copper, zinc, molybdenum, tungsten, silver, antimony, and vanadium and wherein A is in the range of from about 0.50 to about 0.97 and B is in the range of from about 0.03 to about 0.50.
48. The low-sulfur diesel fuel of claim 47 , wherein said promoter metal is nickel, A is in the range of from 0.80 to 0.95, and B is in the range of from 0.05 to 0.20.
49. The desulfurization process of claim 37 , wherein steps (a), (b), (c), and (d) are performed simultaneously.
50. A desulfurized diesel fuel produced by the process of claim 37.
Priority Applications (2)
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US10/738,141 US20040140244A1 (en) | 2000-05-30 | 2003-12-17 | Desulfurization and sorbents for same |
PCT/US2004/041617 WO2005058468A2 (en) | 2003-12-17 | 2004-12-13 | Desulfurization and sorbents for same |
Applications Claiming Priority (31)
Application Number | Priority Date | Filing Date | Title |
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US09/580,611 US6429170B1 (en) | 2000-05-30 | 2000-05-30 | Sorbents for desulfurizing gasolines and diesel fuel |
ARP010102459A AR032338A1 (en) | 2000-05-30 | 2001-05-23 | SORBENTLY SUITABLE COMPOSITION FOR THE REMOVAL OF SULFUR FROM CROSSED GASOLINES AND DIESEL FUELS, PROCESS FOR THEIR PRODUCTION, PROCESS FOR THE REMOVAL OF SULFUR USING AND GASOLINE AND DIESEL FUEL TREATED |
ARP010102159 | 2001-05-23 | ||
NO20025768 | 2001-05-29 | ||
ININ02/01200 | 2001-05-29 | ||
JP587904/01 | 2001-05-29 | ||
ZA7703/02 | 2001-05-29 | ||
BRP10111235-0 | 2001-05-29 | ||
VE001140/01 | 2001-05-29 | ||
KR7013609/02 | 2001-05-29 | ||
HUP0302229 | 2001-05-29 | ||
AU265256/01 | 2001-05-29 | ||
CA002404643A CA2404643C (en) | 2000-05-30 | 2001-05-29 | Desulfurization and sorbents for same |
EP01939774.4 | 2001-05-29 | ||
VE114001 | 2001-05-29 | ||
HU0302229A HU228331B1 (en) | 2000-05-30 | 2001-05-29 | Desulfurization and sorbents for same |
EP01939774A EP1315560B1 (en) | 2000-05-30 | 2001-05-29 | Desulfurization and sorbents for same |
SG200206356-8 | 2001-05-29 | ||
PCT/US2001/017619 WO2001091899A1 (en) | 2000-05-30 | 2001-05-29 | Desulfurization and sorbents for same |
WOPCT/US01/17619 | 2001-05-29 | ||
HRP20020791A | 2001-05-29 | ||
CN01807982.2 | 2001-05-29 | ||
PLP363349 | 2001-05-29 | ||
EG569/20001 | 2001-05-29 | ||
MXPA/A/2002/009728 | 2001-05-29 | ||
CA2404643 | 2001-05-29 | ||
RU2002135590 | 2001-05-29 | ||
US10/072,209 US6864215B2 (en) | 2000-05-30 | 2002-02-06 | Sorbents for desulfurization |
PH1-2002-00690 | 2002-09-30 | ||
CL2978/02 | 2002-12-26 | ||
US10/738,141 US20040140244A1 (en) | 2000-05-30 | 2003-12-17 | Desulfurization and sorbents for same |
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Application Number | Title | Priority Date | Filing Date |
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US10/072,209 Continuation-In-Part US6864215B2 (en) | 2000-05-30 | 2002-02-06 | Sorbents for desulfurization |
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US20040140244A1 true US20040140244A1 (en) | 2004-07-22 |
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US10/738,141 Abandoned US20040140244A1 (en) | 2000-05-30 | 2003-12-17 | Desulfurization and sorbents for same |
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US (1) | US20040140244A1 (en) |
WO (1) | WO2005058468A2 (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060283779A1 (en) * | 2005-06-17 | 2006-12-21 | Feimer Joseph L | Method for reducing the amount of high molecular weight organic sulfur picked-up by hydrocarbon streams transported through a pipeline |
US20070160173A1 (en) * | 2006-01-10 | 2007-07-12 | Nec Electronics Corporation | Clock and data recovery circuit and serdes circuit |
EP1843840A1 (en) * | 2005-01-06 | 2007-10-17 | Research Triangle Institute | Zinc oxide-based sorbents and processes for preparing and using same |
US20070289900A1 (en) * | 2006-06-14 | 2007-12-20 | Alvarez Walter E | Hydrogenation of polynuclear aromatic compounds |
US20080271602A1 (en) * | 2007-05-01 | 2008-11-06 | Auburn University | Doped supported zinc oxide sorbents for regenerable desulfurization applications |
US20080283446A1 (en) * | 2007-05-01 | 2008-11-20 | Auburn University | Silver-based sorbents |
US20090193969A1 (en) * | 2008-01-31 | 2009-08-06 | Conocophillips Company | Contaminant removal from a gas stream |
US20090250411A1 (en) * | 2008-04-08 | 2009-10-08 | China Petroleum & Chemical Corporation | Agglomerate removal system |
US20090311156A1 (en) * | 2008-06-12 | 2009-12-17 | Roland Schmidt | Removal of contaminants from gas streams |
US20100062925A1 (en) * | 2008-09-11 | 2010-03-11 | China Petroleum & Chemical Corporation | Method of inhibiting in situ silicate formation in desulfurization sorbents |
US20100170394A1 (en) * | 2009-01-08 | 2010-07-08 | China Petroleum & Chemical Corporation | Silicate-resistant desulfurization sorbent |
US20100314297A1 (en) * | 2009-06-16 | 2010-12-16 | Exxonmobil Research And Engineering Company | Cyclic petroleum refining |
US20110288354A1 (en) * | 2008-11-26 | 2011-11-24 | Sk Innovation Co., Ltd. | Process for the preparation of clean fuel and aromatics from hydrocarbon mixtures catalytic cracked on fluid bed |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102562687B1 (en) | 2017-08-01 | 2023-08-01 | 리써치 트라이앵글 인스티튜트 | Zinc oxide-based adsorbents using alkali metal hydroxides and methods for making and using the same |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2959538A (en) * | 1956-11-27 | 1960-11-08 | Exxon Research Engineering Co | Hydrodesulfurization of whole crudes |
US4221677A (en) * | 1979-03-19 | 1980-09-09 | Standard Oil Company (Indiana) | Catalytic cracking with reduced emission of noxious gases |
US4260471A (en) * | 1979-07-05 | 1981-04-07 | Union Oil Company Of California | Process for desulfurizing coal and producing synthetic fuels |
US4442221A (en) * | 1982-04-09 | 1984-04-10 | Chevron Research Company | Process for regenerating a spent copper composite sulfur sorbent |
US5157201A (en) * | 1990-06-22 | 1992-10-20 | Exxon Chemical Patents Inc. | Process for adsorbing sulfur species from propylene/propane using regenerable adsorbent |
US5897768A (en) * | 1997-02-28 | 1999-04-27 | Exxon Research And Engineering Co. | Desulfurization process for removal of refractory organosulfur heterocycles from petroleum streams |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6087544A (en) * | 1998-05-07 | 2000-07-11 | Exxon Research And Engineering Co. | Process for the production of high lubricity low sulfur distillate fuels |
US6461497B1 (en) * | 1998-09-01 | 2002-10-08 | Atlantic Richfield Company | Reformulated reduced pollution diesel fuel |
US6150575A (en) * | 1998-11-12 | 2000-11-21 | Mobil Oil Corporation | Diesel fuel |
US6610265B2 (en) * | 2001-07-31 | 2003-08-26 | Utc Fuel Cells, Llc | Method and system for desulfurizing gasoline or diesel fuel for use in a fuel cell power plant |
-
2003
- 2003-12-17 US US10/738,141 patent/US20040140244A1/en not_active Abandoned
-
2004
- 2004-12-13 WO PCT/US2004/041617 patent/WO2005058468A2/en active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2959538A (en) * | 1956-11-27 | 1960-11-08 | Exxon Research Engineering Co | Hydrodesulfurization of whole crudes |
US4221677A (en) * | 1979-03-19 | 1980-09-09 | Standard Oil Company (Indiana) | Catalytic cracking with reduced emission of noxious gases |
US4260471A (en) * | 1979-07-05 | 1981-04-07 | Union Oil Company Of California | Process for desulfurizing coal and producing synthetic fuels |
US4442221A (en) * | 1982-04-09 | 1984-04-10 | Chevron Research Company | Process for regenerating a spent copper composite sulfur sorbent |
US5157201A (en) * | 1990-06-22 | 1992-10-20 | Exxon Chemical Patents Inc. | Process for adsorbing sulfur species from propylene/propane using regenerable adsorbent |
US5897768A (en) * | 1997-02-28 | 1999-04-27 | Exxon Research And Engineering Co. | Desulfurization process for removal of refractory organosulfur heterocycles from petroleum streams |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1843840A1 (en) * | 2005-01-06 | 2007-10-17 | Research Triangle Institute | Zinc oxide-based sorbents and processes for preparing and using same |
EP1843840A4 (en) * | 2005-01-06 | 2013-04-03 | Res Triangle Inst | Zinc oxide-based sorbents and processes for preparing and using same |
US7597798B2 (en) | 2005-06-17 | 2009-10-06 | Exxonmobil Research And Engineering Company | Method for reducing the amount of high molecular weight organic sulfur picked-up by hydrocarbon streams transported through a pipeline |
US20060283779A1 (en) * | 2005-06-17 | 2006-12-21 | Feimer Joseph L | Method for reducing the amount of high molecular weight organic sulfur picked-up by hydrocarbon streams transported through a pipeline |
US20070160173A1 (en) * | 2006-01-10 | 2007-07-12 | Nec Electronics Corporation | Clock and data recovery circuit and serdes circuit |
GB2434283A (en) * | 2006-01-10 | 2007-07-18 | Nec Electronics Corp | A clock-and-data-recovery circuit, especially for a SERDES receiver |
US20070289900A1 (en) * | 2006-06-14 | 2007-12-20 | Alvarez Walter E | Hydrogenation of polynuclear aromatic compounds |
US7833316B2 (en) | 2007-05-01 | 2010-11-16 | Auburn University | Doped supported zinc oxide sorbents for regenerable desulfurization applications |
US20080283446A1 (en) * | 2007-05-01 | 2008-11-20 | Auburn University | Silver-based sorbents |
US8425763B2 (en) | 2007-05-01 | 2013-04-23 | Auburn University | Processes for removing sulfur from a hydrocarbon stream utilizing silver-based sorbents |
US20080271602A1 (en) * | 2007-05-01 | 2008-11-06 | Auburn University | Doped supported zinc oxide sorbents for regenerable desulfurization applications |
US7682424B2 (en) | 2008-01-31 | 2010-03-23 | Conocophillips Company | Contaminant removal from a gas stream |
US20090193969A1 (en) * | 2008-01-31 | 2009-08-06 | Conocophillips Company | Contaminant removal from a gas stream |
US20090250411A1 (en) * | 2008-04-08 | 2009-10-08 | China Petroleum & Chemical Corporation | Agglomerate removal system |
US7931739B2 (en) * | 2008-04-08 | 2011-04-26 | China Petroleum & Chemical Corporation | Agglomerate removal system |
US7776138B2 (en) * | 2008-06-12 | 2010-08-17 | Conocophillips Company | Removal of contaminants from gas streams |
US20090311156A1 (en) * | 2008-06-12 | 2009-12-17 | Roland Schmidt | Removal of contaminants from gas streams |
US7951740B2 (en) | 2008-09-11 | 2011-05-31 | China Petroleum & Chemical Corporation | Method of inhibiting in situ silicate formation in desulfurization sorbents |
US20100062925A1 (en) * | 2008-09-11 | 2010-03-11 | China Petroleum & Chemical Corporation | Method of inhibiting in situ silicate formation in desulfurization sorbents |
US20110288354A1 (en) * | 2008-11-26 | 2011-11-24 | Sk Innovation Co., Ltd. | Process for the preparation of clean fuel and aromatics from hydrocarbon mixtures catalytic cracked on fluid bed |
US8933283B2 (en) * | 2008-11-26 | 2015-01-13 | Sk Innovation Co., Ltd. | Process for the preparation of clean fuel and aromatics from hydrocarbon mixtures catalytic cracked on fluid bed |
US20100170394A1 (en) * | 2009-01-08 | 2010-07-08 | China Petroleum & Chemical Corporation | Silicate-resistant desulfurization sorbent |
US20100314297A1 (en) * | 2009-06-16 | 2010-12-16 | Exxonmobil Research And Engineering Company | Cyclic petroleum refining |
Also Published As
Publication number | Publication date |
---|---|
WO2005058468A3 (en) | 2005-10-06 |
WO2005058468A2 (en) | 2005-06-30 |
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