Heat and hydrogen integrated apparatus for use in a process for regenerative

Abstract

The utility model relates to a heat and hydrogen integration device used in a method for regenerating alkylbenzene products, which comprises a deoxidation unit communicated with a natural oil feeding pipeline and a first hydrogen pipeline; a C9 to C14 pipeline and a C14 + pipeline, wherein the C9 to C14 pipeline and the C14 + pipeline are communicated with the deoxidation unit; the dehydrogenation unit is communicated with the purification pipeline; a dehydrogenation line and a second hydrogen line; wherein the dehydrogenation line and the second hydrogen line are in communication with the dehydrogenation unit; wherein the second hydrogen line is also in communication with the straight-chain selective cracking unit; a selective hydrogenation unit in communication with the dehydrogenation line with a monoolefine line in communication with the selective hydrogenation unit; an alkylation unit in communication with the monoolefine line; and an alkylation effluent line in communication with the alkylation unit. According to the utility model, alkylbenzene is produced from natural oil. Natural oils include those derived from plant or algal material, animal fat, nut and / or seed oil, and / or triglyceride-containing oil, and are generally referred to as renewable oils.

Description

[0001] Priority Claim

[0002] This application claims the priority of U.S. Provisional Patent Application Serial No. 63 / 504,880, filed on May 30, 2023, and U.S. Patent Application Serial No. 18 / 500,162, filed on November 2, 2023, the entire content of which is incorporated herein by reference. Technical Field

[0003] The present utility model relates to an apparatus for producing alkylbenzene from natural oils such as vegetable oils, animal oils, nut oils, seed oils, and / or triglyceride-containing oils. The 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, and are commonly referred to as renewable oils. Background Art

[0004] Linear alkylbenzene is an organic compound having the formula C 6 H 5 C n H 2n+1 Although the alkyl carbon number "n" can have any practical value, detergent manufacturers desire alkylbenzene to have an alkyl carbon number in the range of 9 to 16, and preferably in the range of 9 to 14. These specific ranges are typically required when alkylbenzene is used as an intermediate in the production of surfactants for detergents. An alkyl carbon number in the range of 9 to 14 meets the specifications of the detergent industry.

[0005] Since the surfactants produced from alkylbenzene are biodegradable, the production of alkylbenzene has grown rapidly since its initial use in detergent production in the 1960s. The straight-chain degree of the alkane chain in alkylbenzene is crucial for the biodegradability of the material and its effectiveness as a detergent. The main factor for the final straight-chain degree of alkylbenzene is the straight-chain degree of the alkane component.

[0006] Although detergents prepared using alkylbenzene-based surfactants are biodegradable, the methods previously used to produce alkylbenzene are not based on renewable sources. Specifically, alkylbenzene is currently produced from kerosene refined from crude oil extracted from the earth. Due to the increasing environmental bias against fossil fuel extraction and the economic concerns about depleting fossil fuel deposits, there may be support for alternative sources of biodegradable surfactants in the detergent and other industries.

[0007] Accordingly, there is a desire to provide linear alkylbenzenes having a high degree of linearity made from bio-renewable sources rather than being extracted from the earth. Additionally, there is a desire to provide renewable linear alkylbenzenes from triglycerides and fatty acids that are easily processed from plants, animals, nuts, and / or seed oils. These nC9 to nC14 intermediates can be used to ultimately prepare detergent of the linear alkylbenzene type through additional process steps. There is a further desire that the resulting nC9 to nC14 alkanes be linear products with a minimum of branched isomer products. There is also a desire to reduce the amount of energy used and the amount of hydrogen gas required in the method. Brief Description of the Drawings

[0008] Figure 1 is a schematic diagram of an embodiment of a method for producing alkylbenzene from natural oil incorporating hydrogen and heat integration in accordance with the present invention.

[0009] Figure 2 is a graph of the n-alkane mass % versus the deoxygenation temperature according to Example 2. Summary of the Utility Model

[0010] The present utility model includes the following technical solutions:

[0011] 1. A heat and hydrogen integration device in a method for renewable alkylbenzene products, the heat and hydrogen integration device in the method for renewable alkylbenzene products comprising:

[0012] A deoxygenation unit in communication with a natural oil feed line and a first hydrogen gas line;

[0013] A C9 to C14 line and a C14+ line, wherein the C9 to C14 line and the C14+ line are in communication with the deoxygenation unit;

[0014] A dehydrogenation unit in communication with a purification line;

[0015] A dehydrogenation line and a second hydrogen gas line;

[0016] wherein the dehydrogenation line and the second hydrogen gas line are in communication with the dehydrogenation unit;

[0017] wherein the second hydrogen gas line is also in communication with a linearity selective cracking unit;

[0018] A selective hydrogenation unit in communication with the dehydrogenation line

[0019] A mono-olefin line in communication with the selective hydrogenation unit;

[0020] An alkylation unit in communication with the mono-olefin line; and

[0021] An alkylation effluent line in communication with the alkylation unit.

[0022] 2. The thermal and hydrogen integration device in the method for renewable alkylbenzene products according to Item 1, the thermal and hydrogen integration device in the method for renewable alkylbenzene products further comprises:

[0023] A benzene separation unit, which is communicated with the alkylation effluent pipeline, and the linear alkylbenzene product is in the linear alkylbenzene product pipeline; and

[0024] A benzene recycle pipeline;

[0025] Wherein the linear alkylbenzene product pipeline and the benzene recycle pipeline are communicated with the benzene separation unit.

[0026] 3. The thermal and hydrogen integration device in the method for renewable alkylbenzene products according to Item 2, wherein the benzene recycle pipeline is communicated with the alkylation unit.

[0027] 4. The thermal and hydrogen integration device in the method for renewable alkylbenzene products according to any one of Items 1-3, wherein the linear selective cracking unit is communicated with the C14+ pipeline; the thermal and hydrogen integration device in the method for renewable alkylbenzene products further comprises:

[0028] A first pipeline, which is communicated with the linear selective cracking unit;

[0029] A second pipeline;

[0030] Wherein the first pipeline and the second pipeline are communicated with the linear selective cracking unit.

[0031] 5. The thermal and hydrogen integration device in the method for renewable alkylbenzene products according to any one of Items 1-3, the thermal and hydrogen integration device in the method for renewable alkylbenzene products further comprises:

[0032] A purification unit, which is communicated with the first pipeline; and

[0033] A purification pipeline, which is communicated with the purification unit.

[0034] 6. The thermal and hydrogen integration device in the method for renewable alkylbenzene products according to Item 4, the thermal and hydrogen integration device in the method for renewable alkylbenzene products further comprises:

[0035] A purification unit, which is communicated with the first pipeline; and

[0036] A purification pipeline, which is communicated with the purification unit.

[0037] 7. The thermal and hydrogen integration device in the method for renewable alkylbenzene products according to Item 5, wherein the C9 to C14 pipeline is communicated with the purification unit.

[0038] 8. The thermal and hydrogen integration device in the method for renewable alkylbenzene products according to item 6, wherein the C9 to C14 pipeline is in communication with the purification unit.

[0039] 9. The thermal and hydrogen integration device in the method for renewable alkylbenzene products according to item 1, wherein the selective hydrogenation unit is in communication with the dehydrogenation pipeline, and the thermal and hydrogen integration device in the method for renewable alkylbenzene products further comprises:

[0040] An aromatic compound pipeline and a light fraction pipeline, wherein the aromatic compound pipeline and the light fraction pipeline are in communication with the selective hydrogenation unit.

[0041] 10. The thermal and hydrogen integration device in the method for renewable alkylbenzene products according to item 1, wherein the C9 to C14 pipeline or the C14+ pipeline or the first pipeline or the second pipeline or a combination thereof is in communication with the dehydrogenation pipeline or the alkylation effluent pipeline or both through a heat exchanger.

[0042] 11. The thermal and hydrogen integration device in the method for renewable alkylbenzene products according to item 1, wherein the deoxygenation unit is in communication with the straight-chain selective cracking unit or the dehydrogenation unit or the alkylation unit or a combination thereof or both through a heat exchanger. Detailed Description

[0043] The present invention relates to a process for producing alkylbenzenes from natural oils such as vegetable oils, animal oils, nut oils, seed oils and / or triglyceride-containing oils. The natural oils are not based on kerosene or other fossil fuels. Natural oils include those derived from plant or algal materials, animal fats, nuts and / or seed oils and / or triglyceride-containing oils and are commonly referred to as renewable oils. Natural oils typically contain triglycerides, free fatty acids or combinations thereof. Natural oils include, but are not limited to, peanut oil (Arachis oil) (peanut oil; groundnut oil), babassu oil, coconut oil, cottonseed oil, grapeseed oil, maize oil (corn oil), mustard oil, palm kernel oil, palm oil, palm olein (the liquid fraction obtained by fractionation of palm oil), palm stearin (the high melting point fraction obtained by fractionation of palm oil), rapeseed oil, rapeseed oil – low erucic acid (low erucic acid turnip rape oil; low erucic acid colza oil; canola oil), safflower oil (safflower oil; carthamus oil; kurdee oil), high oleic acid safflower oil (high oleic acid safflower oil; high oleic acid carthamus oil; high oleic acid kurdee oil), sesame seed oil (sesame oil; gingelly oil; benne oil; ben oil; till oil; tillie oil), soya bean oil (soybean oil), sunflower seed oil (sunflower oil) and sunflower seed oil – high oleic acid (high oleic acid sunflower oil).

[0044] The method for preparing alkylbenzene from triglycerides according to the present invention comprises deoxygenating the triglycerides to form alkanes. The alkanes are separated (by fractional distillation, distillation, etc.) into a C9 - C14 stream comprising C9 to C14 alkanes and a C14+ stream comprising C14+ alkanes (i.e., having a carbon chain containing C15 to C28). The C14+ stream is sent to a separate linear-selective cracking unit to crack the C14+ alkanes; the cracked alkanes are fractionated into a first stream comprising C9 to C14 normal alkanes and lightly branched alkanes and a second stream comprising isoalkanes. Optionally, contaminants are removed from the first stream, or the C9 - C14 stream, or both, the contaminants including but not limited to sulfur compounds, or nitrogen compounds, or phosphorus compounds, or oxygen-containing compounds, or aromatic compounds or combinations thereof. The purified stream is dehydrogenated to form olefins, dienes, and aromatic compounds. The dienes are selectively hydrogenated to form additional olefins, and the aromatic compounds are separated and removed, forming an aromatic compound stream comprising aromatic compounds and a mono-olefin stream comprising mono-olefins. Benzene is alkylated with the olefins, and the alkylation effluent contains alkylbenzene and benzene. Then the alkylbenzene is separated.

[0045] The general method can be improved by providing the heat generated in various processes to other processes that require heat addition. For example, the heat generated in dehydrogenating natural oil can be used to reduce the amount of heat required in one or more of the linear-selective cracking unit, dehydrogenation unit, alkylation unit. Additionally, the heat present in certain streams can be used to heat other streams. For example, the heat present in the dehydrogenation stream, or the alkylation effluent stream, or both, can be used to heat one or more of the alkane stream, or the C9 - C14 stream, or the C14+ stream, or the first stream, or the second stream.

[0046] Furthermore, the method can incorporate appropriate hydrogen recycling. The dehydrogenation process generates hydrogen, which can be recycled to the linear-selective cracking unit for cracking the C14+ alkanes.

[0047] The method will be described in more detail below.

[0048] To limit catalyst deactivation, the feed is treated to remove sulfur contaminants prior to hydrodeoxygenation. Otherwise, sulfur accumulates on the catalyst and causes deactivation. High-temperature hydrogenation treatment has shown to restore some of the lost activity. The degree of hydrodeoxygenation can affect the selectivity for each normal alkane in the range of 9 to 14 carbons. A high degree of hydrodeoxygenation can cause the hydrodeoxygenation composition to be strongly biased towards n-dodecane and n-decane to the detriment of n-undecane and n-tridecane. A low degree of hydrodeoxygenation can cause the hydrodeoxygenation composition to be biased towards n-undecane and n-tridecane to the detriment of n-dodecane and n-decane.

[0049] The hydrodeoxygenation reactor temperature is maintained low, less than 343 °C (650 °F) for typical bioregenerable feeds and less than 304 °C (580 °F) for feeds with higher free fatty acid (FFA) concentrations, to avoid polymerization of the olefins present in the FFA. Typically, a hydrodeoxygenation reactor pressure of 700 kPa (100 psig) to 21 MPa (3000 psig) is suitable.

[0050] The linearity of the alkylbenzene product depends primarily on the linearity of the alkane used to alkylate benzene. A common rule of thumb for those skilled in the art is that, after dehydrogenation and alkylation, the linearity of the alkane feed drops by 5 wt% - 7 wt%. Thus, an alkane with 97 wt% linearity (or alternatively 3 wt% isoalkane) will produce an alkylbenzene product with a linearity of about 90 wt% - 92 wt%. This sets a requirement for the linearity of the alkane that is 5 wt% - 7 wt% higher than the specification for the alkylbenzene product. Typically, the linearity of the alkane product is measured by UOP 621, UOP 411, or UOP 732 standard test methods purchased from ASTM, which are hereby incorporated by reference in their entirety. Linear alkylbenzenes can be analyzed using ASTM standard test method D4337, which is hereby incorporated by reference in its entirety.

[0051] In Figure 1 illustrates an exemplary system 100 for producing an alkylbenzene product from a natural oil feed.

[0052] In the illustrated embodiment, a natural oil 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 natural oil feed 105 are deoxygenated and converted to normal alkanes. Triglycerides are structurally formed from three generally different fatty acid molecules that are bonded together by a glycerol bridge. The glycerol molecule includes three hydroxyl groups (HO--) and each fatty acid molecule has a carboxyl group (COOH). In a triglyceride, the hydroxyl groups of the glycerol bond to the carboxyl groups of the fatty acids to form ester bonds. Thus, during deoxygenation, the fatty acids are released from the triglyceride structure and converted to normal alkanes. 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 respectively as:

[0053]

[0054] During the deoxygenation reaction, the resulting alkane chain R nThe length will vary by a value depending on the exact reaction pathway. It should be understood that deoxygenation includes at least one of hydrodeoxygenation, decarboxylation, and decarbonylation reactions 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.

[0055] The operating conditions of the deoxygenation unit include a pressure in the range of 250 psig to 800 psig (1724 kPa to 5516 kPa) and a temperature in one embodiment of 274 °C to 371 °C (525 °F to 700 °F), in another embodiment of 274 °C to 338 °C (525 °F to 640 °F), and in another embodiment of 274 °C to 310 °C (525 °F to 590 °F). The catalyst can include those catalysts 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 1500 to 10,000, 4000 to 9000, and 5000 to 8000 standard cubic feet per barrel of feedstock (scf / B). Suitable space velocities include 0.2 hr -1 -3.0 hr -1 LHSV. The conditions are selected to minimize alkane cracking or isomerization.

[0056] The deoxygenation product containing normal alkanes, water, carbon dioxide, carbon monoxide, and propane is fractionated into a C9 to C14 stream 115 and a C14+ stream 120. The separation can be carried out in a multi-stage fractionation unit, a distillation system, or similar known equipment. In any case, the separator removes water, carbon dioxide, carbon monoxide, and propane from the deoxygenation product. A naphtha stream (not shown) of alkanes having a carbon chain length of C 5 to C 9 can also be formed.

[0057] The C14+ stream 120 is sent to a straight-chain selective cracking unit 125 where the stream is selectively cracked to form a first stream 130 containing C9 to C14 normal alkanes or mildly branched alkanes and a second stream 135 containing isoparaffins. The straight-chain 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+ alkanes are selectively cracked before the C9 to C14 due to their higher absorption energy.

[0058] Selecting specific metal catalysts, including noble metals (such as ruthenium and platinum) and nickel, can produce normal paraffins with 9 to 14 carbons in much higher yields than previous methods. Suitable catalysts include, but are not limited to, Ru / ZrO 2 , Pt - Al 2 O 3 , Ni - alumina or NiO x / clay. Using these catalysts, the C14+ stream can produce straight - chain cracking products without significant amounts of branched - chain isomers being formed.

[0059] Among the preferred catalysts, the Ru catalyst exhibits much higher activity and single - pass nC9 to nC14 yields than other catalysts. Under optimized reaction conditions, it also produces very small amounts of methane and isomerization products. It has been found to be the best catalyst for such chemical conversion methods. The Pt - Al2O3 catalyst can produce even lower methane yields than the Ru - based catalyst, with slightly lower straight - chain product yields.

[0060] Send the C9 to C14 stream 115 from the deoxygenation unit 110 and the first stream 130 from the straight - chain selective cracking unit 125 to the purification unit 140. The purification unit 140 removes contaminants from the C9 to C14 paraffins in the C9 to C14 stream 115 and the first stream 130 in an adsorption separation system. Contaminants include, but are not limited to, sulfur compounds, or nitrogen compounds, or phosphorus compounds, or oxygen - containing compounds, or aromatic compounds or combinations thereof.

[0061] Send the purified stream 145 to the dehydrogenation unit 150, where hydrogen is removed to produce a dehydrogenated stream 155 containing mono - olefins, di - olefins, and aromatic compounds. In the dehydrogenation unit 150, the paraffins are dehydrogenated to mono - olefins having the same number of carbons as the paraffins. Generally, dehydrogenation is carried out by known catalytic methods, such as the commercially popular Pacol method. Di - olefins (i.e., dienes) and aromatic compounds are also produced as unwanted results of the dehydrogenation reaction, as shown by the following reaction equations:

[0062] Formation of mono - olefin: C x H 2x+2 →C x H 2x +H 2

[0063] Formation of di - olefin: C x H 2x →C x H 2x-2 +H 2

[0064] Formation of aromatic compound: C x H 2x-2 →C xH 2x-6 +2H 2

[0065] The operating conditions of the dehydrogenation unit 150 include a space velocity of 5 LHSV to 50 LHSV and 20 LHSV to 32 LHSV; a pressure of 34 kPa(g) to 345 kPa(g) (5 psig to 50 psig) and 103 kPa(g) to 172 kPa(g) (15 psig to 25 psig); a temperature of 400 °C to 500 °C and 440 °C to 490 °C, and a hydrogen to hydrocarbon molar ratio of 1 to 12 and 3 to 7. Examples of suitable catalysts are Pt / alumina catalysts in which the platinum is attenuated with an attenuator metal. Another suitable catalyst is described in U.S. Patent 6,177,381, which is incorporated herein by reference in its entirety. The dehydrogenation unit 150 can be operated dry or with up to 2000 mass ppm of water injected. Hydrogen can be recycled upstream of the deoxygenation unit.

[0066] Hydrogen is also produced in the dehydrogenation reaction. The hydrogen stream 157 is recycled to the linear selective cracking unit 125 to provide hydrogen for the cracking step.

[0067] The dehydrogenation stream 155 is sent to a selective hydrogenation unit 160, such as a DeFine reactor, where at least a portion of the dienes are hydrogenated to form additional monoolefins. As a result, the monoolefin stream 170 has an increased monoolefin concentration compared to the dehydrogenation stream 155. The aromatics are separated and removed in the form of an aromatics stream 165. A light distillate stream 167 containing any light components (such as butane, propane, ethane, and methane) produced by cracking or other reactions during upstream processing can also be removed.

[0068] The monoolefin stream 170 containing monoolefins is sent to the alkylation unit 175 together with the benzene stream 180. The benzene is alkylated with the monoolefins to form alkylbenzenes. The alkylation unit 175 contains a catalyst that supports the alkylation of benzene with monoolefins, such as a solid acid catalyst. Fluorinated silica-alumina, hydrogen fluoride (HF), aluminum chloride (AlCl 3 )), zeolites, and ionic liquid catalysts are examples of the main catalysts commercially used for the alkylation of benzene with linear monoolefins and can be used in the alkylation unit 175. As a result of the alkylation, alkylbenzenes, commonly referred to as linear alkylbenzenes (LAB), are formed according to the following reaction:

[0069] C 6 H 6 +C x H 2x →C 6 H 5 C x H 2x+1

[0070] Suitable operating conditions for the alkylation unit 175 include a space velocity of 1 LHSV to 10 LHSV, a pressure to maintain liquid phase operation such as 2068 kPa(g) to 4137 kPa(g) (300 psig to 600 psig), a temperature in the range of 80 °C to 180 °C and 120 °C to 170 °C, and a molar ratio of benzene to olefin of 3 to 40 and 8 to 35.

[0071] An excess of benzene is supplied to the alkylation unit 175 to achieve the desired high degree of alkylation. Thus, the alkylation effluent 185 leaving the alkylation unit 175 contains alkylbenzene and unreacted benzene. In addition, the alkylation effluent 185 may also include some unreacted paraffins. The alkylation effluent 185 is passed to a benzene separation unit 190, such as a fractionation tower, to separate the unreacted benzene and paraffins from the alkylation effluent 185. The unreacted benzene leaves the benzene separation unit 190 in the form of a benzene recycle stream 195, which can be sent back to the alkylation unit 175 to maintain the desired benzene / olefin ratio (e.g., 1 - 50) to reduce the volume of fresh benzene required. The fresh benzene requirement (i.e., net benzene) is determined by the net olefins entering the alkylation unit. The paraffin stream 200 can also be separated out and recycled to the dehydrogenation unit 150.

[0072] As a result of the post-alkylation separation process, the linear alkylbenzene product 205 is separated out. It should be noted that such a separation method is not necessary in all embodiments for separating the linear alkylbenzene product 205.

[0073] The linear alkylbenzene product 205 is a linear alkylbenzene product that contains: alkylbenzenes having the formula C 6 H 5 C n H 2n+1 where n is from 9 to 14. In some embodiments, at least 80 mass%, or at least 90 mass% of the alkylbenzenes have linear alkyl groups.

[0074] The linear alkylbenzene can be sulfonated to provide a linear alkylbenzene sulfonate product that contains: alkylbenzene sulfonate compounds having the formula C n H 2n+ 1 C 6 H 4 SO 3 H, where n is from 10 to 14, or where n is from 11 to 13.

[0075] As used herein, the term "separator" means a vessel having an inlet and at least one overhead vapor outlet and one bottoms liquid outlet, and may also have an aqueous stream outlet from a boot. A flash drum is a type of separator that may be in downstream communication with a separator that operates at a higher pressure. The term "in communication" means that fluid flow is operably permitted between the recited components, which may be characterized as "in fluid communication". The term "downstream communication" means that at least a portion of the fluid flowing to the body in the downstream communication can operably flow from an object in fluid communication therewith.

[0076] The term "column" means one or more distillation columns for separating one or more components having different volatilities. Unless otherwise specified, each column includes a condenser at the top of the column for condensing a portion of the overhead stream and returning it to the top of the column, and a reboiler at the bottom of the column for vaporizing a portion of the bottoms stream and returning it 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 bottoms liquid outlet temperature. Unless otherwise specified, the overhead line and the bottoms line refer to the net lines from downstream of the column for any reflux or reboiler take-off to the column. A stripper column may omit the reboiler at the bottom of the column and instead provide the heating requirements and separation driving force for a liquefied inert medium such as steam.

[0077] As used herein, the term "component-rich stream" or "component stream" means a stream exiting a vessel having a greater concentration of the component than the feed to the vessel. As used herein, the term "component-lean stream" means a lean stream exiting a vessel having a smaller concentration of the component than the feed to the vessel.

[0078] Embodiment

[0079] Embodiment 1

[0080] Coconut oil feed is deoxygenated to form paraffins, dehydrogenated to form monoolefins, and benzene is alkylated with the monoolefins to form an alkylbenzene product having a modern carbon content of 62 mass% modern carbon as determined by ASTM D6866 compared to a theoretical modern carbon content of 66.4 mass%, a bromine value of 1 g Br per gram of sample as determined by UOP Standard Test Method 304, and a straight-chain degree of 92 mass%.

[0081] Embodiment 2

[0082] The oil is deoxygenated using a catalyst at a pressure of 480 psig H, with a bio-oil ratio of 7200 scf / B and an LHSV of 1 hr⁻¹. During operation, the deoxygenation reaction temperature is gradually increased from 315 °C (600 °F) to 349 °C (660 °F), then to 377 °C (710 °F) and 404 °C (760 °F) to monitor the response of the straight-chain degree in the final product to the reaction temperature. The results are shown in Figure 2 which is a graph of the concentration (in mass %) of C10 - C13 n-alkanes versus the reaction temperature. Figure 2 It clearly shows that as the deoxygenation reaction temperature increases, the concentration of n-alkanes decreases. Controlling the temperature below 404 °C (760 °F) produces more than 92 mass % n-alkanes.

[0083] Note: Examples 1 and 2 were previously included as Examples 3 and 4 in U.S. Patent 9,079,814.

[0084] Specific implementation scheme

[0085] Although the following is described in connection with specific embodiments, it should be understood that the description is intended to illustrate and not limit the scope of the foregoing description and the appended claims.

[0086] A first embodiment of the present invention is a method for producing a linear alkylbenzene product derived from a natural oil, the method comprising deoxygenating the natural oil to form an alkane stream comprising alkanes; separating the alkane stream to form a C9 - C14 stream comprising C9 - C14 alkanes and a C14+ stream comprising C14+ alkanes; subjecting the C14+ stream to linear selective cracking in a separate linear selective cracking unit in the presence of a linear selective cracking catalyst under linear selective cracking conditions to form a first stream comprising C9 - C14 normal alkanes or slightly branched alkanes and a second stream comprising isoalkanes; dehydrogenating the first stream in a dehydrogenation unit to provide a dehydrogenated stream comprising monoolefins, diolefins and aromatic compounds and a hydrogen stream comprising hydrogen; recycling at least a portion of the hydrogen stream to the linear selective cracking unit; selectively hydrogenating the diolefins in the dehydrogenated stream to form additional monoolefins, and separating and removing the aromatic compounds from the monoolefins to form an aromatic compound stream comprising the aromatic compounds and a monoolefin stream comprising the monoolefins; alkylating benzene with the monoolefins in an alkylation unit under alkylation conditions to provide an alkylation effluent comprising alkylbenzenes and benzene; separating the alkylbenzenes to provide the alkylbenzene product derived from the natural oil; and effecting heat exchange between the alkane stream, or the C9 - C14 stream, or the C14+ stream, or the first stream, or the second stream, or a combination thereof and the dehydrogenated stream, or the alkylation effluent stream, or both; or providing heat from deoxygenating the natural oil to the linear selective cracking unit, or the dehydrogenation unit, or the alkylation unit, or a combination thereof; or both of the above. One embodiment of the present invention is one, any or all of the foregoing embodiments in this paragraph to the first embodiment in this paragraph, further comprising removing contaminants from the first stream, or the C9 - C14 stream, or both before dehydrogenating the first stream to form a purified stream, wherein the contaminants comprise sulfur compounds, or nitrogen compounds, or phosphorus compounds, or aromatic compounds, or oxygenated compounds, or fatty acids, or fatty acid esters, or a combination thereof. One embodiment of the present invention is one, any or all of the foregoing embodiments in this paragraph to the first embodiment in this paragraph, wherein the C9 - C14 stream and the first stream are combined to form the purified stream before removing the contaminants from the first stream, or the C9 - C14 stream, or both. One embodiment of the present invention is one, any or all of the foregoing embodiments in this paragraph to the first embodiment in this paragraph, wherein the linear selective cracking catalyst comprises a ruthenium, platinum and nickel supported catalyst or a mixture thereof.One embodiment of the present invention is one, any, or all of the foregoing embodiments in this paragraph to the first embodiment in this paragraph, wherein the straight-chain 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. One embodiment of the present invention is one, any, or all of the foregoing embodiments in this paragraph to the first embodiment in this paragraph, wherein the alkylbenzene product comprises alkylbenzenes having C9 to C14 chains. One embodiment of the present invention is one, any, or all of the foregoing embodiments in this paragraph to the first embodiment in this paragraph, wherein the natural oil is selected from vegetable oils, animal fats, and triglyceride-containing oils.

[0087] A second embodiment of the present invention is a method for producing a linear alkylbenzene product derived from natural oils, the method comprising deoxygenating the natural oil to form an alkane stream comprising alkanes, wherein the natural oil is selected from vegetable oils, animal fats, and triglyceride-containing oils; separating the alkane stream to form a C9 to C14 stream comprising C9 to C14 alkanes and a C14+ stream comprising C14+ alkanes; subjecting the C14+ stream to linear-selective cracking in a separate linear-selective cracking unit in the presence of a linear-selective cracking catalyst under linear-selective cracking conditions to form a first stream comprising C9 to C14 normal alkanes or lightly branched alkanes and a second stream comprising isoalkanes; removing contaminants from the first stream, or the C9 to C14 stream, or both to form a purified stream, wherein the contaminants comprise sulfur compounds, or nitrogen compounds, or phosphorus compounds, or aromatic compounds, or oxygen-containing compounds, or fatty acids, or fatty acid esters, or combinations thereof; dehydrogenating the purified stream in a dehydrogenation unit to provide a dehydrogenated stream comprising monoolefins, diolefins, and aromatic compounds and a hydrogen stream comprising hydrogen; recycling at least a portion of the hydrogen stream to the linear-selective cracking unit; selectively hydrogenating the diolefins in the dehydrogenated stream to form additional monoolefins, and separating and removing the aromatic compounds from the monoolefins to form an aromatic compound stream comprising the aromatic compounds and a monoolefin stream comprising the monoolefins; alkylating benzene with the monoolefins in an alkylation unit under alkylation conditions to provide an alkylation effluent comprising alkylbenzenes and benzene; separating the alkylbenzenes to provide the alkylbenzene product derived from the natural oil; and exchanging heat between the alkane stream, or the C9 to C14 stream, or the C14+ stream, or the first stream, or the second stream, or combinations thereof and the dehydrogenated stream, or the alkylation effluent stream, or both; or providing heat from deoxygenating the natural oil to the linear-selective cracking unit, or the dehydrogenation unit, or the alkylation unit, or combinations thereof; or both of the above. One embodiment of the present invention is one, any, or all of the foregoing embodiments in this paragraph to the second embodiment in this paragraph, wherein the C9 to C14 stream and the first stream are combined to form the purified stream before removing the contaminants from the C9 to C14 stream and the first stream. One embodiment of the present invention is one, any, or all of the foregoing embodiments in this paragraph to the second embodiment in this paragraph, wherein the linear-selective cracking catalyst comprises a ruthenium, platinum, and nickel supported catalyst or a mixture thereof.One embodiment of the present invention is one, any, or all of the foregoing embodiments in this paragraph to the second embodiment in this paragraph, wherein the straight-chain 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. One embodiment of the present invention is one, any, or all of the foregoing embodiments in this paragraph to the second embodiment in this paragraph, wherein the alkylbenzene product contains alkylbenzenes having C9 to C14 chains.

[0088] Although no further detailed description is provided, it is believed that those skilled in the art can make the most of the present invention by using the foregoing description and can easily determine the basic features of the present invention without departing from the essence and scope of the present invention to make various changes and modifications thereto and adapt it to various uses and conditions. Therefore, the foregoing preferred specific embodiments should be construed as merely illustrative and in no way limiting the remainder of the disclosure, and are intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.

[0089] In the foregoing, all temperatures are shown in degrees Celsius and all parts and percentages are by weight unless otherwise indicated.

Claims

1. A heat and hydrogen integrated device for use in a process for regenerating an alkylbenzene product, characterized in that: The heat and hydrogen integration device in the process for regenerating alkylbenzene products includes: a deoxygenation unit in communication with a natural oil feed line and a first hydrogen line; A C9 to C14 pipeline and a C14+ pipeline, wherein the C9 to C14 pipeline and the C14+ pipeline are connected to a deoxygenation unit; a dehydrogenation unit connected to the purification line; a dehydrogenation pipeline and a second hydrogen pipeline; wherein the dehydrogenation pipeline and the second hydrogen pipeline are connected to the dehydrogenation unit; wherein the second hydrogen pipeline is also connected to the linear selective cracking unit; A selective hydrogenation unit connected to the dehydrogenation line a monoolefin line communicating with the selective hydrogenation unit; an alkylation unit in communication with the mono-olefin line; and An alkylation effluent line communicating with the alkylation unit.

2. The heat and hydrogen integrated device in the process for regenerating alkylbenzene products according to claim 1, characterized in that: The heat and hydrogen integration device for the process of regenerating alkylbenzene product further comprises: a benzene separation unit in communication with the alkylation effluent line, the linear alkylbenzene product being in the linear alkylbenzene product line; and Benzene recycle line; The linear alkylbenzene product pipeline and the benzene recycling pipeline are connected to the benzene separation unit.

3. The heat and hydrogen integrated device in the process for regenerating alkylbenzene products according to claim 2, characterized in that: The benzene recycle line is in communication with the alkylation unit.

4. The heat and hydrogen integrated device for the process for regenerating alkylbenzene products according to any one of claims 1 to 3, characterized in that: The linear selective cracking unit is connected to the C14+ pipeline; the heat and hydrogen integrated device in the method for regenerating alkylbenzene products further includes: a first pipeline in communication with a linear selective cracking unit; Second pipeline; The first pipeline and the second pipeline are connected to the linear selective cracking unit.

5. The heat and hydrogen integrated device in the process for regenerating alkylbenzene products according to any one of claims 1 to 3, characterized in that: The heat and hydrogen integration device for the process of regenerating alkylbenzene product further comprises: a purification unit in communication with the first pipeline; and A purification line is communicated with the purification unit.

6. The heat and hydrogen integrated device in the process for regenerating alkylbenzene products according to claim 4, characterized in that: The heat and hydrogen integration device for the process of regenerating alkylbenzene product further comprises: a purification unit in communication with the first pipeline; and A purification line is communicated with the purification unit.

7. The heat and hydrogen integrated device in the process for regenerating alkylbenzene products according to claim 5, characterized in that: The C9 to C14 pipeline is connected to the purification unit.

8. The heat and hydrogen integrated device in the process for regenerating alkylbenzene products according to claim 6, characterized in that: The C9 to C14 pipeline is connected to the purification unit.

9. The heat and hydrogen integrated device in the process for regenerating alkylbenzene products according to claim 1, characterized in that: The selective hydrogenation unit is in communication with the dehydrogenation line, and the heat and hydrogen integration device for the process of regenerating alkylbenzene products further comprises: An aromatics line and a light ends line, wherein the aromatics line and the light ends line are in communication with the selective hydrogenation unit.

10. The heat and hydrogen integrated device in the process for regenerating alkylbenzene products according to claim 1, characterized in that: The C9 to C14 line or the C14+ line or the first line or the second line or a combination thereof is connected to the dehydrogenation line or the alkylation effluent line or both through a heat exchanger.

11. The heat and hydrogen integrated device in the process for regenerating alkylbenzene products according to claim 1, characterized in that: The deoxygenation unit is connected with the linear selective cracking unit or the dehydrogenation unit or the alkylation unit or a combination thereof or both through a heat exchanger.

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