WO2011025803A1 - Reduction of hindered dibenzothiophenes in fcc products via transalkylaton of recycled long-chain alkylated dibenzothiophenes - Google Patents
Reduction of hindered dibenzothiophenes in fcc products via transalkylaton of recycled long-chain alkylated dibenzothiophenes Download PDFInfo
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- WO2011025803A1 WO2011025803A1 PCT/US2010/046571 US2010046571W WO2011025803A1 WO 2011025803 A1 WO2011025803 A1 WO 2011025803A1 US 2010046571 W US2010046571 W US 2010046571W WO 2011025803 A1 WO2011025803 A1 WO 2011025803A1
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- catalyst
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- dibenzothiophenes
- lco
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- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 230000009467 reduction Effects 0.000 title description 9
- 238000000034 method Methods 0.000 claims abstract description 52
- 230000008569 process Effects 0.000 claims abstract description 50
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 33
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 33
- 238000009835 boiling Methods 0.000 claims abstract description 29
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims description 67
- 238000005336 cracking Methods 0.000 claims description 57
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 18
- 239000010457 zeolite Substances 0.000 claims description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims description 17
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 14
- 238000004523 catalytic cracking Methods 0.000 claims description 9
- 239000000571 coke Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims 1
- 150000002790 naphthalenes Chemical class 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 41
- 229910052717 sulfur Inorganic materials 0.000 description 41
- 239000011593 sulfur Substances 0.000 description 41
- 239000000047 product Substances 0.000 description 28
- 238000010555 transalkylation reaction Methods 0.000 description 28
- 230000000694 effects Effects 0.000 description 24
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 23
- 239000003921 oil Substances 0.000 description 21
- 125000000217 alkyl group Chemical group 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- MYAQZIAVOLKEGW-UHFFFAOYSA-N DMDBT Natural products S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 7
- 241000894007 species Species 0.000 description 7
- 239000002283 diesel fuel Substances 0.000 description 6
- 239000003502 gasoline Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000003464 sulfur compounds Chemical class 0.000 description 6
- 230000029936 alkylation Effects 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 5
- -1 aromatic sulfur compounds Chemical class 0.000 description 5
- 229930192474 thiophene Natural products 0.000 description 5
- 150000003577 thiophenes Chemical class 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012013 faujasite Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003137 locomotive effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- LOXRGHGHQYWXJK-UHFFFAOYSA-N 1-octylsulfanyloctane Chemical compound CCCCCCCCSCCCCCCCC LOXRGHGHQYWXJK-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000012420 spiking experiment Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- 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
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
Definitions
- This invention relates to a process for producing low sulfur distillates such as low sulfur road diesel fuel.
- Sulfur is found in refinery streams in a number of different forms including aliphatic and aromatic sulfur compounds; in the lower boiling naphtha streams, mercaptans, sulfides and thiophenes predominate and these can be removed easily by extractive or oxidative/extractive processes such as the commercially available MeroxTM process.
- the sulfur compounds concentrated in the higher boiling distillate fractions is mainly in the form of aromatic heterocyclic compounds such as the thiophenes, benzothiophenes and
- DBTs dibenzothiophenes
- benzothiophenes At higher desulfurization severities, the more refractory sulfur compounds can be removed although with increased cost and with greater difficulty. Certain sulfur compounds are more difficult to remove than others.
- the most difficult compounds to remove by hydroprocessing are the dibenzothiophenes and, of these, the substituted dibenzothiophenes tend to be less amenable to hydrodesulfurization than dibenzothiophene itself; this effect varies according to the extent and type of substitution in the dibenzothiophenes with the sterically-hindered alkyl dibenzothiophenes such as the 4,6-dialkyl dibenzothiophenes being the most refractory. See Chemistry of Catalytic
- LCO light cycle oil
- FCC fluid catalytic cracking
- hydrodesulfurization catalysts Another costly option is hydrotreating the hydrocarbon feedstream to the FCC, which reduces the sulfur content but also alters the composition of the sulfur free hydrocarbons, especially of the high octane olefins which enter the gasoline fraction. This last option is also very costly due to the large (i.e., non-selective) volume of hydrocarbons required to be hydrotreated.
- the commercial success of these additives has, however, been limited. Additionally, as most refineries need additional capital hardware in order to treat any additional SO x loadings in an FCC unit, this option can be very costly in most instances.
- This mitigation is accomplished by a process comprising the recycling a heavy fraction of the full-range LCO cracking product which contains long chain alkylated DBTs (e.g. C ⁇ -DBTs) to allow another round of transalkylation to take place with an equilibrium shift away from the hindered alkyl DBTs.
- long chain alkyl groups split off from the hydrocarbons and the long chain alkylated DBT's (typically Ci 2 -DBTs) present in the heavier LCO fractions may attach to other species in the fraction to produce a net decrease in the proportion of hindered DBTs in the portion that enters the distillate product.
- Transalkylation reactions may form DBTs alkylated with long chain alkyl groups formed by cracking of long alkyl side chains in the heaviest LCO fractions but these long chain DBTs are likely to boil above the distillate product boiling range shown above and so do not need to be hydrotreated with the portion of the distillate which will enter the distillate fuel fraction, e.g. for road diesel, kerojet.
- the long chain alkyl DBTs will be rejected to the heavy fuel oil product to which the stringent sulfur limits do not apply.
- the sulfur content of the middle distillate fraction from an FCC process is reduced by fractionating the cracked liquid products to form a cracked naphtha fraction and a full-range LCO fraction that contains alkylated dibenzothiophenes.
- the full-range LCO (or "distillate") fraction boils substantially in the range from about 395 to about 750 0 F (approximately 200 to 400 0 C).
- the recycled portion of the LCO fraction that contains the long chain alkylated DBT's boils substantially in the range from about 520 to about 68O 0 F (271 to 360 0 C).
- the reaction transferring the alkyl groups from the alkylated DBTs to the other species present is favored by relatively lower temperatures (i.e. lower relative to the cracking temperatures) and for this reason, the recycled fraction of the LCO is preferably re-introduced into the FCC cycle at a point where the temperature is lowered slightly from the original cracking temperature. Re- introduction of the recycled LCO fraction can suitably be made at the top of the FCC riser or even more preferably into the stripper section of the FCC reactor.
- FIGURE 1 is a graph showing the sulfur speciation of a typical light cycle oil (“LCO").
- FIGURE 2 is a graph showing the sulfur speciation of cracking products of a vacuum gas oil (“VGO”) with dibenzothiophene added in three concentrations.
- VGO vacuum gas oil
- FCC fluid catalytic cracking
- LCO fluid catalytic cracking
- conventional FCC catalysts may be used, for example, zeolite based catalysts with a faujasite cracking component as described in the seminal review by Venuto and Habib, Fluid Catalytic Cracking with Zeolite Catalysts, Marcel Dekker, New York 1979, ISBN 0-8247-6870-1 as well as in numerous other sources such as Sadeghbeigi, Fluid Catalytic Cracking Handbook, Gulf Publ. Co. Houston, 1995, ISBN 0-88415-290-1.
- organosulfur compounds will be cracked to lighter products takes place by contact of a hydrocarbon-containing feed (also referred to herein as “heavy hydrocarbon feed”, “hydrocarbon feed”, or simply "feed) in a cyclic catalyst recirculation cracking process with a circulating fluidizable catalytic cracking catalyst inventory consisting of particles having a size ranging from about 20 to about 100 microns.
- a hydrocarbon-containing feed also referred to herein as “heavy hydrocarbon feed”, “hydrocarbon feed”, or simply "feed
- a circulating fluidizable catalytic cracking catalyst inventory consisting of particles having a size ranging from about 20 to about 100 microns.
- the hydrocarbon feed is catalytically cracked in a catalytic cracking zone, normally a riser cracking zone, operating at catalytic cracking conditions by contacting the hydrocarbon feed with a source of hot, regenerated cracking catalyst to produce an effluent comprising cracked products and spent catalyst containing coke and strippable hydrocarbons;
- the effluent from the cracking zone is discharged and separated, normally in one or more cyclones, into a vapor phase rich in cracked hydrocarbon products and a solids rich phase comprising the spent catalyst;
- the spent catalyst is stripped, usually with steam, to remove occluded hydrocarbons from the catalyst, after which the stripped catalyst is oxidatively regenerated to produce hot, regenerated catalyst which is then recycled to the cracking zone for cracking further quantities of feed;
- the cracked hydrocarbon products are separated to produce cracked product fractions including a cracked naphtha fraction and a light cycle oil (LCO) fraction containing alkylated dibenzothiophenes; and
- LCO light cycle oil
- At least a portion of the light cycle oil fraction containing alkylated dibenzothiophenes is recycled to the catalytic cracking process in order to transalkylate at least a portion of the alkylated
- the feed to the FCC process will typically be a high boiling feed of mineral oil origin, normally with an initial boiling point of at least about 55O 0 F (29O 0 C) and in most cases above about 600 0 F (315°C). Most refinery cut points for FCC feed will be at least about 650 0 F (345 0 C). The end point will vary, depending on the exact character of the feed or on the operating characteristics of the refinery.
- FCC feeds can include virgin feeds such as gas oils, e.g.
- Hydrotreated feeds may also be used, for example, hydrotreated gas oils, especially hydrotreated heavy gas oil.
- FCC reactor riser top temperature conditions can be controlled in the range of about 900 to about 1050 0 F (about 482 to 565°C), preferably about 925° to about 1050 0 F (about 496 to 565°C) with typical operation at about 1000 0 F (about 540 0 C).
- most preferred FCC reactor riser top temperatures conditions for use of the present invention are on the lower end of these temperatures, preferably in the range of about 930 to about 970 0 F (510 to 52O 0 C).
- Typical regenerated catalyst temperatures are in the range of about 1250 to about 135O 0 F (about 675 to 73O 0 C).
- Catalystroil ratios from about 1 :1 to 20:1, preferably from 3:1 to 6:1, are typical. Pressures in the FCC reactor riser are normally of about atmospheric to about 350 kPag (50 psig) are preferred. These values are, however, subject to variation as discussed below if the generation of hindered DBTs in the process is to be mitigated according to the present process.
- the feed is usually preheated to about 350° to 700 0 F (175 to 37O 0 C), though operation with feed preheat outside of this range is possible.
- the liquid cracking products from the FCC process typically include cracked naphtha fractions (light gasoline and heavy gasoline) boiling up to about 430 0 F (220 0 C), and a full-range LCO fraction typically boiling in the range of about 395 to about 75O 0 F (200 to about 400 0 C).
- a undercut LCO fraction (such as the recycled LCO fraction herein) may also be drawn directly from an FCC fractionator or may be further separated from a full-range LCO fraction.
- the cracking component of the FCC catalyst which is present to effect the desired cracking reactions and the production of lower boiling cracking products is typically based on a faujasite zeolite active cracking component, which is conventionally zeolite Y in one of its forms such as calcined rare-earth exchanged type Y zeolite (CREY), the preparation of which is disclosed in U.S. Pat. No. 3,402,996, ultrastable type Y zeolite (USY) as disclosed in U.S. Pat. No. 3,293,192, as well as various partially exchanged type Y zeolites as disclosed in U.S. Pat. Nos. 3,607,043 and 3,676,368.
- CREY calcined rare-earth exchanged type Y zeolite
- Cracking catalysts such as these are widely available in large quantities from various commercial suppliers.
- the active cracking component is routinely combined with a matrix material such as silica and/or alumina as well as a clay in order to provide the desired mechanical characteristics (attrition resistance etc.) as well as activity control for the very active zeolite component or components.
- the particle size of the cracking catalyst is typically in the range of 10 to 100 microns for effective fluidization. If separate particle additive catalysts are used, they are normally selected to have a particle size and density comparable to that of the cracking catalyst so as to prevent component segregation during the cracking cycle.
- transalkylation onto the dibenzothiophenes in the present process is favored by the use of catalysts with a large unit cell size in the zeolite component and a high matrix activity and/or high metals content.
- the preferred cracking catalysts are those that have a low unit cell size. Unit cell sizes below 2.427 nm and lower, below 2.425 nm, are therefore preferred for the zeolite component.
- low matrix activity and low metals content may also be favorable for low transalkylation activity, with matrix activity as measured by matrix surface area not more than 40 m 2 /gram, and preferably not more than 35 or 30 m 2 /gram, in order to minimize the extent of transalkylation onto the unhindered DBT molecules present in the feed.
- matrix activity as measured by matrix surface area not more than 40 m 2 /gram, and preferably not more than 35 or 30 m 2 /gram, in order to minimize the extent of transalkylation onto the unhindered DBT molecules present in the feed.
- a strategy of minimizing the generation of hindered DBTs by some reversal of the undesired alkylation is favored by the use of a catalyst that increases the degree of transalkylation, so establishing a tension in the final choice of catalyst.
- the effect of transalkylation onto the DBTs present in the feed is mitigated by a reversal of the process by which they form; in other words, the conditions under which the undesired
- transalkylation takes place are replicated although optionally modified to favor transalkylation away from the hindered alkyl DBTs. If the hindered DBTs are given another chance to react, the equilibrium may be shifted and the amount of hindered sulfur in the resulting LCO changed.
- Figure 1 herein shows that the mono-alkyl and di-alkyl substituted DBTs are found principally in the highest boiling tractions of the LCO; it is these fractions, therefore, that are the most likely to benefit from any treatment which reduces the level of hindered alkyl DBTs.
- the fractions representing the highest boiling 60% of the LCO fraction with boiling points substantially in the range of about 500 to about 75O 0 F (260 to 41O 0 C), and more preferably with boiling points substantially in the range of about 520 to about 750 0 F (271 to 410 0 C) are the ones preferably treated in the present processing scheme.
- substantially as used in the disclosure herein, it is meant that at least 80 wt% of the designated fraction boils in the range of temperatures designated.
- the recycled fraction of LCO has boiling points substantially in the range of about 520 to about 68O 0 F (271 to 36O 0 C). This is explained further in Example 2 herein.
- the optimal final boiling point for the recycled LCO fraction can be determined empirically as a function of base FCC feed composition, catalyst selection, and operating conditions.
- the heavy fraction of the LCO may be recycled to any convenient point in the cracking cycle where cracking products are in contact with the cracking catalyst and the temperature is conducive to transalkylation. It may therefore be recycled to any point of the FCC reactor riser, the reactor
- transalkylation does not require the high temperatures required for the actual cracking, lower temperatures are preferred, favoring the reactions of transalkylation away from the hindered DBTs to the other species present.
- Injection of the recycle LCO no earlier than at the riser top therefore provides the optimal range of solutions. Injection at the riser top will be favored when the unit is operated with closed cyclones or other rapid disengagement systems which separate the catalyst from the cracking products quickly. In this case, a relatively low riser top temperature will be preferred for the now desired transalkylation reactions.
- a preferred target range for the FCC reactor riser top temperature is from about 930 to about 970 0 F (499 to 521 0 C).
- Riser top temperature can be controlled by appropriate selection of catalyst:oil ration and regenerated catalyst temperature. A relatively low catalyst:oil ratio coupled with a high regenerated catalyst temperature may be required to ensure feed vaporization with enough cooling in the riser to attain the desired FCC reactor riser top temperature.
- Resort may also be made to the use of a riser quench to control the riser top temperature, by utilizing quench media such as cycle oil, naphtha, distillate, and/or waste oil.
- Riser quench enables the reactor mix zone temperature to be increased, typically by about 25 to 50 0 F (15 to 30°C) while still retaining the desired riser top temperature.
- the selected recycled LCO fraction utilized herein may be injected into the FCC reactor vessel, especially if a closed cyclone system is not being used.
- a preferred option is injection of the recycled LCO fraction into the stripper section of the FCC reactor which typically operates at a temperature of about 5 to 10 0 F (2 to 5 0 C) lower than the riser top temperature, thereby favoring the transalkylation reactions.
- Preferred operating temperatures for the present invention are from about 900 to about 98O 0 F (about 482 to 527°C), preferably about 920° to about 965 0 F (about 493 to 518°C).
- the catalystioil ratio in the stripper section is relatively high, as compared to the ratios prevailing in the riser and the reactor as a result of separation of cracked products and the injection of the recycle.
- the extended contact time prevailing in the stripper will also tend to increase attainment of the transalkylation equilibrium between the unalkylated recycle and the cracking products, for the desired decrease in hindered DBT levels.
- injection of the recycled LCO is preferably carried out at temperatures which enhance the transalkylation chemistry and minimize cracking and the amount of dry gas and coke make.
- the recycled LCO is preferably injected at a point in the FCC process where the process temperatures are from about 930 to about 97O 0 F (499 to 521 0 C), and more preferably from about 950 to about 97O 0 F (510 to 521 0 C).
- catalyst choice has been found to affect the efficacy of the alkyl transfer reactions.
- Catalysts in which the zeolite component has high unit cell size tend to promote transalkylation onto the DBTs.
- High matrix activity of a catalyst is also believed to be associated with high transalkylation activity.
- catalysts with relatively lower unit cell size are less active for transalkylation and lower matrix activity may also be found to be associated with reduced
- transalkylation activity This implies that if transalkylation of the DBT molecules is to be minimized to the extent feasible during the initial cracking reactions, a catalyst with low transalkylation activity would be the catalyst of choice (low unit cell size possibly coupled with low matrix activity).
- transalkylation activity should desirably be maximized by using a catalyst of high unit cell size coupled potentially with high matrix activity. Because the FCC unit has to be operated with only one circulating catalyst however, a fundamental tension is established as it is not possible to accommodate both requirements simultaneously in one catalyst formulation. A compromise catalyst candidate may therefore be the best choice although a final selection will be made on an empirical basis, taking into account the feed composition, product slate desired, unit characteristics and catalyst availability.
- zeolite unit cell size of at least 2.425 nm, preferably at least 2.428 or even 2.430 nm have been found to confer good transalkylation activity with very notable results achieved with a zeolite unit cell size of at least 2.44 nm.
- Embodiments of the present invention incorporating catalysts with a high activity matrix of at least 40 or even 50 m 2 /gram surface area is also preferred.
- VGO vacuum gas oil
- Dibenzothiophene was added to the feed in amounts of 1%, 3% and 5%, to give nominal total sulfur contents of 1.15 wt%, 1.47 wt%, and 1.77 wt%,
- each feed sample was run in the unit 4 to 5 times under the same conditions using ReduxionTM ECat (BASF) catalyst. Unless otherwise stated, each run in the unit was conducted at 99O 0 F (approximately 53O 0 C) and a cat/oil ratio of 6.
- the total sulfur content in the total liquid product recovered from the process was obtained while the sample was still cold. The presence of the added DBT did not appreciably affect the conversion under the selected reaction conditions.
- a positive number indicates that the 4,6 Dimethyl DBT structure is converted while a negative number indicates that the 4,6 Dimethyl DBT species is generated in the unit.
- This study shows that the most promising way to reduce the concentration of 4,6 dimethyl DBT species is to recycle the 70-90% cut of this LCO (nominal boiling point 325-36O 0 C, 620-680 0 F) at a low temperature.
- the low cracking temperature enhances the transalkylation chemistry and ensures that the amount of dry gas and coke make is minimized.
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Abstract
The level of sterically hindered alkylated dibenzothiophenes in the distillate product fraction from an FCC process is reduced by fractionating the cracked hydrocarbon products of the process to form a cracked naphtha fraction and a light cycle oil fraction that contains naphthalenes and alkylated dibenzothiophenes. A portion of the light cycle oil fraction that primarily contains alkylated dibenzothiophenes, typically the fraction boiling in the range from about 500 to about 75O°F (260 to 400°C), is recycled to transalkylate the alkylated dibenzothiophenes in the recycled light cycle oil fraction.
Description
REDUCTION OF HINDERED DIBENZOTHIOPHENES
IN FCC PRODUCTS VIA TRAN SALKYLATI ON OF RECYCLED LONG-CHAIN ALKYLATED DIBENZOTHIOPHENES
FIELD OF THE INVENTION
[0001] This invention relates to a process for producing low sulfur distillates such as low sulfur road diesel fuel.
BACKGROUND OF THE INVENTION
[0002] Environmental concerns are expected to lead to decreases in the permissible levels of sulfur in hydrocarbon fuels. While reduction in the maximum sulfur level of road diesel oils from about 0.3 weight percent to 0.05 weight percent were implemented in the 1990s, further significant reductions have since come into effect. In the European Union, the Euro IV standard specifying a maximum of 50 wppm (0.005%) of sulfur in diesel fuel for most highway vehicles has applied since 2005; ultra-low sulfur diesel with a maximum of 10 wppm of sulfur was required to be available from 2005 and was, in fact, widely available in 2008. A final target is the 2009 Euro V fuel standard for the final reduction of sulfur to 10 wppm, which is also expected for most non-highway applications.
[0003] In the United States, the Environmental Protection Administration ("EPA") has required most on-highway diesel fuel sold at retail locations in the United States to conform to the Ultra Low Sulfur Diesel ("ULSD") standard of 15 wppm since 2006 except for rural Alaska which will transition all diesel to ULSD in 2010. Non-road diesel fuel, required to conform to 500 wppm sulfur in 2007, will be further limited to conform to ULSD sulfur specifications in 2010
and railroad locomotive and marine diesel fuel will also change to conform with ULSD sulfur specifications in 2012. As of December 1, 2014 all highway, non- road, locomotive and marine diesel fuel produced and imported into the United States will be required to conform with the ULSD specifications.
[0004] The current allowable sulfur content for ULSD in the United States (15 wppm) is much lower than the previous U.S. on-highway standard for low sulfur diesel ("LSD") of 500 wppm. The reduced sulfur content not only reduces emissions of sulfur compounds but also allows advanced emission control systems to be fitted that would otherwise be poisoned by these compounds. These systems can greatly reduce emissions of oxides of nitrogen and particulate matter and according to EPA estimates, emissions of nitrogen oxide will be reduced by 2.3 million metric tonnes (2.6 million short tons) each year and soot or particulate matter will be reduced by 100,000 metric tonnes (110,000 short tons) a year with the adoption of the new standards.
[0005] Sulfur is found in refinery streams in a number of different forms including aliphatic and aromatic sulfur compounds; in the lower boiling naphtha streams, mercaptans, sulfides and thiophenes predominate and these can be removed easily by extractive or oxidative/extractive processes such as the commercially available Merox™ process. The sulfur compounds concentrated in the higher boiling distillate fractions is mainly in the form of aromatic heterocyclic compounds such as the thiophenes, benzothiophenes and
dibenzothiophenes ("DBTs"). Conventional hydrodesulfurization processes are capable of removing sulfur compounds, especially the lower molecular weight materials including the aliphatic sulfur materials, thiophenes and
benzothiophenes. At higher desulfurization severities, the more refractory sulfur compounds can be removed although with increased cost and with greater difficulty. Certain sulfur compounds are more difficult to remove than others. For example, the most difficult compounds to remove by hydroprocessing are
the dibenzothiophenes and, of these, the substituted dibenzothiophenes tend to be less amenable to hydrodesulfurization than dibenzothiophene itself; this effect varies according to the extent and type of substitution in the dibenzothiophenes with the sterically-hindered alkyl dibenzothiophenes such as the 4,6-dialkyl dibenzothiophenes being the most refractory. See Chemistry of Catalytic
Processes, Gates et al. McGraw Hill, pages 407 and 408.
[0006] Hydrogenative removal of the dibenzothiophenes requires high hydrogen partial pressures and circulation rates, low space velocity and high temperature, implying a significant increase in the capacity of the hydrogen circulation system, an increase in the reactor bed size, an increase in operating pressure, a decrease in cycle length or any combination of these. The higher severity operation can also increase cracking and, therefore, light gas production. Conventional hydroprocessing of the fractions which find their way into the light diesel products such as road diesel is therefore economically unattractive as a complete solution.
[0007] One of the fractions which is conventionally used as a blend component for road diesel is light cycle oil ("LCO") which is produced in large quantities in the fluid catalytic cracking ("FCC") units commonly used for gasoline production. Experience has shown, however, that hydrodesulfurization of full-range LCO requires high severity conditions for achieving sulfur levels as low as 500 ppm let alone the far lower levels required by ULSD or Euro V.
These difficulties are, moreover, accentuated by the fact that the other sulfur-and nitrogen- contain ing impurities in the feed react earlier in the reactor, producing ammonia and hydrogen sulfide, which further inhibit the removal of the dibenzothiophenes .
[0008] Improvements in hydroprocessing techniques such as those described in U.S. Patent No. 5,409,599 and 5,730,860, were developed in response to the
previous sulfur limitations and improved management of refinery operations both in FCC units and in the hydroprocessing of middle distillates has achieved worthwhile reductions but at some cost. Refiners may, for example, choose to undercut their LCO to remove the hindered DBTs from the molecules that need to be hydrotreated. Undercutting is a practice of lowering the end boiling point (or "cut point") of a hydrocarbon fraction and thus sends more valuable, lower boiling point hydrocarbons from the LCO to the FCC bottoms resulting in a significant loss in revenue.
[0009] Other refiners choose to use very high pressure hydrogen to desulfurize the hindered DBTs in the FCC products. This process is also very costly absent significant improvements in the activity of diesel
hydrodesulfurization catalysts. Another costly option is hydrotreating the hydrocarbon feedstream to the FCC, which reduces the sulfur content but also alters the composition of the sulfur free hydrocarbons, especially of the high octane olefins which enter the gasoline fraction. This last option is also very costly due to the large (i.e., non-selective) volume of hydrocarbons required to be hydrotreated. Some attention has been given to adding components such as Zn and Ni as additives to FCC catalysts to trap the sulfur in the hydrocarbons. In such instances, the sulfur would be sent to the regenerator as ZnS instead of as organic sulfur in the product streams. The sulfur would then exit the regenerator as SOx where it would need to be further treated. The commercial success of these additives has, however, been limited. Additionally, as most refineries need additional capital hardware in order to treat any additional SOx loadings in an FCC unit, this option can be very costly in most instances.
[0010] Managing sulfur reduction in middle distillate fuels has created an incentive to develop improved methods for removing sulfur compounds, especially the refractory alkylated dibenzothiophenes, in ways which are economical as well as effective.
SUMMARY OF THE INVENTION
[0011] We have found that a significant amount of alkylation of the DBT molecules occurs in the FCC unit. That is that a non-hindered DBT molecule entering the FCC unit is likely to undergo transalkylation with alkyl fragments cracked off from other molecules and leave the unit as a sterically hindered DBT which becomes more difficult to hydrotreat. We have discovered herein a way to mitigate the effect of alkylation of DBT molecules to hindered DBTs in the FCC unit so that the proportion of hindered, refractory DBT molecules in the FCC product fractions can be reduced without incurring the cost of either rejecting useful LCO to the lower-value heavy oil products or without the use of high severity hydroprocessing of the DBT compounds.
[0012] This mitigation is accomplished by a process comprising the recycling a heavy fraction of the full-range LCO cracking product which contains long chain alkylated DBTs (e.g. C^-DBTs) to allow another round of transalkylation to take place with an equilibrium shift away from the hindered alkyl DBTs. Here, long chain alkyl groups split off from the hydrocarbons and the long chain alkylated DBT's (typically Ci2-DBTs) present in the heavier LCO fractions may attach to other species in the fraction to produce a net decrease in the proportion of hindered DBTs in the portion that enters the distillate product. Transalkylation reactions may form DBTs alkylated with long chain alkyl groups formed by cracking of long alkyl side chains in the heaviest LCO fractions but these long chain DBTs are likely to boil above the distillate product boiling range shown above and so do not need to be hydrotreated with the portion of the distillate which will enter the distillate fuel fraction, e.g. for road diesel, kerojet. The long chain alkyl DBTs will be rejected to the heavy fuel oil product to which the stringent sulfur limits do not apply.
[0013] According to the present invention, the sulfur content of the middle distillate fraction from an FCC process is reduced by fractionating the cracked liquid products to form a cracked naphtha fraction and a full-range LCO fraction that contains alkylated dibenzothiophenes. Typically the full-range LCO (or "distillate") fraction boils substantially in the range from about 395 to about 7500F (approximately 200 to 4000C). A portion of the LCO fraction that contains the long chain alkylated DBT's, typically the fraction boiling
substantially in the range from about 500 to about 75O0F (260 to 4000C), and more preferably, the fraction boiling substantially in the range from about 520 to about 75O0F (271 to 4000C), is recycled to transalkylate or dealkylate the sterically-hindered alkyl DBTs in the FCC feed. In a most preferred
embodiment of the present invention, the recycled portion of the LCO fraction that contains the long chain alkylated DBT's, boils substantially in the range from about 520 to about 68O0F (271 to 3600C). By substantially it is meant that at least 80 wt% of the designated fraction boils in the range of temperatures designated.
[0014] The reaction transferring the alkyl groups from the alkylated DBTs to the other species present is favored by relatively lower temperatures (i.e. lower relative to the cracking temperatures) and for this reason, the recycled fraction of the LCO is preferably re-introduced into the FCC cycle at a point where the temperature is lowered slightly from the original cracking temperature. Re- introduction of the recycled LCO fraction can suitably be made at the top of the FCC riser or even more preferably into the stripper section of the FCC reactor.
FIGURES
[0015] FIGURE 1 is a graph showing the sulfur speciation of a typical light cycle oil ("LCO").
[0016] FIGURE 2 is a graph showing the sulfur speciation of cracking products of a vacuum gas oil ("VGO") with dibenzothiophene added in three concentrations.
DETAILED DESCRIPTION
FCC Process
[0017] The predominate commercially utilized catalytic cracking process for gasoline production currently in use is the fluid catalytic cracking ("FCC") process. Apart from the use of the LCO recycle, the manner of operating the FCC process of the present invention will remain essentially unchanged. Thus, conventional FCC catalysts may be used, for example, zeolite based catalysts with a faujasite cracking component as described in the seminal review by Venuto and Habib, Fluid Catalytic Cracking with Zeolite Catalysts, Marcel Dekker, New York 1979, ISBN 0-8247-6870-1 as well as in numerous other sources such as Sadeghbeigi, Fluid Catalytic Cracking Handbook, Gulf Publ. Co. Houston, 1995, ISBN 0-88415-290-1.
[0018] In an embodiment of the present invention, the fluid catalytic cracking process in which the heavy hydrocarbon feed containing the
organosulfur compounds will be cracked to lighter products takes place by contact of a hydrocarbon-containing feed (also referred to herein as "heavy hydrocarbon feed", "hydrocarbon feed", or simply "feed) in a cyclic catalyst recirculation cracking process with a circulating fluidizable catalytic cracking
catalyst inventory consisting of particles having a size ranging from about 20 to about 100 microns. The significant steps in the cyclic process are:
(i) the hydrocarbon feed is catalytically cracked in a catalytic cracking zone, normally a riser cracking zone, operating at catalytic cracking conditions by contacting the hydrocarbon feed with a source of hot, regenerated cracking catalyst to produce an effluent comprising cracked products and spent catalyst containing coke and strippable hydrocarbons;
(ii) the effluent from the cracking zone is discharged and separated, normally in one or more cyclones, into a vapor phase rich in cracked hydrocarbon products and a solids rich phase comprising the spent catalyst;
(iii) the vapor phase is removed as product and fractionated in the FCC main column and its associated side columns to form liquid cracking products including gasoline and light cycle oil;
(iv) the spent catalyst is stripped, usually with steam, to remove occluded hydrocarbons from the catalyst, after which the stripped catalyst is oxidatively regenerated to produce hot, regenerated catalyst which is then recycled to the cracking zone for cracking further quantities of feed;
(v) the cracked hydrocarbon products are separated to produce cracked product fractions including a cracked naphtha fraction and a light cycle oil (LCO) fraction containing alkylated dibenzothiophenes; and
(vi) at least a portion of the light cycle oil fraction containing alkylated dibenzothiophenes is recycled to the catalytic cracking process in order to transalkylate at least a portion of the alkylated
dibenzothiophenes thereby reducing the level of hindered alkylated dibenzothiophenes in the cracking products.
[0019] The feed to the FCC process will typically be a high boiling feed of mineral oil origin, normally with an initial boiling point of at least about 55O0F (29O0C) and in most cases above about 6000F (315°C). Most refinery cut points for FCC feed will be at least about 6500F (3450C). The end point will vary, depending on the exact character of the feed or on the operating characteristics of the refinery. FCC feeds can include virgin feeds such as gas oils, e.g. heavy or light atmospheric gas oil, heavy or light vacuum gas oil as well as cracked feeds such as light coker gas oil, heavy coker gas oil as well as resid (non- distil lab Ie) material. Hydrotreated feeds may also be used, for example, hydrotreated gas oils, especially hydrotreated heavy gas oil. When utilizing the process of the present invention, it may be possible to dispense with initial hydrotreatment where its objective is to reduce sulfur although improvements in crackability will still be achieved.
[0020] FCC reactor riser top temperature conditions can be controlled in the range of about 900 to about 10500F (about 482 to 565°C), preferably about 925° to about 10500F (about 496 to 565°C) with typical operation at about 10000F (about 5400C). However, most preferred FCC reactor riser top temperatures conditions for use of the present invention are on the lower end of these temperatures, preferably in the range of about 930 to about 9700F (510 to 52O0C). Typical regenerated catalyst temperatures are in the range of about 1250 to about 135O0F (about 675 to 73O0C). Catalystroil ratios from about 1 :1 to 20:1, preferably from 3:1 to 6:1, are typical. Pressures in the FCC reactor riser are normally of about atmospheric to about 350 kPag (50 psig) are preferred. These values are, however, subject to variation as discussed below if the generation of hindered DBTs in the process is to be mitigated according to the present process. The feed is usually preheated to about 350° to 7000F (175 to 37O0C), though operation with feed preheat outside of this range is possible.
[0021] The liquid cracking products from the FCC process typically include cracked naphtha fractions (light gasoline and heavy gasoline) boiling up to about 4300F (2200C), and a full-range LCO fraction typically boiling in the range of about 395 to about 75O0F (200 to about 4000C). A undercut LCO fraction (such as the recycled LCO fraction herein) may also be drawn directly from an FCC fractionator or may be further separated from a full-range LCO fraction.
FCC Catalyst
[0022] The cracking component of the FCC catalyst which is present to effect the desired cracking reactions and the production of lower boiling cracking products, is typically based on a faujasite zeolite active cracking component, which is conventionally zeolite Y in one of its forms such as calcined rare-earth exchanged type Y zeolite (CREY), the preparation of which is disclosed in U.S. Pat. No. 3,402,996, ultrastable type Y zeolite (USY) as disclosed in U.S. Pat. No. 3,293,192, as well as various partially exchanged type Y zeolites as disclosed in U.S. Pat. Nos. 3,607,043 and 3,676,368. Cracking catalysts such as these are widely available in large quantities from various commercial suppliers. The active cracking component is routinely combined with a matrix material such as silica and/or alumina as well as a clay in order to provide the desired mechanical characteristics (attrition resistance etc.) as well as activity control for the very active zeolite component or components. The particle size of the cracking catalyst is typically in the range of 10 to 100 microns for effective fluidization. If separate particle additive catalysts are used, they are normally selected to have a particle size and density comparable to that of the cracking catalyst so as to prevent component segregation during the cracking cycle.
Generation of Hindered Dibenzothiophenes
[00231 It has been discovered that a significant portion of the sterically hindered dibenzothiophenes generated during the FCC process arise from the alkylation of simpler dibenzothiophenes ("DBT's) present in the feed with alkyl fragments liberated during the cracking; generation from other sulfur species such as alkylthiophenes, sulfides, mercaptans has not been found to be significant. It was further discovered that the choice of cracking catalyst had an effect on the extent to which the transalkylation took place during the cracking. As a general proposition, transalkylation onto the dibenzothiophenes in the present process is favored by the use of catalysts with a large unit cell size in the zeolite component and a high matrix activity and/or high metals content. For this reason, when the basic process objective is to minimize the generation of hindered DBTs in the initial cracking step, the preferred cracking catalysts are those that have a low unit cell size. Unit cell sizes below 2.427 nm and lower, below 2.425 nm, are therefore preferred for the zeolite component. It is also believed that low matrix activity and low metals content may also be favorable for low transalkylation activity, with matrix activity as measured by matrix surface area not more than 40 m2/gram, and preferably not more than 35 or 30 m2/gram, in order to minimize the extent of transalkylation onto the unhindered DBT molecules present in the feed. As discussed below, however, a strategy of minimizing the generation of hindered DBTs by some reversal of the undesired alkylation is favored by the use of a catalyst that increases the degree of transalkylation, so establishing a tension in the final choice of catalyst.
Hindered DBT Reduction Strategy
[0024] According to the present invention, the effect of transalkylation onto the DBTs present in the feed is mitigated by a reversal of the process by which
they form; in other words, the conditions under which the undesired
transalkylation takes place are replicated although optionally modified to favor transalkylation away from the hindered alkyl DBTs. If the hindered DBTs are given another chance to react, the equilibrium may be shifted and the amount of hindered sulfur in the resulting LCO changed.
[0025] Speciation of a typical light cycle oil fraction (boiling substantially in the range of 350 to 7500F) from a refinery FCC unit has shown that the hindered DBTs are concentrated in the heaviest portions of the LCO. Table 1.1 shows the boiling point distribution of this LCO and Table 1.2. shows the sulfur distribution, by Sulfur Simdist, in the same LCO by boiling point.
Table 1.1
Sim Dist. Boiling Point of LCO Cuts
Table 1.2
Total Sulfur of LCO Cuts by Boiling Point
[0026] Figure 1 herein shows that the mono-alkyl and di-alkyl substituted DBTs are found principally in the highest boiling tractions of the LCO; it is these fractions, therefore, that are the most likely to benefit from any treatment which reduces the level of hindered alkyl DBTs. The fractions representing the highest boiling 60% of the LCO fraction with boiling points substantially in the range of about 500 to about 75O0F (260 to 41O0C), and more preferably with boiling points substantially in the range of about 520 to about 7500F (271 to 4100C) are the ones preferably treated in the present processing scheme. Again, by use of the term "substantially" as used in the disclosure herein, it is meant that at least 80 wt% of the designated fraction boils in the range of temperatures designated.
[0027] It has been found, however, that it in a most preferred embodiment of the present invention, it may not be preferable to recycle the highest boiling fractions of the LCO with boiling points above about 6800F (3600C) since these contain long chain alkyl substituents which on cracking may generate Cl and C2 alkyl fragments which may react with DBT cores and so re-form the hindered DBTs such as 4,6 dimethyl DBT and 4 ethyl DBT which should be removed.
Therefore, in the most preferable embodiment of the present invention the recycled fraction of LCO has boiling points substantially in the range of about 520 to about 68O0F (271 to 36O0C). This is explained further in Example 2 herein. The optimal final boiling point for the recycled LCO fraction can be determined empirically as a function of base FCC feed composition, catalyst selection, and operating conditions.
[0028] The heavy fraction of the LCO may be recycled to any convenient point in the cracking cycle where cracking products are in contact with the cracking catalyst and the temperature is conducive to transalkylation. It may therefore be recycled to any point of the FCC reactor riser, the reactor
(disengager) or to the stripper as conditions in all locations will be conducive to the desired transalkyltion/dealkylation reactions. Because transalkylation does not require the high temperatures required for the actual cracking, lower temperatures are preferred, favoring the reactions of transalkylation away from the hindered DBTs to the other species present. Injection of the recycle LCO no earlier than at the riser top therefore provides the optimal range of solutions. Injection at the riser top will be favored when the unit is operated with closed cyclones or other rapid disengagement systems which separate the catalyst from the cracking products quickly. In this case, a relatively low riser top temperature will be preferred for the now desired transalkylation reactions. IfFCC reactor riser top injection is actually selected, the temperature at this point should be adequate to vaporize the recycled LCO. A preferred target range for the FCC reactor riser top temperature is from about 930 to about 9700F (499 to 5210C). Riser top temperature can be controlled by appropriate selection of catalyst:oil ration and regenerated catalyst temperature. A relatively low catalyst:oil ratio coupled with a high regenerated catalyst temperature may be required to ensure feed vaporization with enough cooling in the riser to attain the desired FCC reactor riser top temperature. Resort may also be made to the use of a riser quench to control the riser top temperature, by utilizing quench media such as
cycle oil, naphtha, distillate, and/or waste oil. Riser quench enables the reactor mix zone temperature to be increased, typically by about 25 to 500F (15 to 30°C) while still retaining the desired riser top temperature.
[0029] Alternatively, the selected recycled LCO fraction utilized herein may be injected into the FCC reactor vessel, especially if a closed cyclone system is not being used. A preferred option, however, is injection of the recycled LCO fraction into the stripper section of the FCC reactor which typically operates at a temperature of about 5 to 100F (2 to 50C) lower than the riser top temperature, thereby favoring the transalkylation reactions. Preferred operating temperatures for the present invention are from about 900 to about 98O0F (about 482 to 527°C), preferably about 920° to about 9650F (about 493 to 518°C). In addition, the catalystioil ratio in the stripper section is relatively high, as compared to the ratios prevailing in the riser and the reactor as a result of separation of cracked products and the injection of the recycle. The extended contact time prevailing in the stripper will also tend to increase attainment of the transalkylation equilibrium between the unalkylated recycle and the cracking products, for the desired decrease in hindered DBT levels.
[0030] If feasible, given the limitations of the unit, injection of the recycled LCO is preferably carried out at temperatures which enhance the transalkylation chemistry and minimize cracking and the amount of dry gas and coke make. The recycled LCO is preferably injected at a point in the FCC process where the process temperatures are from about 930 to about 97O0F (499 to 5210C), and more preferably from about 950 to about 97O0F (510 to 5210C).
[0031] In order to achieve the greatest reduction in the amount of hindered DBTs in the distillate cracking product, recycle of the entire fraction containing these compounds would be preferred although a definite limit may be
established by the accumulation of these materials in the unit. Because it is
unlikely that conditions prevailing in the unit downstream of the riser top will normally be conducive to a significant degree of cracking of the recycled LCO fraction so that significant losses of the LCO will take place in normal operation, recycle of this fraction is unlikely to impose a substantial yield penalty. On the other hand, recycle should not be carried to the point that an accumulation of recycled LCO occurs in the reactor. As such, in most embodiments, only a portion of the FCC product produced in the desired LCO ranges cited need to be recycled back the FCC reactor. Normally, recycle of more than 50 vol% of the portion of the LCO containing these long chain alkylated DBT's (comprising Ci2-DBTs) should not be required given the relatively small amount of hindered DBTs likely to be formed from most crude sources.
[0032] As noted above, catalyst choice has been found to affect the efficacy of the alkyl transfer reactions. Catalysts in which the zeolite component has high unit cell size tend to promote transalkylation onto the DBTs. High matrix activity of a catalyst (as measured, for example, by matrix surface area) is also believed to be associated with high transalkylation activity. Conversely, catalysts with relatively lower unit cell size are less active for transalkylation and lower matrix activity may also be found to be associated with reduced
transalkylation activity. This implies that if transalkylation of the DBT molecules is to be minimized to the extent feasible during the initial cracking reactions, a catalyst with low transalkylation activity would be the catalyst of choice (low unit cell size possibly coupled with low matrix activity). On the other hand, when the LCO fraction herein is recycled, transalkylation activity should desirably be maximized by using a catalyst of high unit cell size coupled potentially with high matrix activity. Because the FCC unit has to be operated with only one circulating catalyst however, a fundamental tension is established as it is not possible to accommodate both requirements simultaneously in one catalyst formulation. A compromise catalyst candidate may therefore be the best choice although a final selection will be made on an empirical basis, taking into
account the feed composition, product slate desired, unit characteristics and catalyst availability.
[0033] Although the trends relating the zeolite cell size and matrix activity of the catalyst to transalkylation activity are not firmly fixed, zeolite unit cell size of at least 2.425 nm, preferably at least 2.428 or even 2.430 nm have been found to confer good transalkylation activity with very notable results achieved with a zeolite unit cell size of at least 2.44 nm. Embodiments of the present invention incorporating catalysts with a high activity matrix of at least 40 or even 50 m2/gram surface area is also preferred.
Example 1
[0034] Model compound spiking experiments in a laboratory scale FCC unit were carried out to better understand the FCC sulfur chemistry. The feed used was, throughout, a vacuum gas oil ("VGO") containing 0.99 wt. pet. sulfur. Dibenzothiophene was added to the feed in amounts of 1%, 3% and 5%, to give nominal total sulfur contents of 1.15 wt%, 1.47 wt%, and 1.77 wt%,
respectively.
[0035] Each feed sample was run in the unit 4 to 5 times under the same conditions using Reduxion™ ECat (BASF) catalyst. Unless otherwise stated, each run in the unit was conducted at 99O0F (approximately 53O0C) and a cat/oil ratio of 6. The sulfur distribution in the total liquid product ("TLP") was determined on the basis of the simulated distillation with the hindered alkyl DBTs (C1 DBT = monosubstituted DBT, C2 DBT = monosubstituted DBT) showing longer retention times in the Simdist chromatogram than the unhindered (C0) DBT. The total sulfur content in the total liquid product recovered from the process was obtained while the sample was still cold. The presence of the added
DBT did not appreciably affect the conversion under the selected reaction conditions.
[0036] The results shown in Figure 2 indicated that dibenzothiophenes (DBTs) in the feed were a major contributor to distillate range sulfur. A significant amount of alkylation occurred in the unit to form hindered DBTs but no substantial cracking of DBTs was observed nor was there any evidence of ring growth to form coke. Formation of DBTs or hindered DBTs was not observed with other experiments in which other sulfides and thiophenes were added to the feed. For example, no olefin and H2S combination to form thiophenes was evident from runs where octyl sulfide was added to the feed.
Example 2
[0037] Individual cuts of the LCO reported in Tables 1.1 and 1.2 above were fed directly into the laboratory scale FCC unit, with a catalyst having a cell size of 2.429 nm and a matrix surface area of 30 m2/g. The reaction was run at two different temperatures, namely 53O0C and 5050C (99O0F and 94O0F). A summary of the results is shown in Table 2.
Table 2
4,6 Dimethyl DBT conversion in FCC
[0038] A positive number indicates that the 4,6 Dimethyl DBT structure is converted while a negative number indicates that the 4,6 Dimethyl DBT species is generated in the unit. This study shows that the most promising way to reduce the concentration of 4,6 dimethyl DBT species is to recycle the 70-90% cut of this LCO (nominal boiling point 325-36O0C, 620-6800F) at a low temperature. The low cracking temperature enhances the transalkylation chemistry and ensures that the amount of dry gas and coke make is minimized. Recycling the heaviest cut (90-100%, nominal 360-4100C, 680-7700F) of LCO results in 4,6 dimethyl DBT generation due to the long alkyl chains (>=C2) cracking to form Ci and C2 species such as 4,6 dimethyl DBT and 4 ethyl DBT.
Claims
1. A fluid catalytic cracking process comprising cracking a heavy hydrocarbon feed in a fluid catalytic cracking (FCC) unit comprising the steps of:
(a) contacting the hydrocarbon feed with a heated circulating catalyst to produce cracked product fractions including a cracked naphtha fraction and a light cycle oil (LCO) fraction containing alkylated
dibenzothiophenes;
(b) recycling at least a portion of the light cycle oil fraction containing alkylated dibenzothiophenes to the catalytic cracking process, wherein the at least 80 wt% of the portion of the light cycle oil fraction that is recycled boils in the range from about 500 to about 75O0F (260 to 41O0C); and
(c) transalkylating at least a portion of the alkylated dibenzothiophenes in the recycled light cycle oil fraction in the presence of the circulating catalyst;
wherein the circulating catalyst comprises a faujasitic zeolite with a unit cell size of at least 2.425 nm; and the level of hindered alkylated dibenzothiophenes in the cracked product fractions is reduced.
2. The process of claim 1, wherein at least 80 wt% of the recycled LCO fraction containing alkylated dibenzothiophenes boils in the range from about 520 to about 68O0F (271 to 3600C).
3. The process of claim 1 , wherein the FCC unit is a unit with a cracking riser and a portion of the LCO fraction containing alkylated dibenzothiophenes is recycled to the top of the cracking riser.
4. The process of claim 3, wherein the riser top temperature is from about 930 to about 97O0F (499 to 5210C).
5. The process of claim 1, wherein the FCC unit is a unit with a reactor-disengager vessel for separating cracked product fractions from the circulating catalyst and at least a portion of the LCO fraction containing alkylated dibenzothiophenes is recycled to the reactor-disengager vessel.
6. The process of claim 1, wherein the FCC unit is a unit with a stripper section for stripping cracked hydrocarbon products from the circulating catalyst, and at least a portion of the LCO fraction containing alkylated dibenzothiophenes is recycled to the stripper section of the FCC unit.
7. The process of claim 1, wherein the surface area of the faujasitic zeolite is at least 40 m2/gram.
8. The process of claim 7, wherein the faujasitic zeolite has a unit cell size of at least 2.430 nm.
9. The process of claim 8, wherein the cracked product fractions are comprised of a full-range LCO fraction that has a boiling range substantially from about 395 to about 5700F (200 to 3000C) and the level of hindered alkylated dibenzothiophenes in the full-range LCO fraction is reduced.
10. A fluid catalytic cracking process in which a heavy hydrocarbon feed containing organosulfur compounds is cracked to lighter products by contact of the hydrocarbon feed in a cyclic catalyst recirculation cracking process with a circulating inventory of a fluidizable catalytic cracking catalyst comprising catalyst particles, comprising the steps of: (a) catalytically cracking the hydrocarbon feed in a riser catalytic cracking zone operating at catalytic cracking conditions by contacting the hydrocarbon feed with a source of hot, regenerated cracking catalyst to produce an effluent comprising cracked hydrocarbon products and spent catalyst which contains coke and strippable hydrocarbons;
(b) separating the effluent from the cracking zone into cracked hydrocarbon products and catalyst;
(c) fractionating the cracked hydrocarbon products to form a light cycle oil fraction comprising alkylated dibenzothiophenes;
(d) stripping the spent catalyst in a stripper section to remove occluded hydrocarbons from the catalyst, thereby producing a stripped catalyst;
(e) oxidatively regenerating the stripped catalyst to produce a regenerated catalyst and recycling the regenerated catalyst to the riser cracking zone for cracking further quantities of the hydrocarbon feed; and
(f) recycling at least a portion of the light cycle oil fraction containing alkylated dibenzothiophenes to the cracking process, wherein the at least 80 wt% of the portion of the light cycle oil fraction that is recycled boils in the range from about 500 to about 75O0F (260 to 41O0C), thereby transalkylating at least a portion of the alkylated dibenzothiophenes in the recycled light cycle oil fraction in the presence of the cracking catalyst;
wherein the regenerated cracking catalyst comprises a faujasitic zeolite with a unit cell size of at least 2.425 nm; and the level of hindered alkylated dibenzothiophenes in the cracked hydrocarbon products is reduced.
11. The process of claim 10, wherein at least 80 wt% of the recycled LCO fraction containing alkylated dibenzothiophenes boils in the range from about 520 to about 68O0F (271 to 36O0C).
12. The process of claim 10, wherein at least a portion of the LCO fraction containing alkylated dibenzothiophenes is recycled to the top of the cracking riser.
13. The process of claim 12, wherein the riser top temperature is from about 930 to about 9700F (499 to 5210C).
14. The process of claim 10, wherein at least a portion of the LCO fraction containing alkylated dibenzothiophenes is recycled to the stripper section of the FCC unit.
15. The process of claim 10, wherein the surface area of the faujasitic zeolite is at least 40 m2/gram.
16. The process of claim 15, wherein the faujasitic zeolite has a unit cell size of at least 2.430 nm.
17. The process of claim 16, wherein the cracked product fractions are comprised of a full-range LCO fraction that has a boiling range substantially from about 395 to about 57O0F (200 to 3000C) and the level of hindered alkylated dibenzothiophenes in the full-range LCO fraction is reduced.
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US9181500B2 (en) | 2014-03-25 | 2015-11-10 | Uop Llc | Process and apparatus for recycling cracked hydrocarbons |
US10385279B2 (en) | 2014-03-25 | 2019-08-20 | Uop Llc | Process and apparatus for recycling cracked hydrocarbons |
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