FCC process useful for the production of petrochemical products

Abstract

A catalytic cracking method for producing light olefins and aromatic gasoline includes the step of contacting a petroleum feedstock with a catalyst in a single riser reactor, the catalyst containing 0 wt% to about 15 wt% of Y-type zeolite and more than 30 wt% of pentasil zeolite, the weight ratio of pentasil zeolite to Y-type zeolite being more than 3, and the weight hourly space velocity (WHSV) being about 40 h -1 ~ about 120 h -1 -1.

Description

Technical Field

[0001]

[0001] This application claims the benefit of priority of U.S. Provisional Patent Application No. 63 / 356,940, filed Jun. 29, 2022, which is hereby incorporated by reference in its entirety for all purposes.

Background Art

[0002]

[0002] This technology generally relates to a catalytic cracking process for producing light olefins and aromatic gasoline.

Summary of the Invention

Means for Solving the Problems

[0003]

[0003] In one aspect, the technology is a catalytic cracking method for producing light olefins and aromatic gasoline, comprising contacting a petroleum feedstock with a catalyst in a single riser reactor at a certain temperature and weight hourly space velocity (WHSV) to convert at least a portion of the petroleum feedstock into light olefins and aromatic gasoline, wherein the temperature is about 530° C. to about 600° C., and the WHSV is about 40 h -1 ~about 120 h -1 . A method is provided. The catalyst comprises 0 wt % to about 15 wt % Y zeolite and more than 30 wt % pentasil zeolite, the weight ratio of pentasil zeolite to Y zeolite exceeds 3, and the weight ratio of the catalyst to the petroleum feedstock is about 10:1 to about 30:1, optionally about 13:1 to about 25:1, and aromatic gasoline with a cut point from C5+ to 221° C. is obtained.

Mode for Carrying Out the Invention

[0004]

[0004] The following describes various embodiments. It should be noted that specific embodiments are not intended as an exhaustive description or as a limitation to the broad aspects discussed herein. One aspect described in conjunction with a specific embodiment is not necessarily limited to that embodiment and can be implemented with any other embodiment.

[0005]

[0005] The terms "a", "an", and "the", as well as similar reference terms, used in the context of describing elements (especially in the context of the following claims), are to be construed to cover both the singular and plural forms, unless otherwise indicated herein or unless clearly contradicted by the context. The recitation of a range of values herein is intended, unless otherwise indicated herein, merely as a shorthand way of referring individually to each separate value that falls within the range, and each separate value is incorporated herein as if it were individually recited herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or unless clearly contradicted by the context. The use of any examples, or exemplary language (e.g., "such as") provided herein is merely intended to better illustrate the embodiments and does not impose a limitation on the claims unless otherwise stated. No language in this specification should be construed as indicating any non-claimed element as essential.

[0006]

[0006] As used herein, the phrase "and / or" means any one of the recited members individually or any combination of two or more of them. For example, "A, B, and / or C" is understood to mean "A, B, C, A and B, A and C, B and C, or the combination of A, B, and C".

[0007] As used herein with respect to numerical ranges, the terms "about," "approximately," "substantially," and similar terms are understood by those skilled in the art and vary to some extent depending on the context in which they are used. If there is any use of a term that is not clear to those skilled in the art from the context in which it is used, the term is understood to mean plus or minus 10% of the disclosed value. For example, "about 10 wt%" means "9 wt% to 11 wt%." When the terms "about," "approximately," and "substantially" (or the like) are attached to a term, the term is understood to disclose not only the term with "about" / "approximately" / "substantially," but also the term without the modification by "about" / "approximately" / "substantially." For example, "about 10 wt%" should be understood to disclose not only "9 wt% to 11 wt%," but also "10 wt%." When the terms "approximately," "about," "substantially," and similar terms are applied to structural features (e.g., to describe its shape, size, orientation, direction, etc.), these terms are intended to cover, for example, minor variations in the structure that may result from the manufacturing or assembly process and have a broad meaning that is consistent with the general and accepted usage by those skilled in the art to which the subject matter of the present disclosure pertains. Accordingly, these terms should be construed to indicate that minor or insignificant changes or modifications to the described and claimed subject matter are considered to be within the scope of the present disclosure as recited in the appended claims.

[0008] The phrase "at least a portion of" with respect to a composition means from about 0.1 wt% to about 100 wt% of the composition.

[0009] As used herein, the term "aromatic" is synonymous with "aromate" and means both non-heteroatom-containing cyclic aromatic hydrocarbons and heteroaromatic compounds. This term includes monocyclic, bicyclic and polycyclic ring systems (such bicyclic and polycyclic ring systems are collectively referred to herein as "polycyclic aromatic" or "polycyclic aromate"). This term also includes aromatic species having alkyl and cycloalkyl groups. Thus, aromatics include, but are not limited to, benzene, azulene, heptalene, phenylbenzene, indacene, fluorene, phenanthrene, triphenylene, pyrene, naphthacene, chrysene, anthracene, indene, indane, pentalene, and naphthalene, as well as alkyl and cycloalkyl substitution variants of these compounds. In some embodiments, the aromatic species contain 6 to 14 carbon atoms in the ring portion of the group, and in other embodiments contain 6 to 12 carbon atoms, or even 6 to 10 carbon atoms. This phrase includes groups containing fused rings such as fused aromatic-aliphatic ring systems (e.g., indane, tetrahydronaphthalene, etc.).

[0009]

[0010] As used herein, the term "C#" (where "#" is a positive integer) means to represent all hydrocarbons having # carbon atoms. Thus, the term "C#+ hydrocarbon" means to represent all hydrocarbon molecules having # or more carbon atoms. For example, the term "C5+" represents a mixture of hydrocarbons having 5 or more carbon atoms, and the term "C4-" represents 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).

[0010]

[0011] Generally, "diesel" refers to a fuel having a boiling point at atmospheric pressure in the range of about 150°C to about 360°C ("diesel boiling point range").

[0012] Generally, "gasoline" refers to a fuel for a spark-ignition engine having a boiling point in the range of about 35°C to about 225°C. "Aromatic gasoline" refers to gasoline containing aromatics. Thus, the phrase "aromatic gasoline having a cut point from C5+ to 221°C can be obtained" will be understood by those skilled in the art, but if this phrase is considered not clear to those skilled in the art, it will be understood to mean "aromatic gasoline having a cut point from 35°C to 221°C can be obtained".

[0011]

[0013] As used herein, the term "olefin" refers to an unsaturated hydrocarbon compound containing at least one carbon-carbon double bond. The term "light olefin" relates to ethylene, propylene, butylene (e.g., 1-butene, cis-2-butene, trans-2-butene, and / or isobutylene), and / or butadiene.

[0012]

[0014] As used herein, the term "paraffin" means an acyclic, branched or unbranched alkane. An unbranched paraffin is an n-paraffin, and a branched paraffin is an isoparaffin. "Cycloparaffin" is a cyclic, branched or unbranched alkane.

[0013]

[0015] As used herein, the term "paraffinic" means a hydrocarbon chain having a region that is mostly an alkane, either branched or unbranched, of both paraffins and cycloparaffins as defined above, regardless of the presence or absence of mono- or di-unsaturation (i.e., one or two double bonds).

[0014]

[0016] As used herein, the "petroleum feedstock" refers to a hydrocarbon-containing composition containing components finally 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 fluid catalytic cracking light cycle oil, hydrotreated coker light gas oil, and / or hydrocracked FCC heavy cycle oil. The "petroleum feedstock" in any embodiment described herein may or may not include a "biorenewable feedstock" and / or a "plastic-derived feedstock" (in addition to components finally produced from crude oil). The "biorenewable feedstock" as used herein is a component not finally produced by humans from crude oil, and can include animal fats, animal oils, vegetable fats, vegetable oils, vegetable fats, vegetable oils, greases, pyrolysis oils produced from biological materials, or any mixture of two or more thereof. The "plastic-derived feedstock" can include oils from the thermal or catalytic conversion of plastics.

[0015]

[0017] This technology

[0018] Gasoline engine-powered automobiles are being replaced by electric vehicles, and the demand for catalytic cracking (e.g., fluid catalytic cracking (FCC)) gasoline as a transportation fuel is expected to decrease dramatically. At some point, the operation of catalytic cracking such as FCC (e.g., the main gasoline production unit in current refineries) will no longer be feasible unless the product yield composition is significantly changed by improving the hardware of the device or changing the catalyst.

[0016]

[0019] Even before it was predicted that future demand for gasoline as a fuel would decline, the demand for propylene as a petrochemical feedstock has been increasing, and as a result of balancing gasoline fuel production for gasoline engines, the number of more stringent FCC units installed has been increasing. Compared to conventional FCC units, more stringent units generally operate at lower weight hourly space velocity (WHSV), higher catalyst-to-oil ratio (C / O), higher reactor outlet temperature, and higher steam velocity. These characteristics are shown in Table 1 below. To further maximize the yield of propylene, refiners generally recycle a portion of the gasoline, typically light cycle naphtha (LCN), and re-crack it in the reactor. To achieve a lower WHSV, the Deep Catalytic Cracking (DCC) process utilizes a fluidized catalyst bed downstream of the riser, while the Ultimate Catalytic Cracking (UCC) process (described, for example, in U.S. Patent No. 5,846,402) utilizes a very high catalyst circulation rate and thus a large catalyst inventory within the riser.

[0017]

Table 1

[0018]

[0020] Catalysts for the DCC and UCC processes generally differ from FCC catalysts. For example, U.S. Patent No. 5,846,402, U.S. Patent Application Publication No. 2010 / 021310 (A1), and U.S. Patent No. 9,365,779 discuss the use of catalysts having the compositions shown in Table 2 (below) in combination with the conditions of the UCC process to maximize light olefins.

[0019]

Table 2

[0020]

[0021] The main objective of the method disclosed in the above literature is to produce propylene and light olefins in high yields. However, the need that the present inventors now recognize to increase gasoline aromatics so that the gasoline stream can be used as a chemical feedstock was not recognized. In fact, high concentrations of aromatics, especially benzene, are considered undesirable in current gasoline specifications in many regions of the world due to health concerns. Therefore, prior to this application, the art in this field has focused on increasing the light olefin yield while maintaining a relatively high gasoline yield and a relatively low aromatic concentration in the gasoline.

[0021]

[0022] The inventors of the present technology have discovered that simultaneously adjusting the operating conditions of the catalytic cracking process, such as temperature, catalyst-to-oil ratio ("C / O"), and weight hourly space velocity ("WHSV"), and the catalyst composition (e.g., Y-zeolite content, ZSM-5 content, and the ratio of the Y-zeolite content to the ZSM-5 content) results in a significant and advantageous change in the product composition. A further advantage provided by the present technology is that by producing a more aromatic gasoline, more feedstock hydrogen migrates to the C4-fraction, and thus the yield of light olefins is improved.

[0022]

[0023] In particular, it was unexpectedly discovered that a catalytic cracking process involving a catalyst with a lower WHSV and higher Y-zeolite and ZSM-5 contents than the catalysts described in U.S. Patent No. 5,846,4402 and U.S. Patent No. 9,365,779 produces high yields of light olefins and gasoline with a high concentration of aromatics. Specifically, a catalyst composition containing 0 wt% to 15 wt% of Y-zeolite, more than 30 wt% of ZSM-5, and a ZSM-5 to Y-zeolite weight ratio of more than 3 is used for 40h -1 ~120h -1When used in a process that utilizes the weight hourly space velocity (WHSV), more than 60% (e.g., 63% or more) of the hydrogen content of the petroleum feedstock (“feed hydrogen”) can be redistributed to the C4-fraction of the product, and 28% or less (e.g., 25% or less) of the feed hydrogen can be redistributed to the aromatic gasoline of the product, resulting in a product in which the atomic ratio of hydrogen to carbon in the aromatic gasoline can be 1.46:1 or less (e.g., 1.40:1 or less). Further, a catalyst composition having more than 50 wt% ZSM-5 and a lower amount of Y-type zeolite (e.g., including the exclusion of Y-type zeolite) advantageously maximizes the ethylene yield and the amount of aromatics in the aromatic gasoline, and has been found to result in a relatively high yield of propylene, butylene, light cycle oil (“LCO”; a type of diesel), and / or fuel oil.

[0023]

[0024] Due to the above unexpected findings, a catalytic cracking process for producing light olefins (e.g., ethylene, propylene, and / or butylene) and aromatics in aromatic gasoline (e.g., benzene, toluene, and / or xylene) from a petroleum feedstock in high yields is provided. This process also has the flexibility to produce LCO and fuel oil in high yields as needed while maintaining high yields of light olefins and high-concentration aromatic gasoline as valuable feedstocks for the petrochemical industry. This process features a single riser configuration, as most existing FCC units are currently configured, and in some cases does not require bed cracking and / or product recycling. Thus, the present disclosure enables the improvement of existing catalytic cracking units at relatively low capital costs.

[0024]

[0025] In one aspect, the technology is a catalytic cracking process for producing light olefins and aromatic gasoline, comprising contacting a petroleum feedstock with a catalyst in a single riser reactor at a certain temperature and weight hourly space velocity (WHSV) to convert at least a portion of the petroleum feedstock into light olefins and aromatic gasoline, wherein the temperature is from about 530 °C to about 600 °C and the WHSV is about 40 h -1~about 120 h -1 Provided is a method which is as follows. The catalyst contains 0 wt% to about 15 wt% of Y-type zeolite and more than 30 wt% of pentasil zeolite. The weight ratio of pentasil zeolite to Y-type zeolite exceeds 3, and the weight ratio of the catalyst to the petroleum feedstock is from about 10:1 to about 30:1, optionally from about 13:1 to about 25:1, and an aromatic gasoline with a cut point from C5+ to 221 °C is obtained. Thus, in any embodiment of the present technology, the weight ratio of the catalyst to the petroleum feedstock 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 any range including and / or between any two of these values. In any embodiment of the present technology, the 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, methylethylbenzene, and / or propylbenzene.

[0025]

[0026] Pentasil zeolite contains silicon and oxygen as the elements constituting the framework, and the framework may be crystalline silica substantially composed of silicon and oxygen, or may be a crystalline metallosilicate further containing another metal element as an element constituting the framework. In the case of crystalline metallosilicates, 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 any mixture of two or more of these. 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, for example, 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; 5,365,002; 5,064,793; 5,409,685; 5,466,432; 4,968,650; 5,158,757; 5,273,737; 4,935,561; 4,299,808; 4,405,502; 4,363,718; 4,732,747; 4,828,812; 5,466,835; 5,374,747; and 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 the pentasil zeolite may 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 can include from about 35 wt% to about 60 wt% of pentasil zeolite. Thus, in any embodiment of the present technology, the catalyst can include about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, or any amount within any range including and / or between any two of these values of pentasil zeolite. For example, in any embodiment, the catalyst can include from about 35 wt% to about 55 wt% of pentasil zeolite. In any embodiment herein, the catalyst can include from about 6 wt% to about 24 wt% of phosphorus (measured as P2O5). Thus, in any embodiment of the present technology, the catalyst can 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 amount within any range including and / or between any two of these values of phosphorus. In any embodiment herein, the catalyst can include from about 1 wt% to about 10 wt% of iron (measured as Fe2O3). Thus, in any embodiment of the present technology, the catalyst can 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 amount within any range including and / or between any two of these values of iron.

[0026]

[0027] Suitable Y zeolites include those commonly used in catalytic cracking processes (e.g., FCC). These zeolites include, but are not limited to, Y zeolite (see, e.g., U.S. Patent No. 3,130,007); ultrastable Y zeolite (USY) (see, e.g., U.S. Patent No. 3,449,070); rare earth exchanged Y (REY) (see, e.g., U.S. Patent No. 4,415,438); rare earth exchanged USY (REUSY); dealuminated Y (DeAlY) (see, e.g., U.S. Patent No. 3,442,792; U.S. Patent No. 4,331,694); ultra-hydrophobic Y (UHPY) (see, e.g., U.S. Patent No. 4,401,556), and any combination of two or more thereof. Typically in the art, such Y zeolites are all collectively referred to as "Y zeolite" or "Y zeolites". Suitable Y zeolites can be large pore molecular sieves having a pore diameter greater than about 7 angstroms, and in current commercial practice, most cracking catalysts contain such zeolites. In any embodiment of the present technology, the catalyst can contain Y zeolite in an amount of 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 two of these values and / or any range therebetween. For example, in any embodiment of the present technology, the catalyst can contain no Y zeolite or about 1 wt% to about 8 wt% of Y zeolite. In any embodiment of the present technology, the Y zeolite may be stabilized with rare earth oxides such as lanthanum oxide and / or cerium oxide (referred to herein and in the claims as "RE2O3").In any embodiment of the present technology, the catalyst can include a weight ratio of RE2O3 to Y-type zeolite of from about 0.04:1 to about 0.15:1. Thus, in any embodiment of the present technology, the catalyst can 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 two of these values and / or any range therebetween.

[0027]

[0028] In any embodiment of the present technology, the WHSV is about 40 h -1 , about 45 h -1 , about 50 h -1 , about 55 h -1 , about 60 h -1 , about 65 h -1 , about 70 h -1 , or can be any two of these values and / or any range therebetween.

[0028]

[0029] In any embodiment of the present technology, the step of 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 a product, and the product may include light olefins and aromatic gasoline. In any embodiment of the present technology, 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 two of these values and / or any range therebetween) or more of the hydrogen content of the petroleum-based feedstock may be redistributed to the C4-product. In any embodiment of the present technology, 28%, 27%, 26%, 25%, 24%, 23%, 22%, 21%, 20%, 19%, 18%, 17%, 16%, 15%, or 14% (or any two of these values and / or any range therebetween) or less of the hydrogen content of the petroleum-based feedstock may be redistributed to the aromatic gasoline.

[0029]

[0030] In any embodiment of the present technology, the atomic ratio of H to C in the aromatic gasoline (also referred to herein as the "atomic H:C ratio") may be 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 any two of these values and / or any range therebetween).

[0030]

[0031] 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 recycle of the product.

[0031]

[0032] In any embodiment of the present technology, the petroleum-based feedstock can include vacuum gas oil, atmospheric gas oil, coker gas oil, decanted oil, atmospheric residue, vacuum residue, or any mixture of two or more of them. In any embodiment of the present technology, the petroleum-based feedstock can include coal liquefied oil, tar sand oil, shale oil, bio-renewable feedstock, plastic-derived feedstock, or any mixture of two or more of them. In any embodiment of the present technology, the bio-renewable feedstock can include animal fat, animal oil, vegetable fat, vegetable oil, vegetable fat, vegetable oil, grease, pyrolysis oil produced from biological materials, or any mixture of two or more of them.

[0032]

[0033] In any embodiment of the present technology, the step of contacting the petroleum-based feedstock with the catalyst can convert at least a portion of the petroleum-based feedstock into dry gas, liquefied petroleum gas (LPG), light cycle oil (LCO), slurry, or any combination of two or more of them. 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 further include one or more fractionation steps for fractionating dry gas and / or LPG to obtain ethylene, propylene, and / or butylene. In any embodiment of the present technology, the method can further include one or more fractionation steps for fractionating aromatic gasoline to obtain benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methyl ethylbenzene, and / or propylbenzene.

[0033]

[0034] The present technology, generally described as such, will be more readily understood by reference to the following examples, which are provided for purposes of illustration and not intended to limit the present technology.

Examples

[0034] Example 1

[0035] Two comparative catalysts (Catalyst 1 and Catalyst 2) were synthesized according to the teachings of U.S. Patent No. 5,846,402 (the “’402 Patent”), while Catalyst 3, Catalyst 4, and Catalyst 5 are examples according to the present technology. Table 3 shows the amounts of the components utilized for each catalyst. For each catalyst, the “bottoms cracking matrix” was obtained by using pseudoboehmite in the range of 3-11% (shown in Table 3) in the production of the catalyst, the Y-zeolite was stabilized with rare earths, the ZSM-5 was stabilized with phosphorus, and the weight ratio of P2O5 / ZSM-5 was kept constant at 0.25 for all catalysts.

[0035]

[0036] Regarding the comparative catalysts, Comparative Catalyst 1 is within the preferred range of the formulation framework disclosed in the ’402 Patent, while Comparative Catalyst 2 is within the upper limit range of the Y-zeolite, ZSM-5, and rare earth specifications claimed by the ’402 Patent.

[0036]

[0037] Notably, each of Catalysts 3-5 utilized more than 28 wt% ZSM-5, and the total amount of Y-zeolite + ZSM-5 (the “Total of ZSM-5 + Y” in Table 3) was higher than 35 wt%. Further, in each of Catalysts 3-5, the amounts of clay and binder utilized were less than 45 wt%, which was less than the amount defined by the ’402 Patent. Further, Catalyst 3 contained approximately 8 wt% Y-zeolite and thus exceeded the range described in the invention of the ’402 Patent regarding this component.

[0037]

Table 3

[0038] Example 2

[0038] In a circulating pilot plant operating under UCC conditions (see Table 1), Catalysts 1-3 were used to crack VGO from the central region of the United States, the riser outlet temperature was set at 1050°F (566°C), the C / O was maintained at 16, and the WHSV was about 59 h -1 ~about 61 h -1It was maintained. Table 4 shows the properties of the VGO in the central region used in this example (and Examples 3 to 4), and the results are shown in Table 5.

[0039]

Table 4

[0040]

Table 5

[0041]

[0039] As shown in Table 5, Catalyst 3 of the present technology resulted in higher yields of ethylene and propylene than the comparative catalysts (Catalyst 1 and Catalyst 2). Furthermore, Catalyst 3 produced gasoline with a higher concentration of aromatics than the gasoline produced by Catalyst 1 and Catalyst 2.

[0042] Example 3

[0040] In a circulating pilot plant operating under UCC conditions (see Table 1), Catalysts 1, 4, and 5 were used to crack the VGO in the central region of the United States (see Table 4), the riser outlet temperature was set at 1050°F (566°C), the C / O was maintained at 13.8, and the WHSV was maintained in the range of about 68 h -1 ~about 70 h -1 The results are shown in Table 6.

[0043]

[0041] As shown in Table 6, the use of Catalyst 4 resulted in higher yields of ethylene and propylene compared to the case of using Catalyst 1. Catalyst 4 also produced gasoline with a higher concentration of aromatics than the gasoline produced by Catalyst 1.

[0044]

[0042] The results obtained by using catalyst 5 demonstrate the flexibility provided by the technology of the present invention, i.e., while shifting the yield of light olefins and / or gasoline towards diesel and / or fuel oil, it still advantageously provides gasoline with a relatively high concentration of aromatics. In particular, the use of catalyst 5 results in a significantly higher yield of LCO / diesel and fuel oil compared to catalysts 1 and 4, and at the same time, a higher ethylene yield than catalyst 1 (and additionally higher than the yield brought about by catalyst 4). Furthermore, catalyst 5 brought about gasoline with an aromatic concentration comparable to that of the gasoline brought about by catalyst 4. Additionally, by varying the ratio of Y-zeolite to ZSM-5, the selectivity of ethylene and propylene can be adjusted.

[0045]

Table 6

[0046] Example 4

[0043] In the patent literature, both DCC and UCC technologies claim to achieve a propylene yield of over 20 wt% by decomposing the "VGO" feedstock. However, there are various types of VGO feedstocks. Since the properties of VGO vary from laboratory to laboratory, a person skilled in the art understands that even if it is claimed that all other process conditions are the same, the product yields of different laboratories cannot be directly compared. The properties of the feedstock strongly affect the amount of LPG olefins that can be produced. Typically, FCC feedstocks contain about 12 wt% to about 13 wt% H (or an H / C atomic ratio between about 1.64 and about 1.8). However, the H / C atomic ratio of each of ethylene, propylene, 1-butene, cis-2-butene, trans-2-butene, and isobutylene is 2. Therefore, the production of such light olefins is limited by the hydrogen content of the feedstock. Generally, as the hydrogen content increases, the conversion increases and the yields of propylene and butylene increase. For example, by decomposing a highly paraffinic VGO feed (having a hydrogen content of over 13 wt%), a higher propylene yield can be obtained. However, under the same process, i.e., the same conditions, the same reactor, the same catalyst, etc., decomposing a VGO feed from the central region (having a hydrogen content of about 12.5 wt%) results in a significant decrease in the propylene yield. The FCC process causes a shift in the carbon distribution from higher molecular weight feedstocks to lower molecular weight products. What has not been fully evaluated 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, in order to enable an appropriate comparison, the hydrogen distribution of the decomposition products based on the feed should be used.

[0047]

[0044] Therefore, Table 7 shows a typical maximum gasoline FCC operation (with a catalyst having 25 wt% Y-zeolite and no ZSM-5, 521 °C, WHSV = 120 h -1) The maximum propylene FCC operation according to the current state-of-the-art technology (catalyst with 18 wt% Y-zeolite and 17 wt% ZSM-5, 566 °C, WHSV = 120 h -1 ) and the operation according to the present technology (catalyst 3 with 8 wt% Y-zeolite and 39 wt% ZSM-5; 566 °C, WHSV = 57 h -1 ) The hydrogen distribution of the decomposition products is shown on the basis of the feed hydrogen. All data were obtained by single riser cracking of the same mid-region VGO (see Table 4) without bed cracking or product recycling. The elemental hydrogen content of the dry gas and LPG streams was calculated directly based on the molecular formulas of the components in these streams and their weight percentages, and the hydrogen content of gasoline, LCO, and slurry was measured by ASTM 5291 "Standard Test Methods for Instrumental Determination of Carbon, Hydrogen, and Nitrogen in Petroleum Products and Lubricants". Here, the liquid product was physically distilled into gasoline (boiling range 59 (15 °C) - 430 °F (221 °C)) and LCO (boiling range 430 (221 °C) - 700 °F (371 °C)), and what remained at the bottom of the distillation column was taken as the slurry fraction. The elemental hydrogen content of the coke was calculated from the CO, CO2, and O2 analyses of the regenerator flue gas of the pilot plant. Here, since elemental hydrogen reacted with oxygen to form water, the total amount of oxygen in CO, CO2, and residual O2 compared to the total oxygen in the inlet air can be calculated as the oxygen deficit. The hydrogen balance results from all the disclosed pilot plant tests were a recovery rate of >96% of the hydrogen content of the VGO feed (see Table 4).

[0048]

[0045] In the maximum gasoline FCC operation, 57.1% of the feed hydrogen reaches the gasoline range, 27.5% of the feed hydrogen reaches LPG (C3 + C4), and only 3.3% of the feed hydrogen reaches dry gas (C2-). The total hydrogen in the C4- range (LPG + dry gas) is 30.8%.

[0049]

[0046] In the current state-of-the-art maximum propylene FCC operation, the hydrogen distribution shifts from gasoline towards LPG and dry gas, such that, compared to the maximum gasoline FCC operation, only about half of the feed hydrogen (28.2%) reaches the gasoline range and about twice the feed hydrogen (60.2%) reaches the C4- range.

[0050]

[0047] The operation using Catalyst 3 (a combination of a lower WHSV and the catalyst of the present technology for promoting light olefin production) shows that the feed hydrogen further shifts from gasoline to the C4- range, i.e., the feed hydrogen content in gasoline further decreases to 20.9% and the feed hydrogen content in C4- further increases to 67.6%.

[0051]

[0048] Table 7 also provides the atomic ratio of hydrogen to carbon (in the present disclosure, also referred to as the “atomic H / C ratio,” “atom H / C ratio,” or simply “H / C”) for various product streams. Desirable products in the C4- fraction include ethylene (C2H4), propylene (C3H6), and butylene (C4H8), each having 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 having an atomic H / C ratio greater than 2. The operation using Catalyst 3 provides a lower atomic H / C ratio of dry gas and LPG compared to the maximum propylene FCC process and a significantly lower atomic H / C ratio of dry gas and LPG compared to the maximum gasoline FCC process. In fact, the LPG atomic H / C ratio provided by the operation using Catalyst 3 is very close to 2, demonstrating that the LPG is highly olefinic. Without being bound by theory, it is believed that the combination of Catalyst 3 and the operating conditions results in a highly olefinic C4- stream because it minimizes hydrogen transfer reactions.

[0052]

[0049] The atomic H / C ratio of gasoline is a good indicator of the degree of aromaticity. Table 8 shows that while the H / C of benzene (C6H6) is 1, the atomic H / C ratio increases with an increase in substitution by alkyl (methyl, ethyl, or propyl) groups. Furthermore, the atomic H / C ratio of gasoline increases as the levels of non-aromatic compounds such as paraffins, olefins, and naphthenes increase. This is because in the cracking process, these non-aromatic compounds could have been cracked into light olefins but represent the compounds that were not cracked. In the operation using Catalyst 3, gasoline with an atomic H / C ratio lower than that of gasoline in maximum propylene FCC operation and significantly lower than that of gasoline H in maximum gasoline FCC operation is provided, demonstrating that this technology results in a very effective conversion of non-aromatic molecules into light olefins. In fact, the atomic H / C ratio of the gasoline obtained in the operation using Catalyst 3 is only 1.33 (note that the atomic H / C ratio of trimethylbenzene is 1.33), and the aromatic compounds in the gasoline are very valuable for use as petrochemical feedstocks.

[0053]

Table 7

[0054]

Table 8

[0055]

[0050] Item 1. A catalytic cracking method for producing light olefins and aromatic gasoline, comprising the step of contacting a petroleum feedstock with a catalyst in a single riser reactor at a certain temperature and weight hourly space velocity (WHSV) to convert at least a portion of the petroleum feedstock into light olefins and aromatic gasoline, wherein the catalyst is 0 wt% to about 15 wt% of Y zeolite, and more than 30 wt% of pentasil zeolite containing, with the weight ratio of pentasil zeolite to Y zeolite exceeding 3, the temperature being from about 530 °C to about 600 °C, the WHSV being from about 40 h -1 to about 120 h -1 and the weight ratio of the catalyst to the petroleum feedstock being from about 10:1 to about 30:1, optionally from about 13:1 to about 25:1, aromatic gasoline with a cut point from C5+ to 221 °C being obtained, a method.

[0056]

[0051] Item 2. The method according to claim 1, wherein the light olefins include ethylene, propylene, butylene, or any combination of two or more thereof.

[0052] Item 3. The method according to item 1 or item 2, wherein the aromatic gasoline includes benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, propylbenzene, or any combination of two or more thereof.

[0057]

[0053] Item 4. The method according to any one of items 1 to 3, wherein the pentasil zeolite includes ZSM-5.

[0054] Item 5. The method according to any one of items 1 to 4, wherein the pentasil zeolite is stabilized with P2O5, and optionally the weight ratio of P2O5 to the pentasil zeolite is from about 0.1:1 to about 0.3:1.

[0058]

[0055] Item 6. The method according to any one of items 1 to 5, wherein the Y zeolite is stabilized with RE2O3, and optionally the weight ratio of RE2O3 to the Y zeolite is from about 0.04:1 to about 0.15:1.

[0059]

[0056] Item 7. The method according to any one of items 1 to 6, wherein the catalyst contains from 0 wt% to about 10 wt% of Y zeolite.

[0057] Item 8. The method according to any one of items 1 to 7, wherein the catalyst contains from about 35 wt% to about 60 wt% of pentasil zeolite.

[0060] Item 9. The WHSV is about 40 h -1 to about 70 h -1 The method according to any one of Items 1 to 8, wherein the WHSV is as defined above. Item 10. The step of contacting the petroleum feedstock with the catalyst redistributes the hydrogen content of the petroleum feedstock by converting at least a portion of the petroleum feedstock to products, and the products include light olefins and aromatic gasoline. The method according to any one of Items 1 to 9.

[0061] Item 11. The method according to Item 10, wherein 60% or more of the hydrogen content of the petroleum feedstock is redistributed to C4-products, and optionally, 63% or more of the hydrogen content of the petroleum feedstock is redistributed to C4-products.

[0062] Item 12. The method according to Item 10 or 11, wherein 28% or less of the hydrogen content of the petroleum feedstock is redistributed to aromatic gasoline, and optionally, 25% or less of the hydrogen content of the petroleum feedstock is redistributed to aromatic gasoline.

[0063] Item 13. The method according to any one of Items 1 to 12, wherein the atomic ratio of H to C in the aromatic gasoline is 1.46 or less, and optionally, the atomic ratio of H to C in the aromatic gasoline is less than 1.40.

[0064] Item 14. The method according to any one of Items 1 to 13, which does not include fluidized bed cracking. Item 15. The method according to any one of Items 1 to 14, which does not include recycling of the products.

[0065] Item 16. The method according to any one of Items 1 to 15, wherein the petroleum feedstock includes vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, atmospheric residue, vacuum residue, or a mixture of any two or more thereof.

[0066] Item 17. The method according to any one of Items 1 to 16, wherein the petroleum-based feedstock comprises liquefied coal oil, tar sand oil, shale oil, or a mixture of any two or more thereof.

[0067] Item 18. The method according to any one of Items 1 to 17, wherein the petroleum-based feedstock further comprises a bio-renewable feedstock and / or a plastic-derived feedstock, and optionally, the bio-renewable feedstock comprises vegetable oil, animal fat, pyrolysis oil, or a mixture of any two or more thereof.

[0067]

[0068] Item 19. The method according to any one of Items 1 to 18, wherein the step of contacting the petroleum-based feedstock with a 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, or any combination of two or more thereof.

[0068]

[0069] Item 20. The method according to Item 19, wherein the dry gas and / or LPG comprises light olefins, and further comprises one or more fractionation steps for fractionating the dry gas and / or LPG to obtain ethylene, propylene, and / or butylene.

[0069]

[0070] Item 21. The method according to any one of Items 1 to 17, further comprising one or more fractionation steps for fractionating aromatic gasoline to obtain benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, and / or propylbenzene.

[0070]

[0071] Item 22. A product comprising light olefins and gasoline produced according to Item 1.

[0072] Item 23. The product according to Item 22, wherein the C4-product is present in an amount of 60% or more of the hydrogen content of the petroleum-based feedstock.

[0071]

[0073] Item 24. The product according to Item 23, wherein the C4-product is present in an amount of 63% or more of the hydrogen content of the petroleum-based feedstock.

[0074] Item 25. The product according to any one of Items 22 to 24, wherein the aromatic gasoline is present in an amount of 28% or less of the hydrogen content of the petroleum-based feedstock.

[0072]

[0075] Item 26. The product according to Item 25, wherein the aromatic gasoline is present in an amount of 25% or less of the hydrogen content of the petroleum-based feedstock.

[0076] Item 27. The product according to any one of Items 22 to 26, wherein the aromatic gasoline has an atomic ratio of H to C of 1.46 or less.

[0073]

[0077] Item 28. The product according to Item 27, wherein the aromatic gasoline has an atomic ratio of H to C of less than 1.40.

[0074] Equivalents

[0078] The present technology should not be limited in terms of the specific embodiments described in this application, and this embodiment is intended as a single exemplification of the individual aspects of the present technology. As will be apparent to those skilled in the art, many modifications and variations of the present technology can be made without departing from its spirit and scope. In addition to those listed herein, functionally equivalent methods and apparatuses within the scope of the present technology will be apparent to those skilled in the art from the foregoing description. Such modifications and variations are intended to be included within the scope of the present technology. It should be understood that the present technology is not limited to a specific method, reagent, compound composition, or biological system, and can of course vary. Also, it should be understood that the terms used herein are for the purpose of describing specific embodiments only and are not intended to be limiting.

[0075]

[0079] In addition, when the features or aspects of the present disclosure are described from the perspective of a Markush group, those skilled in the art will recognize that the present disclosure is also described from the perspective of any individual member or subgroup of members of the Markush group.

[0076]

[0080] As will be understood by those skilled in the art, for all purposes, particularly from the perspective of providing a written description, all ranges disclosed in this specification include any and all possible sub-ranges and combinations thereof. It can be readily recognized that any recited range is made to fully disclose and enable the same range to be decomposed into at least equal halves, thirds, quarters, fifths, tenths, etc. By way of non-limiting example, each range discussed herein can be readily decomposed into lower thirds, middle thirds, and upper thirds, etc. Also, as will be understood by those skilled in the art, all language such as "up to", "at least", "greater than", "less than", etc. includes the recited number and, as described above, refers to ranges that can be subsequently decomposed into sub-ranges. Finally, as will be understood by those skilled in the art, a range includes each and every member thereof. Thus, for example, a group having 1 to 3 cells refers to a group having 1, 2, or 3 cells. Similarly, a group having 1 to 5 cells refers to a group having 1, 2, 3, 4, or 5 cells, etc.

[0077]

[0081] All publications, patent applications, issued patents, and other documents mentioned in this specification are hereby incorporated 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 incorporated by reference text are excluded to the extent that they contradict definitions in the present disclosure.

[0078]

[0082] Other embodiments are set forth in the following claims.

Claims

1. A catalytic cracking method for producing light olefins and aromatic gasoline, The process includes the step of contacting a petroleum-based feedstock with a catalyst in a single riser reactor at a certain temperature and space velocity per weight per hour (WHSV) to convert at least a portion of the petroleum-based feedstock into light olefins and aromatic gasoline. The catalyst, Y-type zeolite in a quantity of 0% to approximately 15% by weight, and Pentasil zeolite exceeding 30% by weight It includes, and the weight ratio of pentasyl zeolite to Y-type zeolite exceeds 3, The temperature is approximately 530°C to approximately 600°C. WHSV is approximately 40 hours －１ ~Approx. 120h －１ And, The weight ratio of the catalyst to the petroleum-based raw materials is approximately 10:1 to 30:1, and in some cases, approximately 13:1 to 25:

1. Aromatic gasoline with a cutoff point from C5+ to 221°C can be obtained. method.

2. The method according to claim 1, wherein the light olefin comprises ethylene, propylene, butylene, or any two or more combinations thereof.

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

4. The method according to any one of claims 1 to 3, wherein the pentasilzeolite comprises ZSM-5.

5. Pentasil zeolite is P ２ O ５ It is stabilized by, and in some cases, P ２ O ５ The method according to any one of claims 1 to 3, wherein the weight ratio of to pentasylzeolite is about 0.1:1 to about 0.3:

1.

6. The Y zeolite is stabilized with RE ２ O ３ and optionally, the weight ratio of RE ２ O ３ to the Y zeolite of is from about 0.04:1 to about 0.15:1, the method according to any one of claims 1 to 3.

7. The method according to any one of claims 1 to 3, wherein the catalyst comprises 0% to about 10% by weight of a Y-type zeolite.

8. The method according to any one of claims 1 to 3, wherein the catalyst comprises about 35% to about 60% by weight of pentasylzeolite.

9. WHSV is approximately 40 hours －１ ~about 70 hours －１ The method according to any one of claims 1 to 3.

10. The method according to any one of claims 1 to 3, wherein the step of contacting a petroleum-based feedstock with a catalyst redistributes the hydrogen content of the petroleum-based feedstock by converting at least a portion of the petroleum-based feedstock into a product, the product comprising a light olefin and aromatic gasoline.

11. The method according to claim 10, wherein 60% or more of the hydrogen content of the petroleum-based raw material is redistributed to the C4 product, and in some cases, 63% or more of the hydrogen content of the petroleum-based raw material is redistributed to the C4 product.

12. The method according to claim 10, wherein 28% or less of the hydrogen content of the petroleum-based raw material is redistributed to aromatic gasoline, and in some cases, 25% or less of the hydrogen content of the petroleum-based raw material is redistributed to aromatic gasoline.

13. The method according to any one of claims 1 to 3, wherein the atomic ratio of H to C in the aromatic gasoline is 1.46 or less, and optionally, the atomic ratio of H to C in the aromatic gasoline is less than 1.

40.

14. The method according to any one of claims 1 to 3, which does not involve floor dismantling.

15. The method according to any one of claims 1 to 3, wherein the product is not recycled.

16. The method according to any one of claims 1 to 3, wherein the petroleum-based supply raw material includes vacuum gas oil, atmospheric gas oil, coker gas oil, deburring oil, atmospheric residue, vacuum residue, or any two or more mixtures thereof.

17. The method according to any one of claims 1 to 3, wherein the petroleum-based raw material supply comprises liquefied coal oil, tar sands oil, shale oil, or a mixture of any two or more thereof.

18. The method according to any one of claims 1 to 3, wherein the petroleum-based feedstock further comprises biorenewable feedstock and / or plastic-derived feedstock, and optionally the biorenewable feedstock comprises vegetable oil, animal fat, pyrolysis oil, or any two or more mixtures thereof.

19. The method according to any one of claims 1 to 3, wherein the step of contacting a petroleum-based feedstock with a 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, or any two or more combinations thereof.

20. The method according to claim 19, wherein the dry gas and / or LPG comprises a light olefin, and the method further comprises one or more fractionation steps for fractionating the dry gas and / or LPG to obtain ethylene, propylene, and / or butylene.

21. The method according to any one of claims 1 to 3, further comprising one or more fractionation steps for fractionating aromatic gasoline to obtain benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, and / or propylbenzene.

22. A product comprising a light olefin and gasoline manufactured according to claim 1.

23. The product according to claim 22, wherein the C4-product is present in an amount of 60% or more of the hydrogen content of the petroleum-based raw material.

24. The product according to claim 23, wherein the C4-product is present in an amount of 63% or more of the hydrogen content of the petroleum-based raw material.

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

26. The product according to claim 25, wherein aromatic gasoline is present in an amount of 25% or less of the hydrogen content of the petroleum-based raw material.

27. The product according to any one of claims 22 to 24, wherein the aromatic gasoline has an atomic ratio of H to C of 1.46 or less.

28. The product according to claim 27, wherein the atomic ratio of H to C in the aromatic gasoline is less than 1.40.