Device for producing monomethyl alkylbenzene product

Abstract

The utility model relates to a device for producing a monomethyl alkylbenzene product, which is characterized by comprising a deoxidation unit, a natural oil feeding pipeline, a gas-liquid separation unit and a gas-liquid separation unit, a C9 to C28 line in communication with the deoxidation unit; the isomerization unit is communicated with the first pipeline; an isomerization line in communication with the isomerization unit, the isomerization line comprising a monomethyl paraffin; the dehydrogenation unit is communicated with the isomerization pipeline; a dehydrogenation line communicating with the dehydrogenation unit; a selective hydrogenation unit in communication with the dehydrogenation line; 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. The utility model provides a material flow rich in monomethyl paraffin relative to normal paraffin, wherein the material flow can be used for producing monomethyl alkylbenzene.

Description

[0001] Priority Claim

[0002] This application claims the priority of U.S. Provisional Patent Application Serial No. 63 / 504,881, filed on May 30, 2023, and U.S. Patent Application Serial No. 18 / 500,166, 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 a stream rich in monomethylalkylbenzenes from natural oils such as vegetable oils, animal oils, nut oils, and / or seed oils, and oils containing triglycerides. The apparatus provides a stream rich in monomethylalkanes relative to n-alkanes, which stream can be used to produce monomethylalkylbenzenes. Background Art

[0004] Linear alkylbenzenes are organic compounds having the formula C 6 H 5 C n H 2n+1 While the alkyl carbon number "n" can have any practical value, detergent manufacturers desire alkylbenzenes having 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 alkylbenzenes are used as intermediates 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 alkylbenzenes are biodegradable, the production of alkylbenzenes has grown rapidly since its initial use in detergent production in the 1960s. The straight-chainness of the alkane chains in alkylbenzenes is key to the biodegradability of the material and its effectiveness as a detergent. The main factor in the ultimate straight-chainness of alkylbenzenes is the straight-chainness of the alkane component.

[0006] While detergents made with alkylbenzene-based surfactants are biodegradable, the methods previously used to produce alkylbenzenes are not based on renewable sources. Specifically, alkylbenzenes are 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] Some detergent manufacturers serve specialized markets based on alkylbenzenes that are rich in monomethylalkylbenzenes (MMAB) relative to more typical linear alkylbenzenes (LAB).

[0008] Accordingly, it is desirable to provide MMAB made from bio-renewable sources rather than extracted from the earth. Additionally, it is desirable to provide renewable linear alkylbenzenes from vegetable oils, animal oils, nut oils, and / or seed oils to reduce the carbon intensity relative to fossil-based monomethylalkane sources. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0010] Figure 2 is a graph of n-alkane mass % versus deoxygenation temperature according to Example 2. SUMMARY OF THE INVENTION

[0011] The present invention relates to the following technical solutions:

[0012] 1. An apparatus for producing a monomethylalkylbenzene product, characterized in that the apparatus for producing a monomethylalkylbenzene product comprises:

[0013] A deoxygenation unit, which is connected to a natural oil feed pipeline;

[0014] A C9 to C28 pipeline, which is connected to the deoxygenation unit;

[0015] An isomerization unit, which is connected to a first pipeline;

[0016] An isomerization pipeline, which is connected to the isomerization unit, and the isomerization pipeline contains monomethylalkanes;

[0017] A dehydrogenation unit, which is connected to the isomerization pipeline;

[0018] A dehydrogenation pipeline, which is connected to the dehydrogenation unit;

[0019] A selective hydrogenation unit, which is connected to the dehydrogenation pipeline;

[0020] A monoolefin pipeline, which is connected to the selective hydrogenation unit;

[0021] An alkylation unit, which is connected to the monoolefin pipeline; and

[0022] An alkylation effluent pipeline, which is connected to the alkylation unit.

[0023] 2. The apparatus for producing a monomethylalkylbenzene product according to item 1, characterized in that the apparatus for producing a monomethylalkylbenzene product further comprises:

[0024] A benzene separation unit, which is connected to the alkylation effluent pipeline, and the linear alkylbenzene product is in the linear alkylbenzene product pipeline; and

[0025] A benzene recycle pipeline;

[0026] Among them, the straight-chain alkylbenzene product pipeline and the benzene recycle pipeline are connected to the benzene separation unit.

[0027] 3. The device for producing monomethylalkylbenzene products according to item 2, characterized in that the benzene recycle pipeline is connected to the alkylation unit.

[0028] 4. The device for producing monomethylalkylbenzene products according to item 2, characterized in that the device for producing monomethylalkylbenzene products further comprises:

[0029] An alkane pipeline, which is connected to the benzene separation unit, and

[0030] Among them, the alkane pipeline is connected to the dehydrogenation unit recycle.

[0031] 5. The device for producing monomethylalkylbenzene products according to item 1, characterized in that the device for producing monomethylalkylbenzene products further comprises:

[0032] A benzene separation unit, which is connected to the alkylation effluent pipeline, and the alkane pipeline is connected to the benzene separation unit;

[0033] Among them, the alkane pipeline is connected to the dehydrogenation unit recycle.

[0034] 6. The device for producing monomethylalkylbenzene products according to any one of items 1-5, characterized in that the device for producing monomethylalkylbenzene products further comprises:

[0035] A straight-chain selective cracking unit, which is connected to the C9 to C28 pipeline;

[0036] A first pipeline, a second pipeline and a third pipeline;

[0037] Among them, the first pipeline, the second pipeline and the third pipeline are connected to the straight-chain selective cracking unit.

[0038] 7. The device for producing monomethylalkylbenzene products according to any one of items 1-5, characterized in that the device for producing monomethylalkylbenzene products further comprises:

[0039] A purification unit, which is connected to the isomerization pipeline;

[0040] A purified isomerization pipeline and a raffinate pipeline;

[0041] Among them, the raffinate pipeline is connected to the isomerization unit, and the purified isomerization pipeline is connected to the purification unit.

[0042] 8. The device for producing monomethylalkylbenzene products according to item 6, characterized in that the device for producing monomethylalkylbenzene products further comprises:

[0043] A purification unit, which is connected to the isomerization pipeline;

[0044] Purify the isomerization pipeline and the raffinate pipeline;

[0045] Wherein the raffinate pipeline is connected to the isomerization unit, and wherein the purified isomerization pipeline is connected to the purification unit.

[0046] 9. The apparatus for producing monomethyl alkylbenzene products according to item 7, characterized in that the purification unit is an adsorption separation unit.

[0047] 10. The apparatus for producing monomethyl alkylbenzene products according to item 8, characterized in that the purification unit is an adsorption separation unit.

[0048] 11. The apparatus for producing monomethyl alkylbenzene products according to any one of items 1-5, characterized in that the selective hydrogenation unit is connected to the dehydrogenation pipeline, and the apparatus for producing monomethyl alkylbenzene products further comprises:

[0049] An aromatic compound pipeline and a light fraction pipeline, wherein the aromatic compound pipeline and the light fraction pipeline are connected to the selective hydrogenation unit.

[0050] 12. The apparatus for producing monomethyl alkylbenzene products according to item 6, characterized in that the selective hydrogenation unit is connected to the dehydrogenation pipeline, and the apparatus for producing monomethyl alkylbenzene products further comprises:

[0051] An aromatic compound pipeline and a light fraction pipeline, wherein the aromatic compound pipeline and the light fraction pipeline are connected to the selective hydrogenation unit.

[0052] 13. The apparatus for producing monomethyl alkylbenzene products according to item 7, characterized in that the selective hydrogenation unit is connected to the dehydrogenation pipeline, and the apparatus for producing monomethyl alkylbenzene products further comprises:

[0053] An aromatic compound pipeline and a light fraction pipeline, wherein the aromatic compound pipeline and the light fraction pipeline are connected to the selective hydrogenation unit.

[0054] 14. The apparatus for producing monomethyl alkylbenzene products according to item 8, characterized in that the selective hydrogenation unit is connected to the dehydrogenation pipeline, and the apparatus for producing monomethyl alkylbenzene products further comprises:

[0055] An aromatic compound pipeline and a light fraction pipeline, wherein the aromatic compound pipeline and the light fraction pipeline are connected to the selective hydrogenation unit.

[0056] 15. The apparatus for producing monomethylalkylbenzene products according to item 9, characterized in that the selective hydrogenation unit is connected to the dehydrogenation pipeline, and the apparatus for producing monomethylalkylbenzene products further comprises:

[0057] An aromatic compound pipeline and a light fraction pipeline, wherein the aromatic compound pipeline and the light fraction pipeline are connected to the selective hydrogenation unit.

[0058] 16. The apparatus for producing monomethylalkylbenzene products according to item 10, characterized in that the selective hydrogenation unit is connected to the dehydrogenation pipeline, and the apparatus for producing monomethylalkylbenzene products further comprises:

[0059] An aromatic compound pipeline and a light fraction pipeline, wherein the aromatic compound pipeline and the light fraction pipeline are connected to the selective hydrogenation unit. Detailed implementation mode

[0060] The present invention relates to a method for producing a monomethylalkylbenzene-rich stream from natural oils such as vegetable oils, animal oils, nut oils, and / or seed oils, and oils containing triglycerides. The method provides a stream that is rich in monomethylalkanes relative to n-alkanes, and this stream can be used to produce monomethylalkylbenzenes.

[0061] The n-alkanes are produced by the deoxygenation and hydrogenation of triglyceride feeds such as palm kernel oil (PKO) and other plant or animal-based oils. The deoxygenation and hydrogenation are carried out in the first step of the method by contacting the natural oil feed with a catalyst and hydrogen at elevated temperature and pressure. Some plant-based oils, such as PKO or coconut oil, already have carbon chains that typically fall within the C9 to C14 range in detergent applications. Longer chains can be selectively hydrocracked to enrich the deoxygenated / hydrogenated n-alkane product in n-alkanes having 9 to 14 carbon atoms. Thus, the n-alkanes can be selectively mildly isomerized in a hydroisomerization step to produce a portion of alkanes having monomethyl branching. The mixture of alkanes can be further enriched in monomethyl-branched alkanes by treatment in an adsorption separation system, and the raffinate can be recycled to the hydroisomerization to further prepare monomethyl-branched alkanes. The adsorption separation process for large-scale processes can use a simulated moving bed design to continuously separate the components in the mixture. For example, the simulated moving bed method is described in U.S. Patent No. 2,985,589. ZSM and X-type zeolites have been widely used in adsorption separation systems, as mentioned in US 6,225,518. Suitable adsorbents for the adsorbent system include, but are not limited to, ZSM or X-type zeolites, such as ZSM-5 or 13X zeolites.

[0062] A feed stream rich in monomethyl paraffins is subjected to contaminant removal, dehydrogenation, selective hydrogenation, and alkylation to produce an MMAB product. The hydroisomerization step is controlled by appropriate selection of catalyst and operating conditions to favor the selective production of monomethyl-branched paraffins over the more highly branched or mis-branched paraffins required for the lightly branched. For feeds having an inherent carbon chain length greater than 9-14, the straight-chain selective cracking step comprises controlling the catalyst and operating conditions to increase the yield of chains in the 9-14 carbon number range.

[0063] 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 oils containing triglycerides, and are commonly 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, 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; benoil; 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).

[0064] A process for preparing monomethylalkylbenzenes from natural oils according to the present invention comprises deoxygenating the natural oil to form paraffins. A C9 to C28 stream is sent to a separate straight-chain selective cracking unit to crack the C14+ paraffins; the cracked paraffins are separated (by fractionation, distillation, etc.) into a first stream comprising C9 to C14 normal paraffins and lightly branched paraffins, a second stream comprising C14+ (i.e., having a carbon chain containing C15 to C28) paraffins, and a third stream comprising isoparaffins. The C9 to C14 paraffins from the straight-chain selective cracking unit are isomerized to produce C9 to C14 monomethyl paraffins. Contaminants are removed from the isomerized C9 to C14 stream, 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, diolefins and aromatic compounds. The diolefins 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 monoolefin stream comprising monoolefins. Benzene is alkylated with the olefins, and the alkylation effluent contains alkylbenzenes and benzene. The alkylbenzenes are then separated.

[0065] The straight-chain selective cracking and isomerization steps will be further described. 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+ paraffins are selectively cracked before the C9 to C14 due to their higher absorption energy.

[0066] Selecting specific metal catalysts, including noble metals (such as ruthenium and platinum) and nickel, can produce much higher yields of normal paraffins having 9 to 14 carbons 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 isomers being produced.

[0067] 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 processes. The Pt-Al 2 O 3 catalyst can produce an even lower methane yield than the Ru-based catalyst, with a slightly lower straight-chain product yield.

[0068] 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.

[0069] Isomerize a first stream containing C9 to C14 paraffins from the straight-chain selective cracking unit to produce C9 to C14 monomethyl paraffins. The weight ratio of monomethyl paraffins to normal paraffins in the isomerized stream is in the range of 3 to 60.

[0070] The isomerization catalyst comprises a zeolite having a 10-ring AEL framework or a combination thereof. The isomerization conditions include a temperature in the range of 280 °C to 400 °C, or a pressure in the range of 2.8 MPa to 17.5 MPa, or a combination thereof.

[0071] The overall process will now be described in more detail.

[0072] 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 been shown to restore some of the lost activity. The degree of hydrodeoxygenation can affect the selectivity for each normal paraffin in the 9- to 14-carbon range. A high degree of hydrodeoxygenation can bias the hydrodeoxygenation composition strongly towards n-dodecane and n-decane to the detriment of n-undecane and n-tridecane. A low degree of hydrodeoxygenation can bias the hydrodeoxygenation composition towards n-undecane and n-tridecane to the detriment of n-dodecane and n-decane.

[0073] The hydrodeoxygenation reactor temperature is kept low, less than 343 °C (650 °F) for typical bioregenerable feeds and less than 304 °C (580 °F) for feeds with a high free fatty acid (FFA) concentration, 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.

[0074] The linearity of the alkylbenzene product mainly depends 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 decreases 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 approximately 90 wt% - 92 wt%. This sets a requirement for the linearity of the alkane that is 5 wt% - 7 wt% higher than the specification of the alkylbenzene product. Generally, the linearity of the alkane product is measured by the 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.

[0075] In Figure 1 it illustrates an exemplary system 100 for producing an alkylbenzene product from a specific triglyceride feed.

[0076] In the illustrated embodiment, a selected 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 into normal alkanes. When the natural oil contains triglycerides, the triglycerides are formed by 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 glycerol bond with 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 into normal alkanes. 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 reactions of fatty acids and triglycerides are shown respectively as:

[0077]

[0078] During the deoxygenation reaction, the length of the resulting alkane chain R n 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.

[0079] 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 hours -1 -3.0 hours -1 LHSV. The conditions are selected to minimize alkane cracking or isomerization.

[0080] The deoxygenation product contains normal alkanes, water, carbon dioxide, carbon monoxide, and propane.

[0081] The C9 to C28 stream 115 from the deoxygenation unit 110 is sent to the straight-chain selective cracking unit 120, where the stream is selectively cracked to form a first stream 125 containing C9 to C14 normal alkanes or lightly branched alkanes as described above, a second stream 130 containing C14+ alkanes 135, and a third stream containing isoalkanes.

[0082] The first stream 125 is sent to the isomerization unit 140, where a portion of the C9 to C14 alkanes are converted to monomethyl alkanes. The isomerization catalyst contains a zeolite with a 10-ring AEL framework or a combination thereof. Suitable isomerization catalysts include, but are not limited to, SAPO-11, AEI, AEL, AFO, AFX, ATO, BEA, CHA, FAU, FER, MEL, MFI, MOR, MRE, MTT, MWW, or TON topologies, such as EU-2, ZSM-11, ZSM-22, ZSM-23, ZSM-48, SAPO-5, SAPO-11, SAPO-31, SAPO-34, SAPO-41, SSZ-13, SSZ-16, SSZ-39, MCM-22, zeolite Y, ferrierite, mordenite, ZSM-5, or zeolite β, and combinations thereof.

[0083] The isomerization conditions include a temperature in the range of 280 °C to 400 °C, or a pressure in the range of 2.8 MPa to 17.5 MPa, 1500 - 10000 standard cubic feet of hydrogen per barrel of feed, 0.25 LHSV - 2.5 LHSV, or a combination thereof.

[0084] The overall process will now be described in more detail.

[0085] The isomerate stream 145 from the isomerization unit 140 is sent to the purification unit 150. The purification unit 150 removes contaminants from the C9 to C14 monomethyl paraffins in the isomerate stream 145 in an adsorption system. The 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.

[0086] The purified stream 155 is sent to the dehydrogenation unit 160, where hydrogen is removed to produce a dehydrogenated stream 165 containing monoolefins, diolefins, and aromatic compounds. In the dehydrogenation unit 160, the paraffins are dehydrogenated to monoolefins having the same number of carbon atoms as the paraffins. Generally, dehydrogenation is carried out by known catalytic methods, 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 by the following reaction equations:

[0087] Formation of monoolefin: C x H 2x+2 →C x H 2x +H 2

[0088] Formation of diolefin: C x H 2x →C x H 2x-2 +H 2

[0089] Formation of aromatic compound: C x H 2x-2 →C x H 2x-6 +2H 2

[0090] The operating conditions of the dehydrogenation unit 160 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 attenuating metal. Another suitable catalyst is described in U.S. Patent 6,177,381, which is hereby incorporated by reference in its entirety. The dehydrogenation unit 160 can be operated dry or with up to 2000 mass ppm of water injected. Hydrogen can be recycled upstream of the deoxygenation unit.

[0091] The dehydrogenated feed stream 165 is sent to a selective hydrogenation unit 170, 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 175 has an increased monoolefin concentration compared to the dehydrogenated feed stream 165. The aromatic compounds are separated and removed in the form of an aromatic stream 180. A light distillate stream 1185 containing any light components (such as butane, propane, ethane, and methane) produced by cracking or other reactions during upstream processing can also be removed.

[0092] The monoolefin stream 175 containing monoolefins is sent to an alkylation unit 190 together with a benzene stream 195. The benzene is alkylated with the monoolefins to form alkylbenzenes. The alkylation unit 190 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 190. As a result of the alkylation, alkylbenzenes, commonly referred to as linear alkylbenzenes (LAB), are formed according to the following reaction:

[0093] C 6 H 6 +C x H 2x →C 6 H 5 C x H 2x+1

[0094] Suitable operating conditions for the alkylation unit 190 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.

[0095] An excess of benzene is supplied to the alkylation unit 190 to achieve the desired high degree of alkylation. Thus, the alkylation effluent 200 leaving the alkylation unit 190 contains alkylbenzene and unreacted benzene. In addition, the alkylation effluent 200 may also include some unreacted paraffins. The alkylation effluent 200 is passed to a benzene separation unit 205, such as a fractionation column, to separate the unreacted benzene and paraffins from the alkylation effluent 200. The unreacted benzene leaves the benzene separation unit 205 in the form of a benzene recycle stream 210, which can be sent back to the alkylation unit 190 to maintain the desired benzene / olefin 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 entering the alkylation unit. The paraffin stream 215 can also be separated and recycled to the dehydrogenation unit 160.

[0096] As a result of the post-alkylation separation process, a linear alkylbenzene product 220 is separated. It should be noted that such a separation method is not necessary in all embodiments for separating the linear alkylbenzene product 220.

[0097] The linear alkylbenzene product 220 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.

[0098] 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.

[0099] In some embodiments, before or after the purification step, the isomerized stream (if before the purification step) or the purified stream (if after the purification step) can be separated in an absorption separation system (not shown), where the monomethyl alkanes are preferentially absorbed by the absorbent and the non - monomethyl alkanes remain in the fluid phase. In some embodiments, the absorbent in the absorption separation system is divided into multiple absorbent beds.

[0100] The term "column" means one or more distillation columns used to separate 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 can be pre - heated. The top pressure is the pressure of the overhead vapor at the vapor outlet of the column. The bottom temperature is the liquid bottoms outlet temperature. Unless otherwise specified, the overhead line and the bottoms line refer to the net lines from downstream of the column to the column from any reflux or reboiler take - offs. A stripper column can 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.

[0101] As used herein, the term "component - rich stream" or "component stream" means a stream exiting a vessel having a greater concentration of a 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 a component than the feed to the vessel.

[0102] Embodiment

[0103] Embodiment 1

[0104] Coconut oil feed is deoxygenated to form alkanes, 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% 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%.

[0105] Embodiment 2

[0106] 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 h⁻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 in Figure 2As shown, the figure is a plot of the concentration (in mass %) of C10 - C13 normal paraffins versus the reaction temperature. Figure 2 It clearly shows that as the deoxygenation reaction temperature increases, the concentration of normal paraffins decreases. Controlling the temperature below 404 °C (760 °F) produces greater than 92 mass % normal paraffins.

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

[0108] Specific implementation

[0109] 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.

[0110] A first embodiment of the present invention is a method for producing a monomethylalkylbenzene product from a natural oil, the method comprising deoxygenating the natural oil to form an alkane stream comprising C9 to C28 carbon chains; subjecting the alkane stream to straight-chain selective cracking in a separate straight-chain selective cracking unit in the presence of a straight-chain selective cracking catalyst under straight-chain selective cracking conditions to form a first stream comprising C9 to C14 normal alkanes or lightly branched alkanes, a second stream comprising C14+ alkanes, and a third stream comprising isoalkanes; isomerizing the first stream in the presence of an isomerization catalyst under isomerization conditions to form an isomerized stream comprising C9 to C14 monomethylalkanes, wherein the isomerization catalyst comprises a zeolite having a 10-ring AEL framework or a combination thereof; removing contaminants from the isomerized stream to form a purified stream, wherein the contaminants comprise sulfur compounds, or nitrogen compounds, or phosphorus compounds, or oxygen-containing compounds, or aromatic compounds or a combination thereof; dehydrogenating the purified stream to provide a dehydrogenated stream comprising monoolefins, diolefins, and aromatic compounds; 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 under alkylation conditions to provide an alkylation effluent comprising alkylbenzene and benzene; and separating the alkylbenzene to provide the alkylbenzene product derived from the natural oil. 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 separating the isomerized stream by a first absorption separation system before removing the contaminants from the isomerized stream, wherein the monomethylalkanes in the mixture are preferentially adsorbed by a first adsorbent, and wherein the non-monomethylalkanes remain in the fluid phase; or separating the purified stream by a second absorption separation system before dehydrogenating the purified stream, wherein the monomethylalkanes in the mixture are preferentially adsorbed by a second adsorbent, and wherein the non-monomethylalkanes remain in the fluid phase. 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 adsorbent in the first absorption separation system is divided into a plurality of adsorbent bed zones; or wherein the adsorbent in the second absorption separation system is divided into a plurality of adsorbent bed zones; 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, wherein the isomerized stream has a weight ratio of monomethylalkanes to normal alkanes of 3 to 60.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, and further includes recycling the second stream containing C14+ paraffins to the straight-chain selective cracking unit. 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 catalyst comprises ruthenium, or platinum, or a 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 1500 - 10000 standard cubic feet of hydrogen per barrel of feed, or 0.25 LHSV - 2.5 LHSV, 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 isomerization conditions include a temperature in the range of 280 °C to 400 °C, or a pressure in the range of 2.8 MPa to 17.5 MPa, or 1500 Scfb - 10000 Scfb of hydrogen feed, 0.25 LHSV - 2.5 LHSV, 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 zeolite containing a 10-ring AEL framework comprises SAPO-11. 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 isomerization catalyst comprises platinum or nickel-tungsten sulfide. One embodiment of the present invention is one, any, or all of the foregoing embodiments in this paragraph to the first embodiment in paragraph 2, wherein the first adsorbent comprises ZSM or type X zeolite.

[0111] A second embodiment of the present invention is a method for producing a monomethylalkylbenzene product from a natural oil, the method comprising deoxygenating the natural oil to form an alkane stream comprising C9 to C28 carbon chains; subjecting the alkane stream to straight-chain selective cracking in a separate straight-chain selective cracking unit in the presence of a straight-chain selective cracking catalyst under straight-chain selective cracking conditions to form a first stream comprising C9 to C14 normal alkanes or lightly branched alkanes, a second stream comprising C14+ alkanes, and a third stream comprising isoparaffins; isomerizing the first stream in the presence of an isomerization catalyst under isomerization conditions to form an isomerized stream comprising C9 to C14 monomethylalkanes, wherein the isomerization catalyst comprises a zeolite having a 10-ring AEL framework or a combination thereof; removing contaminants from the isomerized stream to form a purified stream, wherein the contaminants comprise sulfur compounds, or nitrogen compounds, or phosphorus compounds, or oxygen-containing compounds, or aromatic compounds or a combination thereof; dehydrogenating the purified stream to provide a dehydrogenated stream comprising monoolefins, diolefins, and aromatic compounds; 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 under alkylation conditions to provide an alkylation effluent comprising alkylbenzene and benzene; separating the alkylbenzene to provide the alkylbenzene product derived from the natural oil; and separating the isomerized stream through a first absorption separation system before removing the contaminants from the isomerized stream, wherein the monomethylalkanes in the mixture are preferentially adsorbed by the adsorbent, and wherein the non-monomethylalkanes remain in the fluid phase, wherein the adsorbent in the first absorption separation system is divided into a plurality of adsorbent bed zones; or separating the purified stream through a second absorption separation system before dehydrogenating the purified stream, wherein the monomethylalkanes in the mixture are preferentially adsorbed by the adsorbent, and wherein the non-monomethylalkanes remain in the fluid phase, wherein the adsorbent in the second absorption separation system is divided into a plurality of adsorbent bed zones. 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 isomerized stream has a weight ratio of monomethylalkanes to normal alkanes of 3 to 60. 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, further comprising recycling the second stream comprising C14+ alkanes to the straight-chain selective cracking unit. 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 catalyst comprises ruthenium, or platinum, or a 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 1500 - 10000 standard cubic feet of hydrogen per barrel of feed, 0.25 LHSV - 2.5 LHSV, 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 isomerization conditions include a temperature in the range of 280 °C to 400 °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 zeolite containing the 10-ring AEL framework comprises SAPO-11. 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 first adsorbent comprises ZSM or type X zeolite.

[0112] 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 understood as being merely illustrative and not limiting the remainder of the disclosure in any way, and are intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.

[0113] In the foregoing, all temperatures are shown in degrees Celsius, and all parts and percentages are by weight unless otherwise indicated.

Claims

1. A device for producing a monomethyl alkylbenzene product, characterized in that: The device for producing monomethyl alkylbenzene product comprises: a deoxygenation unit in communication with the natural oil feed line; A C9 to C28 pipeline connected to a deoxygenation unit; an isomerization unit in communication with the first pipeline; an isomerization line in communication with the isomerization unit, the isomerization line comprising monomethyl paraffins; a dehydrogenation unit in communication with the isomerization line; a dehydrogenation pipeline connected to the dehydrogenation unit; a selective hydrogenation unit in communication with 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 device for producing monomethyl alkylbenzene product according to claim 1, characterized in that: The device for producing monomethyl 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 device for producing monomethyl alkylbenzene product according to claim 2, characterized in that: The benzene recycling line is connected to the alkylation unit.

4. The device for producing monomethyl alkylbenzene product according to claim 2, characterized in that: The device for producing monomethyl alkylbenzene product further comprises: a paraffin line communicating with a benzene separation unit, and The paraffin pipeline is recirculatingly connected to the dehydrogenation unit.

5. The device for producing monomethyl alkylbenzene product according to claim 1, characterized in that: The device for producing monomethyl alkylbenzene product further comprises: a benzene separation unit in communication with the alkylation effluent line, and a paraffin line in communication with the benzene separation unit; The paraffin pipeline is recirculatingly connected to the dehydrogenation unit.

6. The device for producing monomethyl alkylbenzene product according to any one of claims 1 to 5, characterized in that: The device for producing monomethyl alkylbenzene product further comprises: a linear selective cracking unit in communication with the C9 to C28 pipeline; A first pipeline, a second pipeline and a third pipeline; The first pipeline, the second pipeline and the third pipeline are connected to the linear selective cracking unit.

7. The device for producing monomethyl alkylbenzene product according to any one of claims 1 to 5, characterized in that: The device for producing monomethyl alkylbenzene product further comprises: a purification unit in communication with the isomerization line; Purification of isomerization and raffinate lines; wherein the raffinate line is in communication with the isomerization unit, and wherein the purge isomerization line is in communication with the purge unit.

8. The device for producing monomethyl alkylbenzene product according to claim 6, characterized in that: The device for producing monomethyl alkylbenzene product further comprises: a purification unit in communication with the isomerization line; Purification of isomerization and raffinate lines; wherein the raffinate line is in communication with the isomerization unit, and wherein the purge isomerization line is in communication with the purge unit.

9. The device for producing monomethyl alkylbenzene product according to claim 7, characterized in that: The purification unit is an adsorption separation unit.

10. The device for producing monomethyl alkylbenzene product according to claim 8, characterized in that: The purification unit is an adsorption separation unit.

11. The device for producing monomethyl alkylbenzene product according to any one of claims 1 to 5, characterized in that: The selective hydrogenation unit is connected to the dehydrogenation pipeline, and the device for producing monomethyl alkylbenzene product 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.

12. The device for producing monomethyl alkylbenzene product according to claim 6, characterized in that: The selective hydrogenation unit is connected to the dehydrogenation pipeline, and the device for producing monomethyl alkylbenzene product 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.

13. The device for producing monomethyl alkylbenzene product according to claim 7, characterized in that: The selective hydrogenation unit is connected to the dehydrogenation pipeline, and the device for producing monomethyl alkylbenzene product 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.

14. The device for producing monomethyl alkylbenzene product according to claim 8, characterized in that: The selective hydrogenation unit is connected to the dehydrogenation pipeline, and the device for producing monomethyl alkylbenzene product 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.

15. The device for producing monomethyl alkylbenzene product according to claim 9, characterized in that: The selective hydrogenation unit is connected to the dehydrogenation pipeline, and the device for producing monomethyl alkylbenzene product 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.

16. The device for producing monomethyl alkylbenzene product according to claim 10, characterized in that: The selective hydrogenation unit is connected to the dehydrogenation pipeline, and the device for producing monomethyl alkylbenzene product 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.

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