EP0432235B1 - Verfahren zur herstellung von benzin mit verbesserten oktanzahlen - Google Patents

Verfahren zur herstellung von benzin mit verbesserten oktanzahlen Download PDF

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Publication number
EP0432235B1
EP0432235B1 EP90908440A EP90908440A EP0432235B1 EP 0432235 B1 EP0432235 B1 EP 0432235B1 EP 90908440 A EP90908440 A EP 90908440A EP 90908440 A EP90908440 A EP 90908440A EP 0432235 B1 EP0432235 B1 EP 0432235B1
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EP
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Prior art keywords
subjected
gasolines
boiling
hydrocarbons
lco
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EP90908440A
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English (en)
French (fr)
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EP0432235A1 (de
Inventor
Michel Melin
Jacques François Grootjans
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Total Research and Technology Feluy SA
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Fina Research SA
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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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen

Definitions

  • the present invention relates to a process for producing gasolines with a high octane number.
  • the present invention relates to the production of gasoline having an improved RON and MON, starting from heavier hydrocarbon feeds, originating from the catalytic cracking in a fluidized bed of vacuum gasels, deasphalted oils and residues.
  • the catalytic cracking process in a fluidized bed of heavy hydrocarbon feedstocks such as vacuum gas oils is a well-known process in particular for producing gasolines. It is also essential to produce gasolines with a high octane number due to the upcoming removal of lead additives. There is therefore a growing need to obtain, at the start of these same charges, gasolines having an octane index or RON indices (octane index "Research”) and particularly MON (octane index "Engine”) improved.
  • Patent EP 184669 describes a process for the production of gasoline with a high octane content in which a catalytic cracking of a heavy carbo-metallic oil is carried out, an LCO fraction is recovered which is subjected to a hydrogenation step and the entire hydrogenated fraction is introduced into an FCC unit.
  • US Patent 4,426,276 describes many processes for converting or upgrading crude oil; these processes are characterized in that a residual oil fraction is catalytically cracked and that the resulting high boiling fraction is then hydrocracked. According to a particular embodiment, after the hydrocracking step, the possibility of recycling the liquid products having a boiling temperature of between 204 and 315 ° C. is described by reintroducing them successively in the flash separation and cracking steps. catalytic.
  • the object of the present invention is a process which makes it possible to produce gasolines having improved RON and MON starting from heavy hydrocarbon charges.
  • the present invention also aims at a process for producing gasolines having improved RON and MON, from hydrogenated LCO, HCO and CLO.
  • FIG. 1 represents a schematic diagram of the process of the invention.
  • a charge of heavy hydrocarbons is introduced via line 10, which may consist of gas oil, vacuum gas oil or other similar charges.
  • This charge is introduced into the FCC reactor 20 in which it is brought into contact with a fluid catalytic cracking catalyst introduced through line 22.
  • the charge and the catalyst are mixed and driven upwards.
  • the catalyst is made up of fine particles so that it acts as a fluidized bed.
  • the reaction takes place in reactor 20, the catalyst falls by gravity and is recovered for regeneration via line 18 and is regenerated in reactor 16, while the various products of the catalytic reaction which include gaseous hydrocarbons, hydrocarbons boiling in the range of gasolines, LCOs, HCOs and CLOs are recovered via line 24, to be sent to a separator (25) to separate the gaseous and light products leaving via line 26, heavier products leaving through line 28.
  • the light products recovered through line 26 consist of hydrocarbons boiling in the range of gasolines.
  • the heavy products leaving via line 28 consist of LCO boiling between 221 and 350 ° C, HCO boiling between 350 and 400 ° C as well as CLO boiling at a temperature above 400 ° C.
  • the LCO, the HCO and the CLO are successively separated and they are subjected separately afterwards to a hydrogenation treatment.
  • the LCOs, HCOs and CLOs are subjected together to a hydrogenation treatment.
  • the current leaving via line 28 is mixed with hydrogen coming from one or the other source defined below and the mixture of charge and hydrogen via line 29 in the hydrogenation reaction zone 30 in the presence of a hydrogenation catalyst at a temperature between 320 and 420 ° C and under a pressure between 30 and 200 bar.
  • the hydrogenation catalyst is in the form of a fixed bed, in the reaction zone 30.
  • the charge to be hydrogenated passes through the catalytic bed maintained under hydrogenation conditions as stated above.
  • the effluent product is withdrawn from the reactor 30 via the line 31 and is introduced into the separator 32, in which the gaseous products and products boiling in the range of gasoline are separated on the one hand by the line 33. that is to say at a temperature below 221 ° C, and on the other hand via line 34, the hydrogenated products boiling at a temperature above 221 ° C.
  • These boiling hydrocarbons are subjected to a temperature above 221 ° C., to a new catalytic cracking in a fluidized bed, in a reactor (36) preferably different from the first reactor (20).
  • the hydrocarbons treated by the line (38) are recovered and separated in the separator (40) between products boiling in the range of gasolines and heavier products, containing LCO, HCO and CLO which are recycled to the reactor d hydrogenation 30 by the pipe (42), while recovering gasolines having an improved RON and MON by the pipe (44).
  • the Applicant has unexpectedly found that by subjecting all of the hydrogenated products having a boiling point above 221 ° C. taken together or separately to an FCC, the total quantity of gasolines formed by the process is increased and the RON and MON of the species formed were considerably increased.
  • the process of the invention can be adapted to the numerous modes of execution of a catalytic cracking in a fluidized bed, the essential being to resubmit the hydrogenated hydrocarbons and boiling above 221 ° C., to a treatment. from FCC.
  • the Applicant has moreover observed that subjecting the hydrogenated LCOs, HCOs and / or CLOs to a new FCC makes it possible to obtain gasolines with better RON and MON. Contrary to what is taught in the state of the art, it is not essential to limit the FCC reaction of LCOs, HCOs and / or CLOs with partially deactivated catalysts, in order to obtain the good gasoline yields, but, and this constitutes an essential element of the invention, it is absolutely necessary to contact it with a fresh FCC catalyst to obtain gasolines having a better RON and MON.
  • the hydrocarbons leaving via line 34 can be recycled to the first FCC reactor (20) in admixture with the charge of VGO (vacuum stars), but the results from the RON and MON point of view of the species obtained are slightly lower than those obtained with the mode of execution of the method presented above.
  • the FCC (20) can be used to crack the loads (normal heavy and hydrogenated LCO, HCO and / or CLO) by campaign.
  • loads normal heavy and hydrogenated LCO, HCO and / or CLO
  • catalysts suitable for use in catalytic cracking processes in particular amorphous silica-alumina, silica-magnesia, catalysts of the crystalline zeolite type such as faujasite or other analogues, such as Y zeolites dispersed in a matrix of silica and another inorganic oxide or in an alumina matrix.
  • the zeolites can also be used pure with or without zeolitic promoters of the ZSM-5 or silicalite type.
  • the matrices consist of silica-alumina in a 90-40 / 10-60 ratio, in which the zeolites are dispersed.
  • Zeolites are generally of the Y zeolite type exchanged with rare earths or of the ultrastable type (the mode of dealumination being variable).
  • Promoters can also be added in an amount of 5 to 15% by weight of the zeolite used.
  • the catalytic cracking is generally carried out at temperatures between 480 and 550 ° C and preferably between 510 and 530 ° C; at pressures between 1 and 4 bar and preferably between 1 and 2 bar.
  • the hydrotreating catalyst is preferably sulfur resistant. Most are Group VI and Group VIII metal catalysts deposited on an alumina or silica-alumina support and other similar supports. Most of the time, we use a Nickel-Molybdenum catalyst deposited on alumina or silica-alumina.
  • the hydrogenation operating conditions are a temperature between 270 and 500 ° C, a pressure between 30 and 200 bars and preferably between 60 and 120 bars, an LHSV between 0.5 and 5 and a H2 / HC ratio included between 500 and 50,000 NL / L.
  • the boiling products in the range of gasolines, LCOs and HCOs and CLOs were separated.
  • the LCOs, HCOs and CLOs were subjected to hydrogenation separately in the presence of a Ni-Mo catalyst and under the conditions indicated in Table 1.
  • the boiling products in the gasoline range were separated. and those with a boiling point above 221 ° C.
  • the products having a boiling point above 221 ° C. were sent directly to a second catalytic cracking reactor under the conditions indicated in Table 1.
  • the properties of the gasolines produced at the outlet of this latter catalytic cracking reactor are indicated in Table 1.
  • the boiling products in the range of gasolines, LCOs and HCOs and CLOs were separated.
  • the HCOs were subjected to hydrogenation at a temperature of 390 ° C. and under a pressure of 120 bar, at an LHSV of 0.6.
  • the products boiling in the gasoline range were separated from those having a boiling point above 221 ° C. and they were sent directly to a second catalytic cracking reactor.
  • Table 1 The properties of the gasolines produced at the outlet of this latter catalytic cracking reactor are shown in Table 1.

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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)

Claims (7)

  1. Verfahren zum Herstellen von Benzinen mit verbesserten ROZ und MOZ, dadurch gekennzeichnet, daß es die folgenden Stufen umfaßt:
    a. katalytisches Cracken einer Charge schwerer Kohlenwasserstoffe im Fließbett durch in Berührung bringen mit einem flüssigen Crack-Katalysator, um gasförmige Produkte, Kohlenwasserstoffe, die im Bereich der Benzine sieden, leichte Kreislauföle, schwere Kreislauföle, und geklärte Öle zu bilden;
    b. Abtrennen des Katalysators von den gebildeten Produkten;
    c. Abtrennen und Überführen der gebildeten leichten Kreislauföle, schweren Kreislauföle und geklärten Öle in einen anderen Reaktor, in dem sie bei einer Temperatur zwischen 270 und 500°C, einem Druck zwischen 30 und 200 bar und in Gegenwart eines Hydrierungskatalysators einer Hydrierung unterworfen werden, um gasförmige Kohlenwasserstoffe, Kohlenwasserstoffe, die im Bereich der Benzine sieden und Kohlenwasserstoffe zu bilden, die bei einer Temperatur von mehr als etwa 221°C sieden;
    d. Abtrennen der in Stufe (c) gebildeten Kohlenwasserstoffe, die bei einer Temperatur von mehr als etwa 221°C sieden;
    e. katalytisches Cracken der in Stufe (d) gebildeten Kohlenwasserstoffe, die bei einer Temperatur von mehr als etwa 221°C sieden, im Fließbett, wobei sich der Reaktor vorzugsweise von dem der Stufe (a) unterscheidet;
    f. Gewinnen der in Stufe (e) gebildeten Kohlenwasserstoffe, die im Bereich der Benzine sieden und bessere ROZ und MOZ aufweisen.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man das in Stufe (c) gebildete hydrierte leichte Kreislauföl einem katalytischen Cracken im Fließbett unterwirft.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man das in Stufe (c) gebildete hydrierte schwere Kreislauföl einem katalytischen Cracken im Fließbett unterwirft.
  4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man das in Stufe (c) gebildete hydrierte geklärte Öl einem katalytischen Cracken im Fließbett unterwirft.
  5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Mischung aus leichtem Kreislauföl, schwerem Kreislauföl und geklärtem Öl der Stufe (c) einem katalytischen Cracken im Fließbett unterwirft.
  6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man das in Stufe (c) gewonnene leichte Kreislauföl, geklärte Öl, schwere Kreislauföl zusammen oder getrennt einer Hydrierungsbehandlung bei einer Temperatur zwischen 320 und 420°C unterwirft.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man das in Stufe (c) gewonnene leichte Kreislauföl, geklärte Öl, schwere Kreislauföl gemeinsam oder getrennt einer Hydrierungsbehandlung bei einem Druck zwischen 60 und 120 bar, bei einer Raumgeschwindigkeit/h der Flüssigkeit zwischen 0,5 und 5 und einem Verhältnis von H₂/Kohlenwasserstoff zwischen 500 und 50.000 Litern unter Normalbedingungen/Liter unterwirft.
EP90908440A 1989-06-09 1990-06-08 Verfahren zur herstellung von benzin mit verbesserten oktanzahlen Expired - Lifetime EP0432235B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
BE8900630 1989-06-09
BE8900630A BE1004277A4 (fr) 1989-06-09 1989-06-09 Procede de production d'essences a indice ron et mon ameliores.
PCT/BE1990/000028 WO1990015121A1 (fr) 1989-06-09 1990-06-08 Procede de production d'essences a indices d'octane ameliores

Publications (2)

Publication Number Publication Date
EP0432235A1 EP0432235A1 (de) 1991-06-19
EP0432235B1 true EP0432235B1 (de) 1994-09-14

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EP90908440A Expired - Lifetime EP0432235B1 (de) 1989-06-09 1990-06-08 Verfahren zur herstellung von benzin mit verbesserten oktanzahlen

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US (1) US5152883A (de)
EP (1) EP0432235B1 (de)
JP (1) JPH04500231A (de)
AT (1) ATE111507T1 (de)
BE (1) BE1004277A4 (de)
DE (1) DE69012526T2 (de)
DK (1) DK0432235T3 (de)
ES (1) ES2060172T3 (de)
WO (1) WO1990015121A1 (de)

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US5582711A (en) * 1994-08-17 1996-12-10 Exxon Research And Engineering Company Integrated staged catalytic cracking and hydroprocessing process
US5770044A (en) * 1994-08-17 1998-06-23 Exxon Research And Engineering Company Integrated staged catalytic cracking and hydroprocessing process (JHT-9614)
US5770043A (en) * 1994-08-17 1998-06-23 Exxon Research And Engineering Company Integrated staged catalytic cracking and hydroprocessing process
US6113776A (en) * 1998-06-08 2000-09-05 Uop Llc FCC process with high temperature cracking zone
US5944982A (en) 1998-10-05 1999-08-31 Uop Llc Method for high severity cracking
US6123830A (en) * 1998-12-30 2000-09-26 Exxon Research And Engineering Co. Integrated staged catalytic cracking and staged hydroprocessing process
EP1050572A3 (de) * 1999-05-05 2001-06-06 Bar-Co Processes Joint Venture Fluidkatalytisches Krackverfahren von Rückstandsöl
US6569316B2 (en) 2000-04-17 2003-05-27 Exxonmobil Research And Engineering Company Cycle oil conversion process incorporating shape-selective zeolite catalysts
US6565739B2 (en) 2000-04-17 2003-05-20 Exxonmobil Research And Engineering Company Two stage FCC process incorporating interstage hydroprocessing
US20010042701A1 (en) 2000-04-17 2001-11-22 Stuntz Gordon F. Cycle oil conversion process
US20010042702A1 (en) 2000-04-17 2001-11-22 Stuntz Gordon F. Cycle oil conversion process
US6569315B2 (en) 2000-04-17 2003-05-27 Exxonmobil Research And Engineering Company Cycle oil conversion process
US20070289899A1 (en) * 2006-06-14 2007-12-20 Fina Technology, Inc. Stacked bed hydrotreating reactor system
CN101210200B (zh) 2006-12-27 2010-10-20 中国石油化工股份有限公司 一种渣油加氢处理与催化裂化组合工艺方法
JP5840840B2 (ja) 2007-12-20 2016-01-06 中国石油化工股▲分▼有限公司 炭化水素油を水素化し接触分解するための、改善された一体的方法
KR101503069B1 (ko) * 2008-10-17 2015-03-17 에스케이이노베이션 주식회사 유동층 접촉 분해 공정의 경질 사이클 오일로부터 고부가 방향족 및 올레핀을 제조하는 방법
JP5339845B2 (ja) * 2008-10-14 2013-11-13 Ｊｘ日鉱日石エネルギー株式会社 流動接触分解方法
BRPI1012237A2 (pt) * 2009-03-27 2016-03-29 Jx Nippon Oil & Energy Corp método para produção de hidrocarbonetos aromáticos
US20110163001A1 (en) * 2010-01-07 2011-07-07 Lourenco Jose J P Upgrading heavy oil by deasphalting
FR2983208B1 (fr) * 2011-11-24 2015-03-06 IFP Energies Nouvelles Procede de production de distillat moyen a partir d'une charge lourde conventionnelle incluant une etape d'hydrogenation selective de la coupe hco ex fcc
JP6278587B2 (ja) * 2012-03-21 2018-02-14 Ｊｘｔｇエネルギー株式会社 高芳香族基油及び高芳香族基油の製造方法
US10626339B2 (en) 2016-09-20 2020-04-21 Uop Llc Process and apparatus for recycling cracked hydrocarbons

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Publication number Publication date
DK0432235T3 (da) 1994-11-21
US5152883A (en) 1992-10-06
DE69012526D1 (de) 1994-10-20
JPH04500231A (ja) 1992-01-16
ATE111507T1 (de) 1994-09-15
WO1990015121A1 (fr) 1990-12-13
EP0432235A1 (de) 1991-06-19
DE69012526T2 (de) 1995-03-30
BE1004277A4 (fr) 1992-10-27
ES2060172T3 (es) 1994-11-16

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