FCC process for production of petrochemicals

Abstract

A catalytic cracking process for the production of light olefins and aromatic gasoline comprising contacting a petroleum-based feedstock with a catalyst in a single riser reactor wherein the catalyst comprises from 0% to about 15% by weight of a Y-type zeolite and greater than 30% by weight of a pentasil zeolite, the weight ratio of the pentasil zeolite to the Y-type zeolite being greater than 3; and a weight hourly space velocity (WHSV) of from about 40 h <-1 > to about 120 h <-1 >.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 356,940, filed on June 29, 2022, which is hereby incorporated by reference in its entirety for any and all purposes. Technical Field

[0003] The present technology generally relates to catalytic cracking processes for producing light olefins and aromatic gasoline.

[0004] Overview of this technology

[0005] In one aspect, the present technology provides a catalytic cracking process for producing light olefins and aromatic gasoline, wherein the process comprises contacting a petroleum-based feedstock with a catalyst in a single riser reactor at a temperature and a weight hourly space velocity (WHSV) to convert at least a portion of the petroleum-based feedstock into light olefins and aromatic gasoline, wherein the temperature is from about 530° C. to about 600° C., the WHSV is about 40 h / min, and the catalyst is contacted with the catalyst in a single riser reactor at a temperature and a weight hourly space velocity (WHSV) to convert at least a portion of the petroleum-based feedstock into light olefins and aromatic gasoline. -1 About 120h -1 The catalyst comprises 0 wt % to about 15 wt % Y-type zeolite and greater than 30 wt % pentasil zeolite, wherein the weight ratio of pentasil zeolite to Y-type zeolite is greater than 3, and the weight ratio of catalyst to petroleum-based feedstock is from about 10:1 to about 30:1, optionally from about 13:1 to about 25:1, and the aromatic gasoline is obtained from a C5+ to 221°C cut point.

[0006] Detailed Description

[0007] Various embodiments are described below. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation of the broader aspects discussed herein. An aspect described in conjunction with a specific embodiment is not necessarily limited to that embodiment and can be practiced with any other (one or more) embodiments.

[0008] Unless otherwise indicated herein or the context is clearly contradictory, in the context of describing elements (especially in the context of the following claims), the use of the terms "a", "an", "the" and similar references should be interpreted as covering both the singular and the plural. Unless otherwise indicated herein, the enumeration of the value range herein is intended only as a shorthand method for individually citing each individual value falling within the range, and each individual value is incorporated into the specification as if it were individually listed herein. Unless otherwise indicated herein or the context is clearly contradictory in other aspects, all methods described herein can be performed in any suitable order. Unless otherwise stated, the use of any and all examples or exemplary terms (e.g., "such as") provided herein is intended only to better illustrate the embodiments and will not limit the scope of the claims. The terms in the specification should not be interpreted as indicating that any unclaimed element is necessary.

[0009] As used in this disclosure, the phrase "and / or" will be understood to refer to any one of the listed members individually or in combination of any two or more thereof - for example, "A, B and / or C" will mean "A, B, C, A and B, A and C, B and C, or a combination of A, B and C."

[0010] As used herein with respect to numerical ranges, the terms "about," "approximately," "substantially," and similar terms will be understood by one of ordinary skill in the art and will vary to some extent depending on the context in which they are used. If the usage of these terms is not clear to one of ordinary skill in the art, these terms will be understood to mean plus or minus 10% of the disclosed value, given the context in which they are used—for example, "about 10% by weight" will mean "9% to 11% by weight." It will be understood that when "about," "approximately," and "substantially" (and the like) precede a term, the term is interpreted to disclose "about" / "approximately" / "substantially" as well as the term without "about" / "approximately" / "substantially" modification—for example, "about 10% by weight" discloses "9% to 11% by weight" as well as discloses "10% by weight." When "approximately," "about," "substantially," and similar terms are applied to structural features (e.g., describing their shape, size, orientation, direction, etc.), these terms are intended to encompass minor variations in structure that may result from, for example, manufacturing or assembly processes, and are intended to have a broad meaning consistent with common and recognized usage by those of ordinary skill in the art to which the disclosed subject matter belongs. Accordingly, these terms should be interpreted as indicating that insubstantial or inconsequential modifications or alterations to the described and claimed subject matter are considered to be within the scope of the present disclosure as described in the appended claims.

[0011] The phrase "at least a portion" with respect to a composition means from about 0.1% to about 100% by weight of the composition.

[0012] As used herein, the term "aromatics" is synonymous with "aromates" and means cyclic aromatic hydrocarbons and heterocyclic aromatic compounds that do not contain heteroatoms. The term includes monocyclic, bicyclic and polycyclic ring systems (such bicyclic and polycyclic ring systems are collectively referred to herein as "polycyclic aromatics" or "polycyclic aromatic compounds (polycyclic aromatictes)"). The term also includes aromatic species having alkyl groups and cycloalkyl groups. Therefore, aromatic hydrocarbons include, but are not limited to, benzene, azulene, heptadene, phenylbenzene, indacene, fluorene, phenanthrene, triphenylene, pyrene, tetracene, anthracene, indene, indane, pentalene and naphthalene, as well as alkyl and cycloalkyl substituted variants of these compounds. In some embodiments, the aromatic species contains 6-14 carbons in the ring portion of the group, and in other embodiments contains 6 to 12 or even 6-10 carbon atoms. The phrase includes groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., indane, tetrahydronaphthene, etc.).

[0013] As used herein, the term "C#" (where "#" is a positive integer) is intended to describe all hydrocarbons having # carbon atoms. Thus, the term "C#+ hydrocarbons" is intended to describe all hydrocarbon molecules having # or more carbon atoms. For example, the term "C5+" describes a mixture of hydrocarbons having 5 or more carbon atoms; the term "C4-" describes a mixture of hydrocarbons having 4 carbon atoms, 3 carbon atoms, 2 carbon atoms, 1 carbon atom, and / or 0 carbon atoms (i.e., H2).

[0014] "Diesel" generally refers to fuels having a boiling point falling within the range of about 150°C to about 360°C at atmospheric pressure (the "diesel boiling range").

[0015] "Gasoline" generally refers to spark-ignition engine fuels having boiling points falling within the range of about 35°C to about 225°C. "Aromatic gasoline" refers to gasoline that includes aromatic hydrocarbons. Thus, while the phrase "aromatic gasoline obtained from a cut point of C5+ to 221°C" will be understood by one of ordinary skill in the art, if the phrase may be considered unclear to one of ordinary skill in the art, the phrase will be understood to mean "aromatic gasoline obtained from a cut point of 35°C to 221°C".

[0016] The term "olefin" as used herein refers to an unsaturated hydrocarbon compound containing at least one carbon-carbon double bond. The term "light olefin" refers to ethylene, propylene, butene (e.g., 1-butene, cis-2-butene, trans-2-butene and / or isobutylene) and / or butadiene.

[0017] As used herein, the term "paraffin" refers to non-cyclic, branched or unbranched alkanes. Unbranched paraffins are normal paraffins; branched paraffins are isoparaffins. "Cycloparaffins" are cyclic, branched or unbranched alkanes.

[0018] As used herein, the term "paraffinic" refers to both paraffins and cycloalkanes as defined above, as well as regions containing predominantly hydrocarbon chains that are alkanes, branched or unbranched, with or without mono- or di-unsaturation (i.e., one or two double bonds).

[0019] As used herein, "petroleum-based feedstock" refers to a hydrocarbon-containing composition including components ultimately produced by humans from natural gas and / or crude oil (e.g., in a crude oil refining facility), such as vacuum gas oil, atmospheric residue, vacuum residue, hydrotreated straight-run diesel, hydrotreated fluidized catalytic cracking light cycle oil, hydrotreated coker light gas oil, and / or hydrocracked FCC heavy cycle oil. "Petroleum-based feedstock" in any embodiment described herein may include or exclude (in addition to components ultimately produced from crude oil) "biorenewable feedstock" and / or "plastic-derived feedstock." As used herein, "biorenewable feedstock" is not a component ultimately produced by humans from crude oil, and it may include animal fats, animal oils, plant fats, vegetable oils, vegetable fats, vegetable oils, greases, pyrolysis oils produced by biomaterials, or any mixture of two or more thereof. "Plastic-derived feedstock" may include oils from thermal or catalytic conversion of plastics.

[0020] This technology

[0021] As gasoline engine powered cars are replaced by electric vehicles, the demand for catalytic cracking (e.g., fluid catalytic cracking (FCC)) gasoline as a transportation fuel is expected to decline substantially. At some point, catalytic cracking operations such as FCC, the primary gasoline producing machine in the current refinery setup, will no longer be viable without major changes in the product yield structure through unit hardware modifications or catalyst changes.

[0022] Even before the expected decline in demand for gasoline as a fuel in the future, the increase in demand for propylene as a petrochemical feedstock, while balancing the gasoline fuel production for gasoline engines, has led to the installation of more and more FCC units with higher severity. Compared with traditional FCC units, units with higher severity are generally operated at lower weight hourly space velocity (WHSV), higher catalyst / oil ratio (C / O), higher reactor outlet temperature and higher steam consumption rate. These characteristics are shown in Table 1 below. In order to further maximize the propylene yield, it is common for refiners to recycle a portion of the gasoline (usually light fraction naphtha (LCN)) to the reactor for re-cracking. In order to achieve lower WHSV, the deep catalytic cracking (DCC) process utilizes a fluidized catalyst bed downstream of the riser, while the final catalytic cracking (UCC) process (e.g., as described in U.S. Patent No. 5,846,402) uses very high catalyst circulation rates, so the catalyst retention in the riser is high.

[0023] Table 1. Comparison of various catalytic cracking processes

[0024] FCC DCC UCC WHSV,1 / h 125 to 200 0.2 to 20 40 to 120 Catalyst / oil ratio 4 to 8 2 to 12 15 to 25 Riser outlet temperature, ℃ 490 to 540 540 to 625 530 to 600 Steam, wt% feed 0 to 10 5 to 50 3 to 50 Propylene yield, weight % 4 to 10 13-20 13-20

[0025] Catalysts used for DCC and UCC processes are generally different from FCC catalysts. For example, U.S. Patent No. 5,846,402, U.S. Patent Application No. 2010 / 021310A1, and U.S. Patent No. 9,365,779 discuss using catalysts having the compositions shown in Table 2 (below) in conjunction with UCC process conditions to maximize light olefins.

[0026] Table 2. Catalyst compositions of U.S. Pat. No. 5,846,402, U.S. Patent Application No. 2010 / 0213102A1, and U.S. Pat. No. 9,365,779

[0027]

[0028] Although the main goal of the method disclosed in the above-mentioned reference is to generate high yields of propylene and light olefins, the inventors have not recognized the need to increase gasoline aromatics so that the gasoline stream can be used as a chemical feedstock. In fact, due to health issues, high concentrations of aromatics (especially benzene) are considered undesirable for current gasoline specifications in many parts of the world. Therefore, before the present application, the technology focused on increasing the yield of light olefins while maintaining a relatively high gasoline yield and a relatively low aromatics concentration in the gasoline.

[0029] The inventors of the present technology have discovered that simultaneously adjusting the operating conditions of the catalytic cracking process, such as temperature, catalyst / oil ratio ("C / O") and weight hourly space velocity ("WHSV"), and catalyst composition (e.g., Y-zeolite content, ZSM-5 content, and the ratio of Y-zeolite to ZSM-5 content) can result in significant and favorable changes in product composition. Another advantage provided by the present technology is that by producing a more aromatic gasoline, more feed hydrogen can be transferred to the C4-fraction, thereby increasing the yield of light olefins.

[0030] In particular, it was unexpectedly discovered that a catalytic cracking process comprising a lower WHSV and comprising a catalyst having a higher Y-zeolite and ZSM-5 content produced a higher yield of light olefins and produced gasoline having a higher aromatics concentration than the catalytic cracking processes described in U.S. Pat. No. 5,846,4402 and U.S. Pat. No. 9,365,779. -1 Up to 120h - 1 A catalyst composition containing 0 wt % to 15 wt % Y-type zeolite, greater than 30 wt % ZSM-5, and a weight ratio of ZSM-5 to Y-type zeolite greater than 3 is used in a process with a weight hourly space velocity (WHSV) of 1000 wt % to 1500 wt % Y-type zeolite, greater than 30 wt % ZSM-5, and a weight ratio of ZSM-5 to Y-type zeolite greater than 3 to produce a product, wherein equal to or greater than 60% (e.g., equal to or greater than 63%) of the hydrogen content of the petroleum-based feedstock ("feed hydrogen") can be redistributed to the C4- fraction of the product, equal to or less than 28% (e.g., equal to or less than 25%) of the feed hydrogen can be redistributed to the aromatic gasoline of the product, and the atomic ratio of hydrogen to carbon in the aromatic gasoline can be equal to or less than 1.46:1 (e.g., equal to or less than 1.40:1). In addition, it has been found that catalyst compositions having greater than 50 wt % ZSM-5 and lower amounts of Y-type zeolite (including, for example, excluding Y-type zeolite) advantageously maximize ethylene yields and the amount of aromatics in aromatic gasoline, as well as provide relatively high yields of propylene, butenes, light cycle oil ("LCO"; a type of diesel), and / or fuel oil.

[0031] The above unexpected discovery provides a catalytic cracking process for producing high yields of light olefins (e.g., ethylene, propylene and / or butylenes) and aromatics (e.g., benzene, toluene and / or xylenes) in aromatic gasoline from petroleum-based raw materials. The method also has the flexibility of producing high yields of LCO and fuel oil (if necessary), while maintaining a high yield of light olefins and highly aromatic gasoline as valuable raw materials for the petrochemical industry. The method is characterized by a single riser configuration, as currently configured by almost all existing FCC units, and optionally does not require bed cracking and / or product recycle. Therefore, the present disclosure can transform existing catalytic cracking units with relatively low capital costs.

[0032] In one aspect, the present technology provides a catalytic cracking process for producing light olefins and aromatic gasoline, the process comprising contacting a petroleum-based feedstock with a catalyst in a single riser reactor at a temperature and a weight hourly space velocity (WHSV) to convert at least a portion of the petroleum-based feedstock into light olefins and aromatic gasoline, wherein the temperature is from about 530° C. to about 600° C., the WHSV is about 40 h / min, and the WHSV is about 100 h / min. -1 About 120h -1 The catalyst comprises 0 wt % to about 15 wt % Y-type zeolite and greater than 30 wt % pentasil zeolite, wherein the weight ratio of pentasil zeolite to Y-type zeolite is greater than 3, and the weight ratio of catalyst to petroleum-based feedstock is from about 10:1 to about 30:1, optionally from about 13:1 to about 25:1, and the aromatic gasoline is obtained from a C5+ to 221°C cut point. Therefore, in any embodiment of the present technology, the weight ratio of catalyst to petroleum-based raw materials can be about 10: 1, about 11: 1, about 12: 1, about 13: 1, about 14: 1, about 15: 1, about 16: 1, about 17: 1, about 18: 1, about 19: 1, about 20: 1, about 21: 1, about 22: 1, about 23: 1, about 24: 1, about 25: 1, about 26: 1, about 27: 1, about 28: 1, about 29: 1, about 30: 1, or include and / or any range between any two of these values. In any embodiment of the present technology, light olefins can include ethylene, propylene, butadiene, 1-butene, cis-2-butene, trans-2-butene and / or isobutylene. In any embodiment of the present technology, the aromatic gasoline can include benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methyl ethylbenzene, and / or propylbenzene.

[0033] The pentasil zeolite contains silicon and oxygen as elements constituting the framework, and may be a crystalline silica whose framework is substantially composed of silicon and oxygen, or may be a crystalline metal silicate that also contains another metal element as an element constituting the framework. In the case of crystalline metal silicates, examples of such metal elements other than silicon and oxygen include, but are not limited to, Be, B, Al, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Sb, La, Hf, Bi, or a mixture of any two or more thereof. In any embodiment of the present technology, the pentasil zeolite may be a ZSM-type zeolite, such as ZSM-5 and / or ZSM-11. See, e.g., U.S. Patent Nos. 3,308,069; 3,702,886; 3,709,979; 3,832,449; 4,016,245; 4,788,169; 3,941,871; 5,013,537; 4,851,602; 4,564,511; 5,137,706; 4,962,266; 4,329,328; 5,354,719; 5,365, 5,354,875. In any embodiment of the present technology, the pentasil zeolite can be stabilized with P2O5. In any embodiment of the present technology, the weight ratio of P2O5 to pentasil zeolite can be about 0.1:1, about 0.2:1, about 0.3:1, or any range including and / or between any two of these values. In any embodiment of the present technology, the catalyst may include about 35 wt% to about 60 wt% pentasil zeolite; thus, in any embodiment of the present technology, the catalyst may include about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, or any range of pentasil zeolite including and / or between any two of these values. For example, in any embodiment, the catalyst may include about 35 wt% to about 55 wt% pentasil zeolite.In any embodiment herein, the catalyst may include about 6 wt % to about 24 wt % phosphorus (measured as P2O5); thus, in any embodiment of the present technology, the catalyst may include about 6 wt %, about 8 wt %, about 10 wt %, about 12 wt %, about 14 wt %, about 16 wt %, about 18 wt %, about 20 wt %, about 22 wt %, about 24 wt %, or any range of amounts of phosphorus including and / or between any two of these values. In any embodiment herein, the catalyst may include about 1 wt % to about 10 wt % iron (measured as Fe2O3); thus, in any embodiment of the present technology, the catalyst may include about 1 wt %, about 2 wt %, about 3 wt %, about 4 wt %, about 5 wt %, about 6 wt %, about 7 wt %, about 8 wt %, about 9 wt %, about 10 wt %, or any range of amounts of iron including and / or between any two of these values.

[0034] Suitable Y-type zeolites include those commonly used in catalytic cracking processes (e.g., FCC). These zeolites include, but are not limited to, Y zeolites (see, e.g., U.S. Pat. No. 3,130,007); ultrastable Y zeolite (USY) (see, e.g., U.S. Pat. No. 3,449,070); rare earth exchanged Y (REY) (see, e.g., U.S. Pat. No. 4,415,438); rare earth exchanged USY (REUSY); dealuminated Y (DeAlY) (see, e.g., U.S. Pat. No. 3,442,792; U.S. Pat. No. 4,331,694); ultrahydrophobic Y (UHPY) (see, e.g., U.S. Pat. No. 4,401,556), and any combination of two or more thereof, wherein such Y-type zeolites are generally referred to as "Y zeolites" or "Y-type zeolites" in the art. Suitable Y-type zeolites may be macroporous molecular sieves having a pore size greater than about 7 angstroms; in current commercial practice, most cracking catalysts contain such zeolites. In any embodiment of the present technology, the catalyst can include about 0 wt%, about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, about 15 wt%, or any range of amounts of Y-type zeolite including and / or between any two of these values. For example, in any embodiment of the present technology, the catalyst can include no Y-type zeolite, or can include about 1 wt% to about 8 wt% of Y-type zeolite. In any embodiment of the present technology, the Y-type zeolite can be stabilized with rare earth oxides (referred to herein and in the claims as "RE2O3") such as lanthanum oxide and / or cerium oxide. In any embodiments of the present technology, the catalyst may include a weight ratio of RE2O3 to Y-type zeolite of about 0.04:1 to about 0.15:1; therefore, in any embodiments of the present technology, the catalyst may include a weight ratio of RE2O3 to Y-type zeolite of about 0.04:1, about 0.05:1, about 0.06:1, about 0.07:1, about 0.08:1, about 0.09:1, about 0.10:1, about 0.11:1, about 0.12:1, about 0.13:1, about 0.14:1, about 0.15:1, or any range including and / or between any two of these values.

[0035] In any embodiment of the present technology, the WHSV may be about 40h -1 , about 45h -1 , about 50h - 1 , about 55h -1 , about 60h -1 , about 65h -1 , about 70h -1, or any range including and / or between any two of these values.

[0036] In any embodiment of the present technology, contacting the petroleum-based feedstock with a catalyst can redistribute the hydrogen content of the petroleum-based feedstock by converting at least a portion of the petroleum-based feedstock into products, such products including light olefins and aromatic gasoline. In any embodiments of the present technology, equal to or greater than 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98% or 99% (or any range including and / or between any two of these values) of the hydrogen content of the petroleum based feedstock can be reallocated into the C4-product. In any embodiments of the present technology, the hydrogen content of a petroleum-based feedstock equal to or less than 28%, 27%, 26%, 25%, 24%, 23%, 22%, 21%, 20%, 19%, 18%, 17%, 16%, 15% or 14% (or any range including and / or between any two of these values) can be redistributed into aromatic gasoline.

[0037] In any embodiments of the present technology, the atomic ratio of H / C in the aromatic gasoline (also referred to herein as the "atomic H:C ratio") can be equal to or less than 1.46:1, 1.45:1, 1.44:1, 1.43:1, 1.42:1, 1.41:1, 1.40:1, 1.40:1, 1.39:1, 1.38:1, 1.37:1, 1.36:1, 1.35:1, 1.34:1, 1.33:1, 1.32:1, 1.31:1 or 1.30:1 (or can be any range including and / or between any two of these values).

[0038] In any embodiment of the present technology, the method may or may not include bed cracking. In any embodiment of the present technology, the method may or may not include product recycle.

[0039] In any embodiment of the present technology, the raw material based on petroleum can include vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, atmospheric residue, vacuum residue, or any two or more mixtures thereof. In any embodiment of the present technology, the raw material based on petroleum can include coal liquefaction oil, tar sand oil, shale oil, bio-renewable raw materials, plastic derived raw materials, or any two or more mixtures thereof. In any embodiment of the present technology, the bio-renewable raw materials can include animal fat, animal oil, vegetable fat, vegetable oil, vegetable fat, vegetable oil, grease, the pyrolysis oil produced by biomaterial, or any two or more mixtures thereof.

[0040] In any embodiment of the present technology, make the raw material based on petroleum contact with catalyst can be converted into dry gas, liquefied petroleum gas (LPG), light cycle oil (LCO), slurry oil or any two or more combination thereof based on at least a portion of the raw material of petroleum.In any embodiment of the present technology, light olefins can be included in dry gas and / or LPG.In any embodiment of the present technology, the method can also include one or more fractionation steps to fractionate dry gas and / or LPG to produce ethene, propylene and / or butylene.In any embodiment of the present technology, the method can also include one or more fractionation steps to fractionate aromatic gasoline to produce benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methyl ethylbenzene and / or propylbenzene.

[0041] The present technology thus generally described will be more readily understood by reference to the following examples, which are provided by way of illustration and are not intended to limit the present technology. Example

[0042] Embodiment 1:

[0043] Two comparative catalysts (Catalyst 1 and Catalyst 2) were synthesized according to the teachings of U.S. Pat. No. 5,846,402 ("the '402 patent"), while Catalysts 3, 4, and 5 are examples according to the present technology. Table 3 provides the amounts of the components used for each catalyst. For each catalyst, the catalyst was generated by using pseudo-boehmite in the range of 3 to 11% to provide a "bottom cracking matrix" (as shown in Table 3), Y-zeolite was stabilized with rare earths, and ZSM-5 was stabilized with phosphorus, wherein the P2O5 / ZSM-5 weight ratio was kept constant at 0.25 for all catalysts.

[0044] Regarding the comparative catalysts, Comparative Catalyst 1 is within the preferred range of the formulation window disclosed in the '402 patent, while Comparative Catalyst 2 is at the upper end of the range of Y-zeolite, ZSM-5, and rare earth specifications claimed in the '402 patent.

[0045] Notably, each of Catalysts 3-5 utilizes greater than 28 wt% ZSM-5, with the total amount of Y-zeolite plus ZSM-5 ("ZSM-5+Y Total" in Table 3) being greater than 35 wt%. In addition, for each of Catalysts 3-5, the amount of clay and binder utilized is less than 45 wt%, which is less than the amount specified in the '402 patent. In addition, Catalyst 3 includes approximately 8 wt% Y-zeolite, thus exceeding the range specified in the '402 patent for this component.

[0046] Table 3. Catalyst formulation

[0047]

[0048] Embodiment 2:

[0049] Catalysts 1-3 were used to crack U.S. Mid-Continent VGO in a cycle pilot unit operating under UCC conditions (see Table 1) with a riser outlet temperature of 1050°F (566°C), C / O maintained at 16, and WHSV maintained at approximately 59 h -1 to about 61h -1 The properties of the mid-continent VGO used in this example (as well as Examples 3-4) are provided in Table 4; the results are shown in Table 5.

[0050] Table 4. Properties of Mid-Continent VGO Feedstock

[0051] test unit result API 24.03 proportion 0.9098 Aromatic ring carbon, Ca weight% 19.6 Cycloalkane carbon, Cn weight% 18.3 Alkane carbon, Cp weight% 62.1 hydrogen weight% 12.5 sulfur weight% 0.5 Basic nitrogen weight% 0.05 Total Nitrogen weight% 0.14 Conradson Carbon weight% 0.4 Distillation, initial boiling point °F 587 Distilled, 5% °F 671 Distilled, 10% °F 703 Distilled, 20% °F 746 Distilled, 30% °F 780 Distilled, 40% °F 811 Distilled, 50% °F 844 Distilled, 60% °F 879 Distilled, 70% °F 919 Distilled, 80% °F 961 Distilled, 90% °F 1016 Distilled, 95% °F 1059 Distillation, end point °F 1153 Distillation recovery rate ％ 99.6

[0052] Table 5. Comparison of yields at constant catalyst / oil ratio

[0053]

[0054]

[0055] As shown in Table 5, Catalyst 3 of the present technology provides higher yields of ethylene and propylene than the comparative catalysts (Catalysts 1 and 2). In addition, the gasoline produced by Catalyst 3 has a higher aromatics concentration than the gasoline provided by Catalysts 1 and 2.

[0056] Embodiment 3:

[0057] Catalysts 1, 4, and 5 were used to crack U.S. Mid-Continent VGO (see Table 4) in a cycle pilot unit operating under UCC conditions (see Table 1) with a riser outlet temperature of 1050°F (566°C), C / O maintained at 13.8, and WHSV maintained at approximately 68 h -1 About 70h -1 The results are shown in Table 6.

[0058] As shown in Table 6, the use of Catalyst 4 provided higher yields of ethylene and propylene than when Catalyst 1 was used. Catalyst 4 also produced a gasoline having a higher aromatics concentration than the gasoline provided by Catalyst 1.

[0059] The results provided using Catalyst 5 illustrate the flexibility provided by the present technology: shifting the yield of light olefins and / or gasoline toward diesel and / or fuel oil, while still advantageously providing gasoline with a relatively high concentration of aromatics. Specifically, the use of Catalyst 5 provides significantly higher yields of LCO / diesel and fuel oil compared to Catalysts 1 and 4, while providing a higher ethylene yield than Catalyst 1 (and higher than that provided by Catalyst 4). In addition, the gasoline provided by Catalyst 5 has a similar aromatics concentration compared to the gasoline provided by Catalyst 4. In addition, the selectivity of ethylene and propylene can be adjusted by changing the ratio of Y-zeolite to ZSM-5.

[0060] Table 6. Comparison of yields at constant catalyst / oil ratio

[0061]

[0062] Embodiment 4:

[0063] In the patent literature, both DCC and UCC technologies claim to achieve a propylene yield greater than 20 wt % by cracking "VGO" feedstock (although there are various VGO feedstocks). Due to the differences in VGO properties between laboratories, those of ordinary skill in the art recognize that even if all other process conditions are said to remain the same, people cannot directly compare the product yields from different laboratories. The nature of the feedstock strongly affects the amount of LPG olefins that can be produced. Typically, FCC feedstocks contain about 12 wt % to about 13 wt % H (or H / C atomic ratios between about 1.64 and about 1.8). However, ethylene, propylene, 1-butene, cis-2-butene, trans-2-butene and isobutylene each have an H / C atomic ratio of 2. Therefore, the production of such light olefins is limited by the hydrogen content of the feedstock. In general, as the hydrogen content increases, the conversion rate increases, and the yields of propylene and butene increase. For example, a higher propylene yield can be obtained by cracking a highly paraffinic VGO feed (hydrogen content greater than 13 wt%), whereas the same process (same conditions, same reactor, same catalyst, etc.) will provide a much lower propylene yield when cracking a mid-continent VGO feed (hydrogen content of about 12.5 wt%). The FCC process causes a shift in carbon distribution from higher molecular weight feedstocks to lower molecular weight products. Less appreciated in the scientific literature is the fact that the shift in hydrogen distribution to lower molecular weight products is even more significant than the shift in carbon distribution. This is because the H / C ratio increases as the molecular weight decreases. Instead, to allow for proper comparison, one should use the hydrogen distribution of the cracked products on a feed basis.

[0064] Thus, Table 7 shows a representative maximum gasoline FCC run (catalyst with 25 wt% Y-zeolite and no ZSM-5, 521°C, WHSV=120h -1 ), the state-of-the-art maximum propylene FCC operation (catalyst with 18 wt% Y-zeolite and 17 wt% ZSM-5, 566°C, WHSV=120h -1 ) and operation according to the present technique (Catalyst 3 with 8 wt% Y-zeolite and 39 wt% ZSM-5; 566°C, WHSV=57h -1) based on feed hydrogen. All data were generated by single riser cracking of the same Mid-Continent VGO (see Table 4) without bed cracking or product recycle. The elemental hydrogen content in the dry gas and LPG streams was calculated directly based on the molecular formulas of the components in these streams and their weight percentages; the hydrogen content in gasoline, LCO and slurry oil was determined by ASTM 5291 "Standard Test Methods for Instrumental Determination of Carbon, Hydrogen, and Nitrogen in Petroleum Products and Lubricants", in which the liquid products are physically distilled into gasoline (59°F (15°C) - 430°F (221°C) as boiling point range) and LCO (430°F (221°C) - 700°F (371°C) as boiling point range), with the remainder at the bottom of the distillation column as the slurry oil fraction. The elemental hydrogen content of the coke is calculated from the CO, CO2 and O2 analysis of the pilot plant regenerator flue gas, where elemental hydrogen reacts with oxygen to form water, so it can be calculated as the missing portion of oxygen when the total oxygen output in CO, CO2 and remaining O2 is compared to the total oxygen in the inlet air. The hydrogen balance results for all published pilot plant tests were >96% recovery of the hydrogen content of the VGO feed (see Table 4).

[0065] In maximum gasoline FCC operation, 57.1% of the feed hydrogen ends up in the gasoline range, 27.5% ends up in LPG (C3+C4), and only 3.3% ends up in dry gas (C2-). The total hydrogen in the C4-range (LPG+dry gas) is 30.8%.

[0066] In state-of-the-art maximum propylene FCC operations, the hydrogen distribution deviates from gasoline and shifts to LPG and dry gas, which results in about half more feed hydrogen (28.2%) ending up in the gasoline range, and about twice as much feed hydrogen (60.2%) in the C4-range compared to maximum gasoline FCC operations.

[0067] Operation with Catalyst 3 (combining a lower WHSV with a catalyst of the present technology designed to increase light olefin production) showed a further shift in feed hydrogen from gasoline to the C4- range: the feed hydrogen content in gasoline was further reduced to 20.9%, while the feed hydrogen content of C4- was further increased to 67.6%.

[0068] Table 7 also provides the atomic ratio of hydrogen to carbon (also referred to as "H / C atomic ratio", "atomic H / C ratio" or simply "H / C" in this disclosure) for various product streams. Desired products in the C4- fraction include ethylene (C2H4), propylene (C3H6) and butene (C4H8), each of which has an atomic H / C ratio of 2, and butadiene (C4H6) having an atomic H / C ratio of less than 2. Undesirable products include H2, methane, ethane, propane and butane, each of which has an atomic H / C ratio greater than 2. The atomic H / C ratio of dry gas and LPG provided by operation with Catalyst 3 is lower than that of the maximum propylene FCC process and much lower than that of the maximum gasoline FCC process. In fact, the atomic H / C ratio of LPG provided by operation with Catalyst 3 is very close to 2, which proves that the LPG is highly olefinic. Without being bound by theory, it is believed that the combination of Catalyst 3 and operating conditions minimizes hydrogen transfer reactions, thereby producing a highly olefinic C4- stream.

[0069] The atomic H / C ratio of gasoline is a good indicator of aromaticity. Table 8 shows that the H / C of benzene (C6H6) is 1, but with the increase of substitution through alkyl (methyl, ethyl or propyl) groups, the atomic H / C ratio increases. In addition, the atomic H / C ratio of gasoline increases with the increase of non-aromatic compounds (such as paraffins, olefins and cycloalkanes) levels in the cracking process, which represent compounds that could have been cracked into light olefins but were not cracked. The operation of catalyst 3 provides gasoline with an atomic H / C ratio lower than that of gasoline operated with maximum propylene FCC, and far lower than that of gasoline H operated with maximum gasoline FCC, proving that the present technology provides very effective conversion of non-aromatic molecules to light olefins. In fact, the atomic H / C ratio of gasoline provided by the operation of catalyst 3 is only 1.33 (note that trimethylbenzene has an atomic H / C ratio of 1.33), and the aromatic compounds of gasoline are very valuable for being used as petrochemical raw materials.

[0070] Table 7. Hydrogen distribution in cracking products

[0071]

[0072]

[0073] Table 8. Atomic H / C ratios of various aromatic compounds in gasoline

[0074]

[0075]

[0076] Paragraph 1. A catalytic cracking process for producing light olefins and aromatic gasoline, the process comprising:

[0077] contacting a petroleum-based feedstock with a catalyst in a single riser reactor at a temperature and weight hourly space velocity (WHSV) to convert at least a portion of the petroleum-based feedstock into light olefins and aromatic gasoline;

[0078] in:

[0079] The catalyst comprises

[0080] 0% to about 15% by weight of Y-type zeolite, and

[0081] greater than 30% by weight of pentasil zeolite,

[0082] wherein the weight ratio of the pentasil zeolite to the Y-type zeolite is greater than 3;

[0083] The temperature is from about 530°C to about 600°C;

[0084] The WHSV is about 40h -1 About 120h -1 ;

[0085] a weight ratio of catalyst to petroleum-based feedstock of about 10:1 to about 30:1, optionally about 13:1 to about 25:1; and

[0086] The aromatic gasoline is obtained from a C5+ to 221°C cut point.

[0087] Paragraph 2. The method of claim 1, wherein the light olefin comprises ethylene, propylene, butene, or a combination of any two or more thereof.

[0088] Paragraph 3. The method according to paragraph 1 or paragraph 2, wherein the aromatic gasoline comprises benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, propylbenzene, or a combination of any two or more thereof.

[0089] Paragraph 4. The process of any of paragraphs 1-3, wherein the pentasil zeolite comprises ZSM-5.

[0090] Paragraph 5. The method of any of paragraphs 1-4, wherein the pentasil zeolite is stabilized with P2O5, optionally wherein the weight ratio of P2O5 to the pentasil zeolite is from about 0.1:1 to about 0.3:1.

[0091] Paragraph 6. The method according to any of paragraphs 1-5, wherein the Y-type zeolite is stabilized with RE2O3, optionally wherein the weight ratio of RE2O3 to the Y-type zeolite is from about 0.04:1 to about 0.15:1.

[0092] Paragraph 7. The process of any of paragraphs 1-6, wherein the catalyst comprises 0 wt % to about 10 wt % of the Y-type zeolite.

[0093] Paragraph 8. The process of any of paragraphs 1-7, wherein the catalyst comprises from about 35 wt % to about 60 wt % of the pentasil zeolite.

[0094] Paragraph 9. The method according to any one of paragraphs 1-8, wherein the WHSV is about 40h -1 About 70h -1 .

[0095] Paragraph 10. A method according to any of paragraphs 1-9, wherein the petroleum-based feedstock is contacted with the catalyst to redistribute the hydrogen content of the petroleum-based feedstock by converting at least a portion of the petroleum-based feedstock into products, wherein the products include the light olefins and the aromatic gasoline.

[0096] Paragraph 11. A method according to paragraph 10, wherein 60% or more of the hydrogen content of the petroleum-based feedstock is reallocated to C4-products, optionally wherein 63% or more of the hydrogen content of the petroleum-based feedstock is reallocated to C4-products.

[0097] Paragraph 12. A method according to paragraph 10 or paragraph 11, wherein 28% or less of the hydrogen content of the petroleum-based feedstock is redistributed to the aromatic gasoline, optionally wherein 25% or less of the hydrogen content of the petroleum-based feedstock is redistributed to the aromatic gasoline.

[0098] Paragraph 13. The process according to any of paragraphs 1-12, wherein the H / C atomic ratio in the aromatic gasoline is equal to or less than 1.46, optionally wherein the H / C atomic ratio in the aromatic gasoline is less than 1.40.

[0099] Paragraph 14. The process of any of paragraphs 1-13, wherein the process does not include bed cracking.

[0100] Paragraph 15. The method of any of paragraphs 1-14, wherein the method does not comprise product recycle.

[0101] Paragraph 16. The method of any one of paragraphs 1-15, wherein the petroleum-based feedstock comprises vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, atmospheric residue, vacuum residue, or a mixture of any two or more thereof.

[0102] Paragraph 17. The method according to any one of paragraphs 1-16, wherein the petroleum-based feedstock comprises coal liquefaction oil, tar sand oil, shale oil, or a mixture of any two or more thereof.

[0103] Paragraph 18. A method according to any one of paragraphs 1-17, wherein the petroleum-based feedstock further comprises a biorenewable feedstock and / or a plastic-derived feedstock, optionally wherein the biorenewable feedstock comprises vegetable oil, animal fat, pyrolysis oil, or a mixture of any two or more thereof.

[0104] Paragraph 19. A method according to any one of paragraphs 1-18, wherein contacting the petroleum-based feedstock with the catalyst converts at least a portion of the petroleum-based feedstock into a product comprising dry gas, liquefied petroleum gas (LPG), light cycle oil (LCO), slurry oil, or a combination of any two or more thereof.

[0105] Paragraph 20. The method according to paragraph 19, wherein the dry gas and / or the LPG contains the light olefins, and wherein the method further comprises one or more fractionation steps to fractionate the dry gas and / or LPG to produce ethylene, propylene and / or butenes.

[0106] Paragraph 21. The method according to any of paragraphs 1-17, wherein the method further comprises one or more fractionation steps to fractionate the aromatic gasoline to produce benzene, toluene, xylenes, ethylbenzene, trimethylbenzenes, methylethylbenzene and / or propylbenzene.

[0107] Paragraph 22. A product comprising light olefins produced by paragraph 1 and gasoline.

[0108] Paragraph 23. The product of paragraph 22, wherein the C4-product is present in an amount equal to or greater than 60% of the hydrogen content of the petroleum-based feedstock.

[0109] Paragraph 24. The product of paragraph 23, wherein the C4-product is present in an amount equal to or greater than 63% of the hydrogen content of the petroleum-based feedstock.

[0110] Paragraph 25. The product of any of paragraphs 22-24, wherein aromatic gasoline is present in an amount equal to or less than 28% of the hydrogen content of the petroleum-based feedstock.

[0111] Paragraph 26. The product of paragraph 25, wherein aromatic gasoline is present in an amount equal to or less than 25% of the hydrogen content of the petroleum-based feedstock.

[0112] Paragraph 27. The product of any of paragraphs 22-26, wherein the aromatic gasoline has an H / C atomic ratio equal to or less than 1.46.

[0113] Paragraph 28. The product according to paragraph 27, wherein the aromatic gasoline has an H / C atomic ratio of less than 1.40.

[0114] Equivalent

[0115] The present technology is not limited to the specific embodiments described in this application, which are intended to be a single illustration of a single aspect of the present technology. As will be apparent to those skilled in the art, many modifications and changes may be made to the present technology without departing from the spirit and scope of the present technology. In addition to those listed herein, functionally equivalent methods and devices within the scope of the present technology will be apparent to those skilled in the art through the foregoing description. Such modifications and changes are intended to fall within the scope of the present technology. It should be understood that the present technology is not limited to ad hoc methods, reagents, compound compositions or biological systems, which can certainly vary. It should also be understood that the terms used herein are only for the purpose of describing specific embodiments and are not intended to be limiting.

[0116] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0117] As will be understood by those skilled in the art, for any and all purposes, particularly in providing a written description, all ranges disclosed herein also encompass any and all possible sub-ranges and combinations of sub-ranges thereof. Any listed range can be easily understood to fully describe and be able to decompose the same range into at least equal half, one-third, one-quarter, one-fifth, one-tenth, etc. As a non-limiting example, each range discussed herein can be easily decomposed into a lower third, a middle third, and an upper third, etc. As will be understood by those skilled in the art, all terms such as "at most", "at least", "greater than", "less than", etc. include the listed numbers and refer to the ranges that can be subsequently decomposed into sub-ranges as described above. Finally, as will be understood by those skilled in the art, the range includes each individual member. Therefore, for example, a group with 1-3 units refers to a group with 1, 2 or 3 units. Similarly, a group with 1-5 units refers to a group with 1, 2, 3, 4 or 5 units, and so on.

[0118] All publications, patent applications, issued patents, and other documents mentioned in this specification are incorporated herein by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions contained in text incorporated by reference are excluded to the extent they conflict with definitions in this disclosure.

[0119] Other embodiments are set forth in the following claims.

Claims

1. A catalytic cracking process for producing light olefins and aromatic gasoline, the process comprising: contacting a petroleum-based feedstock with a catalyst in a single riser reactor at a temperature and weight hourly space velocity (WHSV) to convert at least a portion of the petroleum-based feedstock into light olefins and aromatic gasoline; in: The catalyst comprises 0% to about 15% by weight of Y-type zeolite, and greater than 30% by weight of pentasil zeolite, wherein the weight ratio of pentasil zeolite to Y-type zeolite is greater than 3; The temperature is from about 530°C to about 600°C; The WHSV is about 40h -1 About 120h -1 ; a weight ratio of catalyst to petroleum-based feedstock of about 10:1 to about 30:1, optionally about 13:1 to about 25:1; and The aromatic gasoline is obtained from a C5+ to 221°C cut point.

2. The method according to claim 1, wherein the light olefin comprises ethylene, propylene, butene, or a combination of any two or more thereof.

3. The method according to claim 1 or claim 2, wherein the aromatic gasoline comprises benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, propylbenzene, or a combination of any two or more thereof.

4. The process of any one of claims 1-3, wherein the pentasil zeolite comprises ZSM-5.

5. The method of any one of claims 1-4, wherein the pentasil zeolite is stabilized with P2O5, optionally wherein the weight ratio of P2O5 to the pentasil zeolite is from about 0.1:1 to about 0.3:

1.

6. The method of any one of claims 1-5, wherein the Y-type zeolite is stabilized with RE2O3, optionally wherein the weight ratio of RE2O3 to the Y-type zeolite is from about 0.04:1 to about 0.15:

1.

7. The process of any one of claims 1-6, wherein the catalyst comprises 0 wt% to about 10 wt% of the Y-type zeolite.

8. The process of any one of claims 1-7, wherein the catalyst comprises from about 35 wt% to about 60 wt% of the pentasil zeolite.

9. The method according to any one of claims 1 to 8, wherein the WHSV is about 40 h -1 About 70h -1 .

10. The method of any one of claims 1-9, wherein contacting the petroleum-based feedstock with the catalyst redistributes the hydrogen content of the petroleum-based feedstock by converting at least a portion of the petroleum-based feedstock into products, the products comprising the light olefins and the aromatic gasoline.

11. The method of claim 10, wherein 60% or more of the hydrogen content of the petroleum-based feedstock is redistributed to C4-products, optionally wherein 63% or more of the hydrogen content of the petroleum-based feedstock is redistributed to C4-products.

12. The method of claim 10 or claim 11, wherein 28% or less of the hydrogen content of the petroleum-based feedstock is redistributed to the aromatic gasoline, optionally wherein 25% or less of the hydrogen content of the petroleum-based feedstock is redistributed to the aromatic gasoline.

13. The method according to any one of claims 1 to 12, wherein the H / C atomic ratio in the aromatic gasoline is equal to or less than 1.46, optionally wherein the H / C atomic ratio in the aromatic gasoline is less than 1.

40.

14. The process according to any one of claims 1 to 13, wherein the process does not comprise bed cracking.

15. The process of any one of claims 1-14, wherein the process does not comprise product recycle.

16. The method of any one of claims 1-15, wherein the petroleum-based feedstock comprises vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, atmospheric residue, vacuum residue, or a mixture of any two or more thereof.

17. The method of any one of claims 1-16, wherein the petroleum-based feedstock comprises coal liquefaction oil, tar sand oil, shale oil, or a mixture of any two or more thereof.

18. The method of any one of claims 1-17, wherein the petroleum-based feedstock further comprises a biorenewable feedstock and / or a plastic-derived feedstock, optionally wherein the biorenewable feedstock comprises vegetable oil, animal fat, pyrolysis oil, or a mixture of any two or more thereof.

19. The method of any one of claims 1-18, wherein contacting the petroleum-based feedstock with the catalyst converts at least a portion of the petroleum-based feedstock into a product comprising dry gas, liquefied petroleum gas (LPG), light cycle oil (LCO), slurry oil, or a combination of any two or more thereof.

20. The method according to claim 19, wherein the dry gas and / or the LPG comprises the light olefins, and wherein the method further comprises one or more fractionation steps to fractionate the dry gas and / or LPG to produce ethylene, propylene and / or butenes.

21. The process of any one of claims 1-17, wherein the process further comprises one or more fractionation steps to fractionate the aromatic gasoline to produce benzene, toluene, xylenes, ethylbenzene, trimethylbenzenes, methylethylbenzene and / or propylbenzene.

22. A product comprising light olefins produced by claim 1 and gasoline.

23. The product of claim 22, wherein C4-product is present in an amount equal to or greater than 60% of the hydrogen content of the petroleum-based feedstock.

24. The product of claim 23, wherein C4-product is present in an amount equal to or greater than 63% of the hydrogen content of the petroleum-based feedstock.

25. The product of any one of claims 22-24, wherein aromatic gasoline is present in an amount equal to or less than 28% of the hydrogen content of the petroleum-based feedstock.

26. The product of claim 25 wherein aromatic gasoline is present in an amount equal to or less than 25% of the hydrogen content of the petroleum-based feedstock.

27. The product of any one of claims 22-26, wherein the aromatic gasoline has an H / C atomic ratio equal to or less than 1.

46.

28. The product of claim 27, wherein the aromatic gasoline has an H / C atomic ratio of less than 1.40.

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