Process for producing renewable alkylbenzene products

Abstract

To provide a method for production of a linear alkylbenzene product derived from a triglyceride.SOLUTION: Described herein is a process for producing alkylbenzenes from triglycerides, specifically, triglycerides having 60% or more of alkyl chains having less than 16 carbon atoms. The process includes a linear selective cracking process to crack C14+ chains into C9-C14 chains which are useful for making linear alkylbenzene for use in detergents.SELECTED DRAWING: None

Description

[Technical Field]

[0001] (Priority statement) This application claims priority to U.S. Provisional Patent Application No. 63 / 504,879, filed May 30, 2023, and U.S. Patent Application No. 18 / 500,161, filed November 02, 2023, which are incorporated by reference herein in their entireties. [Background technology]

[0002] Linear alkylbenzenes have the formula C6H5C n H 2n+1 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 9 to 14. These specific ranges are often required when alkyl benzenes are used as intermediates in the production of detergent surfactants. Alkyl carbon numbers in the range of 9 to 14 meet detergent industry specifications.

[0003] Since their initial use in detergent production in the 1960s, alkylbenzene production has grown rapidly because surfactants made from alkylbenzenes are biodegradable. 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.

[0004] Detergents made using alkylbenzene surfactants are biodegradable, but previous processes for making alkylbenzenes are not based on renewable sources. In particular, alkylbenzenes are currently produced from kerosene refined from crude oil extracted from the earth. Due to increasing environmental prejudice against fossil fuel extraction and economic concerns about depleting fossil fuel deposits, the use of alternative sources of biodegradable surfactants in detergent and other industries may be advocated. Summary of the Invention [Means for solving the problem]

[0005] Therefore, it is desirable to provide linear alkylbenzenes with high linearity made from biorenewable sources instead of those extracted from the earth. Furthermore, it is 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 a high composition of C9-C14 n-paraffins in the desirable range, matching the alkyl carbon number range desired in the detergent industry. Such renewable sources also have large amounts of nC16-nC18 feed, and it is desirable to convert these feeds to nC9-nC14 feeds with high per-pass yields. These nC9-nC14 intermediate products are ultimately useful for producing linear alkylbenzene-type detergents through additional process steps. It is further desirable that the resulting nC9-nC14 paraffins be linear products with minimal branched isomer products. [Brief explanation of the drawings]

[0006] [Figure 1] FIG. 1 is a schematic diagram of one embodiment of a process for producing alkylbenzenes from triglycerides in accordance with the present invention. [Figure 2] 1 is a plot of normal paraffins mass % versus deoxygenation temperature according to Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0007] The present invention relates to a process for producing alkylbenzenes from triglycerides, specifically from triglycerides that, after hydrogenation, produce 60% or more by weight of normal paraffins having fewer than 16 carbon atoms. Some of these triglycerides also, after dehydrogenation, produce substantial amounts, e.g., 20-30%, of normal paraffins having 16-24 carbon atoms. These paraffins are longer than desired for producing detergent products.

[0008] In some embodiments, the amount of normal paraffins having 16 carbon atoms after dihydrogenation is less than 20%, or less than 15%, or less than 10%.

[0009] The triglycerides are derived from natural oils. Natural oils are not based on kerosene or other fossil fuels. Natural oils include those derived from plant or algae materials, or animal fats, nut oils and / or seed oils, and triglyceride-containing oils, often referred to as renewable oils. Natural oils typically contain triglycerides, free fatty acids, or a combination thereof. Natural oils include, but are not limited to, arachis oil (peanut oil; groundnut oil), babassu oil, palm oil, cottonseed oil, grapeseed oil, corn oil (maize oil), mustard seed oil, palm kernel oil, palm oil, palm olein (a liquid fraction derived from the fractional distillation of palm oil), palm stearin (a high melting point fraction derived from the fractional distillation of palm oil), rapeseed oil, rapeseed oil-low erucic acid (low erucic acid rapeseed oil; low erucic acid rapeseed oil; canola oil), safflower seed oil ( safflower oil; safflower (carthamus) oil; safflower (kurdee) oil), safflower seed oil-high oleic (high oleic safflower oil; high oleic safflower (carthamus) oil; high oleic safflower (kurdee) oil), sesame seed oil (sesame oil; gingelly oil; bene oil; ben oil; til oil; tillie oil), soybean oil (soybean) oil, sunflower seed oil (helianthus annuus), and sunflower seed oil-high oleic (high oleic sunflower oil).

[0010] In some embodiments, the triglycerides yield 15% or more by weight of normal paraffins having 12 or 14 carbon atoms after deoxygenation, hi some embodiments, the triglycerides yield 10% or more by weight of normal paraffins having 12 carbon atoms after deoxygenation.

[0011] A process for producing alkylbenzenes from triglycerides according to the present invention includes deoxygenating triglycerides to form paraffins. The paraffins are separated (by fractionation, distillation, etc.) into a C9-C14 stream containing C9-C14 paraffins and a C14+ stream containing C14+ (i.e., containing carbon chains from C15 to C28) paraffins. The C14+ stream is sent to a separate linear selective cracking unit to crack the C14+ paraffins, and the cracked paraffins are fractionated into a first stream containing C9-C14 normal paraffins and lightly branched paraffins, and a second stream containing isoparaffins. Contaminants, including but not limited to sulfur compounds, nitrogen compounds, phosphorus compounds, oxygenates, aromatics, or combinations thereof, are removed from the C9-C14 stream and the first stream. The decontaminated stream is dehydrogenated to form olefins, di-olefins, and aromatics. The di-olefins are selectively hydrogenated to form additional olefins, and the aromatics are separated and removed to form an aromatic stream comprising aromatics and a mono-olefin stream comprising mono-olefins. Benzene is alkylated with the olefins, and the alkylation effluent comprises alkylbenzenes and benzene. The alkylbenzenes are then isolated.

[0012] The linear selective cracking step is further described. Because sulfur and nitrogen contaminants from the first stage can poison the metal-based hydrocracking catalyst, the linear selective cracking is performed in a separate unit rather than in the bottom bed of the first-stage hydrocracking reactor. C14+ paraffins are cracked more selectively than C9-C14 due to their higher absorption energy.

[0013] By selecting specific metal catalysts, including noble metals (such as ruthenium and platinum) and nickel, it is possible to produce normal paraffins with 9 to 14 carbon atoms in much higher yields than previous processes. Suitable catalysts include, but are not limited to, Ru / ZrO2, Pt-Al2O3, Ni-alumina, or NiO x Using these catalysts, C14+ streams can produce linear cracking products without producing significant amounts of branched isomers.

[0014] Among the preferred catalysts, the Ru catalyst exhibits much higher activity and nC9-nC14 yields per pass than other catalysts. Also, under optimized reaction conditions, the production of methane and isomerized products is very low. This has been found to be the best catalyst for such chemical conversion processes. The Pt-Al2O3 catalyst can produce even lower methane yields and slightly lower linear product yields than the Ru-based catalyst.

[0015] To limit catalyst deactivation, the feed is treated to remove sulfur, chloride, and metal contaminants prior to hydrodeoxygenation. Otherwise, sulfur, chloride, and metals accumulate on the catalyst, leading to deactivation. High-temperature hydrotreating has been shown to restore some of the lost activity. The extent of hydrodeoxygenation can affect the selectivity to each of the normal paraffins in the 9-14 carbon range. A high degree of hydrodeoxygenation can result in the hydrodeoxygenated composition being heavily biased toward normal dodecane and normal decane, to the detriment of normal undecane and normal tridecane. A low degree of hydrodeoxygenation can result in the hydrodeoxygenated composition being heavily biased toward normal undecane and normal tridecane, to the detriment of normal dodecane and normal decane.

[0016] Hydrodeoxygenation reactor temperatures are 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 the olefins found in the FFA. Generally, hydrodeoxygenation reactor pressures of 700 kPa (100 psig) to 21 MPa (3000 psig) are suitable.

[0017] The entire process is described below.

[0018] The linearity of the alkylbenzene product depends largely on the linearity of the paraffins used to alkylate the benzene. A general rule of thumb for those skilled in the art is that the linearity of the paraffin feed decreases by 5-7% by mass after dehydrogenation and alkylation. Thus, a paraffin with 97% by mass linearity (or alternatively 3% by mass isoparaffins) will produce an alkylbenzene product with approximately 90-92% by mass linearity. This sets the paraffin linearity requirement 5-7% by mass higher than the alkylbenzene product specification. Typically, the linearity of the paraffin product is measured by standard test methods UOP621, UOP411, or UOP732 available from ASTM, which are incorporated herein by reference in their entirety. Linear alkylbenzenes can be analyzed using ASTM standard test method D4337, which is incorporated herein by reference in its entirety.

[0019] Illustrated is an exemplary system 100 for producing an alkylbenzene product from a particular triglyceride feed.

[0020] In the illustrated embodiment, the selected triglyceride feed 105 is delivered to a deoxygenation unit 110, which also receives a hydrogen feed (not shown). In the deoxygenation unit 110, the fatty acids in the selected triglyceride feed 105 are deoxygenated and converted to normal paraffins. Structurally, triglycerides are formed by three, typically different, fatty acid molecules linked together with a glycerol bridge. The glycerol molecule contains three hydroxyl groups (HO--), and each fatty acid molecule has a carboxyl group (COOH). In triglycerides, the hydroxyl groups of glycerol combine with the carboxyl groups of the fatty acids to form ester bonds. Thus, during deoxygenation, the fatty acids are liberated from the triglyceride structure and converted to normal paraffins. The glycerol is converted to propane, and the oxygen in the hydroxyl and carboxyl groups is converted to water, carbon dioxide, or carbon monoxide. The deoxygenation reactions for fatty acids and triglycerides are shown below, respectively:

[0021] [ka]

[0022] During the deoxygenation reaction, the paraffin chains R n The length of the chain will vary by a value of 1 depending on the exact reaction pathway. It is understood that deoxygenation includes at least one of hydrodeoxygenation, decarboxylation, and decarbonylation, or any combination thereof. For example, if carbon dioxide is formed, the chain will have one less carbon than the fatty acid source. If water is formed, the chain will match the length of the fatty acid source.

[0023] Operating conditions for the deoxygenation unit include pressures ranging from 250 to 800 psig (1724 to 5516 kPa), and temperatures ranging from 274°C to 371°C (525°F to 700°F) in one embodiment, from 274°C to 338°C (525°F to 640°F) in another embodiment, and from 274°C to 310°C (525°F to 590°F) in another embodiment. Catalysts can include one or more of Ni, Mo, Co, P, such as Ni--Mo, Ni--Mo--P, Ni--Co--Mo, or Co--Mo on alumina, silica, titania, zirconia, and mixtures thereof. Suitable hydrogen to hydrocarbon molar ratios include 1500 to 10,000, 4000 to 9000, and 5000 to 8000 standard cubic feet per barrel of feedstock (scf / B). Suitable space velocities are 0.2 to 3.0 hr -1 Conditions are selected to minimize the cracking or isomerization of paraffins.

[0024] The deoxygenated product, containing normal paraffins, water, carbon dioxide, carbon monoxide, and propane, is fractionated into a C9-C14 stream 115 and a C14+ stream 120. The separation may be carried out in a multi-stage fractionation unit, a distillation system, or similar known equipment. In either event, the separator removes the water, carbon dioxide, carbon monoxide, and propane from the deoxygenated product. A naphtha stream (not shown) of paraffins having carbon chain lengths of C5 to C9 may also be formed.

[0025] The C14+ stream 120 is sent to a linear selective cracking unit 125 where it is selectively cracked to form a first stream 130 containing normal or lightly branched C9 to C14 paraffins and a second stream 135 containing isoparaffins, as described above.

[0026] The C9 to C14 stream 115 from the deoxygenation unit 110 and the first stream 130 from the linear selective cracking unit 125 are sent to a decontamination unit 140. The decontamination unit 140 removes contaminants from the C9 to C14 stream 115 and the C9 to C14 paraffins in the first stream 130 in an adsorption system. The contaminants include, but are not limited to, sulfur compounds, or nitrogen compounds, or phosphorus compounds, or oxygenates, or aromatics, or combinations thereof.

[0027] The decontaminated stream 145 is sent to a dehydrogenation unit 150 where hydrogen is removed to produce a dehydrogenated stream 155 containing mono-olefins, di-olefins, and aromatics. In the dehydrogenation unit 150, the paraffins are dehydrogenated to mono-olefins of the same carbon number as the paraffins. Typically, the dehydrogenation is carried out via a known catalytic process, such as the commercially available Pacol process. Di-olefins (i.e., dienes) and aromatics are also produced as undesired results of the dehydrogenation reaction, which is represented by the following equation: Mono-olefin formation: C x H 2x+2 →C x H 2x +H2 Di-olefin formation: C x H 2x →C x H 2x-2 +H2 Aromatic formation:C x H 2x-2 →C x H 2x-6 +2H2

[0028] Operating conditions for the dehydrogenation unit 150 include space velocities of 5 to 50 LHSV and 20 to 32 LHSV, pressures of 1 kPa(g) to 1013 kPa(g) (0.1 psig to 150 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 a Pt-alumina catalyst in which platinum is damped with a damping metal. Another suitable catalyst is described in U.S. Pat. No. 6,177,381, the entire contents of which are incorporated herein by reference. The dehydrogenation unit 150 can be operated dry or with water injection of up to 2000 mass-ppm. Hydrogen can be recycled to the upstream deoxygenation unit.

[0029] Dehydrogenated stream 155 is sent to a selective hydrogenation unit 160, such as a Define reactor, where at least a portion of the di-olefins are hydrogenated to form additional mono-olefins. As a result, mono-olefin stream 170 has an increased mono-olefin concentration compared to dehydrogenated stream 155. Aromatics are separated and removed as aromatics stream 165. Light ends stream 167, containing any lights such as butane, propane, ethane, and methane resulting from cracking or other reactions during upstream processing, may also be removed.

[0030] Mono-olefin stream 170, which contains mono-olefins, is sent to alkylation unit 175 along with benzene stream 180. Benzene is alkylated with the mono-olefins to form alkylbenzenes. Alkylation unit 175 contains a catalyst, such as a solid acid catalyst, that supports the alkylation of benzene with mono-olefins. Fluorinated silica-alumina, hydrogen fluoride (HF), aluminum chloride (AlCl), zeolites, and ionic liquid catalysts are some of the main catalysts in commercial use for the alkylation of benzene with linear mono-olefins and may be used in alkylation unit 175. 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

[0031] Suitable operating conditions for alkylation unit 175 include space velocities of 1 to 10 LHSV, pressures to maintain liquid phase operation such as 2068 kPa(g) to 4137 kPa(g) (300 psig to 600 psig), temperatures ranging from 80°C to 180°C and 120°C to 170°C, and benzene to olefin molar ratios of 3 to 40 and 8 to 35.

[0032] An excess amount of benzene is fed to the alkylation unit 175 to achieve the desired high degree of alkylation. Thus, the alkylation effluent 185 exiting the alkylation unit 175 contains alkylbenzenes and unreacted benzene. Additionally, the alkylation effluent 185 may also contain some unreacted paraffins. The alkylation effluent 185 is sent to a benzene separation unit 190, such as a fractionation column, to separate the unreacted benzene and paraffins from the alkylation effluent 185. The unreacted benzene exits the benzene separation unit 190 as a benzene recycle stream 195, which can be sent back to the alkylation unit 175 to maintain a desired benzene / olefin ratio (e.g., 1 to 50) and reduce the volume of benzene produced required. The required amount of benzene produced (i.e., net benzene) is determined by the net olefins for the alkylation unit. Alternatively, a paraffin stream 200 can be separated and recycled to the dehydrogenation unit 150.

[0033] As a result of the post-alkylation separation process, a linear alkylbenzene product 205 is isolated. Note that such a separation process to isolate the linear alkylbenzene product 205 is not required in all embodiments.

[0034] The linear alkylbenzene product 205 is represented by the formula C6H5C n H 2n+1In some embodiments, at least 80% by weight, or at least 90% by weight, of the alkylbenzenes have linear alkyl groups.

[0035] The linear alkylbenzene is sulfonated to form a compound of formula C, wherein n is 10-14, or n is 11-13. n H 2n+1 A linear alkylbenzene sulfonate product can be provided that includes an alkylbenzene sulfonate compound having C6H4SO3H.

[0036] 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 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.

[0037] The term "column" refers to one or more distillation 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 a 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, overhead and bottom lines refer to the net lines from column to column downstream of any reflux or reboil removal. 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.

[0038] As used herein, the term "component-rich stream" or "component stream" means that the stream exiting a vessel has a higher concentration of the 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 the component than the feed to the vessel. [Example]

[0039] Example 1 The palm oil feed was deoxygenated to form paraffins, dehydrogenated to form mono-olefins, and benzene was alkylated with the mono-olefins to form an alkylbenzene product having a modern carbon content of 62 mass % of 96 modern carbon as determined by ASTM D6866, a Bromine Number of Br / g of Br per gram of sample as determined by UOP Standard Test Method 304, and a linearity of 92 mass % compared to a theoretical modern carbon content of 66.4 mass %.

[0040] Example 2 The oil was deoxygenated using a catalyst at a pressure of 480 psig, an H2O-to-bio-oil ratio of 7200 scf / B, and an LHSV of 1 hr. During operation, the deoxygenation reaction temperature was increased stepwise from 600°F (315°C) to 660°F (34.9°C), then to 710°F (377°C) and 760°F (404°C), and the response of the linearity of the final product to reaction temperature was monitored. The results are shown in Figure 2, which is a plot of the concentration of normal C10-C13 paraffins in mass percent versus reaction temperature. Figure 2 clearly shows that the concentration of linear paraffins decreases as the deoxygenation reaction temperature increases. By controlling the temperature below 760°F (404°C), greater than 92 mass percent linear paraffins were produced.

[0041] Note: Examples 1 and 2 were previously included as Examples 3 and 4 in U.S. Patent No. 9,079,814.

[0042] 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.

[0043] A first embodiment of the present invention is a method for producing linear alkylbenzene products derived from triglycerides, comprising: deoxygenating triglycerides to produce 60% or more normal paraffins having fewer than 16 carbon atoms after deoxygenation to form a paraffin stream comprising 60% or more normal paraffins having fewer than 16 carbon atoms; fractionating the paraffin stream to form a C9 to C14 stream comprising C9 to C14 paraffins and a C14+ stream comprising C14+ paraffins; linear selective cracking the C14+ stream in a separate linear selective cracking unit under linear selective cracking conditions in the presence of a linear selective cracking catalyst to form a first stream comprising normal or lightly branched C9 to C14 paraffins and a second stream comprising isoparaffins; and removing contaminants from the C9 to C14 stream and the first stream to form a decontaminated stream. forming a decontaminated stream, the contaminants comprising sulfur compounds, or nitrogen compounds, or phosphorus compounds, or oxygenates, or aromatics, or a combination thereof; dehydrogenating the decontaminated stream to provide a dehydrogenated stream comprising mono-olefins, di-olefins, and aromatics; selectively hydrogenating the di-olefins in the dehydrogenated stream to form additional mono-olefins and separating and removing the aromatics from the mono-olefins to form an aromatic stream comprising aromatics, and a mono-olefin stream comprising the mono-olefins; alkylating benzene with the mono-olefins under alkylation conditions to provide an alkylation effluent comprising alkylbenzenes and benzene; and isolating the alkylbenzenes to provide a triglyceride-derived alkylbenzene product. One embodiment of the present invention is one, any, or all of the first embodiment of this paragraph through the preceding embodiment of this paragraph, wherein the C9 to C14 stream and the first stream are combined and then the contaminants are removed from the C9 to C14 stream and the first stream to form the decontaminated stream. An embodiment of the present invention is one, any, or all of the first embodiment of this paragraph through the preceding embodiments of this paragraph, wherein the linear selective cracking catalyst comprises a ruthenium, platinum, and nickel supported catalyst, or a mixture thereof.An embodiment of the present invention is one, any, or all of the first embodiment of this paragraph through the preceding embodiments of this paragraph, where the linear selective cracking conditions include a temperature in the range of 290°C to 455°C, or a pressure in the range of 2.8 MPa to 17.5 MPa, or a combination thereof. An embodiment of the present invention is one, any, or all of the first embodiment of this paragraph through the preceding embodiments of this paragraph, where the amount of alkylbenzene product is greater than the amount of alkylbenzene produced in a process without a linear selective cracking step. An embodiment of the present invention is one, any, or all of the first embodiment of this paragraph through the preceding embodiments of this paragraph, where the alkylbenzene product comprises alkylbenzenes having C9 to C14 chains. An embodiment of the present invention is one, any, or all of the first embodiment of this paragraph through the preceding embodiments of this paragraph, where the alkylbenzene product comprises alkylbenzenes having C10 to C13 chains. An embodiment of the present invention is any one, any, or all of the first embodiment of this paragraph through the preceding embodiments of this paragraph, wherein the triglycerides, after dehydrogenation, yield 0.1 wt. % to 20 wt. % normal paraffins having 16 carbon atoms. An embodiment of the present invention is any one, any, or all of the first embodiment of this paragraph through the preceding embodiments of this paragraph, wherein the C14+ stream comprises C16-C18 paraffins. An embodiment of the present invention is any one, any, or all of the first embodiment of this paragraph through the preceding embodiments of this paragraph, wherein the triglycerides, after deoxygenation, yield 15 wt. % or more normal paraffins having either 12 or 14 carbon atoms. An embodiment of the present invention is any one, any, or all of the first embodiment of this paragraph through the preceding embodiments of this paragraph, wherein the triglycerides, after deoxygenation, yield 10 wt. % or more normal paraffins having 12 carbon atoms.

[0044] A second embodiment of the present invention is a method for producing alkylbenzene products derived from triglycerides, comprising: deoxygenating triglycerides to produce 60% or more normal paraffins having fewer than 16 carbon atoms after deoxygenation to form a paraffin stream comprising 60% or more normal paraffins having fewer than 16 carbon atoms; fractionating the paraffin stream to form a C9 to C14 stream comprising C9 to C14 paraffins and a C14+ stream comprising C14+ paraffins; linearly selectively cracking the C14+ stream in a separate linear selective cracking unit under linear selective cracking conditions in the presence of a linear selective cracking catalyst to form a first stream comprising normal or lightly branched C9 to C14 paraffins and a second stream comprising isoparaffins, wherein the linear selective cracking catalyst comprises a ruthenium, platinum, and nickel supported catalyst, or a mixture thereof, to form the second stream; and removing contaminants from the C9 to C14 stream and the first stream to form decontaminated streams. forming a decontaminated stream, wherein the contaminants comprise sulfur compounds, or nitrogen compounds, or phosphorus compounds, or oxygenates, or aromatics, or combinations thereof; dehydrogenating the decontaminated stream to provide a dehydrogenated stream comprising mono-olefins, di-olefins, and aromatics; selectively hydrogenating the di-olefins in the dehydrogenated stream to form additional mono-olefins and separating and removing the aromatics from the mono-olefins to form an aromatic stream comprising aromatics, and a mono-olefin stream comprising the mono-olefins; alkylating benzene with the mono-olefin under alkylation conditions to provide an alkylation effluent comprising alkylbenzene and benzene; and isolating the alkylbenzene to provide an alkylbenzene product derived from triglycerides, wherein the alkylbenzene product comprises alkylbenzenes having C9 to C14 chains. An embodiment of the present invention is one, any, or all of the second embodiment of this paragraph through the preceding embodiment of this paragraph, wherein the C9-C14 stream and the first stream are combined and then contaminants are removed from the C9-C14 stream and the first stream to form a decontaminated stream.An embodiment of the present invention is one, any, or all of the second embodiment of this paragraph through the preceding embodiment of this paragraph, where the linear selective cracking conditions include a temperature in the range of 290°C to 455°C, or a pressure in the range of 2.8 MPa to 17.5 MPa, or a combination thereof. An embodiment of the present invention is one, any, or all of the second embodiment of this paragraph through the preceding embodiment of this paragraph, where the amount of alkylbenzene product is greater than the amount of alkylbenzene produced in a process without a linear selective cracking step. An embodiment of the present invention is one, any, or all of the second embodiment of this paragraph through the preceding embodiment of this paragraph, where the triglyceride, after deoxygenation, produces 0.1 wt. % to 20 wt. % normal paraffins having 16 carbon atoms. An embodiment of the present invention is one, any, or all of the second embodiment of this paragraph through the preceding embodiment of this paragraph, where the triglyceride, after deoxygenation, produces 15 wt. % or more normal paraffins having either 12 or 14 carbon atoms. One embodiment of the present invention is one, any, or all of the second embodiment of this paragraph through the preceding embodiment of this paragraph, wherein the triglyceride yields 10% or more by weight of normal paraffins having 12 carbon atoms after deoxygenation.

[0045] Without further elaboration, it is believed that one skilled in the art can, using the preceding description, readily ascertain the essential characteristics of the present invention and make various changes and modifications to the present invention to adapt it to various uses and conditions, all without departing from the spirit and scope of the present invention. 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.

[0046] 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 producing a linear alkylbenzene product derived from triglycerides, comprising: deoxygenating triglycerides (105) that produce 60% or more normal paraffins having less than 16 carbon atoms after deoxygenation to form a paraffin stream comprising 60% or more normal paraffins having less than 16 carbon atoms; fractionating the paraffin stream to form a C9-C14 stream (115) comprising C9-C14 paraffins and a C14+ stream (120) comprising C14+ paraffins; linearly selectively cracking said C14+ stream (120) in a separate linear selective cracking unit (125) under linear selective cracking conditions in the presence of a linear selective cracking catalyst to form a first stream (130) comprising normal or lightly branched C9 to C14 paraffins and a second stream (135) comprising isoparaffins; removing contaminants from the C9-C14 stream (115) and the first stream (130) to form a decontaminated stream (145), wherein the contaminants comprise sulfur compounds, or nitrogen compounds, or phosphorus compounds, or oxygenates, or aromatics, or a combination thereof; dehydrogenating the decontaminated stream (145) to provide a dehydrogenated stream (155) comprising mono-olefins, di-olefins, and aromatics; selectively hydrogenating the di-olefins in the dehydrogenated stream (155) to form additional mono-olefins and separating and removing the aromatics from the mono-olefins to form an aromatics stream (165) comprising the aromatics and a mono-olefins stream (170) comprising the mono-olefins; alkylating benzene (180) with said mono-olefin under alkylation conditions to provide an alkylation effluent (185) comprising alkylbenzenes and benzene; and isolating the alkylbenzene to provide the alkylbenzene product (205) derived from the triglycerides; wherein the triglycerides (105) are derived from natural oils that are not based on kerosene or other fossil fuels, including those derived from plant or algal materials, or animal fats, nut and / or seed oils, and triglyceride-containing oils; method.

2. 10. The method of claim 1, wherein the linear selective cracking catalyst comprises a ruthenium, platinum, and nickel supported catalyst, or a mixture thereof.

3. 3. The method of claim 1 or 2, wherein the linear selective cracking conditions comprise a temperature in the range of 290°C to 455°C, or a pressure in the range of 2.8 MPa to 17.5 MPa, or a combination thereof.

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