• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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    • 专利摘要:

    公开号:BR112012001656B1
    申请号:R112012001656
    申请日:2010-05-28
    公开日:2018-10-16
    发明作者:Al-Dugathier Abdullah；Meiswinkel Andreas；Wöhl Anina；H Müller Bernd；Reddy Aluri Bhaskar；Taube Carsten；Winkler Florian；Mosa Fuad；BÖLT Heinz；Fritz Helmut；Al-Hazmi Mohammed；Peulecke Normen；M FRITZ Peter；Schneider Richard；Majeed Azam Shahid；Peitz Stephan；Rosenthal Uwe；Göke Volker；Müller Wolfgang
    申请人:Linde Ag；Saudi Basic Ind Corp；
    IPC主号:
    专利说明:

    (54) Title: METHOD FOR THE PREPARATION OF LINEAR ALPHA-OLEFINS (51) lnt.CI .: C07C 2/30; C07C 11/02 (30) Unionist Priority: 24/07/2009 EP 09 009599.3 (73) Holder (s): LINDE AG. SAUDI BASIC INDUSTRIES CORPORATION (72) Inventor (s): PETER M. FRITZ; HEINZ BÕLT; ANDREAS MEISWINKEL; CARSTEN TAUBE; FLORIAN WINKLER; VOLKER GÕKE; WOLFGANG MÜLLER; ANINA WÕHL; RICHARD SCHNEIDER; UWE ROSENTHAL; HELMUT FRITZ; BERND H. MÜLLER; NORMEN PEULECKE; STEPHAN PEITZ; BHASKAR REDDY ALURI; MOHAMMED AL-HAZMI; SHAHID MAJEED AZAM; FUAD MOSA; ABDULLAH AL-DUGATHIER (85) National Phase Start Date: 24/01/2012
    1/9
    Descriptive Report of the Invention Patent for METHOD FOR THE PREPARATION OF LINEAR ALPHA-OLEFINS ”.
    Description [001] The present invention relates to a method for preparing linear alpha-olefins (LAO).
    [002] The processes for ethylene oligomerization using homogeneous catalysts are widely known. For example, DE 43 38 414 C1 discloses a process for the oligomerization of ethylene to obtain linear alpha-olefins, where ethylene is catalytically converted into an empty tubular reactor using a catalyst comprising a zirconium component and an aluminum component. The process is advantageously carried out in a continuous manner in which the gaseous and liquid outflow currents are obtained. The liquid outlet stream usually contains solvent, catalyst, dissolved ethylene and linear alpha-olefins. The catalyst can preferably be caustic deactivated. Preferably, the deactivated catalyst is also extracted from the phase containing solvent, ethylene and alpha-olefins.
    [003] DE 198 07 226 A1 discloses the deactivation of the oligomerization catalyst with an aqueous solution of sodium hydroxide (caustic), in which the deactivated catalyst is transferred from the organic phase to the aqueous phase.
    [004] From operational experience, it was known that the decommissioning step must be performed quickly and effectively. Otherwise, there is a chance of degradation of the product through unwanted side reactions that have an influence on the purity of the product. The efficiency of removing the catalyst can be enhanced by static or active mixing devices. However, these systems turned out not to be ideal for the application due to the high installation costs, respective requirements of intensive maintenance.
    Petition 870180053372, of 6/21/2018, p. 13/25
    2/9 [005] As another disadvantage of known processes, it was observed that both the formation of organic chlorides as well as alkylated toluenes by Friedel-Crafts alkylation occur.
    [006] It is, therefore, an objective of the present invention to provide a method for the preparation of linear alpha-olefins that overcome the drawbacks of the prior art, especially to provide a method including deactivation and removal of the catalyst resulting in better product purity , suppression of unwanted side reactions, less energy requirements for mixing, no requirement for sophisticated mixing devices and which allows on-line cleaning of piping and equipment. Likewise, the formation of organic chlorides and toluenes alkylated by Friedel-Crafts alkylation must be avoided.
    [007] This objective is achieved by a method for the preparation of linear alpha-olefins (LAO) through the oligomerization of ethylene in the presence of a homogeneous solvent and catalyst, comprising the steps of:
    (i) feeding ethylene, solvent and catalyst into an oligomerization reactor, (ii) oligomerizing ethylene in the reactor, (iii) removing a stream from the reactor comprising solvent, linear alpha-olefins, optionally unreacted ethylene and catalyst of the reactor through a reactor outlet piping system, (iv) administer in doses at least one additive selected from the group consisting of alcohols, polyethylene glycols, polyethylene glycol monoethers, polyethylene glycol diethers, polyamines, amines, amino alcohols and surfactants, (v) transfer the reactor output current containing the additive to a catalyst deactivation and removal section, and
    Petition 870180053372, of 6/21/2018, p. 14/25
    3/9 (vi) deactivate the catalyst with caustic and remove the deactivated catalyst from the reactor output current, where the additive dwell time in the reactor output current before mixing with caustic is at least 1 second, preferably at least 5 seconds, more preferably at least 10 seconds.
    [008] It is preferable that the additive is selected from MOR, HO (CH 2 -CH 2 ) n-OH, HO- (CH 2 -CH 2 ) n -OR, RO- (CH 2 -CH 2 ) n -OR , R ' 2 N [(CH 2 ) n ] -NR' 2 , R ' 3 N, R' 2 N - [(CH 2 ) n ] -OR 'with M = alkali metal, R = alkyl or aryl, R '= H, alkyl or aryl and n = 3 - 300.
    [009] Preferably, the amine is an organic amine, preferably a primary, secondary, tertiary or cyclic amine, more preferably selected from t-butyl amine, triethyl amine, cyclopentyl amine, t-octyl amine, n-heptyl amine, 2-heptyl amine, hexyl amine, 2-ethylexyl amine, diexyl amine, 1,6-diamino hexane, tributyl amine, 1,8-diamino octane, n-dodecyl amine, 3-ethylptyl amine and tris-2-ethyl hexyl amine .
    [0010] More preferably, the additive is added continuously to the reactor output current.
    [0011] In one embodiment, the additive is added in an amount of 500 to 5000 ppm by weight with reference to the flow rate of the reactor output current.
    [0012] The dosage amount is determined by the following two questions:
    • The amount required in a certain stoichiometric ratio right for the catalyst and the co-catalyst rates as introduced in the LAO reactor • The amount obtained from practical operational experience in order to carry out the online cleaning effects described for the reactor outlet piping.
    Still preferable, the additive is soluble in an organic phase
    Petition 870180053372, of 6/21/2018, p. 15/25
    4/9 containing linear alpha-olefins.
    [0013] In another preferred embodiment the additive is substantially insoluble or has a low solubility in water or a mixture of water and caustic.
    [0014] The additive can preferably be removed from the reactor outlet current or a fraction of the product through distillation, extraction, adsorption or ion exchange.
    [0015] More preferably, the removed additive is recycled to the reactor outlet stream when removed from the reactor.
    [0016] In a preferred embodiment, the additive is mixed with the outflow of the reactor by means of a mixing device, preferably a static mixer, a dynamic mixer, a supersonic mixer or a Venturi mixing nozzle.
    [0017] It is preferable that the catalyst comprises a zirconium salt of organic acid and at least one organoaluminium compound. [0018] Still preferable, the zirconium salt has the formula ZrCU-mXm, where X = OCOR or OSOeR 'with R and R' being independently alkyl, alkene or aryl, preferably phenyl, and where 0 <m <4 .
    [0019] It is still preferable that the at least one aluminum compound has the general formula R 1 nAl3-n or AbYsRS, where R 1 represents an alkyl group having from 1 to 20 carbon atoms, Y represents Cl, Br or I, n is any number within the range of 1 <n <2. [0020] Surprisingly, it was observed that the dosage of an additive selected from the group as disclosed above for the reactor output current before mixing the output current of the reactor with aqueous caustic only under certain very specific conditions significantly improves the efficiency of the catalyst removal section without obtaining any unwanted side reactions. Thus, the purity of the product can be improved. It was surprisingly observed that there is a minimum residence time required for
    Petition 870180053372, of 6/21/2018, p. 16/25
    5/9 the additive until its impact on the system is evolved. This minimum dwell time is at least 1 second.
    [0021] It has also been observed that a simple combination of amine dosage and caustic deactivation will in no way be sufficient for the intended purpose. It is a main feature of the invention that surprisingly a certain minimum residence time between dosing the additive and the caustic is required.
    [0022] All the disclosed additives are observed to be responsible for avoiding Friedel-Crafts alkylations of the solvent used, as well as the formation of organic chlorides, especially by preventing the formation of HCI that forms organic chlorides with LAOs, or with the formed organic chlorides and the solvent, preferably toluene, alkylated solvents.
    [0023] In addition, it is important to note that the place of addition of the additive is essential. For example, the dosing of additives in the caustic stream will not work, as well as the simultaneous mixing of all currents, that is, the additive current, reactor output current and caustic current, will not solve all these issues. Rather, it is absolutely necessary for the additive to be introduced into the reactor outlet current close to the LAO reactor outlet, with a sufficient dwell time before the point of mixing with the caustic stream.
    [0024] Without wishing to be limited to any theory, it is believed that the additive used in the method of the invention can reduce the interfacial tension between the hydrocarbon LAO phase and the aqueous caustic phase, leading to the formation of smaller droplet sizes, and finally improving the solubility of the catalyst deactivation products in the aqueous caustic phase.
    [0025] Only in the case where the additive is dosed in the reactor output current as illustrated, the following benefits can be
    Petition 870180053372, of 6/21/2018, p. 17/25
    6/9 achieved:
    - the effective mixture of LAO / caustic has become much easier,
    - the purities of the product have been improved due to the suppression of unwanted side reactions,
    - heterogeneity and critical points in the l_AO / caustic mixing stage have not yet been observed, and
    - maintenance requirements for a mixer are reduced.
    - fouling / clogging of LAO reactor outlet piping is avoided due to the online cleaning effect (ie, removal of rust particles and materials from the equipment surfaces and pipe walls, using the surfactant effects) . [0026] The additional aspects and advantages of the present invention will now become apparent from the detailed description of a preferred embodiment thereof.
    [0027] Ethylene is oligomerized in a suitable reactor, for example, an empty tubular reactor as disclosed in DE 43 38 414 C1, using a catalyst comprising a zirconium compound and an aluminum component. A suitable zirconium component is zirconium tetraisobutyrate, and a suitable aluminum component is ethyl aluminum sesquichloride.
    [0028] Oligomerization is carried out under conditions (temperature, pressure, etc.) known in the art. Ethylene, solvent and catalyst are introduced and oligomerization is started. From the reactor, a liquid organic outlet stream is discharged into a reactor outlet piping system containing solvent, for example, toluene, catalyst, ethylene dissolved in the solvent, and linear alpha-olefins. To this liquid organic outlet stream, an additive selected from the group of non-ionic surfactants and amines, for example, n-dodecyl amine, is administered in doses. The mixing of the reactor output current and
    Petition 870180053372, of 6/21/2018, p. 18/25
    7/9 of the additive is for at least 1 second, before adding lye to a catalyst deactivation and removal section. However, the residence time should not exceed a period of 100 seconds, since otherwise the additive is already deactivated because it suffers from different stages of unwanted reaction and has lost its activity due to the expected positive effects. The catalyst is then caustically deactivated and removed from the outlet stream. The caustic phase may contain alkali metal hydroxide, preferably NaOH and / or KOH. After deactivation, the deactivated catalyst will be present in the aqueous phase and can be removed as is known in the art. [0029] After the catalyst deactivation and removal section, the amine can be removed from the LAO products (the remaining reactor output current) through conventional distillation, extraction or adsorption. The remaining traces of the amine in the products can be additionally removed by suitable protective adsorbents, depending on the required product specification.
    [0030] Friedel-Crafts alkylation prevention has been demonstrated by the following experiments:
    Laboratory Experiment No. 1: Basic experiment without additive [0031] In the laboratory 20 mL of toluene, 10 mL of 1-hexene, 5 mL of EASC solution and 20 mL of ZrCI4 solution were mixed in a flask at room temperature and under inert nitrogen atmosphere.
    [0032] Under intense agitation the mixture was quenched with 50 ml of 20% by weight sodium hydroxide solution.
    [0033] Then the agitation was turned off. After phase separation of the hydrocarbon phase and the aqueous phase by gravity, the hydrocarbon phase was analyzed and presented high amounts of alkylated toluene.
    Laboratory Experiment No. 2: Experiment with an amine as a
    Petition 870180053372, of 6/21/2018, p. 19/25
    8/9 additive (residence time 30 seconds) [0034] In the laboratory 20 ml of toluene, 10 ml of 1-hexene, 5 ml of EASC solution and 20 ml of ZrCI4 solution and 1 ml of ethylexyl amine were mixed in a flask at room temperature and under an inert nitrogen atmosphere for 30 seconds.
    [0035] Under intense agitation the mixture was quenched with 50 ml of 20% by weight sodium hydroxide solution.
    [0036] Then the agitation was turned off. After the phase separation of the hydrocarbon phase and the aqueous phase by gravity, the hydrocarbon phase was analyzed and showed no alkylated toluene.
    Laboratory Experiment No. 3: Experiment with amine as an additive (simultaneous addition) [0037] In the laboratory 10 mL of toluene, 10 mL of 1-hexene, 5 mL of EASC solution and 20 mL of ZrCI4 solution were mixed in a flask at room temperature and under an inert nitrogen atmosphere. In a second flask 10 ml of toluene and 1 ml of ethylhexyl amine were mixed.
    [0038] Under intense agitation, both mixtures were poured into a 50 ml solution of sodium hydroxide of 20% by weight simultaneously.
    [0039] Then the agitation was turned off. After the phase separation of the hydrocarbon phase and the aqueous phase by gravity, the hydrocarbon phase was analyzed and showed a little alkylated toluene, but less than in Experiment No. 1.
    Laboratory Experiment No. 4: Experiment with amine as an additive in the sodium hydroxide solution [0040] In the laboratory 20 mL of toluene, 10 mL of 1-hexene, 5 mL of EASC solution and 20 mL of ZrCI4 solution were mixed in a flask at room temperature and under a nitrogen atmosphere
    Petition 870180053372, of 6/21/2018, p. 20/25
    9/9 inert.
    [0041] Under intense agitation the mixture was quenched with a mixture of 50 ml of 20% by weight sodium hydroxide solution and 1 ml of ethylhexyl amine.
    [0042] Then the agitation was turned off. After phase separation of the hydrocarbon phase and the aqueous phase by gravity, the hydrocarbon phase was analyzed and presented almost the same amount of alkylated toluene as in Experiment No. 1.
    [0043] These simple experiments clearly confirm the importance and the positive effect of the combination of an additive and the caustic for the prevention of undesirable side reactions in the deactivation and catalyst removal section of the LAO process. It becomes clear that the positive effect of the additive is also a function of the additive's residence time in the reactor output stream before mixing with caustic.
    [0044] The need for an adequate residence time in order to have a positive impact on the formation of toluene alkyl can also be seen in the attached graph, which was prepared based on the analysis of the laboratory experiments.
    [0045] The aspects disclosed in the following description and in the claims may, both separately and in any combination thereof, be material for the realization of the invention in its various forms.
    Petition 870180053372, of 6/21/2018, p. 21/25
    1/3
    权利要求:
    Claims (13)
    [1]
    1. Method for the preparation of linear alpha-olefins (LAO) by means of ethylene oligomerization in the presence of a solvent and a homogeneous catalyst, characterized by the fact that it comprises the steps of:
    (i) feeding ethylene, solvent and catalyst into an oligomerization reactor, (ii) oligomerizing ethylene in the reactor, (iii) removing a stream from the reactor comprising solvent, linear alpha-olefins, optionally unreacted ethylene and catalyst of the reactor through a reactor outlet piping system, (iv) administer in doses at least one additive selected from the group consisting of polyamines, amines and amino alcohols.
    (v) transfer the reactor output current containing the additive to a catalyst deactivation and removal section, and (vi) caustic deactivate the catalyst and remove the deactivated catalyst from the reactor output current; and since the additive dwell time in the reactor output current, before mixing with caustic, is at least 10 seconds and does not exceed a period of 100 seconds.
    [2]
    2. Method, according to claim 1, characterized by the fact that the additive is selected from R'2N - [(CH2) n] -NR'2, R'3N, or R ' 2 N - [(CH 2 ) n] -OR ', where R' = H, alkyl or aryl, and n = 3 - 300.
    [3]
    3. Method according to claim 1 or 2, characterized by the fact that the amine is an organic amine.
    [4]
    Method according to any one of claims 1 to 3, characterized in that the additive is added continuously to the reactor output stream.
    [5]
    5. Method according to any of the claims
    Petition 870180053372, of 6/21/2018, p. 22/25
    2/3
    1 to 4, characterized by the fact that the additive is added in an amount of 500 to 5000 ppm by weight.
    [6]
    Method according to any one of claims 1 to 5, characterized in that the additive is soluble in an organic phase containing linear alpha-olefins.
    [7]
    Method according to any one of claims 1 to 6, characterized in that the additive is substantially insoluble or has a solubility in water or a mixture of water and caustic of less than 5 mol%.
    [8]
    Method according to any one of claims 1 to 7, characterized by the fact that the additive is removed from the reactor outlet stream or a fraction of the product by distillation, extraction, adsorption or ion exchange.
    [9]
    9. Method according to claim 8, characterized by the fact that the removed additive is recycled in the reactor output stream removed from the reactor.
    [10]
    Method according to any one of claims 1 to 9, characterized in that the additive is mixed with the reactor outlet current by means of a mixing device.
    [11]
    11. Method according to any one of claims 1 to 10, characterized in that the catalyst comprises a zirconium salt of organic acid and at least one organoaluminium compound.
    [12]
    12. Method, according to claim 11, characterized by the fact that the zirconium salt has the formula
    ZrCU-mXm, in which
    X = OCOR or OSOeR ', with R and R' independently being alkyl, alkene or aryl, preferably phenyl, and
    0 <m <4.
    Petition 870180053372, of 6/21/2018, p. 23/25
    3/3
    [13]
    13. Method according to claim 11 or 12, characterized by the fact that at least one aluminum compound has the general formula
    R 1 nAl3-n or AI 2 Y 3 R 1 3, in which
    R 1 represents an alkyl group having from 1 to 20 carbon atoms,
    Y represents Cl, Br or I, and n is any number within the range of 1 <n <2.
    Petition 870180053372, of 6/21/2018, p. 24/25
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    法律状态:
    2018-03-27| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2018-07-24| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2018-10-16| 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 28/05/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP09009599.3A|EP2287142B1|2009-07-24|2009-07-24|Method for preparing linear alpha-olefins|
    PCT/EP2010/003285|WO2011009509A1|2009-07-24|2010-05-28|Method for preparing linear alpha-olefins|
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