US20020014438A1 - Recracking mixture of cycle oil and cat naphtha for maximizing light olefins yields - Google Patents

Recracking mixture of cycle oil and cat naphtha for maximizing light olefins yields Download PDF

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Publication number
US20020014438A1
US20020014438A1 US09/811,165 US81116501A US2002014438A1 US 20020014438 A1 US20020014438 A1 US 20020014438A1 US 81116501 A US81116501 A US 81116501A US 2002014438 A1 US2002014438 A1 US 2002014438A1
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Prior art keywords
catalyst
cycle oil
steam
reaction zone
naphtha
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Abandoned
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US09/811,165
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George Swan
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ExxonMobil Technology and Engineering Co
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Individual
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Priority to US09/811,165 priority Critical patent/US20020014438A1/en
Priority to EP01926744A priority patent/EP1274810A2/en
Priority to CA002402052A priority patent/CA2402052A1/en
Priority to CN01808100.2A priority patent/CN1423686A/zh
Priority to AU2001253259A priority patent/AU2001253259A1/en
Priority to JP2001577367A priority patent/JP2003531242A/ja
Priority to PCT/US2001/011443 priority patent/WO2001079383A2/en
Assigned to EXXONMOBIL RESEARCH AND ENGINEERING COMPANY reassignment EXXONMOBIL RESEARCH AND ENGINEERING COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SWAN III, GEORGE A.
Publication of US20020014438A1 publication Critical patent/US20020014438A1/en
Abandoned legal-status Critical Current

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    • 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
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only

Definitions

  • This invention relates to a fluid catalytic cracking process. More particularly, a mixture of cycle oil, light cat naphtha, and steam are added to the reaction zone to improve yields of light olefins.
  • Fluid catalytic cracking is a well-known method for converting high boiling hydrocarbon feedstocks to lower boiling, more valuable products.
  • the high boiling feedstock is contacted with fluidized catalyst particles in the substantial absence of hydrogen at elevated temperatures.
  • the cracking reaction typically occurs in the riser portion of the catalytic cracking reactor.
  • Cracked products are separated from catalyst by means of cyclones and coked catalyst particles are steam-stripped and sent to a regenerator where coke is burned off the catalyst. The regenerated catalyst is then recycled to contact more high-boiling feed at the beginning of the riser.
  • Typical FCC catalysts contain active crystalline aluminosilicates such as zeolites and active inorganic oxide components such as clays of the kaolin type dispersed within an inorganic metal oxide matrix formed from amorphous gels or sols that bind the components together on drying. It is desirable that the matrix be active, attrition resistant, selective with regard to the production of hydrocarbons without excessive coke make and not readily deactivated by metals.
  • Current FCC catalysts may contain in excess of 40 wt. % zeolites.
  • U.S. Pat. No. 4,051,013 describes a cat cracking process for simultaneously cracking a gas oil feed and upgrading a gasoline-range feed to produce high quality motor fuel.
  • the gasoline-range feed is contacted with freshly regenerated catalyst in a relatively upstream portion of a short-time dilute-phase riser reactor zone maintained at first catalytic cracking conditions and the gas oil feed is contacted with used catalyst in a relatively downstream portion of the riser reaction zone which is maintained at second catalytic cracking conditions.
  • U.S. Pat. No. 5,043,522 relates to the conversion of paraffinic hydrocarbons to olefins. A saturated paraffin feed is combined with an olefin feed and the mixture contacted with a zeolite catalyst.
  • the feed mixture may also contain steam.
  • U.S. Pat. No. 4,892,643 discloses a cat cracking operation utilizing a single riser reactor in which a relatively high boiling feed is introduced into the riser at a lower level in the presence of a first catalytic cracking catalyst and a naphtha charge is introduced at a higher level in the presence of a second catalytic cracking catalyst.
  • U.S. Pat. No. 5,846,403 discloses an FCC reaction wherein a mixture of light catalytically cracked naphtha (“light cat naphtha” or “LCN”) and steam is injected into an FCC riser at a point upstream of gas oil or residual oil injection. Such LCN and steam coinjection results in augmented light olefin production in the FCC unit.
  • LCN light cat naphtha
  • the present invention relates to a fluid catalytic cracking process for upgrading feedstocks to increase yields of C 3 and C 4 olefins, the process comprising:
  • step (b) separating from the cracked products a cycle oil fraction, a light cat naphtha fraction, and steam from spent catalyst and recycling at least a portion of the cycle oil fraction and light cat naphtha fraction to the upstream reaction zone in step (b),
  • the invention is related to a product formed in accord with such a process.
  • FIG. 1 is a flow diagram showing the two zone feed injection system in the riser reactor.
  • FIG. 2 shows the selectivity for olefins compared to dry gas for various LCN:cycle oil ratios.
  • the invention is based on the discovery that increased C 3 and C 4 olefin production over conventional (i.e., base) FCC operation and decreased dry gas production compared to neat LCN recycle in an FCC process may be obtained by injecting cycle oil, LCN, and steam at a point upstream of heavy feed injection. More particularly, the invention is related to an FCC riser reactor having at least one two-zone riser reactor wherein cycle oil, LCN, and steam are injected into a second zone upstream of a first zone, the heavy feed being injected into the first zone.
  • the riser reactor of a typical FCC unit receives hot regenerated catalyst from the regenerator.
  • Fresh catalyst may be included in the catalyst feed to the riser reactor.
  • a lift gas such as light hydrocarbon vapors, or steam may be added to the riser reactor to assist in fluidizing the hot catalyst particles.
  • cycle oil, light cat naphtha, and steam are added in an upstream zone of the riser reactor.
  • the cycle oil may include heavy cycle oil, light cycle oil, and mixtures thereof.
  • Heavy cycle oil refers to a hydrocarbon stream boiling in the range of 240° C. to 370° C. (about 465° F. to about 700° F.).
  • Light cycle oil refers to a hydrocarbon stream boiling in the range of 190° C. to 240° C.
  • Light cat naphtha refers to a hydrocarbon stream having a final boiling point less than about 150° C. (300° F.) and containing olefins in the C 5 to C 9 range, single ring aromatics (C 6 -C 9 ) and paraffins in the C 5 to C 9 range.
  • Cycle oil and light cat naphtha (“LCN”) is injected into the upstream reactor zone together with 2 to 50 wt. % of steam, based on total weight of cycle oil and LCN.
  • the cycle oil, LCN, and steam have a vapor residence time in the upstream zone of less than about 1.5 sec., preferably less than about 1.0 sec, and more preferably less than 0.5 seconds.
  • Cat/oil ratios range from 75-150 (wt/wt) at pressures of 100 to 400 kPa and temperatures in the range of 620-775° C.
  • the addition of cycle oil, steam, and LCN in this upstream zone results in increased C 3 and C 4 olefins yields by cracking C 5 to C 9 olefins in the LCN feed and cracking principally saturated species in cycle oil to produce naphtha and lighter products.
  • Suitable catalysts include any catalyst 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 aluminophosphates (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. Included among the synthetic zeolites are 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.
  • 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 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, November 1949, are desirable.
  • Alumina, silica-alumina and silica-alumina-zirconia compounds are preferred.
  • the inert catalyst framework component densities, 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 ⁇ -alumina, boehmite, diaspore, and transitional aluminas such as ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, and ⁇ -alumina can be employed.
  • the alumina species is an aluminum trihydroxide such as gibbsite, bayerite, nordstrandite, or doyelite.
  • Coked catalyst particles and cracked hydrocarbon products from the upstream and downstream reaction zones in the riser reactor are conducted from the riser reactor into the main reactor vessel which contains cyclones.
  • the cracked hydrocarbon products are separated from coked catalyst particles by the cyclone(s).
  • Coked catalyst particles from the cyclones are conducted to a stripping zone where strippable hydrocarbons are stripped from coked catalyst particles under stripping conditions. In the stripping zone, coked catalyst is typically contacted with steam. Stripped hydrocarbons may be combined with cracked hydrocarbon products and recovered for storage or further processing.
  • the catalyst is then conducted to a regenerator.
  • Suitable regeneration temperatures include a temperature ranging from about 1100 to about 1500° F. (593 to about 816° C.), and a pressure ranging from about 0 to about 150 psig (101 to about 1136 kPa).
  • the oxidizing agent used to contact the coked catalyst will generally be an oxygen-containing gas such as air, oxygen and mixtures thereof.
  • the coked catalyst is contacted with the oxidizing agent for a time sufficient to remove, by combustion, at least a portion of the carbonaceous deposit and thereby regenerate the catalyst.
  • hot catalyst 10 from the regenerator (not shown) is conducted through regenerated catalyst standpipe 12 and slide valve 14 into the “J” bend pipe 16 which connects the regenerator standpipe 12 to the riser reactor 32 .
  • Lift gas 20 is injected into pipe 16 through injection nozzle 18 thereby fluidizing hot catalyst particles 10 .
  • Cycle oil and light cat naphtha 22 together with steam 24 are injected into upstream reaction zone 34 through nozzle 26 ; multiple injection nozzles may be employed.
  • C 5 to C 9 olefins in the LCN are cracked to C 3 and C 4 olefins.
  • at least a portion of the saturated species present in the cycle oil is converted to lower boiling point products including light olefins.
  • This reaction is favored by short residence times and high temperatures. Cracked hydrocarbon products, partially deactivated catalyst and steam from reaction zone 34 are conducted to downstream reaction zone 36 .
  • reaction zone 36 conventional heavy FCC feedstocks 28 are injected through multiple injection nozzles 30 and combined with the cracked hydrocarbon products, catalyst and steam from reaction zone. Residence times in zone 36 are longer which favor conversion of feed 28 . Cracked products from zone 34 and 36 together with coked catalyst and steam are then conducted to the reactor vessel containing cyclones (not shown) where cracked products are separated from coked catalyst particles.
  • the LCN:cycle oil ratio at injection should range from 0.1 to 0.75, based on the combined weight of cycle oil and LCN. Preferably the ratio ranges from about 0.1 to about 0.6, and more preferably from about 0.2 to about 0.5.
  • Comparative recycle options for short contact time FCC units were evaluated using a process model based on an existing FCC unit. Accordingly, the calculation directly compared existing unit performance with calculated results reflecting LCN and cycle oil injection in admixture with the heavy feed and approximately two meters upstream of the primary feed injectors.
  • a cat cycle oil (“CCO”) with boiling range of 240/370° C., light cat naphtha (LCN) with 10/100° C. boiling range, a constant fresh feed rate of 172 m 3 hr, and nominal recycle rate of 10 m 3 /hr were used in this example.
  • the heavy feed employed contained VGO and about 4 wt. % vacuum resid.
  • Feed properties are summarized in Table I. TABLE I FEEDSTOCK PROPERTIES VGO VAC RESID Gravity, API 23.8 11.4 Sulfur, wt. % 1.10 1.40 Thiophenic sulfur, wt. % 0.88 1.12 Nitrogen, wppm 1369 4111 Basic nitrogen, wppm 413 1247 Conradson carbon, wt. % N.A. 15.3
  • Catalyst properties are set forth in Table II: TABLE II CATALYST PROPERTIES Unit Cell, ⁇ 24.27 Surface area, m 2 /gm 0.80 ABD, gm/cc 0.40 Pore Vol., cc/gm 1.52 REO, wt. % 1930 V, wppm 4150 Ni, wppm 61
  • Feed pre-heat and riser outlet temperatures are constant for each example.
  • the highest light olefin yields and the highest olefin to dry gas selectivity are achieved with LCN and CCO recycle. Cases with recycle of LCN and CCO streams in admixture with base gas oil feed results in improvements that are much less pronounced. Dry gas yields increase with increasing LCN recycle. There is a 2 wt. % 430° F. conversion penalty for the neat LCN recycle case (and large LCN volume reduction), whereas the neat CCO recycle option gives a minimal conversion debit. In essence, examples 2 and 3 bracket the ideal situation wherein light olefins yields are increased without a large dry gas penalty and conversion of fresh feed is maximized.
  • FIG. 2 shows that the ratio of light olefin yield increase to dry gas yield increase may be adjusted by including cycle oil with LCN recycle, in accord with the invention.
  • the ordinate in FIG. 2 shows the increase in light olefin yield divided by the increase in dry gas yield plotted for various LCN:cycle oil ratios on the abscissa.
  • the preferred blend composition contains about 30 wt. % LCN.
  • the calculated pre-injection vapor residence time for all examples is approximately constant at only 0.35-0.4 second. Extremely high (120-160) cat/oil ratios are realized at these elevated temperatures, and both catalytic and thermal reactions occur. While not wishing to be bound by any theory, it is believed that CCO injected into the upstream zone may provide an in situ quench for LCN cracking at this extraordinary intensity.

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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)
US09/811,165 2000-04-17 2001-03-16 Recracking mixture of cycle oil and cat naphtha for maximizing light olefins yields Abandoned US20020014438A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US09/811,165 US20020014438A1 (en) 2000-04-17 2001-03-16 Recracking mixture of cycle oil and cat naphtha for maximizing light olefins yields
EP01926744A EP1274810A2 (en) 2000-04-17 2001-04-06 Recracking mixtures of cycle oil and cat naphtha for maximizing light olefin yields
CA002402052A CA2402052A1 (en) 2000-04-17 2001-04-06 Recracking mixtures of cycle oil and cat naphtha for maximizing light olefin yields
CN01808100.2A CN1423686A (zh) 2000-04-17 2001-04-06 循环油和催化石脑油的混合物再裂化使轻烯烃产率最大
AU2001253259A AU2001253259A1 (en) 2000-04-17 2001-04-06 Recracking mixtures of cycle oil and cat naphtha for maximizing light olefin yields
JP2001577367A JP2003531242A (ja) 2000-04-17 2001-04-06 軽質オレフィン収率を最大限にするための循環油と接触ナフサとの再分解混合物
PCT/US2001/011443 WO2001079383A2 (en) 2000-04-17 2001-04-06 Recracking mixtures of cycle oil and cat naphtha for maximizing light olefin yields

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US19792000P 2000-04-17 2000-04-17
US09/811,165 US20020014438A1 (en) 2000-04-17 2001-03-16 Recracking mixture of cycle oil and cat naphtha for maximizing light olefins yields

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CN (1) CN1423686A (zh)
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CA (1) CA2402052A1 (zh)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090020454A1 (en) * 2007-07-17 2009-01-22 Cunningham Brian A Reduced elevation catalyst return line for a fluid catalytic cracking unit
US20100158767A1 (en) * 2008-12-22 2010-06-24 Mehlberg Robert L Fluid catalytic cracking system
WO2012123571A1 (en) 2011-03-16 2012-09-20 Aker Process Systems As Method and system for gas purification with first direct absorption step and second absorption step by means of membrane contactor
WO2013136310A1 (en) 2012-03-16 2013-09-19 Aker Process Systems As Hydrocarbon gas treatment
WO2018200650A1 (en) * 2017-04-25 2018-11-01 Saudi Arabian Oil Company Enhanced light olefin yield via steam catalytic downer pyrolysis of hydrocarbon feedstock

Families Citing this family (7)

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Publication number Priority date Publication date Assignee Title
US7425258B2 (en) 2003-02-28 2008-09-16 Exxonmobil Research And Engineering Company C6 recycle for propylene generation in a fluid catalytic cracking unit
US7270739B2 (en) 2003-02-28 2007-09-18 Exxonmobil Research And Engineering Company Fractionating and further cracking a C6 fraction from a naphtha feed for propylene generation
CN1333046C (zh) * 2004-04-29 2007-08-22 中国石油化工股份有限公司 一种石油烃类催化转化方法
US9181146B2 (en) 2010-12-10 2015-11-10 Exxonmobil Chemical Patents Inc. Process for the production of xylenes and light olefins
US8937205B2 (en) 2012-05-07 2015-01-20 Exxonmobil Chemical Patents Inc. Process for the production of xylenes
US9181147B2 (en) 2012-05-07 2015-11-10 Exxonmobil Chemical Patents Inc. Process for the production of xylenes and light olefins
US8921633B2 (en) 2012-05-07 2014-12-30 Exxonmobil Chemical Patents Inc. Process for the production of xylenes and light olefins

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1327177C (en) * 1988-11-18 1994-02-22 Alan R. Goelzer Process for selectively maximizing product production in fluidized catalytic cracking of hydrocarbons
US5846403A (en) * 1996-12-17 1998-12-08 Exxon Research And Engineering Company Recracking of cat naphtha for maximizing light olefins yields

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090020454A1 (en) * 2007-07-17 2009-01-22 Cunningham Brian A Reduced elevation catalyst return line for a fluid catalytic cracking unit
US8202412B2 (en) 2007-07-17 2012-06-19 Exxonmobil Research And Engineering Company Reduced elevation catalyst return line for a fluid catalytic cracking unit
US20100158767A1 (en) * 2008-12-22 2010-06-24 Mehlberg Robert L Fluid catalytic cracking system
US8246914B2 (en) 2008-12-22 2012-08-21 Uop Llc Fluid catalytic cracking system
WO2012123571A1 (en) 2011-03-16 2012-09-20 Aker Process Systems As Method and system for gas purification with first direct absorption step and second absorption step by means of membrane contactor
US9155989B2 (en) 2011-03-16 2015-10-13 Aker Process Systems Ag Method and system for gas purification with first direct absorption step and second absorption step by means of membrane contactor
WO2013136310A1 (en) 2012-03-16 2013-09-19 Aker Process Systems As Hydrocarbon gas treatment
WO2018200650A1 (en) * 2017-04-25 2018-11-01 Saudi Arabian Oil Company Enhanced light olefin yield via steam catalytic downer pyrolysis of hydrocarbon feedstock
US10767117B2 (en) 2017-04-25 2020-09-08 Saudi Arabian Oil Company Enhanced light olefin yield via steam catalytic downer pyrolysis of hydrocarbon feedstock
US11306258B2 (en) 2017-04-25 2022-04-19 Saudi Arabian Oil Company Enhanced light olefin yield via steam catalytic downer pyrolysis of hydrocarbon feedstock

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AU2001253259A1 (en) 2001-10-30
EP1274810A2 (en) 2003-01-15
JP2003531242A (ja) 2003-10-21
CN1423686A (zh) 2003-06-11
WO2001079383A2 (en) 2001-10-25
CA2402052A1 (en) 2001-10-25
WO2001079383A3 (en) 2002-04-04

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