EP0610168A1 - 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
EP0610168A1
EP0610168A1 EP94870015A EP94870015A EP0610168A1 EP 0610168 A1 EP0610168 A1 EP 0610168A1 EP 94870015 A EP94870015 A EP 94870015A EP 94870015 A EP94870015 A EP 94870015A EP 0610168 A1 EP0610168 A1 EP 0610168A1
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EP
European Patent Office
Prior art keywords
transalkylation
fraction
process according
heavy
reforming
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.)
Granted
Application number
EP94870015A
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English (en)
French (fr)
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EP0610168B1 (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 process for improving the yield of gasoline with a high octane number.
  • the present invention relates to a process for increasing the yield of gasolines with a high octane number during the step of reforming naphtha.
  • Naphtha is a fraction that has a boiling temperature between 80 and 200 ° C and which consists mainly of paraffins, naphthenes and aromatics.
  • the most important reaction that takes place during the reforming of naphtha is the dehydrocyclization of paraffins to aromatics.
  • catalytic reforming tends to increase the end point of the reformate compared to naphtha and to favor the formation of benzene.
  • these phenomena are all the more marked.
  • those skilled in the art know that the end point of the reformate must be sufficiently low and that the benzene content must be limited
  • the object of the present invention is a process which makes it possible to increase the yield of gasolines with a high octane number, namely the intermediate fraction originating from the step of reforming naphtha.
  • FIG. 1 represents a schematic diagram of the process of the invention.
  • a charge of naphtha is introduced via line (11). This charge is subjected to a reforming step (2) during which it is brought into contact with a reforming catalyst under appropriate conditions.
  • the effluent recovered from the reforming step via line (21) is introduced into the separation step (3) and separated into three fractions: the light fraction (31), rich in benzene, and whose temperature boiling is generally less than 90 ° C, the intermediate fraction (32) whose boiling temperature is generally between 90 and 180 ° C and the heavy fraction (33) whose boiling temperature is generally greater than 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 essential; in certain cases they allow the relative proportions of the heavy and light fractions to be adjusted before introduction into the transalkylation reactor.
  • 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 150-300m2 / 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.
  • the Applicant has unexpectedly found that by subjecting the mixture of heavy and light fractions to a transalkylation step and by reintroducing the resulting effluent in the separation step, the total amount of intermediate fraction is increased. ie the yield of gasoline with a high octane number.
  • step c step of mixing the light fraction and the heavy fraction
  • any other source of dilute benzene and / or any other source of polyalkylbenzene any other source of dilute benzene and / or any other source of polyalkylbenzene.
  • This patent describes a process for transalkylating a feedstock containing at least one polyalkylbenzene in a reactor in the presence of a transalkylation catalyst in order to produce at least one monoalkylbenzene characterized in that the reaction is carried out in the presence of hydrogen.
  • the hydrogen: alkyl groups molar ratios are preferably between 1:10 and 1: 1.
  • transalkylation catalysts can be used.
  • Large pore molecular sieves will be particularly suitable; preferably those with a stress index less than 1.
  • the definition of the stress index and its calculation are given in column 5 of US Pat. No. 4,211,886.
  • mordenite type catalysts are used, in particular type catalysts. Mordenite slightly deficient in aluminum and having a silica / alumina molar ratio of 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 US Patents 4,665,258 and US 4,723,048.
  • One of the advantages provided by the process of the present invention consists in the recovery of the heavy fraction resulting from the reforming step.
  • Another advantage of the process of the present invention consists in that it makes it possible to treat charges 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 charge of starting naphtha by removing the compounds at high boiling temperatures. According to the process of the present invention, this step of pretreatment of naphtha is no longer necessary, which represents a considerable advantage.
  • the light fraction obtained is rich in benzene.
  • this light fraction was incorporated into gasolines which very often required treatment in order to limit the benzene content of the gasolines. This additional step is no longer necessary according to the process of the present invention since the benzene content is automatically limited following the conversion of the benzene during the transalkylation step.
  • the catalyst used is based on nickel (1.6% by weight) deposited on a mordenite whose silica / alumina molar ratio is 8.8. This catalyst was activated in the following way: at 6 MPa, with a flow of hydrogen, the temperature gradually rose to 200 ° C. and maintained for 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)
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 true EP0610168A1 (de) 1994-08-10
EP0610168B1 EP0610168B1 (de) 1999-04-07

Family

ID=3886829

Family Applications (1)

Application Number Title Priority Date Filing Date
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)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0763002A1 (de) * 1993-03-08 1997-03-19 Mobil Oil Corporation Verfahren zur herstellung von benzin mit niedrigesm benzolgehalt und distillationsendpunkt

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7708956B2 (en) * 2007-09-07 2010-05-04 Uop Llc Combination hot separator and reactor vessel for simultaneously desulfurizing two vapor streams
WO2013166235A2 (en) 2012-05-02 2013-11-07 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
PL3167026T3 (pl) * 2014-07-07 2019-11-29 Albemarle Europe Sprl Sposób alkilowania przy użyciu katalizatora zawierającego bogate w cer zeolity z zawartością pierwiastków ziem rzadkich i metal uwodorniający
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
RU2762589C2 (ru) * 2017-03-01 2021-12-21 Альбемарл Юроп Срл Способ алкилирования с улучшенным октановым числом
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

Citations (5)

* 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
EP0422727A1 (de) * 1989-10-06 1991-04-17 Enichem Anic S.r.l. Verfahren zur Rückgewinnung von Trimethylbenzolen aus den enthaltenden Mischungen
US5053573A (en) * 1990-09-14 1991-10-01 Mobil Oil Corporation Reduction of benzene content of reformate by reaction with cycle oils

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (5)

* 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
EP0422727A1 (de) * 1989-10-06 1991-04-17 Enichem Anic S.r.l. Verfahren zur Rückgewinnung von Trimethylbenzolen aus den enthaltenden Mischungen
US5053573A (en) * 1990-09-14 1991-10-01 Mobil Oil Corporation Reduction of benzene content of reformate by reaction with cycle oils

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0763002A1 (de) * 1993-03-08 1997-03-19 Mobil Oil Corporation Verfahren zur herstellung von benzin mit niedrigesm benzolgehalt und distillationsendpunkt
EP0763002A4 (de) * 1993-03-08 1998-07-08 Mobil Oil Corp Verfahren zur herstellung von benzin mit niedrigesm benzolgehalt und distillationsendpunkt

Also Published As

Publication number Publication date
ES2131660T3 (es) 1999-08-01
DK0610168T3 (da) 1999-10-18
DE69417607D1 (de) 1999-05-12
DE69417607T2 (de) 1999-10-14
JPH06271871A (ja) 1994-09-27
EP0610168B1 (de) 1999-04-07
BE1006675A3 (fr) 1994-11-16
ATE178647T1 (de) 1999-04-15
US6281398B1 (en) 2001-08-28
GR3030656T3 (en) 1999-10-29
JP3469625B2 (ja) 2003-11-25

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