Heat and hydrogen accumulation in processes for renewable alkylbenzene products.

Abstract

To provide a method for producing linear alkylbenzenes from natural oils incorporating hydrogen and heat integration.SOLUTION: The method includes: a step of recycling at least a portion of a hydrogen stream to a linear selective cracking unit; and a step of heat-exchanging either a paraffin stream, a C9 to C14 stream, a C14+ stream, a first stream, a second stream, or a combination thereof with either a dehydrogenated stream, an alkylation effluent stream, or both, and / or a step of providing heat from deoxygenating a natural oil to either the linear selective cracking unit, a dehydrogenation unit, an alkylation unit, or a combination thereof.SELECTED DRAWING: None

Description

[Technical field]

[0001] (Statement of priority) This application claims priority to U.S. Provisional Patent Application No. 63 / 504,880, filed May 30, 2023, and U.S. Patent Application No. 18 / 500,162, filed November 02, 2023, the entireties of which are incorporated by reference herein. [Background technology]

[0002] Linear alkylbenzenes have the formula C6H5C n H 2n+1 The alkyl benzenes are organic compounds having the formula: n=1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 70, 72, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 112, 113, 114, 120, 121, 132, 143, 144, 145, 146, 147, 148, 149, 151, 162, 173, 174, 185, 196, 197, 198, 199, 102, 113, 124, 136, 147, 148,

[0003] The production of alkylbenzenes has grown rapidly since their first use in detergent manufacture in the 1960s, because the surfactants produced from alkylbenzenes are biodegradable. The linearity of the paraffin chains in alkylbenzenes 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] Although detergents made using alkylbenzene-based surfactants are biodegradable, the process for making alkylbenzene prior to their creation is not based on renewable sources. In particular, alkylbenzene is currently produced from kerosene refined from crude oil extracted from the earth. Increasing environmental bias against fossil fuel extraction and increasing economic concerns about depleting fossil fuel deposits may support the use of alternative sources of biodegradable surfactants in detergent and other industries.

[0005] It is therefore desirable to provide linear alkylbenzenes with a high degree of linearity that are produced from bio-renewable resources rather than mined from the earth. Additionally, it is desirable to provide renewable linear alkylbenzenes from easily processed triglycerides and fatty acids from vegetable, animal, nut, and / or seed oils. These nC9-nC14 intermediate products are useful for the ultimate production of linear alkylbenzene type detergents through additional processing steps. Additionally, it is desirable that the resulting nC9-nC14 paraffins are linear products with minimal branched isomer products. It is also desirable to reduce the amount of energy used in the process as well as the amount of hydrogen required. [Brief description of the drawings]

[0006] [Figure 1] FIG. 1 is a schematic diagram of one embodiment of a process for producing alkylbenzenes from natural oil incorporating hydrogen and heat accumulation according to the present invention. [Diagram 2] 1 is a plot of mass % normal paraffins versus deoxygenation temperature according to Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] The present invention relates to a method for producing alkylbenzenes from natural oils, such as vegetable oils, animal oils, nut oils, seed oils, and / or triglyceride-containing oils. Natural oils are not based on kerosene or other fossil fuels. Natural oils include those derived from plant or algal materials, animal fats, nut and / or seed oils, and / or triglyceride-containing oils, often referred to as renewable oils. Natural oils typically contain triglycerides, free fatty acids, or combinations thereof. Natural oils include peanut oil (groundnut oil; peanut oil), babassu oil, coconut oil, cottonseed oil, grapeseed oil, maize oil (corn 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 turnip oil; low erucic acid rapeseed oil; canola oil), and oleic acid-low erucic acid (low erucic acid rapeseed oil; low erucic acid rapeseed oil). oil), safflower seed oil (safflower oil; carthamus oil; safflower oil), safflower seed oil-high oleic (high oleic safflower oil; high oleic safflower oil; high oleic safflower oil), sesame seed oil (sesame oil; ginger oil; benne oil; ben oil; chilli oil; chilli oil), soybean oil (soybean oil), sunflower seed oil (helianthus annuus oil), and sunflower seed oil-high oleic (high oleic sunflower oil).

[0008] The method for producing alkylbenzenes from triglycerides according to the present invention includes deoxygenating the 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 linear paraffins and light branched paraffins and a second stream containing isoparaffins. Optionally, contaminants, including but not limited to sulfur compounds, or nitrogen compounds, or phosphorus compounds, or oxygenates, or aromatic compounds, or combinations thereof, are removed from the first stream, or the C9-C14 stream, or both. The decontaminated stream is dehydrogenated to form olefins, diolefins, and aromatic compounds. The diolefins are selectively hydrogenated to form additional olefins and the aromatics are separated and removed to form an aromatics stream comprising aromatics and a monoolefin stream comprising monoolefins. Benzene is alkylated with the olefins and the alkylation effluent comprises alkylbenzenes and benzene. The alkylbenzenes are then isolated.

[0009] This general process can be improved by providing heat generated in various processes to other processes that require additional heat. For example, heat generated in dehydrogenating natural oils can be used to reduce the amount of heat required in one or more of the linear selective cracking unit, the dehydrogenation unit, and the alkylation unit. Additionally, heat present in one stream can be used to heat another stream. For example, heat present in the dehydrogenation stream, or the alkylation effluent stream, or both, can be used to heat one or more of the paraffin stream, or the C9-C14 stream, or the C14+ stream, or the first stream, or the second stream.

[0010] In addition, the process can incorporate appropriate hydrogen recycle. The dehydrogenation process produces hydrogen that can be recycled to the linear selective cracking unit used to crack the C14+ paraffins.

[0011] This process is explained in more detail below.

[0012] To limit catalyst deactivation, the feedstock is treated to remove sulfur contaminants prior to hydrodeoxygenation. Otherwise, sulfur will accumulate on the catalyst, resulting in deactivation. High temperature hydrotreating has been found 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 atom 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.

[0013] The temperature of the hydrodeoxygenation reactor 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 the olefins found in the FFA. Generally, hydrodeoxygenation reactor pressures of 700 kPa (100 psig) to 21 MPa (3000 psig) are suitable.

[0014] The linearity of the alkylbenzene product depends mostly on the linearity of the paraffins used to alkylate the benzene. A general rule of thumb by those skilled in the art is that the linearity of the paraffin feedstock 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 result in an alkylbenzene product with about 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 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.

[0015] FIG. 1 illustrates an exemplary system 100 for producing alkylbenzene products from a natural oil feedstock.

[0016] In the illustrated embodiment, the natural oil feedstock 105 is delivered to a deoxygenation unit 110, which also receives a hydrogen feedstock (not shown). In the deoxygenation unit 110, the fatty acids in the natural oil feedstock 105 are deoxygenated and converted to linear paraffins. Structurally, triglycerides are formed by three, typically different, fatty acid molecules bound 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 are combined 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 linear 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 respectively shown as follows:

[0017] [ka]

[0018] During the deoxygenation reaction, the paraffin chain R n The length of the chain varies by 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 has one less carbon atom than the fatty acid source. If water is formed, the chain matches the length of the fatty acid source.

[0019] 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 yet another embodiment. Catalysts include those containing one or more of Ni, Mo, Co, P, such as, for example, 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 feed (scf / B). The preferred space velocity is 0.2 to 3.0 hr -1 LHSV. Conditions are selected to minimize cracking or isomerization of paraffins.

[0020] 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. Separation can be accomplished in a multi-stage fractionation unit, a distillation system, or similar known equipment. In either case, 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.

[0021] 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 linear or lightly branched C9-C14 paraffins and a second stream 135 containing isoparaffins. The linear selective cracking is carried out in a separate unit rather than in the bottom bed of the first stage hydrocracking reactor because sulfur and nitrogen contaminants from the first stage can poison the metal-based hydrocracking catalyst. The C14+ paraffins are selectively cracked over the C9-C14 paraffins due to their higher absorption energy.

[0022] Selection of specific metal catalysts, including precious metals (e.g., ruthenium and platinum) and nickel, can produce linear paraffins having 9 to 14 carbon atoms in much higher yields than previous processes. Suitable catalysts include 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 chain isomers.

[0023] Among the preferred catalysts, the Ru catalyst exhibits much higher activity and much higher nC9-nC14 yield per pass than the other catalysts. Under optimized reaction conditions, it also produces very small amounts of methane and isomerized products. It has been found to be the best catalyst for such chemical conversion processes. The Pt-Al2O3 catalyst may result in even lower methane yields and slightly lower linear product yields than the Ru-based catalysts.

[0024] 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 adsorptive separation system. The contaminants include, but are not limited to, sulfur compounds, nitrogen compounds, phosphorus compounds, oxygenates, or aromatic compounds, or combinations thereof.

[0025] 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 having the same number of carbon atoms as the paraffins. Typically, the dehydrogenation is carried out by 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: Monoolefin formation: C x H 2x+2 →C x H 2x +H2 Diolefin formation: C x H 2x →C x H 2x-2 +H2 Aromatic compound formation:C x H 2x-2 →C x H 2x-6+2H2

[0026] Operating conditions for the dehydrogenation apparatus 150 include space velocities of 5-50 LHSV and 20-32 LHSV; pressures of 34 kPa(g)-345 kPa(g) (5 psig-50 psig) and 103 kPa(g)-172 kPa(g) (15 psig-25 psig); temperatures of 400° C.-500° C. and 440° C.-490° C.; and hydrogen to hydrocarbon molar ratios of 1-12 and 3-7. An example of a suitable catalyst is a Pt on alumina catalyst, where the platinum is attenuated with an attenuator metal. Another suitable catalyst is described in U.S. Pat. No. 6,177,381, which is incorporated herein by reference in its entirety. The dehydrogenation unit 150 can be operated dry or with injection of up to 2000 ppm water by weight. Hydrogen can be recycled to an upstream deoxygenation unit.

[0027] Hydrogen is also produced in the dehydrogenation reaction. Hydrogen stream 157 is recycled to the linear selective cracking unit 125 to provide hydrogen for the cracking step.

[0028] The dehydrogenated stream 155 is sent to a selective hydrogenation unit 160, such as a Define reactor, where at least a portion of the diolefins are hydrogenated to form additional mono-olefins. As a result, mono-olefin stream 170 has an increased mono-olefin concentration compared to the dehydrogenated stream 155. 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.

[0029] Monoolefin stream 170, which contains monoolefins, is sent to alkylation unit 175 along with benzene stream 180. Benzene is alkylated with monoolefins to form alkylbenzenes. Alkylation unit 175 includes 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 (AlCl3) catalysts, zeolite catalysts, and ionic liquid catalysts are examples of major catalysts in commercial use for the alkylation of benzene with linear monoolefins 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

[0030] 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 within the ranges of 80° C. to 180° C. and 120° C. to 170° C., and benzene to olefin molar ratios of 3:40 and 8:35.

[0031] 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 returned to the alkylation unit 175 to maintain the desired benzene / olefins ratio (e.g., 1-50) and reduce the volume of fresh benzene required. The fresh benzene requirement (i.e., net benzene) is determined by the net olefins to the alkylation unit. A paraffin stream 200 may also be separated and recycled to the dehydrogenation unit 150.

[0032] 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 is not required in all embodiments to isolate the linear alkylbenzene product 205.

[0033] The linear alkylbenzene product 205 has the formula C6H5C n H 2n+1 where n is from 9 to 14. In some embodiments, at least 80% by weight, or at least 90% by weight, of the alkylbenzene have a linear alkyl group.

[0034] Linear alkylbenzenes are sulfonated to form the compounds of formula C n H 2n+1 A linear alkylbenzene sulfonate product may be provided, comprising an alkylbenzene sulfonate compound having the formula C6H4SO3H, where n is 10-14, or n is 11-13.

[0035] 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 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 may operably flow from the object in fluid communication.

[0036] The term "column" refers to a distillation column or 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. The top 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 noted, 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 a reboiler at the bottom of the column and instead provide the required heat and driving force for the separation as a stream from a fluidized inert medium such as steam.

[0037] 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. EXAMPLES

[0038] Example 1 The coconut oil feedstock 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 62.96 mass % modern carbon as measured by ASTM D6866, a bromine number of 1 g Br per gram sample as measured by UOP Standard Test Method 304, and a linearity of 92 mass % compared to a theoretical modern carbon content of 66.4 mass %.

[0039] Example 2 Pressure of 480 psig, H to bio-oil ratio of 7200 scf / B, and 1hr ’ The oil was deoxygenated using a catalyst at an LHSV of 1000°F. 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 further to 404°C (760°F), and the response of the linearity of the final product to the reaction temperature was monitored. The results are shown in Figure 2, which is a plot of the concentration (mass%) of linear C10-C13 paraffins versus reaction temperature. Figure 2 clearly shows that as the deoxygenation reaction temperature increases, the concentration of linear paraffins decreases. When the temperature was controlled below 404°C (760°F), more than 92 mass% of linear paraffins was obtained.

[0040] Note: Examples 1 and 2 were previously included as Examples 3 and 4 in US Pat. No. 9,079,814.

[0041] 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.

[0042] A first embodiment of the present invention is a method for producing a linear alkylbenzene product derived from a natural oil, comprising: deoxygenating the natural oil to form a paraffin stream comprising paraffins; separating 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 linear or lightly branched C9-C14 paraffins, and a second stream comprising isoparaffins; dehydrogenating the first stream in a dehydrogenation unit to provide a dehydrogenated stream comprising mono-olefins, di-olefins, and aromatics, and a hydrogen stream comprising hydrogen; recycling at least a portion of the hydrogen stream to the linear selective cracking unit; and separating the di-olefins in the dehydrogenated stream from the linear selective cracking unit. selectively hydrogenating olefins to form additional mono-olefins and separating and removing aromatics from the mono-olefins to form an aromatics stream comprising aromatics and a mono-olefin stream comprising mono-olefins; alkylating benzene with the mono-olefins under alkylation conditions in an alkylation unit to provide an alkylbenzene and an alkylation effluent comprising benzene; isolating the alkylbenzene to provide an alkylbenzene product derived from a natural oil; heat exchanging the paraffin stream, or the C9-C14 stream, the C14+ stream, the first stream, or the second stream, or a combination thereof, with the dehydrogenation stream, or the alkylation effluent stream, or both; or providing heat from deoxygenating the natural oil to a linear selective cracking unit, a dehydrogenation unit, or an alkylation unit, or a combination thereof; or both.An embodiment of the invention is any one, any or all of the first embodiment through the embodiments up to this paragraph, further comprising removing contaminants from the first stream, or the C9-C14 stream, or both, to form a decontaminated stream, prior to dehydrogenating the first stream, where the contaminants include sulfur compounds, nitrogen compounds, phosphorus compounds, aromatic compounds, oxygenates, fatty acids, or fatty esters, or combinations thereof. An embodiment of the invention is any one, any or all of the first embodiment through the embodiments up to this paragraph, where the C9-C14 stream and the first stream are combined prior to removing contaminants from the first stream, or the C9-C14 stream, or both, to form a decontaminated stream. An embodiment of the invention is any one, any or all of the first embodiment through the embodiments up to this paragraph, where the linear selective cracking catalyst includes a ruthenium supported catalyst, a platinum supported catalyst, or a nickel supported catalyst, or a mixture thereof. An embodiment of the present invention is any one, any or all of the first embodiment through to the present embodiment in 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 2.8MPa to 17.5MPa, or a combination thereof. An embodiment of the present invention is any one, any or all of the first embodiment through to the present embodiment in this paragraph, where the alkylbenzene product includes alkylbenzenes having C9 to C14 chains. An embodiment of the present invention is any one, any or all of the first embodiment through to the present embodiment in this paragraph, where the natural fat is selected from vegetable oils, animal fats, and triglyceride-containing oils.

[0043] A second embodiment of the present invention is a method for producing a linear alkylbenzene product derived from a natural oil, comprising: deoxygenating the natural oil to form a paraffin stream comprising paraffins, the natural oil being selected from vegetable oils, animal fats and triglyceride-containing oils; separating 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 linear or lightly branched C9-C14 paraffins and a second stream comprising isoparaffins; removing contaminants from the first stream, or the C9-C14 stream, or both, the contaminants comprising sulfur compounds, nitrogen compounds, phosphorus compounds, aromatic compounds, oxygenates, fatty acids, or fatty esters, or combinations thereof; dehydrogenating the decontaminated stream. dehydrogenating in the unit to provide a dehydrogenation stream comprising mono-olefins, di-olefins, and aromatics, and a hydrogen stream comprising hydrogen; recycling at least a portion of the hydrogen stream to the linear selective cracking unit; selectively hydrogenating the di-olefins in the dehydrogenation stream to form additional mono-olefins and separating and removing the aromatics from the mono-olefins to form an aromatics stream comprising aromatics and a mono-olefin stream comprising mono-olefins; alkylating benzene with the mono-olefins under alkylation conditions in the alkylation unit to provide alkylbenzenes and an alkylation effluent comprising benzene; isolating the alkylbenzenes to provide an alkylbenzene product derived from the natural oil; heat exchanging the paraffin stream, or the C9-C14 stream, the C14+ stream, the first stream, or the second stream, or a combination thereof, with the dehydrogenation stream, or the alkylation effluent stream, or both;or providing heat from deoxygenating the natural oil to a linear selective cracking unit, a dehydrogenation unit, or an alkylation unit, or a combination thereof; or both. One embodiment of the present invention is any one, any or all of the second embodiment to the present embodiment in this paragraph, where the C9-C14 stream and the first stream are combined prior to removing contaminants from the C9-C14 stream and the first stream to form a decontamination stream. One embodiment of the present invention is any one, any or all of the second embodiment to the present embodiment in this paragraph, where the linear selective cracking catalyst comprises a ruthenium supported catalyst, a platinum supported catalyst, or a nickel supported catalyst, or a mixture thereof. One embodiment of the present invention is any one, any or all of the second embodiment to the present embodiment in this paragraph, where 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. One embodiment of the present invention is one, any, or all of the second embodiment of this paragraph through the embodiments up to this point in this paragraph, wherein the alkylbenzene product comprises C9-C14 chains;

[0044] 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, and can make various changes and modifications to the present invention to adapt it to various uses and conditions, 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, but are intended to cover various modifications and equivalent arrangements falling within the scope of the appended claims.

[0045] Above, all temperatures are listed in degrees Celsius and all parts and percentages are by weight unless otherwise stated.

Claims

1. 1. A process for the production of a linear alkylbenzene product derived from a natural oil comprising: deoxygenating the natural oil (105) to form a paraffin stream comprising paraffins; separating the paraffin stream to form a C9-C14 stream (115) comprising C9-C14 paraffins and a C14+ stream (120) comprising C14+ paraffins; linear selective 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 linear or lightly branched C9 to C14 paraffins, and a second stream (135) comprising isoparaffins; dehydrogenating said first stream (130) in a dehydrogenation unit (150) to provide a dehydrogenated stream (155) comprising mono-olefins, di-olefins, and aromatics, and a hydrogen stream (157) comprising hydrogen; recycling at least a portion of said hydrogen stream (157) to said linear selective cracking unit; selectively hydrogenating the diolefins 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 monoolefins under alkylation conditions in an alkylation unit (175) to provide an alkylation effluent (185) comprising alkylbenzenes and benzene; isolating the alkylbenzene to provide the alkylbenzene product (205) derived from the natural oil; exchanging heat between the paraffin stream, the C9-C14 stream (115), the C14+ stream (120), the first stream (130), or the second stream (135), or a combination thereof, with the dehydrogenation stream (155), or the alkylation effluent stream (185), or both; or providing heat from the deoxygenation of the natural oil to the linear selective cracking unit (125), the dehydrogenation unit (150), or the alkylation unit (175), or a combination thereof; or both.

2. 10. The method of claim 1, further comprising removing contaminants from the first stream (130), or the C9-C14 stream (115), or both, prior to dehydrogenating the first stream (130), to form a decontaminated stream (145), wherein the contaminants include sulfur compounds, nitrogen compounds, phosphorus compounds, aromatic compounds, oxygenates, fatty acids, or fatty esters, or combinations thereof.

3. 3. The method of claim 2, wherein the C9-C14 stream (115) and the first stream (130) are combined to form the decontaminated stream (145) prior to removing the contaminants from the first stream (130) or the C9-C14 stream (115), or both.

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