CA2953853C - Upgrading of hydrocarbon material - Google Patents
Upgrading of hydrocarbon material Download PDFInfo
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- CA2953853C CA2953853C CA2953853A CA2953853A CA2953853C CA 2953853 C CA2953853 C CA 2953853C CA 2953853 A CA2953853 A CA 2953853A CA 2953853 A CA2953853 A CA 2953853A CA 2953853 C CA2953853 C CA 2953853C
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- Canada
- Prior art keywords
- fraction
- olefin
- treatment
- olefinic
- upgraded
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- 239000000463 material Substances 0.000 title claims abstract description 381
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 254
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 254
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 254
- 238000000034 method Methods 0.000 claims abstract description 121
- 230000008569 process Effects 0.000 claims abstract description 111
- 238000005336 cracking Methods 0.000 claims abstract description 67
- 239000001257 hydrogen Substances 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims description 83
- 150000001336 alkenes Chemical class 0.000 claims description 71
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 41
- 238000005804 alkylation reaction Methods 0.000 claims description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 230000029936 alkylation Effects 0.000 claims description 22
- 238000009835 boiling Methods 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 230000002152 alkylating effect Effects 0.000 claims description 10
- 238000004227 thermal cracking Methods 0.000 claims description 9
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000047 product Substances 0.000 description 89
- 239000003054 catalyst Substances 0.000 description 82
- 238000000926 separation method Methods 0.000 description 37
- 238000010977 unit operation Methods 0.000 description 32
- 239000010426 asphalt Substances 0.000 description 23
- 230000000694 effects Effects 0.000 description 23
- 239000003921 oil Substances 0.000 description 23
- 150000001925 cycloalkenes Chemical class 0.000 description 20
- 238000006356 dehydrogenation reaction Methods 0.000 description 19
- 239000000852 hydrogen donor Substances 0.000 description 19
- 239000011148 porous material Substances 0.000 description 16
- 239000000295 fuel oil Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000010586 diagram Methods 0.000 description 14
- 230000009467 reduction Effects 0.000 description 12
- 239000003377 acid catalyst Substances 0.000 description 10
- 150000001924 cycloalkanes Chemical class 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000003085 diluting agent Substances 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 125000005842 heteroatom Chemical group 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000010779 crude oil Substances 0.000 description 7
- 230000005484 gravity Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000001491 aromatic compounds Chemical class 0.000 description 5
- 150000007514 bases Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 5
- 238000007323 disproportionation reaction Methods 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000002203 pretreatment Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000013557 residual solvent Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- -1 pyridine Chemical class 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229910003294 NiMo Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 239000011959 amorphous silica alumina Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000012993 chemical processing Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000386 donor Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000001991 steam methane reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
- C10G57/005—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process with alkylation
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1096—Aromatics or polyaromatics
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
- C10G2300/206—Asphaltenes
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
There is provided a process for upgrading a hydrocarbon material. The process includes: (a) treating a hydrocarbon material-comprising feed, wherein the treating includes cracking a hydrocarbon material-comprising feed, such that an upgraded intermediate is produced; and (b) in the absence, or the substantial absence, of adscititious diatomic hydrogen, reducing the content of olefinic material within at least a fraction of the upgraded intermediate such that an olefinic material content-reduced product is produced.
Description
UPGRADING OF HYDROCARBON MATERIAL
FIELD
[0001] The present disclosure relates to the upgrading of hydrocarbon materials, including the upgrading of heavy hydrocarbon materials.
BACKGROUND
FIELD
[0001] The present disclosure relates to the upgrading of hydrocarbon materials, including the upgrading of heavy hydrocarbon materials.
BACKGROUND
[0002] Commonly, heavy oils and/or bitumen are difficult to transport from their production areas due to their high viscosities at typical handling temperatures. For example in Canada, there are typically three specifications that must be met by any oil to be acceptable for pipeline transport. The viscosity should be below the maximum viscosity limit (e.g. <350 cSt at 7.5 C), the density should be below the maximum density limit (e.g. <940 kg=m-
3 at 15.6 C, or >19 API), and the olefins (including di-olefins) content should be below the maximum limit (e.g. < 1 wt% as 1-decene equivalent).
[0003] As is well known, light oils generally have much lower viscosity values and therefore flow easier through pipelines than heavy oils. Regardless of the recovery method used for their extraction, including costly thermal enhanced oil recovery (EOR) methods, heavy oils and bitumen generally need to be diluted by blending the oil with low density and low viscosity diluents, typically gas condensate, naphtha and/or lighter oil to make the heavy oils and/or bitumen transportable over long distances. For example in Canada, when adding diluent to bitumen to produce transportable oil (also known as "DilBit"), the volume of diluent is typically 30 to 35% of the total product. There are several disadvantages of adding diluent to bitumen to produce transportable oil, including:
[0003] As is well known, light oils generally have much lower viscosity values and therefore flow easier through pipelines than heavy oils. Regardless of the recovery method used for their extraction, including costly thermal enhanced oil recovery (EOR) methods, heavy oils and bitumen generally need to be diluted by blending the oil with low density and low viscosity diluents, typically gas condensate, naphtha and/or lighter oil to make the heavy oils and/or bitumen transportable over long distances. For example in Canada, when adding diluent to bitumen to produce transportable oil (also known as "DilBit"), the volume of diluent is typically 30 to 35% of the total product. There are several disadvantages of adding diluent to bitumen to produce transportable oil, including:
[0004] Higher capital cost - Well remoteness makes the construction of pipelines for sending or returning of the diluents to the bitumen production zone considerably more expensive;
[0005] Higher operating cost - The use of diluents constitutes the single largest component of the operating cost of running a bitumen extraction facility;
[0006] Higher capital and operating costs - The added diluent occupies valuable pipeline space that otherwise could be used to transport more partially upgraded bitumen;
[0007] Lower value ¨ product - bitumen sells at a lower price vs. partially upgraded bitumen.
[0008] The upgrading of heavy oil and/or bitumen to a product that meets the specifications for pipeline transport is known in the industry. Upgrading has become an attractive alternative for converting heavy oil and/or bitumen into transportable oil or oil that requires less diluent to be transportable, and in some cases upgrading is the only viable alternative in order to transport heavy oil to refineries and market places.
[0009] One upgrading approach involves the chemical processing of the heavy oil and/or bitumen by a suitable combination of conversion and separation steps. Most chemical processing for converting heavy oil and/or bitumen into transportable oil are cracking based systems and usually include at least one form of cracking, e.g. thermal cracking, and at least one form of hydro-proccssing. The cracking step is employed to reduce the viscosity and density of the heavy oil and/or bitumen. The hydro-processing step is employed to reduce the olefin and di-olefin content of the heavy oil and/or bitumen.
[0010] Moderate thermal cracking such as visbreaking or more severe thermal processes such as coking systems have been proposed in the prior art to reduce the viscosity and density of heavy oils and/or bitumen.
[0011] A disadvantage of these processes is the production of cracked material comprising olefins and di-olefins. If left untreated, olefins, and more particularly the more reactive conjugated C4 and C5 di-olefins (i.e. butadiene, 1,3-pentadiene, 2-methyl-1,3-butadiene) may react with each other, with oxygen (such as oxygen in the air) or other reactive compounds (e.g. organic acids, carbonyls, amines, etc.), to form long chain polymers (polymerization reaction) commonly referred to as gums. Gums of this nature are known to foul process equipment. It has been reported in U.S. Patent 6,210,560 assigned to Exxon Research and Engineering Company, that these polymerization reactions occur at a significant rate for petroleum oils having a di-olefins value per UOP-326 of 4 grams iodine/110 grams oil or greater in the temperature range of 232 C to 324 C; particularly 260 C to 304 C. Below this temperature range, the reaction rate is too slow for significant polymerization formation to occur and above this temperature range the chemical bonds are broken thermally faster than they are formed. It has also been reported in U.S. Patent Application Publication No.
2012/0273394 Al assigned to UOP LLC, that the fouling tendencies of oils having a di-olefins value per UOP-326 of less than about 2 grams iodine/110 grams oil are deemed acceptable.
2012/0273394 Al assigned to UOP LLC, that the fouling tendencies of oils having a di-olefins value per UOP-326 of less than about 2 grams iodine/110 grams oil are deemed acceptable.
[0012] As excessive olefins content in hydrocarbon streams can lead to fouling of refining equipment and pipelines, methods to reduce the amount of olefins in a hydrocarbon stream are sought in the industry. A particular challenge is to reduce the amount of olefins in facilities where it is impractical to supply or generate sufficient adscititious hydrogen to make use of hydro-processing.
SUMMARY
SUMMARY
[0013] In one aspect, there is provided a process for upgrading a hydrocarbon material comprising: treating a hydrocarbon material-comprising feed, wherein the treating includes cracking a hydrocarbon material-comprising feed, such that an upgraded intermediate is produced; and in the absence, or the substantial absence, of adscititious diatomic hydrogen, reducing the content of olefinic material within at least a fraction of the upgraded intermediate such that an olefinic material content-reduced product is produced.
[0014] In another aspect, there is provided a process for upgrading a hydrocarbon material comprising: treating a hydrocarbon material-comprising feed, wherein the treating includes cracking the hydrocarbon material-comprising feed within a reaction zone, such that an upgraded intermediate is produced; separating a feed material into at least an olefin-comprising treatment fraction and a treatment bypass fraction, wherein the feed material includes at least a fraction of the upgraded intermediate reducing the content of olefinic material within the olefin-comprising treatment fraction such that an olefin-depleted intermediate is produced; separating the treatment bypass fraction into a heavier hydrocarbon material-comprising fraction and a lighter hydrocarbon material-comprising fraction; combining at least the lighter hydrocarbon material-comprising fraction and the olefin¨depleted intermediate such that an olefinic material content-reduced product is produced; producing an upgraded product including the olefinic material content-reduced product; and supplying at least a fraction of the heavier hydrocarbon material-comprising fraction to the reaction zone, such that the hydrocarbon material-comprising feed includes at least a fraction of the heavier hydrocarbon material-comprising fraction.
[0014 a] In a further aspect, there is provided a process for upgrading a heavy hydrocarbon feed material to an upgraded product comprising: thermally cracking the heavy hydrocarbon feed material within a reaction zone disposed at a temperature of at least 300 degrees Celsius, such that an upgraded intermediate is produced, separating the upgraded intermediate into at least an olefin-comprising treatment fraction and a treatment bypass fraction, wherein, at a pressure of one (1) atmosphere, the boiling point range of the olefin-comprising treatment fraction is between 25 degrees Celsius and 365 degrees Celsius, reducing the content of olefinic material within the olefin-comprising treatment fraction by alkylating the olefin-comprising treatment fraction such that an olefin-depleted intermediate is produced; separating the treatment bypass fraction into a heavier hydrocarbon material-comprising fraction and a lighter hydrocarbon material-comprising fraction; the boiling point range of the lighter hydrocarbon material-comprising fraction is between 80 degrees Celsius and 450 degrees Celsius;
combining at least the lighter hydrocarbon material-comprising fraction and the olefin¨depleted intermediate such that an olefinic material content-reduced product is produced; producing the upgraded product including the olefinic material content-reduced product; and supplying at least a fraction of the heavier hydrocarbon material-comprising fraction upstream the reaction zone, such that the heavy hydrocarbon material-comprising feed includes at least a fraction of the heavier hydrocarbon material-comprising fraction.
[0014 b] In still another aspect, there is provided a process for upgrading a heavy hydrocarbon feed material to an upgraded product comprising: thermally cracking the heavy hydrocarbon feed material within a reaction zone disposed at a temperature of at least 300 degrees Celsius, such that an upgraded intermediate is produced; separating the upgraded intermediate into at least an olefin-comprising treatment fraction, a heavier hydrocarbon material-comprising fraction, and a lighter hydrocarbon material-comprising fraction, wherein the heavy hydrocarbon feed material includes at least a fraction of the upgraded intermediate, reducing the content of olefinic material within the olefin-comprising treatment fraction by alkylating the olefin-comprising treatment fraction such that an olefin-depleted intermediate is 3a Date Recue/Date Received 2020-08-21 produced; wherein, at a pressure of one (1) atmosphere, the boiling point range of the olefin-comprising treatment fraction is between 25 degrees Celsius and 365 degrees Celsius, combining at least the lighter hydrocarbon material-comprising fraction and the olefin¨depleted intermediate such that an olefinic material content-reduced product is produced; wherein the boiling point range of the lighter hydrocarbon material-comprising fraction is between 80 degrees Celsius and 450 degrees Celsius, producing the upgraded product including the olefinic material content-reduced product; and supplying at least a fraction of the heavier hydrocarbon material-comprising fraction upstream of the reaction zone, such that the heavy hydrocarbon feed material includes at least a fraction of the heavier hydrocarbon material-comprising fraction.
[0014 c] In yet another aspect, there is provided a process for upgrading a heavy hydrocarbon feed material to an upgraded product comprising: thermally cracking the heavy hydrocarbon feed material in a reaction zone disposed at a temperature of at least 300 degrees Celsius, such that an upgraded intermediate is produced, wherein the thermal cracking is effected; separating the upgraded intermediate into at least a light olefin-comprising treatment fraction and a treatment bypass fraction, wherein the heavy hydrocarbon feed material includes at least a fraction of the upgraded intermediate; wherein, at a pressure of one (1) atmosphere, the boiling point range of the light olefin-comprising treatment fraction is between 25 degrees Celsius and 200 degrees Celsius; reducing the content of light olefinic material within the olefin-compri sing treatment fraction by alkylating the olefin-comprising treatment fraction such that a light olefinic material-depleted intermediate is produced; combining the light olefinic material-depleted intermediate and the treatment bypass fraction so as to produce a light olefinic material content-reduced product; and producing the upgraded product including the light olefinic material content-reduced product 3b Date Recue/Date Received 2020-08-21
[0014 a] In a further aspect, there is provided a process for upgrading a heavy hydrocarbon feed material to an upgraded product comprising: thermally cracking the heavy hydrocarbon feed material within a reaction zone disposed at a temperature of at least 300 degrees Celsius, such that an upgraded intermediate is produced, separating the upgraded intermediate into at least an olefin-comprising treatment fraction and a treatment bypass fraction, wherein, at a pressure of one (1) atmosphere, the boiling point range of the olefin-comprising treatment fraction is between 25 degrees Celsius and 365 degrees Celsius, reducing the content of olefinic material within the olefin-comprising treatment fraction by alkylating the olefin-comprising treatment fraction such that an olefin-depleted intermediate is produced; separating the treatment bypass fraction into a heavier hydrocarbon material-comprising fraction and a lighter hydrocarbon material-comprising fraction; the boiling point range of the lighter hydrocarbon material-comprising fraction is between 80 degrees Celsius and 450 degrees Celsius;
combining at least the lighter hydrocarbon material-comprising fraction and the olefin¨depleted intermediate such that an olefinic material content-reduced product is produced; producing the upgraded product including the olefinic material content-reduced product; and supplying at least a fraction of the heavier hydrocarbon material-comprising fraction upstream the reaction zone, such that the heavy hydrocarbon material-comprising feed includes at least a fraction of the heavier hydrocarbon material-comprising fraction.
[0014 b] In still another aspect, there is provided a process for upgrading a heavy hydrocarbon feed material to an upgraded product comprising: thermally cracking the heavy hydrocarbon feed material within a reaction zone disposed at a temperature of at least 300 degrees Celsius, such that an upgraded intermediate is produced; separating the upgraded intermediate into at least an olefin-comprising treatment fraction, a heavier hydrocarbon material-comprising fraction, and a lighter hydrocarbon material-comprising fraction, wherein the heavy hydrocarbon feed material includes at least a fraction of the upgraded intermediate, reducing the content of olefinic material within the olefin-comprising treatment fraction by alkylating the olefin-comprising treatment fraction such that an olefin-depleted intermediate is 3a Date Recue/Date Received 2020-08-21 produced; wherein, at a pressure of one (1) atmosphere, the boiling point range of the olefin-comprising treatment fraction is between 25 degrees Celsius and 365 degrees Celsius, combining at least the lighter hydrocarbon material-comprising fraction and the olefin¨depleted intermediate such that an olefinic material content-reduced product is produced; wherein the boiling point range of the lighter hydrocarbon material-comprising fraction is between 80 degrees Celsius and 450 degrees Celsius, producing the upgraded product including the olefinic material content-reduced product; and supplying at least a fraction of the heavier hydrocarbon material-comprising fraction upstream of the reaction zone, such that the heavy hydrocarbon feed material includes at least a fraction of the heavier hydrocarbon material-comprising fraction.
[0014 c] In yet another aspect, there is provided a process for upgrading a heavy hydrocarbon feed material to an upgraded product comprising: thermally cracking the heavy hydrocarbon feed material in a reaction zone disposed at a temperature of at least 300 degrees Celsius, such that an upgraded intermediate is produced, wherein the thermal cracking is effected; separating the upgraded intermediate into at least a light olefin-comprising treatment fraction and a treatment bypass fraction, wherein the heavy hydrocarbon feed material includes at least a fraction of the upgraded intermediate; wherein, at a pressure of one (1) atmosphere, the boiling point range of the light olefin-comprising treatment fraction is between 25 degrees Celsius and 200 degrees Celsius; reducing the content of light olefinic material within the olefin-compri sing treatment fraction by alkylating the olefin-comprising treatment fraction such that a light olefinic material-depleted intermediate is produced; combining the light olefinic material-depleted intermediate and the treatment bypass fraction so as to produce a light olefinic material content-reduced product; and producing the upgraded product including the light olefinic material content-reduced product 3b Date Recue/Date Received 2020-08-21
[0015] In another aspect, there is provided a process for upgrading a hydrocarbon material comprising: treating a hydrocarbon material-comprising feed, wherein the treating includes cracking the hydrocarbon material-comprising feed within a reaction zone, such that an upgraded intermediate is produced; separating a feed material into at least an olefin-comprising treatment fraction, a heavier hydrocarbon material-comprising fraction, and a lighter hydrocarbon material-comprising fraction, wherein the feed material includes at least a fraction of the upgraded intermediate reducing the content of olefinic material within the olefin-comprising treatment fraction such that an olefin-depleted intermediate is produced; combining at least the lighter hydrocarbon material-comprising fraction and the olefin¨depleted intermediate such that an olefinic material content-reduced product is produced; producing an upgraded product including the olefinic material content-reduced product; and supplying at least a fraction of the heavier hydrocarbon material-comprising fraction to the reaction zone, such that the hydrocarbon material-comprising feed includes at least a fraction of the heavier hydrocarbon material-comprising fraction.
[0016] In another aspect, there is provided a process for upgrading a hydrocarbon material comprising: treating a hydrocarbon material-comprising feed, wherein the treating includes cracking the hydrocarbon material-comprising feed, such that an upgraded intermediate is produced; separating a feed material into at least a light olefin-comprising treatment fraction and a treatment bypass fraction, wherein the feed material includes at least a fraction of the upgraded intermediate; reducing the content of light olefinic material within the olefin-comprising treatment fraction such that a light olefinic material-depleted intermediate is produced; combining the light olefinic material-depleted intermediate and the treatment bypass fraction so as to produce a light olefinic material content-reduced product;
and producing an upgraded product including the light olefinic material content-reduced product.
and producing an upgraded product including the light olefinic material content-reduced product.
[0017] In another aspect, there is provided a process for upgrading a hydrocarbon material comprising: supplying a hydrogen donor material to a reaction zone;
supplying a Date Recue/Date Received 2020-08-21 hydrocarbon material-comprising feed to the reaction zone; treating the hydrocarbon material-comprising feed, wherein the treating includes cracking the hydrocarbon material-comprising feed in the presence of a hydrogen donor material within the reaction zone, such that an upgraded hydrocarbon material is produced.
BRIEF DESCRIPTION OF DRAWINGS
supplying a Date Recue/Date Received 2020-08-21 hydrocarbon material-comprising feed to the reaction zone; treating the hydrocarbon material-comprising feed, wherein the treating includes cracking the hydrocarbon material-comprising feed in the presence of a hydrogen donor material within the reaction zone, such that an upgraded hydrocarbon material is produced.
BRIEF DESCRIPTION OF DRAWINGS
[0018] The preferred embodiments will now be described with the following accompanying drawings, in which:
[0019] Figure 1 is a process flow diagram of a process according to one embodiment;
[0020] Figure 1A is a process flow diagram of a process according to another embodiment;
[0021] Figure 2 is a process flow diagram of a process according to another embodiment;
[0022] Figure 3 is a process flow diagram of a process according to another embodiment;
[0023] Figure 4 is a process flow diagram of a process according to another embodiment;
[0024] Figure 5 is a process flow diagram of a process according to another embodiment;
[0025] Figure 5A is a process flow diagram of a process according to another embodiment;
[0026] Figure 6 is a process flow diagram of a process according to another embodiment;
[0027] Figure 7 is a process flow diagram of a process according to another embodiment;
[0028] Figure 8 is a process flow diagram of a process according to another embodiment;
[0029] Figure 9 is a process flow diagram of a process according to another embodiment;
[0030] Figure 10 is a process flow diagram of a process according to another embodiment;
[0031] Figure 11 is a process flow diagram of a process according to another embodiment; and
[0032] Figure 12 is a process flow diagram of a process according to another embodiment.
DETAILED DESCRIPTION
DETAILED DESCRIPTION
[0033] The present disclosure relates to the upgrading of hydrocarbon material. In some embodiments, for example, the upgrading is of heavy hydrocarbon material.
Exemplary embodiments may relate to heavy hydrocarbon materials, but it is understood, unless the context suggests otherwise, that such embodiments are also applicable to hydrocarbon materials, generally.
Exemplary embodiments may relate to heavy hydrocarbon materials, but it is understood, unless the context suggests otherwise, that such embodiments are also applicable to hydrocarbon materials, generally.
[0034] As used herein, the following terms have the following meanings:
[0035] "Hydrocarbon" is an organic compound consisting primarily of hydrogen and carbon, and, in some instances, may also contain heteroatoms such as sulfur, nitrogen and oxygen.
[0036] "Hydrocarbon material" is a material consisting of at least one hydrocarbon.
[0037] "Heavy hydrocarbon material" is, in some embodiments, for example, hydrocarbon material that includes at least 10 weight percent of hydrocarbon material that boils above 500 C. In some of these embodiments, for example, the heavy hydrocarbon material is a hydrocarbon material that includes at least 20 weight percent of hydrocarbon material that boils above 500 C. In some of these embodiments, for example, the heavy hydrocarbon material is a hydrocarbon material includes at least 40 weight percent of hydrocarbon material that boils above 500 C. In some of these embodiments, for example, the heavy hydrocarbon material is a hydrocarbon material includes at least 60 weight percent of hydrocarbon material that boils above 500 C. In some of these embodiments, for example, the heavy hydrocarbon material is a hydrocarbon material includes at least 80 weight percent of hydrocarbon material that boils above 500 C. In some of these embodiments, for example, the heavy hydrocarbon material is a hydrocarbon material that boils above 500 C.
[0038] In some embodiments, for example, the heavy hydrocarbon material is a hydrocarbon material having an API (American Petroleum Institute) gravity of less than 22 . In some embodiments, for example, the heavy hydrocarbon material is a hydrocarbon material having an API gravity of less than 20 . In some embodiments, for example, the heavy hydrocarbon material is a hydrocarbon material having an API gravity of less than 150. In some embodiments, for example, the heavy hydrocarbon material is a hydrocarbon material having an API gravity of less than 10 . In some embodiments, for example, the heavy hydrocarbon material has an API gravity of less than 5 . In some embodiments, for example, the heavy hydrocarbon material is a hydrocarbon material having an API gravity of less than 0 . In some embodiments, for example, the heavy hydrocarbon material is a hydrocarbon material having an API gravity of less than -5 .
[0039] In some embodiments, for example, the heavy hydrocarbon material includes, or in some embodiments, consists of, residuum or resid. Exemplary residuum includes various heavy crude and refinery fractions. In this respect, in some embodiments, for example, the heavy hydrocarbon material includes, or in some embodiments, consists of, fresh resid hydrocarbon feeds, a bottoms stream from any refinery process, such as petroleum atmospheric tower bottoms, vacuum tower bottoms, or a bottoms stream from a coker or a thermal cracking unit, or a bottoms stream from a fluid catalytic cracking ("FCC") unit operation or a resid fluid catalytic cracking (RFCC) unit operation, hydrocracked atmospheric tower, vacuum tower, FCC, or RFCC bottoms, straight run vacuum gas oil, hydrocracked vacuum gas oil, fluid catalytically cracked slurry oils or cycle oils, as well as other similar hydrocarbon materials, or any combination thereof, each of which may be straight run, process derived, hydrocracked, or otherwise partially treated (for example, desulfurized). The above-described heavy hydrocarbon material may also include various impurities, such as sulphur, nitrogen, oxygen, halides, and metals.
[0040] In some embodiments, for example, the heavy hydrocarbon material includes, or in some embodiments, consists of, a crude, such as an heavy and/or an ultra-heavy crude. Crude refers to hydrocarbon material which have been produced and/or retorted from hydrocarbon-containing formations and which has not yet been distilled and/or fractionally distilled in a treatment facility to produce multiple components with specific boiling range distributions, such as atmospheric distillation methods and/or vacuum distillation methods.
Exemplary crudes include coals, bitumen, oil sands, heavy oil or crude oil.
Exemplary crudes include coals, bitumen, oil sands, heavy oil or crude oil.
[0041] In some embodiments, for example, the heavy hydrocarbon material is included within an asphaltene-comprising heavy hydrocarbon-comprising material includes an asphaltene content of less than 40 weight %, based on the total weight of the heavy hydrocarbon material. In some of these embodiments, for example, the asphaltene-comprising heavy hydrocarbon-comprising material includes an asphaltene content of less than 20 weight %, based on the total weight of the heavy hydrocarbon material. In some of these embodiments, for example, the asphaltene-comprising heavy hydrocarbon-comprising material includes an asphaltene content of less than 15 weight %, based on the total weight of the heavy hydrocarbon material.
[0042] The term "asphaltenes" as used herein refers to the heaviest and most polar molecules component of a carbonaceous material such as crude oil, bitumen or coal and are defined as a solubility class of materials that are insoluble in an n-alkane (usually npentane or n-heptane) but soluble in aromatic solvents such as toluene. In crude oil, asphaltenes are found, along with saturated and aromatic hydrocarbons and resins ("SARA").
Asphaltenes consist primarily of carbon, hydrogen, nitrogen, oxygen, and sulfur, as well as trace amounts of vanadium and nickel. The density is approximately 1.2 g/cc and the hydrogen to carbon atomic ratio is approximately 1.2, depending on the asphaltenes source and the solvent used for extraction. The asphaltenes fraction is also responsible for a large percentage of the contaminants contained in the bitumen (for example Athabasca bitumen is typically 72%-76%
w/w of the metals, 53%-58% w/w of coke precursors, and 26%-31% w/w of the heteroatoms -sulphur, nitrogen and oxygen), making bitumen very challenging to process into clean and valuable products.
Asphaltenes consist primarily of carbon, hydrogen, nitrogen, oxygen, and sulfur, as well as trace amounts of vanadium and nickel. The density is approximately 1.2 g/cc and the hydrogen to carbon atomic ratio is approximately 1.2, depending on the asphaltenes source and the solvent used for extraction. The asphaltenes fraction is also responsible for a large percentage of the contaminants contained in the bitumen (for example Athabasca bitumen is typically 72%-76%
w/w of the metals, 53%-58% w/w of coke precursors, and 26%-31% w/w of the heteroatoms -sulphur, nitrogen and oxygen), making bitumen very challenging to process into clean and valuable products.
[0043] In some embodiments, for example, the heavy hydrocarbon material is included within deasphalted heavy hydrocarbon-comprising material. In this respect, to produce deasphalted heavy hydrocarbon-comprising material, an asphaltene-comprising heavy hydrocarbon-comprising material is deasphalted.
[0044] Deasphalting effects production of the deasphalted heavy hydrocarbon-comprising material, such that the asphaltene content of the deasphalted heavy hydrocarbon-comprising material is less than the asphaltene content of the asphaltene-comprising heavy hydrocarbon-comprising material. In some embodiments, for example, the deasphalting is effected by at least a solvent extraction process. In some embodiments, for example, the deasphalting is effected by at least a reactive process.
[0045] As alluded to above, in some embodiments, for example, the deasphalting is effected by solvent extraction, as is well known in the art, and is described in, and amongst other sources, the article by Billon and others published in 1994 in Volume 49, No.
5 of the journal of the French Petroleum Institute, pages 495 to 507, in the book "Raffinage et conversion des produits lourds du petrole [Refining and Conversion of Heavy Petroleum Products]" by J. F. Le Page, S. G. Chatila, and M. Davidson, Edition Technip, pages 17-32. In some embodiments, for example, the solvent material is a supercritical fluid at the operating conditions of the zone within which the solvent material is separated (for recycling and re-use) from the heavy hydrocarbon material which it has previously extracted.
5 of the journal of the French Petroleum Institute, pages 495 to 507, in the book "Raffinage et conversion des produits lourds du petrole [Refining and Conversion of Heavy Petroleum Products]" by J. F. Le Page, S. G. Chatila, and M. Davidson, Edition Technip, pages 17-32. In some embodiments, for example, the solvent material is a supercritical fluid at the operating conditions of the zone within which the solvent material is separated (for recycling and re-use) from the heavy hydrocarbon material which it has previously extracted.
[0046] "Olefin" means an unsaturated hydrocarbon containing one or more carbon-carbon double bonds that are not part of an aromatic ring, and, for greater certainty, includes di-olefins and cyclo-olefins.
[0047] "Olefinic material" means a material consisting of one or more olefins.
[0048] "Light olefinic material" means any one or both of the following:
(a) olefinic material that has a weight average molecular weight of less than 150 g/mol; or (b) olefinic material that has a normal boiling point temperature (i.e., boiling point at one (1) atmosphere) of less than 200 degrees Celsius.
(a) olefinic material that has a weight average molecular weight of less than 150 g/mol; or (b) olefinic material that has a normal boiling point temperature (i.e., boiling point at one (1) atmosphere) of less than 200 degrees Celsius.
[0049] "Pipeline specification" refers to a characteristic of an oil that effects whether it can be transported by pipeline, and varies from jurisdiction to jurisdiction.
In Canada, for example, there are three critical specifications that must be met by an oil to be acceptable for pipeline transport:
= The viscosity should be below the maximum viscosity limit (e.g. <350 cSt at the pipeline reference temperature, which could be as low as 7.5 C during the winter months);
= The density should be below the maximum density limit (e.g. <940 kg.m3 at 15.6 C, or >19 API);
= The olefins content should be below the maximum limit (e.g. < 1 wt% as 1-decene equivalent) per CAPP olefins in crude oil by proton NMR test.
In Canada, for example, there are three critical specifications that must be met by an oil to be acceptable for pipeline transport:
= The viscosity should be below the maximum viscosity limit (e.g. <350 cSt at the pipeline reference temperature, which could be as low as 7.5 C during the winter months);
= The density should be below the maximum density limit (e.g. <940 kg.m3 at 15.6 C, or >19 API);
= The olefins content should be below the maximum limit (e.g. < 1 wt% as 1-decene equivalent) per CAPP olefins in crude oil by proton NMR test.
[0050] The term "fraction of', with reference to a material, means, depending on the context, one of (a) a portion of the material with the same, or substantially the same, composition as the material as a whole, or (b) a portion of the material that is compositionally different than the material as a whole, or either one of (a) or (b).
[0051] The upgrading of the heavy hydrocarbon material includes cracking of the heavy hydrocarbon material. Cracking refers to any process for breaking down heavier hydrocarbon molecules into lighter hydrocarbon molecules. Exemplary methods of cracking include thermal cracking, steam cracking, catalytic cracking, and coking. "Thermal cracking"
refers to an example of a cracking process that uses heat to perform such breaking of heavier molecules into smaller ones. Exemplary thermal cracking processes include visbreaking.
In some embodiments, for example, the cracking is effected within a cracking unit operation. In some of these embodiments, for example, the cracking unit operation effects visbreaking, and includes a heater and a soaker.
refers to an example of a cracking process that uses heat to perform such breaking of heavier molecules into smaller ones. Exemplary thermal cracking processes include visbreaking.
In some embodiments, for example, the cracking is effected within a cracking unit operation. In some of these embodiments, for example, the cracking unit operation effects visbreaking, and includes a heater and a soaker.
[0052]
Conversion technologies that accomplish cracking may generate olefins. The presence of excessive quantities of olefins is undesirable. Olefins (including, in particular, the more reactive conjugated diolefins) are considered to be deleterious materials due to their impact on refineries:
fouling of heaters, heat exchangers and catalyst beds;
negatively impacting the oxidation stability of refined products such as gasoline, jet fuel and diesel; and increasing the refinery hydrogen demand.
Conversion technologies that accomplish cracking may generate olefins. The presence of excessive quantities of olefins is undesirable. Olefins (including, in particular, the more reactive conjugated diolefins) are considered to be deleterious materials due to their impact on refineries:
fouling of heaters, heat exchangers and catalyst beds;
negatively impacting the oxidation stability of refined products such as gasoline, jet fuel and diesel; and increasing the refinery hydrogen demand.
[0053]
Accordingly, it is desirable to reduce the olefins content of hydrocarbon material to achieve appropriate operational and pipeline specifications.
Accordingly, it is desirable to reduce the olefins content of hydrocarbon material to achieve appropriate operational and pipeline specifications.
[0054] In this respect, and referring to Figure 1, the process includes treating a heavy hydrocarbon material-comprising feed 112. The treating is such that an upgraded product 200 is produced. The treating includes cracking the heavy hydrocarbon material-comprising feed 112 within a reaction zone 111. In some embodiments, for example, the reaction zone 111 is disposed at a temperature of at least 300 degrees Celsius, such as, for example, at least 350 degrees Celsius.
[0055]
Referring to Figure 1A, the heavy hydrocarbon material-comprising feed may be derived from a heavy hydrocarbon material-comprising supply stream 1012 from which a portion has bypassed the process as bypass stream 1014 and then combined with the upgraded product 20D.
Referring to Figure 1A, the heavy hydrocarbon material-comprising feed may be derived from a heavy hydrocarbon material-comprising supply stream 1012 from which a portion has bypassed the process as bypass stream 1014 and then combined with the upgraded product 20D.
[0056]
Generally, cracking of the heavy hydrocarbon material-comprising feed produces olefinic material within an upgraded intermediate product 114. In one aspect, the process further includes, within a reaction zone 120, effecting a reduction in content of olefinic material within the upgraded intermediate 114. In this respect, after the upgraded intermediate 114 is produced, a reduction of the content of olefinic material within the upgraded intermediate 114 is then effected to produce an olefinic material content-reduced product 115. An upgraded product 200 is produced including the olefinic material content-reduced product 115.
Generally, cracking of the heavy hydrocarbon material-comprising feed produces olefinic material within an upgraded intermediate product 114. In one aspect, the process further includes, within a reaction zone 120, effecting a reduction in content of olefinic material within the upgraded intermediate 114. In this respect, after the upgraded intermediate 114 is produced, a reduction of the content of olefinic material within the upgraded intermediate 114 is then effected to produce an olefinic material content-reduced product 115. An upgraded product 200 is produced including the olefinic material content-reduced product 115.
[0057] In another aspect, the process further includes creating conditions which suppress the formation of olefinic material during the cracking within the reaction zone 111.
[0058] In some embodiments, for example, it may be useful to pre-treat the upgraded intermediate 114, prior to supplying the upgraded intermediate to the reaction zone 120, such as by effecting a reduction in the content of di-olefins within the upgraded intermediate. In some embodiments, for example, di-olefins (and, particularly, the conjugated diolefins) are particularly reactive and may effect fouling of any catalyst material that is disposed within the reaction zone 120. The pre-treatment may include, for example, catalytic conversion, adsorption, precipitation, or extraction. Where the pre-treatment includes catalytic conversion, the catalyst material being used for the pre-treatment may be different than the catalyst material that is used for effecting, in the absence, or the substantial absence, of adscititious diatomic hydrogen, the reducing of the content of olefinic material within at least a fraction of the upgraded intermediate. If the pre-treatment is effected, in the absence, or the substantial absence, of adscititious diatomic hydrogen, and results in the reducing of the content of olefinic material within at least a fraction of the upgraded intermediate, then the pre-treatment is considered to be included within the step of reducing the content of olefinic material within at least a fraction of the upgraded intermediate in the absence, or the substantial absence, of adscititious diatomic hydrogen.
(a) Reducing olefinic material content without adscititious diatomic hydrogen
(a) Reducing olefinic material content without adscititious diatomic hydrogen
[0059] In one aspect, the reducing of the content of olefinic material within at least a fraction of the upgraded intermediate 114 is effected in the absence, or the substantial absence, of adscititious diatomic hydrogen (H2).
[0060] In a related aspect, the reducing of the content of olefinic material within at least a fraction of the upgraded intermediate 114 is effected within a reaction zone 120, and the ratio of the weight of adscititious diatomic hydrogen within the reaction zone 120 to the weight of olefinic material within at least a fraction of the upgraded intermediate within the reaction zone is less than 0.25, such as, for example, less than 0.1, and includes zero or substantially zero. In some embodiments, for example adscititious diatomic hydrogen is absent, or substantially absent within the reaction zone 120.
[0061] In some embodiments, for example, the reduction of the content of olefinic material within at least a fraction of the upgraded intermediate 114 is effected by alkylating one or more aromatic compounds, that are present within the at least a fraction of the upgraded intermediate, with the olefinic material. Advantageously, aromatic compounds are typically present within heavy hydrocarbon material, and are, therefore, available to effect conversion of the olefinic material such that the content of olefinic material within the at least a fraction of the upgraded intermediate is reduced. In this respect, the one or more aromatic compounds with which the olefinic material participates in the alkylation reaction is present within the heavy hydrocarbon material being upgraded. In some embodiments, for example, the one or more aromatic compounds are present within the bitumen or heavy oil from which the heavy hydrocarbon material, being upgraded, is derived.
[0062] The alkylation reaction is a reaction comprising the addition of an olefinic group to an aromatic group (e.g. the aromatic group is essentially the alkyl acceptor and would be available within the hydrocarbon feed). The olefins-aromatics alkylation reaction produces an alkylated aromatic compound and effects a reduction in olefinic material content of the upgraded intermediate. The reaction can occur without the use of an external source of olefins, di-olefins, aromatics and/or hydrogen and, without substantial loss of the volume of material as compared to the hydrocarbon feed. The difference between the volume of the reaction product and the volume of the upgraded intermediate, whose olefinic material content is being reduced, is about 0.1% to 10% v/v. Thus, the volume of the product is substantially similar to the original feed.
The exact volume decrease or increase is dependent on the olefinic material content of the upgraded intemediate and other reaction conditions. As would be appreciated, the olefinic group that takes part in the reaction may be a sole olefin, or it may be attached to and/or form part of a molecule containing at least one other functional group. Similarly, the aromatic group may he a sole aromatic hydrocarbon or may be attached to, and/or form part of a molecule that contains at least one other functional group.
The exact volume decrease or increase is dependent on the olefinic material content of the upgraded intemediate and other reaction conditions. As would be appreciated, the olefinic group that takes part in the reaction may be a sole olefin, or it may be attached to and/or form part of a molecule containing at least one other functional group. Similarly, the aromatic group may he a sole aromatic hydrocarbon or may be attached to, and/or form part of a molecule that contains at least one other functional group.
[0063] In some embodiments, for example, the alkylation is conducted within a reaction zone 120 (such as, for example, within a reactor 121) at a pressure and temperature which facilitates olefin alkylation with aromatics (olefins-aromatics alkylation).
In this respect, a fraction of the upgraded intermediate 114, produced by the cracking of the heavy hydrocarbon material-comprising feed 112 within the cracking unit operation 110, is supplied to the reaction zone 120 so as to effect olefin alkylation with aromatics. In some embodiments, for example, the temperature within the reaction zone is below about 380 C. In some embodiments, for example, the temperature within the reaction zone ranges from about 50 C to about 380 C, such as, for example, from about 150 C to about 350 C. The pressure within the reaction zone 200 is such that the reactants and resultant reaction product are disposed in a liquid, or substantially liquid, state. While the transition phase from liquid to vapour is pressure and temperature dependent, the methods disclosed herein can be carried out within a reaction zone at a pressure from about 0 to about 8 MPa, such as for example, from about 2 MPa to about 5 MPa.
In this respect, a fraction of the upgraded intermediate 114, produced by the cracking of the heavy hydrocarbon material-comprising feed 112 within the cracking unit operation 110, is supplied to the reaction zone 120 so as to effect olefin alkylation with aromatics. In some embodiments, for example, the temperature within the reaction zone is below about 380 C. In some embodiments, for example, the temperature within the reaction zone ranges from about 50 C to about 380 C, such as, for example, from about 150 C to about 350 C. The pressure within the reaction zone 200 is such that the reactants and resultant reaction product are disposed in a liquid, or substantially liquid, state. While the transition phase from liquid to vapour is pressure and temperature dependent, the methods disclosed herein can be carried out within a reaction zone at a pressure from about 0 to about 8 MPa, such as for example, from about 2 MPa to about 5 MPa.
[0064] In some embodiments, for example, the alkylation has a weight hourly space velocity of from about 0.01 to about 201-1, such as, for example, from about 0.02 to about 20h-1.
[0065] In some embodiments, for example, the alkylation is catalyzed with a catalyst material disposed within the reaction zone 120. The catalyst material includes at least one acid catalyst, and the reaction zone 120 is disposed at a temperature below around 380 C and at a pressure sufficient for the reactants and resultant product to be disposed in a liquid, or substantially liquid, state.
[0066] The catalyst material, operating conditions, and reactor are selected to allow this process to achieve desirable olefins content reduction. It is possible to select different combinations of the reactor, catalyst material and operating conditions that will convert the olefins in the feed to a sufficient degree to meet the desired operating and/or pipeline specifications objective(s). The catalyst material is selected such that the catalyst material can catalyze the reaction without being poisoned or otherwise inhibited to an extent that the reaction cannot occur. In practice, this means that if the catalyst material includes an acid catalyst, the reaction conditions are chosen such that the acid catalyst would not become irreversibly poisoned with basic compounds present in the feed. The temperature can be chosen to prevent the acid catalyst from reacting with basic compounds, or at least, from becoming irreversibly bound to the basic compounds.
[0067] Because the upgraded intermediate 114 would generally be produced as a result of an upgrading process, such as an upgrading process for the processing of heavy oils, the upgraded intermediate 114 may have species that include heteroatoms such as sulfur, nitrogen and oxygen. These types of heteroatoms can sometimes be problematic for acid catalysis because strong bonds or strong adsorption can be formed between the compounds in the feed and the acid sites on the catalyst material, thereby rendering the catalyst material neutralized or inactive. In some embodiments, for example, the acid strength of the catalyst material is selected in such a way that the compounds in the feed adsorb to form a bond with the acid sites that do not persist at the operating temperature of the catalyst material and hence the catalyst material is not rendered inactive. In some embodiments, for example, the acid strength of the catalyst material is within the range of strength characterized by temperature programmed ammonia desorption within the temperature range of 150 degrees Celsius to 350 degrees Celsius.
[0068] The catalyst material may be a heterogeneous catalyst material selected from the group consisting of supported liquid phase catalyst material, solid catalyst materials, and supported homogeneous catalyst materials.
[0069] In some embodiments, for example, the supported liquid phase catalyst material includes Bronsted acids (e.g. H2SO4, HF) and Lewis acids (e.g. BF3).
[0070] In some embodiments, for example, the heterogeneous catalyst material has a particle size and particle morphology suitable for use in a packed bed may be used. Catalyst materials that are suitable for use in packed bed reactors are known in the art. Such catalyst materials have a smaller chance of contaminating the hydrocarbon product as the catalyst material-product separation tends to be easier, allowing for simpler reactor and operating configurations. This may be advantageous when used in a field upgrading application (e.g. when the upgrading occurs on site), as such field upgrading applications are most economical when there is less complex equipment set-up.
[0071] In some embodiments, for example, the heterogeneous catalyst material includes large pore catalyst materials that can accommodate bulky olefin and the potentially bulky aromatics. The desirable pore size mainly depends on the size of the molecules being treated and the size of the materials being produced. In some embodiments, for example, the catalyst material includes a pore network with a pore diameter of greater than 0.5 nanometres. In some embodiments, for example, the pore diameter is within the range of 0.5 to ten (10) nanometres.
If the pore diameter is too small, larger molecules will not be able to travel through the pore network. On the other hand, large pore diameter, as a necessary incident, reduces the available surface area for catalyst activity, and also compromises mechanical integrity of the catalyst structure.
If the pore diameter is too small, larger molecules will not be able to travel through the pore network. On the other hand, large pore diameter, as a necessary incident, reduces the available surface area for catalyst activity, and also compromises mechanical integrity of the catalyst structure.
[0072] The catalyst material has acidic properties and, therefore, includes at least one acid catalyst. The acid catalyst may be promoted with metals, even though metal promoters are not specifically required by the processes disclosed herein. In some embodiments, for example, the acid catalyst has sufficient acid strength to catalyze the olefins-aromatics alkylation reaction, as well as an acid strength distribution to retain sufficient activity in contact with the basic compounds that are present in the upgraded intermediate. The temperature and acid catalyst are selected such that an optimal combination of olefins-aromatics alkylation activity and smallest amount of catalyst inhibition by compounds that are strongly adsorbing, or are basic in nature in the reaction product (with reduced olefins levels) is achieved.
[0073] It is known that among others, the following heterogeneous catalysts are catalytically active materials for liquid phase aromatic alkylation:
[0074] (b.1) Zeolites of the framework type FAU, like Y-zeolite (e.g. J.
Mol. Catal. A
2007, 277:1-14 and Appl. Catal. A 1999, 182:407-411);
Mol. Catal. A
2007, 277:1-14 and Appl. Catal. A 1999, 182:407-411);
[0075] (b.2) Zeolites of the framework type BEA, like Beta-zeolite (e.g.
Appl. Catal. A
1997, 153:233-241);
Appl. Catal. A
1997, 153:233-241);
[0076] (b.3) Zeolites of the framework type MOR, like mordenite (e.g. J.
Mol. Catal. A
2004, 223:305-311);
Mol. Catal. A
2004, 223:305-311);
[0077] (b.4) Zcolites of the framework type MFI, like ZSM-5 (e.g. Energy Fuels 2008, 22:1449-1455);
[0078] (b.5) Zeolites of the framework type MWW, like MCM-22 (e.g. App!.
Catal. A
2005, 292:68-75 and J. Catal. 2005, 236:45-54);
Catal. A
2005, 292:68-75 and J. Catal. 2005, 236:45-54);
[0079] (b.6) Zeolites of the framework type MTW, like ZSM-12 (e.g. Catal.
Rev.-Sci.
Eng. 2002, 44:375-421);
Rev.-Sci.
Eng. 2002, 44:375-421);
[0080] (b.7) Amorphous silica-alumina based catalysts (e.g. Ind. Eng.
Chem. Res. 2005, 44:5535-5541);
Chem. Res. 2005, 44:5535-5541);
[0081] (b.8) Natural clays, such as montmorillonite (e.g. Hely. Chim. Acta 1987, 70:577-586);
[0082] (b.9) Solid phosphoric acid (e.g. Ind. Eng. Chem. Res. 2006, 45:7399-7408 and J.
Am. Chem. Soc. 1945, 67:1060-1062);
Am. Chem. Soc. 1945, 67:1060-1062);
[0083]
(b.10) Acidic resins, such as sulfonated styrene-divinylbenzene copolymers (e.g.
React. Func. F'olym. 2000, 44:1-7).
(b.10) Acidic resins, such as sulfonated styrene-divinylbenzene copolymers (e.g.
React. Func. F'olym. 2000, 44:1-7).
[0084] The aforementioned list is by no means exhaustive. However, this process can be performed using appropriate catalysts despite the presence of contaminants typically found in industrial feed materials and which may be deleterious to acid catalysts in general. Thus, in contrast to some known methods of alkylation, the process of the present invention can be used at temperatures below about 380 degrees Celsius with a hydrocarbon feed that contains potential catalyst poisons in the feed.
[0085] In some embodiments, for example, an amorphous silica-alumina catalyst, material or a crystalline silica-alumina catalyst material, may be used in this process. The silica-alumina catalyst material may have a SiO2 to Al2O3 ratio of 0-99 wt% for example, but in some circumstances, it may be appropriate to use a catalyst having a SiO2 to Al2O3 ratio ratio of 5-75 wt%. The silica-alumina catalyst material is generally activated by calcination at a temperature in the range 500 to 600 degrees Celsius.
[0086] The choice of catalyst type is based on accessibility and performance in the presence of basic compounds, such as pyridine, which may be acid catalyst poisons. Basic nitrogen compounds are typically present in most hydrocarbon feed materials that have not been hydro-processed.
[0087] The type of catalyst material affects the selection of the reactor and operating conditions.
[0088] The operating conditions are selected to match the catalyst employed. There are a number of guiding principles in selecting appropriate operating conditions.
These are as follows:
These are as follows:
[0089] (a) The temperature range depends on the catalyst selected and the contaminants present in the hydrocarbon feed.
Olefin-aromatic alkylation reactions are favored thermodynamically by low temperature. However, the contaminants present in the hydrocarbon feed, in particular basic nitrogen species, tend to deactivate the acid sites in the catalyst and render it ineffective after a short exposure time. It has been found however, that operating the catalyst at higher temperatures the catalyst can perform the reaction without being poisoned or otherwise inhibited to an extent that the reaction cannot occur. If too high a temperature is used however the rate of olefins polymerization reactions that promote fouling and catalyst deactivation will prevail. Furthermore, the operating temperature needs to consider the rate of catalytic or thermal cracking such that the amount of olefins produced during the cracking process does not exceed the target olefins concentration at the outlet of the reactor. The maximum operating temperature is in the range of about 320 to 380 degrees Celsius for silica-alumina catalysts. The lower operating temperature limit is determined by the activity of the catalyst in the presence of basic heteroatom feed contaminants, where below this point olefin-aromatic alkylation reactions are too slow for significant olefins conversion to occur. In order to perform acid catalysis at an industrially meaningful rate, the minimum operating temperature must be sufficiently high to avoid excessive catalyst poisoning by irreversible adsorption of compounds. In the presence of nitrogen bases in the feed, the minimum operating temperature is in the range of from about 200 to 300 degrees Celsius for silica-alumina catalysts. The temperature conditions appropriate for acidic resin and SPA catalysts are from about 50 to 380 degrees Celsius, and more particularly, from about 150 to 350 degrees Celsius.
Olefin-aromatic alkylation reactions are favored thermodynamically by low temperature. However, the contaminants present in the hydrocarbon feed, in particular basic nitrogen species, tend to deactivate the acid sites in the catalyst and render it ineffective after a short exposure time. It has been found however, that operating the catalyst at higher temperatures the catalyst can perform the reaction without being poisoned or otherwise inhibited to an extent that the reaction cannot occur. If too high a temperature is used however the rate of olefins polymerization reactions that promote fouling and catalyst deactivation will prevail. Furthermore, the operating temperature needs to consider the rate of catalytic or thermal cracking such that the amount of olefins produced during the cracking process does not exceed the target olefins concentration at the outlet of the reactor. The maximum operating temperature is in the range of about 320 to 380 degrees Celsius for silica-alumina catalysts. The lower operating temperature limit is determined by the activity of the catalyst in the presence of basic heteroatom feed contaminants, where below this point olefin-aromatic alkylation reactions are too slow for significant olefins conversion to occur. In order to perform acid catalysis at an industrially meaningful rate, the minimum operating temperature must be sufficiently high to avoid excessive catalyst poisoning by irreversible adsorption of compounds. In the presence of nitrogen bases in the feed, the minimum operating temperature is in the range of from about 200 to 300 degrees Celsius for silica-alumina catalysts. The temperature conditions appropriate for acidic resin and SPA catalysts are from about 50 to 380 degrees Celsius, and more particularly, from about 150 to 350 degrees Celsius.
[0090] (b) The pressure should be sufficient to keep most of the hydrocarbon feed material in the liquid phase at the operating temperature. This limits the amount of light olefins that may be present in the vapour phase and that may pass through the reactor unconverted. A
typical operating pressure is in the range 0-8 MPa. For operating temperatures in the range of about 300 to 380 degrees Celsius, which is typical for silica-alumina catalysts, the pressure range is about 2-5 MPa.
typical operating pressure is in the range 0-8 MPa. For operating temperatures in the range of about 300 to 380 degrees Celsius, which is typical for silica-alumina catalysts, the pressure range is about 2-5 MPa.
[0091] (c) The flow rate is determined by the olefins conversion requirements for the selected combination of catalyst and operating conditions. The range of weight hourly space velocity (WHSV) is 0.01 to 20 111. The WHSV range is generally in the range of 0.02 to 2 111.
Optimum conditions for olefins conversion are adjusted to meet final product specifications and may be determined empirically, depending on changes in feed composition, selected catalyst types (i.e. one or more catalyst types used in conjunction) and aging, number of reactor beds (i.e.
single vs. multiple with interstage cooling) and other unit constraints.
Process operating conditions can be optimized using strategies known in the art.
Optimum conditions for olefins conversion are adjusted to meet final product specifications and may be determined empirically, depending on changes in feed composition, selected catalyst types (i.e. one or more catalyst types used in conjunction) and aging, number of reactor beds (i.e.
single vs. multiple with interstage cooling) and other unit constraints.
Process operating conditions can be optimized using strategies known in the art.
[0092] (d) Depending on the catalyst, it may be beneficial to add water, or compounds that may produce water, such as alcohols, to the feed.
[0093] The process may be conducted in a conventional packed bed reactor.
The catalyst is contained and retained in a process vessel that is designed according to principles known in the art. In one embodiment, a single adiabatic packed bed (fixed bed) reactor is employed. The use of multiple catalyst beds within the reactor, the use of inter-bed quench feed stream, the use of more than one reactor and product recycling may all be considered.
The catalyst is contained and retained in a process vessel that is designed according to principles known in the art. In one embodiment, a single adiabatic packed bed (fixed bed) reactor is employed. The use of multiple catalyst beds within the reactor, the use of inter-bed quench feed stream, the use of more than one reactor and product recycling may all be considered.
[0094] The adiabatic temperature increase should be controlled. Aromatic alkylation with olefins and olefins dimerization (a possible side-reaction) are both exothermic.
Implementation of heat management strategies in the reactor design is known in the art.
Implementation of heat management strategies in the reactor design is known in the art.
[0095] The reactor may be operated either in down flow or up flow configuration. The operation of the reactor in an up flow configuration with a liquid filled catalyst bed improves heat transfer and catalyst wetting, and maximizes liquid holdup. This configuration also facilitates removal of heavy products (gums) typical of di-olefins reactions from the catalyst by dissolving it in the liquid product, as described in patents related to the buildup of fouling agents (e.g. U.S. Patent No. 4,137,274). The operation of the reactor in a down flow configuration facilitates maintenance and catalyst replacement, since the contaminated portion of the catalyst will be concentrated at the top of the reactor where it is easier to access and replace.
[0096] From an operational point of view, the reactor may further be designed for easy maintenance and catalyst replacement in the field.
[0097] In some embodiments, for example, the olefinic material may include one or more cyclo-olefins, and the reducing of the content of olefinic material within the at least a fraction of the upgraded intermediate is effected by dehydrogenation of the one or more cyclo-olefins. The dehydrogenation of a cyclo-olefin produces an aromatic. In some embodiments, for example, the cyclo-olefin includes one or more heteroatoms In some embodiments, for example, the dehydrogenation is effected within a reaction zone 120 disposed at a temperature of from about 100 degrees Celsius to about 300 degrees Celsius, such as, for example, from about 125 degrees Celsius to about 275 degrees Celsius. In some embodiments, for example, the cyclo-olefin is a five-membered ring or a six-membered ring, and may include one or more heteroatoms.
[0098] In some embodiments, for example, the reaction zone 120 includes a catalyst material (including a supported catalyst material) that is active for hydrogenation-dehydrogenation, and includes catalysts that are active for hydrogenation-dehydrogenation in the presence of heteroatom-containing cyclo-olefins (e.g. Ni/A1203, Ni/SiO2, NiMo/A1203, CoMo/A1203, FeS, or MoS2).
[0099]
Advantageously, as a result of the dehydrogenation, some diatomic hydrogen is produced, which can be exploited to effect hydrogenation of di-olefins to produce mono-olefins.
This has downstream benefits related to the removal of the di-olefins. There are also immediate benefits in that the consumption of the produced diatomic hydrogen favours the equilibrium towards dehydrogenation of the cyclo-olefins to aromatics.
Advantageously, as a result of the dehydrogenation, some diatomic hydrogen is produced, which can be exploited to effect hydrogenation of di-olefins to produce mono-olefins.
This has downstream benefits related to the removal of the di-olefins. There are also immediate benefits in that the consumption of the produced diatomic hydrogen favours the equilibrium towards dehydrogenation of the cyclo-olefins to aromatics.
[00100] In some embodiments, for example, the catalyst material for the dehydrogenation includes large pore catalyst materials that can accommodate bulky olefin and the potentially bulky aromatics. The desirable pore size mainly depends on the size of the molecules being treated and the size of the materials being produced. In some embodiments, for example, the catalyst material includes a pore network with a pore diameter of greater than 0.5 nanometres. In some embodiments, for example, the pore diameter is within the range of 0.5 to ten (10) nanometres. If the pore diameter is too small, larger molecules will not be able to travel through the pore network. On the other hand, large pore diameter, as a necessary incident, reduces the available surface area for catalyst activity, and also compromises mechanical integrity of the catalyst structure.
[00101] In some embodiments, for example, the olefinic material includes one or more cyclo-olefins, and the reducing of the content of the olefinic material within the at least a fraction of the upgraded intermediate is effected by hydrogen disproportionation of the one or more cyclo-olefins. The hydrogen disproportionation converts the one or more cyclo-olefins to cyclo-paraffin structures or aromatic structures. In some embodiments, for example, the hydrogen disproportionation is effected within the reaction zone 111. In some embodiments, for example, to effect the hydrogen disproportionation, the temperature within the reaction zone 111 is at least 300 degrees Celsius.
[00102] Referring to Figure 2, in some embodiments, for example, the heavy hydrocarbon material-comprising feed, that is the subject of the treating that includes cracking of the heavy hydrocarbon material-comprising feed, includes at least a fraction of a heavier hydrocarbon material-comprising fraction 134A that has been, along with a lighter hydrocarbon material-comprising fraction 134B, separated from a feed material 150. In this respect, a feed material 150 is provided, and the feed material 150 is separated (for example, by a separator 130, such as a fractionator) into at least the heavier hydrocarbon material-comprising fraction 134A and the lighter hydrocarbon material-comprising fraction 134B. The heavier hydrocarbon material-comprising fraction 134A has a weight average molecular weight that is greater than that of the lighter hydrocarbon material-comprising fraction 134B. In some embodiments, for example, the separation is effected based on differences in volatilities between the heavier hydrocarbon material-comprising fraction 134A and the lighter hydrocarbon material-comprising fraction 134B. Suitable separation processes that are based on differences in volatilities between the heavier hydrocarbon material-comprising fraction 134A and the lighter hydrocarbon material-comprising fraction 134B include stripping and distillation. In some embodiments, for example, at a predetermined pressure and temperature at which the separation is effected, the heavier hydrocarbon material-comprising fraction 134A has a higher boiling point than the lighter hydrocarbon material-comprising fraction 134B. In some embodiments, for example, at a predetermined temperature at which the separation is effected, the heavier hydrocarbon material-comprising fraction 134A has a lower vapour pressure than the lighter hydrocarbon material-comprising fraction 134B. In some embodiments, for example, at a predetermined temperature at which the separation is effected, the vapour pressure of the heavier hydrocarbon material-comprising fraction 134A is less than 90% (such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the lighter hydrocarbon material-comprising fraction 134B. In this respect, it is recognized that the additional incremental cost in configuring a cracking unit operation 110 for effecting the cracking of lighter hydrocarbon material may not be justified, having regard to the fact that, relative to heavier hydrocarbon material, cracking of lighter hydrocarbon material is not pronounced and does not significantly contribute to the production of a hydrocarbon material having a pipeline specification Instead of being processed through the cracking unit operation 110, the lighter hydrocarbon material-comprising fraction 134B is combined with at least a fraction of the olefinic material content-reduced product 115, such that the upgraded product 200 is produced.
[00103] Referring to Figure 3, the reducing of the content of olefinic material within the upgraded intermediate 114 is effected by separating at least a fraction of the upgraded intermediate 114 into at least an olefin-comprising treatment fraction 132 and a treatment by-pass fraction 134. In some embodiments, for example, the separating is effected within a separator 130, such as a fractionator. In some embodiments, for example, the separation is effected based on differences in volatilities between the olefin-comprising treatment fraction 132 and the treatment by-pass fraction 134. Suitable separation processes that are based on differences in volatilities between the olefin-comprising treatment fraction 132 and the treatment by-pass fraction 134 include stripping and distillation. In some embodiments, for example, at a predetermined temperature at which the separation is effected, the olefin-comprising treatment fraction 132 has a higher vapour pressure than the treatment by-pass fraction 134. In some embodiments, for example, at a predetermined temperature at which the separation is effected, the vapour pressure of the treatment by-pass fraction 134 is less than 90%
(such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the olefin-comprising treatment fraction 132. The content of olefinic material within the olefin-comprising treatment fraction 132 is reduced such that an olefin depleted intermediate 136 is produced. In this respect, in some embodiments, for example, the reducing of the content of olefinic material within the olefin-comprising treatment fraction 132 includes effecting conversion of the olefinic material within the olefin-comprising treatment fraction 132, such as by the processes effected within the reaction zone 120, as explained above, including, in particular, those which are carried out in the absence, or the substantial absence, of adscititious diatomic hydrogen. The treatment by-pass fraction 134 may then be combined with at least the olefin-depleted intermediate 136 to produce the olefinic material content-reduced product 115, which then may be produced as at least a part of the upgraded product 200.
(such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the olefin-comprising treatment fraction 132. The content of olefinic material within the olefin-comprising treatment fraction 132 is reduced such that an olefin depleted intermediate 136 is produced. In this respect, in some embodiments, for example, the reducing of the content of olefinic material within the olefin-comprising treatment fraction 132 includes effecting conversion of the olefinic material within the olefin-comprising treatment fraction 132, such as by the processes effected within the reaction zone 120, as explained above, including, in particular, those which are carried out in the absence, or the substantial absence, of adscititious diatomic hydrogen. The treatment by-pass fraction 134 may then be combined with at least the olefin-depleted intermediate 136 to produce the olefinic material content-reduced product 115, which then may be produced as at least a part of the upgraded product 200.
[00104] Referring to Figure 4, in some of these embodiments, for example, the upgraded intermediate 114 may not have been sufficiently cracked by a single pass through the cracking unit operation 110, such that excessive amounts of heavy hydrocarbon material remain present within the upgraded intermediate 114. It may be desirable, therefore, to recycle a fraction of the upgraded intermediate 114 through the cracking unit operation 110 so as to further reduce the content of heavy hydrocarbon material within the upgraded intermediate 114. In this respect, instead of combining the entirety of the treatment by-pass fraction 134 with the olefin-depleted intermediate 136 to effect production of the upgraded product 200, the treatment by-pass fraction 134 is separated into at least fractions 138A, 138B, with the fraction 138B
being combined with the olefin-depleted intermediate, and the fraction 138A being supplied to the cracking unit operation. In this respect, the heavy hydrocarbon material-comprising feed includes a combination of the heavy hydrocarbon material-comprising supply stream 150 and the fraction 138A.
being combined with the olefin-depleted intermediate, and the fraction 138A being supplied to the cracking unit operation. In this respect, the heavy hydrocarbon material-comprising feed includes a combination of the heavy hydrocarbon material-comprising supply stream 150 and the fraction 138A.
[00105] By reducing the content of olefinic material, without requiring any amount, or any substantial amount, of diatomic hydrogen supplied from an external source, cost and complexities of producing and supplying such diatomic hydrogen are mitigated.
In particular, most methods to reduce olefinic material content currently involve expensive hydro-processing infrastructures such as hydrotreaters and associated equipment, which require an extraneous source of hydrogen. Also, many methods to reduce the olefinic material content of a hydrocarbon stream require the addition of extraneous components such as diatomic hydrogen and/or another hydrocarbon. For example, when upgrading is employed to treat a feed material, separate equipment is needed for diatomic hydrogen generation to enable hydro-processing. In addition to the required hydro-processing unit, units needed to produce diatomic hydrogen (e.g. steam methane reforming) increase the complexity and cost of the oil upgrading facility and increase the carbon footprint of the overall process.
(b) Separating olefinic material from the upgraded intermediate prior to converting the olefinic material, and then separating lighter hydrocarbon material from the residual upgraded intermediate prior to cracking
In particular, most methods to reduce olefinic material content currently involve expensive hydro-processing infrastructures such as hydrotreaters and associated equipment, which require an extraneous source of hydrogen. Also, many methods to reduce the olefinic material content of a hydrocarbon stream require the addition of extraneous components such as diatomic hydrogen and/or another hydrocarbon. For example, when upgrading is employed to treat a feed material, separate equipment is needed for diatomic hydrogen generation to enable hydro-processing. In addition to the required hydro-processing unit, units needed to produce diatomic hydrogen (e.g. steam methane reforming) increase the complexity and cost of the oil upgrading facility and increase the carbon footprint of the overall process.
(b) Separating olefinic material from the upgraded intermediate prior to converting the olefinic material, and then separating lighter hydrocarbon material from the residual upgraded intermediate prior to cracking
[00106] In another aspect, because the upgraded intermediate 114 may not have been sufficiently cracked by a single pass through the cracking unit operation 110, such that excessive amounts of heavy hydrocarbon material remain present within the upgraded intermediate 114, it may be desirable to recycle at least a fraction of the upgraded intermediate 114 through the cracking unit operation 110. This may be desirable if the upgraded intermediate 114 contains cyclo-olefins. The recycling of at least a fraction of the upgraded intermediate 114 may be effected by separating the treatment by-pass fraction 134 from the upgraded intermediate 114, and then supplying a fraction 138A of the treatment by-pass fraction 134 to the reaction zone 111 of the cracking unit operation 110 (see, for example, Figure 4). However, the fraction 134 may include not an insubstantial content of lighter hydrocarbon material, whose recycling through the reaction zone 111 may not be justifiable, as it is recognized that additional incremental cost in configuring the cracking unit operation 110 for effecting the cracking of recycled lighter hydrocarbon material may not be justified, having regard to the fact that, relative to heavier hydrocarbon material, cracking of lighter hydrocarbon material is not pronounced and does not significantly contribute to the production of a hydrocarbon material having a pipeline specification. It is, therefore, desirable to separate, from the treatment by-pass fraction 134, at least a heavier hydrocarbon material-comprising fraction 134A and a lighter hydrocarbon material-comprising fraction 134B, and recycle only at least some material (i.e. fraction 138A) of the heavier hydrocarbon material-comprising fraction 134A through the cracking unit operation 110, as opposed to simply recycling the entirety of the treatment by-pass fraction 134 (including the lighter hydrocarbon material-comprising fraction) through the reaction zone 111.
Advantageously, where the upgraded intermediate 114 includes cyclo-olefins, cyclo-olefins being recycled within the fraction 138A may undergo hydrogen disproportionation within the reaction zone 111, thereby further reducing the olefinic content of the upgraded product 200 being produced.
Advantageously, where the upgraded intermediate 114 includes cyclo-olefins, cyclo-olefins being recycled within the fraction 138A may undergo hydrogen disproportionation within the reaction zone 111, thereby further reducing the olefinic content of the upgraded product 200 being produced.
[00107] In this respect, and referring to Figure 5, the process includes supplying a heavy hydrocarbon material-comprising supply stream 150 to the cracking unit operation such that the intermediate upgraded product 114 is produced. At least a fraction of the intermediate upgraded product 114 is separated into a olefin-comprising treatment fraction 132 and a treatment by-pass fraction 134. In some embodiments, for example, the separating is effected within a separator 130, such as a fractionator. In some embodiments, for example, the separation is effected based on differences in volatilities between the olefin-comprising treatment fraction 132 and the treatment by-pass fraction 134. Suitable separation processes that are based on differences in volatilities between the olefin-comprising treatment fraction 132 and the treatment by-pass fraction 134 include stripping and distillation. In some embodiments, for example, at a predetermined temperature at which the separation is effected, the olefin-comprising treatment fraction 132 has a higher vapour pressure than the treatment by-pass fraction 134. In some embodiments, for example, at a predetermined temperature at which the separation is effected, the vapour pressure of the treatment by-pass fraction 134 is less than 90%
(such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the olefin-comprising treatment fraction 132. In some embodiments, for example, at a pressure of one (1) atmosphere, the boiling point range of the olefin-comprising treatment fraction is between 25 degrees Celsius and 365 degrees Celsius, such as, for example, between 25 degrees Celsius and 200 degrees Celsius, such as, for example, 25 degrees Celsius and 100 degrees Celsius. The content of olefinic material within the olefin-comprising treatment fraction is reduced such that an olefin-depleted intermediate 136 is produced. In this respect, in some embodiments, for example, the reducing of the content of olefinic material within the olefin-comprising treatment fraction 132 includes effecting conversion of the olefinic material within the olefin-comprising treatment fraction 132, such as by the processes effected within the reaction zone 120, as explained above, including, in particular, those which are carried out in the absence, or the substantial absence, of adscititious diatomic hydrogen.
(such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the olefin-comprising treatment fraction 132. In some embodiments, for example, at a pressure of one (1) atmosphere, the boiling point range of the olefin-comprising treatment fraction is between 25 degrees Celsius and 365 degrees Celsius, such as, for example, between 25 degrees Celsius and 200 degrees Celsius, such as, for example, 25 degrees Celsius and 100 degrees Celsius. The content of olefinic material within the olefin-comprising treatment fraction is reduced such that an olefin-depleted intermediate 136 is produced. In this respect, in some embodiments, for example, the reducing of the content of olefinic material within the olefin-comprising treatment fraction 132 includes effecting conversion of the olefinic material within the olefin-comprising treatment fraction 132, such as by the processes effected within the reaction zone 120, as explained above, including, in particular, those which are carried out in the absence, or the substantial absence, of adscititious diatomic hydrogen.
[00108] The treatment by-pass fraction 134 is then separated (such as by the separator 130) into at least a heavier hydrocarbon material-comprising fraction 134A and a lighter hydrocarbon material-comprising fraction 134B. In some embodiments, for example, the separation is effected based on differences in volatilities between the heavier hydrocarbon material-comprising fraction 134A and the lighter hydrocarbon material-comprising fraction 134B. Suitable separation processes that are based on differences in volatilities between the heavier hydrocarbon material-comprising fraction 134A and the lighter hydrocarbon material-comprising fraction 134B include stripping and distillation. In some embodiments, for example, at a predetermined temperature at which the separation is effected, the heavier hydrocarbon material-comprising fraction 134A has a lower vapour pressure than that of the lighter hydrocarbon material-comprising fraction 134B. In some embodiments, for example, at a predetermined temperature at which the separation is effected, the vapour pressure of the heavier hydrocarbon material-comprising fraction 134A is less than 90% (such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the lighter hydrocarbon material-comprising fraction 134B.
[00109] In some embodiments, for example, where the above-described separations are effected based on differences in volatilities, as a necessary incident, the lighter hydrocarbon material-comprising fraction 134B has a lower vapour pressure than that of the olefin-comprising treatment fraction 132. In some embodiments, for example, at a predetermined temperature at which the separation is effected, the vapour pressure of the lighter hydrocarbon material-comprising fraction 134B is less than 90% (such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the olefin-comprising treatment fraction 132.
In some embodiments, for example, at a pressure of one (1) atmosphere, the boiling point range of the olefin-comprising treatment fraction 132 is between 25 degrees Celsius and 365 degrees Celsius (such as, for example, between 25 degrees Celsius and 200 degrees Celsius, such as, for example, 25 degrees Celsius and 100 degrees Celsius), and the boiling point range of the lighter hydrocarbon material-comprising fraction 134B is between 80 degrees Celsius and 450 degrees Celsius (such as, for example, 200 degrees Celsius and 450 degrees Celsius, such as, for example, between 360 degrees Celsius and 450 degrees Celsius). In some of these embodiments, for example, the lighter hydrocarbon material-comprising fraction 134B
includes hydrocarbon material that is equivalent to light vacuum gas oil.
In some embodiments, for example, at a pressure of one (1) atmosphere, the boiling point range of the olefin-comprising treatment fraction 132 is between 25 degrees Celsius and 365 degrees Celsius (such as, for example, between 25 degrees Celsius and 200 degrees Celsius, such as, for example, 25 degrees Celsius and 100 degrees Celsius), and the boiling point range of the lighter hydrocarbon material-comprising fraction 134B is between 80 degrees Celsius and 450 degrees Celsius (such as, for example, 200 degrees Celsius and 450 degrees Celsius, such as, for example, between 360 degrees Celsius and 450 degrees Celsius). In some of these embodiments, for example, the lighter hydrocarbon material-comprising fraction 134B
includes hydrocarbon material that is equivalent to light vacuum gas oil.
[00110] In a related aspect, the treating includes, separating at least a fraction of the upgraded intermediate into at least an olefin-comprising treatment fraction 132, a light hydrocarbon material-comprising fraction 134B, and a heavy hydrocarbon material-comprising fraction 134A. In some embodiments, for example, the separating is effected within a separator 130, such as a fractionator. In some embodiments, for example, the separation is effected based on differences in volatilities between the olefin-comprising treatment fraction 132, the light hydrocarbon material-comprising fraction 134B, and the heavy hydrocarbon material-comprising fraction 134A. Suitable separation processes that are based on differences in volatilities between these components include stripping and distillation. In some embodiments, for example, at a predetermined temperature at which the separation of the olefin-comprising treatment fraction 132 is effected, the heavier hydrocarbon material-comprising fraction 134A has a lower vapour pressure than that of the lighter hydrocarbon material-comprising fraction 134B, and the lighter hydrocarbon material-comprising fraction 134B has a lower vapour pressure than that of the olefin-comprising treatment fraction 132. In some embodiments, for example, at a predetermined temperature at which the separation is effected, the vapour pressure of the heavier hydrocarbon material-comprising fraction 134A is less than 90% (such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the lighter hydrocarbon material-comprising fraction 134B, and the vapour pressure of the lighter hydrocarbon material-comprising fraction 134B is less than 90% (such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the olefin-comprising treatment fraction 132.
[00111] A
fraction 138A of the produced heavier hydrocarbon material-comprising fraction 134A may be recycled through the cracking unit operation 110. With respect to the produced lighter hydrocarbon material-comprising fraction 134B, instead of being processed through the cracking unit operation 110, the lighter hydrocarbon material-comprising fraction 134B may be combined with at least the produced olefin-depleted intermediate 136 (and, in some embodiments, for example, a fraction 138B of the heavier hydrocarbon material-comprising fraction 134A) to create an olefinic material content-reduced product 115, which may then be produced as the upgraded product 200.
fraction 138A of the produced heavier hydrocarbon material-comprising fraction 134A may be recycled through the cracking unit operation 110. With respect to the produced lighter hydrocarbon material-comprising fraction 134B, instead of being processed through the cracking unit operation 110, the lighter hydrocarbon material-comprising fraction 134B may be combined with at least the produced olefin-depleted intermediate 136 (and, in some embodiments, for example, a fraction 138B of the heavier hydrocarbon material-comprising fraction 134A) to create an olefinic material content-reduced product 115, which may then be produced as the upgraded product 200.
[00112]
Referring to Figure 5A, instead of supplying the heavy hydrocarbon material-comprising supply stream 150 directly to the cracking unit operation 110, the heavy hydrocarbon material-comprising supply stream 150 may be combined with the upgraded intermediate 114 to form the feed to the separator 130.
(c) Removing light olefinic material from the upgraded intermediate
Referring to Figure 5A, instead of supplying the heavy hydrocarbon material-comprising supply stream 150 directly to the cracking unit operation 110, the heavy hydrocarbon material-comprising supply stream 150 may be combined with the upgraded intermediate 114 to form the feed to the separator 130.
(c) Removing light olefinic material from the upgraded intermediate
[00113] Referring to Figure 6, in another aspect, the reducing of the content of olefinic material within the upgraded intermediate 114 is defined by a reduction in the content of light olefinic material within at least a fraction of the upgraded intermediate 114 such that the content of light olefinic material within the olefinic material content-reduced product is less than the content of light olefinic material within the at least a fraction of the upgraded intermediate 114.
In this respect, the ratio of the weight of light olefinic material within the olefinic material content-reduced product to the total weight of the olefinic material content-reduced product is less than the ratio of the weight of light olefinic material within the upgraded intermediate 114 to the total weight of the upgraded intermediate 114.
In this respect, the ratio of the weight of light olefinic material within the olefinic material content-reduced product to the total weight of the olefinic material content-reduced product is less than the ratio of the weight of light olefinic material within the upgraded intermediate 114 to the total weight of the upgraded intermediate 114.
[00114] It is recognized that, in some embodiments, it is not necessary to reduce the content of all of the olefinic material, as the presence of some of the olefinic material may not necessarily be as detrimental to the further processing of the upgraded product 200, including the olefinic material content-reduced product, as other fractions of the olefinic material. In some embodiments, for example, light olefinic material may be a more significant contributor to the problems associated with olefinic material, generally (and as above-described), relative to other kinds of olefinic material. In this respect, in some of these embodiments, for example, it may be sufficient to effect a reduction of the content of at least the light olefinic material.
[00115] By not making it a requirement to effect a reduction in the content of all of the olefinic material, and just a portion of the olefinic material (and, specifically, the light olefinic material portion), costs and complexities relating to the processing of the upgraded intermediate 114 are reduced.
[00116] In some of these embodiments, for example, the reducing of the content of light olefinic material within the at least a fraction of the upgraded intermediate 114 includes effecting conversion of the light olefinic material within at least a fraction of the upgraded intermediate 114, such as by the processes effected within the reaction zone 120, as explained above with respect to olefinic material generally, including, in particular, those processes which are carried out in the absence, or the substantial absence, of adscititious diatomic hydrogen.
[00117] Referring to Figure 7, in some of these embodiments, for example, the reducing of the content of olefinic material within the upgraded intermediate 114 is effected by separating at least a fraction of the upgraded intermediate 114 into at least a lighter olefin-comprising fraction 142 and a heavier fraction 144, and then effecting a reduction in the content of light olefinic material within the light olefin-comprising fraction 142 (such as by the processes effected within the reaction zone 120, as explained above with respect to olefinic material generally) such that a light olefin-depleted intermediate 146 is produced, and then combining the heavier fraction 144 with at least the light olefin-depleted intermediate 146 to produce a light olefinic material content-reduced product. In this respect, the ratio of the weight of light olefinic material within the lighter olefin-comprising fraction 142 to the total weight of the lighter olefin-comprising fraction 142 is greater than the ratio of the weight of light olefinic material within the heavier fraction 144 to the total weight of the heavier fraction 144. An upgraded product 200 may be produced including the light olefin content material-reduced product In some embodiments, for example, the separation is effected within a separator 130, such as a fractionator. In some embodiments, for example, the separation is effected based on differences in volatilities between the lighter olefin-comprising fraction 142 and the heavier fraction 144.
Suitable separation processes that are based on differences in volatilities of the lighter olefin-comprising fraction 142 and the heavier fraction 144 include stripping and distillation. In some embodiments, for example, at a predetermined temperature at which the separation is effected, the lighter olefin-comprising fraction 142 has a higher vapour pressure than the heavier fraction 144. In some embodiments, for example, at a predetermined temperature at which the separation is effected, the vapour pressure of the heavier fraction 144 is less than 90% (such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the lighter olefin-comprising fraction 142.
Suitable separation processes that are based on differences in volatilities of the lighter olefin-comprising fraction 142 and the heavier fraction 144 include stripping and distillation. In some embodiments, for example, at a predetermined temperature at which the separation is effected, the lighter olefin-comprising fraction 142 has a higher vapour pressure than the heavier fraction 144. In some embodiments, for example, at a predetermined temperature at which the separation is effected, the vapour pressure of the heavier fraction 144 is less than 90% (such as, for example, less than 80%, such as, for example, less than 70%, such as, for example, less than 60%, such as, for example, less than 50%) of the vapour pressure of the lighter olefin-comprising fraction 142.
[00118] Referring to Figure 8, in a related aspect, the reducing of the content of olefinic material within the upgraded intermediate 114 is effected by separating at least a fraction of the upgraded intermediate 114 into a more volatile fraction 162 and a less volatile fraction 164, wherein the more volatile fraction 164 has a boiling point range, at a pressure of one (1) atmosphere, of between 25 degrees Celsius and 200 degrees Celsius, such boiling point range being characteristic of a lighter olefinic material. A reduction in the content of olefinic material within the more volatile fraction 164 (such as by the processes effected within the reaction zone 120, as explained above with respect to olefinic material generally) such that an olefin-depleted intermediate 166 is produced, and then combining at least a fraction of the less volatile fraction 164 with at least the olefin-depleted intermediate 166 to produce an olefinic material content-reduced product 115. An upgraded product 200 may be produced including the olefin content material-reduced product 115. In some embodiments, for example, the separation is effected within a separator 130, such as a fractionator. In some embodiments, for example, the separation is effected based on differences in volatilities between the more volatile fraction and the less volatile fraction. Suitable separation processes that are based on differences in volatilities of the more volatile fraction and the less volatile fraction include stripping and distillation.
(d) Cracking in the presence of a hydrogen donor material
(d) Cracking in the presence of a hydrogen donor material
[00119]
Referring to Figure 9, in some embodiments, for example, the treating of the heavy hydrocarbon material-comprising feed 112 includes cracking the heavy hydrocarbon material-comprising feed within the reaction zone 111, of the cracking unit operation 110, in the presence of a hydrogen donor material 108. In some embodiments, for example, the hydrogen donor material 108 is another hydrocarbon material-comprising feed that has hydrogen transfer or hydrogen donor properties. The treating is such that an upgraded product 200 is produced.
The presence of the hydrogen donor material 108 discourages the production of olefinic material, and thereby renders the upgraded product 200 of a quality that meets at least one pipeline specification or come closer to meeting at least one pipeline specification.
In some embodiments, for example, the hydrogen donor material 108 is supplied to the reaction zone 111.
Referring to Figure 9, in some embodiments, for example, the treating of the heavy hydrocarbon material-comprising feed 112 includes cracking the heavy hydrocarbon material-comprising feed within the reaction zone 111, of the cracking unit operation 110, in the presence of a hydrogen donor material 108. In some embodiments, for example, the hydrogen donor material 108 is another hydrocarbon material-comprising feed that has hydrogen transfer or hydrogen donor properties. The treating is such that an upgraded product 200 is produced.
The presence of the hydrogen donor material 108 discourages the production of olefinic material, and thereby renders the upgraded product 200 of a quality that meets at least one pipeline specification or come closer to meeting at least one pipeline specification.
In some embodiments, for example, the hydrogen donor material 108 is supplied to the reaction zone 111.
[00120] In some embodiments, for example, the ratio of weight of hydrogen donor material supplied to the reaction zone 111 to weight of heavy hydrocarbon material is at least 1:20. In some of these embodiments, for example, the ratio is at least 1:5, such as, for example, at least 1:4. In some embodiments, for example, the ratio is between 1:20 and 4:1, such as, for example, between 1:6 and 1:3.
[00121] In some embodiments, for example, the hydrogen donor material includes synthetic crude oil.
[00122] In some embodiments, for example, the hydrogen donor material includes (or, in some embodiments, for example, is defined by) one or more cycloalkanes, one or more naptheno-aromatics, or one or more cycloalkanes and one or more naptheno-aromatics. The cycloalkane may be substituted or unsubstituted. The naphtheno-aromatic may be substituted or unsubstituted. In some embodiments, for example, the hydrogen donor material includes a hydrocarbon including a six-membered ring structure that is attached to an aromatic. In some embodiments, for example, the hydrogen donor material is substantially free of five-membered ring structures that cannot form aromatic rings as a consequence of their hydrogen donor activity.
[00123] In some embodiments, for example, the hydrogen donor material includes tetralin (i.e. 1,2,3 ,4-tetrahydrohaphthalene).
[00124] The cracking of the heavy hydrocarbon material-comprising feed in the presence of a hydrogen donor material, that includes a cycloalkane (such as a five-membered cyclo-alkane, and also, in some embodiments, and to some extent, a six-membered cyclo-alkane) or a naphtheno-aromatic, produces an intermediate product 114 including a cyclo-olefin material that includes one or more cyclo-olefins. In such embodiments, for example, the treating further includes effective a reactive process, such that the intermediate product 114 participates within the reactive process as a reactant and is consumed within the reactive process. The reactive process includes dehydogenation of an olefinic material within a reaction zone 170 (such as within a reactor 172) to produce an olefinic material content-reduced product 115. In some embodiments, for example the treating includes dehydrogenating at least a fraction of the cyclo-olefin material of the intermediate product 114. In this respect, the reactive process is effected within the reaction zone 170 disposed at a temperature that is thermodynamically more favourable to the dehydrogenation of cyclo-olefins than to the dehydrogenation of cyclo-alkanes.
Where the cyclo-olefin material is cyclohexene, the temperature of the reaction zone is from about 125 degrees Celsius and 275 degrees Celsius. Within this temperature range, it is believed that it is thermodynamically favourable to dehydrogenate cyclohexene and thermodynamically unfavourable to dehydrogenate cyclohexane. In some embodiments, for example, a suitable catalyst material, that is active for dehydrogenation and hydrogenation, is disposed within the reaction zone 170. In some embodiments, for example, the catalyst material may include a supported metal catalyst that is active for dehydrogenation and hydrogenation in the presence of heteroatom-comprising compounds (e.g. Ni/A1203, Ni/SiO2, NiMo/A1203, CoMo/A1203). In some embodiments, for example, the catalyst material includes a dispersed catalyst.
(e) Upgraded product
Where the cyclo-olefin material is cyclohexene, the temperature of the reaction zone is from about 125 degrees Celsius and 275 degrees Celsius. Within this temperature range, it is believed that it is thermodynamically favourable to dehydrogenate cyclohexene and thermodynamically unfavourable to dehydrogenate cyclohexane. In some embodiments, for example, a suitable catalyst material, that is active for dehydrogenation and hydrogenation, is disposed within the reaction zone 170. In some embodiments, for example, the catalyst material may include a supported metal catalyst that is active for dehydrogenation and hydrogenation in the presence of heteroatom-comprising compounds (e.g. Ni/A1203, Ni/SiO2, NiMo/A1203, CoMo/A1203). In some embodiments, for example, the catalyst material includes a dispersed catalyst.
(e) Upgraded product
[00125] In some embodiments, for example, an upgraded product 200 is produced and includes the olefinic material content-reduced product 115. The upgraded product 200 meets at least one pipelines specification. In this respect, in some embodiments, for example, the upgraded product 200 is supplied to a pipeline for transporting to a refinery.
In some of these embodiments, for example, the process also includes transporting the upgraded product 200, via the pipeleine, to the refinery.
(fi Other exemplary embodiments
In some of these embodiments, for example, the process also includes transporting the upgraded product 200, via the pipeleine, to the refinery.
(fi Other exemplary embodiments
[00126] It is understood that any two or more of the above-described aspects, and any one of their respective exemplary embodiments, may be combined to create other embodiments of the present disclosure, such as the embodiment illustrated in Figures 10, 11, and 12.
[00127] Each one of illustrate feed material 150 that is derived, in part, from a deasphalting process. In this respect, the feed material 150 includes a deasphalted heavy hydrocarbon-comprising material.
[00128] Referring to Figures 10, 11, and 12, an asphaltene-comprising heavy hydrocarbon-comprising material 300 is supplied to a separator 302 to effect phase separation of gaseous material 304 and aqueous material 306 from the raw asphaltene-comprising heavy hydrocarbon-comprising material such that a dewatered/degassed asphaltene-comprising heavy hydrocarbon-comprising material 308 is produced. The material 308 is admixed with solvent material 310, 312 in mixers 314, 316 to produce a mixture 318.
[00129] The mixture 318 is separated, within a separator 320, into at least an asphaltene-depleted heavy hydrocarbon-comprising material fraction 322 and an asphaltene-enriched material fraction 324. The asphaltene content of the asphaltene-depleted heavy hydrocarbon-comprising fraction 322 is less than the asphaltene content of the mixture 318. The asphaltene-enriched material fraction 324, being denser than the asphaltene-depleted heavy hydrocarbon-comprising material fraction 322, is recovered as an underflow product, and the asphaltene-depleted heavy hydrocarbon-comprising material fraction is recovered as an overhead product in the form of the deasphalted heavy hydrocarbon-comprising material which defines the feed material 150.
[00130] In some embodiments, for example, the asphaltene-enriched material fraction 324 is admixed with solvent material 326 within a mixer 328 and then separated within a separator 330 into an overflow material mixture 332, including deasphalted heavy hydrocarbon-comprising material and solvent material, and an underflow asphaltene-enriched material fraction 334.
[00131] The material 332 is recycled to upstream of the separator 320 to increase recovery of the deasphalted heavy hydrocarbon-comprising material fraction.
[00132] The underflow asphaltene-enriched material fraction 334 is supplied to a separator 336, such as a fractionator, to effect separation of the asphaltene-enriched material fraction 334 into a gaseous solvent-enriched material fraction 338 and a further-enriched asphaltene material fraction 340. The gaseous solvent-enriched material fraction 338 may be re-used within the process, while the further-enriched asphaltcnc material fraction 340 may be further treated to recover water.
[00133] In each one of the embodiments illustrated in Figures 10, 11, and 12, the feed material 150, which includes at least a fraction of an upgraded intermediate 114 produced by the cracking unit operation 110, is supplied to a separator 130 (such as a fractionator), for effecting separation of at least the lighter hydrocarbon material-comprising fraction 134B (for example, in the form of a distillate).
[00134] In the embodiment, illustrated in Figure 10, the presence of olefinic material within the upgraded product 200 is minimized by effecting a reduction in content of the olefinic material within the upgraded intermediate 114. In this respect, the separator 130 additionally effects separation of the olefm-comprising treatment fraction 132 (such as, for example, the lighter olefinic material-comprising fraction) as a distillate. The olefin-comprising treatment fraction 132 is converted into an olefin-depleted intermediate 136 (such as a light olefin material-depleted intermediate), such as by the processes effected within the reaction zone 120, as explained above with respect to olefinic material generally, namely, any one of, or any combination of alkylation and dehydrogenation (with incidental hydrogenation, as explained above). The heavier bottoms product 134A is also recovered. The fraction 138B
of the bottoms product 134A is combined with both of the olefin-depleted intermediate 136 and the lighter hydrocarbon material-comprising fraction 134B to produce the upgraded product 200. A
fraction 138A of the bottoms product 134A is supplied to the cracking unit operation 110. The cracking unit operation may comprise, in series, a heater 110a and a soaker 110b, which effects cracking of the bottoms product fraction 138A to produce the upgraded intermediate 114 which is then combined into the feed material 150. In this respect, at least a fraction of the upgraded intermediate 114 is recycled through the cracking unit operation 110 in the form of the fraction 138A of the bottoms product 134A. Because the feed material 150 includes a deasphalted heavy hydrocarbon-comprising material, the feed material 150 also typically includes residual solvent material deriving from the deasphalting process, and most of the residual solvent material may be recovered as a top distillate product 308 from the separator 130.
of the bottoms product 134A is combined with both of the olefin-depleted intermediate 136 and the lighter hydrocarbon material-comprising fraction 134B to produce the upgraded product 200. A
fraction 138A of the bottoms product 134A is supplied to the cracking unit operation 110. The cracking unit operation may comprise, in series, a heater 110a and a soaker 110b, which effects cracking of the bottoms product fraction 138A to produce the upgraded intermediate 114 which is then combined into the feed material 150. In this respect, at least a fraction of the upgraded intermediate 114 is recycled through the cracking unit operation 110 in the form of the fraction 138A of the bottoms product 134A. Because the feed material 150 includes a deasphalted heavy hydrocarbon-comprising material, the feed material 150 also typically includes residual solvent material deriving from the deasphalting process, and most of the residual solvent material may be recovered as a top distillate product 308 from the separator 130.
[00135] In some embodiments, for example, steam stream 1311 supplies steam to the separator to reduce partial pressure of hydrocarbon material, and thereby improve the separation between distillate cuts to optimize the yields of desired product from the separator 130.
[00136] In some embodiments, for example, solvent stream 133 is merged with the treatment material 132 for purging the solvent loop from olefins and also for adding diluent to the upgraded product 200.
[00137] In the embodiment illustrated in Figure 11, the presence of olefinic material within the upgraded product 200 is minimized by mitigating formation of the olefinic material within the cracking unit operation 110. In this respect, a bottoms product 134A is recovered and a fraction 138B of the bottoms product 134A is combined with the lighter hydrocarbon material-comprising fraction 134B and the stream 312 to produce the upgraded product 200, while a fraction 138A of the bottoms product 134A is combined with a hydrogen donor material 310 (such as synthetic crude oil that includes cycloalkanes) to produce a cracking unit operation feed 3102, and is then supplied to the cracking unit operation 110. The presence of the hydogen donor material 310 mitigates formation of olefinic material within the cracking unit operation 110. The cracking unit operation 110 may comprise, in series, a heater 110a and a soaker 110b, which effects cracking of the feed 3102 to produce the upgraded intermediate 114 which is then combined into the feed material 150. In this respect, at least a fraction of the upgraded intermediate 114 is recycled through the cracking unit operation in the form of the second fraction 306 of the bottoms product 134A. Because the feed material 150 includes a deasphalted heavy hydrocarbon-comprising material, the feed material 150 also typically includes residual solvent material deriving from the deasphalting process, and most of the residual solvent material may be recovered as a top distillate product 308 from the separator 130.
[00138] In the embodiment illustrated in Figure 12, the process embodiment illustrated in Figure 11 is modified such that the presence of olefinic material within the upgraded product 200 is further minimized by one or both of aromatic alkylation and dehydrogenation (with incidental hydrogenation), as described above. The dehydrogenation is also helpful for converting cyclo-olefins that may be derived from the supplied hydrogen donor material (such as from five-membered cyclo-alkanes). In those embodiments where both of aromatic alkylation and dehydrogenation (with incidental hydrogenation) is effected within the reaction zone 170 of an olefin treating unit 172, in some of these embodiments, for example, the reaction zone 170 is configured such that, as the received treatment material 132 is conducted through the reaction zone 170, the treatment material 132 is contacted, sequentially, with a dehydrogenation/hydrogenation catalyst, and then with an olefin-aromatic alkylation catalyst. In this respect, in some embodiments, for example, the olefin treating unit 172 includes an inlet 174 for receiving the treatment material 132 and an outlet 176 for discharging the olefin-depleted intermediate 136, and the dehydrogenation/hydrogenation catalyst is disposed closer to the inlet 174 than the olefin-aromatic alkylation catalyst, and the olefin-aromatic alkylation catalyst is disposed closer to the outlet 136 than the dehydrogenation/hydrogenation catalyst. A fraction 138A of the bottoms product 134A is combined with the hydrogen donor material 310 (such as synthetic crude oil that contains cycloalkanes) to produce a cracking unit operation feed 3102 which is then supplied to the cracking unit operation.
[00139] In the above description, for purposes of explanation, numerous details are set forth in order to provide a thorough understanding of the present disclosure.
However, it will be apparent to one skilled in the art that these specific details are not required in order to practice the present disclosure.
Although certain dimensions and materials are described for implementing the disclosed example embodiments, other suitable dimensions and/or materials may be used within the scope of this disclosure. All such modifications and variations, including all suitable current and future changes in technology, are believed to be within the sphere and scope of the present disclosure.
Date Recue/Date Received 2020-08-21
However, it will be apparent to one skilled in the art that these specific details are not required in order to practice the present disclosure.
Although certain dimensions and materials are described for implementing the disclosed example embodiments, other suitable dimensions and/or materials may be used within the scope of this disclosure. All such modifications and variations, including all suitable current and future changes in technology, are believed to be within the sphere and scope of the present disclosure.
Date Recue/Date Received 2020-08-21
Claims (27)
- CLAIMS:
I. A process for upgrading a heavy hydrocarbon feed material to an upgraded product comprising:
thermally cracking the heavy hydrocarbon feed material within a reaction zone disposed at a temperature of at least 300 degrees Celsius, such that an upgraded intermediate is produced, separating the upgraded intermediate into at least an olefin-comprising treatment fraction and a treatment bypass fraction, wherein, at a pressure of one (1) atmosphere, the boiling point range of the olefin-comprising treatment fraction is between 25 degrees Celsius and 365 degrees Celsius, reducing the content of olefinic material within the olefin-comprising treatment fraction by alkylating the olefin-comprising treatment fraction such that an olefin-depleted intermediate is produced;
separating the treatment bypass fraction into a heavier hydrocarbon material-comprising fraction and a lighter hydrocarbon material-comprising fraction; the boiling point range of the lighter hydrocarbon material-comprising fraction is between 80 degrees Celsius and 450 degrees Celsius combining at least the lighter hydrocarbon material-comprising fraction and the olefin¨depleted intermediate such that an olefinic material content-reduced product is produced;
producing the upgraded product including the olefinic material content-reduced product; and supplying at least a fraction of the heavier hydrocarbon material-comprising fraction upstream the reaction zone, such that the heavy hydrocarbon material-comprising feed includes at least a fraction of the heavier hydrocarbon material-comprising fraction. - 2. The process as claimed in claim 1;
wherein both of the separating of the upgraded intermediate and the separating of the bypass treatment fraction is effected within a separator;
and further comprising:
supplying the heavy hydrocarbon feed material to the separator. - 3. The process as claimed in claim 1 or 2;
wherein both of the separating of the upgraded intermediate and the separating of the treatment bypass fraction is effected based on differences in volatilities between the olefin-comprising treatment fraction, the lighter hydrocarbon material-comprising fraction, and the heavier hydrocarbon material-comprising fraction. - 4. The process as claimed in any one of claims 1 to 3;
wherein, at a predetermined temperature at which the separating of the olefin-comprising treatment fraction from the treatment bypass fraction is effected, the heavier hydrocarbon material-comprising fraction has a lower vapour pressure than that of the lighter hydrocarbon material-comprising fraction, and the lighter hydrocarbon material-comprising fraction has a lower vapour pressure than that of the olefin-comprising treatment fraction. - 5. The process as claimed in any one of claims 1 to 4;
wherein the combining at least the lighter hydrocarbon material-comprising fraction and the olefin¨depleted intermediate includes combining at least the lighter hydrocarbon material-comprising fraction, the olefin¨depleted intermediate and another fraction of the heavier hydrocarbon material-comprising fraction. - 6. The process as claimed in any one of claims 1 to 5, further comprising:
supplying the upgraded product to a pipeline for transporting to a refinery. - 7. The process as claimed any one of claims 1 to 6, wherein the alkylating the olefin-comprising treatment fraction is through an olefinic-aromatic alkylation reaction comprising addition of an olefinic group to an aromatic group.
- 8. The process as claimed in any one of claims 1 to 7, wherein the olefinic-aromatic alkylation occurs without an external source of olefins, di-olefins, aromatic and/or hydrogen.
- 9. The process as claimed in any one of claims 1 to 8, wherein the olefinic-aromatic alkylation occurs at a temperature from about 50 C to about 380 C.
- 10. The process as claimed in any one of claims 1 to 9, wherein the olefinic-aromatic alkylation reaction has a weight hourly space velocity of from about 0.02 to about 20h-1.
- 11. A process for upgrading a heavy hydrocarbon feed material to an upgraded product comprising:
thermally cracking the heavy hydrocarbon feed material within a reaction zone disposed at a temperature of at least 300 degrees Celsius, such that an upgraded intermediate is produced;
separating the upgraded intermediate into at least an olefin-comprising treatment fraction, a heavier hydrocarbon material-comprising fraction, and a lighter hydrocarbon material-comprising fraction, wherein the heavy hydrocarbon feed material includes at least a fraction of the upgraded intermediate reducing the content of olefinic material within the olefin-comprising treatment fraction by alkylating the olefin-comprising treatment fraction such that an olefin-depleted intermediate is produced; wherein, at a pressure of one (1) atmosphere, the boiling point range of the olefin-comprising treatment fraction is between 25 degrees Celsius and 365 degrees Celsius combining at least the lighter hydrocarbon material-comprising fraction and the olefin¨depleted intermediate such that an olefinic material content-reduced product is produced; wherein the boiling point range of the lighter hydrocarbon material-comprising fraction is between 80 degrees Celsius and 450 degrees Celsius producing the upgraded product including the olefinic material content-reduced product; and supplying at least a fraction of the heavier hydrocarbon material-comprising fraction upstream of the reaction zone, such that the heavy hydrocarbon feed material includes at least a fraction of the heavier hydrocarbon material-comprising fraction. - 12. The process as claimed in claim 11;
wherein both of the separating of the upgraded intermediate and the separating of the bypass treatment fraction is effected within a separator;
and further comprising:
supplying the feed material to the separator. - 13. The process as claimed in claim 11 or 12;
wherein both of the separating of the upgraded intermediate and the separating of the treatment bypass fraction is effected based on differences in volatilities between the olefin-comprising treatment fraction, the lighter hydrocarbon material-comprising fraction, and the heavier hydrocarbon material-comprising fraction. - 14. The process as claimed in any one of claims 11 to 13, at a predetermined temperature at which the separating of the olefin-comprising treatment fraction from the treatment bypass fraction is effected, the heavier hydrocarbon material-comprising fraction has a lower vapour pressure than that of the lighter hydrocarbon material-comprising fraction, and the lighter hydrocarbon material-comprising fraction has a lower vapour pressure than that of the olefin-comprising treatment fraction.
- 15. The process as claimed in any one of claims 11 to 14;
wherein the combining at least the lighter hydrocarbon material-comprising fraction and the olefin¨depleted intermediate includes combining at least the lighter hydrocarbon material-comprising fraction, the olefin¨depleted intermediate and another fraction of the heavier hydrocarbon material-comprising fraction. - 16. The process as claimed in any one of claims 11 to 15, further comprising:
supplying the upgraded product to a pipeline for transporting to a refinery. - 17. The process as claimed in any one of claims 11 to 16, wherein the alkylating the olefin-comprising treatment fraction is through an olefinic-aromatic alkylation reaction comprising addition of an olefinic group to an aromatic group.
- 18. The process claimed in any one of claims 11 to 17, wherein the olefinic-aromatic alkylation occurs without an external source of olefins, di-olefins, aromatic and/or hydrogen.
- 19. The process as claimed in any one of claims 11 to 18, wherein the olefinic-aromatic alkylation occurs at a temperature from about 50 C to about 380 C.
- 20. The process as claimed in any one of claims 11 to 20, wherein the olefinic-aromatic alkylation reaction has a weight hourly space velocity of from about 0.02 to about 20h-1.
- 21. A process for upgrading a heavy hydrocarbon feed material to an upgraded product comprising:
thermally cracking the heavy hydrocarbon feed material in a reaction zone disposed at a temperature of at least 300 degrees Celsius, such that an upgraded intermediate is produced, wherein the thermal cracking is effected;
separating the upgraded intermediate into at least a light olefin-comprising treatment fraction and a treatment bypass fraction, wherein the heavy hydrocarbon feed material includes at least a fraction of the upgraded intermediate; wherein, at a pressure of one (1) atmosphere, the boiling point range of the light olefin-comprising treatment fraction is between 25 degrees Celsius and 200 degrees Celsius reducing the content of light olefinic material within the olefin-comprising treatment fraction by alkylating the olefin-comprising treatment fraction such that a light olefinic material-depleted intermediate is produced;
combining the light olefinic material-depleted intermediate and the treatment bypass fraction so as to produce a light olefinic material content-reduced product; and producing the upgraded product including the light olefinic material content-reduced product. - 22. The process as claimed in claim 21, wherein the separating of the feed material is effected based on differences in volatilities between the light olefin-comprising treatment fraction and the treatment bypass fraction.
- 23. The process as claimed in claim 21 or 22, wherein at a predetermined temperature at which the separating of the olefin-comprising treatment fraction from the treatment bypass fraction is effected, the treatment bypass fraction has a lower vapour pressure than that of the light olefin-comprising treatment fraction.
- 24. The process as claimed in any one of claims 21 to 23, wherein the alkylating the olefin-comprising treatment fraction is through an olefinic-aromatic alkylation reaction comprising addition of an olefinic group to an aromatic group.
- 25. The process as claimed in any one of claims 21 to 24, wherein the olefinic-aromatic alkylation occurs without an external source of olefins, di-olefins, aromatic and/or hydrogen.
- 26. The process as claimed in any one of claims 21 to 25, wherein the olefinic-aromatic alkylation occurs at a temperature from about 50 C to about 380 C.
- 27. The process as claimed in any one of claims 21 to 26, wherein the olefinic-aromatic alkylation reaction has a weight hourly space velocity of from about 0.02 to about 20"-1.
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PCT/CA2014/000541 WO2015000061A1 (en) | 2013-07-04 | 2014-07-04 | Olefins reduction of a hydrocarbon feed using olefins- aromatics alkylation |
PCT/CA2014/000915 WO2016000060A1 (en) | 2014-07-04 | 2014-12-23 | Upgrading of hydrocarbon material |
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AU2013207783B2 (en) | 2012-01-13 | 2017-07-13 | Lummus Technology Llc | Process for providing C2 hydrocarbons via oxidative coupling of methane and for separating hydrocarbon compounds |
US9670113B2 (en) | 2012-07-09 | 2017-06-06 | Siluria Technologies, Inc. | Natural gas processing and systems |
WO2014089479A1 (en) | 2012-12-07 | 2014-06-12 | Siluria Technologies, Inc. | Integrated processes and systems for conversion of methane to multiple higher hydrocarbon products |
WO2015081122A2 (en) | 2013-11-27 | 2015-06-04 | Siluria Technologies, Inc. | Reactors and systems for oxidative coupling of methane |
CN106068323B (en) | 2014-01-08 | 2019-09-06 | 希路瑞亚技术公司 | Ethylene at liquid system and method |
US9701597B2 (en) | 2014-01-09 | 2017-07-11 | Siluria Technologies, Inc. | Oxidative coupling of methane implementations for olefin production |
US10377682B2 (en) | 2014-01-09 | 2019-08-13 | Siluria Technologies, Inc. | Reactors and systems for oxidative coupling of methane |
US9334204B1 (en) | 2015-03-17 | 2016-05-10 | Siluria Technologies, Inc. | Efficient oxidative coupling of methane processes and systems |
US10793490B2 (en) | 2015-03-17 | 2020-10-06 | Lummus Technology Llc | Oxidative coupling of methane methods and systems |
US20160289143A1 (en) | 2015-04-01 | 2016-10-06 | Siluria Technologies, Inc. | Advanced oxidative coupling of methane |
US9328297B1 (en) | 2015-06-16 | 2016-05-03 | Siluria Technologies, Inc. | Ethylene-to-liquids systems and methods |
US20170107162A1 (en) | 2015-10-16 | 2017-04-20 | Siluria Technologies, Inc. | Separation methods and systems for oxidative coupling of methane |
WO2017180910A1 (en) | 2016-04-13 | 2017-10-19 | Siluria Technologies, Inc. | Oxidative coupling of methane for olefin production |
KR20190031440A (en) * | 2016-05-16 | 2019-03-26 | 메그 에너지 코오퍼레이션 | Direct olefin reduction of the pyrolyzed hydrocarbon stream |
EP3554672A4 (en) | 2016-12-19 | 2020-08-12 | Siluria Technologies, Inc. | Methods and systems for performing chemical separations |
CA2963436C (en) | 2017-04-06 | 2022-09-20 | Iftikhar Huq | Partial upgrading of bitumen |
PL3630707T3 (en) | 2017-05-23 | 2024-02-19 | Lummus Technology Llc | Integration of oxidative coupling of methane processes |
RU2020102298A (en) | 2017-07-07 | 2021-08-10 | Люммус Текнолоджи Ллс | SYSTEMS AND METHODS FOR OXIDATIVE COMBINATIONS OF METHANE |
EA202090153A1 (en) * | 2017-07-18 | 2020-05-06 | ЛАММУС ТЕКНОЛОДЖИ ЭлЭлСи | UNITED METHOD OF THERMAL CRACKING AND DEHYDRATION FOR PRODUCING OLEFINS |
US11078431B2 (en) * | 2019-12-16 | 2021-08-03 | Saudi Arabian Oil Company | Modified ultra-stable Y (USY) zeolite catalyst for deolefinization of hydrocarbon streams |
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US2248677A (en) * | 1939-06-05 | 1941-07-08 | Garman Reed Waldo | Apparatus for coking petroleum |
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JPH07286183A (en) * | 1994-03-22 | 1995-10-31 | Shell Internatl Res Maatschappij Bv | Method for conversion of hydrocarbon bottom oil |
FR2741888B1 (en) * | 1995-12-04 | 1998-02-20 | Total Raffinage Distribution | IMPROVEMENTS IN PROCESSES AND DEVICES FOR VISCOREDUCING HEAVY HYDROCARBON LOADS |
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CA2916767C (en) | 2019-01-15 |
CN106661466B (en) | 2022-08-23 |
CN105492580B (en) | 2018-11-02 |
CA2953853A1 (en) | 2016-01-07 |
US20170152451A1 (en) | 2017-06-01 |
CN106661466A (en) | 2017-05-10 |
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