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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
• • 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
  • C07C2/24—Catalytic processes with metals
• • 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/74—Iron group metals
  • B01J23/755—Nickel
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C11/00—Aliphatic unsaturated hydrocarbons
  • C07C11/02—Alkenes
  • C07C11/04—Ethylene
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
  • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
  • C07C2521/04—Alumina
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
  • C07C2523/74—Iron group metals
  • C07C2523/755—Nickel
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
  • C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • C07C2527/06—Halogens; Compounds thereof
  • C07C2527/135—Compounds comprising a halogen and titanum, zirconium, hafnium, germanium, tin or lead
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • C07C2531/14—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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/10—Process efficiency

Definitions

• the present invention relates to manufacture of higher olefins by oligomerization of a lower olefin, and in particular to oligomerization of ethylene, with simultaneous separation of the higher olefins, using catalytic distillation conditions.
• the process is operated without the need for added solvent, in contrast to the prior art.
• the higher olefins initially so formed normally are terminal (alpha) olefins ie. olefins having a single double bond at the first carbon atom.
• the terminal olefins may then isomerize to one or more internal olefins ie olefins having a double bond on an interior carbon atom.
• the terminal olefins usually have higher commercial utility and value than the internal olefins.
• SHOP Shell Higher Olefins Process
• Solid state catalyst processes used in slurry reactor systems allow for easier separation of the catalyst from the reaction mixtures but present several challenges. There is strong adsorption of the products on the catalyst surfaces, as well as on the reactant. Also, there is a negative thermodynamic influence on selectivity to the desired terminal olefin products at high reaction temperatures, with internal olefins being formed. There is a need for more active catalysts. Each of these factors including catalyst deactivation by the formation of decomposition and isomerisation products, must be overcome.
• Nickel/Sulfonated Alumina Catalyst hid. Eng. Chem. Res., 36, 3433-3438 (1997), the disclosure of which is incorporated herein by reference.
• oligomerization of lower olefins and in particular for oligomerization of ethylene, without use of an added solvent, so that there is no need for separation of the higher olefins product from a fluid such as a hydrocarbon solvent.
• the process operates under catalytic distillation conditions such that the product higher olefins are in liquid form, so that the product is easily separated from the reaction mixture as liquid..
• a process for making higher olefins of formula C n H 2n , wherein n is an integer greater than two through catalytic oligomerization of lower olefins wherein n is an integer from 2 to 5, and in particular to oligomerization of ethylene, and simultaneous separation of the higher olefins as liquid using catalytic distillation conditions e.g. in a catalytic distillation column.
• the process which can be continuous, is operated at a temperature and a pressure such that the higher olefins are primarily in the liquid phase and the ethylene is present both as gas and dissolved phase, to form a solution with the liquid higher olefins.
• Suitable catalysts include the homogeneous and heterogeneous catalysts described above e.g. a catalyst comprising nickel dispersed on a non-porous alumina support is highly active and has good selectivity to terminal olefins at low temperatures.
• a catalyst comprising nickel dispersed on a non-porous alumina support is highly active and has good selectivity to terminal olefins at low temperatures.
• ALON the above-described catalyst known as ALON has been found to be useful
• FIG. 1 is a schematic diagram of a catalytic distillation for concurrent oligomerization of ethylene and separation of higher olefins.
• FIG. 2 shows a first profile of composition and temperature from modeling of the process of ethylene oligomerization using a catalytic distillation column.
• Stage 1 is at the top of the column.
• FIG. 3 shows a second profile of composition and temperature from modeling of the process of ethylene oligomerization using a catalytic distillation column.
• P 40 atm
• RXN 0.45
• Equilibrium conversion 0.05
• Total conversion of Ethylene 44.03%.
• FIG. 4 shows a third profile of composition and temperature from modeling of the process of ethylene oligomerization using a catalytic distillation column.
• P 40 atm
• Equilibrium conversion 0.05
• Total conversion of Ethylene 44.03%.
• FIG. 5 shows a fourth profile of composition and temperature from modeling of the process of ethylene oligomerization using a catalytic distillation column.
• P 40 atm
• RR I 5
• D/F 0.35
• RXN Stage 3
• Equilibrium conversion 0.10
• Total conversion of Ethylene 61.27%.
• FIG. 6 shows a fifth profile of composition and temperature from modeling of the process of ethylene oligomerization using a catalytic distillation column.
• P 40 atm
• RR 79
• D/F 0.05
• RXN Stage 3
• Equilibrium conversion 0.50
• Total conversion of Ethylene 96.88%.
• FIG. 7 shows a sixth profile of composition and temperature from modeling of the process of ethylene oligomerization using a catalytic distillation column.
• an apparatus 10 having a catalytic distillation column 12 is provided for the present process.
• Column 12 has an upper first portion 14, a middle second portion 16 and a lower third portion 18.
• a condenser 20 is provided at first portion 14 for condensation of condensable components of a gas phase reaction mixture 27 for their return as liquids to first portion 14 of column 12.
• a reboiler 22 is provided at third portion 18 of column 12 for vaporization of the more volatile components of a liquid reaction mixture 28 there collected for return as volatiles to third portion 18 of column 12.
• Second portion 16 of column 12 includes a catalyst bed 24 having therein an oligomerization catalyst 26.
• catalyst 26 is an acidic catalyst.
• the catalyst is considered to be acidic if it consumes a significant amount of base during titration.
• the sulfated nickel/alumina(ALON) will consume NH 3 during a titration experiment. This finding is in agreement with that for a different system by Espinoza et al. in "Catalytic Oligomerization of Ethylene over Nickel- exchanged Amorphous Silica-alumina: Effect of the Acid Strength of the Support" Appl. Catal. 29, 295 (1987).
• One preferred catalyst 26 comprises nickel (Ni) well-dispersed and supported on a non-porous alumina support, for example the commercial product ALON.
• ALON nickel
• a non-porous alumina support for example the commercial product ALON.
• ALON nickel
• Such a catalyst has highly active Ni sites that enable the oligomerization process to be conducted under very mild conditions (about -10 0 C to about 8 0 C) for oligomerization of substantially pure ethylene(see below) as feed 30 when operated at, for example, about 40 to 50 atmospheres pressure.
• the desirable surface acidity is achieved via surface sulphation. Since ALON has only external surfaces and the reaction products are large molecules, the desorption of reaction products is enhanced(less products adsorbed on catalyst surface) resulting in higher reaction rate and improved catalyst stability.
• Feed 30 is more volatile than products 36.
• products 36 are present primarily in liquid phase 28.
• feed 30 is fed as liquid, and it is present as gas and liquid in equilibrium within the refluxing reaction mixture.
• the ethylene feed 30 may be selected from substantially pure ethylene, typically 99.9% ethylene with 0.1% ethane as used in polyethylene manufacture, or a mixture rich in ethylene, for example an unfractionated industrial ethylene stream comprising, typically, about 80.5% ethylene, 18.2% ethane and 1.3% acetylene.
• the acetylene may be removed or converted before being fed to the oligomerization reactor. It will be appreciated by those skilled in the art that the reaction parameters to provide the low olefin feed in liquid form at its boiling point will vary somewhat for different compositions of the feed mixture rich in ethylene.
• feed 30 comprises the above unfractionated industrial ethylene stream
• the mixture flashes between 16 0 C and 17.5 0 C at 50 atm.
• the low olefin feed composition includes C3, C4, C5, etc., the temperature and pressure required to provide the feed in the requisite liquid form, will be different ie different boiling points.
• Liquid ethylene 30 is fed via an inlet line 32 to upper portion 14 of column at a position above an upper surface 34 of catalyst bed 24.
• Ethylene 30 is oligomerized to a series of higher olefins CnH 2 n 36 which mix with ethylene to form liquid phase reaction mixture 28 that descends via a bottom surface 38 of catalyst bed 24 to collect in third portion 18 of column 12.
• Liquid ethylene 30 supplied via line 32 washes liquid phase products 36 off the catalyst surface as liquid mixture 28.
• ethylene 30 is continuously supplied, reacts within catalyst bed 24, and with products 36 descends as liquid mixture 28.
• inlet line 32 As shown in Figure 1 is above catalyst bed 24. It will be recognized by those skilled in the art that inlet line 32 may be positioned above, below, or at some point within the vertical extent of catalyst bed 24. Further, there may be more than one feed line 32 positioned at different heights on column 12. The product distribution is affected by the positioning of inlet line 32. The distribution within the slate of products can be controllably varied by amending the position of inlet line 32, and controlling the reflux rate and the reboiler duty. It should be noted that line 42 is optional. It is required only if there present impurities in the gas phase at the condenser.
• Liquid product mixture 28 is removed via reboiler 22, from which the more volatile components, and in particular ethylene, are returned as volatiles to column 12. The remaining portion is liquid products 36 that are removed via line 40.
• the rate of feed of ethylene 30, the process operating conditions, and the rate of removal of liquid products determines the composition of the product liquid removed from column 12.
• the reaction is operated at elevated pressure, for example 40 atmospheres, so as to maintain ethylene 30 at its boiling point.
• the process operates at low temperatures, preferably from about -20 0 C to about 8 0 C, and more preferably at -10 0 C to 8 0 C, when operated at 40 to 50 atmospheres pressure. Under these conditions ethylene is present primarily as liquid at its boiling point in first portion 14 of column 12, and as a solution with products 36 as a condensed phase 28 within catalyst bed 24 and in third portion 18 of column 12.
• the new process for oligomerization of olefins, and in particular oligomerization of ethylene has the following beneficial characteristics.
• catalysts are active for oligomerization of ethylene, including homogeneous catalysts and heterogeneous catalysts.
• One preferred catalyst has highly active Ni sites that enable oligomerization process at very mild conditions.
• the desirable surface acidity is achieved via surface sulphation.
• This preferred catalyst comprises Ni well dispersed and supported on a non-porous alumina support, thus facilitating product desorption, consequently minimizing isomer formation, and so enhancing selectivity to desirable terminal linear olefins (alpha-olefms).
• Both liquid feed and higher olefins formed through oligomerization of the feed also serve as the liquid medium, without added solvent, thus facilitating product desorption from the catalyst surface.
• At least one fixed catalyst bed 24 is used as the reactor in catalytic distillation column 12, and there is no need to provide another column for separation of catalyst from the reaction mixtures, in contrast to possible highly acidic homogeneous reactive distillation systems that may be used without solvent.
• the heterogeneous reaction is substantially similar to the liquid phase reaction used in several present commercial processes, the catalyst and catalytic distillation process described herein confer significant additional benefits.
• Example 1 Activity of catalyst comprising Ni supported on alumina.
• Catalyst charge 0.2, 0.3, 0.4, 0.5 g
• the catalyst is highly active for oligomerization. It was found that the process has first order kinetics with respect to ethylene (Eq. 2) and the activation energy is 16.3 kJ/mol. Neither inter- nor intra-particle resistances may be ignored with this catalyst.
• Eq. 3 The combined resistance to external diffusion, internal diffusion and reaction, expressed as in Eq. 3, is the controlling step.
• Example 2 Simulation of the process with different operating parameters.
• the following are data obtained through simulations using ASPEN PLUS® software.
• the design was based on a column equipped with 20 equilibrium stages.
• Figures 2-6 Figure 7 is another simulation run with only 10 equilibrium stages in the column, all other conditions are identical to those used in Figure 6.
• the temperature profile provides the design data for choosing the reboiler and the condenser.
• Figures 2 through 7 show the concentration and temperature profiles throughout column 12 using different sets of process operating parameters for oligomerization of ethylene to higher olefins. In each case, the reactions occurred over catalyst 26 within catalyst bed 24.
• reaction occurs sufficiently rapidly that there is little ethylene present in third portion 18 of column, and ethylene dissolved in liquid phase 28 is returned to column 12 as volatiles from reboiler 22.
• ethylene dissolved in liquid phase 28 is returned to column 12 as volatiles from reboiler 22.
• the small proportion of olefin products 36 present in the vapor phase at first portion 14 of column 12 are returned as liquid from condenser 20.
• the catalytic distillation column can be operated with a homogeneous catalyst.
• the catalyst is mixed with feed ethylene and introduced at the top of the column.

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