MXPA06004122A - Preparation of branched aliphatic alcohols using a process stream from an isomerization unit with recycle to a dehydrogenation unit - Google Patents

Abstract

Systems and methods to produced branched aliphatic alcohols are described. Systems may include an olefin isomerization unit, a hydrofo rmylation unit, a dehydrogenation unit, and/or combinations thereof Methods for producing branched aliphatic alcohols may include isomerization of olefins in a process stream. The isomerized olefins may be hydroformylated to produce aliphatic alcohols. After hydroformylation of the aliphatic alcohols, unreacted components from the hydroformylation process may be separated from the aliphatic alcohols products. The unreacted components from the hydroformylation process may be recycled back into the main process stream or sent to other processing units. Addition of multiple streams to the units may be performed to control reaction conditions in the units

Description

PREPARATION OF BRANCHED ALIPHATIC ALCOHOLS USING A PROCESS CURRENT OF AN ISOMERIZATION UNIT WITH RECIRCULATION TO A DEHYDROGENATION UNIT Field of the Invention The present invention relates generally to systems and methods for preparing aliphatic alcohols. More particularly, the embodiments described herein relate to systems and methods for preparing branched aliphatic alcohols using an isomerization unit. BACKGROUND OF THE INVENTION Aliphatic alcohols are important compounds that can be used in a variety of applications or that convert to other chemical compounds (e.g., surfactants, sulfates). Surfactants can be used in a variety of applications (eg, detergents, soaps, oil recovery). The structural composition of the aliphatic alcohol can influence the properties of the surfactant and / or detergent (eg, water solubility, biodegradability and detergent effect in cold water) produced from aliphatic alcohol. For example, the solubility of water can be affected by the linearity of the aliphatic portion of the aliphatic alcohol. As it is REF: 172163 increases the linearity of the aliphatic portion, the hydrophilicity (ie affinity for water) of the surfactant of the aliphatic alcohol can decrease. In this way, the solubility in water and / or performance of detergent effect of the aliphatic alcohol surfactant can decrease. The incorporation of branches in the aliphatic portion of the aliphatic alcohol surfactant can increase the solubility in cold water and / or the detergent effect of the aliphatic alcohol surfactant. However, the biodegradability of the aliphatic alcohol surfactants can be reduced if the branches in the aliphatic portion of the alcohol surfactant include a large number of quaternary carbons. The incorporation of branches with a minimum number of quaternary carbon atoms in the aliphatic portion of the aliphatic alcohol surfactant can increase the solubility and / or detergent effect in cold water of the alcohol surfactants while maintaining the degradability properties of the detergents. The aliphatic portion of an aliphatic alcohol used to make a surfactant may include one or more aliphatic alkyl groups as branches. Alkaliphatic groups that can form branches in the aliphatic portion can 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. As used herein, the phrase "aliphatic quaternary carbon atom" refers to a carbon atom that does not bind to any hydrogen atom. In U.S. Patent No. 5,849,960 to Singleton et al. , titled? ighly Branched Primary Alcohol Compositions, and Biodegradable Detergents Made Therefrom "and U.S. Patent No. 6,150,322 to Singleton et al., Entitled" Highly Branched Primary Alcohol Compositions, and Biodegradable Detergents Made Therefrom. "Processes for making compositions of branched primary alcohols are described. BRIEF DESCRIPTION OF THE INVENTION In one embodiment, aliphatic alcohols can be produced by a method including isomerization of olefins.The isomerization of olefins in a process stream can occur in an isomerization unit. The process entering an isomerization unit is derived from a Fischer-Tropsch process.At least a portion of the linear olefins in a process feed stream can be isomerized to branched olefins in the isomerization unit.The resulting branched olefins can have an average number of branches per m olefin olefin from 0.7 to 2.5. The branched olefins can include, enunciatively and without limitation, branched methyl and / or ethyl olefins. The isomerization process can produce branched olefins that include less than 0.5 aliphatic quaternary carbon atoms. After the feed stream is processed in the isomerization unit, the resulting stream containing branched olefins is passed to a hydroformylation unit. One or more hydrocarbon streams can be combined with the branched olefin-containing stream to alter the concentration of the olefins entering the hydroformylation unit. After the hydroformylation of the olefins, the unreacted components of the hydroformylation process of the aliphatic alcohol products can be separated. Unreacted paraffins and olefins in the separated stream can be sent to a dehydrogenation unit. The dehydrogenation of the paraffins can occur in a dehydrogenation unit. In one embodiment, at least a portion of a stream of unreacted paraffins and olefins can enter a dehydrogenation unit. In the dehydrogenation unit, at least a portion of the. Paraffins in the stream of unreacted paraffins and olefins can be dehydrogenated to produce olefins. At least a portion of the olefins produced can leave the dehydrogenation unit to form an olefinic hydrocarbon stream. The olefinic hydrocarbon stream resulting from the dehydrogenation process can be recirculated back to the isomerization unit and / or in a stream entering the isomerization unit. In one embodiment, one or more hydrocarbon streams may be combined with the feed stream entering an isomerization unit, a hydroformylation unit and / or a >; dehydrogenation unit. The hydrocarbon stream can be mixed with the feed stream to alter the concentration of the olefins entering the isomerization unit, hydroformylation unit and / or a dehydrogenation unit. In certain embodiments, at least a portion of the aliphatic alcohols can be sulfated to form aliphatic sulfates. In some embodiments, the aliphatic sulfates may include branched alkyl groups. In certain embodiments, at least a portion of the aliphatic alcohols produced can be oxyalkylated to form oxyalkyl alcohols. In some embodiments, the oxyalkyl alcohols may include branched alkyl groups. In some embodiments, at least a portion of the branched aliphatic alcohols produced can be ethoxylated to form branched ethoxyalkyl alcohols. At least a portion of the oxyalkyl alcohols can be sulfated to form oxyalkyl sulfate. In some embodiments, the oxyalguile sulfates may include branched alkyl groups. BRIEF DESCRIPTION OF THE DRAWINGS The advantages of the present invention will become apparent to those skilled in the art with the benefit of the following detailed description of the embodiments and with reference to the accompanying figures, in which: Figure 1 represents a diagram Schematic of one embodiment of a system for producing branched aliphatic alcohols using an olefin isomerization unit. Figure 2 depicts a schematic diagram of one embodiment of a system for producing branched aliphatic alcohols using a .isomerization unit and a separation unit for separating branched olefins from linear olefins and paraffins. Figure 3 depicts a schematic diagram of one embodiment of a system for producing branched aliphatic alcohols using an olefin isomerization unit with the addition of an additional hydrocarbon stream.

While the invention is susceptible to various modifications and alternative forms, the specific embodiments thereof are shown by way of example in the figures and will be described herein in detail. It should be understood that the figures and the detailed description thereof are not intended to limit the invention to the particular form described, but on the contrary, the invention will cover all modifications, equivalents and alternatives that fall within the spirit and scope of the present invention as referred to in the appended claims. Detailed Description of the Invention Hydrocarbon products can be synthesized from synthesis gas (ie, a mixture of hydrogen and carbon monoxide) using a Fischer-Tropsch process. The synthesis gas can be derived by partial combustion of oil (for example, coal, hydrocarbons), by reforming natural gas or by partial oxidation of natural gas. The Fischer-Tropsch process catalytically converts synthesis gas into a product mix that includes saturated hydrocarbons, unsaturated hydrocarbons and a smaller amount of oxygen-containing products. The products of a Fischer-Tropsch process can be used for the production of fuels (for example, gasoline, diesel), lubricating oils and waxes.

Fischer-Tropsch process streams can also be used to prepare commodity products, which have economic value. For example, linear olefins are commodity products that are useful for the production of surfactants. The use of a portion of the process stream to produce linear olefins can increase the economic value of a Fischer-Tropsch process stream. The surfactants derived from branched olefins may have different properties of the surfactants derived from linear olefins. For example, surfactants derived from branched olefins may have improved detergent effect properties and / or increased water solubility compared to surfactants derived from linear olefins. The biodegradable properties of the surfactant, however, can 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 can have biodegradable properties similar to surfactants derived from linear olefins. The production of branched olefins from a Fischer-Tropsch process stream can increase the economic value of the current. In some embodiments, linear olefins can be converted to 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 can 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 a certain amount of olefins, thereby increasing the economic value of the process stream. These 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 constituted of linear paraffins and olefins having at least 4 carbon atoms and up to 18 carbon atoms. A hydrocarbon feed stream can be obtained from a Fischer-Tropsch process or from an ethylene oligomerization process. The Fischer-Tropsch catalysts and the reaction conditions can be selected to provide a particular mixture of products in the stream of reaction products. For example, a Fischer-Tropsch catalyst and reaction conditions can be selected to increase the amount of olefins and decrease the amount of paraffins of oxygenated products in the stream. Alternatively, the catalyst and the reaction conditions may be selected to increase the amount of parafams and decrease the amount of olefins and oxygenates in the stream. The catalyst used in a Fischer-Tropsch process can be Mo,, Group VIII compounds or combinations thereof. The Group VIII compounds include, without limitation, iron, cobalt, ruthenium, rhodium, platinum, palladium, iridium and osmium. Combinations of Mo, and compounds of Group VIII can be prepared in the free metal form. In one embodiment, combinations of Mo, W, and Group VIII compounds can be formed as alloys. The combinations of Mo, W and compounds of Group VIII can be formed, in some embodiments, as oxides, carbides or other compounds. In other embodiments, combinations of Mo, W and Group VIII compounds may be formed as salts. Commercially based iron and cobalt-based catalysts have been used as Fischer-Tropsch catalysts. Ruthenium catalysts tend to favor the formation of serous species of high melting point under high pressure conditions. The synthetic Fischer-Tropsch catalysts can include combined iron. In some embodiments, a combined iron-Fischer-Tropsch catalyst may include a promoter (eg, potassium or oxides in a silicon support, alumina support or silica-alumina support). The cobalt material can also be used in a Fischer-Tropsch catalyst. With the appropriate selection of supports, promoters and other metal combinations, a cobalt catalyst can be adjusted to make a composition enriched in the desired hydrocarbon species. Other catalysts, such as iron-cobalt alloy catalysts, are known for their selectivity towards the production of olefins. Catalysts and combinations for the production of hydrocarbon species by a Fischer-Tropsch process are generally known. As long as there is a reference to a current of Fischer-Tropsch, any stream of olefins and saturated hydrocarbons may be adequate. Many Fischer-Tropsch streams can contain from 5 percent to 80 percent olefins, the rest being saturated hydrocarbons that comprise paraffins and other compounds. In some embodiments, the feed streams containing olefins and paraffins are obtained through the fractionation of paraffin wax or the oligomerization of olefins. Commercial olefin products made by oligomerization of ethylene are marketed in the United States of America by Chevron Phillips Chemical Company, Shell Chemical Company (as NEODENEMR) and by British Petroleum. The fractionation of the paraffin wax to produce alpha-olefin and olefin feed streams is described in the Patent of the United States No. 4,579,986 to Sie, entitled "Process For The Preparation Of Hydrocarbons "and U.S. Patent Application Serial No. 10 / 153,955 to Ansorge et al., Entitled" Process For The Preparation of Linear Olefins and Use Thereof To Prepare Linear Alcohols. "Specific Procedures for Preparing Olefins Linearities from ethylene are described in U.S. Patent No. 3,676,523 to Mason entitled "Alpha-Olefin Production"; U.S. Patent No. 3,686,351 to Mason entitled "Alpha-Olefin Production"; No. 3,737,475 to Mason entitled "Alpha-Olefin Production" and U.S. Patent No. 4,020,121 to Kister et al., Entitled "Oligomerization Reaction System." Most of the processes mentioned above produce alpha-olefins. commercial way higher linear internal olefins (for example, paraffin chlorination-dehydrochlorination, dehydrogenation of paraffins, isomerization of alpha-olefins). d, a feed stream is processed to produce a hydrocarbon stream that includes branched olefins. These branched olefins can be converted to branched aliphatic alcohols using various techniques. The feed stream may have a range of paraffin content between 50 weight percent to 90 weight percent of the feed stream.

In certain embodiments, a feed stream may have a paraffin content greater than 90 weight percent paraffins. The feed stream may also include olefins. The olefin content of the feed stream may be between 10 weight percent to 50 weight percent. In other embodiments, a feed stream may have an olefin content greater than 90 weight percent olefins. The feed stream may include hydrocarbons having an average carbon number ranging from 4 to 30. In one embodiment, an average carbon number of the hydrocarbons in a feed stream may vary from 4 to 24. In other embodiments, a The average carbon number of the feed stream can vary from 4 to 18. An average carbon number of the hydrocarbons in a feed stream can vary from 7 to 18. In certain embodiments, an average carbon number of the hydrocarbons in a feed stream may vary from 10 to 17. In some embodiments, an average number of carbons or hydrocarbons in a feed stream may vary from 10 to 13. In other embodiments, the average number of hydrocarbon carbons in a feed stream may vary from 14 to 17. In one embodiment, a feed stream for an isomerization unit includes mono-olefins and paraffins, the mono-o Lefines can 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 molecules of olefin molecules present may be alpha-olefins of a linear carbon structure (straight string). In certain embodiments, at least 70 percent of the olefins are alpha-olefins of a linear carbon structure. A hydrocarbon stream in which more than 70 percent of all olefin molecules are alpha-olefins of a linear carbon structure can be used in certain embodiments to convert olefins to aliphatic alcohols. This current could be derived from a Fischer-Tropsch process. In some embodiments, a feed stream includes olefins in which at least 50 percent of the olefin molecules present are internal olefins. The branched chain olefins can be converted to branched aliphatic alcohols (eg, branched primary alcohols) by a hydroformylation process. "Hydroformylation", as used herein, refers to the production of alcohols from olefins via a carbonization and a hydrogenation process.

Other processes can be used to produce aliphatic alcohols from olefins. Examples of these processes for producing aliphatic alcohols from olefins include, but are not limited to, hydration, oxidation and hydrolysis, sulfation and hydration, and epoxylation and hydration. The composition of a product stream of alcohol may include aliphatic alcohols having an average carbon number that varies from 5 to 31. In one embodiment, the average carbon number of the aliphatic alcohols in a product stream of alcohol may vary from 7 to 20. In certain embodiments, an average carbon number of the aliphatic alcohols in a product stream of alcohol may vary from 11 to 18. In some embodiments, an average number of carbons of aliphatic alcohols in a product stream of alcohol may vary from 11 to 14. In other embodiments, an average carbon number of the aliphatic alcohols in a product stream of alcohol may vary from 15 to 18. In certain embodiments, to reduce the production costs of producing branched aliphatic alcohols, A stream containing a significant amount of paraffins and a smaller amount of olefins could then first be isomerized, then hydrophobic rmila to form branched aliphatic alcohols. The processing of a stream containing a lower amount of olefins through an isomerization unit prior to hydroformylation can save production time, cost of dehydrogenation catalyst and / or improve the total economic viability of the stream. In some embodiments, after hydroformylation, unreacted paraffins and olefins may be recirculated to a hydrogenation unit to produce a stream enriched in olefins. The enriched olefin stream can be recycled or reprocessed to an isomerization unit. With reference to System 100 in Figure 1, a first hydrocarbon stream can be introduced into the isomerization unit 110 via the first conduit 112. In the isomerization unit 110, at least a portion of the olefins in the first hydrocarbon stream it can be isomerized to branched olefins to produce a second hydrocarbon stream. The conditions for the isomerization of olefins in the isomerization unit 110 can be controlled such that the number of carbon atoms in the olefins before and after the isomerization is substantially the same. Catalysts and process conditions for structurally isomerizing linear olefins to branched olefins are described in U.S. Patent No. 5,648,582 to Murray, entitled "Process for Isomerizing Linear Olefins to Isoolefins" and U.S. Patent No. 5,648,585 to Murray et al. ., entitled "Process for Isomerizing Linear Olefins to Isoolefins. "In one embodiment, linear olefins are isotylated in a first stream and hydrocarbon in unit 110 and isomerization by contacting at least a portion of the first hydrocarbon stream with a zeolite catalyst. less a channel with a free crystallographic channel diameter that varies from more than 4.2 A and less than 7 A. The zeolite catalyst may have an elliptical pore size large enough to allow the entry of a linear olefin and diffusion, at least partial, of a branched olefin. The pore size of the zeolite catalyst may also be small enough to retard coke formation. The temperatures at which the isomerization of olefins can be carried out vary from 200 ° C to 500 ° C. The temperatures in the isomerization unit 110 are maintained, in some embodiments, below the temperature at which the olefin is extensively fractionated. To inhibit fractionation, low temperatures can be used at low feed rates. In certain embodiments, lower temperatures may be used when the amount of oxygenates present in the process stream is low. Larger feed rates may be desirable to increase the production rate of the isomerized products. Higher feed rates can be used, in some embodiments, when operating at higher reaction temperatures. The reaction temperature, however, must be adjusted such that the fractionation to products of lower weight and boiling is minimized. For example, more than 90 percent of the linear olefins can be converted to branched olefins at 260 ° C at a feed rate of 60 grams per hour with minimal fractionation. The pressures maintained in the isomerization unit 110 may be at a hydrocarbon partial pressure ranging from 0.1 atmosphere (10 kPa) to 20 atmospheres (20 to 26 kPa). In one embodiment, the partial pressure may vary from above 0.5 atmospheres (51 kPa) to 10 atmospheres (1013 kPa). The branched olefin produced in the isomerization unit 110 may include methyl, ethyl and / or longer carbon chain branches. The isomerized olefin composition can be analyzed by XE NMR. In one embodiment, an average number of branches per olefin molecule present in the produced composition of branched olefins may be greater than 0.7. In certain embodiments, an average number of branches per olefin molecule present in the branched olefin composition is from 0.7 to 2.5. In some embodiments, an average number of branches per olefin molecule present in the branched olefin composition is from 0.7 to 2.2. In certain embodiments, an average number of branches per olefin molecule present in the branched olefin composition is from 1.0 to 2.2. The degree of branching in the product can be controlled by controlling the process conditions of the isomerization unit. For example, high reaction temperatures and lower feed rates may result in a higher degree of branching. The methyl branches can represent between 20 percent and 99 percent of the total number of branches present in the olefin molecules. In some embodiments, the methyl branches may represent more than 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 30 percent of the total number of branches. In other embodiments, a number of ethyl branches, if present, may be between 0.1 percent and 2 percent of the total number of branches. The different methyl or ethyl branches, if present, may be less than 5 percent the total number of branches. The isomerization unit 110 can produce a second hydrocarbon stream that includes olefins and paraffins. At least a portion of the second hydrocarbon stream contains branched olefins. The second hydrocarbon stream can leave the isomerization unit 10 via the second conduit 114 and is introduced into the hydroformylation unit 116. At least a portion of the olefins in the second hydrocarbon stream can be hydroformylated. In one embodiment, olefins can be separated, if desired, of the second hydrocarbon stream through generally known techniques (eg, distillation, molecular screening, extraction, adsorption, adsorption / desorption, and / or membranes). With reference to Figure 2, a second hydrocarbon stream can leave the isomerization unit 110 and enter the separation unit 118 via the separation conduit 120. The separation unit 118 can produce at least a current, a branched olefin stream and a stream of linear olefins and paraffins. In the separation unit 118, the second hydrocarbon stream can be contacted with molecular sieves (for example, zeolite or urea) of the correct size for the absorption of branched olefins and / or linear olefins and paraffins. The subsequent desorption of at least a portion of the branched olefins and / or at least a portion of the linear olefins and paraffins of the molecular sieves can produce at least two streams, a stream of branched olefins and a stream of linear olefins and paraffins. The separation unit 118 may include a fixed bed containing adsorbent for the separation of the second hydrocarbon stream to produce a branched olefin stream and a stream of linear olefins and paraffins. The separation temperatures in the separation unit 118 may vary from 100 ° C to 400 ° C. In some embodiments, the separation temperatures may vary from 180 ° C or 380 ° C. The separations in the separation unit 118 can be carried out at a pressure ranging from 2 atmospheres (202 kPa) to 7 atmospheres (710 kPa). In some embodiments, a pretreatment of the second hydrocarbon stream can be performed to prevent contamination of the adsorbent. At least a portion of the stream of linear olefins and paraffins can be recycled, transported to other processing units and / or stored at the site. In one embodiment, at least a portion of the stream of linear olefins and paraffins can be combined with the first hydrocarbon stream in the first conduit 112 via the recirculation conduit 122 of linear olefins and paraffins. The combined current can enter the unit 110 isomerization via the first conduit 112 to continue the process to produce isomerized olefins. In some embodiments, a stream of linear olefins and paraffins can be introduced directly into the isomerization unit 110. In some embodiments, a stream of linear olefins and paraffins can be introduced into a dehydrogenation unit. At least a portion of the branched olefin stream can be transported and used in other processing streams and / or stored on site via conduit 124 of branched olefins. In some embodiments, at least a portion of a branched olefin stream can leave the separation unit 118 and combine with the second hydrocarbon stream in the second conduit 114 upstream of the hydroformylation unit 16 via the olefin conduit 124 branched In other embodiments, at least a portion of a stream of branched olefins can exit a separation unit and is directly introduced into a hydroformylation unit. The second hydrocarbon stream can leave the isomerization unit 110 via the second conduit 114 and enter the hydroformylation unit 116 as depicted in Figures 1 and 2. As used herein, an "Oxo process" refers to 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 or more carbon atoms than the starting olefin. In other hydroformylation processes, a "modified Oxo process" is used. As used herein, a "modified Oxo process" refers to an oxo process using a cobalt or rhodium catalyst modified by phosphine ligand, phosphite, arsine or pyridine. The preparation and use of oxo modified catalysts are described in US Patent No. 3,231,621 to Slaugh, entitled "Reaction Rates In Catalytic Hydroformilation"; U.S. Patent No. 3,239,566 to Slaught et al., Entitled "Hydroformylation Of Olefins"; U.S. Patent No. 3,239,569 to Slaught et al. , entitled "Hydroformylation Of Olefins"; U.S. Patent No. 3,239,570 to Slaught et al., Entitled "Hydroformylation Of Olefins"; U.S. Patent No. 3,239,571 to Slaught et al., Entitled "Hydroformylation Of Olefins"; U.S. Patent No. 3,400,163 to Mason et al., Entitled "Bicyclic Heterocyclic Sec- And Ter-Phosphines", - U.S. Patent No. 3,420,898 to Van inkle et al., Entitled "Single Stage Hydroformilation Of Olefins To Alcohols Single Stage Hydroformylation of Olefins To Alcohols "; U.S. Patent No. 3,440,291 to Van Winkle et al., Entitled "Single Stage Hydroformilation Of Olefins To Alcohols"; U.S. Patent No. 3,448,157 to Slaugh et al., Entitled "Hydroformylation Of Olefins"; Patent of the United States No. 3,488,158 to Slaugh et al., Entitled "Hydroformilation of Olefins", Patent of the United States No. 3,496,203 to Morris et al., Entitled "Tertiary Organophosphine-Cobalt-Carbonyl Complexes"; U.S. Patent No. 3,496,204 to Morris et al., Entitled "Tertiary Organophosphine-Cobalt-Carbonyl Complexes", U.S. Patent No. 3,501,515 to Van inkle et al., Entitled "Bibyclic Heterocyclic Tertiary Phosphine-Cobalt-Carbonyl Complexes" ", United States Patent No. 3,527,818 to Mason et al., Entitled" Oxo Alcohols Using Catalysts Comprising Ditertiary Phosphines "; United States Patent Application Serial No. 10/075682, entitled" A Process For Preparing A Branched Olefin, A Method of Using The Branched Olefin For Making A Surfactant, and a Surfactant "and U.S. Patent Application Serial No. 10/167209 entitled" Process for the Preparation of A Highly Linear Alcohol Composition. " methods of alcohol production by Othmer, in "Encyclopedia of Chemical Technology" 2000, and by Wickson, in "Monohydric Alcohols; Manufacture, Applications and Chemistry "Ed. Am. Chem. Soc. 1981. A hydroformylation catalyst used in the hydroformylation unit 130 may include a metal of the Group VIII of the Periodic Table. Examples of Group VIII metals include cobalt, rhodium, nickel, palladium or platinum. The Group VIII metal can be used as a complex compound. A complex compound can be a Group VIII metal combined with a ligand. Examples of ligands include, but are not limited to, a phosphine, phosphite, arsine, stibin or pyridine ligand. Examples of hydroformylation catalysts include, but are not limited to, cobalt hydrocarbon catalyst, phosphine-cobalt ligand catalyst, phosphine-rhodium ligand catalyst or combinations thereof. In the hydroformylation unit 116, the olefins in the third hydrocarbon stream can be hydroformylated using a continuous, semi-continuous or batch process. In the case of a continuous mode of operation, the space velocities per hour of the line may be in the range of 0.1 h "1 to 10 h" 1. When the hydroformylation unit 116 is operated as a batch process, the reaction times may vary from 0.1 hours to 10 hours or even longer.

The reaction temperatures in the hydroformylation unit 116 may vary from 100 ° C to 300 ° C. In certain embodiments, reaction temperatures in the hydroformylation unit can be used ranging from 125 ° C to 250 ° C.

The pressure in the hydroformylation unit 120 may vary from one atmosphere (101 kPa) to 300 atmospheres (30,398 kPa). In one embodiment, a pressure of 20 (2027 kPa) can be used 150 atmospheres (15199 kPa). A quantity of the catalyst can vary with respect to the amount of olefin to be hydroformylated. Typical molar ratios of catalyst to olefin in the third hydrocarbon stream can vary from 1: 1000 to 10: 1. A ratio between 1:10 and 5: 1 can be used in certain modalities. In one embodiment, a diluent stream can be added to the hydroformylation unit 116 to control the reaction conditions. The diluent stream may include solvents that do not substantially interfere with the desired reaction. Examples of these solvents include, without limitation, alcohols, ethers, acetonitrile, sulfolane and paraffins. The mono-alcohol selectivities of at least 90 percent and even less than 92 percent can be achieved in the hydroformylation unit 116. In addition, conversions of olefin to aliphatic alcohols can vary from 50 weight percent to more than 95 weight percent. In certain embodiments, the conversion of olefin to aliphatic alcohols may be greater than 75 weight percent. In some embodiments, the conversion of olefin to aliphatic alcohols may be greater than 99 weight percent. The isolation of aliphatic alcohols produced from the hydroformylation reaction product stream can be achieved by generally known methods. In one embodiment, the isolation of the aliphatic alcohols includes subjecting the aliphatic alcohols produced to a first distillation, a saponification, a washing treatment with water and a second distillation. The reaction mixture stream may enter the separator 128 via the fourth conduit 126. In the separator 130, the stream of the hydroformylation reaction product may be subjected to a first distillation step (eg, flash distillation or a distillation route). short) . In one embodiment, a short path distillation can be used to produce at least two streams, a bottom current and a top stream. At least a portion of the bottom stream can be recirculated to the hydroformylation unit 116 via the bottom stream recirculation duct 130, in certain embodiments. The top stream may include, without limitation, paraffins, unreacted olefins and a crude aliphatic alcohol product.

In one embodiment, a higher stream may be subjected to a saponification treatment to remove any acid and ester present in the stream. Saponification can be carried out by contacting the upper stream with an aqueous solution of a hydroxide base (for example, sodium hydroxide or potassium hydroxide at elevated temperatures with agitation). The saponification can be carried out by contacting the top stream with a 0.5 to 10 percent aqueous 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. The saponification of the upper stream can be carried out batchwise or continuously. The upper stream can be subjected to one or more saponification processes. The saponification reaction temperatures can be from 40 ° C to 99 ° C. In one embodiment, the saponification temperatures may vary from 60 ° C to 95 ° C. The mixing of the upper stream with the basic water layer can be carried out during the saponification reaction. The separation of the upper stream from the basic water layer can be carried out using known methods. The upper stream is subjected to a water wash after separation to remove any sodium salt present. The overhead stream can be separated using generally known techniques (eg, fractional distillation) to produce at least two streams, a stream of crude alcohol product, and a stream of unreacted parafams and olefms. As used herein, "fractional distillation" refers to the distillation of liquids and subsequent collection of fractions of liquids determined by boiling point.

The stream of unreacted paraffins and olefins can be recirculated, transported to other units for processing, stored on site, transported off-site and / or sold. In certain embodiments, a product stream of crude aliphatic alcohol may contain undesired byproducts (eg, aldehydes, hemi-acetals). The by-products can be removed by subjecting the raw alcohol product stream to a hydrofinishing treatment step to produce a stream of aliphatic alcohol product. "Hydrofinishing" as used herein, refers to a hydrogenation reaction carried out under relatively moderate conditions. Hydrofinishing can be carried out using conventional hydrogenation processes. Conventional hydrogenation processes may include passing the crude alcohol feed together with a flow of hydrogen onto a bed of a suitable hydrogenation catalyst. The product stream of aliphatic alcohol may include more than 50 weight percent of the aliphatic alcohols produced. In some embodiments, the product stream of aliphatic alcohol may include more than 80 weight percent of the aliphatic alcohols produced. In other embodiments, the product stream of aliphatic alcohol may include more than 95 weight percent of aliphatic alcohols produced. The product stream of aliphatic alcohol may include branched aliphatic primary alcohols. The resulting aliphatic alcohols in the aliphatic alcohol product stream can be sold commercially, transported off-site, stored on site and / or used in other processing units by the product conduit 132. The composition of an aliphatic alcohol product stream may include hydrocarbons with an average carbon number ranging from 8 to 20. In one embodiment, an average carbon number of the hydrocarbons in the aliphatic alcohol product stream may vary from about 10 to about 10% by weight. 18. In certain embodiments, an average carbon number of the feed stream may vary from 10 to 13. In other embodiments, an average carbon number of the feed stream may vary from 14 to 17. In some embodiments, the branched primary alcohol products can be used as the precursor for the preparation of anionic sulfates, including aliphatic sulfates and oxyalkyl sulfates and oxyalkyl alcohols. The aliphatic alcohols may have slightly higher aliphatic branching and a slightly higher number of quaternary carbons such as the olefin precursor. In some modalities, the aliphatic branching may include methyl and / or ethyl branching. In other embodiments, the aliphatic branching may include aliphatic methyl, ethyl and higher branching. In certain embodiments, a number of quaternary carbon atoms in the aliphatic alcohol product may be less than 0.5. In other embodiments, a number of quaternary carbon atoms in the aliphatic alcohol product may be less than 0.3. The branching of the alcohol product can be determined by XH NMR analysis. The number of quaternary carbon atoms can be determined by 13 C NMR. 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 Made Therefrom Detergents". At least a portion of the stream of unreacted paraffins and olefins can be exited from the separation unit 126 and transported via the fourth conduit 134 and another processing unit and / or storage vessel. At least a portion of the stream separated from paraffins and olefins in react can enter the dehydrogenation unit 136 via the fourth conduit 134. An average carbon number of the hydrocarbons in the stream of unreacted paraffins and olefins can vary from 7 to 18. In certain embodiments, an average carbon number 0 of the Unreacted paraffin and olefin streams can vary from 10 to 17. In some embodiments, an average number of carbons in the stream of unreacted paraffins and olefins can vary from 10 to 13. In other embodiments, an average carbon number of 5 is the hydrocarbons in the stream of unreacted paraffins and olefins can range from 14 to 17. In one embodiment, at least a portion of the stream of unreacted paraffins and olefins can be introduced into the dehydrogenation unit 136 via the fourth or through conduit 134. At least a portion of the unreacted paraffins in the hydrocarbon stream can be dehydrogenated to produce an olefinic hydrocarbon stream by the use of hydrocarbons. e a catalyst selected from a wide variety of catalyst types. For example, the catalyst may be based on a metal and / or a metal compound deposited on a porous support. The metal or metal compound may include, but are not limited to, chromium oxide, iron oxide and noble metals. The techniques for preparing catalysts, for performing the dehydrogenation step and for carrying out the associated separation steps are known in the art. For example, suitable methods for preparing catalysts and for performing the dehydrogenation step are described in U.S. Patent No. 5,012,021 to Vora et al., Entitled "Process For The Production of Alkyl Aromatic Hydrocarbons Usin Solid Catalysts"; U.S. Patent No. 3,274,287 to Moore et al., Entitled "Hydrocarbon Conversion Process And Catalyst"; U.S. Patent No. 3,315,007 to Abell et al., Entitled "Dehydrogenation Of Saturated Hydrocarbons Over Noble-Metal Catalyst"; U.S. Patent No. 3,315,008 to Abell et al. , entitled "Dehydrogenation Of Saturated Hydrocarbons Over Noble-Metal Catalyst"; U.S. Patent No. 3,745,112 to Rausch, entitled "Platinum-Tin Uniformly Dispersed Hydrocarbon Conversion Catalyst And Process"; U.S. Patent No. 4,506,032 to Imai et al. , entitled "Dehydrogenation Catalyst Composition" and U.S. Patent No. 4,430,517 to Imai et al., entitled "Dehydrogenation Process Using a Catalytic Composition".

The reaction conditions in the dehydrogenation unit 136 can be varied to control unwanted by-products (eg, coke, diene oligomers, cyclized hydrocarbons) and to control the position of the double bond in the olefin. In certain modalities, temperatures may vary from more than 300 ° C to less than 700 ° C. In other embodiments, a dehydrogenation reaction temperature may vary from 450 ° C to 550 ° C.

During dehydrogenation, the pressures in the dehydrogenation unit 136 may vary from more than 0.010 atmospheres (1 kPa) at 25.0 atmospheres (2534 kPa). In one embodiment, a total pressure of the dehydrogenation unit 136 during the reaction may vary from 0.10 atmospheres (10 kPa) to 15.0 atmospheres (15200 kPa). In certain embodiments, the pressure in the dehydrogenation unit 136 may vary from 1.0 atmosphere (101 kPa) to 1.5 atmosphere 510 kPa). In order to prevent the formation of coke, s can feed hydrogen into the dehydrogenation unit 136 together with the stream of unreacted paraffins and olefins. The molar ratio of hydrogen to paraffin can be adjusted between 0.1 mol of hydrogen to 20 mol of paraffins. In some embodiments, a molar ratio of hydrogen to paraffin is from 1 to 10. The amount of time (e.g., residence time) that a process stream remains in the dehydrogenation unit 136 may determine, to some degree., the amount of olefins produced. In general, the longer a process stream remains in the dehydrogenation unit 136, the level of conversion of paraffins to olefins is increased until an olefin-paraffin thermodynamic equilibrium is obtained. The residence time of the stream of unreacted paraffins and olefins in the dehydrogenation unit 136 can be such that the level of conversion of paraffins to olefins can be maintained below 50 mole percent. In certain embodiments, the level of conversion of paraffins to olefins in the range of 5 to 30 mole percent can be maintained. By keeping the conversion level low, secondary reactions (eg, diene formation and cyclizapion reactions) can be prevented. In certain embodiments, at least a portion of the unconverted paraffins can be separated from the olefinic stream and, if desired, the unconverted paraffins can be recycled to the dehydrogenation unit 136 to undergo dehydrogenation. This separation can be achieved by extraction, distillation or adsorption techniques. In some embodiments, at least a portion of the paraffinic hydrocarbon stream can be introduced upstream of the dehydrogenation unit 136 to produce a combined stream. The combined stream can enter the dehydrogenation unit 136 to undergo dehydrogenation. In other embodiments, a paraffinic hydrocarbon stream is introduced directly into the dehydrogenation unit 136 through one or more entry points. The olefinic hydrocarbon stream can be combined with the first hydrocarbon stream in the first conduit 112 of the isomerization unit 110 via the fifth conduit 138. The combined stream can enter the isomerization unit 110 and at least a portion of the olefins present in the combined stream can be isomerized to branched olefins. In some embodiments, an olefinic hydrocarbon stream can leave the dehydrogenation unit 136 and is introduced directly into the isomerization unit 110 through one or more entry points. In certain embodiments, additional hydrocarbon streams may be used to control the reaction conditions and / or to optimize the concentration of unreacted fines and olefins in the isomerization unit 110, the hydroformylation unit 116, the dehydrogenation unit 136, and / or other processing units used to produce aliphatic alcohols. With reference to Figure 3, a first hydrocarbon stream can be introduced into the isomerization unit 110 via the first conduit 112. The first hydrocarbon stream can include olefins and paraffins. The conditions of the olefin isomerization can be controlled, as described above for system 100, such that the number of carbon atoms in the olefin before and subsequent to the isomerization conditions is substantially the same. At least a portion of a paraffinic hydrocarbon stream may be introduced into the first conduit 112 via the sixth conduit 140 upstream of the isomerization unit 110 to produce a combined stream. The combined stream can enter the isomerization unit 110 via the first conduit 112. In other embodiments, a paraffinic hydrocarbon stream is introduced directly into the isomerization unit 110 through one or more entry points. At least a portion of the olefins in the combined stream can be isomerized to branched olefins in the isomerization unit 110 to produce a second hydrocarbon stream. The addition of the hydrocarbon paraffinic stream can be used to optimize the olefin concentration in the isomerization unit 110 and to control the degree of branching in the olefins produced. The concentration of paraffins in the paraffinic hydrocarbon stream can be between 10 percent and 99 percent by weight. In certain modalities, a paraffin concentration can vary between 10 percent and 50 percent by weight. In some embodiments, a paraffin concentration can vary between 25 percent and 75 percent by weight. In other embodiments, a paraphorm stream may include olefmas. An • concentration of olefin in the hydrocarbon stream can be between 20 and 80 percent. The second hydrocarbon stream can leave the isomerization unit 110 and be introduced into the hydroformylation unit 116 via the second conduit 114 to continue the process to produce aliphatic alcohols. The second hydrocarbon stream can include branched olefins. At least a portion of a third stream of hydrocarbons can enter the second conduit 114 via the septic conduit 142 upstream of the hydroformylation unit 116 to form a mixed stream. The mixed stream can then be introduced into the hydroformylation unit 116 via the second conduit 114. At least a portion of the olefins in the mixed stream can be hydroformylated using process conditions as described above. In some embodiments, a third hydrocarbon stream can be introduced directly into the hydroformylation unit 116 through one or more entry points. It should be understood that an olefin concentration in the process streams can be adjusted by adding a stream through the sixth conduit 140 only, the seventh conduit 142 only, directly in the unit 116 of hydroformylation alone or by combination thereof. The third hydrocarbon stream in line 142 can be used to optimize the concentration of olfactory in the hydroformylation unit 116 to maximize hydroformylation of the olefins. The third hydrocarbon stream can be from the same source as the first hydrocarbon stream. Alternatively, the third hydrocarbon stream may be a hydrocarbon stream that includes olefins, paraffins, and / or hydrocarbon solvents derived from another source. The third hydrocarbon stream may include olefins and paraffins. In certain embodiments, an average carbon number of the hydrocarbons in the third hydrocarbon stream varies from 7 to 18. In certain embodiments, a third hydrocarbon stream may include olefins and paraffins. In some embodiments, a paraffin content of the third hydrocarbon stream may be between 60 percent and 90 percent by weight. In other embodiments, a paraffin content of the third hydrocarbon stream may be greater than 90 weight percent. In one embodiment, the olefma content of a third hydrocarbon stream varies between 1 percent and 99 percent in relation to the total hydrocarbon content. In certain embodiments, an olefin content of the third hydrocarbon stream may be between 45 percent and 99 percent by weight. In other embodiments, an olefin concentration of the third hydrocarbon stream may be greater than 80 weight percent. In some embodiments, a third hydrocarbon stream may include linear olefins. The addition of a stream that includes linear olefins downstream of the isomerization unit allows the creation of a hydroformylation feed stream that includes a mixture of linear and branched olefins. By introducing a stream that includes branched and linear olefins in the hydroformylation unit 116, a mixture of branched and linear aliphatic alcohol products can be obtained. By varying the amount of linear olefins added to the stream of. Hydroformylation feed can control the ratio of aliphatic alcohol products, linear to branched. A mixture of linear and branched aliphatic alcohols can have improved properties when converted to surfactants or other products. Examples of improved surfactant properties include, without limitation, limitation., low irritation to the skin and eyes, foaming properties, biodegradability, solubility in cold water and detergent effect in cold water. Applications for these surfactants include, but are not limited to, personal care products, pet and industrial laundry products, process washing products, machine lubricant additives and lubricating oil formulations. The hydroformylation reaction mixture stream can enter the separator 126 via the third conduit 128. The separation of the aliphatic alcohol product from at least a portion of the hydroformylation reaction stream can be performed in the separation unit 126 as described previously. The separation can produce at least two currents, a bottom current and a higher current using generally known techniques (eg, distillation). At least a portion of the bottom stream can be recycled to the hydroformylation unit 116 via the recycling unit 130. The overhead stream can be further purified and separated to produce at least two streams, a stream of unreacted olefin paraffins and a stream of crude aliphatic alcohol product. At least a portion of the crude aliphatic alcohol product stream can be further purified to produce an aliphatic alcohol product stream using generally known techniques, the aliphatic alcohol product stream can leave the separation unit 126 and be transported via unit 132 of product to be stored on the site, sold commercially transported off-site and / or used in other processing units. The aliphatic alcohols produced in the aliphatic alcohol product stream may have an average carbon number of from 8 to 19. In certain In certain embodiments, the aliphatic alcohols produced in the aliphatic alcohol product stream may have an average carbon number of 11 to 18. In some embodiments, the aliphatic alcohols produced in the aliphatic alcohol product stream may have an average carbon number of 11 to 14. In other embodiments, the aliphatic alcohols produced in the aliphatic alcohol product stream may have an average number of carbons of 15 to 18. At least a portion of the stream of unreacted paraffins and olefins can leave the separation unit 126 and be transported via the fourth conduit 134 to another processing unit and / or storage vessel . At least a portion of the separated paraffins and unreacted olefins can enter the dehydrogenation unit 136 via the fourth conduit 134. An average carbon number of the hydrocarbons in the stream of unreacted paraffins and olefins can vary from 7 to 18. .

In certain embodiments, an average number of carbons in the stream of unreacted paraffins and olefins can vary from 10 to 17. In some embodiments, an average number of carbons in the stream of unreacted paraffins and olefins can vary from 10 to 13. In other embodiments, an average carbon number of the hydrocarbons in the unreacted paraffin and olefin stream can vary from 14 to 17. At least a portion of the paraffins in the hydrocarbon stream can be dehydrogenated using process conditions such as described above. At least a portion of the resulting olefinic hydrocarbon stream may leave the dehydrogenation unit 136 and be transported to another processing unit and / or a storage vessel via the fifth conduit 138. At least a portion of a hydrocarbon paraffin stream it can be introduced into the fourth conduit 134 via the eighth conduit 144 upstream of the dehydrogenation unit 136 to produce a combined stream. The combined stream can enter the dehydrogenation unit 136 via the fourth conduit 134. In other embodiments, a paraffinic hydrocarbon stream is introduced directly into the dehydrogenation unit 136 through one or more entry points. In certain embodiments, at least a portion of the unconverted paraffins can be separated from the dehydrogenated compounds in the olefinic stream. This separation can be achieved by extraction, distillation or adsorption techniques. At least a portion of the unconverted paraffins can be recycled to the dehydrogenation unit 136 to undergo further dehydrogenation. At least a portion of the olefinic hydrocarbon stream can leave the dehydrogenation unit 136 via the fifth conduit 138 and be combined with the first hydrocarbon stream in the first conduit 112 upstream of the isomerization unit 110 to produce a combined stream . The combined stream can be introduced into the isomerization unit 110 via the first conduit 112 and at least a portion of the olefins in the combined stream can be isomerized to branched olefins. In some embodiments, an olefinic hydrocarbon stream may be directly introduced into the isomerization unit 110 via one or more entry points. At least a portion of the hydrocarbon olefin stream can be combined with a second hydrocarbon stream in the second conduit 114 upstream of the isomerization unit 110 to produce a mixed stream. Depending on the dehydrogenation conditions, the mixed stream may include linear olefins. The addition of the olefinic hydrocarbon stream with the second hydrocarbon stream can produce a mixed stream that includes both linear and branched olefins. The aliphatic alcohols can be converted to oxy-alcohols, sulfates or other commercial products. At least a portion of the aliphatic alcohols in the alcohol product stream can be reacted in an oxyalkylation unit with an epoxide (for example, ethylene oxide, propylene oxide, butylene oxide, in the presence of a base for producing an oxyalkyl alcohol The condensation of an alcohol with an oxide allows the functionality of the alcohol to be expanded by one or more oxy groups.The number of oxy groups may vary from 3 to 12. For example, the reaction of an alcohol with oxide of ethylene can produce alcohol products having between 3 to 12 ethoxy groups The reaction of an alcohol with ethylene oxide and propylene oxide can produce alcohols with an ethoxy / propoxy ratio of ethoxy or propoxy groups of 4: 1 to 12 : 1. In some modalities, a substantial proportion of portions of alcohol can be combined with more than three portions of ethylene oxide. likewise with less than three portions of ethylene oxide. In a typical mixture of oxyalkylation product, a lower proportion of unreacted alcohol may be present in the product mixture. In one embodiment, at least a portion of the aliphatic alcohol product stream can be formed by condensing a C5 to C3X aliphatic alcohol with an epoxide. In certain embodiments, a branched primary alcohol of C5 to C15 can be condensed with ethylene oxide and / or propylene oxide. In other embodiments, a branched primary alcohol of Cu to C? 7 can be condensed with ethylene oxide and / or propylene oxide. The resulting oxyalkyl alcohols can be sold commercially, transported off-site, stored on site and / or used in other processing units. In some embodiments, an oxyalkyl alcohol can be sulfated to form an anionic surfactant. In one embodiment, at least a portion of the alcohols in the aliphatic alcohol product stream can be added to a base. The base may be an alkali metal or alkaline earth metal hydroxide (for example sodium hydroxide or potassium hydroxide). The base can act as a catalyst for the oxyalkylation reaction. An amount of 0.1 weight percent to 0.6 weight percent of a base, based on the total weight of the alcohol, may be used for the oxyalkylation of an alcohol. In one embodiment, a weight percent of a base can vary from 0.1 weight percent to 0.4 weight percent based on the total amount of alcohol. The reaction of the alcohol with the base can result in the formation of an alkoxide. The resulting alkoxide can be dried to remove any water present. The dry alkoxide can be reacted with an epoxide. An amount of epoxide used can be from 1 mole to 12 moles of epoxide per mole of alkoxide. A resulting mixture of alkoxide-epoxide can be allowed to react until the epoxide is consumed. A decrease in the total reaction pressure may indicate that the reaction is complete. The reaction temperatures in an oxyalkylation unit can vary from 120 ° C to 220 ° C. In one embodiment, the reaction temperatures may vary from 140 ° C to 160 ° C. Reaction pressures can be achieved by introducing the required amount of epoxide into the reaction vessel. Epoxides have a high vapor pressure at the desired reaction temperature. Due to the safety of the process, the partial pressure of the epoxide reagent can be limited, for example, to less than 4 atmospheres (413 kPa). Other safety measures may include diluting the reagent with an inert gas such as nitrogen. For example, dilution with inert gas can result in a reagent vapor phase concentration of 50 percent or less. In some embodiments, an alcohol-epoxide reaction can be safely achieved at a higher epoxide concentration, a higher total pressure and a higher epoxide partial pressure, if adequate, generally known, safety precautions are taken to handle the risks of explosion. With respect to ethylene oxide, a total pressure of 3 atmospheres (304 kPa) to 7 atmospheres (709 kPa) can be used. The total pressures of ethylene oxide from one atmosphere (101 kPa) to atmospheres (415 kPa) can be used in certain embodiments. In one embodiment, total pressures of 1.5 atmospheres ((150 kPa) to 3 atmospheres (304 kPa) can be used with respect to ethylene oxide.The pressure can serve as a measure of the degree of reaction.The reaction can be considered substantially complete when the pressure does not decrease for more time over time Aliphatic alcohols and oxyalkyl alcohols can be derivatized to form compositions (eg sulfonates, sulfates, phosphates) useful in formulations of commercial products (eg, detergents, surfactants, additives) of oil, lubricating oil formulations.) For example, alcohols can be sulfided with S03 to produce sulphates.The term "sulfur" refers to a sulfur atom or sulfur-containing functionality that is added to a carbon or oxygen. Sulforization processes are described in U.S. Patent No. 6, 462,251 by Jacobson et al., Entitled "Sulfonation, Sulfation and Sulfamation "; U.S. Patent No. 6,448,435 of Jacobson et al., "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. Patent No. 3,428,654 to Rubinfeld et al., Entitled" Alkene Sulfonation Process and Products; "U.S. Patent No. 3,420,875 to DiSalvo et al., Entitled" Olefin Sulfonates "; US Pat. No. 3,506,580 to Rubinfeld et al., Entitled "Heat-Treatment Of Sulfonated Olefin Products"; and U.S. Patent No. 3,579,537 to Rubinfeld, entitled "Process For Separation Of Sultons, From Alkenyl Sulfonic Acoids." characterize a general class of aliphatic alcohol sulfates by the chemical formula: (R-0- (A) x-S03) nM.R 'represents the aliphatic portion. "A" represents a portion of an alkylene oxide; average number of portions of A per portion R-0 and may vary from 0 to 15, and n is an integer that depends on the valence of the cation M. Examples of the cation M include, without limitation, metal ions alkali, alkali metal ions carriers, ammonium ions and / or mixtures thereof. Examples of cations include, but are not limited to, magnesium, potassium, monoethanolamine, diethanolamine or triethianolamine. The aliphatic and oxyalkyl alcohols can be sulfated in a sulfation unit. Sulfation procedures may include the reaction of sulfur trioxide (S03), chlorosulfonic acid (C1S03H), sulfamic acid (NH2S03H) or sulfuric acid with an alcohol. In one embodiment, sulfur trioxide can be used in concentrated sulfuric acid (eg, smoking) to sulphonate alcohols. The concentrated sulfuric acid can have a concentration of 75 weight percent to 100 weight percent in water. In one embodiment, concentrated sulfuric acid may have a concentration of 85 weight percent to 98 weight percent in water. The amount of sulfur trioxide can vary from 0. 3 mol to 1. 3 mole of sulfur trioxide per mole of alcohol. In certain modalities, an amount of sulfur trioxide may vary from 0.4 moles to 1.0 moles of sulfur trioxide per mole of alcohol. In one embodiment, a sulfur trioxide sulfating process may include contacting a liquid alcohol or an oxyalkyl alcohol and sulfur trioxide gas in a falling film sulfater to produce a sulfuric acid ester of the alcohol. The reaction zone of the falling film sulfator can be operated at atmospheric pressure and a temperature in the range of 25 ° C to 70 ° C. The sulfuric acid ester of the alcohol can leave the falling film sulfater and enter a neutralization reactor. The sulfuric acid ester can be neutralized by an alkali metal solution to form the alkyl sulfate salt or the oxyalkyl sulfate salt. Examples of an alkali metal solution may include sodium or potassium hydroxide solutions. Derivatized alcohols can 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 formulation, liquid dishwashing formulation, and miscellaneous formulations. Examples of miscellanea formulation may include general purpose cleaning agents, liquid soaps, shampoos and liquid scouring agents. Granular laundry detergent formulations may include several components in addition to the derivatized alcohols (eg, surfactants, additives, co-additives, bleaching agents, bleach activators, foam control agents, enzymes, anti-gray agents, optical brighteners and stabilizers). Examples of other surfactants may include ionic, nonionic, amphoteric or cationic surfactants. Liquid laundry detergent formulations can include the same components as granular laundry detergent formulations. In certain embodiments, liquid laundry detergent formulations may include less of an inorganic additive component than granular laundry detergent formulations. Hydrotropes of the liquid detergent formulations may be present. General purpose cleaning agents can include other surfactants, additives, foam control agents, hydrotropes and solubilizing alcohols. The formulations may typically include one or more inert components, for example, the remainder of the liquid detergent formulations may typically be an inert solvent or diluent (e.g., water). Granular or powder detergent formulations typically contain amounts of inert carrier or filler materials.

EXAMPLES Example 1: Isomerization of olefins in hydrocarbon stream derived from Fischer-Tropsch. Carbon monoxide and hydrogen were reacted under Fischer-Tropsch process conditions to produce a hydrocarbon mixture of linear paraffins, linear olefins, a lower amount of dienes and a smaller amount of oxygenated products. The Fischer-Tropsch hydrocarbon stream was separated into different hydrocarbon streams using fractional distillation techniques. The hydrocarbon stream containing olefins and paraffins with an average number of carbon atoms of 8 to 10 was obtained. The composition of the resulting C 8 -C 0 hydrocarbon stream was analyzed by gas chromatography and tabulated in the Table. 1. Table 1 A zeolite catalyst used for isomerization of linear olefins in the hydrocarbon stream was prepared in the following manner. In a Lancaster mixing mixer, ammonium-ferrierite (645 grams) was charged which exhibits a 5.4% loss in ignition and exhibits the following properties: silica to alumina molar ratio of 62: 1, surface area of 369 square meters per gram (P / Po = 0.03), soda content of 480 ppm and n-hexane adsorption capacity of 7.3 g per 100 g of ammonium-ferrierite. CATAPAL ^ D alumina kneader (91 grams) was added to the alumina kneader, which exhibits an ignition loss of 25.7%. During a five-minute kneading period, 152 milliliters of deionized water was added to the alumina / ammonium-ferrierite mixture. Then, a mixture of 6.8 grams of 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 kneader to peptize the alumina. The resulting mixture of alumina / ammonium-ferrierite / acid was kneaded for 10 minutes. Over a period of 15 minutes, a mixture of 0.20 grams of tetraamine-palladium nitrate in 153 grams of deionized water was slowly added to the kneaded mixture of alumina / ammonium-ferrierite / acid. The resulting mixture exhibited a 90:10 ratio of zeolite to alumina and an ignition loss of 43.5%. The zeolite / alumina mixture was formed by extruding the mixture through a stainless steel nozzle plate (1/16 inch holes) of a Bonnot 2.25 inch extruder. The wet extruded product of zeolite / alumina was dried at 125 ° C for 16 hours. After drying, the extruded product of zeolite / alumina was broken along manually. The extruded product of zeolite / alumina was calcined in flowing air, at 200 ° C for 2 hours. The temperature was increased to a maximum temperature of 500 ° C and the extruded product of zeolite / alumina was calcined for two additional hours to produce an isomerization catalyst. The isomerization catalyst was allowed to cool in a desiccator under a nitrogen atmosphere. Isomerization reactor was used as stainless steel pipe, 1 inch outside diameter, 0.6 inch inside diameter and 26 inches long. A thermo cavity was extended 20 inches from the top of the stainless steel reactor tube. To load the reactor tube, the head tube was inverted and a piece of glass wool was transferred down to the wall of the reactor tube, over the thermocavity and placed on the bottom of the reactor tube to serve as a plug for the tube reactor.

Silicon carbide (20 mesh) was added to a depth of approximately 6 inches to the reactor tube. A second piece of glass wool was placed on the silicon kangaroo. A mixture of 6.0 grams of isomerization catalyst particles (6-20 mesh) and 45 grams of fresh silicon carbide (60-80 mesh) was added to the reactor tube in two parts. The two-part addition distributed the isomerization catalyst evenly in the reactor tube and resulted in an isomerization catalyst bed approximately 10 inches long. A third piece of glass wool was added to the top of the catalyst in the reactor tube. The silicon kangaroo (20 mesh) was stratified on the third piece of glass wool. An additional piece of glass wool was placed on the silicon carbide to serve as a plug for the bottom of the reactor tube. To monitor the temperature of the reaction at several points in the reactor tube, a thermocouple of multiple points was inserted into the thermo cavity 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 for a period of four hours under flowing nitrogen. Once the temperature of 280 ° C was obtained, the reactor tube was maintained at the operating temperature for two additional hours to condition the isomerization catalyst. After conditioning of the isomerization catalyst, the hydrocarbon stream was pumped through the reactor tube at a flow rate of 60 g / hr. Nitrogen was passed, at a flow rate of 6 L / hr, over the isomerization catalyst simultaneously with the hydrocarbon stream. The hydrocarbon stream was evaporated before being brought into contact with the isomerization catalyst. The reactor tube was operated at an outlet pressure of 20 kPa above atmospheric pressure. In Table 2, the percent by weight of branched olefins of C8-C0, linear olefins of C8-C0, and C8-C0 paraffins in the hydrocarbon stream at 0 hours and in the effluent are tabulated. of the reactor tube after 24 to 48 hours of isomerization. More than 90% of the linear olefins in the hydrocarbon stream were converted to branched olefins in the isomerization reactor. During the isomerization step, a small amount of boiling material was generated below C8 of the fractionation side reactions. In addition, a portion of the C9-Cn alcohols present in the feed were dehydrated to produce additional olefins in the product. The average number of alkyl branches in the C8-C10 olefins in the product was found to be 1.0 as determined by 1 H NMR analysis. Table 2 Example 2. Isomerization of 1-dodecene. 1-Dodecene was obtained from Shell Chemical Co. The 1-dodecene composition, as assessed by gas chromatography, is tabulated in Table 3.

Table 3 The 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 was passed, at a flow rate of 6 L / hr over the isomerization catalyst simultaneously with the 1-dodecene stream. The 1-dodecene stream was evaporated 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 molecules of less than C? 0, C? 0-C? and less than Ci 4 in 1-dodecene at 0 hours and the effluent from reactor tube after 168 and 849 hours. Linear olefins of C10-C? 4 were converted to a yield of 94% to branched olefins of Cio- after a processing time of 168 hours. During the isomerization step, less than 3 weight percent of boiling material was generated below C10 of the fractionation side reactions. The average number of alkyl branches in the olefins of C? 0-C? in the product it was found to be 1.3 as determined by XH NMR analysis. Table 4 Example 3. Dehydrogenation of dodecane with minimal isomerization. Dodecene was obtained from Aldrich Chemical Company and stored under nitrogen before being processed. The dodecene composition, as assessed by gas chromatography, is tabulated in Table 5.

Table 5 A paraffin dehydrogenation catalyst was prepared according to Example 1 (catalyst A) of U.S. Patent No. 4,430,517 to Imai et al. , entitled "Dehydrogenation Process Using A Catalytic Composition". The resulting catalyst included 0.8% by weight of platinum, 0.5% by weight of tin, 2.7% by weight of tin, 2.7% by weight of potassium and 1.3% by weight of 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 granules in a hydrochloric acid solution. An amount of stannic chloride was added to the resulting solution to provide a compound 2 final containing 0.5% by weight of tin and stirred to distribute the tin component evenly throughout the entire mixture. Hexamethylenetetramine was added to the resulting tin mixture and the resulting tin-amine mixture was added dropwise to 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 ammonia solution, dried and calcined to form a spherical carrier material of gamma-alumina. The resulting spheres contained approximately 0.5% by weight of tin in the tin oxide form. US Pat. No. 2,620,314 to Hoesktra entitled "Spheroidal Alumina" describes more details about the method for preparing the alumina carrier material. The tin-alumina composite product was contacted with a deionized solution of chloroplatinic acid and hydrochloric acid (2 weight percent based on the weight of the alumina) in a rotary dryer for 15 minutes at room temperature. The amount of chloroplatinic acid used was the amount needed to incorporate 0.8% by weight of platinum in the tin-alumina composite product. The solution was then heated and purged with nitrogen to remove water, resulting in a product composed of platinum-chloro-tin-alumina. The incorporated chlorine was removed by heating the composite platinum-chloro-tin-alumina product at 550 ° C and by treating the composite product with an air / steam mixture at 80 ° C, 50/50 at a space velocity per hour of gas (GHSV) of 300 hr "1. After treatment with the air / steam mixture, the platinum-tin-alumina composite contained less than 0.1 wt% chlorine.The compound platinum-tin-alumina was contacted with a deionized potassium nitrate water solution The amount of potassium nitrate used was the amount needed to incorporate 2.7 percent by weight of potassium into the platinum-tin-alumina composite product Water was removed from the platinum compound tin-potassium-alumina by heating the compound product to 100 ° C under a dry air purge (GHSV of 1000 hr "1) for 0.5 hours. The temperature was increased to 525 ° C and the compound product of platinum-tin-potassium-alumina was treated with a stream of hydrochloric acid (12 cc / hr, HCl 0.9 M) and a stream of an air / steam mixture at 80 ° C. ° C, 50/50 (GHSV of 300 hr "1) to incorporate chlorine into the compound product of platinum-tin-potassium-alumina The compound product of platinum-tin-potassium-chlorine-alumina was dried at 525 ° C a dry air purge (GHSV of 1000 hr "1). The resulting spheres of catalyst have an average particle diameter of 1/16 inch and were crushed and sized to a 6-20 mesh particle before the test. It was used as a reactor isomerization stainless steel pipe 1 inch outside diameter, 0.6 inches inside and 26 inches long. A thermocavity was extended 20 inches from the top of the stainless steel reactor tube. To load the reactor tube, the reactor tube was inverted and a piece of glass wool was transferred down to the wall of the reactor tube, over the thermocavity and placed in the bottom of the reactor tube to serve as a plug for the head tube. Silicon carbide (20 mesh) was added to a depth of approximately 6 inches to the reactor tube. A second piece of glass wool was placed on the silicon carbide. A mixture of 6.0 grams of platinum-tin in alumina catalyst particles (6-20 mesh) and 45 grams of fresh silicon carbide (60-80 mesh) was added to the two-part reactor tube. The two-part addition distributed the catalyst evenly in the reactor tube and resulted in a catalyst bed about 10 inches long. A third piece of glass wool was added to the top of the catalyst in the reactor tube. The silicon carbide (20 mesh) was stratified on the third piece of glass wool. A fourth piece of glass wool was placed on the silicon carbide to serve as a plug for the bottom of the reactor tube. To monitor the temperature of the reaction at several points in the reactor tube, a multi-point thermocouple was inserted into the thermocavity 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 for a period of four hours under nitrogen flowing (250 normal liters per hour). Once the temperature of 425 ° C was obtained, the reactor tube was maintained at the operating temperature for two additional hours. The catalyst was pre-sulphided by flowing a 1% mixture of hydrogen sulfide gas in hydrogen gas at 425 ° C for 5 minutes through the reactor tube. After 5 minutes, the hydrogen sulfide in the flow of hydrogen gas was changed to a flow of hydrogen gas through the reactor tube. After pre-sulfurization of the catalyst, the reactor tube was maintained at 425 ° C for eight hours. After eight hours, the reactor tube pressure was increased to 25 pounds / in2 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 normal liters per hour. After four hours, The dodecane current was increased to 80 g / hr. After obtaining a flow rate of 80 g / hr, the temperature of the reactor tube was increased to 460 ° C. The reactor tube was sampled every eight hours to obtain the operating temperature of 460 ° C. After twenty-four hours the% by weight of dodecane was 11.4% by weight as shown in Table 6. At a -temperature of 479 ° C, the conversion of dodecane to olefins was 16 weight percent after twenty-four hours . Of the olefins, 84% formed were mono-olefins, 4.1% by weight were aromatic compounds and 7.5% by weight were di-olefins. In the total amount of olefins formed, 6% was branched, as determined by 1 H NMR analysis.

Table 6 It is noted that with respect to this date, the best method known by the applicant to carry out the present invention is that which is clear from the present description of the invention.

Claims (24)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. Method for the production of aliphatic alcohols, characterized in that it comprises: introducing a first hydrocarbon stream comprising olefins and paraffins in an isomerization unit, wherein the isomerization unit is configured to isomerize at least a portion of linear olefins in the first hydrocarbon stream to branched olefins, and wherein at least a portion of the unreacted components of the first hydrocarbon stream and at least one portion of the branched olefins produced form a second hydrocarbon stream; introducing the second hydrocarbon stream into a hydroformylation unit, wherein the hydroformylation unit is configured to hydroformilate at least a portion of the olefins in the second hydrocarbon stream to produce aliphatic alcohols, and wherein at least a portion of the alcohols produced aliphatics comprises a branched alkyl group, and wherein at least a portion of the unreacted components of the second hydrocarbon stream, and at least a portion of the aliphatic alcohols produced form a hydroformylation reaction stream; separating at least a portion of the hydroformylation reaction stream to produce a stream of aliphatic alcohol product and a stream of unreacted paraffm and olefins; and introducing at least a portion of the stream of unreacted paraffins and olefins into a dehydrogenation unit, wherein the dehydrogenation unit is configured to dehydrogenate at least a portion of the paraffins in the stream of unreacted paraffins and olefins to produce olefins , and wherein at least a portion of the defines produced leaves the dehydrogenation unit to form an olefinic hydrocarbon stream; and introducing at least a portion of the olefinic hydrocarbon stream into the isomerization unit.
2. 2. Method according to claim 1, characterized in that the first hydrocarbon stream is produced from an oligomerization process of olefins.
3. Method according to claim 1, characterized in that the first hydrocarbon stream is produced from a Fischer-Tropsch process.
4. 4. Method according to any of claims 1 to 3, characterized in that the first hydrocarbon stream comprises olefins and paraffins having a carbon number of 10 to 17, particularly 10 to 13.
5. 5. Method of conformance with any of Claims 1 to 4, characterized in that the isomerization unit is operated at a reaction temperature between 200 ° C and 500 ° C.
6. 6. Method according to any of claims 1 to 5, characterized in that the isomerization unit is operated at a reaction pressure between 0.1 atmospheres and 20 atmospheres.
7. Method according to any of claims 1 to 6, characterized in that the hydroformylation unit is configured to produce more than 50 percent aliphatic alcohols.
8. 8. Method according to any of claims 1 to 7, characterized in that the hydroformylation unit is configured to produce more than 95 percent aliphatic alcohols.
9. 9. Method according to any of claims 1 to 8, characterized in that the hydroformylation unit is operated at a reaction temperature of 100 ° C to 300 ° C.
10. 10. The method according to claim 1, further comprising adjusting an olefin to paraffin ratio introduced into the isomerization unit by adding at least a portion of a paraffinic hydrocarbon stream to the isomerization unit.
11. 11. Method according to any of claims 1 to 10, characterized in that it further comprises: adjusting a ratio of olefins to paraffins introduced in the isomerization unit by combining a paraffinic hydrocarbon stream with at least a portion of the first hydrocarbon stream upstream of the isomerization unit to form a combined stream; and introduce the combined current in the isomerization unit.
12. 12. Method according to any of claims 1 to 10, characterized in that it further comprises: adjusting a ratio of olefins to paraffins introduced in the isomerization unit by combining at least a portion of a paraffinic hydrocarbon stream with at least a portion of the first hydrocarbon stream upstream of the isomerization unit to form a combined stream; introduce the combined current in the isomerization unit; adjusting an olefin to paraffin ratio introduced into the hydroformylation unit by combining at least a portion of a third hydrocarbon stream with at least a portion of the second hydrocarbon stream upstream of the hydroformylation unit to form a combined stream; and introducing the combined stream in the hydroformylation unit.
13. 13. Method according to any of claims 1 to 12, characterized in that it further comprises adjusting a ratio of olefins to paraffins introduced in the hydroformylation unit by adding at least a portion of a third hydrocarbon stream in the hydroformylation unit.
14. 14. Method according to any of claims 1 to 12, characterized in that it further comprises adjusting a ratio of olefins to paraffins introduced in the hydroformylation unit by adding at least a portion of a third hydrocarbon stream in the hydroformylation unit , wherein the third hydrocarbon stream comprises more than 80 weight percent olefins.
15. 15. Method according to any of claims 1 to 12, characterized in that it further comprises: adjusting a ratio of olefins to paraffins introduced in the hydroformylation unit by combining at least a portion of a third hydrocarbon stream with at least a portion of the second hydrocarbon stream upstream of the hydroformylation unit to form a combined stream; and introducing the combined stream in the hydroformylation unit.
16. 16. Method according to any of claims 1 to 12, characterized in that it further comprises: adjusting a ratio of olefins to paraffins introduced in the hydroformylation unit by combining at least a portion of a third hydrocarbon stream with at least a portion of the second hydrocarbon stream upstream of the hydroformylation unit to form a combined stream, wherein the third hydrocarbon stream comprises more than 80 weight percent olefins; and introducing the combined stream in the hydroformylation unit.
17. 17. Method according to any of claims 1 to 12, characterized in that it further comprises: adjusting a ratio of olefins to paraffins introduced in the hydroformylation unit by combining at least a portion of a third hydrocarbon stream with at least a portion of the second hydrocarbon stream upstream of the hydroformylation unit to form a combined stream, wherein the third hydrocarbon stream comprises linear olefins; and introducing the combined stream in the hydroformylation unit.
18. 18. Method according to any of claims 1 to 12, characterized in that it further comprises: adjusting a ratio of olefins to paraffins introduced in the hydroformylation unit by combining at least a portion of a third hydrocarbon stream with at least a portion of the second hydrocarbon stream upstream of the hydroformylation unit to form a combined stream, wherein at least a portion of the second hydrocarbon stream comprises branched olefins; and introducing the combined stream in the hydroformylation unit.
19. 19. Method of compliance with any of claims 1 to 12, characterized in that it further comprises: adjusting a ratio of olefins to paraffins introduced into the hydroformylation unit by combining at least a portion of a third hydrocarbon stream with at least a portion of the second stream of 5 hydrocarbon stream upstream of the hydroformylation unit to form a combined stream, wherein at least a portion of the third hydrocarbon stream comprises linear olefins and at least a portion of the second hydrocarbon stream comprises 0 branched olefins; and introduce the combined stream in the hydroforming unit.
20. Method according to any of claims 1 to 19, characterized in that the dehydrogenation unit is operated at a temperature between 300 ° C and 700 ° C.
21. 21. Method according to any of claims 1 to 20, characterized in that the dehydrogenation unit is operated at a pressure between 0.01 atmospheres 0 and 25 atmospheres.
22. 22. Method according to any of claims 1 to 21, characterized in that it further comprises introducing at least a portion of the product stream of aliphatic alcohol in a sulphation unit, ~ wherein the sulfation unit is configured to sulfate at least a portion of the aliphatic alcohols in the aliphatic alcohol product stream to produce aliphatic sulfates, and wherein at least a portion of the aliphatic sulfates produced comprises branched aliphatic sulphates.
23. 23. Method according to any of claims 1 to 21, characterized in that it further comprises introducing at least a portion of the product stream of aliphatic alcohol into an oxyalkylation unit, wherein the oxyalkylation unit is configured to oxyalkylate at least one portion of the aliphatic alcohols in the aliphatic alcohol product stream to produce oxyalkyl alcohols, wherein at least a portion of the oxyalkyl alcohols produced comprises branched oxyalkyl alcohols.
24. 24. System for the production of aliphatic alcohols, characterized in that it is configured to perform the method according to any of claims 1 to 23.