EP0552069B1 - Réduction de la teneur en benzène dans les essences par un procédé d'isomérisation - Google Patents

Réduction de la teneur en benzène dans les essences par un procédé d'isomérisation Download PDF

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Publication number
EP0552069B1
EP0552069B1 EP93400020A EP93400020A EP0552069B1 EP 0552069 B1 EP0552069 B1 EP 0552069B1 EP 93400020 A EP93400020 A EP 93400020A EP 93400020 A EP93400020 A EP 93400020A EP 0552069 B1 EP0552069 B1 EP 0552069B1
Authority
EP
European Patent Office
Prior art keywords
isomerization
process according
charge
fraction
catalyst
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
EP93400020A
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German (de)
English (en)
French (fr)
Other versions
EP0552069A1 (fr
Inventor
Christine Travers
Patrick Sarrazin
Jean-Marie Deves
Christian Marcilly
Philippe Travers
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Publication of EP0552069A1 publication Critical patent/EP0552069A1/fr
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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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • 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 the gasoline pool by a process of isomerization of the light reformate and / or of a C5-C coupe cut generally of direct distillation.
  • Catalytic reforming used under conditions of high severity, and isomerization of normal C5-C6 paraffins with low octane number are the most commonly used processes today to obtain high octane numbers without the addition of lead.
  • 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 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 the light fraction is then sent to a hydrogenation unit which makes it possible to transform the benzene into naphthene, which is 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 the hydro-isomerization of cyclic hydrocarbons which uses a group VIII metal supported on zeolite as a catalyst for opening rings under severe operating conditions and as an isomerization catalyst under 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 the C5-C6 cut, generally paraffinic and resulting from direct distillation.
  • the process of the present invention therefore comprises the isomerization of the mixture of the filler defined below and of a C5-C6 cut.
  • EP-A-0 552 070 and EP-A-0 552 072 the isomerization step is preceded by a hydrogenation step.
  • the feed concerned by the present invention contains a light fraction of the reformate and a C5-C6 cut generally resulting from direct distillation.
  • Benzene is essentially the only aromatic compound included in said fraction.
  • said fraction can comprise between 1 and 3% of olefinic hydrocarbons.
  • the weight composition of the C5-C6 cut generally resulting from direct distillation is variable. It depends on the nature of the crude to be treated in the case where the C5-C6 cut is obtained from direct distillation.
  • the paraffin content of said cut is generally greater than 90% by weight, the naphthene content less than 10% by weight and the benzene content less than 1.5% by weight. Its research octane number is between 60 and 75.
  • the isomerization zone includes one or more isomerization reactors.
  • the isomerization zone is implemented under the usual conditions of isomerization: the temperature is generally between 150 ° C and 300 ° C and preferably between 230 and 280 ° C, and the partial pressure of hydrogen is included generally between atmospheric pressure and 70 bar and preferably between 5 and 50 bar.
  • the space velocity is generally 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 generally 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 can be a catalyst based on platinum on chlorinated alumina, containing from 1 to 10% of chlorine and preferably from 2 to 9% of chlorine, but preferably uses 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.
  • 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 comprised between 2.78 and 2.73 nm3 and preferably between 2.77 and 2.74 nm3, a benzene absorption capacity 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, or in the form of acid.
  • hexachloroplatinic in the case of platinum or 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 thus obtained then has an octane number high enough to be incorporated into the gasoline fractions after stabilization and is practically completely free of benzene (content in the effluent less than 0.1%).
  • the example which follows specifies the invention without limiting its scope. In this example, the isomerization is carried out in a single reactor (or unit).
  • the light reformate obtained after distillation at 85 ° C, containing 21.5% of benzene and having an octane number of 80.3 is mixed in an amount of 50% by weight with a C5-C6 cut of direct distillation containing 0.7 % of benzene and having an octane number of 65.
  • the compositions of these 2 products are shown in Table I.
  • the charge from the mixture, the composition of which also appears in Table I, is sent to an isomerization unit at a temperature of 250 ° C, a pressure of 30 bar with an LHSV equal to 2 h ⁇ 1 and a hydrogen molar ratio on hydrocarbons with a charge equal to 4.
  • the effluent leaving the isomerization unit has the composition given in Table I; it contains very little benzene and has an octane number of 78.2. It can therefore be directly incorporated into the gasoline fractions after stabilization.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (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)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP93400020A 1992-01-15 1993-01-07 Réduction de la teneur en benzène dans les essences par un procédé d'isomérisation Expired - Lifetime EP0552069B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9200436A FR2686095B1 (fr) 1992-01-15 1992-01-15 Production de base pour carburant exempt de benzene, presentant un indice d'octane eleve.
FR9200436 1992-01-15

Publications (2)

Publication Number Publication Date
EP0552069A1 EP0552069A1 (fr) 1993-07-21
EP0552069B1 true EP0552069B1 (fr) 1996-04-24

Family

ID=9425704

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93400020A Expired - Lifetime EP0552069B1 (fr) 1992-01-15 1993-01-07 Réduction de la teneur en benzène dans les essences par un procédé d'isomérisation

Country Status (9)

Country Link
EP (1) EP0552069B1 (enrdf_load_stackoverflow)
KR (1) KR930016525A (enrdf_load_stackoverflow)
CA (1) CA2087384A1 (enrdf_load_stackoverflow)
DE (1) DE69302287T2 (enrdf_load_stackoverflow)
ES (1) ES2089739T3 (enrdf_load_stackoverflow)
FR (1) FR2686095B1 (enrdf_load_stackoverflow)
MY (1) MY109121A (enrdf_load_stackoverflow)
RU (1) RU2091441C1 (enrdf_load_stackoverflow)
TW (1) TW238298B (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103464210A (zh) * 2013-09-27 2013-12-25 凯瑞化工股份有限公司 一种轻烃异构化催化剂及其制备方法

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2714305B1 (fr) * 1993-12-29 1996-02-02 Inst Francais Du Petrole Catalyseur pour la réduction de la teneur en benzène dans les essences.
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
US5830345A (en) * 1996-02-28 1998-11-03 Chinese Petroleum Corporation Process of producing a debenzenated and isomerized gasoline blending stock by using a dual functional catalyst
RU2322478C2 (ru) * 2006-05-10 2008-04-20 Государственное образовательное учреждение высшего профессионального образования Самарский государственный технический университет Способ снижения содержания бензола в бензиновых фракциях
EP2277980B1 (fr) * 2009-07-21 2018-08-08 IFP Energies nouvelles Procédé de réduction sélective de la teneur en benzène et en composés insatures legers de differentes coupes hydrocarbures
FR2948380B1 (fr) * 2009-07-21 2011-08-12 Inst Francais Du Petrole Procede de reduction selective de la teneur en benzene et en composes insatures legers de differentes coupes hydrocarbures
US8808533B2 (en) * 2010-04-23 2014-08-19 IFP Energies Nouvelles Process for selective reduction of the contents of benzene and light unsaturated compounds of different hydrocarbon fractions

Family Cites Families (4)

* 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
US4457832A (en) * 1983-01-19 1984-07-03 Chevron Research Company Combination catalytic reforming-isomerization process for upgrading naphtha
FR2579906B1 (enrdf_load_stackoverflow) * 1985-04-05 1987-05-15 Inst Francais Du Petrole
US5003118A (en) * 1989-12-29 1991-03-26 Uop Isomerization of benzene-containing feedstocks

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103464210A (zh) * 2013-09-27 2013-12-25 凯瑞化工股份有限公司 一种轻烃异构化催化剂及其制备方法
CN103464210B (zh) * 2013-09-27 2015-07-22 凯瑞环保科技股份有限公司 一种轻烃异构化催化剂及其制备方法

Also Published As

Publication number Publication date
MY109121A (en) 1996-12-31
CA2087384A1 (fr) 1993-07-16
DE69302287D1 (de) 1996-05-30
EP0552069A1 (fr) 1993-07-21
FR2686095B1 (fr) 1994-04-29
DE69302287T2 (de) 1996-09-12
ES2089739T3 (es) 1996-10-01
TW238298B (enrdf_load_stackoverflow) 1995-01-11
KR930016525A (ko) 1993-08-26
FR2686095A1 (fr) 1993-07-16
RU2091441C1 (ru) 1997-09-27

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