Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
  • B01J8/12—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by gravity in a downward flow
  • B01J8/125—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by gravity in a downward flow with multiple sections one above the other separated by distribution aids, e.g. reaction and regeneration sections
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
  • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
  • B01J8/085—Feeding reactive fluids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
  • B01J8/087—Heating or cooling the reactor
• • 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
  • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
• • 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
  • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
  • C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1088—Olefins
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
• • 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
  • C10G2400/04—Diesel oil

Definitions

• the present invention relates to a reaction device inside which is carried out at least one catalytic reaction having a significant thermal effect, generally a release of heat (so-called exothermic reactions) or sometimes a heat absorption (so-called endothermic reactions). It also relates to a process for oligomerization of olefinic feedstocks (that is to say polymerization or addition limited to essentially 2 to 6 monomers or base molecules). It relates in particular to the reactions of addition of an olefin to another compound present in the feedstock, for example an olefin, a sulfur compound, a nitrogen compound or an aromatic molecule, said addition reactions intended to increase the molecular weight of the feedstock. this compound.
• It relates more particularly to oligomerization reactions from olefinic hydrocarbon cuts containing from 2 to 12 carbon atoms, preferentially from 3 to 7 carbon atoms, and more particularly from 4 to 6 carbon atoms, the oligomerization reactions allowing to produce gasoline, diesel or lubricant cuts, and more particularly hydrocarbons of the diesel cut.
• the invention relates to a reaction device comprising a reactor with several reaction zones, stacked vertically and separated by heat exchange zones, and comprising the possibility of supplying each reaction zone with catalyst comprising a regenerated or fresh catalyst booster.
• US Patent 2002/0011428 A1 discloses a multi-stage moving bed reactor for carrying out hydrotreatment reactions.
• a system which is the subject of other patents (in particular US Pat. No. 5,076,908) makes it possible to add and remove catalyst continuously or semi-continuously from each reactor stage. The load flows from one floor to another. In contrast, the one-stage catalyst does not flow into the next stage. It has been found that such a system can also be used to carry out an oligomerization reaction. However, the described system does not effectively control the temperature profile within each reaction section.
• Patent WO 02/04575 describes a zeolite oligomerization process using a fixed-bed type reactor of tabular type, or any other reactor that can be used to carry out the oligomerization reaction.
• the patent describes a method for adding and withdrawing catalyst continuously or semi-continuously from the reactor.
• the problem of controlling the exothermicity of the reaction is not addressed.
• EP 1236506A1 discloses a multi-stage low bed reactor with internal heat exchanger, used mainly in the context of dehydrogenation reactions of long paraffins. This system makes it possible to precisely control the temperature in each reaction section.
• the catalyst grains often have a substantially spherical shape to facilitate their flow, and typical dimensions between 0.5 and 5 mm in diameter, and preferably between 1 to 4 mm. This technology allows a progressive replacement of the catalyst during the reactor operation, with fresh or regenerated catalyst at the reactor head.
• the present invention describes a reaction device, and a process for the chemical conversion of hydrocarbons using this device, making it possible to prevent or limit disparities in catalytic activity, especially with a given catalyst regeneration capacity (necessarily limited) and to treat at better the problems associated with the implementation of highly exothermic or endothermic reactions, in particular oligomerization reactions.
• the present device is particularly suitable for carrying out an oligomerization reaction of olefinic hydrocarbon cuts containing from 2 to 12 carbon atoms, preferably from 3 to 7 carbon atoms, and more preferably still from 4 to 6 carbon atoms, making it possible to obtain hydrocarbons in the range of petrol, diesel or lubricating oil cuts, and more particularly hydrocarbons of the diesel fraction, with a typical distillation range of between 160 and 370 ° C., in particular between 200 and 370 ° C. and 365 ° C. It is important to avoid significant disparities in the catalytic activity between the different reaction zones, which generate conversion losses.
• the oligomerization reaction is highly exothermic. Too high a temperature favors the cracking reactions of the oligomerized compounds and is therefore undesirable.
• a temperature too low in certain reaction zones limits the conversion into sufficiently heavy compounds sought in the composition of a diesel cut. It is therefore desirable to precisely control the temperatures within the various reaction zones. In particular, it is advantageous to adjust the temperature level of a catalytic reaction zone as a function of the activity of the catalyst within said zone.
• the invention proposes a reaction device comprising means for maintaining a significant catalytic activity, with small disparities between the different reaction zones, implementing, typically at the inlet of each reaction zone, an addition of fresh or regenerated catalyst, for its mixing with at least a portion of the spent catalyst (partially) from the upstream reaction zone. It also proposes a preferred variant of the device with integration of thermal means for heating or cooling the reaction fluid at a catalyst passage narrowing used for the implementation of this fresh or regenerated catalyst booster. This considerably increases the selectivity and the conversion compared with the prior art, in particular for oligomerization reactions.
• the invention also proposes a method for carrying out chemical reactions in this device, in particular a process for oligomerizing olefinic charges.
• FIG. 1 shows a view of the reaction device in its basic configuration.
• FIG. 2 represents a view of the reaction device in a variant comprising an injection of an additional reaction fluid between two reaction zones.
• FIG. 3 represents a view of the reaction device in a variant comprising at least a part of the heat exchange means outside the reaction chamber.
• FIGS. 1 to 3 illustrate the different embodiments of the invention without however limiting its scope.
• the invention is illustrated in its basic configuration in FIG.
• the invention relates to a reaction device comprising a catalytic reactor of elongate shape along a substantially vertical axis, this reactor comprising in the same chamber several catalytic reaction zones staggered vertically, this reactor being adapted to the circulation of at least one moving-bed granular catalyst sequentially descending into each of the reaction zones, and comprising means (100) for introducing and (101) discharging the reaction fluid, means (102) for supplying fresh catalyst or regenerated at the top of the reaction chamber, and means (105) for removing used catalyst in the lower part of the chamber, this reactor comprising in particular: a) an upper reaction zone Za (3a), and a reaction zone Zb (3b), located just below the upper reaction zone Za, these reaction zones Za and Zb being two reaction zones successiv they are directly connected on the one hand by a passage of the reaction fluid, and on the other hand by a catalyst passage from zone Za to zone Zb.
• the two zones Za and Zb are, according to the invention, successive reaction zones, which means that the effluents from one of these zones supply the other zone without passing through another reaction zone. They are typically separated by a narrowing of the catalyst passage, located at the collection of spent catalyst (typically partially) from Za.
• the invention makes it possible to increase the catalytic activity of the catalyst supplying the zone Zb by adding a regenerated catalyst to the feedstock . . ej; _dQnc..jie._reducing - the - disparities - d-a catalytic activity between the reaction zones.
• the device represented in FIG. 1 comprises means for withdrawing and discharging (104) a portion of said spent catalyst from the upper reaction zone. Za connected to the collection means. This makes it possible to eliminate a portion (for example from 10 to 70%, and often from 15 to 50%) of the spent catalyst, before the introduction of regenerated and / or fresh catalyst.
• the average activity of the mixed catalyst feeding Zb is increased, without generally appreciably increasing the total flow rate of catalyst entering Zb, or even keeping the flow rate of circulating catalyst in Za and Zb constant.
• the invention makes it possible to obtain a certain rebalancing of the catalytic activity between the different reaction zones.
• This extra regenerated and / or fresh catalyst can also represent for example from 10 to 70%, and often from 15 to 50% of the catalyst feeding Za at the reactor head, or feeding Zb.
• the two successive reaction zones Za and Zb are connected by a circulation circuit of the reaction fluid passing through a heat exchange means (8), internal or external to said reactor, for example a reheat furnace or a heat exchanger (typically with an auxiliary thermal fluid) for heating or cooling the reaction fluid.
• a heat exchange means (8) is disposed inside the reactor, in an intermediate zone located between the two successive reaction zones Za and Zb. It can advantageously be a heat exchanger disposed in the intermediate zone, at a narrowing of the catalyst passage from zone Za to zone Zb.
• the intermediate zone comprises means for introducing (10) one or more additional reaction fluids (106), and for mixing this or these fluids with the reaction fluid flowing between the successive reaction zones Za and Zb. It may be in particular useful to add a new chemical reagent, to carry out a reaction subsequent to that carried out in the upstream zone, for example an alkylation reaction of an aromatic molecule or a mixture of aromatics, and / or or introducing a hydrogen-rich recycle gas (comprising more than 50% and often more than 70 mol% H 2) to increase the amount of hydrogen present. This gas can also have a thermal effect, heating or more frequently downstream reaction.
• the device of the invention may be used in particular in the context of a chemical conversion process of hydrocarbons, and in particular of a process for oligomerization of olefinic charges having 2 to 12 carbon atoms, this or these method (s) constituting another object of the invention.
• the typical conditions are as follows: the pressure is between 0.1 and 10 MPa and preferably between 0.3 and 7 MPa, the temperature is between 40 and 600 ° C and preferably between 60 and 400 ° C, the hourly space velocity VVH is between 0.01 and 100 h -1 and preferably between 0.4 and 30 h " , and the catalyst circulates in each reaction zone at a speed (average) of between 1 cm / hour and 200 cm / hour and preferably between 2 cm / hour and 100 cm / hour.
• L 1 invention is particularly suitable for processes in which the operating conditions are selected: temperature, pressure, LHSV, so as to limit the temperature variation in each of the reaction zones in one or more values between 2 ° C and 50 ° C.
• the catalyst travels all the downstream reaction zones, and the charge also travels all the reaction zones but against the current of the catalyst.
• the reaction zones shown are of the axial reactor type. However, a configuration in which the reaction fluid circulates co-current of the catalyst, ie from top to bottom is also perfectly possible within the scope of the invention. Moreover, the reaction zones can also be of the radial reactor type (and not only of the axial reactor type).
• the fresh and / or regenerated catalyst is fed, mainly in general, at the top of the reactor via the line (102) and then the conduit (2a). This catalyst flows slowly, continuously or discontinuously in a zone Za, referenced (3a) in FIG. 1, which is the upper reaction zone.
• the chamber (5) may be provided with means (not shown) to facilitate the extraction of a granular product such as catalyst, for example an extraction screw, or a pneumatic transport container, or a fluidized bed or any another means known to those skilled in the art. It is also possible to use a duct (104) inclined at least 60 ° with respect to the horizontal and optionally aeration of catalyst aeration gases (for example nitrogen) to facilitate the removal of the catalyst.
• a duct (104) inclined at least 60 ° with respect to the horizontal and optionally aeration of catalyst aeration gases (for example nitrogen) to facilitate the removal of the catalyst.
• the non-extracted part of the catalyst present in the chamber (5) flows into the mixing chamber (7), to be mixed with another part of the fresh and / or regenerated catalyst, introduced via the line (103), via the valve (6). It is possible to use a duct (103) inclined at least 60 ° with respect to the horizontal, including in its end part, and optionally injections of aeration gas of the catalyst (for example nitrogen) to facilitate introducing the fresh and / or regenerated catalyst.
• the mixing chamber (7) may be provided with means (not shown) to facilitate the mixing of fresh / regenerated catalyst and partially spent catalyst.
• the catalyst mixture thus formed has a catalytic activity increased compared to that of the spent catalyst from zone Za.
• This mixture passes through a narrowing passage (2b), then feeds the zone Zb, referenced (3b) in Figure 1, which is immediately below Za (from the point of view of the reaction zones).
• the spent catalyst from zone Zb (3b) circulates in an extraction pipe (4b) and is then discharged from the reactor via the pipe (105) on which the valve (9) is located.
• a particle transport system by means of a liquid or gaseous transport fluid (for example nitrogen), according to well-known technologies. of the person skilled in the art concerning the moving bed. It is particularly possible to use, at the level of the duct (105) or below the valve (9), a spent catalyst recipe for the storage of a predetermined quantity of catalyst before its sequential evacuation by pneumatic transport, by means generally a primary aeration fluid of the catalyst, and a secondary transport fluid.
• the technologies to be introduced, rip, mix, or transport granular products are technologiej_génichers_bien_coiinues-Dej-'ans - -métier v of which the invention is not related.
• the regeneration zone of the catalyst may be equipped with an elutriator or any other means for separating the fine particles created during the various catalyst transport operations.
• the regenerated catalyst (after in particular a controlled oxidation of the carbonaceous deposits) is typically recycled through the conduits (102) and (103), with a supplement of fresh catalyst.
• a fraction of the loop catalyst (often spent catalyst) is generally removed to allow the addition of fresh catalyst while keeping the total amount of catalyst employed constant.
• the reaction fluid E.g. olefinic hydrocarbon feedstock C4-C6 (having essentially of 4 to 6 carbon atoms), is fed through line (100) into the feed chamber 5 I through the reaction zone Zb (3b) filled with catalyst, then the intermediate zone (22) containing no catalyst, then enters the reaction zone Za (3a) filled with catalyst, then enters the chamber (23) before being discharged through the conduit (101).
• the reaction zones Za and Zb are advantageously provided at the top and bottom of perforated grids (shown in dotted lines in the figures) to allow the passage of the reaction fluid. These grids can be inclined at an angle of 60 ° or more, at the bottom, to facilitate the flow of the catalyst.
• a heat exchanger (8) with a thermal fluid circulation is placed inside the reactor, in the intermediate zone (22) (itself located inside the reactor), in order to carry out a heat exchange with the reaction fluid between Zb and Za.
• This heat exchanger is advantageously arranged at the level of the narrowing 2b of the catalyst passage, because of the space thus released inside the reactor.
• This heat exchanger generally uses a heating or cooling fluid circulating inside tubes, the set of tubes forming for example one or more pins dipping within the reaction fluid in the intermediate zone (22).
• the exchanger may however be of any type known to those skilled in the art, the invention being in no way related to the particular technology of this exchanger.
• Various fluids under pressure can be used as heating or cooling fluid: water vapor, air, water, hydrogen or hydrogen-rich recycle gas, nitrogen, molten salts, aromatic oil, etc.
• FIG. (2) represents another reaction device according to the present invention, comprising the same elements as those of the device of FIG. 1. It comprises a-conduit (-106) for supplying an additional reaction fluid, for an addition of reagent and / or an addition of hydrogen, this fluid is distributed in the intermediate zone (22) via a distribution manifold (10) to facilitate its homogeneous mixing with the reaction fluid resulting from the zone Zb.
• the mixture is also favored by the fact that the intermediate zone (22) is free of catalyst.
• the reaction device comprises a heat exchanger
• reaction fluid from the zone Zb is collected via the conduit (11), feeds the exchanger (8), and is then reintroduced into the reactor, after addition of the additional reaction fluid, via the conduit (108) and the distribution manifold (12), which are also part of the reaction device.
• a typical operation of the device of FIG. 1 is as follows:
• the flow rate of the regenerated catalyst booster, or possibly of fresh catalyst, is defined so as to maintain a determined level of activity on each reaction zone.
• this catalyst make-up rate is defined as a function of a characteristic of the reaction fluid at the outlet of the reaction zone. This characteristic can be a temperature, a composition, a conversion, or any other measurable physico-chemical characteristic in line. Correlations that relate one or more of these in-line measurable quantities to the level of catalyst activity depend on the reaction being performed, the type of catalyst, and its rate of flow.
• a simple way is notably to control the conversion in zone Zb, or the temperature variation (delta T) of the reaction fluid in this zone, or the exit temperature of this zone, by acting on the catalyst make-up flow rate.
• regenerated and / or fresh If the measured value of the delta T is lower than the expected value (typically depending on the initial composition of the charge), or if the value of the exit temperature of the zone corresponds to an insufficient reaction, then the regenerated and / or new catalyst back-up rate in this zone, and inversely, the back-up is reduced if the conversion in the zone (deduced from the delta T or from the outlet temperature) is too great.
• the same amount of used catalyst can be removed as that of the catalyst booster, before mixing, to keep constant the overall flow of catalyst in the zone Zb.
• the flow rate of makeup catalyst can therefore be fully automated. Alternatively, it can be adjusted at certain times (for example once or twice a day) by the operator, especially in view of the temperatures and / or delta T above.
• the reheating or cooling of the reaction fluid in the exchanger (8) can be controlled by, in particular, the flow rate or the temperature level of the thermal fluid circulating in the exchanger (8).
• the catalyst flowing in the reaction device according to the invention can be of various types.
• an oligomerization reaction device it is possible to use, in particular, any type of acidic catalyst which makes it possible to oligomerize, for example an amorphous silica-alumina or solid phosphoric acid type or ion exchange resin type catalyst, or when a catalyst having shape selectivity, for example a zeolitic catalyst, for example a zeolitic catalyst with structure type MFI, FER, EUO 5 TON, LTL, MOR, MTT, MEL, MWW, MTW and zeolites NU-86, NU-87, NU-88, IM-5.
• These zeolitic acid catalysts may be used in the state or after modifications, the said modifications preferably affecting the acidity of the catalyst, the term acidity denoting both the strength of the acidic sites and the concentration in acidic sites.
• These modifications can affect the framework of the zeolite, for example if it is a dealumination by vapotraitement or by acid treatment, and / or affect the surface of the zeolite, for example (i) by proton exchanges by alkaline type cations, (ii) inert phase deposits on the surface of the zeolites.
• the preferred operating conditions are those used in standard manner for the oligomerization of olefins by catalvseurs_de_t ⁇ p.e.solides acids: - - a temperature between 100 0 C and 300 ° C
• the device according to the invention is particularly suitable for oligomerization reactions of olefins, but it can be more generally used for any type of exothermic or endothermic reaction, taking place in the gas phase and / or liquid, and for which a fine control of the temperature profile in each reaction zone is necessary, in particular the reactions of addition of one olefin to another compound present in the feed, for example an olefin, a sulfur compound, a nitrogen compound, an aromatic molecule, said reactions of addition to increase the molecular weight of this compound, in particular the alkylation reactions of thiophene compounds with olefins, the metathesis of olefins.
• the device according to the invention can also be used for skeletal isomerization reactions of light olefins such as, for example, olefins with 4 or 5 carbon atoms.
• the cooling thermal fluid can be any fluid adapted to perform the heat exchange under good conditions, in particular by respecting an average temperature difference between the reaction fluid and the cooling fluid of at least 5 ° C and preferably at least 10 ° C.
• the invention is in no way related to a particular cooling or heating fluid.
• Examples 1, 3 and 5 are according to the prior art.
• Examples 2, 4 and 6 are according to the invention, and are respectively associated with Examples 1, 3 and 5 to highlight the effect of the device according to the invention with respect to a fixed bed implementation.
• This example relates to the oligomerization reaction of a C3Jnaturated cut on ⁇ bed-fixed.
• a dealuminated zeolite mordenite catalyst having an Si / Al molar ratio of 57 was tested for the propene oligomerization reaction, after being formed into beads with an alumina binder.
• the reaction is carried out in a conventional fixed bed reactor.
• the catalyst used is shaped into spherical beads 3 mm in diameter.
• the feed used for this test is a steam cracker feed which contains 94% by weight of propene and 6% by weight of propane.
• the conditions were chosen so as to optimize the formation of the diesel fraction in the oligomer product.
• the operating conditions are as follows:
• VVH volume flow rate of charge per volume of catalyst
• Example 2 corresponds to the same reaction as that of Example 1, using the same catalyst used in a reaction device according to the invention, such as that of FIG. 1.
• the reactor comprises two reaction zones denoted Zb ( initial zone (3b)) and Za (final zone (3 a)), in series, separated by an intermediate zone comprising a water cooling system constituting the heat exchanger.
• the charge, the test conditions and the catalyst are the same as for example 1.
• VVH volume flow rate of charge per volume of catalyst
• 20% of the spent catalyst from the upper reaction zone is withdrawn, which is replaced by regenerated catalyst in the same amount, to increase the catalytic activity in the lower reaction zone.
• the coolant temperature is set so that the reaction temperature at the inlet of the second reaction zone is 210 ° C.
• the cooling fluid used is water introduced at 25 ° C.
• Example 3 consists of an oligomerization reaction of an unsaturated C4 cut implemented in a fixed bed.
• the catalyst used is in the form of spherical beads 3 mm in diameter.
• This dealuminated zeolite mordenite catalyst having a Si / Al molar ratio of 57 is used for the oligomerization reaction of a slice containing 60% by weight of unsaturated butene, 3% by weight of iso-butene, 11% by weight of n-butanol. butane and 26% by weight of isobutane.
• the reaction is conducted in a conventional fixed bed reactor.
• the conditions were chosen so as to optimize the formation of the diesel fraction in the oligomer product.
• the operating conditions are as follows:
• VVH volume flow rate of charge per volume of catalyst
• Reactor inlet temperature (° C) 210 Reactor outlet temperature ( 0 C) at the beginning of the test 233
• Example 4 consists of carrying out the same reaction as that of example 3 in a reaction device according to the invention, such as that of FIG. 1, using the same catalyst.
• the reaction is carried out in a reactor comprising two reaction zones in series, denoted Zb (initial zone (3b)) and Za (final zone (3a)), separated by an intermediate zone comprising a water cooling system constituting the exchanger thermal.
• Zb initial zone (3b)
• Za final zone (3a)
• the charge, the test conditions and the catalyst are the same as for example 3.
• VVH volume flow rate of charge per volume of catalyst
• 20% of the spent catalyst from the upper reaction zone is withdrawn, which is replaced by regenerated catalyst in the same amount, to increase the catalytic activity in the lower reaction zone.
• the temperature of the cooling liquid (water at 25 ° C.) is set so that the reaction temperature at the inlet of the second reaction zone is equal to 210 ° C.
• Example 5 consists in carrying out the oligomerization reaction of an unsaturated C6 cut using a dealuminated zeolite mordenite catalyst having a Si / Al molar ratio of 57. This catalyst is used in the form of spherical beads. 3 mm in diameter. The reaction is carried out in a conventional fixed bed reactor.
• the feed used for this test contains 72% by weight olefinic unsaturated C6, 7% by weight unsaturated paraffinic C6, 18% olefinic unsaturated C9, 3% olefinic unsaturated C12.
• the conditions were chosen so as to optimize the formation of the diesel fraction in the oligomer product.
• the operating conditions are as follows: Temperature of the inlet charge of the reactor 230 ° C. Pressure 6.0 MPa
• VVH volume flow rate of charge per volume of catalyst
• Example 6 consists of carrying out the same reaction as that of Example 5 in a reaction device according to the invention, such as that of FIG.
• the reaction is conducted in a reactor comprising two series reaction zones marked Zb (initial zone (3b)) and Za (final zone (3a)), separated by an intermediate zone comprising a water cooling system constituting the heat exchanger.
• VVH volume flow rate of charge per volume of catalyst
• the addition of new catalyst allows at least partial rebalancing of the catalytic activity between the reaction zones, which is favorable to the efficiency of the diesel cut.
• the system for the continuous regeneration of part of the catalyst makes it possible to operate without having to stop the unit in order to change the catalyst.
• the heat exchange zone situated between the two reaction zones makes it possible to improve the homogeneity of the temperature in the two reaction zones.
• the temperature difference between the inlet and the outlet of each of the zones is 8 ° C. (Zone 1) and 5 ° C. (Zone 2), in comparison with a difference in temperature. 14 0 C in the case of a fixed bed.
• the reactor is compact, has a high catalytic volume and may however comprise an integrated heat exchanger.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
• Catalysts (AREA)
• Physical Or Chemical Processes And Apparatus (AREA)

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• 2004
  • 2004-11-09 FR FR0411961A patent/FR2877590B1/fr not_active Expired - Fee Related
• 2005
  • 2005-10-28 JP JP2007540670A patent/JP5235414B2/ja not_active Expired - Lifetime
  • 2005-10-28 CN CN200580046232XA patent/CN101163541B/zh not_active Expired - Fee Related
  • 2005-10-28 KR KR1020077012962A patent/KR101240836B1/ko not_active Expired - Fee Related
  • 2005-10-28 EP EP05815267.9A patent/EP1814654B1/fr not_active Ceased
  • 2005-10-28 WO PCT/FR2005/002721 patent/WO2006051185A1/fr not_active Ceased
  • 2005-11-09 US US11/269,883 patent/US7611678B2/en not_active Expired - Fee Related

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