WO2017187289A1 - Procédé d'élimination de chaleur d'une réaction d'oligomérisation - Google Patents

Procédé d'élimination de chaleur d'une réaction d'oligomérisation Download PDF

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WO2017187289A1
WO2017187289A1 PCT/IB2017/052158 IB2017052158W WO2017187289A1 WO 2017187289 A1 WO2017187289 A1 WO 2017187289A1 IB 2017052158 W IB2017052158 W IB 2017052158W WO 2017187289 A1 WO2017187289 A1 WO 2017187289A1
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reactor
reaction
temperature
cooling liquid
oligomerization
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PCT/IB2017/052158
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English (en)
Inventor
Abdullah Saad AL-DUGHAITHER
Shahid Azam
Dafer Mubarak ALSHAHRANI
Abdulmajeed Mohammed AL-HAMDAN
Anina Wohl
Wolfgang Muller
Andreas Meiswinkel
Heinz Bolt
Ralf Noack
Andreas Metzner
Tobias Meier
Gabriel WAURICK
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Sabic Global Technologies B.V.
Linde Ag
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Publication of WO2017187289A1 publication Critical patent/WO2017187289A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0231—Halogen-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0239—Quaternary ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
    • B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1885—Ligands comprising two different formal oxidation states of phosphorus in one at least bidentate ligand, e.g. phosphite/phosphinite
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00121—Controlling the temperature by direct heating or cooling
    • B01J2219/00123—Controlling the temperature by direct heating or cooling adding a temperature modifying medium to the reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0258—Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1088—Olefins
    • C10G2300/1092—C2-C4 olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/22—Higher olefins

Definitions

  • An exothermic reaction is a chemical reaction which is accompanied by evolution of heat.
  • the reaction temperature of an exothermic reaction can be controlled by indirect or direct cooling of the reactor, balancing the heat released from the reaction and the heat removed by the cooling system.
  • Heat of reaction can be removed by introduction of a gaseous ethylene cycle over the reactor, which is generally introduced into the reactor at a temperature that is significantly below the reaction temperature.
  • the ethylene cycle leaves the reactor at the reaction temperature (i.e., heat of reaction is removed by the sensible heat of the ethylene cycle).
  • the specific heat capacity of gaseous ethylene is relatively low, so large flow rates of ethylene are generally required for reaction cooling to be achieved.
  • a runaway reaction As the removable heat by a cooling system is normally linearly dependent on the reaction temperature, reaching a certain temperature can lead to an irreversible accelerating reaction, commonly referred to as a runaway reaction. Runaway reactions can be difficult to prevent, and certain measures for handling runaway reactions have been established. These measures, however, suffer from major draw backs. For example, a catalyst poison for catalytically driven exothermic reactions can be added. This approach generally results in loss of product as well as contamination of the reactor with the poison. Complete shutdown and cleaning of the reactor subsequent to adding the catalyst poison is also generally required.
  • a further measure relies on depressurization or draining of the reactor vessels by valves or bursting discs. This measure also results in loss of product and the necessity of complete reactor shutdown and cleaning of the reactor of the runaway products. There is often also a need for further treatment of the runaway product due to unwanted properties such as polymerization or toxicity.
  • a process for removing heat from an oligomerization reaction comprises introducing a gaseous ethylene stream at a first temperature to an oligomerization reactor having a liquid phase and a gas phase and being at a reaction temperature; oligomerizing at least a portion of the ethylene to provide a linear alpha olefin product, wherein the oligomerizing generates a heat of reaction; and continuously injecting a cooling liquid comprising a C 2 _ 4 olefin into the reactor to remove at least a portion of the heat of reaction generated during the oligomerization reaction.
  • a process for removing heat from an oligomerization reaction comprises introducing a gaseous ethylene stream at temperature of 10 to 60°C to an oligomerization reactor having a liquid phase and a gas phase and being at a reaction temperature; oligomerizing the ethylene to provide a linear alpha olefin product comprising C 4 _i 8 linear alpha olefins, wherein the oligomerizing generates a heat of reaction; injecting a cooling liquid comprising a C 2 _ 4 olefin preferably a C 2 _ 4 olefin that has been separated from the linear alpha olefin product into the reactor to remove 60 to 80% of the total heat of reaction; measuring the reaction
  • an exothermic reaction e.g., an exothermic oligomerization reaction.
  • An example of an exothermic reaction that could particularly benefit from an improved method for removing heat is an oligomerization reaction.
  • the process for removing heat from the oligomerization reaction can include injecting a cooling liquid into the reactor, where the generated heat from the oligomerization reaction can be removed by vaporization of the cooling liquid.
  • a small gaseous ethylene cycle can be used. This process can further aid in preventing runaway reactions by adjusting the ethylene cycle or the cooling liquid to efficiently cool the reaction and avoid reactor runaway. Using the process described herein, the probability of preventing a runaway reaction is higher, thus increasing overall plant availability, reducing production losses, and improving the overall plant economics.
  • a process for removing heat from an oligomerization reaction can include introducing a gaseous ethylene stream at a first temperature to an oligomerization reactor.
  • the first temperature can be 0 to 100°C, for example, 0 to 60°C, for example, 10 to 60°C, for example, 10 to 20°C.
  • introducing the gaseous ethylene stream at the first temperature removes 20 to 40% of the total heat of reaction generated by the oligomerization.
  • the reactor can be any oligomerization reactor.
  • the reactor can be a loop reactor, a plug-flow reactor, a bubble column reactor, or a tubular reactor.
  • the oligomerization reactor is a bubble column reactor.
  • the oligomerization reactor can include a liquid phase and a gas phase, and can be at a reaction temperature.
  • the reaction temperature can be any temperature at which oligomerization can occur. Oligomerization can occur at temperatures of 10 to 200°C, for example, 20 to 100°C, for example, 50 to 90°C, for example, 55 to 80°C, for example, 60 to 70°C.
  • Operating pressures can be 1 to 5 MegaPascals (MPa), for example, 2 to 4 MPa.
  • MPa MegaPascals
  • the process can be continuous and mean residence times can be 10 minutes to 20 hours, for example 30 minutes to 4 hours, for example, 1 to 2 hours. Residence times can be chosen so as to achieve the desired conversion at high selectivity.
  • the process can further comprise oligomerizing at least a portion of the ethylene to provide a linear alpha olefin product.
  • the linear alpha olefin products can generally be addition products containing greater than or equal to two ethylene units, but not as many ethylene units as in the relatively high molecular weight addition product referred to as polyethylene.
  • the oligomerization is a selective oligomerization process, for example a selective ethylene trimerization or tetramerization process.
  • the oligomerization is a trimerization process.
  • the linear alpha olefin products comprise C 4 _i 8 linear alpha olefins.
  • the linear alpha olefin products comprise C 4 _ 8 linear alpha olefins.
  • the linear alpha olefins can include at least one of 1-butene, 1-hexene, or 1-octene.
  • Oligomerizing the ethylene to provide the linear alpha olefin product generates a heat of reaction. At least a portion of the heat of reaction generated by oligomerizing ethylene can be removed by continuously injecting a cooling liquid comprising a C 2 _ 4 olefin into the reactor.
  • the cooling liquid can be C 2 _ 4 olefins that have been recovered from the oligomerization process, for example in a separation section downstream from an
  • the cooling liquid comprising the C 2 _ 4 olefins can be routed from a separation section, any suitable process vessel, or from a dedicated storage facility.
  • the cooling liquid can be introduced to the reactor at a temperature of -20 to 0°C, preferably -10 to -1°C, more preferably -4 to -1°C.
  • the cooling liquid can be introduced into the liquid phase of the reactor, the gas phase of the reactor, or both. Injecting the cooling liquid into the reactor can remove 60 to 80% of the total heat of reaction generated by the oligomerization.
  • the cooling liquid can further comprise C 6+ olefins, for example, in some embodiments, the cooling liquid can comprise C 2-1 o olefins. In some embodiments, the cooling liquid comprises less than or equal to 10 weight percent of C 6+ olefins, or less than or equal to 8 weight percent C 6+ olefins, or less than or equal to 5 weight percent C 6+ olefins, based on the total weight of the cooling liquid. In some embodiments, the cooling liquid can optionally further comprise an aromatic solvent.
  • the aromatic solvent when present, can be toluene, benzene, ethyl benzene, isopropylbenzene, xylene, mesitylene, monochlorobenzene, dichlorobenzene, chlorotoluene, and the like, or a combination comprising at least one of the foregoing.
  • the aromatic solvent can be present in the cooling liquid in an amount of less than or equal to 10 weight percent, or less than or equal to 8 weight percent, or less than or equal to 5 weight percent, or less than or equal to 2 weight percent, based on the total weight of the cooling liquid.
  • the C 2 _ 4 olefins of the cooling liquid are the main contributor for removing the heat of reaction and suppressing a runaway reaction, despite the presence of C 6+ olefins and/or an aromatic solvent.
  • the cooling liquid excludes higher olefins, for example C 6+ olefins. In some embodiments, the cooling liquid does not include any solvent, for example an aromatic solvent. Thus, in some embodiments, the cooling liquid consists of C 2 _ 4 olefins, preferably C 2 _ 4 olefins that have been recovered from the oligomerization process, for example in a separation section downstream from an oligomerization reactor.
  • the process can further include measuring the reaction temperature.
  • gaseous ethylene can be introduced to the reactor at a second temperature, wherein the second temperature is lower than the first temperature.
  • the second temperature can be 0 to 30°C, for example, 0 to 10°C, for example, 0°C. If the measured reaction
  • the process can optionally further include increasing the amount of cooling liquid injected into the reactor.
  • the gaseous ethylene can be introduced at the second temperature and the amount of cooling liquid injected into the reactor can be increased if the measured reaction temperature is greater than the oligomerization reaction temperature, for example, it can be desriable if the measured reaction temperature is at least 5°C greater than the oligomerization reaction temperature.
  • the oligomerization reaction is further carried out in the presence of a solvent and a catalyst composition.
  • the solvent can be any organic solvent capable of dissolving the reaction components.
  • the solvent can also be non-reactive with the catalyst composition.
  • desirable organic solvents can include, but are not limited to, aromatic hydrocarbon solvents which can be unsubstituted or substituted, for example, toluene, benzene, ethyl benzene, isopropylbenzene, xylene, mesitylene, monochlorobenzene,
  • dichlorobenzene chlorotoluene
  • aliphatic paraffin hydrocarbons for example, pentane, hexane, heptane, octane, nonane, decane
  • alicyclic hydrocarbon compounds for example, cyclohexane, decahydronaphthalene, and halogenated alkanes, for example, dichloroethane and
  • dichlorobutane or a combination comprising at least one of the foregoing.
  • the solvent can be toluene, xylene, benzene, mesitylene, ethyl benzene, isopropylbenzene, or a combination comprising at least one of the foregoing.
  • the catalyst composition can be any catalyst system that can oligomerize ethylene.
  • the catalyst composition can include a chromium source, a heteroatomic multidentate ligand, and an activator, also known as a co-catalyst.
  • a catalyst modifier is not required, but is also preferably present.
  • the chromium compound can be an organic or inorganic salt, coordination complex, or organometallic complex of Cr(II) or Cr(III).
  • the chromium compound is CrCl 3 (tetrahydrofuran)3, Cr(III)acetylacetonate, Cr(III)octanoate, chromium hexacarbonyl, Cr(III)-2-ethylhexanoate, benzene(tricarbonyl) -chromium, or Cr(III)chloride.
  • CrCl 3 tetrahydrofuran
  • Cr(III)acetylacetonate Cr(III)octanoate
  • Crmium hexacarbonyl Cr(III)-2-ethylhexanoate
  • benzene(tricarbonyl) -chromium or Cr(III)chloride.
  • a combination of different chromium compounds can be used.
  • the heteroatomic multidentate ligand includes two or more heteroatoms (P, N, O, S, As, Sb, Bi, O, S, or Se) that can be the same or different, wherein the two or more heteroatoms (P, N, O, S, As, Sb, Bi, O, S, or Se) that can be the same or different, wherein the two or more heteroatoms (P, N, O, S, As, Sb, Bi, O, S, or Se) that can be the same or different, wherein the two or more
  • heteroatoms are linked via a linking group.
  • the linking group is a Ci- 6 hydrocarbylene group or one of the foregoing heteroatoms. Any of the heteroatoms in the ligand can be substituted to satisfy the valence thereof, with a hydrogen, halogen, C 18 hydrocarbyl group, Cno
  • heteroatoms of the multidentate ligand are preferably a combination comprising phosphorus with nitrogen and sulfur or a combination comprising phosphorous and nitrogen, linked by at least one additional phosphorus or nitrogen heteroatom.
  • the ligand can have the backbone PNP, PNPN, NPN, NPNP, NPNPN, PNNP, or cyclic derivatives containing these backbones wherein one or more of the heteroatoms is linked by a Cno hydrocarbylene to provide a heterocyclic group.
  • a combination of different ligands can be used.
  • the ligand has the backbone PNPNH, which as used herein has the general structure R 1 R 2 P-N(R 3 )-P(R 4 )-N(R 5 )-H wherein each of R 1 , R 2 , R 3 , R 4 , and R 5 is independently a hydrogen, halogen, Cns hydrocarbyl group, amino group of the formula NR a R b wherein each of R a and R b is independently hydrogen or a Cns hydrocarbyl group, a silyl group of the formula SiR a R b R c wherein each of R a , R b , and R c is independently hydrogen or a Ci-18 hydrocarbyl group, or two of R 1 , R 2 , R 3 , R 4 , R 5 , R a , or R b taken together are a substituted or unsubstituted Cno hydrocarbylene group linked to the same or different heteroatoms to form
  • each R , R , R 3 , R 4 , R 5 are independently hydrogen, substituted or unsubstituted Ci-C 8 alkyl, substituted or unsubstituted C6-C 20 aryl, more preferably unsubstituted Ci-C 6 alkyl or unsubstituted C 6 -Cio aryl.
  • a specific example of the ligand is (phenyl) 2 PN(iso-propyl)P(phenyl)N(iso-propyl)H, commonly abbreviated Ph 2 PN(i-Pr)P(Ph)NH(i-Pr).
  • Activators can include aluminum compounds, for example a tri(Ci-C 6 alkyl) aluminum such as triethyl aluminum, (Ci-C 6 alkyl) aluminum sesquichloride, di(Ci-C 6 alkyl) aluminum chloride, or (Ci-C 6 -alkyl) aluminum dichloride, or an aluminoxane such as methylaluminoxane (MAO).
  • Each alkyl group can be the same or different, and in some embodiments is methyl, ethyl, isopropyl, or isobutyl. A combination of different activators can be used.
  • the modifier can modify the activator, and serve as a chlorine source.
  • Modifiers can include an ammonium or phosphonium salt of the type (H 4 E)X, (H 3 ER)X, (H 2 ER 2 )X, (HER 3 )X, or (ER 4 )X wherein E is N or P, X is CI, Br, or I, and each R is independently a Ci-C 22 hydrocarbyl, preferably a substituted or unsubstituted Ci-Ci 6 -alkyl, C 2 - Ci6-acyl, or substituted or unsubstituted C6-C 2 o-aryl- In some embodiments the modifier is dodecyltrimethylammonium chloride or tetraphenylphosphonium chloride.
  • the catalyst composition is often pre-formed (i.e., formed prior to contacting other reaction components in the oligomerization reactor), for example by combining the components in a solvent before contacting with ethylene in an oligomerization process.
  • solvents examples include toluene, benzene, ethylbenzene, cumenene, xylenes, mesitylene, C 4 -Cis paraffins, cyclohexane, C 4 -Ci 2 olefins such as butene, hexene, heptene, octene, or ethers or multiethers such as diethylether, tetrahydrofuran, dioxane, di(Ci-C 8 alkyl)ethers.
  • the solvent is an aromatic solvent such as toluene.
  • each component selected for use in the catalyst composition and relative amount of each component depend on the desired product and desired selectivity.
  • the concentration of the chromium compound is 0.01 to 100 millimole per liter (mmol/1), or 0.01 to 10 mmol/1, or 0.01 to 1 mmol/1, or 0.1 to 1.0 mmol/1; and the mole ratio of multidentate ligand:Cr compound:activator is 0.1: 1: 1 to 10: 1: 1,000, or 0.5: 1:50 to 2: 1:500, or 1: 1: 100 to 5: 1:300.
  • Desirable catalyst systems are described, for example, in EP2489431 B l; EP2106854 B l; and WO2004/056479.
  • the residual catalyst can include a zirconium-containing catalyst and an organoaluminum co-catalyst.
  • the zirconium-containing catalyst can be a zirconium carboxylate having the formula Zr(OOCR) m X 4 _ m , where R is alkyl, alkenyl, aryl, aralkyl or cycloalkyl, X is halide, for example X is chlorine or bromine, and m is 0 to 4.
  • R can be an alkyl group having 1 to 20 carbon atoms, for example, 1 to 5 carbon atoms.
  • the catalyst can be zirconium tetraisobutyrate.
  • the organoaluminum compound can be, for example, an alkyl aluminum halide.
  • the organoaluminum compound can be of the formula R' n AlX 3 _ n , wherein R' is a C 1-2 o alkyl and X is a halide, preferably chlorine or bromine, and n is 1 or 2.
  • the co-catalyst can comprise ethylaluminum sesquichloride (EASC), diethyl aluminum chloride (DEAC), or a combination comprising at least one of the foregoing.
  • the process can further comprise discontinuing feeding the catalyst composition to the reactor when the temperature exceeds the predetermined value.
  • the process can further comprise reducing the reactor level when the temperature exceeds the predetermined value.
  • the process can further comprise increasing the solvent flowrate when the temperature exceeds the predetermined value.
  • the process for removing heat from an oligomerization reaction comprises introducing a gaseous ethylene stream at a temperature of 10 to 60°C to an oligomerization reactor having a liquid phase and a gas phase and being at a reaction
  • the ethylene is oligomerized to provide a linear alpha olefin product comprising C 4 _i8 linear alpha olefins, and the oligomerization generates a heat of reaction.
  • the process further comprises injecting a cooling liquid comprising a C 2 _ 4 olefin, preferably a C 2 _ 4 olefin that has been separated from the linear alpha olefin product and recycled back into the reactor to remove 60 to 80% of the total heat of reaction.
  • the reaction temperature can be measured, and in the reaction temperature exceeds a predetermined value, the process can further include introducing the gaseous ethylene stream at a temperature of 0 to 30°C and increasing the amount of cooling liquid injected into the reactor.
  • the process also includes discontinuing feeding the catalyst composition to the reactor when the temperature exceeds the predetermined value.
  • the process for removing heat from an oligomerization reaction comprises introducing a gaseous ethylene stream at a temperature of 10 to 60°C to an oligomerization reactor having a liquid phase and a gas phase and being at a reaction
  • the ethylene is oligomerized to provide a linear alpha olefin product comprising C 4 _i8 linear alpha olefins, and the oligomerization generates a heat of reaction.
  • the process further comprises injecting a cooling liquid comprising a C 2-1 o olefin and optionally and aromatic solvent, preferably wherein the cooling liquid has been separated from the linear alpha olefin product and recycled back into the reactor to remove 60 to 80% of the total heat of reaction.
  • the reaction temperature can be measured, and in the reaction temperature exceeds a predetermined value, the process can further include introducing the gaseous ethylene stream at a temperature of 0 to 30°C and increasing the amount of cooling liquid injected into the reactor.
  • the process also includes discontinuing feeding the catalyst composition to the reactor when the temperature exceeds the predetermined value.
  • the process for removing heat from an oligomerization reaction comprises introducing a gaseous ethylene stream at a temperature of 10 to 60°C to an oligomerization reactor having a liquid phase and a gas phase and being at a reaction
  • the ethylene is oligomerized to provide a linear alpha olefin product comprising C 4 _i8 linear alpha olefins, and the oligomerization generates a heat of reaction.
  • the process further comprises injecting a cooling liquid comprising a C 2 _ 4 olefin, preferably a C 2 _ 4 olefin that has been separated from the linear alpha olefin product and recycled back into the reactor to remove 60 to 80% of the total heat of reaction.
  • the reaction temperature can be measured, and if the reaction temperature exceeds a predetermined value, the process can further include introducing the gaseous ethylene stream at a temperature of 0 to 30°C and increasing the amount of cooling liquid injected into the reactor.
  • the process also includes discontinuing feeding the catalyst composition to the reactor, reducing the reactor level, and increasing the flowrate of a solvent to the reactor when the temperature exceeds the predetermined value.
  • the present disclosure provides an improved process for removing heat from an oligomerization reaction.
  • the process can advantageously be used for preventing a runaway reaction from occurring.
  • the probability of preventing a runaway reaction is higher, thus increasing overall plant availability, reducing production losses, and improving the overall plant economics. Therefore, a substantial improvement in removing heat from an oligomerization reaction and preventing runaway reaction is provided.
  • the reaction temperature is maintained at a predetermined value, for example, 50°C.
  • a cooling liquid and gaseous ethylene are routed to the reactor.
  • the reaction temperature is controlled by the inlet temperature of the gaseous ethylene stream, which is for example 10°C.
  • the inlet temperature of the gaseous ethylene stream is decreased to the minimum possible temperature, for example, to a temperature of 0°C. If the cooling capacity of the gaseous ethylene stream is insufficient to prevent a further temperature increase, additional cooling liquid is supplied to the reactor. The introduction of the additional cooling liquid into the reactor is stopped as soon as the reaction temperature is within a range such that feeding ethylene is sufficient to prevent a temperature increase.
  • Embodiment 1 A process for removing heat from an oligomerization reaction, comprising: introducing a gaseous ethylene stream at a first temperature to an oligomerization reactor having a liquid phase and a gas phase and being at a reaction temperature; oligomerizing at least a portion of the ethylene to provide a linear alpha olefin product, wherein the
  • oligomerizing generates a heat of reaction; and continuously injecting a cooling liquid comprising a C 2 _ 4 olefin into the reactor to remove at least a portion of the heat of reaction generated during the oligomerization reaction.
  • Embodiment 2 The process of embodiment 1, wherein the cooling liquid further comprises one or both of C 6+ olefins, preferably C6 io olefins, and an aromatic solvent.
  • Embodiment 3 The process of embodiment 1 or 2, wherein the process further comprises measuring the reaction temperature; and introducing the gaseous ethylene stream at a second temperature that is lower than the first temperature and, optionally, increasing the amount of the cooling liquid if the reaction temperature exceeds a predetermined value.
  • Embodiment 4 The process of any of embodiments 1 to 3, wherein the C 2 _ 4 olefin is obtained from a separation section, a process vessel, or a dedicated storage facility.
  • Embodiment 5 The process of any of embodiments 1 to 4, wherein the cooling liquid is introduced to the reactor at a temperature of -20 to 0°C, preferably -10 to -1°C, more preferably -4 to -1°C.
  • Embodiment 6 The process of any of embodiments 1 to 5, wherein the first temperature is 0 to 100°C, preferably 0 to 60°C, more preferably 10 to 60°C, even more preferably 10 to 20°C.
  • Embodiment 7 The process of any of embodiments 1 to 6, wherein the oligomerization reactor is a bubble column reactor.
  • Embodiment 8 The process of any of embodiments 1 to 7, wherein the linear alpha olefin product comprises C 4 _i 8 linear alpha olefins.
  • Embodiment 9 The process of any of embodiments 1 to 8, wherein the oligomerization is a selective trimerization or tetramerization, preferably a selective
  • Embodiment 10 The process of any of embodiments 1 to 9, wherein the second temperature is 0 to 30°C, preferably 0 to 10°C, more preferably 0°C.
  • Embodiment 11 The process of any of embodiments 1 to 10, wherein the oligomerizing is further in the presence of a solvent and a catalyst composition.
  • Embodiment 12 The process of embodiment 11, wherein the solvent is an aromatic solvent, preferably toluene, xylenes, benzene, mesitylene, ethylbenzene,
  • aromatic solvent preferably toluene, xylenes, benzene, mesitylene, ethylbenzene,
  • isopropylbenzene or a combination comprising at least one of the foregoing.
  • Embodiment 13 The process of embodiment 11 or 12, wherein the catalyst composition comprises a chromium source, a heteroatomic multidentate ligand, an activator, and optionally, a modifier, preferably wherein the chromium source is at least one of
  • the heteroatomic multidentate ligand is (phenyl) 2 PN(iso-propyl)P(phenyl)N(iso-propyl)H;
  • the activator is a tri(Ci_ 6 alkyl) aluminum; and the modifier comprises tetraphenylphosphonium chloride,
  • dodecyltrimethylammonium chloride isopropylamine hydrochloride, triethylamine
  • tetraethylammonium bromide p-toluidine hydrochloride, dimethyldistearylammonium chloride, (tri-n-butyl)-n-tetradecylphosphonium chloride, benzoyl chloride and acetyl chloride, or a combination comprising at least one of the foregoing.
  • Embodiment 14 The process of embodiment 11 or 12, wherein the catalyst composition comprises a zirconium-containing catalyst and an organoaluminum co-catalyst.
  • Embodiment 15 The process of any of embodiments 11 to 14, further comprising discontinuing feeding the catalyst composition to the reactor when the temperature exceeds a predetermined value.
  • Embodiment 16 The process of any of embodiments 1 to 15, further comprising reducing the reactor level when the temperature exceeds a predetermined value.
  • Embodiment 17 The process of any of embodiments 11 to 16, further comprising increasing the flowrate of solvent into the reactor when the temperature exceeds a predetermined value.
  • Embodiment 18 The process of any of embodiments 1 to 17, wherein injecting the cooling liquid into the reactor removes 60 to 80% of the total heat of reaction.
  • Embodiment 19 The process of any of embodiments 1 to 18, wherein introducing the gaseous ethylene stream at the first temperature removes 20 to 40% of the total heat of reaction.
  • Embodiment 20 The process of any of embodiments 1 to 19, wherein the cooling liquid is introduced into the liquid phase of the reactor.
  • Embodiment 21 The process of any of embodiments 1 to 20, wherein the cooling liquid is introduced into the gas phase of the reactor.
  • Embodiment 22 The process of any of embodiments 3 to 21, wherein introducing the gaseous ethylene stream at the second temperature and increasing the amount of the cooling liquid injected into the reactor is continued until the reaction temperature is at or below the predetermined value.
  • Embodiment 23 A process for removing heat from an oligomerization reaction comprising, introducing a gaseous ethylene stream at a temperature of 10 to 60°C to an oligomerization reactor having a liquid phase and a gas phase and being at a reaction
  • Embodiment 24 A process for removing heat from an oligomerization reaction comprising, introducing a gaseous ethylene stream at a temperature of 10 to 60°C to an oligomerization reactor having a liquid phase and a gas phase and being at a reaction
  • Embodiment 25 A process for removing heat from an oligomerization reaction comprising, introducing a gaseous ethylene stream at a temperature of 10 to 60°C to an oligomerization reactor having a liquid phase and a gas phase and being at a reaction
  • compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate components or steps herein disclosed.
  • the compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any steps, components, materials, ingredients, adjuvants, or species that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.
  • alkyl means a branched or straight chain, unsaturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s- pentyl, and n- and s-hexyl.
  • Alkoxy means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups.
  • Alkylene means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH 2 -) or, propylene (-(CH 2 )3- )).
  • Cycloalkylene means a divalent cyclic alkylene group, -C n H 2n -x, wherein x is the number of hydrogens replaced by cyclization(s).
  • Cycloalkenyl means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl).
  • Aryl means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl.
  • halo means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo groups (e.g., bromo and fluoro), or only chloro groups can be present.
  • hetero means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P.

Abstract

La présente invention décrit un procédé d'élimination de chaleur d'une réaction d'oligomérisation comprenant l'introduction d'un écoulement d'éthylène gazeux à une première température vers un réacteur d'oligomérisation, et l'oligomérisation d'au moins une partie de l'éthylène pour fournir un produit linéaire d'alpha oléfine, l'oligomérisation générant une chaleur réactionnelle. Le procédé comprend en outre l'injection de manière continue d'un liquide de refroidissement comprenant des oléfines en C2-4 dans le réacteur. L'injection du liquide de refroidissement dans le réacteur élimine au moins une partie de la chaleur réactionnelle générée durant la réaction d'oligomérisation.
PCT/IB2017/052158 2016-04-25 2017-04-13 Procédé d'élimination de chaleur d'une réaction d'oligomérisation WO2017187289A1 (fr)

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WO2023196322A1 (fr) * 2022-04-06 2023-10-12 ExxonMobil Technology and Engineering Company Procédés de conversion d'oléfines c2+ en oléfines à nombre de carbones plus élevé

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WO2023196322A1 (fr) * 2022-04-06 2023-10-12 ExxonMobil Technology and Engineering Company Procédés de conversion d'oléfines c2+ en oléfines à nombre de carbones plus élevé

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