WO2014062314A1 - Slurry hydrocracking process - Google Patents
Slurry hydrocracking process Download PDFInfo
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- WO2014062314A1 WO2014062314A1 PCT/US2013/059428 US2013059428W WO2014062314A1 WO 2014062314 A1 WO2014062314 A1 WO 2014062314A1 US 2013059428 W US2013059428 W US 2013059428W WO 2014062314 A1 WO2014062314 A1 WO 2014062314A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- slurry
- catalyst
- iron
- slurry catalyst
- Prior art date
Links
- 239000002002 slurry Substances 0.000 title claims abstract description 107
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 90
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 37
- 229910052742 iron Inorganic materials 0.000 claims abstract description 22
- 238000009835 boiling Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000011575 calcium Substances 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011734 sodium Substances 0.000 claims abstract description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 150000004677 hydrates Chemical class 0.000 claims description 4
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000004215 Carbon black (E152) Substances 0.000 description 21
- 239000007789 gas Substances 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- -1 e.g. Substances 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910001570 bauxite Inorganic materials 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021532 Calcite Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241000209149 Zea Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 229910014813 CaC2 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910017356 Fe2C Inorganic materials 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- OTCGCPARNNLRKH-UHFFFAOYSA-N calcium;oxalic acid;hydrate Chemical compound O.[Ca].OC(=O)C(O)=O OTCGCPARNNLRKH-UHFFFAOYSA-N 0.000 description 1
- 229910052663 cancrinite Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- MSNWSDPPULHLDL-UHFFFAOYSA-K ferric hydroxide Chemical compound [OH-].[OH-].[OH-].[Fe+3] MSNWSDPPULHLDL-UHFFFAOYSA-K 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910001700 katoite Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 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 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002688 soil aggregate Substances 0.000 description 1
- 239000002881 soil fertilizer Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/04—Oxides
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
Definitions
- This invention generally relates to a slurry hydrocracking process.
- Catalysts are often used in hydroconversion processes. In the hydroconversion of heavy oils, biofuels, and coal liquids, a catalytic slurry system typically is utilized with large amounts of catalyst.
- these catalysts are relatively inexpensive and do not contain valuable metals, such as groups 8-10 metals.
- the catalyst is used in large quantities, and availability and cost are issues. Thus, finding another suitable source of inexpensive catalyst that can be available in large quantities is desired.
- One exemplary embodiment can be a slurry hydrocracking process.
- the process can include providing one or more hydrocarbon compounds having an initial boiling point temperature of at least 340° C, and a slurry catalyst to a slurry hydrocracking zone.
- the slurry catalyst may have 32 to 50%, by weight, iron; 3 to 14%, by weight, aluminum; no more than 10%), by weight, sodium; and 2 to 10%>, by weight, calcium.
- all catalytic component percentages are as metal and based on the weight of the dried slurry catalyst.
- Another exemplary embodiment can be a slurry hydrocracking process.
- the process may include providing one or more hydrocarbon compounds having an initial boiling point temperature of at least 340° C, and a slurry catalyst to a slurry hydrocracking zone.
- the slurry catalyst includes 15 to 25%, by weight, iron; 1.5 to 7%, by weight, aluminum; no more than 5%, by weight, sodium; and greater than 1 to 5%, by weight, calcium.
- all catalytic component percentages are as metal and based on the weight of the slurry catalyst with a loss on ignition at 900° C of 40 to 60%, by weight.
- a further exemplary embodiment can be a slurry hydrocracking process.
- the process may include providing one or more hydrocarbon compounds having an initial boiling point temperature of at least 340° C, and a slurry catalyst to a slurry hydrocracking zone.
- the slurry catalyst includes 46 to 72%, by weight, iron oxide; 6 to 27%, by weight, aluminum oxide; no more than 14%, by weight, sodium oxide; and 3 to 14%, by weight, calcium oxide.
- all catalytic component percentages are as oxide and based on the weight of the dried slurry catalyst.
- the embodiments disclosed herein can provide a slurry hydrocracking catalyst minimizing low toluene insoluble organic residue, including mesophase.
- One potential benefit can provide a product with a lower weight of total solids, including material from the catalyst, in the product.
- red mud as a catalyst is particularly beneficial as red mud currently has no commercial value and is often landfilled.
- the term "stream” can include various hydrocarbon molecules, such as straight-chain, branched, or cyclic alkanes, alkenes, alkadienes, and alkynes, and optionally other substances, such as gases, e.g., hydrogen, or impurities, such as heavy metals, and sulfur and nitrogen compounds.
- the stream can also include aromatic and non- aromatic hydrocarbons.
- the hydrocarbon molecules may be abbreviated CI, C2, C3...Cn where "n” represents the number of carbon atoms in the one or more hydrocarbon molecules.
- the term “stream” may also include catalyst.
- zone can refer to an area including one or more equipment items and/or one or more sub-zones.
- Equipment items can include one or more reactors or reactor vessels, heaters, exchangers, pipes, pumps, compressors, and controllers. Additionally, an equipment item, such as a reactor, dryer, or vessel, can further include one or more zones or sub-zones.
- the term “substantially” can mean an amount of generally at least 80%), preferably 90%, and optimally 99%, by weight, of a compound, class of compounds, or catalyst.
- LOI loss on ignition
- ICP inductively-coupled plasma
- HVGO heavy vacuum gas oil
- the boiling temperatures can be the atmospheric equivalent boiling point as calculated from the observed boiling temperature and the distillation pressure, for example using the equations furnished in ASTM Dl 160-06.
- the term "dried slurry catalyst” can mean a slurry catalyst that has been dried to remove one or more liquids.
- the term “pitch” or “vacuum bottoms” can mean a hydrocarbon material boiling above 524° C and can include one or more C40 + hydrocarbons.
- KPa kilopascal
- MPa megapascal
- process flow lines in the figures can be referred to interchangeably as, e.g., lines, pipes, slurries, feeds, products, or streams.
- FIGURE is a schematic depiction of an exemplary hydrocarbon conversion zone.
- one exemplary hydrocarbon conversion zone 100 can be a slurry reaction or bubble column system including a reservoir 120, a holding tank 130, a heater 140, and a hydroprocessing reaction zone 150.
- a slurry reaction or bubble column system including a reservoir 120, a holding tank 130, a heater 140, and a hydroprocessing reaction zone 150.
- Exemplary systems are disclosed in, e.g., US 5,755,955 and US 5,474,977.
- a hydrocarbon feed 104 can be provided, which may be a light vacuum gas oil, a heavy vacuum gas oil, a vacuum residue, a fluid catalytic cracking slurry oil, a pitch, or other heavy hydrocarbon-derived oils.
- the hydrocarbon feed 104 can be at least one of coal liquid or a biofuel feedstock such as lignin, one or more plant parts, one or more fruits, one or more vegetables, a plant processing waste, one or more woodchips, chaff, one or more grains, one or more grasses, a corn, one or more corn husks, one or more weeds, one or more aquatic plants, hay, paper, and any cellulose-containing biological material.
- the hydrocarbon feed 104 can include one or more hydrocarbon compounds having an initial boiling point temperature of at least 340° C.
- a reservoir 120 can provide a catalyst to be combined with the hydrocarbon feed 104.
- a resultant slurry 108 i.e., a combination of the catalyst and the hydrocarbon feed 104 having a solids content of 0.01 to 10%, by weight, can pass to a holding tank 130 before being combined with a gas 112.
- the slurry catalyst has an average particle size of no more than 75 microns, or of 10 to 75 microns.
- the catalyst can include red mud, which can be a waste stream from a bauxite process.
- red mud is generated as a waste during the processing of bauxite, the most common ore of aluminum used in the process.
- the ore can be washed, ground and dissolved in sodium hydroxide under heat and pressure.
- the resulting products are sodium aluminate liquor, that may be further processed and a large quantity of undissolved solid waste called 'red mud' or 'bauxite waste'.
- the amount of red mud generated per ton of alumina produced may vary from 0.3 tons for a high- grade ore to 2.5 tons for a low-grade ore. Over 12 million tons can be produced annually at various sites around the world.
- the red mud is highly alkaline, but can be neutralized.
- One preferred source is a spent bauxite product sold under the trade designation CAJUNITE by Kaiser Aluminum and Chemical Corporation. Kaiser Aluminum and
- Chemical Corporation has disclosed the red mud to be used for engineered earthen products such as a synthetic landfill cover, road base, and levee construction material; agricultural soil enhancers, soil aggregates, and fertilizers; absorbents and solidification agents used for treating effluents; and fill used for reclamation.
- Red mud can have a variety of compositions depending on the source.
- the main constituents of red mud can include iron oxide (Fe 2 0 3 ), aluminum oxide (A1 2 0 3 ), silicon oxide (Si0 2 ), titanium oxide (Ti0 2 ), sodium oxide (Na 2 0), calcium oxide (CaO), and magnesium oxide (MgO) and optionally a number of minor constituents like potassium, chromium, vanadium, nickel, copper, manganese, and zinc, and oxides thereof.
- iron oxide (Fe 2 0 3 ) is the major constituent of red mud and gives the red mud a characteristic red brick color.
- Metals can be present in reduced form, or as oxides, hydroxides, and/or oxide hydrates.
- Red mud can include other mineralogical constituents, such as a hematite (a- Fe 2 0 3 ), an iron hydroxide (Fe(OH) 3 ), a magnetite (Fe 3 0 4 ), a rutile (Ti0 2 ), an anatase (Ti0 2 ), a bayerite (Al(OH) 3 ), a halloysite (Al 2 Si 2 0 5 (OH) 4 ), a boehmite (AIO(OH)), a diaspore (AIO(OH)), a gibbsite (Al(OH) 3 ), a kaolinite (Al 2 Si 2 0 5 (OH) 4 ), a quartz (Si0 2 ), a calcite (CaC0 3 ), a perovskite (CaTi0 3 ), a sodalite (Na 4 Al 3 Si 3 0i 2 Cl), a cancrinite
- One exemplary red mud can include the following components:
- All catalytic component percentages can be as metal and based on the weight of the dried slurry catalyst.
- the dried slurry catalyst can include no more than 1%, by weight, water.
- the dried slurry catalyst can have a loss on ignition at 900° C of no more than 0.01%, by weight.
- a washed slurry catalyst after drying can have a loss on ignition of no more than 15%, preferably 5 to 15%, and optimally 12.3% at 900° C.
- Another exemplary red mud can include the following components:
- All catalytic component percentages can be as oxide and based on the weight of the wet slurry catalyst with a loss on ignition at 900° C of 50%.
- the wet slurry catalyst can have a loss on ignition at 900° C of 40 to 60%>, preferably 50%>, by weight.
- a further exemplary red mud may include the following components:
- All catalytic component percentages can be as oxide and based on the weight of the dried slurry catalyst.
- the dried slurry catalyst can include no more than 1%, by weight, water.
- the dried slurry catalyst can have a loss on ignition at 900° C of no more than 0.01%, by weight.
- a washed slurry catalyst after drying can have a loss on ignition of no more than 15%, preferably 5 to 15%, and optimally 12.3% at 900° C.
- Yet another exemplary red mud can include the following components:
- All catalytic component percentages can be as oxide and based on the weight of the wet slurry catalyst with a loss on ignition at 900° C of 50%.
- the wet slurry catalyst can have a loss on ignition at 900° C of 40 to 60%, preferably 50%>, by weight.
- the gas 112 typically contains hydrogen, which can be once-through hydrogen optionally with no significant amount of recycled gases. Alternatively, the gas 112 can contain recycled hydrogen gas optionally with added hydrogen as the hydrogen is consumed during the one or more hydroprocessing reactions.
- the gas 112 may be essentially pure hydrogen or may include additives such as hydrogen sulfide or light hydrocarbons, e.g., methane and ethane. Reactive or non-reactive gases may be combined with the hydrogen introduced into the hydroprocessing reaction zone 150 at the desired pressure to achieve the desired product yields.
- a combined feed 116 including the slurry 108 and the gas 112 can enter the heater 140.
- the heater 140 is a heat exchanger using any suitable fluid such as the hydroprocessing reaction zone 150 effluent or high pressure steam to provide the requisite heating requirement. Afterwards, the heated combined feed 116 can enter the heater 140.
- hydroprocessing reaction zone 150 including an up flow tubular reactor 160.
- slurry hydroprocessing is carried out using reactor conditions sufficient to crack at least a portion of the hydrocarbon feed 104 to lower boiling products, such as one or more distillate
- Conditions in the hydroprocessing reaction zone 150 can include a temperature of 340 to 600° C, a hydrogen partial pressure of 3.5 to 10.5 MPa, and a space velocity of 0.1 to 30 volumes of hydrocarbon feed 104 per hour per reactor or reaction zone volume.
- a reaction product 170 can exit the hydroprocessing reaction zone 150.
- the iron present as iron oxide in the slurry hydrocracking catalyst may convert to iron sulfide, as disclosed in, e.g., US 7,820,135, in the hydroprocessing reaction zone 150.
- the iron oxide in the presence of alumina can quickly convert to active iron sulfide without presenting excess sulfur to the catalyst in the presence of a heavy
- the iron sulfide can have several molecular forms, so is generally represented by the formula, Fe x S, where x can be 0.7-1.3.
- essentially all the iron oxide may convert to iron sulfide upon heating the mixture of hydrocarbon and catalyst to 410° C in the presence of hydrogen and sulfur.
- "essentially all” means no peak for iron oxide is generated on an XRD plot of intensity versus two theta degrees at 33.1 or no less than 99%, by weight, conversion to iron sulfide.
- Sulfur may be present in the hydrocarbon feed as organic sulfur compounds. Consequently, the iron in the catalyst may be added to the heavy hydrocarbon feed in the plus three oxidation state, preferably as Fe 2 C>3.
- the catalyst may be added to the feed in the reaction zone or prior to entry into the reaction zone without pretreatment. After heating the mixture to reaction temperature, organic sulfur compounds in the feed may convert to hydrogen sulfide and sulfur-free hydrocarbons.
- the iron in the plus three oxidation state in the catalyst may quickly react at reaction temperature with hydrogen sulfide produced in the reaction zone by the reaction of organic sulfur and hydrogen. The reaction of iron oxide and hydrogen sulfide produce iron sulfide that may be the active form of the catalyst. Iron may then be present in the plus two oxidation state in the reactor.
- the efficiency of conversion of iron oxide to iron sulfide can enable operation without adding sulfur to the feed if sufficient available sulfur is typically present in the feed to ensure complete conversion to iron sulfide. Because the iron oxide and alumina can be efficient in converting iron oxide to iron sulfide and in promoting the slurry hydrocracking reaction, less iron may be added to the slurry hydrocracking reactor. Consequently, less sulfur is typically required to convert the iron oxide to iron sulfide minimizing the need for sulfur addition. Generally, the iron oxide and alumina do not have to be subjected to elevated temperature in the presence of hydrogen to obtain conversion to iron sulfide. Conversion may also occur at below the slurry hydrocracking reaction temperature. By avoiding thermal and sulfiding pretreatments, process simplification and material cost reduction can be achieved. Additionally, less hydrogen may be required and less hydrogen sulfide and other sulfur can be removed from the slurry hydrocracking product.
- the iron content of catalyst as metal in the upflow tubular reactor 160 is typically 0.1 to 4.0 %, by weight, and usually no more than 2.0%, by weight, of the catalyst and liquid in the upflow tubular reactor 160.
- iron content is the weight ratio of iron on the catalyst relative to the non-gas materials in the upflow tubular reactor 160.
- the non-gas materials in the upflow tubular reactor 160 are the hydrocarbon liquids, solids, and the catalyst; and do not include reactor and ancillary equipment.
- pretreatments for enhancing performance to the red mud can be conducted, which may include an addition of a small amount of a promoter, mixing with a fly ash, a carbon, or one or more iron compounds, such as ferrous sulfate, and/or mixing with other mineral catalysts. Additionally, a thorough acid washing with sulfuric, phosphoric and/or hydrochloric acid can be conducted. Furthermore, presulfiding the red mud may also enhance performance and/or for low sulfur feeds if desired to convert all the iron oxide to iron sulfide. What is more, cations, such as calcium and sodium, can be removed and solids may be recovered by a post-reaction water-wash electrostatic separation.
- the red mud catalyst as described herein can minimize coking.
- the red mud catalyst can perform similarly as other slurry hydrocracking catalyst, particularly with respect to toluene insoluble organic residue, which may include coke and mesophase, as described in, e.g., US 2012/0085680.
- red mud often does not require grinding to blend with the feed.
- red mud is provided grounded and hence blending costs may be lowered.
- less total catalyst is typically required because red mud often has a higher iron concentration as compared to other slurry hydrocracking catalyst on a dry basis.
- a first embodiment of the invention is a slurry hydrocracking process, comprising providing one or more hydrocarbon compounds having an initial boiling point temperature of at least 340° C, and a slurry catalyst to a slurry hydrocracking zone, wherein the slurry catalyst comprises: 1) 32 to 50%, by weight, iron; 2) 3 to 14%, by weight, aluminum; 3) no more than 10%, by weight, sodium; and 4) 2 to 10%, by weight, calcium; wherein all catalytic component percentages are as metal and based on the weight of the dried slurry catalyst.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the slurry
- hydrocracking zone comprises an upflow tubular reactor.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the iron, aluminum, sodium, and calcium are present as oxides, hydroxides, or oxide hydrates.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the slurry catalyst comprises 40 to 50%, by weight, iron as metal and based on the weight of the dried slurry catalyst.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the dried slurry catalyst comprises no more than 1%, by weight, water.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the dried slurry catalyst has a loss on ignition at 900°C of no more than 0.01%, by weight.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the one or more hydrocarbons comprises a light vacuum gas oil, a heavy vacuum gas oil, or a pitch.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the slurry catalyst comprises a red mud.
- An embodiment of the invention is one, any or all of prior
- the slurry catalyst has an average particle size of no more than 75 microns.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the slurry catalyst comprises 45 to 50%>, by weight, iron as metal and based on the weight of the dried slurry catalyst.
- a second embodiment of the invention is a slurry hydrocracking process, comprising providing one or more hydrocarbon compounds having an initial boiling point temperature of at least 340° C, and a slurry catalyst to a slurry hydrocracking zone, wherein the slurry catalyst comprises 1) 15 to 25%, by weight, iron; 2) 5 to 7%, by weight, aluminum; 3) no more than 5%, by weight, sodium; and 4) greater than 1 to 5%, by weight, calcium; wherein all catalytic component percentages are as metal and based on the weight of the slurry catalyst with a loss on ignition at 900° C of 40 to 60%, by weight.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the slurry catalyst has a loss on ignition at 900° C of 50%, by weight.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the slurry catalyst comprises 2 to 5%, by weight, calcium and 5 to 5%, by weight, titanium as metal based on the weight of the slurry catalyst.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the slurry hydrocracking zone comprises an upflow tubular reactor.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the iron, aluminum, sodium, and calcium are present as oxides, hydroxides, or oxide hydrates.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the one or more hydrocarbons comprises a light vacuum gas oil, a heavy vacuum gas oil, or a pitch.
- a third embodiment of the invention is a slurry hydrocracking process, comprising providing one or more hydrocarbon compounds having an initial boiling point temperature of at least 340° C, and a slurry catalyst to a slurry hydrocracking zone, wherein the slurry catalyst comprises 1) 46 to 72%, by weight, iron oxide; 2) 6 to 27%, by weight, aluminum oxide; 3) no more than 14%, by weight, sodium oxide; and 4) 3 to 14%, by weight, calcium oxide; wherein all catalytic component percentages are as oxide and based on the weight of the dried slurry catalyst.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the dried slurry catalyst comprises no more than 1%, by weight, water.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the dried slurry catalyst has a loss on ignition at 900°C of no more than 0.01%, by weight.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the slurry hydrocracking zone comprises an upflow tubular reactor.
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Priority Applications (4)
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EP13847245.1A EP2906665A4 (en) | 2012-10-15 | 2013-09-12 | SLUDGE HYDROCRACKING METHOD |
CN201380052440.5A CN104704085B (zh) | 2012-10-15 | 2013-09-12 | 淤浆加氢裂化方法 |
RU2015118126A RU2606117C2 (ru) | 2012-10-15 | 2013-09-12 | Способ гидрокрекинга со взвешенным слоем катализатора |
IN2258DEN2015 IN2015DN02258A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 2012-10-15 | 2013-09-12 |
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US13/652,439 | 2012-10-15 | ||
US13/652,439 US8999145B2 (en) | 2012-10-15 | 2012-10-15 | Slurry hydrocracking process |
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WO2014062314A1 true WO2014062314A1 (en) | 2014-04-24 |
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PCT/US2013/059428 WO2014062314A1 (en) | 2012-10-15 | 2013-09-12 | Slurry hydrocracking process |
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CN109126799A (zh) * | 2018-08-07 | 2019-01-04 | 淮阴工学院 | 一种用于生物质焦油裂解重整的红砖粉负载镍催化剂及制备方法 |
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CA2972066A1 (en) | 2015-01-30 | 2016-08-04 | Halliburton Energy Services, Inc. | Lost circulation materials comprising red mud |
MX2017008644A (es) * | 2015-01-30 | 2017-10-11 | Halliburton Energy Services Inc | Materiales de circulacion perdida que comprenden lodo marron. |
CA3021229C (en) * | 2016-04-25 | 2022-08-09 | Sherritt International Corporation | Process for partial upgrading of heavy oil |
US10703990B2 (en) * | 2017-08-24 | 2020-07-07 | Uop Llc | Process for slurry hydrocracking using catalyst with low diaspore alumina |
CN107858173B (zh) * | 2017-11-24 | 2019-06-07 | 福州大学 | 一种劣质重油悬浮床加氢裂化脱硫方法 |
CN107892941B (zh) * | 2017-11-24 | 2019-08-09 | 福州大学 | 一种重油悬浮床加氢裂化工艺方法 |
CN107841336B (zh) * | 2017-11-24 | 2019-08-09 | 福州大学 | 一种重油悬浮床加氢裂化方法 |
CN107903937B (zh) * | 2017-11-24 | 2019-06-07 | 福州大学 | 一种悬浮床加氢裂化方法 |
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Also Published As
Publication number | Publication date |
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EP2906665A4 (en) | 2016-06-08 |
RU2606117C2 (ru) | 2017-01-10 |
US8999145B2 (en) | 2015-04-07 |
EP2906665A1 (en) | 2015-08-19 |
RU2015118126A (ru) | 2016-12-10 |
IN2015DN02258A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 2015-08-21 |
US20140102944A1 (en) | 2014-04-17 |
CN104704085A (zh) | 2015-06-10 |
CN104704085B (zh) | 2017-03-08 |
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