EP0552070B1 - Erniedrigung des Benzolgehaltes von Benzinen - Google Patents

Erniedrigung des Benzolgehaltes von Benzinen Download PDF

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Publication number
EP0552070B1
EP0552070B1 EP93400021A EP93400021A EP0552070B1 EP 0552070 B1 EP0552070 B1 EP 0552070B1 EP 93400021 A EP93400021 A EP 93400021A EP 93400021 A EP93400021 A EP 93400021A EP 0552070 B1 EP0552070 B1 EP 0552070B1
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EP
European Patent Office
Prior art keywords
isomerization
catalyst
hydrogenation
process according
charge
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
EP93400021A
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English (en)
French (fr)
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EP0552070A1 (de
Inventor
Christine Travers
Patrick Sarrazin
Jean-Marie Deves
Jean-Paul Boitiaux
Pierre Auboir
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Publication date
Priority claimed from FR9200435A external-priority patent/FR2686094B1/fr
Priority claimed from FR929209758A external-priority patent/FR2694565B1/fr
Application filed by IFP Energies Nouvelles IFPEN filed Critical IFP Energies Nouvelles IFPEN
Publication of EP0552070A1 publication Critical patent/EP0552070A1/de
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Publication of EP0552070B1 publication Critical patent/EP0552070B1/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
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • the invention relates to a process allowing the reduction of the benzene content in gasoline fractions by a process combining the hydrogenation of the benzene contained in the light reformate and optionally the hydrogenation of a C 5 -C 6 cut and isomerization. effluent from hydrogenation and possibly from said cut.
  • the catalytic reforming used under conditions of severe severity, and the isomerization of normal C 5 -C 6 paraffins of low octane number are the most commonly used processes currently for obtaining high octane numbers without the addition of lead.
  • the catalytic reforming process produces large quantities 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.
  • 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 cutting point of the naphtha 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).
  • a conventional isomerization process US-A 5,003,118.
  • the naphthenes adsorb on the catalyst and thus contribute to deteriorating its activity.
  • US-A-3,611,117 also describes a process for hydroisomerization 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 carry out jointly the reduction of the benzene content contained in the light reformate and the isomerization of the paraffins contained on the one hand in this light reformate and on the other hand in a C 5 -C cut 6 generally paraffinic and resulting from direct distillation.
  • the process of the present invention therefore comprises the hydrogenation of benzene contained in the charge defined below in a zone hydrogenation and then isomerization of the effluent from the hydrogenation in an isomerization zone, the process being characterized in that one mixing said effluent a C5-C6 cut.
  • EP-A-0 552 072 relates to a similar process but without the addition of a C5-C6 cut to the effluent resulting from the hydrogenation.
  • 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.
  • the conditions under which the hydrogenation is carried out and isomerization i.e. the operating conditions, the catalyst, etc.
  • the conditions known to those skilled in the art are the conditions known to those skilled in the art. They are nevertheless specified below.
  • Benzene is generally essentially the only compound aromatic included in said fraction.
  • said fraction can comprise between 1 and 3% of hydrocarbons olefinic.
  • the weight composition of the C 5 -C 6 cut is variable. It depends on the nature of the crude to be treated in the case where the C 5 -C 6 cut is obtained from direct distillation.
  • the paraffin content of said cut is generally greater than 90% by weight, its naphthene content generally less than 10% by weight and the benzene content generally less than 1.5% by weight.
  • His index typically research octane is between 60 and 75.
  • the C 5 -C 6 cut is mixed with the effluent from the hydrogenation, that is to say with the saturated light reformate leaving the hydrogenation zone, the effluent content from the hydrogenation of the charge entering the isomerization zone being between 10 and 90% and preferably between 20 and 80%.
  • the pressure required for this step hydrogenation is generally between 1 and 60 bar absolute, particularly between 2 and 50 bar and more advantageously between 5 and 45 bar.
  • the operating temperature is generally between 100 and 400 ° C, more advantageously between 150 and 350 ° C and preferably between 160 and 320 ° C.
  • the space velocities calculated with respect to the catalyst are generally 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 generally between 1 and 2000 volumes (gas under normal conditions) per volume of catalyst and per hour.
  • the heat released at this stage is advantageously used to preheat the isomerization charge.
  • the catalyst used in the hydrogenation zone according to the process of 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 aluminous cements.
  • 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 effluent from the hydrogenation zone generally contains less 0.1% aromatics and generally has between 4 and 6 octane points less than the load entering said area.
  • the isomerization zone is fed by the effluent from the hydrogenation zone comprising the light reformate mixture plus the non-hydrogenated C 5 -C 6 cut.
  • the isomerization is generally carried out in said isomerization zone under the following usual conditions: the temperature is between 230 and 280 ° C., and the partial pressure of hydrogen is between atmospheric pressure and 70 bar and preferably between 5 and 50 bar.
  • the space velocity is between 0.2 and 10 liters and preferably between 0.5 and 5 liters of liquid hydrocarbons per liter of catalyst per hour.
  • the hydrogen / charge molar ratio is normally between 0.5 and 10 and preferably between 1 and 3.
  • 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 either in the 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 effluent obtained at the exit from the isomerization zone has an index octane high enough to be incorporated into gasoline fractions after stabilization and generally has a maximum benzene content equal to 0.1% by weight. Preferably, it is completely free of benzene.
  • the single figure shows an arrangement of the method according to the invention, in which hydrogenation and isomerization are carried out in two reactors (or units) separate.
  • the stabilized reformate (1) is sent to a distillation column (6), which is a heavy reformate (3) comes out at the bottom 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).
  • a direct distillation C 5 -C 6 cut (10) is mixed with the saturated light reformate (4) just before the isomerization unit (8).
  • the cut obtained is treated in an isomerization unit (8) giving the final product (5) which, after stabilization, can be incorporated into the gasoline fractions.
  • the molar ratio of hydrogen to hydrocarbons contained in the charge is equal to 0.85, and the liquid space speed is 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 mixed in an amount of 50% by weight with a C 5 -C 6 cut of direct distillation containing 0.7% of benzene and having an octane number of 65.
  • the composition of this cut as well as the composition of the mixture which constitutes the charge of the isomerization unit are given in table II.
  • the isomerization unit operates at a temperature of 260 ° C., a pressure of 30 bar with an LHSV equal to 2 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 II; it no longer contains benzene and has an octane number of 78.1. 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)

Claims (7)

  1. Verfahren zur Erniedrigung des Benzolgehaltes in Benzinfraktionen, bei dem man in einer Hydrierungszone eine Hydrierung der Charge vornimmt, gekennzeichnet durch:
    eine Gewichtszusammensetzung in den folgenden Intervallen:
    zwischen 40 und 80% Paraffine
    zwischen 0,5 und 7% Naphtene
    zwischen 6 und 45% Aromate
    und eine maximale Destillationstemperatur zwischen 70 und 90 °C,
    gefolgt von einer Isomerisierung in einer Isomerisierungszone des aus der Hydrierungszone stammenden Abstroms, wobei das Verfahren sich dadurch auszeichnet, daß der Hydrierungskatalysator wenigstens ein Metall umfaßt, das aus der durch Nickel, Platin und Palladium gebildeten Gruppe gewählt ist, trägergestützt, daß der Isomerisierungskatalysator einen Zeolith und wenigstens ein Metall der Gruppe VIII umfaßt und daß die Isomerisierung bei einer Temperatur zwischen 230°C und 280°C durchgeführt wird und daß man mit diesem Abstrom eine C5-C6 Fraktion mischt.
  2. Verfahren nach Anspruch 1, bei dem das Gemisch 10 bis 90% dieses Abstroms umfaßt.
  3. Verfahren nach einem der Ansprüche 1 oder 2, bei dem das Metall der Gruppe VIII des Isomerisierungskatalysators gewählt ist aus der Gruppe, die durch Platin, Palladium und Nickel gebildet ist.
  4. Verfahren nach einem der Ansprüche 1 bis 3, derart, daß der Zeolith ein Mordenit- oder ein Omega-Zeolith ist.
  5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem die Hydrierungsstufe entsprechend den folgenden Arbeitsbedingungen erfolgt: die Temperatur liegt zwischen 100 und 400 °C, der Druck zwischen 1 und 60 Bar, die Raumgeschwindigkeit zwischen 1 und 50 Volumen Charge pro Volumen Katalysator und Stunde und der Wasserstoffdurchsatz liegt zwischen 1 und 2000 Volumen pro Volumen Katalysator und Stunde.
  6. Verfahren nach einem der Ansprüche 1 bis 5, bei dem die Isomerisierungsstufe bei einem Wasserstoffpartialdruck zwischen dem atmosphärischen Druck und 70 Bar bei einer Raumgeschwindigkeit zwischen 0,2 und 10 Liter Charge pro Liter Katalysator und Stunde und mit einem Molverhältnis von Wasserstoff zu Charge zwischen 0,5 und 10 durchgeführt wird.
  7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem die C5-C6 Fraktion eine Fraktion der direkten Destillation ist.
EP93400021A 1992-01-15 1993-01-07 Erniedrigung des Benzolgehaltes von Benzinen Expired - Lifetime EP0552070B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR9200435A FR2686094B1 (fr) 1992-01-15 1992-01-15 Production de base pour carburant exempt de benzene, presentant un indice d'octane eleve.
FR9200435 1992-01-15
FR929209758A FR2694565B1 (fr) 1992-08-04 1992-08-04 Réduction de la teneur en benzène dans les essences.
FR9209758 1992-08-04

Publications (2)

Publication Number Publication Date
EP0552070A1 EP0552070A1 (de) 1993-07-21
EP0552070B1 true EP0552070B1 (de) 1999-08-18

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ID=26229197

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Application Number Title Priority Date Filing Date
EP93400021A Expired - Lifetime EP0552070B1 (de) 1992-01-15 1993-01-07 Erniedrigung des Benzolgehaltes von Benzinen

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EP (1) EP0552070B1 (de)
CA (1) CA2087385A1 (de)
DE (1) DE69326030T2 (de)
ES (1) ES2137974T3 (de)
MY (1) MY109122A (de)
TW (1) TW218377B (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2714388B1 (fr) * 1993-12-29 1996-02-02 Inst Francais Du Petrole Procédé de réduction de la teneur en benzène dans les essences.
US5599997A (en) * 1995-03-14 1997-02-04 Chemical Research & Licensing Company Process for the production of cyclohexyl amine
US5773670A (en) * 1995-03-06 1998-06-30 Gildert; Gary R. Hydrogenation of unsaturated cyclic compounds
FR2743079B1 (fr) * 1995-12-27 1998-02-06 Inst Francais Du Petrole Procede et dispositif d'hydrogenation selective par distillation catalytique comportant une zone reactionnelle a co-courant ascendant liquide-gaz
FR2743080B1 (fr) * 1995-12-27 1998-02-06 Inst Francais Du Petrole Procede de reduction selective de la teneur en benzene et en composes insatures legers d'une coupe d'hydrocarbures
FR2743081B1 (fr) * 1995-12-27 1998-01-30 Inst Francais Du Petrole Procede de reduction selective de la teneur en benzene et en composes insatures legers d'une coupe d'hydrocarbures
FR2776667B1 (fr) * 1998-03-31 2000-06-16 Total Raffinage Distribution Procede et dispositif d'isomerisation d'essences a teneur elevee en benzene
EP0953626A1 (de) * 1998-04-27 1999-11-03 FE Forschungs & Entwicklung GmbH Verfahren zur Herstellung eines benzolarmen, hochoktanigen Kohlenwasserstoffgemischs
US6855853B2 (en) 2002-09-18 2005-02-15 Catalytic Distillation Technologies Process for the production of low benzene gasoline
US11697777B2 (en) 2019-08-02 2023-07-11 Abu Dhabi Oil Refining Company—Takreer Single reactor process for benzene-saturation/isomertzation of light reformates

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3009002A (en) * 1960-06-20 1961-11-14 Phillips Petroleum Co High purity cyclohexane from natural cyclohexane-containing fraction
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
DE69326030T2 (de) 2000-01-05
TW218377B (de) 1994-01-01
EP0552070A1 (de) 1993-07-21
DE69326030D1 (de) 1999-09-23
MY109122A (en) 1996-12-31
ES2137974T3 (es) 2000-01-01
CA2087385A1 (fr) 1993-07-16

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