Process for producing renewable product streams

Abstract

By hydrodeoxygenating biorenewable feedstocks enriched in free fatty acids having 10-13 carbon atoms at moderate hydrodeoxygenation ratios lower than those utilized for conventional biorenewable feedstocks such as vegetable oils or even mineral feedstocks, normal paraffins in the range desired by the detergent industry can be produced. Either hydroisomerization or isononal separation can be performed to provide green fuel streams. Two reactors are proposed, one for hydrodeoxygenation of biorenewable feedstocks enriched in free fatty acids having 10-13 carbon atoms and the other for conventional biorenewable feedstocks or even mineral feedstocks operated at higher hydrodeoxygenation ratios.

Description

[Technical Field]

[0001] (Priority statement) This application claims priority to U.S. Patent Application No. 17 / 513,651, filed October 28, 2021, which is incorporated herein by reference in its entirety.

[0002] FIELD OF THE INVENTION The field is processes for producing product streams from renewable feed streams. Specifically, the field is processes for producing detergent and fuel streams from renewable feed streams. [Background technology]

[0003] Linear alkylbenzenes have the formula C6H5C n H 2n+1 The alkyl benzenes are organic compounds having the following structure: The alkyl carbon number "n" can have any practical value, but detergent manufacturers prefer alkyl benzenes to have alkyl carbon numbers in the range of 9 to 16, preferably 10 to 13. These specific ranges are often required when alkyl benzenes are used as intermediates in the manufacture of detergent surfactants. Alkyl carbon numbers in the range of 10 to 13 meet detergent industry specifications.

[0004] Because surfactants produced from alkylbenzenes are biodegradable, the production of alkylbenzenes has grown rapidly since their first use in detergent manufacturing in the 1960s. The linearity of the paraffin chains in alkylbenzenes is important to the material's biodegradability and effectiveness as a cleaning agent. The primary factor in the final linearity of the alkylbenzene is the linearity of the paraffin component.

[0005] While cleaning agents made utilizing alkylbenzene-based surfactants are biodegradable, the process for making alkylbenzenes is not based on renewable resources. In particular, alkylbenzenes are currently produced from kerosene refined from crude oil extracted from the earth. Increasing environmental bias against fossil fuel extraction and growing economic concerns about depleting fossil fuel deposits may support the use of alternative sources of biodegradable surfactants in detergent and other industries.

[0006] Therefore, it would be desirable to provide linear alkylbenzenes with a high degree of linearity that are produced from biorenewable sources rather than mined from the earth. It would also be desirable to provide renewable linear alkylbenzenes from easily processed triglycerides and fatty acids from vegetable, animal, nut, and / or seed oils. Palm kernel oil, coconut oil, and babassu oil have compositions that match the alkyl carbon number range desired in the detergent industry.

[0007] Biofuel can be co-produced with linear alkylbenzenes. Other desirable features and characteristics of the present invention will become apparent from the subsequent detailed description of the invention and the appended claims, taken in conjunction with the accompanying drawings and this background. Summary of the Invention

[0008] The inventors have discovered that biorenewable feedstocks enriched in free fatty acids having 10-13 carbon atoms can be converted to paraffinic compositions favorable for detergent alkylation by moderate hydrodeoxygenation ratios less than those utilized for conventional biorenewable feedstocks such as vegetable oils. This disclosure proposes two reactors, one for the hydrodeoxygenation of biorenewable feedstocks enriched in free fatty acids having 12 and 14 carbon atoms, and the other for conventional biorenewable feedstocks or even mineral feedstocks operated at higher deoxygenation ratios.

[0009] Further details and embodiments of the present disclosure will become apparent from the following detailed description of the present disclosure. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 2 is a schematic diagram of a conversion unit of the present disclosure. [Figure 2] FIG. 2 is a schematic diagram of another conversion unit of FIG. 1; [Figure 3] FIG. 3 is a schematic diagram of a benzene alkylation unit useful with either the conversion unit of FIG. 1 or FIG. 2. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present disclosure seeks to produce alkylbenzenes from renewable resources for detergent manufacturing and jet fuel and / or diesel. Many vegetable oils have fatty acids that, when hydrodeoxygenated, produce normal paraffins with 16 to 18 carbons, which are longer than desired by detergent manufacturers. However, some renewable resources, such as palm kernel oil (PKO), coconut oil, and babassu oil, have fatty acids that, when deoxygenated, produce normal paraffins with 10 to 13 carbons. Normal paraffins with 10 to 13 carbons are the desired number of carbons that detergent manufacturers want for the alkyl groups on alkylbenzenes used in detergents.

[0012] We found that the degree of hydrodeoxygenation can affect the selectivity to each of the normal paraffins in the 10-13 carbon range. For biorenewable feedstocks with fatty acids having 12 and 14 carbon atoms, hydrodeoxygenation converts them to the corresponding numbers of normal paraffins with 12 and 14 carbon atoms, respectively. For example, hydrodeoxygenation of neutral fats with fatty acids of 14 carbon atoms produces tetradecane.

[0013] [ka]

[0014] However, upon decarboxylation or decarbonylation, fatty acids with 12 and 14 carbon atoms are converted to normal paraffins, which have one less carbon atom than fatty acids with 11 and 13 carbon atoms. For example, decarboxylation of a triglyceride with a 14 carbon atom fatty acid produces tridecane and carbon dioxide.

[0015] [ka]

[0016] If the degree of hydrodeoxygenation is too great, the hydrodeoxygenated composition may be heavily biased toward normal tetradecane and normal dodecane, to the detriment of normal tridecane and normal undecane. If the degree of hydrodeoxygenation is too small, the hydrodeoxygenated composition may be heavily biased toward normal tridecane and normal undecane, to the detriment of normal tetradecane and normal dodecane. The hydrodeoxygenation ratio is determined by the following formula:

[0017]

number

[0018] The inventors have found that hydrodeoxygenation at percentages of 35 to 60%, preferably 40 to 55%, provides a hydrodeoxygenation composition having n-undecane, n-dodecane, and n-tridecane in the ranges desired by detergent specifications for at least n-paraffins, although n-decane may be low in some cases and may need to be replenished to meet detergent specifications.

[0019] Other vegetable oils with fatty acids in the 15-20 carbon range are typically subjected to advanced hydrodeoxygenation to obtain jet fuel or diesel-range paraffins. Advanced hydrodeoxygenation is not equivalent to the moderate hydrodeoxygenation of PKO, coconut oil, and babassu oil, which are best suited for detergent production. Therefore, we propose to separate the hydrodeoxygenation of other feedstock streams from the hydrodeoxygenation of biorenewable streams that produce 10-13 carbon, especially 11-13 carbon, normal paraffins, such as PKO, palm oil, and babassu oil, to achieve higher yields of the hydrodeoxygenated compositions desired in detergent production.

[0020] In FIG. 1, we propose to decouple the hydrodeoxygenation of a biorenewable feed stream having a large amount of fatty acids with 12 and 14 carbons from the hydrodeoxygenation of another biorenewable feed stream having a large amount of fatty acids with 14-20 carbons by utilizing two hydrodeoxygenation reactors.

[0021] A process 10 for treating a biorenewable feedstock stream is shown according to an exemplary embodiment. A first feedstock line 12 may transport a first biorenewable feedstock stream. The term "biorenewable feedstock stream" is intended to include feedstocks other than those derived from crude oil. The biorenewable feedstock stream may include any of these feedstocks containing glycerides and / or free fatty acids. Most of the glycerides will be triglycerides, but monoglycerides and diglycerides may be present and similarly processed. The free fatty acids may be derived from phospholipids, which may be a source of phosphorus in the feedstock. The first biorenewable feedstock stream in line 12 may include a biological oil substantially enriched in free fatty acids having 12 and 14 carbon atoms. The free fatty acids may be derived from glycerin bridges. As used herein, the terms "substantial," "substantially," or "substantially" mean greater than 30%, suitably greater than 40%, and preferably greater than 50%.

[0022] Examples of such biorenewable oils include PKO, palm oil, and babassu oil. The biorenewable feedstock may be pretreated to remove contaminants and filtered to remove solids. The biorenewable feedstock stream in line 12 may be mixed with hydrogen from line 14, heated, and fed to a first hydrodeoxygenation reactor 16.

[0023] The second feedstock line 18 transports a second feedstock stream. The second feedstock stream in line 18 may include a second biorenewable feedstock stream of biological oil containing free fatty acids having 10 to 20 carbon atoms derived from glycerol bridges. The second feedstock stream may also be a conventional biorenewable oil, such as a vegetable oil, that is not enriched in free fatty acids having 12 or 14 carbon atoms. The second feedstock stream in line 18 may include a biological oil that is substantially enriched in free fatty acids not having 12 or 14 carbon atoms. A variety of different biorenewable feedstocks may be suitable for the second biorenewable feedstock stream in second feedstock line 18. Examples of these biorenewable feedstocks include, but are not limited to, camelina oil, canola oil, corn oil, soy oil, rapeseed oil, soybean oil, rapeseed oil, tall oil, sunflower oil, hempseed oil, olive oil, linseed oil, castor oil, peanut oil, mustard oil, tallow, yellow and brown grease, lard, whale oil, milk fat, fish oil, algae oil, sewage sludge, etc. Further examples of biorenewable feedstocks include non-edible vegetable oils from the group including Jatropha curcas (ratanjo, wildcaster, jangulierandi), Madhuca indica (mowa), Pongamia pinnata (karanji, hongji), calophyllum inophyllum, moringa oleifera, and Azadirachta indica (neem). Typical vegetable or animal fat triglycerides and FFAs contain aliphatic hydrocarbon chains with 8 to 30 carbon atoms in their structure. As will be appreciated, the biorenewable feedstock may include a mixture of one or more of the foregoing examples. The second feedstock stream in line 18 may be mixed with hydrogen from line 20, heated, and fed to hydrotreating reactor 22.

[0024] The first hydrodeoxygenation reactor 16 may include a bed of a hydrodeoxygenation catalyst for hydrodeoxygenating the first bio-feedstock stream in the presence of hydrogen to provide a first hydrodeoxygenated stream. The hydrotreating reactor 22 may include a bed of a hydrotreating catalyst for hydrotreating the second feedstock stream in the presence of hydrogen to provide a hydrotreated stream. In the embodiment of Figure 1, the hydrotreating reactor may include a second hydrodeoxygenation reactor 22 including a bed of a hydrodeoxygenation catalyst for hydrodeoxygenating the second bio-renewable feedstock stream in the presence of hydrogen to provide a second hydrodeoxygenated stream.

[0025] The hydrodeoxygenation reactions that occur in the hydrodeoxygenation reactors 16, 22 include hydrodecarbonylation and hydrodecarboxylation. Additionally, other hydrotreating reactions occur in the hydrodeoxygenation reactors 16, 22, including olefin saturation, hydrodemetallization to remove phosphorus, hydrodesulfurization, and hydrodenitrogenation.

[0026] Conditions within the first hydrodeoxygenation reactor 16 may include temperatures between 250°C (482°F) and 400°C (752°F) and pressures between 700 kPa (absolute) (100 psig) and 21 MPa (absolute) (3000 psig). The hydrodeoxygenation reactor temperature is kept low, below 343°C (650°F) for typical biorenewable feedstocks, and below 304°C (580°F) for feedstocks with higher free fatty acid (FFA) concentrations to avoid polymerization of olefins found in the FFA. Generally, hydrodeoxygenation reactor pressures between 1.9 MPa (absolute) (285 psia) and 14.7 MPa (absolute) (2133 psia) are suitable.

[0027] The first hydrodeoxygenation reactor 16 and the second hydrotreating reactor 22 may contain guard bed catalysts comprising base metals on supports. Base metals usable in this process include nickel, chromium, molybdenum, and tungsten. Other base metals that may be used include tin, indium, germanium, lead, cobalt, gallium, and zinc. The base metals are active in the sulfide form. In further embodiments, the guard bed catalyst may contain a second metal, which may include one or more of the following metals: tin, indium, ruthenium, rhodium, rhenium, osmium, iridium, germanium, lead, cobalt, gallium, zinc, and thallium. An alumina-supported nickel-molybdenum catalyst may be a suitable catalyst within the guard bed. A hydrogen quench stream may be injected at spaced or interbed locations to control temperature exotherms.

[0028] The first hydrodeoxygenation reactor 16 and the second hydrotreating reactor 22 may also contain beds of hydrodeoxygenation catalysts to further hydrodemetallize, hydrodeoxygenate (including hydrodecarbonylation and hydrodecarboxylation), hydrodenitrogenate, and hydrodesulfurize the respective feed streams. Metals removed include alkali and alkaline earth metals and phosphorus. The olefinic or unsaturated portions of n-paraffin chains in the biorenewable feedstock are also saturated. Hydrodeoxygenation reactions, including hydrodecarboxylation and hydrodecarbonylation, remove oxygenated functional groups from the biorenewable feedstock molecules, which are converted to water and carbon oxides. The hydrodeoxygenation catalysts also catalyze the desulfurization of organic sulfur and the denitrification of organic nitrogen in the biorenewable feedstock stream.

[0029] The hydrodeoxygenation catalyst may comprise nickel, nickel / molybdenum, or cobalt / molybdenum dispersed on a high surface area support such as alumina. Suitable hydrotreating catalysts include BDO 200 or BDO 300, available from UOP LLC (Des Plaines, Illinois). The hydrodeoxygenation catalyst should be in sulfided form. Hydrogen sulfide from the recycle stream in line 24 may provide sulfur for catalyst sulfiding.

[0030] The first hydrodeoxygenation reactor 16 produces a hydrodeoxygenated stream in line 26. The hydrodeoxygenated stream comprises a hydrocarbon fraction having a substantial n-paraffin concentration in the 10-13 carbon atom range, preferably in the 11-13 carbon atom range. The oxygenate concentration in the hydrocarbon fraction is essentially zero, while the olefin concentration is substantially reduced relative to the first biorenewable feedstock stream. The organic sulfur concentration in the hydrocarbon fraction can be 500 wppm or less, and the organic nitrogen concentration in the hydrocarbon fraction can be 10 wppm or less. Conditions in the first hydrodeoxygenation reactor 16 are operated to achieve a hydrodeoxygenation ratio of 35-60%, preferably 40-55%.

[0031] The second hydrotreating reactor 22 produces a hydrotreated stream in line 28. The hydrotreated stream may be a second hydrodeoxygenated stream in line 28, in which case the hydrodeoxygenated stream in line 26 is the first hydrodeoxygenated stream. The hydrotreated stream includes a hydrocarbon fraction having a substantial n-paraffin concentration in the 14 to 20 carbon atom range. The oxygenate concentration in the hydrocarbon fraction is essentially zero, while the olefin concentration is substantially reduced relative to the first biorenewable feedstock stream. The organic sulfur concentration in the hydrocarbon fraction may be 500 wppm or less, and the organic nitrogen concentration in the hydrocarbon fraction may be 10 wppm or less. Conditions in hydrotreating reactor 22 may include temperatures of from 250°C (482°F) to 400°C (752°F) and pressures of from 700 kPa (absolute) (100 psig) to 21 MPa (absolute) (3000 psig), preferably from 1.9 MPa (absolute) (285 psia) to 14.7 MPa (absolute) (2133 psia). Conditions in second hydrotreating reactor 22 are operated to achieve a hydrodeoxygenation ratio higher than that in first hydrodeoxygenation reactor 16 and / or to achieve a hydrodeoxygenation ratio of greater than 55%, suitably greater than 60%, and preferably at least 90%.

[0032] The hydrodeoxygenated stream in line 26 can be cooled and separated in first separator 30 to provide a hydrogen gas stream in overhead line 18 and a liquid hydrodeoxygenated stream in bottoms line 32. An aqueous stream can be removed from a boot descending from separator 30. First separator 30 can be in downstream communication with hydrodeoxygenation reactor 16 and an upstream high-temperature separator, not shown. First separator 30 can be operated at a temperature between 30°C (116°F) and 70°C (158°F). First separator 30 can be operated at a slightly lower pressure than hydrodeoxygenation reactor 32, taking into account pressure drops due to intervening equipment. First separator 30 can be operated at a pressure between 1.9 MPa (absolute) (285 psig) and 14.7 MPa (absolute) (2133 psia).

[0033] The hydrotreated stream in line 28 may be cooled and separated in second separator 34 to provide a hydrogen gas stream in overhead line 18 and a liquid hydrodeoxygenated stream in bottoms line 36. An aqueous stream may be removed from a boot descending from separator 34. Second separator 34 may be in downstream communication with hydrotreating reactor 28 and an upstream high-temperature separator, not shown. Second separator 34 may be operated at a temperature between 30°C (116°F) and 70°C (158°F). Second separator 34 may be operated at a slightly lower pressure than hydrotreating reactor 22, taking into account pressure drops due to intervening equipment. Second separator 34 may be operated at a pressure between 1.9 MPa (absolute) (285 psig) and 14.7 MPa (absolute) (2133 psia).

[0034] In one embodiment, the first separator 30 and the second separator 34 may be in the same vessel with a baffle that separates the liquid in the first separator from the liquid in the second separator 34. The baffle may have a bottom edge sealed to the bottom of the vessel, but may have an upper edge spaced apart from the top of the vessel. Thus, the first separator 30 and the second separator 34 may share the same overhead outlet 24, but may have separate bottom outlets 32 and 36 and separate boot outlets.

[0035] As used herein, the term "separator" means a vessel having an inlet and at least an overhead vapor outlet and a bottoms liquid outlet, and may also have an aqueous stream outlet from a boot. A flash drum is a type of separator that may be in downstream communication with a separator that may be operated at a higher pressure. The term "communication" means that fluid flow is operably permitted between the listed components, which may be characterized as "fluid communication." The term "downstream communication" means that at least a portion of the fluid flowing to an object in downstream communication can operably flow from the object in fluid communication.

[0036] The liquid hydrodeoxygenated stream in line 32 may be fractionated in splitter column 40 to produce three streams. Alternatively, multiple columns may be used. A splitter overhead stream is withdrawn from splitter column 40 in an overhead line, condensed in a cooler, and fed to a separator. The condensed overhead stream is recycled to splitter column 40 as reflux through a reflux line, and a net vapor stream containing C9-hydrocarbons, including green LPG and naphtha, is withdrawn in net overhead line 42. The green LPG and naphtha may be separated downstream. A liquid side stream containing a light normal paraffin stream in the C10 to C13 carbon range is removed from side 41 of splitter column 40 in line 44. The composition of the light normal paraffin stream meets applicable detergent alkylation specifications for at least C11 to C13 normal paraffins. The term "Cx" should be understood to refer to a molecule having the number of carbon atoms represented by the subscript "x". Similarly, the term "Cx-" refers to a molecule containing less than or equal to x, preferably x and less, carbon atoms. x+ " refers to a molecule having more than or equal to x, preferably x and more, carbon atoms. The light normal paraffin stream in line 44 may be transported to a detergent alkylation unit 200 in FIG. 3.

[0037] A splitter bottoms stream is withdrawn from splitter column 40 through a bottoms line, from which a portion of the splitter bottoms stream flows through a reboiler line, is heated in a reboiler heater, and returns to splitter fractionation column 40. The remaining portion of the splitter bottoms stream flows through net bottoms stream line 46, which contains a heavy normal paraffin stream in the C14 to C20 carbon range. Splitter fractionation column 40 operates at a bottoms temperature range of 230 to 270°C and an overhead pressure of 20 kPa to 400 mmHg absolute to a slight vacuum. It is envisioned that instead of a single column producing a side stream, two fractionation columns could be used to provide three streams.

[0038] The term "column" refers to a distillation column or columns for separating one or more components of different volatility. Unless otherwise specified, each column includes a condenser at the top of the column for condensing and refluxing a portion of the overhead stream that returns to the top of the column, and a reboiler at the bottom of the column for vaporizing a portion of the bottom stream and returning it to the bottom of the column. The feed to the column may be preheated. The overhead pressure is the pressure of the overhead vapor at the vapor outlet of the column. The bottom temperature is the liquid bottom outlet temperature. Unless otherwise specified, the overhead and bottom lines refer to the net lines from column to column downstream of any reflux or reboil. A stripper column may omit the reboiler at the bottom of the column and instead provide the required heat and driving force for separation from a fluidized inert medium such as steam.

[0039] A portion of the hydrotreated stream is combined with a heavy normal paraffin stream in net bottoms line 46. Specifically, the liquid hydrotreated stream in second bottoms line 36 is combined with the heavy normal paraffin stream in the embodiment of Figure 1 to provide a hydroisomerization feed stream in line 48. The hydroisomerization feed stream in line 48 can be combined with a recycle stream in line 56 and a hydroisomerized hydrogen stream in line 52 and fed to hydroisomerization reactor 50. To improve cold flow properties, the hydrotreated stream can be contacted with a hydroisomerization catalyst under hydroisomerization conditions in hydroisomerization reactor 50 to hydroisomerize the normal paraffins to branched paraffins.

[0040] The hydroisomerization, also known as hydrodewaxing, of normal hydrocarbons in hydroisomerization reactor 50 may be accomplished over one or more beds of hydroisomerization catalyst, which may be operated in a co-current mode of operation.

[0041] Suitable hydroisomerization catalysts may include metals from Group VIII of the periodic table (IUPAC 8-10) and support materials. Suitable Group VIII metals include platinum and palladium, each of which may be used alone or in combination. The support material may be amorphous or crystalline. Suitable support materials include amorphous alumina, amorphous silica-alumina, ferrierite, ALPO-31, SAPO-11, SAPO-31, SAPO-37, SAPO-41, SM-3, MgAPSO-31, FU-9, NU-10, NU-23, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, MeAPO-11, MeAPO-31, MeAPO-41, MgAPSO-11, Examples of suitable slags include MgAPSO-31, MgAPSO-41, MgAPSO-46, ELAPO-11, ELAPO-31, ELAPO-41, ELAPSO-11, ELAPSO-31, ELAPSO-41, laumontite, cancrinite, offretite, hydrogen-form stilbite, magnesium or calcium-form mordenite, and magnesium or calcium-form persite, each of which may be used alone or in combination. ALPO-31 is described in U.S. Patent No. 4,310,440. SAPO-11, SAPO-31, SAPO-37, and SAPO-41 are described in U.S. Patent No. 4,440,871. SM-3 is described in U.S. Patent Nos. 4,943,424, 5,087,347, 5,158,665, and 5,208,005. MgAPSO is MeAPSO, an acronym for metal aluminum silicophosphate molecular sieve, where the metal Me is magnesium (Mg). Suitable MgAPSO-31 catalysts include MgAPSO-31. MeAPSO is described in U.S. Pat. No. 4,793,984, and MgAPSO is described in U.S. Pat. No. 4,758,419. MgAPSO-31 is a preferred MgAPSO, where 31 refers to MgAPSO having the structure type 31.As taught in U.S. Patent Nos. 4,795,623 and 4,924,027, many naturally occurring zeolites, such as ferrierite, which initially have reduced pore size, can be converted to a form suitable for olefin skeletal hydroisomerization by ammonium ion exchange and calcination to remove associated alkali or alkaline earth metals and produce substantially the hydrogen form. Additional catalysts and conditions for skeletal hydroisomerization are disclosed in U.S. Patent Nos. 5,510,306, 5,082,956, and 5,741,759. The hydroisomerization catalyst may also contain a modifier selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, and mixtures thereof, as described in U.S. Patent Nos. 5,716,897 and 5,851,949. Other suitable support materials include ZSM-22, ZSM-23, and ZSM-35, which are described for use in dewaxing in U.S. Patent No. 5,246,566 and in an article by S.J. Miller entitled "New Molecular Sieve Process for Lube Dewaxing by Wax Isomerization," 2 Microporous Materials 439-449 (1994). U.S. Patent Nos. 5,444,032 and 5,608,968 teach suitable bifunctional catalysts composed of amorphous silica-alumina gel and one or more metals belonging to Group VIIIA, which are effective in the hydroisomerization of long-chain normal paraffins containing more than 15 carbon atoms. U.S. Patent Nos. 5,981,419 and 5,908,134 teach suitable bifunctional catalysts comprising (a) a porous crystalline material isostructural with beta zeolite selected from borosilicates (BOR-B) and boroaluminosilicates (Al-BOR-B) having a SiO2:Al2O3 ratio greater than 300:1, and (b) one or more metals belonging to Group VIIIA selected from platinum and palladium in an amount ranging from 0.05 to 5% by weight. V. Calemma et al., App. Catal. A: Gen., 190 (2000), 207 teaches yet another suitable catalyst.DI-100, available from UOP LLC (Des Plaines, Ill.), may be a suitable catalyst.

[0042] Hydroisomerization conditions typically include temperatures from 250°C (482°F) to 400°C (752°F) and pressures from 1.9 MPa (absolute) (285 psia) to 14.7 MPa (absolute) (2133 psia). In another embodiment, hydroisomerization conditions include temperatures from 300°C (572°F) to 360°C (680°F) and pressures from 3102 kPa (absolute) (450 psia) to 6895 kPa (absolute) (1000 psia).

[0043] The hydroisomerized stream in hydroisomerization line 54 from hydroisomerization reactor 50 is a branched paraffin-rich stream. The term "rich" means that the effluent stream has a higher concentration of branched paraffins than the stream entering hydroisomerization reactor 84, and preferably contains greater than 50% by weight of the total paraffin content. It is contemplated that the hydroisomerized effluent may contain 70, 80, or 90% by weight of the total paraffin content of branched paraffins.

[0044] The hydroisomerize stream in line 54 may be separated in separators, not shown, and stripped of lights in hydroisomerization stripper 60 to provide a light gas stream in overhead line 62 and a green fuel stream in bottoms line 64. Hydroisomerization stripper 60 strips the hydroisomerize stream with steam from line 66 and may be operated at a bottoms temperature of 149°C (300°F) to 288°C (550°F) and an overhead pressure just below the pressure of hydroisomerization reactor 50, accounting for intervening equipment pressure drops of 0.35 MPa (gauge) (50 psig) to 2.0 MPa (gauge) (290 psig) or less.

[0045] The liquid green fuel stream in line 64 may be dried and fractionated in product column 70 to produce three streams. A product overhead stream is withdrawn from product column 70 in an overhead line, fully condensed in a cooler, and sent to a separator. A portion of the condensed overhead stream is recycled to product fractionation column 70 as reflux through a reflux line, and a net liquid stream containing green naphtha is withdrawn in net overhead liquid line 72. A liquid side stream is withdrawn from side 71 of product column 70 in line 74 containing a paraffin stream in the jet fuel range with an initial boiling point of 80°C to 120°C and an end point of 290°C to 310°C. As used herein, the term "initial boiling point" (IBP) refers to the temperature at which a sample begins to boil, as the case may be, using ASTM D-86. As used herein, the term "end point" (EP) refers to the temperature at which a sample has completely evaporated, as the case may be, using ASTM D-86.

[0046] A product bottoms stream is withdrawn from product column 70 through a bottoms line, from which a portion of the splitter bottoms stream flows through a reboiler line, a reboiler heater, and back to product fractionation column 70. The remaining portion of the product bottoms stream flows through net bottoms line 76, which contains green diesel in the C17 to C20 carbon range. Some or all of the green diesel stream may be recycled in line 56, combined with the hydroisomerization feed stream in line 48, and hydroisomerized in hydroisomerization reactor 50. Some or all of the green diesel may be recovered in line 78. Product fractionation column 70 operates at a bottoms temperature range of 250°C (482°F) to 350°C (662°F) and an overhead pressure of 200 mmHg (absolute pressure at 0°C) (3.9 psia) to less than 1.0 MPa (absolute pressure) (145 psia).

[0047] Figure 2 shows an embodiment in which the second feed stream in line 18' is a mineral oil stream such as kerosene, and second hydrotreating reactor 22' contains a hydrotreating catalyst. Many of the elements in Figure 2 have the same configuration and bear the same reference numbers as Figure 1. Elements in Figure 2 that correspond to elements in Figure 1 but have a different configuration bear the same reference numbers as Figure 1 but are prefixed with a prime symbol (').

[0048] The second feed stream in line 18' may be a conventional hydrocarbon feed stream extracted from the earth, such as a mineral oil stream. In one embodiment, the hydrocarbon feed stream in line 18' is preferably a kerosene stream. The second feed stream may contain hydrocarbons boiling in the range of 70°C to 120°C IBP and 280°C to 320°C EP. The first feed stream is hydrodeoxygenated, and the hydrodeoxygenated stream is recovered and processed as described for the first embodiment, except that the second feed stream is hydrotreated to remove heteroatoms and saturated olefins that may be present in the mineral oil feed stream. The hydrotreated stream in line 28 is fed to a second separator 34, which may be in the same vessel as the first separator 30, while the liquid hydrotreated stream in line 36' may be fed to an adsorptive separation unit 80 to separate normal paraffins from isoparaffins. Normal paraffins are desirable for detergent alkylation, and isoparaffins are desirable for fuel streams.

[0049] Suitable hydrotreating catalysts are any known conventional hydrotreating catalysts, including those consisting of at least one Group VIII metal, preferably iron, cobalt, and nickel, more preferably cobalt and / or nickel, and at least one Group VI metal, preferably molybdenum and tungsten, on a high surface area support material, preferably alumina. Other suitable hydrotreating catalysts include zeolite catalysts and noble metal catalysts in which the noble metal is selected from palladium and platinum. It is within the scope of the present invention to use two or more hydrotreating catalysts in hydrotreating reactor 22'. The Group VIII metal is typically present in an amount ranging from 2 to 20 wt. %, preferably from 4 to 12 wt. %. The Group VI metal is typically present in an amount ranging from 1 to 25 wt. %, preferably from 2 to 25 wt. %.

[0050] Preferred hydrotreating reaction conditions are a temperature of 290°C (550°F) to 455°C (850°F), suitably 316°C (600°F) to 427°C (800°F), preferably 343°C (650°F) to 399°C (750°F), a pressure of 2.8 MPa (gauge) (400 psig) to 17.5 MPa (gauge) (2500 psig), and a reaction pressure of 0.1 hr. -1 , appropriately 0.5 hours -1 ~5hr -1 , preferably 1.5 to 4 hours -1 and the liquid hourly space velocity of the fresh hydrocarbon feedstock of 84 Nm 3 / m 3 (500scf / bbl)~1011Nm 3 / m 3 Oil (6,000 scf / bbl), preferably 168 Nm 3 / m 3 Oil (1,000scf / bbl)~1250Nm 3 / m 3 Includes hydrogen rate of oil (7,500 scf / bbl).

[0051] The liquid hydrotreated stream in line 36' is sent to an adsorbent separation unit 80. The feed stream in feed line 36' passes through a valve 101 in adsorbent separation unit 80, which routes the feed to the appropriate bed in an adsorbent vessel 86.

[0052] The liquid hydrodeoxygenated stream in line 32 is fractionated in splitter column 40 as in the embodiment of Figure 1. The heavy normal paraffin stream in net bottoms line 46', along with the raffinate bottoms stream in net bottoms line 128, is fed to the product column and fractionated into a fuel stream.

[0053] As used herein, the term "component-rich stream" or "component stream" means that the stream exiting a vessel has a higher concentration of that component than the feed to the vessel. As used herein, the term "component-lean stream" means that the stream exiting a vessel has a lower concentration of that component than the feed to the vessel.

[0054] In the adsorbent separation unit 80, the liquid hydrotreated stream in line 36' is separated into a normal paraffin stream and an isoparaffin stream. The normal paraffins in the liquid hydrotreated stream selectively enter or are occluded in the porous structure of the adsorbent component, while the branched hydrocarbons typically do not enter the pores. The isoparaffins exit the process as a raffinate stream. To provide a useful method for separating normal paraffins from isoparaffins, it is necessary to desorb the occluded normal paraffins. In the disclosed process, iso- or normal pentane, hexane, heptane, or octane, and mixtures thereof, can be suitably used as desorbents to desorb the normal paraffins in the extract-desorbent stream.

[0055] The adsorbent used in the adsorbent vessel preferably comprises an aluminosilicate molecular sieve having a relatively uniform pore size of 5 Angstroms. A preferred adsorbent is provided by commercially available Type 5A molecular sieves manufactured and sold by UOP LLC (Des Plaines, Illinois).

[0056] The adsorber vessel 86 may include a series of vertically spaced, separate beds interconnected by pipes 115 between the bottom of one bed and the top of its downstream adjacent bed. Valves 101 may include a manifold configuration or rotary valves for downstream advancement of the inlet and outlet points of each stream. The adsorber vessel 86 operates in a downflow mode, although upflow may also be suitable. For simplicity, the adsorber vessel 86 is shown as having four main zones I-IV, although these zones may be further subdivided to accommodate different flushing schemes. The overall process may have other numbers of beds, e.g., 8, 12, or 24 beds, divided among the four main zones I-IV.

[0057] The hydrotreated stream is introduced through line 36' through valve 101 arranged to pass the feed stream through line 47 to adsorber vessel 86 between zones I and II. An extract is withdrawn between zones II and III in line 33 and transported through valve 101 in extract line 88 to extract fractionation column 90 to separate the desorbent from the extract. The desorbent is introduced through desorbent line 92 through valve 101 arranged to send the desorbent through desorbent line 94 to the process between zones III and IV. A raffinate is withdrawn between zones IV and I through raffinate line 21, through valve 101, and through line 23 to raffinate fractionation column 110.

[0058] Simulated countercurrent flow is achieved by cyclically advancing the introduction points of the feed stream and desorbent stream downstream while simultaneously and equally advancing the withdrawal points of the raffinate stream and extract stream downstream. Zone I is defined as the zone bounded between the feed stream inlet and the raffinate outlet. Zone II is defined as the zone bounded between the extract stream outlet and the desorbent inlet. Zone III is defined as the zone bounded between the desorbent inlet and the extract outlet, and Zone IV is defined as the zone bounded between the raffinate stream outlet and the desorbent stream inlet. Typical liquid-phase operation is preferred, for example, at temperatures between 50°C and 300°C, more specifically, up to 260°C, and at pressures from slightly superatmospheric to 30 atmospheres.

[0059] A raffinate characterized by fewer molecules adsorbed in adsorber vessel 86 is withdrawn from the adsorber vessel in raffinate line 21 through valve 101 and enters raffinate fractionation column 110 via line 23. Because it is desired to obtain a normal paraffin product, raffinate fractionation column 24 is operated to separate two fractions: a raffinate bottoms stream enriched in isoparaffins, and in one embodiment, C10 to C14 isoparaffins, and a desorbent bottoms stream enriched in light paraffin desorbent, and in one embodiment, C5 or C6 normal paraffins. The desorbent overhead bottoms stream is withdrawn from raffinate fractionation column 110 in overhead line 112, condensed in cooler 113, and fed to separator 114. A portion of the condensed raffinate overhead is recycled as reflux through reflux line 115 to raffinate fractionation column 110, and the remaining portion of the condensed raffinate overhead is withdrawn through net raffinate overhead line 116. The net raffinate overhead stream is rich in normal pentane or hexane desorbent, which may be combined with the extractive desorbent stream in line 98. Both may be recycled in desorbent line 92 through valve 101 to adsorber vessel 86 in desorbent line 94.

[0060] A raffinate bottoms stream is withdrawn from raffinate fractionation column 110 through bottoms line 125, from which a portion of the raffinate bottoms stream flows through reboiler line 126, is heated in reboiler heater 127, and returns to raffinate fractionation column 110. The remaining portion of the raffinate bottoms stream flows through net bottoms line 128 as an isoparaffin-rich stream, particularly a C10 to C14 isoparaffin-rich stream. Because the raffinate bottoms stream is rich in isoparaffins, it makes an excellent fuel feedstock and is fed to product column 70. Raffinate fractionation column 110 operates at a bottoms temperature range of 200 to 280°C and an overhead pressure of about atmospheric.

[0061] The extract stream contains molecules selectively adsorbed by the adsorbent in adsorber vessel 86. The desorbent displaces the selectively adsorbed normal paraffins from the solid adsorbent in desorbent bed III of adsorber vessel 86. The extract and desorbent are withdrawn in line 33, and valve 101 connects line 33 to line 88. The extract and desorbent withdrawn from the adsorber vessel in extract line 33, connected via valve 101, are sent in line 88 to extract fractionation column 90. Because it is desired to obtain a normal paraffin product, extract fractionation column 90 is operated to separate two fractions: an extract overhead stream enriched in normal paraffins, and in one embodiment, enriched in normal pentane or hexane desorbent, and a bottoms stream enriched in normal paraffin extract, and in one embodiment, enriched in C10 to C14 normal paraffins. A desorbent overhead stream is withdrawn from extract fractionation column 90 in overhead line 94, condensed in cooler 95, and fed to separator 96. A portion of the condensed desorbent overhead stream is recycled to extract fractionation column 90 as reflux through reflux line 97, and the remaining portion of the condensed desorbent overhead stream is withdrawn through net desorbent extract overhead line 98. The desorbent overhead stream is rich in normal pentane or hexane desorbent and can be combined with a raffinate desorbent stream in line 116 containing a raffinate desorbent stream. Both can be recycled in desorbent line 92 via valve 101 to adsorber vessel 86 in desorbent line 94.

[0062] An extract bottoms stream is withdrawn from extract fractionation column 90 through bottoms line 104, from which a portion of the extract bottoms stream flows through reboiler line 106, is heated in reboiler heater 105, and returns to extract fractionation column 90. The remaining portion of the extract bottoms stream flows through line 108 as a normal paraffin-rich stream, specifically rich in normal C10 to C14 paraffins. Extract fractionation column 90 operates at a bottoms temperature range of 200 to 280°C and an overhead pressure of atmospheric pressure.

[0063] The extract bottoms stream in extract bottoms line 108 contains a substantial concentration of normal paraffins, which, along with the light normal paraffins stream in side line 44 from splitter column 40, can be transported to the detergent alkylation unit of FIG. 3.

[0064] FIG. 3 shows alkylbenzene unit 200 to which a liquid side stream from side 41 of splitter column 40 in line 44 containing the light normal paraffin stream in the C10 to C13 carbon range from FIGS. 1 and 2, and / or an extract bottoms stream containing a substantial concentration of normal paraffins in extract bottoms line 108 from FIG. 2 may be fed in line 130.

[0065] As shown in FIG. 3 , a light normal paraffin stream in the C10 to C13 carbon range from line 44 and possibly line 108 is mixed with a recycled paraffin stream in line 282 before being introduced into alkylbenzene unit 200. The light normal paraffin streams in lines 44 and 108 may also be supplemented with a normal decane stream in line 132 to meet detergent alkylation specifications, and the combined light normal paraffin stream in line 130 may be fed to dehydrogenation reactor 210 in alkylbenzene unit 200. In dehydrogenation reactor 210, the light paraffins in line 130 are dehydrogenated to monoolefins of the same carbon number as the light normal paraffin stream. Typically, dehydrogenation is carried out by known catalytic processes, such as the commercially available Pacol Process available from UOP LLC (Des Plaines, Illinois). Diolefins (i.e., dienes) and aromatics are also produced as undesirable results of the dehydrogenation reaction, represented by the following equation: Monoolefin formation: C X H 2X+2 →C X H 2X +H2 Diolefin formation: C X H 2X →C X H 2X-3 +H2 Aromatic formation:C X H 2X-2 →C X H 2X-6 +2H2

[0066] Operating conditions for the dehydrogenation reactor 210 include space velocities of 5 to 50 LHSV and 20 to 32 LHSV, pressures of 35 kPa (5 psig) to 350 kPa (50 psig) and 105 kPa (15 psig) to 175 kPa (25 psig), temperatures of 400°C to 500°C and 440°C to 490°C, and hydrogen-to-hydrocarbon molar ratios of 1 to 12 and 3 to 7. One example of a suitable catalyst is platinum on alumina, where the platinum is attenuated with an attenuator metal. Another suitable catalyst is described in U.S. Patent No. 6,177,381. The unit can be operated dry or with water injection of up to 2000 ppm by weight.

[0067] In Figure 3, a dehydrogenated light normal olefins stream 212 exits dehydrogenation reactor 210 containing monoolefins and hydrogen, as well as some diolefins and aromatics. The dehydrogenated stream in line 212 is sent to separator 220 to remove hydrogen from the dehydrogenated light normal olefins stream in line 212. As shown, hydrogen exits separator 220 as hydrogen recycle stream 222, which can be recycled to line 20 of Figure 1 or Figure 2 to support an upstream hydrodeoxygenation or hydrotreating process.

[0068] Separator 220 produces a dehydrogenated liquid light normal olefins stream in bottoms line 224 containing mono-olefins and any di-olefins and aromatics formed during dehydrogenation. Dehydrogenated liquid light normal olefins stream 224 exits separator 220 and enters selective hydrogenation reactor 230, such as a DeFine reactor available from UOP, LLC. Selective hydrogenation reactor 230 selectively hydrogenates at least a portion of the di-olefins in dehydrogenated liquid light normal olefins stream 224 to form additional mono-olefins. As a result, selectively dehydrogenated light normal olefins stream 232 is formed with an increased mono-olefin concentration.

[0069] As shown, the selectively dehydrogenated stream 232 passes from the selective hydrogenation reactor 230 to a lights separator 240, such as a stripper column, which removes a light ends stream in overhead line 242 containing any lights, such as butane, propane, ethane, and methane, resulting from cracking or other reactions during upstream processing. With the lights removed, the de-lighted light normal olefins stream in bottoms line 244 may be sent to an aromatics removal unit 250, such as the Pacol Enhancement Process available from UOP, LLC. The aromatics removal unit 250 removes aromatics in line 252 from the de-lighted light normal olefins stream in bottoms line 244, possibly by contact with a solvent, to produce a de-aromatized light normal olefins stream in line 254 in the C10 to C13 range.

[0070] The light normal olefin stream in line 254 and the benzene 256 stream are fed to alkylation unit 260. Alkylation unit 260 contains a catalyst, such as a solid acid catalyst, that supports the alkylation of benzene with monoolefins. Fluorinated silica-alumina catalysts, hydrogen fluoride (HF) catalysts, aluminum chloride (AlCl) catalysts, and zeolite catalysts are examples of major catalysts in commercial use for the alkylation of benzene with linear monoolefins and may be used in alkylation unit 260. As a result of the alkylation, alkylbenzenes, typically referred to as linear alkylbenzenes (LABs), are formed according to the following reaction: C6H6+C X H 2X →C6H5C X H 2X+1 present in the alkylation effluent in line 262.

[0071] Suitable operating conditions for the alkylation unit include a space velocity of 1 to 10 LHSV, a pressure to maintain liquid phase operation such as 2.1 MPa (300 psig) to 4.2 MPa (600 psig), a temperature in the range of 80°C to 180°C and preferably 120°C to 170°C, and a benzene to olefin molar ratio of 3 to 40 and preferably 8 to 35.

[0072] An excess amount of benzene in line 256 is fed to alkylation unit 260 to achieve the desired high degree of alkylation. Thus, alkylation effluent 262 exiting alkylation unit 260 contains alkylbenzenes and unreacted benzene. Additionally, alkylation effluent 262 may also contain some unreacted paraffins. The alkylation effluent in line 262 is sent to a benzene separation unit 270, such as a fractionation column, to separate the unreacted benzene from the alkylation effluent. The unreacted benzene exits benzene separation unit 270 as benzene recycle stream 272, which is returned to alkylation unit 260 in benzene line 256 to reduce the volume of fresh benzene therein.

[0073] As shown, the benzene stripping stream exits the benzene separation unit 270 in line 274 and enters a paraffin separation unit 280, such as a fractionation column. In the paraffin separation unit 280, unreacted paraffins are removed from the benzene stripping stream 274 in a recycle paraffin stream in line 282 and sent to be combined with the light normal paraffin stream in line 44 and the extract bottoms stream in line 108 to provide a light normal paraffin stream in line 130 for dehydrogenation as described above. Additionally, the alkylbenzene stream 284 is separated by the paraffin separation unit 280 and fed to an alkylate separation unit 290. The alkylate separation unit 290 may be, for example, a multi-column fractionation unit, and separates a heavy alkylate bottoms stream 294 from the alkylbenzene product stream in line 292.

[0074] As a result of the post-alkylation separation process, linear alkylbenzene product in line 292 is isolated and exits alkylbenzene unit 200 .

[0075] Biorenewable feedstocks enriched in free fatty acids having 12 and 14 carbon atoms can be hydrodeoxygenated at moderate hydrodeoxygenation ratios, lower than those utilized for conventional biorenewable feedstocks such as vegetable oils or even mineral feedstocks, to produce normal paraffins in the range desired by the detergent industry. Either hydroisomerization or isonon separation can be performed to produce green fuel streams. [Example]

[0076] The inventors charged the PKO feedstock to a hydrodeoxygenation pilot plant operated at the hydrodeoxygenation ratios shown in Table 1. The hydrodeoxygenation ratios were adjusted by adjusting the catalyst and selecting the reaction temperature.

[0077] [Table 1]

[0078] Hydrodeoxygenation ratios of 40, 50, and 55% in the pilot plant provided nC11-13 selectivities and molecular weights within the ranges specified by the exemplary detergent manufacturer in Table 2.

[0079] [Table 2]

[0080] To meet the specifications of an exemplary detergent manufacturer, normal C10 was added in the specified weight ranges in Table 2 to produce nC10-13, as shown in Table 3.

[0081] [Table 3]

[0082] Isoparaffins were produced at a maximum of less than 1.5 wt % and the resulting average molecular weights met the detergent specifications in Table 2. By manipulating the hydrodeoxygenation reaction to achieve the desired hydrodeoxygenation ratio, suitable biorenewable feedstocks can be hydrodeoxygenated to the desired selectivity, particularly to meet detergent production specifications.

[0083] Specific Embodiments While the following will be described in conjunction with specific embodiments, it will be understood that this description is illustrative, but not intended to limit the scope of the foregoing description and appended claims.

[0084] A first embodiment of the present invention is a process for hydrotreating two feedstreams, the process comprising: hydrodeoxygenating a biorenewable feedstream in the presence of hydrogen and a hydrodeoxygenation catalyst to produce a hydrodeoxygenated stream; hydrotreating a second feedstream in the presence of hydrogen and a hydrotreating catalyst to provide a hydrotreated stream; fractionating the hydrodeoxygenated stream to provide a light normal paraffin stream and a heavy normal paraffin stream; and blending a portion of the hydrotreated stream with either the light normal paraffin stream or the heavy normal paraffin stream. One embodiment of the present invention is one, any, or all of the previous embodiment of this paragraph through the first embodiment of this paragraph, comprising: blending the heavy normal paraffin stream with a liquid hydrotreated stream to provide an isomerized feedstream; and hydroisomerizing the hydroisomerized feedstream in the presence of hydrogen and a hydroisomerization catalyst to produce a hydroisomerate stream.

[0014] An embodiment of the present invention is one, any, or all of the preceding embodiments through the first embodiment of this paragraph, further comprising dehydrogenating the light normal paraffin stream to produce a light normal olefin stream and alkylating the light normal olefin stream with a benzene stream to produce an alkylbenzene stream.

[0015] An embodiment of the present invention is one, any, or all of the preceding embodiments through the first embodiment of this paragraph, wherein the biorenewable feed stream is enriched in free fatty acids having 12 and 14 carbon atoms.

[0016] An embodiment of the present invention is one, any, or all of the preceding embodiments through the first embodiment of this paragraph, wherein the second feed stream is a biorenewable feed stream comprising conventional biorenewable oil.An embodiment of the present invention is one, any, or all of the previous embodiments through the first embodiment of this paragraph, further comprising separating a normal paraffin-rich stream from the liquid hydrotreated stream, blending the normal paraffin-rich stream with a light normal paraffin stream, dehydrogenating the light normal paraffin stream to produce a light normal olefin stream, and alkylating the light normal olefin stream with a benzene stream to produce an alkylbenzene stream. An embodiment of the present invention is one, any, or all of the previous embodiments through the first embodiment of this paragraph, wherein the second feed stream is a kerosene feed stream. An embodiment of the present invention is one, any, or all of the previous embodiments through the first embodiment of this paragraph, further comprising operating the hydrodeoxygenation step at a hydrodeoxygenation ratio of 35 to 60%. An embodiment of the present disclosure is one, any, or all of the preceding embodiments to the first embodiment of this paragraph, further comprising operating the hydrotreating step at a higher hydrodeoxygenation ratio than the hydrodeoxygenation step. An embodiment of the present disclosure is one, any, or all of the preceding embodiments to the first embodiment of this paragraph, further comprising separating the hydroisomerized stream into naphtha and jet fuel.

[0085] A second embodiment of the present invention is a process for hydrodeoxygenating two feedstreams, the process comprising: hydrodeoxygenating a biorenewable feedstream in the presence of hydrogen and a first hydrodeoxygenation catalyst to produce a first hydrodeoxygenated stream; hydrodeoxygenating the second feedstream in the presence of hydrogen and a second hydrodeoxygenation catalyst to provide a second hydrodeoxygenated stream; fractionating the first hydrodeoxygenated stream to provide a light normal paraffin stream and a heavy normal paraffin stream; and blending a portion of the second hydrodeoxygenated stream with the light normal paraffin stream or the heavy normal paraffin stream. One embodiment of the present invention is one, any, or all of the previous embodiment to the second embodiment of this paragraph, wherein the first hydrodeoxygenation step is carried out at a different hydrodeoxygenation ratio than the second hydrodeoxygenation step.

[0013] An embodiment of the present invention is one, any, or all of the previous through second embodiments of this paragraph, further comprising combining the heavy normal paraffin stream with a liquid second hydrodeoxygenated stream to provide a hydroisomerized feed stream, and hydroisomerizing the hydroisomerized feed stream in the presence of hydrogen and a hydroisomerization catalyst to produce a hydroisomerate stream. An embodiment of the present invention is one, any, or all of the previous through second embodiments of this paragraph, further comprising dehydrogenating the light normal paraffin stream to produce a light normal olefin stream, and alkylating the light normal olefin stream with a benzene stream to produce an alkylbenzene stream. An embodiment of the present invention is one, any, or all of the previous through second embodiments of this paragraph, wherein the biorenewable feed stream is enriched with 12 and 14 carbon atoms. An embodiment of the present invention is one, any, or all of the previous embodiment of this paragraph through the second embodiment of this paragraph, wherein the second feed stream is a biorenewable feed stream comprising conventional vegetable oil.

[0086] A third embodiment of the present invention is a process for producing alkylbenzenes from renewable feedstocks, the process comprising: hydrodeoxygenating a biorenewable feedstock stream at a first hydrodeoxygenation ratio in the presence of hydrogen and a first hydrodeoxygenation catalyst to produce a first hydrodeoxygenated stream; hydrodeoxygenating a second feedstock stream at a second hydrodeoxygenation ratio in the presence of hydrogen and a second hydrodeoxygenation catalyst to produce a second hydrodeoxygenated stream; and combining at least a portion of the first hydrodeoxygenated stream with at least a portion of the second hydrodeoxygenated stream. One embodiment of the present invention is one, any, or all of the previous through third embodiments of this paragraph, further comprising fractionating the first hydrodeoxygenated stream to provide a light normal paraffin stream and a heavy normal paraffin stream; dehydrogenating the light normal paraffin stream to produce a light normal olefin stream; and alkylating the light normal olefin stream with a benzene stream to produce an alkylbenzene stream. An embodiment of the present invention is one, any, or all of the preceding through third embodiments of this paragraph, further comprising: combining a liquid second hydrodeoxygenated stream removed from the second hydrodeoxygenation stream with a heavy normal paraffin stream to provide a hydroisomerization feed stream; hydroisomerizing the hydroisomerization feed stream in the presence of hydrogen and a hydroisomerization catalyst to produce a hydroisomerate stream; and separating the hydroisomerate stream into naphtha and jet fuel or diesel. An embodiment of the present invention is one, any, or all of the preceding through third embodiments of this paragraph, further comprising operating the first hydrodeoxygenation step at a hydrodeoxygenation ratio of 35 to 60%.

[0087] Without further elaboration, it is believed that, using the preceding description, one skilled in the art can utilize the present disclosure to its fullest extent and easily ascertain the essential characteristics of the present disclosure, and can make various changes and modifications to the present disclosure to adapt it to various uses and conditions, without departing from the spirit and scope of the present disclosure. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way, and are intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.

[0088] Above, all temperatures are set forth in degrees Celsius and all parts and percentages are by weight unless otherwise stated.

Claims

1. 1. A process for hydrotreating two feed streams, comprising: hydrodeoxygenating the biorenewable feedstock stream in the presence of hydrogen and a hydrodeoxygenation catalyst to produce a hydrodeoxygenated stream; hydrotreating the second feed stream in the presence of hydrogen and a hydrotreating catalyst to provide a hydrotreated stream; operating the hydrotreating step at a hydrodeoxygenation ratio greater than that of the hydrodeoxygenation step, the hydrodeoxygenation ratio being the ratio of the mass flow rate of normal paraffins having even carbon numbers to the mass flow rate of normal paraffins in the hydrodeoxygenation reaction product; fractionating the hydrodeoxygenated stream to provide a light normal paraffin stream and a heavy normal paraffin stream; dehydrogenating the light normal paraffin stream to produce a light normal olefin stream; alkylating said light normal olefin stream with a benzene stream to produce an alkylbenzene stream.

2. 1. A process for hydrotreating two feed streams, comprising: hydrodeoxygenating a first biorenewable feedstock stream selected from palm kernel oil, coconut oil, and babassu oil, enriched in free fatty acids containing 12 to 14 carbon atoms in the presence of hydrogen and a hydrodeoxygenation catalyst to produce a hydrodeoxygenated stream; hydrotreating a second biorenewable feedstock stream comprising conventional biorenewable oil in the presence of hydrogen and a hydrotreating catalyst to provide a hydrotreated stream; operating the hydrotreating step at a hydrodeoxygenation ratio greater than that of the hydrodeoxygenation step, the hydrodeoxygenation ratio being the ratio of the mass flow rate of normal paraffins having even carbon numbers to the mass flow rate of normal paraffins in the hydrodeoxygenation reaction product; fractionating the hydrodeoxygenated stream to provide a light normal paraffin stream and a heavy normal paraffin stream; blending a portion of the hydrotreated stream with the light normal paraffin stream or the heavy normal paraffin stream; the second biorenewable feed stream comprises less than 30 wt.% free fatty acids having 12 and 14 carbon atoms; process.

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