EP0654520A1 - Integriertes katalytisches Krack- und Olefinen Herstellungsverfahren - Google Patents
Integriertes katalytisches Krack- und Olefinen Herstellungsverfahren Download PDFInfo
- Publication number
- EP0654520A1 EP0654520A1 EP94308423A EP94308423A EP0654520A1 EP 0654520 A1 EP0654520 A1 EP 0654520A1 EP 94308423 A EP94308423 A EP 94308423A EP 94308423 A EP94308423 A EP 94308423A EP 0654520 A1 EP0654520 A1 EP 0654520A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- catalytic cracking
- dehydrogenation
- olefin
- plug flow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 43
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 43
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 121
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 41
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 24
- 238000005336 cracking Methods 0.000 claims abstract description 24
- 230000008929 regeneration Effects 0.000 claims abstract description 23
- 238000011069 regeneration method Methods 0.000 claims abstract description 23
- 229930195733 hydrocarbon Natural products 0.000 claims description 24
- 150000002430 hydrocarbons Chemical class 0.000 claims description 24
- 239000004215 Carbon black (E152) Substances 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000010457 zeolite Substances 0.000 claims description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 5
- 239000001282 iso-butane Substances 0.000 claims description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003209 petroleum derivative Substances 0.000 claims description 4
- YUHZIUAREWNXJT-UHFFFAOYSA-N (2-fluoropyridin-3-yl)boronic acid Chemical class OB(O)C1=CC=CN=C1F YUHZIUAREWNXJT-UHFFFAOYSA-N 0.000 claims description 3
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical class CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical class CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical class CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 229910052809 inorganic oxide Inorganic materials 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 9
- 239000000571 coke Substances 0.000 description 9
- 238000004231 fluid catalytic cracking Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- -1 dachiardite Chemical compound 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 235000013847 iso-butane Nutrition 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 229910052663 cancrinite Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910001683 gmelinite Inorganic materials 0.000 description 1
- 229910052677 heulandite Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052667 lazurite Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001723 mesolite Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052674 natrolite Inorganic materials 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 229910001682 nordstrandite Inorganic materials 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 235000020030 perry Nutrition 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052679 scolecite Inorganic materials 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- 229910052645 tectosilicate Inorganic materials 0.000 description 1
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
-
- 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
- C10G2400/20—C2-C4 olefins
Definitions
- This invention relates to a combined catalytic cracking and olefin producing process.
- U.S. Patent No. 4,830,728 discloses a fluid catalytic cracking (FCC) unit which is operated to maximize olefin production.
- the FCC unit has two separate risers in which different feed streams are introduced.
- the operation of the risers is designed so that a certain catalyst will act to convert a heavy gas oil in one riser and a different catalyst will act to crack a lighter olefin/naphtha feed in the other riser.
- Conditions within the heavy gas oil riser are modified to maximize either gasoline or olefin production.
- the primary means of maximizing production of the desired product is by using a specified catalyst.
- a problem inherent in producing olefin products using FCC units is that the process depends upon a specific catalyst balance to maximize production.
- olefin selectivity is generally low due to undesirable side reactions such as extensive cracking, isomerization, aromatization and hydrogen transfer reactions. It is, therefore, desirable that olefin production be maximized in a process which allows a high degree of control over olefin selectivity.
- the present invention provides an integrated catalytic cracking and alkane dehydrogenation process which comprises catalytically cracking a petroleum hydrocarbon with an active catalytic cracking catalyst to form a deactivated cracking catalyst and a cracked hydrocarbon product; regenerating the deactivated cracking catalyst under regeneration conditions in a plug flow regeneration system to form a dehydrogenation catalyst and a reactivated catalytic cracking catalyst within the plug flow regeneration system; and dehydrogenating a C2-C10 alkane feed stream with the dehydrogenation catalyst.
- the catalytic cracking catalyst comprises a zeolite crystalline framework oxide
- the alkane feed stream comprises at least one component selected from the group consisting of ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentanes, isohexanes, isoheptanes and iso-octanes
- the dehydrogenation catalyst comprises about 0.2-10 wt % carbon
- the alkane feed stream is dehydrogenated to an olefin product stream which comprises at least 1 wt % total olefin
- the reactivated catalytic cracking catalyst comprises less than about 0.2 wt % carbon
- the dehydrogenation of the alkane feed stream with the dehydrogenation catalyst forms a coked dehydrogenation catalyst and the coked dehydrogenation catalyst is regenerated under regeneration conditions in the plug flow regeneration system
- Fig. 1 is a schematic representation of a preferred embodiment of the invention.
- Catalytic cracking is a process which is well known in the art of petroleum refining and generally refers to converting a large hydrocarbon molecule to a smaller hydrocarbon molecule by breaking at least one carbon to carbon bond.
- large paraffin molecules can be cracked to a paraffin and an olefin, and a large olefin molecule can be cracked to two or more smaller olefin molecules.
- Long side chain molecules which may be present on aromatic rings or naphthenic rings can also be cracked.
- a coked catalytic cracking catalyst can be used to enhance the dehydrogenation of an alkane feed stream to produce an olefin stream.
- this aspect of the invention can be integrated into the catalytic cracking process to increase olefin yield in the overall reaction scheme.
- This increased olefin yield is advantageous since the olefin product can be used as a feedstock in other reaction processes to either increase the octane pool in a refinery, or the olefins can be used in the manufacture of gasoline additives which are required to reduce undesirable hydrocarbon emissions.
- the process of this invention allows for high olefin selectivity such that a portion of the olefin stream can also be used in other chemicals processes such as polyolefin production.
- the hydrocarbon feed is preferably a petroleum hydrocarbon.
- the hydrocarbon is preferably a distillate fraction having an initial ASTM boiling range of about 400°F.
- Such hydrocarbon fractions include gas oils, thermal oils, residual oils, cycle stocks, topped and whole crudes, tar sand oils. shale oils, synthetic fuels, heavy hydrocarbon fractions derived from the destructive hydrogenation of coal, tar, pitches, asphalts, and hydrotreated feed stocks derived from any of the foregoing.
- the hydrocarbon feed is preferably introduced into a riser which feeds a catalytic cracking reactor vessel.
- the feed is mixed in the riser with catalytic cracking catalyst that is continuously recycled.
- the hydrocarbon feed can be mixed with steam or an inert type of gas at such conditions so as to form a highly atomized stream of a vaporous hydrocarbon-catalyst suspension.
- this suspension flows through the riser into the reactor vessel.
- the reactor vessel is preferably operated at a temperature of about 800-1200°F and a pressure of about 0-100 psig.
- the catalytic cracking reaction is essentially quenched by separating the catalyst from the vapor.
- the separated vapor comprises the cracked hydrocarbon product, and the separated catalyst comprises a carbonaceous material (i.e., coke) as a result of the catalytic cracking reaction.
- the coked catalyst is preferably recycled to contact additional hydrocarbon feed after the coke material has been removed.
- the coke is removed from the catalyst in a regenerator vessel by combusting the coke from the catalyst under standard regeneration conditions.
- the coke is combusted at a temperature of about 900-1400°F and a pressure of about 0-100 psig. After the combustion step, the regenerated catalyst is recycled to the riser for contact with additional hydrocarbon feed.
- the catalyst which is used in this invention can be any catalyst which is typically used to catalytically "crack" hydrocarbon feeds. It is preferred that the catalytic cracking catalyst comprise a crystalline tetrahedral framework oxide component. This component is used to catalyze the breakdown of primary products from the catalytic cracking reaction into clean products such as naphtha for fuels and olefins for chemical feedstocks.
- the crystalline tetrahedral framework oxide component is selected from the group consisting of zeolites, tectosilicates, tetrahedral aluminophophates (ALPOs) and tetrahedral silicoaluminophosphates (SAPOs). More preferably, the crystalline framework oxide component is a zeolite.
- Zeolites which can be employed in accordance with this invention include both natural and synthetic zeolites. These zeolites include gmelinite, chabazite, dachiardite, clinoptilolite, faujasite, heulandite, analcite, levynite, erionite, sodalite, cancrinite, nepheline, lazurite, scolecite, natrolite, offretite, mesolite, mordenite, brewsterite, and ferrierite.
- zeolites X, Y, A, L, ZK-4, ZK-5, B, E, F, H, J, M, Q, T, W, Z, alpha and beta, ZSM-types and omega are included among the synthetic zeolites.
- aluminosilicate zeolites are effectively used in this invention.
- the aluminum as well as the silicon component can be substituted for other framework components.
- the aluminum portion can be replaced by boron, gallium, titanium or trivalent metal compositions which are heavier than aluminum. Germanium can be used to replace the silicon portion.
- the catalytic cracking catalyst used in this invention can further comprise an active porous inorganic oxide catalyst framework component and an inert catalyst framework component.
- an active porous inorganic oxide catalyst framework component Preferably, each component of the catalyst is held together by attachment with an inorganic oxide matrix component.
- the active porous inorganic oxide catalyst framework component catalyzes the formation of primary products by cracking hydrocarbon molecules that are too large to fit inside the tetrahedral framework oxide component.
- the active porous inorganic oxide catalyst framework component of this invention is preferably a porous inorganic oxide that cracks a relatively large amount of hydrocarbons into lower molecular weight hydrocarbons as compared to an acceptable thermal blank.
- a low surface area silica e.g., quartz
- the extent of cracking can be measured in any of various ASTM tests such as the MAT (microactivity test, ASTM # D3907-8). Compounds such as those disclosed in Greensfelder. B. S., et al. , Industrial and Engineering Chemistry , pp. 2573-83, Nov. 1949, are desirable.
- Alumina, silica-alumina and silica-alumina-zirconia compounds are preferred.
- the inert catalyst framework component densifies, strengthens and acts as a protective thermal sink.
- the inert catalyst framework component used in this invention preferably has a cracking activity that is not significantly greater than the acceptable thermal blank.
- Kaolin and other clays as well as ⁇ -alumina, titania, zirconia, quartz and silica are examples of preferred inert components.
- the inorganic oxide matrix component binds the catalyst components together so that the catalyst product is hard enough to survive interparticle and reactor wall collisions.
- the inorganic oxide matrix can be made from an inorganic oxide sol or gel which is dried to "glue" the catalyst components together.
- the inorganic oxide matrix will be comprised of oxides of silicon and aluminum. It is also preferred that separate alumina phases be incorporated into the inorganic oxide matrix.
- Species of aluminum oxyhydroxides- ⁇ -alamina, boehmite, diaspore, and transitional aluminas such as ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, and ⁇ -alumina can be employed.
- the alumina species is an aluminum trihydroxide such as gibbsite, bayerite, nordstrandite, or doyelite.
- an olefin reaction is commenced by contacting an alkane feed stream with a dehydrogenation catalyst.
- the alkane feed stream of this invention is preferably a C2-C10 alkane composition.
- the alkane composition can be either branched or unbranched. Such compositions include ethane. propane. butane, pentane, hexane, heptane, octane, nonane, decane, isobutane, isopentanes, isohexanes, isoheptanes and iso-octanes.
- a coked catalytic cracking catalyst serves as the dehydrogenation catalyst.
- the coked catalytic cracking catalyst is a catalytic cracking catalyst, as described above, which contains a measurable content of carbonaceous material (i.e., coke) on the catalyst, and which will effectively enhance dehydrogenation of the alkane feed stream to selectively form an olefin product.
- the carbon content of the dehydrogenation catalyst will be about 0.2-10 wt %, more preferably from about 0.3-5.0 wt %, most preferably from about 0.4-2.5 wt %.
- the dehydrogenation catalyst can be obtained by any of numerous means.
- the dehydrogenation catalyst can be obtained as a result of a partial or incomplete regeneration of at least a portion of the spent catalyst stream in a FCC unit.
- One of ordinary skill in the art will be able to attain the desired concentration of coke on the catalytic cracking catalyst using well known means of adjusting temperature, oxygen content or burn time within the regenerator portion of the FCC unit.
- the conversion of alkane to olefin in this invention generally involves a dehydrogenation reaction.
- alkanes are converted to olefins and molecular hydrogen.
- This reaction is highly endothermic.
- the dehydrogenation reaction is carried out at a temperature of about 800-1600°F, more preferably about 800-1400°F.
- the dehydrogenation reaction is somewhat dependent upon pressure. In general, the higher the pressure, the lower the conversion of alkane to olefin. Preferably, the process is carried out at about 0-100 psig.
- the contact time between the alkane stream and the dehydrogenation catalyst will also affect the yield of olefin product.
- optimal contact between the coked catalyst and the alkane stream is attained when the olefin product stream contains a concentration of at least about 1 wt % total iso-olefin.
- alkane vapor residence time will range from about 0.5-10 seconds, more preferably, about 1.0-5.0 seconds.
- FIG. 1 A preferred embodiment of this invention is shown in Fig. 1 in which the dehydrogenation reaction is incorporated into a catalytic cracking process.
- a petroleum hydrocarbon is catalytically cracked with an active catalytic cracking catalyst to form a cracked hydrocarbon product.
- the active catalytic cracking catalyst becomes coked (i.e., coated with a carbonaceous material).
- the activity of the catalytic cracking catalyst decreases as the concentration of the coke deposited on the catalyst increases.
- the catalytic cracking catalyst is deactivated to the point where the catalyst is essentially ineffective in enhancing the equilibrium balance of the cracking reaction under the standard cracking conditions. At this point. the catalytic cracking catalyst is considered to be a deactivated cracking catalyst.
- the deactivated cracking catalyst can be reactivated by regenerating the catalyst under standard regeneration conditions.
- part of the deactivated catalyst can be regenerated and reused as the dehydrogenation catalyst.
- part of the deactivated catalyst can be fully reactivated and reused in a continuous catalytic cracking reaction.
- regeneration and recovery of a plurality of catalyst streams need be performed in only one regenerator vessel.
- the plug flow regeneration system of this invention comprises a regenerator in which there is little or no significant back mixing of the reaction mixture, including catalyst components.
- the plug flow regenerator is of a tubular or empty tower design which provides for effectively overall laminar flow of the reaction mixture.
- regenerators are of the same type of general configuration as typical tubular and tower reactors, such as those described in Perry's Chemical Engineers' Handbook , sixth edition, McGraw-Hill, 1984.
- the plug flow regenerator has means for distributing an oxygen containing stream throughout the entire length of the regenerator. This will provide a balanced flow of oxygen within the regenerator to evenly combust carbonaceous material from the deactivated cracking catalyst. Since there is no significant back mixing, the amount of carbon material combusted from the spent catalyst increases as the catalyst progressively flows through the regeneration system. Therefore. the amount of carbonaceous material that is desired to be removed from the deactivated catalyst can be primarily controlled by the residence time within the regenerator as long as the other operating conditions remain relatively constant. Residence times can be selected according to the amount of carbon material that is desired to be removed.
- At least two regenerated streams are recovered requiring at least two different residence times.
- One regenerated stream is partially regenerated for use as a dehydrogenation catalyst, and another regeneration stream is a fully regenerated catalyst.
- the partially regenerated catalyst has a carbon content of about 0.2-10 wt %
- the fully reactivated catalyst has a carbon content of less than about 0.2 wt%, based on the total weight of the catalyst.
- FIG. 1 A preferred embodiment is shown in Fig. 1 in which the integrated catalytic cracking and alkane dehydrogenation process takes place generally in a FCC unit 10 which includes a tubular or empty tower plug flow regenerator 11, a cracking reactor 12 and a satellite reactor 13.
- the cracking reactor 12 comprises a main reactor vessel and preferably includes a riser conduit where hydrocarbon feed is injected and initially contacts reactivated catalytic cracking catalyst from the plug flow regenerator 11.
- the catalytic cracking reaction is initiated as the hydrocarbon feed contacts the catalyst, and continues until the catalyst is separated from the hydrocarbon, typically within the cracking reactor 12. Separation can be accomplished using any of the acceptable FCC separation devices such as cyclone separators.
- the cracked hydrocarbon product leaves the reactor 12 through a product line 14.
- the separated catalyst which has become coked (i.e.. spent) in the cracking reaction, leaves the reactor 12 through a recycle line 15 where the catalyst is sent to the plug flow regenerator 11.
- the plug flow regenerator 11 preferably includes a series of injection means 16a-d for distributing an oxygen containing stream evenly throughout the plug flow regenerator 11 to minimize back mixing.
- injection means 16a-d for distributing an oxygen containing stream evenly throughout the plug flow regenerator 11 to minimize back mixing.
- any of various designs for injecting an oxygen containing stream can be used as long as back mixing is kept to a minimum.
- the satellite reactor 13 can be any type of reactor vessel that is operable under dehydrogenation conditions.
- the satellite reactor 13 can be a transfer line riser reactor, a slumped bed reactor, a spouting bed reactor or a moving bed reactor.
- the satellite reactor 13 will be capable of supporting a fluid bed catalyst at a density of about 1-45 lbs of catalyst per cubic foot of reactor volume.
- alkane feed is injected to initiate the dehydrogenation reaction.
- the reaction continues until the catalyst is separated from the olefin products within the satellite reactor 13. Separation can be accomplished using any of the acceptable fluidized type of catalyst separation devices such as cyclone separators.
- the olefin product leaves the satellite reactor 13 through an olefin product line 18.
- the separated catalyst which is further spent in the dehydrogenation reaction leaves the reactor 13 through a recycle line 19 where it is combined with the spent catalyst in the recycle line 15 and sent back to the plug flow regenerator 11 to repeat the cycle.
- An equilibrium zeolite beta FCC catalyst (SiO2 65.1 wt %; Al2O3 wt %; Na2O 0.28 wt %; REO2 2.14 wt %) was placed in a fixed bed quartz reactor. The temperature of the reactor was maintained at 1250°F, and the pressure was maintained at 0 psig. Six runs were made varying the total carbon content on the catalyst from 0.2 wt % to 2.7 wt %. The catalyst in runs 2-6 was pretreated with a hydrocarbon to increase the base level carbon content, thereby representing a partially regenerated spent catalyst. Iso-butane feed was passed through the reactor at 1 second residence time and GHSV of 1066. The results are shown in Table 1.
- Spent zeolite catalytic cracking catalyst is passed through a tubular plug flow regenerator, which is operated at 1 atm and 1280°F. At various residence times within the regenerator, cracking catalyst is recovered and the amount of carbon material removed during the regeneration process is calculated. The results are shown in Table 1. Table 1 Time, min. wt% coke removed 0 0 1.25 43.8 2.5 74.0 3.75 86.3 5.0 92.3
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- 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)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15482993A | 1993-11-19 | 1993-11-19 | |
US154829 | 1993-11-19 |
Publications (2)
Publication Number | Publication Date |
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EP0654520A1 true EP0654520A1 (de) | 1995-05-24 |
EP0654520B1 EP0654520B1 (de) | 1999-08-04 |
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Application Number | Title | Priority Date | Filing Date |
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EP19940308423 Expired - Lifetime EP0654520B1 (de) | 1993-11-19 | 1994-11-15 | Integriertes katalytisches Krack- und Olefinen Herstellungsverfahren |
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EP (1) | EP0654520B1 (de) |
CA (1) | CA2135102C (de) |
DE (1) | DE69419872T2 (de) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3894935A (en) * | 1973-11-19 | 1975-07-15 | Mobil Oil Corp | Conversion of hydrocarbons with {37 Y{38 {0 faujasite-type catalysts |
EP0168185A2 (de) * | 1984-07-13 | 1986-01-15 | Exxon Research And Engineering Company | Verbesserung der Lebensdauer von Zeolithkatalysatoren |
EP0259156A1 (de) * | 1986-09-03 | 1988-03-09 | Mobil Oil Corporation | Verfahren zur katalytischen Wirbelschichtspaltung mit reaktiven Bruchstücken |
EP0325437A2 (de) * | 1988-01-19 | 1989-07-26 | Mobil Oil Corporation | Umwandlung von Alkanen zu Alkylenen in einem externen Katalysatorkühler für einen Regenerator einer FCC-Anlage |
US4968401A (en) * | 1988-06-27 | 1990-11-06 | Mobil Oil Corp. | Aromatization reactor design and process integration |
EP0577280A1 (de) * | 1992-06-18 | 1994-01-05 | Exxon Research And Engineering Company | Verfahren zur Dehydrierung von Kohlenwasserstoffen unter Verwendung eines Kohlenstoff enthaltenden Katalysators |
-
1994
- 1994-11-04 CA CA 2135102 patent/CA2135102C/en not_active Expired - Fee Related
- 1994-11-15 DE DE1994619872 patent/DE69419872T2/de not_active Expired - Fee Related
- 1994-11-15 EP EP19940308423 patent/EP0654520B1/de not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3894935A (en) * | 1973-11-19 | 1975-07-15 | Mobil Oil Corp | Conversion of hydrocarbons with {37 Y{38 {0 faujasite-type catalysts |
EP0168185A2 (de) * | 1984-07-13 | 1986-01-15 | Exxon Research And Engineering Company | Verbesserung der Lebensdauer von Zeolithkatalysatoren |
EP0259156A1 (de) * | 1986-09-03 | 1988-03-09 | Mobil Oil Corporation | Verfahren zur katalytischen Wirbelschichtspaltung mit reaktiven Bruchstücken |
EP0325437A2 (de) * | 1988-01-19 | 1989-07-26 | Mobil Oil Corporation | Umwandlung von Alkanen zu Alkylenen in einem externen Katalysatorkühler für einen Regenerator einer FCC-Anlage |
US4968401A (en) * | 1988-06-27 | 1990-11-06 | Mobil Oil Corp. | Aromatization reactor design and process integration |
EP0577280A1 (de) * | 1992-06-18 | 1994-01-05 | Exxon Research And Engineering Company | Verfahren zur Dehydrierung von Kohlenwasserstoffen unter Verwendung eines Kohlenstoff enthaltenden Katalysators |
Also Published As
Publication number | Publication date |
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DE69419872D1 (de) | 1999-09-09 |
DE69419872T2 (de) | 2000-04-20 |
CA2135102C (en) | 2004-05-25 |
EP0654520B1 (de) | 1999-08-04 |
CA2135102A1 (en) | 1995-05-20 |
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