US20150136656A1 - Process for pyrolysis of coal - Google Patents
Process for pyrolysis of coal Download PDFInfo
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- US20150136656A1 US20150136656A1 US14/464,300 US201414464300A US2015136656A1 US 20150136656 A1 US20150136656 A1 US 20150136656A1 US 201414464300 A US201414464300 A US 201414464300A US 2015136656 A1 US2015136656 A1 US 2015136656A1
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- United States
- Prior art keywords
- stream
- pitch
- hydrogenating
- pitch stream
- group
- Prior art date
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- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000003245 coal Substances 0.000 title claims abstract description 26
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 25
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 45
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 39
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 26
- 239000011280 coal tar Substances 0.000 claims abstract description 25
- 238000010555 transalkylation reaction Methods 0.000 claims abstract description 14
- 239000000571 coke Substances 0.000 claims abstract description 10
- 230000029936 alkylation Effects 0.000 claims abstract description 8
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 8
- 238000004231 fluid catalytic cracking Methods 0.000 claims abstract description 8
- 238000003442 catalytic alkylation reaction Methods 0.000 claims abstract 3
- 239000003054 catalyst Substances 0.000 claims description 46
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims description 19
- 150000002739 metals Chemical class 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 10
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910003465 moissanite Inorganic materials 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 150000002790 naphthalenes Chemical class 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052713 technetium Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 24
- 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000005804 alkylation reaction Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 150000001336 alkenes Chemical class 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
- 238000000926 separation method Methods 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
- 239000007789 gas Substances 0.000 description 4
- 239000000463 material Substances 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
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- 239000003915 liquefied petroleum gas Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-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
- 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003208 petroleum Substances 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
- 239000000376 reactant Substances 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
- 238000009901 transfer hydrogenation reaction Methods 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
- 241000169624 Casearia sylvestris Species 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
- 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
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- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 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
- 238000004939 coking Methods 0.000 description 1
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- 150000001924 cycloalkanes Chemical class 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
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- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
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- 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
- 239000011148 porous material Substances 0.000 description 1
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- 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
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 150000003739 xylenols Chemical class 0.000 description 1
Images
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
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
-
- 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
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
-
- 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
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
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 can be 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 pitch stream While lighter hydrocarbon streams from coal tar can be more easily processed to produce desirable products, the pitch stream includes aromatic cores that make the pitch more difficult to react in further processing.
- the residual pitch left from the separation conventionally is used for paving, roofing, waterproofing, and insulation.
- One aspect of the invention involves a process for pyrolyzing a coal feed.
- the coal feed is pyrolyzed into a coal tar stream and a coke stream in a pyrolysis zone.
- the coal tar stream is separated into at least a pitch stream.
- the pitch stream is hydrogenated, and the hydrogenated pitch stream is recycled into the pyrolysis zone.
- Another aspect of the invention includes a process for removing at least one product from coal tar.
- a coal feed is introduced into a pyrolysis zone, and the coal feed is pyrolyzed in the pyrolysis zone to produce a coal tar stream and a coke stream.
- the coal tar stream is separated into at least one hydrocarbon stream and a pitch stream.
- the pitch stream is hydrogenated, and the hydrogenated pitch stream is recycled to the pyrolysis zone.
- the hydrogenated pitch stream is pyrolyzed. At least one product is recovered from the hydrocarbon stream.
- the FIGURE is an illustration of one embodiment of the process of the present invention.
- the Figure shows one embodiment of a coal conversion process 5 of the present invention.
- a coal feed 10 is sent to a pyrolysis zone 15 .
- all or a portion of the coal feed 10 is also sent to a gasification zone (not shown), where the coal feed is mixed with oxygen and steam and reacted under heat and pressure 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 feed 10 can be sent to the pyrolysis zone 15 , the gasification zone, or the coal feed 10 can be split into two parts and sent to both.
- the coal feed 10 is heated at high temperature, e.g., up to about 2,000° C. (3,600° F.), in the absence of oxygen to drive off the volatile components. Pyrolysis 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 is sent to a separation zone 30 where it is separated at least a pitch stream.
- the coal tar stream 20 is separated into two or more fractions 35 , 40 , 45 , 50 , 55 .
- Suitable separation processes include, but are not limited to fractionation, solvent extraction, and adsorption.
- 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 stream 20 into four to six streams. For example, there can be a fraction 35 comprising NH 3 , CO, and light hydrocarbons, a light oil fraction 40 with boiling points between 0° C.
- a middle oil fraction 45 with boiling points between 180° C. to 230° C. a heavy oil fraction 50 with boiling points between 230 to 270° C.
- an anthracene oil fraction (not shown) with boiling points between 270° C. to 350° C.
- a pitch stream 55 a pitch stream 55 .
- the light oil fraction 40 contains compounds such as benzenes, toluenes, xylenes, naphtha, coumarone-indene, dicyclopentadiene, pyridine, and picolines.
- the middle oil fraction 45 contains compounds such as phenols, cresols and cresylic acids, xylenols, naphthalene, high boiling tar acids, and high boiling tar bases.
- the heavy oil fraction 50 contains creosotes.
- the anthracene oil fraction (not shown) contains anthracene.
- the pitch stream 55 is the residue of the coal tar distillation containing primarily aromatic hydrocarbons and heterocyclic compounds.
- the pitch stream 55 includes polynuclear aromatic (PNA) cores that are difficult to react for further processing, as compared to lighter hydrocarbon fractions.
- PNA polynuclear aromatic
- the pitch stream 55 is sent to a hydrogenation zone 60 for hydrogenating the pitch stream 55 .
- 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.
- the hydrogenatable hydrocarbon compounds are introduced into the hydrogenation zone 60 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 hydrogenation zone 60 may contain a fixed, ebulated or fluidized catalyst bed.
- An example hydrogenation process in the hydrogenation zone 60 takes place at a temperature between about 250° C. and about 500° C., and at a pressure between about 1.72 MPa (about 250 psig) and about 20.7 MPa (about 3,000 psig).
- the hydrogenation includes contacting the pitch stream 55 with a hydrogenation catalyst consisting of metal selected from the group consisting of Group VI metals (Cr, Mo, W), Group VII metals (Mn, Tc, Re) or Group VIII metals (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) metals and combinations thereof supported on an inorganic oxide, carbide or sulfide support, including Al 2 O 3 , SiO 2 , SiO 2 —Al 2 O 3 , zeolites, non-zeolitic molecular sieves, ZrO 2 , TiO 2 , ZnO, and SiC.
- a hydrogenation catalyst consisting of metal selected from the group consisting of Group VI metals (Cr,
- the liquid hourly space velocity (LHSV) is typically in the range from about 0.2 hr ⁇ 1 to about 10 hr ⁇ 1 and hydrogen circulation rates from about 200 standard cubic feet per barrel (SCFB) (35.6 m 3 /m 3 ) to about 10,000 SCFB (1,778 m 3 /m 3 ).
- SCFB standard cubic feet per barrel
- the hydrogenation zone 60 hydrogenates at least a portion of the aromatic cores in the pitch stream 55 to make them more reactive; for instance, the hydrogenated aromatic cores can crack open more easily in a subsequent thermal reaction.
- the hydrogenated pitch stream 65 with hydrogenated aromatic cores is recycled to the pyrolysis zone 15 .
- Additional coal feed 10 can also be fed to the pyrolysis zone 15 .
- the hydrogenated pitch stream 65 can be combined with the new coal feed 10 , and this combined feed can be fed to the pyrolysis zone 15 , or the hydrogenated pitch stream 65 and new coal feed 10 can separately be delivered to the pyrolysis zone 15 .
- Pyrolyzing the recycled hydrogenated pitch stream 65 alone or with additional coal feed 10 , provides a coal tar stream 20 output having lighter fractions.
- the pyrolysis zone 15 , the fractionation zone 30 , and the hydrogenation zone 60 with new coal feed 10 for pyrolysis, can provide a cycle that is repeated multiple times to provide an increased amount of the lighter fractions for additional processing.
- fractions 35 , 40 , 45 , 50 , 55 can be recovered as at least one product, or may be further processed as desired to recover at least one product.
- fraction 45 is sent to a hydrocarbon conversion zone 80 .
- hydrocarbon conversion zone 80 includes a catalyst which is sensitive to sulfur
- the fraction 35 , 40 , 45 , 50 , 55 can be sent to a hydrotreating zone 70 for treating to remove contaminants sulfur and nitrogen.
- the hydrotreating effluent 75 is then sent to the hydrocarbon conversion zone 80 for hydrocracking, for example, to recover at least one product 85 .
- 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.
- Typical hydrotreating reaction conditions include a temperature of about 290° C. (550° F.) to about 455° C.
- 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.
- Suitable hydrocarbon conversion zones include, but are not limited to, hydrotreating zones, hydrocracking zones, fluid catalytic cracking zones, alkylation zones, transalkylation zones, oxidation zones, and hydrogenation zones.
- Example hydrotreating processes are described above.
- 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 about 290° C. (550° F.) to about 468° C. (875° F.), a pressure of about 3.5 MPa (500 psig) to about 20.7 MPa (3,000 psig), a liquid hourly space velocity (LHSV) of about 1.0 to less than about 2.5 hr ⁇ 1, and a hydrogen rate of about 421 to about 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 about 400° C. to about 800° C., a pressure of about 0 to about 688 kPag (about 0 to 100 psig), and contact times of about 0.1 seconds to about 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.
- 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 about 200 to about 7,100 kPa absolute.
- the temperature range covered by this set of conditions is from about ⁇ 20° C. to about 200° C.
- the temperature range is about from 100° C. to 200° C. at the pressure range of about 200 to about 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.
- 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 about 130° C. to about 540° C.
- the transalkylation zone is typically operated at moderately elevated pressures broadly ranging from about 100 kPa to about 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 about 0.1 to about 30 hr ⁇ 1 .
- 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 alcohols, aldehydes, ketones, carboxylic acids and epoxides.
- 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 fluidized-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 oxidants including hydrogen peroxide, organic peroxides, or peroxy-acids.
- the molar ratio of oxygen (O 2 ) to alkane can range from about 5:1 to about 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 about 10:1.
- the catalyst and feed stream are reacted at oxidation conditions which include a temperature of about 100° C. to about 600° C., a pressure of about 101 kPa to about 5,066 kPa and a gas hourly space velocity of about 100 to about 100,000 hr ⁇ 1.
- An additional hydrogenation process 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 about 689 kPag (100 psig) to about 13,790 kPag (2,000 psig) with a maximum catalyst bed temperature in the range of about 177° C.
- the liquid hourly space velocity is typically in the range from about 0.2 hr ⁇ 1 to about 10 hr ⁇ 1 and hydrogen circulation rates from about 200 standard cubic feet per barrel (SCFB) (35.6 m 3 /m 3 ) to about 10,000 SCFB (1,778 m 3 /m 3 ).
- SCFB standard cubic feet per barrel
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Abstract
A process for pyrolyzing a coal feed is described. The coal feed is pyrolyzed into a coal tar stream and a coke stream in a pyrolysis zone. The coal tar stream is fractionated into at least a pitch stream. The pitch stream is hydrogenated, and the hydrogenated pitch stream is recycled into the pyrolysis zone. The hydrocarbon stream may be processed further by at least one of hydrotreating, hydrocracking, fluid catalytic cracking, alkylation, and transalkylation.
Description
- This application claims priority to U.S. Provisional Application No. 61/906,010, filed on Nov. 19, 2013, the entirety of which is incorporated by reference.
- 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 can be 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.
- While lighter hydrocarbon streams from coal tar can be more easily processed to produce desirable products, the pitch stream includes aromatic cores that make the pitch more difficult to react in further processing. The residual pitch left from the separation conventionally is used for paving, roofing, waterproofing, and insulation.
- There is a need for improved processes for making value-added products from coal tar.
- One aspect of the invention involves a process for pyrolyzing a coal feed. The coal feed is pyrolyzed into a coal tar stream and a coke stream in a pyrolysis zone. The coal tar stream is separated into at least a pitch stream. The pitch stream is hydrogenated, and the hydrogenated pitch stream is recycled into the pyrolysis zone.
- Another aspect of the invention includes a process for removing at least one product from coal tar. A coal feed is introduced into a pyrolysis zone, and the coal feed is pyrolyzed in the pyrolysis zone to produce a coal tar stream and a coke stream. The coal tar stream is separated into at least one hydrocarbon stream and a pitch stream. The pitch stream is hydrogenated, and the hydrogenated pitch stream is recycled to the pyrolysis zone. The hydrogenated pitch stream is pyrolyzed. At least one product is recovered from the hydrocarbon stream.
- The FIGURE is an illustration of one embodiment of the process of the present invention.
- The Figure shows one embodiment of a coal conversion process 5 of the present invention. A
coal feed 10 is sent to apyrolysis zone 15. In some processes, all or a portion of thecoal feed 10 is also sent to a gasification zone (not shown), where the coal feed is mixed with oxygen and steam and reacted under heat and pressure 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. Thecoal feed 10 can be sent to thepyrolysis zone 15, the gasification zone, or thecoal feed 10 can be split into two parts and sent to both. - In the
pyrolysis zone 15, thecoal feed 10 is heated at high temperature, e.g., up to about 2,000° C. (3,600° F.), in the absence of oxygen to drive off the volatile components. Pyrolysis produces acoke stream 25 and acoal tar stream 20. Thecoke stream 25 can be used in other processes, such as the manufacture of steel. - The
coal tar stream 20 is sent to aseparation zone 30 where it is separated at least a pitch stream. Preferably, thecoal tar stream 20 is separated into two ormore fractions coal tar stream 20 into four to six streams. For example, there can be afraction 35 comprising NH3, CO, and light hydrocarbons, alight oil fraction 40 with boiling points between 0° C. and 180° C., amiddle oil fraction 45 with boiling points between 180° C. to 230° C., aheavy oil fraction 50 with boiling points between 230 to 270° C., an anthracene oil fraction (not shown) with boiling points between 270° C. to 350° C., and apitch stream 55. - The
light oil fraction 40 contains compounds such as benzenes, toluenes, xylenes, naphtha, coumarone-indene, dicyclopentadiene, pyridine, and picolines. Themiddle oil fraction 45 contains compounds such as phenols, cresols and cresylic acids, xylenols, naphthalene, high boiling tar acids, and high boiling tar bases. Theheavy oil fraction 50 contains creosotes. The anthracene oil fraction (not shown) contains anthracene. Thepitch stream 55 is the residue of the coal tar distillation containing primarily aromatic hydrocarbons and heterocyclic compounds. - The
pitch stream 55 includes polynuclear aromatic (PNA) cores that are difficult to react for further processing, as compared to lighter hydrocarbon fractions. In the process 5, thepitch stream 55 is sent to ahydrogenation zone 60 for hydrogenating thepitch stream 55. - 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. The hydrogenatable hydrocarbon compounds are introduced into the
hydrogenation zone 60 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. Thehydrogenation zone 60 may contain a fixed, ebulated or fluidized catalyst bed. - An example hydrogenation process in the
hydrogenation zone 60 takes place at a temperature between about 250° C. and about 500° C., and at a pressure between about 1.72 MPa (about 250 psig) and about 20.7 MPa (about 3,000 psig). The hydrogenation includes contacting thepitch stream 55 with a hydrogenation catalyst consisting of metal selected from the group consisting of Group VI metals (Cr, Mo, W), Group VII metals (Mn, Tc, Re) or Group VIII metals (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) metals and combinations thereof supported on an inorganic oxide, carbide or sulfide support, including Al2O3, SiO2, SiO2—Al2O3, zeolites, non-zeolitic molecular sieves, ZrO2, TiO2, ZnO, and SiC. The liquid hourly space velocity (LHSV) is typically in the range from about 0.2 hr−1 to about 10 hr−1 and hydrogen circulation rates from about 200 standard cubic feet per barrel (SCFB) (35.6 m3/m3) to about 10,000 SCFB (1,778 m3/m3). - The
hydrogenation zone 60 hydrogenates at least a portion of the aromatic cores in thepitch stream 55 to make them more reactive; for instance, the hydrogenated aromatic cores can crack open more easily in a subsequent thermal reaction. The hydrogenatedpitch stream 65 with hydrogenated aromatic cores is recycled to thepyrolysis zone 15.Additional coal feed 10 can also be fed to thepyrolysis zone 15. For example, the hydrogenatedpitch stream 65 can be combined with thenew coal feed 10, and this combined feed can be fed to thepyrolysis zone 15, or thehydrogenated pitch stream 65 andnew coal feed 10 can separately be delivered to thepyrolysis zone 15. - Pyrolyzing the recycled hydrogenated
pitch stream 65, alone or withadditional coal feed 10, provides acoal tar stream 20 output having lighter fractions. Thepyrolysis zone 15, thefractionation zone 30, and thehydrogenation zone 60, withnew coal feed 10 for pyrolysis, can provide a cycle that is repeated multiple times to provide an increased amount of the lighter fractions for additional processing. - One or more of the
fractions fraction 45 is sent to ahydrocarbon conversion zone 80. Wherehydrocarbon conversion zone 80 includes a catalyst which is sensitive to sulfur, thefraction hydrotreating zone 70 for treating to remove contaminants sulfur and nitrogen. Thehydrotreating effluent 75 is then sent to thehydrocarbon conversion zone 80 for hydrocracking, for example, to recover at least oneproduct 85. - 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. Typical hydrotreating reaction conditions include a temperature of about 290° C. (550° F.) to about 455° C. (850° F.), a pressure of about 3.4 MPa (500 psig) to about 26.7 MPa (4,000 psig), a liquid hourly space velocity of about 0.5 hr−1 to about 4 hr−1, and a hydrogen rate of about 168 to about 1,011 Nm3/m3 oil (1,000-6,000 scf/bbl). 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.
- Suitable hydrocarbon conversion zones include, but are not limited to, hydrotreating zones, hydrocracking zones, fluid catalytic cracking zones, alkylation zones, transalkylation zones, oxidation zones, and hydrogenation zones. Example hydrotreating processes are described above.
- 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 about 290° C. (550° F.) to about 468° C. (875° F.), a pressure of about 3.5 MPa (500 psig) to about 20.7 MPa (3,000 psig), a liquid hourly space velocity (LHSV) of about 1.0 to less than about 2.5 hr−1, and a hydrogen rate of about 421 to about 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 about 400° C. to about 800° C., a pressure of about 0 to about 688 kPag (about 0 to 100 psig), and contact times of about 0.1 seconds to about 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. 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 about 200 to about 7,100 kPa absolute. The temperature range covered by this set of conditions is from about −20° C. to about 200° C. For at least alkylation of aromatic compounds, the temperature range is about from 100° C. to 200° C. at the pressure range of about 200 to about 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 about 130° C. to about 540° C. The transalkylation zone is typically operated at moderately elevated pressures broadly ranging from about 100 kPa to about 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 about 0.1 to about 30 hr−1. 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 alcohols, aldehydes, ketones, carboxylic acids and epoxides. 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 fluidized-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 oxidants including hydrogen peroxide, organic peroxides, or peroxy-acids. The molar ratio of oxygen (O2) to alkane can range from about 5:1 to about 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 about 10:1. The catalyst and feed stream are reacted at oxidation conditions which include a temperature of about 100° C. to about 600° C., a pressure of about 101 kPa to about 5,066 kPa and a gas hourly space velocity of about 100 to about 100,000 hr−1.
- An additional hydrogenation process 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 about 689 kPag (100 psig) to about 13,790 kPag (2,000 psig) with a maximum catalyst bed temperature in the range of about 177° C. (350° F.) to about 454° C. (850° F.). The liquid hourly space velocity is typically in the range from about 0.2 hr−1 to about 10 hr−1 and hydrogen circulation rates from about 200 standard cubic feet per barrel (SCFB) (35.6 m3/m3) to about 10,000 SCFB (1,778 m3/m3).
- 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 (20)
1. A process comprising:
pyrolyzing a coal feed into a coal tar stream and a coke stream in a pyrolysis zone;
separating the coal tar stream into at least a pitch stream;
hydrogenating the pitch stream; and
recycling the hydrogenated pitch stream into the pyrolysis zone.
2. The process of claim 1 wherein hydrogenating the pitch stream comprises contacting the pitch stream with a hydrogenation catalyst consisting of metal selected from the group consisting of Group VI metals (Cr, Mo, W), Group VII metals (Mn, Tc, Re), or Group VIII metals (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) and combinations thereof supported on an inorganic oxide, carbide or sulfide support, including Al2O3, SiO2, SiO2—Al2O3, zeolites, non-zeolitic molecular sieves, ZrO2, TiO2, ZnO, and SiC.
3. The process of claim 1 wherein hydrogenating the pitch stream takes place at a temperature between about 250° C. and about 500° C.
4. The process of claim 1 wherein the hydrogenation takes place at a pressure between about 1.72 MPa (about 250 psig) and about 20.7 MPa (about 3,000 psig).
5. The process of claim 1 wherein separating the coal tar stream further provides a hydrocarbon stream.
6. The process of claim 5 further comprising:
recovering at least one product from the hydrocarbon stream.
7. The process of claim 1 further comprising:
feeding additional coal feed into the pyrolysis zone; and
pyrolyzing the recycled pitch stream.
8. The process of claim 6 further comprising:
processing the hydrocarbon stream to produce at least one product.
9. The process of claim 8 wherein the hydrocarbon stream is processed by at least one of hydrotreating, hydrocracking, fluid catalytic cracking, alkylation, and transalkylation.
10. The process of claim 9 further comprising:
treating at least one product to remove contaminants.
11. A process for recovering at least one product from coal tar comprising:
introducing a coal feed into a pyrolysis zone;
pyrolyzing the coal feed in the pyrolysis zone to produce a coal tar stream and a coke stream;
separating the coal tar stream into at least one hydrocarbon stream and a pitch stream;
hydrogenating the pitch stream;
recycling the hydrogenated pitch stream to the pyrolysis zone;
pyrolyzing the hydrogenated pitch stream; and
recovering at least one product from the hydrocarbon stream.
12. The process of claim 11 wherein the recovering comprises:
processing the hydrocarbon stream by at least one of hydrotreating, hydrocracking, fluid catalytic cracking, alkylation, and transalkylation.
13. The process of claim 11 wherein hydrogenating the pitch stream comprises contacting the pitch stream with a hydrogenation catalyst consisting of metal selected from the group consisting of Group VI metals (Cr, Mo, W), Group VII metals (Mn, Tc, Re) or Group VIII metals (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) metals and combinations thereof supported on an inorganic oxide, carbide or sulfide support, including Al2O3, SiO2, SiO2—Al2O3, zeolites, non-zeolitic molecular sieves, ZrO2, TiO2, ZnO, and SiC.
14. The process of claim 11 , wherein hydrogenating the pitch stream takes place at a temperature between about 250° C. and about 500° C.
15. The process of claim 11 , wherein hydrogenating the pitch stream takes place at a pressure between about 1.72 MPa (about 250 psig) and about 20.7 MPa (about 3,000 psig).
16. The process of claim 11 wherein pyrolyzing the hydrogenated pitch stream further comprises pyrolyzing additional coal feed with the hydrogenated pitch stream.
17. The process of claim 11 wherein hydrogenating the pitch stream uses hydrogen provided in a hydrogen-containing compound selected from the group consisting of tetralin, alcohols, and hydrogenated naphthalenes.
18. The process of claim 1 wherein hydrogenating the pitch stream comprises adding hydrogen to a hydrogenation zone.
19. The process of claim 11 wherein separating the coal tar stream provides a plurality of hydrocarbon streams and the pitch stream.
20. The process of claim 11 wherein hydrogenating the pitch stream uses a catalyst bed selected from the group consisting of a fixed catalyst bed, an ebulated catalyst bed, and a fluidized catalyst bed.
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US201361906010P | 2013-11-19 | 2013-11-19 | |
US14/464,300 US20150136656A1 (en) | 2013-11-19 | 2014-08-20 | Process for pyrolysis of coal |
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US20170355911A1 (en) * | 2016-06-14 | 2017-12-14 | Fluor Technologies Corporation | Processing of gasification tars to high yields of btx |
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CN105670666B (en) * | 2016-04-01 | 2018-06-15 | 太原理工大学 | The combined unit of low-order coal catalytic degradation and use its method |
CN106318430B (en) * | 2016-10-14 | 2018-03-23 | 神雾科技集团股份有限公司 | A kind of system and method using low-order coal |
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US4324640A (en) * | 1980-08-26 | 1982-04-13 | Occidental Research Corporation | Pyrolysis process |
US20100147743A1 (en) * | 2008-12-16 | 2010-06-17 | Macarthur James B | Process for upgrading coal pyrolysis oils |
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US4101416A (en) * | 1976-06-25 | 1978-07-18 | Occidental Petroleum Corporation | Process for hydrogenation of hydrocarbon tars |
US4406744A (en) * | 1981-11-16 | 1983-09-27 | Clyde Berg | Process for the production of hydrogenated tar and distillates and low sulfur coke from coal |
JPS62277491A (en) * | 1986-05-26 | 1987-12-02 | Maruzen Petrochem Co Ltd | Production of meso-phase pitch |
US5266184A (en) * | 1992-02-07 | 1993-11-30 | Reilly Industries, Inc. | Process for increasing pitch yield from coal tar |
CN101643654B (en) * | 2009-08-31 | 2013-03-06 | 中煤能源黑龙江煤化工有限公司 | Processing technology of non-caked coal or weakly caking coal |
-
2014
- 2014-08-20 US US14/464,300 patent/US20150136656A1/en not_active Abandoned
- 2014-10-29 WO PCT/US2014/062817 patent/WO2015076992A1/en active Application Filing
Patent Citations (2)
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US4324640A (en) * | 1980-08-26 | 1982-04-13 | Occidental Research Corporation | Pyrolysis process |
US20100147743A1 (en) * | 2008-12-16 | 2010-06-17 | Macarthur James B | Process for upgrading coal pyrolysis oils |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170355911A1 (en) * | 2016-06-14 | 2017-12-14 | Fluor Technologies Corporation | Processing of gasification tars to high yields of btx |
WO2017218557A1 (en) * | 2016-06-14 | 2017-12-21 | Fluor Technologies Corporation | Processing of gasification tars to high yields of btx |
CN109415279A (en) * | 2016-06-14 | 2019-03-01 | 氟石科技公司 | Gasification tar is processed into BTX with high yield |
US10590349B2 (en) * | 2016-06-14 | 2020-03-17 | Fluor Technologies Corporation | Processing of gasification tars to high yields of BTX |
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