WO2014082689A1 - Process for oligomerization of ethylene - Google Patents
Process for oligomerization of ethylene Download PDFInfo
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- WO2014082689A1 WO2014082689A1 PCT/EP2013/002670 EP2013002670W WO2014082689A1 WO 2014082689 A1 WO2014082689 A1 WO 2014082689A1 EP 2013002670 W EP2013002670 W EP 2013002670W WO 2014082689 A1 WO2014082689 A1 WO 2014082689A1
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- 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
- C07C2/34—Metal-hydrocarbon complexes
-
- 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
- C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/20—Carbonyls
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
- C07C2531/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of chromium, molybdenum or tungsten
Definitions
- the present invention relates to a process for the oligomerization of ethylene.
- LAOs linear alpha olefins
- comonomer-grade 1- hexene comonomer-grade 1- hexene
- catalyst compositions are known in the oligomerization of ethylene which can predominantly prepare 1-hexene oligomers.
- US 2010/0190939 Al discloses a catalyst composition comprising a chromium compound, a ligand of the general structure PNPN or PNPNP, and an activator or co-catalyst, which can be used in the oligomerization of ethylene to produce predominantly hexene oligomers.
- US 2012/0029258 Al discloses a quite similar catalyst composition additionally comprising a modifier containing organic or inorganic halide, or a modifier containing a free amine group, respectively.
- the commercial processes for ethylene trimerization known in the state of the art involve feeding a solvent, preferably toluene, ethylene recycle with fresh ethylene make-up, and the respective catalyst solution into a reactor, preferably a multi-tubular reactor, more preferably a bubble- column reactor.
- a reactor preferably a multi-tubular reactor, more preferably a bubble- column reactor.
- Un-reacted ethylene and light ends LAO that have partitioned into vapour phase exit from the top of the reactor as reactor overhead effluent and are flashed to recover only ethylene, while the condensed LAO, here mostly C 4 and minor C 6 , are combined with the liquid stream from the reactor bottom for further purification.
- the bottom reactor effluents containing the LAO products (> C4), together with dissolved ethylene, solvent and catalyst, are continuously withdrawn from the bottom of the reactor. Because the catalyst is still active, a quench medium, preferably n-decanol, is immediately added and blended with the reactor liquid effluents. This stream is sent to an ethylene recovery column where dissolved ethylene is recovered and recycled back into the reactor.
- a quench medium preferably n-decanol
- the bottom-ends of a C2 stripper comprising of LAOs, solvent, spent catalyst, quenching medium, is sent to a product recovery section, where it is fractionated in a series of about 4 to 5 distillation columns to individually separate butenes, hexenes, solvent, octenes, decenes and > C12 products, as well as polymers, etc.
- FIG. 1 A process known in the art is illustrated in figure 1.
- solvent 2, catalyst 3 and ethylene 4 are entered via respective lines to conduct an oligomerization process.
- Gaseous reactor overhead effluent is removed from the reactor and transferred to an externally located cooling device 5, such as a condenser.
- Ethylene obtained is transferred back into the reactor, if necessary with a fresh ethylene make-up 6.
- Reactor bottom effluent is quenched with a quenching medium 7 and combined with linear alpha-olefins liquefied in the cooling device 5. This quenched reactor bottom effluent is then sent to a series of fractionation columns 8-13.
- fractionation column 8 ethylene dissolved in the solvent is removed and separated, which can then be also recycled into the reactor.
- fractionation column 9 butenes may be separated, while in the fractionation column 10, hexenes can be removed and further processed afterwards. If, for example, toluene is utilized as solvent in the oligomerization reaction, this can be separated in fractionation column 1 1, while higher linear alpha-olefins, i.e. octenes and decenes, can be individually separated in fractionation columns 12 and 13. Any further residues, such as > C12 fractions, spent catalyst, polymer materials and quench media can be further processed, which is not described here in detail.
- solvent can be chosen so that the solvent removal step falls together with any of the steps i)-iv) or solvent can be chosen, like toluene, to add an additional step into the process.
- the catalyst comprises (1) a chromium compound, (2) a ligand of the general structure (A) R 1 R 2 P-N(R 3 )-P(R 4 )-N(R 5 )-H or (B) RiR 2 P-N(R 3 )-P(R 4 )-N(R 5 )-PR 6 R 7 , wherein Ri, R 2 , R 3 , R4, R 5 , R and R 7 are independently selected from halogen, amino, trime- thylsilyl, Cl-ClO-alkyl, C 6 -C 20 aryl and substituted C 6 -C 20 aryl, and (3) an activator or co- catalyst.
- a chromium compound (2) a ligand of the general structure (A) R 1 R 2 P-N(R 3 )-P(R 4 )-N(R 5 )-H or (B) RiR 2 P-N(R 3 )-P(R 4 )-N(R 5 )-
- the chromium compound is selected from the group consisting of CrCl 3 (THF) 3 , Cr(III) acetyl acetonate, Cr(III) octanoate, chromium hexacarbonyl, Cr(III)-2- ethyl hexanoate, benzene (tricarbonyl)-chromium, Cr(III) chloride.
- the activator or co-catalyst is selected from trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, ethylaluminumsesquichloride, diethyl aluminum chloride, ethyl aluminum dichloride, methyl aluminoxane (MAO) or mixtures thereof.
- the process is the trimerization of ethylene.
- a solvent should be chosen which is not simultaneously removed in the C 6 recovery step.
- the reactor overhead transferred and recycled in step b) preferably comprises unreacted ethylene or unreacted ethylene and butenes.
- the cooling device is preferably a condenser or a series of heat exchangers.
- the reactor overhead effluent is cooled in the cooling device to a temperature of - 30°C to +10°C, preferably -10°C to +5°C, more preferably -5°C to 0°C, and is then recycled into the reactor.
- Make-up ethylene can be added to the condensed reactor overhead effluent to be recycled into the reactor.
- the C8 and CIO fractions obtained in step iii) are preferably recycled into the reactor at a temperature of about 10-20°C.
- step iv) The residue obtained in step iv) can be sent to incineration or is used as fuel in an adjacent plant.
- the content of C4 in the reactor preferably is from 5 to 30 weight percent, the content of C8 is from 1 to 2 weight percent, and/or the content of CIO in the reactor is from 5-10 weight percent, all weight percentages given based on the total weight of liquids contained in the reactor.
- the total content of linear alpha-olefins in the liquid is from 30-75 wt.%, preferably 30-55 wt.% based on the total weight of liquids contained in the reactor.
- the total LAO content without ethylene (i.e. liquid product) is about 38%.
- the LAO/solvent ratio is preferably about 50%.
- the reactor may be a multi tubular reactor and/or a bubble column reactor.
- the process for the oligomerization of ethylene, preferably the trimerization of ethylene, according to the present invention provides reduced capital and operational expenditures, allows easy removal of heavy wax formed in the reactor or the reactor equipment, and improves heat removal of the exothermic oligomerization.
- the two separate distillation columns each for C8 and CIO used in the art, are according to the present invention combined in one single column.
- This can be advantageously utilized as the process of the present invention is preferably chromium catalyzed and produces a very limited amount of other oligomers apart from C6. Saving one column definitely reduces the overall investment cost of the entire process.
- chromium-based ethylene oligomerization catalyst a well known inherent disadvantage of chromium-based ethylene oligomerization catalyst is the formation of heavy wax. This solid residue (mostly polyethylene and heavy wax- es) tends to cause plugging/fouling inside the reactor and reactor equipment. This is especially the case in a bubble column reactor in which the condenser is located within the reactor.
- the internal condenser serves as additional surface for solid accumulations, such that the reactor needs to be periodically shut down for cleaning.
- the inventive process overcomes the disadvantage and avoids any internals within the ethylene trimerization reactor, while at the same time providing same cooling capacity to maintain the reactor temperature and/or mobilizing the solid residues out of the reactor to reduce fouling.
- the process of the present invention is practiced in a way that reactor plugging by polymer materials or waxes is significantly reduced by dissolving the polymer materials in higher fractions of C8 and CIO present within the reactor equipment.
- Polymer materials are known to be more soluble in heavier than lighter-end olefins.
- the inventive process can be operated at a reduced temperature by adjusting the reactor content in view of both fractions, C8 and CIO, which also enhances ethylene solubility. This will potentially benefit catalyst activity as well.
- Fig. 1 discloses a schematic illustration of a state of the art commercial process for oligomerization
- Fig. 2 is a schematic illustration of the process of the present invention.
- solvent 20 (optionally with fresh make-up solvent), catalyst 30 and ethylene 40 (optionally with fresh make-up ethylene 60) are entered into a reactor 10 for oligomerization.
- Reactor overhead effluent preferably containing ethylene and butenes, is transferred to an externally located cooling device 50 and is recycled, either with fresh make-up ethylene or directly, into the reactor 10.
- Reactor bottom effluent is discharged from the reactor 10 and transferred to a quenching unit 70 were quenching medium is added.
- the quenched reactor bottom effluent is then transferred to a series of fractionation columns 80-1 10, wherein in the first fractionation column 80 ethylene dissolved in the solvent and butenes are separated jointly and transferred to the cooling device 50 to be finally recycled into the reactor 10.
- fractionation column 90 hexenes are separated and discharged for further processing. If, for example, toluene is used as solvent, this can be removed and separated in fractionation column 100.
- C8 and CIO fractions are removed and separated simultaneously (jointly) in fractionation column 1 10. C8 and CIO fractions are recycled into the reactor 10, while any further residues can be then transferred for further processing.
- a multi compartment reactor model was developed to account for detailed hydrodynamics, thermodynamics and the variable gas flow-rate resulting from chemical/physical contraction, and gas/liquid re-circulation in a bubble-column reactor.
- the reactor model was coupled to a mechanistic kinetic model developed specifically for the novel ethylene trimerization catalyst system described by US 20120029258.
- the model was used to analyze one embodiment of the present invention.
- the performance of a pilot-scale bubble-column reactor for ethylene trimerization process for this embodiment of the present invention was verified with the developed rigorous reactor model.
- a comparative example is provided illustrating a process for oligomerization known in the art, however utilizing an externally located condenser with a total reflux to separate uncon- verted ethylene from reactor top effluents.
- the separated ethylene is combined with make-up ethylene and ethylene from C2 column, which is recycled back to the reactor.
- the feed gas composition is mostly ethylene, i.e., 98-99 wt.% C2.
- 1-butene is not present in the ethylene recycle stream, nor is there any recycling of C8 and CIO fractions into the reactor.
- Table 1 Stream analysis for the comparative example with an overhead condenser having total reflux and without C 4 recycle
- Ethylene and 1 -butene are sent directly to the externally located condenser after passing through an heat exchanger to reduce temperature to about 35°C.
- the condensed ethylene/ 1-butene enters the reactor as liquid streams preferably from the top of a disengagement zone, even more preferably from the side towards the reaction zone for effective cooling.
- the ethylene/ 1-butene content in the reactor can be maintained between 5-30 wt% via a purge stream.
- decenes/l-octene from the top of 1-C 8 /Ci 0 fractionation column are routed back to the reactor after been cooled from 170°C to 10 ⁇ 20°C.
- the decenes content in the reactor can be maintained between 5-10% via a purge stream. Additional duty to cool the recycled l-Cg/Cio to lower temperatures may have to be considered. Notwithstanding, the extra benefits provided by the recycled heavy fraction for polymer mobilization and reactor cooling in form of sensible heats may offset this duty.
- Table 3 shows the stream analysis, while Table 4 illustrates the key process indicators for this inventive process.
- Table 3 Stream analysis for the preferred embodiment of present invention with C 2 /C 4 as recycled as liquid streams and 1-octene/decenes recycled
- Condenser temperature 274.150 As shown in the illustrative example, ethylene per pass conversion is ⁇ 8% with condenser duty of -5kW operated at 1°C. This embodiment typify the lower ethylene feed rate at 50 kg/hr.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract
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Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015544367A JP6141441B2 (en) | 2012-11-28 | 2013-09-05 | Ethylene oligomerization process |
MX2015006560A MX2015006560A (en) | 2012-11-28 | 2013-09-05 | Process for oligomerization of ethylene. |
IN3293DEN2015 IN2015DN03293A (en) | 2012-11-28 | 2013-09-05 | |
SG11201503088QA SG11201503088QA (en) | 2012-11-28 | 2013-09-05 | Process for oligomerization of ethylene |
RU2015124111A RU2635551C9 (en) | 2012-11-28 | 2013-09-05 | Method of ethylene oligomerization |
US14/125,805 US10112876B2 (en) | 2012-11-28 | 2013-09-05 | Process for oligomerization of ethylene |
BR112015012012-1A BR112015012012B1 (en) | 2012-11-28 | 2013-09-05 | process for ethylene oligomerization |
KR1020157012774A KR101951268B1 (en) | 2012-11-28 | 2013-09-05 | Process for oligomerization of ethylene |
CN201380056522.7A CN104781216B (en) | 2012-11-28 | 2013-09-05 | The method of ethylene oligomerization |
CA2889817A CA2889817C (en) | 2012-11-28 | 2013-09-05 | Process for oligomerization of ethylene |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12194589.3 | 2012-11-28 | ||
EP12194589.3A EP2738151B8 (en) | 2012-11-28 | 2012-11-28 | Process for oligomerization of ethylene |
Publications (1)
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WO2014082689A1 true WO2014082689A1 (en) | 2014-06-05 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2013/002670 WO2014082689A1 (en) | 2012-11-28 | 2013-09-05 | Process for oligomerization of ethylene |
Country Status (15)
Country | Link |
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US (1) | US10112876B2 (en) |
EP (1) | EP2738151B8 (en) |
JP (1) | JP6141441B2 (en) |
KR (1) | KR101951268B1 (en) |
CN (1) | CN104781216B (en) |
BR (1) | BR112015012012B1 (en) |
CA (1) | CA2889817C (en) |
ES (1) | ES2524905T3 (en) |
IN (1) | IN2015DN03293A (en) |
MX (1) | MX2015006560A (en) |
MY (1) | MY169037A (en) |
RU (1) | RU2635551C9 (en) |
SG (1) | SG11201503088QA (en) |
TW (1) | TWI598322B (en) |
WO (1) | WO2014082689A1 (en) |
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Also Published As
Publication number | Publication date |
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KR101951268B1 (en) | 2019-02-22 |
KR20150088249A (en) | 2015-07-31 |
RU2635551C2 (en) | 2017-11-14 |
US10112876B2 (en) | 2018-10-30 |
IN2015DN03293A (en) | 2015-10-09 |
CA2889817A1 (en) | 2014-06-05 |
RU2635551C9 (en) | 2017-12-06 |
EP2738151B8 (en) | 2014-12-17 |
EP2738151A1 (en) | 2014-06-04 |
MY169037A (en) | 2019-02-07 |
ES2524905T3 (en) | 2014-12-15 |
BR112015012012B1 (en) | 2020-12-08 |
CN104781216A (en) | 2015-07-15 |
CA2889817C (en) | 2016-10-11 |
MX2015006560A (en) | 2015-08-05 |
JP6141441B2 (en) | 2017-06-07 |
TW201420550A (en) | 2014-06-01 |
EP2738151B1 (en) | 2014-11-12 |
TWI598322B (en) | 2017-09-11 |
RU2015124111A (en) | 2017-01-11 |
JP2015535529A (en) | 2015-12-14 |
BR112015012012A2 (en) | 2017-07-11 |
CN104781216B (en) | 2016-11-09 |
SG11201503088QA (en) | 2015-05-28 |
US20150299069A1 (en) | 2015-10-22 |
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