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    • 专利摘要:
    processes for separating a hydrocarbon stream from multiple components, and ethylene oligomerization. a process (8, 108) for separating a multi-component hydrocarbon stream (10.1) that includes ethylene and other components, with at least some components being present in a plurality of phases, is disclosed. the process (8, 108) includes, in a first flash vaporization stage (16), flash vaporization of the multi-component hydrocarbon stream (10.1) from an elevated pressure and temperature to a pressure in the range of 10 to 18 bar, producing a first steam stream containing ethylene (16.1) at a pressure in the range of 10 to 18 bar and a multi-band stream (16.2) that includes some ethylene. in a second instantaneous vaporization stage (20), the multiphase stream (16.2) is instantaneously vaporized at a pressure of less than 6 bar, producing a second vapor stream (20.1) at a pressure of less than 6 bar and an undercurrent (20.2). the first steam stream containing ethylene (16.1) is removed from the first flash vaporization stage (16), the second stream of steam (20.1) is removed from the second flash vaporization stage (20) and the bottom stream (20.2) is removed from the second flash vaporization stage (20).
    公开号:BR112012008987B1
    申请号:R112012008987-0
    申请日:2010-10-01
    公开日:2021-08-24
    发明作者:Johannes Jochemus Gildenhuys；Andrew Kenneth Stone；William Francis Revelt
    申请人:Sasol Technology (Proprietary) Limited；
    IPC主号:
    专利说明:

    [0001] This invention relates to the separation of the components of a multi-component hydrocarbon stream that includes ethylene. In particular, the invention relates to a process for separating a multi-component hydrocarbon stream, which includes components in a plurality of phases and ethylene, and to an ethylene oligomerization process that includes this separation process.
    [0002] Distillation is a method of choice for many processes to separate a hydrocarbon stream from multiple components into different fractions. When the multi-component hydrocarbon stream includes solids, whether molten, dissolved or undissolved, such as polymers and waxes, it is undesirable to feed the multi-component hydrocarbon stream through distillation trays, as solids can block the trays. An example of such a multi-component hydrocarbon stream is the oligomeric product stream obtained from the oligomerization of an olefinic feedstock. An effective and economical process for separating a hydrocarbon stream from multiple components, which may include solids, should therefore be desirable.
    [0003] According to one aspect of the invention, there is provided a process for separating a multi-component hydrocarbon stream that includes ethylene and other components with at least some of the components being present in a plurality of stages, the process including: in a first stage of instantaneous vaporization, the burning of the multi-component hydrocarbon stream, at a high pressure (ie a pressure of more than 18 bar) and a high temperature (ie a temperature of more than 180 °C ) up to a pressure in the range of 10 to 18 bar, producing a first steam stream containing ethylene at a pressure in the range of 10 to 18 bar and a multiphase stream that includes some ethylene; in a second stage of instantaneous vaporization, the burning the multiphase stream at a pressure of less than 6 bar, producing a second stream of steam at a pressure of less than 6 bar and an underflow; apor containing ethylene from the first flash vaporization stage and the second stream of vapor from the second flash vaporization stage; and remove the undercurrent from the second instantaneous vaporization stage.
    [0004] In at least one embodiment of the invention, the process includes reheating the multistage stream of the first instantaneous vaporization stage before burning the multistage stream in the second instantaneous vaporization stage.
    [0005] According to a second aspect of the invention, there is provided a process for oligomerizing ethylene, the process including: in an oligomerization stage, oligomerizing ethylene and removing a multi-component hydrocarbon stream from different phases that includes the oligomeric product , the polymeric product and unreacted ethylene; heating the multi-component hydrocarbon stream in accordance with a separation process as hereinbefore described producing said first steam stream containing ethylene; and feeding the first steam stream containing ethylene to an ethylene recovery stage producing an ethylene rich stream and an ethylene-poor multicomponent hydrocarbon stream that includes oligomeric and/or polymeric product.
    [0006] The process may include the step of recovering energy from the first stream containing ethylene by heat exchange with a second stream, the second stream being or may include the multi-component hydrocarbon stream, another process stream or a stream of utility. Typically, the first steam stream containing ethylene is at least partially condensed during such a heat exchange step.
    [0007] The multiphase stream can be predominantly a liquid stream that includes solids and optionally entrained gas.
    [0008] In this specification the term "solids" is intended to include materials such as polyethylene, waxes, catalysts and catalyst deactivation products, whether molten, partially molten or dissolved under the process conditions of the multi-component hydrocarbon stream. Also, in this specification, the term “condense” includes a phase change from gas to liquid and the term “compress” does not include a phase change.
    [0009] The multiphase stream is preferably instantaneously vaporized in the second instant vaporization stage at a pressure between about 1 bar and about 6 bar, more preferably between about 2 bar and about 5 bar, for example between about 2 bar and about 4 bar. In some embodiments of the invention, however, a negative gauge pressure, i.e. a subatmospheric pressure, can be used in the second stage of instantaneous vaporization.
    [0010] Preferably, in the first flash vaporization stage, the multi-component hydrocarbon stream is flash vaporized from an elevated temperature of at least 185 °C, preferably an elevated temperature of at least 190 °C, more preferably a temperature high pressure of at least 195 °C, and a high pressure of more than 30 bar. The first steam stream containing ethylene is thus typically defining a higher mass flow of ethylene and is at a higher pressure than the second stream of steam.
    [0011] Typically, in the first flash vaporization stage the multi-component hydrocarbon stream is flash vaporized at a temperature of at least 120 °C, preferably at least 150 °C, more preferable at least 170 °C, for example between about 175 °C and about 190 °C.
    The high pressure may be between about 30 bar and about 50 bar, preferably between about 40 bar and about 50 bar, more preferably between about 46 bar and about 50 bar.
    [0013] The process according to the first aspect of the invention may include separating at least a portion of the ethylene from the first steam stream containing ethylene. Thus, the first steam stream containing ethylene can be subjected to at least one ethylene recovery stage producing an ethylene rich stream and an ethylene-poor multicomponent hydrocarbon stream.
    [0014] Typically, the ethylene recovery stage employs at least one distillation column. The ethylene recovery stage and, in particular, said distillation column, can be operated at the same pressure as the first flash vaporization stage, minus any pressure drop caused by the intervening process equipment. The ethylene recovery stage, and in particular said distillation column, can thus operate at a pressure in the range of about 10 to 18 bar, preferably of about 10 to 15 bar.
    [0015] The first steam stream containing ethylene is typically not recompressed before being fed to the ethylene recovery stage, but is preferably at least partially condensed before being fed to said ethylene recovery stage.
    [0016] The process according to the second aspect of the invention may include the additional step of recycling the ethylene rich stream to the oligomerization stage.
    [0017] The ethylene-poor multi-component hydrocarbon stream may include a solvent for an ethylene oligomerization catalyst.
    [0018] The process may include combining the low ethylene multi-component hydrocarbon stream from the ethylene recovery stage and the second steam stream from the second flash vaporization stage. Typically, the pressure of the low ethylene multi-component hydrocarbon stream is thus weakened to the pressure of the second steam stream.
    [0019] The process may include solvent recovery from the combined ethylene-poor multi-component hydrocarbon stream streams from the ethylene recovery stage and the second steam stream from the flash vaporization second stage, for example, by distillation .
    [0020] The process with the first aspect of the invention may include heating the multi-component hydrocarbon stream to a desired temperature, prior to instantaneously vaporizing the multi-component hydrocarbon stream in the first instantaneous vaporization stage.
    [0021] The heating of the multi-component hydrocarbon stream can be carried out in a heat exchanger, for example, with the use of high pressure steam or hot oil. Alternatively, or in addition, heating the multi-component hydrocarbon stream can be effected by direct contact heating or mixing with a hot process stream, producing a combined stream that is then instantaneously vaporized in the first instantaneous vaporization stage .
    [0022] In at least one embodiment of the invention, at least some of the heat for heating the multi-component hydrocarbon stream is provided by the first steam stream containing ethylene.
    [0023] The ethylene-poor multi-component hydrocarbon stream from the ethylene recovery stage may include 1-hexene, 1-octene and 1-butene. The multi-component hydrocarbon stream can also include cyclic by-products, aliphatic or aromatic solvent, ethane, very little, if any amount, of methane, and polymer(s). Most methane and ethane, in fact, concerns the first steam stream containing ethylene.
    [0024] In the oligomerization stage, ethylene is preferably oligomerized at an elevated pressure of at least 30 bar, and at an elevated temperature, typically at least 40 °C. The elevated pressure can be between about 30 bar and about 50 bar, preferably between about 40 bar and about 50 bar, more preferably between about 46 bar and about 50 bar. The elevated temperature of the oligomerization stage is typically between about 40°C and about 80°C, for example about 60°C.
    [0025] In an embodiment of the invention, the process according to the second aspect of the invention is a process of oligomerization of ethylene over a wide range, employing a catalyst system and producing a Schulz Flory or Poisson distribution of olefins . The process olefins find application as a feedstock for detergents, plasticizing alcohols, linear alkyl benzenes and as comonomers for the production of polyethylene. Non-limiting examples of such catalyst systems are nickel-based systems, carrying α-diimine ligands and activated by a dialkyl aluminum halide cocatalyst (for example, as described in WO 0010945), or nickel-based systems. nickel having chelating ligands such as 2-diphenylphosphine benzoic acid in combination with a borohydride reducing agent (for example, as described in US 3,676,523). Equally possible is the use of aluminum trialkyl catalysts to produce a wide range of alpha-olefins.
    [0026] In another embodiment of the invention, the process according to the second aspect of the invention is predominantly a trimerization of the ethylene process. The trimerization of ethylene in 1-hexane is a significant commercial operation. In addition to its use as a specific chemical, 1-hexene is extensively used in polymerization processes or as a monomer or comonomer. Non-limiting examples of ethylene trimerization catalyst systems are provided in a review by J.T. Dixon, M.J. Green, F.M. Hoss and D.H. Morgan, Journal of Organometallic Chemistry, 2004, 689, 3641-3668. A few examples include the Phillips Cr/pyrolide/TEA system, the Cp/MAO system replaced by Ti/benzyl from the Dutch Polymer Institute, the BP Cr/o-methoxyphenylPNP/MAO system, and the Sasol Cr/SNS/MAO and Cr/ systems the alkylphenylPNP/MAO. Examples of ligand-free tantalum-based catalyst systems have also been reported by R. Arteaga-Muller, H. Tsurugi, T. Saito, M. Yanagawa, S. Oda and K. Mashima, JACS Communications, 2009, 131, 5370-5371.
    [0027] In another embodiment of the invention, the process according to the second aspect of the invention is predominantly a tetramerization of the ethylene process. As in the case of 1-hexene described above, 1-octene is also used as a comonomer in the production of linear low density polyethylene. Selective non-limiting examples of ethylene tetramerization catalyst systems include the ubiquitous Cr/PNP/MAO systems, starting with the PNP ligands containing no substituent on the phenyl rings attached to the P atoms (for example, as described in WO 2004/056479) and those with p-methoxy groups on the phenyl rings (for example, as described in WO 2004/056480). Furthermore, PNP systems containing o-fluoro groups on the phenyl rings are described in U.S. 2008/0242811, and PNP systems carrying donor atoms pendant on the nitrogen linker are described in WO 2007/088329. Multi-site PNP ligands are examined in U.S. 2008/0027188.
    [0028] In addition to Cr/PNP systems, chromium systems carrying the N,N-bidentate ligands (for example, as described in US 2006/0247399), as well as systems containing the PPN ligands (for example, as described in WO 2008/077911 and in WO 2008/077908) can be used. PNPNH ligands as well as PNPNP are described in WO 2009/006979. Finally, chromium/PCCP/MAO systems are described in WO 2008/088178 and WO 2009/022770.
    [0029] In another embodiment, the process according to the second aspect of the invention is predominantly both a trimerization process and a tetramerization process. In yet another embodiment, the process according to the second aspect of the invention is a tetramerization of the ethylene process in combination with a trimerization of the ethylene process, or wide range oligomerization of the ethylene process as described in WO 2005/ 123884. The process can be a combination of a tetramerization of ethylene with a trimerization of the ethylene process as described in WO 2005/123884, WO 2007/057455 and WO 2006/108803. The process can also be an oligomerization/polymerization process as described in WO 2004/056480.
    [0030] In an embodiment of the process according to the second aspect of the invention, the catalyst is a catalyst composed of dissolved transition metal, for example a chromium catalyst, with a heteroatomic or homoatomic ligand, typically used with an activator . Various dissolved transition metal composite catalysts have been developed for use to trimerize or tetramerize olefins, for example, as disclosed in US 4,668,838, EP 0668105, US 5,750,817, US 6,031,145, US 5,811,618, WO 03/ 053890, WO 2004/056478, WO 2004/056477, WO 2004/056479, WO 2004/056480, WO 2005/123633 and WO 2007/007272, all of which are incorporated herein by reference.
    [0031] Some of these catalysts are selective for C6 and C8 oligomeric products, for example 1-hexene and 1-octene, and the Applicant believes that such catalysts are particularly advantageous for use with the process according to the second aspect of the invention, since the selective production of 1-hexene and 1-octene from ethylene is commercially important.
    [0032] In a preferred embodiment of the process according to the second aspect of the invention, the catalyst also includes one or more activators. Such an activator can be a compound that produces an active catalyst when the activator is combined with a transition metal source and a binding compound.
    Suitable activators include aluminum compounds, organoboron compounds, organic salts such as methyl lithium and methyl magnesium bromide, inorganic acids and salts such as tetrafluoroboric acid etherate, silver tetrafluoroborate, sodium hexafluoroantimonate and others .
    Suitable aluminum compounds include compounds of the formula Al(R1)3 (R1 being the same or different), wherein each R1 is independently a C1-C12 alkyl, an oxygen-containing component or a halide, aluminoxanes, and such compounds such as LiAlH4 and others. Aluminoxanes are well known in the art as typically oligomeric compounds which can be prepared by the controlled addition of water to an alkylaluminum compound, for example trimethylaluminum. Such compounds can be linear, cyclic, caged, or mixtures thereof. Examples of suitable aluminum compounds in the form of organoaluminum activators include trimethylaluminum (TMA), triethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n-octylaluminum, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, chloride diethylaluminum, aluminum isopropoxide, ethylaluminumskichloride, methylaluminumski-chloride, [Ph3C][Al{OC(CF3)3}], methylaluminoxane (MAO), ethylaluminoxane (EAO), isobutylaluminoxane (iBuAO), alkylaluminoxane modified methylaluminoxanes MMAO) and mixtures of the aforementioned compounds.
    [0035] Examples of suitable organoboron compounds are boroxines, NaBH4, triethylborane, tris(pentafluorophenyl)borane, triethyltetrakis(pentafluorophenyl) borate, dimethylanilinium tetrakis(pentafluorophenyl) borate, tributyl borate, dialkylmethylammonium borate tetrakis(pentafluorophenyl) , where alkyl = C2 to C22 and others. These boron-containing compounds can be used in combination with the Al(R1)3 compounds discussed above.
    [0036] The activator can also be or contain a compound that acts as a reducing or oxidizing agent, such as sodium or zinc metal and others, or hydrogen or oxygen and others.
    In this specification the term "aluminoxanes" is used to denote a compound represented by the general formulas (Ra-Al-O)n and Rb(Rc-Al-O)n-AlRd2 wherein Ra, Rb, Rc and Rd are independently a C1-C30 alkyl or halo-alkyl radical, for example methyl, ethyl, propyl, butyl, 2-methyl-propyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, isohexyl, cyclohexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, decyl, 2-phenyl-propyl, 2-(4-fluorophenyl)-propyl, 2,3-dimethyl-butyl, 2,4,4-trimethyl-pentyl and dodecyl; and n has the value from 2 to 50. Preferably n is at least 4.
    The activator can be selected from alkylaluminoxanes such as methylaluminoxane (MAO), high stability methylaluminoxane (MAO HS), ethylaluminoxane (EAO), isobutylaluminoxane (iBuAO), as well as modified alkylaluminoxanes such as modified methylaluminoxane (MMAO).
    [0039] The transition metal source and the aluminoxane can be combined in proportions to provide Al/transition metal molar ratios of from about 1:1 to 10,000:1, preferably from about 1:1 to 1000:1, and more preferably from 1:1 to 500:1.
    The process according to the second aspect of the invention may include the step of adding to the catalyst system a trialkylaluminum compound in amounts between 0.01 to 1000 mol per mol of alkylaluminoxane.
    [0041] In an embodiment of the process according to the second aspect of the invention, the oligomerization catalyst includes a combination of: i) a source of Cr; eii) a binding compound of the formula (R1)m X1 (Y) X2 (R2)nor wherein: X1 and X2 are independently selected from the group consisting of N, P, As, Sb, Bi, O, S and Se;Y is a linking group between X1 and X2; men are independently 0, 1 or a higher integer; and R1 and R2 are independently hydrogen, a hydrocarbyl group or a heterohydrocarbyl group, and R1 being the same or different when m>1, and R2 being the same or different when n>1.
    [0042] In this specification, a heterohydrocarbyl group is a hydrocarbyl group that includes at least one heteroatom (not being H or C), and whose organic compound binds to one or more other components through one or more carbon atoms of the compound organic and/or one or more heteroatoms of the organic compound, organoetheryl groups and organyl groups (which include at least one heteroatom) are examples of heterohydrocarbyl groups.
    [0043] Preferably, the binding compound has the formula:
    with R3 to R7 as defined above.
    [0044] Preferably, each of R3 to R6 is an alkyl (preferably methyl, ethyl or isopropyl) or aromatic (preferably phenyl or substituted phenyl).
    [0045] Non-limiting examples of the linking compound are:phenyl2PN(methyl)Pphenyl2; phenyl2PN(ethyl)Pphenyl2; phenyl2PN(propyl)Pphenyl2 phenyl2PN(tertiary butyl)Pphenyl2; phenyl2PN(neopentyl)Pphenyl2; phenyl2PN(1,2-dimethylpropyl)Pphenyl2; phenyl2PN(allyl)Pphenyl2; phenyl2PN(methylheptyl)Pphenyl2; phenyl2PN(1,5-dimethylheptyl)Pphenyl2; phenyl2PN(2-methylhexyl)Pphenyl2;phenyl2PN(adamantyl)Pphenyl2; phenyl2PN(adamantylmethyl)Pphenyl2;phenyl2PN(3-trimethoxysilanepropyl)Pphenyl2; phenyl2PN(indanyl)Pphenyl2;phenyl2PN(cyclohexylmethyl)Pphenyl2; phenyl2PN(2-methylcyclohexyl)Pphenyl2;phenyl2PN(cyclohexanemethyl)Pphenyl2; phenyl2PN(benzyl)Pphenyl2; phenyl2PNphenylPphenyl2;phenyl2PN(4-methoxy)phenyl)Pphenyl2; phenyl2PN((3-methoxy)-phenyl)Pphenyl2; phenyl2PN((2-methoxy)phenyl)Pphenyl2;phenyl2PN((4-t-butyl)phenyl)Pphenyl2; phenyl2PN((4-nitro)-phenyl)Pphenyl2; phenyl2PN(1-naphthyl)Pphenyl2; phenyl2PN(2-naphthyl)Pphenyl2; phenyl2PN(4-pyridyl)Pphenyl2phenyl2PN(3-(N-morpholine)-propyl)Pphenyl2;phenyl2PN(2-naphthyl-methyl)Pphenyl2; phenyl2PN(1-naphthylmethyl)Pphenyl2;phenyl2PN(diphenylmethyl)Pphenyl2;phenyl2PN(1,2-diphenyl-methyl)Pphenyl2; phenyl2PN(phenylmethyl)Pphenyl2; phenyl2PN((2-methyl)phenyl)Pphenyl2; phenyl2PN((3-methyl)phenyl)Pphenyl2;phenyl2PN((4-methyl)phenyl)Pphenyl2;phenyl2PN((2,6-dimethyl)phenyl)Pphenyl2;phenyl2PN((2-methyl)phenyl)Pphenyl2;phenyl2PN(1 ,2,3,4-Tetrahydronaphthyl)Pphenyl2;phenyl2PN((2-methyl)cyclohexyl)Pphenyl2;phenyl2PN((3-methyl)cyclohexyl)Pphenyl2; phenyl2PN((4-methyl)cyclohexyl)Pphenyl2;phenyl2PN((2-methyl)cyclohexyl)Pphenyl2;phenyl2PN((2-isopropyl)cyclohexyl)Pphenyl2;phenyl2PN((2,6-dimethyl)cyclohexyl)Pphenyl2;phenyl2PN(exo- 2-norbornanyl)Pphenyl2; phenyl2PN(isopinocampheil)Pphenyl2;phenyl2PN(dimethylamino)Pphenyl2; phenyl2PN(phthalimido)Pphenyl2; phenyl2PN(pyrrolyl)Pphenyl2;phenyl2PN(trimethylsilyl)Pphenyl2; phenyl2PN(tertiary dimethylbutyl silyl)Pphenyl2;[henyl2P]2N(1,1'-bis(cyclohexyl)-4,4'-methylene))N[Pphenyl2]2;([henyl2P]2N(1,6-hexylene-) N[Pphenyl2]2;(2,2',2''-trimethylamino)[N[Pphenyl2]2]3;(4-biphenyl)PN(methyl)P(4-biphenyl)2;(2-naphthyl)2PN(methyl)P(2-naphthyl)2;(4-methylphenyl)2PN(methyl)P(4-methylphenyl)2;(3-methylphenyl)2PN(methyl)P(3-methylphenyl)2;(2-naphthyl)2PN(methyl)Pphenyl2;(2-naphthyl)phenylPN(methyl)P(2-naphthyl)phenyl;(2-naphthyl)2PN(methyl)P(2-naphthyl)phenyl;(2-naphthyl)phenylPN(methyl)Pphenyl2;(2-methylphenyl)2PN(methyl)P(2-methylphenyl)2;(2-methylphenyl)2PN(methyl)P(2-methylphenyl)2;(2-isopropylphenyl)2PN(methyl)P(2-isopropylphenyl)2;(2-methylphenyl)2PN(methyl)P(2-methylphenyl)2;(2-methylphenyl)2PN(methyl)P(2-methylphenyl)phenyl;(2-methylphenyl)phenylPN(isopropyl)P(2-methylphenyl))phenyl;(2-methylphenyl)2PN(methyl)Pphenyl2;(2-methylphenyl)phenylPN(isopropyl)Pphenyl2;(methyl)2PN(methyl)P(methyl)2;(methyl)2PN(isopropyl)P(methyl)2; (methyl)2PN(tertiary butyl)P(methyl)2; (methyl)2PN(isopropyl)P(methyl)2; (isopropyl)2PN(methyl)P(isopropyl)2; (methyl)2PN(isopropyl)P( methyl)phenyl; (methyl)phenylPN(isopropyl)P(methyl)phenyl; (methyl)2PN(isopropyl)Pphenyl2; (methyl)phenylPN(isopropyl)Pphenyl2;(2-thiophenyl)2PN(isopropyl)P(2-thiophenyl)2; (diphenylphosphonite)N(isopropyl)(diphenylphosphonite);(dibenzophosphonitephosphonine)N(isopropyl)(dibenzothiaphosphonine); (dibenzooxaphosphonine)N(isopropyl)(dibenzooxaphosphonine);phenyl2PN(methyl)N(methyl)Pphenyl2; phenyl2PN(methyl)N(methyl)Pphenyl2;phenyl2PNphenylNphenylPphenyl2; phenyl2PN(isopropyl)N(isopropyl)Pphenyl2;phenyl2PN(isopropyl)N(methyl)Pphenyl2; phenyl2PN(isopropyl)N(methyl)Pphenyl2;(4-methylphenyl)2P-N(CH3)N(CH3)-P(4-methylphenyl)2;(3-methylphenyl)2P-N(CH3)N(CH3)- P(3-methylphenyl)2;(2-methylphenyl)2P-N(CH3)N(CH3)-P(2-methylphenyl)2;(2-methylphenyl)2P-N(CH3)N(CH3)-P( 2-methylphenyl)2;(2-isopropylphenyl)2P-N(CH3)N(CH3)-P(2-isopropylphenyl)2;(2-methylphenyl)2P-N(CH3)N(CH3)-P(2- methylphenyl)phenyl;(2-methylphenyl)2P-N(CH3)N(CH3)-Pphenyl2;(methyl)2P-N(CH3)N(CH3)-P(methyl)2; (methyl)2P-N(CH3)N(CH3)-P(methyl)2;(isopropyl)2P-N(CH3)N(CH3)-P(isopropyl)2;(methyl)2P-N(CH3)N (CH3)-P(methyl)phenyl;(methyl)phenylP-N(CH3)N(CH3)-P(methyl)phenyl;(methyl)2P-N(CH3)N(CH3)-Pphenyl2; (methyl)phenylP-N(CH3)N(CH3)-Pphenyl2;(2-thiophenethyl)2P-N(CH3)N(CH3)-P(2-thiophenethyl)2;(2-naphthyl)2P-N(CH3 )N(CH3)-P(2-naphthyl)2;(4-biphenyl)2P-N(CH3)N(CH3)-P(4-biphenyl)2; phenyl2P-1,8-naphthyl-Pphenyl2; phenyl2P-9,10-phenanthrene-Pphenyl2; phenyl2P-4,5-phenanthrene-Pphenyl2;phenyl2P-C(CH3)2-Pphenyl2; phenyl2P-C(CH2)2-Pphenyl2;phenyl2P-1,2-benzene-Pphenyl2;(4-methylphenyl)2P-1,2-benzene-P(4-methylphenyl)2;(3-methylphenyl)2P-1, 2-benzene-P(3-methylphenyl)2;(2-methylphenyl)2P-1,2-benzene-P(2-methylphenyl)2;(2-methylphenyl)2P-1,2-benzene-P(2- methylphenyl)2;(2-isopropylphenyl)2P-1,2-benzene-P(2-isopropylphenyl)2;(2-methylphenyl)2P-1,2-benzene-P(2-methylphenyl)phenyl; (2-methylylphenyl)2P-1,2-benzene-Pphenyl2; (methyl)2P-1,2-benzene-P(methyl)2;(methyl)2P-1,2-benzene-P(methyl)2;(isopropyl)2P-1,2-benzene-P(isopropyl)2 ;(methyl)2P-1,2-benzene-P(methyl)phenyl;(methyl)phenylP-1,2-benzene-P(methyl)phenyl;(methyl)2P-1,2-benzene-Pphenyl2; (methyl)phenylP-1,2-benzene-Pphenyl2;(2-thiopheneyl)2P-1,2-benzene-P(2-thiopheneyl)2;(2-naphthyl)2P-1,2-benzene-P(2 -naphthyl)2;(4-biphenyl)2P-1,2-benzene-P(4-biphenyl)2; phenyl2P-CH2CH2-Pphenyl2;(4-methylphenyl)2P-CH2CH2-P(4-methylphenyl)2;(3-methylphenyl)2P-CH2CH2-P(3-methylphenyl)2;(4-methylphenyl)2P-CH2CH2-P (4-methylphenyl)phenyl;(4-methylphenyl)phenylP-CH2CH2-P(4-methylphenyl)phenyl;(4-methylphenyl)2P-CH2CH2-Pphenyl2;(4-methylphenyl)phenylP-CH2CH2-Pphenyl2;(2-methylphenyl) )2P-CH2CH2-P(2-methylphenyl)2;(2-methylphenyl)2P-CH2CH2-P(2-methylphenyl)2;(2-isopropylphenyl)2P-CH2CH2-P(2-isopropylphenyl)2;(2- methylphenyl)2P-CH2CH2-P(2-methylphenyl)phenyl;(2-methylphenyl)2P-CH2CH2-Pphenyl2; (methyl)2P-CH2CH2-P(methyl)2;(methyl)2P-CH2CH2-P(methyl)2; (isopropyl)2P-CH2CH2-P(isopropyl)2;(methyl)2P-CH2CH2-P(methyl)phenyl; (methyl)phenylP-CH2CH2-P(methyl)phenyl;(methyl)2P-CH2CH2-Pphenyl2; (methyl)phenylP-CH2CH2-Pphenyl2;(2-thiophenethyl)2P-CH2CH2-P(2-thiophenethyl)2; phenyl2PBphenylPphenyl2;phenyl2PPphenylPphenyl2; phenyl2PSi(methyl)2Pphenyl2; phenyl2AsN(isopropyl)Asphenyl2; phenylSN(isopropyl)Sphenyl; phenyl2PN(isopropyl)Sphenyl; phenyl2PN(isopropyl)Asphenyl2;phenyl2PN(isopropyl)P(=O)phenyl2; phenyl2P(=O)N(isopropyl)P(=O)phenyl2;phenyl2PN(isopropyl)P(=S)phenyl2; phenyl2P(=S)N(isopropyl)P(=S)phenyl2;phenyl2P(=O)N(isopropyl)P(=S)phenyl2;(4-trifluoromethylphenyl)2PN(isopropyl)P(4-trifluoromethylphenyl)2; (4-chlorophenyl)2PN(isopropyl)P(4-chlorophenyl)2;(4-methoxyphenyl)2PN(methyl)P(4-methoxyphenyl)2;(4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)2 ;(3-methoxyphenyl)2PN(methyl)P(3-methoxyphenyl)2;(4-methoxyphenyl)2PN(isopropyl)P(4-methoxyphenyl)phenyl;(4-methoxyphenyl)phenylPN(isopropyl)P(4-methoxyphenyl) phenyl;(4-methoxyphenyl)2PN(isopropyl)Pphenyl2;(4-methoxyphenyl)phenylPN(isopropyl)Pphenyl2;(4-methoxyphenyl)2P-N(CH3)N(CH3)-P(4-methoxyphenyl)2;(3 -methoxyphenyl)2P-N(CH3)N(CH3)-P(3-methoxyphenyl)2;(4-methoxyphenyl)2P-N(CH3)N(CH3)-P(4-methoxyphenyl)phenyl;(4-methoxyphenyl) )phenylP-N(CH3)N(CH3)-P(4-methoxyphenyl)phenyl;(4-methoxyphenyl)2P-N(CH3)N(CH3)-Pphenyl2;(4-methoxyphenyl)phenylP-N(CH3)N (CH3)-Pphenyl2;(4-methoxyphenyl)2P-1,2-benzene-P(4-methoxyphenyl)2;(3-methoxyphenyl)2P-1,2-benzene-P(3-methoxyphenyl)2;(4 -methoxyphenyl)2P-1,2-benzene-P(4-methoxyphenyl)phenyl;(4-methoxyphenyl)phenylP-1,2-benzene-P(4-methoxyphenyl)phenyl;(4-methoxyphenyl)2P-1,2 -benzene-Pphenyl2;(4-methoxyphenyl)phenylP-1,2-benzene-Pphenyl2;(3-methoxyphenyl)2P(CH2CH2)P(3-methoxyphenyl)2;(3-methoxyphenyl)2P(CH 2CH2)P(3-methoxyphenyl)phenyl;(3-methoxyphenyl)phenylP(CH2CH2CH2)P(3-methoxyphenyl)phenyl;(3-methoxyphenyl)phenylP(CH2CH2)P(3-methoxyphenyl)phenyl;(3-methoxyphenyl)phenylP (CH2)P(3-methoxyphenyl)phenyl;(3-methoxyphenyl)2P(CH2CH2)Pphenyl2;(3-methoxyphenyl)phenylP(CH2CH2)Pphenyl2;(4-methoxyphenyl)2P(CH2CH2)P(4-methoxyphenyl)2; (4-methoxyphenyl)2P(CH2CH2)P(4-methoxyphenyl)phenyl;(4-methoxyphenyl)phenylP(CH2CH2CH2)P(4-methoxyphenyl)phenyl; (4-methoxyphenyl)phenylP(CH2CH2)P(4-methoxyphenyl)phenyl;(4-methoxyphenyl)phenylP(CH2)P(4-methoxyphenyl)phenyl;(4-methoxyphenyl)2P(CH2CH2)Pphenyl2;(4-methoxyphenyl) phenylP(CH2CH2)Pphenyl2;(2-methoxyphenyl)2PN(methyl)P(2-methoxyphenyl)2;(2-methoxyphenyl)2PN(methyl)P(2-methoxyphenyl)2;(2-methoxyphenyl)2PNphenylP(2-methoxyphenyl) )2;(2-methoxyphenyl)2PN(methyl)N(methyl)P(2-methoxyphenyl)2;(2-methoxyphenyl)2P(CH2)P(2-methoxyphenyl)2;(2-methoxyphenyl)2P(CH2CH2) P(2-methoxyphenyl)2;tri(2-methoxyphenyl)phosphane; tri(2-methoxymethoxyphenyl)phosphane; (2-methoxyphenyl)2PN(isopropyl)P(2-methoxyphenyl)phenyl;(2-methoxyphenyl)phenylPN(isopropyl)P(2-methoxyphenyl)phenyl;(2-methoxyphenyl)2PN(isopropyl)Pphenyl2;(2-methoxyphenyl) phenylPN(isopropyl)Pphenyl2;(2-methoxyphenyl)2PN(methyl)P(2-methoxyphenyl)phenyl;(2-methoxyphenyl)phenylPN(methyl)P(2-methoxyphenyl)phenyl;(2-methoxyphenyl)2PN(methyl)Pphenyl2 ;(2-methoxyphenyl)phenylPN(methyl)Pphenyl2;(2-ethoxyphenyl)2PN(methyl)P(2-ethoxyphenyl)2;(2-isopropoxyphenyl)2PN(methyl)P(2-isopropoxyphenyl)2;(2-hydroxyphenyl) )2PN(methyl)P(2-hydroxyphenyl)2;(2-nitrophenyl)2PN(methyl)P(2-nitrophenyl)2;(2-(dimethylamino)phenyl)2PN(methyl)P(2-(dimethylamino)phenyl )2;(2,3-dimethoxyphenyl)2PN(methyl)P(2,3-dimethoxyphenyl)2;(2,4-dimethoxyphenyl)2PN(methyl)P(2,4-dimethoxyphenyl)2;(2,6- dimethoxyphenyl)2PN(methyl)P(2,6-dimethoxyphenyl)2;(2,4,6-trimethoxyphenyl)2PN(methyl)P(2,4,6-trimethoxyphenyl)2;(2-methoxyphenyl)(2-methylphenyl) )PN(methyl)P(2-methylphenyl)2;(2-methoxymethoxyphenyl)2PN(methyl)P(2-methoxymethoxyphenyl)2; (2-methoxyphenyl)2PN(methyl)P(2-methoxyphenyl)phenyl;(2-methoxyphenyl)phenylPN(methyl)P(2-methoxyphenyl)phenyl;(2-methoxyphenyl)2PN(methyl)Pphenyl2;(2-methoxyphenyl) phenylPN(methyl)Pphenyl2;(2-methoxyphenyl)2P-N(CH3)N(CH3)-P(2-methoxyphenyl)2;(2-methoxyphenyl)2P-1,2-benzene-P(2-methoxyphenyl)2 ;(2-methoxyphenyl)2P(CH2CH2)P(2-methoxyphenyl)2;(2-methoxyphenyl)2P(CH2CH2)P(2-methoxyphenyl)phenyl;(2-methoxyphenyl)phenylP(CH2CH2CH2)P(2-methoxyphenyl) phenyl;(2-methoxyphenyl)phenylP(CH2CH2)P(2-methoxyphenyl)phenyl;(2-methoxyphenyl)phenylP(CH2)P(2-methoxyphenyl)phenyl;(2-methoxyphenyl)2P(CH2CH2)Pphenyl2;(2- methoxyphenyl)phenylP(CH2CH2)Pphenyl2;(2-ethoxyphenyl)2P(CH2CH2)P(2-ethoxyphenyl)2;(2-ethoxyphenyl)2P(CH2CH2)P(2-ethoxyphenyl)phenyl;(2-ethoxyphenyl)phenylP(CH2CH2CH2 )P(2-ethoxyphenyl)phenyl;(2-ethoxyphenyl)phenylP(CH2CH2)P(2-ethoxyphenyl)phenyl;(2-ethoxyphenyl)phenylP(CH2)P(2-ethoxyphenyl)phenyl;(2-ethoxyphenyl)2P( CH2CH2)Pphenyl2;(2-ethoxyphenyl)phenylP(CH2CH2)Pphenyl2;(2-isopropoxyphenyl)2P(CH2CH2)P(2-isopropoxyphenyl)2;(2-isopropoxyphenyl)2P(CH2CH2)P(2-isopropoxyphenyl)phenyl;( 2-isopropoxy nyl)phenylP(CH2CH2CH2)P(2-isopropoxyphenyl)phenyl;(2-isopropoxyphenyl)phenylP(CH2CH2)P(2-isopropoxyphenyl)phenyl;(2-isopropoxyphenyl)phenylP(CH2)P(2-isopropoxyphenyl)phenyl;(2-isopropoxyphenyl)phenyl;(2-isopropoxyphenyl)phenyl; -isopropoxyphenyl)2P(CH2CH2)Pphenyl2;(2-isopropoxyphenyl)phenylP(CH2CH2)Pphenyl2; phenyl2PCH2CH2NHCH2CH2Pphenyl2;(methyl)2PCH2CH2NHCH2CH2P(methyl)2; phenyl2PCH2CH2NHCH2CH2P(methyl)2;phenyl(methyl)PCH2CH2NHCH2CH2Pphenyl2;phenylSCH2CH2NHCH2CH2Sphenyl; (methyl)2PCH2CH2NHCH2CH2P(methyl)2; (decyl)2PCH2CH2NHCH2CH2P(decyl)2; phenyl2PCH2CH2NHCH2CH2S(methyl);phenyl2PCH2CH2PphenylCH2CH2Pphenyl2 and phenyl2PCH2CH2CH2NHCH2CH2Pphenyl2.(2-fluorophenyl)2PN(isopropyl)P(2-fluorophenyl)2, Ph2PN(Me)P(2-methoxyphenyl)2,phenyl2PN(isopropyl)PphenylNH(isopropyl), )PphenylNphenylH,phenyl2PN(isopropyl)PphenylN(t-butyl)H, phenyl2PN(isopropyl)PphenylN(CH(CH3)phenyl)H,phenyl2PN(CH2)(2-methoxyphenyl)Pphenyl2,phenyl2PN(CH2)2(2-methoxyphenyl) Pphenyl2,phenyl2PN(CH2)3(2-methoxyphenyl)Pphenyl2,

    Suitable ligand systems may also include mixtures of the aforementioned ligands.
    [0047] The binding compound may include a polymeric component to render the reaction product of the transition metal source and said binding compound as being soluble at higher temperatures and insoluble at lower temperatures, for example, 25 °C . This approach can make it possible to recover the complex from the reaction mixture for reuse and has been used for another catalyst as described by D.E. Bergbreiter et al., J. Am. Chem. Soc., 1987, 109, 177-179. In a similar trend, these transition metal catalysts can also be immobilized by bonding the compound to a silica, silica gel, polysiloxane or alumina backbone as, for example, demonstrated by C. Yuanyin et al., Chinese J. React . Pol. 1992, 1(2), 152-159 to immobilize platinum complexes.
    [0048] The binding compound may include multiple binding units or derivatives thereof. Non-limiting examples of such ligands include dendritic ligands, as well as ligands in which the individual linking moieties are coupled either through one or more of the R groups or through the linking group Y. More specific, but not limiting, the examples of such ligands may include 1,2-di-(N(P(phenyl)2)2)-benzene, 1,4-di-(N(P(phenyl)2)2)-benzene, N(CH2CH2N-(P (phenyl)2)2)3, 1,4-di-(P(phenyl)N(methyl)P(phenyl)2)-benzene, 1,2-di-(N(P(p-methoxyphenyl)2) 2)-benzene, 1,4-di-(N(P(p-methoxyphenyl)2)2)-benzene, N(CH2CH2N(P(p-methoxyphenyl)2)2)3 and 1,4-di-( P(p-methoxyphenyl)N(methyl)P-(p-methoxyphenyl)2)-benzene.
    Binding compounds can be prepared using procedures known to a person skilled in the art and procedures that are part of the prior art.
    [0050] The invention will now be described by means of non-limiting examples, with reference to the accompanying diagrammatic drawings, in which:
    [0051] Figure 1 shows an embodiment of a process according to the invention, for separating a multi-component hydrocarbon stream that includes ethylene and other components with at least some of the components being present in a plurality of phases; and
    [0052] Figure 2 shows another embodiment of a process according to the invention for separating a multi-component hydrocarbon stream that includes ethylene and other components with at least some of the components being present in a plurality of phases.
    [0053] Referring to Figure 1 of the drawings, reference numeral 8 generally indicates a process according to the invention for separating a multi-component hydrocarbon stream that includes ethylene and other components with at least some of the components being present in a plurality of phases. Such a process 8 can be incorporated into an ethylene oligomerization process (not shown) which would include an oligomerization stage in which a multi-component hydrocarbon stream is produced, separation process 8 in which the components of the multi-component stream are produced. components are separated and in which the ethylene is recovered, and other stages of the process, which may be entirely conventional and known to those skilled in the art.
    [0054] Separation process 8 includes a first burn drum 16, a second burn drum 20, and a devolatilizer system 22. Separation process 8 further includes an ethylene recovery section 26.
    [0055] A dissolved catalyst system including a transition metal source, optionally a binding compound, a solvent and optionally a catalyst activator, is used in the oligomerization stage of the ethylene together with ethylene oligomerization process. In particular, the catalyst system includes a catalyst system, a trimerization or tetramerization catalyst as described herein, an aliphatic solvent and an aluminoxane activator as described in this specification.
    [0056] The oligomerization stage of the ethylene oligomerization process with the particular catalysis system mainly produces 1-hexene and 1-octene of ethylene. In other words, mainly the trimerization and tetramerization of ethylene takes place in the reactor. A multi-component, multi-phase hydrocarbon stream, including 1-octene, ethane, methane, 1-butene, 1-hexene, hydrogen, solids and solvent, as well as unreacted ethylene, is removed from the ethylene oligomerization stage and flows through a 10.1 flow line to the separation process 8. The multi-component, multi-phase hydrocarbon stream is typically at a temperature of about 60 °C and a pressure of about 48 bar.
    [0057] In separation process 8, the multi-component, multi-phase hydrocarbon stream in flow line 10.1, is heated in a heat exchanger 12 and then fed via flow line 12.1 to a heater. high pressure steam 14, in which the multi-component hydrocarbon stream is heated to a temperature of about 220 °C (using 42 bar steam or high pressure steam). The heated, multi-component, multi-phase hydrocarbon stream is instantaneously vaporized through a valve (not shown) at a pressure typically between about 10 bar and about 18 bar, more typically between about 10 bar and about 16 bar, and fed through a flow line 14.1 to the first burner drum 16 when the multi-component, multi-phase hydrocarbon stream is separated.
    [0058] The first burner drum 16 separates the multi-component, multi-phase hydrocarbon stream into a first ethylene-containing vapor stream (which thus includes most of the unreacted ethylene from the oligomerization stage) removed by means of a flow line 16.1 and a multiphase stream which is predominantly liquid but which includes both solid and gaseous components. The multi-phase stream is removed from the first firing drum 16 by means of a flow line 16.2.
    [0059] The pressure of the firing drum 16 is determined by economic considerations, taking into account the loss of ethylene to the multiphase stream, the cost of recompression of the recovered ethylene, the capital expense and the operating cost, and the utility temperature restrictions in relation to the bottom boil 26 of the ethylene recovery section. The pressure of the firing drum 16 in the illustrated embodiment of Figure 1 is, however, 14 bar.
    [0060] Conventionally, a stream such as a multi-component, multi-phase hydrocarbon stream is instantaneously vaporized in a united step of the process. This ensures that the product is recovered under less severe conditions. However, the introduction of the two firing drums 16, 20 in series in accordance with the invention ensures that the first ethylene-containing vapor stream from the first firing drum 16, flowing through the flow line 16.1, is in a higher pressure, for example 14 bar. This has the advantageous effect that a small compression ratio is required in order to recycle the ethylene vapor back to the oligomerization stage.
    [0061] The introduction of the first stage of burning is thus enabling the ethylene to be recycled in a cost-effective way.
    [0062] The multiphase current in flow line 16.2 is heated again in a heat exchanger 18 to a temperature range of about 220 to 300 °C (typically using steam or hot oil) and instantaneously vaporized to a pressure of about 2 bar in the second firing drum 20 which separates the multiphase stream into a second steam stream removed by means of a flow line 20.1 and a bottom stream predominantly containing solids and gases which are removed by means of of a flow line 20.2.
    [0063] It is important to note that the heat exchanger 14 can use hot oil instead of steam. In such a case, the temperature of the multiphase current in flow line 16.2 may be sufficiently high (preferably at least 220 °C and even as high as 285 °C) for purposes of the second firing step, such that the second heat exchanger 18 is not needed.
    [0064] The underflow in flow line 20.2 is fed to the devolatilizer system 22 that produces a solids stream that is removed by means of a flow line 22.2, and a steam stream that is removed by a line of flow 22.1. The steam stream in flow line 22.1 can be instantaneously vaporized, or combined with the second steam stream in flow line 20.1 to be used still in process 8 or separately recovered. The solids can be sent to a solids processing section 24, which can, for example, employ an underwater pelletizer to pellet the solids.
    [0065] The first steam stream containing ethylene in flow line 16.1 of the first burn drum 16 is partially condensed in heat exchanger 12 by heat exchange with the multi-component, multi-phase hydrocarbon stream in flow line 10.1, and then enters the ethylene recovery section 26 as a partially condensed stream through the flow line 17. The ethylene recovery section 26 typically employs a distillation column operating at a pressure of about 10 to 18 bar, preferable of about 10 to 15 bar, to generate an ethylene rich vapor separated by means of a flow line 26.1 and an ethylene-poor multicomponent hydrocarbon stream separated by means of a flow line 26.2. The main purpose of the ethylene recovery section 26 is to give a predetermined required ethylene recovery for recycling back (via flow line 26.1) to the oligomerization stage.
    [0066] The bottoms stream of ethylene recovery section 26 (i.e., the ethylene-poor multi-component hydrocarbon stream) includes the oligomeric product, by-products and solvent, and it is necessary to separate the solvent from the oligomeric product and by-products. Conventional separation techniques known to those skilled in the science can be employed to effect such separation.
    [0067] Process 8, as illustrated, economically removes solids such as polyethylene, waxes, catalysts, and catalyst deactivation products from a multi-component, multi-phase hydrocarbon stream that includes ethylene and desirable oligomeric products. This allows the multi-component, multi-phase hydrocarbon stream to be subjected to distillation to recover unreacted ethylene (thereby improving the economics of the ethylene oligomerization process) and separate the oligomeric products into desirable fractions.
    [0068] Referring to Figure 2 of the drawings, another embodiment of a process according to the invention, for separating a multi-component hydrocarbon stream that includes ethylene and other components, with at least some of the components being present in a The plurality of steps is shown and indicated by reference numeral 108. In process 108 of Figure 2, the same reference numerals are used to indicate the same or similar aspects of the process as are used in Figure 1 in relation to process 8, a unless otherwise indicated.
    Unlike process 8, process 108 includes another pump 110 in flow line 16.2, and flow line 16.2 downstream of pump 110 branches to join flow line 10.1. Other differences are that heat exchanger 12 in process 108 is not located in flow line 10.1, and heat exchanger 14 is located in flow line 16.2 downstream of pump 110.
    [0070] Process 108 is operated similarly to process 8, with a few changes. In process 108, the multi-phase stream separated from the first burner drum 16 via flow line 16.2 is first routed to pump 110, where the multi-phase stream is filled to a pressure sufficient to overcome any pressure drop. in flow line 16.2 and heat exchanger 14 to bring the pressure in flow line 16.2 to the pressure in flow line 10.1 (eg 48 bar), so that when flow lines 10.1 and 16.2 come together , the pressures are substantially equal.
    [0071] In the heat exchanger 14, the multiple phase stream in the flow line 16.2 of the first firing drum 16 is heated to a temperature of more than 190 °C (eg 199 °C) using high pressure steam and a portion of said heated stream in flow line 16.2 is combined with the multi-component multi-phase hydrocarbon stream in flow line 10.1 coming from an ethylene oligomerization stage (not shown). The mass flow rate through flow line 16.2 that joins flow line 10.1, is about ten times the mass flow rate through flow line 10.1. The flow rate and temperature of the heated stream in flow line 16.2 are sufficiently high so that when the heated stream in flow line 16.2 is mixed with the multi-component hydrocarbon stream in flow line 10.1 coming from one stage of ethylene oligomerization, results in a combined current temperature typically between 180 and 220 °C, for example 190 °C. The combined multi-component, multi-phase hydrocarbon stream, heated to about 190°C, is ignited through a valve (not shown) at a pressure typically between about 10 bar and about 16 bar, for example 15.5 bar, and a temperature of about 186°C, and then fed to the first burner drum 16, where the multi-component, multi-phase hydrocarbon stream is separated.
    [0072] The remaining portion of the multiphase stream that leaves the heat exchanger 14 and not recycled to the burning drum 16, is passed through the flow line 16.2 to be further heated in the heat exchanger 18, as was the case as to process 8.
    [0073] The recycle flow rate of the multi-phase stream to the burn drum 16, and the exit temperature of the heat exchanger 14, can be manipulated to vary the temperature of the multi-component, multi-phase hydrocarbon stream , in flow line 10.1 to the first firing drum 16.
    [0074] The first burner drum 16 separates the multi-component, multi-phase hydrocarbon stream into a first stream of ethylene vapor (which thus includes most of the unreacted ethylene from the oligomerization stage) separated through the line. stream 16.1 and the multiphase stream which is predominantly liquid but which includes both solid and gaseous components. The multi-phase stream is separated from the first burner drum 16 via flow line 16.2, as described hereinbefore.
    [0075] With respect to process 8, the pressure of the burner drum 16 is determined by economic considerations, taking into account the loss of ethylene to the multi-phase stream, the cost of recompression of the recovered ethylene, the capital expenditure and the operating cost, and the utility temperature in relation to the bottom boil 26 of the ethylene recovery section. The pressure of the firing drum 16 in the embodiment illustrated in Figure 2 is, however, 15.5 bar.
    [0076] Conventionally, as mentioned hereinbefore, a stream such as a multi-component multi-phase hydrocarbon stream is instantaneously vaporized in a single process step. This ensures that the product is recovered under less severe conditions. However, the introduction of the two firing drums 16, 20 in series, according to the invention, ensures that the first ethylene-containing steam stream from the first burning drum 16 flowing through the flow line 16.1 advantageously has a pressure of 15 .5 bar, which means that only a small compression ratio is required in order to recycle the ethylene vapor back to the oligomerization stage.
    [0077] As is the case with process 8, the introduction of the first firing step is thus enabling the ethylene to be recycled in a cost-effective manner.
    [0078] The multiple phase current in flow line 16.2 is further heated in heat exchanger 18 to a temperature of about 285 °C (typically using hot oil) and instantaneously vaporized at a pressure of about 4 bar in the second burner drum 20, which separates the multi-phase stream into a second separate vapor stream via flow line 20.1 and a bottom stream predominantly containing solids and gases that are withdrawn via flow line 20.2.
    [0079] It is important to note that the heat exchanger 14 can also employ hot oil rather than steam as a means of transferring heat. In such a case, the temperature of the multiple-phase stream in the flow lines 16.2 downstream of the heat exchanger 14 can be high enough for the purposes of the second firing step such that the heat exchanger 18 is not needed. .
    [0080] The underflow in flow line 20.2 of process 108 is treated in the same way as the underflow in flow line 20.2 of process 8.
    [0081] The first stream of steam containing ethylene in flow line 16.1 of the first burning drum 16 is partially condensed in heat exchanger 12 by heat exchange with low pressure steam condensate, producing low pressure steam, and subsequently enters the ethylene recovery section 26 as a partially condensed stream through flow line 17. The ethylene recovery section 26 of process 108 operates in the same manner as the ethylene recovery section 26 of process 8.
    [0082] Similar to process 8, process 108, as illustrated, economically removes solids such as polyethylene, waxes, catalysts, and catalyst deactivation products, from a multi-phase, multi-component hydrocarbon stream that includes ethylene and desirable oligomeric products . This enables the multi-phase, multi-component hydrocarbon stream to be subjected to distillation to recover unreacted ethylene (thereby improving the economics of the ethylene oligomerization process) and separate the oligomeric products into desirable fractions.
    [0083] The process 8, 108 of the invention, as illustrated, ensures the recovery of ethylene at a relatively high intermediate pressure, which is cost-effective. The thermodynamically optimal path should be to take the multi-phase, multi-component hydrocarbon stream from an ethylene oligomerization stage, and burn it in a single step-down stream burning separation to 1 to 2 bar. In this way, the reactor products can be recovered under less severe conditions. However the ethylene must have to be compressed to the pressure of the oligomerization stage again at a high compression ratio which is expensive. To overcome this problem, an intermediate instantaneous vaporization is introduced (ie, burner drum 16) in which the multi-phase, multi-component hydrocarbon stream is instantaneously vaporized at a medium pressure so that most of the ethylene is recovered in a higher pressure of at least 10 bar, for example about 14 bar to 16 bar, and a lower compression ratio is therefore required to ensure that recycled ethylene is fed into the oligomerization stage at the required pressure. In addition, the process 8, 108 recovers heat, which is reintegrated into the process. This further improves the operating costs of the process 8, 108.
    权利要求:
    Claims (12)
    [0001]
    1. Process for separating a multi-component hydrocarbon stream that includes ethylene and other components with at least some of the components being present in a plurality of phases, characterized in that it includes: in a first instantaneous vaporization stage, instantaneously vaporizing the multi-component hydrocarbon stream, of an elevated pressure and temperature of more than 180°C at a pressure in the range of 10 to 18 bar, producing a first steam stream containing ethylene at a pressure in the range of 10 to 18 bar, and a multiphase stream that includes some ethylene; in a second instantaneous vaporization stage, instantaneously vaporize the multiphase stream at a pressure of less than 6 bar, producing a second stream of vapor at a pressure of less than 6 bar and an underflow; removing the first stream of ethylene-containing vapor from the first instantaneous vaporization stage and the second stream of v. affixing the second instantaneous vaporization stage; separating at least a portion of the ethylene from the first ethylene-containing steam stream by subjecting the first ethylene-containing steam stream to at least one ethylene recovery stage producing an ethylene-rich stream and a stream of ethylene-poor multi-component hydrocarbon; and remove the undercurrent from the second instantaneous vaporization stage.
    [0002]
    2. Process according to claim 1, characterized in that the multiphase stream is instantaneously vaporized in the second instantaneous vaporization stage at a pressure between 1 bar and 6 bar.
    [0003]
    3. Process according to any one of claims 1 or 2, characterized in that, in the first instantaneous vaporization stage, the multi-component hydrocarbon stream is instantaneously vaporized from an elevated temperature of at least 185 °C and a pressure higher than 30 bar, the first steam stream containing ethylene defining a higher mass flow of ethylene and being at a higher pressure than the second steam stream.
    [0004]
    4. Process according to any one of claims 1 to 3, characterized in that the ethylene recovery stage employs at least one distillation column operated at a pressure in the range of 10 to 18 bar, with the first steam stream containing ethylene not being recompressed before being fed to the ethylene recovery stage, but being at least partially condensed before being fed to the ethylene recovery stage.
    [0005]
    5. A process according to any one of claims 1 to 4, characterized in that the ethylene-poor multi-component hydrocarbon stream includes a solvent for an ethylene oligomerization catalyst, the process further including combining the ethylene hydrocarbon stream. multiple ethylene-poor components from the ethylene recovery stage, and the second steam stream from the second stage flash flash, and recover solvent from the combined streams by distillation.
    [0006]
    6. Process according to claim 5, characterized in that the pressure of the ethylene-poor multi-component hydrocarbon stream is weakened to the pressure of the second steam stream.
    [0007]
    7. Process according to any one of claims 1 or 2, characterized in that it includes heating the multi-component hydrocarbon stream to a temperature of at least 180 °C prior to instantaneous vaporization of the multi-component hydrocarbon stream in the first stage of instantaneous vaporization, with at least some of the heat for heating the multi-component hydrocarbon stream being supplied by the first steam stream containing ethylene.
    [0008]
    8. Process according to claim 7, characterized in that the heating of the multi-component hydrocarbon stream is done by means of indirect heat exchange with a heating medium or hot process stream, or by direct contact heating or mixing with a hot process stream.
    [0009]
    9. Ethylene oligomerization process, characterized in that it includes: in one stage of oligomerization, oligomerize ethylene and remove a multi-component hydrocarbon stream from different phases that includes oligomeric product, polymeric product, and unreacted ethylene; of multi-component hydrocarbon at a temperature of more than 180°C; separating the multi-component hydrocarbon stream according to a separation process as defined in any one of claims 1 to 6, producing said first stream of steam containing ethylene; and feeding the first ethylene-containing steam stream to said ethylene recovery stage producing said ethylene-rich stream and said ethylene-poor multi-component hydrocarbon stream including oligomeric and/or polymeric product.
    [0010]
    10. Process according to claim 9, characterized in that the multi-component hydrocarbon stream is heated to a temperature of at least 180 °C before flash vaporization of the multi-component hydrocarbon stream in the first flash vaporization stage , with at least some of the heat for heating the multi-component hydrocarbon stream being supplied by the first steam stream containing ethylene.
    [0011]
    11. Process according to any one of claims 9 or 10, characterized in that it includes recycling the ethylene-rich stream to the oligomerization stage.
    [0012]
    12. Process according to any one of claims 9 to 11, characterized in that, in the oligomerization stage, ethylene is oligomerized at a high pressure of at least 30 bar and at a high temperature of at least 40 °C.
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    同族专利:
    公开号 | 公开日
    US9017522B2|2015-04-28|
    CN102666443B|2014-09-03|
    MY161612A|2017-04-28|
    KR20130004237A|2013-01-09|
    BR112012008987A2|2021-02-02|
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    ZA201202558B|2013-01-30|
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    法律状态:
    2021-02-17| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2021-02-23| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-07-20| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-08-24| 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 01/10/2010, OBSERVADAS AS CONDICOES LEGAIS. PATENTE CONCEDIDA CONFORME ADI 5.529/DF, QUE DETERMINA A ALTERACAO DO PRAZO DE CONCESSAO. |
    优先权:
    申请号 | 申请日 | 专利标题
    ZA2009/07265|2009-10-16|
    ZA200907265|2009-10-16|
    PCT/IB2010/054444|WO2011045701A1|2009-10-16|2010-10-01|Separation of components from a multi-component hydrocarbon stream which includes ethylene|
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