Classifications

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  • 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
  • C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
  • C10G57/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process with polymerisation
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  • 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
  • C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
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  • 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
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  • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
  • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
  • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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  • 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
  • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
  • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
  • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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  • 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
  • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • C07C2521/08—Silica
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • C07C2523/20—Vanadium, niobium or tantalum
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • C07C2523/20—Vanadium, niobium or tantalum
  • C07C2523/22—Vanadium
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  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • C07C2523/24—Chromium, molybdenum or tungsten
  • C07C2523/28—Molybdenum
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  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • C07C2523/24—Chromium, molybdenum or tungsten
  • C07C2523/30—Tungsten
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  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • C07C2523/32—Manganese, technetium or rhenium
  • C07C2523/34—Manganese
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  • 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
• • C—CHEMISTRY; METALLURGY
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
  • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
  • C07C2529/46—Iron group metals or copper
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
  • C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• • 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
  • C10G2300/1025—Natural gas
• • 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
  • C10G2300/1081—Alkanes
• • 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
  • C10G2400/02—Gasoline
• • 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
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

• the present disclosure relates to upgrading ethane-containing light paraffin (C5-) streams, particularly natural gas liquid streams.
• NGL natural gas liquid
• An alternative process for converting alkanes to alkenes is by selective oxidation, in which the alkane is catalytically dehydrogenated in the presence of oxygen.
• the process is also called oxidative dehydrogenation (ODH) and can be carried out at lower reaction temperatures than reductive dehydrogenation processes discussed above, and without the same problem of coke formation.
• ODH oxidative dehydrogenation
• US Patent No. 8,519,210 discloses a process for the oxidative dehydrogenation of gaseous hydrocarbons, particularly ethane, to olefins, particularly ethylene.
• the present disclosure resides in a process for upgrading an ethane-containing C5- paraffin stream, the process comprising:
• C n hydrocarbon wherein n is a positive integer, e.g., 1, 2, 3, 4, or 5, means a hydrocarbon having n number of carbon atom(s) per molecule.
• Cn+ hydrocarbon wherein n is a positive integer, e.g., 1, 2, 3, 4, or 5, means a hydrocarbon having at least n number of carbon atom(s) per molecule.
• d- hydrocarbon wherein n is a positive integer, e.g., 1, 2, 3, 4, or 5, means a hydrocarbon having no more than n number of carbon atom(s) per molecule.
• hydrocarbon encompasses mixtures of hydrocarbon having different values of n. As used herein, the numbering scheme for the groups of the Periodic Table of the Elements is as disclosed in Chemical and Engineering News, 63(5), 27 (1985).
• ethane-containing light paraffin (Cs-) stream particularly a natural gas liquid stream or fraction thereof, to gasoline and/or distillate boiling range hydrocarbons.
• the ethane-containing light paraffin (C5-) stream is reacted with an oxygen containing gas in the presence of a selective oxidation catalyst under conditions to convert at least part of the ethane to ethylene.
• At least part of the resultant ethylene is then oligomenzed in a single stage or in multiple stages to produce the desired gasoline and/or distillate boiling range hydrocarbons. Residual C5- paraffins can be separated from the selective oxidation effluent and/or the oligomerization effluent and recycled back to the selective oxidation step.
• the present process can be used to upgrade any ethane-containing light paraffin (C5-) feedstock, but is particularly effective for upgrading natural gas liquid (NGL) streams and fractions thereof.
• NGL natural gas liquid
• the as-produced natural gas is initially subjected to multiple pretreatment steps to remove condensate, water, nitrogen and reactive gaseous impurities, such as hydrogen sulfide and carbon oxides, before being fed to the demethanizer.
• the NGL can be treated, for example by fractionation, to remove part or all of the C3+ hydrocarbons.
• Preferred ethane-containing light paraffin (C5-) streams useful in the present process contain at least 80 wt%, such as at least 85 wt%. for example at least 90 wt%, such as at least 95 wt%, even up to 100 wt%, ethane; less than 20 wt %, such as less than 15 wt%, for example less than 10 wt%, such as less than 5wt % methane and/or less than 20 wt %, such as less than 15 wt%, for example less than 10 wt%, such as less than 5wt % propane.
• most light paraffin streams employed in the present process will contain at least 0.5 wt% methane and/or at least 0.5 wt% propane.
• Any catalyst effective for the oxydehydrogenation of ethane in a C5- mixed paraffin stream to produce ethylene can be used in the present process.
• the effectiveness of the catalyst is usually primarily determined by two parameters: the activity of the catalyst for ethane conversion, and selectivity (efficiency) of the conversion to ethylene rather than acetic acid.
• Suitable oxydehydrogenation catalysts with a desirable combination of activity and selectivity are frequently mixed metal oxides, especially mixed oxides of molybdenum and vanadium, optionally with one or more other metal oxides.
• One such preferred oxide is niobium oxide.
• X Cr, Mn, Nb, Ta, Ti, V, and/or W
• Y Bi, Ce, Co, Cu, Fe, K, Mg, Ni, P, Pb, Sb, Si, Sn, TI, and/or U
• a l
• U. S. Patent No. 9,409, 156 discloses the oxidative dehydrogenation of light paraffins, such as ethane, at moderate temperatures ( ⁇ 500° C ) to produce ethylene without the formation of side products, such as acetic acid and/or other oxygenated hydrocarbons, using a tellurium-free, multimetallic catalyst possessing orthorhombic Ml phase having the formula:
• A represents Nb, W, Ga, Bi, Sn, Cu, Ti, Fe, Co, Ni, Cr, Zr, rare earth metals or rare earth alkaline metals or mixtures of thereof, h and i, respectively, are each between 0.001 and 4.0, 0 ⁇ j ⁇ 2.0, the ratio i/h is between 0.3 and 10 0, and x represents the number determined by and consistent with the valence requirements of the other elements present in the multimetallic mixed oxide.
• any or all of the above mixed metal oxide catalyst compositions may be used in the ethane oxidative dehydrogenation step of the present process.
• the mixed metal oxide catalyst is preferably prepared from a solution of soluble compounds (salts, complexes or other compounds) of each of the desired elements.
• the solution is preferably an aqueous system having a pH of 1 to 7, and preferably 2 to 6.
• the solution of the element containing compounds is prepared by dissolving sufficient quantities of soluble compounds of each of the elements, so as to provide the desired gram-atom ratios of the elements.
• the selected compounds of the various elements should be mutually soluble. Where any of the selected compounds of such elements are not mutually soluble with the other compounds, they can be added last to the solution system.
• the catalyst composition is then prepared by removing the water or other solvent from the mixture of the compounds in the solution system, such as by evaporation.
• the dried mixture may then be calcined by being heated at about 220 to 550°C in air or oxygen for 1/2 to 24 hours to produce the final catalyst.
• the mixed metal oxide catalyst can be used with or without a support.
• Suitable supports include silica, aluminum oxide, silicon carbide, zirconia, titania and mixtures thereof.
• the supported catalyst When used on a support, the supported catalyst usually comprises about 10 to 50 weight % of the mixed metal oxide catalyst composition, with the remainder being the support.
• the compounds of the desired elements are deposited on a particulate porous support by immersing the support individually or collectively in a solution of each of the compounds, evaporating off the major portion of the solvent, and then drying the system at about 80 to 220°C for 2 to 60 hours. Again the dried composition may then be calcined by being heated at about 220 to 550°C in air or oxygen for 1/2 to 24 hours to produce the final catalyst.
• one or more of the metal components in the mixed metal oxide catalyst should be slightly reduced below its highest possible oxidation state. This may be accomplished by thermal treatment of the catalyst in the presence of reducing agents such as NH3 or organic reducing agents, such as the organic complexing agents, which are introduced into the solution systems from which the catalysts are prepared.
• the catalyst may also be reduced in the reactors in which the oxidation reaction is to be conducted by the passage of hydrogen or hydrocarbon reducing agents such as ethane, ethylene, or propylene through the catalyst bed.
• the oxydehydrogenation reaction is conducted by contacting the ethane-containing light paraffin (C5-) with any oxygen containing gas, such as air, in the presence of one or more mixed metal oxide catalysts as described above under conditions effective to selectively oxidize at least part of the ethane to produce ethylene.
• Suitable conditions include a temperature from 200 °C to 700 °C, such as from 300 to 550°C and a pressure from 100 kPa-a to 6895 kPa-a, such as from 100 to 5000 kPa-a.
• the reaction can be conducted in any suitable reactor, such as a fixed bed reactor or fluidized bed reactor.
• the amount of oxygen added to the light paraffin (C5-) feed is not critical but generally is selected such that the total feed to the oxydehydrogenation reaction is from 0.01 to 0.7 mole, such as from 0.1 to 0.6 mole of molecular oxygen (as pure oxygen or in the form of air) per mole of ethane in the feed. Since the reaction is exothermic, diluents can also be supplied to the reaction to moderate heat generation. Suitable diluents include water, nitrogen, helium, CO2, and methane. It will be appreciated that water is an inherent by-product of the reaction.
• the oxidative dehydrogenation step can be conducted so as to selectively convert at least 50%, such as at least 60%, such as at least 70%, such as at least 80%, even as much as 90%, of the ethane in the feed to ethylene.
• any propane and/or butane in the feed will be at least partly converted to propylene and butenes.
• the product of the oxidative dehydrogenation step may contain various organic oxygenates, for example carboxylic acids, such as acetic acid and acrylic acid; alcohols such as methanol and ethanol; aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, and acrylic aldehyde; esters, such as ethyl acetate and propane acetate and ketones, such as acetone.
• the product may also contain unreacted C5- hydrocarbons, as well as inert impurities present in the initial feedstock, such as N2 and CO2.
• the product of the oxidative dehydrogenation step may be fed to the next stage in the process, namely ethylene oligomenzation, without intermediate separation or may initially be subjected to one or more separation steps, for example, to remove unreacted C5- hydrocarbons for recycle to the dehydrogenation step or to recover valuable organic oxygenates, such as acetic acid and acrylic acid.
• separation steps for example, to remove unreacted C5- hydrocarbons for recycle to the dehydrogenation step or to recover valuable organic oxygenates, such as acetic acid and acrylic acid.
• organic oxygenates such as acetic acid and acrylic acid.
• intermediate separation is avoided since propene and higher olefins as well as many organic oxygenates can be converted to gasoline and/or distillate boiling range hydrocarbons in the oligomenzation process.
• Oligomerization of at least part of the ethylene component in the oxidative dehydrogenation effluent to produce gasoline and/or distillate boiling range hydrocarbons may be achieved by contacting the ethylene with one or more oligomerization catalysts in one or multiple stages.
• the oligomerization catalyst employed in at least one oligomerization stage comprises at least one medium pore molecular sieve having a Constraint Index of 2-12 (as defined in U. S. Patent No. 4,016,218).
• Suitable medium pore molecular sieves include ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48.
• ZSM-5 is described in detail in U. S. Patent Nos. 3,702,886 and Re. 29,948.
• ZSM-11 is described in detail in U. S. Patent No. 3,709,979.
• ZSM-12 is described in U.S. Patent No. 3,832,449.
• ZSM-22 is described in U.S. Patent No.
• Suitable oligomerization catalysts comprise one or more large pore molecular sieves having a Constraint Index less than 2.
• Suitable large pore molecular sieves include zeolite beta, zeolite Y, Ultrastable Y (USY), Ultrahydrophobic Y (UHP-Y), Dealuminized Y (Deal Y), mordenite, ZSM-3, ZSM-4, ZSM-14, ZSM-18, ZSM-20 and mixtures thereof.
• Zeolite ZSM-3 is described in U. S. Patent No. 3,415,736.
• Zeolite ZSM-4 is described in U.S. Patent No. 4,021,947.
• Zeolite ZSM-14 is described in U.S. Patent No. 3,923,636.
• Zeolite ZSM-18 is described in U. S. Patent No. 3,950,496.
• Zeolite ZSM-20 is described in U. S. Patent No. 3,972,983.
• Zeolite Beta is described in U.S. Patent Nos. 3,308,069, and Re. No. 28,341.
• Low sodium Ultrastable Y molecular sieve (USY) is described in U.S. Patent Nos. 3,293, 192 and 3,449,070.
• Ultrahydrophobic Y (UHP-Y) is described in U.S. Patent No. 4,401,556.
• Dealuminized Y zeolite (Deal Y) may be prepared by the method found in U.S. Patent No. 3,442,795.
• Zeolite Y and mordenite are naturally occurring materials but are also available in synthetic forms, such as TEA-mordenite (i.e., synthetic mordenite prepared from a reaction mixture comprising a tetraethylammonium directing agent).
• TEA-mordenite is disclosed in U.S. Patent Nos. 3,766,093 and 3,894, 104.
• Suitable oligomerization catalysts comprise at least one molecular sieve of the MCM-22 family.
• the term "molecular sieve of the MCM-22 family" includes one or more of:
• molecular sieves made from a common second degree building block, being a 2- dimensional tiling of such MWW framework topology unit cells, forming a monolayer of one unit cell thickness, preferably one c-unit cell thickness;
• molecular sieves made from common second degree building blocks being layers of one or more than one unit cell thickness, wherein the layer of more than one unit cell thickness is made from stacking, packing, or binding at least two monolayers of one unit cell thickness.
• the stacking of such second degree building blocks can be in a regular fashion, an irregular fashion, a random fashion, or any combination thereof; and • molecular sieves made by any regular or random 2-dimensional or 3 -dimensional combination of unit cells having the MWW framework topology.
• Molecular sieves of the MCM-22 family include those molecular sieves having an X- ray diffraction pattern including d-spacing maxima at 12.4 ⁇ 0.25, 6.9 ⁇ 0.15, 3.57 ⁇ 0.07 and 3.42 ⁇ 0.07 Angstrom.
• the X-ray diffraction data used to characterize the material are obtained by standard techniques using the K-alpha doublet of copper as incident radiation and a diffractometer equipped with a scintillation counter and associated computer as the collection system.
• Materials of the MCM-22 family include MCM-22 (described in U.S. Patent No. 4,954,325), PSH-3 (described in U.S. Patent No. 4,439,409), SSZ-25 (described in U. S. Patent No. 4,826,667), ERB-1 (described in European Patent No. 0293032), ITQ-1 (described in U.S. Patent No 6,077,498), ITQ-2 (described in International Patent Publication No. WO97/17290), MCM-36 (described in U.S. Patent No. 5,250,277), MCM-49 (described in U.S. Patent No. 5,236,575), MCM-56 (described in U.S. Patent No. 5,362,697), UZM-8 (described in U.S. Patent No. 6,756,030), UZM-8HS (described in U.S. Patent No. 7,713,513) and mixtures thereof.
• the molecular sieves described above are employed in the oligomerization catalyst as an aluminosilicate material having a silica to alumina molar ratio of at least 10, such as at least 25 to 100.
• Preferred molecular sieves for use in the oligomerization reaction are those having a Constraint Index of 2-12 as described above, especially ZSM-5 and more partivularly ZSM-5 having a homogeneous crystal size of ⁇ 0.05 micron and a relatively high activity (alumina content) characterized by a S1O2/AI2O3 molar ratio of around 50: 1 or less.
• the above molecular sieves may be employed in their acid forms, ion exchanged or impregnated with one or more suitable metals, such as Ga, Pd, Zn, Ni, Co and/or other metals of Periodic Groups 3 to 14.
• the molecular sieve may include a hydrogenation-dehydrogenation component (sometimes referred to as a hydrogenation component) which is generally one or more metals of Groups 5, 6 and 8 to 13 of the Periodic Table, especially aromatization metals such as Ga, Pd, etc.
• Useful hydrogenation components include the noble metals of Groups 9 to 11, especially platinum, gold, silver, rhenium, and rhodium.
• the catalyst material may include two or more catalytic components, such as metallic oligomerization component (e.g., ionic Ni +2 and a shape-selective medium pore acidic oligomerization catalyst, such as ZSM-5 zeolite) which components may be present in admixture or combined in a unitary bifunctional solid particle.
• metallic oligomerization component e.g., ionic Ni +2
• a shape-selective medium pore acidic oligomerization catalyst such as ZSM-5 zeolite
• the above molecular sieves may be used as the oligomerization catalyst without any binder or matrix, i.e., in so-called self-bound form.
• the molecular sieve may be composited with another material which is resistant to the temperatures and other conditions employed in the oligomerization reaction.
• Such materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays and/or oxides such as alumina, silica, silica-alumina, zirconia, titania, magnesia or mixtures of these and other oxides.
• clays and/or oxides such as alumina, silica, silica-alumina, zirconia, titania, magnesia or mixtures of these and other oxides.
• the latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides.
• Clays may also be included with the oxide type binders to modify the mechanical properties of the catalyst or to assist in its manufacture.
• Use of a material in conjunction with the molecular sieve, i.e., combined therewith or present during its synthesis, which itself is catalytically active may change the conversion and/or selectivity of the catalyst.
• Inactive materials suitably serve as diluents to control the amount of conversion so that products may be obtained economically and orderly without employing other means for controlling the rate of reaction.
• These materials may be incorporated into naturally occurring clays, e.g., bentonite and kaolin, to improve the crush strength of the catalyst under commercial operating conditions and function as binders or matrices for the catalyst.
• the relative proportions of molecular sieve and inorganic oxide matrix vary widely, with the sieve content ranging from about 1 to about 90 percent by weight and more usually, particularly, when the composite is prepared in the form of beads, in the range of about 2 to about 80 weight percent of the composite.
• Oligomerization over the molecular sieves described above may be conducted over a wide range of temperatures and pressures, for example at temperatures from about 20°C to 300°C (preferably 50°C to 200°C) and pressures from ambient to about 5500 kPa (preferably about 250 to 2900 kPa).
• temperatures from about 20°C to 300°C (preferably 50°C to 200°C) and pressures from ambient to about 5500 kPa (preferably about 250 to 2900 kPa).
• higher severity conditions generally favor ethylene conversion and the production of gasoline (Cs-Cio) boiling-range products, whereas less severe conditions favor production of heavier distillate boiling-range products at the expense of ethylene conversion activity.
• the oligomerization may be conducted in two or more stages, with one stage being conducted at higher severity conditions to produce olefinic gasoline and pari or all of the gasoline being fed to a later oligomerization stage to produce distillate.
• the oligomerization over the molecular sieves described above may be preceded by, or occur simulataneously with, an ethylene dimerization step, in which part or all of the oxidative dehydrogenation product is contacted with a metal dimerization catalyst under conditions effective to convert ethylene to C4+ olefins, especially 1-butene.
• ethylene dimerization step in which part or all of the oxidative dehydrogenation product is contacted with a metal dimerization catalyst under conditions effective to convert ethylene to C4+ olefins, especially 1-butene.
• dimerization is used in the present specification to mean a specific case of oligomerization so that the broader term "oligomerization" is intended to include dimerization.
• oligomerization is also intended to processes in which the oligomerization is accompanied by cyclization to produce aromatic and non-aromatic cyclic olefins as well as non- cyclic linear or branched C4+ olefins.
• Suitable ethylene dimerization catalysts comprise one or more metals or compounds thereof selected from the group consisting of nickel, manganese, iron and copper deposited on a suitable support, such as silica. Where ethylene dimerization occurs simultanoeusly with oligomerization, the support may be one or more of the molecular sieves described above, especially ZSM-5.
• ethylene dimerization/oligomerization catalysts include mixed metal oxides containing, such as, as an oxide of a Group 4 metal, for example, Zr, and oxide of a Group 6 metal, such as W, optionally together with one or more oxides of Group 7 to 11 metals, such as Fe, Cu, Mn and Ce.
• a description of the production of such mixed metal oxides and their use in olefin oligomerization can be found in U.S. Patent No. 5,608,133, the entire contents of which are incorporated herein by reference.
• the oligomerization reaction can be conducted in any suitable reactor or series of reactors, including one or more fixed bed reactors, moving bed reactors and/or fluidized bed reactors.
• the effluent from the oligomerization reaction will contain gasoline and/or distillate boiling range hydrocarbons, together with unreacted ethylene and/or C4+ olefins and potentially water, unreacted C5- hydrocarbons, organic oxygenates from the oxidative dehydrogenation reaction.
• the oligomerization effluent can be fed to a separation system, such as a distillation train, where gasoline and/or distillate boiling range hydrocarbons may be recovered, while the unreacted ethylene and/or C4+ olefins can be separated for recycle to the oligomerization step, and unreacted C5- paraffins can be separated for recycle to the oxidative dehydrogenation step.
• a separation system such as a distillation train
• isoparaffins and aromatic compounds can be cofed with the C2+ olefins to the oligomerization reactor(s) so that some of the ethylene and, if present, propene and butenes, can react with the isoparaffin to generate alkylate, or can alkylate benzene to generate high octane product and also chemicals.
• the presence of propene/butenes in the feed is particularly advantageous in that it speeds up alkylation of the isoparaffins with the ethylene.

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