WO2019118228A1

WO2019118228A1 - Processes for isomerizing alpha olefins

Info

Publication number: WO2019118228A1
Application number: PCT/US2018/063745
Authority: WO
Inventors: Renyuan YU; Elizabeth G. MAHONEY; Anatoly L KRAMER; Wenyih F. Lai; Paul F. Keusenkothen
Original assignee: Exxonmobil Chemical Patents Inc.
Priority date: 2017-12-14
Filing date: 2018-12-04
Publication date: 2019-06-20

Abstract

Processes are described for isomerizing one or more C4-C24 alpha olefins to produce an isomerization mixture comprising one or more C4-C24 internal olefins comprising contacting an olefinic feed comprising the one or more C4-C24 alpha olefins with a catalyst under isomerization conditions, wherein the catalyst comprises a mesoporous material having a collidine uptake of greater than about 100 μmol/g. The resulting isomerization mixture typically exhibits a low pour point with maintained biodegradability properties as compared to the olefinic feed, and is particularly useful in drilling fluid and paper sizing compositions.

Description

PROCESSES FOR ISOMERIZING ALPHA OLEFINS

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority from U.S. Provisional Application No. 62/598,629, filed December 14, 2017, which is incorporated herein by reference.

FIELD

[0002] The present disclosure relates to processes for isomenzing alpha olefins to produce an isomerization mixture comprising internal olefins.

BACKGROUND

[0003] Internal olefins are commercially valuable for use in a variety of applications, such as paper sizing agents and drilling fluids. For example, internal olefin based drilling fluids exhibit a number of enhanced properties, such as lower pour point, compared to alpha olefin based drilling fluids. For instance, U.S. Pat. No 5,589,442 discloses synthetic hydrocarbon- based drilling fluids comprising mostly linear C 14 to Cis olefins.

[0004] Internal olefins may be produced via the isomerization of alpha olefins. In the isomerization of alpha olefins to internal olefins for use in drilling fluids, it is desirable to produce an isomerization mixture having a combination of a reduced pour point while maintaining acceptable biodegradability. The pour point of the isomerization mixture generally decreases with increasing conversion of alpha olefins to internal olefins and with increasing formation of branched olefins. In contrast, the biodegradability of the isomerization mixture generally increases with decreased formation of branched olefins, particularly those having extended branching.

[0005] Accordingly, there is a need for highly active and selective methods of isomenzing alpha olefins to internal olefins at high conversion and with a controlled amount of branched olefin formation. References of potential interest may include: U.S. Pat. No. 5,741 ,759; U.S. Pat. No. 5,965,783; U.S. Pat. No. 6,054,629; U.S. Pat. No. 7,956,229; U.S. Pat. No. 5,107,047; U.S. Pat. 5,246,566; U.S. Pat. No. 4,749,819; U.S. Pat. No. 5,177,281; and U.S. Pub. No. U.S. 2005/0070747.

SUMMARY

[0006] According to the present disclosure, it has now been found that employing mesoporous materials having high surface Bronsted acidity, and therefore high activity, as the isomerization catalyst in the isomerization of C4-C24 alpha olefins advantageously allows for the isomerization to be conducted under mild process conditions, particularly at low temperature.

[0007] Thus, in one aspect, the present disclosure relates to a process for isomerizmg one or more C4-C24 alpha olefins to produce an isomerization mixture comprising one or more C4- C24 internal olefins, the process comprising contacting an olefinic feed comprising the one or more C4-C2.4 alpha olefins with a catalyst under isomerization conditions, wherein the catalyst comprises a mesoporous material having a collidine uptake of greater than about 100 pmol/g.

[0008] In a further aspect, the present disclosure relates to a drilling fluid comprising the isomerization mixture produced by the foregoin process.

[0009] In a further aspect, the present disclosure relates to a paper sizing composition comprising the isomerization mixture produced by the foregoing process.

[0010] In a further aspect, the present disclosure relates to a process for isornerizing one or more C14-C2₀ alpha olefins to produce an isomerization mixture comprising one or more Cj_4~ C₂₀ internal olefins, the process comprising contacting an olefinic feed comprising the one or more C14-C2₀ alpha olefins with a catalyst under isomerization conditions, wherein the catalyst comprises a mesoporous material having a collidine uptake of greater than about 100 pmol/g, and wherein the mesoporous material comprises a member of the M41S family.

[0011] In a further aspect, the present disclosure relates to a process for isornerizing one or more C₁₄-C₂₀ alpha olefins to produce an isomerization mixture comprising one or more Cj₄- C₂₀ internal olefins, the process comprising contacting an olefinic feed comprising the one or more C14-C2₀ alpha olefins with a catalyst under isomerization conditions, wherein the catalyst comprises a mesoporous material having a collidine uptake of greater than about 100 pmol/g, and wherein the mesoporous material comprises an amorphous mixed metal oxide.

BRIEF DESCRIPTION OF THE FIGURE

[0012] The Figure depicts the linear internal olefin, branched olefin, and linear alpha olefin concentrations of the isomerization effluent against time on stream (TOS) in the isomerization reaction conducted in Example 6.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] All numerical values within the detailed description and the claims herein are modified by “about” or “approximately” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art. Unless otherwise indicated, room temperature is about 23°C. [0014] As used herein,“wt%” means percentage by weight,“vol%” means percentage by volume,“moI%” means percentage by mole,“ppm” means parts per million, and“ppm wt” and“wppm” are used interchangeably to mean parts per million on a weight basis. All“ppm” as used herein are ppm by weight unless specified otherwise. Ail concentrations herein are expressed on the basis of the total amount of the composition in question. Thus, the concentrations of the various components of the first mixture are expressed based on the total weight of the first mixture. All ranges expressed herein should include both end points as two specific embodiments unless specified or indicated to the contrary.

Definitions

[0015] For the purpose of this specification and appended claims, the following terms are defined.

[0016] Tire term“hydrocarbon” means a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds; (ii) unsaturated hydrocarbon compounds; and (iii) mixtures of hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different values of n, i.e. differing carbon numbers.

[0017] As used herein, a“carbon number” refers to the number of carbon atoms in a hydrocarbon. Likewise, a“C_x” hydrocarbon is one having x carbon atoms (i.e., carbon number of x), and a“C_{x -} C_y” or“C_{x - y}” hydrocarbon is one having from x to y carbon atoms.

[0018] The term“alkane” refers to non-aromatic saturated hydrocarbons with the general formula C_nH_(2n+2), where n is 1 or greater. An alkane may be straight chained or branched. Examples of alkanes include, but are not limited to methane, ethane, propane, butane, pentane, hexane, heptane and octane. “Alkane” is intended to embrace all structural isomeric forms of an alkane. For example, butane encompasses n-butane and isobutane; pentane encompasses n- pentane, isopentane and neopentane.

[0019] The term“olefin,” alternatively referred to as“a!kene,” refers to a branched or unbranched unsaturated hydrocarbon having one or more carbon-carbon double bonds. A simple olefin comprises the general formula C_nH_2n, where n is 2 or greater. Examples of olefins include, but are not limited to ethylene, propylene, butylene, pentene, hexene and heptene. “Olefin” is intended to embrace all structural isomeric forms of an olefin. For example, butylene encompasses but-l-ene, (Z)-but-2-ene, etc.

[0020] As used herein, the term“reactor” refers to any vessel(s) in which a chemical reaction occurs. Reactor includes both distinct reactors, as well as reaction zones within a single reactor apparatus and, as applicable, reactions zones across multiple reactors. For example, a single reactor may have multiple reaction zones. Where the description refers to a first and second reactor, the person of ordinary skill in the art will readily recognize such reference includes two reactors, as well as a single reactor vessel having first and second reaction zones. Likewise, a first reactor effluent and a second reactor effluent will be recognized to include the effluent from the first reaction zone and the second reaction zone of a single reactor, respectively.

[0021] As used herein, kinematic viscosity (KV) is measured using ASTM standard D-445 and reported at temperatures of 100°C (KV100).

[0022] As used herein, pour point is measured according to ASTM D5950

[0023] In the present disclosure, the“collidine uptake' of a catalyst is measured on a TA Instruments Q5000 model TGA machine (available from TA Instruments, 159 Lukens Drive, New Castle, DE 19720, U.S.A.) with a modified gas and vapor delivery system. A catalyst sample of 10 to 50 mg is first dried under flowing N₂ (90 cnrVmin) at 200°C for 60 minutes or until a stable weight is achieved. Then a N stream (90 cm in) flowing through a reservoir of collidine (2,4,6-trimethylpyridine, held at 35°C) and a condenser (held at 26°C) is delivered to the sample. The partial pressure of collidine is set by the temperature of the condenser and the N^t2 flow rate. The sparged collidine was delivered over the sample for 60 minutes, followed by 60 minutes of stripping with flowingN The increase in sample weight indicates adsorption of collidine. Uptake is reported in /imo! (i.e., micromole) collidine per gram of catalyst.

[0024] Various embodiments described herein pro vide processes for the production of one or more C4-C24 internal olefins via isomerization, typically catalytic isomerization, of one or more C4-C24 alpha olefins. It has been found that employing mesoporous materials having high surface Bronsted acidity, and therefore high activity', as the isomerization catalyst advantageously allows for the isomerization to be conducted under mild process conditions, particularly at low' temperature. Conducting the isomerization at a low temperature provides several benefits, such as reducing energy' usage of the process and improving selectivity' to desired products in the resulting isomerization mixture.

Supply of Alpha Olefins

[0025] Generally, the alpha olefins supplied to the isomerization have a carbon number ranging from 4 to 24, more preferably from 14 to 20, more preferably from 15 to 18, and ideally from 16 to 18 Preferably, the alpha olefins supplied to the isomerization are linear alpha olefins. [0026] Typically, the one or more C4-C24 alpha olefins are provided in an olefinic feed. Suitable olefinic feeds for use in various embodiments of the present invention comprise (or consist essentially of, or consist of) C4-C24 alpha olefins, preferably C 14-C20 alpha olefins, such as C15-C18 alpha olefins, ideally C16-C18 alpha olefins. In any embodiment, at least about 50 wt%, preferably at least about 60 wt%, more preferably at least about 80 wt%, more preferably at least about 85 wt%, more preferably at least about 95 wt%, more preferably at least about 99 wt% of the olefinic feed is composed of alpha olefins, preferably alpha olefins, having any of the aforementioned (V(\ ranges (i.e., any of the aforementioned numbers of carbon atoms) based on the total weight of the olefinic feed. For example, in any embodiment the olefinic feed may comprise from about 50 wt% to about 100 wt%, such as from about 75 wt% to about 90 wt%, of alpha olefins, preferably linear al pha olefins, having any of the aforementioned C_x- C_y ranges based on the total weight of the olefinic feed. Particularly preferable olefinic feeds may comprise Cie-Cig alpha olefins, ideally Cie/C g linear alpha olefin mixtures. In such aspects, the olefinic feed typically comprises at least about 40 wt% of Ci₆ alpha olefins, more preferably at least about 60 wt%, such as at least about 65 wt% of C_l6 alpha olefins (preferably linear C c, alpha olefins) based on the total weight of the olefinic feed and, additionally or alternatively, at most about 60 wt%, more preferably at most about 40 wt%, such as at most about 35 wt% of Cis alpha olefins (preferably linear C_l8 alpha olefins) based on the total weight of the olefinic feed, such as from about 60 wt% or from about 65 wt% to 75 wt% C -₆ alpha olefins and from about 25% to about 40 wt% or to about 35 wt% Cis alpha olefins based on the total weight of the olefinic feed.

[0027] In any embodiment, the olefinic feed preferably has an average carbon number (by weight, as measured by GC-MS) of greater than or equal to 14, preferably greater than or equal to 16, such as from 14 to 24.

[0028] Typically, the olefinic feed is substantially linear. For example, the olefinic feed typically has a branched olefin content of less than 10 wt% based on the total weight of the olefinic feed, preferably less than about 8 wt%, more preferably less about 4 wt%, such as from 0 wt% to 10 wt% branched olefin content based on the total weight of the olefinic feed.

[0029] Preferably, the olefinic feed is pretreated prior to isomerization to remove moisture, oxygenates, nitrates, and other impurities that could deactivate the isomerization catalyst. Typically, the pretreatment is performed by passing the feed can be through a guard bed that contains a molecular sieve. Typically, the preheated feed comprises less than about 50 ppmw water based on the weight of the feed, more preferably less than about 25 ppmw water.

- S - Isomerization Catalvst

|0030] Generally, the isomerization is conducted in the presence of a catalyst. Typically, the isomerization catalyst comprises (or consists essentially of, or consists of) a mesoporous material. In this respect, the term‘mesoporous” is used herein to refer to porous material having a maximum perpendicular cross-section pore dimension of at least about 13 Angstroms, and generally within the range of from about 13 Angstroms to about 200 Angstroms. In one embodiment, the mesoporous material can be in the range of about 20 to about 60 Angstroms. In another embodiment, the mesoporous material can be in the range of about 20 to about 50 angstroms, about 20 to about 40 angstroms, about 20 to about 30 angstroms, about 30 to about 60 angstroms, about 30 to about 50 angstroms, about 30 to about 40 angstroms, and about 25 to about 55 angstroms.

[0031] Often, the mesoporous material comprises a crystalline phase material. In such aspects, the mesoporous material may be layered or non-layered, wherein non-layered is herein defined as non-iamellar. In layered (i.e., lamellar) materials, the interatomic bonding in two directions of the crystalline lattice is substantially different from that in the third direction, resulting in a structure that contains cohesive units resembling sheets. Usually, the bonding between the atoms within these sheets is highly covalent, while adjacent layers are held together by ionic forces or van der Waals interactions. These latter forces can frequently be neutralized by relatively modest chemical means, while the bonding between atoms within the layers remains intact and unaffected. Preferred mesoporous materials having a crystalline framework exhibit an X-ray diffraction pattern, after calcination, with at least one peak at a position greater than about 18 Angstrom Units, d-spacing with a relative intensity of 100, and have a benzene adsorption capacity of greater than about 15 grams benzene per 100 grams of the anhydrous material at 50 torr (6.7 kPa) and 25°C. Preferred examples of such mesoporous materials are those belonging to the M41S class or family of catalysts. The M41S family of catalysts are mesoporous materials having high silica contents whose preparation is further described in I. Amer. Chem. Soc., 1992, 114, 10834. Example members of the M41S family of catalysts include MCM-41, MCM-48, and MCM-50. A preferred member of this class is MCM-41 , which has a hexagonal arrangement of uniformly-sized pores and is described in U.S. Pat. Nos. 5,098,684 and 5,057,296, the entire contents of which are incorporated herein by reference. Other suitable members include MCM-48, which has a cubic symmetry and is described in U.S. Pat. No. 5,198,203, and MCM-50, which has a lamellar structure and is described in U.S. Pat. No. 5,304,363. The entire contents of both of these patents are incorporated herein by reference. In an especially preferred embodiment, the isomerization catalyst comprises (or consists essentially of, or consists of) a mesoporous material selected from the group consisting of MCM-41, MCM-48, and MCM-50, in particular Vi ( VI -4 1

[0032] Alternatively, the mesoporous material may comprises an amorphous phase material. Preferred amorphous phase materials include silica, alumina, and mixed metal oxides, such as silica-alumina and/or silica-titania. Exemplary amorphous materials include silica- alumina hydrates available under the trade name Siral™ from Sasoi Performance Chemicals GmbH. In any embodiment, the amorphous material may further comprise a dopant. Suitable dopants include zirconium, magnesium, thorium, beryllium, titanium, and sulfate, preferably sulfate (SG4). Typically, the dopant may be present in an amount ranging from about 0.1 wt% to about 20 wt% based on the weight of the isomerization catalyst, such as from about 1 wt% to about 10 wt%. The dopant may be added via any method known in the art, preferably by impregnating the amorphous material with a solution containing the dopant. For example, convenient sources of zirconium include zirconyl chloride hydrate and zirconium acetate solutions, while a convenient source of sulfate is ammonium sulfate solution. In another especially preferred embodiment, the isomerization catalyst comprises (or consists essentially of, or consists of) an amorphous mesoporous material selected from the group consisting of silica-alumina and/or silica-titania, optionally comprising a dopant selected from the group consisting of zirconium, magnesium, thorium, beryllium, titanium, and sulfate, and mixtures or combinations thereof; in particular silica-alumina and/or silica-titania comprising a zirconium and/or sulfate dopant.

[0033] In any embodiment, the isomerization catalyst may comprise a binder or matrix material from about 0 wt% to about 90 wt% based on the weight of the isomerization catalyst, such as from about 20 wt% to about 50 wt%. The presence of a binder or matrix material is particularly preferred in aspects where the mesoporous material comprises a crystalline phase material. Additionally or alternatively, the isomerization catalyst may be free or substantially free from a binder or matrix material (i.e., be self-bound), particularly in aspects where the mesoporous material is amorphous. For example, binder or matrix material may be present at less than about 10 wt%, or less than about 5 wt%, such as from about 0 to about 1 wt% based on the weight of the isomerization catalyst. Preferred binder or matrix materials include clay and/or inorganic oxides that are resistant to the temperatures and other conditions employed in the present process. Suitable inorganic oxide binders may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Naturally occurring clays which can be used as a binder include those of the montmorillonite and kaolin families, which families include the subbentonites and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolimte, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. Suitable inorganic oxide binders include silica, alumina, zirconia, titania, silica-alumina, silica- magnesia, sihca-zirconia, silica-thoria, silica-beryilia, silica-titania as well as ternary compositions such as silica-alumina-thoria, sihca-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.

[0034] Typically, the isomerization catalyst is free or substantially free from promoters, such as noble metals and transition metals in metal or metal oxide form, e.g., platinum, palladium, ruthenium, iron, cobalt, and nickel. For instance, preferably the isomerization catalyst may comprise a combined platinum, palladium, ruthenium, iron, cobalt, and nickel content of less than about 0.5 wt% based on the weight of the isomerization catalyst, more preferably less than about 0.1 wt% or less than about 0.01 wt%.

[0035] In any embodiment, preferred isomerization catalysts are highly acidic. For example, the isomerization catalyst generally exhibits a collidine uptake as measured using the characterization protocol disclosed above of above 100 pmol/g, such as in a range from CU1 to CU2, where CU1 can be 100, 110, 120, 130, 140, 145, 150, 155, 160, 170, 180, or 190; and CU2 can be 500, 400, 350, 300, 290, 280, 270, 260, 250, 240, 230, 220, 210, or 200 Additionally, where the isomerization catalyst comprises a mesoporous material comprising a crystalline phase material, e.g., a member of the M41S family of catalysts, the mesoporous material may preferably be an aluminosilicate having a SiCh/AbQ_?, molar ratio of less than about 100, such as less than about 50, or less than about 30, or less than about 20, such as from about 15 to about 50

Isomerization of Alpha Olefins

[0036] The isomerization reaction can be conducted in a wide range of reactor configurations including fixed bed (single or m series) and fluidized bed, preferably fixed bed. In addition, the isomerization can be conducted in a single reaction zone or in a plurality of reaction zones.

[0037] Typically, the isomerization is conducted under conditions suitable to maintain the reaction medium in the liquid phase. Preferably, the isomerization is conducted under mild process conditions, particularly at low temperature. Suitable reaction temperatures range from about 50°C to about 200°C, such as from about l00°C to about 180°C, or from about 1 lO°C to about 170°C, or from about 130°C to about l 50°C, while suitable isomerization pressures range from about 2 kPa absolute to about 7,000 kPa absolute, such as from about 5 psig (136 kPa-a) to about 200 psig (1480 kPa-a). Preferably, the olefinic feed is supplied to the reaction at a weight hourly space velocity (WHSV) ranging from about 1 If¹ to about 50 h ¹, more preferably from about 2 lr^] to about 20 h ¹.

[0038] Typically, the isomerization exhibits a high single-pass rate of conversion (measured as 100 minus the remaining amount of LAO expressed in wt%, as measured by GC-MS). For example, preferably the single-pass rate of conversion of the one or more C4-C24 alpha olefins is at least about 40%, more preferably at least about 50%, and ideally at least about 75%. In such aspects, the isomerization can be conveniently conducted in the absence of recycle, i.e., without recycling any portion of the produced isomerization mixture. Preferably, conducting die isomerization without recycle provides several process advantages, such as increasing process reliability and reducing operating costs.

[0039] Preferably, the isomerization reaction is highly selective to the desired internal olefin products, particularly linear internal olefins, and exhibits minimal side reactions, such as skeletal isomerization, oligomerization, and cracking. For example, typically less than about 10 wt% of C4-C24 alpha olefins present in the olefinic feed are converted to product having a lower or higher carbon number. Additionally or alternatively, typically from about 5 wt% to about 30 wt% of linear C4-C24 alpha olefins present (if any) in the olefinic feed are converted to branched olefins.

Isomerization Mixture

[0040] Tire resultin isomerization mixture obtained via isomerization of the one or more C4-C24 alpha olefins according to any one or more of the foregoing embodiments typically comprises (or consists essentially of, or consists of) linear internal olefins, and optionally, branched olefins, e.g., branched internal olefins. For example, the isomerization mixture typically comprises at least about 40 wt%, preferably at least about 60 wt%, more preferably at least about 80 wt%, such as at least about 85 wt%, or at least about 95 wt%, or even at least about 99 wt% of linear internal olefins based on the total weight of the isomerization mixture. The isomerization mixture preferably has a branched olefin content of less than about 35 wt%, preferably less than about 20 wt%, such as less than about 10 wt%, or less than about 8 wt% based on the total weight of the isomerization mixture, such as from about 5 wt% to about 30 wt%, or from about 8 wt% to about 15 wt%, or from about 0 wt% to about 10 wt%. [0041] The isomerization product may also contain some amount of residual C4-C24 alpha olefins. Preferably, the isomerization mixture comprises a residual alpha olefin content of less than about 35 wt%, preferably less than about 10 wt%, and ideally less than about 5 wt% based on the total weight of the isomerization mixture.

[0042] The obtained isomerization mixture may be particularly useful in drilling fluid compositions and paper sizing compositions. Preferred isomerization mixtures suitable for drilling fluid compositions generally comprise 50 wt% or more of C16-C3» linear internal olefins. Such mixtures may be particularly useful as the oil-phase m drilling fluid compositions comprising oil-based drilling emulsions.

[0043] When used for drilling fluid compositions, the isomerization mixture may generally exhibit any one or more of the following properties:

* KV100 within the range from about 1 cSt to about 2 cSt, preferably from about 1 to about 1.1 cSt to about 1.5 cSt;

« Pour point of ~6°C or less, such as ~U^)CC or less, such as -l2°C or less, such as - 15°C or less.

[0044] Additionally or alternatively, when used for drilling fluid compositions the isomerization mixture is typically biodegradable under aerobic and preferably anaerobic conditions. Particularly preferably, the isomerization mixture and drilling fluid compositions comprising the same meet or exceed the anaerobic biodegradability' standard set forth in the Marine Closed Bottle Biodegradation Test System: EPA METHOD 1647.

[0045] The following examples illustrate the present invention. Numerous modifications and variations are possible and it is to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.

EXAMPLES

Gas Chromatography Procedure

[0046] Liquid samples from the reactor effluent were analyzed on an Agilent 7890 Gas Chromatograph (GC) equipped with FID detectors and automatic liquid samplers (ALS). TWO GC methods were employed to analyze the samples - one for measuring the linear alpha olefin (LAO) content and the other for measuring the branched olefin (BO) content. The typical injection size for both methods was about 0.2 mΐ.

[0047] For the LAO content measurement method, the column used was Agil ent DB-WAX (60 m x 250 pm x 0.25 pm). The GC was operated in constant flow mode at 40 psi (280 kPa) inlet pressure and with column flow of 1.839 mL/min using helium as a carrier gas. The following oven procedure was used:

• Initial temperature of 140°C, hold for 17 minutes;

^» Ramp at 25°C/min to 240°C, hold for 8 minutes;

Total analysis time of 29 minutes.

[0048] For the BO content measurement method, liquid sample was first fully hydrogenated to saturated material, from which the BO content was determined by analyzing the total branched aliphatic material. The column used was Agilent HP-1 (60 m x 250 pm x 1 pm) and the inlet liner was a split inlet liner (obtained from Agilent) that was pre-packed with 1 cm height 1% RΪ/ΆI₂O₃. The GC was operated in ramped pressure mode with an initial pressure of 20 psi (140 kPa) to 50 psi (340 kPa) at 7 psi/min (50 kPa/min) using hydrogen as a carrier gas. The following oven procedure was used:

• Initial temperature of 140°C, hold for 17 minutes;

* Ramp at 25°C/min to 240°C, hold for 8 minutes;

* Total analysis time of 29 minutes.

[0049] The LIO content can be assessed as LIO ^::: 100 - LAO content - BO content.

Cie/Cis LAO Isomerization Procedure

[0050] In the following examples, the isomerization of a Cie/C -g LAO feed was conducted in a continuous, isothermal, tubular fixed bed reactor in accordance with the following procedure.

[0051] In each experiment, 1.00 g of the formulated catalyst was loaded between -15-20 g of silicon carbide so that the catalyst was located in the isothermal zone of the reactor. A 65 wt% Ci_6/'35 wt% Gig LAO feed (a blend of A!phap!us™ l-Hexadecene and Alphaplus™ 1- Octadecene, both available from ChevronPhillips Chemical Company LLC) containing ~ 7 wt% vinylidene (as determined by GC) was then introduced into the reactor at a WHSV of 2.5 h ¹. The isomerization reaction was conducted at a pressure of 20 psig (239 kPa-a) at a temperature indicated in the relevant example.

[0052] The resulting isomerization product mixtures were sampled online. The collected samples were analyzed by GC for composition.

Measurement of Alpha Value

[0053] The Alpha Value tests for the materials or compositions in the Examples were performed in accordance with the methods described in U.S. Pat. No. 3,354,078 and in the Journal of Catalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966) and Vol. 61, p. 395 (1980), each incorporated herein by reference. The experimental conditions of the test included a constant temperature of 538°C and a variable flow rate as described in detail in the Journal of Catalysis, Vol. 61, p. 395 (1980).

Measurement of Total Surface Area bv BET

[0054] The total BET was measured by nitrogen adsorption/desorption with a Micromeritics Tristar II 3020 instrument after degassing of the calcined mesoporous materials for 4 hrs at 350°C. More information regarding the method can be found, for example, in “Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density”, S. Lowell el al., Springer, 2004.

Example 1 : LAO Isomerization using Zr-Doped Mixed Silica- Alumina Extrudate

Catalyst Composition

[0055] A Zr-doped mixed silica-alumina extrudate catalyst composition exhibiting a low collidine uptake was prepared in accordance with the following procedure. First, 80 parts by weight, on a calcined at 538°C basis, of Versal-300 pseudoboehmite alumina binder (commercially available from HOP LLC) were mixed and mulled with 20 parts by weight, on a calcined at 538°C basis, of Ultrasil™ silica. Zirconyl chloride hydrate and water were added to the mull mixture in in amounts sufficient to produce an extrudabie paste, after which the mull mixture was extruded into 1/16” (0.16 cm) quadrulobe extrudates. The prepared extrudates were dried at 120°C for 3 hours and then calcined in air at 500°C for 3 hours. The final catalyst composition exhibited a collidine uptake of 27 pmol/'g and Zr content of about 5 wd%.

[0056] The prepared Zr-doped mixed silica-alumina extrudate catalyst composition was used to isomerize a 65 wt% C _G / 35 wt% C g LAO feed in accordance with the above referenced isomerization procedure at an isomerization temperature of 150°C and 170°C. Table 1 summarizes the relative amounts of unreacted LAO, linear internal olefins (LIO), and branched olefins (BO) in the produced isomerization mixtures at the two isomerization temperatures.

Table 1

[0057] As can be seen from Table 1, conducting the isomerization with a catalyst composition having a low collidine uptake resulted in low conversion of LAO feed and accompanying low yield of the desired LIO product.

Example 2: LAO Isomerization using Zr-Doped Self-Bound Silica-Alumina Hydrate

Extrudate Catalyst Composition

[0058] A Zr-doped self-bound silica-alumina hydrate extrudate catalyst composition exhibiting a high collidine uptake was prepared in accordance with the following procedure. First, a sample of Siral™-20 amorphous silica-alumina hydrate m pow'der form (obtained from Sasol Performance Chemicals GmbH) was mulled. A solution of zirconyl chloride in water was added to the mulled silica-alumina hydrate in an amount sufficient to produce an extrudable paste, after which the resulting paste was extruded into 1/16” (0.16 cm) quadrulobe extrudates. The prepared extrudates were dried at 120°C for 3 hours, and then calcined in air at 500°C for 3 hours. The final catalyst composition exhibited a Zr content of 18.2 wt% and a collidine uptake of 131 pmol/g.

[0059] The prepared Zr-doped self-bound amorphous silica-alumina hydrate extrudate catalyst composition was used to isomerize a 65 wt% Cu, / 35 wt% C g LAO feed in accordance with the above referenced isomerization procedure at an isomerization temperature of l30°C and 150°C. Table 2 summarizes the relative amounts of unreacted LAO, LIO, and BO in the produced isomerization mixtures at the two isomerization temperatures.

Table 2

[0060] As can be seen from Table 2, conducting the isomerization with a catalyst composition having a high collidine uptake resulted in significantly higher LAO conversion and LIO yield as compared to the results achieved using the low' collidine catalyst composition of Example 1.

Example 3: SQ₄-Doped Self-Bound Amorphous Silica-Alumina Hydrate Extrudate Catalyst Composition Synthesis (1.49 wt% S content)

[0061] A S0₄-doped self-bound silica-alumina hydrate extrudate catalyst composition exhibiting a high collidine uptake was prepared in accordance ith the following procedure. First, a sample of Siral™-20 amorphous silica-alumina hydrate in powder form (obtained from Sasol Performance Chemicals GmbH) was mulled. Water was added to the mulled silica- alumina hydrate in an amount sufficient to produce an extrudable paste, after which the resulting paste was extruded into 1/16’ (0.16 cm) quadrulobe extradates. The prepared extrudates were dried at 120°C for 3 hours, and subsequently calcined in air at 500°C for 3 hours. The calcined extrudates were then impregnated with a desired amount of ammonium sulfate solution, dried, and subsequently calcined in air at 538°C for 3 hours. The final catalyst composition exhibited a S content of 1.49 wt% and a collidine uptake of 253 pmol/g.

Example 4: SQi-Doped Self-Bound Silica-Alumina Hydrate Extrudate Catalyst Composition Synthesis (2.6 wt% S content)

[0062] A S0₄-doped self-bound amorphous silica-alumina hydrate extrudate catalyst composition exhibiting a high collidine uptake was prepared in accordance with the following procedure. First, a sample of Siral™-20 amorphous silica-alumina hydrate in powder form (obtained from Sasol Performance Chemicals GmbH) was mulled. Water was added to the mulled silica-alumina hydrate in an amount sufficient to produce an extrudable paste, after which the resulting paste was extruded into 1 /16” (0.16 cm) quadrulobe extradates. The prepared extradates were dried at 120°C for 3 hours, and subsequently calcined in air at 500°C for 3 hours. The calcined extrudates were then impregnated with additional ammonium sulfate solution, dried, and subsequently calcined in air at 538°C for 3 hours. The final catalyst composition exhibited a S content of 2.6 wt% and a collidine uptake of 286 pmol/g. As can be seen from a comparison of Examples 3 and 4, a higher collidine uptake was observed on the mesoporous material containing a higher level of sulfate dopant.

Example 5: Al-MCM-41 Alumina-Bound Extrudate Catalyst Composition Synthesis iSiQ?/AbO, of - 50)

[0063] Al-MCM-41 crystals prepared in accordance with the methods of U. S. Pat. No. 7,538,065 having 3qA pores and a SiCh/AhO, molar ratio of -50 were used to prepare a 65 wt% zeolite/35 wt% alumina particle in accordance with the following procedure. First, 65 parts by weight, on a calcined at 538°C basis, of the Al-MCM-41 crystals were mulled with 35 parts by weight, on a calcined at 538°C basis, of Versal-300 pseudoboehmite alumina binder (commercially available from UOP LLC). Deionized w¾ter was added to the mull mixture in an amount sufficient to produce an extrudable paste, after which the mull mixture w¾s extruded into 1/16” (0.16 cm) quadrulobe extrudates. The prepared extrudates were dried at 120°C for 3 hours, and subsequently calcined in air at 540°C for 3 hours. The final catalyst composition exhibited a hexane sorption of 54.2 mg/g, surface area of 535 m²/g, and a collidine uptake of 217 pmol/'g.

Example 6: C ^'Cis LAO isomerization using Al-MCM-41 Alumina-Bound Extrudate Catalyst Composition 25)

[0064] Al-MCM-41 crystals prepared in accordance with the methods of U.S. Pat. No. 7,538,065 having 3qA pores and a SiCh/AbXL molar ratio of~25 were used to prepare a 65 wt% zeolite/35 wt% alumina particle in accordance with the following procedure. First, 65 parts by weight, on a calcined at 538°C basis, of the Al-MCM-41 crystals were mulled with 35 parts by weight, on a calcined at 538°C basis, of Versal-300 pseudoboehmite alumina hinder (commercially available from UOP LLC). Deionized water was added to the mull mixture in an amount sufficient to produce an extrudable paste, after which the mull mixture w¾s extruded into 1/16” (0.16 cm) quadrulobe extrudates. The prepared extrudates were dried at 120°C for 3 hours, and subsequently calcined in air at 540°C for 3 hours. The final catalyst composition exhibited a hexane sorption of 59.7 mg/g, surface area of 814 m²/g, and a collidine uptake of 260 pmol/g. As can be seen from a comparison of Examples 5 and 6, a higher collidine uptake was observed on the mesoporous material formulated from Al-MCM-41 crystals having a lower SiQyAhChjnolar ratio.

[0065] Tire prepared Al-MCM-41 alumina-bound extrudate catalyst composition of this example was used to isomerize a 65 wt% C_½ / 35 wt% Cis LAO feed in accordance with the above referenced isomerization procedure at an isomerization temperature of 130°C for 232 hours. Tire relati ve amounts of unreacted LAO, LIO, and BO in the produced isomerization mixture of the produced isomerization mixture against time on stream (TOS) is summarized in the Figure. Additionally, the mixture sampled at 232 hours TOS was analyzed for pour point, winch was determined as -11.1°C.

[0066] As seen from the Figure, high LAO conversion and selectivity towards the desired LIO was observed over the duration of the reaction. Moreover, the produced isomerization mixtures, containing a branched olefin content of ~8 wt%, exhibited a favorable balance between a branched olefin content low' enough to maintain biogradability properties while high enough to attain a reduced pour point of -11.1°C.

[0067] All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited thereby. Likewise, the term "comprising" is considered synonymous with the term "including" for purposes of United States law. Likewise whenever a composition, an element or a group of elements is preceded with the transitional phrase "comprising", it is understood that it is also contemplated that the same composition or group of elements with transitional phrases "consisting essentially of," "consisting of, "selected from the group of consisting of," or "is" preceding the recitation of die composition, element, or elements and vice versa.

[0068] Additionally or alternately, embodiments disclosed herein relate to:

[0069] Embodiment 1 : A process for isomerizmg one or more C4-C24 alpha olefins to produce an isomerization mixture comprising one or more C4-C24 internal olefins, the process comprising contacting an olefini c feed comprising the one or more C4-C24 alpha olefins with a catalyst under isomerization conditions, wherein the catalyst comprises a mesoporous material having a collidine uptake of greater than about 100 pmol/g.

[007Q] Embodiment 2: The process of embodiment 1, wherein the mesoporous material comprises a crystalline phase material.

[0071] Embodimetn 3 : The process of embodiment 1 or 2, wherein the mesoporous material comprises a member of the M41S family.

[0072] Embodiment 4: The process of any one of embodiments 1 to 3, wherein the mesoporous material is selected from the group consisting of MCM-41, MCM-48, MCM-50, and mixtures or combinations thereof.

[0073] Embodiment 5: The process of any one of embodiments 1 to 4, wherein the mesoporous material comprises an amorphous phase material.

[0074] Embodiment 6: The process of any one of embodiments 1 to 5, wherein the mesoporous material comprises a mixed metal oxide.

[0075] Embodiment 7: The process of any one of embodiments 1 to 6, wherein the mesoporous material comprises silica-alumina and/or silica-titania.

[0076] Embodiment 8: The process of any one of embodiments 5 to 7, wherein the mesoporous material further comprises a dopant selected from the group consisting of zirconium, magnesium, thorium, beryllium, titanium, and sulfate, and mixtures or combinations thereof.

[QQ77] Embodiment 9: The process of any one of embodiments 1 to 8, wherein the mesoporous material has a colli dine uptake of greater than about 200 pmol/'g. [0078] Embodiment 10: The process of any one of embodiments 1 to 9, wherein the catalyst further comprises a binder selected from the group consisting of clay, inorganic oxides, and mixtures or combinations thereof.

[0079] Embodiment 11 : The process of any one of embodiments 1 to 9, wherein the catalyst is free or substantially free of a binder.

[0080] Embodiment 12: The process of any one of embodiments 1 to 1 1, wherein the olefinic feed has an average carbon number of greater than or equal to 14.

[0081] Embodiment 13: The process of any one of embodiments 1 to 12, further comprising passing the olefinic feed through a guard bed prior to contacting with the catalyst.

[0082] Embodiment 14: The process of any one of embodiments 1 to 13, wherein the olefinic feed comprises C_l6 alpha olefins at a concentration of at least about 40 wt% based on the total weight of the olefinic feed.

[0083] Embodiment 15: The process of embodiment 14, wherein the olefinic feed comprises Cie alpha olefins at a concentration of at least about 60 wt%, preferably at least about 65 wt% based on the total weight of the olefinic feed, and wherein the olefinic feed comprises Cig alpha olefins at a concentration of at most about 40 wt%, preferably at most about about 35 wt% based on the total weight of the olefinic feed.

[0084] Embodiment 16: The process of any one of embodiments 1 to 15, wherein the isomerization conditions comprise a temperature from about 50°C to about 200°C.

[0085] Embodiment 17: The process of embodiment 16, wherein the temperature ranges from about 100°C to about 180°C.

[QQ86] Embodiment 18: The process of any one of embodiments 1 to 17, wherein the olefinic feed is supplied at a weight hourly space velocity (WHSV) from about 1 h:¹ to about 50 h ¹.

[0087] Embodiment 19: The process of any one of embodiments 1 to 18, wherein the rate of conversion of the C4-C24 alpha olefins to the C4-C24 internal olefins is at least about 40%.

[0088] Embodiment 20: The process of any one of embodiments 1 to 19, wherein the isomerization mixture comprises linear internal olefins at a concentration of about 40 wt% or more based on the total weight of the isomerization mixture, and optionally comprises linear alpha olefins at a concentration of less than about 35 wt% based on the total weight of the isomerization mixture. [0089] Embodiment 21: The process of any one of embodiments 1 to 20, wherein the isomerization mixture comprises branched olefins at a concentration of about 35 wt% or less based on the total weight of the isomerization mixture.

[0090] Embodiment 22: The process of embodiment 21, wherein the isomerization mixture comprises branched olefins at a concentration ranging from about 5 wt% to about 35 wt% based on the total weight of the isomerization mixture.

[0091] Embodiment 23: The process of any one of embodiments 1 to 22, wherein the isomerization mixture has a pour point of about -6°C or less.

[0092] Embodiment 24: A drilling fluid or a paper sizing composition comprising the isomerization mixture produced by any one of embodiments 1 to 23.

[0093] Embodiment 25: A process for isomerizing one or more C14-C20 alpha olefins to produce an isomerization mixture comprising one or more C14-C20 internal olefins, the process comprising contacting an olefimc feed comprising the one or more C 14-C20 alpha olefins with a catalyst under isomerization conditions, wherein the catalyst comprises a mesoporous material having a collidine uptake of greater than about 100 pmol/g, and wherein the mesoporous material comprises a member of the M41 S family.

[QQ94] Embodiment 26: A process for isomerizing one or more C i4-C₂o alpha olefins to produce an isomerization mixture comprising one or more C14-C20 internal olefins, the process comprising contacting an olefinic feed comprising the one or more C_M-C20 alpha olefins with a catalyst under isomerization conditions, wherein the catalyst comprises a mesoporous material having a collidine uptake of greater than about 100 pmol/g, and wherein the mesoporous material comprises an amorphous mixed metal oxide.

Claims

CLAIMS:

1. A process for isomerizing one or more C4-C24 alpha olefins to produce an isomerization mixture comprising one or more C4-C24 internal olefins, the process comprising contacting an olefinic feed comprising the one or more C₄-C2₄ alpha olefins with a catalyst under isomerization conditions, wherein the catalyst comprises a mesoporous material having a collidine uptake of greater than about 100 pmol/g.

2. The process of claim 1, wherein the mesoporous material comprises a crystalline phase material.

3. The process of claim 1 or 2, wherein the mesoporous material comprises a member of the M41 S family.

4. The process of any one of claims 1 to 3, wherein the mesoporous material is selected from the group consisting of MCM-41, MCM-48, MCM-50, and mixtures or combinations thereof, preferably MCM-41.

5. The process of claim 1, wherein the mesoporous material comprises an amorphous phase material.

6. The process of claim 5, wherein the mesoporous material comprises a mixed metal oxide.

7. The process of claim 6, wherein the mesoporous material comprises silica-alumina and/or si!ica-titania.

8. The process of any one of claims 5 to 7, wherein the mesoporous material further comprises a dopant selected from the group consisting of zirconium, magnesium, thorium, beryllium, titanium, and sulfate, and mixtures or combinations thereof.

9. The process of any one of claims 1 to 8, wherein the mesoporous material has a collidine uptake of greater than about 200 pmol/g.

10. The process of any one of claims 1 to 9, wherein the catalyst further comprises a binder selected from the group consisting of clay, inorganic oxides, and mixtures or combinations thereof.

11. The process of any one of claims 1 to 9, wherein the catalyst is free or substantially free of a binder.

12. The process of any one of claims 1 to 1 1 , wherein the olefimc feed has an average carbon number of greater than or equal to 14.

13. The process of any one of claims 1 to 12, further comprising passing the olefinic feed through a guard bed prior to contacting with the catalyst.

14. The process of any one of claims 1 to 13, wherein the olefimc feed comprises Cie alpha olefins at a concentration of at least about 40 wt% based on the total weight of the olefinic feed.

15. The process of claim 14, wherein the olefinic feed comprises Ci6 alpha olefins at a concentration of at least about 60 wt%, preferably at least about 65 wt% based on the total weight of the olefinic feed, and wherein the olefinic feed comprises Cig alpha olefins at a concentration of at most about 40 wt%, preferably at most about about 35 wt% based on the total weight of the olefi c feed.

16. The process of any one of claims 1 to 15, wherein the isomerization conditions comprise a temperature from about 50°C to about 200°C.

17. The process of claim 16, wherein the temperature ranges from about 100°C to about 180°C.

18. The process of any one of claims 1 to 17, wherein the olefinic feed is supplied at a weight hourly space velocity (WHSV) from about 1 h ^] to about 50 h ¹.

19. The process of any one of claims 1 to 18, wherein the rate of conversion of the C4-C24 alpha olefins to the C₄-C₂₄ internal olefins is at least about 40%.

20. The process of any one of claims 1 to 19, wherein the isomerization mixture comprises linear internal olefins at a concentration of about 40 wt% or more based on the total weight of the isomerization mixture, and optionally comprises linear alpha olefins at a concentration of less than about 35 wt% based on the total weight of the isomerization mixture.

21. The process of any one of claims 1 to 20, wherein the isomerization mixture comprises branched olefins at a concentration of about 35 wt% or less based on the total weight of the isomerization mixture.

22. The process of claim 21 , wherein the isomerization mixture comprises branched olefins at a concentration ranging from about 5 wt% to about 35 with» based on the total weight of the isomerization mixture.

23. The process of any one of claims 1 to 22, wherein the isomerization mixture has a pour point of about ~6°C or less.

24. A drilling fluid or a paper sizing composition comprising the isomerization mixture produced by any one of claims 1 to 23.

25. A process for isomerizmg one or more C_l4-C₂o alpha olefins to produce an isomerization mixture comprising one or more C1₄-C20 internal olefins, the process comprising contacting an olefime feed comprising the one or more C14-C20 alpha olefins with a catalyst under isomerization conditions, wherein the catalyst comprises a mesoporous material having a collidine uptake of greater than about 100 pmol/g, and wherein the mesoporous material comprises a member of the M41S family.

26. A process for isomerizing one or more C14-C20 alpha olefins to produce an isomerization mixture comprising one or more C14-C20 internal olefins, the process comprising contacting an olefime feed comprising the one or more C1₄-C2₀ alpha olefins with a catalyst under isomerization conditions, wherein the catalyst comprises a mesoporous material having a collidine uptake of greater than about 100 pmol/g, and wherein the mesoporous material comprises an amorphous mixed metal oxide.