EP0953626A1 - Procédé de préparation d'un mélange hydrocarburé à haut indice d'octane et pauvre en benzène - Google Patents

Procédé de préparation d'un mélange hydrocarburé à haut indice d'octane et pauvre en benzène Download PDF

Info

Publication number
EP0953626A1
EP0953626A1 EP98107643A EP98107643A EP0953626A1 EP 0953626 A1 EP0953626 A1 EP 0953626A1 EP 98107643 A EP98107643 A EP 98107643A EP 98107643 A EP98107643 A EP 98107643A EP 0953626 A1 EP0953626 A1 EP 0953626A1
Authority
EP
European Patent Office
Prior art keywords
stage
mixture
benzene
isomerization
bar
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.)
Withdrawn
Application number
EP98107643A
Other languages
German (de)
English (en)
Inventor
Hermann Voss
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.)
FE ENGINEERING GMBH
Original Assignee
Fe Forschungs & Entwicklung GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fe Forschungs & Entwicklung GmbH filed Critical Fe Forschungs & Entwicklung GmbH
Priority to EP98107643A priority Critical patent/EP0953626A1/fr
Publication of EP0953626A1 publication Critical patent/EP0953626A1/fr
Withdrawn legal-status Critical Current

Links

Images

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
    • 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
    • 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 method for producing a Low-benzene, high-octane hydrocarbon mixture.
  • benzene is a special ingredient high octane number up to about 8%. Because benzene is carcinogenic is its maximum content in the carburetor fuel in Europe is currently limited to 5%, in the future there will be a reduction of the limit at 1%.
  • benzene is required by distillation and / or extractive treatment from the reformate to remove. This goes hand in hand with a reduction in Octane number in the reformate and a loss of quantity of gasoline. Becomes benzene from the reformate by distillation separated, contains this separated fraction in addition to aliphatic and naphthenic hydrocarbons in one Proportion of usually about 20 to a maximum of about 50%.
  • EP-A-0 552 070 discloses a process in which first a benzene hydrogenation is carried out and then the effluent of the hydrogenation stage is fed to the isomerization stage together with a low-aromatic C 5 to C 6 distillation cut.
  • the selected process conditions in particular the very different pressures and temperatures in the hydrogenation and isomerization stage) do not allow a common gas cycle in which the hydrogen-rich gas component of the effluent of the isomerization stage is returned directly to the inlet of the hydrogenation stage.
  • the present invention is based on the object To create procedures of the type mentioned, the one simplified and cost-effective compared to the prior art Process control allowed and a high yield of isoparaffins having.
  • the heated mixture fed to the hydrogenation stage only has a gas phase according to the invention on.
  • the invention allows the hydrogenation of KW mixtures with significantly higher benzene proportions than in State of the art.
  • the combination of parameters according to the invention does the exothermic benzene hydrogenation even at high benzene concentrations manageable.
  • maximum 4 to 5% Benzene may be included to locally overheat the catalyst and to avoid resulting side reactions and damage.
  • the benzene concentration in the feed of the hydrogenation stage is preferred at least 5%, more preferably at least 10%, more preferably at least 15%, more preferably at least 20%, more preferably at least 30%.
  • the invention makes it possible to use a feed mixture a water content of up to 100 ppm and a sulfur content up to 50 ppm.
  • the waiver of one chlorine-containing catalyst allows comparatively high water contents, furthermore avoids or reduces the invention Combination of features a catalyst poisoning itself at relatively high sulfur levels. Assigns the feed mix Sulfur levels above 10 ppm, a platinum-doped Catalyst preferred in the hydrogenation stage.
  • the effluent of the isomerization stage it is possible from the effluent of the isomerization stage to the hydrogen-rich one Separate the gas portion (e.g. by distillation) and immediately attributed to the entrance of the hydrogenation stage. This is especially possible without special effort if the Isomerization stage, as described later, between Input and output only have a small pressure difference.
  • the specific catalyst loading in the hydrogenation stage is 1 to 7 v / v h. This means that 1 to 7 m 3 of hydrocarbon mixture (volume calculated for the liquid state) flow through the hydrogenation stage per hour and per m 3 of catalyst. This measure is also known as LHSV (liquid hourly space velocity).
  • the specific catalyst load in the isomerization stage is preferably 0.3 to 2.5 v / v h.
  • a platinum-doped catalyst support composition is preferably used in the hydrogenation stage. If the sulfur content is somewhat lower (up to about 10 ppm), a nickel-doped catalyst support composition is preferably used.
  • Such a catalyst can be shaped as a tablet or extrudate and preferably has about 50 to 80% by weight of nickel on an acidic support material containing silicon oxide.
  • the specific metallic nickel surface of the catalyst is preferably at least 20 m 2 / g, the pore volume is at least 0.2 cm 3 / g, and the density is preferably between 1,000 and 1,500 kg / m 3 .
  • a tube or plate reactor is preferably used as the hydrogenation stage Use, the shaped catalyst (pills or extrudate) is in the tubes or thin between the Panels arranged.
  • the exothermic hydrogenation reaction released heat can be caused by the walls of the tubes or Plates are derived, the are particularly preferred Tubes or walls for this purpose from a heat exchange medium flowed, with the help of a regulated heat dissipation to maintain a desired temperature in the hydrogenation stage can take place.
  • Can be used as a heat exchange medium use a heat exchanger oil. Alternatively, this can be done in the feed mixture to be used or its hydrocarbon fraction used and preheated in this way become. Also KW currents for a downstream distillation can be preheated in this way.
  • the controlled heat dissipation allows by setting the reaction temperature an influence on the residual benzene content of the effluent of the hydrogenation stage and avoids local unwanted Temperature peaks that favor cracking reactions and possibly lead to coking of the catalyst can. If necessary, almost isothermal reaction conditions be created in the entire reactor bed of the hydrogenation stage.
  • the targeted temperature setting also enables Extensive splitting of naphthenic rings, so that at the entrance the subsequent isomerization step a higher proportion of n-paraffins is available.
  • the effluent from the hydrogenation stage can be fed directly to the isomerization stage. If necessary, an intermediate heat exchanger is used to preheat to the temperature desired at the entrance to the isomerization stage.
  • a further low-benzol hydrocarbon mixture for example a mineral oil cut obtained by distillation, which is rich in n-paraffins, primarily C 5 - and C 6 contains hydrocarbons and can therefore also be subjected to an octane-increasing isomerization.
  • a platinum-doped is preferred in the isomerization stage Catalyst support mass used. It is preferred around a shaped carrier mass (e.g. pills or extrudate), which is preferably of the mordenite type.
  • the Si / Al atomic ratio in the mordenite is preferably 10 to 60.
  • the carrier can be doped with 0.2 to 0.5, preferably about 0.3% by weight of platinum his.
  • a radial flow reactor is preferred for the isomerization stage used.
  • Such a type of reactor is only suitable for single-phase reaction mixtures and enables flow through of the catalyst bed with low pressure loss.
  • the feed mix flows through the ring arranged around the central tube Catalyst bed radially from the outside to the center and will derived from the reactor through a central tube.
  • the effluent of a catalytic reforming plant becomes a benzene-containing fraction A with a boiling range of 70 separated up to 90 ° C.
  • This fraction A is filled with a hydrogen Purgegas B of a reformer in one molar mixing ratio of 0.8 added.
  • the mixture will set to a pressure of 28 bar (g) and in the heat exchanger E1 (see Fig. 1) heated to 180 ° C.
  • the mixture goes completely into the gas phase. It becomes the hydrogenation stage R1 fed.
  • the hydrogenation stage R1 has a reactor which works like a Shell and tube heat exchanger is constructed.
  • a catalyst an extruded alumina carrier used with 0.3 % By weight of platinum is doped. It is placed in the pipes. The feed mixture flows through these tubes in an amount that the catalyst is subjected to a load of 5 v / v h.
  • the feed mixture fed to the hydrogenation stage R1 flows through the reactor from top to bottom. Benzene and hydrogen react with each other to cyclohexane. The exothermic at this Reaction heat is dissipated to the extent that from the entrance to the exit of the reactor from 180 ° C to 205 ° C increasing temperature profile results. The low-benzol reaction mixture C thus leaves the hydrogenation stage R1 at a temperature of 205 ° C.
  • the mixture C is then heated to 255 ° C. in the preheater F1 and the isomerization stage R2.
  • the isomerization stage R2 has a radial flow reactor on.
  • the catalyst bed is ring-shaped around a central tube arranged around.
  • the mixture C is fed so that it the catalyst bed radially from the outside to the central tube can flow through.
  • the reaction mixture is through the central tube derived from the reactor. Training as a radial flow reactor causes a slight pressure drop across this Reactor.
  • An extrudate is used as the catalyst in the isomerization stage from mordenite (Si / Al atomic ratio 10:60) used with an aluminum binder mechanically stabilized and with 0.4% by weight of platinum is doped.
  • This acidic catalyst works a quick adjustment of the chemical balance between n- and isoparaffins.
  • it causes one partial conversion of cyclohexane present in the reaction mixture in methylcyclopentane, which has a higher octane number than Has cyclohexane. Because that fed to the isomerization stage Feed C is low in benzene, takes place in the isomerization stage no noteworthy due to exothermic reactions caused heating instead, so that undesirable side reactions are largely avoided.
  • the reaction mixture emerging from the isomerization stage R2 is cooled in the heat exchanger E1 and partially condensed. A further cooling to 35 ° C takes place in the water cooler E2.
  • the two-phase cooled mixture is in the separation tank D1 headed.
  • the hydrogen-rich gas phase is at a pressure of 26 bar (g) from the separator tank D1 With the help of the compressor C1 and sucked together with the one supplied at E. fresh hydrogen again as an input product of Hydrogenation stage R1 supplied. It becomes the one essential Advantage of the invention forming closed gas circuit both reaction stages (hydrogenation and isomerization) educated.
  • the liquid phase collecting in the separating container D1 is freed of dissolved gases in the stabilizing column D1 and broken down into three fractions by distillation.
  • the partially condensed top product D2, cooled to 35 ° C., is passed into a top product receiver. It mainly contains hydrogen, methane and ethane in the gas phase F and propane and butane in the liquid phase G.
  • a side stream H which predominantly contains C 5 hydrocarbons, is removed from the stabilization column T1 (also called debutanizer). This stream H is fed to the deisopentanizer D2, which splits the C 5 fraction into an isopentane-rich top product I and an n-pentane-rich bottom product J.
  • the top product I can be added directly to a gasifier fuel, the bottom product J can be returned to the inlet either to the hydrogenation stage R1 or directly to the isomerization stage R2.
  • the bottom product K of the Debutanizer D1 is a C 6 hydrocarbon-rich fraction, which is broken down into three fractions in the Deisohexanizer D3.
  • the top product L of the Deisohexanizer T3 is an isoparaffin-rich C 6 fraction (usable as a component of gasoline).
  • the side draw M consists mainly of n-hexane, which is recycled to the hydrogenation or isomerization stage.
  • the bottom product N contains predominantly methylcyclopentane and cyclohexane.
  • the product composition of the benzene-rich feed A, the hydrogen-rich gas mixture B, the effluent C of the hydrogenation stage and the effluent D of the isomerization stage can be seen from Table 1 below.
  • the engine octane number (MON) is also given in the last line of the table.
  • the stream A is mixed with a hydrogen-rich gas C, so that a ratio of 500 to 1,000 Nm 3 hydrogen per 1 m 3 liquid hydrocarbon is established.
  • the mixture is adjusted to a pressure of 29 bar (g) and heated to a temperature between 150 and 280 ° C until it has completely passed into the gas phase. This mixture is fed to the hydrogenation stage.
  • the hydrogenation stage has a reactor which is constructed as described in Example 1.
  • a tablet-shaped catalyst material is used which contains 50 to 80% by weight of nickel on an acidic silica-containing support material.
  • the catalyst has a specific metallic nickel surface area of at least 20 m 2 / g, a pore volume of at least 0.2 cm 3 / g and a density of 1,000 to 1,500 kg / m 3 .
  • the feed stream is adjusted so that the specific catalyst load is 3 to 7 v / vh.
  • benzene is converted to cyclohexane with hydrogen and implemented methylcyclohexane.
  • the exothermic reaction released heat is through the pipe wall in the a heat exchanger liquid through which the jacket space flows Derived from the reactor.
  • a heat exchanger liquid is at this example the bottom product of the one described below Deisobutanizers T1 uses this this way is warmed up.
  • the heat dissipation is regulated so that at least 95%, preferably at least 99% of that in the feed mixture contained benzene converted to cyclohexane or methylcyclopentane becomes.
  • the effluent stream D of the hydrogenation stage is the low-benzol Hydrocarbon stream B mixed, this hydrocarbon stream B contains mainly aliphatic and cyclic Paraffins.
  • the mixture produced is at a pressure of Set 27.3 bar (g) and at a temperature of 230 to 330 ° C heated so that any liquid components evaporate completely are and a single-phase gas mixture is formed.
  • This mixture is fed to the isomerization stage.
  • she is constructed as described in Example 1 and contains one Catalyst of the mordenite type, containing 0.2 to 0.5% by weight of platinum is endowed.
  • the isomerization stage essentially prevails adiabatic reaction conditions.
  • the reactions taking place in the isomerization stage are equilibrium reactions in which, depending on temperature and pressure, ratios of isopentane to n-pentane of 2: 1, isohexane to n-hexane of 4: 1 and cyclohexane to methylcyclopentane of 1: 3 can be achieved.
  • C 7 hydrocarbons present in the feed mixture are largely converted to C 1 to C 4 hydrocarbons.
  • the effluent F of the isomerization stage is partially condensed, a gas phase G and a liquid phase H being obtained.
  • the hydrogen-rich gas phase G becomes after pressure increase and mixing with hydrogen-rich fresh gas again as hydrogen-rich Gas C the benzene-rich hydrocarbon stream A mixed in before the hydrogenation stage.
  • the composition of the various products described is shown in Table 2.
  • the Debutanizer T1 is preferably operated at 16 to 22 bar (g), the Deisopentanizer T2 at 6 to 12 bar (g) and the Deisohexanizer preferably at 2 to 5 bar (g).

Landscapes

  • 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)
EP98107643A 1998-04-27 1998-04-27 Procédé de préparation d'un mélange hydrocarburé à haut indice d'octane et pauvre en benzène Withdrawn EP0953626A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP98107643A EP0953626A1 (fr) 1998-04-27 1998-04-27 Procédé de préparation d'un mélange hydrocarburé à haut indice d'octane et pauvre en benzène

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP98107643A EP0953626A1 (fr) 1998-04-27 1998-04-27 Procédé de préparation d'un mélange hydrocarburé à haut indice d'octane et pauvre en benzène

Publications (1)

Publication Number Publication Date
EP0953626A1 true EP0953626A1 (fr) 1999-11-03

Family

ID=8231834

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98107643A Withdrawn EP0953626A1 (fr) 1998-04-27 1998-04-27 Procédé de préparation d'un mélange hydrocarburé à haut indice d'octane et pauvre en benzène

Country Status (1)

Country Link
EP (1) EP0953626A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1992673A1 (fr) * 2007-05-18 2008-11-19 Uop Llc Isomérisation de produits de départ contenant du benzène

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR954644A (fr) * 1950-01-04
US3791960A (en) * 1971-04-19 1974-02-12 British Petroleum Co Isomerization of paraffin hydrocarbons
EP0504510A1 (fr) * 1989-12-29 1992-09-23 Uop Procédé combiné d'hydrogénation et d'isomérisation en charges contenant du benzène et des paraffines
EP0552070A1 (fr) * 1992-01-15 1993-07-21 Institut Français du Pétrole Réduction de la teneur en benzène dans les essences
EP0552072A1 (fr) * 1992-01-15 1993-07-21 Institut Français du Pétrole Réduction de la teneur en benzène dans les essences
EP0661370A1 (fr) * 1993-12-29 1995-07-05 Institut Français du Pétrole Catalyseur pour la réduction de la teneur en benzène dans les essences

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR954644A (fr) * 1950-01-04
US3791960A (en) * 1971-04-19 1974-02-12 British Petroleum Co Isomerization of paraffin hydrocarbons
EP0504510A1 (fr) * 1989-12-29 1992-09-23 Uop Procédé combiné d'hydrogénation et d'isomérisation en charges contenant du benzène et des paraffines
EP0552070A1 (fr) * 1992-01-15 1993-07-21 Institut Français du Pétrole Réduction de la teneur en benzène dans les essences
EP0552072A1 (fr) * 1992-01-15 1993-07-21 Institut Français du Pétrole Réduction de la teneur en benzène dans les essences
EP0661370A1 (fr) * 1993-12-29 1995-07-05 Institut Français du Pétrole Catalyseur pour la réduction de la teneur en benzène dans les essences

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1992673A1 (fr) * 2007-05-18 2008-11-19 Uop Llc Isomérisation de produits de départ contenant du benzène

Similar Documents

Publication Publication Date Title
DE2526887C2 (de) Verfahren zur Herstellung von aromatischen Kohlenwasserstoffen
DE2753937A1 (de) Verfahren zur gewinnung aromatischer verbindungen aus naphtha
DE2262797A1 (de) Verfahren zum kracken unter wasserstoffdruck fuer die herstellung von olefinen
WO2019158687A1 (fr) Procédé et installation de production d'une essence synthétique
DE69917363T2 (de) Verfahren zur Isomerisation von Benzinen mit erhöhtem Benzolgehalt
DE2061945C3 (de) Verfahren zur Herstellung von hochoctanigem Benzin
DE2840986A1 (de) Verfahren zur aufarbeitung der bei der spaltung von kohlenwasserstoffen entstehenden ueber 200 grad siedenden kohlenwasserstoff-fraktion
EP0953626A1 (fr) Procédé de préparation d'un mélange hydrocarburé à haut indice d'octane et pauvre en benzène
DE2134155A1 (de) Verfahren zur Herstellung von hochoktanigem unverbleiten Benzin
DE2239282B2 (de) Verfahren zur gleichzeitigen Herstellung eines Aromatenkonzentrates und eines Isobutankonzentrates
DE2620854A1 (de) Verfahren zur trennung des aus einer kohlenwasserstoffumwandlungsanlage austretenden reaktionsproduktes
DE1668774A1 (de) Verfahren zur Herstellung olefinischer Kohlenwasserstoffe
DE112021000068T5 (de) Methoden für eine butanhydrogenolyse unter wasserstoffarmen bedingungen
DE2937376C2 (fr)
DE2227740A1 (de) Kohlenwasserstoffumwandlungsverfahren
DE2001134C2 (de) Verfahren zur Herstellung von Düsenbrennstoffkerosinfraktionen
DE3002209C2 (de) Verfahren zur Umwandlung von Kohlenwasserstoffen
DE1964146A1 (de) Verfahren zur Erhoehung der Klopffestigkeit von Benzin-Kohlenwasserstoffen durch katalytisches Reformieren
DE2055728C3 (fr)
DE2247297C3 (de) Verfahren zur Herstellung eines aromatische Kohlenwasserstoffe und Isobutan enthaltenden unverbleiten Motortreibstoffes hoher Octanzahl
DE1645776C (de) Kohlenwasserstoff Umwandlungs verfahren
DE1545415C2 (de) Verfahren zur Umwandlung von Kohlenwasserstoffen
AT233707B (de) Kontinuierliches Kohlenwasserstoffumwandlungsverfahren
DE1042800B (de) Verfahren zur Herstellung von fluessigen Kohlenwasserstoffgemischen mit hoher Octanzahl
DE2001134A1 (de) Verfahren zur Herstellung von Duesenbrennstoffkerosinfraktionen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CY DE DK ES FI FR GB GR IT NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: FE ENGINEERING GMBH

17P Request for examination filed

Effective date: 20000420

AKX Designation fees paid

Free format text: AT BE CY DE DK ES FI FR GB GR IT NL PT SE

AXX Extension fees paid

Free format text: AL PAYMENT 20000420;RO PAYMENT 20000420

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20011101