CROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U.S. Application Serial No 16/156,616 filed on October 10, 2018, the entire disclosure of which is hereby incorporated by reference.

TECHNICAL FIELD

[0002] Embodiments of the present disclosure generally relate to propylene production, and more specifically relate to catalyst systems used for converting butene to propylene via metathesis.

BACKGROUND

[0003] In recent years, there is a dramatic increase in the demand for propylene to feed the growing markets for polypropylene, propylene oxide and acrylic acid. Currently, most of the propylene produced worldwide is a by-product from steam cracking units, which primarily produce ethylene, or a by-product from Fluid Catalytic Cracking (FCC) units, which primarily produce gasoline. These processes cannot respond adequately to a rapid increase in propylene demand. However, the processing of lower-cost butenes co produced by these processes gives the refiner or the petrochemical producer an opportunity to add value depending on downstream integration and relative economics. However, propylene demand growth has exceeded ethylene and gasoline and distillate demand growth, and propylene supply has not kept pace with this increase in demand

[0004] Olefin metathesis is considered a useful reaction to shift the composition of a pool of low- value butenes to meet market demand for propylene. With ne capacity coming on-stream in the Middle East and Asia, propylene production via metathesis is expected to increase.

SUMMARY

[0005] Catalytic olefin metathesis is a useful chemical reaction that is able to transform simple and cheap organic molecules into complex and valuable molecules. In olefin metathesis, two olefin molecules exchange the groups around the double bonds in the presence of a catalyst. The olefins can be of different molecules by structure and composition, or two identical molecules. In general, reaction temperatures for olefin metathesis reactions can be as low as at room temperature or can be at temperatures up to about 550 °C or greater, depending on the type of starting materials, the catalyst used, and the media in which the reaction is carried out.

[0006] However, metathesis catalysts often do not have the requisite selectivity to yield propylene and other products. Additionally, metathesis catalysts are subject to deactivation due to coking from aromatic products.

[0007] Accordingly, ongoing needs exist for metathesis catalyst systems for the selective production of propylene using butenes metathesis. Embodiments of the present disclosure are directed to the production of propylene via metathesis using metathesis catalyst systems comprising a large pore silica support impregnated with tungsten and doped with a solid metal co-catalyst.

[0008] Moreover, conventional metathesis catalyst systems may include a co-catalyst, such as aluminum, that is added to the base catalyst that includes a metal oxide and a support. However, in these conventional catalyst systems, when the aluminum is simply added to the base catalyst, the metal oxide of the base catalyst may cover the aluminum co-catalyst, thereby causing a crystallite. The crystallite may then cause the catalyst system to quickly deactivate, which is costly and inefficient in propylene production applications.

[0009] Accordingly, ongoing needs exist for metathesis catalyst systems, which include metal-based co-catalysts that increase the selective product of propylene yet do not cause crystallite formation that deactivates the system. Further embodiments of the present disclosure are directed to methods of synthesizing a metathesis catalyst system, which disperse a metal-based co-catalyst onto a base catalyst. According to one embodiment, a method of synthesizing a metathesis catalyst system is disclosed, which may include impregnating tungsten oxide on silica support in the presence of a precursor to produce a base catalyst; calcining the base catalyst, dispersing a solid metal-based co-catalyst onto the surface of the base catalyst to produce a doped catalyst; and calcining the doped catalyst to produce a metathesis catalyst system. As a result, the sequential calcination steps prevent the disclosed metathesis catalyst systems from deactivating as fast as conventional metathesis catalyst systems

[0010] According to another embodiment, a process for the production of propylene is disclosed, which includes contacting a hydrocarbon feedstock comprising a mixture of 1- butene and 2-butene with embodiments of the metathesis catalyst system to produce, via metathesis conversion, a product stream comprising propylene.

[0011] Additional features and advantages of the present embodiments will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the described embodiments, including the detailed description which follows, the claims, as well as the appended drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

[0012] FIG. 1 is graph that illustrates the X-ray diffraction (XRD) analysis carried out for an embodiment of a large pore silica support.

[0013] FIG. 2 is a graph that il lustrates the XRD analysis of tungsten oxide versus a 10 wt. % WO ₃ /S1O ₂ base catalyst denoted by dotted and solid lines, respectively.

[0014] FIG. 3 is a graph illustrating the effect of weight percent of the co-metal in embodiments of the metathesis catalyst system on propylene yield at 450 °C.

[0015] FIG. 4 is a graph illustrating the effect of weight percent of the co-metal on propylene yield at 500 °C.

[0016] FIG. 5 is a graph illustrating the effect of weight percent of the co-metal on propylene yield at 550 °C.

DETAILED DESCRIPTION

[0017] Embodiments of the present disclosure are directed to systems and methods for converting a butene stream to propylene via catalyzed metathesis. As used in the application,“metathesis” is generally a two-step process: 2-butene isomerization and then cross-metathesis using the metathesis catalyst as depicted as follows in Formulas 1 and 2

[0018] Formula 1 : 2-Butene Isomerization tvtetai e-sis

0019] Formula 2: Cross-Metathesis

Penisns Butene Buteni Prapene

[0020] As shown in Formulas 1 and 2, the“metathesis” reactions are not limited to these reactants and products; however, this is the basic illustration of the reaction methodology. As shown, metathesis reactions take place between two alkene molecules. The groups bonded to the carbon atoms of the double bond are exchanged between the molecules to produce two new alkenes with the swapped groups. The specific metathesis catalyst system that is selected for the metathesis reaction helps to determine whether a cis-isomer or trans-isomer is formed, as the coordination of the olefin molecules with the metathesis catalyst system play an important role, as do the steiic influences of the substituents on the double bond of the newly formed molecule.

[0021] Here, methods of synthesizing a metathesis catalyst system may include impregnating tungsten oxide on silica support in the presence of a precursor to produce a base catalyst, calcining the base catalyst, dispersing a solid metal-based co-catalyst onto the surface of the base catalyst to produce a doped catalyst, and calcining the doped catalyst to produce a metathesis catalyst system. As stated previously in this disclosure, sequential calcination steps of this method prevent the disclosed metathesis catalyst systems from deactivating as fast as conventional metathesis catalyst systems. [0022] The metathesis catalyst system includes a base catalyst. In some embodiments, the base catalyst includes tungsten oxide impregnated on a large pore silica support in the presence of a precursor. As used in this application,‘"silica support” means a large pore silica catalyst that has been calcined. As used in this application“large pore” means a pore volume of at least 0.700 cnrVg. In other embodiments, a large pore silica support may have a pore volume from at least 0.700 cm g to about 2.5 cm g, from about 0 800 em ³ /g to about 2.5 cm7g, from about 0.800 cm/Vg to about 1.5 cm /g, from about 0.800 cmVg to about 1.25 cm7g, from about 0.800 cm’/g to about 1.0 cm’/g, or from about 0.850 cm’/g to about 1 0 cnrVg. In some embodiments, for example, the large pore silica catalyst may be a commercial spherical catalyst, such as Q-10, provided by Fuji Silysia Chemical, Ltd., which has an average pore diameter of about 10 nm, an average pore volume of about 1.00 mL/g, and a surface area of about 300 m ² /g.

[0023] In some embodiments, the large pore silica support may be an amorphous silica. As used in this application,“amorphous” means an amorphous silica support with a non- ordered structure and a narrow pore size distribution. This non-ordered structure may be random and thus different than the disclosed hexagonal or cubic structures of conventional silica supports. Specifically, the amorphous silica has a narrow pore size distribution of at least 3 nm to about 40 nm and a total pore volume of at least 0.700 em ³ /g. In other embodiments, the pore size distribution may range from at least 3 nm to about 40 nm, from about 3 nm to about 20 nm, from about 4 nm to about 10 nm, from about 4 nm to about 8 nm, or from about 4 nm to about 6 nm. In further embodiments, the total pore volume may be from at least 0.700 cnrVg to about 2.5 cm ³ /g, from about 0.800 cm7g to about 2.5 cm’/g, from about 0.800 cm g to about 1.5 cm7g, from about 0.800 cm7g to about 1.25 cnrVg, from about 0.800 cm ³ /g to about 1.0 cm ³ /g, or from about 0.850 cm’/g to about 1.0 cm’/g.

[0024] As stated previously, the large pore silica support may be prepared by placing a desired amount of a large pore silica catalyst on a ceramic plate and calcining the large pore silica catalyst. In some embodiments, the large pore silica catalyst may be calcined at a temperature of at least 100 °C. In other embodiments, the large pore silica catalyst may be calcined at from about 100 °C to about 700 °C, from about 100 °C to about 600 °C, from about 100 °C to about 500 °C, from about 100 °C to about 400 °C, from about 100 °C to about 300 °C, from about 100 °C to about 200 °C, from about 200 °C to about 700 °C, from about 200 °C to about 600 °C, from about 200 °C to about 500 °C, from about 200 °C to about 400 °C, from about 200 °C to about 300 °C, from about 300 °C to about 700 °C, from about 300 °C to about 600 °C, from about 300 °C to about 500 °C, from about 300 °C to about 400 °C, from about 400 °C to about 700 °C, from about 400 °C to about 600 °C, from about 400 °C to about 500 °C, from about 500 °C to about 700 °C, from about 500 °C to about 600 °C, or from about 600 °C to about 700 °C.

[0025] Additionally, in some embodiments, the large pore silica catalyst may be calcined at a temperature for at least 1 hour. In other embodiments, the large pore silica catalyst may be calcined at a temperature for about 1 hour to about 7 hours, about 1 hour to about 6 hours, about 1 hour to about 5 hours, about 1 hour to about 4 hours, about 1 hour to about 3 hours, about 1 hour to about 2 hours, for about 2 hours to about 7 hours, about 2 hours to about 6 hours, about 2 hours to about 5 hours, about 2 hours to about 4 hours, about 2 hours to about 3 hours, for about 3 hours to about 7 hours, about 3 hours to about 6 hours, about 3 hours to about 5 hours, about 3 hours to about 4 hours, for about 4 hours to about 7 hours, about 4 hours to about 6 hours, about 4 hours to about 5 hours, for about 5 hours to about 7 hours, or about 5 hours to about 6 hours, about 6 hours to about 7 hours.

[0026] Also, the large pore silica catalyst may calcined at ramping rate of at least

1 ° C/minute. In other embodiments, the ramping rate may be from about 1 ° C/minute to about 5 °C/minute, from about 1 °C/minute to about 4 °C/minute, from about 1 ° C/minute to about 3 °C/minute, from about 1 ° C/minute to about 2 °C/minute, from about

2 °C/minute to about 5 °C/minute, from about 2 °C/minute to about 4 °C/minute, from about 2 °C/minute to about 3 °C/minute, from about 3 °C/minute to about 5 ° C/minute, from about 3 °C/minute to about 4 °C/minute, or from about 4 ° C/minute to about 5 °C/minute.

[0027] In further embodiments, the large pore silica catalyst may be calcined at multiple ramping rates and temperatures for various amounts of times to produce the large pore silica support. For example, in some embodiments of producing the large pore silica support, the large pore silica catalyst may be calcined at 200 °C for three hours and again at 575 °C for five hours, with a ramping rate of 3 ^c C/minute, resulting in the large pore silica support.

[0028] Without being bound by theory, the pore size distribution and pore volume of the large pore silica support are sized to achieve better catalytic activity and reduced blocking of pores by metal oxides, whereas smaller pore volume and pore size silica supports are susceptible to pore blocking and thereby reduced catalytic activity. Reduced blocking leads to higher dispersion of metal oxide species, such as tungsten oxide, on the large pore silica support. Higher tungsten oxide dispersion leads to higher metathesis activity and thus higher propylene yield.

[0029] The metal oxide of the base catalyst may comprise one or oxides of a metal from the Periodic Table RIP AC Group Numbers 6-10. In one or more embodiments, the metal oxide may be an oxide of molybdenum, rhenium, tungsten, or combinations. In some embodiments, the metal oxide is tungsten oxide (W0 ₃ ). It is contemplated that various amounts of metal oxide may be impregnated into the large pore silica support. For example and not by way of limitation, the molar ratio of silica to metal oxide, for example, W0 ₃ , is about 1 to about 50, about l to about 40, about 5 to about 30, about 5 to about 15. In some embodiments, the base catalyst may include from about 5 wt.% to about 15 wt.%, about 5 wt.% to about 12 wt.%, about 5 wt.% to about 8 wt.%, about 8 wt.% to about 15 wt.%, about 8 wt.% to about 12 wt.%, or about 8 wt.% to about 10 wt.% of metal oxide based on the total weight of the base catalyst. Moreover, the metathesis catalyst system may include from about 1 to about 50% by weight, or from about 2 to about 25% by weight, or from about 5 to about 15% by weight metal oxide, for example, WO ₃ , based on the total weight of the metathesis catalyst system.

[0030] As stated previously, in some embodiments, the base catalyst includes tungsten oxide impregnated on a large pore silica support in the presence of a precursor. A precursor may be any nonporous material that participates in a chemical reaction of the large pore silica support to produce the metal oxide that is impregnated onto the large pore silica support. In some embodiments, the metal precursor may be ammonium metatungstate hexahydrate. In other embodiments, the metal precursor may include tungsten chlorides. In other embodiments, the metal precursor may include tungsten hexaearbonyi

[0031] To prepare the base catalyst, a large pore silica support may be impregnated with a metal oxide in the presence of the precursor. In some methods of impregnating the large pore silica support, the large pore silica support and water may be placed in a flask to produce a large pore silica support and water solution. In some embodiments, an amount of precursor may be weighed and mixed with the large pore silica support and water solution. The large pore silica support and water solution with precursor may then be stirred for to produce a homogeneous mixture in which the precursor is dispersed in the large pore silica support. The mixture may then be rotated and heated. In some embodiments, a vacuum may be applied to the mixture to remove excess water. After vacuuming the water from the mixture, this may produce a slurry material. In some embodiments, the slurry material may be cooled to room temperature. In further embodiments, the slurry material may be dried, for example, in an oven, producing a dried material. In further embodiments, the dried material may be crushed into powder and calcined, for example, in a furnace.

[0032] As stated previously in this disclosure, conventional metathesis catalyst systems may include a co-catalyst, such as aluminum, that is added to the base catalyst. However, in these conventional catalyst systems, when the aluminum is simply added to the base catalyst, the tungsten oxide of the base catalyst may cover the aluminum, thereby causing a crystallite. The crystallite may then cause the catalyst to quickly deactivate. Here, the calcination of the base catalyst prior to adding the metal -based co-catalyst prevents the formation of such crystallites. As such, the presently disclosed metathesis catalyst systems are commercially advantageous in propylene production applications, because they do not deactivate as fast as conventional catalyst systems

[0033] In some embodiments of preparing the base catalyst, the base catalyst may be calcined after it has been impregnated with the metal oxide. In some embodiments, the base catalyst may be calcined at a temperature of at least 100 °C. In other embodiments, the base catalyst may be calcined at from about l 00 °C to about 700 °C, from about 100 °C to about 600 °C, from about 100 °C to about 500 °C, from about 100 °C to about 400 °C, from about 100 °C to about 300 °C, from about 100 °C to about 200 °C, from about 200 °C to about 700 °C, from about 200 °C to about 600 °C, from about 200 °C to about 500 °C, from about 200 °C to about 400 °C, from about 200 °C to about 300 °C, from about 300 °C to about 700 °C, from about 300 °C to about 600 °C, from about 300 °C to about 500 °C, from about 300 °C to about 400 °C, from about 400 °C to about 700 °C, from about 400 °C to about 600 °C, from about 400 °C to about 500 °C, from about 500 °C to about 700 °C, from about 500 °C to about 600 °C, or from about 600 °C to about 700 °C.

[0034] Additionally, in some embodiments, the base catalyst may be calcined at a temperature for at least 1 hour. In other embodiments, the base catalyst may be calcined at a temperature for about 1 hour to about 7 hours, about 1 hour to about 6 hours, about 1 hour to about 5 hours, about 1 hour to about 4 hours, about 1 hour to about 3 hours, about

1 hour to about 2 hours, for about 2 hours to about 7 hours, about 2 hours to about 6 hours, about 2 hours to about 5 hours, about 2 hours to about 4 hours, about 2 hours to about 3 hours, for about 3 hours to about 7 hours, about 3 hours to about 6 hours, about 3 hours to about 5 hours, about 3 hours to about 4 hours, for about 4 hours to about 7 hours, about 4 hours to about 6 hours, about 4 hours to about 5 hours, for about 5 hours to about 7 hours, or about 5 hours to about 6 hours, about 6 hours to about 7 hours.

[0035] Also, the base catalyst may calcined at ramping rate of at least 1 °C/minute. In other embodiments, the ramping rate may be from about l °C/minute to about 5 °C/minute, from about 1 °C/minute to about 4 °C/minute, from about 1 °C/minute to about 3 °C/minute, from about 1 °C/minute to about 2 °C/minute, from about 2 °C/minute to about 5 °C/minute, from about 2 °C/minute to about 4 °C/minute, from about

2 °C/minute to about 3 °C/minute, from about 3 °C/minute to about 5 °C/minute, from about 3 °C/minute to about 4 °C/minute, or from about 4 °C/minute to about 5 ° C/minute. [0036] In further embodiments, the base catalyst may be calcined at multiple ramping rates and temperatures for various amounts of times. For example, in some embodiments of producing the base catalyst, the base catalyst may be calcined at 250 °C for two hours and at 550 °C for 8 hours, with a ramping rate of 1 ° C/minute until the temperature of 250 °C is reached and 3 °C/minute until the temperature of 550 °C is reached, therefore producing the base catalyst.

[0037] Embodiments of the metathesis catalyst system also include a doped catalyst, which includes a co-metal doped onto the base catalyst via a solid metal-based co-catalyst. In some embodiments, the co-metal may be platnium (Pt), palladium (Pd), or aluminum (Al). In further embodiments, the doped catalyst includes a solid metal-based co-catalyst dispersed onto the base catalyst. In some embodiments, the solid metal -based co-catalyst may be Pt0 ₂ , PdCl ₂ , gamma- Al ₂ 0 ₃ , or combinations of these.

[0038] To prepare the doped catalyst, a base catalyst may be prepared as previously described, and a solid metal -based co-catalyst may be dispersed onto the base catalyst. In some embodiments, the solid metal-based co-catalyst may be dispersed by ball milling. In embodiments of a ball milling method, a ball mill mechanical stirrer may be used, which includes a vessel with steel balls inside. The ball mill mechanical stirrer may mix or stir or disperse the base catalyst with the solid metal -based co-catalyst in the vessel with the steel balls. In further embodiments, the ball mill mechanical stirrer may be packed.

[0039] In further embodiments, dispersing the solid metal-based co-catalyst onto the base catalyst may require mixing, stirring, or dispersing for about 5 minutes to 1 hour. In other embodiments, mixing, stirring, or dispersing may be for about 5 minutes to about 50 minutes, about 5 minutes to about 40 minutes, about 5 minutes to about 30 minutes, about 5 minutes to about 20 minutes, about 5 minutes to about 10 minutes, about 10 minutes to about 1 hour, about 10 minutes to about 50 minutes, about 10 minutes to about 40 minutes, about 10 minutes to about 30 minutes, about 10 minutes to about 20 minutes, about 20 minutes to about 1 hour, about 20 minutes to about 50 minutes, about 20 minutes to about 40 minutes, about 20 minutes to about 30 minutes, about 30 minutes to about 1 hour, about 30 minutes to about 50 minutes, about 30 minutes to about 40 minutes, about 40 minutes to about 1 hour, about 40 minutes to about 50 minutes, or about 50 minutes to about 1 hour.

[0040] In further embodiments, dispersing the solid metal-based co-catalyst onto the base catalyst may require mixing, stirring, or dispersing at about a frequency of 5 Hz to about 50 Hz. In other embodiments, mixing, stirring, or dispersing may be for a frequency of about 5 Hz to about 40 Hz, about 5 Hz to about 30 Hz, about 5 Hz to about 20 Hz, about 5 Hz to about 10 Hz, 10 Hz to about 50 Hz, about 10 Hz to about 40 Hz, about 10 Hz to about 30 Hz, about 10 Hz to about 20 Hz, 20 Hz to about 50 Hz, about 20 Hz to about 40 Hz, about 20 Hz to about 30 Hz, 30 Hz to about 50 Hz, about 30 Hz to about 40 Hz, 40 Hz to about 50 Hz.

[0041] For example, in some embodiments, dispersing the solid metal-based co- catalyst onto the base catalyst may require mixing, stirring, or dispersing using a ball mill mechanical mixer for 25 min at 20 Hz frequency to produce the doped catalyst.

[0042] Additionally, in some embodiments, the doped catalyst may be calcined to produce the metathesis catalyst system. The doped catalyst may be calcined at a temperature for at least 1 hour. In other embodiments, the base catalyst may be calcined at a temperature for about 1 hour to about 7 hours, about 1 hour to about 6 hours, about 1 hour to about 5 hours, about 1 hour to about 4 hours, about 1 hour to about 3 hours, about 1 hour to about 2 hours, for about 2 hours to about 7 hours, about 2 hours to about 6 hours, about 2 hours to about 5 hours, about 2 hours to about 4 hours, about 2 hours to about 3 hours, for about 3 hours to about 7 hours, about 3 hours to about 6 hours, about 3 hours to about 5 hours, about 3 hours to about 4 hours, for about 4 hours to about 7 hours, about 4 hours to about 6 hours, about 4 hours to about 5 hours, for about 5 hours to about 7 hours, or about 5 hours to about 6 hours, about 6 hours to about 7 hours.

[0043] Also, the doped catalyst may calcined at ramping rate of at least 1 °C/minute. In other embodiments, the ramping rate may be from about 1 °C/minute to about 5 °C/minute, from about 1 °C/minute to about 4 °C/minute, from about 1 °C/minute to about 3 °C/minute, from about 1 °C/minute to about 2 °C/minute, from about 2 °C/minute to about 5 °C/minute, from about 2 °C/minute to about 4 °C/minute, from about 2 °C/minute to about 3 °C/minute, from about 3 °C/minute to about 5 °C/minute, from about 3 °C/minute to about 4 °C/minute, or from about 4 °C/minute to about 5 ° C/minute.

[0044] In further embodiments, the doped catalyst may be calcined at multiple ramping rates and temperatures for various amounts of times. For example, in some embodiments of producing the metathesis catalyst system, the doped catalyst may be calcined at 250 °C for two hours and at 550 °C for 8 hours, with a ramping rate of 1 °C/minute until the temperature of 250 °C is reached and 3 °C/minute until the temperature of 550 °C is reached, therefore producing the base catalyst.

[0045] In further embodiments, the doped catalyst may be calcined at multiple ramping rates and temperatures for various amounts of times. For example, in some embodiments of producing the metathesis catalyst system, the doped catalyst may be calcined at 250 °C for two hours and at 550 °C for 8 hours, with a ramping rate of 1 °C/minute until the temperature of 250 °C is reached and 3 °C/minute until the temperature of 550 °C is reached, therefore producing the metathesis catalyst system.

[0046] The metathesis catalyst system may comprise at least 0.5 weight percent (wt.%) co-catalyst based on the total weight of the metathesis catalyst system. In further embodiments, metathesis catalyst system may comprise from about 0.5 wt.% to about 5 wt.% co-catalyst, from about 0.5 wt.% to about 4 wt.% co-catalyst, from about 0 5 wt.% to about 3 wt.% co-catalyst, from about 0.5 wt.% to about 2 wt.% co-catalyst, from about 0.5 wt.% to about 1 wt.% co-catalyst, from about 1 wt.% to about 5 wt.% co-catalyst, from about 1 wt.% to about 4 wt.% co-catalyst, from about 1 wt.% to about 3 wt.% co-catalyst, from about 1 wt.% to about 2 wt.% co-catalyst, from about 2 wt.% to about 5 wt.% co- catalyst, from about 2 wt.% to about 4 wt.% co-catalyst, from about 2 wt.% to about 3 wt.% co-catalyst, from about 3 wt.% to about 5 wt.% co-catalyst, from about 3 wt.% to about 4 wt.% co-catalyst, or from about 4 wt.% to about 5 wt.% co-catalyst based on the total weight of the metathesis catalyst system.

[0047] Additionally, other optional components may be included into the metathesis catalyst system. For example, the metathesis catalyst system may include a structuring agent. In one embodiment, the structuring agent is a tri -block copolymer structuring agent. In a further embodiment, the tri-block copolymer structuring agent is a poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) structure, which may be also called a poloxamer structure. In some embodiments, the surfactant tri-block copolymer structuring agent is Pluronic® P123 by BASF Corporation

[0048] The metathesis catalyst system has a total acidity from about 0.125 millimole/gram (mmol/g) to about 0.500 mmol/g. Without being bound by theory, if the material exceeds 0.500 mmol/g, other detrimental side reactions may result, such as cracking and hydrogen transfer reactions. In further embodiments, the metathesis catalyst system may have a total acidity from about 0.125 mmol/g to about 0.250 mmol/g, or from about 0.125 mmol/g to about 0.150 mmol/g.

[0049] While various surface areas are contemplated, the metathesis catalyst system may, in one or more embodiments, have a surface area of at least about 400 meters ² /gram (m /g), or from about 400 m /g about 800 m ² /g, or from about 400 m ^z /g to about 500 m /g, or from about 400 mVg to about 450 m ^z /g, or from about 425 mVg to about 450 m ^z /g.

[0050] The metathesis catalyst system has a pore size distribution of pore size distribution of at least 3 nm to about 40 nm. In other embodiments, the pore size distribution may range fro at least 3 nm to about 40 nm, from about 3 nm to about 20 nm, from about 4 nm to about 10 nm, from about 4 nm to about 8 nm, or from about 4 nm to about 6 nm.

[0051] The metathesis catalyst system has a total pore volume of total pore volume of at least 0 700 cm ³ /g. In further embodiments, the total pore volume may be fro at least 0 700 cnrVg to about 2 5 cnr/g, from about 0.800 cnrVg to about 2 5 cnrVg, from about 0.800 cm g to about 1.5 cmVg, from about 0.800 cnr/g to about 1.25 cm ³ /g, from about 0.800 cnr/g to about 1.0 cm’/g, or from about 0 850 cnrVg to about 1.0 cnrVg.

[0052] In operation, a hydrocarbon feedstock compri sing a mixture of 1 -butene and 2- butene is contacted with embodiments of the metathesis catalyst system to produce, via metathesis conversion, a product stream comprising propylene. The hydrocarbon feedstock comprises a mixture of 1 -butene and 2-butene, and optionally comprises one or more isomers, such as trans-2-butene and cis-2-butene. In some embodiments, the hydrocarbon feedstock comprises more 2 -butene than 1-butene. The present discussion is specifically directed to butene-based hydrocarbon feedstock streams; however, it is known that other C _r- C ₆ components may also be present in the hydrocarbon feedstock stream. As shown previously, metathesis involves isomerization of 2 -butene to 1 -butene followed by cross-metathesis of the 2-butene and 1-butene into a metathesis product stream comprising propylene, and other alkenes and alkanes such as pentene.

[0053] Various operating conditions are contemplated for the contacting of the hydrocarbon feedstock with the metathesis catalyst system. For example, the hydrocarbon feedstock may contact the metathesis catalyst system at a space hour velocity of about 10 to about 10,000 hr ¹ or about 300 to about 1200 hr . Moreover, the hydrocarbon feedstock may contact the metathesis catalyst system at a temperature of about 200 °C to about 600 °C, or about 300 °C to about 600 °C, or about 400 °C to about 600 °C, or about 400 °C to about 550 °C, or about 450 °C to about 600 °C, or about or about 450 °C to about 550 °C. Furthermore, the hydrocarbon feedstock may contact the metathesis catalyst system at a pressure of about 1 to about 30 bars, or about 1 to about 10 bars.

[0054] Optionally, the metathesis catalyst system may, in some embodiments, be pretreated prior to metathesis. For example, the metathesis catalyst may be pretreated with N ₂ for about 1 hours to about 5 hours before metathesis at a temperature of at least about 400 °C, or at least about 500 °C

[0055] Without being bound by theory, it is desired that the aromatics yield be low as it causes coke formation, which can lead to catalyst deactivation. Without being bound by theory, the improved propylene yield and reduced side reactions is due in part to the high selectivity of the isomerization from 2-butene to 1 -butene. Moreover, by increasing the yield of 1-butene via isomerization, the subsequent cross-metathesis of 2-butene and 1- butene is able to yield more propylene in the product stream. For example, in some embodiments, the propylene yield for processes that utilize the metathesis catalyst systems may be at least 10 %. In other embodiments, the propylene yield may be from about 10 % to about 60 %, about 10 % to about 50 %, about 10 % to about 40 %, about 10 % to about 30 %, about 10 % to about 20 %, about 20 % to about 60 %, about 20 % to about 50 %, about 20 % to about 40 %, about 20 % to about 30 %, about 30 % to about 60 %, about 30 % to about 50 %, about 30 % to about 40 %, about 40 % to about 60 %, about 40 % to about 50 %, or about 50 % to about 60 % for processes that utilize the metathesis catalyst systems.

[0056] As will be demonstrated in the examples which follow, methods using the metathesis catalyst system show a higher 2-butene conversion and better propylene yield compared to conventional metathesis catalysts. Reiterating the prior statements, the selective isomerization of 2-butene to 1 -butene and less hydrogen transfer reactions (less aromatics formation) are additional advantages of the metathesis catalyst systems compared to conventional metathesis catalysts. The formation of undesirable isobutylene is also reduced in the metathesis catalyst systems compared to conventional metathesis catalysts.

Test Methods

[0057] Determination of "Conversion” was calculated according to Formula. 1, where rp is the number of moles of component“i” (2 -butenes) entering or leaving the reactor. 100 (1)

0058] Similarly, determination of "Conversion C ₄ " was calculated according to

Formula 2.

Conversion C ₄ = 100 - (Cis Butene Yield + Trans Butene Yield + Iso Butene Yield + 1-Butene Yield)

0059] Determination of "Selectivity" was calculated according to Formula 3.

Yield of Product

Selectivity X 100

Conversion [0060] The surface area of the samples was measured by nitrogen adsorption at 77 Kelvin (K) using AUTOSORB-1 (Quanta Chrome). Before adsorption measurements, samples (ea. 0.1 g) were heated at 220°C for 2 hours under nitrogen flow. The nitrogen adsorption isotherms of catalysts were measured at liquid nitrogen temperature (77 K) The surface areas were calculated by the Brunauer Emmett-Teller (BET) method. The total relative pore volume was estimated from the amount of N2 adsorbed at R/R0 = 0.99. Barret EP, Joyner LJ, Halenda PH, J. Am. Chem. Soc. 73 (1951) 373-380. The percent improvement, such as the percent change presented in Table 7, is equal to the difference between the improved value and the initial value divided by the initial value. The quotient is then multiplied by 100 to convert the improvement to percent improvement. The initial value could also be a reference value.

Examples

[0061] The following examples illustrate one or more additional features of the present disclosure. It should be understood that these examples are not intended to limit the scope of the disclosure or the appended claims in any manner.

[0062] To compare the effect of the metathesis catalyst system on propylene production, samples of metathesis catalyst systems were prepared and tested under various process conditions.

[0063] Preparation of the Large Pore Silica Support

[0064] A large pore silica support was prepared by placing a 50 grams of a large pore silica catalyst on a ceramic plate. Here, the large pore silica catalyst was a commercial spherical catalyst, Q-10, provided by Fuji Silysia Chemical, Ltd. The commercial spherical catalyst had an average pore diameter of about 10 nm, an average pore volume of about 1.00 rnL/g, and a surface area of about 300 m ² /g. The spherical catalyst was then calcined at 200 °C for three hours and again at 575 °C for five hours, with a ramping rate of 3 °C/minute, resulting in the large pore silica support. [0065] Preparation of the Base Catalyst (in the Inventive Examples): The Comparative Example

[0066] In a typical synthesis of the base catalyst, samples of a large pore silica support were impregnated with a metal oxide in the presence of the precursor. Here, the metal oxide was tungsten oxide. To prepare the base catalyst, 50 grams of the large pore silica support were placed in a 500 mL round-bottom flask and 200 mL of deionized water were added to the large pore silica support to produce a large pore silica support and water solution. Then, approximately 5.896 grams of precursor, which rvas ammonium metatungstate hydrate 99.99% trace metals basis, was weighed and mixed with the large pore silica support and water solution. The large pore silica support and water solution with precursor was then stirred for about 30 minutes at 400 rotations per minute (RPM) to produce a homogeneous mixture in which the precursor was dispersed in the large pore silica support. The flask was then placed in on vacuum rotary evaporator wiiere the mixture was rotated and heated at 80 °C using a water bath. Then, a vacuum was applied to the mixture to remove excess water, producing a slurry material. After vacuuming the water from the solution, the slurry material was left in the flask, which was cooled to room temperature and subsequently dried overnight at 80 °C in an oven. The following day, the dried material was crushed into powder and left for calcination in a furnace. The material was calcined at 250 °C for 2 hours and at 550 °C for 8 hours, with a ramping rate of 1 ° C/minute until the first temperature is reached and 3 ° C/minute until the second temperature was reached, therefore producing the base catalyst. The metal loading was calculated to be 10 wt% W0 ₃ /Si0 _2.

[0067] The surface area and pore volume of the silica support and base catalyst were analyzed using an Autosorb iQ2 from Quantachrome Instruments. The measured BET surface area and pore volume are provided in Table 1. Table 1. BET Surface Area Analysis for Blank Silica and Tungsten Loaded Silica.

[0068] The X-ray Diffraction (XRD) for the silica support was carried out after calcining at 200 °C for three hours and then at 575 °C for five hours, with a ramping rate of 3 °C/minute. As shown in FIG 1, the XRD shows a simple amorphous structure, characterized by the peak in the 263 range from 18° to 30°.

[0069] FIG. 2 shows the XRD of blank tungsten oxide compared to the XRD of the Comparative Example. The red diffraction graph shows the characteristic peaks of crystalline W0 ₃ which are in line with JCPDS card No. 00-005-0364 with the monoclinic crystal structure. The blue diffraction graph demonstrates the XRD pattern of the blank silica support with 10wt% tungsten on it. After loading tungsten oxide on the silica support’s surface, the structure of the silica morphology holds. This is because the tungsten oxide is finely dispersed on the surface of the silica support.

[0070] Preparation of the Metathesis Catalyst System: The Inventive Examples A C

[0071] To first prepare the doped catalyst, platinum, palladium and gamma alumina metals were doped onto the base catalyst using a ball mill mechanical stirrer. For each sample, 5 grams of the base catalyst was prepared according to the methods previously described. To dope the base catalyst, a calculated amount of solid metal -based co-catalyst was mixed with the base catalyst in a 25 niL capacity vessel (ball mill mechanical stirrer) with steel balls inside. The calculation was based on the total weight percentage of the base catalyst and the data provided in Table 1. The solid metal -based co-catalysts were platinum oxide, palladium (II) chloride, and gamma alumina. The ball mill mechanical stirrer was packed and stirred for 25 min at 20 Hz frequency, producing the doped catalyst. The solid metal-based co-catalysts and their calculated amount are listed below; rsors.

[0072] Finally, to prepare the inventive examples of embodiments of the metathesis catalyst system, each doped catalyst sample was dried and calcined. Each doped catalyst sample was placed in a drying oven overnight at 80 °C. The doped catalyst samples were then calcined at 250 °C for 2 hours and at 550 °C for 8 hours, with a ramping rate of 1 °C/minute until the first temperature (250 °C) was reached and 3 °C/minute until the second temperature (550 °C) was reached, and thus, Inventive Examples A-l, A-2, B-l, B- 2, C-l, C-2, C-3, C-4, C-5 were produced.

[0073] In the following tables (Table 3, Table 4, and Table 5), Examples A-l and A-2 provide examples of embodiments of the metathesis catalyst that include platinum as the co-metal (where platinum oxide was used as the solid-metal based co-catalyst). As shown in Table 2, Inventive Example A-l (Inv. A-l) contained 0.05 grams of co-metal, resulting in 1 wt.% co-metal. Inventive Example A-2 (Inv. A-2) contained 0.10 grams of co-metal, resulting in 2 wt.% co-metal. Examples B-l and B-2 provide examples of embodiments of the metathesis catalyst that include palladium as the co-metal (where palladium (II) oxide was used as the solid-metal based co-catalyst). As shown in Table 2, Inventive Example B-l (Inv. B-l) contained 0.07 grams of co-metal, resulting in 1 wt.% co-metal. Inventive Example B-2 (Inv. B-2) contained 0.144 grams of co-metal, resulting in 2 wt.% co-metal. Finally, Examples C-L C-2, C-3, C-4, and C-5 provide examples of embodiments of the metathesis catalyst that include aluminum oxide as the co-metal (where gamma alumina was used as the solid-metal based co-catalyst). Inventive Example C-l (Inv. C-l) contained 0 05 grams of co-metal, resulting in 1 wt.% co-metal. Inventive Example C-2 (Inv. C-2) contained 0.10 grams of co-metal, resulting in 2 wt.% co-metal, Inventive Example C-3 (Inv. C-3) contained 0.15 grams of co-metal, resulting in 3 wt.% co-metal, Inventive Example C-4 (Inv. C-4) contained 0.20 grams of co-metal, resulting in 4 wt.% co-metal, and Inventive Example C-5 (Inv. C-5) contained 0 25 grams of co-metal, resulting in 5 wt.% co-metal. Again, the Comparative Example contains no co-metal or solid metal-based co-catalyst. The Comparative Example is also the base catalyst for the embodiments of the Inventive Examples on which the solid metal -based co-catalysts were dispersed.

{0074] Metathesis Catalyst System Evaluation

[0075] The prepared catalysts were tested for their activity and selectivity to the butenes metathesis reaction in a fixed bed continuous flow reactor (ID 0.25 in, Autoclave Engineers, Ltd.) at atmospheric pressure. Fixed amount of catalyst samples, 1 mL of each Comparative or Inventive Example was packed in the reactor tube with 1 mL Grade 20 Silicon Carbide at the bottom of the reactor, for a total of 2 mL.

[0076] The catalysts were pretreated under N ₂ at 550 °C for 150 minutes. All reactions were carried out at three temperatures of 450 °C, 500 °C, and 550 °C and atmospheric pressure. At each temperature point, the reaction was held for 3 5 hours A gas hourly space velocity (GHSV) of 900 h ¹ was maintained using 2-butene (5 rnL/min) as feed with nitrogen as diluent (25 mL/min). The quantitative analysis of the reaction products were carried out on-line using an Agilent GC-7890B with an FID equipped with HP-A1/KCL (50 m x 0 53 mm x 15 microns) Column

[0077] Table 3, Table 4, and Table 5 provide the propylene yield, selectivity and 2- butene conversion for each of the Comparative and Inventive Examples at 450 °C, 500 °C, and 550 °C, respectively. Table 3. Conversion ami Product Distribution for Different Dopants at 450 °C.

Table 4. Conversion and Prodnct Distribntion for Different Dopants at 500 °C. 99

Table 5. Conversion and Product Distribution for Different Dopants at 550 °C.

[0078] After screening each of the Comparative and Inventive Examples, it was observed that some co-metals allowed for a higher activity for propylene yield at various temperatures

[0079] For the Inventive Examples containing platinum as the co-metal, A-l and A-2, it was observed that at 500 °C, Inv. A-l showed improved conversion (75.53 % versus 72.34 % for the Comparative Catalyst), and Inv. A-2 showed improved conversion (74 76 % versus 72.34 % for the Comparative Catalyst), yield (25.44 % versus 24.4 % for the Comparative Catalyst), and selectively (34.03 % versus 33.72 % for the Comparative Catalyst). (See Table 4) Also, at 550 °C, Inv. A-l showed improved conversion (79 % versus 78.56 % for the Comparative Catalyst), and Inv. A-2 showed improved conversion (79.39 % versus 78.56 % for the Comparative Catalyst), yield (28.13 % versus 27.9 % for the Comparative Catalyst), and selectively (35.43 % versus 35.54 % for the Comparative Catalyst). (See Table 5).

[0080] For the Inventive Examples containing palladium as the co-metal, B-l and B-2, it was observed that at 450 °C, both Inv. B-l and Inv. B-2 showed improved yield (22,69 % and 20.94 %, respectively, compared to 19.9 %), and Inv. B-l showed improved conversion (65.74 % compared to 60 %). (See Table 3). Also, at 550 °C, Inv. B-l and Inv. B-2 both showed an improved conversion (81.26 % and 80.71, respectively, compared to 72.34 %) and yield (28.13 % and 27 13, respectively, compared to 24.4 %), and B-l also showed improved selectivity (34.62 % compared to 33.72 %). (See Table 4). Finally, at 550 °C, both Inv. B-l and Inv. B-2 showed improved conversion (80.71 % and 79.83 %, respectively, compared to 78.56 %), yield (28.84 % and 28.77 %, respectively, compared to 27.9 %), and selectivity (35.73 % and 36.04 %, respectively, compared to 35.54 %). (See Table 5).

[0081] For the Inventive Examples containing aluminum oxide as the co-metal, Inv. C- I, Inv. C-2, Inv. C-3, Inv. C-4, and Inv. C-5, it was observed that at all temperatures, a higher conversion and yield was observed compared to the Comparative Example. (See generally Table 3, Table 4, and Table 5).

[0082] Furthermore, FIGs. 3, 4, and 5 provide a clear view about how each embodiment of the metathesis catalyst system may perform at various temperatures. From the figures, one may observe how each co-metal can be utilized to increase the overall propylene yield when compared a process that only utilizes the base catalyst. From FIG. 3, it was observed that at 450 °C, almost all of the Inventive Examples (except Inv. A-l and Inv. A-2), provided a higher propylene yield. Also, as shown in FIG 4, at 500 °C, it was further observed the trend that only 1% of the co-metals was needed to increase the propylene yield compared to the Comparative Example. Finally, as shown in FIG. 5, at 550 °C, a similar trend was observed that only 1% of the co-metals was needed to increase the propylene yield compared to the Comparative Example. For the results that show a decrease the propylene yield at higher temperatures, this could he the result of the reaction reaching an equilibrium state of electronic transition. Moreover, at higher temperatures, the formation of unwanted side products may led to decrease in propylene yield as well.

[0083] From these results, it may be apparent that using a co-metal on the base catalyst (the disclosed metathesis catalyst system) would boost the propylene yield formation compared to conventional catalyst systems (the base catalyst without a co-metal). In some situations, embodiments of the metathesis catalyst system may be preferred where less co- metal is required to produce a higher yield. One example, as stated previously, can be seen in Inv. B-l v. Inv. B-2 at 500 °C. This data is particularly useful because palladium is expensive, and therefore, a metathesis catalyst syste that requires less palladium— yet still produces a higher propylene yield— is commercially advantageous

[0084] Moreover, these results show' that embodiments of the metathesis catalyst system that include aluminum oxide as the co-metal may be particularly advantageous in industrial applications. Aluminum is not as expensive, yet it still may produce improved results when compared to the Comparative Catalyst {see, for example, the conversion and yield results for Inv. Examples Inv. C-l, Inv. C-2, and Inv. C-3 versus the Comparative Example for all temperatures). In addition, the disclosed methods provide the most- effective way to disperse an alumninum oxide co-metal onto a base catalyst. It is known that when aluminum is simply added to the base catalyst, the tungsten oxide of the base catalyst may cover the aluminum, therefore causing a crystallite. The crystallite may then cause the catalyst to quickly deactivate. Here, by adding the co-metal stepwise after producing and calcining the base catalyst, the crystallite problem is not observed. Therefore, the disclosed metathesis catalyst systems also do not deactivate as fast, which is another commercial advantage. [0085] It should be understood that any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure. It should be appreciated that compositional ranges of a chemical constituent in a composition or formulation should be appreciated as containing, in some embodiments, a mixture of isomers of that constituent. It should be appreciated that the examples supply compositional ranges for various compositions, and that the total amount of isomers of a particular chemical composition can constitute a range.

[0086] It is noted that one or more of the following claims utilize the term“where” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.”

[0087] Having described the subject matter of the present disclosure in detail and by reference to specific embodiments, it is noted that the various details described in this disclosure should not be taken to imply that these details relate to elements that are essential components of the various embodiments described in this disclosure, even in cases where a particular element is illustrated in each of the drawings that accompany the present description. Rather, the claims appended hereto should be taken as the sole representation of the breadth of the present disclosure and the corresponding scope of the various embodiments described in this disclosure. Further, it should be apparent to those skilled in the art that various modifications and variations can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter. Thus it is intended that the specification cover the modifications and variations of the various described embodiments provided such modification and variations come within the scope of the appended claims and their equivalents.

[0088] The present disclosure includes one or more non-limiting aspects. A first aspect may include a method of synthesizing a metathesis catalyst system comprising: impregnating a metal oxide on silica support in the presence of a precursor to produce a base catalyst; calcining the base catalyst, dispersing a solid metal-based co-catalyst onto the surface of the base catalyst to produce a doped catalyst; and calcining the doped catalyst to produce a metathesis catalyst system.

[0089] A second aspect may include the first aspect, wherein the large pore silica support comprises large pore silica.

[0090] A third aspect may include any of the preceding aspects, wherein the co-catalyst is selected from the group consisting of Pt0 ₂ , PdCl ₂ , gamma-Al ₂ 0 ₃ , or combinations.

[0091] A fourth aspect may include any of the preceding aspects, wherein the metal oxide is tungsten oxide.

[0092] A fifth aspect may include any of the preceding aspects, wherein the metathesis catalyst system comprises at least 0.5 weight percent (wt. %) co-catalyst.

[0093] A sixth aspect may include any of the preceding aspects, wherein the metathesis catalyst system comprises from about 1 wt.% to about 2 wt.% co-catalyst.

[0094] A seventh aspect may include any of the preceding aspects, wherein the base catalyst comprises from about 8 wt. % to about 12 wt. % of tungsten oxide.

[0095] An eighth aspect may include any of the preceding aspects, wherein the precursor comprises ammonium metatungstate hexa ydrate.

[0096] A ninth aspect may include any of the preceding aspects, wherein the metathesis catalyst system has a surface area of about 400 m ² /g to about 800 m ² /g.

[0097] A tenth aspect may include any of the preceding aspects, wherein the metathesis catalyst system has a pore size distribution of about 3 nm to about 40 nm. [0098] An eleventh aspect may include any of the preceding aspects, wherein the metathesis catalyst system has a total pore volume of at least 0.700 cm ³ /g to about 2,5 cm ³ /g.

[0099] A twelfth aspect may include a process for the production of propylene comprising: contacting a hydrocarbon feedstock comprising a mixture of 1 -butene and 2- butene with a metathesis catalyst system comprising a base catalyst comprising tungsten, a support comprising silica, and a metal-based co-catalyst dispersed and calcined on the surface of the base catalyst and support; to produce propylene.

[00100] A thirteenth aspect may include the twelfth aspect, wherein the propylene yield is from about 10 % to about 60 %.

[00101] A fourteenth aspect may include any of the twelfth through thirteenth aspects, wherein the hydrocarbon feedstock comprises more 2-butene than 1 -butene.

[00102] A fifteenth aspect may include any of the twelfth through fourteenth aspects, further comprising contacting the hydrocarbon feedstock with the catalyst system at a temperature greater than 400 degrees Celsius (°C).

[00103] A sixteenth aspect may include any of the twelfth through fifteenth aspects, further comprising contacting the hydrocarbon feedstock with the catalyst system at a temperature from about 450 °C to about 550 °C.

[00104] A seventeenth aspect may include any of the twelfth through sixteenth aspects, wherein the metathesis catalyst system comprises at least 0.5 wt. % metal -based co- catalyst.

[00105] An eighteenth aspect may include any of the twelfth through seventeent aspects, wherein the metathesis catalyst system comprises from about 1 wt.% to about 2 wt.% metal-based co-catalyst. [00106] A nineteenth aspect may include any of the twelfth through eighteenth aspects, wherein the base catalyst comprises from about 8 wt. % to about 12 wt. % of tungsten oxide.

[00107] A twentieth aspect may include any of the twelfth through nineteenth aspects, wherein the catalyst system has a surface area of about 400 m ² /g to about 800 m g, a pore size distribution of about 3 nm to about 40 nm, and a total pore volume of at least 0.700 cm ³ /g to about 2.5 cm7g.