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    • 专利摘要:
    METHOD FOR ETHYLENE OLIGOMERIZATION The present invention relates to a method for the oligomerization of ethylene, which comprises the steps: a) feeding ethylene, solvent and a catalyst composition comprising catalyst and cocatalyst in a reactor, b) oligomerize the ethylene into the reactor, c) discharge a reactor effluent comprising linear alpha-olefins, including 1-butene, solvent, uneaten ethylene dissolved in the reactor effluent and reactor catalyst composition, d) separate ethylene and 1-butene from the remaining reactor effluent, and e) recycle at least part of the ethylene and 1-butene separated in step d) in the reactor.
    公开号:BR112015000387B1
    申请号:R112015000387-7
    申请日:2013-06-05
    公开日:2020-11-10
    发明作者:Anina Wöhl；Wolfgang Müller；Heinz Bölt；Andreas Meiswinkel；Marco Harff；Anton Wellenhofer；Karl-Heinz Hofmann；Hans-Jörg Zander；Abduljelil Iliyas；Shehzada Khurram；Shahid Azam；Abdullah Al-Qahtani
    申请人:Saudi Basic Industries Corporation；Linde Ag；
    IPC主号:
    专利说明:

    [001] The present invention relates to a method for the oligomerization of ethylene.
    [002] Methods for oligomerization of ethylene using various catalyst compositions are well known in the art. Typically, if very nonspecific catalysts are used, a broad product distribution is obtained from C4 to higher olefins and even polymeric materials. Higher linear alpha-olefins and polymeric materials can cause clogging and fouling of the oligomerization reactor and pipes connected to it. Recently, catalyst compositions for ethylene oligomerization have been developed, which are more specific for, for example, trimerization or tetramerization, thus resulting in a more accurate product distribution, but still producing alpha-olefins superior linear and polymeric materials.
    [003] WO 2009/006979 A2 describes a process and a corresponding catalyst system for the di-, tri- and / or tetramerization of ethylene, based on a chromium complex with a heteroatomic ligand, which typically presents a chain main component of PNPNH, and activated by an organoaluminium compound, such as, for example, trialkylaluminum or methylaluminoxane. Among other possible embodiments of this invention, CrCl3 (THF) 3 (thf tetrahydrofuran) is preferably used as a source of chromium.
    [004] EP 2 239 056 A1 describes a catalyst composition and a process for oligomerization, in particular, for the selective trimerization of ethylene in 1-hexene, with the use of a modification of the catalyst system disclosed in WO 2009. / 006979 A2. Although they also depend on types of binders that feature the PNPNH main chain, these modified systems show distinct advantages over the original catalyst compositions in terms of stability, activity, selectivity and the permissible window of operability regarding process parameters in a technical environment .
    [005] According to EP 2 239 056 A1, modifiers containing halogen are used, together with, for example, Cr (acac) 3 (acac acetylacetonate), the PNPNH ligand and triethyl aluminum as an activator. Typical modifiers are, for example, tetrafenylphosphonium tetraalkylammonium halides, preferably chlorides. Unlike catalyst systems that use CrCl3 (THF) 3 as a chromium source, these modified systems allow free and independent adjustment of the chromium / halogen / aluminum ratio. This is a very advantageous strategy, since basic mechanistic investigations have shown that halogen is an indispensable constituent of the catalytically active species, thereby influencing overall catalytic performance.
    [006] A typical oligomer product distribution for that catalyst system mentioned above is: C4 2.9% by weight C6 91.4% by weight (> 99.0% by weight) 1-hexene C8 0.5% by weight CIO 5.1% by weight> C12 0.1% by weight
    [007] A typical process for a homogeneous catalyzed ethylene oligomerization technology of the prior art is shown in Fig. 1.
    [008] The homogeneous catalyst system 1 is transferred together with solvent 2 (for example, toluene) to reactor 3. Linear alpha-olefins, mainly 1-hexene, are formed by means of trimerization of ethylene dissolved in the liquid phase . Inside the reactor, the heat of the reaction from the exothermic reaction has to be removed and a rapid phase transfer of the ethylene gas to the solvent has to be carried out. Various types of reactor are conceivable. Some examples are: 1. Bubble column reactor: to avoid internal heat exchange surfaces, ethylene can be used both as a reaction feed and as a cooling medium. At the same time, mixing is achieved by means of the bubbles emerging above a suitable spray plate. 2. Loop reactor with external heat exchanger. 3. Piston flow reactor: the heat of the reaction can be removed through the reactor wall.
    [009] A preferred reactor for ethylene oligomerization is the bubble column reactor. The ethylene is introduced through a gas distribution system to the bottom section, while the heavy liquid LAOs, together with the solvent and the catalyst, are removed from the bottom. The oligomerization reaction is highly exothermic. By removing this heat with ethylene, the surfaces of the heat exchanger inside the reaction area, which would be susceptible to heavy encrustation, are avoided. A portion of the formed linear a-olefins, which are gaseous under reaction conditions, is condensed at the top of the reactor and works as a reflux for cooling purposes, taking advantage of their respective heat of evaporation. Typical reaction conditions are: 30 to 70 ° C at 1 to 10 MPa (10 to 100 bar).
    [010] After the reaction section, the liquid product that includes the solvent (eg toluene) with the dissolved ethylene is fed into the separation section. In a first column 4, the uneaten ethylene is separated from the product and the solvent. The ethylene is recycled back to the reactor via line 5. A polishing of ethylene 6 can take place in line 5. The heavier fractions are conducted to the subsequent separation 7, where they are divided into the different fractions (C4, C6, solvent , C8, CIO,> C12). The solvent is recovered and recycled back to the reactor.
    [011] Starting with the very advantageous modified catalyst system class, as described, for example, in EP 2 239 056 A1, the question arises as to an economic process for ethylene oligomerization, especially the selective trimerization of ethylene in 1-hexene, must be designed. The following challenges must be considered in this regard: 1. The heat of the reaction from the exothermic reaction must be removed from the reactor. Due to the fact that the catalyst is very sensitive to high temperatures, a reaction temperature, preferably between 30 and 70 ° C, has to be maintained and controlled very precisely. Due to the fact that small amounts of polyethylene are formed during the reaction, the internal heat exchange surfaces show a tendency to scale. This inevitably results in unstable and / or dangerous operation of the reactor only in a very limited flow time. Therefore, such internal heat exchange surfaces must be avoided. 2. Unfortunately, the formation of high molecular weight polymer or oligomers cannot be avoided completely during ethylene oligomerization, as this is an inherent channeled side reaction.
    [012] These solid materials can be dissolved or suspended in the liquid product and, thus, finally passed to the separation section or they can accumulate on the internal surface of the reactor and in its peripheral equipment. The latter is the worst case, as this can lead to fouling and blockage of the reactor. Consequently, the reactor and its associated equipment have to be cleaned periodically to remove deposits. This results in shutdowns and, consequently, loss of production. Consequently, the polymer that is dissolved or suspended in the product stream is preferred.
    [013] Thus, it is an objective of the present invention to provide a method for the oligomerization of ethylene, which overcomes the disadvantages of the prior art. In particular, the method must be an economical process in terms of operating and investment costs and should preferably provide a stable and safe reactor operation with good heat removal and preventing clogging and fouling.
    [014] This objective is achieved by a method for ethylene oligomerization, which comprises the steps: a) feeding ethylene, solvent and a catalyst composition comprising catalyst and cocatalyst in a reactor, b) oligomerizing ethylene in the reactor, c ) discharge a reactor effluent comprising linear alpha-olefins, including 1-butene, solvent, uneaten ethylene dissolved in the reactor effluent and catalyst composition from the reactor, d) collectively separate ethylene and 1-butene from the reactor effluent remainder, e) recycle at least part of the ethylene and 1-butene separated in step d) in the reactor.
    [015] In a more preferred embodiment, there is a catalyst composition deactivation step between steps c) and d).
    [016] In principle, the total amount of ethylene, which has not been consumed, should be recycled back to the reactor in order to improve the overall yield of the method. Since it is preferable to adjust a constant 1-butene content during the method, a purge current is then required. Consequently, through a purge, a part of the ethylene is discharged. Once a preferred concentration of 1-butene in the liquid phase in the reactor is reached, the amount of 1-butene that is formed during trimerization has to be purged. Due to the high selectivity, especially using the trimerization catalyst, as described below, the loss of ethylene over the purge is comparatively low.
    [017] Preferably, the reactor is a bubble column reactor.
    [018] Most preferably, the ethylene and 1-butene recycling stream from step e) is purged at least partially by a purge stream.
    [019] In a more preferred embodiment, a stable state of the oligomerization is achieved, that is, having a constant content of 1-butene in the reactor. This constant 1-butene content can be achieved by adjusting the respective amounts of 1-butene that are removed from the reactor with the reactor effluent and recycled in the reactor in step e), and these amounts are purged from, preferably ethylene recycling.
    [020] In the steady state of the process, the entire amount of 1-butene, which is formed during oligomerization, has to be removed from the process. Conversely, 1-butene will accumulate more and the concentration of 1-butene will increase. Due to the fact that there is only a division of C4 / C6, the only possibility to remove 1-butene from the process is to remove it with ethylene in recycling. In the steady state, a constant amount of 1-butene is formed. This also means that a constant amount of the recycled chain has to be removed. Consequently, a part of the recycled chain has to be purged. The amount of the purged current is in the steady state, therefore substantially constant. Through the amount of the purge stream, the concentration of 1-butene in the reactor and the composition of the purge stream can be adjusted. For example, in the case of a high purge current, recycling consists mostly of ethylene and a lower amount of 1-butene, since a large amount of fresh / replacement ethylene is required for the process. Consequently, less 1-butene is sent back to the reactor and larger amounts of pure / fresh ethylene as a replacement dilute the reactor composition. Thus, the concentration of 1-butene is lower. The opposite occurs in a lower purge current.
    [021] Due to the fact that the recycled stream can be gaseous as well as liquid, the purge stream can also be gaseous or liquid. An amount can be controlled by a mass flow controller. In the event that the recycled stream is condensed in a heat exchanger before it is sent to the reactor, it may be energetically more beneficial to remove the purge stream before the recycle stream is condensed.
    [022] More preferably, the amount of 1-butene in the reactor is at least 1 weight percent, more preferably 5 weight percent, more preferably 10 weight percent, most preferably 25 weight percent , based on the total weight of liquids in the reactor.
    [023] Even the preferred 1-butene is present in the reactor in a maximum amount of 30 weight percent, based on the total weight of liquids in the reactor. In principle, even higher levels of 1-butene are conceivable, as a maximum amount of 50 or even 70 weight percent in the liquid phase, with such levels being possible at a reaction pressure of 3 MPa (30 bar ).
    [024] In a more preferred embodiment, a stable oligomerization state is achieved since equal amounts of 1-butene are removed from the reactor with the reactor effluent and are recycled in the reactor in step e).
    [025] Step b) can preferably be carried out at a temperature of 10 to 100 ° C, preferably 30 to 70 ° C and / or a pressure of about 1 to 10 MPa (10 to 100 bar) .
    [026] In a preferred embodiment, more 1-butene is fed into the reactor from an external source, preferably at an initial start-up period of the method for oligomerization.
    [027] Even more preferably, the separation of step d) is carried out at a pressure below the reaction pressure of step b). In this modality, the product stream (reactor effluent) is depressurized before being sent to a separation section. The advantage is obtained that the separation step can be improved. Operating and investment costs are reduced when the separation section (distillation column) is operated at a lower pressure. The C2 + C4 product that is recycled back to the reactor has to be re-compressed at the reaction pressure or it can be liquefied and pumped back to the reactor.
    [028] Ethylene and 1-butene can be advantageously recycled in the reactor in liquid form. The advantage of using a liquid recycling stream is that a pump can be used for the recycling stream instead of an expensive compressor. At the same time, the reactor's cooling capacity is increased. Evaporation of the C2 + C4 current in the reactor removes a significant part of the heat from the exothermic reaction. Consequently, the recycling of ethylene gas, which is necessary to cool the reactor, can be reduced. This is again beneficial for operating and investment costs of the method.
    [029] Preferably, the method for oligomerization is a trimerization to substantially prepare, then, 1-hexene.
    [030] The catalyst composition may comprise a catalyst comprising a chromium compound and a linker of the general structure (A) RIR2P-N (R3) -P (R4) - N (R5) -H OR (B) R4R2P- N (R3) -P (R4) -N (R5) -PR6R7, where RI-R7 are independently selected from halogen, amino, trimethylsilyl, C1-C10-alkyl, C6-C20 aryl or any cyclic derivatives of ( A) and (B), in which at least one of the P or N atoms of the PNPN unit or PNPNP unit is a member of a ring system, the ring system being formed from one or more compounds constituents of structures (A) or (B) by substitution.
    [031] As should be understood, any cyclic derivatives of (A) and (B) can be used as a linker, in which at least one of the P or N atoms of the PNPN unit (structure (A)) or unit of PNPNP (structure (B)) is a ring member, the ring being formed from one or more constituent compounds of the structures (A) or (B) by substitution, that is, formally eliminating, by constituent compound , two total RI-R7 groups (as defined) or H, one atom from each of the two RI-R7 groups (as defined) or a total R4-R7 group (as defined) or H and one atom from another RI- R7 (as defined), and joining the unsaturated valence sites then formally created through a covalent bond by constituent compound to provide the same valence as initially present at the given location.
    [032] Preferably, the chromium compound is selected from organic or inorganic salts, coordination complexes and organometallic complexes of Cr (II) or Cr (III), preferably CrCl3 (THF) 3, Cr (III) acetyl acetonate, Cr (III) octanoate, chromium hexacarbonyl, Cr (III) - 2-ethylhexanoate, benzene (tricarbonyl) -chromium or Cr (III) chloride.
    [033] The cocatalyst can be selected from trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, ethyl aluminum sesqui-chloride, diethyl aluminum chloride, ethyl aluminum dichloride, methyl aluminoxane (MAC) or mixtures thereof.
    [034] The catalyst composition may additionally comprise a modifier that contains organic or inorganic halide.
    [035] More preferably, the linker can be selected from Ph2P-N (i-Pr) -P (Ph) -N (i-Pr) -H, Ph2P-N (i-Pr) -P (Ph) -N (Ph) -H, Ph2P-N (i-Pr) -P (Ph) -N (tert-butyl) - H and Ph2P-N (i-Pr) -P (Ph) -N (CH- ( CH3) (Ph)) - H.
    [036] In principle, it is preferred that any of the catalyst compositions, as disclosed in documents W02009 / 006979 A2 or EP 2 239 056 A1, including any modifiers, can be used successfully, which are now incorporated by way of reference.
    [037] Finally, the solvent can be selected from aromatic hydrocarbons, cyclic and straight chain aliphatic hydrocarbons and ethers, preferably toluene, benzene, ethylbenzene, cumene, xylenes, mesitylene, hexane, octane, cyclohexane, methylcyclohexane, ether diethyl, tetrahydrofuran, and mixtures thereof, with maximum preference, toluene.
    [038] Surprisingly, it was found, in the method of the present invention, that the 1-butene produced during oligomerization can be used successfully as a "co-solvent" to improve heat removal and removal of polymeric compounds or high molecular weight of the reactor.
    [039] In detail, since the amount of C4 produced in an oligomerization reaction is usually comparatively low, especially as a side reaction during ethylene trimerization, the design of a separation section without a separation of C2 / C4. This means that, after the reactor, the liquid product (reactor effluent) is sent directly to a liquid C4 / C6 separation column. Although it is, in principle, conceivable to recycle only a part of the 1-butene back to the reactor, it is one of the main advantages of the present invention to guarantee a process step, namely the C2 / C4 division. Consequently, to obtain this advantage, it is then necessary to substantially recycle the total amount of uneaten ethylene and prepared 1-butene. Although some C4 may end up in the C6 fraction, which is not preferred due to the negative impact on the quality of 1- hexene, in the purge current, especially in the purge rate, the best option is to adjust the concentration of 1- butene in the reactor to ideal values. The heavier products, together with the solvent, are sent to the subsequent separation section, as usual, where the solvent is recovered and the main product, 1-hexene, is separated.
    [040] It is clear to a person skilled in the art that, in a very preferred embodiment, there is a catalyst deactivation step between steps c) and d) of the method of the invention. Usually, for these purposes, after discharging the reactor effluent from the reactor, a deactivating agent is added to the product / toluene / catalyst solution. All established / revealed deactivation methods are conceivable for this catalyst system: alcohol, water, caustic soda, air / O2, amine, CO / CO2. It is important that the deactivating agent is added at molar stoichiometric rates in relation to the catalyst and cocatalyst, that is, for example, Cr catalyst and alkyl aluminum activator, that is, [Cat] + [Cocat]. This guarantees complete deactivation of the catalyst. Conversely, side reactions in separation columns, for example, olefin isomerization, are possible. The most preferred deactivating agent is a long-chain alcohol, especially 1-decanol, which, after separation, does not end up in the 1-hexene fraction of the desired product or solvent.
    [041] In addition, a mixture of 1-butene and ethylene is recycled back to the reactor from the light product of the first separation step (the C4 / C6 column). The recycled current can be injected / distributed from the top of the reactor through a distributor plate or a nozzle. Alternatively, it can also be injected from the side into the fluid bed. The effect is that 1-butene, which is formed as a by-product during the trimerization reaction (1 to 4% by weight), is accumulated in the reactor. Consequently, a significant amount of the liquid reactor phase mixture is 1-butene. This amount can vary from 1 to 30% by weight, compared to only 1 to 4% by weight of net production.
    [042] Since 1-butene is usually a by-product of the oligomerization reaction, especially trimerization, it has to be discharged from the process. In this way, a purge current may be required. The purge stream may preferably consist of between 10 and 90% by weight of 1-butene, while the rest of the stream is mainly ethylene. The purge stream can be sent back, for example, to a steam cracker where ethylene and 1-butene can be recovered. In the event that no cracker is available, this chain can be sold separately or used energetically. Depending on the situation, the purge stream can be used as fuel for boilers. Due to the fact that the catalyst produces 1-hexene very selectively with only a small amount of 1-butene as a by-product, the loss of ethylene through the purge is comparatively low.
    [043] The high 1-butene content in the reactor has a significant benefit in removing heat from the reaction. Through recycling, ethylene gas and evaporated 1-butene are condensed and recycled back to the reactor. In this way, the enthalpy of evaporation of 1-butene is used for the removal of heat. Consequently, the stream of ethylene gas, which also functions as a cooling medium, can be reduced.
    [044] Interestingly, several laboratory experiments show that the catalyst system is very selective in relation to the ethylene substrate. This means that, despite the large amount of 1-butene in the liquid phase, catalytic activity, 1-hexene selectivity and 1-hexene purity are not affected. This is especially surprising, since the mechanistic knowledge regarding the underlying metallocycle mechanism implies a certain possibility of deterioration of 1-hexene selectivities if high concentrations of 1-butene are present in the reaction mixture. However, such a detrimental effect is entirely avoided here as a direct consequence of the very high selectivity of the catalytically active species, largely caused by the preferred ligand that presents the PNPNH main chain.
    [045] It is even more surprising that the high content of 1-butene in the reactor advantageously changes the mobilization behavior of the polymer. This means that a significant portion of polymer that normally remains in the reactor as a sticky layer on the internal surfaces of the reactor is now dissolved and suspended in the product stream. This means that at higher concentrations of 1-butene in the reactor, a greater amount of secondary product polyethylene is discharged together with the product.
    [046] In subsequent examples, it becomes clear that higher C4 contents in the reaction mixture lead to better polymer mobilization and more of this unwanted material is discharged together with the liquid product. Evidently, high concentrations of 1-butene lead to the formation of small flakes of polymer, which have a lower affinity to accumulate and precipitate on the wall or internal part of the reactor. The agglomeration of polyethylene particles is largely impeded by the improved solvent properties, resulting in less particle size distribution. Then, the reactor operating time until the reactor has to be cleaned can be extended by increasing the steady state concentration of 1-butene.
    [047] It is conceivable that the high concentration of light olefin changes the solvent properties. In principle, a new solvent (solvent + 1-butene) with significantly improved solvent properties is now used in the reaction section. These altered solvent characteristics support the formation of smaller particles, which are better suspended in the liquid.
    [048] In summary, with the use of a high content of 1-butene in the liquid phase, the cooling capacity of the reactor can be significantly improved. Through recycling, in which the 1-butene-rich gas phase is condensed and recycled to the reactor, the enthalpy of evaporation of 1-butene can be used for cooling. Consequently, the stream of ethylene gas, which also functions as a cooling medium, can be reduced. This is beneficial as fewer requirements for recompression and cooling are required.
    [049] No heat exchange surface in the liquid phase of the reactor is necessary, since the cooling of the reactor can be achieved through evaporation of 1-butene and through the injection of cold ethylene.
    [050] The investment cost can be reduced, since the concept of the invention of the distillation column for the C2 / C4 division is no longer needed. In addition, ethylene recycling equipment is less.
    [051] Reactor operating times can be extended. Due to the better mobilization of the by-product polymer, the scale of the reactor is reduced. Consequently, the interval before the reactor has to be cleaned again is extended.
    [052] Finally, due to the high content of 1-butene, the process stability against thermal disruptions is improved. An increasing reaction temperature causes a greater amount of 1-butene to evaporate, thereby removing more heat. Consequently, the system is somewhat inhibitory in itself to some extent.
    [053] Additional features and advantages of the method of the invention can be obtained from the following detailed description of a preferred embodiment in conjunction with the drawings, where
    [054] Fig. 1 is a flow chart for a conventional process for an ethylene oligomerization technology,
    [055] Fig. 2 is a schematic for the ethylene oligomerization technology according to the present invention; and
    [056] Fig. 3 is a graph showing the initial C4-dependent polymer distribution in the liquid phase, based on a method of the present invention.
    [057] According to Fig. 1, in which a conventional process scheme for ethylene oligomerization is illustrated, the catalyst, solvent and ethylene are fed into a reactor in which oligomerization, for example, trimerization occurs. A reactor effluent liquid comprising solvent, unreacted ethylene, linear alpha-olefins and catalyst, is transferred to a first separation section in which the ethylene is separated. This ethylene can be recycled back to the reactor and the recycling cycle can comprise polishing ethylene. The heavier fractions are taken to a second section and other separation sections in which separation into different fractions, such as C4, C6, solvent, C8, Cio,> Ci2, is carried out.
    [058] According to the method of the invention, which is illustrated in Figure 2, catalyst 10, solvent 11 and ethylene 12 are also fed into a reactor 13 for oligomerization, for example, trimerization, of ethylene. Unlike the prior art method, the reactor effluent is sent directly to a C4 / C6 14 separation section, in which both ethylene and C4 are separated from the rest. Ethylene and C4 (at least partially) are recycled in the reactor via line 16. The recycling step can include a purge stream 17 and polishing 18 of ethylene. As in the prior art, the heavier fractions can be transferred to other separation sections 15.
    [059] Examples
    [060] A 300 ml pressure reactor, equipped with immersion tube, thermowell, gas entrainment agitator, cooling coil, control units for temperature, pressure and agitator speed (all connected to a data acquisition system ), was inertized with dry argon. The supply of isobaric ethylene was maintained by a cylinder of gas pressurized by aluminum in an equilibrium to monitor the consumption of ethylene over time through a computerized data acquisition system.
    [061] Before conducting an experiment, the reactor was heated to 100 ° C under reduced pressure for several hours to eliminate waste water, oxygen and oxygenated impurities. Before the reaction, the reactor was cooled to a reaction temperature of 50 ° C.
    [062] For the preparation of the catalyst, adequate amounts of PNPNH binder (14.7 mg (Ph) 2P- N (1Pr) -P (Ph) -N (1Pr) -H, Ph = phenyl, iPr = isopropyl) , chromium precursor (Cr (acac) 3, 10.5 mg) and modifier dodecyltrimethylammonium chloride (CH3 (CH2) nN (CH3) 3C1, 63.5 mg) were weighed and loaded and a Schlenk tube under an inert atmosphere. A 50/100 ml volume of anhydrous toluene was added and the solution was stirred using a magnetic stirrer. After dissolving the Cr compound, the binder and the modifier, the required amount of 93% by weight of triethyl aluminum (AlEt3, 100 pl) was added. The solution was immediately transferred to the reactor.
    [063] The volumes and masses chosen correspond to a chromium concentration of 0.3 / 0.6 mmol / 1 at a molar binder to chromium ratio of 1.2 mol / mol, an Al / Cr ratio of 24 mol / mol and a Cl / Cr ratio of 8 mol / mol.
    [064] To investigate the effect of accumulated gas on ethylene recycling, the existing test probe was extended by a 2 1 gas cylinder. For good quantification, this cylinder was stored on a scale. The desired amount of 1-butene was filled in the reactor shortly after the reaction was started. After filling, the agitator was turned on and the ethylene supply was opened and the reactor was pressurized to 3 MPa (30 bar) of ethylene. The ethylene was fed on demand to maintain a constant pressure at 3 MPa (30 bar). Ethylene consumption was monitored by the data acquisition system and an electronic scale by constantly weighing the ethylene pressure cylinder. The total amount of 1-butene dosed was determined by quantifying and characterizing the liquid and gaseous product by GC-FID and the loss of balance weight. The weight content of 1-butene in the liquid phase was calculated using the UniSim process simulation tool.
    [065] Following the procedure, a series of trimerization reactions were conducted with different amounts of 1-butene and different volumes of toluene to adjust different ratios of toluene / 1-butene mixtures.
    [066] After the residence time of 1 h, the reaction in the liquid phase was abruptly cooled by transferring the liquid stock through the pressure of ethylene to a glass vessel filled with approximately 100 ml of water. The mass balance of the experiment was determined by quantification and GC-FID analysis of the liquid and gaseous product separately, followed by comparison with the ethylene absorption data. Based on the measured data, overall yields and selectivity were determined.
    [067] The results of the experiments are summarized in Table 1.
    [068] Table 1: Standard experimental performance tests with different amounts of 1-butene (Conditions: 50 ° C, 3 MPa (30 bar), 1 h)

    1) The initial 1-C4 weight ratio was determined by UniSim (50/100 ml of toluene with an additional mass of 1-butene, saturated with ethylene at 3 MPa (30 bar), 50 0 C) Woluene = 50 ml, [Cr] = - 0.6 mmol / 1
    [069] Surprisingly, the yield of 1-hexene is very high, despite the higher content of 1-butene in the liquid. In addition, the purity of 1-hexene, which means that the content of 1-C6 in the C6 fraction, remains at 99.0% by weight, unaffected by the high concentrations of 1-butene. These results show the extraordinary selectivity of the homogeneous ethylene trimerization catalyst, greatly favoring the incorporation of the ethylene raw material in the product during the analogous reaction with 1-butene.
    [070] However, curiously and surprisingly, the polymer mobilization behavior is significantly changed with the concentration of 1-butene in the liquid phase. As shown in Fig. 3, it becomes evident that, at a high C4 content, the polymer is better mobilized and is discharged from the reactor together with the liquid product.
    [071] The features disclosed in the previous description, the claims and the accompanying drawings can be, both separately and in any combination thereof, important for carrying out the invention in various forms thereof.
    权利要求:
    Claims (15)
    [0001]
    1. METHOD FOR ETHYLENE OLIGOMERIZATION, characterized by comprising the steps: a) feeding ethylene, solvent and a catalyst composition comprising catalyst and cocatalyst in a reactor, b) oligomerizing ethylene in the reactor, c) discharging a reactor effluent comprising linear alpha-olefins, including linear Ce + alpha-olefins, 1-butene, solvent, uneaten ethylene dissolved in the reactor effluent, and catalyst composition from the reactor, d) collectively separate ethylene and 1-butene from the remaining reactor effluent which comprises linear Ce + alpha-olefins, and e) recycling at least a part of the ethylene and 1-butene separated in step d) in the reactor, where there is a constant content of 1-butene in the reactor.
    [0002]
    Method according to claim 1, characterized in that the ethylene and 1-butene recycling stream of step e) is purged at least partially by a purge stream.
    [0003]
    METHOD according to either of claims 1 or 2, characterized in that the amount of 1-butene in the reactor is at least 1 weight percent, based on the total weight of the liquids in the reactor.
    [0004]
    4. METHOD according to any one of the preceding claims, characterized in that 1-butene is present in the reactor in a maximum amount of 30 weight percent, based on the total weight of the liquids in the reactor.
    [0005]
    5. METHOD according to any one of the preceding claims, characterized by step b) being carried out at a temperature of 10 to 100 ° C, and / or a pressure of 1 to 10 MPa (10 to 100 bar).
    [0006]
    6. METHOD, according to any one of the preceding claims, characterized in that the additional 1-butene is fed into the reactor, from an external source in an initial start-up period of the method for oligomerization.
    [0007]
    7. METHOD, according to any one of the preceding claims, characterized in that the separation of step d) is carried out at a pressure below the reaction pressure of step b).
    [0008]
    8. METHOD, according to any one of the preceding claims, characterized in that ethylene and 1-butene are recycled in the reactor in liquid form.
    [0009]
    9. METHOD, according to any one of the preceding claims, characterized by being a trimerization.
    [0010]
    METHOD according to any one of the preceding claims, characterized in that the catalyst composition comprises a catalyst comprising a chromium compound and a binder of the general structure (A) R1R2P-N (R3) -P (R4) -N ( R5) -H or (B) R1R2P-N (R3) -P (R4) —N (R5) -PR6R7, where R1-R7 are independently selected from halogen, amino, trimethylsilyl, Ci-Cio-alkyl, C6-C20 aryl or any cyclic derivatives of (A) and (B), with at least one of the P or N atoms of the PNPN unit or PNPNP unit being a member of a ring system, where the system ring is formed from one or more compounds constituting the structures (A) or (B) by substitution.
    [0011]
    11. METHOD, according to claim 10, characterized in that the chromium compound is selected from organic or inorganic salts, coordination complexes and organometallic complexes of Cr (II) or Cr (III).
    [0012]
    12. METHOD, according to any one of the preceding claims, characterized in that the cocatalyst is selected from trimethylaluminum, triethylalumin, triisopropylalumin, triisobutylaluminum, ethylaluminium sesqui-chloride, diethylaluminium chloride, ethylaluminium dichloride, methylaluminoxane (MAO) mixtures thereof.
    [0013]
    13. METHOD according to any one of the preceding claims, characterized in that the catalyst composition further comprises a modifier containing organic or inorganic halide.
    [0014]
    14. METHOD according to any of the preceding claims 10 to 13, characterized in that the linker is selected from PI12P-N (i-Pr) -P (Ph) -N (i-Pr) -H, Ph2P-N (i-Pr) -P (Ph) - N (Ph) -H, PI12P-N (i-Pr) -P (Ph) -N (tert-butyl) -H and Ph2P-N (i-Pr) - P (Ph) -N (CH (CH3) (Ph)) - H.
    [0015]
    15. METHOD according to any one of the preceding claims, characterized in that the solvent is selected from aromatic hydrocarbons, cyclic and straight chain aliphatic hydrocarbons and ethers.
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    法律状态:
    2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-11-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-07-07| B09A| Decision: intention to grant|
    2020-11-10| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 05/06/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP12175732.2A|EP2684857A1|2012-07-10|2012-07-10|Method for oligomerization of ethylene|
    EP12175732.2|2012-07-10|
    PCT/EP2013/001658|WO2014008964A1|2012-07-10|2013-06-05|Method for oligomerization of ethylene|
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