WO2005037750A1 - Preparation d'alcools aliphatiques ramifies au moyen d'un courant de procede provenant d'une unite de dimerisation - Google Patents

Preparation d'alcools aliphatiques ramifies au moyen d'un courant de procede provenant d'une unite de dimerisation Download PDF

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WO2005037750A1
WO2005037750A1 PCT/US2004/033899 US2004033899W WO2005037750A1 WO 2005037750 A1 WO2005037750 A1 WO 2005037750A1 US 2004033899 W US2004033899 W US 2004033899W WO 2005037750 A1 WO2005037750 A1 WO 2005037750A1
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olefins
stream
branched
unit
aliphatic
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PCT/US2004/033899
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English (en)
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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
    • 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
    • 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
    • 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 dimerization unit Description of Related Art 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 maybe 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, biodegradabihty 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.
  • Biodegradabihty, 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 biodegradabihty 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 branching 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 made by a process that includes a dimerization of olefins.
  • the produced dimerized olefins may include branched dimerized olefins.
  • a feed stream entering the dimerization unit includes alpha-olefins having an average carbon number from 4 to 9.
  • a process feed stream entering a dimerization unit is derived, in some embodiments, from a Fischer-Tropsch process. 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.
  • 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. At least a portion of the unreacted components and the produced dimerized olefins 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.
  • the produced dimerized olefins may be converted to aliphatic alcohols, i some embodiments, dimerized olefins may be hydroformylated to produce aliphatic alcohols.
  • 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 aliphatic alcohols may be sulfated to form aliphatic sulfates.
  • aliphatic sulfates may include branched alkyl groups, certain embodiments, at least a portion of the produced aliphatic alcohols may be oxyalkylated to form oxyalkyl alcohols.
  • oxyalkyl alcohols may include branched alkyl groups, hi some embodiments, 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. ha some embodiments, oxyalkyl sulfates may include branched alkyl groups.
  • FIG. 1 depicts a schematic diagram of an embodiment of a system for producing branched aliphatic alcohols using a dimerization 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. It should be understood that the drawings and detailed description thereto are not intended to limit the invention to the particular form disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present invention as defined by the appended claims.
  • Hydrocarbon products maybe 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.
  • Production of branched olefins from a Fischer- Tropsch process stream may increase the economic value of the stream.
  • linear olefins may be converted into branched olefins with a minimum number of quaternary carbon atoms using an isomerization catalyst.
  • a hydrocarbon feed stream composition may include paraffins and olefins. At least a portion of the hydrocarbon stream maybe made up of linear paraffins and olefins having at least 4 carbon atoms and up to 9 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.
  • 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 may be 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 may be Mo, W, Group VIJI compounds or combinations thereof.
  • Group VUI 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 VUI compounds may be formed as alloys.
  • Combinations of Mo, W and Group Vlfl compounds may be formed, in some embodiments, as oxides, carbides or other compounds, hi other embodiments, combinations of Mo, W and Group VUI compounds may be 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.
  • 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. Other catalysts, such as iron-cobalt alloy catalysts, are known for their selectivity toward the production of olefins. Catalysts and combinations for manufacture of hydrocarbon species by a Fischer- Tropsch process are generally known.
  • 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 hydro
  • 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.
  • 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-olefin 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. 10/153,955 of Ansorge et al., entitled “Process For The Preparation of linear Olefins and Use Thereof To Prepare Linear Alcohols.”
  • Specific procedures for preparing linear olefins from ethylene are described in U.S. Patent No. 3,676,523 to Mason, entitled “Alpha-Olefm Production;” U.S. Patent No. 3,686,351 to Mason, entitled “Alpha-Olefm Production;” U.S. Patent No. 3,737,475 to Mason, entitled “Alpha-Olefm Production” and U.S. Patent 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.
  • a feed stream may have a paraffin content greater than about 90 percent by weight paraffins.
  • 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 average carbon number of the hydrocarbons in a feed stream may range from 4 to 9. hi certain embodiments, an average carbon number of the hydrocarbons in a feed stream ranges from 5 to 8. In 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 may include mono-olefins and/or paraffins.
  • the mono-olefins may be of a linear or branched structure.
  • the mono-olefins 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, i certain embodiments, 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.
  • 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, hydration, 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 9 to 19. hi certain embodiments, an average carbon number of aliphatic alcohols in an alcohol product stream may range from 11 to 17. i some embodiments, an average carbon number of aliphatic alcohols in an alcohol product stream may range from 11 to 15. In other embodiments, an average carbon number of aliphatic alcohols in an alcohol product stream may range from 15 to 19.
  • a Fischer-Tropsch feed stream may contain olefins and paraffins of low carbon number (e.g., 4, 5, 6, 7, 8, 9).
  • a low carbon number feed stream may be sold as fuel, sent to waste and/or recycled to other processing units.
  • the low carbon number feed stream may be less useful in the production of detergents.
  • detergents are made from olefins having a carbon number greater than 7.
  • a first hydrocarbon stream, including olefins and paraffins may be transported to dimerization unit 110 via first conduit 112 as depicted for System 100 in FIG. 1. In dimerization unit 110, at least a portion of the olefins may be dimerized.
  • dimerization unit 110 may have several points of entry to accommodate process streams that vary in composition.
  • Process streams may be from other processing units and/or storage units. Examples of process streams include a diluent hydrocarbon stream, and/or other hydrocarbon streams that include olefins and paraffins derived from other processes. Examples of other processes may include Shell Higher Olefins Process or wax cracking process.
  • "entry into the dimerization unit” refers to entry of process streams into the dimerization unit through one or more entry points.
  • a dimerization catalyst used in dimerization unit 110 maybe a homogeneous or heterogeneous catalyst.
  • a dimerization catalyst used in dimerization unit 110 may be a catalyst that includes oxides of Group HI, Group IV A,
  • 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. hi 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 may be 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. In some embodiments, 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 trivalent metal oxide, which may include, but is not limited to, aluminum, gallium and indium or combinations thereof.
  • a nickel oxide and/or silica catalyst may be active for olefin dimerization, it may deactivate quickly. 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). In 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, i 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, 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 frivalent 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, i 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.
  • Conversion of olefins in the first hydrocarbon feed stream to dimers in dimerization unit 110 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)
  • evaporative cooling e.g., the evaporation of lighter hydrocarbon fractions from the reaction mixture may control the reaction temperature
  • At least a portion of the produced dimerized olefins may be transported to other processing units (e.g., an alkylation unit and hydroformylation unit) via second conduit 114.
  • Produced dimerized olefins may include olefins with an average carbon number from 8 to 18.
  • produced dimerized olefins may include olefins with an average carbon number from 10 to 16.
  • produced dimerized olefins may include olefins with an average carbon number from 10 to 14.
  • produced dimerized olefins may include olefins with an average carbon number from 14 to 18. Depending on the choice of catalyst, the resulting dimer may be branched. Branched olefins produced in dimerization unit 110 may include methyl, ethyl and/or longer carbon chain branches. Hydrogen Nuclear Magnetic Resonance (1H NMR) analysis of the isomerized olefin composition may be performed. Branched olefins may include quaternary and/or tertiary aliphatic carbons, hi certain embodiments, an amount of quaternary aliphatic carbons produced in a unit in which olefin isomerization occurs may be minimized.
  • 1H NMR Hydrogen Nuclear Magnetic Resonance
  • 1H NMR analysis of the olefins may indicate the extent of isomerization of the olefins in the hydrocarbon stream. 1H NMR analysis may be capable of differentiating a wide range of olefin structures. The presence of quaternary carbon atoms may be determined using carbon 13 ( 13 C) NMR techniques. i an embodiment, an average number of branches per olefin molecule present in the produced branched olefin composition may be greater than 0.7. certain embodiments, an average number of branches per olefin molecule present in the branched olefin composition is from about 0.7 to about 2.5.
  • an average number of branches per olefin molecule present in the branched olefin composition is from about 0.7 to about 2.2. h certain embodiments, an average number of branches per olefin molecule present in the branched olefin composition is from about 1.0 to about 2.2.
  • the degree of branching in the product may be controlled by controlling process conditions used in the dimerization unit. For example, high reaction temperatures and lower feed rates may result in a higher degree of branching.
  • Methyl branches may represent between about 20 percent to about 99 percent of the total number of branches present in the olefin molecules. In some embodiments, methyl branches may represent greater than about 50 percent of the total number of branches in the olefin molecules.
  • the number of ethyl branches in the olefin molecules may represent, in certain embodiments, less than about 30 percent of the total number of branches, other embodiments, a number of ethyl branches, if present, maybe between about 0.1 percent and about 2 percent of the total number of branches. Branches other than methyl or ethyl, if present, maybe less than about 5 percent of the total number of branches.
  • Aliphatic quaternary carbon atoms present in the branched olefin composition may be less than about 2 percent of the carbon atoms present, ha an embodiment, a number of aliphatic quaternary carbon atoms present is less than about 1 percent of the carbon atoms present.
  • the number of aliphatic quaternary carbon atoms may be less than about 0.5 percent of the carbon atoms present. In an embodiment, a number of aliphatic quaternary carbon atoms is less than about 0.3 percent of the carbon atoms present, hi other embodiments, a number of aliphatic quaternary carbon atoms present in the branched olefin composition is between about 0.01 percent and about 0.3 percent of the aliphatic carbon atoms present. In 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.
  • At least a portion of the paraffins and unreacted olefins may be separated and recycled back to the dimerization unit and/or sent to other processing units.
  • Produced dimerized olefins may be separated, if desired, from the reaction mixture through techniques known in the art (e.g., distillation, adsorption/desorption).
  • at least a portion of the second hydrocarbon stream may exit dimerization unit 110 and enter separation unit 116 via separation conduit 118 as depicted in FIG. 2.
  • Separation unit 116 may produce at least two streams, a branched olefins stream and a linear olefins and paraffins stream.
  • the second hydrocarbon stream may be contacted with organic and/or inorganic molecular sieves (e.g., zeolite or urea) with the conect pore size for branched olefins and/or linear olefins and paraffins.
  • organic and/or inorganic molecular sieves e.g., zeolite or urea
  • Separation unit 116 may include a fixed bed containing adsorbent for separation of the second hydrocarbon stream to produce a branched olefin and paraffins stream and a linear olefins and paraffins stream. Separation temperatures in separation unit 116 may range from about 100 °C to about 400 °C.
  • separation temperatures may range from 180 °C to about 380 °C.
  • Separation in separation unit 116 may be conducted at a pressure ranging from about 2 atmospheres (202 kPa) to about 7 atmospheres (710 kPa).
  • a pretreatment of a second 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.
  • At least a portion of the linear olefins and paraffins stream may be transported to other processing units and/or stored on site. In an embodiment, at least a portion of the linear olefins and paraffins stream may be combined with the first hydrocarbon stream in first conduit 112 via linear olefin and paraffin recycle conduit 120.
  • the linear olefins and paraffins stream may have a carbon number less than 9.
  • the combined stream may enter dimerization unit 110 via first conduit 112 to continue the process to produce aliphatic alcohols, hi some embodiments, a linear olefins and paraffins stream may be introduced directly into dimerization unit 110. 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 122. hi some embodiments, at least a portion of a branched olefins stream may exit separation unit 116 and be introduced into second conduit 114 via branched olefins conduit 122.
  • At least a portion of a branched olefins stream may exit separation unit 116 and be introduced directly into a hydroformylation unit.
  • a second hydrocarbon stream may exit dimerization unit 110 and enter hydroformylation unit 124 via second conduit 114.
  • "entry into the hydroformylation unit” refers to entry of process streams into the hydroformylation unit through one or more entry points.
  • 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” is used.
  • a “modified Oxo process” refers to an Oxo process that uses a phosphine, phosphite, arsine or pyridine ligand modified cobalt or rhodium catalyst. Preparation and use of modified Oxo catalysts are described in U.S. Patent No.
  • a hydroformylation catalyst used in hydroformylation unit 124 may include a metal from Group VUI of the Periodic Table. Examples of Groups VUI metals include cobalt, rhodium, nickel, palladium or platinum. The Group V_H metal may be used as a complex compound. A complex compound may be a Group VUI 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.
  • olefins may be hydroformylated using a continuous, semi-continuous or batch process, hi 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 124 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 124 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 sfream 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, h an embodiment, a second stream may be added to hydroformylation unit 124 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 124.
  • olefin conversions to aliphatic alcohols may range from about 50 percent by weight to greater than about 95 percent by weight, h certain embodiments, olefin conversion to aliphatic alcohols may be greater than 75 percent by weight, hi 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 hydroformylation reaction mixture stream may enter separator 128 via third conduit 130.
  • hi separator 128 at least two streams, bottom stream and a top stream maybe produced.
  • the bottom stream may be recycled back to hydroformylation unit 124 via recycle conduit 132.
  • the top stream may be purified and separated to produce at least two streams, a paraffins and unreacted olefins stream and a crude aliphatic alcohol product stream.
  • 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.
  • a hydroxide base e.g., sodium hydroxide or potassium hydroxide
  • the saponification may be 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 canied out batch- wise or continuously.
  • the top stream may be subjected to one or more saponification processes.
  • Saponification reaction temperatures may be from about 40 °C to about 99 °C. In an embodiment, 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.
  • paraffins and unreacted olefins sfream may be recycled, transported to other units for processing, stored on site, transported offsite and/or sold. At least a portion of the paraffins and unreacted olefins stream may exit separator 128 and be recycled, combined with other process streams, sent to other processing units and/or be stored on site via fourth conduit 136. h certain embodiments, 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.
  • a crude aliphatic alcohol product stream may contain unwanted by-products (e.g., aldehydes, hemi-acetals).
  • the by-products may be removed by subjecting the crude alcohol product stream to a hydro finishing treatment step to produce an aliphatic alcohol product stream.
  • Hydrofinishing refers to a hydrogenation reaction carried out under relatively mild conditions. Hydrofinishing 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, i 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 aliphatic alcohol product stream may exit separator 128 via product conduit 134 to be stored on site, sold commercially, transported off-site, and/or utilized in other processing units.
  • 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 sfream may range from 10 to 17. In certain embodiments, an average carbon number of hydrocarbons in aliphatic alcohol product stream may range from 10 to 13. In other embodiments, an average carbon number of hydrocarbons in aliphatic alcohol product stream may range from 14 to 17.
  • the aliphatic alcohol product stream may include branched aliphatic alcohols (e.g., branched primary alcohols).
  • the branched alcohol product may be suitable for the manufacture of anionic, nonionic and cationic surfactants, hi 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 olefin precursor.
  • aliphatic branching may include methyl and/or ethyl branches, i other embodiments, aliphatic branching may include methyl, ethyl and higher aliphatic branching, hi certain embodiments, a number of quaternary carbon atoms in the aliphatic alcohol product may be less than 0.5 percent, i other embodiments, a number of quaternary carbon atoms in the aliphatic alcohol product may be 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 13 C NMR analysis.
  • a 13 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 third hydrocarbon stream may be used to regulate the olefin concentration in hydroformylation unit 124 at a concentration sufficient to maximize hydroformylation of the olefin.
  • a third hydrocarbon stream may optimize the ratio of linear to branched aliphatic alcohols.
  • the third hydrocarbon stream may be, but is not limited to, a hydrocarbon sfream containing olefins, paraffins and/or hydrocarbon solvents.
  • a third hydrocarbon sfream may include olefins and paraffins.
  • an average carbon number of the hydrocarbons in the third hydrocarbon stream ranges from 7 to 18.
  • a paraffin content of the third hydrocarbon stream may be between about 60 percent and about 90 percent by weight, hi other embodiments, a paraffin content of the third hydrocarbon stream may be greater than about 90 percent by weight.
  • an olefin content of a third hydrocarbon sfream ranges between about 1 percent and about 99 percent relative to the total hydrocarbon content.
  • an olefin content of the third hydrocarbon stream may be between about 45 percent and about 99 percent by weight, hi other embodiments, an olefin concentration of the third hydrocarbon sfream may be greater than about 80 percent by weight.
  • 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. Condensation of an alcohol with an epoxide allows the alcohol functionality to be expanded by one or more oxy groups.
  • epoxide e.g., ethylene oxide, propylene oxide, butylene oxide
  • 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.
  • an approximately equal proportion may be combined with less than three ethylene oxide moieties, hi a typical oxyalkylation product mixture, a minor proportion of unreacted alcohol may be present in the product mixture, hi an embodiment, at least a portion of the aliphatic alcohol product stream may be formed by condensing a C 5 to C 3 ⁇ aliphatic alcohol with an epoxide.
  • a C 5 to C 15 branched primary alcohol may be condensed with ethylene oxide and/or propylene oxide
  • a C ⁇ to C 17 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, hi some embodiments, an oxyalkyl alcohol may be sulfated to form an anionic surfactant. hi an embodiment, at least a portion of the alcohols in the aliphatic alcohol product sfream 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. h 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) may be used.
  • Total pressures of ethylene oxide from about 1 atmosphere (101 kPa) to about 4 atmospheres (415 kPa) may be used in certain embodiments, hi an embodiment, 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 forai 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.
  • SO 3 sulfurized
  • the term "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.
  • a general class of aliphatic alcohol sulfates may be characterized by the chemical formula: (R-O-(A) x -SO ) souM.
  • R' 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 ), 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, i an embodiment, 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 fonnulations 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, hi 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. 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.
  • EXAMPLES Example 1. 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 aluminosilicate cogel (100 gram, 87% by weight SiO 2 -13% by weight Al 2 O 3 ) was dispersed in distilled water (2000 mL).
  • Aluminosilicate cogel may be obtained from Ineos 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 aluminosilicate solid washed with distilled water until the filtrate exhibited a pH of 5.7.
  • the recovered aluminosilicate 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 aluminosilicate solid was washed with distilled water until the filtrate exhibited a pH of 5.7.
  • the recovered aluminosilicate 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 ) -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 aluminosilicate 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 ) 2 CO 3 (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 stined 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, stined 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. The temperature was raised to 371 °C and the solid heated for 2 hours. After 2 hours, the temperature was raised to 592 °C and the solid was heated for 16 hours.
  • the resulting NiO catalyst dispersed on an aluminosilicate support was crushed and carefully sized to slightly greater than 60 mesh before testing.
  • a 15 mL reactor tube of an autoclave unit was charged with the NiO catalyst (0.335 grams), 1-hexene (3.35 grams), and a gas chromatography standard (0.67 grams linear tetradecane).
  • Autoclave units of the type "Endeavour" from Argonaut Technologies, United Kingdom, were used to perform the dimerization experiments.
  • 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 10 hours and then cooled to room temperature.
  • the reaction mixture was filtered to remove the NiO catalyst and the filtrate was analysed by gas chromatography.
  • the dimerization results are tabulated in Table 1.
  • Example 2 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.
  • Table 2 Table 2

Abstract

L'invention concerne un système et des procédés de production d'alcools aliphatiques ramifiés. Les alcools aliphatiques sont des composé importants pouvant être utilisés dans une grande variété d'applications ou pouvant être transformés en autres composés chimiques (ex. tensioactifs, sulfates). Le système de l'invention peut comprendre une unité de dimérisation et une unité d'hydroformylation. Les conditions du procédé dans l'unité de dimérisation peuvent se caractériser en ce que les oléfines ramifiées résultantes possèdent un nombre moyen de ramifications par molécule d'oléfine compris entre environ 0,7 et environ 2,5. Les oléfines ramifiées peuvent être, entre autres, des oléfines ramifiées méthyles et/ou éthyles. Une unité de dimérisation peut produire des oléfines ramifiées contenant moins d'environ 0,5 pour cent d'atomes de carbone quaternaire. Les oléfines dimérisées peuvent être hydroformylées en vue de la production d'alcools aliphatiques. Après l'hydroformylation d'alcools aliphatiques, les composants n'ayant pas réagi du procédé d'hydroformylation peuvent être séparés des produits d'alcools aliphatiques.
PCT/US2004/033899 2003-10-15 2004-10-14 Preparation d'alcools aliphatiques ramifies au moyen d'un courant de procede provenant d'une unite de dimerisation WO2005037750A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8383873B2 (en) 2010-02-16 2013-02-26 The Chinese University Of Hong Kong Terminal 1,1-disubstituted alkenes, method of making and using thereof
US9073804B2 (en) 2010-12-21 2015-07-07 Dow Global Technologies Llc Enhanced conversion of syngas to propylene
WO2018132626A1 (fr) 2017-01-13 2018-07-19 The Procter & Gamble Company Compositions comprenant des tensioactifs sulfonés ramifiés
CN111892482A (zh) * 2020-06-24 2020-11-06 万华化学集团股份有限公司 一种异构十三醇的制备方法

Citations (4)

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Publication number Priority date Publication date Assignee Title
US5169824A (en) * 1991-01-22 1992-12-08 Exxon Chemical Patents Inc. Catalyst comprising amorphous NiO on silica/alumina support
US5849960A (en) * 1996-11-26 1998-12-15 Shell Oil Company Highly branched primary alcohol compositions, and biodegradable detergents made therefrom
WO2000039058A1 (fr) * 1998-12-23 2000-07-06 Basf Aktiengesellschaft Procede de production d'alcools tensioactifs et d'ethers d'alcools tensioactifs, produits ainsi obtenus et leur utilisation
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 (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5169824A (en) * 1991-01-22 1992-12-08 Exxon Chemical Patents Inc. Catalyst comprising amorphous NiO on silica/alumina support
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
WO2000039058A1 (fr) * 1998-12-23 2000-07-06 Basf Aktiengesellschaft Procede de production d'alcools tensioactifs et d'ethers d'alcools tensioactifs, produits ainsi obtenus et leur utilisation

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8383873B2 (en) 2010-02-16 2013-02-26 The Chinese University Of Hong Kong Terminal 1,1-disubstituted alkenes, method of making and using thereof
US9073804B2 (en) 2010-12-21 2015-07-07 Dow Global Technologies Llc Enhanced conversion of syngas to propylene
WO2018132626A1 (fr) 2017-01-13 2018-07-19 The Procter & Gamble Company Compositions comprenant des tensioactifs sulfonés ramifiés
CN111892482A (zh) * 2020-06-24 2020-11-06 万华化学集团股份有限公司 一种异构十三醇的制备方法

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