EP0949317A1 - Verfahren und Vorrichtung zur Isomerizierung von Benzinen mit hohem Benzolgehalt - Google Patents

Verfahren und Vorrichtung zur Isomerizierung von Benzinen mit hohem Benzolgehalt Download PDF

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Publication number
EP0949317A1
EP0949317A1 EP99400568A EP99400568A EP0949317A1 EP 0949317 A1 EP0949317 A1 EP 0949317A1 EP 99400568 A EP99400568 A EP 99400568A EP 99400568 A EP99400568 A EP 99400568A EP 0949317 A1 EP0949317 A1 EP 0949317A1
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EP
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Prior art keywords
reactor
fluid
isomerization
make
charge
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EP99400568A
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English (en)
French (fr)
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EP0949317B1 (de
Inventor
Marc Fersing
Pedro Nascimento
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Total Marketing Services SA
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Total Raffinage Distribution 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
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • the present invention relates to a method and a improved device for the isomerization of gasolines high benzene content.
  • gasoline isomerization processes which aim to increase the octane number of these gasolines by transformation of linear paraffins which they contain branched paraffins (or isoparaffins).
  • the load to be treated is mainly composed of hydrocarbons saturated at five or six carbon atoms, as well as lower proportions of hydrocarbons at four or seven carbon atoms, and benzene which, as everyone knows, is relatively difficult to separate from other hydrocarbons to six carbon atoms.
  • the charge at most often is mixed with hydrogen and a possible recycle, then directed to at least one reactor containing a suitable catalyst in a fixed bed.
  • the temperature prevailing in this reactor is usually between 120 and 190 ° C.
  • effluents are routed to one or more separation columns.
  • isoparaffins are then separated from paraffins not isomerized: the first ones are sent in principle to the pool essences, to serve as bases for the formulation of fuels, while the seconds are eventually recycled to the reactor for processing.
  • the first reactor in which product, in addition to the isomerization of paraffins, the hydrogenation of traces of benzene present in the load, operates at slightly higher temperature than the second, where the isomerization reaction ends proper. Indeed, from a kinetic point of view, the paraffin isomerization reaction is slower than the benzene hydrogenation reaction. In addition, the lower temperature prevailing in the second reactor is thermodynamically favorable for product formation branched trees sought.
  • the benzene content of the fillers isomerization remains relatively limited. Indeed, a commonly accepted rule considers that an increase in the benzene content of 1% in the feed to be treated a 10 ° C rise in temperature within the first isomerization reactor. Knowing that other reactions that the hydrogenation of benzene already produce to them only a temperature rise of around 15 ° C, the benzene content of the feedstock entering this reactor must then be limited to 4%. Beyond this content, the temperature in the reactor is too high, which ultimately damages not only the catalyst but also the unit, designed to operate at room temperature limited. Furthermore, at high temperature, reactions unwanted side effects occur, such as, by example, hydrocracking reactions of the charge.
  • An ingenious solution then consists in admitting in the isomerization unit, in addition to the conventional charges, cuts of benzene-rich gasolines, such as some fuel cuts from reforming units or catalytic cracking: the benzene present in these cuts is thus hydrogenated in the isomerization unit, and this ultimately reduces the content of benzene of the said cuts before sending them to the "pool essences ", term by which we designate all the bases used to make petroleum products.
  • the patent US N ° 5,003,118 proposes to introduce, upstream of the isomerization reactors themselves, a charge pretreatment, specifically intended for perform the hydrogenation of the benzene present in this charge. In this way, the unit is able to deal with charges with higher benzene content.
  • This solution has the disadvantage of being of high cost, linked to the necessary construction of additional equipment. Besides, it is absolutely not flexible, insofar as the hydrogenation reactor is of no useful in the case of a load with a low benzene content.
  • the present invention therefore aims to propose a method isomerization of gasoline with a high benzene content, allowing a simple and inexpensive remedy to problems encountered in the prior art.
  • the present invention also aims to provide a particularly flexible isomerization process, allowing to adapt quickly to different charges intended for him.
  • the subject of the present invention is a process for the isomerization of a hydrocarbon feedstock containing a substantial amount of paraffinic hydrocarbons with 5 or 6 carbon atoms and of benzene at a content greater than or equal to 2% by weight, in which the charge to be treated passes, in the presence of hydrogen, at a total pressure greater than or equal to 10.10 5 Pa (10 bars) and at an average temperature between 100 and 200 ° C, in at least one reactor containing a catalyst of isomerization of paraffinic hydrocarbons, this process being characterized in that one introduces, in the upstream part of the reaction zone, a make-up fluid which, at 40 ° C and under atmospheric pressure (1.0134.10 5 Pa ), is in the gaseous state and has a density less than or equal to that of normal-pentane considered under the same conditions.
  • density of a gaseous fluid is meant the ratio between the density of this fluid and the density dry air with normal carbon dioxide content, these two densities being measured in the same temperature and pressure conditions.
  • the density of the make-up fluid will be measured, at 40 ° C and under a pressure of 1.0134.10 5 Pa (1 atmosphere), by applying to any fluid any of the standardized measurement methods described in standard ASTM D1070-85 (R94). The same is true for normal-pentane.
  • the densities of said makeup fluid and of pentane will be considered by reference to the same measurement method.
  • the makeup fluid is in the gaseous state at 40 ° C under a pressure of 1.0134.10 5 Pa (1 atmosphere).
  • it is introduced into the upstream part of the reaction zone under temperature and pressure conditions directly dependent on the operating conditions of the process. Depending on its composition, it can then be in the liquid or gaseous state or in an intermediate state.
  • said makeup fluid contains a substantial amount of hydrogen and / or hydrocarbons having one to five carbon atoms.
  • this makeup fluid contains a substantial amount of hydrogen and / or hydrocarbons containing from one to four carbon atoms, the preferred hydrocarbons being methane and ethane.
  • This fluid can thus, for example, be made of natural gas.
  • This fluid can also comprise, in quantity minority, hydrocarbons with six or seven atoms of carbon, and / or inert gases such as nitrogen, or any other suitable light fluid.
  • said makeup fluid contains a substantial amount of: light compounds from fractionation column located downstream of the unit isomerization.
  • the introduction of light makeup fluid has the effect of create, in the upstream part of the reaction zone, a vaporization of part of the liquid fraction of the hydrocarbon feed. This phenomenon is endothermic and helps restore the heat balance within the reactor. We can thus compensate for the excess heat that is released in the upstream part of the first reactor, following the hydrogenation of the benzene present in a higher quantity in charge.
  • the drop in temperature within the reactor, resulting from the injection of said fluid may be perfectly determined. Indeed, this injection has for consequence a change in the balances between liquid and vapor fractions of the constituent hydrocarbons of load, balances which are governed by the laws of thermodynamic.
  • This drop in temperature therefore depends only on the following parameters: flow rates and load compositions and make-up fluid, pressure, temperature, fraction vaporized charge at the reactor inlet and report mass between hydrogen and charge in the mixture reaction allowed in the unit. So it can be perfectly controlled and optimized according to the content into benzene of the charge to be isomerized.
  • the process according to the invention is precise and extremely flexible, since the flow of the makeup fluid can be adjusted to compensate exactly the temperature rise due to the content of benzene higher than the maximum generally accepted content.
  • the method according to the invention proves to be very advantageous for units which do not have, downstream of the isomerization unit, a deisohexanizer (column of separation of the branched paraffins sought and the linear paraffins), with recycle of a cut rich in linear paraffins upstream of the isomerization unit.
  • One of the aims of this recycling is to dilute the fresh load allowed in the unit, in order to lower the benzene content. Thanks to the invention, since it is it is possible to admit more content to the unit high in benzene, this dilution is no longer necessary.
  • the method according to the invention therefore represents a very valid alternative to the costly installation of a deisohexanizer and a system of recycle.
  • the process according to the invention has been found to provide increased recovery light hydrocarbons containing not more than four atoms of carbon, and in particular propane and butane.
  • LPG Petroleum Gas Liquefied
  • the isomerization unit can be so operated with a view to increased production of these LPGs.
  • the make-up fluid is injected into the upstream part of the reaction zone. This means that said fluid can be injected into the part upstream of the first reactor proper, and / or immediately upstream of the latter.
  • make-up fluid is injected in the upstream part of the first isomerization reactor, at know in the area extending from the level of introduction into the reaction mixture reactor (feed and hydrogen) halfway up the catalytic bed.
  • Make-up fluid can then be injected into the reactor area included between the introduction of the reaction mixture and the start of the dense bed of catalyst.
  • fluid can also be injected directly into the dense bed of catalyst, in the first half of this latest.
  • make-up fluid When make-up fluid is injected immediately in upstream of the first reactor, we introduce it immediately before the introduction of the reaction mixture (charge and hydrogen) in the first reactor, i.e. after complete preheating of this mixture and before injection of this in the first reactor.
  • This injection of makeup fluid has a purely thermal and therefore has nothing to do with the injection, in large quantities, of the hydrogen necessary for the actual isomerization reaction, which takes place, in a manner known per se, upstream of the unit isomerization, i.e. upstream of the heat exchangers heat in which the reaction mixture (charge and hydrogen) is heated before being introduced into the reactor.
  • make-up fluid is therefore carried out, moreover, compared to the usual injection of hydrogen in upstream of the unit, in a completely different location, and with a much lower volume flow.
  • this make-up fluid which has a purely thermal effect, can consist of any gas light compatible with the process, while hydrogen introduced upstream of the isomerization unit has an effect chemical at the level of the actual reaction.
  • This make-up fluid is advantageously injected at a rate of 5 to 150 Nm 3 per m 3 of charge to be isomerized and, preferably, from 5 to 60 Nm 3 per m 3 of charge.
  • the starting charge is considered here, before mixing with hydrogen and heating of the reaction mixture thus obtained.
  • the make-up fluid either injected at a temperature below or above that of the reaction medium. That said, it is better injecting said fluid at a lower temperature or equal to that of the reaction medium and, preferably, between 20 and 180 ° C.
  • a particularly variant advantageous of the invention consists in recycling, immediately downstream of the first reactor, a rich section in slightly branched paraffins with 5 or 6 carbon atoms and which usually contains naphthenes. This cut comes, in a manner known per se, from a fractionation existing in advanced isomerization units, which is located downstream of the reactors, and which separates the isoparaffins sought from other compounds.
  • this recycle cut which does not contains no benzene, is traditionally introduced upstream of the first reactor, in order not only to perform an additional passage in the isomerization unit, but also to dilute the fresh charge allowed in the unit, to so as to lower the benzene content of the feed combined thus obtained.
  • the invention also aims to propose a device allowing the implementation of the process described above.
  • the subject of the invention is a device for isomerizing a hydrocarbon charge containing a substantial quantity of paraffinic hydrocarbons with 5 or 6 carbon atoms and benzene at a content greater than or equal to 2% by weight, said device comprising at least one reactor charged with a catalyst in a fixed bed, a line for supplying the reaction mixture consisting of the charge mixed with a hydrogen-rich gas to the reactor, at least one system for heating said reaction mixture upstream of the reactor, and an evacuation line from the reactor of the charge enriched in isoparaffins, this device being characterized in that, in the upstream part of the reaction zone opens at least one means for introducing a make-up fluid, which is in the gaseous state at 40 ° C, at atmospheric pressure (1.0134.10 5 Pa).
  • a make-up fluid supply line opens into the finish line at the first reactor of the mixture reaction (charge and hydrogen), between the warming of the most downstream reaction mixture and the injection point of said mixture in the first reactor.
  • the make-up fluid When the make-up fluid is introduced into the breast of the first reactor, at least one means of introducing make-up fluid flows into this reactor, upstream of the bed dense catalyst and / or within the first half of this last.
  • the one or more means can then be constituted by any known means allowing, downstream of the injection of the charge itself, the introduction of a light fluid in a reactor.
  • a cane or even a single tube with side slits or more orifices, in order to allow a better distribution of the make-up fluid.
  • a diffuser is used allowing to introduce the make-up fluid so homogeneous over the entire section of the reactor.
  • said means for introducing make-up fluid can lead into the reactor in multiple ways.
  • said means open out transversely in the reactor, substantially perpendicular to the axis of the latter.
  • At least one means of introduction of make-up fluid opens into the reactor substantially parallel to the axis of the latter.
  • said means then enters the reactor by the orifice allowing the introduction of the reaction mixture.
  • the invention does not relate to catalysts capable of to intervene in its implementation.
  • We can, in fact, employ any known catalyst exhibiting activity for isomerization of linear paraffins into paraffins branched.
  • many catalysts are known to those skilled in the art. They usually have a or more acid type functions, as well as a function hydrogenating (hydrogenating transition metal).
  • FIG. 1 represents a unit for the isomerization of sections containing linear paraffins with 5 or 6 atoms of carbon.
  • This charge arrives via line 1, in which hydrogen and possibly recycle gases are introduced via line 2.
  • the reaction mixture thus obtained is routed by line 33 to two heat exchangers heat 3 and 4, against the effluent from both unit isomerization reactors.
  • the reaction mixture thus reheated is then introduced into a first reactor 5, or upstream reactor.
  • the latter contains a isomerization catalyst distributed in a catalytic bed 6, which occupies most of the height of the reactor 5.
  • the effluent of the latter, after passing through the exchanger 4 is then introduced via line 7 into the second reactor 8, or downstream reactor, which is also loaded with an isomerization catalyst distributed in a catalytic bed 9.
  • the load to be treated flows from high down in reactors 5 and 8, but it could naturally circulate there from bottom to top.
  • the device further includes valve systems, not represented, allowing to interrupt independently the supply of reactors 5 and 8 and / or reverse the direction circulation of the reaction mixture.
  • a make-up fluid is injected into the upstream reactor 5, via a rod 11 substantially perpendicular to the axis of the reactor and which leads directly into the catalytic bed, into the first half of it.
  • This rod is provided with side slits, not shown, allowing better distribution.
  • the catalytic bed 6 of the upstream reactor 5 can be separated into an upstream section 12 and a downstream section 13, which contain the same isomerization catalyst.
  • the rod 11 a for introducing make-up fluid then enters the reactor between the two catalytic sections 12 and 13.
  • a stepped injection system 11b allows the introduction of make-up fluid at several levels in the first half of the catalytic bed 6 of the reactor 5.
  • an injection system 11 c of make-up fluid opens into the reactor 5 in a manner substantially parallel to the axis of the latter, at the level of the orifice allowing the introduction of the reaction mixture (feed and hydrogen) supplied to the reactor via line 33.
  • a line 11 d for supplying make-up fluid opens into the inlet line 33 of the reaction mixture (feed and hydrogen), immediately upstream of the first reactor. isomerization 5.
  • the unit isomerization comprises at least two reactors in series
  • make-up fluid injection always takes place at the upstream reactor, insofar as the hydrogenation of benzene is much faster than isomerization of paraffins itself and takes place only within the reactor upstream.
  • FIG. 6 shows how the invention can allow improve the relationships between the unit isomerization and other petroleum units.
  • the fraction rich in isopentane which is a compound with high octane number therefore requiring no treatment isomerization, is discharged via line 19.
  • Light petrol depleted in isopentane then crosses the two reactors isomerization 5 and 8 as described above, and the load enriched in isoparaffins is extracted therefrom by line 10.
  • This charge is then separated, within the stabilizer 20, in a head section 21, consisting of compounds with up to four carbon atoms, and a cut background 22 of heavier compounds .: The latter is then directed to the deisohexanizer 23, where it found divided into an isomerate 26, consisting of isoparaffins with 5 or 6 carbon atoms, and a heavy cut 25, consisting essentially of naphthenes and paraffins at 7 carbon atoms or more.
  • the essence heavy discharged from separator 15 via line 17 is directed towards the reforming unit 27, within which it undergoes among others aromatization reactions, which contribute to increase its content of aromatic products, including benzene.
  • the reformate thus produced is then separated at level of fractionation 28 into a heavy reformate 29, the boiling point is above about 90 ° C, which is routed to the gasoline pool, and a light reformate 31, whose boiling point is between approximately 30 ° C and 90 ° C.
  • a means 11 for injecting a make-up fluid enters the catalytic bed of the upstream reactor 5.
  • the make-up fluid consists of compounds comprising at most 4 carbon atoms derived from the line 35 of the head section, discharged at 21, from stabilizer 20.
  • the isomerization unit is likely to deal with charges with content if necessary higher in benzene than in the prior art. So the Doubling the amount of benzene present in the charge can be thermally compensated by adding fluid light (density less than or equal to that of normal-pentane), the flow rate of which will be adjusted according to the benzene content of the feed to be isomerized.
  • the purpose of this example is to illustrate the limits of conventional gasoline isomerization processes, in the case treatment of loads with high benzene content.
  • This charge is combined with a gaseous mixture rich in hydrogen (20% by weight of hydrogen), introduced at a flow rate of 2 t / h.
  • This reaction mixture is then warmed up to 133 ° C., then treated in a conventional gasoline isomerization unit comprising two reactors in series, operating at a pressure of 31 ⁇ 10 5 Pa.
  • the temperature recorded at the outlet of the first reactor is 180 ° C.
  • this charge No. 2 has a content of benzene of 7.66% by weight and a density at 15 ° C of 0.687. The other properties remain globally unchanged by in relation to charge # 1.
  • This charge n ° 2 is treated under the same conditions than those mentioned above for the treatment of charge # 1, except gas flow rich in hydrogen, which is brought to 3.5 t / h (so known per se, the isomerization of charges rich in benzene requires an increased amount of hydrogen in the medium reactive, taking into account the additional consumption hydrogen induced by the hydrogenation of benzene).
  • the temperature recorded at the outlet of the first reactor is then 193 ° C. So there was an increase in temperature of 13 ° C in this reactor, due to the high quantity of heat given off by the hydrogenation of the supplement benzene present in charge # 2. Ultimately, this temperature increase in the first reactor risk not only damage the catalyst and the unit, but also to decrease the reaction yields isomerization (better at low temperature).
  • charge rich in benzene described above (charge n ° 2) is treated this time according to the isomerization process according to the invention.
  • a fluid make-up is therefore introduced into the catalytic bed of the first reactor, at the level of the first third of the bed catalytic (exactly 2/7 of this bed), and with a flow of 30Nm3 per m3 of load.
  • Two introduction temperatures make-up fluid have been tested: 30 ° C (temperature lower than that of the reaction medium) and 145 ° C. (temperature of the order of that of the reaction medium).
  • Fluid Composition (in% by weight) Density (40 ° C, 1.0134 Pa) F1 2% H 2 + 12% CH 4 + 18% C 2 H 6 + 25% C 3 H 8 + 43% C 4 H 10 1.04.10 -3 F2 2% H 2 + 80% CH 4 + 16% C 2 H 6 + 2% C 3 H 8 0.59.10 -3 F3 100% H 2 0.08.10 -3 F4 100% CH 4 0.62.10 -3 F5 100% C 2 H 6 1.16.10 -3 F6 100% C 3 H 8 1.72.10 -3 F7 100% nC 4 H 10 2.28.10 -3 F8 100%% nC 5 H 12 2.87.10 -3
  • the fluid F1 corresponds to a gaseous mixture of the type of those that can be recovered at the head of a column of fractionation located downstream of the isomerization unit (so-called stabilization column).
  • the operating conditions are identical to those described in Example 1 for the treatment of the charge n ° 2, and the inlet temperature of the reaction mixture in the first isomerization reactor is notably maintained at 133 ° C.
  • Test 1 corresponds to a zero makeup fluid flow rate (prior art).
  • Test Make-up fluid flow (Nm3 per m3 of charge) First reactor outlet temperature (° C) 1 0 193 2 10 188 3 30 181 4 60 173
  • This example illustrates the excellent thermal control to which the invention gives access.
  • This control is extremely precise and flexible, since the fluid flow can be optimized according to the characteristics the load to be treated and, in particular, its content benzene.
  • This example specifies the conditions in which the process according to the invention must be implemented work, and in particular the nature of the make-up fluids likely to be employed.
  • thermodynamic effect described is not produces more and the injection of make-up fluid does not allow more to lower the temperature of the first reactor.
  • the thermodynamic effect described is not produces more and the injection of make-up fluid does not allow more to lower the temperature of the first reactor.

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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)
EP99400568A 1998-03-31 1999-03-09 Verfahren zur Isomerizierung von Benzinen mit hohem Benzolgehalt Expired - Lifetime EP0949317B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9803958A FR2776667B1 (fr) 1998-03-31 1998-03-31 Procede et dispositif d'isomerisation d'essences a teneur elevee en benzene
FR9803958 1998-03-31

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EP0949317A1 true EP0949317A1 (de) 1999-10-13
EP0949317B1 EP0949317B1 (de) 2004-05-19

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US (2) US6416657B1 (de)
EP (1) EP0949317B1 (de)
JP (1) JP4112114B2 (de)
AT (1) ATE267239T1 (de)
DE (1) DE69917363T2 (de)
ES (1) ES2221327T3 (de)
FR (1) FR2776667B1 (de)
ZA (1) ZA992450B (de)

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US8692046B2 (en) 2011-01-13 2014-04-08 Uop Llc Process for isomerizing a feed stream including one or more C4-C6 hydrocarbons
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FR3015514B1 (fr) 2013-12-23 2016-10-28 Total Marketing Services Procede ameliore de desaromatisation de coupes petrolieres
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ATE267239T1 (de) 2004-06-15
JPH11323356A (ja) 1999-11-26
DE69917363T2 (de) 2005-05-12
US20020139712A1 (en) 2002-10-03
FR2776667B1 (fr) 2000-06-16
JP4112114B2 (ja) 2008-07-02
DE69917363D1 (de) 2004-06-24
ZA992450B (en) 1999-10-01
ES2221327T3 (es) 2004-12-16
US6416657B1 (en) 2002-07-09
EP0949317B1 (de) 2004-05-19
US6881385B2 (en) 2005-04-19
FR2776667A1 (fr) 1999-10-01

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