WO2005037416A2 - Preparation d'alcools aliphatiques ramifies a partir de circuits de traitement combines d'une unite d'hydrogenation, d'une unite de deshydrogenation, d'une unite de dimerisation et d'une unite d'isomerisation - Google Patents

Preparation d'alcools aliphatiques ramifies a partir de circuits de traitement combines d'une unite d'hydrogenation, d'une unite de deshydrogenation, d'une unite de dimerisation et d'une unite d'isomerisation Download PDF

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WO2005037416A2
WO2005037416A2 PCT/US2004/034037 US2004034037W WO2005037416A2 WO 2005037416 A2 WO2005037416 A2 WO 2005037416A2 US 2004034037 W US2004034037 W US 2004034037W WO 2005037416 A2 WO2005037416 A2 WO 2005037416A2
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unit
olefins
stream
hydrocarbon stream
paraffins
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WO2005037416A3 (fr
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Paul Marie Ayoub
Hendrik Dirkzwager
Brendan Dermot Murray
Steven Clois Sumrow
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Shell Internationale Research Maatschappij B.V.
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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
    • C07C2/10—Catalytic processes with metal oxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/125—Monohydroxylic acyclic alcohols containing five to twenty-two carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2767—Changing the number of side-chains
    • C07C5/277—Catalytic processes
    • C07C5/2775—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • 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
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • 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

Definitions

  • the present invention generally relates to systems and methods for preparing aliphatic alcohols. More particularly, embodiments described herein relate to systems and methods for preparing branched aliphatic alcohols using a hydrogenation unit, a dehydrogenation unit, a dimerization unit, an isomerization unit and/or combinations thereof.
  • Aliphatic alcohols are important compounds that may be used in a variety of applications or converted to other chemical compounds (e.g., surfactants, sulfates). Surfactants may be used in a variety of applications (e.g., detergents, soaps, oil recovery).
  • the structural composition of the aliphatic alcohol may influence the properties of the surfactant and/or detergent (e.g., water solubility, biodegradability and cold water detergency) produced from the aliphatic alcohol.
  • water solubility may be affected by the linearity of the aliphatic portion of the aliphatic alcohol. As the linearity of the aliphatic portion increases, the hydrophilicity (i.e., affinity for water) of the aliphatic alcohol surfactant may decrease. Thus, the water solubility and/or detergency performance of the aliphatic alcohol surfactant may decrease.
  • Incorporating branches into the aliphatic portion of the aliphatic alcohol surfactant may increase the cold-water solubility and/or detergency of the aliphatic alcohol surfactant. Biodegradability, however, of the aliphatic alcohol surfactants may be reduced if the branches in the aliphatic portion of the alcohol surfactant include a high number of quaternary carbons. Incorporation of branches with a minimum number of quaternary carbon atoms into the aliphatic portion of the aliphatic alcohol surfactant may increase cold-water solubility and/or detergency of the alcohol surfactants while maintaining the biodegradability properties of the detergents.
  • the aliphatic portion of an aliphatic alcohol used to manufacture a surfactant may include one or more aliphatic alkyl groups as branches.
  • Aliphatic alkyl groups that may form branches in the aliphatic portion may include methyl, ethyl, propyl or higher alkyl groups.
  • Quaternary and tertiary carbons may be present when the aliphatic portion is branched. The number of quaternary and tertiary carbons may result from the brandling pattern in the aliphatic portion.
  • the phrase "aliphatic quaternary carbon atom" refers to a carbon atom that is not bound to any hydrogen atoms.
  • aliphatic alcohols may be produced by a method that include hydrogenation of paraffins a feed stream containing olefins and paraffins may be processed in a hydrogenation unit.
  • a process feed stream entering a hydrogenation unit may include linear olefins and paraffins having an average carbon number from 7 to 18.
  • a process feed stream entering a hydrogenation unit includes linear olefins and paraffins having an average carbon number from 10 to 17.
  • carbon number refers to the total number of carbon atoms in a molecule.
  • a process feed stream entering a hydrogenation unit is derived, in some embodiments from a Fischer- Tropsch process. i the hydrogenation unit at least a portion of the olefins in the feed stream may be hydrogenated to form paraffins. The resulting paraffinic feed stream may be fed into a dehydrogenation unit. At least a portion of the paraffins in the feed stream may be dehydrogenated to form an olefin hydrocarbon stream. At least a portion of the olefmic hydrocarbon stream produced f om the dehydrogenation unit maybe fed into a dimerization unit. In certain embodiments, a feed stream is fed into a dimerization unit that produces dimerized olefins.
  • the produced dimerized olefins may include branched dimerized olefins.
  • a process feed stream entering a dimerization unit is derived, in some embodiments, from a Fischer-Tropsch process.
  • produced dimerized olefins may be separated from the unreacted components after leaving the dimerization unit.
  • the unreacted components in some embodiments, may be recycled back into the dimerization unit.
  • Process conditions in the dimerization unit may be such that the resulting branched olefins have an average number of branches per olefin molecule from about 0.7 to about 2.5.
  • the branched olefins may include, but are not limited to, methyl and/or ethyl branched olefins.
  • a dimerization unit may produce branched olefins that include less than about 0.5 percent of quaternary carbon atoms.
  • a feed stream entering the dimerization unit includes alpha-olefins having an average carbon number from 4 to 9.
  • the branched olefins produced from the dimerization of alpha-olefins having an average carbon number from 4 to 9 will have an average carbon number from 8 to 18.
  • the produced dimerized olefins may be converted to aliphatic alcohols.
  • dimerized olefins may be hydroformylated to produce aliphatic alcohols. After hydroformylation of the dimerized olefins, at least a portion of unreacted components from the hydroformylation process may be separated from the produced aliphatic alcohol products. At least a portion of the unreacted components may be separated to produce an unreacted hydrocarbon stream and a produced dimerized olefins stream. At least a portion of the unreacted hydrocarbon stream may be recycled to the dimerization unit. In an embodiment, an isomerization unit may be used to produce branched olefins.
  • At least a portion of the product stream exiting a dimerization unit may be combined with at least a portion of the product stream exiting an isomerization unit and the combined stream directed to a hydroformylation unit.
  • At least a portion of the olefins in the combined stream may be hydroformylated in the hydroformylation unit to produce aliphatic alcohols.
  • at least a portion of unreacted components from the hydroformylation process may be separated from the aliphatic alcohol products. At least a portion of the unreacted components may be separated.
  • Isomerization of olefins in a process stream may occur in an isomerization unit, hi certain embodiments, a process feed stream entering an isomerization unit is derived from a Fischer-Tropsch process. At least a portion of the linear olefins in a process feed stream may be isomerized to branched olefins in the isomerization unit. The resulting branched olefins may have an average number of branches per olefin molecule from about 0.7 to about 2.5.
  • the branched olefins may include, but are not limited to, methyl and/or ethyl branched olefins.
  • the isomerization process may produce branched olefins that include less than about 0.5 percent of aliphatic quaternary carbon atoms.
  • one or more hydrocarbon streams may be combined with the feed stream entering an isomerization unit.
  • the hydrocarbon stream may be mixed with the feed stream to alter the concentration of the olefins entering the isomerization unit.
  • the resulting branched olefin- containing stream is passed into a hydroformylation unit.
  • One or more hydrocarbon streams may be combined with the branched olefin-containing stream to alter the concentration of olefins entering the hydroformylation unit.
  • unreacted components from the hydroformylation process may be separated from the aliphatic alcohol products. Paraffins and unreacted olefins in the separated stream may be sent to a dehydrogenation unit.
  • on e or more hydrocarbons streams may be coined with the feed streams entering an isomerization unit and/or a hydroformylation unit.
  • the hydrocarbon stream may be mixed with the feed streams to alter the concentration of the olefins entering the isomerization unit and/or hydroformylation unit.
  • at least a portion of the aliphatic alcohols may be sulfated to form aliphatic sulfates.
  • aliphatic sulfates may include branched alkyl groups.
  • at least a portion of the produced aliphatic alcohols may be oxyalkylated to form oxyalkyl alcohols.
  • oxyalkyl alcohols may include branched alkyl groups.
  • at least a portion of the produced branched aliphatic alcohols may be ethoxylated to form branched ethoxyalkyl alcohols.
  • At least a portion of the oxyalkyl alcohols may be sulfated to from oxyalkyl sulfates.
  • oxyalkyl sulfates may include branched alkyl groups.
  • FIG. 1 depicts a schematic diagram of an embodiment of a system for producing aliphatic alcohols using a hydrogenation unit, a dehydrogenation unit, a dimerization unit and an isomerization unit.
  • FIG. 2 depicts a schematic diagram of an embodiment of a separation unit to separate produced dimerized olefins from a reaction mixture. While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawing and will herein be described in detail.
  • Hydrocarbon products may be synthesized from synthesis gas (i.e., a mixture of hydrogen and carbon monoxide) using a Fischer-Tropsch process.
  • Synthesis gas may be derived by partial combustion of petroleum (e.g., coal, hydrocarbons), by reforming of natural gas or by partial oxidation of natural gas.
  • the Fischer-Tropsch process catalytically converts synthesis gas into a mixture of products that includes saturated hydrocarbons, unsaturated hydrocarbons and a minor amount of oxygen-containing products.
  • the products from a Fischer-Tropsch process may be used for the production of fuels (e.g., gasoline, diesel oil), lubricating oils and waxes.
  • Fischer-Tropsch process streams may also be used to prepare commodity products, which have economic value.
  • linear olefins are commodity products that are useful for the production of surfactants. Using a portion of the process stream to produce linear olefins may increase the economic value of a Fischer-Tropsch process stream.
  • Surfactants derived from branched olefins may have different properties than surfactants derived from linear olefins.
  • surfactants derived from branched olefins may have increased water solubility and/or improved detergency properties compared to surfactants derived from linear olefins.
  • Biodegradable properties of the surfactant may be affected by the presence of quaternary carbon atoms in the branched portion of the surfactant.
  • Surfactants made from branched olefins with a minimum number of quaternary carbon atoms may have similar biodegradable properties to surfactants derived from linear olefins.
  • Linear olefins may be converted into branched olefins with a minimum number of quaternary carbon atoms using an isomerization catalyst.
  • Increasing the amount of branched olefins derived from a Fischer-Tropsch process stream may increase the economic value of the process streams.
  • Methods are described for increasing the amount of branched olefins derived from a process stream that includes certain amount of olefins, thus increasing the economic value of the process stream. Such methods are useful for both Fischer-Tropsch process streams and product streams from other sources that include hydrocarbons.
  • a hydrocarbon feed stream composition may include paraffins and olefins. At least a portion of the hydrocarbon stream may be made up of linear paraffins and olefins having at least 4 carbon atoms and up to 18 carbon atoms.
  • a hydrocarbon feed stream may be obtained from a Fischer-Tropsch process or from an ethylene oligomerization process. Fischer-Tropsch catalysts and reaction conditions may be selected to provide a particular mix of products in the reaction product stream. For example, a Fischer-Tropsch catalyst and reaction conditions may be selected to increase the amount of olefins and decrease the amount of paraffins and oxygenates in the stream.
  • the catalyst and reaction conditions maybe selected to increase the amount of paraffins and decrease the amount of olefins and oxygenates in the stream.
  • the catalyst used in a Fischer-Tropsch process maybe Mo, W, Group VHI compounds or combinations thereof.
  • Group VIII compounds include, but are not limited to, iron, cobalt, ruthenium, rhodium, platinum, palladium, iridium and osmium.
  • Combinations of Mo, W and Group VIH compounds may be prepared in the free metal form.
  • combinations of Mo, W and Group VIE compounds may be formed as alloys.
  • Combinations of Mo, W and Group VIII compounds may be formed, in some embodiments, as oxides, carbides or other compounds.
  • combinations of Mo, W and Group VHI compounds maybe formed as salts.
  • Iron based and cobalt based catalysts have been used commercially as Fischer-Tropsch catalysts. Ruthenium catalysts tend to favor the formation of high melting waxy species under high- pressure conditions.
  • Synthetic Fischer-Tropsch catalysts may include fused iron, hi some embodiments, a fused iron Fischer-Tropsch catalyst may include a promoter (e.g., potassium or oxides on a silica support, alumina support or silica-alumina support).
  • Cobalt metal may also be used in a Fischer-Tropsch catalyst. With the proper selection of supports, promoters and other metal combinations, a cobalt catalyst may be tuned to manufacture a composition enriched in the desired hydrocarbon species.
  • catalysts such as iron-cobalt alloy catalysts
  • Catalysts and combinations for manufacture of hydrocarbon species by a Fischer- Tropsch process are generally known. While reference is made to a Fischer-Tropsch stream, any stream of olefins and saturated hydrocarbons may be suitable. Many Fischer-Tropsch streams may contain from 5 percent to 80 percent olefins, the remainder being saturated hydrocarbons comprising paraffins and other compounds. The Fischer-Tropsch' stream may be separated into several streams. For example, one stream may include hydrocarbons with an average carbon number from 4 to 9 for streams used in a dimerization unit.
  • a second stream may include hydrocarbons with an average carbon number from 7 to 18 for processes that involve an isomerization unit.
  • feed streams containing olefins and paraffins are obtained through cracking of paraffin wax or the oligomerization of olefins.
  • Commercial olefin products manufactured by ethylene oligomerization are marketed in the United States by Chevron Phillips Chemical Company, Shell Chemical Company (as NEODENE ® ) and by British Petroleum. Cracking of paraffin wax to produce alpha-olefm and paraffin feed streams is described in U.S. Patent No. 4,579,986 to Sie, entitled "Process For The Preparation Of Hydrocarbons" and U.S. Patent Application Serial No.
  • a feed stream is processed to produce a hydrocarbon stream that includes branched olefins. These branched olefins may be converted to branched aliphatic alcohols using various techniques.
  • the feed stream may have a paraffin content range between about 50 percent by weight to about 90 percent by weight of the feed stream. In certain embodiments, a feed stream may have a paraffin content greater than about 90 percent by weight paraffins.
  • the feed stream may also include olefins.
  • the olefin content of the feed stream may be between about 10 percent by weight to about 50 percent by weight, hi other embodiments, a feed stream may have an olefin content greater than 90 percent by weight olefins.
  • the composition of the feed stream may include hydrocarbons having an average carbon number ranging from 4 to 30. In an embodiment, an average carbon number of the hydrocarbons in a feed stream may range from 4 to 24. In other embodiments, an average carbon number of the feed stream may range from 4 to 18. An average carbon number of the hydrocarbons in a feed stream may range from 7 to 18 for processes that involve an isomerization unit. In certain embodiments, an average carbon number of the hydrocarbons in a feed stream may range from 10 to 17 for processes that involve an isomerization unit.
  • an average carbon number of hydrocarbons in a feed stream may range from 10 to 13 for processes that involve an isomerization unit, hi other embodiments, an average carbon number of hydrocarbons in a feed stream may range from 14 to 17 for processes that involve an isomerization unit.
  • the average carbon number of the hydrocarbons in a feed stream may range from 4 to 9 for processes that use a dimerization unit.
  • an average carbon number of the hydrocarbons in a feed stream ranges from 5 to 8 for processes that use a dimerization unit, hi some embodiments, an average carbon number of hydrocarbons in a feed stream may range from 5 to 7. In other embodiments, an average carbon number of hydrocarbons in a feed stream may range from 7 to 9.
  • a feed stream may include minor amounts of hydrocarbons having a carbon number that is higher or lower than the desired carbon number range.
  • a feed stream may be derived from distillation of a process stream that includes a broader range of carbon numbers.
  • a feed stream for a dimerization unit and/or an isomerization unit includes mono-olefms and/or paraffins.
  • the mono-olefms may be of a linear or branched structure.
  • the mono-olefms may have an alpha or internal double bond position.
  • the feed stream may include olefins in which 50 percent or more of the olefin molecules present may be alpha-olefins of a linear (straight chain) carbon skeletal structure.
  • At least about 70 percent of the olefins are alpha-olefins of a linear carbon skeletal structure.
  • a hydrocarbon stream in which greater than about 70 percent of all of the olefin molecules are alpha-olefins of a linear carbon skeletal structure may be used in certain embodiments to convert olefins to aliphatic alcohols. Such a stream may be derived from a Fischer-Tropsch process.
  • a feed stream includes olefins in which at least about 50 percent of the olefin molecules present are internal olefins.
  • Branched chain olefins may be converted to branched aliphatic alcohols (e.g., branched primary alcohols) by a hydroformylation process.
  • Hydroformylation refers to the production of alcohols from olefins via a carbonylation and a hydrogenation process.
  • Other processes may be used to produce aliphatic alcohols from olefins. Examples of other processes to produce aliphatic alcohols from olefins include, but are not limited to, hydradration, oxidation and hydrolysis, sulfation and hydration, and epoxidation and hydration.
  • the composition of an alcohol product stream may include aliphatic alcohols having an average carbon number ranging from 5 to 31. In an embodiment, an average carbon number of the aliphatic alcohols in an alcohol product stream may range from 7 to 18. In certain embodiments, an average carbon number of the aliphatic alcohols in an alcohol product stream may range from 11 to 18. In some embodiments, an average carbon number of aliphatic alcohols in an alcohol product stream may range from 11 to 14. hi other embodiments, an average carbon number of aliphatic alcohols in an alcohol product stream may range from 15 to 18.
  • a first hydrocarbon stream may contain unwanted compounds (e.g., oxygenates and dienes) that may reduce catalyst selectivity in a dimerization process used to produce aliphatic alcohols.
  • Removal of the unwanted compounds may be performed by hydrogenation of the first hydrocarbon stream.
  • Hydrogenation of the first hydrocarbon stream in certain embodiments, may produce a hydrocarbon stream that includes greater than about 90 percent paraffins.
  • the hydrogenated hydrocarbon stream may be dehydrogenated to produce an olefinic stream.
  • the catalyst used in the dehydrogenation process may control the position of the olefin double bond.
  • an olefinic hydrocarbon stream may include olefins in which greater than 70 percent of the olefins are alpha-olefins of a linear carbon skeletal structure.
  • an olefinic hydrocarbon stream may include olefins in which 50 percent or more of the olefin molecules present may be internal olefins.
  • a first hydrocarbon stream may be introduced into hydrogenation unit 110 via first conduit 112.
  • the first hydrocarbon stream includes olefins and paraffins.
  • Hydrocarbons in the first hydrocarbon stream may have an average carbon number from 4 to 9. i certain embodiments, hydrocarbons in a first hydrocarbon stream may have an average carbon number from 5 to 8. In some embodiments, hydrocarbons in a first hydrocarbon stream may have an average carbon number from 5 to 7. In other embodiments, hydrocarbons in a first hydrocarbon stream may have an average carbon number from 5 to 9.
  • hi hydrogenation unit 110 at least a portion of the olefins in the first hydrocarbon stream maybe hydrogenated to paraffins to produce a second hydrocarbon stream.
  • Reaction conditions in hydrogenation unit 110 may be controlled to hydrogenate olefins and dienes and to remove oxygenates.
  • An operating temperature of hydrogenation unit 110 may range between about 100 °C and about 300 °C. hi some embodiments, an operating temperature may range between about 150°C and about 275 °C. In other embodiments, an operating temperature may range between about 175 °C and 250 °C.
  • An operating pressure may range from about 5 atmospheres (506 kPa) to about 150 atmospheres (1520 kPa).
  • an operating pressure may range from 10 atmospheres psi (1013 kPa) to about 50 atmospheres (5065 kPa).
  • Hydrogenation processes may be carried out using any type of catalyst bed arrangement (e.g., fluidized bed, moving bed, slurry phase bed or a fixed bed).
  • a fixed bed arrangement may be used.
  • hydrogen may be supplied to the hydrogenation stage at a gas hourly space velocity in the range from about 100 normal liter gas/liter catalyst/hour (NL/L/hr) to about 1000 NL/L/hr.
  • hydrogen may be supplied at a gas hourly space velocity in the range from about 250 NL/L/hr to 5000 NL/L/hr.
  • Hydrogenation catalysts are generally known and are commercially available in a large variety of compositions, hi some embodiments, a hydrogenation catalyst may include one or more metals from Groups VIB and VII of the periodic Table of the Elements, h certain embodiments, metals may include, but are not limited to, molybdenum, tungsten, cobalt, nickel, ruthenium, iridium, osmium, platinum and palladium.
  • the hydrogenation catalyst may include a refractory oxide or a silicate as a binder.
  • Hydrogenation reaction conditions and catalysts are described in European Patent No. 0 583 836 to Eilers et al., entitled “Process For The Preparation of Hydrocarbon Fuels;” European Patent No. 0 668 342 to Eilers et al., entitled “Lubricating Base Oil Preparation Process.” Hydrogenation reaction conditions and catalysts are also described in U.S. Patent No. 5,371,308 to Gosselink et al, entitled “Process For The Preparation Of Lower Olefins.” At least a portion of the second hydrocarbon stream may exit hydrogenation unit
  • the catalyst 110 may be dehydrogenated to produce an olefinic hydrocarbon stream by use of a catalyst selected from a wide range of catalyst types.
  • the catalyst may be based on a metal or metal compound deposited on a porous support.
  • the metal or metal compound may be selected from, but is not limited to, chrome oxide, iron oxide and noble metals.
  • Reaction conditions in dehydrogenation unit 114 may be varied to control unwanted side products (e.g., coke, dienes, oligomers, cyclized hydrocarbons) and control double bond position in the olefin.
  • unwanted side products e.g., coke, dienes, oligomers, cyclized hydrocarbons
  • temperatures may range from greater than about 300 °C to less than about 700 °C.
  • a reaction temperature may range from about 450 °C to about 550 °C.
  • the pressures in dehydrogenation unit 114 may range from greater 0.010 atmosphere (1 kPa) to about 25.0 atmospheres (2534 kPa).
  • a total pressure of dehydrogenation unit 114 during the reaction may range from about 0.010 atmosphere (1 kPa) to about 15.0 atmospheres (15200 kPa).
  • pressure in dehydrogenation unit 114 may range from about 1.0 atmosphere (101 kPa) to about 5.0 atmospheres (510 kPa).
  • hydrogen may be fed into dehydrogenation unit 114 together with the paraffins and unreacted olefins stream in order to prevent coke from forming.
  • the hydrogen to paraffins molar ratio maybe set between about 0.1 moles of hydrogen to about 20 moles of paraffins, hi some embodiments, hydrogen to paraffin molar ratio is about 1 to 10.
  • the amount of time (e.g., the residence time) that a process stream remains in dehydrogenation unit 114 may determine, to some extent, the amount of olefins produced. Generally, the longer a process stream remains in dehydrogenation unit 114, the conversion level of paraffins to olefins increases until an olefin-paraffm thermodynamic equilibrium is obtained.
  • the residence time of the paraffins and unreacted olefins stream in dehydrogenation unit 114 may be selected such that the conversion level of paraffins to olefins may be kept below 50 mole percent. In certain embodiments, a conversion level of paraffins to olefins may be kept in the range from 5 to 30 mole percent. By keeping the conversion level low, side reactions maybe prevented (e.g., diene formation and cyclization reactions). In certain embodiments, at least a portion of non-converted paraffins may be separated from a third hydrocarbon stream using generally known techniques. Such separation may be accomplished by extraction, distillation or adsorption techniques.
  • the paraffins may be recycled to dehydrogenation unit 114 to undergo dehydrogenation to continue the process to produce aliphatic alcohols.
  • At least a portion of the third hydrocarbon steam may exit the dehydrogenation unit 114 and enter dimerization unit 118 via third conduit 120.
  • hi dimerization unit 118 at least a portion of the olefins in the third hydrocarbon stream may be dimerized.
  • the resulting dimerized olefins and the unreacted hydrocarbons in the third hydrocarbon stream may exit dimerization unit 118 as a fourth hydrocarbon stream.
  • a dimerization catalyst used in dimerization unit 118 may be a homogeneous or heterogeneous catalyst, i certain embodiments, a dimerization catalyst used in dimerization unit 118 maybe a catalyst that includes oxides of Group HI, Group IV A, Group IVB, Group VIEA, or combinations thereof. Examples of such oxides include, but are not limited to, nickel oxide, silicon dioxide, titanium dioxide, aluminum oxide or zirconium dioxide.
  • the dimerization catalyst may include an amorphous nickel oxide (NiO) present as a dispersed substantial monolayer on the surfaces of a silica (SiO 2 ) support.
  • the silica support may also include on the surface minor amounts of an oxide of aluminum, gallium or indium such that the ratio of nickel oxide to metal oxide present in the catalyst is within the range from about 4: 1 to about 100: 1.
  • the dimerization catalyst may be prepared by precipitating a water insoluble nickel salt onto the surface of a silica support.
  • the silica support may be impregnated with a metal oxide.
  • a dimerization catalyst may be prepared by precipitating a water insoluble nickel salt onto a silica-alumina support.
  • the silica-alumina support may be dealuminized such that the resulting nickel oxide/alumina ratio falls within the range from about 4: 1 to about 100: 1.
  • the catalyst may be activated by calcination in the presence of oxygen at a temperature with a temperature range from about 300 °C to about 700 °C. In some embodiments, the catalyst may be activated by calcination in the presence of oxygen at a temperature with a temperature range from about 500 °C to about 600 °C.
  • Silica useful as a support material may have a surface area within a range from about 100 m 2 /g to about 450 m 2 /g. In an embodiment, a silica surface area may be within the range from about 200 m 2 /g to about 400 m 2 /g.
  • a range of nickel oxide content maybe from about 7 percent to about 70 percent by weight, hi certain embodiments, a nickel oxide content may be from about 20 percent to about 50 percent by weight, depending on the surface area of the particular support utilized in preparing the catalyst.
  • a nickel oxide content may, in some embodiments, range from about 21 percent to about 35 percent by weight.
  • a nickel oxide content may, in other embodiments, be about 28 percent by weight.
  • the silica support may be in dry granular form or in a hydrogel form prior to precipitation of the nickel oxide precursor compound on the surfaces thereof.
  • Silica hydrogel may be prepared by mixing a water-soluble silicate, (e.g., a sodium or potassium silicate) with a mineral acid.
  • the water-soluble silicate may be washed with water to remove water-soluble ions.
  • the resulting silica hydrogel may be partially dried.
  • a silica hydrogel may be completely dried.
  • a nickel oxide precursor may include a water-insoluble nickel salt, such as nickel carbonate, nickel phosphate, nickel nitrate or nickel hydroxide.
  • a water-insoluble nickel salt may be generated in-situ by forming an aqueous mixture of the silica gel and a water- soluble nickel salt.
  • the nickel salt may include, but is not limited to, nickel nitrate, nickel sulfonate, nickel carbonylate, nickel halide.
  • a base may be added to the aqueous mixture to induce precipitation of the water-insoluble nickel salt.
  • the water-insoluble nickel salt may be precipitated in finely divided form within the interstices and on the surface of the silica support.
  • the treated silica support may then be recovered, washed several times and dried.
  • a second component in the catalyst may be a trfvalent metal oxide, which may include, but is not limited to, aluminum, gallium and indium or combinations thereof.
  • Deactivation may be from formation of large oligomers that remain attached to the catalyst surface. Large oligomers may act as coke precursors, in some embodiments.
  • a presence of a small amount of the trivalent metal oxide within the catalyst may form acid sites. Acidic sites may promote catalytic activity without promoting unwanted and/or excessive oligomer formation.
  • a trivalent metal oxide may be incorporated into the silica support by generally known techniques (e.g., precipitation, impregnation), hi an embodiment, a trivalent metal oxide may be impregnated into the silica support as an aqueous solution by the addition of a water-soluble salt.
  • the water-soluble metal salt may include, but is not limited to, metal nitrates, metal chlorides or metal sulfates.
  • the silica support may be dried and calcinated to reduce the metal salt to the oxide form.
  • the silica- trivalent oxide support may further treated to incorporate a nickel oxide layer onto the silica-trivalent metal oxide support.
  • silica-trivalent metal oxide e.g., silica/alumina, silica/gallia or silica/india gel
  • a content of metal oxide (e.g., alumina) present in the support may be low in comparison with the content of nickel oxide.
  • Dealuminization of the silica/alumina gel of relatively high alumina content may be necessary to reduce the content of alumina.
  • Dealuminization may be accomplished by known techniques (e.g., extraction of the aluminum with an organic or inorganic acid).
  • Organic or inorganic acids may include, but are not limited to, nitric acid, sulfuric acid, hydrochloric acid, chloroacetic acid or ethylene diamine tetraacetic acid. Extraction may be accomplished by adding the acid to an aqueous dispersion of the alumino silicate followed by stirring, decantation and washing with water. The process may be repeated one or more times until the desired alumina content is achieved.
  • a content of trivalent metal oxide with respect to the content of the nickel oxide present in the silica support may be significant, hi certain embodiments, when the content of trivalent metal oxide is too low (e.g., above a nickel oxide to trivalent metal oxide ratio of about 100 to 1) then the yield of dimer decreases and the catalyst may tend to deactivate quickly, hi certain embodiments, a content of trivalent metal oxide may be high (e.g., below a nickel oxide to trivalent metal oxide ratio of about 4 to 1). A high trivalent metal oxide content may lower the yield of dimer.
  • a high trivalent metal oxide content may raise an average content of methyl branching in the dimerized olefin product.
  • a content of trivalent metal oxide may be such that the ratio of nickel oxide to trivalent metal oxide falls within the range from about 4:1 to about 30:1.
  • a content of trivalent metal oxide may be such that the ratio of nickel oxide to trivalent metal oxide is between about 5:1 to about 20:1.
  • a ratio of nickel oxide to trivalent metal oxide may be between about 8 : 1 to about 15:1.
  • a dimerization catalyst may contain from about 21 percent to about 35 percent by weight of nickel oxide and about 1 percent to about 5 percent by weight of trivalent metal oxide, based on the total weight of nickel oxide, trivalent metal oxide and silica, hi certain embodiments, a dimerization catalyst may include from about 1.5 percent to about 4 percent by weight trivalent metal oxide based on the total weight of nickel oxide, trivalent metal oxide and silica. Preparation of dimerization catalysts are described in U.S. Patent No. 5,849, 972 to Vicari et al., entitled "Oligomerization Of Olefins To Highly Linear Oligomers, and Catalyst For This Purpose," and U.S.
  • dimerization unit 118 may include methyl, ethyl and/or longer carbon chains, hi an embodiment, dimerized olefins may contain greater than about 50 percent methyl branches. In certain embodiments, dimerized olefins may contain greater than about 90 percent methyl branches.
  • the dimerized olefins may be separated from the unreacted products through techniques known in the art. One such technique is fractional distillation.
  • Conversion of olefins to dimers in dimerization unit 118 may be carried out as a batch, continuous (e.g., using a fixed bed), semi-batch or multi-step process, hi a batch process, the catalyst may be slurried with the first hydrocarbon feed stream.
  • Temperature conditions for the dimerization reaction may range from about 120 °C to about 200 °C.
  • a reaction temperature may range from about 150 °C to about 165 °C.
  • Reaction temperatures may be controlled with evaporative cooling (e.g., the evaporation of lighter hydrocarbon fractions from the reaction mixture may control the reaction temperature).
  • Produced dimerized olefins may be separated, if desired, from the reaction mixture through techniques known in the art (e.g., distillation, adsorption/desorption and/or molecular sieves).
  • a fourth hydrocarbon stream may exit dimerization unit 118 and enter separation unit 122 via separation conduit 124.
  • Separation unit 122 may produce at least two streams, a branched olefins stream and a linear olefins and paraffins stream.
  • the fourth hydrocarbon stream may be contacted with organic and/or inorganic molecular sieves (e.g., zeolite or urea) with the correct pore size for branched olefins and/or linear olefins and paraffins.
  • organic and/or inorganic molecular sieves e.g., zeolite or urea
  • Subsequent desorption e.g., solvent desorption
  • at least a portion of the branched olefins and/or at least a portion of the linear olefins and paraffins from the molecular sieves may produce at least two streams (e.g., a branched olefins stream and a linear olefins and paraffins stream).
  • Separation unit 122 may include a fixed bed containing adsorbent for separation of the fourth hydrocarbon stream to produce a branched olefin and paraffins stream and a linear olefins and paraffins stream. Separation temperatures in separation unit 122 may range from about 100 °C to about 400 °C. hi some embodiments, separation temperatures may range from 180 °C to about 380 °C. Separation in separation unit 122 may be conducted at a pressure ranging from about 2 atmospheres (202 kPa) to about 7 atmospheres (710 kPa). In some embodiments, a pretreatment of a fourth hydrocarbon stream may be performed to prevent adsorbent poisoning.
  • An example of an adsorption/desorption process is a Molex process using Sorbex® separations technology (UOP process, UOP, Des Plaines, IL).
  • Adsorption desorption processes are described in U.S. Patent No. 6,225,518 to Sohn et al., entitled “Olefinic Hydrocarbon Separation Process;” U.S. Patent No. 5,292,990 to Kantner et al., entitled, "Zeolite Compositions For Use in Olefinic Separations" and U.S. Patent No.
  • At least a portion of the linear olefins and paraffins stream may be transported to other processing units and/or stored on site.
  • the paraffins and unreacted olefins stream may contain hydrocarbons with a carbon number less than 9.
  • at least a portion of the linear olefins and paraffins stream may be combined with the second hydrocarbon stream in second conduit 116 via linear olefm and paraffin recycle conduit 126.
  • the combined stream may enter dehydrogenation unit 114 via second conduit 116 to continue the process to produce aliphatic alcohols.
  • a linear olefins and paraffins stream may be introduced directly into dehydrogenation unit 114. At least a portion of the branched olefins stream may be transported and utilized in other processing streams and/or stored on site via branched olefins conduit 128.
  • the paraffins and unreacted olefins stream may contain hydrocarbons with a carbon number less than about 8. hi some embodiments, at least a portion of a branched olefins stream may exit separation unit 122 and be introduced into fourth conduit 130 via branched olefins conduit 128.
  • a branched olefins stream may exit separation unit 122 and be introduced directly into hydroformylation unit 132. At least a portion of the fourth hydrocarbon stream may exit dimerization unit 118 and be introduced into hydroformylation unit 132 via fourth conduit 130.
  • the fourth hydrocarbon stream includes branched olefins. At least a portion of the olefins in the fourth hydrocarbon stream may be hydroformylated to produce aliphatic alcohols.
  • a hydrocarbon stream from a dimerization unit may be combined with a hydrocarbon stream from an isomerization unit to produce a combined stream. The combined stream may be introduced into a hydroformylation unit.
  • a sixth hydrocarbon stream may be introduced directly into hydroformylation unit 132 through one or more hydroformylation unit ports. At least a portion of a sixth hydrocarbon stream may be introduced into fourth conduit 130 via fifth conduit 134 upstream of hydroformylation unit 124 to produce a combined stream.
  • the sixth hydrocarbon stream may be a stream exiting from isomerization unit 136. Isomerization unit 136 maybe fed by a fifth hydrocarbon stream containing paraffins and unreacted olefins via sixth conduit 138.
  • a fifth hydrocarbon stream may include hydrocarbons with an average carbon number from 7 to 18. In certain embodiments, a fifth hydrocarbon stream may include hydrocarbons with an average carbon number from 10 to 17. In some embodiments, a fifth hydrocarbon stream may include hydrocarbons with an average carbon number from 10 to 13. In other embodiments, a fifth hydrocarbon stream may include hydrocarbons with an average carbon number from 14 to 17. In some embodiments, a fifth hydrocarbon stream includes alpha-olefins.
  • a fifth hydrocarbon stream is a stream derived from a Fischer-Tropsch process.
  • the alpha- olefin content of the fifth hydrocarbon stream may be greater than about 70 percent of the total amount of olefins in the third hydrocarbon stream.
  • isomerization unit 136 at least a portion of the olefins in the fifth hydrocarbon stream may be isomerized to branched olefins (e.g., isoolefms) to produce a sixth hydrocarbon stream.
  • isomerization unit 136 may have several points of entry to accommodate process streams, which may vary in composition. Process streams may be from other processing units and/or storage units.
  • process streams include, but are not limited to, a diluent hydrocarbon stream, and/or other hydrocarbon streams that include olefins and paraffins derived from other processes.
  • entity into the isomerization unit refers to entry of process streams into the isomerization unit through one or more entry points.
  • Conditions for olefin isomerization in isomerization unit 136 may be controlled such that the number of carbon atoms in the olefins before and after the isomerization is substantially the same. Process conditions to skeletally isomerize linear olefins to branched olefins are described in U. S. Patent No.
  • linear olefins in a fifth hydrocarbon stream are isomerized in isomerization unit 136 by contacting at least a portion of the fifth hydrocarbon stream with a zeolite catalyst.
  • the zeolite catalyst may have at least one channel with a crystallographic free channel diameter ranging from greater than 4.2 A and less than about 7 A.
  • the zeolite catalyst may have an elliptical pore size large enough to permit entry of a linear olefin and diffusion, at least partially, of a branched olefin.
  • the pore size of the zeolite catalyst may also be small enough to retard coke formation.
  • Olefin isomerization may be conducted in isomerization unit 136 at temperatures ranging from about 200 °C to about 500 °C. Temperatures in isomerization unit 136 are, in some embodiments, kept below the temperature at which the olefm will crack extensively.
  • “cracking” refers to the process of thermally degrading molecules into smaller molecules. To inhibit cracking, low temperatures may be used at low feed rates.
  • lower temperatures may be used when the amount of oxygenates present in the process stream is low.
  • Higher feed rates may be desirable to increase the production rate of isomerised products.
  • Higher feed rates may be used, in some embodiments, when operating at higher reaction temperatures.
  • the reaction temperature should be set such that cracking to lower boiling weight products is minimized.
  • greater than 90 percent of linear C ⁇ 2 -C ⁇ 4 olefins maybe converted to branched olefins at 230 °C at a feed rate of 60 grams per hour per 6 grams of catalyst with minimal cracking.
  • Pressures maintained in isomerization unit 136 may be at a hydrocarbon partial pressure ranging from about 0.1 atmospheres (10 kPa) to about 20 atmospheres (2026 kPa).
  • a partial pressure may range from above about 0.5 atmospheres (51 kPa) to about 10 atmospheres (1013 kPa).
  • a seventh hydrocarbon stream may be introduced into hydroformylation unit 132 through one or more hydroformylation ports. In certain embodiments, at least a portion of a seventh hydrocarbon stream may be introduced into fourth conduit 130 upstream of hydro fonnylation unit 132 via seventh conduit 140 to produce a combined stream.
  • the combined stream may enter hydroformylation unit 132 and at least a portion of the olefins in the combined stream may be hydroformylated to produce a hydroformylation reaction stream, hi an embodiment, a paraffin content of the seventh hydrocarbon stream may be greater than about 50 percent and less than about 99 percent relative to the total hydrocarbon content, h certain embodiments, a paraffin content of the seventh hydrocarbon stream may be between about 60 percent and about 90 percent relative to the total hydrocarbon content, i an embodiment, an olefm content of a seventh hydrocarbon stream ranges between about 1 percent and about 99 percent relative to the total hydrocarbon conteni hi certain embodiments, an olefin content of a seventh hydrocarbon stream ranges between about 45 percent and about 95 percent, hi other embodiments, an olefm content of a seventh hydrocarbon stream may be greater than 80 percent relative to the total hydrocarbon stream.
  • At least a portion of an eighth hydrocarbon stream may be introduced into sixth conduit 138 upstream of isomerization unit 136 via eighth conduit 142 to produce a combined stream.
  • the combined stream may enter isomerization unit 136 and at least a portion of the olefins in the combined stream may be isomerized to produce a sixth hydrocarbon stream, hi an embodiment, a paraffin content of the eighth hydrocarbon stream may be greater than about 50 percent and less than about 99 percent relative to the total hydrocarbon content.
  • a paraffin content of the eighth hydrocarbon stream may be between about 60 percent and about 90 percent relative to the total hydrocarbon content, hi an embodiment, an olefm content of an eighth hydrocarbon stream ranges between about 1 percent and about 99 percent relative to the total hydrocarbon content. In certain embodiments, an olefin content of an eighth hydrocarbon stream ranges between about 45 percent and about 95 percent, h other embodiments, an olefin content of an eighth hydrocarbon stream may be greater than 80 percent relative to the total hydrocarbon stream.
  • the sixth and seventh hydrocarbon streams may be used to regulate the olefin concentration in hydroformylation unit 132 at a concentration sufficient to maximize hydroformylation of the olefin.
  • the sixth and seventh hydrocarbon streams may be, but are not limited to, a hydrocarbon stream containing olefm, paraffins and/or hydrocarbon solvents.
  • a combined stream may include, but is not limited to, a fourth hydrocarbon stream, a sixth hydrocarbon stream, a seventh hydrocarbon stream and/or combinations thereof, may be introduced into hydroformylation unit 132 via fourth conduit 130.
  • An advantage of combining the streams may be that overall production of aliphatic alcohols may be increased with fewer throughputs. At least a portion of the olefins in the combined stream may be hydroformylated to produce aliphatic alcohols.
  • olefins are converted to aldehydes, alcohols or a combination thereof by reaction of at least a portion of the olefins with carbon monoxide and hydrogen according to an Oxo process.
  • an "Oxo process” refers to the reaction of an olefin with carbon monoxide and hydrogen in the presence of a metal catalyst (e.g., a cobalt catalyst) to produce an alcohol containing one more carbon atom than the starting olefin.
  • a metal catalyst e.g., a cobalt catalyst
  • a "modified Oxo process” refers to an Oxo process that uses a phosphine, phosphite, arsine or pyridine ligand modified cobalt or rhodium catalyst.
  • modified Oxo catalysts are described in U.S. Patent No. 3,231, 621, to Slaugh, entitled “Reaction Rates In Catalytic Hydroformylation”; U.S. Patent No. 3,239,566 to Slaugh et al, entitled “Hydroformylation Of Olefins;" U.S. Patent No.
  • a hydroformylation catalyst used in hydroformylation unit 132 may include a metal from Group VIII of the Periodic Table. Examples of Groups VIJI metals include cobalt, rhodium, nickel, palladium or platinum.
  • the Group VHI metal may be used as a complex compound.
  • a complex compound may be a Group Vin metal combined with a ligand.
  • ligands include, but are not limited to, a phosphine, phosphite, arsine, stibine or pyridine ligand.
  • hydroformylation catalysts include, but are not limited to, cobalt hydrocarbonyl catalyst, cobalt-phosphine ligand catalyst, rhodium-phosphine ligand catalyst or combinations thereof.
  • hi hydroformylation unit 132, olefins may be hydroformylated using a continuous, semi-continuous or batch process. In case of a continuous mode of operation, the liquid hourly space velocities maybe in the range of about 0.1 h "1 to about 10 h "1 .
  • reaction times may vary from about 0.1 hours to about 10 hours or even longer.
  • Reaction temperatures in hydroformylation unit 132 may range from about 100 °C to about 300 °C. In certain embodiments, reaction temperatures in the hydroformylation unit ranging from about 125 °C to about 250 °C may be used.
  • Pressure in hydroformylation unit 132 may range from about 1 atmosphere (101 kPa) to about 300 atmospheres (30398 kPa). In an embodiment, a pressure from about 20 (2027 kPa) to about 150 atmospheres (15199 kPa) maybe used.
  • An amount of catalyst relative to the amount of olefin to be hydroformylated may vary.
  • Typical molar ratios of catalyst to olefin in the hydrocarbon stream may range from about 1 : 1000 to about 10: 1. A ratio of between about 1:10 and about 5:1 maybe used in certain embodiments.
  • a second stream may be added to hydroformylation unit 132 to control reaction conditions.
  • the second stream may include solvents that do not interfere substantially with the desired reaction. Examples of such solvents include, but are not limited to, alcohols, ethers, acetonitrile, sulfolane and paraffins.
  • Mono-alcohol selectivities of at least 90 percent and even of at least 92 percent may be achieved in hydroformylation unit 132.
  • olefin conversions to aliphatic alcohols may range from about 50 percent by weight to greater than about 95 percent by weight, i certain embodiments, olefm conversion to aliphatic alcohols may be greater than 75 percent by weight. In some embodiments, olefin conversion to aliphatic alcohols may be greater than about 99 percent by weight.
  • Isolation of aliphatic alcohols produced from the hydroformylation reaction product stream may be achieved by generally known methods. In an embodiment, isolation of the aliphatic alcohols includes subjecting the produced aliphatic alcohols to a first distillation, a saponification, a water washing treatment and a second distillation. The hydro formylation reaction mixture stream may enter separator 144 via ninth conduit 146.
  • the hydroformylation reaction product stream may be subjected to a first distillation step (e.g., flash distillation or a short path distillation).
  • a short path distillation may be used to produce at least two streams, a bottom stream and a top stream. At least a portion of the bottom stream may be recycled to hydroformylation unit 132 via bottom stream recycle conduit 148, in certain embodiments.
  • the top stream may include, but is not limited to, paraffins, unreacted olefins and a crude aliphatic alcohol product.
  • a top stream may be subjected to a saponification treatment to remove any acids and esters present in the stream.
  • Saponification may be performed by contacting the top stream with an aqueous solution of a hydroxide base (e.g., sodium hydroxide or potassium hydroxide) at elevated temperatures with agitation.
  • the saponification maybe carried out by contacting the top stream with an aqueous 0.5 percent to 10 percent hydroxide base solution at a crude alcohol/water ratio of 10: 1 to 1 : 1.
  • the amount of hydroxide base used may depend on an estimated amount of esters and acids present.
  • Saponification of the top stream may be carried out batch- wise or continuously.
  • the top stream may be subjected to one or more saponification processes. Saponification reaction temperatures maybe from about 40 °C to about 99 °C.
  • saponification temperatures may range from about 60 °C to about 95 °C.
  • Mixing of the top stream with the basic water layer may be performed during the saponification reaction. Separation of the top stream from the basic water layer may be performed using known methods.
  • the top stream may be subjected to a water wash after separation to remove any sodium salts present.
  • the top stream may be separated using generally known techniques (e.g., fractional distillation) to produce at least two streams, a crude alcohol product stream and a paraffins and unreacted olefins stream.
  • fractional distillation refers to the distillation of liquids and subsequent collection of fractions of liquids determined by boiling point.
  • the paraffins and unreacted olefins stream may be recycled, transported to other units for processing, stored on site, transported offsite and/or sold.
  • a crude aliphatic alcohol product stream may contain unwanted by-products (e.g., aldehydes, hemi-acetals).
  • the by-products maybe removed by subjecting the crude alcohol product stream to a hydro finishing treatment step to produce an aliphatic alcohol product stream.
  • Hydro finishing refers to a hydrogenation reaction carried out under relatively mild conditions. Hydrofmishing may be carried out using conventional hydrogenation processes. Conventional hydrogenation processes may include passing the crude alcohol feed together with a flow of hydrogen over a bed of a suitable hydrogenation catalyst.
  • the aliphatic alcohol product stream may include greater than about 50 percent by weight of the produced aliphatic alcohols, hi some embodiments, the aliphatic alcohol product stream may include greater than 80 percent by weight of the produced aliphatic alcohols. In other embodiments, the aliphatic alcohol product stream may include greater than 95 percent by weight of the produced aliphatic alcohols.
  • the aliphatic alcohol product stream may include branched aliphatic primary alcohols.
  • the resulting aliphatic alcohols in the aliphatic alcohol product stream may be sold commercially, transported off-site, stored on site and/or used in other processing units via product conduit 150.
  • the composition of an aliphatic alcohol product stream may include hydrocarbons with an average carbon number ranging from 8 to 19.
  • an average carbon number of the hydrocarbons in aliphatic alcohol product stream may range from 10 to 17. In certain embodiments, an average carbon number of the feed stream may range from 10 to 13. In other embodiments, an average carbon number of the feed stream may range from 14 to 17.
  • the aliphatic alcohol product stream may include branched primary alcohols.
  • the branched primary alcohol product may be suitable for the manufacture of anionic, nonionic and cationic surfactants. In some embodiments, branched primary alcohol products may be used as the precursor for the manufacture of anionic sulfates, including aliphatic sulfates and oxyalkyl sulfates and oxyalkyl alcohols.
  • Aliphatic alcohols may have slightly higher aliphatic branching and slightly higher number of quaternary carbons as the olefm precursor.
  • aliphatic branching may include methyl and/or ethyl branches.
  • aliphatic branching may include methyl, ethyl and higher aliphatic branching.
  • a number of quaternary carbon atoms in the aliphatic alcohol product may be less than 0.5 percent. In other embodiments, a number of quaternary carbon atoms in the aliphatic alcohol product maybe less than 0.3 percent. Branching of the alcohol product may be determined by 1H NMR analysis. The number of quaternary carbon atoms may be determined by C NMR.
  • a C NMR method for determining quaternary carbon atoms for branched aliphatic alcohols is described in U.S. Patent No. 6,150,322 to Singleton et al., entitled, "Highly Branched Primary Alcohol Compositions and Biodegradable Detergents Made Therefrom.”
  • at least a portion of the paraffins and unreacted olefins stream may exit separator 144 and be recycled, combined with other process streams, sent to other processing units and/or be stored on site via tenth conduit 152.
  • a paraffins and unreacted olefins stream may be further separated into a hydrocarbons stream including paraffins and unreacted olefins with a carbon number less than 9.
  • the hydrocarbon stream including paraffins and unreacted olefins with a carbon number less than 9 may be introduced upstream of and/or into the dimerization unit.
  • Aliphatic alcohols may be converted to oxy alcohols, sulfates or other commercial products.
  • At least a portion of the aliphatic alcohols in the alcohol product stream may be reacted in an oxyalkylation unit with an epoxide (e.g., ethylene oxide, propylene oxide, butylene oxide) in the presence of a base to produce an oxyalkyl alcohol.
  • an epoxide e.g., ethylene oxide, propylene oxide, butylene oxide
  • Condensation of an alcohol with an epoxide allows the alcohol functionality to be expanded by one or more oxy groups.
  • the number of oxy groups may range from 3 to 12.
  • reaction of an alcohol with ethylene oxide may produce alcohol products having between 3 to 12 ethoxy groups.
  • Reaction of an alcohol with ethylene oxide and propylene oxide may produce alcohols with an ethoxy/propoxy ratio of ethoxy to propoxy groups from about 4:1 to about 12:1.
  • a substantial proportion of alcohol moieties may become combined with more than three ethylene oxide moieties. In other embodiments, an approximately equal proportion may be combined with less than three ethylene oxide moieties. In a typical oxyalkylation product mixture, a minor proportion of unreacted alcohol may be present in the product mixture.
  • at least a portion of the aliphatic alcohol product stream may be formed by condensing a C 5 to C 31 aliphatic alcohol with an epoxide. hi certain embodiments, a C 5 to C ⁇ 5 branched primary alcohol may be condensed with ethylene oxide and/or propylene oxide.
  • a C ⁇ to C 1 branched primary alcohol may be condensed with ethylene oxide and/or propylene oxide.
  • the resulting oxyalkyl alcohols may be sold commercially, transported off-site, stored on site and/or used in other processing units.
  • an oxyalkyl alcohol may be sulfated to form an anionic surfactant.
  • at least a portion of the alcohols in the aliphatic alcohol product stream may be added to a base.
  • the base may be an alkali metal or alkaline earth metal hydroxide (e.g., sodium hydroxide or potassium hydroxide).
  • the base may act as a catalyst for the oxyalkylation reaction.
  • An amount from about 0.1 percent by weight to about 0.6 percent by weight of a base, based on the total weight of alcohol, may be used for oxyalkylation of an alcohol, hi an embodiment, a weight percent of a base may range from about 0.1 percent by weight to 0.4 percent by weight based on the total alcohol amount.
  • the reaction of the alcohol with the base may result in formation of an alkoxide.
  • the resulting alkoxide may be dried to remove any water present.
  • the dried alkoxide may be reacted with an epoxide.
  • An amount of epoxide used may be from about 1 mole to about 12 moles of epoxide per mole of alkoxide.
  • reaction temperatures in an oxyalkylation unit may range from about 120 °C to about 220 °C. hi an embodiment, reaction temperatures may range from about 140 °C to about 160 °C.
  • Reaction pressures may be achieved by introducing to the reaction vessel the required amount of epoxide.
  • Epoxides have a high vapor pressure at the desired reaction temperature.
  • the partial pressure of the epoxide reactant may be limited, for example, to less than about 4 atmospheres (413 kPa).
  • Other safety measures may include diluting the reactant with an inert gas such as nitrogen.
  • inert gas dilution may result in a vapor phase concentration of reactant of about 50 percent or less
  • an alcohol-epoxide reaction may be safely accomplished at a greater epoxide concentration, a greater total pressure and a greater partial pressure of epoxide if suitable, generally known, safety precautions are taken to manage the risks of explosion.
  • ethylene oxide a total pressure from about 3 atmospheres (304 kPa) to about 7 atmospheres (709 kPa) maybe used. Total pressures of ethylene oxide from about 1 atmosphere (101 kPa) to about 4 atmospheres (415 kPa) may be used in certain embodiments.
  • total pressures from about 1.5 atmospheres (150 kPa) to about 3 atmospheres (304 kPa) with respect to ethylene oxide may be used.
  • the pressure may serve as a measure of the degree of the reaction.
  • the reaction may be considered substantially complete when the pressure no longer decreases with time.
  • Aliphatic alcohols and oxyalkyl alcohols may be derivatized to form compositions (e.g., sulfonates, sulfates, phosphates) useful in commercial product formulations (e.g., detergents, surfactants, oil additives, lubricating oil formulations).
  • alcohols may be sulfurized with SO 3 to produce sulfates.
  • sulfurized refers to a sulfur atom or sulfur containing functionality being added to a carbon or oxygen. Sulfurization processes are described in U.S. Patent No. 6,462,215 to Jacobson et al., entitled “Sulfonation, Sulfation and Sulfamation”; U.S. Patent No. 6,448,435 to Jacobson et al., entitled “Sulfonation, Sulfation and Sulfamation”; U.S. Patent No. 3,462,525 to Levinsky et al, entitled, "Dental Compositions Comprising Long-Chain Olefin Sulfonates;" U.S. Pat. No.
  • a general class of aliphatic alcohol sulfates may be characterized by the chemical formula: (R-O-(A) -SO 3 ),.M- R 1 represents the aliphatic moiety.
  • A represents a moiety of an alkylene oxide; x represents the average number of A moieties per R-O moiety and may range from 0 to 15; and n is a number depending on the valence of cation M.
  • Examples of cation M include, but are not limited to, alkali metal ions, alkaline earth metal ions, ammonium ions and/or mixtures thereof.
  • cations include, but are not limited to, magnesium, potassium, monoethanol amine, diethanol amine or triethanol amine.
  • Aliphatic and oxyalkyl alcohols may be sulfated in a sulfation unit. Sulfation procedures may include the reaction of sulfur trioxide (SO 3 ), chlorosulfonic acid (ClSO 3 H), sulfamic acid (NH 2 SO 3 H) or sulfuric acid with an alcohol.
  • sulfur trioxide in concentrated (e.g., fuming) sulfuric acid may be used to sulfate alcohols. The concentrated sulfuric acid may have a concentration of about 75 percent by weight to about 100 percent by weight in water.
  • concentrated sulfuric acid may have a concentration of about 85 percent by weight to about 98 percent by weight in water.
  • the amount of sulfur trioxide may range from about 0.3 mole to about 1.3 moles of sulfur trioxide per mole of alcohol, hi certain embodiments, an amount of sulfur trioxide may range from about 0.4 moles to about 1.0 moles of sulfur trioxide per mole of alcohol.
  • a sulfur trioxide sulfation procedure may include contacting a liquid alcohol or an oxyalkyl alcohol and gaseous sulfur trioxide in a falling film sulfator to produce a sulfuric acid ester of the alcohol.
  • the reaction zone of the falling film sulfator may be operated at about atmospheric pressure and at a temperature in the range from about 25 °C to about 70 °C.
  • the sulfuric acid ester of the alcohol may exit the falling film sulfator and enter a neutralization reactor.
  • the sulfuric acid ester may be neutralized with an alkali metal solution to form the alkyl sulfate salt or the oxyalkyl sulfate salt.
  • Examples of an alkali metal solution may include solutions of sodium or potassium hydroxide.
  • the derivatized alcohols may be used in a wide variety of applications. An example of an application includes detergent formulations.
  • Detergent formulations include, but are not limited to, granular laundry detergent formulation, liquid laundry detergent formulations, liquid dishwashing detergent formulations and miscellaneous formulations.
  • miscellaneous formulations may include general purpose cleaning agents, liquid soaps, shampoos and liquid scouring agents.
  • Granular laundry detergent formulations may include a number of components besides the derivatized alcohols (e.g., surfactants, builders, co-builders, bleaching agents, bleaching agent activators, foam controlling agents, enzymes, anti-graying agents, optical brighteners and stabilizers).
  • surfactants may include ionic, nonionic, amphoteric or cationic surfactants.
  • Liquid laundry detergent formulations may include the same components as granular laundry detergent formulations, h certain embodiments, liquid laundry detergent formulations may include less of an inorganic builder component than granular laundry detergent formulations. Hydrotropes may be present in the liquid detergent formulations. General purpose cleaning agents may include other surfactants, builders, foam control agents, hydrotropes and solubilizer alcohols. The formulations may typically include one or more inert components. For example, the balance of liquid detergent formulations may typically be an inert solvent or diluent (e.g., water). Powdered or granular detergent formulations typically contain quantities of inert filler or carrier materials.
  • Example 1 Isomerization of Olefins in a Fischer-Tropsch derived Hydrocarbon Stream. Carbon monoxide and hydrogen were reacted under Fischer-Tropsch process conditions to yield a hydrocarbon mixture of linear paraffins, linear olefins, a minor amount of dienes and a minor amount of oxygenates.
  • the Fischer-Tropsch hydrocarbon stream was separated into different hydrocarbon streams using fractional distillation techniques. A hydrocarbon stream containing olefins and paraffins with an average number of carbon atoms from 8 to 10 was obtained. The composition of the resulting C 8 - Cio hydrocarbon stream was analysed by gas chromatography and is tabulated in Table 1.
  • a zeolite catalyst used for isomerization of linear olefins in the hydrocarbon stream was prepared in the following manner.
  • CATAPAL® D alumina (91 grams) exhibiting a loss on ignition of 25.7% was added to the muller.
  • alumina ammonium-ferrierite mixture 152 milliliters was added to the alumina ammonium-ferrierite mixture.
  • a mixture of 6.8 grams glacial acetic acid, 7.0 grams of citric acid and 152 milliliters of deionized water was slowly added to the alumina/ammonium-ferrierite mixture in the muller to peptize the alumina.
  • the resulting alumina/ammonium-ferrierite/acid mixture was mulled for 10 minutes.
  • a mixture of 0.20 grams of tetraamine palladium nitrate in 153 grams of deionized water was slowly added to mulled alumiiia/ammonium-ferrierite/acid mixture.
  • the resulting mixture exhibited a 90:10 ratio of zeolite to alumina and a loss on ignition of 43.5%.
  • the zeolite/alumina mixture was shaped by extruding the mixture through a stainless steel die plate (1/16" holes) of a 2.25 inch Bonnot extruder.
  • the moist zeolite/alumina extrudate was dried at 125°C for 16 hours. After drying, the zeolite/alumina extrudate was longsbroken manually.
  • the zeolite/alumina extrudate was calcined in flowing air at 200°C for two hours. The temperature was raised to a maximum temperature of 500°C and the zeolite/alumina extrudate was calcined for an
  • the isomerization catalyst was allowed to cool in a dessicator under a nitrogen atmosphere.
  • Stainless steel tubing 1 inch OD, 0.6 inch ID and 26 inches long, was used as an isomerization reactor.
  • a thermowell extended 20 inches from the top of the stainless steel reactor tube.
  • Silicon carbide (20 mesh) was added to a depth of about 6 inches to the reactor tube.
  • a second piece of glass wool was placed over the silicon carbide.
  • a fourth piece of glass wool was positioned over the silicon carbide to serve as a plug for the bottom of the reactor tube.
  • a multipoint thermocouple was inserted into the thermowell of the reactor tube.
  • the temperature above, below and at three different places in the catalyst bed was monitored.
  • the reactor tube was inverted and installed in the furnace.
  • the reactor tube was heated to the operating temperature of 280 °C over a four-hour period under flowing nitrogen. Once the temperature of 280 °C was obtained, the reactor tube was held at the operating temperature for an additional two hours to condition the isomerization catalyst.
  • the hydrocarbon stream was pumped through the reactor tube at a flow rate of 60 g/hr. Nitrogen, at a flow rate of 6 L/hr, was passed over the isomerization catalyst simultaneously with the hydrocarbon stream. The hydrocarbon stream was vaporized before contacting the isomerization catalyst.
  • the reactor tube was operated at an outlet pressure of 20 kPa above atmospheric pressure.
  • Example 2 Isomerization of 1-Dodecene.
  • 1-Dodecene was obtained from Shell Chemical Co.
  • the composition of 1-dodecene, as assayed by gas chromatography, is tabulated in Table 3.
  • 1-dodecene was isomerized using the same reactor tube design and isomerization catalyst preparation as described in Example 1.
  • a stream of 1-dodecene was pumped through a reactor tube at a flow rate of 90 g/hr. Nitrogen, at a flow rate of 6 L/lrr, was passed over the isomerization catalyst simultaneously with the stream of 1-dodecene.
  • the stream of 1-dodecene was vaporised before contacting the isomerization catalyst.
  • the reactor tube was operated at an outlet pressure of 20 kPa above atmospheric pressure and a temperature of 290°C.
  • Table 4 is a tabulation of the weight percent of less than Cio, C1 0 - 4 and greater than C ⁇ 4 molecules in 1-dodecene at 0 hours and the reactor tube effluent after 168 and 849 hours.
  • Linear C ⁇ o-C 14 olefins were converted in a 94% yield to branched C_o-C_ 4 olefins after a 168 hr processing time.
  • less than 3 weight percent of material boiling below Cio was generated from cracking side reactions.
  • the average number of alkyl branches on the o-Cu olefins in the product was determined to be 1.3 by 1H NMR analysis. Table 4
  • Example 3 Dehydrogenation of Dodecane with Minimal Isomerization: Dodecane was obtained from Aldrich Chemical Company and stored under nitrogen before being processed. The composition of dodecane, as assayed by gas chromatography, is tabulated in Table 5.
  • a paraffin dehydrogenation catalyst was prepared according to Example 1 (catalyst A) of U.S. Patent No. 4,430,517 to hnai et al, entitled "Dehydrogenation Process Using A Catalytic Composition.”
  • the resulting catalyst included 0.8 wt.% platinum, 0.5 wt.% tin, 2.7 wt.% tin, 2.7 wt.% potassium and 1.3 wt.% chlorine on a gamma-alumina support.
  • the atomic ratio of potassium to platinum for this catalyst was 16.8.
  • the dehydrogenation catalyst was prepared by dissolving substantially pure aluminum pellets in a hydrochloric acid solution.
  • stannic chloride An amount of stannic chloride was added to the resulting solution to provide a final composite containing 0.5 weight % tin and stirred to distribute the tin component evenly throughout the mixture.
  • Hexamethyleneteframine was added to the resulting tin mixture and the resulting tin-amine mixture was dropped into an oil bath in a manner to form spherical particles having an average particle diameter of about 1/16 inch.
  • the spheres were aged, washed with an ammoniacal solution, dried and calcined to form a spherical gamma-alumina carrier material.
  • the resulting spheres contained about 0.5 weight % tin in the form of tin oxide.
  • the incorporated chlorine was removed by heating the platmum-chlorine-tin-alumina composite to 550 °C and treating the composite with a 50/50 air/80 °C steam mixture at a gas hourly space velocity (GHSV) of 300 hr "1 . After treatment with the air/steam mixture, the platinum-tin-alumina composite contained less than 0.1 weight percent chlorine.
  • the platinum-tin- alumina composite was contacted with a deionized water solution of potassium nitrate. The amount of potassium nitrate used was the amount necessary to incorporate 2.7 weight percent of potassium in the platinum-tin-alumina composite.
  • the water was removed from the platinum-tin-potassium-alumina composite by heating the composite to 100 °C under a purge of dry air (1000 hr ⁇ GHSV) for 0.5 hour.
  • the temperature was raised to 525 °C and the platinum-tin-potassium alumina composite was treated with a stream of hydrochloric acid (12 cc/hr, 0.9 M HC1) and a stream of 50/50 air/80 °C steam mixture (300 hr "1 GHSV) to incorporate chlorine into the platinum-tin- potassium-alumina composite.
  • the platinum-tin-potassium-chlorine-alumina composite was dried at 525 °C under a purge of dry air (1000 hr "1 GHSV).
  • the resulting catalyst spheres had an average particle diameter of 1/16 inch and were crushed and sized into 6-20 mesh particle before testing.
  • Stainless steel tubing 1 inch OD, 0.6 inch ID and 26 inches long, was used as an isomerization reactor.
  • a thermowell extended 20 inches from the top of the stainless steel reactor tube.
  • Silicon carbide (20 mesh) was added to a depth of about 6 inches to the reactor tube.
  • a second piece of glass wool was placed over the silicon carbide.
  • a fourth piece of glass wool was positioned over the silicon carbide to serve as a plug for the bottom of the reactor tube.
  • a multipoint thermocouple was inserted into the thermowell of the reactor tube. The temperature above, below and at three different places in the catalyst bed was monitored.
  • the reactor tube was inverted and installed in the furnace.
  • the reactor tube was purged with nitrogen.
  • the reactor tube was heated to the operating temperature of 425°C over a four-hour period under flowing nitrogen (250 standard liters per hour). Once the temperature of 425°C was obtained, the reactor tube was held at the operating temperature for an additional two hours.
  • the catalyst was presulfided by flowing a 1% mixture of hydrogen sulfide gas in hydrogen gas at 425 °C for five minutes through the reactor tube. After 5 minutes, the hydrogen sulfide in hydrogen gas flow was switched to a hydrogen gas flow through the reactor tube. After presulfiding the catalyst, the reactor tube was maintained at 425 °C for eight hours.
  • the reactor tube pressure was increase to 25 psig with hydrogen gas.
  • Dodecane was pumped through the reactor tube at a flow rate of 40 g/hr at a hydrogen flow rate of 125 standard liters per hour. After four hours, the dodecane stream was increased to 80 g/hr. After obtaining a flow rate of 80 g/hr, the reactor tube temperature was raised to 460 °C. The reactor tube was sampled every eight hours after obtaining the operating temperature of 460°C. After twenty-four hours the weight percent of dodecane was 11.4 weight percent as depicted in Table 6. At a temperature of 479 °C, the conversion of dodecane to olefins was 16 weight percent after twenty- four hours.
  • Example 4 Dimerization of 1-Hexene.
  • a dimerization catalyst for the dimerization of a C 6 olefin stream was prepared by the method for Example 1 in U.S. Patent No. 5,169,824 to Saleh et al., entitled, "Catalyst Comprising Amorphous NiO On Silica/ Alumina Support.”
  • An aluminosihcate cogel (100 gram, 87% by weight SiO 2 -13% by weight Al 2 O 3 ) was dispersed in distilled water (2000 mL).
  • Aluminosihcate cogel may be obtained from hieos Silicas, Netherlands BV, as Synclist-13.
  • Nitric acid (65%) was added to the aluminosilicate/water dispersion with stirring until a pH of 2.7 was obtained.
  • the resulting acidic mixture was filtered and the aluminosihcate solid washed with distilled water until the filtrate exhibited a pH of 5.7.
  • the recovered aluminosihcate solid was dispersed again in distilled water and nitric acid (65%) was added until a pH of 2.7 was obtained.
  • the resulting acidic mixture was filtered and the resulting aluminosihcate solid was washed with distilled water until the filtrate exhibited a pH of 5.7.
  • the recovered aluminosihcate solid was dried for 16 hours at 110 °C in an air atmosphere and thereafter calcined at 500 °C for 16 hours under an air atmosphere.
  • Ni(NO 3 ) 2 -6 H 2 O (67.38 gram) was dissolved in distilled water (700 mL) and heated to a temperature of 32 °C to result in a solution having a pH of 5.7.
  • the aluminosihcate solid (35 gram) was added over time to the nickel solution resulting in a nickel/aluminosilicate slurry.
  • the pH of the nickel/aluminosilicate slurry was approximately 3.9.
  • the nickel/aluminosilicate slurry was neutralized by adding a solution of (NH 4 ) 2 CO (33.69 gram) in distilled water (200 mL) drop wise over 30 minutes until the pH of the slurry was approximately 6.9. The neutral slurry was stirred for 30 minutes at 32 °C and then filtered to obtain a solid. The recovered solid was slurried twice with water to the original volume of the nickel/aluminosilicate slurry, stirred for 5 minutes and then filtered to obtain a solid. The resulting solid was dried at 110 °C for 16 hours in an air atmosphere. Calcination of the solid was performed by heating the solid under an air atmosphere at increasing temperatures. Initially, the solid was heated to 232 °C for 1 hour.
  • Example 5 Dimerization of Diluted 1-Hexene.
  • a 15 mL reactor tube of the autoclave unit was charged with the NiO catalyst (0.335 grams) prepared according to the method for Example 7, 1-hexene (1.675 grams), hexane (1.675 grams) and a gas chromatography standard (0.67 grams linear tetradecane).
  • the gas cap of the reactor tube was flushed with nitrogen and the reactor tube was heated to 160 °C. Once the reaction temperature of 160 °C was obtained, the reaction temperature was maintained for eight hours and then cooled to room temperature.
  • the reaction mixture was filtered to remove the NiO catalyst and the filtrate was analyzed by gas chromatography.
  • the dimerization results are tabulated in Table 8.

Abstract

L'invention concerne des systèmes et des procédés destinés à la production d'alcools aliphatiques ramifiés. Ces systèmes peuvent comprendre une unité d'hydrogénation, une unité de déshydrogénation, une unité de dimérisation d'oléfines, une unité d'isomérisation d'oléfines, une unité d'hydroformylation et/ou des combinaisons de ces dernières. L'invention concerne également des procédés destinés à la production d'alcools aliphatiques ramifiés pouvant comprendre une dimérisation et une isomérisation d'oléfines dans un circuit. Ces oléfines isomérisées peuvent être hydroformylées pour produire des alcools aliphatiques. Après l'étape d'hydroformylation des alcools aliphatiques, les composants inaltérés peuvent être séparés des produits à base d'alcools aliphatiques. Les composants inaltérés suite à l'étape d'hydroformylation peuvent être renvoyés dans le circuit principal ou envoyés vers d'autres unités de traitement. Plusieurs circuits peuvent être ajoutés aux unités pour contrôler les conditions de réaction dans les unités.
PCT/US2004/034037 2003-10-15 2004-10-14 Preparation d'alcools aliphatiques ramifies a partir de circuits de traitement combines d'une unite d'hydrogenation, d'une unite de deshydrogenation, d'une unite de dimerisation et d'une unite d'isomerisation WO2005037416A2 (fr)

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Citations (7)

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Publication number Priority date Publication date Assignee Title
US2930763A (en) * 1956-03-05 1960-03-29 Universal Oil Prod Co Hydrocarbon conversion catalyst
US4430517A (en) * 1981-12-02 1984-02-07 Uop Inc. Dehydrogenation process using a catalytic composition
EP0211381A1 (fr) * 1985-07-30 1987-02-25 Phillips Petroleum Company Procédé pour la purification d'hydrocarbures
WO1997038957A1 (fr) * 1996-04-16 1997-10-23 The Procter & Gamble Company Fabrication d'un tensioactif ramifie
WO1998023566A1 (fr) * 1996-11-26 1998-06-04 Shell Internationale Research Maatschappij B.V. Compositions d'alcool primaire fortement ramifie et detergents biodegradables fabriques a partir de telles compositions
US5849960A (en) * 1996-11-26 1998-12-15 Shell Oil Company Highly branched primary alcohol compositions, and biodegradable detergents made therefrom
US6222077B1 (en) * 1996-11-26 2001-04-24 Shell Oil Company Dimerized alcohol compositions and biodegradible surfactants made therefrom having cold water detergency

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2930763A (en) * 1956-03-05 1960-03-29 Universal Oil Prod Co Hydrocarbon conversion catalyst
US4430517A (en) * 1981-12-02 1984-02-07 Uop Inc. Dehydrogenation process using a catalytic composition
EP0211381A1 (fr) * 1985-07-30 1987-02-25 Phillips Petroleum Company Procédé pour la purification d'hydrocarbures
WO1997038957A1 (fr) * 1996-04-16 1997-10-23 The Procter & Gamble Company Fabrication d'un tensioactif ramifie
WO1998023566A1 (fr) * 1996-11-26 1998-06-04 Shell Internationale Research Maatschappij B.V. Compositions d'alcool primaire fortement ramifie et detergents biodegradables fabriques a partir de telles compositions
US5849960A (en) * 1996-11-26 1998-12-15 Shell Oil Company Highly branched primary alcohol compositions, and biodegradable detergents made therefrom
US6222077B1 (en) * 1996-11-26 2001-04-24 Shell Oil Company Dimerized alcohol compositions and biodegradible surfactants made therefrom having cold water detergency

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Title
"SASOL DETERGENT ALCOHOLS" PRELIMINARY SASOL R&D TECHNICAL BULLETIN, XX, XX, 25 November 1996 (1996-11-25), pages 1-13, XP002932342 *

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