BR112021012703B1 - PROCESSPROCESS FOR PREPARING C2 TO C4 OLEFINS - Google Patents

Abstract

PROCESS. It is a process for preparing C2 to C4 olefins that includes introducing a feed stream comprising hydrogen gas and a carbon-containing gas selected from the group consisting of carbon monoxide, carbon dioxide, and mixtures thereof, to a reaction zone of a reactor. The feed stream is converted to a product stream that includes C2 to C4 olefins in the reaction zone in the presence of the hybrid catalyst. The hybrid catalyst includes a metal oxide catalyst component comprising phase pure zirconia and gallium oxide and a microporous catalyst component.

Description

FIELD

[001] The present specification generally refers to catalysts that efficiently convert various carbon-containing streams into C2 to C4 olefins. In particular, the present specification relates to the preparation of hybrid catalysts and the application of process methods to achieve high synthesis gas feed conversion, resulting in good carbon conversion and high yield of desired products. Synthesis gas comprises hydrogen gas and a carbon-containing gas selected from the group consisting of carbon monoxide, carbon dioxide and mixtures thereof. A hybrid catalyst generally comprises a combination of a metal oxide component and a microporous catalyst component operating in tandem.

BACKGROUND OF THE TECHNIQUE

[002] For a number of industrial applications, olefins are used, or starting materials are used, to produce plastics, fuels and various subsequent chemicals. Such olefins include C2 to C4 materials such as ethylene, propylene and butylenes (also commonly referred to as ethene, propylene and butenes, respectively). A variety of processes to produce these lower olefins have been developed, including petroleum cracking and various synthetic processes.

[003] Synthetic processes for converting feed carbon into desired products, such as olefins, are known. Some of these synthetic processes begin with the use of a hybrid catalyst. Different types of catalysts were also explored, as well as different types of feed streams and feed stream component ratios. However, many of these synthetic processes have low carbon conversion, and much of the feed carbon is either (1) not converted, and leaves the process in the same form as the feed carbon; or (2) is converted to CO2; or (3) these synthetic processes have low stability over time, and the catalyst quickly loses its activity for converting carbon into desirable products. For example, many synthetic processes tend to have an increase in methane production - and thus decrease the production of C2 to C4 olefins - over time.

[004] Therefore, there is a need for processes and catalytic systems that have a high conversion of feed carbon into desired products, such as, for example, C2 to C4 olefins in combination with a high in catalyst current stability.

SUMMARY

[005] According to one embodiment, a process for preparing C2 to C4 olefins comprises: introducing a feed stream comprising hydrogen gas and a carbon-containing gas selected from the group consisting of carbon monoxide, carbon dioxide and mixtures of them in a reaction zone of a reactor; and converting the feed stream into a product stream comprising C2 to C4 olefins in the reaction zone in the presence of a hybrid catalyst, wherein the hybrid catalyst comprises: a metal oxide catalyst component comprising gallium oxide and zirconia phase pure; and a microporous catalyst component.

[006] Additional features and advantages of the modalities will be presented in the following detailed description, and in part will be readily apparent to those skilled in the art from this description or recognized by the practice of the modalities described herein, including the following detailed description and the demands.

[007] It should be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter.

DETAILED DESCRIPTION

[008] Reference will now be made in detail to modalities of hybrid catalysts and methods using the hybrid catalyst to prepare C2 to C4 olefins. In one embodiment, a process for preparing C2 to C4 olefins comprises: introducing a feed stream comprising hydrogen gas and a carbon-containing gas selected from the group consisting of carbon monoxide, carbon dioxide and mixtures thereof into a zone reaction of a reactor; and converting the feed stream into a product stream comprising C2 to C4 olefins in the reaction zone in the presence of the hybrid catalyst, wherein the hybrid catalyst comprises: a metal oxide catalyst component comprising gallium oxide and pure zirconia phase; and a microporous catalyst component.

[009] The use of hybrid catalysts to convert feed streams comprising carbon into desired products, such as, for example, C2 to C4 olefins, is known. However, many known hybrid catalysts are inefficient as they exhibit low feed carbon conversion and/or rapidly deactivate as they are used, such as, for example, by having an increase in methane production, which leads to to a low olefin yield and low stability for a given set of operating conditions over a given amount of time. In contrast, the hybrid catalysts disclosed and described herein exhibit a high and constant yield of C2 to C4 olefins, even as the catalyst time in the stream increases. The composition of such hybrid catalysts used in the embodiments is discussed below.

[010] In summary, hybrid catalysts tightly couple independent reactions in each of the two independent catalysts. In the first step, a feed stream comprising hydrogen gas (H2) and at least one of carbon monoxide (CO), carbon dioxide (CO2) or a mixture of CO and CO2, such as, for example, carbon dioxide (CO2) synthesis, is converted into an intermediate (or intermediates) such as oxygenated hydrocarbons. In the subsequent step, these intermediates are converted into hydrocarbons (mainly short-chain hydrocarbons, such as, for example, C2 to C4 olefins). The continuous formation and consumption of the oxygenated intermediates formed in the first stage by the second stage reactions ensures that there is no thermodynamic limit on the conversions. With careful selection of the hybrid catalytic bed components, high conversions of the syngas feed can be achieved.

[011] Hybrid catalyst systems comprise a metal oxide catalyst component that converts the feed stream into oxygenated hydrocarbons, and a microporous catalyst component (such as, for example, a silicoaluminophosphate or a molecular sieve component of the type SAPO), which converts oxygenated hydrocarbons into hydrocarbons. Known hybrid catalyst systems based on the chromium-zinc mixed metal oxide catalyst generally exhibit an imbalance between initial yield of C2 to C4 olefins and sustained yield of C2 to C4 olefins as catalyst time in the stream increases (also referred to as stability). There is therefore a need for a metal oxide catalyst component that results in a high initial yield as well as high stability when combined with a microporous catalyst component in a hybrid catalyst process. It should be understood that, as used herein, the “metal oxide catalyst component” includes metals in various oxidation states. In some embodiments, the metal oxide catalyst component may comprise more than one metal oxide, and individual metal oxides within the metal oxide catalyst component may have different oxidation states. Thus, the metal oxide catalyst component is not limited to comprising metal oxides with homogeneous oxidation states.

[012] Embodiments of hybrid catalysts and systems for the use of hybrid catalysts disclosed herein comprise a metal oxide catalyst component comprising: (1) gallium (Ga) and (2) phase pure zirconia (ZrO2) . In some embodiments, the phase pure zirconia may be crystalline, and in some embodiments, the phase pure zirconia may be monoclinic crystalline phase pure zirconia. The metal oxide catalyst component is combined with a microporous catalyst component. The microporous catalyst component is, according to some embodiments, an 8-MR microporous catalyst component, such as, for example, SAPO-34 molecular sieve.

[013] Metal oxide catalyst components for use in a hybrid catalyst, according to embodiments, will now be described. As mentioned above, metals commonly used as constituents of the metal oxide catalyst component of some hybrid catalysts include combinations of zinc (Zn) and chromium (Cr). However, catalysts comprising zinc and chromium, which are known as high-temperature methanol synthesis catalysts, do not have a combination of good olefin yield and good stability when kept in the stream for an extended period of time. Although other metal combinations have been used, zinc and chromium have long been considered the most efficient metal oxide components for producing lower olefins, such as C2 to C4 olefins.

[014] Gallium oxide (gallium, Ga2O3) is a very capable promoter for palladium, copper or nickel based methanol forming catalysts. In such roles, it is believed that upon reduction in the presence of hydrogen, gallium oxide forms suboxides and surface hydrides. Eventually, the reduction process can lead to the alloying of the Ga metal with the active catalyst component (Pd, Cu or Ni), creating a better performing intermetallic phase (e.g. Pd-Ga). In contrast, gallium oxides and supported gallium oxides perform very poorly in synthesis gas conversion. Furthermore, bulk pure gallium used as a metal oxide component of a hybrid catalyst usually produces a high percentage of paraffins. However, it was unexpectedly found that when gallium was combined with a phase pure zirconia, this combination promoted both high olefin yield and high process stability of the hybrid catalyst.

[015] As used herein, the zirconia used in the embodiments disclosed and described herein in the metal oxide catalyst component of the hybrid catalyst is “phase pure zirconia”, which is defined herein as zirconia to which no other material was intentionally added during formation. Thus, “phase pure zirconia” includes zirconia with small amounts of components other than zirconia (including oxides other than zirconia) that are unintentionally present in the zirconia as a natural part of the zirconia formation process, such as, for example, hafnium (Hf ). Therefore, as used herein, “zirconia” and “phase pure zirconia” are used interchangeably unless specifically indicated otherwise.

[016] Without being bound by any particular theory, it is believed that the high surface area of zirconia allows the gallium oxide catalyst to act as part of a hybrid catalyst to convert carbon-containing components into C2 to C4 olefins. Gallium oxide and zirconia oxide are believed to help activate each other, which results in improved yield of C2 to C4 olefins.

[017] Surprisingly, along with the high activity and high selectivity of the unique combination of the Ga/ZrO2 component used to prepare hybrid catalysts with a molecular sieve, it was found that such hybrid catalysts comprising gallium oxide and zirconia as their oxide component metal have improved stability over extended process times. It has also been discovered, in embodiments, that crystalline zirconia is a particularly effective carrier for gallium oxide. Furthermore, in some embodiments, monoclinic zirconia has been found to be a particularly good carrier for gallium oxide that provides very high combined activity without compromising selectivity for C2 to C4 olefins.

[018] In embodiments disclosed herein, the composition of the metal oxide catalyst component is designated by a weight percentage of gallium metal to pure zirconia (accounting for ZrO2 stoichiometry). In one or more embodiments, the composition of the metal oxide catalyst component is designated by the weight of gallium per 100 grams (g) of zirconia. According to embodiments, the metal oxide catalyst component comprises from more than 0.0 g of gallium to 30.0 g of gallium per 100 g of zirconia, such as 5.0 g of gallium to 30.0 g of of gallium per 100 g of zirconia, 10.0 g of gallium to 30.0 g of gallium per 100 g of zirconia, 15.0 g of gallium to 30.0 g of gallium per 100 g of zirconia, 20.0 g of gallium to 30.0 g of gallium per 100 g of zirconia or 25.0 g of gallium to 30.0 g of gallium per 100 g of zirconia. In some embodiments, the metal oxide catalyst component comprises from more than 0.0 g of gallium to 25.0 g of gallium per 100 g of zirconia, such as from more than 0.0 g of gallium to 20.0 g of gallium. g of gallium per 100 g of zirconia, from more than 0.0 g of gallium to 15.0 g of gallium per 100 g of zirconia, from more than 0.0 g of gallium to 10.0 g of gallium per 100 g of zirconia, or from more than 0.0 g of gallium to 5.0 g of gallium per 100 g of zirconia. In some embodiments, the metal oxide catalyst component comprises from 5.0 g of gallium to 25.0 g of gallium per 100 g of zirconia, such as from 10.0 g of gallium to 20.0 g of gallium per 100 g of zirconia. In some embodiments, the metal oxide catalyst component comprises from 0.01 g of gallium per 100 g of zirconia to 5.00 g of gallium per 100 g of zirconia, such as from 0.50 g of gallium per 100 g of zirconia to 5.00 g of gallium to 100 g of zirconia, of 1.00 g of gallium per 100 g of zirconia to 5.00 g of gallium to 100 g of zirconia, of 1.50 g of gallium per 100 g of zirconia to 5, 00 g gallium to 100 g zirconia, from 2.00 g gallium per 100 g zirconia to 5.00 g gallium to 100 g zirconia, from 2.50 g gallium per 100 g zirconia to 5.00 g gallium to 100 g of zirconia, from 3.00 g of gallium per 100 g of zirconia to 5.00 g of gallium per 100 g of zirconia, from 3.50 g of gallium per 100 g of zirconia to 5.00 g of gallium at 100 g of zirconia, from 4.00 g of gallium per 100 g of zirconia to 5.00 g of gallium per 100 g of zirconia, or from 4.50 g of gallium per 100 g of zirconia to 5.00 g of gallium a 100 g of zirconia.

[019] As disclosed herein above, and without being bound by any particular theory, it is understood that high surface area zirconia acts as a support or carrier for the gallium constituent of the metal oxide component, which yields a of gallium metal oxide zirconia catalyst that will have selectivity to produce C2 to C4 olefins. Therefore, it has been found that processes for preparing gallium zirconia metal oxide catalyst that require intimate contact of the gallium and zirconia components produce metal oxide catalyst components that have better selectivity for C2 to C4 olefins. .

[020] In view of the above, a method for producing the zirconia gallium metal oxide component of the hybrid catalyst is by incipient moisture impregnation. In such a method, an aqueous mixture of a gallium precursor material, which, in embodiments, may be gallium nitrate (Ga(NO3)3), is added to zirconia particles in a metered amount (such as dropwise) while stirring. vigorously remove the zirconia particles. It should be understood that the total amount of gallium precursor that is mixed with the zirconia particles will be determined by the desired target amount of gallium in the metal oxide catalyst component.

[021] As discussed previously, according to some embodiments, zirconia particles comprise zirconia particles with a crystalline structure. In embodiments, the zirconia particles comprise zirconia particles with a monoclinic structure. In one or more embodiments, the zirconia particles essentially consist of or consist of crystalline zirconia particles, and in some embodiments, the zirconia particles essentially consist of or consist of monoclinic zirconia particles. According to some embodiments, the zirconia particles have a BET surface area that is greater than or equal to 5 square meters per gram (m2/g), such as greater than 10 m2/g, greater than 20 m2/g, greater than 30 m2/g, greater than 40 m2/g, greater than 50 m2/g, greater than 60 m2/g, greater than 70 m2/g, greater than 80 m2/g, greater than 90 m2/g, greater than 100 m2/g, greater than 110 m2/g, greater than 120 m2/g, greater than 130 m2/g or greater than 140 m2/g. According to some embodiments, the maximum BET surface area of zirconia particles is 150 m2/g. Accordingly, in some embodiments, the BET surface area of the zirconia particles is from 5 m2/g to 150 m2/g, from 10 m2/g to 150 m2/g, from 20 m2/g to 150 m2/g, such as 30 m2/g to 150 m2/g, from 40 m2/g to 150 m2/g, from 50 m2/g to 150 m2/g, from 60 m2/g to 150 m2/g, from 70 m2/g to 150 m2/g, from 80 m2/g to 150 m2/g, from 90 m2/g to 150 m2/g, from 100 m2/g to 150 m2/g, from 110 m2/g to 150 m2/g, from 120 m2/g to 150 m2/g, from 130 m2/g to 150 m2/g, or from 140 m2/g to 150 m2/g. In some embodiments, the BET surface area of the zirconia particles is from 5 m2/g to 140 m2/g, such as from 5 m2/g to 130 m2/g, from 5 m2/g to 120 m2/g, from 5 m2/g g to 110 m2/g, from 5 m2/g to 100 m2/g, from 5 m2/g to 90 m2/g, from 5 m2/g to 80 m2/g, from 5 m2/g to 70 m2/g, from 5 m2/g g to 60 m2/g, from 5 m2/g to 50 m2/g, from 5 m2/g to 40 m2/g, from 5 m2/g to 30 m2/g, from 5 m2/g to 20 m2/g, or from 5 m2 /g to 10 m2/g. In some embodiments, the BET surface area of the zirconia particles is 10 m2/g to 140 m2/g, 20 m2/g to 130 m2/g, 30 m2/g to 120 m2/g, 40 m2/g to 110 m2/g, from 50 m2/g to 100 m2/g, from 60 m2/g to 90 m2/g, or from 70 m2/g to 80 m2/g.

[022] Once the gallium precursor and zirconia particles are suitably mixed, the metal oxide catalyst component can be dried at temperatures below 200 degrees Celsius (°C), such as below 175 °C or below 150°C. Subsequent to drying, the metal oxide catalyst component is calcined at temperatures of 400°C to 800°C, such as 425°C to 775°C, 450°C to 750°C, 475°C to 725°C, from 500°C to 700°C, from 525°C to 675°C, from 550°C to 650°C, or from 575°C to 625°C or about 600°C. After calcination, the composition of the mixed metal oxide catalyst component is determined and reported as a weight of elemental gallium referenced per 100 g of phase pure zirconia (simplified to ZrO2 stoichiometry), as previously disclosed above.

[023] In embodiments, the metal oxide catalyst component can be produced by mixing powders or slurries of a gallium precursor (such as gallium nitrate or gallium oxide) and zirconia. According to some embodiments, the zirconia particles comprise zirconia particles having a crystalline structure. In embodiments, the zirconia particles comprise zirconia particles with a monoclinic structure. In one or more embodiments, the zirconia particles essentially consist of or consist of crystalline zirconia particles, and in some embodiments, the zirconia particles essentially consist of or consist of monoclinic zirconia particles. The zirconia particles may, in embodiments, have the BET surface areas disclosed above. Powders or slurries can be vigorously mixed at high temperatures, such as from room temperature (approximately 23°C) to 100°C. After the powders or slurries are suitably mixed, the metal oxide catalyst component may be dried and calcined at temperatures of 400°C to 800°C, such as 425°C to 775°C, 450°C to 750 °C, from 475 °C to 725 °C, from 500 °C to 700 °C, from 525 °C to 675 °C, from 550 °C to 650 °C, or from 575 °C to 625 °C or around 600°C. After calcination, the composition of the mixed metal oxide catalyst component is determined and reported as a weight of elemental gallium in reference to 100 g of phase pure zirconia (simplified to ZrO2 stoichiometry) as disclosed above.

[024] It should be understood that, according to the embodiments, the metal oxide catalyst component can be made by other methods that eventually lead to intimate contact between the gallium and the zirconia. Some non-limiting cases include vapor phase deposition of Ga-containing precursors (of organic or inorganic nature), followed by their controlled decomposition. Similarly, processes for dispersing liquid gallium metal can be modified by those skilled in the art to develop Ga-ZrO2.

[025] Elements other than zirconia and gallium may, in some embodiments, be present in the metal oxide catalyst component containing gallium and phase pure zirconia. These elements can be introduced into phase pure zirconia before, during or after the introduction of gallium into the composition. Sometimes these elements are added to direct and stabilize the crystallization of the zirconia phase (e.g., Y-stabilized tetragonal ZrO2). In other cases, additional elements from the rare earth group, alkali and/or transition metals are co-deposited with the gallium precursor or introduced only when the mixed Ga-ZrO2 composition has first been prepared. Likewise, the metal oxide catalyst component may also contain residue or be purposefully modified with non-metallic dopants such as, for example, sulfur (present as, for example, oxyanion SO4), chlorine (Cl), phosphorus (P). or mixtures thereof may be present in the zirconia support or remain after use as a precursor element intended to introduce gallium or other metals into phase pure zirconia.

[026] In one or more embodiments, after the metal oxide catalyst component has been formed - such as, for example, by the methods disclosed above - the metal oxide catalyst component is physically mixed with a microporous catalyst component . The microporous catalyst component is, in embodiments, selected from molecular sieves with 8-MR pore openings and a structure type selected from the group consisting of the following structure types CHA, AEI, AFX, ERI, LTA, UFI, RTH, EDI, GIS, MER, RHO and combinations thereof, where the structure types correspond to the International Zeolite Association naming convention. It should be understood that, in embodiments, both aluminosilicate and silicoaluminophosphate structures can be used. Some embodiments may include tetrahedral aluminosilicates, ALPOs (such as, for example, tetrahedral aluminophosphates), SAPOs (such as, for example, tetrahedral silicoaluminophosphates) and tectosilicates based solely on silica. In certain embodiments, the microporous catalyst component may be silicoaluminophosphate with a Chabazite (CHA) type of structure. Examples of the same may include, but are not necessarily limited to: CHA modalities selected from SAPO-34 and SSZ-13; and AEI modalities, such as SAPO-18. Combinations of microporous catalyst components that have any of the above structure types can also be employed. It should be understood that the microporous catalyst component may have a different membered ring pore opening depending on the desired product. For example, microporous catalyst component with pore openings from 8-MR to 12-MR can be used depending on the desired product. However, to produce C2 to C4 olefins, a microporous catalyst component with 8-MR pore openings is used in the embodiments.

[027] The metal oxide catalyst component and the microporous catalyst component of the hybrid catalyst can be mixed by any suitable means, such as, for example, physical mixing — such as shaking, rocking or other agitation. The metal oxide catalyst component may, in embodiments, comprise from 1.0 wt% to 99.0 wt% of the hybrid catalyst, such as from 5.0 wt% to 99.0 wt%, of 10.0% by weight to 99.0% by weight, from 15.0% by weight to 99.0% by weight, from 20.0% by weight to 99.0% by weight, from 25.0% by weight weight to 99.0% by weight, from 30.0% by weight to 99.0% by weight, from 35.0% by weight to 99.0% by weight, from 40.0% by weight to 99.0 % by weight, from 45.0% by weight to 99.0% by weight, from 50.0% by weight to 99.0% by weight, from 55.0% by weight to 99.0% by weight, from 60.0% by weight to 99.0% by weight, from 65.0% by weight to 99.0% by weight, from 70.0% by weight to 99.0% by weight, from 75.0% by weight weight to 99.0% by weight, from 80.0% by weight to 99.0% by weight, from 85.0% by weight to 99.0% by weight, from 90.0% by weight to 99.0 % by weight or from 95.0% by weight to 99.0% by weight. In some embodiments, the metal oxide catalyst component comprises from 1.0 wt% to 95.0 wt% of the hybrid catalyst, such as from 1.0 wt% to 90.0 wt%, of 1 .0% by weight to 85.0% by weight, from 1.0% by weight to 80.0% by weight, from 1.0% by weight to 75.0% by weight, from 1.0% by weight to 70.0% by weight, from 1.0% by weight to 65.0% by weight, from 1.0% by weight to 60.0% by weight, from 1.0% by weight to 55.0% by weight, from 1.0% by weight to 50.0% by weight, from 1.0% by weight to 45.0% by weight, from 1.0% by weight to 40.0% by weight, from 1 .0% by weight to 35.0% by weight, from 1.0% by weight to 30.0% by weight, from 1.0% by weight to 25.0% by weight, from 1.0% by weight to 20.0% by weight, from 1.0% by weight to 15.0% by weight, from 1.0% by weight to 10.0% by weight or from 1.0% by weight to 5.0% in weight. In some embodiments, the metal oxide catalyst component comprises from 5.0 wt% to 95.0 wt% of the hybrid catalyst, such as from 10.0 wt% to 90.0 wt%, of 15. .0% by weight to 85.0% by weight, from 20.0% by weight to 80.0% by weight, from 25.0% by weight to 75.0% by weight, from 30.0% by weight to 70.0% by weight, from 35.0% by weight to 65.0% by weight, from 40.0% by weight to 60.0% by weight or from 45.0% by weight to 55.0% in weight.

[028] After the metal oxide catalyst component is formed and combined with a microporous catalyst component to form a hybrid catalyst, the hybrid catalyst can be used in methods of converting carbon in a feed stream containing carbon in C2 to C4 olefins. Such processes will be described in more detail below.

[029] According to embodiments, a feed stream is fed to a reaction zone, wherein the feed stream comprises hydrogen gas (H2) and a carbon-containing gas selected from carbon monoxide (CO), carbon dioxide carbon (CO2) and combinations thereof. In some embodiments, H2 gas is present in the feed stream in an amount of from 10 volume percent (vol%) to 90 volume%, based on the combined volume of H2 gas and the gas selected from CO, CO2 and combinations thereof. The feed stream is contacted with a hybrid catalyst, as disclosed and described herein, in the reaction zone. The hybrid catalyst comprises a metal oxide catalyst component comprising gallium oxide and zirconia; and a microporous catalyst component.

[030] It should be understood that the activity of the hybrid catalyst will be greater for feed streams containing CO as the carbon-containing gas, and that the activity of the hybrid catalyst decreases as a greater portion of the carbon-containing gas in the feed stream is CO2. However, this does not mean that the hybrid catalyst disclosed and described herein cannot be used in methods in which the feed stream comprises CO2 as the whole, or as a large portion, of the carbon-containing gas.

[031] The feed stream is contacted with the hybrid catalyst in the reaction zone under reaction conditions sufficient to form a product stream comprising C2 to C4 olefins. The reaction conditions comprise a temperature within the reaction zone ranging, according to one or more embodiments, from 300 °C to 500 °C, such as from 300 °C to 475 °C, from 300 °C to 450 °C, from 300 °C to 425 °C, from 300 °C to 400 °C, from 300 °C to 375 °C, from 300 °C to 350 °C, or from 300 °C to 325 °C. In other embodiments, the temperature within the reaction zone is from 325 °C to 500 °C, from 350 °C to 500 °C, from 375 °C to 500 °C, from 400 °C to 500 °C, from 425 °C to 500 °C, from 450 °C to 500 °C, or from 475 °C to 500 °C. In still other embodiments, the temperature within the reaction zone is from 300 °C to 500 °C, such as from 325 °C to 475 °C, from 350 °C to 450 °C, or from 360 °C to 440 °C.

[032] Reaction conditions also, in embodiments, include a pressure within the reaction zone of at least 1 bar (100 kilopascals (kPa), such as at least 5 bar (500 kPa), at least 10 bar (1,000 kPa ), at least 15 bar (1,500 kPa), at least 20 bar (2,000 kPa), at least 25 bar (2,500 kPa), at least 30 bar (3,000 kPa), at least 35 bar (3,500 kPa), at least 40 bar (4,000 kPa), at least 45 bar (4,500 kPa), at least 50 bar (5,000 kPa), at least 55 bar (5,500 kPa), at least 60 bar (6,000 kPa), at least 65 bar (6,500 kPa) , at least 70 bar (7,000 kPa), at least 75 bar (7,500 kPa), at least 80 bar (8,000 kPa), at least 85 bar (8,500 kPa), at least 90 bar (9,000 kPa), at least 95 bar (9,500 kPa), or at least 100 bar (10,000 kPa), in other embodiments, the reaction conditions include a pressure within the reaction zone of 5 bar (500 kPa) to 100 bar (10,000 kPa), such as 10). bar (1,000 kPa) to 95 bar (9,500 kPa), from 15 bar (1,500 kPa) to 90 bar (9,000 kPa), from 20 bar (2,000 kPa) to 85 bar (8,500 kPa), from 25 bar (2,500 kPa) at 80 bar (8,000 kPa), from 30 bar (3,000 kPa) to 75 bar (7,500 kPa), from 35 bar (3,500 kPa) to 70 bar (7,000 kPa), from 40 bar (4,000 kPa) to 65 bar (6,500 kPa), from 45 bar (4,500 kPa) to 60 bar (6,000 kPa) or from 50 bar (5,000 kPa) to 55 bar (5,500 kPa). In some embodiments, the pressure within the reaction zone is 20 bar (2000 kPa) to 60 bar (6000 kPa).

[033] According to the embodiments, the gas hourly space velocity (GHSV) within the reaction zone is from 1,200 per hour (/h) to 12,000/h, such as from 1,500/h to 10,000/h, from 2,000/h h to 9,500/h, from 2,500/h to 9,000/h, from 3,000/h to 8,500/h, from 3,500/h to 8,000/h, from 4,000/h to 7,500/h, from 4,500/h to 7,000/h, from 5,000/h to 6,500 /h, or from 5,500/h to 6,000/h. In some embodiments, the GHSV within the reaction zone is 1,800/h to 3,600/h, such as 2,000/h to 3,600/h, 2,200/h to 3,600/h, 2,400/h to 3,600/h, 2,600/h to 3,600/h, from 2,800/h to 3,600/h, from 3,000/h to 3,600/h, from 3,200/h to 3,600/h, or from 3,400/h to 3,600/h. In some embodiments, the GHSV within the reaction zone is 1,800/h to 3,400/h, such as 1,800/h to 3,200/h, 1,800/h to 3,000/h, 1,800/h to 2,800/h, 1,800/h to 2,600/h, from 1,800/h to 2,400/h, from 1,800/h to 2,200/h, or from 1,800/h to 2,000/h. In some embodiments, the GHSV within the reaction is 2,000/h to 3,400/h, such as 2,200/h to 3,200/h, 2,400/h to 3,000/h, or 2,600/h to 2,800/h.

[034] With the use of hybrid catalysts disclosed and described in this document, together with the process conditions disclosed and described in this document, improved C2 to C4 olefin yields and carbon conversion can be achieved. For example, in embodiments where the ratios of hydrogen to carbon monoxide H2/CO range from 2 to 5, such as greater than 2.2 and less than 3.8, or greater than 2.8 and less than 3.4 , where temperatures vary from 360 °C to 460 °C, such as from 380 °C to 440 °C, or from 400 °C to 420 °C, and pressure varies from 5 to 100 bar, such as from 20 to 80 bar, or from 30 to 60 bar. Using such conditions, the yield of C2 to C4 olefins is greater than or equal to 4.0 mol%, such as greater than or equal to 5.0 mol%, greater than or equal to 7.0% in mol, greater than or equal to 10.0 mol%, greater than or equal to 12.0 mol%, greater than or equal to 15.0 mol%, greater than or equal to 17.0 mol% , greater than or equal to 20.0 mol%, greater than or equal to 22.0 mol%, greater than or equal to 25.0 mol%, greater than or equal to 27.0 mol%, greater that or equal to 30.0 mol%, greater than or equal to 32.0 mol%, or greater than or equal to 35.0 mol%. In some embodiments, the maximum yield of C2 to C4 olefin is 50.0 mol%. Thus, in some embodiments, the yield of C2 to C4 olefins is greater than or equal to 4.0 mol% to 50.0 mol%, such as 5.0 mol% to 50.0 mol%, from 7.0 mol% to 50.0 mol%, from 10.0 mol% to 50.0 mol%, from 12.0 mol% to 50.0 mol%, from 15.0% in mol to 50.0 mol%, from 17.0 mol% to 50.0 mol%, from 20.0 mol% to 50.0 mol%, from 22.0 mol% to 50, 0 mol%, from 25.0 mol% to 50.0 mol%, from 27.0 mol% to 50.0 mol%, from 30.0 mol% to 50.0 mol%, from 32.0 mol% to 50.0 mol%, from 35.0 mol% to 50.0 mol%, from 37.0 mol% to 50.0 mol%, from 40.0% mol to 50.0 mol%, from 42.0 mol% to 50.0 mol%, from 45.0 mol% to 50.0 mol%, or from 47.0 mol% to 50 .0 mol%.

[035] In embodiments, with the use of hybrid catalysts disclosed and described herein, together with the process conditions disclosed and described herein, carbon conversion can be improved. Within the disclosed process ranges, conversion of the feed containing carbon and hydrogen oxides can be carried out in a series of reactors with a water by-product intermediate KNOCK-OUT through, for example, phase separation, membrane separation or some type of selective water absorption process. Further directing the partially converted and water-free effluent to the subsequent reactor in series and repeating this manner of technological operations will have an overall effect of increasing olefin yield. For example, in embodiments in which two to four such operations are performed, the total olefin yield may be greater than or equal to 50.0 mol%, such as greater than or equal to 52.0 mol%, greater than or equal to 55.0 mol%, greater than or equal to 57.0 mol%, greater than or equal to 60.0 mol%, greater than or equal to 62.0 mol%, greater than or equal to 65.0 mol%, greater than or equal to 67.0 mol%, greater than or equal to 70.0 mol%, greater than or equal to 72.0 mol%, greater than or equal to 75 .0 mol%, greater than or equal to 77.0 mol%, greater than or equal to 80.0 mol%, or greater than or equal to 85.0 mol%. In some embodiments, the maximum carbon conversion is 95.0 mol%. Therefore, in embodiments, the carbon conversion may be greater than or equal to 50.0 mol% to 95.0 mol%, such as 52.0 mol% to 95.0 mol%, of 55 .0 mol% to 95.0 mol%, from 57.0 mol% to 95.0 mol%, from 60.0 mol% to 95.0 mol%, from 62.0 mol% to 95.0 mol%, from 65.0 mol% to 95.0 mol%, from 67.0 mol% to 95.0 mol%, from 60.0 mol% to 95.0% in mol, from 72.0 mol% to 95.0 mol%, from 75.0 mol% to 95.0 mol%, from 77.0 mol% to 95.0 mol%, from 80 .0 mol% to 95.0 mol%, from 82.0 mol% to 95.0 mol%, from 85.0 mol% to 95.0 mol%, from 87.0 mol% to 95.0 mol%, from 90.0 mol% to 95.0 mol%, or from 92.0 mol% to 95.0 mol%.

EXAMPLES

[036] Modalities will be better clarified by the examples and comparative examples below. In all examples and comparative examples, hybrid catalysts were prepared by mixing the given amount of mixed oxide catalyst component (60 to 80 mesh) with the SAPO-34 microporous catalyst component (60 to 80 mesh). The values are found in the tables below. However, it should be understood that in some comparative examples, SAPO-34 is not included. This is indicated by a value of zero (“0”) in the tables below.

COMPARATIVE EXAMPLE 1

[037] Composite catalysts with SAPO-34 microporous catalyst components and bulk In2O3, bulk Ga2O3 or bulk ZrO2; physical mixture of bulk Ga2O3 and ZrO2 without microporous catalyst component.

[038] Table 1a shows the results of a synthesis gas conversion process into olefins with the following process conditions: H2/CO of approximately 2.0; pressure of 20 bar (2,000 kPa); temperature of 390 °C and GHSV is equal to 1,200/h. The metal oxide catalyst used in the comparative example is a bulk metal oxide as shown in Table 1a. The indium oxide used in this comparative example was commercially available from Aldrich, product number 63 2317, and the gallium oxide used was commercially available from Aldrich, product number 20333-5. Prior to this testing, each of the initial components was compacted, crushed, and sized to provide 60 to 80 mesh fractions for preparing physical mixtures. Then, by combining 150 μl of SAPO-34 (approximately measured, particle size) and adding 150 μl of indium oxide or gallium oxide (each approximately measured, particle size), the hybrid catalysts were prepared by gently stirring the particles together in a bottle. The table below references the catalytic performance of the SAPO-34 double particle bed mixed by addition with any of the pure oxides including the weight of each component.

[039] Table 1b shows the results of a synthesis gas conversion process into olefins, under the following process conditions: H2/CO of approximately 3.0; pressure of 40 bar (4,000 kPa); temperature of 420 °C; and GHSV is equal to 2,400/h and compares the intrinsic performance of zirconia or gallia mixed by addition with SAPO-34. The zirconium oxide used in this comparative example was commercially available monoclinic ZrO2 (norpro supplier, product code SZ39114) and contains some Hf impurity (approximately 2.45% by weight). Before use, zirconium oxide was dispersed in water, dried and calcined at 550 °C. The gallium oxide used in this comparative example was commercially available gallium oxide (available as AlfaAesar, product number 10508). Before use, gallium oxide is dispersed in water, dried and calcined at 550 °C. Prior to this test, the oxides and sieve were compacted, crushed, and sieved to provide 60 to 80 mesh fractions of the initial components. Then, by volumetrically measuring approximately 200 μl of SAPO-34 (sized particles) and adding 200 μl of zirconium oxide (sized particles) or 200 μl of gallium oxide (sized particles), hybrid catalysts were prepared by gentle stirring. The table below references the catalytic performance of the SAPO-34 double particle bed mixed with any of the pure oxides.

[040] Table 1c shows the results of a synthesis gas conversion process under the following process conditions: H2/CO of approximately 3.0; pressure of 40 bar (4,000 kPa); temperature of 420 °C; and GHSV is equal to 2,400/h. To prepare a dual-particle catalyst bed, zirconium oxide (20 mg) and gallium oxide (80 mg) were physically mixed to form a particle mixture (100 mg). To prepare this combination, the materials ZrO2 and Ga2O3 referenced in example 1b were used. To further differentiate this combination, the catalyst bed did not contain any SAPO-34 components.

[041] Comparative Example 1a demonstrates intrinsic properties of pure oxides of elements from Group 13 of the periodic table of elements after double particle bed formulation with SAPO-34. Comparative example 1b marks the intrinsic properties of pure zirconia versus pure galia in combination with SAPO-34 in dual particle bed application. This comparative example shows that different pure oxides in combination with SAPO-34 result in very different catalytic behavior in the conversion of syngas to hydrocarbons. Notably, (1) pure In2O3 has a certain high initial activity and selectivity towards olefins, but a short process lifetime and the hybrid system deactivates quickly; (2) Pure monoclinic ZrO2 showed high selectivity for olefins and long current life, but low activity; (3) Pure Ga2O3 showed moderate activity and very low selectivity for olefins and high selectivity for paraffins and at the same time can convert synthesis gas in longer process times than indium oxide. Furthermore, comparative example 1c shows that a physical mixture of gallium and zirconium oxides without microporous catalyst component (SAPO-34) also has weak activity and low selectivity for olefins.

COMPARATIVE EXAMPLE 2

[042] Table 2a shows the results of a synthesis gas to olefins conversion process with the following process conditions: H2/CO of approximately 2; temperature of 390 °C; pressure of 20 bar (2,000 kPa); and GHSV equal to 1,200/h. Hybrid catalysts were prepared from particle sizes (60 to 80 mesh) of SAPO-34 (volumetric measurement of 150 μL of particle sizes or approximately 75 mg at a time) and particle sizes of various mixed metal oxide catalysts. The mixed oxides featured gallium and lacked zirconium. The oxides were prepared by incipient wet impregnation of aqueous solutions of gallium nitrate precursor into silicon, titanium, or niobium oxide followed by drying and calcination (500 dig). The amounts of 60 to 80 mesh mixed oxide particles used to prepare hybrid catalyst beds with SAPO-34 were approximately 150 μL volumetric measurement at a time. Because of the varying bulk densities of different carrier oxides, the weight of the oxides also varied. Hybrid catalysts were prepared by gently shaking sized particles together in a vial.

[043] Table 2b shows the results of a synthesis gas conversion process into olefins with the following process conditions: H2/CO of approximately 3; temperature of 420 °C; pressure of 40 bar (4,000 kPa); and GHSV is equal to 2,400/h. The amounts of the 60 to 80 mesh mixed oxide particles used to prepare hybrid catalyst beds with SAPO-34 were approximately 200 μl volumetric measurement at a time. Hybrid catalysts were prepared by gently stirring sized particles together in a flask.

[044] For composite catalysts with SAPO-34 as the microporous catalyst component and a Ga-MOx metal oxide catalyst component. Each of the components of the Ga-MOx metal oxide catalyst was prepared by processing crystalline powders of Y2O3, La2O3, CeO2, Cr2O3, MgAl2O4 or MgO and Ga2O3 into fine slurry particles in deionized water, drying and calcining at 550° W.

[045] Table 2c shows the results of a synthesis gas conversion process into olefins with the following process conditions: H2/CO approximately 3; temperature of 420 °C; pressure of 40 bar (4,000 kPa); and GHSV is equal to 2,400/h. The amounts of the 60 to 80 mesh mixed oxide particles used to prepare hybrid catalyst beds with SAPO-34 were approximately 200 μl volumetric measurement at a time. Hybrid catalysts were prepared by gently stirring sized particles together in a flask.

EXAMPLE 1

[046] This example shows the effects of hybrid catalysts formed from a microporous SAPO-34 catalyst component and a metal oxide catalyst component comprising ZrO2-supported gallium catalysts (monoclinic ZrO2, BET surface area of approximately 50 m2/g). The amounts of the 60 to 80 mesh mixed oxide particles used to prepare hybrid catalyst beds are reported in Table 3a and 3b. The hybrid catalysts were prepared by gently shaking the particles together in a flask.

[047] Table 3a shows the results of a synthesis gas conversion process into olefins with the following process conditions: H2/CO approximately 2; temperature 390 °C; pressure of 20 bar (2,000 kPa); and GHSV is equal to 1,200/h.

[048] Table 3b shows the results of a synthesis gas conversion process into olefins with the following process conditions: synthesis gas process H2/CO approximately 3; temperature of 420 °C; pressure of 40 bar; and GHSV is equal to 2,400/h.

[049] Example 1 demonstrates that microporous Ga-ZrO2 prepared at various loadings deposited on monoclinic zirconia and tested with SAPO-34 as the microporous catalyst component under varying feed (H2/CO approximately 2 or approximately 3) and process (temperature and pressure) conditions. This example shows the effectiveness of lower Ga loadings as well as the effectiveness of a zirconia support in the metal oxide catalyst component.

EXAMPLE 2

[050] This example included catalysts with SAPO-34 as the microporous catalyst component and featuring ZrO2-supported gallium as the metal oxide catalyst component (monoclinic ZrO2, BET surface area of approximately 100 m2/g) using a impregnation approach. The amounts of the 60 to 80 mesh mixed oxide particles used to prepare hybrid catalyst beds are reported in Table 4a and 4b. The hybrid catalysts were prepared by gently shaking the particles together in a flask.

[051] Table 4a shows the results of a synthesis gas conversion process into olefins with the following process conditions: H2/CO approximately 2; temperature 390 °C; pressure of 20 bar (2,000 kPa); and GHSV is equal to 1,200/h. TABLE 4a

[052] Table 4b shows the results of a synthesis gas conversion process into olefins with the following process conditions: H2/CO approximately 3; temperature of 420 °C; pressure of 40 bar (4,000 kPa); and GHSV is equal to 2,400/h.

[053] Example 2 further demonstrates that Ga deposited on monoclinic zirconia allows very high olefin yields from composite catalysts in various syngas feeds (2, 3) and process conditions. Very low Ga loadings may allow for a monoclinic ZrO2-active material of a high surface area.

EXAMPLE 3

[054] This example included composite catalysts with SAPO-34 as the microporous catalyst component and featuring ZrO2-supported gallium catalysts (tetragonal ZrO2, BET surface area of approximately 130 m2/g). The amounts of the 60 to 80 mesh mixed oxide particles used to prepare hybrid catalyst beds are reported in Tables 5a and 5b. The hybrid catalysts were prepared by gently shaking the particles together in a flask.

[055] Table 5a shows the results of a synthesis gas conversion process into olefins with the following process conditions: H2/CO approximately 2; temperature 390 °C; pressure 20 bar (2,000 kPa); and GHSV is equal to 1,200/h.

[056] Table 5b shows the results of a synthesis gas conversion process into olefins with the following process conditions: H2/CO approximately 3; temperature of 420 °C; pressure of 40 bar (4,000 kPa); and GHSV is equal to 2,400/h.

[057] This example demonstrated that Ga deposited on tetragonal zirconia is an active component for the catalyst composite (double particle bed). However, the overall performance is inferior to Ga-ZrO2 prepared in monoclinic ZrO2 as for the operations shown in Example 2.

EXAMPLE 4

[058] This example included hybrid catalysts with ZrO2-supported gallium oxide catalyst components that also comprise other elements in the zirconia carrier and/or co-impregnated with the gallium precursor. In the first case (Table 6a), the zirconia carrier was identified as tetragonal zirconia that contained some lanthanum (La) (NORPRO, product number SZ61156, containing approximately 7.3 g of La per 100 g of ZrO2). Gallium was impregnated into this support alone or co-impregnated with an additional amount of lanthanum. The latter case is evidenced with an increased amount of La in the sample (the first versus the second entry in the table). The amounts of the 60 to 80 mesh mixed oxide particles used to prepare hybrid catalyst beds are reported in Table 6a. The hybrid catalysts were prepared by gently shaking the particles together in a flask.

[059] Table 6a shows the results of a synthesis gas conversion process into olefins with the following process conditions: H2/CO = 3; temperature 390 °C; pressure 30 bar; and GHSV is equal to 1,200/h.

[060] Table 6b shows the results of a process to convert carbon oxide and carbon dioxide (COx Conversion) into olefins with the following process conditions: H2/CO/CO2 equals 69.1/13.6 /6.9% by volume; temperature 390 °C; pressure 30 bar, GHSV is equal to 1,200/h. In addition to the catalytic materials referenced in Table 6a, the test also included additional samples prepared on the zirconia carrier identified as tetragonal zirconia that contained some tungsten (W) (NORPRO, product number SZ61143, contains approximately 11 wt% W). The Ga precursor was impregnated into this support alone or co-impregnated with the La precursor (third vs fourth entry in Table 6b).

[061] Example 4 demonstrates that Ga-deposited on tetragonal zirconia with La on the support is an active and stable composite catalyst. In contrast, tetragonal zirconia with W present significantly impairs its catalytic behavior. Co-impregnated La can mitigate some adverse effects of the presence of W (i.e., an effect on methane selectivity). EXAMPLE 5

[062] This example included catalysts with microporous SAPO-34 catalyst components and gallium/lanthanum catalyst with ZrO2 support. As a carrier to prepare this, a commercial sample of monoclinic ZrO2 (NORPRO product number SZ31108, BET surface area of approximately 70 m2/g) was used. The catalyst was tested in a long process under various process conditions.

[063] Table 7a shows the results for the conversion of synthesis gas to olefins for a hybrid catalyst in a process study during which the process conditions were changed during the process. The hybrid catalyst was prepared from 123 mg of SAPO-34 component and 185 mg of Ga-La/ZrO2 mixed oxide component mixed after gently stirring the 60 to 80 mesh size particles of both components together in a bottle. Average catalytic results are reported for each process segment and include the start and end of each process segment (Min ToS [hs] - Max ToS [hs]). Note that time in the stream was counted from the start of syngas exposure. Each process segment had different process operating parameters, such as H2/CO ratio and space velocity, while the process temperature and pressure were kept constant.

[064] Table 7b shows the results of a process for converting synthesis gas into olefins with the following process conditions: H2/CO approximately 3; temperature 390 to 400 °C; pressure equal to 30 bar; and GHSV is equal to 1,200/h to 2,400/h.

[065] Table 7b shows the results for the conversion of synthesis gas to olefins for the hybrid catalyst in a long process study, where the process conditions were changed during the process. The hybrid catalyst was prepared from 147 mg of SAPO-34 component and 130 mg of Ga-La/ZrO2 mixed oxide component after gently stirring 60 to 80 mesh size particles of both components together in a flask. Average catalytic results are reported for each process segment and include the start and end of each process segment (Min ToS [hs] - Max ToS [hs]). Note that time in the stream was counted from the start of syngas exposure. Each process segment had different process operating parameters, such as H2/CO ratio, space velocity or temperature, while the process pressure was kept constant (30 bar).

[066] Example 5 demonstrates that Ga/La-ZrO2 can sustain the synthesis gas to olefins process over extended times and in high olefin yields under various process conditions (p, T, GHSV).

EXAMPLE 6

[067] This example included hybrid catalysts with SAPO-34 microporous catalyst components featuring Ga-ZrO2 metal oxide catalyst component. It compares a Ga-ZrO2 coprecipitated semicrystalline mixed oxide (an alternative synthetic methodology to impregnation), where an intimate Ga-ZrO2 junction may exist, but ZrO2 shows poor crystallinity, effectively making an inferior catalytic system. It also compares Ga-ZrO2 prepared through slurry processing and calcination of crystalline monoclinic ZrO2 and a Ga precursor in the form of Ga2O3 (an alternative synthetic methodology to impregnation), where crystalline powders produce the desired catalytic effect. Furthermore, it compares a physical mixture of powders without any processing to create an intimate junction of Ga2O3 and ZrO2, where the hybrid system with SAPO-34 shows an underdeveloped catalytic performance. The amounts of the 60 to 80 mesh mixed oxide particles used to prepare hybrid catalyst beds are reported in Table 8a. The hybrid catalysts were prepared by gently shaking the particles together in a flask.

[068] Table 8a shows the results of a process for converting synthesis gas into olefins with the following process conditions: H2/CO approximately 3; temperature of 420 °C; the pressure is equal to 40 bar (4,000 kPa); and GHSV is equal to 2,400/h.

[069] Example 6 demonstrated that Ga-ZrO2 can be created with different preparation technologies; however, care must be taken to ensure that ZrO2 is administered in a well-crystalline form, such as the monoclinic polymorph. Methods for obtaining a very active Ga-ZrO2 component for double particle catalyst bed with SAPO-34 appear to be impregnation (Examples 1 to 5). However, after certain process operations, physical mixtures of ZrO2 and Ga2O3 can also gain activity with prolonged process exposure, affecting the redistribution of elements in the presence of reactants and product gases.

[070] It will be evident to those skilled in the art that various modifications and variations can be made to the embodiments described herein 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 modalities described in this document, provided that such modifications and variations are within the scope of the attached claims and their equivalents.

Claims (15)

1. Process for preparing C2 to C4 olefins characterized by the fact that it comprises: - introducing a feed stream comprising hydrogen gas and a carbon-containing gas selected from the group consisting of carbon monoxide, carbon dioxide and mixtures thereof into a reaction zone of a reactor; and - converting the feed stream into a product stream comprising C2 to C4 olefins in the reaction zone in the presence of a hybrid catalyst, the hybrid catalyst comprising: a metal oxide catalyst component comprising gallium oxide and pure zirconia of phase; and a microporous catalyst component. 2. Process according to claim 1, characterized in that the pure phase zirconia comprises pure crystalline phase zirconia. 3. Process according to any one of claims 1 or 2, characterized in that the pure phase zirconia comprises pure monoclinic phase zirconia. 4. Process according to any one of claims 1 to 3, characterized in that the phase pure zirconia has a BET surface area greater than or equal to 40 m2 / g. 5. Process according to any one of claims 1 to 4, characterized in that the phase pure zirconia has a BET surface area greater than or equal to 100 m2/g. 6. Process according to any one of claims 1 to 5, characterized in that the metal oxide catalyst component comprises more than 0.0 gallium per 100 g of phase pure zirconia to 30.0 g of gallium per 100 g of pure phase zirconia. 7. Process according to any one of claims 1 to 6, characterized in that the metal oxide catalyst component comprises more than 0.0 gallium per 100 g of phase pure zirconia to 15.0 g of gallium per 100 g of pure phase zirconia. 8. Process according to any one of claims 1 to 7, characterized in that the microporous catalyst component comprises an 8-membered ring structure. 9. Process according to any one of claims 1 to 8, characterized in that the microporous catalyst component comprises SAPO-34. 10. Process according to any one of claims 1 to 9, characterized in that the metal oxide catalyst component comprises from 1.0% by weight to 99.0% by weight of the hybrid catalyst. 11. Process according to any one of claims 1 to 10, characterized in that the metal oxide catalyst component comprises from 60.0% by weight to 90.0% by weight of the hybrid catalyst. 12. Process according to any one of claims 1 to 11, characterized in that the temperature within the reaction zone during conversion is 350 °C to 450 °C. 13. Process according to any one of claims 1 to 12, characterized in that the pressure within the reaction zone during conversion is at least 1 bar (100 kPa). 14. Process according to any one of claims 1 to 13, characterized in that a GHSV within the reaction zone during conversion is from 1,200/h to 12,000/h. 15. Process according to any one of claims 1 to 14, characterized in that the metal oxide catalyst component is formed by an impregnation method.