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] (Statement of priority) 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 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 that alkylbenzenes have alkyl carbon numbers in the range of 9 to 16, preferably 9 to 14. These specific ranges are often required when alkylbenzenes 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 first use in detergent production in the 1960s, the production of alkylbenzenes has grown rapidly because surfactants made from alkylbenzenes are biodegradable. The linearity of the paraffin chains in the alkylbenzene is important to the biodegradability of the material and its 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 alkylbenzene are not based on renewable sources. In particular, alkylbenzene is 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 supported. Summary of the Invention [Means for solving the problem]

[0005] It is therefore desirable to provide linear alkylbenzenes with high linearity made from bio-renewable sources instead of those extracted from the earth. It is further desirable to provide linear alkylbenzenes that are renewable from easily processed triglycerides and fatty acids from vegetable, animal, nut, and / or seed oils. Palm kernel, coconut, and babassu oils have a high composition of C9-C14 n-paraffins in the desirable range, which coincides with the alkyl carbon number range desired in the detergent industry. Such renewable sources also have large amounts of nC16-nC18 feeds, and it is desirable to convert these feeds to nC9-nC14 feeds at high per pass yields. These nC9-nC14 intermediate products are useful through additional process steps to ultimately produce linear alkylbenzene type detergents. It is further desirable that the resulting nC9-nC14 paraffins are linear products with minimal branched isomer products. [Brief description 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. [Diagram 2] 1 is a plot of normal paraffins mass % versus deoxygenation temperature according to Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[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 less than 16 carbon atoms. Some of these triglycerides also produce substantial amounts, e.g., 20-30%, of normal paraffins having 16-24 carbon atoms after dehydrogenation. These paraffins are longer than desired for the production of 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] 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 combinations thereof. Natural oils include, but are not limited to, arachis oil (peanut oil; groundnut oil), babassu oil, coconut 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 fractionation of palm oil), palm stearin (a high melting point fraction derived from the fractionation 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; carthamus oil; kurdee oil), safflower seed oil-high oleic (high oleic safflower oil; high oleic safflower oil; carthamus oil; high oleic safflower 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 oil), and sunflower seed oil-high oleic (high oleic sunflower oil).

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

[0011] The process for making 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 of C15-C28) paraffins. The C14+ stream is sent to another 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, or nitrogen compounds, or phosphorus compounds, or oxygenates, or 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 carried out in a separate unit rather than in the bottom bed of the first stage hydrocracking reactor. C14+ paraffins are more selectively cracked than C9-C14 due to their higher absorption energy.

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

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

[0015] To limit catalyst deactivation, the feed is treated to remove sulfur, chloride, and metal contaminants prior to hydrodeoxygenation. Otherwise, sulfur, chloride, and metals will accumulate on the catalyst, which leads 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 large extent of hydrodeoxygenation can result in the hydrodeoxygenated composition being heavily biased towards normal dodecane and normal decane, to the detriment of normal undecane and normal tridecane. A small extent of hydrodeoxygenation can result in the hydrodeoxygenated composition being heavily biased towards 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% linearity (or alternatively 3% isoparaffins) will produce an alkylbenzene product with about 90-92% linearity by mass. This sets the paraffin linearity requirement 5-7% higher by mass than the alkylbenzene product specification. Typically, the linearity of the paraffin product is measured by UOP621, UOP411, or UOP732 standard test methods 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 embodiment shown, 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 of fatty acids and triglycerides are shown as follows, respectively:

[0021] [ka]

[0022] During the deoxygenation reaction, the paraffin chain 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 those containing 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 standard cubic feet per barrel of feedstock (scf / B) of 1500 to 10,000, 4000 to 9000, and 5000 to 8000. Suitable space velocities are 0.2 to 3.0 hr -1 LHSV. Conditions are selected to minimize degradation 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 performed 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-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-C14 stream 115 and the C9-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 known catalytic processes such as the commercially popular Pacol process. Di-olefins (i.e., dienes) and aromatics are also produced as undesirable 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 5-50 LHSV and 20-32 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 1-12 and 3-7. One example of a suitable catalyst is a Pt-alumina catalyst in which platinum is attenuated with a attenuating metal. Another suitable catalyst is described in U.S. Pat. No. 6,177,381, the entirety of which is incorporated herein by reference. The dehydrogenation unit 150 may be operated dry or with injection of up to 2000 mass-ppm water. Hydrogen may be recycled to the upstream deoxygenation unit.

[0029] The 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-olefins stream 170 has an increased mono-olefin concentration compared to the dehydrogenated stream 155. The aromatics are separated and removed as aromatics stream 165. A 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] The mono-olefin stream 170 containing mono-olefins is sent to the alkylation unit 175 together with the benzene stream 180. The benzene is alkylated with the mono-olefins to form alkylbenzenes. The 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 (AlCl3), zeolite, 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 the 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 in the ranges of 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 leaving 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 leaves 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 / olefins ratio (e.g., 1-50) and reduce the volume of benzene produced required. The required amount of benzene produced (i.e., net benzene) is determined by the net olefins to the alkylation unit. Also, 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. It should be noted that such a separation process to isolate the linear alkylbenzene product 205 is not required for 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 alkylbenzene have a linear alkyl group.

[0035] The linear alkylbenzene is sulfonated to give a benzene ring having the formula C, wherein n is 10 to 14, or n is 11 to 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 bottom 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 the object in downstream communication may 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 noted, each column includes a condenser at the top of the column to condense and reflux a portion of the overhead stream returning to the top of the column, and a reboiler at the bottom of the column to vaporize and return a portion of the bottom stream to the bottom of the column. The feed to the column may be preheated. Top pressure is the pressure of the overhead vapor at the vapor outlet of the column. Bottom temperature is the liquid bottom outlet temperature. Unless otherwise noted, 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 a reboiler at the bottom of the column and instead provide the required heat and driving force for the 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. EXAMPLES

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

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

[0042] Specific Embodiments While the following will be described in conjunction with specific embodiments, it will be understood that this description is illustrative and is not intended to limit the scope of the foregoing description and appended claims.

[0043] A first embodiment of the invention is a method for producing linear alkylbenzene products derived from triglycerides, comprising: deoxygenating triglycerides to 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 comprising C9-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-C14 paraffins and a second stream comprising isoparaffins; and removing contaminants from the C9-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 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 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 embodiments of this paragraph, where the C9-C14 stream and the first stream are combined and then the 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 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 any 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 any 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 any 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 any 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, where the triglyceride after dehydrogenation produces 0.1% to 20% by weight of 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, where 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, where the triglyceride after deoxygenation produces 15% or more by weight of 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, where the triglyceride after deoxygenation produces 10% or more by weight of 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 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 comprising C9-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-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-C14 stream and the first stream to form a decontaminated stream. 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-olefins under alkylation conditions to provide an alkylation effluent comprising alkylbenzenes and benzene; and isolating the alkylbenzenes to provide a triglyceride-derived alkylbenzene product, 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 embodiments of this paragraph, where 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 any one, any or all of the second 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 any one, any or all of the second 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 any one, any or all of the second embodiment of this paragraph through the preceding embodiments of this paragraph, where the triglyceride produces 0.1 wt % to 20 wt % normal paraffins having 16 carbon atoms after deoxygenation. An embodiment of the present invention is any one, any or all of the second embodiment of this paragraph through the preceding embodiments of this paragraph, where the triglyceride produces 15 wt % or more normal paraffins having either 12 or 14 carbon atoms after deoxygenation. An embodiment of the present invention is one, any, or all of the second embodiment of this paragraph through the preceding embodiments 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, using the preceding description, one skilled in the art can utilize the present invention to its fullest extent and easily ascertain the essential characteristics of the present invention without departing from the spirit and scope of the present invention, and can make various changes and modifications to the present invention to adapt it to various uses and conditions. The preceding preferred specific embodiments are therefore to be construed as merely illustrative, and are not limitative of the remainder of the disclosure in any way, but are intended to cover various modifications and equivalent arrangements falling 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 after deoxygenation produce 60% or more normal paraffins having less than 16 carbon atoms 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 (130) comprising isoparaffins; removing contaminants from said C9-C14 stream (115) and said first stream (130) to form a decontaminated stream (145), said contaminants comprising sulfur compounds, or nitrogen compounds, or phosphorus compounds, or oxygenates, or aromatics, or combinations 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-olefin 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.

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 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.

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