EP0610168B1 - Verfahren zur Herstellung von Benzin mit hoher Oktanzahl - Google Patents

Verfahren zur Herstellung von Benzin mit hoher Oktanzahl Download PDF

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Publication number
EP0610168B1
EP0610168B1 EP94870015A EP94870015A EP0610168B1 EP 0610168 B1 EP0610168 B1 EP 0610168B1 EP 94870015 A EP94870015 A EP 94870015A EP 94870015 A EP94870015 A EP 94870015A EP 0610168 B1 EP0610168 B1 EP 0610168B1
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EP
European Patent Office
Prior art keywords
stage
transalkylation
fraction
reforming
heavy
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
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EP94870015A
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English (en)
French (fr)
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EP0610168A1 (de
Inventor
Pierre Belloir
Eric Romers
Christian Lamotte
Jacques Grootjans
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Total Petrochemicals Research Feluy SA
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
    • C10G63/00—Treatment of naphtha by at least one reforming process and at least one other conversion process
    • C10G63/02—Treatment of naphtha by at least one reforming process and at least one other conversion process plural serial stages only
    • 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
    • C10G59/00—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha
    • C10G59/02—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha plural serial stages only

Definitions

  • the present invention relates to a method for improving the yield of high octane number gasolines.
  • the present invention is relates to a process for increasing the yield of high index species octane during the naphtha reforming step.
  • Naphtha is a fraction that has its temperature boiling range between 80 and 200 ° C and which consists essentially of paraffins, naphthenes and aromatics.
  • the most important reaction that takes place during naphtha reforming consists of the dehydrocyclization of paraffins in aromatics.
  • catalytic reforming has tendency to increase the end point of the reformate with respect to naphtha and promote the formation of benzene.
  • these phenomena are all the more marked.
  • those skilled in the art know that the endpoint of the reformate must be sufficiently low and that the content of benzene should be limited
  • the object of the present invention is a method which makes it possible to increase the gasoline yield with high octane number, namely the fraction intermediate from the naphtha reforming step.
  • FIG. 1 represents a schematic diagram of the method of the invention.
  • a charge of naphtha is subject to a reforming step (2) during which is brought into contact with a reforming catalyst in appropriate conditions.
  • the effluent recovered from the reforming step by the line (21) is introduced into the separation stage (3) and separated into three fractions: the light fraction (31), rich in benzene, and whose boiling point is generally less than 90 ° C, the fraction intermediate (32) whose boiling point is generally understood between 90 and 180 ° C and the heavy fraction (33) whose temperature boiling point is generally above 180 ° C.
  • the heavy and light fractions are then mixed and introduced into a transalkylation reactor (4) in which it is brought into contact with a transalkylation catalyst under suitable conditions.
  • This transalkylation step can be carried out in ascending or descending mode.
  • the effluent from this transalkylation step is sent via line (41) to line (21) where it is mixed with the effluent from catalytic reforming.
  • the whole is sent to the separation step at the end of which a larger intermediate fraction is recovered.
  • the pipes (311) and (331) indicated in FIG. 1 are not used.
  • Catalytic reforming of hydrocarbons is well known to those skilled in the art.
  • the objective of catalytic reforming is the selective conversion of saturated hydrocarbons to aromatics. This process makes it possible to obtain gasolines with high octane number as well as aromatic hydrocarbons. Many reactions take place during catalytic reforming, the main one being dehydrogenation.
  • the catalysts generally used have a double function: a metallic element makes it possible to catalyze dehydrogenation / hydrogenation and an acid function catalyzes the rearrangements of hydrocarbons.
  • These catalysts usually contain a small amount of highly dispersed platinum (preferably less than 1% by weight) supported on alumina with a high specific surface (of the order of 150-300m 2 / g); a second metal such as rhenium is also often used. It also happens that the catalyst used is dispersed on a basic support.
  • the operating conditions used are generally a temperature between 400 and 550 ° C and a pressure between 0.3 and 3.5 MPa.
  • the reaction is generally carried out in reactors with fixed or moving beds.
  • U.S. Patent 3,927,136 submits a mixture of a light fraction and a portion of heavy fractions at a transalkylation stage.
  • the Applicant unexpectedly found that by submitting the mixing of the heavy and light fractions in a transalkylation stage and in reintroducing the effluent resulting in the separation step, we increased the total amount of intermediate fraction i.e. the yield of gasoline with high octane number.
  • step c step of mixture of the light fraction and the heavy fraction
  • any other source diluted benzene and / or any other source of polyalkylbenzene it is also possible to introduce in step c (step of mixture of the light fraction and the heavy fraction) any other source diluted benzene and / or any other source of polyalkylbenzene.
  • This patent describes a process for transalkylating a charge containing at least one polyalkylbenzene in a reactor in the presence of a catalyst transalkylation to produce at least one characterized monoalkylbenzene in that the reaction is carried out in the presence of hydrogen.
  • transalkylation catalysts all kinds.
  • these are the molecular sieve catalysts doped with hydrogenation compounds metals based on group VIII metals of the periodic table elements, such as, in particular, nickel, palladium and platinum.
  • Large pore molecular sieves will be particularly suitable; we preferably use those with a stress index less than 1.
  • the definition of the stress index and its calculation are given in column 5 of US Patent 4,211,886.
  • mordenite type catalysts in particular type catalysts Mordenite slightly deficient in aluminum and having a molar ratio silica / alumina up to 30, preferably up to 20.
  • mordenite catalysts which can be used according to the present invention, mention may also be made of those described in the US patents 4,665,258 and US 4,723,048.
  • One of the advantages brought about by the process of the present invention consists in the recovery of the heavy fraction from the reforming step.
  • Another advantage of the process of the present invention consists in that that it allows to treat loads of naphtha without treatment prior to reforming. Indeed, it is known to those skilled in the art that in order to minimize the amount of heavy fraction after reforming, it is preferable to treat the starting naphtha charge by removing the compounds with high boiling temperatures. According to the process of the present invention this naphtha pre-treatment step is no longer necessary which represents a considerable advantage.
  • the light fraction obtained is rich in benzene.
  • this light fraction was incorporated into essences which often required treatment in order to limit the benzene content of gasolines. This additional step is no longer necessary according to the process of the present invention because the content of benzene is automatically limited following the conversion of benzene during of the transalkylation step.
  • the catalyst used is based on nickel (1.6% by weight) deposited on a mordenite with a silica / alumina molar ratio of 8.8.
  • This catalyst was activated in the following way: under 6 MPa, with a flow of hydrogen, the temperature gradually rose to 200 ° C and maintained 12 hours. Then, the temperature rose to 360 ° C and stabilized for 4 hours. Then, the reactor is cooled to 200 ° C.
  • the operating conditions of the transalkylation are indicated in Table 2.
  • the composition of the transalkylation effluent is also indicated in Table 2.

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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 zum Erhöhen der Ausbeute von Kraftstoffen mit hohem Octanindex, welches die Stufen umfaßt, die bestehen aus
    a. Aussetzen einer Naphthaladung einem katalytischen Reforming durch in Kontakt bringen mit einem Katalysator von katalytischem Reforming zum Bilden von drei Fraktionen, einer leichten, einer intermediären und einer schweren,
    b. Trennen der drei Fraktionen während einer Trennungsstufe,
    c. Mischen von mindestens einem Teil der leichten Fraktion mit mindestens einem Teil der schweren Fraktion,
    d. Aussetzen der Mischung, abstammend von Punkt c, einer Transalkylierungsstufe und
    e. Einführen des Ausflusses in die Stufe b, der aus der Stufe d stammt, und Gewinnen einer wichtigeren intermediären Fraktion nach dieser Stufe b, dadurch gekennzeichnet, daß der aus der Reformingstufe gewonnene Ausfluß direkt in die Trennungsstufe eingeführt wird, und dadurch, daß die Gesamtheit der leichten Fraktion und der schweren Fraktion in die Stufe d eingeführt wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Transalkylierungsstufe sich in Gegenwart von Wasserstoff abspielt.
  3. Verfahren nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß eine Quelle unterschiedlich von Benzol und/oder von Polyalkylbenzol in Stufe c hinzugegeben wird.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß sich die Transalkylierungsstufe in Gegenwart eines Transalkylierungskatalysators abspielt, ausgewählt unter den Molekülsieben mit großen Poren mit einem Spannungsindex unterhalb von 1.
  5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß der Transalkylierungskatalysator ein Mordenit ist.
EP94870015A 1993-02-02 1994-01-31 Verfahren zur Herstellung von Benzin mit hoher Oktanzahl Expired - Lifetime EP0610168B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE9300104 1993-02-02
BE9300104A BE1006675A3 (fr) 1993-02-02 1993-02-02 Procede de production d'essences a haut indice d'octane.

Publications (2)

Publication Number Publication Date
EP0610168A1 EP0610168A1 (de) 1994-08-10
EP0610168B1 true EP0610168B1 (de) 1999-04-07

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EP94870015A Expired - Lifetime EP0610168B1 (de) 1993-02-02 1994-01-31 Verfahren zur Herstellung von Benzin mit hoher Oktanzahl

Country Status (9)

Country Link
US (1) US6281398B1 (de)
EP (1) EP0610168B1 (de)
JP (1) JP3469625B2 (de)
AT (1) ATE178647T1 (de)
BE (1) BE1006675A3 (de)
DE (1) DE69417607T2 (de)
DK (1) DK0610168T3 (de)
ES (1) ES2131660T3 (de)
GR (1) GR3030656T3 (de)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5347061A (en) * 1993-03-08 1994-09-13 Mobil Oil Corporation Process for producing gasoline having lower benzene content and distillation end point
US7708956B2 (en) * 2007-09-07 2010-05-04 Uop Llc Combination hot separator and reactor vessel for simultaneously desulfurizing two vapor streams
US9109169B2 (en) 2012-05-02 2015-08-18 Saudi Arabian Oil Company Maximizing aromatics production from hydrocracked naphtha
FR3014894B1 (fr) * 2013-12-17 2017-02-10 Ifp Energies Now Procede de reformage catalytique
FR3014895B1 (fr) * 2013-12-17 2017-02-10 Ifp Energies Now Procede de reformage catalytique
CA2954346C (en) * 2014-07-07 2020-06-30 Albemarle Europe Sprl Alkylation process using a catalyst comprising cerium rich rare earth containing zeolites and a hydrogenation metal
US10633596B2 (en) * 2016-06-17 2020-04-28 Basf Corporation FCC catalyst having alumina derived from crystalline boehmite
US10093873B2 (en) 2016-09-06 2018-10-09 Saudi Arabian Oil Company Process to recover gasoline and diesel from aromatic complex bottoms
US11066344B2 (en) 2017-02-16 2021-07-20 Saudi Arabian Oil Company Methods and systems of upgrading heavy aromatics stream to petrochemical feedstock
WO2018158377A1 (en) * 2017-03-01 2018-09-07 Albemarle Europe Sprl Alkylation process with improved octane number
FR3068967B1 (fr) * 2017-07-13 2019-06-28 IFP Energies Nouvelles Methode et procede pour convertir l'ethylene present dans l'effluent de tete d'un fcc de maniere a augmenter la production de propylene
US11613714B2 (en) 2021-01-13 2023-03-28 Saudi Arabian Oil Company Conversion of aromatic complex bottoms to useful products in an integrated refinery process
US11591526B1 (en) 2022-01-31 2023-02-28 Saudi Arabian Oil Company Methods of operating fluid catalytic cracking processes to increase coke production

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3927136A (en) * 1974-07-05 1975-12-16 Texaco Inc Treatment of hydrocarbons
US4078990A (en) * 1977-03-04 1978-03-14 Mobil Oil Corporation Manufacture of lower aromatic compounds
US4211886A (en) * 1978-09-25 1980-07-08 Mobil Oil Corporation Manufacture of benzene, toluene and xylene
JPH03501975A (ja) 1988-06-23 1991-05-09 エービービー　ルーマス　クレスト　インコーポレーテッド 改良されたポリアルキルベンゼンのアルキル交換反応法
IT1236511B (it) * 1989-10-06 1993-03-11 Eniricerche Spa Metodo per il recupero di trimetilbenzeni da miscele che li contengono.
US5053573A (en) * 1990-09-14 1991-10-01 Mobil Oil Corporation Reduction of benzene content of reformate by reaction with cycle oils

Also Published As

Publication number Publication date
JP3469625B2 (ja) 2003-11-25
US6281398B1 (en) 2001-08-28
EP0610168A1 (de) 1994-08-10
GR3030656T3 (en) 1999-10-29
DK0610168T3 (da) 1999-10-18
BE1006675A3 (fr) 1994-11-16
ATE178647T1 (de) 1999-04-15
DE69417607D1 (de) 1999-05-12
DE69417607T2 (de) 1999-10-14
ES2131660T3 (es) 1999-08-01
JPH06271871A (ja) 1994-09-27

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