EP0559518B1 - Verfahren zur Isomerisierung von n-C5/C6-Paraffinen mit Recyclierung von n-Paraffinen und Methylpentanen - Google Patents

Verfahren zur Isomerisierung von n-C5/C6-Paraffinen mit Recyclierung von n-Paraffinen und Methylpentanen Download PDF

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EP0559518B1
EP0559518B1 EP93400443A EP93400443A EP0559518B1 EP 0559518 B1 EP0559518 B1 EP 0559518B1 EP 93400443 A EP93400443 A EP 93400443A EP 93400443 A EP93400443 A EP 93400443A EP 0559518 B1 EP0559518 B1 EP 0559518B1
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stage
paraffins
isomerization
effluent
pressure
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French (fr)
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EP0559518A1 (de
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Ari Minkkinen
André Deschamps
Jean-Paul Cariou
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IFP Energies Nouvelles IFPEN
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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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
    • 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
    • C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
    • C10G61/02—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural serial stages only
    • C10G61/06—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen plural serial stages only the refining step being a sorption process

Definitions

  • the invention relates to a process for the isomerization of n-paraffins into isoparaffins, the aim of which is in particular to improve the octane number of certain petroleum fractions, more particularly those which contain pentanes and normal hexanes as well as pentanes and branched hexanes (cuts C 5 / C 6 ).
  • a well-known isomerization process using molecular sieves for the vapor phase separation of unconverted n-paraffins, incorporates the adsorption step by molecular sieve into the reaction step.
  • This is the so-called “Total Isomerization Process” (or “TIP”) described for example in patent US-A-4210771. It combines the implementation of an isomerization reactor fed by the mixture of the feedstock, a desorption effluent and hydrogen, and the implementation of a separation section by adsorption of n-paraffins on molecular sieve, desorption being effected by hydrogen stripping.
  • the reaction system cannot consist of a step with high activity chlorinated alumina, because of the risks of contamination by hydrochloric acid of the integrated molecular sieves.
  • a less efficient catalytic system is then used, based on a zeolite that does not use chlorine.
  • the result is a product with an index octane lower by 1 to 2 points than that which would have been obtained with a catalyst based on chlorinated alumina.
  • the catalyst based on chlorinated alumina impregnated with platinum makes it possible to carry out the isomerization reaction at a lower temperature than the catalysts of non-chlorinated zeolite type, which are more stable.
  • the object of the invention is to propose a new process making it possible to increase as much as possible the octane number of an oil cut containing normal paraffins while limiting the energy expenditure.
  • the present invention makes it possible in particular to overcome the drawbacks of known processes, by combining the high activity system using for example a catalyst consisting of a chlorinated alumina impregnated with platinum with an original adsorption-desorption system on molecular sieve in the vapor phase (system not integrated).
  • a catalyst consisting of a chlorinated alumina impregnated with platinum
  • an original adsorption-desorption system on molecular sieve in the vapor phase system not integrated
  • the desorption of n-paraffins is carried out under advantageous conditions from the energy point of view by combining a pressure reduction and a stripping operation using a vapor rich in methyl pentanes which are also recycled and converted into dimethylbutanes during passage through the isomerization reactor.
  • a desisohexanization column is incorporated downstream of the system which splits the effluent from the adsorption step into 2 sections: a distillate section containing only isomers with a very high octane number having a high concentration of dimethyl butanes and a bottom section of the column having a high concentration of methylpentanes with an octane number much lower than that of the distillate.
  • the judicious use of methyl pentanes provided by the deisohexanization in the desorption step makes it possible to omit a purging step at the end of the latter.
  • the adsorbent column then filled with methyl pentanes can be immediately reused for adsorption, the adsorption effluent then not containing n-paraffins, even at the start of the latter. This leads to a significant simplification of the unit, in particular allowing the use of a system containing only two adsorbent beds, each operating alternately in adsorption and in desorption.
  • step (1) the charge of light naphtha (line 1) mixed with at least one recycling is sent to an isomerization zone 1, via line 2 a stream rich in normal paraffins and in methylpentanes originating from the desorption step (3) (line 11) and optionally recycling part of the liquid residue from the deisohexanization step (4) (line 12).
  • the isomerization reaction is carried out at a temperature of 140 to 300 ° C in the presence of hydrogen under a pressure of 10 to 40 bars.
  • the charge to be treated is mixed with an addition of hydrogen and possibly with a recycling of hydrogen arriving via line 3, then is heated for example to a temperature of 140 to 300 ° C. by means of a charge / heat exchange. effluent, in the exchanger E 1 and a final heating in an oven H.
  • the isomerization reaction is preferably carried out on a high activity catalyst, such as for example a catalyst based on chlorinated alumina and platinum, operating at low temperature, for example between 130 and 220 ° C, at high pressure, by example from 20 to 35 bars, and with a low hydrogen / hydrocarbon molar ratio, for example between 0.1 / 1 and 1/1.
  • a high activity catalyst such as for example a catalyst based on chlorinated alumina and platinum, operating at low temperature, for example between 130 and 220 ° C, at high pressure, by example from 20 to 35 bars, and with a low hydrogen / hydrocarbon molar ratio, for example between 0.1 / 1 and 1/1.
  • Known catalysts which can be used consist, for example, of an alumina support g and / or h of high purity containing from 2 to 10% by weight of chlorine, from 0.1 to 0.35% by weight of platinum and optionally other metals. They can be implemented with a space speed of 0.5 to 10 h -1 ,
  • a well known catalyst consists of a mordenite with an SiO 2 / Al 2 O 3 ratio of between 10 and 40, preferably between 15 and 25 and containing from 0.2 to 0.4% by weight of platinum.
  • the catalysts belonging to this family are less advantageous than those to based on chlorinated alumina because they operate at higher temperature (240 to 300 ° C) and lead to less extensive conversion of normal paraffins into high octane isoparaffins.
  • n-paraffins is converted into isoparaffins and part of the methyl pentanes is transformed into dimethylbutanes; however, there remains in the effluent leaving the isomerization reactor via line 4 a large proportion of n-paraffins and methyl pentanes, which can range up to about 50 mol% and which is preferably between 25 and 40% by moles.
  • the effluent from the isomerization step (1) after cooling, can pass through a separator S 1 , the vapor of which is recycled by line 3 at the inlet of the isomerization reactor I and the liquid effluent (isomerate) leaving by line 6 is vaporized and superheated in the exchanger E 2 before being sent to the adsorption step (2) by line 8.
  • the vapor mixture is passed upward through the adsorber A, in which the n-paraffins are retained.
  • the isomerate freed from the n-paraffins leaves via line 9, can be at least partially condensed in the exchanger E 3 then sent to the deisohexanization column.
  • other adsorbents such as chabazite or erionite can be used.
  • the preferred operating conditions are a temperature of 200 to 400 ° C and a pressure of 10 to 40 bar.
  • the adsorption cycle generally lasts from 2 to 10 minutes.
  • the effluent collected at the outlet of the adsorber A by line 9 contains practically only isoparaffins (isopentane and isohexane). It is condensed, by exchange of heat, for example by heat exchange with one of the reboilers E3 from step (4) of deisohexanization.
  • n-paraffins adsorbed during step (2) are then desorbed in desorption step (3) represented in FIG. 2 by the adsorber D, which is none other than the absorber A saturated with n -paraffins and working in desorption.
  • the operation is carried out by lowering the pressure to a value less than 5 bars, preferably less than 3 bars, and by stripping by means of a gas stream rich in methyl pentanes, withdrawn at a level of the column of desisohexanisation suitable and brought by line 10 to cross the adsorber D in downflow.
  • This gas flow is generally brought to a temperature of 250 to 350 ° C in the exchanger E 7 .
  • the proportion of the stream rich in methyl pentanes necessary for the desorption advantageously corresponds to 0.5 to 2 moles of vapor rich in methyl pentanes per mole of n-paraffins to be desorbed.
  • the operation generally lasts from 2 to 10 minutes: the effluent from the desorption step (3) is recycled to the isomerization step via line 11; it is condensed directly in an ejector J in contact with the fresh charge of light naphtha arriving via line 1 and with a liquid circulating in line 13 and cooled by the exchanger E 6 .
  • the adsorber D after desorption, is again used in adsorption.
  • the effluent leaving the adsorption step is then sent under adsorption pressure to step (4) deisohexanization.
  • step (4) a desisohexanization column is supplied via line 9 by means of the effluent from the adsorption step (2) described above, for example, at a pressure of 1 to 2 bars (pressure absolute).
  • the deisohexanization column generally consists of a distillation column comprising internal fractionation (structured packing or trays).
  • the deisohexanization operation separates the load into one distillate rich in dimethyl butanes containing, for example, from 20 to 40% by moles of dimethylbutanes and in a residue poor in dimethylbutanes containing for example from 5 to 10% by moles of dimethylbutane.
  • the charge Before being introduced into the deisohexanization column, the charge can be condensed and cooled, for example, to a temperature of 100 to 120 ° C., possibly by heat exchange with one of the reboilers of the desisohexanization column in the exchanger E 3 .
  • the deisohexanization column generally operates between a bottom temperature of 80 to 100 ° C and a head temperature of 20 to 60 ° C.
  • the hot residue from the desisohexanization column leaving via line 12 is then recycled and sent to the isomerization reactor after mixing with the fresh feed (line 1) and the desorption effluent (line 11) in the ejector / mixer J.
  • a lateral withdrawal makes it possible to take a vapor stream rich in methylpentanes sent by line 10 to the adsorber D during desorption.
  • the overhead vapors (distillates) leaving via line 7 are generally condensed by means of a heat exchanger with the cooling water in a condenser E4.
  • the condensate is partially recycled at the top of the deisohexanizer (reflux) and partly sent by pumping via line 14 as the main isomerization product or isomerisate.
  • the overhead vapors (distillates) leaving via line 7 can be compressed in a compressor (heat pump) at a sufficient pressure (from 5 to 6 bars) so that they condense at a temperature 10 to 25 ° C higher than the temperature required for reboiling the bottom of the column.
  • the condensation of these vapors can then be used to supply the energy necessary for the reboiler through the exchanger E5, avoiding an external energy supply. Much of the condensation this way, which saves on the cooling means necessary for the total condensation of the reflux and the distillate.
  • a step for stabilizing the isomerization effluent intended essentially for removing hydrochloric acid from the catalyst at the same time as hydrogen and light hydrocarbons from C 1 to C 4 .
  • the effluent from the isomerization reactor consisting of a two-phase mixture is sent by line 4 directly to a stabilization column S 2 operating in generally at a pressure of 10 to 20 bars, advantageously at around 15 bars.
  • the stabilizer S 2 is shown diagrammatically in FIG. 3.
  • the stabilizer at the top eliminates the lightest products as well as any excess hydrogen which leaves via line 15.
  • the distillate is partially condensed by cooling with water in the exchanger E 8 , the condensate obtained possibly being at less partially recycled to the stabilizer head via line 16. If desired, an LPG can also be collected as a net distillate via line 17.
  • the hydrochloric acid possibly present (when the isomerization catalyst is based on chlorinated alumina impregnated with platinum) is sufficiently volatile to pass entirely at the top of the stabilizer and is evacuated with the gaseous products via line 15.
  • the product of bottom of the stabilizer, free of hydrochloric acid, is drawn off via line 6 in the form of a vapor flow at the pressure of the stabilizer and is sent to the adsorber after additional heating in the exchanger E 2 .
  • the stabilizer reboiler thus serves to vaporize the charge of the adsorber A, at a temperature of about 150 to 200 ° C., allowing the latter to be supplied in the vapor phase.
  • the process of the invention makes it possible to obtain, from fillers of light naphthas rich in C 5 / C 6 having an Octane Research Index (IOR) of 65 to 75, an isomerate having an IOR of 89 to 92.
  • IOR Octane Research Index
  • the filler F is constituted by a light naphtha previously desulphurized and dried having the following molar composition: Component % Molar Isobutane (iC 4 ) 0.4 Normalbutane (nC 4 ) 2.4 Isopentane (iC 5 ) 21 Normalpentane (nC 5 ) 29 Cyclopentane (CP) 2.2 2-2 dimethylbutane (22 DMB) 0.5 2-3 dimethylbutane (23 DMB) 0.9 2 methylpentane (2 MP) 12.7 3 methylpentane (3 MP) 10 Normal hexane (nC 6 ) 14 Methylcyclopentane (MCP) 5 Cyclohexane (CH) 0.5 Benzene 1.3 K 7 + 0.1
  • the liquid charge is introduced via line 1 into an ejector / mixer J with a flow rate of 77.6 kg / h.
  • a recycling flow from the desorption zone D via line 11 is sucked into this ejector / mixer, at an average flow rate of 44 kg / h, the line 11.
  • the ejector / mixer operates at a pressure of 2 bars and the fresh and recycled liquid charge, introduced therein as a working fluid, is preheated to a temperature of about 80 ° C. by direct contact with the vapor resulting from the desorption.
  • the steam is fully condensed and cooled to the same temperature.
  • a recycling stream from the bottom of the distillation column D 1 is also injected into this mixer, at an average flow rate of 25 kg / h, via line 12.
  • the reactor contains 62 liters of an alumina-based isomerization catalyst h containing 7% by weight of chlorine and 0.23% by weight of platinum. To maintain the activity of the catalyst, a continuous addition of 42 g / hour of carbon tetrachloride is carried out in the feed, which corresponds to a content of 500 ppm by weight.
  • the isomerization reaction is carried out under an average pressure of 30 bars and at a temperature of 140 ° C. (inlet) to 160 ° C. (outlet). Under these conditions, the hydrocarbon effluent from the isomerization reactor contains approximately 8% by mole of nC 5 , 5.5% by mole of nC 6 and approximately 26% by mole of methylpentanes.
  • the complete effluent from the isomerization reactor is sent directly via line 4 to the stabilization column S 2 (FIG. 3) operating under a pressure of 15.5 bars, with a temperature of around 200 ° C. at the reboiler and a temperature of 30 ° C with reflux flask.
  • the bottom fraction containing less than 0.5 ppm by weight of HCl is withdrawn in the vapor phase at the reboiler via line 6. It is preheated to a temperature of 300 ° C., is introduced in the vapor phase at the bottom of the adsorber A via line 8. This operates under an average pressure of 15 bars and at an average temperature of 300 ° C.
  • the adsorber with an internal diameter of 16 cm and a height of 4 m contains 60 kg of 5A zeolite in the form of extrudates of 1.6 mm in diameter.
  • At the outlet of the adsorber is recovered via line 9, with an average flow rate of approximately 123 kg / h, an isomer containing less than 1% by moles of normal paraffins C 5 and C 6 and having an IOR of 88 to 88.5 which is then sent under pressure to the reboiler E3 of the distillation column DI.
  • the adsorbent bed contained in the adsorber D is in the desorption phase. This is carried out by lowering the pressure from 15 bars to 2 bars and injecting from the top of the reactor, at a temperature of 300 ° C. and with an average flow rate of 20 kg / h, of a vapor withdrawal from the column. DI rich in methylpentanes (line 10). The temperature of the adsorbent bed is close to 300 ° C. during the whole desorption phase which lasts 6 minutes. The desorption effluent withdrawn at the bottom of the adsorber D contains approximately 29 mol% of nC 5 and 21 mol% of nC 6 . It is recycled by line 11 to the ejector / mixer J.
  • the adsorbers A and D are swapped by means of a set of valves, so as to operate alternately in the adsorption and desorption phase.
  • the effluent from adsorber A (line 9) fully condensed in reboiler E3 of the distillation column is expanded in a pressure control valve and the expanded mixture is introduced into the distillation column DI.
  • the column filled with a structured packing having an efficiency of about 40 theoretical stages operates under a pressure of 2 bars with a reflux rate of 4 relative to the net distillate.

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  • Engineering & Computer Science (AREA)
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Claims (9)

  1. Verfahren zur Isomerisierung von n-Paraffinen in Isopraffine in einer Charge, welche im wesentlichen aus einer C5/C6-Fraktion besteht, dadurch gekennzeichnet, daß es umfaßt:
    - einen Schritt (1) zur Isomerisierung, bei welchem man eine C5/C6-Fraktion, welche die frische Charge darstellt, in einen Reaktor zur Isomerisierung einführt, welche mit wenigstens einem rückgeführten Strom eines an normalen Paraffinen und an aus dem Schritt (3) zur Desorption stammenden Methyl-Pentanen reichen Flusses gemischt wird, wobei der Abstrom dieses Schrittes in einen Abscheider eingeführt wird, in welchem man eine Dampfphase, welche zum Einlaß des Reaktors zur Isomerisierung zurückgeführt wird, und eine Flüssigphase, welche das Rohisomerat bildet, abtrennt;
    - einen Schritt (2) zur Adsorption, bei welchem man die Flüssigphase verdampft, man den erhaltenen Dampffluß durch einen mit einem Molekularsieb versehenen Adsorber strömen läßt, derart, daß darin die n-Paraffine zurückgehalten werden, und man als Dampfabstrom ein von n-Paraffinen befreites Isomerat auffängt;
    - einen Schritt (3) zur Desorption, welcher sich mit dem Schritt (2) abwechselt und bei welchem man den Druck in dem Adsorber absenkt und man einen an Methyl-Pentanen reichen und an n-Paraffinen armen Gasfluß, welcher in dem Schritt (4) zur Entfernung von Isohexan abgezogen wird, durch das Molekularsieb strömen läßt, wobei der Gasfluß die adsorbierten n-Paraffine des Molekularsiebes mitnimmt, der Abstrom dieses Schrittes zur Desorption dem Schritt (1) zur Isomerisierung zugeführt wird; und
    - ein Schritt (4) zur Entfernung von Isohexan, bei welchem man eine Destillationskolonne mittels des Dampfabstromes des Schrittes (2) zur Adsorption speist und man einen flüssigen Rückstand und einen an Methyl-Pentanen reichen Dampffluß sowie ein das Endisomerat bildendes Destillat erhält, wobei der an Methyl-Pentanen reiche Dampffluß als Desorptionsmittel dem Schritt (3) zur Desorption zugeführt wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die C5/C6-Fraktion leichtes Naphta ist.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man bei dem Schritt (1) zur Isomerisierung die frische Charge, welche mit dem rückgeführten Strom der Methyl-Pentane und der normalen Paraffine in Anwesenheit von Wasserstoff über einen Katalysator strömen läßt, der im wesentlichen aus einem Zeolith besteht, welcher wenigstens ein Metall, welches aus denjenigen der Gruppe VIII des Periodensystems ausgewählt wird, oder ein mit Platin imprägniertes, chloriertes Aluminiumoxid enthält, unter einem Druck von 10 bis 40 bar und bei einer Temperatur von 140 bis 300°C.
  4. Verfahren nach irgendeinem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der Schritt (2) zur Adsorption bei einer Temperatur von 200 bis 400°C und bei einem Druck von 10 bis 40 bar über eine Dauer von 2 bis 10 Minuten durchgeführt wird.
  5. Verfahren nach irgendeinem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß der Druck bei dem Schritt (3) zur Desorption auf einen Wert kleiner als 5 bar abgesenkt wird und man den auf eine Temperatur von 250 bis 350°C gebrachten, aus dem Schritt (4) abgezogenen an Methyl-Pentanen reichen Gasfluß in einem Verhältnis, welches 0,5 bis 2 Mol Dampf pro Mol zu desorbierenden n-Paraffinen entspricht, während 2 bis 10 Minuten strömen läßt.
  6. Verfahren nach irgendeinem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man bei dem Schritt (4) zur Entfernung von Isohexan bei einem Druck von 1 bis 2 bar zwischen einer Bodentemperatur von 80 bis 100°C und einer Kopftemperatur von 20 bis 60°C arbeitet, derart, daß das Destillat 5 bis 10 Mol-% Dimethyl-Pentane enthält und daß der Rückstand 5 bis 10 Mol-% Dimethyl-Butane enthält.
  7. Verfahren nach irgendeinem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Destillat aus dem Schritt (4) zur Entfernung von Isohexan auf einen Druck von 5 bis 6 bar komprimiert wird und dessen Kondensation die für ein Abkochen des Bodens der Kolonne zur Entfernung von Isohexan notwendige Wärme liefert.
  8. Verfahren nach irgendeinem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß der flüssige Rückstand des Schrittes (4) zur Entfernung von Isohexan teilweise dem Schritt (1) zur Isomerisierung zurückgeführt wird.
  9. Verfahren nach irgendeinem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß der Abstrom des Schrittes (1) zur Isomerisierung in eine Kolonne zur Stabilisierung bei einem Druck von 10 bis 20 bar eingeführt wird, in welcher am Kopf die leichtesten Produkte und mögliche Salzsäure aus dem Katalysator zur Isomerisierung stammt und am Boden ein Abstrom, welcher dem Schritt (2) zur Adsorption geführt wird, evakuiert wird.
EP93400443A 1992-03-06 1993-02-22 Verfahren zur Isomerisierung von n-C5/C6-Paraffinen mit Recyclierung von n-Paraffinen und Methylpentanen Expired - Lifetime EP0559518B1 (de)

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FR9202812 1992-03-06
FR9202812A FR2688213B1 (fr) 1992-03-06 1992-03-06 Procede d'isomerisation de paraffines normales en c5/c6 avec recyclage de paraffines normales et methyl-pentanes.

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EP0559518A1 EP0559518A1 (de) 1993-09-08
EP0559518B1 true EP0559518B1 (de) 1997-05-02

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US (1) US5602291A (de)
EP (1) EP0559518B1 (de)
JP (1) JPH0641550A (de)
KR (1) KR930019595A (de)
CN (1) CN1037111C (de)
CA (1) CA2091122A1 (de)
DE (1) DE69310251T2 (de)
ES (1) ES2104084T3 (de)
FR (1) FR2688213B1 (de)
ZA (1) ZA931588B (de)

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CN103785474B (zh) * 2014-01-20 2015-12-09 中国石油天然气集团公司 一种用于c5/c6烷烃异构化的催化剂及其制备和使用方法
US9663721B2 (en) 2014-09-04 2017-05-30 Uop Llc Heat recovery from a naphtha fractionation column
CN106278781A (zh) * 2015-06-04 2017-01-04 中国石油化工股份有限公司 一种轻质烷烃异构化方法
CN106833738B (zh) * 2015-12-03 2019-03-22 中国石油化工股份有限公司 一种提高c5/c6烷烃辛烷值的方法
US20180215683A1 (en) * 2017-01-27 2018-08-02 Saudi Arabian Oil Company Isomerization process using feedstock containing dissolved hydrogen
US11597883B2 (en) * 2021-06-07 2023-03-07 Uop Llc Process for removing olefins from normal paraffins in an isomerization effluent stream

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2945909A (en) * 1955-12-30 1960-07-19 Standard Oil Co Isomerization process and catalyst therefor
US2958644A (en) * 1957-05-01 1960-11-01 Exxon Research Engineering Co Production of high octane motor fuels
GB876730A (en) * 1958-08-04 1961-09-06 Universal Oil Prod Co Production of branched-chain aliphatic hydrocarbons
US3755144A (en) * 1971-10-13 1973-08-28 Universal Oil Prod Co Hydrocarbon isomerization and separation process
US4210771A (en) 1978-11-02 1980-07-01 Union Carbide Corporation Total isomerization process
US4414101A (en) * 1981-08-17 1983-11-08 Standard Oil Company (Indiana) Hydrocarbon conversion method and apparatus
US5043525A (en) * 1990-07-30 1991-08-27 Uop Paraffin isomerization and liquid phase adsorptive product separation

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CN1076715A (zh) 1993-09-29
JPH0641550A (ja) 1994-02-15
CN1037111C (zh) 1998-01-21
FR2688213A1 (fr) 1993-09-10
ES2104084T3 (es) 1997-10-01
EP0559518A1 (de) 1993-09-08
US5602291A (en) 1997-02-11
KR930019595A (ko) 1993-10-18
FR2688213B1 (fr) 1995-05-24
DE69310251D1 (de) 1997-06-05
DE69310251T2 (de) 1997-08-21
CA2091122A1 (fr) 1993-09-07
ZA931588B (en) 1994-09-05

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