Apparatus for dehydrogenation of n-paraffins to olefins

Abstract

The present invention relates to an apparatus for dehydrogenation of n-paraffins to olefins. The paraffins are from renewable feedstocks including natural oils such as vegetable oils, animal fats, nut oils and / or seed oils, and triglyceride-containing oils. The utility model relates to a device for dehydrogenating n-alkane into olefin, which is used in production of linear alkylbenzene and is characterized by comprising a deoxidizing unit, a dehydrogenating unit, a dehydrogenating unit, a dehydrogenating unit, a dehydrogenating unit, a dehydrogenating unit and a dehydrogenating unit, 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; a first adsorbent bed containing a first adsorbent comprising an alkali metal cation or alkaline earth metal cation-exchanged X-zeolite, in communication with the first line; a purge line in communication with the first adsorbent bed; the dehydrogenation unit is communicated with the purification pipeline; and a dehydrogenation line communicating with the dehydrogenation unit.

Description

[0001] Priority declaration

[0002] This application claims priority to U.S. Provisional Patent Application Serial No. 63 / 504,884, filed on May 30, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The utility model relates to a device for dehydrogenating normal paraffin to olefin. Paraffin comes from renewable raw materials, which include natural oils, such as vegetable oils, animal fats, nut oils and / or seed oils, and oils containing triglycerides. Background Art

[0004] Linear alkylbenzene is a compound with the formula C6H5C n H 2n+1 An organic compound of the type described herein. While the alkyl carbon number "n" can have any practical value, detergent manufacturers desire alkylbenzenes to have alkyl carbon numbers in the range of 9 to 16, and preferably in the range of 9 to 14. These specific ranges are often desired when the alkylbenzenes are used as intermediates in the production of surfactants for detergents. Alkyl carbon numbers in the range of 9 to 14 meet the specifications of the detergent industry.

[0005] Because surfactants produced from alkylbenzenes are biodegradable, the production of alkylbenzenes has grown rapidly since their initial use in detergent production in the 1960s. The linearity of the paraffin chains in the alkylbenzenes is key to the biodegradability of the material and its effectiveness as a detergent. The primary factor in the final linearity of the alkylbenzene is the linearity of the paraffin component.

[0006] Although detergents prepared using alkylbenzene-based surfactants are biodegradable, previous methods for producing alkylbenzenes are not based on renewable sources. Specifically, alkylbenzenes are currently produced from kerosene refined from crude oil extracted from the earth. Due to growing environmental prejudice against fossil fuel mining and economic concerns about depleting fossil fuel deposits, alternative sources of biodegradable surfactants may be supported for use in detergents and other industries.

[0007] The C9 to C14 paraffins produced from raw materials based on vegetable oils or animal fats contain pollutants that can poison the dehydrogenation catalyst. Pollutants can also cause discoloration of linear alkylbenzenes and linear alkylbenzene sulfonates. Pollutants can include aromatic compounds, light oxygenates, fatty acids, fatty acid esters, etc. These pollutants need to be removed before dehydrogenating C9 to C14 paraffins.

[0008] Therefore, it is desirable to provide the C9 to C14 paraffins of the purification of the triglyceride and lipid acid of the renewable easy processing of vegetable oil, animal oil, nut oil and / or seed oil to the dehydrogenation unit.The composition of palm kernel oil, coconut oil and babassu oil is higher in the expected range of C9-C14 normal paraffins, which is consistent with the required alkyl carbon number range of detergent industry.This type of renewable source also has a large amount of nC16 to nC18 feeds, and it is desirable that those feeds are converted into nC9 to nC14 feeds with high single pass yield.These nC9 to nC14 intermediate products can be used for the final preparation of the detergent of linear alkyl benzene type by other processing steps.It is further desirable that the gained nC9 to nC14 paraffins are the straight chain products with minimum branched isomer products. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Figure 1 is a schematic diagram of one embodiment of a method for producing alkylbenzenes from triglycerides according to the present invention.

[0010] Figure 2 is a graph of normal paraffin mass % versus deoxygenation temperature according to Example 2. Utility Model Content

[0011] The utility model includes the following technical solutions:

[0012] 1. A device for dehydrogenating normal paraffins to olefins, used in the production of linear alkylbenzenes, characterized in that the device for dehydrogenating normal paraffins to olefins comprises:

[0013] a deoxygenation unit in communication with the triglyceride feed line;

[0014] 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;

[0015] a first adsorbent bed containing a first adsorbent comprising an alkali metal cation or alkaline earth metal cation exchange X-zeolite in communication with the first line;

[0016] a purge line in communication with the first adsorbent bed;

[0017] a dehydrogenation unit, which is in communication with the purification line;

[0018] A dehydrogenation pipeline is communicated with the dehydrogenation unit.

[0019] 2. The device for dehydrogenating normal paraffins to olefins according to item 1, characterized in that the device for dehydrogenating normal paraffins to olefins further comprises:

[0020] a selective hydrogenation unit in communication with the dehydrogenation line, and

[0021] A mono-olefin line is connected to the selective hydrogenation unit.

[0022] 3. The device for dehydrogenating normal paraffins to olefins according to item 1 or 2, characterized in that the device for dehydrogenating normal paraffins to olefins further comprises:

[0023] an alkylation unit in communication with the mono-olefin line; and

[0024] An alkylation effluent line communicating with the alkylation unit.

[0025] 4. The device for dehydrogenating normal paraffins to olefins according to item 1 or 2, characterized in that the device for dehydrogenating normal paraffins to olefins further comprises:

[0026] a benzene separation unit in communication with the alkylation effluent line; and

[0027] a linear alkylbenzene product line; and

[0028] Benzene recycle pipeline;

[0029] The linear alkylbenzene product pipeline and the benzene recycling pipeline are connected to the benzene separation unit.

[0030] 5. The device for dehydrogenating normal paraffins to olefins according to item 3, characterized in that the device for dehydrogenating normal paraffins to olefins further comprises:

[0031] a benzene separation unit in communication with the alkylation effluent line; and

[0032] a linear alkylbenzene product line; and

[0033] Benzene recycle pipeline;

[0034] The linear alkylbenzene product pipeline and the benzene recycling pipeline are connected to the benzene separation unit.

[0035] 6. The device for dehydrogenating normal paraffins to olefins according to item 1 or 2, characterized in that the device for dehydrogenating normal paraffins to olefins further comprises:

[0036] a linear selective cracking unit in communication with the C14+ pipeline;

[0037] A first pipeline communicating with a linear selective cracking unit; and

[0038] Second pipeline;

[0039] The first pipeline and the second pipeline are connected to the linear selective cracking unit.

[0040] 7. The device for dehydrogenating normal paraffins to olefins according to item 3, characterized in that the device for dehydrogenating normal paraffins to olefins further comprises:

[0041] a linear selective cracking unit in communication with the C14+ pipeline;

[0042] A first pipeline communicating with a linear selective cracking unit; and

[0043] Second pipeline;

[0044] The first pipeline and the second pipeline are connected to the linear selective cracking unit.

[0045] 8. The device for dehydrogenating normal paraffins to olefins according to item 4, characterized in that the device for dehydrogenating normal paraffins to olefins further comprises:

[0046] a linear selective cracking unit in communication with the C14+ pipeline;

[0047] A first pipeline communicating with a linear selective cracking unit; and

[0048] Second pipeline;

[0049] The first pipeline and the second pipeline are connected to the linear selective cracking unit.

[0050] 9. The device for dehydrogenating normal paraffins to olefins according to item 5, characterized in that the device for dehydrogenating normal paraffins to olefins further comprises:

[0051] a linear selective cracking unit in communication with the C14+ pipeline;

[0052] A first pipeline communicating with a linear selective cracking unit; and

[0053] Second pipeline;

[0054] The first pipeline and the second pipeline are connected to the linear selective cracking unit.

[0055] 10. The device for dehydrogenating normal paraffins to olefins according to item 1, characterized in that the device for dehydrogenating normal paraffins to olefins further comprises:

[0056] An optional second adsorbent bed containing a second adsorbent comprising 5A zeolite.

[0057] 11. The device for dehydrogenating normal paraffins to olefins according to item 1, characterized in that the device for dehydrogenating normal paraffins to olefins further comprises:

[0058] An optional third adsorbent bed containing a third adsorbent comprising 13X zeolite, 5A zeolite, alumina zeolite, or a combination thereof.

[0059] 12. The device for dehydrogenating normal paraffins to olefins according to item 1 or 2, characterized in that the device for dehydrogenating normal paraffins to olefins further comprises:

[0060] The adsorbent bed is regenerated at a predetermined time to remove at least a portion of the oxygenates or aromatic compounds, or both, adsorbed onto the adsorbent.

[0061] 13. The device for dehydrogenating normal paraffins to olefins according to item 3, characterized in that the device for dehydrogenating normal paraffins to olefins further comprises:

[0062] The adsorbent bed is regenerated at a predetermined time to remove at least a portion of the oxygenates or aromatic compounds, or both, adsorbed onto the adsorbent. DETAILED DESCRIPTION

[0063] The present invention relates to a process for dehydrogenating normal paraffins to olefins. The paraffins are derived from renewable raw materials, including natural oils such as vegetable oils, animal fats, nut oils and / or seed oils, and triglyceride-containing oils. A purification process for a renewable bio-paraffin stream comprises passing the stream through one or more adsorbent beds comprising an adsorbent.

[0064] Natural oils are not based on kerosene or other fossil fuels. Natural oils include those derived from plant or algae materials or animal fats, nuts and / or seed oils, and triglyceride-containing oils, and are generally referred to as renewable oils. Natural oils typically contain triglycerides, free fatty acids, or a combination thereof. Natural oils include, but are not limited to, Arachis oil (peanut oil; groundnut oil), babassu oil, coconut oil, cottonseed oil, grapeseed oil, maize oil (corn oil), mustard oil, palm kernel oil, palm oil, palm olein (a liquid fraction obtained by fractionating palm oil), palm stearin (a high melting point fraction obtained by fractionating 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 safflower oil (high oleic acid safflower oil; high oleic acid safflower oil). acidcarthamus oil); high oleic acid safflower oil(high oleic acid kurdee oil)), sesame oil(sesame oil; gingelly oil; benne oil; bene oil; till oil; tilllie oil), soybean oil(soya bean oil)(soybean oil), sunflowerseed oil(sunflower oil) and high oleic sunflowerseed oil(sunflowerseed oil–high oleic acid)(high oleic acid sunflower oil).

[0065] The feed stream derived from a natural oil comprises normal paraffins, iso-paraffins, olefins, oxygenates and up to 10 wt % aromatics.

[0066] Pollutants in the feed stream can include oxygenates and / or aromatic compounds and / or fatty acids and fatty acid esters. Alkali metal cations or alkaline earth metal cation exchange X-zeolites can be used to remove at least a portion of oxygenates, aromatic compounds and fatty acids and fatty acid esters in the paraffin stream derived from natural oil. Suitable adsorbents for removing oxygenates and aromatic compounds include but are not limited to alkali metal cations or alkaline earth metal cation exchange X-zeolites.

[0067] After removal of contaminants, the treated stream contains no more than 6000 ppm of aromatic compounds and no more than 100 ppm of oxygenates.

[0068] A second adsorbent bed may optionally be included to further reduce the levels of oxygenates, aromatic compounds, and fatty acids and fatty acid esters in the treated stream.The second adsorbent includes, but is not limited to, 5A zeolite.

[0069] The first adsorbent bed and / or the second adsorbent bed may be regenerated at a predetermined time to remove at least a portion of the oxygenates or aromatic compounds or both adsorbed onto the first adsorbent and / or the second adsorbent.

[0070] There may be one or more first adsorbent beds and one or more second adsorbent beds.

[0071] The paraffin stream from the renewable raw material comprising vegetable oil and animal fat can also contain other pollutants, such as sulfur compounds, or nitrogen compounds, or phosphorus compounds, or combinations thereof. These pollutants can be removed by passing the treated stream through the third adsorbent bed containing the third adsorbent. The third adsorbent can include but is not limited to 13X zeolite, 5A zeolite, alumina-zeolite or combinations thereof.

[0072] After the feed stream derived from the natural oil has passed through the first adsorbent bed and the optional second and / or third adsorbent beds, the treated stream is dehydrogenated to convert at least a portion of the paraffins in the treated stream into olefins. The dehydrogenated stream comprises mono-olefins, di-olefins, and aromatic compounds.

[0073] The pollutant removal method can be incorporated into a method for preparing alkylbenzenes from natural oils. The method includes deoxygenating natural oils to form paraffins. Paraffins are separated (by fractionation or distillation, etc.) into a C9 to C14 stream containing C9 to C14 paraffins and a C14+ stream containing C14+ paraffins. The C14+ stream is sent to a separate straight chain selective cracking unit to crack the C14+ paraffins; the cracked paraffins are fractionated into a first stream containing C9 to C14 normal paraffins and lightly branched paraffins and a second stream containing isoparaffins. Contaminants are removed from the C9 to C14 stream and the first stream, the contaminants including but not limited to oxygenates and / or aromatic compounds and / or fatty acids and fatty acid esters, and / or sulfur compounds, and / or nitrogen compounds, and / or phosphorus compounds, or combinations thereof. The purified stream is dehydrogenated to form olefins, diolefins and aromatic compounds. The dienes 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 olefins, and the alkylation effluent comprises alkylbenzenes and benzene. The alkylbenzenes are then separated.

[0074] In order to limit catalyst deactivation, the feed is treated to remove sulfur contaminants before hydrodeoxygenation. Otherwise, sulfur accumulates on the catalyst and causes deactivation. High temperature hydrotreatment has been shown to restore some of the lost activity. The degree of hydrodeoxygenation can affect the selectivity for each normal paraffin in the range of 9 to 14 carbons. A large degree of hydrodeoxygenation can make the hydrodeoxygenation composition largely biased towards n-dodecane and n-decane to the disadvantage of n-undecane and n-tridecane. A small degree of hydrodeoxygenation can make the hydrodeoxygenation composition biased towards n-undecane and n-tridecane to the disadvantage of n-dodecane and n-decane.

[0075] The hydrodeoxygenation reactor temperature is kept low, less than 343°C (650°F) for typical biorenewable feedstocks and less than 304°C (580°F) for feedstocks with higher free fatty acid (FFA) concentrations, to avoid polymerization of olefins present in the FFAs. Typically, a hydrodeoxygenation reactor pressure of 700 kPa (100 psig) to 21 MPa (3000 psig) is suitable.

[0076] The linearity of alkylbenzene product depends mainly on the linearity of the paraffin 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 paraffin feed drops by 5%-7% by mass. Therefore, paraffins with 97% by mass linearity (or alternatively 3% by mass isoparaffins) will produce an alkylbenzene product with a linearity of about 90%-92% by mass. This sets a requirement for a linearity of 5%-7% by mass of paraffins higher than the specification of the alkylbenzene product. Typically, the linearity of the paraffin product is measured by UOP 621, UOP411 or UOP732 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.

[0077] In the accompanying drawing, an exemplary system 100 for producing an alkylbenzene product from a particular triglyceride feed is illustrated.

[0078] In the illustrated embodiment, the selected triglyceride feed 105 is delivered to a deoxygenation unit 110, which also receives a hydrogen feed (not shown). In the deoxygenation unit 110, the fatty acids in the selected triglyceride feed 105 are deoxygenated and converted into normal paraffins. Triglyceride is formed by three usually different fatty acid molecules in structure, and the fatty acid molecules are bonded together by glycerol bridges. The glycerol molecule includes three hydroxyl groups (HO--) and each fatty acid molecule has a carboxyl group (COOH). In triglyceride, the hydroxyl group of glycerol engages with the carboxyl group of fatty acid to form an ester bond. Therefore, during deoxygenation, fatty acids are released from the triglyceride structure and converted into normal paraffins. Glycerol is converted into propane, and the oxygen in the hydroxyl and carboxyl groups is converted into water, carbon dioxide or carbon monoxide. The deoxygenation reaction of fatty acid and triglyceride is shown as:

[0079]

[0080] During the deoxygenation reaction, the resulting alkane chain R n The length of will change a value according to definite reaction pathway.It should be understood that deoxygenation comprises at least one of hydrodeoxygenation, decarboxylation and decarbonylation reaction 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.

[0081] The operating conditions of the deoxygenation unit include pressures in the range of 250 psig to 800 psig (1724 kPa to 5516 kPa) and temperatures in the range of 274°C to 371°C (525°F to 700°F) in one embodiment, 274°C to 338°C (525°F to 640°F) in another embodiment, and 274°C to 310°C (525°F to 590°F) in another embodiment. The catalyst may 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 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 -3.0hr -1 LHSV. Conditions are selected to minimize cracking or isomerization of paraffins.

[0082] The deoxygenated product containing normal paraffins, 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 deoxygenated product. A naphtha stream (not shown) of paraffins with carbon chain lengths of C5 to C9 can also be formed.

[0083] The C14+ stream 120 is sent to a linear selective cracking unit 125 where it is selectively cracked to form a first stream 130 comprising C9 to C14 normal paraffins or lightly branched paraffins and a second stream 135 comprising 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 before the C9 to C14 due to their higher absorption energy.

[0084] Selecting specific metal catalysts, including noble metals (such as ruthenium and platinum) and nickel, can produce n-paraffins with 9 to 14 carbons in much higher yields than previous methods. Suitable catalysts include, but are not limited to, Ru / ZrO2, Pt-Al2O3, Ni-alumina or NiOx / clay. Using these catalysts, C14+ streams can produce straight chain cracking products without significant amounts of branched isomers.

[0085] Among the preferred catalysts, the Ru catalyst exhibits much higher activity and single pass nC9 to nC14 yield than the other catalysts. It also produces very small amounts of methane and isomerized products under optimized reaction conditions. It has been found to be the best catalyst for this type of chemical conversion process. The Pt-Al2O3 catalyst can produce even lower methane yields than the Ru-based catalysts, with slightly lower linear product yields.

[0086] The C9 to C14 stream 115 from the deoxygenation unit 110 and the first stream 130 from the linear selective cracking unit 125 are sent to a purification unit 140, as described herein. The purification unit 140 removes contaminants from the C9 to C14 paraffins in the C9 to C14 stream 115 and the first stream 130. The contaminants include, but are not limited to, oxygenates and / or aromatic compounds and / or fatty acids and fatty acid esters, and / or sulfur compounds, and / or nitrogen compounds, and / or phosphorus compounds, or combinations thereof.

[0087] The purified stream 145 is sent to a dehydrogenation unit 150 where hydrogen is removed to produce a dehydrogenated stream 155 comprising monoolefins, diolefins and aromatic compounds. In the dehydrogenation unit 150, paraffins are dehydrogenated to monoolefins having the same carbon number as the paraffins. Typically, dehydrogenation is performed by known catalytic processes, such as the commercially popular Pacol process. Diolefins (i.e., dienes) and aromatic compounds are also produced as undesirable results of the dehydrogenation reaction, as shown in the following reaction formula:

[0088] Formation of monoolefins: C x H 2x+2 →C x H 2x +H2

[0089] Formation of dienes: C x H 2x →C x H 2x-2 +H2

[0090] Formation of aromatic compounds: C x H 2x-2 →C x H 2x-6 +2H2

[0091] The operating conditions of the dehydrogenation unit 150 include space velocities of 5 LHSV to 50 LHSV and 20 LHSV to 32 LHSV; pressures 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); temperatures of 400° C. to 500° C. and 440° C. to 490° C., and molar ratios of hydrogen to hydrocarbon of 1 to 12 and 3 to 7. An example of a suitable catalyst is a Pt / alumina catalyst in which the platinum is attenuated with an attenuator metal. Another suitable catalyst is described in U.S. Pat. No. 6,177,381, which is hereby incorporated by reference in its entirety. The dehydrogenation unit 150 can be operated dry or with water injection of up to 2000 mass ppm water. The hydrogen can be recycled upstream of the deoxygenation unit.

[0092] 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 monoolefins. As a result, the monoolefin stream 170 has an increased monoolefin concentration compared to the dehydrogenated stream 155. The aromatics are separated and removed as an aromatics stream 165. If desired, a light ends stream 167 containing any light components (such as butane, propane, ethane, and methane) produced by cracking or other reactions during upstream processing may also be removed.

[0093] A monoolefin stream 170 comprising monoolefins is sent to an alkylation unit 175 along with a benzene stream 180. Benzene is alkylated with the monoolefins to form alkylbenzenes. The alkylation unit 175 contains a catalyst, such as a solid acid catalyst, that supports the alkylation of benzene with the monoolefins. Fluoridated silica-alumina, hydrogen fluoride (HF), aluminum chloride (AlCl3), zeolites, and ionic liquid catalysts are examples of the main catalysts used commercially 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 (LABs), are formed according to the following reaction:

[0094] C6H6+C x H 2x →C6H5C x H 2x+1

[0095] 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.

[0096] Excess benzene is supplied to the alkylation unit 175 to achieve the desired high degree of alkylation. Therefore, the alkylation effluent 185 leaving the alkylation unit 175 contains alkylbenzenes and unreacted benzene. In addition, the alkylation effluent 185 may also include some unreacted paraffins. The alkylation effluent 185 is passed into a benzene separation unit 190, such as a fractionating tower, for separating unreacted benzene and paraffins from the alkylation effluent 185. 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 a desired benzene / olefin ratio (e.g., 1-50) to reduce the volume of fresh benzene required. Fresh benzene demand (i.e., clean benzene) is determined by the clean olefins entering the alkylation unit. Paraffin stream 200 may also be separated and recycled to the dehydrogenation unit 150.

[0097] As a result of the post-alkylation separation process, a linear alkylbenzene product 205 is separated. It should be noted that in order to separate the linear alkylbenzene product 205, such separation methods are not necessary in all embodiments.

[0098] The linear alkylbenzene product 205 is a linear alkylbenzene product comprising: n H 2n+1 wherein n is from 9 to 14. In some embodiments, at least 80 mass %, or at least 90 mass % of the alkylbenzene has a linear alkyl group.

[0099] The linear alkylbenzene may be sulfonated to provide a linear alkylbenzene sulfonate product comprising: n H 2n+ An alkylbenzene sulfonate compound of 1C6H4SO3H, wherein n is 10 to 14, or wherein n is 11 to 13.

[0100] The term "tower" means one or more distillation columns for separating one or more components with different volatilities. Unless otherwise specified, each tower includes a condenser at the top of the tower for condensing a portion of the overhead stream and refluxing it back to the top of the tower, and a reboiler at the bottom of the tower for vaporizing a portion of the bottom stream and sending it back to the bottom of the tower. The feed to the tower can be preheated. The top pressure is the pressure of the overhead vapor at the vapor outlet of the tower. The bottom temperature is the liquid bottom outlet temperature. Unless otherwise specified, the top line and the bottom line refer to the net line from the tower downstream of any reflux or reboiled takeout to the tower. The stripping tower can omit the reboiler at the bottom of the tower, and instead provide the heating requirements and separation power for the liquefied inert medium (such as steam).

[0101] As used herein, the term "component-rich stream" or "component stream" refers to a stream coming out of a container having a greater component concentration than the feed to the container. As used herein, the term "component-depleted stream" refers to a lean stream coming out of a container having a smaller component concentration than the feed to the container.

[0102] Example

[0103] Example 1

[0104] The coconut oil feed is deoxygenated to form paraffins, dehydrogenated to form mono-olefins, and benzene is alkylated with the mono-olefins to form an alkylbenzene product having a modern carbon content of 62 mass 96 modern carbon as determined by ASTM D6866 compared to a theoretical modern carbon content of 66.4 mass %, a bromine number of 1 g Br per gram of sample as determined by UOP Standard Test Method 304, and a linearity of 92 mass %.

[0105] Example 2

[0106] The oil was deoxygenated using the catalyst at a pressure of 480 psig H, a bio-oil ratio of 7200 scf / B, and a LHSV of 1 hr'. During the 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 linearity in the final product to the reaction temperature. The results are Figure 2 , which is a graph of the concentration of C10-C13 normal paraffins (in mass %) versus the reaction temperature. Figure 2 It is clearly shown that as the deoxygenation reaction temperature increases, the concentration of linear alkanes decreases. Controlling the temperature below 404°C (760°F) produces greater than 92 mass % linear alkanes.

[0107] Note: Examples 1 and 2 were previously included as Examples 3 and 4 in US Patent 9,079,814.

[0108] Specific implementation plan

[0109] While the following is described in conjunction with specific embodiments, it should be understood that this description is intended to illustrate and not to limit the scope of the foregoing description and the appended claims.

[0110] The first embodiment of the present invention is a method for dehydrogenating normal paraffins to olefins, the method comprising passing a feed stream derived from a natural oil comprising C9 to C14 normal paraffins, isoparaffins, olefins, oxygenates, and up to 10 wt% aromatics through a first adsorbent bed containing a first adsorbent comprising an alkali metal cation or alkaline earth metal cation exchange X-zeolite, wherein the adsorbent removes at least a portion of the oxygenates and aromatics from the paraffin stream by adsorption to form a treated stream; and dehydrogenating the treated stream to convert at least a portion of the treated stream into olefins and provide a dehydrogenated stream comprising monoolefins, diolefins, and aromatics. An embodiment of the present invention is one, any one, or all of the previous embodiments of this paragraph to the first embodiment of this paragraph, further comprising regenerating the adsorbent bed at a predetermined time to remove at least a portion of the oxygenates or aromatics or both adsorbed on the adsorbent. One embodiment of the invention is one, any one, or all of the previous embodiments in this paragraph to the first embodiment in this paragraph, further comprising: passing the treated stream through a second adsorbent bed containing a second adsorbent comprising 5A zeolite to remove additional oxygenates and aromatic compounds, thereby forming a second treated stream. One embodiment of the invention is one, any one, or all of the previous embodiments in this paragraph to the first embodiment in this paragraph, further comprising regenerating the second adsorbent bed at a predetermined time to remove at least a portion of the oxygenates or aromatic compounds or both adsorbed to the second adsorbent. One embodiment of the present invention is one, any one or all of the previous embodiments of this paragraph to the first embodiment of this paragraph, wherein the feed stream is formed by deoxygenating a natural oil to form a paraffin stream comprising C9 to C28 paraffins; the paraffin stream is subjected to linear selective cracking in the presence of a linear selective cracking catalyst and under linear selective cracking conditions in a linear selective cracking unit to form a first stream comprising C9 to C14 normal paraffins or lightly branched paraffins and a second stream comprising isoparaffins. One embodiment of the present invention is one, any one or all of the previous embodiments of this paragraph to the first embodiment of this paragraph, further comprising removing contaminants from the treated stream in a third adsorbent bed comprising a third adsorbent to form a purified stream before dehydrogenating the treated stream, wherein the contaminants comprise sulfur compounds, or nitrogen compounds, or phosphorus compounds, or combinations thereof, wherein the third adsorbent comprises 13X zeolite, 5A zeolite, alumina-zeolite, or combinations thereof.One embodiment of the present invention is one, any one or all of the previous embodiments in this paragraph to the first embodiment in this paragraph, further comprising selectively hydrogenating the dienes 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 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. One embodiment of the present invention is one, any one or all of the previous embodiments in this paragraph to the first embodiment in this paragraph, wherein the treated stream contains no more than 6000 ppm of the aromatic compounds and no more than 100 ppm of the oxygen-containing compounds.

[0111] A second embodiment of the present invention is a process for dehydrogenating normal paraffins to olefins, the process comprising passing a feed stream comprising normal paraffins, isoparaffins, olefins, up to 10 wt% aromatics and oxygenates through an adsorbent bed containing an adsorbent comprising an alkali metal cation or alkaline earth metal cation exchange X-zeolite, wherein the adsorbent removes at least a portion of the oxygenates and the aromatics from the paraffin stream by adsorption to form a treated stream; removing contaminants from the treated stream in a third adsorbent bed containing a third adsorbent to form a purified stream, wherein the contaminants comprise sulfur compounds, or nitrogen compounds, or phosphorus compounds, or combinations thereof, wherein the adsorbent comprises 13X zeolite, 5A zeolite, alumina-zeolite, or combinations thereof; and dehydrogenating the purified stream to convert at least a portion of the purified stream into olefins and provide a dehydrogenated stream comprising mono-olefins, di-olefins and aromatics; regenerating the adsorbent bed at a predetermined time to remove at least a portion of the oxygenates or aromatics or both adsorbed on the adsorbent. One embodiment of the invention is one, any one, or all of the previous embodiments in this paragraph to the second embodiment in this paragraph, further comprising: passing the treated stream through a second adsorbent bed containing a second adsorbent comprising 5A zeolite to remove additional oxygenates and aromatic compounds to form a second treated stream before removing the contaminants in the third adsorbent bed. One embodiment of the invention is one, any one, or all of the previous embodiments in this paragraph to the second embodiment in this paragraph, further comprising regenerating the second adsorbent bed at a predetermined time to remove at least a portion of the oxygenates or aromatic compounds or both adsorbed to the second adsorbent. One embodiment of the present invention is one, any one or all of the previous embodiments in this paragraph to the second embodiment in this paragraph, wherein the feed stream is formed by deoxygenating a natural oil to form a paraffin stream comprising C9 to C28 paraffins; the paraffin stream is linearly selectively cracked in a linear selective cracking unit under linear selective cracking conditions in the presence of a linear selective cracking catalyst to form a first stream comprising C9 to C14 normal paraffins or lightly branched paraffins and a second stream comprising isoparaffins. One embodiment of the invention is one, any one or all of the prior embodiments in this paragraph to the second embodiment in this paragraph, further comprising selectively hydrogenating the dienes 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 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.An embodiment of the invention is one, any or all of prior embodiments in this paragraph through the second embodiment in this paragraph wherein the treated stream comprises no more than 6000 ppm of the aromatic compounds and no more than 100 ppm of the oxygenates.

[0112] A third embodiment of the present invention is a method for dehydrogenating normal paraffins to olefins, the method comprising: deoxygenating a natural oil to form a paraffin stream comprising C9 to C28 paraffins; subjecting the paraffin stream to linear selective cracking in the presence of a linear selective cracking catalyst and under linear selective cracking conditions in a linear selective cracking unit to form a first stream comprising C9 to C14 normal paraffins or lightly branched paraffins and a second stream comprising isoparaffins; passing the first stream comprising normal paraffins, isoparaffins, olefins, oxygenates and up to 10 wt % of aromatic compounds through a first adsorbent bed comprising a first adsorbent comprising an alkali metal cation or alkaline earth metal cation exchange X-zeolite, wherein the adsorbent removes at least a portion of the oxygenates and the aromatic compounds from the first stream by adsorption to form a treated stream; before dehydrogenating the treated stream, subjecting the first stream to a third adsorbent; The method further comprises: removing contaminants from the treated stream in a third adsorbent bed, the third adsorbent bed comprising a third adsorbent to form a purified stream, wherein the contaminants comprise sulfur compounds, or nitrogen compounds, or phosphorus compounds, or combinations thereof, wherein the third adsorbent comprises 13X zeolite, 5A zeolite, alumina-zeolite, or combinations thereof, dehydrogenating the purified stream to convert at least a portion of the purified stream into olefins and providing a dehydrogenated stream comprising mono-olefins, di-olefins, and aromatic compounds; selectively hydrogenating the di-olefins in the dehydrogenated stream to form additional mono-olefins, and separating and removing the aromatic compounds from the mono-olefins to form an aromatics stream comprising the 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 separating the alkylbenzenes to provide the alkylbenzene product derived from the natural oil. One embodiment of the present invention is one, any one or all of the previous embodiments in this paragraph to the third embodiment in this paragraph, and further includes: regenerating the first adsorbent bed at a predetermined time to remove at least a portion of the oxygen-containing compounds or aromatic compounds or both adsorbed on the first adsorbent. One embodiment of the present invention is one, any one or all of the previous embodiments in this paragraph to the third embodiment in this paragraph, and further includes: passing the treated stream through a second adsorbent bed containing a second adsorbent comprising 5A zeolite to remove additional oxygen-containing compounds and aromatic compounds, thereby forming a second treated stream. One embodiment of the present invention is one, any one or all of the previous embodiments in this paragraph to the third embodiment in this paragraph, and further includes: regenerating the second adsorbent bed at a predetermined time to remove at least a portion of the oxygen-containing compounds or aromatic compounds or both adsorbed on the second adsorbent.An embodiment of the invention is one, any or all of prior embodiments in this paragraph through the third embodiment in this paragraph wherein the treated stream comprises no more than 6000 ppm of the aromatic compounds and no more than 100 ppm of the oxygenates.

[0113] Although there is no further detailed description, it is believed that those skilled in the art can utilize the present invention to the greatest extent by using the foregoing description and can easily determine the essential characteristics of the present invention without departing from the spirit and scope of the present invention to make various changes and modifications of the present invention and adapt it to various usages and conditions. Therefore, the aforementioned preferred specific embodiments should be understood as merely illustrative and not to limit the rest of the present disclosure in any way, and are intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.

[0114] In the foregoing, all temperatures are set forth in degrees Celsius and all parts and percentages are by weight unless otherwise indicated.

Claims

1. A device for dehydrogenating normal paraffins to olefins, used in the production of linear alkylbenzenes, characterized in that: The device for dehydrogenating normal paraffins to olefins comprises: a deoxygenation unit in communication with the triglyceride feed 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 first adsorbent bed containing a first adsorbent comprising an alkali metal cation or alkaline earth metal cation exchanged X-zeolite in communication with the first line; a purge line in communication with the first adsorbent bed; a dehydrogenation unit connected to the purification line; A dehydrogenation pipeline is communicated with the dehydrogenation unit.

2. The device for dehydrogenating normal paraffins to olefins according to claim 1, characterized in that: The device for dehydrogenating normal paraffins to olefins further comprises: a selective hydrogenation unit in communication with the dehydrogenation line, and A mono-olefin line is connected to the selective hydrogenation unit.

3. The device for dehydrogenating normal paraffins to olefins according to claim 1 or 2, characterized in that: The device for dehydrogenating normal paraffins to olefins further comprises: an alkylation unit in communication with the mono-olefin line; and An alkylation effluent line communicating with the alkylation unit.

4. The device for dehydrogenating normal paraffins to olefins according to claim 1 or 2, characterized in that: The device for dehydrogenating normal paraffins to olefins further comprises: a benzene separation unit in communication with the alkylation effluent line; and a linear alkylbenzene product line; and Benzene recycle pipeline; The linear alkylbenzene product pipeline and the benzene recycling pipeline are connected to the benzene separation unit.

5. The device for dehydrogenating normal paraffins to olefins according to claim 3, characterized in that: The device for dehydrogenating normal paraffins to olefins further comprises: a benzene separation unit in communication with the alkylation effluent line; and a linear alkylbenzene product line; and Benzene recycle pipeline; The linear alkylbenzene product pipeline and the benzene recycling pipeline are connected to the benzene separation unit.

6. The device for dehydrogenating normal paraffins to olefins according to claim 1 or 2, characterized in that: The device for dehydrogenating normal paraffins to olefins further comprises: a linear selective cracking unit in communication with the C14+ pipeline; A first pipeline communicating with a linear selective cracking unit; and Second pipeline; The first pipeline and the second pipeline are connected to the linear selective cracking unit.

7. The device for dehydrogenating normal paraffins to olefins according to claim 3, characterized in that: The device for dehydrogenating normal paraffins to olefins further comprises: a linear selective cracking unit in communication with the C14+ pipeline; A first pipeline communicating with a linear selective cracking unit; and Second pipeline; The first pipeline and the second pipeline are connected to the linear selective cracking unit.

8. The device for dehydrogenating normal paraffins to olefins according to claim 4, characterized in that: The device for dehydrogenating normal paraffins to olefins further comprises: a linear selective cracking unit in communication with the C14+ pipeline; A first pipeline communicating with a linear selective cracking unit; and Second pipeline; The first pipeline and the second pipeline are connected to the linear selective cracking unit.

9. The device for dehydrogenating normal paraffins to olefins according to claim 5, characterized in that: The device for dehydrogenating normal paraffins to olefins further comprises: a linear selective cracking unit in communication with the C14+ pipeline; A first pipeline communicating with a linear selective cracking unit; and Second pipeline; The first pipeline and the second pipeline are connected to the linear selective cracking unit.

10. The device for dehydrogenating normal paraffins to olefins according to claim 1, characterized in that: The device for dehydrogenating normal paraffins to olefins further comprises: An optional second adsorbent bed containing a second adsorbent comprising 5A zeolite.

11. The device for dehydrogenating normal paraffins to olefins according to claim 1, characterized in that: The device for dehydrogenating normal paraffins to olefins further comprises: An optional third adsorbent bed containing a third adsorbent comprising 13X zeolite, 5A zeolite, alumina zeolite, or a combination thereof.

12. The device for dehydrogenating normal paraffins to olefins according to claim 1 or 2, characterized in that: The device for dehydrogenating normal paraffins to olefins further comprises: The adsorbent bed is regenerated at a predetermined time to remove at least a portion of the oxygenates or aromatic compounds, or both, adsorbed onto the adsorbent.

13. The device for dehydrogenating normal paraffins to olefins according to claim 3, characterized in that: The device for dehydrogenating normal paraffins to olefins further comprises: The adsorbent bed is regenerated at a predetermined time to remove at least a portion of the oxygenates or aromatic compounds, or both, adsorbed onto the adsorbent.

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