• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    PROCESS FOR ETHYLENE OLIGOMERIZATION The present invention relates to a process for the ethylene oligomerization that comprises the steps of: a) oligomerizing ethylene in a reactor in the presence of solvent and catalyst; b) transfer the surplus effluent from the reactor to an externally located cooling device and recycle the condensed effluent in the reactor; c) transfer the reactor bottom effluent to a series of fractionation columns and, in the following order, i) optionally separate the C6 fraction, ii) separate the C6 fraction, iii) simultaneously separate the C8 and C10 fractions and recycle them in the reactor, and iv) separate residues comprising fractions of (Major equal) C12, spent catalyst, polymer material and cooling media, from the process, in which the solvent is separated in any of steps i) to iv ) and / or an additional step.
    公开号:BR112015012012B1
    申请号:R112015012012-1
    申请日:2013-09-05
    公开日:2020-12-08
    发明作者:Heinz Bölt；Abduljelil Iliyas；Shahid Azam；Abdullah Alqahtani；Shehzada Khurram；Anina Wöhl；Wolfgang Müller；Marco Harff；Andreas Meiswinkel
    申请人:Linde Ag；Saudi Basic Industries Corporation；
    IPC主号:
    专利说明:

    [001] The present invention relates to a process for the oligomerization of ethylene.
    [002] Processes for the production of linear alpha-olefins (LAOs), including comonomer-grade 1-hexene, are widely known and depend on ethylene oligomerization using various catalyst compositions. These processes have in common the fact that they result in a product distribution of ethylene oligomers with a chain length of 4, 6, 8 and so on.
    [003] In addition, catalyst compositions are known for ethylene oligomerization, which can predominantly prepare 1-hexene oligomers.
    [004] For example, US 2010/0190939 A1 discloses a catalyst composition comprising a chromium compound, a PNPN or PNPNP general structure binder and an activator or cocatalyst, which can be used in ethylene oligomerization to produce predominantly hexene oligomers.
    [005] In addition, US 2012/0029258 A1 discloses a very similar catalyst composition that further comprises a modifier containing organic or inorganic halide and, or a modifier containing a free amine group, respectively.
    [006] US 2010/0190939 A1 and US 2012/0029258 A1 describe both oligomerization reactions that have a typical 1-hexene selectivity of more than 92 weight percent (1-hexene purity> 99 percent percent by weight), butenes ~ 3 percent by weight, ten ~ 5 percent by weight, octenes ~ 0.5 percent by weight and polymer «0.3 percent by weight, where all percentages by weight are based on the total weight of the oligomers / polymers obtained. The typical process conditions for this oligomerization are in the range of 1 to 10 MPa (10 to 100 bar) of pressure and 30 to 70 ° C of temperature.
    [007] The commercial processes for ethylene trimerization known in the art involve feeding a solvent, preferably toluene, recycling ethylene with fresh ethylene composition, and the respective catalyst solution in a reactor, preferably a multi-reactor -bular, more preferably, a bubble column reactor. Unreacted ethylene and light-ended LAO that split into a gaseous phase leave the top of the reactor as surplus effluent from the reactor and are washed to recover only ethylene, while the condensed LAO, here, for the most part, C4 and lower C6, is combined with the liquid flow from the bottom of the reactor for further purification.
    [008] The bottom reactor effluents containing LAO products (> C4), together with dissolved ethylene, solvent and catalyst, are continuously removed from the bottom of the reactor. Due to the fact that the catalyst is still active, a cooling medium, preferably n-decanol, is immediately added and mixed with the liquid effluent from the reactor. This flow is sent to an ethylene recovery column where the dissolved ethylene is recovered and recycled back to the reactor.
    [009] The lower ends of a C2 remover comprising LAOs, solvent, spent catalyst and cooling medium are sent to a product recovery assignment, where it is divided into a series of about 4 to 5 distillation columns in products of butenes, hexenes, solvents, octenes, decenes and> C12 individually separated, as well as polymers, etc.
    [010] A process known in the art is illustrated in figure 1. In a reactor 1, solvent 2, catalyst 3 and ethylene 4 are introduced by means of respective lines to conduct an oligomerization process. The surplus gaseous effluent from the reactor is removed from the reactor and transferred to an externally located cooling device 5, such as a condenser. The obtained ethylene is transferred back to the reactor, if necessary, with a fresh ethylene composition 6. The reactor bottom effluent is cooled with a cooling medium 7 and combined with liquefied linear alpha-olefins in the cooling device. 5. This cooled reactor bottom effluent is then sent to a series of fractionation columns 8 to 13. In fractionation column 8, the ethylene dissolved in the solvent is removed and separated, which can also be -so, recycled in the reactor. In the fractionation column 9, the butenes can be separated, while in the fractionation column 10, the hexenes can be removed and further processed further. If, for example, toluene is used as a solvent in the oligomerization reaction, it can be separated in the fractionation column 11, while higher linear alpha-olefins, ie octenes and decines, can be individually separated in the columns. fractionation 12 and 13. Any additional residues, such as fractions of> C12, spent catalyst, polymer materials and air-cooling media, can be further processed, which are not described in detail in this document.
    [011] The disadvantages of prior art processes for ethylene oligomerization are high capital and operating expenses, for example, the costs of several fractionation columns in the separation section for product recovery, the formation of heavy wax that results in encrustation / obstruction of the reactor and the reactor equipment, as well as the difficulty of removing heat for the exothermic o-ligomerization process.
    [012] Therefore, it is an object of the present invention to overcome the disadvantages of the prior art, especially by providing a process for the ethylene oligomerization that has reduced capital and operating expenses, reduced heavy wax formation or easy removal, as well as removal improved heat.
    [013] This objective is achieved by a process for the oligomerization of ethylene, which comprises the steps of: a) oligomerization of ethylene in a reactor in the presence of solvent and catalyst; b) transfer the surplus effluent from the reactor to an externally located cooling device and recycle the condensed effluent in the reactor; c) transfer the reactor bottom effluent to a series of fractionation columns and, in the order below, i) optionally separate the C4 fraction, ii) separate the C6 fraction, iii) simultaneously separate the C8 and C10 fractions and recycle them in the reactor, and iv) separate the residues comprising fractions of> C12, spent catalyst, polymer material and air-cooling means, from the process, in which the solvent is separated in any of the steps i) a iv) and / or in an additional step.
    [014] It is evident to a person skilled in the art that, depending on the choice of a solvent, it can be removed in several positions. For example, if toluene is used as a solvent, there is a solvent removal step between steps ii) and iii) preferably. The solvents can be chosen so that the solvent removal step occurs together with any of the steps i) to iv) or the solvent can be chosen, such as toluene, so that an additional step is added in the process.
    [015] While the surplus effluent from the condensed reactor, as well as the C8 and C10 fractions, are recycled in the reactor, all other fractions obtained can be further processed, as desired, however, cannot be recycled in the reactor. In particular, the most desirable C6 fraction is preferably further processed for purification to allow its use, for example, in copolymerizing it with ethylene.
    [016] In a preferred embodiment, the catalyst comprises (1) a chromium compound, (2) 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, R2, R3, R4, R5, R6 and R7 are independently selected from halogen, amino, trimethylsilyl, C1-C10 -alkyl, C6-C20 aryl and substituted C6-C20 aryl, and (3) an activator or cocatalyst.
    [017] In another preferred embodiment, the chromium compound is selected from the group consisting of CrCl3 (THF) 3, Cr (III) acetylacetonate, Cr (III) octanoate, chromium hexacarbonyl, Cr 2-ethylhexanoate (III), benzene (tricarbonyl) -chromium, Cr (III) chloride.
    [018] Preferably, the activator or cocatalyst is selected from trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, ethyl aluminum sesquichloride, diethyl aluminum chloride, dichloride ethyl aluminum, methylaluminoxane (MAO) or mixtures thereof.
    [019] Most preferably, the process is ethylene trimerization. As the process is preferably the trimerization of ethylene to result in the production of 1-hexene, a solvent must be chosen, which is not simultaneously removed in the C6 recovery step.
    [020] The surplus of the reactor transferred and recycled in step b) preferably comprises unreacted ethylene or unreacted ethylene and butenes.
    [021] The cooling device is preferably a condenser or a series of heat exchangers.
    [022] Preferably, the surplus effluent from the reactor is cooled in the cooling device to a temperature of -30 ° C to +10 ° C, preferably -10 ° C to +5 ° C, more preferably, -5 ° C to 0 ° C, and is then recycled to the reactor.
    [023] Composition ethylene can be added to the surplus effluent from the condensed reactor to be recycled in the reactor.
    [024] The C8 and C10 fractions obtained in step iii) are preferably recycled in the reactor at a temperature of about 10 to 20 ° C.
    [025] The waste obtained in step iv) can be sent for incineration or used as fuel in an adjacent plant.
    [026] The C4 content in the reactor is preferably 5 to 30 weight percent, the C8 content is 1 to 2 weight percent, and / or the C10 content in the reactor is 5 to 10 weight percent, all weight percentages are given based on the total weight of liquids contained in the reactor.
    [027] Preferably, the total content of linear alpha-olefins in the liquid is 30 to 75% by weight, preferably 30 to 55% by weight, based on the total weight of the liquids contained in the reactor. As can be seen in Table 3, below, the total LAO content without ethylene (ie liquid product) is about 38%. In addition, the LAO / solvent ratio is preferably about 50%.
    [028] Finally, the reactor can be a multitubular reactor and / or a bubble column reactor.
    [029] Surprisingly, it was found that the process for the oligomerization of ethylene, preferably the trimerization of ethylene, according to the present invention, provides reduced operational and capital expenses, allows an easy removal of heavy wax formed in the reactor or reactor e-equipment, and improves heat removal from exothermic oligo- merization.
    [030] According to the present invention, the two separate distillation columns, each for C8 and C10 used in the art, are, according to the present invention, combined into a single column. This can be used advantageously and the process of the present invention is preferably catalyzed by chromium and produces a very limited amount of oligomers other than C6. Saving a column definitely reduces the overall investment cost of the entire process.
    [031] In addition, the biggest challenge of existing ethylene oligomerization processes is the efficient removal of heat from the exothermic reaction. Some commercial processes used, until now, excess ethylene to cool the reactor to the desired temperature that favors the activity and selectivity of the catalyst. However, with such excess ethylene, the ethylene conversion per pass is very low for bubble column reactors, resulting in a significant load on the C2 recovery column and, therefore, higher operating costs. The invention process can be conceived now that some of the heat of the reaction is removed by the latent heat of evaporation of C2 / C4 condensed from the bottom of the condenser, as well as the sensitive heat from heavy LAO that are routed back to the reactor.
    [032] Additionally, a well-known inherent disadvantage of chromium-based ethylene oligomerization catalyst is the formation of heavy wax. This solid residue (mostly polyethylene and heavy waxes) tends to cause clogging / fouling inside the reactor and the reactor equipment. This is especially the case when it comes to a bubble column reactor in which the condenser is located inside the reactor.
    [033] In such projects, the internal condenser acts as an additional surface for accumulations of solids, in such a way that the reactor needs to be periodically deactivated for cleaning. A situation that causes interruption of continuous operation. The process of the invention overcomes disadvantage and prevents the use of any internal equipment in the ethylene trimerization reactor, while at the same time providing the same cooling capacity to maintain the reactor temperature and / or mobilize waste solids out of the reactor to reduce fouling.
    [034] The process of the present invention is practiced in a way that the blocking of the reactor by polymer materials or waxes is significantly reduced by dissolving the polymer materials in higher fractions of C8 and C10 present inside the reactor equipment . Polymer materials are known to be more soluble in heavier end olefins than in lighter end olefins. By recycling the C8 and C10 fractions in the reactor, the flow time of the process of the invention can be significantly extended. In addition, the process of the invention can be operated at a reduced temperature by adjusting the reactor content in view of both fractions, C8 and C10, which also improve the ethylene solubility. This will also potentially benefit the catalyst activity.
    [035] In a preferred embodiment, if condensed C2 and C4 are sent to the reactor as liquid flows, instead of gaseous flows, this will significantly improve the cooling of the oligomerization reactor using a significant portion of the reaction heat, such as heat latent evaporation.
    [036] The advantages and additional resources of the process of the invention can be obtained from the following detailed description of a preferred modality, along with the drawings, in which
    [037] Fig. 1 shows a schematic illustration of a state of the art commercial process for o-ligomerization; and
    [038] Fig. 2 is a schematic illustration of the process of the present invention.
    [039] As for the process illustrated in Fig. 1, also in Fig. 2, solvent 20 (optionally with fresh composition solvent), catalyst 30 and ethylene 40 (optionally with fresh composition ethylene 60) are introduced -zones in a reactor 10 for oligomerization. The effluent from ex-transferor from the reactor, which preferably contains ethylene and butenes, is transferred to a cooling device located externally 50 and is recycled, with fresh ethylene composition or directly, in the reactor 10. The reactor bottom effluent is discharged from the reactor 10 and transferred to a cooling unit 70 where the cooling medium is added. The cooled reactor bottom effluent is then transferred to a series of fractionation columns 80 to 110, in which, in the first fractionation column 80, the ethylene dissolved in the solvent and the butenes are separated together and transferred to the cooling device 50 to finally be recycled in the reactor 10. In the fractionation column 90, the hexenes are separated and discharged for further processing. If, for example, toluene is used as a solvent, it can be removed and separated in the fractionation column 100. Finally, the fractions of C8 and C10 are removed and separated simultaneously (together) in the fractionation column 110. The C8 and C10 fractions are recycled to the reactor 10, while any additional waste can then be transferred for further processing.
    [040] Illustrative modalities
    [041] A multi-compartment reactor model was developed to handle detailed hydrodynamics, thermodynamics and the variable gas flow rate resulting from chemical / physical contraction, and gas / liquid recirculation in a gas reactor. bubble column. The re-actor model was coupled with a mechanistic kinetic model developed specifically for the new ethylene trimerization catalyst system described in US 20120029258. The model was used to analyze a modality of the present invention. The performance of a pilot scale bubble column reactor for the ethylene trimerization process for this modality of the present invention was verified with the developed rigorous reactor model.
    [042] In addition, a comparative example is provided, which illustrates a process for oligomerization known in the art, however, which uses an extermally located condenser with a total reflux to separate unconverted ethylene from effluent from the top of the reactor. The separated ethylene is combined with composition ethylene and ethylene from the C2 column, which is recycled back to the reactor. Thus, in this comparative example, the feed gas composition is, for the most part, ethylene, that is, 98 to 99% by weight of C2. 1-butene is not present in the ethylene recycling stream and there is no recycling of C8 and C10 fractions in the reactor. Comparative example
    [043] Table 1: Flow analysis for the comparative example with a suspended condenser that has full reflux and no C4 recycling

    [044] The flow analysis of comparative example 1 is shown in Table 1. The key process performance indicators (KPIS) are shown in Table 2. Table 2

    [045] As shown in Table 2, the conversion of ethylene by passing ~ 6% by weight was achieved with a condenser operation of -7.5 kW operated at -2 ° C. Example of the invention
    [046] Ethylene and 1-butene are sent directly to the externally located condenser after passing through a heat exchanger to reduce the temperature to about 35 ° C. Condensed ethylene / 1-butene enters the reactor as flows of liquid, preferably from the top of a disengagement zone, even more preferably from the side facing the reaction zone for effective cooling. The ethylene / 1-butene content in the reactor can be maintained between 5 to 30% by weight through a purge flow.
    [047] Similarly, decenos / 1-octene from the top of the 1-C8 / C10 fractionation column is routed back to the reactor after being cooled from 170 ° C to 10 ~ 20 ° C. The decene content in the reactor can be maintained between 5 to 10% by means of a purge flow. An additional operation to cool the recycled 1-C8 / C10 to lower temperatures can be considered. Nevertheless, the extra benefits provided by the recycled heavy fraction for the mobilization of polymer and the reactor cooling in the form of sensitive heat prevent this operation.
    [048] Table 3 shows the flow analysis, while Table 4 illustrates the key process indicators for this invention process.
    [049] Table 3: Flow analysis for the preferred embodiment of the present invention with recycled C2 / C4 as liquid flows and recycled 1-octene / decades.
    Table 4


    [050] As shown in the illustrative example, the ethylene conversion per pass is ~ 8% with -5 kW condenser operation operated at 1 ° C. This modality features an ethylene feed rate of less than 50 kg / h.
    [051] The features of the invention presented in the description above and in the claims can be essential to implement the invention in its various modalities, both individually and in any combination.
    权利要求:
    Claims (14)
    [0001]
    1. PROCESS FOR ETHYLENE OLIGOMERIZATION, characterized by comprising: a) oligomerization of ethylene in a reactor in the presence of solvent and catalyst; b) transfer a surplus effluent from the reactor to an externally located cooling device and recycle the condensed effluent in the reactor; c) transfer a reactor bottom effluent to a series of fractionation columns and, in the following order, i) optionally separate a fraction of C4, ii)) separate a fraction of C6, iii)) simultaneously separate the fractions of C8 and C10 and recycle the fractions of C8 and C10 in the reactor, and iv) separate residues comprising fractions of> C12, spent catalyst, polymer material and cooling media, from the process, in which the solvent is separated in any of the steps i ) to iv) and / or in an additional step.
    [0002]
    2. PROCESS according to claim 1, characterized in that the catalyst comprises (1) a chromium compound, (2) 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, R2, R3, R4, R5, R6 and R7 are independently selected from halogen, amino, trimethylsilyl, C1-C10 alkyl, C6-C20 aryl and substituted C6-C20 aryl, and (3) an activator or cocatalyst.
    [0003]
    3. PROCESS, according to claim 2, characterized in that the chromium compound is selected from the group consisting of CrCl3 (THF) 3, Cr (III) acetylacetonate, Cr (III) octanoate, chromium hexacarbonyl, 2- Cr (III) ethylhexanoate, benzene (tricarbonyl) -chromium and Cr (III) chloride.
    [0004]
    4. PROCESS, according to claim 2, characterized in that the activator or cocatalyst is selected from trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, ethyl aluminum sesquichloride, diethyl aluminum chloride, dichloride ethyl aluminum, methylaluminoxane (MAO) or mixtures thereof.
    [0005]
    PROCESS, according to claim 1, characterized by the oligomerization of ethylene comprising the trimerization of ethylene.
    [0006]
    6. PROCESS, according to claim 1, characterized by the surplus of the reactor transferred and recycled in step b) comprising unreacted ethylene.
    [0007]
    7. PROCESS, according to claim 1, characterized in that the cooling device located externally is a condenser or a series of heat exchangers.
    [0008]
    8. PROCESS, according to any one of the preceding claims, characterized in that the surplus effluent from the reactor is cooled in the cooling device located externally to a temperature of - 30 ° C to + 10 ° C, preferably -10 ° C to + 5 ° C, more preferably -5 ° C to 0 ° C, and then be recycled in the reactor.
    [0009]
    9. PROCESS, according to claim 1, characterized in that the composition ethylene is added to the surplus effluent from the condensed reactor to be recycled in the reactor.
    [0010]
    10. PROCESS, according to claim 1, characterized in that the fractions of C8 and C10 obtained in step iii) are recycled in the reactor at a temperature of about 10 to 20 ° C.
    [0011]
    11. PROCESS, according to claim 1, characterized in that the waste obtained in step iv) is sent for incineration or used as fuel in an adjacent plant.
    [0012]
    12. PROCESS, according to claim 1, characterized in that the C4 content in the reactor is 5 to 30 weight percent, the C8 content is 1 to 2 weight percent, and / or the C10 content in the reactor is 5 to 10 weight percent, all weight percentages given are based on the total weight of the liquids contained in the reactor.
    [0013]
    13. PROCESS, according to claim 1, characterized in that the total content of linear alpha-olefins in the liquids contained in the reactor is 30 to 75 weight percent based on the total weight of the liquids contained in the reactor.
    [0014]
    14. PROCESS, according to claim 1, characterized in that the reactor is a multitubular reactor and / or a bubble column reactor.
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    法律状态:
    2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-08-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-08| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 05/09/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP12194589.3|2012-11-28|
    EP12194589.3A|EP2738151B8|2012-11-28|2012-11-28|Process for oligomerization of ethylene|
    PCT/EP2013/002670|WO2014082689A1|2012-11-28|2013-09-05|Process for oligomerization of ethylene|
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