EP0552072B1 - Erniedrigung des Benzolgehaltes von Benzinen - Google Patents

Erniedrigung des Benzolgehaltes von Benzinen Download PDF

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Publication number
EP0552072B1
EP0552072B1 EP93400023A EP93400023A EP0552072B1 EP 0552072 B1 EP0552072 B1 EP 0552072B1 EP 93400023 A EP93400023 A EP 93400023A EP 93400023 A EP93400023 A EP 93400023A EP 0552072 B1 EP0552072 B1 EP 0552072B1
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EP
European Patent Office
Prior art keywords
isomerization
catalyst
hydrogenation
process according
zeolite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP93400023A
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English (en)
French (fr)
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EP0552072A1 (de
Inventor
Christine Travers
Patrick Sarrazin
Philippe Travers
Jean-Marie Deves
Jean Cosyns
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Publication of EP0552072A1 publication Critical patent/EP0552072A1/de
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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
    • 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
    • C10G69/08—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 reforming naphtha
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons

Definitions

  • the invention relates to the reduction of the benzene content in fractions gasolines by a process associating the hydrogenation of the benzene contained in the light reformate and the isomerization of the effluent from the hydrogenation.
  • Catalytic reforming used under severe conditions and the isomerization of normal C 5 -C 6 paraffins with low octane numbers are the most commonly used processes currently used to obtain high octane numbers without the addition of lead.
  • the catalytic reforming process produces significant amounts of high octane benzene. This is why it is necessary to develop new processes which make it possible to reduce the benzene content of gasolines while meeting the specifications for the octane number.
  • catalytic reforming and isomerization processes consisting in separating the C 5 -C 6 fraction from the reformate, in isomerizing it and in introducing it directly into the gasoline fractions to improve the octane number is well known. ; it is described for example in patents US-A 4,457,832, US-A 4,181,599 and US-A 3,761,392.
  • the reduction of the benzene content of the reformate can also be carried out in various ways, such as for example the modification of the naphtha cutting point between reforming and isomerization or the separation of the reformate into two fractions: a heavy reformate and a light reformate in which all the benzene is concentrated.
  • This light fraction is then sent to a hydrogenation unit which makes it possible to transform the benzene into naphthenes, which are then decyclized in an isomerization unit working under severe conditions.
  • the normal paraffins thus formed are isomerized by a conventional isomerization process (US-A 5,003,118).
  • US-A 5,003,118 a conventional isomerization process
  • the naphthenes adsorb on the catalyst and thus contribute to deteriorating its activity.
  • US-A 3,611,117 also describes a process for hydro-isomerization cyclic hydrocarbons that uses a Group VIII metal supported on zeolite as a catalyst for opening cycles in severe operating conditions and as an isomerization catalyst in mild operating conditions.
  • the object of the present invention is to reduce the benzene content in the gasolines without significant decrease in the octane number.
  • the process of present invention therefore comprises the hydrogenation of benzene contained in the charge defined below in a hydrogenation zone and then the isomerization effluent from hydrogenation in an isomerization zone.
  • EP-A-0 552 070 a cut C5-C6 is mixed with said effluent.
  • the hydrogenation zone and the isomerization zone according to the invention can be included in the same reactor, or in separate reactors such that each of said zones is included in at least one reactor.
  • Benzene is essentially the only aromatic compound included in said fraction.
  • said fraction can comprise between 1 and 3% of hydrocarbons olefinic.
  • the hydrocarbon feedstock concerned by the present invention is the fraction slight from a reformate or any other filler from another process or set of processes and having characteristics similar to those described above.
  • the pressure is between 1 and 60 bar (absolute), particularly from 2 to 50 bar and more advantageously from 5 to 45 bar.
  • the temperature is between 100 and 400 ° C, more advantageously between 150 (even 110) and 350 ° C and preferably between 160 (even 110) and 320 ° C.
  • the space velocity calculated relative to the catalyst is between 1 and 50 h -1 and more particularly between 1 and 30 h -1 (volume of charge per volume of catalyst and per hour).
  • the flow of hydrogen, relative to the catalyst is between 1 and 2000 volumes (gas at normal conditions) by volume of catalyst and by hour.
  • the heat released at this stage is advantageously used to preheat the isomerization charge.
  • the catalyst used in the hydrogenation zone which is the subject of the present invention comprises at least one metal M chosen from the group formed by nickel, platinum and palladium, deposited on a support.
  • Metal M must be in reduced form at less for 50% of its totality.
  • nickel or platinum is used, and even more preferably platinum.
  • the catalyst may contain advantageously at least one halogen in a proportion by weight per ratio to the catalyst of between 0.5 and 2%.
  • halogen in a proportion by weight per ratio to the catalyst of between 0.5 and 2%.
  • the proportion of metal M relative to the total weight of catalyst is between 0.1 and 60%, more particularly between 5 and 60% and preferably between 5 and 30%.
  • the total proportion of metal M by relative to the total weight of catalyst is between 0.1 and 10% and so preferred between 0.05 and 5%.
  • the support can be chosen from the group formed by alumina, silica-aluminas, silica, zeolites, activated carbon, clays and cements aluminous.
  • An alumina is preferably used, with a specific surface at least equal to 50 m 2 / g and a pore volume at least equal to 0.4 cm 3 / g, for example with a specific surface of between 50 and 350 m 2 / g and of pore volume between 0.4 and 1.2 cm 3 / g.
  • the value of the research octane number (RON) of this effluent is included between 70 and 85.
  • Said effluent is sent with hydrogen to the isomerization zone and is brought into contact with an isomerization catalyst under the conditions of the isomerization specified below.
  • the catalyst used in the isomerization zone according to the process of the present invention is a catalyst comprising at least one group VIII metal and a zeolite.
  • Different zeolites can be used for said catalyst, such as, for example, mordenite or ⁇ zeolite.
  • Use is preferably made of a mordenite having an Si / Al (atomic) ratio of between 5 and 50 and preferably between 5 and 30, a sodium content of less than 0.2% and preferably of less than 0.1% ( relative to the weight of dry zeolite), a volume of mesh V of the elementary mesh of between 2.78 and 2.73 nm 3 and preferably between 2.77 and 2.74 nm 3 , an absorption capacity of benzene greater than 5% and preferably greater than 8% (relative to the weight of dry solid).
  • the mordenite thus prepared is then mixed with a generally amorphous matrix (alumina, silica alumina, kaolin, etc.) and shaped by any method known to those skilled in the art (extrusion, pelletizing, coating).
  • the mordenite content of the support thus obtained must be greater than 40% and preferably greater than 60% by weight.
  • At least one hydrogenating metal from group VIII preferably chosen from the group formed by platinum, palladium, and nickel, is then deposited on this support, either in the form of a tetramine complex by cation exchange, either in the form of hexachloroplatinic acid in the case of platinum or in form of palladium chloride by anion exchange.
  • the content by weight is between 0.05 and 1% and preferably between 0.1 and 0.6%.
  • the weight content is between 0.1 and 10% and preferably between 0.2 and 5%.
  • the isomerization process is carried out between 230 and 280 ° C, at a partial pressure of hydrogen between atmospheric pressure and 70 bar and preferably between 5 and 50 bar.
  • the space velocity is between 0.2 and 10 and preferably between 0.5 and 5 liters of liquid hydrocarbons per liter of catalyst and per hour.
  • the hydrogen / charge molar ratio is normally between 0.5 and 10 and preferably between 1 and 3.
  • the effluent thus obtained in addition to its low benzene content, then has a research octane number practically equivalent to that of the reformate light before hydrogenation; it can thus be directly incorporated into the essence fractions.
  • the method according to the invention therefore does not lead to a notable decrease in the research octane number and it makes it possible to decrease the benzene content.
  • the single figure shows an arrangement of the method according to the invention, in which the hydrogenation and isomerization reactions are carried out in two separate reactors (or units).
  • the stabilized reformate (1) is sent to a distillation column (6) which is comes out, in the background a heavy reformate (3) which can be used directly in the essence fractions and at the top a slight reformate (2).
  • the latter is sent to a hydrogenation unit (7) then the cut obtained (4) is treated in a isomerization unit (8) giving the final product (5) which, after stabilization, can be used in essence fractions.
  • the hydrogen to hydrocarbons molar ratio contained in the charge is equal to 0.85, and the liquid space velocity equal to 4 h -1 .
  • the catalyst used in the hydrogenation section consists of 15% of Ni deposited on alumina.
  • the effluent from the hydrogenation unit no longer contains benzene but has an octane number of 76.5. It is then sent to an isomerization unit operating at a temperature of 260 ° C., a pressure of 30 bars with an LHSV equal to 2 h -1 and a hydrogen to hydrocarbon molar ratio of the charge equal to 4.
  • the effluent leaving the isomerization unit has the composition given in Table I; it no longer contains benzene and has an octane number of 80, practically equivalent to the octane number of the light reformate. This effluent can be directly incorporated into the gasoline fractions after stabilization.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (5)

  1. Verfahren zur Herabsetzung des Benzolgehaltes in den Benzinfraktionen, ohne die Octan-Zahl merklich zu verringern, bei dem man in einer Hydrierungszone eine Hydrierung und danach in einer lsomerisierungszone eine Isomerisierung einer Beschickung (Charge) mit einer Gewichts-Zusammensetzung innerhalb der nachstehend angegebenen Bereiche:
    40 bis 80 % Paraffine
    0,5 bis 7 % Naphthene
    6 bis 45 % Aromaten
    bei einer maximalen Destillations-Temperatur zwischen 70 und 90°C durchführt,
    dadurch gekennzeichnet, daß der Hydrierungs-Katalysator mindestens ein Metall, ausgewählt aus der Gruppe, die besteht aus Nickel, Platin und Palladium, auf einem Träger aufweist und daß der lsomerisierungs-Katalysator ein Zeolith und mindestens ein Metall der Gruppe VIII aufweist und daß die Isomerisierung bei einer Temperatur zwischen 230 und 280°C durchgeführt wird.
  2. Verfahren nach Anspruch 1, bei dem der Zeolith ein Mordenit oder ein Ω-Zeolith ist.
  3. Verfahren nach einem der Ansprüche 1 oder 2, bei dem das Metall der Gruppe VIII des lsomerisierungs-Katalysators ausgewählt wird aus der Gruppe, die besteht aus Platin, Palladium und Nickel.
  4. Verfahren nach den Ansprüchen 1 bis 3, bei dem die Hydrierung unter den folgenden Betriebsbedingungen durchgeführt wird: die Temperatur liegt zwischen 100 und 400°C, der Druck liegt zwischen 1 und 60 bar, die Raumgeschwindigkeit liegt zwischen 1 und 50 Volumenteilen Beschickung pro Volumenteil Katalysator und pro Stunde und der Wasserstoffdurchsatz liegt zwischen 1 und 2000 Volumenteilen pro Volumenteil Katalysator und pro Stunde.
  5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem die Isomerisierung bei einem Wasserstoffpartialdruck zwischen Atmosphärendruck und 70 bar, bei einer Raumgeschwindigkeit zwischen 0,2 und 10 l Beschickung pro l Katalysator und pro Stunde und bei einem Molverhältnis Wasserstoff/Beschickung zwischen 0,5 und 10 durchgeführt wird.
EP93400023A 1992-01-15 1993-01-07 Erniedrigung des Benzolgehaltes von Benzinen Expired - Lifetime EP0552072B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9200433 1992-01-13
FR9200433A FR2686096B1 (fr) 1992-01-15 1992-01-15 Reduction de la teneur en benzene dans les essences.

Publications (2)

Publication Number Publication Date
EP0552072A1 EP0552072A1 (de) 1993-07-21
EP0552072B1 true EP0552072B1 (de) 1998-10-28

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ID=9425702

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93400023A Expired - Lifetime EP0552072B1 (de) 1992-01-15 1993-01-07 Erniedrigung des Benzolgehaltes von Benzinen

Country Status (9)

Country Link
EP (1) EP0552072B1 (de)
KR (1) KR100242918B1 (de)
CA (1) CA2087229A1 (de)
DE (1) DE69321741T2 (de)
ES (1) ES2125959T3 (de)
FR (1) FR2686096B1 (de)
ID (1) ID852B (de)
MY (1) MY106926A (de)
TW (1) TW237474B (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0953626A1 (de) * 1998-04-27 1999-11-03 FE Forschungs & Entwicklung GmbH Verfahren zur Herstellung eines benzolarmen, hochoktanigen Kohlenwasserstoffgemischs
BR0010212A (pt) * 1999-05-13 2002-02-13 Mobil Oil Corp Processo para hidrocraqueamento de suprimentos de nafta
EP2277980B1 (de) 2009-07-21 2018-08-08 IFP Energies nouvelles Verfahren zur selektiven reduzierung des benzolgehalts und des gehalts an leichten ungesättigten verbindungen von verschiedenen kohlenwasserstoffverschnitten

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA975384A (en) * 1971-04-19 1975-09-30 Graham K. Hilder Isomerisation of paraffin hydrocarbons
US5003118A (en) * 1989-12-29 1991-03-26 Uop Isomerization of benzene-containing feedstocks

Also Published As

Publication number Publication date
KR930016527A (ko) 1993-08-26
ID852B (id) 1996-08-02
DE69321741T2 (de) 1999-03-18
FR2686096B1 (fr) 1994-04-29
ES2125959T3 (es) 1999-03-16
DE69321741D1 (de) 1998-12-03
KR100242918B1 (ko) 2000-02-01
CA2087229A1 (fr) 1993-07-14
EP0552072A1 (de) 1993-07-21
TW237474B (de) 1995-01-01
MY106926A (en) 1995-08-30
FR2686096A1 (fr) 1993-07-16

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