WO2015077045A1 - Process for hydrotreating a coal tar stream - Google Patents
Process for hydrotreating a coal tar stream Download PDFInfo
- Publication number
- WO2015077045A1 WO2015077045A1 PCT/US2014/064466 US2014064466W WO2015077045A1 WO 2015077045 A1 WO2015077045 A1 WO 2015077045A1 US 2014064466 W US2014064466 W US 2014064466W WO 2015077045 A1 WO2015077045 A1 WO 2015077045A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- paragraph
- coal tar
- stream
- tar stream
- hydrotreating
- Prior art date
Links
- 239000011280 coal tar Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 39
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 47
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000010555 transalkylation reaction Methods 0.000 claims description 14
- 238000005804 alkylation reaction Methods 0.000 claims description 12
- 239000003245 coal Substances 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 230000029936 alkylation Effects 0.000 claims description 8
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 8
- 239000000571 coke Substances 0.000 claims description 8
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000001282 iso-butane Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 239000003915 liquefied petroleum gas Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical class CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 235000006173 Larrea tridentata Nutrition 0.000 description 1
- 244000073231 Larrea tridentata Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000011285 coke tar Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- -1 diesel Substances 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 150000003739 xylenols Chemical class 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including oxidation as the refining step in the absence of hydrogen
-
- 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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
-
- 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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
Definitions
- Coke Pyrolysis of coal produces coke and coal tar.
- the coke-making or "coking” process consists of heating the material in closed vessels in the absence of oxygen to very high temperatures.
- Coke is a porous but hard residue that is mostly carbon and inorganic ash, which is used in making steel.
- Coal tar is the volatile material that is driven off during heating, and it comprises a mixture of a number of hydrocarbon compounds. It can be separated to yield a variety of organic compounds, such as benzene, toluene, xylene, naphthalene, anthracene, and phenanthrene. These organic compounds can be used to make numerous products, for example, dyes, drugs, explosives, flavorings, perfumes, preservatives, synthetic resins, and paints and stains. The residual pitch left from the separation is used for paving, roofing, waterproofing, and insulation. Coal tar includes many contaminants. For many processes, it is desirable to treat a coal stream to remove such contaminants. However, some treatment processes for coal tar insufficiently remove contaminants or produce undesirable results, such as saturated aromatic rings. There is a need to improve treatment of coal tar streams.
- One aspect of the invention involves a process for hydrotreating a coal tar stream.
- a coal tar stream is provided, and the coal tar stream is expanded with an inert gas stream to provide an expanded liquid coal tar stream.
- the expanded liquid coal tar stream is hydrotreated.
- the Figure shows one embodiment of a basic coal conversion process 5.
- a coal feed 10 is sent to a pyro lysis zone 15.
- a portion of the coal feed 10 is sent to a gasification zone (not shown), where the coal feed is mixed with oxygen and steam and reacted under heat and pressure in the gasification zone to form syngas, which is a mixture of carbon monoxide and hydrogen.
- the syngas can be further processed using the Fischer-Tropsch reaction to produce gasoline or using the water- gas shift reaction to produce more hydrogen.
- the coal In the pyrolysis zone 15, the coal is heated at high temperature, e.g., up to paragraph 2,000°C (3600°F), in the absence of oxygen to drive off the volatile components. Coking produces a coke stream 25 and a coal tar stream 20.
- the coke stream 25 can be used in other processes, such as the manufacture of steel.
- the coal tar stream 20 from the pyrolysis zone, or coal tar streams from other sources, is subjected to a treatment process to provide a treated stream that can be used in various downstream processes.
- the coal tar stream 20 can be sent to a reaction zone 35, where the coal tar stream 20 is reacted with added hydrogen in the presence of a hydrocarbon solvent 30.
- the reaction zone 35 can be, for instance, a continuous stirred-tank reactor (CSTR), a slurry hydrocracking reactor, or a fixed bed reactor.
- the hydrocarbon solvent 30 can include, for instance, a petroleum cut or other aromatic-type hydrocarbon.
- Example reaction conditions include a pressure ranging from paragraph 4.8 MPa (paragraph 700 psig) to paragraph 8.3 MPa (paragraph 1200 psig) and a temperature ranging from paragraph 232 °C (450°F) to paragraph 371 °C (700°F).
- a catalyst such as a Ni/Mo hydrotreating catalyst for heavy feeds, or if S level is low enough a Pt/Al 2 03 catalyst, can be used in the reaction zone 35, but is not required in all embodiments.
- the reaction zone 35 produces a liquid coal tar stream 40 that is reduced in aromaticity with respect to the coal tar stream 20.
- the liquid coal tar stream 40 is fed to an expansion zone 50.
- the coal tar stream 40 is expanded with an inert gas stream 45 that is fed into the expansion zone 50.
- the expansion preferably takes place at high pressure, such as between paragraph 10.3 MPa (paragraph 1500 psi) and paragraph 17.2 MPa (paragraph 2500 psi), with an example range of paragraph 2000 psi (13.8 MPa).
- Suitable inert gases include, but are not limited to, carbon dioxide, nitrogen, and light hydrocarbons such as CH 4 , C 2 H 4 , C 3 H 8 , and C 4 Hi 0 .
- the inert gas stream 45 provides a vapor phase solvent in the expansion zone 50, and improves solubility of hydrogen in later hydrotreating, making the liquid phase more reactive.
- the expanded liquid coal tar stream 55 includes the hydrocarbon solvent 30 from the reaction zone 35.
- reaction zone 35 can be omitted, and the coal tar stream 20 can be fed into the expansion zone 50.
- the expanded liquid coal tar stream would not include the hydrocarbon solvent 30.
- Hydrotreating is a process in which hydrogen gas is contacted with a hydrocarbon stream in the presence of suitable catalysts which are primarily active for the removal of heteroatoms, such as sulfur, nitrogen, and metals from the hydrocarbon feedstock.
- suitable catalysts which are primarily active for the removal of heteroatoms, such as sulfur, nitrogen, and metals from the hydrocarbon feedstock.
- hydrocarbons with double and triple bonds may be saturated.
- Aromatics may also be saturated.
- the hydrotreating in the hydrotreating zone 60 preferably takes place at paragraph 4.8 MPa (paragraph 700 psi) to paragraph 8.3 MPa (paragraph 1200 psi), and at a temperature range of paragraph 260 C (paragraph 500 F) to paragraph 370 C (paragraph 700 F), a liquid hourly space velocity of paragraph 0.5 hr -1 to paragraph 4 hr -1 , and a hydrogen rate of paragraph 168 to paragraph 1,011 Nm 3 /m 3 oil (1,000-6,000 scf/bbl). Conditions can vary depending on the solvent.
- the hydrogenation can take place in the presence of a catalyst.
- Typical hydrotreating catalysts include at least one Group VIII metal, preferably iron, cobalt and nickel, and at least one Group VI metal, preferably molybdenum and tungsten, on a high surface area support material, preferably alumina.
- Other typical hydrotreating catalysts include zeolitic catalysts, as well as noble metal catalysts where the noble metal is selected from palladium and platinum.
- Hydrotreating can include hydrodesulfurization, hydrodenitrogenation, or both.
- the resulting hydrotreated stream 65 provides a pre -treated stream that can be subject to a processing zone 70 to provide one or more products 75. This pre-treated stream can be relatively free of contaminants such as sulfur and nitrogen.
- Example hydrotreated streams 65 have a sulfur content of paragraph 50 ppm or less, and a nitrogen content of paragraph 10 ppm or less. Hydrotreating, reaction, and/or expansion conditions can be tuned to provide a desirable decontamination of the coal tar stream 40.
- the processing zone 70 can process the hydrotreated stream 65 by hydrocracking, fluid catalytic cracking, alkylation, transalkylation, oxidation, hydrogenation, or a combination of such processes.
- the hydrotreated stream 65 can also be blended in fuel.
- the hydrotreated stream 65 may be fractionated.
- the coal tar stream 20, 40 may be fractionated before treatment.
- Coal tar comprises a complex mixture of heterocyclic aromatic compounds and their derivatives with a wide range of boiling points.
- the number of fractions and the components in the various fractions can be varied as is well known in the art.
- a typical separation process involves separating the coal tar into four to six streams.
- a fraction comprising NH3, CO, and light hydrocarbons, a light oil fraction with boiling points between 0°C and 180°C, a middle oil fraction with boiling points between 180°C to 230°C, a heavy oil fraction with boiling points between 230 to 270°C, an anthracene oil fraction with boiling points between 270°C to 350°C, and pitch.
- the light oil fraction contains compounds such as benzenes, toluenes, xylenes, naphtha, coumarone-indene, dicyclopentadiene, pyridine, and picolines.
- the middle oil fraction contains compounds such as phenols, cresols and cresylic acids, xylenols, naphthalene, high boiling tar acids, and high boiling tar bases.
- the heavy oil fraction contains benzene absorbing oil and creosotes.
- the anthracene oil fraction contains anthracene.
- Pitch is the residue of the coal tar distillation containing primarily aromatic hydrocarbons and heterocyclic compounds.
- Hydrocracking is a process in which hydrocarbons crack in the presence of hydrogen to lower molecular weight hydrocarbons.
- Typical hydrocracking conditions may include a temperature of paragraph 290°C (550°F) to paragraph 468°C (875°F), a pressure of paragraph 3.5 MPa (500 psig) to paragraph 20.7 MPa (3000 psig), a liquid hourly space velocity (LHSV) of paragraph 1.0 to less than paragraph 2.5 hr-1, and a hydrogen rate of paragraph 421 to paragraph 2,527 Nm3/m3 oil (2,500-15,000 scf/bbl).
- Typical hydrocracking catalysts include amorphous silica-alumina bases or low-level zeolite bases combined with one or more Group VIII or Group VIB metal hydrogenating components, or a crystalline zeolite cracking base upon which is deposited a Group VIII metal hydrogenating component. Additional hydrogenating components may be selected from Group VIB for incorporation with the zeolite base.
- Fluid catalytic cracking is a catalytic hydrocarbon conversion process accomplished by contacting heavier hydrocarbons in a fluidized reaction zone with a catalytic particulate material.
- the reaction in catalytic cracking is carried out in the absence of substantial added hydrogen or the consumption of hydrogen.
- the process typically employs a powdered catalyst having the particles suspended in a rising flow of feed hydrocarbons to form a fluidized bed.
- cracking takes place in a riser, which is a vertical or upward sloped pipe.
- a pre-heated feed is sprayed into the base of the riser via feed nozzles where it contacts hot fluidized catalyst and is vaporized on contact with the catalyst, and the cracking occurs converting the high molecular weight oil into lighter components including liquefied petroleum gas (LPG), gasoline, and a distillate.
- LPG liquefied petroleum gas
- the catalyst- feed mixture flows upward through the riser for a short period (a few seconds), and then the mixture is separated in cyclones.
- the hydrocarbons are directed to a fractionator for separation into LPG, gasoline, diesel, kerosene, jet fuel, and other possible fractions.
- the cracking catalyst While going through the riser, the cracking catalyst is deactivated because the process is accompanied by formation of coke which deposits on the catalyst particles.
- Contaminated catalyst is separated from the cracked hydrocarbon vapors and is further treated with steam to remove hydrocarbon remaining in the pores of the catalyst.
- the catalyst is then directed into a regenerator where the coke is burned off the surface of the catalyst particles, thus restoring the catalyst's activity and providing the necessary heat for the next reaction cycle.
- the process of cracking is endothermic.
- the regenerated catalyst is then used in the new cycle.
- Typical FCC conditions include a temperature of paragraph 400°C to paragraph 800°C, a pressure of paragraph 0 to paragraph 688 kPa g (paragraph 0 to 100 psig), and contact times of paragraph 0.1 seconds to paragraph 1 hour. The conditions are determined based on the hydrocarbon feedstock being cracked, and the cracked products desired.
- Zeolite-based catalysts are commonly used in FCC reactors, as are composite catalysts which contain zeolites, silica-aluminas, alumina, and other binders.
- Alkylation is typically used to combine light olefins, for example mixtures of alkenes such as propylene and butylene, with isobutane to produce a relatively high-octane branched-chain paraffinic hydrocarbon fuel, including isoheptane and isooctane.
- an alkylation reaction can be performed using an aromatic compound such as benzene in place of the isobutane.
- the product resulting from the alkylation reaction is an alkylbenzene (e.g. toluene, xylenes, ethylbenzene, etc.).
- the reactants are mixed in the presence of a strong acid catalyst, such as sulfuric acid or hydrofluoric acid.
- a strong acid catalyst such as sulfuric acid or hydrofluoric acid.
- the alkylation reaction is carried out at mild temperatures, and is typically a two-phase reaction. Because the reaction is exothermic, cooling is needed. Depending on the catalyst used, normal refinery cooling water provides sufficient cooling. Alternatively, a chilled cooling medium can be provided to cool the reaction.
- the catalyst protonates the alkenes to produce reactive carbocations which alkylate the isobutane reactant, thus forming branched chain paraffins from isobutane .
- Aromatic alkylation is generally now conducted with solid acid catalysts including zeolites or amorphous silica-aluminas
- the alkylation reaction zone is maintained at a pressure sufficient to maintain the reactants in liquid phase.
- a general range of operating pressures is from paragraph 200 to paragraph 7100 kPa absolute.
- the temperature range covered by this set of conditions is from paragraph -20°C to paragraph 200°C.
- the temperature range is paragraph from 100-200C at the pressure range of paragraph 200 to paragraph 7100 kPa.
- Transalkylation is a chemical reaction resulting in transfer of an alkyl group from one organic compound to another. Catalysts, particularly zeolite catalysts, are often used to effect the reaction.
- the transalkylation catalyst may be metal stabilized using a noble metal or base metal, and may contain suitable binder or matrix material such as inorganic oxides and other suitable materials.
- a polyalkylaromatic hydrocarbon feed and an aromatic hydrocarbon feed are provided to a transalkylation reaction zone.
- the feed is usually heated to reaction temperature and then passed through a reaction zone, which may comprise one or more individual reactors. Passage of the combined feed through the reaction zone produces an effluent stream comprising unconverted feed and product monoalkylated hydrocarbons.
- This effluent is normally cooled and passed to a stripping column in which substantially all C5 and lighter hydrocarbons present in the effluent are concentrated into an overhead stream and removed from the process.
- the transalkylation reaction can be effected in contact with a catalytic composite in any conventional or otherwise convenient manner and may comprise a batch or continuous type of operation, with a continuous operation being preferred.
- the transalkylation catalyst is usefully disposed as a fixed bed in a reaction zone of a vertical tubular reactor, with the alkylaromatic feed stock charged through the bed in an upflow or downflow manner.
- the transalkylation zone normally operates at conditions including a temperature in the range of paragraph 130°C to paragraph 540°C.
- the transalkylation zone is typically operated at moderately elevated pressures broadly ranging from paragraph 100 kPa to paragraph 10 MPa absolute.
- the transalkylation reaction can be effected over a wide range of space velocities. That is, volume of charge per volume of catalyst per hour; weight hourly space velocity (WHSV) generally is in the range of from paragraph 0.1 to paragraph 30hr-l .
- WHSV weight hourly space velocity
- the catalyst is typically selected to have relatively high stability at a high activity level.
- Oxidation involves the oxidation of hydrocarbons to oxygen-containing compounds, such as aldehydes.
- the hydrocarbons include alkanes, alkenes, typically with carbon numbers from 2 to 15, and alkyl aromatics, Linear, branched, and cyclic alkanes and alkenes can be used.
- Oxygenates that are not fully oxidized to ketones or carboxylic acids can also be subjected to oxidation processes, as well as sulfur compounds that contain -S-H moieties, thiophene rings, and sulfone groups.
- the process is carried out by placing an oxidation catalyst in a reaction zone and contacting the feed stream which contains the desired hydrocarbons with the catalyst in the presence of oxygen.
- the type of reactor which can be used is any type well known in the art such as fixed-bed, moving-bed, multi-tube, CSTR, fluidized bed, etc.
- the feed stream can be flowed over the catalyst bed either up-flow or down-flow in the liquid, vapor, or mixed phase. In the case of a fiuidized-bed, the feed stream can be flowed co-current or counter-current.
- the feed stream In a CSTR the feed stream can be continuously added or added batch-wise.
- the feed stream contains the desired oxidizable species along with oxygen. Oxygen can be introduced either as pure oxygen or as air, or as liquid phase oxididents including hydrogen peroxide, organic peroxides, or peroxy-acids.
- the molar ratio of oxygen (02) to alkane can range from paragraph 5: 1 to paragraph 1 : 10.
- the feed stream can also contain a diluent gas selected form nitrogen, neon, argon, helium, carbon dioxide, steam or mixtures thereof.
- the oxygen can be added as air which could also provide a diluent.
- the molar ratio of diluent gas to oxygen ranges from greater than zero to paragraph 10: 1.
- the catalyst and feed stream are reacted at oxidation conditions which include a temperature of paragraph 300°C to paragraph 600°C, a pressure of paragraph 101 kPa to paragraph 5,066 kPa and a space velocity of paragraph 100 to paragraph 100,000 hr-1.
- Hydrogenation involves the addition of hydrogen to hydrogenatable hydrocarbon compounds.
- hydrogen can be provided in a hydrogen-containing compound with ready available hydrogen, such as tetralin, alcohols, hydrogenated naphthalenes, and others via a transfer hydrogenation process with or without a catalyst.
- the hydrogenatable hydrocarbon compounds are introduced into a hydrogenation zone and contacted with a hydrogen-rich gaseous phase and a hydrogenation catalyst in order to hydrogenate at least a portion of the hydrogenatable hydrocarbon compounds.
- the catalytic hydrogenation zone may contain a fixed, ebulated or fluidized catalyst bed.
- This reaction zone is typically at a pressure from paragraph 689 k Pa gauge (100 psig) to paragraph 13790 k Pa gauge (2000 psig) with a maximum catalyst bed temperature in the range of paragraph 177°C (350°F) to paragraph 454°C (850°F).
- the liquid hourly space velocity is typically in the range from paragraph 0.2 hr-1 to paragraph 10 hr-1 and hydrogen circulation rates from paragraph 200 standard cubic feet per barrel (SCFB) (35.6 m3 /m3) to paragraph 10,000 SCFB (1778 m3 /m3).
- a first embodiment of the invention is a process comprising providing a coal tar stream; expanding the coal tar stream with an inert gas stream to provide an expanded liquid coal tar stream; and hydrotreating the expanded liquid coal tar stream.
- 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 hydrotreating the expanded liquid coal tar stream comprises subjecting the expanded liquid coal tar stream to hydrodesulfurization, or hydrodenitrogenation, or both.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising processing the hydrotreated stream by one or more of hydrocracking, fluid catalytic cracking, alkylation, transalkylation, oxidation, and hydrogenation to provide at least one product.
- 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 inert gas is selected from the group consisting of carbon dioxide, nitrogen, and light hydrocarbons.
- 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 hydrotreating takes place at a temperature range of paragraph 260°C (paragraph 500°F) to paragraph 370°C (paragraph 700°F).
- 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 hydrotreating takes place at a pressure range of paragraph 4.8 MPa (paragraph 700 psi) to paragraph 8.3 MPa (paragraph 1200 psi).
- 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 hydrotreating takes place in the presence of a 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 further comprising feeding the coal tar stream and a hydrocarbon solvent into a reaction zone; reacting the coal tar stream and the hydrocarbon solvent in the reaction zone to provide a liquid coal tar stream; and wherein expanding the coal tar stream comprises expanding the liquid coal tar stream.
- 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 hydrocarbon solvent comprises an aromatic hydrocarbon.
- 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 coal tar stream and the hydrocarbon solvent are reacted at a pressure ranging from paragraph 4.8 MPa (paragraph 700 psig) to paragraph 8.3 MPa (paragraph 1200 psig).
- 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 providing the coal tar stream comprises pyrolyzing a coal feed into at least the coal tar stream and a coke stream.
- a second embodiment of the invention is a process comprising providing a coal tar stream; feeding the coal tar stream and a hydrocarbon solvent into a reaction zone; reacting the coal tar stream and the hydrocarbon solvent in the reaction zone to provide a liquid coal tar stream; and expanding the reacted coal tar stream with an inert gas stream to provide an expanded liquid coal tar stream; and hydrotreating the expanded liquid coal tar stream.
- 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 hydrotreating takes place at a temperature range of paragraph 260°C (paragraph 500°F) to paragraph 370°C (paragraph 700°F) and a pressure range of paragraph 4.8 MPa (paragraph 700 psi) to paragraph 8.3 MPa (paragraph 1200 psi).
- 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 inert gas is selected from the group consisting of carbon dioxide, nitrogen, and light hydrocarbons.
- 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 hydrotreating the expanded liquid coal tar stream comprises subjecting the expanded liquid coal tar stream to hydrodesulfurization, or hydrodenitrogenation, or both.
- An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising processing the hydrotreated stream by one or more of hydrocracking, fluid catalytic cracking, alkylation, transalkylation, oxidation, and hydrogenation to provide at least one product.
- 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 hydrotreating takes place in the presence of a 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 hydrocarbon solvent comprises an aromatic hydrocarbon.
- 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 coal tar stream and the hydrocarbon solvent are reacted at a pressure ranging from paragraph 4.8 MPa (paragraph 700 psig) to paragraph 8.3 MPa (paragraph 1200 psig).
- 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 providing the coal tar stream comprises pyrolyzing a coal feed into at least the coal tar stream and a coke stream.
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Abstract
A process for hydrotreating a coal tar stream is described. A coal tar stream is provided, and the coal tar stream is expanded with an inert gas stream to provide an expanded liquid coal tar stream. The expanded liquid coal tar stream is hydrotreated. The coal tar stream can be reacted with a hydrocarbon solvent before it is expanded.
Description
PROCESS FOR HYDROTREATING A COAL TAR STREAM
STATEMENT OF PRIORITY
This application claims the benefit of Provisional Application Serial No. 61/905,980 filed November 19, 2013, the contents of which are hereby incorporated by reference in its entirety.
BACKGROUND OF THE INVENTION
Many different types of chemicals are produced from the processing of petroleum. However, petroleum is becoming more expensive because of increased demand in recent decades. Therefore, attempts have been made to provide alternative sources for the starting materials for manufacturing chemicals. Attention is now being focused on producing liquid hydrocarbons from solid carbonaceous materials, such as coal, which is available in large quantities in countries such as the United States and China.
Pyrolysis of coal produces coke and coal tar. The coke-making or "coking" process consists of heating the material in closed vessels in the absence of oxygen to very high temperatures. Coke is a porous but hard residue that is mostly carbon and inorganic ash, which is used in making steel.
Coal tar is the volatile material that is driven off during heating, and it comprises a mixture of a number of hydrocarbon compounds. It can be separated to yield a variety of organic compounds, such as benzene, toluene, xylene, naphthalene, anthracene, and phenanthrene. These organic compounds can be used to make numerous products, for example, dyes, drugs, explosives, flavorings, perfumes, preservatives, synthetic resins, and paints and stains. The residual pitch left from the separation is used for paving, roofing, waterproofing, and insulation. Coal tar includes many contaminants. For many processes, it is desirable to treat a coal stream to remove such contaminants. However, some treatment processes for
coal tar insufficiently remove contaminants or produce undesirable results, such as saturated aromatic rings. There is a need to improve treatment of coal tar streams.
SUMMARY OF THE INVENTION
One aspect of the invention involves a process for hydrotreating a coal tar stream. A coal tar stream is provided, and the coal tar stream is expanded with an inert gas stream to provide an expanded liquid coal tar stream. The expanded liquid coal tar stream is hydrotreated.
BRIEF DESCRIPTION OF THE DRAWING The Figure is an illustration of one embodiment of the process of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The Figure shows one embodiment of a basic coal conversion process 5. A coal feed 10 is sent to a pyro lysis zone 15. Alternatively or additionally, in some processes, a portion of the coal feed 10 is sent to a gasification zone (not shown), where the coal feed is mixed with oxygen and steam and reacted under heat and pressure in the gasification zone to form syngas, which is a mixture of carbon monoxide and hydrogen. The syngas can be further processed using the Fischer-Tropsch reaction to produce gasoline or using the water- gas shift reaction to produce more hydrogen.
In the pyrolysis zone 15, the coal is heated at high temperature, e.g., up to paragraph 2,000°C (3600°F), in the absence of oxygen to drive off the volatile components. Coking produces a coke stream 25 and a coal tar stream 20. The coke stream 25 can be used in other processes, such as the manufacture of steel. The coal tar stream 20 from the pyrolysis zone, or coal tar streams from other sources, is subjected to a treatment process to provide a treated stream that can be used in various downstream processes. To reduce the aromaticity of the coal tar stream 20, the coal tar stream 20 can be sent to a reaction zone 35, where the coal tar stream 20 is reacted with added hydrogen in the presence of a hydrocarbon solvent 30. The reaction zone 35 can be, for instance, a continuous stirred-tank reactor (CSTR), a slurry hydrocracking reactor, or a fixed bed reactor.
The hydrocarbon solvent 30 can include, for instance, a petroleum cut or other aromatic-type hydrocarbon. Example reaction conditions include a pressure ranging from paragraph 4.8 MPa (paragraph 700 psig) to paragraph 8.3 MPa (paragraph 1200 psig) and a temperature ranging from paragraph 232 °C (450°F) to paragraph 371 °C (700°F). A catalyst such as a Ni/Mo hydrotreating catalyst for heavy feeds, or if S level is low enough a Pt/Al203 catalyst, can be used in the reaction zone 35, but is not required in all embodiments. The reaction zone 35 produces a liquid coal tar stream 40 that is reduced in aromaticity with respect to the coal tar stream 20.
The liquid coal tar stream 40 is fed to an expansion zone 50. The coal tar stream 40 is expanded with an inert gas stream 45 that is fed into the expansion zone 50. The expansion preferably takes place at high pressure, such as between paragraph 10.3 MPa (paragraph 1500 psi) and paragraph 17.2 MPa (paragraph 2500 psi), with an example range of paragraph 2000 psi (13.8 MPa). Suitable inert gases include, but are not limited to, carbon dioxide, nitrogen, and light hydrocarbons such as CH4, C2H4, C3H8, and C4Hi0. The inert gas stream 45 provides a vapor phase solvent in the expansion zone 50, and improves solubility of hydrogen in later hydrotreating, making the liquid phase more reactive. The expanded liquid coal tar stream 55 includes the hydrocarbon solvent 30 from the reaction zone 35.
In other processes, the reaction zone 35 can be omitted, and the coal tar stream 20 can be fed into the expansion zone 50. In this arrangement, the expanded liquid coal tar stream would not include the hydrocarbon solvent 30.
The expanded liquid coal tar stream 55 is then hydrotreated in the hydrotreating zone 60. Hydrotreating is a process in which hydrogen gas is contacted with a hydrocarbon stream in the presence of suitable catalysts which are primarily active for the removal of heteroatoms, such as sulfur, nitrogen, and metals from the hydrocarbon feedstock. In hydrotreating, hydrocarbons with double and triple bonds may be saturated. Aromatics may also be saturated. The hydrotreating in the hydrotreating zone 60 preferably takes place at paragraph 4.8 MPa (paragraph 700 psi) to paragraph 8.3 MPa (paragraph 1200 psi), and at a temperature range of paragraph 260 C (paragraph 500 F) to paragraph 370 C (paragraph 700 F), a liquid hourly space velocity of paragraph 0.5 hr-1 to paragraph 4 hr-1, and a
hydrogen rate of paragraph 168 to paragraph 1,011 Nm3/m3 oil (1,000-6,000 scf/bbl). Conditions can vary depending on the solvent.
The hydrogenation can take place in the presence of a catalyst. Typical hydrotreating catalysts include at least one Group VIII metal, preferably iron, cobalt and nickel, and at least one Group VI metal, preferably molybdenum and tungsten, on a high surface area support material, preferably alumina. Other typical hydrotreating catalysts include zeolitic catalysts, as well as noble metal catalysts where the noble metal is selected from palladium and platinum. Hydrotreating can include hydrodesulfurization, hydrodenitrogenation, or both. The resulting hydrotreated stream 65 provides a pre -treated stream that can be subject to a processing zone 70 to provide one or more products 75. This pre-treated stream can be relatively free of contaminants such as sulfur and nitrogen. Example hydrotreated streams 65 have a sulfur content of paragraph 50 ppm or less, and a nitrogen content of paragraph 10 ppm or less. Hydrotreating, reaction, and/or expansion conditions can be tuned to provide a desirable decontamination of the coal tar stream 40.
The processing zone 70 can process the hydrotreated stream 65 by hydrocracking, fluid catalytic cracking, alkylation, transalkylation, oxidation, hydrogenation, or a combination of such processes. The hydrotreated stream 65 can also be blended in fuel.
The hydrotreated stream 65 may be fractionated. Alternatively, the coal tar stream 20, 40 may be fractionated before treatment. Coal tar comprises a complex mixture of heterocyclic aromatic compounds and their derivatives with a wide range of boiling points. The number of fractions and the components in the various fractions can be varied as is well known in the art. A typical separation process involves separating the coal tar into four to six streams. For example, there can be a fraction comprising NH3, CO, and light hydrocarbons, a light oil fraction with boiling points between 0°C and 180°C, a middle oil fraction with boiling points between 180°C to 230°C, a heavy oil fraction with boiling points between 230 to 270°C, an anthracene oil fraction with boiling points between 270°C to 350°C, and pitch.
The light oil fraction contains compounds such as benzenes, toluenes, xylenes, naphtha, coumarone-indene, dicyclopentadiene, pyridine, and picolines. The middle oil
fraction contains compounds such as phenols, cresols and cresylic acids, xylenols, naphthalene, high boiling tar acids, and high boiling tar bases. The heavy oil fraction contains benzene absorbing oil and creosotes. The anthracene oil fraction contains anthracene. Pitch is the residue of the coal tar distillation containing primarily aromatic hydrocarbons and heterocyclic compounds.
Hydrocracking is a process in which hydrocarbons crack in the presence of hydrogen to lower molecular weight hydrocarbons. Typical hydrocracking conditions may include a temperature of paragraph 290°C (550°F) to paragraph 468°C (875°F), a pressure of paragraph 3.5 MPa (500 psig) to paragraph 20.7 MPa (3000 psig), a liquid hourly space velocity (LHSV) of paragraph 1.0 to less than paragraph 2.5 hr-1, and a hydrogen rate of paragraph 421 to paragraph 2,527 Nm3/m3 oil (2,500-15,000 scf/bbl). Typical hydrocracking catalysts include amorphous silica-alumina bases or low-level zeolite bases combined with one or more Group VIII or Group VIB metal hydrogenating components, or a crystalline zeolite cracking base upon which is deposited a Group VIII metal hydrogenating component. Additional hydrogenating components may be selected from Group VIB for incorporation with the zeolite base.
Fluid catalytic cracking (FCC) is a catalytic hydrocarbon conversion process accomplished by contacting heavier hydrocarbons in a fluidized reaction zone with a catalytic particulate material. The reaction in catalytic cracking is carried out in the absence of substantial added hydrogen or the consumption of hydrogen. The process typically employs a powdered catalyst having the particles suspended in a rising flow of feed hydrocarbons to form a fluidized bed. In representative processes, cracking takes place in a riser, which is a vertical or upward sloped pipe. Typically, a pre-heated feed is sprayed into the base of the riser via feed nozzles where it contacts hot fluidized catalyst and is vaporized on contact with the catalyst, and the cracking occurs converting the high molecular weight oil into lighter components including liquefied petroleum gas (LPG), gasoline, and a distillate. The catalyst- feed mixture flows upward through the riser for a short period (a few seconds), and then the mixture is separated in cyclones. The hydrocarbons are directed to a fractionator for separation into LPG, gasoline, diesel, kerosene, jet fuel, and other possible fractions. While going through the riser, the cracking catalyst is deactivated because the process is accompanied by formation of coke which deposits on the catalyst particles. Contaminated
catalyst is separated from the cracked hydrocarbon vapors and is further treated with steam to remove hydrocarbon remaining in the pores of the catalyst. The catalyst is then directed into a regenerator where the coke is burned off the surface of the catalyst particles, thus restoring the catalyst's activity and providing the necessary heat for the next reaction cycle. The process of cracking is endothermic. The regenerated catalyst is then used in the new cycle. Typical FCC conditions include a temperature of paragraph 400°C to paragraph 800°C, a pressure of paragraph 0 to paragraph 688 kPa g (paragraph 0 to 100 psig), and contact times of paragraph 0.1 seconds to paragraph 1 hour. The conditions are determined based on the hydrocarbon feedstock being cracked, and the cracked products desired. Zeolite-based catalysts are commonly used in FCC reactors, as are composite catalysts which contain zeolites, silica-aluminas, alumina, and other binders.
Alkylation is typically used to combine light olefins, for example mixtures of alkenes such as propylene and butylene, with isobutane to produce a relatively high-octane branched-chain paraffinic hydrocarbon fuel, including isoheptane and isooctane. Similarly, an alkylation reaction can be performed using an aromatic compound such as benzene in place of the isobutane. When using benzene, the product resulting from the alkylation reaction is an alkylbenzene (e.g. toluene, xylenes, ethylbenzene, etc.). For isobutane alkylation, typically, the reactants are mixed in the presence of a strong acid catalyst, such as sulfuric acid or hydrofluoric acid. The alkylation reaction is carried out at mild temperatures, and is typically a two-phase reaction. Because the reaction is exothermic, cooling is needed. Depending on the catalyst used, normal refinery cooling water provides sufficient cooling. Alternatively, a chilled cooling medium can be provided to cool the reaction. The catalyst protonates the alkenes to produce reactive carbocations which alkylate the isobutane reactant, thus forming branched chain paraffins from isobutane .Aromatic alkylation is generally now conducted with solid acid catalysts including zeolites or amorphous silica-aluminas
The alkylation reaction zone is maintained at a pressure sufficient to maintain the reactants in liquid phase. For a hydrofluoric acid catalyst, a general range of operating pressures is from paragraph 200 to paragraph 7100 kPa absolute. The temperature range covered by this set of conditions is from paragraph -20°C to paragraph 200°C. For at least alkylation of aromatic compounds, the temperature range is paragraph from 100-200C at the pressure range of paragraph 200 to paragraph 7100 kPa.
Transalkylation is a chemical reaction resulting in transfer of an alkyl group from one organic compound to another. Catalysts, particularly zeolite catalysts, are often used to effect the reaction. If desired, the transalkylation catalyst may be metal stabilized using a noble metal or base metal, and may contain suitable binder or matrix material such as inorganic oxides and other suitable materials. In a transalkylation process, a polyalkylaromatic hydrocarbon feed and an aromatic hydrocarbon feed are provided to a transalkylation reaction zone. The feed is usually heated to reaction temperature and then passed through a reaction zone, which may comprise one or more individual reactors. Passage of the combined feed through the reaction zone produces an effluent stream comprising unconverted feed and product monoalkylated hydrocarbons. This effluent is normally cooled and passed to a stripping column in which substantially all C5 and lighter hydrocarbons present in the effluent are concentrated into an overhead stream and removed from the process. An aromatics-rich stream is recovered as net stripper bottoms, which is referred to as the transalkylation effluent. The transalkylation reaction can be effected in contact with a catalytic composite in any conventional or otherwise convenient manner and may comprise a batch or continuous type of operation, with a continuous operation being preferred. The transalkylation catalyst is usefully disposed as a fixed bed in a reaction zone of a vertical tubular reactor, with the alkylaromatic feed stock charged through the bed in an upflow or downflow manner. The transalkylation zone normally operates at conditions including a temperature in the range of paragraph 130°C to paragraph 540°C. The transalkylation zone is typically operated at moderately elevated pressures broadly ranging from paragraph 100 kPa to paragraph 10 MPa absolute. The transalkylation reaction can be effected over a wide range of space velocities. That is, volume of charge per volume of catalyst per hour; weight hourly space velocity (WHSV) generally is in the range of from paragraph 0.1 to paragraph 30hr-l . The catalyst is typically selected to have relatively high stability at a high activity level.
Oxidation involves the oxidation of hydrocarbons to oxygen-containing compounds, such as aldehydes. The hydrocarbons include alkanes, alkenes, typically with carbon numbers from 2 to 15, and alkyl aromatics, Linear, branched, and cyclic alkanes and alkenes can be used. Oxygenates that are not fully oxidized to ketones or carboxylic acids can also be subjected to oxidation processes, as well as sulfur compounds that contain -S-H
moieties, thiophene rings, and sulfone groups. The process is carried out by placing an oxidation catalyst in a reaction zone and contacting the feed stream which contains the desired hydrocarbons with the catalyst in the presence of oxygen. The type of reactor which can be used is any type well known in the art such as fixed-bed, moving-bed, multi-tube, CSTR, fluidized bed, etc. The feed stream can be flowed over the catalyst bed either up-flow or down-flow in the liquid, vapor, or mixed phase. In the case of a fiuidized-bed, the feed stream can be flowed co-current or counter-current. In a CSTR the feed stream can be continuously added or added batch-wise. The feed stream contains the desired oxidizable species along with oxygen. Oxygen can be introduced either as pure oxygen or as air, or as liquid phase oxididents including hydrogen peroxide, organic peroxides, or peroxy-acids. The molar ratio of oxygen (02) to alkane can range from paragraph 5: 1 to paragraph 1 : 10. In addition to oxygen and alkane or alkene, the feed stream can also contain a diluent gas selected form nitrogen, neon, argon, helium, carbon dioxide, steam or mixtures thereof. As stated, the oxygen can be added as air which could also provide a diluent. The molar ratio of diluent gas to oxygen ranges from greater than zero to paragraph 10: 1. The catalyst and feed stream are reacted at oxidation conditions which include a temperature of paragraph 300°C to paragraph 600°C, a pressure of paragraph 101 kPa to paragraph 5,066 kPa and a space velocity of paragraph 100 to paragraph 100,000 hr-1.
Hydrogenation involves the addition of hydrogen to hydrogenatable hydrocarbon compounds. Alternatively, hydrogen can be provided in a hydrogen-containing compound with ready available hydrogen, such as tetralin, alcohols, hydrogenated naphthalenes, and others via a transfer hydrogenation process with or without a catalyst. The hydrogenatable hydrocarbon compounds are introduced into a hydrogenation zone and contacted with a hydrogen-rich gaseous phase and a hydrogenation catalyst in order to hydrogenate at least a portion of the hydrogenatable hydrocarbon compounds. The catalytic hydrogenation zone may contain a fixed, ebulated or fluidized catalyst bed. This reaction zone is typically at a pressure from paragraph 689 k Pa gauge (100 psig) to paragraph 13790 k Pa gauge (2000 psig) with a maximum catalyst bed temperature in the range of paragraph 177°C (350°F) to paragraph 454°C (850°F). The liquid hourly space velocity is typically in the range from paragraph 0.2 hr-1 to paragraph 10 hr-1 and hydrogen circulation rates from
paragraph 200 standard cubic feet per barrel (SCFB) (35.6 m3 /m3) to paragraph 10,000 SCFB (1778 m3 /m3).
SPECIFIC EMBODIMENTS
While the following is described in conjunction with specific embodiments, it will be understood that this description is intended to illustrate and not limit the scope of the preceding description and the appended claims.
A first embodiment of the invention is a process comprising providing a coal tar stream; expanding the coal tar stream with an inert gas stream to provide an expanded liquid coal tar stream; and hydrotreating the expanded liquid coal tar stream. 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 hydrotreating the expanded liquid coal tar stream comprises subjecting the expanded liquid coal tar stream to hydrodesulfurization, or hydrodenitrogenation, or both. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising processing the hydrotreated stream by one or more of hydrocracking, fluid catalytic cracking, alkylation, transalkylation, oxidation, and hydrogenation to provide at least one product. 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 inert gas is selected from the group consisting of carbon dioxide, nitrogen, and light hydrocarbons. 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 hydrotreating takes place at a temperature range of paragraph 260°C (paragraph 500°F) to paragraph 370°C (paragraph 700°F). 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 hydrotreating takes place at a pressure range of paragraph 4.8 MPa (paragraph 700 psi) to paragraph 8.3 MPa (paragraph 1200 psi). 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 hydrotreating takes place in the presence of a 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 further comprising feeding the coal tar stream and a hydrocarbon solvent into a
reaction zone; reacting the coal tar stream and the hydrocarbon solvent in the reaction zone to provide a liquid coal tar stream; and wherein expanding the coal tar stream comprises expanding the liquid coal tar stream. 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 hydrocarbon solvent comprises an aromatic hydrocarbon. 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 coal tar stream and the hydrocarbon solvent are reacted at a pressure ranging from paragraph 4.8 MPa (paragraph 700 psig) to paragraph 8.3 MPa (paragraph 1200 psig). 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 providing the coal tar stream comprises pyrolyzing a coal feed into at least the coal tar stream and a coke stream.
A second embodiment of the invention is a process comprising providing a coal tar stream; feeding the coal tar stream and a hydrocarbon solvent into a reaction zone; reacting the coal tar stream and the hydrocarbon solvent in the reaction zone to provide a liquid coal tar stream; and expanding the reacted coal tar stream with an inert gas stream to provide an expanded liquid coal tar stream; and hydrotreating the expanded liquid coal tar stream. 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 hydrotreating takes place at a temperature range of paragraph 260°C (paragraph 500°F) to paragraph 370°C (paragraph 700°F) and a pressure range of paragraph 4.8 MPa (paragraph 700 psi) to paragraph 8.3 MPa (paragraph 1200 psi). 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 inert gas is selected from the group consisting of carbon dioxide, nitrogen, and light hydrocarbons. 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 hydrotreating the expanded liquid coal tar stream comprises subjecting the expanded liquid coal tar stream to hydrodesulfurization, or hydrodenitrogenation, or both. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising processing the hydrotreated stream by one or more of hydrocracking, fluid catalytic cracking, alkylation, transalkylation, oxidation, and
hydrogenation to provide at least one product. 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 hydrotreating takes place in the presence of a 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 hydrocarbon solvent comprises an aromatic hydrocarbon. 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 coal tar stream and the hydrocarbon solvent are reacted at a pressure ranging from paragraph 4.8 MPa (paragraph 700 psig) to paragraph 8.3 MPa (paragraph 1200 psig). 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 providing the coal tar stream comprises pyrolyzing a coal feed into at least the coal tar stream and a coke stream.
While at least one exemplary embodiment has been presented in the foregoing detailed description of the invention, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the invention in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment of the invention. It being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the invention as set forth in the appended claims.
Claims
CLAIMS 1. A process (5) comprising: providing a coal tar stream (20); expanding the coal tar stream (20) with an inert gas stream (45) to provide an expanded liquid coal tar stream (55); and hydrotreating (60) the expanded liquid coal tar stream (55).
2. The process of claim 1 wherein hydrotreating (60) the expanded liquid coal tar stream (55) comprises subjecting the expanded liquid coal tar stream (55) to hydrodesulfurization, or hydrodenitrogenation, or both.
3. The process of any of claims 1-2 further comprising: processing (70) the hydrotreated stream (65) by one or more of hydrocracking, fluid catalytic cracking, alkylation, transalkylation, oxidation, and hydrogenation to provide at least one product (75).
4. The process of any of claims 1-2 wherein the inert gas is selected from the group consisting of carbon dioxide, nitrogen, and light hydrocarbons.
5. The process of any of claims 1-2 wherein the hydrotreating (60) takes place in the presence of a catalyst.
6. The process of any of claims 1-2 wherein the hydrotreating (60) takes place at a temperature range of paragraph 260°C (paragraph 500°F) to paragraph 370°C
(paragraph 700°F) and in a pressure range of paragraph 4.8 MPa (paragraph 700 psi) to paragraph 8.3 MPa (paragraph 1200 psi).
7. The process of any of claims 1-2 further comprising: feeding the coal tar stream (20) and a hydrocarbon solvent (30) into a reaction zone (35); reacting the coal tar stream (20) and the hydrocarbon solvent (30) in the reaction zone (35) to provide a liquid coal tar stream (40); and wherein expanding the coal tar stream (20) comprises expanding the liquid coal tar stream (40).
8. The process of claim 7 wherein the hydrocarbon solvent (30) comprises an aromatic hydrocarbon.
9. The process of claim 7 wherein the coal tar stream (20) and the hydrocarbon solvent (30) are reacted at a pressure ranging from paragraph 4.8 MPa
(paragraph 700 psig) to paragraph 8.3 MPa (paragraph 1200 psig).
10. The process of any of claims 1-2 wherein providing the coal tar stream (20) comprises pyrolyzing (15) a coal feed (10) into at least the coal tar stream (20) and a coke stream (25).
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CN201480061925.5A CN105745310A (en) | 2013-11-19 | 2014-11-07 | Process for hydrotreating a coal tar stream |
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AU2016286296B2 (en) * | 2015-07-02 | 2021-12-09 | Haldor Topsøe A/S | Demetallization of hydrocarbons |
WO2020086394A1 (en) * | 2018-10-25 | 2020-04-30 | Exxonmobil Chemical Patents Inc. | Solvent and temperature assisted dissolution of solids from steam cracked tar |
CN117844525A (en) * | 2024-03-07 | 2024-04-09 | 陕西煤业化工集团神木天元化工有限公司 | Method for preparing chemicals and special fuel from medium-temperature coal tar |
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CN101033410A (en) * | 2007-02-16 | 2007-09-12 | 西安交通大学 | Method of hydrogenation treatment for coal tar by hypercritical solvent |
US20080256852A1 (en) * | 2007-04-20 | 2008-10-23 | Schobert Harold H | Integrated process and apparatus for producing coal-based jet fuel, diesel fuel, and distillate fuels |
CN102899088A (en) * | 2012-09-19 | 2013-01-30 | 王小英 | Hydrogenation method for medium and low temperature coal tar |
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US4356077A (en) * | 1980-12-31 | 1982-10-26 | Occidental Research Corporation | Pyrolysis process |
JP2006306742A (en) * | 2005-04-26 | 2006-11-09 | Jfe Chemical Corp | Method for producing methyldecalin |
CN102703115B (en) * | 2012-05-22 | 2014-06-25 | 韩钊武 | Hydrotreating method for preparing gasoline by high-temperature coal tar |
CN102899087B (en) * | 2012-09-19 | 2014-12-24 | 王小英 | Deep processing method for medium and low temperature coal tar |
-
2014
- 2014-08-26 US US14/469,289 patent/US20150136652A1/en not_active Abandoned
- 2014-11-07 WO PCT/US2014/064466 patent/WO2015077045A1/en active Application Filing
- 2014-11-07 CN CN201480061925.5A patent/CN105745310A/en active Pending
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US4101416A (en) * | 1976-06-25 | 1978-07-18 | Occidental Petroleum Corporation | Process for hydrogenation of hydrocarbon tars |
CN101033410A (en) * | 2007-02-16 | 2007-09-12 | 西安交通大学 | Method of hydrogenation treatment for coal tar by hypercritical solvent |
US20080256852A1 (en) * | 2007-04-20 | 2008-10-23 | Schobert Harold H | Integrated process and apparatus for producing coal-based jet fuel, diesel fuel, and distillate fuels |
CN102766477B (en) * | 2012-07-13 | 2013-09-18 | 韩钊武 | Method for preparing clean fuel oil from coal tar |
CN102899088A (en) * | 2012-09-19 | 2013-01-30 | 王小英 | Hydrogenation method for medium and low temperature coal tar |
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