US20080202985A1 - Method for recovery of hydrocarbon oils from oil shale and other carbonaceous solids - Google Patents
Method for recovery of hydrocarbon oils from oil shale and other carbonaceous solids Download PDFInfo
- Publication number
- US20080202985A1 US20080202985A1 US11/710,389 US71038907A US2008202985A1 US 20080202985 A1 US20080202985 A1 US 20080202985A1 US 71038907 A US71038907 A US 71038907A US 2008202985 A1 US2008202985 A1 US 2008202985A1
- Authority
- US
- United States
- Prior art keywords
- reactor
- solid feedstock
- gas
- hydrogen
- hydrocarbons
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 85
- 239000007787 solid Substances 0.000 title claims abstract description 73
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 48
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 48
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 15
- 239000004058 oil shale Substances 0.000 title claims description 15
- 238000011084 recovery Methods 0.000 title abstract description 13
- 239000003921 oil Substances 0.000 title description 14
- 239000007789 gas Substances 0.000 claims abstract description 83
- 239000001257 hydrogen Substances 0.000 claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 55
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 230000008569 process Effects 0.000 claims abstract description 36
- 238000012545 processing Methods 0.000 claims abstract description 36
- 239000003245 coal Substances 0.000 claims abstract description 29
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 25
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 19
- 239000000446 fuel Substances 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000002485 combustion reaction Methods 0.000 claims abstract 3
- 239000007788 liquid Substances 0.000 claims description 37
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 claims description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 25
- 239000010880 spent shale Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000003546 flue gas Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002407 reforming Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000000295 complement effect Effects 0.000 claims description 3
- -1 gilsonite Substances 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004568 cement Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000003209 petroleum derivative Substances 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims 5
- 239000002826 coolant Substances 0.000 claims 2
- 239000012530 fluid Substances 0.000 claims 1
- 239000008236 heating water Substances 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 238000002309 gasification Methods 0.000 abstract description 22
- 230000015572 biosynthetic process Effects 0.000 abstract 2
- 238000003786 synthesis reaction Methods 0.000 abstract 2
- 239000006227 byproduct Substances 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 description 29
- 239000003079 shale oil Substances 0.000 description 21
- 239000003502 gasoline Substances 0.000 description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 8
- 239000002956 ash Substances 0.000 description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-IGMARMGPSA-N oxygen-16 atom Chemical compound [16O] QVGXLLKOCUKJST-IGMARMGPSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 230000035899 viability Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010020400 Hostility Diseases 0.000 description 1
- 206010038743 Restlessness Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012717 electrostatic precipitator Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000004391 petroleum recovery Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 229910021654 trace metal Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000002699 waste material Substances 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/007—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 in the presence of hydrogen from a special source or of a special composition or having been purified by a special treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B47/00—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion
- C10B47/28—Other processes
- C10B47/30—Other processes in rotary ovens or retorts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/06—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of oil shale and/or or bituminous rocks
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
- C10J3/485—Entrained flow gasifiers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/86—Other features combined with waste-heat boilers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/005—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/007—Removal of contaminants of metal compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/02—Dust removal
- C10K1/024—Dust removal by filtration
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/02—Dust removal
- C10K1/026—Dust removal by centrifugal forces
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/101—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids with water only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
- C10K1/14—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic
- C10K1/143—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic containing amino groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0415—Purification by absorption in liquids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
- C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0495—Composition of the impurity the impurity being water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/063—Refinery processes
- C01B2203/065—Refinery processes using hydrotreating, e.g. hydrogenation, hydrodesulfurisation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0872—Methods of cooling
- C01B2203/0888—Methods of cooling by evaporation of a fluid
- C01B2203/0894—Generation of steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
- C01B2203/84—Energy production
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0903—Feed preparation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0903—Feed preparation
- C10J2300/0906—Physical processes, e.g. shredding, comminuting, chopping, sorting
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/093—Coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0959—Oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
- C10J2300/0989—Hydrocarbons as additives to gasifying agents to improve caloric properties
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
- C10J2300/1618—Modification of synthesis gas composition, e.g. to meet some criteria
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1671—Integration of gasification processes with another plant or parts within the plant with the production of electricity
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1671—Integration of gasification processes with another plant or parts within the plant with the production of electricity
- C10J2300/1675—Integration of gasification processes with another plant or parts within the plant with the production of electricity making use of a steam turbine
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1678—Integration of gasification processes with another plant or parts within the plant with air separation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1687—Integration of gasification processes with another plant or parts within the plant with steam generation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/169—Integration of gasification processes with another plant or parts within the plant with water treatments
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
- C10J2300/1838—Autothermal gasification by injection of oxygen or steam
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
- C10J2300/1861—Heat exchange between at least two process streams
- C10J2300/1884—Heat exchange between at least two process streams with one stream being synthesis gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
- C10J2300/1861—Heat exchange between at least two process streams
- C10J2300/1892—Heat exchange between at least two process streams with one stream being water/steam
Definitions
- This invention relates to methods for recovering hydrocarbon oils from various solid materials. More specifically, this invention is directed to methods for recovering hydrocarbon oils from oil shale, tar sands and other carbonaceous materials.
- Oil has been produced commercially from shale since at least as early as the mid-nineteenth century.
- oil production from shale is being pursued in eighteen different countries world-wide.
- the extensive oil shale deposits of the western United States have been viewed as being a potential solution to the nation's energy problems.
- the economic viability of oil production from shale deposits has been affected by the expansion of crude oil availability.
- As the price for crude oil has risen due to political instability in the Middle East, a renewed interest in oil shale production has emerged.
- Carter Administration the President announced a massive program to produce 2.5 million barrels of crude oil per day from coal and oil shale by 1990.
- Past oil shale recovery techniques have typically made use of some form of heating to drive off the oil from the rock. Both in-situ (below ground) and above ground heating processes have been used. The advantages of the in-situ processes include:
- a process suited for thermally removing liquid hydrocarbons from a solid feedstock and upgrading these liquids is disclosed.
- the process is specifically directed to continuously removing condensable hydrocarbons from such feedstocks as oil shale.
- the process is utilized on the surface as opposed to below the surface of the earth.
- the process may include the following steps:
- the quantity of second solid feedstock which is processed is limited to the amount sufficient to solely produce an amount of hydrogen sufficient to hydro treat the hydrocarbons liberated from the first solid feedstock and to provide the thermal energy requirements for operating the reactor vessel.
- first solid feedstock which may be oil shale or tar sands.
- first solid feedstocks are also within contemplation.
- the processing of the second solid feedstock may include the use of a gasifer or alternatively may include the reforming of the second solid feedstock to produce the requisite hydrogen. Processing steps may be incorporated downstream of such a gasifier to remove carbon dioxide from the syngas produced by the gasifier in order to reduce carbon dioxide emissions.
- Various gasifier constructions may be utilized in the process, including but not limited to entrained gasifiers, fixed bed gasifiers and fluidized bed type gasifiers.
- the second solid feedstock is processed by steam reforming.
- the process may utilize a number of solid, liquid and/or gases for second solid feedstocks such as, but not limited to, coal, gilsonite, petroleum and natural gas.
- the reactor vessel utilized in the process may be an indirectly heated rotary kiln, or a stationary, i.e., non-rotating reactor with solid screw feed system and transport system.
- the reactor vessel may be constructed for operation at or near atmospheric pressure conditions.
- the reactor may be adapted for use at elevated pressures to thereby increase the capacity of the reactor.
- FIG. 1 is a schematic diagram of an embodiment of the process of the invention
- FIG. 2 is a flow sheet illustrating various procedural steps of an embodiment of the invention directed to coal gasification to produce hydrogen.
- FIG. 3 is a flow sheet illustrating various procedural steps of an embodiment of the invention directed to the drying and preheating of oil shale;
- FIG. 4 is a flow sheet which illustrates various procedural steps of an embodiment of the invention directed to shale oil recovery in a rotary kiln;
- FIG. 5 is a flow sheet illustrating various procedural steps of an embodiment of the invention concerning shale oil separation
- FIG. 6 is a flow sheet illustrating various procedural steps of an embodiment of the invention directed to shale oil upgrading.
- FIG. 1 presents a simplified block diagram of an embodiment of the method of the invention.
- An abbreviated disclosure of the process utilizing the schematic diagram of FIG. 1 will now be discussed. Hereinafter, a more detailed description of the various components of the process will be provided.
- coal 10 is ground to a preselected size in coal preparation unit 12 .
- Coal preparation unit 12 may include a conventional coal pulverizer.
- the pulverized coal is fed to coal gasification reactor 18 together with oxygen 16 , recycled off-gas 69 and steam 17 A.
- Oxygen 16 is produced by air separation process 15 .
- Steam 17 A is produced in syngas cooling and cleaning unit 21 and in heat recovery steam generation unit 35 .
- Off-gas 69 is produced in syngas processing unit 25 , shale oil recovery unit 60 and hydro treating and reforming process unit 65 .
- Hot syngas 19 and ash 20 flow from the coal gasification reactor 18 .
- Hot syngas 19 containing fine particulates produced by the coal gasification reactions is directed to syngas cooling and cleaning process 21 where particulates 20 A are removed and steam 17 is generated as shown in FIG. 2 .
- Clean syngas 22 and steam 17 B enters processing unit 25 where carbon monoxide is shifted to carbon dioxide and hydrogen and sulfur 26 , carbon dioxide 27 , hydrogen 28 and an off-gas mixture 30 are separated.
- the sulfur 26 is further processed to produce elemental sulfur.
- the carbon dioxide 27 may be compressed for sequestration or other use rather than emitted to the atmosphere.
- Hydrogen 28 is divided and hydrogen 28 A is used in the shale oil hydro treating and reforming unit 65 and hydrogen 28 B is used as fuel for the shale ore processing unit 50 .
- Excess hydrogen 28 C and the off-gas 30 are used as fuel in a heat recovery steam generator (hereinafter a “HRSG”) unit 35 .
- Water and waste products 24 produced in syngas process unit 25 are directed to treatment and disposal.
- HRSG heat recovery steam generator
- Shale ore 40 is mined and then crushed to a preselected size in processing step 41 .
- the crushed shale ore 42 which forms the feedstock of the overall recovery process is introduced into preheating and drying unit 45 where, in direct contact with flue gas 48 from shale oil processing rotary kiln unit 50 , it is dried and pre-heated.
- the cooled flue gas 37 enters flue gas cleaning unit 36 where solid particulates 38 are separated before the gas is vented to the atmosphere 39 .
- Gas cleaning unit 36 may be a baghouse.
- the dry and preheated shale 46 then enters shale ore processing rotary kiln unit 50 together with sweep steam 47 .
- the shale is heated and pyrolysed sufficiently in unit 50 to liberate shale oil liquid, vapor and gas 53 from spent shale 51 .
- Spent shale 51 is contacted and partially combusted with air 57 in spent shale processing unit 55 .
- Spent shale processing unit 55 may be a fluidized bed. Heated and oxygen containing gas 56 from unit 55 enters a burner assembly surrounding shale ore processing unit 50 where it combusts with hydrogen 28 B to indirectly heat the oil shale 46 .
- Shale oil liquid, vapor, shale gas and steam 53 are then cooled and separated in shale oil separation unit 60 .
- a mixture 62 of light hydrocarbons, carbon monoxide, carbon dioxide, hydrogen and hydrogen sulfide are removed and sent to the gasification reactor 18 to produce hydrogen and to separate sulfur and carbon dioxide.
- Condensed water 64 is sent to spent shale processing unit 55 and disposed of with combusted spent shale 52 .
- Crude shale oil fractions 61 are sent to the hydro treating and reforming unit 65 (See FIG. 6 ) where it is reacted with hydrogen 28 A to produce motor fuels 70 and residual products, e.g. asphalt, 71 .
- Off-gas stream 66 from processing unit 65 is recycled to the gasification reactor 18 .
- FIG. 2 illustrates an embodiment of the coal gasification and hydrogen production portion of the process.
- Coal 10 is delivered to the processing site by truck, rail or other conventional means.
- the coal is unloaded and transferred directly into storage silo 105 .
- it can be stockpiled on site and then transferred to the silo 105 .
- It is fed from silo 105 into pulverizer 110 where the particle sizes are reduced until at least 70% of the particles pass through a 200 mesh screen.
- Air is blown by fan 106 into combustor 108 , where it reacts with recycled off-gas 69 B.
- the hot flue gas 109 then passes through pulverizer 110 , heating and drying the coal particles.
- the flue gas then transports coal particles through cyclone 111 , where oversize particles are removed and recycled, and the fine particles 112 are directed to storage vessel 113 .
- the flue gas then passes out of vessel 113 and through bag house 114 before venting to the atmosphere 115 .
- the pulverized coal within vessel 113 passes into lock hopper vessel 116 , where it is pressurized by recycled off-gas 69 D. Following pressurization it passes into feed vessel 117 then through feeding device 122 where it is picked up by recycled off-gas 69 C and blown into the gasification reactor 18 .
- Oxygen 16 from oxygen separator 15 is fed into gasification reactor 18 together with steam 17 A.
- Ash produced in the gasification reactor drops into ash lock 131 where is picked up by a water stream 155 and periodically discharged 132 to separator 151 .
- a particulate and ash stream 20 from separator 151 is combined with spent shale stream 52 for landfill disposal. (See FIG. 4 .)
- Separator 151 may be a gravity separator.
- Syngas stream 19 flows out of the gasification reactor 18 and through gas cooler 140 , filter 141 , scrubber 146 and into shift reactor 142 . There it reacts with steam 17 B to convert carbon monoxide to carbon dioxide and hydrogen.
- the shifted syngas passes into cooler and knock-out unit 143 where the excess steam is condensed.
- Knock-out unit 143 may be a heat exchanger. From unit 143 the syngas passes through an amine selective absorption unit 144 where sulfur and carbon dioxide are removed and then into pressure swing absorbing (“PSA”) unit 145 where the final hydrogen product 28 is separated.
- PSA pressure swing absorbing
- FIG. 2 depicts dry coal feeding of coal into gasification reactor 18 .
- Slurry coal feeding as is well known in the art of coal gasification is an alternative embodiment.
- off-gas 69 C would be fed separately into gasification reactor 18 and steam 17 A would be reduced or eliminated.
- hot cyclones are positioned upstream of gas cooler 140 or filter 141 .
- the cyclones are used to remove the coarser ash and carbon particles.
- Wet scrubber 146 removes the final traces of particulates. Ammonia and trace metal compounds like lead, mercury and arsenic, present in very small amounts, are also removed at wet scrubber 146 .
- Steam is produced in cooling passages of coal gasification reactor 18 , in gas cooler 140 and HRSG 35 .
- sulfur in the form of H 2 S is then removed in a dual amine unit 144 . It is typically removed in three steps.
- the first step is the contacting of the H 2 S with an acid gas solvent, such as methyldiethanolamine [MDEA], whereby H 2 S is extracted from the gas stream and regenerated as a fairly pure H 2 S stream.
- MDEA methyldiethanolamine
- the H 2 S goes to a classical Claus Sulfur plant 110 where solid sulfur is formed and removed from the system. This sulfur is usually sold as a fertilizer additive for the use with alkaline soils.
- carbon dioxide 27 also is removed in amine unit 144 .
- the absorbed CO 2 is then stripped and subsequently pressurized or condensed by compressor 149 depending on the intended underground disposal method or for purposes of secondary petroleum recovery. This step in processing of the syngas may be eliminated in a plant having unrestricted CO 2 emissions requirements.
- the syngas stream from amine unit 144 contains hydrogen, carbon monoxide, carbon dioxide and small amounts of methane, nitrogen and argon.
- the hydrogen is separated from this mixture in a pressure swing absorption unit 145 that produces 99% pure hydrogen 28 for plant hydro-processing 28 A and fuel needs 28 B and 28 C.
- Off-gas 30 A from the PSA unit 145 is combined with off-gas 69 .
- the combined off gases are directed to the shift reactor 142 and to the gasification reactor 69 A.
- a portion of the combined compressed off gases are also directed through the ejector 154 where they are combined with particulates 20 A and subsequently directed to the gasification reactor 18 . Further the combined off gases are directed to combuster 108 .
- FIG. 3 illustrates an embodiment of the shale ore drier and pre-heater portion of the process.
- Shale ore is typically mined from deposits which typically lie near the surface. In some instances, the overburden covering a shale ore deposit may be 1000 feet in depth.
- the ore is conventionally mined and thereafter crushed to a processing size of minus 3 ⁇ 8 inch by conventional techniques. As shown, the crushed shale ore 40 is delivered to the processing site by truck, rail or other conventional means.
- the shale ore can be delivered to an on-site stock pile or conveyed directly into a storage silo 77 via conveyor 73 and elevator 74 .
- the shale ore is moved by conveyor 76 and elevator 78 to a first screw 76 which transfers the ore to rotary drier and heater 80 .
- the ore is then heated by direct contact with hot flue gas 48 from indirect-fired rotary kiln 90 . (See FIG. 4 )
- the flue gas typically flows co-currently with the flow of shale ore and the ore is heated to a temperature less than that corresponding to the onset of pyrolysis reactions, e.g. 400-500 degrees F.
- Flue gas 37 is drawn from drier and heater 80 and through cyclones 82 and dust bag house 83 by fan 84 and then exhausted to the atmosphere through stack 85 .
- Dust 38 from the cyclones and bag house is transported to the dry, pre-heated ore stream 46 by conveyors 85 and 86 .
- FIG. 4 illustrates an embodiment of the shale recovery unit. It shows shale ore 46 from the preheater 80 is directed by screw 86 into an indirect-fired rotary kiln 90 . A stream of sweep steam 17 from HSRG 35 is passed through the screw 86 with the shale ore.
- An alternative embodiment might employ two or more parallel indirectly heated rotary kilns rather than the single kiln depicted in FIG. 4 .
- the shale ore is indirectly heated to a temperature typically between 900 F and 1100 F resulting in pyrolysis reactions releasing oil liquid, vapor, hydrocarbon gases, hydrogen, carbon monoxide, carbon dioxide and hydrogen sulfide.
- This final temperature must be closely controlled in order to release the hydrocarbon material while not releasing significant amounts of CO 2 by decomposition of the calcite and dolomite (carbonate) materials present in the shale ore.
- Kiln 90 is heated by burning hydrogen 28 B with pre-heated oxygen rich flue gas 56 from the spent shale processor 55 , which may be a fluidized bed contactor 94 .
- Flue gas 56 is produced by blowing air with fan 95 through spent shale processor 94 where it is heated and reacts with charred hydrocarbon material in the spent shale.
- Coal ash slurry 20 is fed into the lower outlet of kiln 90 to enable disposal with the spent shale.
- the spent shale and ash are discharged through screw 89 into spent shale processor 94 .
- Waste water stream 64 enters the lower section of processor 94 to enable disposal of waste water with the spent shale and the cooled, moist spent shale and ash 52 is discharged through screw 98 .
- the feed rate of water in stream 64 may be adjusted and proportioned so as to obtain a moisture content of about 20% in the resultant mixture.
- Shale oil, liquids, vapors and gases 53 pass through cyclone 91 before leaving kiln 90 in order to remove entrained particulates. Fine particulates are removed from the gases 53 using electrostatic precipitator 92 . In an alternative embodiment precipitator 92 may be eliminated.
- FIG. 5 depicts an embodiment of cooling the stream of vapors and gases 53 from kiln 90 and separating them into oil and gas fractions.
- Stream 53 is partially cooled and the dust removed by a sprayed diesel fraction 61 B 1 .
- the vapors and gases are then further cooled to about 400 F in a pump around system using refinery type air coolers and a packed tower (Residual & Diesel Knockout Vessel 160 ) where a large part of the shale oil is condensed as a diesel boiling fraction 61 B.
- the diesel fraction is initially passed into Diesel Receiver 180 and thereafter through pump 171 and then through cooler 165 .
- a portion of the diesel fraction is directed to Diesel Air Cooler 161 and thereafter returned to the Knockout Vessel 160 .
- the Residual Fraction 61 A is removed from the Knockout Vessel 160 and is then cooled in cooler 165 . Subsequently the Residual Fraction passes through pump 173 and thereafter through Residual
- the shale gas 166 is then further cooled to 150-175 F using a water stream (condensed steam) in gasoline condenser 170 .
- a gasoline boiling cut 61 C is condensed out in this step, along with most of the steam 64 A.
- Gasoline boiling cut 61 C is thereafter directed through cooler 165 C and pump 174 .
- Steam 64 A is directed through pump 175 .
- a portion of stream 64 A is directed to an air cooler 162 and subsequently reintroduced into condenser 170 .
- a gas and water vapor mixture 167 is withdrawn from condenser 170 and is The gas is next compressed to 100 psig by gas compressor 178 and cooled in a water-cooled heat exchanger 165 D, where the remainder of the steam [water] and a fraction of the shale oil is condensed.
- Gases 62 composed of C1, C2, C3, CO, CO 2 , H 2 , and H2S, are sent to the coal gasification and hydrogen production and purification section of the plant.
- the C4, C5 and C6 fraction 61 D is directed to further processing.
- the condensate gases are directed to a receiver gravity separator vessel 190 which functions to separate light gases 62 from liquids 61 D (C4-C6 fractions) (and water 64 B. Water 64 B is thereafter directed through pump 176 and thereafter mixed with water 64 A, which is exiting pump 175 , to form water stream 64 .
- a portion of residual product 70 A is recycled through compressor 211 to heater 201 and hydro cracker 204
- FIG. 6 illustrates an embodiment of the process for shale oil upgrading.
- Residual fraction 61 A and hydrogen stream 28 A 1 pass through heater 201 and then through hydro cracker 204 .
- the resulting upgraded liquids are then separated in cooler and knock-out 207 from unreacted excess hydrogen and off-gases.
- the unreacted excess hydrogen 28 A 2 is compressed and recycled by compressor 216 and the off-gas 66 A is compressed by compressor 218 and recycled to the coal gasification and hydrogen production section of the plant.
- the upgraded liquid 219 from cooler and knock-out 207 is separated in distillation column 215 into diesel fraction 191 , gasoline fraction 192 and final residual product 70 A.
- Diesel fraction 61 B, diesel fraction stream 191 and hydrogen stream 28 A 2 pass through heater 202 and then pass through hydro pyrolysis unit 205 .
- the resulting upgraded liquids are then separated in cooler and knock-out 208 from unreacted excess hydrogen 222 and off-gases 66 B.
- the unreacted excess hydrogen is compressed and recycled by compressor 217 and the off-gas 66 B is compressed in compressor 218 and recycled to the coal gasification and hydrogen production section of the plant.
- the final upgraded diesel product is stream 70 B.
- Gasoline fraction 61 C, C4-C6 fraction 61 D and gasoline fraction stream 192 pass with hydrogen stream 28 A 3 through heater 203 and then through hydro pyrolysis unit 206 .
- the resulting upgraded liquids 223 are then separated in cooler and knock-out 209 into unreacted excess hydrogen 224 and off-gases 66 C and gasoline product 225 .
- the gasoline product 225 is then passed through reformer 210 to form gasoline product 70 C.
- the unreacted excess hydrogen 224 is compressed and recycled by compressor 217 and the off-gas 66 C is compressed in compressor 218 . Both gases are recycled, with some of the gases being directed to the coal gasification and hydrogen production section of the plant.
- the upgraded liquid 225 is sent to reformer 70 C to produce the final gasoline product, stream 70 C.
- the off gases 66 A, 66 B, 66 C and 220 are compressed by compressor 218 and a portion thereof is used as fuel for heaters 201 , 202 and 203 .
- the balance of the gases 66 is combined with off gas 62 to form stream 69 (See FIG. 1 ).
- Water 155 is directed through a water treatment unit 156 , which may be an ion exchanger. Thereafter the water 155 is directed through a deaerator 157 forming boiling feed water (BFW) 240 which is introduced into boiler 35 .
- BFW boiling feed water
- All hydrogen produced in the process is used either for liquid upgrading or for producing process heating, with any excess being used for generating steam. Any steam so generated which is not needed for the process would be sent to a turbine for purposes of electrical power generation.
Abstract
Description
- This invention was made with government support under DOE/SBIR Grant DF-FG-02-06ER84596. The Government has certain rights to this invention.
- 1. Field
- This invention relates to methods for recovering hydrocarbon oils from various solid materials. More specifically, this invention is directed to methods for recovering hydrocarbon oils from oil shale, tar sands and other carbonaceous materials.
- 2. Statement of the Art
- Oil has been produced commercially from shale since at least as early as the mid-nineteenth century. Currently, oil production from shale is being pursued in eighteen different countries world-wide. Over the past century, the extensive oil shale deposits of the western United States have been viewed as being a potential solution to the nation's energy problems. The economic viability of oil production from shale deposits has been affected by the expansion of crude oil availability. As the price for crude oil has risen due to political instability in the Middle East, a renewed interest in oil shale production has emerged. During the Carter Administration, the President announced a massive program to produce 2.5 million barrels of crude oil per day from coal and oil shale by 1990. However, a subsequent drop in oil prices resulted in a substantial discontinuation in investment in oil shale technology and research. Recently, political unrest and hostilities in the Arabian Gulf have again resulted in significant increases in the price of crude oil thereby reinvigorating the interest in the processing of the national reserves of oil shale and tar sands.
- Past oil shale recovery techniques have typically made use of some form of heating to drive off the oil from the rock. Both in-situ (below ground) and above ground heating processes have been used. The advantages of the in-situ processes include:
-
- (1) Mining of the shale is typically minimal or not required;
- (2) no disposal of the spent shale is mandated;
- (3) the process permits access to resources which are otherwise not minable;
- (4) the process allows for the use of lower quality shale; and
- (5) the process requires no crushing of the shale or transportation of the shale to a processing facility.
- Although past in-situ shale recovery processes have significant advantages, they are not, however, devoid of disadvantages. Some of these disadvantages are as follows:
-
- (1) such processes involve significant drilling costs;
- (2) control of the recovery process is oftentimes difficult;
- (3) such processes typically recover a low percentage of the available shale oil;
- (4) the oil shale treated typically has low permeability restricting flow rates of the shale oil and gas;
- (5) such processes carry the possibility of water contamination in the area in which the processes are employed;
- (6) control of the shale bed boundaries and operating conditions are difficult;
- (7) such processes typically have very long residence times; and
- (8) such processes conventionally consume high quantities of expensive energy, especially those processes which utilize electricity as the heating source.
- The alternative approach of above ground processing offers the following notable advantages:
-
- (1) high recovery efficiency;
- (2) improved control of process conditions;
- (3) easy product recovery; and
- (4) continuous processing capability.
- Despite these advantages, prior development of methods for surface processing of U.S. shale ore to recover shale oil have not resulted in commercial viability and they have been criticized for producing unacceptable air emissions.
- Another consideration of importance in the economical recovery and use of shale oil is the difference between shale oil and the oil produced from conventional oil wells. The conjugated olefin structure of the hydrocarbon molecule of crude shale oil requires substantial upgrading before it can be efficiently used as a motor fuel. Relatively large quantities of hydrogen and high temperature and high pressure catalytic operating conditions are required for the processing of the shale oil. The upgrading requirements and the availability of the hydrogen to carry out the upgrading often render such oil unamenable to the processing capabilities of existing conventional oil refineries.
- It is readily apparent that there continues to be a need for more efficient and more environmentally acceptable processing methods for producing high quality oil products from solid feedstocks such as oil shale.
- A process suited for thermally removing liquid hydrocarbons from a solid feedstock and upgrading these liquids is disclosed. The process is specifically directed to continuously removing condensable hydrocarbons from such feedstocks as oil shale. In preferred embodiments, the process is utilized on the surface as opposed to below the surface of the earth.
- The process may include the following steps:
-
- (1) Preparing a first solid feedstock to a predetermined size and moisture content;
- (2) Preparing a second solid feedstock to complement first solid feedstock;
- (3) Drying and pre-heating the first solid feedstock;
- (4) Providing a reactor suited for processing the first solid feedstock at an elevated temperature;
- (5) Providing sufficient clean burning fuel to heat the reactor;
- (6) Providing a heated reactor sweep gas;
- (7) Feeding the first solid feedstock into the reactor to thermally liberate hydrocarbons from the first solid feedstock;
- (8) Directing the heated reactor sweep gas through the reactor to remove the hydrocarbons from the reactor;
- (9) Cooling the hydrocarbons to condense liquid hydrocarbons;
- (10) Separating the liquid hydrocarbons from gaseous hydrocarbons, other reactor off-gases and reactor sweep gas;
- (11) Treating the liquid hydrocarbon with hydrogen to produce a hydro treated and/or hydro cracked liquid hydrocarbon;
- (12) Processing the second solid feedstock and the reactor off-gases to produce a syngas;
- (13) Processing the syngas to produce an amount of hydrogen sufficient to hydro treat the liquid hydrocarbons producing the hydro treated liquid hydrocarbons and also to provide the clean burning fuel to heat the reactor.
- In an alternative embodiment, the quantity of second solid feedstock which is processed is limited to the amount sufficient to solely produce an amount of hydrogen sufficient to hydro treat the hydrocarbons liberated from the first solid feedstock and to provide the thermal energy requirements for operating the reactor vessel.
- In a preferred embodiment the process is utilized to process a first solid feedstock which may be oil shale or tar sands. Other first solid feedstocks are also within contemplation.
- The processing of the second solid feedstock may include the use of a gasifer or alternatively may include the reforming of the second solid feedstock to produce the requisite hydrogen. Processing steps may be incorporated downstream of such a gasifier to remove carbon dioxide from the syngas produced by the gasifier in order to reduce carbon dioxide emissions. Various gasifier constructions may be utilized in the process, including but not limited to entrained gasifiers, fixed bed gasifiers and fluidized bed type gasifiers. In an alternative embodiment of the process, the second solid feedstock is processed by steam reforming. The process may utilize a number of solid, liquid and/or gases for second solid feedstocks such as, but not limited to, coal, gilsonite, petroleum and natural gas.
- The reactor vessel utilized in the process may be an indirectly heated rotary kiln, or a stationary, i.e., non-rotating reactor with solid screw feed system and transport system. The reactor vessel may be constructed for operation at or near atmospheric pressure conditions. Alternatively, the reactor may be adapted for use at elevated pressures to thereby increase the capacity of the reactor.
-
FIG. 1 is a schematic diagram of an embodiment of the process of the invention; -
FIG. 2 is a flow sheet illustrating various procedural steps of an embodiment of the invention directed to coal gasification to produce hydrogen. -
FIG. 3 is a flow sheet illustrating various procedural steps of an embodiment of the invention directed to the drying and preheating of oil shale; -
FIG. 4 is a flow sheet which illustrates various procedural steps of an embodiment of the invention directed to shale oil recovery in a rotary kiln; -
FIG. 5 is a flow sheet illustrating various procedural steps of an embodiment of the invention concerning shale oil separation; and -
FIG. 6 is a flow sheet illustrating various procedural steps of an embodiment of the invention directed to shale oil upgrading. -
FIG. 1 presents a simplified block diagram of an embodiment of the method of the invention. An abbreviated disclosure of the process utilizing the schematic diagram ofFIG. 1 will now be discussed. Hereinafter, a more detailed description of the various components of the process will be provided. - As shown in
FIG. 1 ,coal 10 is ground to a preselected size incoal preparation unit 12.Coal preparation unit 12 may include a conventional coal pulverizer. The pulverized coal is fed tocoal gasification reactor 18 together withoxygen 16, recycled off-gas 69 andsteam 17A.Oxygen 16 is produced byair separation process 15.Steam 17A is produced in syngas cooling andcleaning unit 21 and in heat recoverysteam generation unit 35. Off-gas 69 is produced insyngas processing unit 25, shaleoil recovery unit 60 and hydro treating and reforming process unit 65.Hot syngas 19 andash 20 flow from thecoal gasification reactor 18.Hot syngas 19 containing fine particulates produced by the coal gasification reactions is directed to syngas cooling andcleaning process 21 whereparticulates 20A are removed andsteam 17 is generated as shown inFIG. 2 .Clean syngas 22 andsteam 17B enters processingunit 25 where carbon monoxide is shifted to carbon dioxide and hydrogen andsulfur 26,carbon dioxide 27,hydrogen 28 and an off-gas mixture 30 are separated. Thesulfur 26 is further processed to produce elemental sulfur. Thecarbon dioxide 27 may be compressed for sequestration or other use rather than emitted to the atmosphere.Hydrogen 28 is divided andhydrogen 28A is used in the shale oil hydro treating and reforming unit 65 andhydrogen 28B is used as fuel for the shaleore processing unit 50.Excess hydrogen 28C and the off-gas 30 are used as fuel in a heat recovery steam generator (hereinafter a “HRSG”)unit 35. Water andwaste products 24 produced insyngas process unit 25 are directed to treatment and disposal. -
Shale ore 40 is mined and then crushed to a preselected size in processingstep 41. The crushedshale ore 42, which forms the feedstock of the overall recovery process is introduced into preheating and dryingunit 45 where, in direct contact withflue gas 48 from shale oil processingrotary kiln unit 50, it is dried and pre-heated. The cooledflue gas 37 enters fluegas cleaning unit 36 wheresolid particulates 38 are separated before the gas is vented to theatmosphere 39.Gas cleaning unit 36 may be a baghouse. - The dry and
preheated shale 46 then enters shale ore processingrotary kiln unit 50 together withsweep steam 47. The shale is heated and pyrolysed sufficiently inunit 50 to liberate shale oil liquid, vapor andgas 53 from spentshale 51.Spent shale 51 is contacted and partially combusted withair 57 in spentshale processing unit 55. Spentshale processing unit 55 may be a fluidized bed. Heated andoxygen containing gas 56 fromunit 55 enters a burner assembly surrounding shaleore processing unit 50 where it combusts withhydrogen 28B to indirectly heat theoil shale 46. - Shale oil liquid, vapor, shale gas and
steam 53 are then cooled and separated in shaleoil separation unit 60. (SeeFIG. 5 .) Amixture 62 of light hydrocarbons, carbon monoxide, carbon dioxide, hydrogen and hydrogen sulfide are removed and sent to thegasification reactor 18 to produce hydrogen and to separate sulfur and carbon dioxide.Condensed water 64 is sent to spentshale processing unit 55 and disposed of with combusted spentshale 52. Crudeshale oil fractions 61 are sent to the hydro treating and reforming unit 65 (SeeFIG. 6 ) where it is reacted withhydrogen 28A to producemotor fuels 70 and residual products, e.g. asphalt, 71. Off-gas stream 66 from processing unit 65 is recycled to thegasification reactor 18. -
FIG. 2 illustrates an embodiment of the coal gasification and hydrogen production portion of the process.Coal 10 is delivered to the processing site by truck, rail or other conventional means. The coal is unloaded and transferred directly intostorage silo 105. Alternatively, it can be stockpiled on site and then transferred to thesilo 105. It is fed fromsilo 105 intopulverizer 110 where the particle sizes are reduced until at least 70% of the particles pass through a 200 mesh screen. Air is blown byfan 106 intocombustor 108, where it reacts with recycled off-gas 69B. Thehot flue gas 109 then passes throughpulverizer 110, heating and drying the coal particles. The flue gas then transports coal particles through cyclone 111, where oversize particles are removed and recycled, and thefine particles 112 are directed tostorage vessel 113. The flue gas then passes out ofvessel 113 and throughbag house 114 before venting to theatmosphere 115. - The pulverized coal within
vessel 113 passes intolock hopper vessel 116, where it is pressurized by recycled off-gas 69D. Following pressurization it passes intofeed vessel 117 then throughfeeding device 122 where it is picked up by recycled off-gas 69C and blown into thegasification reactor 18.Oxygen 16 fromoxygen separator 15 is fed intogasification reactor 18 together withsteam 17A. Ash produced in the gasification reactor drops intoash lock 131 where is picked up by awater stream 155 and periodically discharged 132 toseparator 151. A particulate andash stream 20 fromseparator 151 is combined with spentshale stream 52 for landfill disposal. (SeeFIG. 4 .)Separator 151 may be a gravity separator.Syngas stream 19 flows out of thegasification reactor 18 and throughgas cooler 140,filter 141,scrubber 146 and intoshift reactor 142. There it reacts withsteam 17B to convert carbon monoxide to carbon dioxide and hydrogen. The shifted syngas passes into cooler and knock-outunit 143 where the excess steam is condensed. Knock-outunit 143 may be a heat exchanger. Fromunit 143 the syngas passes through an amineselective absorption unit 144 where sulfur and carbon dioxide are removed and then into pressure swing absorbing (“PSA”)unit 145 where thefinal hydrogen product 28 is separated. -
FIG. 2 depicts dry coal feeding of coal intogasification reactor 18. Slurry coal feeding as is well known in the art of coal gasification is an alternative embodiment. In this alternative embodiment off-gas 69C would be fed separately intogasification reactor 18 andsteam 17A would be reduced or eliminated. - In another embodiment of the invention, hot cyclones are positioned upstream of gas cooler 140 or
filter 141. The cyclones are used to remove the coarser ash and carbon particles.Wet scrubber 146 removes the final traces of particulates. Ammonia and trace metal compounds like lead, mercury and arsenic, present in very small amounts, are also removed atwet scrubber 146. - Steam is produced in cooling passages of
coal gasification reactor 18, in gas cooler 140 andHRSG 35. - As shown in
FIG. 2 , sulfur in the form of H2S is then removed in adual amine unit 144. It is typically removed in three steps. The first step is the contacting of the H2S with an acid gas solvent, such as methyldiethanolamine [MDEA], whereby H2S is extracted from the gas stream and regenerated as a fairly pure H2S stream. The H2S goes to a classicalClaus Sulfur plant 110 where solid sulfur is formed and removed from the system. This sulfur is usually sold as a fertilizer additive for the use with alkaline soils. - As further shown in
FIG. 2 ,carbon dioxide 27 also is removed inamine unit 144. A CO2 selective solvent similar to that in the sulfur contactor unit, absorbs the CO2 from the syngas stream. The absorbed CO2 is then stripped and subsequently pressurized or condensed bycompressor 149 depending on the intended underground disposal method or for purposes of secondary petroleum recovery. This step in processing of the syngas may be eliminated in a plant having unrestricted CO2 emissions requirements. - The syngas stream from
amine unit 144 contains hydrogen, carbon monoxide, carbon dioxide and small amounts of methane, nitrogen and argon. The hydrogen is separated from this mixture in a pressureswing absorption unit 145 that produces 99%pure hydrogen 28 for plant hydro-processing 28A and fuel needs 28B and 28C. (SeeFIG. 1 ) Off-gas 30A from thePSA unit 145 is combined with off-gas 69. The combined off gases are directed to theshift reactor 142 and to thegasification reactor 69A. A portion of the combined compressed off gases are also directed through theejector 154 where they are combined withparticulates 20A and subsequently directed to thegasification reactor 18. Further the combined off gases are directed tocombuster 108. -
FIG. 3 illustrates an embodiment of the shale ore drier and pre-heater portion of the process. Shale ore is typically mined from deposits which typically lie near the surface. In some instances, the overburden covering a shale ore deposit may be 1000 feet in depth. The ore is conventionally mined and thereafter crushed to a processing size of minus ⅜ inch by conventional techniques. As shown, the crushedshale ore 40 is delivered to the processing site by truck, rail or other conventional means. The shale ore can be delivered to an on-site stock pile or conveyed directly into astorage silo 77 viaconveyor 73 andelevator 74. Thereafter the shale ore is moved byconveyor 76 andelevator 78 to afirst screw 76 which transfers the ore to rotary drier andheater 80. The ore is then heated by direct contact withhot flue gas 48 from indirect-firedrotary kiln 90. (SeeFIG. 4 ) The flue gas typically flows co-currently with the flow of shale ore and the ore is heated to a temperature less than that corresponding to the onset of pyrolysis reactions, e.g. 400-500 degrees F. -
Flue gas 37 is drawn from drier andheater 80 and throughcyclones 82 anddust bag house 83 byfan 84 and then exhausted to the atmosphere throughstack 85.Dust 38 from the cyclones and bag house is transported to the dry,pre-heated ore stream 46 byconveyors -
FIG. 4 illustrates an embodiment of the shale recovery unit. It showsshale ore 46 from thepreheater 80 is directed byscrew 86 into an indirect-firedrotary kiln 90. A stream ofsweep steam 17 fromHSRG 35 is passed through thescrew 86 with the shale ore. An alternative embodiment might employ two or more parallel indirectly heated rotary kilns rather than the single kiln depicted inFIG. 4 . - In
rotary kiln 90 the shale ore is indirectly heated to a temperature typically between 900 F and 1100 F resulting in pyrolysis reactions releasing oil liquid, vapor, hydrocarbon gases, hydrogen, carbon monoxide, carbon dioxide and hydrogen sulfide. This final temperature must be closely controlled in order to release the hydrocarbon material while not releasing significant amounts of CO2 by decomposition of the calcite and dolomite (carbonate) materials present in the shale ore. -
Kiln 90 is heated by burninghydrogen 28B with pre-heated oxygenrich flue gas 56 from the spentshale processor 55, which may be afluidized bed contactor 94.Flue gas 56 is produced by blowing air withfan 95 through spentshale processor 94 where it is heated and reacts with charred hydrocarbon material in the spent shale. -
Coal ash slurry 20 is fed into the lower outlet ofkiln 90 to enable disposal with the spent shale. The spent shale and ash are discharged throughscrew 89 into spentshale processor 94.Waste water stream 64 enters the lower section ofprocessor 94 to enable disposal of waste water with the spent shale and the cooled, moist spent shale andash 52 is discharged throughscrew 98. In an alternate embodiment, in order to take advantage of the cement like properties of the spent shale and ash the feed rate of water instream 64 may be adjusted and proportioned so as to obtain a moisture content of about 20% in the resultant mixture. - Shale oil, liquids, vapors and
gases 53 pass throughcyclone 91 before leavingkiln 90 in order to remove entrained particulates. Fine particulates are removed from thegases 53 usingelectrostatic precipitator 92. In analternative embodiment precipitator 92 may be eliminated. -
FIG. 5 depicts an embodiment of cooling the stream of vapors andgases 53 fromkiln 90 and separating them into oil and gas fractions.Stream 53 is partially cooled and the dust removed by a sprayed diesel fraction 61B1. The vapors and gases are then further cooled to about 400 F in a pump around system using refinery type air coolers and a packed tower (Residual & Diesel Knockout Vessel 160) where a large part of the shale oil is condensed as adiesel boiling fraction 61B. As shown the diesel fraction is initially passed intoDiesel Receiver 180 and thereafter throughpump 171 and then through cooler 165. A portion of the diesel fraction is directed toDiesel Air Cooler 161 and thereafter returned to theKnockout Vessel 160. TheResidual Fraction 61A is removed from theKnockout Vessel 160 and is then cooled in cooler 165. Subsequently the Residual Fraction passes throughpump 173 and thereafter throughResidual Filter 192. - The
shale gas 166 is then further cooled to 150-175 F using a water stream (condensed steam) ingasoline condenser 170. A gasoline boiling cut 61C is condensed out in this step, along with most of thesteam 64A. Gasoline boiling cut 61C is thereafter directed through cooler 165C and pump 174.Steam 64A is directed throughpump 175. A portion ofstream 64A is directed to anair cooler 162 and subsequently reintroduced intocondenser 170. A gas andwater vapor mixture 167 is withdrawn fromcondenser 170 and is The gas is next compressed to 100 psig bygas compressor 178 and cooled in a water-cooledheat exchanger 165D, where the remainder of the steam [water] and a fraction of the shale oil is condensed.Gases 62, composed of C1, C2, C3, CO, CO2, H2, and H2S, are sent to the coal gasification and hydrogen production and purification section of the plant. The C4, C5 andC6 fraction 61D is directed to further processing. The condensate gases are directed to a receivergravity separator vessel 190 which functions to separatelight gases 62 fromliquids 61D (C4-C6 fractions) (andwater 64B.Water 64B is thereafter directed throughpump 176 and thereafter mixed withwater 64A, which is exitingpump 175, to formwater stream 64. A portion ofresidual product 70A is recycled through compressor 211 toheater 201 andhydro cracker 204. -
FIG. 6 illustrates an embodiment of the process for shale oil upgrading.Residual fraction 61A and hydrogen stream 28A1 pass throughheater 201 and then throughhydro cracker 204. The resulting upgraded liquids are then separated in cooler and knock-out 207 from unreacted excess hydrogen and off-gases. The unreacted excess hydrogen 28A2 is compressed and recycled bycompressor 216 and the off-gas 66A is compressed bycompressor 218 and recycled to the coal gasification and hydrogen production section of the plant. The upgraded liquid 219 from cooler and knock-out 207 is separated indistillation column 215 intodiesel fraction 191,gasoline fraction 192 and finalresidual product 70A. -
Diesel fraction 61B,diesel fraction stream 191 and hydrogen stream 28A2 pass throughheater 202 and then pass throughhydro pyrolysis unit 205. The resulting upgraded liquids are then separated in cooler and knock-out 208 from unreactedexcess hydrogen 222 and off-gases 66B. The unreacted excess hydrogen is compressed and recycled bycompressor 217 and the off-gas 66B is compressed incompressor 218 and recycled to the coal gasification and hydrogen production section of the plant. The final upgraded diesel product isstream 70B. -
Gasoline fraction 61C, C4-C6 fraction 61D andgasoline fraction stream 192 pass with hydrogen stream 28A3 throughheater 203 and then throughhydro pyrolysis unit 206. The resulting upgradedliquids 223 are then separated in cooler and knock-out 209 into unreacted excess hydrogen 224 and off-gases 66C andgasoline product 225. Thegasoline product 225 is then passed throughreformer 210 to formgasoline product 70C. The unreacted excess hydrogen 224 is compressed and recycled bycompressor 217 and the off-gas 66C is compressed incompressor 218. Both gases are recycled, with some of the gases being directed to the coal gasification and hydrogen production section of the plant. The upgradedliquid 225 is sent toreformer 70C to produce the final gasoline product,stream 70C. The offgases compressor 218 and a portion thereof is used as fuel forheaters gases 66 is combined with offgas 62 to form stream 69 (SeeFIG. 1 ).Water 155 is directed through awater treatment unit 156, which may be an ion exchanger. Thereafter thewater 155 is directed through adeaerator 157 forming boiling feed water (BFW) 240 which is introduced intoboiler 35. - All hydrogen produced in the process is used either for liquid upgrading or for producing process heating, with any excess being used for generating steam. Any steam so generated which is not needed for the process would be sent to a turbine for purposes of electrical power generation.
- Changes may be made to the embodiments described in this disclosure without departing from the broad inventive concepts they illustrate. Accordingly, this invention is not limited to the particular embodiments disclosed, but is intended to cover all modifications that are within the scope of the invention as defined by the appended claims.
Claims (38)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/710,389 US20080202985A1 (en) | 2007-02-23 | 2007-02-23 | Method for recovery of hydrocarbon oils from oil shale and other carbonaceous solids |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/710,389 US20080202985A1 (en) | 2007-02-23 | 2007-02-23 | Method for recovery of hydrocarbon oils from oil shale and other carbonaceous solids |
Publications (1)
Publication Number | Publication Date |
---|---|
US20080202985A1 true US20080202985A1 (en) | 2008-08-28 |
Family
ID=39714680
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/710,389 Abandoned US20080202985A1 (en) | 2007-02-23 | 2007-02-23 | Method for recovery of hydrocarbon oils from oil shale and other carbonaceous solids |
Country Status (1)
Country | Link |
---|---|
US (1) | US20080202985A1 (en) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090095659A1 (en) * | 2007-10-12 | 2009-04-16 | Enshale, Inc. | Petroleum products from oil shale |
US20100005710A1 (en) * | 2008-07-09 | 2010-01-14 | Pipal Energy Resources, Llc | Upgrading Carbonaceous Materials |
US20100313475A1 (en) * | 2008-02-13 | 2010-12-16 | Outotec Oyj | Process for plant for refining raw materials containing organic constituents |
CN101942333A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Shale oil single-stage serial hydrocracking technology method |
US20120137583A1 (en) * | 2009-08-12 | 2012-06-07 | Thyssenkrupp Uhde Gmbh | Method for supplying an entrained-flow gasification reactor with carbonaceous fuels |
US20140026483A1 (en) * | 2012-07-30 | 2014-01-30 | General Electric Company | Systems for preheating feedstock |
US20140209447A1 (en) * | 2011-09-01 | 2014-07-31 | Guradoor, S.L. | Gasification-pyrolysis dual reactor device |
US20160312697A1 (en) * | 2015-04-27 | 2016-10-27 | Korea Institute Of Energy Research | Gasification Combined Generation System Through Coal and Industrial Waste Water |
US20160322660A1 (en) * | 2015-05-02 | 2016-11-03 | Aerojet Rocketdyne, Inc. | Gas generator and process therefor |
US9914879B2 (en) | 2015-09-30 | 2018-03-13 | Red Leaf Resources, Inc. | Staged zone heating of hydrocarbon bearing materials |
US10787362B2 (en) | 2016-05-16 | 2020-09-29 | Christopher L. de Graffenried, SR. | Hydrogen co-firing with carbon pre-capture for higher carbon ratio fossil fuels |
CN112877083A (en) * | 2021-01-19 | 2021-06-01 | 烟台世玛泰自动化设备有限公司 | Rotary dry distillation complete equipment and production process thereof |
WO2022035960A1 (en) * | 2020-08-12 | 2022-02-17 | David Johnson | Kinetic oil processing system |
US11401476B2 (en) * | 2017-06-14 | 2022-08-02 | Gidara Energy B.V. | Aftertreatment arrangement and method for the aftertreatment of at least gases downstream of a fluid bed gasification system, and logic unit and use |
US11851618B2 (en) | 2020-07-21 | 2023-12-26 | Red Leaf Resources, Inc. | Staged oil shale processing methods |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4094767A (en) * | 1976-11-10 | 1978-06-13 | Phillips Petroleum Company | Fluidized bed retorting of tar sands |
US4725350A (en) * | 1981-02-13 | 1988-02-16 | Smith Anthon L | Process for extracting oil and hydrocarbons from crushed solids using hydrogen rich syn gas |
US4971683A (en) * | 1987-06-08 | 1990-11-20 | Carbon Fuels Corporation | Method of refining coal by short residence time hydrodisproportionation to co-produce coal-based petroleum substitutes and methanol |
US6139722A (en) * | 1995-10-31 | 2000-10-31 | Chattanooga Corporation | Process and apparatus for converting oil shale or tar sands to oil |
-
2007
- 2007-02-23 US US11/710,389 patent/US20080202985A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4094767A (en) * | 1976-11-10 | 1978-06-13 | Phillips Petroleum Company | Fluidized bed retorting of tar sands |
US4725350A (en) * | 1981-02-13 | 1988-02-16 | Smith Anthon L | Process for extracting oil and hydrocarbons from crushed solids using hydrogen rich syn gas |
US4971683A (en) * | 1987-06-08 | 1990-11-20 | Carbon Fuels Corporation | Method of refining coal by short residence time hydrodisproportionation to co-produce coal-based petroleum substitutes and methanol |
US6139722A (en) * | 1995-10-31 | 2000-10-31 | Chattanooga Corporation | Process and apparatus for converting oil shale or tar sands to oil |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8002972B2 (en) * | 2007-10-12 | 2011-08-23 | Enshale, Inc. | Petroleum products from oil shale |
US20090095659A1 (en) * | 2007-10-12 | 2009-04-16 | Enshale, Inc. | Petroleum products from oil shale |
US8936657B2 (en) * | 2008-02-13 | 2015-01-20 | Outotec Oyj | Process and plant or refining raw materials containing organic constituents |
US20100313475A1 (en) * | 2008-02-13 | 2010-12-16 | Outotec Oyj | Process for plant for refining raw materials containing organic constituents |
US9764300B2 (en) | 2008-02-13 | 2017-09-19 | Outotec Oyj | Process and plant for refining raw materials containing organic constituents |
US20100005710A1 (en) * | 2008-07-09 | 2010-01-14 | Pipal Energy Resources, Llc | Upgrading Carbonaceous Materials |
US8021445B2 (en) * | 2008-07-09 | 2011-09-20 | Skye Energy Holdings, Inc. | Upgrading carbonaceous materials |
US8778036B2 (en) | 2008-07-09 | 2014-07-15 | Skye Energy Holdings, Inc. | Upgrading carbonaceous materials |
CN101942333A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Shale oil single-stage serial hydrocracking technology method |
US20120137583A1 (en) * | 2009-08-12 | 2012-06-07 | Thyssenkrupp Uhde Gmbh | Method for supplying an entrained-flow gasification reactor with carbonaceous fuels |
US8932375B2 (en) * | 2009-08-12 | 2015-01-13 | Thyssenkrupp Uhde Gmbh | Method for supplying an entrained-flow gasification reactor with carbonaceous fuels |
US20140209447A1 (en) * | 2011-09-01 | 2014-07-31 | Guradoor, S.L. | Gasification-pyrolysis dual reactor device |
US20140026483A1 (en) * | 2012-07-30 | 2014-01-30 | General Electric Company | Systems for preheating feedstock |
US20160312697A1 (en) * | 2015-04-27 | 2016-10-27 | Korea Institute Of Energy Research | Gasification Combined Generation System Through Coal and Industrial Waste Water |
US20160322660A1 (en) * | 2015-05-02 | 2016-11-03 | Aerojet Rocketdyne, Inc. | Gas generator and process therefor |
US9917319B2 (en) * | 2015-05-02 | 2018-03-13 | Aerojet Rocketdyne, Inc. | Gas generator and process therefor |
US9914879B2 (en) | 2015-09-30 | 2018-03-13 | Red Leaf Resources, Inc. | Staged zone heating of hydrocarbon bearing materials |
US10208254B2 (en) | 2015-09-30 | 2019-02-19 | Red Leaf Resources, Inc. | Stage zone heating of hydrocarbon bearing materials |
US10787362B2 (en) | 2016-05-16 | 2020-09-29 | Christopher L. de Graffenried, SR. | Hydrogen co-firing with carbon pre-capture for higher carbon ratio fossil fuels |
US11401476B2 (en) * | 2017-06-14 | 2022-08-02 | Gidara Energy B.V. | Aftertreatment arrangement and method for the aftertreatment of at least gases downstream of a fluid bed gasification system, and logic unit and use |
US11851618B2 (en) | 2020-07-21 | 2023-12-26 | Red Leaf Resources, Inc. | Staged oil shale processing methods |
WO2022035960A1 (en) * | 2020-08-12 | 2022-02-17 | David Johnson | Kinetic oil processing system |
US11884889B2 (en) | 2020-08-12 | 2024-01-30 | David Johnson | Kinetic oil processing system |
CN112877083A (en) * | 2021-01-19 | 2021-06-01 | 烟台世玛泰自动化设备有限公司 | Rotary dry distillation complete equipment and production process thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20080202985A1 (en) | Method for recovery of hydrocarbon oils from oil shale and other carbonaceous solids | |
US9234149B2 (en) | Steam generating slurry gasifier for the catalytic gasification of a carbonaceous feedstock | |
CA1152533A (en) | Production of methanol | |
CA2624626C (en) | Catalytic steam gasification of petroleum coke to methane | |
CA2192350C (en) | Improved pyrolytic conversion of organic feedstock and waste | |
CN108026459B (en) | All-steam gasification with carbon capture | |
KR101643792B1 (en) | Two stage dry feed gasification system and process | |
US20080016769A1 (en) | Conversion of carbonaceous materials to synthetic natural gas by pyrolysis, reforming, and methanation | |
JP6371809B2 (en) | Two-stage gasification with double quenching | |
WO2008077233A1 (en) | Method for low-severity gasification of heavy petroleum residues. | |
KR19980023905A (en) | Methods and apparatus for treating waste through vaporization | |
JP2012500297A (en) | Two-stage entrained gasifier and method | |
US20080016756A1 (en) | Conversion of carbonaceous materials to synthetic natural gas by reforming and methanation | |
US3909212A (en) | Removal of sulfur from carbonaceous fuels | |
JPH0770569A (en) | Gasification of carbonaceous substance | |
US20230383203A1 (en) | Process and apparatus | |
JPS621784A (en) | Gasification of hydrocarbon fuel | |
EP2940105B1 (en) | Gasification combined facility for carbon fuel including pneumatic conveying dryer | |
JPS6150995B2 (en) | ||
US4530752A (en) | Oil shale retorting process | |
Cavanaugh et al. | Environmental assessment data base for low/medium-Btu gasification technology. Volume II. Appendices A--F | |
US7261873B2 (en) | Power generation from sulphur-containing fuels | |
Higman | Gasification processes and synthesis gas treatment technologies for carbon dioxide (CO2) capture | |
MX2008004832A (en) | Catalytic steam gasification of petroleum coke to methane | |
DESIGN | CLEAN COKE PROCESS J |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: COMBUSTION RESOURCES, L.L.C., UTAH Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HATFIELD, KENT E.;COATES, RALPH L.;SMOOT, L. DOUGLAS;REEL/FRAME:018988/0553 Effective date: 20070222 Owner name: COMBUSTION RESOURCES, L.L.C.,UTAH Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HATFIELD, KENT E.;COATES, RALPH L.;SMOOT, L. DOUGLAS;REEL/FRAME:018988/0553 Effective date: 20070222 |
|
AS | Assignment |
Owner name: COMBUSTION HOLDINGS, LLC, UTAH Free format text: CHANGE OF NAME;ASSIGNOR:COMBUSTION RESOURCES, L.L.C.;REEL/FRAME:024647/0883 Effective date: 20021226 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |