WO1999059942A1 - Alkylation directe d'hydrocarbures aromatiques au moyen de paraffines et isomerisation de paraffines - Google Patents

Alkylation directe d'hydrocarbures aromatiques au moyen de paraffines et isomerisation de paraffines Download PDF

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WO1999059942A1
WO1999059942A1 PCT/US1999/010828 US9910828W WO9959942A1 WO 1999059942 A1 WO1999059942 A1 WO 1999059942A1 US 9910828 W US9910828 W US 9910828W WO 9959942 A1 WO9959942 A1 WO 9959942A1
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extrudate
mcm
benzene
zsm
catalyst
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PCT/US1999/010828
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English (en)
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Jane Chi-Ya Cheng
Terry Eugene Helton
Randall David Partridge
Margaret May-Som Wu
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Mobil Oil Corporation
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Priority to AU39971/99A priority Critical patent/AU3997199A/en
Publication of WO1999059942A1 publication Critical patent/WO1999059942A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65

Definitions

  • the invention relates to the direct alkylation of aromatic hydrocarbons with paraffins to produce linear alkylbenzenes, lubricant base stocks or chemical intermediates.
  • an aromatic hydrocarbon is alkylated with a reactive agent such as olefin, alkyl halide or alkyl alcohol, in a Friedel-Crafts type reaction.
  • a reactive agent such as olefin, alkyl halide or alkyl alcohol
  • a Friedel-Crafts type reaction Processes of this type are described, e.g., in U.S. Patent Nos. 3,755,483 to Burress, 4,301,316 and 4,301,317 to Young, 4,871,444 to Chen et al. and 4,990,718 to Pelrine.
  • U.S. Patent No. 3,755,483 utilizes zeolites in the hydrogen form.
  • U.S. Patent No. 4,871,444 utilizes rare earth exchanged zeolite.
  • U.S. Patent No. 4,990,718 describes utilizing a Group VLB metal oxide such as chromium oxide to produce olefin dimers, followed by Friedel-Crafts type aromatics alkylation over zeolites in the ammonium form.
  • U.S. Patent No. 4,358,628 describes benzene alkylation with detergent range olefins over tungsten oxide on silica-alumina.
  • U.S. Patent No. 4,524,230 to Haensel describes an indirect aromatics alkylation which involves decomposing a paraffinic hydrocarbon on the surface of a nonacid-active catalyst which includes nickel, cobalt, or iron on a non-acid-acting support such as kieselguhr, silica or neutralized zeolite. Paraffins are fragmented and the fragments scavenged by an aromatic compound. Because of the fragmentation, the product alkylaromatic always contains an alkyl group which has fewer carbons than the paraffin feed.
  • Lube base stocks are conventionally obtained from the refining of petroleum through a series of operations which remove unwanted components. These operations are directed towards obtaining a lubricant base stock of suitable boiling point, viscosity, viscosity index and other characteristics.
  • Lubricants should be highly paraffinic since paraffins possess the desirable combination of low viscosity and high viscosity index.
  • Waxy n-paraffins and slightly branched paraffins, e.g., n-methyl paraffins are waxy materials which confer an unacceptably high pour point on the lubricant base stock and are therefore catalytically dewaxed or removed during solvent dewaxing operations.
  • Less waxy isoparaffins have relatively high viscosity index with low pour point properties.
  • the waxy components are converted to relatively less waxy isoparaffins and at the same time, the slightly branched chain paraffins undergo isomerization to more highly branched aliphatics.
  • a measure of cracking can take place during the operation so that not only is the pour point reduced by reason of the isomerization but, in addition, the heavy ends undergo some cracking or hydrocracking to form liquid range materials which can contribute to a low viscosity product.
  • the degree of cracking is limited so as to maintain as much of the feedstock as possible in the desired boiling range.
  • alkylaromatic compounds useful in the production of detergents, as precursors for plastics and as lubricating oil base stocks can be produced by direct aromatic alkylation with paraffins, optionally with concurrent paraffin isomerization, by contacting a hydrocarbon feed containing aromatics and C15+ alkanes with a metal-containing molecular sieve catalyst under aromatics alkylation conditions.
  • Alkanes are used directly as the alkylating agent for aromatics and at the same time, alkanes may be isomerized.
  • direct alkylation means a process where the paraffin, which is usually inactive under prior art Friedel-Crafts reaction conditions, is used directly as an alkylating agent without the need for functionalizing the paraffin.
  • the invention resides a process for direct alkylation of an aromatic hydrocarbon with an alkane comprising contacting a feed comprising an aromatic hydrocarbon and an alkane having at least 15 carbon atoms with a catalyst comprising a molecular sieve material having an incorporated metal component.
  • the molecular sieve catalyst has a pore/channel channel system having openings of 10 or more oxygen ring members.
  • the preferred metal component is selected from Groups VIA, Nil A and NIIIA of the Periodic Table of the Elements (IUPAC version), and most preferably is a noble metal.
  • the invention provides an efficient way to produce alkylaromatics which bypasses the use of the more expensive olefins or fiinctionalized paraffins that are required in Friedel-Crafts type reactions. Therefore alkylation of aromatics with alkanes takes place in the absence of the addition of fiinctionalized alkanes such as olefins, alkyl halides or alkyl alcohols. Aromatics can be reacted directly with paraffins without significant paraffin cracking. Furthermore, when applied to lubricant base stock production, by adjusting reaction conditions and catalysts such that the alkylaromatics produced have desirable lubricant properties, the process not only isomerizes linear paraffins but also adds aromatic components into the product. This way of incorporating aromatics provides lubricant base stocks with better pour point, better low temperature viscometric properties, and better additive solubility than catalytically or solvent dewaxed lubricant base stock.
  • the aromatic component of the feed to the process can be any mononuclear or polynuclear aromatic hydrocarbon. These feeds can be available from petroleum, coal or synthetic fuel or byproducts from chemical processing. Suitable aromatic hydrocarbons include, for example, benzene, naphthalene, anthracene and their alkylated analogs, such as methylated or ethylated benzenes or napthalenes, etc. Preferred aromatics for the feed include benzene and naphthalene.
  • the alkane component of the feed to the process comprises at last one paraffinic hydrocarbon having at least 15 carbon atoms and may range from a linear or very slightly branched paraffin having from 15 to 22 carbon atoms, to light, medium or heavy slack wax, paraffinic FCC bottoms, deasphalted hydrocracked bottoms, Fischer-Tropsch synthetic distillate and wax, deoiled wax or polyethylene wax, light or heavy cycle oil.
  • Other sources include waxy shale oil, tar sands and synthetic fuels.
  • Lower molecular weight paraffins may also be present in the alkane component of the feed. Slack waxes are generally described in U.S. Patent ⁇ os. 5, 110,445 to Chen and
  • Highly paraffinic streams such as those obtained from the solvent dewaxing of distillates and other lube fractions are commonly referred to as slack wax.
  • These highly paraffinic streams comprising mostly straight chain and mono-methyl paraffins, generally have a paraffin content of at least 50 wt. percent, more usually at least 70 wt. percent or above, with the balance from the occluded oil being divided between aromatics and naphthenics.
  • These waxy, highly paraffinic stocks usually have much lower viscosities than vacuum distilled neutral or residual stocks because of their relatively low content of aromatics and naphthenes which are high viscosity components.
  • Slack waxes are obtained, for example, as the waxy product obtained directly from a solvent dewaxing process, e.g., an MEK or propane dewaxing process.
  • Fischer-Tropsch wax is another preferred feed.
  • Fischer-Tropsch synthesis involves the catalytic hydrogenation of carbon monoxide.
  • Fischer-Tropsch liquid obtained, e.g., with cobalt-containing catalysts, is roughly equivalent to a very paraffinic sulfur free natural petroleum oil. Straight-chain, saturated aliphatic molecules predominate.
  • the molar ratio of aromatics to paraffins in the feed useful herein may vary from 0.1 to 30.
  • the preferred molar feed ratio of aromatics to paraffins varies from 1.5 to 10. If the feeds are benzene and hexadecane, for example, the preferred feed composition will contain 34 wt.% to 78 wt.% benzene. If the feeds are benzene and heavy neutral slack wax (with average molecular weight of 492), the preferred feed composition will contain 19 wt.% to 61 wt.% benzene.
  • the feeds contain paraffins in an amount of at least 5 weight percent (wt.%), preferably at least 20 wt.%, more preferably 50 wt.% and higher. More particularly, the feeds contain paraffins in an amount preferably greater than 10 mole percent (mole.%), more preferably, 20-80 mole.%, and most preferably, 40-60 mole.% consistent with the amount of aromatics. CATA
  • the catalysts of the present invention are bifunctional in character, comprising a metal hydrogenation-dehydrogenation component on a molecular sieve which supplies an acidic functionality.
  • the catalysts of the present invention include as non-limiting examples, ZSM-5 (U.S. Pat. No. 3,702,886 and Re. 29,948), mordenite, ZSM-12 (U.S. Pat. No. 3,832,449), ZSM-23 (U.S. Pat. No. 4,076,842), ZSM-48 (U.S. Pat. No. 4,397,827), Zeolite Beta (U.S. Pat. Nos. 3,308,069 and Re. 28,341), USY (U.S. Pat.
  • MCM- 22 U.S. Pat. No. 4,954,325
  • MCM-36 U.S. Pat. No. 5,229,341
  • MCM-49 U.S. Pat. No. 5,236,575
  • MCM-56 U.S. Pat. No. 5,362,697
  • mesoporous materials such as M41S (U.S. Pat. No. 5,102,643) and MCM-41 (U.S. Pat. No. 5,098,684).
  • the catalysts are incorporated with a metal having a strong hydrogenation function, particularly noble metals and other metals from Groups VTA, VILA and VIII A of the Periodic Table of the Elements (IUPAC Version) including chromium, molybdenum, tungsten, manganese, technitium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, gold, silver, zinc and cadmium; especially platinum, palladium, rhenium, rhodium, iridium, and combinations thereof; and preferably platinum or palladium.
  • a metal having a strong hydrogenation function particularly noble metals and other metals from Groups VTA, VILA and VIII A of the Periodic Table of the Elements (IUPAC Version) including chromium, molybdenum, tungsten, manganese, technitium, rhenium, iron, ruthenium, osmium,
  • the metal component can be incorporated by methods known in the art, e.g., by impregnation or cation exchange, usually in amounts of from 0.01 to 10 wt.% of the total catalyst and preferably from 0.1 to 2.0 wt.% of the catalyst.
  • a metal stabilizer or promoter such as tin, indium, gallium, thorium or lead, e.g., in an amount of 0.01 wt.% to 10 wt.% of the catalyst, may also be added to the system, such as is described in U.S. Patent No. 5,012,021.
  • the crystalline molecular sieve may also be composited with a matrix material, including synthetic and naturally occurring substances, e.g., clay, silica, alumina, zirconia, titania, silica-alumina and other metal oxides.
  • a matrix material including synthetic and naturally occurring substances, e.g., clay, silica, alumina, zirconia, titania, silica-alumina and other metal oxides.
  • Naturally-occurring clays include those of the montmorillonite and kaolin families.
  • the matrix itself may possess catalytic properties, often of an acid nature.
  • porous matrix materials include silica-magnesia, silica-zirconia, silica- thoria, silica-beryllia, silica-titania, as well as ternary compositions such as silica-alumina- thoria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-alumina-zirconia.
  • ternary compositions such as silica-alumina- thoria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-alumina-zirconia.
  • the relative proportions of crystalline molecular sieve material and matrix may vary widely from 1 to 90 wt.%, usually 20 to 80 wt.%.
  • the catalyst can also be used in the absence of matrix or binder, i.e., in unbound form.
  • the catalyst can be used in the form of an extrudate, lobed form
  • the catalyst is usually pretreated with flowing H 2 at 100-500°C, H 2 flow rate of 1- 1000 cc/min., pressure of atm.-500 psi for 1 min. to 16 hrs.
  • the catalyst can be regenerated by treating with H 2 at high temperature, e.g., over 350°C, H 2 flow rate of 1-1000 cc/min., pressure of atm.-500 psi for 1 min. to 16 hrs.; or the catalyst can be regenerated by air or oxygen calcination at over 350°C for 0.5 to 24 hrs., followed by H 2 pretreatment as described above.
  • the process is operated under conditions including an elevated temperature preferably ranging from 100°C or 150°C to 400°C (212°F or 302°F to 752°F), more preferably 200°C to 350°C (392°F to 662°F), most preferably 200°C to 300°C (392°F to 572°F); a pressure preferably ranging from atmospheric to 2500 psig, more preferably 200 to 2000 psig, and most preferably 300 to 1500 psig; a space velocity preferably ranging from 0.01 to 100 LHSV, more preferably 0.1 to 50 LHSV, and most preferably 0.1 to 10 LHSV; a molar feed ratio of aromatics/paraffins preferably ranging from 0.1 to 30, more preferably 0.5 to 15, and most preferably 1.5 to 10.
  • an elevated temperature preferably ranging from 100°C or 150°C to 400°C (212°F or 302°F to 752°F), more preferably 200°C to 350°C (392°F to 662°F), most preferably
  • Hydrogen may be used but is not required, and the process is preferably carried out in the absence of added hydrogen.
  • Conditions may be adjusted toward aromatics alkylation or toward paraffin isomerization. This can be accomplished by selecting the catalyst or reaction conditions. For example, some catalysts, e.g., ZSM-5, ZSM-12, ZSM-23, mordenite or ZSM-48, promote more isomerization, whereas other catalysts, e.g., MCM-22 type, zeolite beta, M41S, and USY, promote more alkylation.
  • the process can be carried out in several different types of reactors, e.g., fixed-bed continuous flow, batch, continuous stir tank, or bubble-column type reactors.
  • reactors e.g., fixed-bed continuous flow, batch, continuous stir tank, or bubble-column type reactors.
  • PRODUCTS A notable feature of the present process is that the aromatic is alkylated with a paraffin with various degrees of isomerization to produce linear alkylaromatics, branched alkylaromatics and iso-paraffins.
  • the useful products include chemical intermediates such as polymer precursors, high-quality lubricant base stocks and detergent precursors.
  • the lubricant base stock products When using slack wax, FT wax or hydrocracked bottoms as paraffin feed, the lubricant base stock products contain alkylated aromatics and isomerized paraffins. These components enhance the quality of a lubricant base stock offering advantages of feedstock flexibility, better pour point and low-temperature viscometric properties and better additive solubility. Therefore, the lubricant base stock products have desirable properties of pour point, viscosity and viscosity index. Pour point is the lowest temperature at which a petroleum oil will flow or pour when it is chilled without disturbance at a controlled rate. Pour point is a critical specification of lubricant oils used in cold climates.
  • Viscosity is the property of liquids under flow conditions which causes the oil to resist instantaneous change of shape or rearrangement of their ports due to internal friction. Viscosity is generally measured as the number of seconds, at a definite temperature, required for a standard quantity of oil to flow through a standard apparatus. Common viscosity scales are Saybolt Universal (SU), Saybolt Fural, and Kinematic (Stokes).
  • the Viscosity Index (V.I.) is a quality parameter of lubricating oils which indicates the rate of change of viscosity with change in the temperature. The higher the V.I., the smaller its change in viscosity for a given change in temperature. A high V.I.
  • the process of the invention produces lubricant base stock with high V.I., low pour point, and additive solubility suitable for high performance lubricant product formulation.
  • long-chain paraffins such as Cis to C 22 , preferably Cisto C 18
  • the corresponding alkylaromatics useful as detergent alkylates can be produced, preferably over metal-containing MCM-22 type catalysts, particularly Pt MCM-22.
  • Detergent alkylate generally includes mostly linear alkylbenzenes which are later sulfonated to yield detergent.
  • Detergents are commonly anionic surfactants which include linear sodium alkyl benzene sulfonate (LAS), linear alkyl sulfates, and linear alkyl ethoxy sulfates.
  • LAS linear sodium alkyl benzene sulfonate
  • linear alkyl sulfates linear alkyl ethoxy sulfates.
  • alkylbenzenesulfonic acid based detergents is enhanced when the average substituent position of the benzene ring on the alkyl chain is lower, e.g., a detergent based on (2- alkyl)benzenesulfonic acid is more easily biodegraded than one based on (3- alkyl)benzenesulfonic acid, etc.
  • the higher content of 2-phenyl-alkane also improves the solubility of the sulfonated linear alkylbenzenes.
  • the alkylbenzenes produced over metal- containing MCM-22 type catalysts in the invention contain, e.g., 40% of 2-alkyl benzene and 96% or more of linear alkylbenzenes.
  • EXAMPLE 3 0.6%Pt/[B] zeolite beta/35% SiO 2 as 1/20" quadrulobe.
  • 65 parts of boron containing zeolite beta and 35 parts LaRoche Versal alumina was extruded into a 1/20" quadrulobe shape.
  • the extrudate was calcined in nitrogen at 482°C followed by air calcination at 538°C.
  • the alpha activity of the calcined extrudate was 7.
  • the extrudate was exchanged with platinum tetraammine chloride and ammonium nitrate (competitive exchange) to a concentration of 0.6 wt.% Pt metal.
  • the extrudate was washed with deionized water to remove chlorides and dried at 121°C. After drying, the extrudate was calcined in air at 360°C.
  • EXAMPLE 4 0.6% Pt/zeolite beta/35% Al 2 O 3 as 1/16" quadrulobe (50 alpha). 65 parts of zeolite beta and 35 parts LaRoche Versal alumina was extruded into a 1/20" quadrulobe shape. After drying at 121°C, the extrudate was calcined in nitrogen at 482°C followed by air calcination at 538°C. After calcination, the extrudate was steamed to an alpha activity of 50. After steaming, the extrudate was exchanged with platinum tetraammine chloride to a concentration of 0.6 wt.% Pt metal. After ion exchange, the extrudate was washed with deionized water to remove chlorides and dried at 121°C. After drying, the extrudate was calcined in air at 360°C. EXAMPLE 5
  • Pt/MCM-22 0.6% Pt/MCM-22 as 1/16" extrudate.
  • 100 parts of MCM-22 was extruded into a 1/16" cylindrical shape.
  • the binderless MCM-22 extrudate was exchanged with ammonium nitrate to remove any exchangeable sodium.
  • the binderless extrudate was calcined in nitrogen at 482°C for 3 hours followed by calcination in air at 538°C for 12 hours. After calcination, the binderless extrudate was impregnated with 0.6 wt.% Pt using platinum tetraammine nitrate salt. After drying at 121°C, the platinum containing extrudate was calcined in air at 360°C.
  • ZSM-12 100 parts was extruded with sodium hydroxide into a 1/16" cylindrical shape. After drying at 121°C, the binderless ZSM-12 extrudate was exchanged with ammonium nitrate to remove sodium. After rinsing with deionized water to remove residual nitrate, the binderless extrudate was calcined in nitrogen at 482°C for 3 hours followed by calcination in air at 538°C for 12 hours. This zeolite was steamed to an alpha of 1. After calcination, the binderless extrudate was impregnated with 0.5 wt.% Pt using platinum tetraammine nitrate salt.
  • the sodium-free extrudate was impregnated with 0.6 wt.% Pt using platinum tetraammine nitrate salt. After drying at 121°C, the platinum containing extrudate was calcined in air at 360°C.
  • M41S (80 A)/35% Al 2 O 3 0.5% M41S (80 A)/35% Al 2 O 3 as 1/16" extrudate.
  • 65 parts of M41S (pore diameter 80 A) and 35 parts LaRoche Versal alumina was extruded into a 1/16" cylindrical shape. After drying at 121°C, the extrudate was calcined in nitrogen at 482°C. The extrudate was exchanged with ammonium mtrate to remove any exchangeable sodium. After rinsing with deionized water to remove residual nitrate, the extrudate was calcined in air at 538°C. After calcination, the alumina bound extrudate was impregnated with 0.5 wt.% Pt using platinum tetraammine chloride salt. After drying at 121 °C, the platinum containing extrudate was calcined in air at 360°C.
  • EXAMPLE 18 Fixed-Bed Catalyst Screening Using n-Hexadecane and Benzene Molecular sieve catalysts as prepared in Examples 1 to 14 were tested for n- hexadecane/benzene reaction in fixed-bed reactors. The following general procedures were used for the fixed-bed experiments.
  • the catalyst (extrudate or quadrulobe) was broken into pieces about 1/8" long.
  • the catalyst screening test was carried out in a down-flow fixed-bed reactor in the liquid phase.
  • the reactor was heated with a 3-zone furnace.
  • the catalyst bed (5, 10, or 15 cc of catalyst diluted with sand) was located in the mid-zone. Top and bottom portions of the reactor were filled with sand.
  • the catalyst was pretreated with 100-200 cc/min flowing hydrogen for 2 hr at 350°C and ambient pressure. Hydrogen was turned off and the reactor temperature was reduced to desired reaction temperature ranging from 210°C to 300°C depending on catalyst activity.
  • the reactor pressure was set to 750 psig with a grove loader.
  • Feed (benzene alone or as a 6:1 benzene/n-hexadecane molar ratio mixture) was introduced to the reactor at 60 cc/hr for 1 hr. After reaching the desired pressure, benzene and n- hexadecane were fed in a 6:1 molar ratio with n-hexadecane flow rate adjusted between 0.1 to 0.3 LHSV based on total catalyst volume. After lineout, the reactor effluent was collected in a cold trap and analyzed with an off-line GC. Catalyst results are summarized in Example 19.
  • n-Hexadecane utilization 22 type catalysts in Table 7, ZSM-12 catalysts in Table 8, and ZSM-5, ZSM-23, and mordenite catalysts are in Table 9.
  • One representative reaction condition for each catalyst is given along with observed n-hexadecane conversion, benzene conversions, n-hexadecane utilization, and benzene utilization.
  • n-Hexadecane utilization and benzene utilization are defined below: n-Hexadecane utilization
  • alkylbenzenes For light alkylbenzenes, it is assumed that the alkyl groups are originated from n- hexadacane and the phenyl group is originated from benzene.
  • Pt/zeolite beta and Pt/USY catalyzed n-hexadecane isomerization and n- hexadecane/benzene alkylation simultaneously.
  • the hexadecylbenzene products produced from these catalysts consisted 39-81% of linear hexadecylbenzenes (8-16% being 2- phenylhexadecane), and the balance of the hexadecylbenzene products was branched hexadecylbenzenes (19-61%).
  • Pt/zeolite beta and Pt/USY can be used for simultaneous paraffins isomerization and paraffin/aromatics alkylation where alkylation is the main reaction.
  • These catalysts can also be used for incorporation of aromatic hydrocarbons into linear and branched paraffins during lube dewax process.
  • Comparison of Product Properties Table 6 below compares properties of hexadecylbenzene concentrates generated from hexadecane/benzene reaction over Pt/USY and Pt/MCM-22 with those of severely hydrocracked base stocks (U.S. Patent No. 4,419,220) and those generated from regular 1- hexadecene/benzene reaction over Pt-free MCM-22.
  • the hexadecylbenzene concentrates were obtained by removing excess benzene from the total product mixture with a rotavapor, followed by a Kugelrohr separation under vacuum to remove unreacted n-hexadecane or 1- hexadecene. A small fraction of linear hexadecylbenzene was evaporated with unreacted n- hexadecane or 1-hexadecene during the Kugelrohr separation.
  • hexadecylbenzene products produced with Pt/USY or Pt/MCM-22 has lower pour points (-35 to -36°C) than the severely hydrocracked base stocks (XHQ) or simple linear hexadecylbenzene. (-12 to -18°C or -21°C).

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Abstract

L'invention concerne un procédé servant à effectuer l'alkylation directe d'hydrocarbures aromatiques au moyen de paraffines et consistant à mettre en contact une charge d'hydrocarbures contenant un hydrocarbure aromatique et une paraffine possédant au moins 15 atomes de carbone avec un catalyseur à tamis moléculaire incorporant un métal. L'isomérisation des paraffines peut s'effectuer simultanément à l'alkylation des hydrocarbures aromatiques.
PCT/US1999/010828 1998-05-18 1999-05-18 Alkylation directe d'hydrocarbures aromatiques au moyen de paraffines et isomerisation de paraffines WO1999059942A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004074407A1 (fr) 2003-02-20 2004-09-02 Shell Internationale Research Maatschappij B.V. Procede pour preparer des composes detergents
WO2006015798A1 (fr) * 2004-08-05 2006-02-16 Basf Aktiengesellschaft Procede de production de composes alkyle aromatiques par alkylation directe d'hydrocarbures aromatiques avec des alcanes
EP2321040A1 (fr) * 2008-07-22 2011-05-18 ExxonMobil Chemical Patents Inc. Préparation d'un catalyseur contenant un tamis moléculaire et son utilisation dans la production d'hydrocarbures alkylaromatiques
EP2540691A1 (fr) 2011-06-29 2013-01-02 Stamicarbon B.V. acting under the name of MT Innovation Center Procédé et catalyseur pour l'alkylation des composés aromatiques avec des alcanes légers
WO2013002638A1 (fr) 2011-06-29 2013-01-03 Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center Procédé et catalyseur pour l'alkylation de composés aromatiques avec des alcanes
EP2610325A1 (fr) 2011-12-30 2013-07-03 Shell Internationale Research Maatschappij B.V. Processus de préparation de composés de détergent
CN105536862A (zh) * 2016-01-11 2016-05-04 江苏正丹化学工业股份有限公司 稀土杂多酸改性mcm-41催化剂及其在甲乙苯生产中的使用方法

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US4899008A (en) * 1986-06-27 1990-02-06 Mobil Oil Corporation Direct catalytic alkylation of mononuclear aromatics with lower alkanes

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004074407A1 (fr) 2003-02-20 2004-09-02 Shell Internationale Research Maatschappij B.V. Procede pour preparer des composes detergents
US7674940B2 (en) 2003-02-20 2010-03-09 Shell Oil Company Process for the preparation of detergent compounds
WO2006015798A1 (fr) * 2004-08-05 2006-02-16 Basf Aktiengesellschaft Procede de production de composes alkyle aromatiques par alkylation directe d'hydrocarbures aromatiques avec des alcanes
EP2321040A1 (fr) * 2008-07-22 2011-05-18 ExxonMobil Chemical Patents Inc. Préparation d'un catalyseur contenant un tamis moléculaire et son utilisation dans la production d'hydrocarbures alkylaromatiques
EP2540691A1 (fr) 2011-06-29 2013-01-02 Stamicarbon B.V. acting under the name of MT Innovation Center Procédé et catalyseur pour l'alkylation des composés aromatiques avec des alcanes légers
WO2013002638A1 (fr) 2011-06-29 2013-01-03 Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center Procédé et catalyseur pour l'alkylation de composés aromatiques avec des alcanes
EP2610325A1 (fr) 2011-12-30 2013-07-03 Shell Internationale Research Maatschappij B.V. Processus de préparation de composés de détergent
CN105536862A (zh) * 2016-01-11 2016-05-04 江苏正丹化学工业股份有限公司 稀土杂多酸改性mcm-41催化剂及其在甲乙苯生产中的使用方法
CN105536862B (zh) * 2016-01-11 2018-07-03 江苏正丹化学工业股份有限公司 稀土杂多酸改性mcm-41催化剂及其在甲乙苯生产中的使用方法

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