Methods for producing BIO-olefins by fluidized catalytic cracking

Abstract

Methods for producing bio-olefins by fluidized catalytic cracking (FCC) may comprise introducing a feedstock comprising a C2-C4 bio-alcohol and a petroleum-based hydrocarbon feed into an FCC reactor containing a catalyst, wherein a concentration of the C2-C4 bio-alcohol in the feedstock is about 0.5 wt% to about 99.5 wt% and the C2-C4 bio-alcohol is introduced to a first reaction zone of the FCC reactor and the petroleum-based hydrocarbon feed is introduced to a second reaction zone of the FCC reactor, the first reaction zone being located spatially below the second reaction zone; dehydrating at least a portion of the C2-C4 bio-alcohol in the first reaction zone to produce a bio-olefin; cracking at least a portion of the petroleum-based hydrocarbon feed in the second reaction zone to produce a cracking product; and obtaining an FCC product comprising the bio-olefin and the cracking product.

Description

METHODS FOR PRODUCING BIO-OLEFINS BY FLUIDIZED CATALYTIC CRACKING CROSS-REFERNCE TO RELATED APPLICATION

[0001] This application claims priority to and the benefit of U.S. Provisional Application No. 63 / 633,456 having a filing date of April 12, 2024, the disclosure of which is incorporated herein by reference in its entirety. FIELD

[0002] The present disclosure relates to bio-alcohol dehydration and, more particularly, to methods for producing bio-olefins from bio-alcohols using fluidized catalytic cracking. BACKGROUND

[0003] Bio-alcohols are a class of renewable organic compounds generated from biological sources or processes, such as by the fermentation of sugars or starches derived from plant materials, or through the chemical conversion of cellulose. A prominent bio-alcohol includes bio-ethanol, which may be produced from agricultural feedstocks such as corn, sugarcane, and wheat, or from lignocellulosic materials (plant-based materials that comprise lignin, carbohydrate polymers, and cellulose or hemicellulose).

[0004] Catalytic cracking, including fluidized catalytic cracking (FCC), is a widely used process in the petroleum industry to convert heavy, high-boiling hydrocarbons into more valuable, lower-boiling products such as gasoline and diesel fuel. FCC processes begin with a feedstock, typically a heavy crude oil or vacuum gas oil that may be preheated and introduced into a reactor and mixed with fluidizable catalyst particles. The fluidizable catalyst particles may comprise at least one zeolite as a catalytic material. As long-chain hydrocarbons in the feedstock break apart due to high temperatures in the reactor, the resulting cracked molecular fragments contact the catalytic material and undergo further cracking and rearrangement into smaller hydrocarbons. FCC processes may be tailored to maximize the yield of particular light hydrocarbons, commonly propylene, through manipulation of the hydrocarbon feedstock composition, the properties of the catalyst, and various reaction conditions.

[0005] Production of ethylene, including bio-ethylene from biogenic feedstocks, poses a challenge in traditional catalytic cracking processes, which are usually oriented toward the generation of gasoline-range hydrocarbons starting from a heavy hydrocarbon source. Ethylene may exhibit rapid and complex reaction kinetics within a catalytic cracking unit that leads to further transformation of ethylene into other products, thereby reducing its yield. These factors make catalytic cracking and, particularly FCC, not naturally conducive toward affording high ethylene yields.SUMMARY

[0006] In various aspects, methods for producing bio-olefins by fluidized catalytic cracking (FCC) may include introducing a feedstock comprising a C2-C4bio-alcohol and a petroleum-based hydrocarbon feed into an FCC reactor containing a catalyst, wherein a concentration of the C2-C4bio- alcohol in the feedstock is about 0.5 wt% to about 99.5 wt% and the C2-C4bio-alcohol is introduced to a first reaction zone of the FCC reactor and the petroleum-based hydrocarbon feed is introduced to a second reaction zone of the FCC reactor, the first reaction zone being located spatially below the second reaction zone; dehydrating at least a portion of the C2-C4bio-alcohol in the first reaction zone to produce a bio-olefin; cracking at least a portion of the petroleum-based hydrocarbon feed in the second reaction zone to produce a cracking product; and obtaining an FCC product comprising the bio-olefin and the cracking product.

[0007] In other various aspects, methods for producing bio-olefins by FCC may include introducing a feedstock comprising a bio-ethanol and a petroleum-based hydrocarbon feed into an FCC reactor containing a catalyst comprising an FAU structure, wherein a concentration of the bio-ethanol in the feedstock is about 0.5 wt% to about 99.5 wt% and the bio-ethanol is introduced to a first reaction zone of the FCC reactor and the petroleum-based hydrocarbon feed is introduced to a second reaction zone of the FCC reactor, the first reaction zone being located spatially below the second reaction zone; wherein the first reaction zone has a catalyst / bio-ethanol weight ratio of about 5:300, a residence time in the first reaction zone is about 0.5 s to about 30 s, the first reaction zone has a temperature of about 850°F to about 1100°F, and the first reaction zone has a pressure of about 30 psig to about 95 psig, and wherein a residence time in the second reaction zone is about 0.25 s to about 8 s, the second reaction zone has a temperature of about 900°F to about 1300°F, and the second reaction zone has a pressure of about 10 psig to about 100 psig; dehydrating at least a portion of the bio-ethanol in the first reaction zone to produce bio-ethylene; cracking at least a portion of the petroleum-based hydrocarbon feed in the second reaction zone to produce a cracking product comprising at least some ethane; obtaining an FCC product comprising the bio-ethylene and the cracking product; separating the bio-ethylene and the ethane as separate streams from the FCC product; steam cracking the ethane to convert at least a portion of the ethane into ethylene; combining the ethylene with the bio-ethylene to produce a composite ethylene stream, wherein the composite ethylene stream has a biogenic carbon concentration of about 1 wt% to about 50 wt%; and optionally, converting the composite ethylene into a polyethylene, a linear alpha olefin, or any combination thereof.

[0008] These and other features and attributes of the disclosed methods of the present disclosure and their advantageous applications and / or uses will be apparent from the detailed description that follows. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] To assist those of ordinary skill in the relevant art in making and using the subject matter hereof, reference is made to the appended drawings. The following figures are included to illustrate certain aspects of the disclosure, and should not be viewed as exclusive configurations. The subject matter disclosed is capable of considerable modifications, alterations, combinations, and equivalents in form and function, as will occur to those skilled in the art and having the benefit of this disclosure.

[0010] FIG.1 is a diagram of a method for producing polyethylene and polyalphaolefins from bio- ethanol.

[0011] FIG.2 is a graph of an ethylene production rate as a function of an ethanol injection rate for an ethanol conversion system.

[0012] FIG.3 is a graph of an ethane production rate as a function of an ethanol injection rate for an ethanol conversion system. DETAILED DESCRIPTION

[0013] The present disclosure relates to bio-alcohol dehydration and, more particularly, to methods for producing bio-olefins from bio-alcohols using fluidized catalytic cracking (FCC).

[0014] FCC processes do not typically favor high ethylene yields. Ethanol, including bio-ethanol, when subjected to the high temperatures and catalytic conditions of FCC, predominantly dehydrates to form ethylene. Unfortunately, the ethylene undergoes further conversion under the FCC reaction conditions to decrease the ethylene yield. Surprisingly, co-processing an alcohol (e.g., ethanol) with a conventional petroleum feed (petroleum-based hydrocarbon feed or petroleum feedstock) under FCC reaction conditions may increase the ethylene yield.

[0015] Bio-ethanol is a reactive feedstock that may rapidly undergo conversion into ethylene and water vapor under catalytic cracking conditions, with the potential to increase the selectivity towards ethylene production. The resultant ethylene, when produced through the catalytic transformation of bio-ethanol, contains biogenic carbon and constitutes bio-ethylene. Introduction of bio-ethanol into a hydrocarbon feed modifies the reaction environment, potentially altering the catalyst’s activity and selectivity toward forming lighter olefins. Such co-processing may leverage the unique properties of ethanol to influence the catalytic cracking reactions favorably and increase overall ethylene yields.

[0016] To further enhance the production of ethylene (e.g., bio-ethylene) via co-processing, the operation strategy within the FCC unit (reactor) may involve the strategic injection of ethanol (e.g., bio-ethanol) at a location spatially below where the petroleum feedstock is introduced. This deliberate placement means that the ethanol enters the FCC reactor in a zone that has a higher temperature and is more hydrogen deficient. The lack of hydrogen (or decreased hydrogen content) may be favorable for dehydration reactions that lead to the formation of ethylene, while the higher temperatures are able to supply the necessary energy for the endothermic dehydration of ethanol. The hydrogen- deficient environment may also reduce the likelihood of hydrogenation reactions that may otherwise convert olefins back into saturated hydrocarbons. By increasing the residence time of ethanol in the lower portion of the FCC reactor, there may be an increased potential that the ethanol may be converted to ethylene before reacting further or undergoing dilution by the petroleum feedstock.

[0017] Alongside the enhancement of ethylene yields through the co-processing of bio-ethanol, the FCC process may concurrently produce ethane from both the petroleum feedstock and the ethanol. Ethane, a saturated hydrocarbon, may be further re-processed to produce additional ethylene, potentially through steam cracking wherein the ethane is subjected to high-temperature steam to produce ethylene. Upon production, ethylene derived from steam cracking of ethane may be re- combined with bio-ethylene generated from bio-ethanol co-processing to create a composite ethylene stream. The composite ethylene stream may have both biogenic and petrochemical carbon sources, thereby yielding a product that may carry the benefits of renewable carbon content while utilizing existing petrochemical infrastructure and feedstocks. The composite ethylene stream, containing biogenic carbon originating from bio-ethanol, may serve as a versatile precursor for various downstream petrochemical products. One primary pathway may include polymerization of ethylene to produce polyethylene containing at least some bio-ethylene. Additionally, the composite ethylene stream may be used to manufacture linear alpha olefins (LAOs), such as through ethylene oligomerization, which may be subsequently converted into polyalphaolefins (PAOs). The incorporation of biogenic carbon from bio-ethylene into the production of LAOs and PAOs may likewise lead to a lower overall carbon footprint for these materials.

[0018] Accordingly, methods for producing bio-olefins by FCC may comprise: introducing a feedstock comprising a C2-C4bio-alcohol and a petroleum-based hydrocarbon feed into an FCC reactor containing a catalyst; wherein a concentration of the C2-C4bio-alcohol in the feedstock is up to about 99 wt%; and wherein the bio-alcohol is introduced to a first reaction zone of the FCC reactor and the petroleum-based hydrocarbon feed is introduced to a second reaction zone of the FCC reactor,the first reaction zone being located spatially below the second reaction zone; dehydrating at least a portion of the bio-alcohol in the first reaction zone to produce a bio-olefin; cracking at least a portion of the petroleum-based hydrocarbon feed in the second reaction zone to produce a cracking product; and obtaining an FCC product comprising the bio-olefin and the cracking product.

[0019] Preferably, the C2-C4bio-alcohol is bio-ethanol, which may be obtained from processes including, but not limited to, sugar fermentation, starch-based fermentation, enzymatic hydrolysis proceeding fermentation of cellulosic biomass, co-productions of the bio-diesel industry, the like, and any combination thereof. In this instance, the bio-olefin produced by the dehydration of the C2-C4bio-alcohol in the first reaction zone of the FCC reactor may be bio-ethylene. Other suitable C2-C4bio-alcohols may include bio-propanol, bio-butanol, bio-glycerol, or any combination thereof.

[0020] The C2-C4bio-alcohol may comprise a majority of the alcohol in the feedstock. For example, a concentration of the C2-C4bio-alcohol in the feedstock may about 0.5 wt% to about 99.5 wt%, or about 0.5 wt% to about 90 wt%, or about 0.5 wt% to about 50 wt%, or about 0.5 wt% to about 10 wt%, or about 10 wt% to about 99.5 wt%, or about 10 wt% to about 90 wt%, or about 10 wt% to about 50 wt%, or about 50 wt% to about 99.5 wt%, or about 50 wt% to about 90 wt%, or about 90 wt% to about 99.5 wt%. The foregoing ranges may be representative of the amount of bio-ethanol present in the feedstock.

[0021] A wide tolerance in purity of the C2-C4bio-alcohol may be realized in the present disclosure. Impurity levels up to 20 wt% may be tolerable in some cases. Impurities that may be present in the C2-C4bio-alcohol may include, but are not limited to, methanol, benzene, water, metals, sulfur, sulfate, and the like. Denatured bio-ethanol may be suitably processed.

[0022] In addition to the C2-C4bio-alcohol, alcohols from non-biogenic sources may also be present in the feedstock. For example, the feedstock may comprise non-biogenic alcohols including, but not limited to, denatured fuel ethanol, crude and / or refined ethanol comprising denaturants, the like, and any combination thereof. Additionally, water may be present in the feedstock, potentially enabling rapid vaporization of the bio-ethanol and minimizing coke formation.

[0023] The petroleum-based hydrocarbon feed portion of the feedstock may comprise any suitable non-biogenic FCC feed. For example, the petroleum-based hydrocarbon feed may include, but is not limited to, vacuum gas oil, atmospheric residue, vacuum residue, heavy crude oil, slurry oil, hydrotreated oil, coker gas oil, light cycle oil, deasphalted oil, the like, and any combination thereof. Cracking the petroleum-based hydrocarbon feed in the second reaction zone may, for example, produce gasoline (e.g., high-octane gasoline), olefins (e.g., ethylene, propylene, and / or butylene),cycle oils, light saturated hydrocarbons found in liquefied petroleum gas, gasoil, coke, fuel gasses, or any combination thereof.

[0024] In addition to bio-ethylene, the FCC product may further comprise ethane due to the catalytic cracking of the petroleum-based hydrocarbon feed or over-cracking of the bio-ethanol. Consequently, the FCC product may then be further treated by steam cracking, for example, to convert the ethane into ethylene. Preferably, the ethane may be separated from the ethylene as separate streams from the FCC product prior to performing steam cracking. Details concerning the steam cracking will be familiar to persons having ordinary skill in the art. The bio-ethylene produced from FCC and the ethylene produced from steam cracking may be combined. Combined bio-ethylene produced by the dehydration of the C2-C4bio-alcohol under FCC and ethylene produced by steam cracking of ethane may be combined to produce a composite ethylene stream. At least a portion of the composite ethylene stream may comprise biogenic carbon. For example, the composite ethylene stream may have a biogenic carbon concentration of about 1 wt% to about 50 wt%, or about 1 wt% to about 25 wt%, or about 1 wt% to about 10 wt%, or about 10 wt% to about 50 wt%, or about 10 wt% to about 25 wt%, or about 25 wt% to about 50 wt%.

[0025] The composite ethylene stream may be further processed through conversion into polyethylene by any suitable polymerization reaction, a linear alpha olefin by methods such as oligomerization, or a combination thereof. In the instance that the polyethylene is converted into a linear alpha olefin, the linear alpha olefin may be further converted into a polyalphaolefin. Suitable polymerization and oligomerization processes for producing the foregoing will be familiar to one having ordinary skill in the art.

[0026] Due to the enhancements from the co-processing of the C2-C4bio-alcohol with the petroleum-based hydrocarbon feed, the FCC reactor may have an elevated capacity for producing bio-olefins. For example, the FCC reactor may afford an FCC product in which 90% or more of the FCC product contains biogenic carbon, such as up to about 99%, or up to about 99.5%, or even up to about 99.9%. Alternately, the FCC product may comprise up to about 50 wt% bio-olefins, or up to about 60 wt% bio-olefins, or up to about 70 wt% bio-olefins, or up to 80 wt% bio-olefins, or up to 90 wt% biolefins.

[0027] FIG.1 is a diagram showing a non-limiting example of method 100 of the present disclosure for producing polyethylene and polyalphaolefins from bio-ethanol. Method 100 utilizes FCC reactor 102 having a fluidized catalyst (e.g., a zeolite) therein and comprising first reaction zone 104 located spatially below second reaction zone 106. First reaction zone 104 may be considered a dehydrationzone in which bio-ethanol 108 is injected and at least a portion is dehydrated to form bio-ethylene. Second reaction zone 106 may be a cracking zone in which petroleum-based hydrocarbon feed 110 is injected and at least a portion is cracked to form a cracking product. The bio-ethylene and the cracked product may exit the FCC reactor 102 together as FCC product 112. FCC product 112 is introduced to C2splitter 111 to obtain ethylene stream 113b and ethane stream 113a. Ethane stream 113a may be further treated in steam cracker 114 to convert the ethane into additional ethylene, which is combined with ethylene stream 113b to produce composite ethylene stream 116. At least a portion of composite ethylene stream 116 may be introduced into polyethylene polymerization unit 118 to produce polyethylene 120. Alternately or in addition, at least a portion of composite ethylene stream 116 may be introduced into oligomerization unit 122 to produce linear alpha olefin(s) 124. Linear alpha olefin(s) 124 may be further processed by introduction to polyalphaolefin oligomerization unit 126 to produce polyalphaolefin(s) 128.

[0028] First reaction zone 104 is located spatially below second reaction zone 106 and contains a lower amount of hydrogen than does second reaction zone 106. First reaction zone 104 may be substantially depleted of hydrogen in some cases. First reaction zone 104 and second reaction zone 106 may define a U-bend structure and it may be ideal to avoid injection and reaction of the C2-C4bio-alcohol in the upper portion of the U-bend as buoyancy may raise the C2-C4bio-alcohol and minimize its contact with the hot catalyst, possibly resulting in incomplete dehydration. Furthermore, the C2-C4bio-alcohol may be optimally injected in an outer portion of the U-bend. The injection nozzles used for injection of the C2-C4bio-alcohol into the U-bend may be positioned at about 25° to about 35°, or about 25° to about 30°, or about 30° to about 35° relative to the vertical axis. Additionally, the injection nozzles may preferably contain straight-pipe nozzles lacking internals for atomization and / or shear. Example injection nozzle types include, but are not limited to, aeration nozzles, the like, and any combination thereof.

[0029] Any suitable catalyst capable of cracking C2-C4bio-alcohols and / or petroleum-based hydrocarbon feeds under catalytic cracking conditions may be used in the FCC reactor. The catalyst, for example, may comprise a zeolite having an FAU structure.

[0030] In any embodiment, the first reaction zone may be maintained at conditions conducive to the dehydration of the C2-C4bio-alcohol. For example, the first reaction zone may have a catalyst / C2-C4bio-alcohol weight ratio of about 5:300, or about 5:250, or about 5:200, or about 5:150, or about 5:100, or about 100:300, or about 100:250, or about 100:200, or about 100:150, or about 150:300, or about 150:250, or about 150:200, or about 200:300, or about 200:250, or about 250:300.

[0031] The first reaction zone may, for example, have a residence time of about 0.5 s to about 30 s, or about 0.5 s to about 20 s, or about 0.5 s to about 15 s, or about 0.5 s to about 10 s, or about 0.5 s to about 8 s, or about 0.5 to about 1 s, or about 1 s to about 30 s, or about 1 s to about 20 s, or about 1 s to about 10 s, or about 1 s to about 8 s, or about 8 s to about 30 s, or about 8 s to about 20 s, or about 8 s to about 10 s, or about 10 s to about 30 s, or about 10 s to about 20 s, or about 20 s to about 30 s.

[0032] The first reaction zone may, for example, have a temperature of about 850°F to about 1100°F, or about 850°F to about 1050°F, or about 850°F to about 1000°F, or about 850°F to about 950°F, or about 900°F to about 1100°F, or about 900°F to about 1050°F, or about 900°F to about 1000°F, or about 900°F to about 950°F, or about 950°F to about 1100°F, or about 950°F to about 1050°F, or about 950°F to about 1000°F, or about 1000°F to about 1100°F, or about 1000°F to about 1050°F, or about 1050°F to about 1100°F.

[0033] The first reaction zone may, for example, have a pressure of about 30 psig to about 95 psig, or about 30 psig to about 75 psig, or about 30 psig to about 50 psig, or about 50 psig to about 95 psig, or about 50 psig to about 75 psig, or about 75 psig to about 95 psig.

[0034] Similarly, in any embodiment, the second reaction zone may be maintained at conditions conducive to cracking the petroleum-based hydrocarbon feed. For example, the second reaction zone may have a residence time of about 0.03 s to about 8 s, or about 0.25 s to about 8 s, or about 0.25 to about 5 s, or about 0.5 s to about 3 s, or about 0.03 s to about 3 s, or about 0.03 s to about 2 s, or about 0.03 s to about 1 s, or about 0.03 s to about 0.5 s, or about 0.03 s to about 0.1 s, or about 0.1 s to about 3 s, or about 0.1 s to about 2 s, or about 0.1 s to about 1 s, or about 0.1 s to about 0.5 s, or about 0.5 s to about 3 s, or about 0.5 s to about 2 s, or about 0.5 s to about 1 s, or about 1 s to about 3 s, or about 1 s to about 2 s.

[0035] The second reaction zone may, for example, be at a temperature of about 900°F to about 1300°F, or about 1000°F to about 1300°F, or about 1100°F to about 1300°F, or about 1100°F to about 1250°F, or about 1100°F to about 1200°F, or about 1100°F to about 1150°F, or about 1150°F to about 1300°F, or about 1150°F to about 1250°F, or about 1150°F to about 1200°F, or about 1200°F to about 1300°F, or about 1200°F to about 1250°F, or about 1250°F to about 1300°F,.

[0036] The second reaction zone may, for example, be at a pressure of about 10 psig to about 100 psig, or about 10 psig to about 75 psig, or about 10 psig to about 50 psig, or about 10 psig to about 25 psig, or about 20 psig to about 50 psig, or about 25 psig to about 100 psig, or about 25 psig to about 75 psig, or about 25 psig to about 50 psig, or about 50 psig to about 100 psig, or about 50 psig to about 75 psig, or about 75 psig to about 100 psig.Additional Embodiments

[0037] Embodiments disclosed herein include:

[0038] A. Methods for producing bio-olefins by fluidized catalytic cracking (FCC) comprising: introducing a feedstock comprising a C2-C4bio-alcohol and a petroleum-based hydrocarbon feed into an FCC reactor containing a catalyst; wherein a concentration of the C2-C4bio-alcohol in the feedstock is about 0.5 wt% to about 99.5 wt%; wherein the C2-C4bio-alcohol is introduced to a first reaction zone of the FCC reactor and the petroleum-based hydrocarbon feed is introduced to a second reaction zone of the FCC reactor, the first reaction zone being located spatially below the second reaction zone; dehydrating at least a portion of the C2-C4bio-alcohol in the first reaction zone to produce a bio-olefin; cracking at least a portion of the petroleum-based hydrocarbon feed in the second reaction zone to produce a cracking product; and obtaining an FCC product comprising the bio-olefin and the cracking product.

[0039] B. Methods for producing bio-olefins by fluidized catalytic cracking (FCC) comprising: introducing a feedstock comprising a bio-ethanol and a petroleum-based hydrocarbon feed into an FCC reactor containing a catalyst comprising an FAU structure; wherein a concentration of the bio- ethanol in the feedstock is about 0.5 wt% to about 99.5 wt%; wherein the bio-ethanol is introduced to a first reaction zone of the FCC reactor and the petroleum-based hydrocarbon feed is introduced to a second reaction zone of the FCC reactor, the first reaction zone being located spatially below the second reaction zone; wherein the first reaction zone has a catalyst / bio-ethanol weight ratio of about 5:300, a residence time in the first reaction zone is about 0.5 s to about 30 s, the first reaction zone has a temperature of about 850°F to about 1100°F, and the first reaction zone has a pressure of about 30 psig to about 95 psig; wherein a residence time in the second reaction zone is about 0.25 s to about 8 s, the second reaction zone has a temperature of about 900°F to about 1300°F, and the second reaction zone has a pressure of about 10 psig to about 100 psig; dehydrating at least a portion of the bio-ethanol in the first reaction zone to produce bio-ethylene; cracking at least a portion of the petroleum-based hydrocarbon feed in the second reaction zone to produce a cracking product comprising at least some ethane; obtaining an FCC product comprising an ethylene and an ethane; obtaining an FCC product comprising the bio-ethylene and the cracking product; separating the bio- ethylene and the ethane from the FCC product; steam cracking the ethane to convert at least a portion of the ethane into ethylene, and combining the ethylene with the bio-ethylene to produce a composite ethylene stream; wherein the composite ethylene has a biogenic carbon concentration of about 1 wt%to about 50 wt%; and optionally, converting the composite ethylene stream into a polyethylene, a linear alpha olefin, or any combination thereof.

[0040] Each of embodiments A and B may have one or more of the following additional elements in any combination:

[0041] Element 1: wherein the first reaction zone has a catalyst / C2-C4bio-alcohol weight ratio of about 5:300.

[0042] Element 2: wherein a residence time in the first reaction zone is about 0.5 s to about 30 s.

[0043] Element 3: wherein the first reaction zone has a temperature of about 850°F to about 1100°F.

[0044] Element 4: wherein the first reaction zone has a pressure of about 30 psig to about 95 psig.

[0045] Element 5: wherein a residence time in the second reaction zone is about 0.25 s to about 8 s.

[0046] Element 6: wherein the second reaction zone has a temperature of about 900°F to about 1300°F.

[0047] Element 7: wherein the second reaction zone has a pressure of about 10 psig to about 100 psig.

[0048] Element 8: wherein 90% or more of the FCC product contains biogenic carbon.

[0049] Element 9: wherein the C2-C4bio-alcohol comprises bio-ethanol.

[0050] Element 10: wherein the bio-olefin comprises bio-ethylene.

[0051] Element 11: wherein the bio-olefin comprises bio-ethylene and the FCC product further comprises ethane.

[0052] Element 12: wherein the method further comprises separating the bio-ethylene and the ethane from the FCC product; steam cracking the ethane to convert at least a portion of the ethane into ethylene; and combining the ethylene with the bio-ethylene to produce a composite ethylene stream.

[0053] Element 13: wherein the composite ethylene stream has a biogenic carbon concentration of about 1 wt% to about 50 wt%.

[0054] Element 14: wherein the method further comprises converting the composite ethylene stream into a polyethylene, a linear alpha olefin, or a combination thereof.

[0055] Element 15: wherein the composite ethylene stream is converted into a linear alpha olefin, and the linear alpha olefin is further converted into a polyalphaolefin.

[0056] Element 16: wherein the petroleum-based hydrocarbon feed comprises a vacuum gas oil, an atmospheric residue, a vacuum residue, a heavy crude oil, a hydrotreated oil, a coker gas oil, a light cycle oil, a deasphalted oil, or any combination thereof.

[0057] Element 17: wherein the catalyst comprises a zeolite catalyst having an FAU structure.

[0058] Element 18: wherein the first reaction zone has a lower hydrogen content than the second reaction zone.

[0059] By way of non-limiting example, exemplary embodiment combinations applicable to A and B include: 1 and 2; 1 and 3; 1 and 4; 1 and 5; 1 and 6; 1 and 7; 1 and 8; 1 and 9; 1 and 10; 1 and 11; 1 and 16; 1 and 17; 2 and 3; 2 and 4; 2 and 5; 2 and 6; 2 and 7; 2 and 8; 2 and 9; 2 and 10; 2 and 11; 2 and 16; 2 and 17; 3 and 4; 3 and 5; 3 and 6; 3 and 7; 3 and 8; 3 and 9; 3 and 10; 3 and 11; 3 and 16; 3 and 17; 4 and 5; 4 and 6; 4 and 7; 4 and 8; 4 and 9; 4 and 10; 4 and 11; 4 and 16; 4 and 17; 5 and 6; 5 and 7; 5 and 8; 5 and 9; 5 and 10; 5 and 11; 5 and 16; 5 and 17; 6 and 7; 6 and 8; 6 and 9; 6 and 10; 6 and 11; 6 and 16; 6 and 17; 7 and 8; 7 and 9; 7 and 10; 7 and 11; 7 and 16; 7 and 17; 8 and 9; 8 and 10; 8 and 11; 8 and 16; 8 and 17; 9 and 10; 9 and 11; 9 and 16; 9 and 17; 10 and 11; 10 and 16; 10 and 17; 11 and 12; 11 and 16; 11 and 17; 12 and 13; 12 and 14; 12 and 16; 12 and 17; 13 and 14; 13 and 16; 13 and 17; 14 and 15; 14 and 16; 14 and 17; 15 and 16; 15 and 17; 16 and 17; 1, 2, and 3; 2, 3, and 4; 3, 4, and 5; 4, 5, and 6; 5, 6, and 7; 6, 7, and 8; 7, 8, and 9; 8, 9, and 10; and 9, 10, and 11.

[0060] The present disclosure is further directed to the following non-limiting clauses: Clause 1. A method comprising: introducing a feedstock comprising a C2-C4bio-alcohol and a petroleum-based hydrocarbon feed into a fluidized catalytic cracking (FCC) reactor containing a catalyst; wherein a concentration of the C2-C4bio-alcohol in the feedstock is about 0.5 wt% to about 99.5 wt%; and wherein the C2-C4bio-alcohol is introduced to a first reaction zone of the FCC reactor and the petroleum-based hydrocarbon feed is introduced to a second reaction zone of the FCC reactor, the first reaction zone being located spatially below the second reaction zone; dehydrating at least a portion of the C2-C4bio-alcohol in the first reaction zone to produce a bio-olefin; cracking at least a portion of the petroleum-based hydrocarbon feed in the second reaction zone to produce a cracking product; and obtaining an FCC product comprising the bio-olefin and the cracking product. Clause 2. The method of clause 1, wherein the first reaction zone has a catalyst / C2-C4bio-alcohol weight ratio of about 5:300. Clause 3. The method of clause 1 or clause 2, wherein a residence time in the first reaction zone is about 0.5 s to about 30 s.Clause 4. The method of any one of clauses 1-3, wherein the first reaction zone has a temperature of about 850°F to about 1100°F. Clause 5. The method of any one of clauses 1-4, wherein the first reaction zone has a pressure of about 30 psig to about 95 psig. Clause 6. The method of any one of clauses 1-5, wherein a residence time in the second reaction zone is about 0.25 s to about 8 s. Clause 7. The method of any one of clauses 1-6, wherein the second reaction zone has a temperature of about 900°F to about 1300°F. Clause 8. The method of any one of clauses 1-7, wherein the second reaction zone has a pressure of about 10 psig to about 100 psig. Clause 9. The method of any one of clauses 1-8, wherein 90% or more of the FCC product contains biogenic carbon. Clause 10. The method of any one of clauses 1-9, wherein the C2-C4bio-alcohol comprises bio- ethanol. Clause 11. The method of any one of clauses 1-10, wherein the bio-olefin comprises bio-ethylene. Clause 12. The method of any one of clauses 1-11, wherein the bio-olefin comprises bio-ethylene and the FCC product further comprises ethane. Clause 13. The method of clause 12, further comprising: separating the bio-ethylene and the ethane from the FCC product; steam cracking the ethane to convert at least a portion of the ethane into ethylene; and combining the ethylene with the bio-ethylene to produce a composite ethylene stream. Clause 14. The method of any one of clauses 1-12, wherein the composite ethylene has a biogenic carbon concentration of about 1 wt% to about 50 wt%. Clause 15. The method of clause 13, further comprising: converting the composite ethylene stream into a polyethylene, a linear alpha olefin, or any combination thereof. Clause 16. The method of clause 15, converting the composite ethylene stream into a linear alpha olefin; wherein the linear alpha olefin is further converted into a polyalphaolefin. Clause 17. The method of any one of clauses 1-16, wherein the petroleum-based hydrocarbon feed comprises a vacuum gas oil, an atmospheric residue, a vacuum residue, a heavy crude oil, a hydrotreated oil, a coker gas oil, a light cycle oil, a deasphalted oil, or any combination thereof.Clause 18. The method of any one of clauses 1-17, wherein the catalyst comprises a zeolite catalyst having an FAU structure. Clause 19. The method of any one of clauses 1-18, wherein the first reaction zone has a lower hydrogen content than the second reaction zone. Clause 20. A method comprising: introducing a feedstock comprising a bio-ethanol and a petroleum-based hydrocarbon feed into a fluidized catalytic cracking (FCC) reactor containing a catalyst comprising an FAU structure; wherein a concentration of the bio-ethanol in the feedstock is about 0.5 wt% to about 99.5 wt%; and wherein the bio-ethanol is introduced to a first reaction zone of the FCC reactor and the petroleum-based hydrocarbon feed is introduced to a second reaction zone of the FCC reactor, the first reaction zone being located spatially below the second reaction zone; wherein the first reaction zone has a catalyst / bio-ethanol weight ratio of about 5:300, a residence time in the first reaction zone is about 0.5 s to about 30 s, the first reaction zone has a temperature of about 850°F to about 1100°F, and the first reaction zone has a pressure of about 30 psig to about 95 psig; wherein a residence time in the second reaction zone is about 0.25 s to about 8 s, the second reaction zone has a temperature of about 900°F to about 1300°F, and the second reaction zone has a pressure of about 10 psig to about 100 psig; dehydrating at least a portion of the bio-ethanol in the first reaction zone to produce bio- ethylene; cracking at least a portion of the petroleum-based hydrocarbon feed in the second reaction zone to produce a cracking product comprising at least some ethane; obtaining an FCC product comprising the bio-ethylene and the cracking product; separating the bio-ethylene and the ethane from the FCC product; steam cracking the ethane to convert at least a portion of the ethane into ethylene, and combining the ethylene with the bio-ethylene to produce a composite ethylene stream; wherein the composite ethylene has a biogenic carbon concentration of about 1 wt% to about 50 wt%; and optionally, converting the composite ethylene stream into a polyethylene, a linear alpha olefin, or any combination thereof.

[0061] To facilitate a better understanding of the embodiments of the present invention, the following examples of preferred or representative embodiments are given. In no way should the following examples be read to limit, or to define, the scope of the invention. EXAMPLES

[0062] Pilot plants were used to compare the ethylene and biogenic carbon yield of a 30,000 bpd FCC process utilizing vacuum gas oil (35 kbpd) or a combination of vacuum gas oil (30 kbpd) and denatured fuel ethanol (DFE) (1.5 kbpd) as feedstocks. FIGS.2 and 3 are graphs of an ethylene and an ethane production rate, respectively, as a function of an ethanol injection rate for the 30,000 bpd FCC process. Ethanol injection rates are in barrels per hour (bph), and ethylene or ethane production rates are in kilopounds per hour (kpph) The ethane and ethylene yields were measured using online GC measurements (analyzer data points) and mass balances of liquid and gas samples collected at various locations in the plant (samples data points), which were analyzed at an offline laboratory. Table 1 shows the composition of the FCC product for the processed comparative feedstock containing only vacuum gas oil and Table 2 shows the composition of the FCC product for the co- processed feedstock containing both vacuum gas oil and ethanol.Table 1 Component Concentration (wt%) H20.04Table 2 Component Concentration (wt%) H20.09

[0063] As shown in Table 2, the feedstock containing both vacuum gas oil and ethanol led to an FCC product containing more ethylene and less propylene than the feedstock containing only vacuum gas oil, demonstrating the potential effectiveness of ethanol co-processing in FCC to increase ethylene yield.

[0064] Carbon-14 (14C) testing was performed according to ASTM D6866 on the FCC product of the experimental feedstock to determine the biogenic carbon content of the FCC product. Table 3 shows the14C analysis-based mass balance of the FCC product of the experimental feedstock. Theyields presented in Table 3 are on a 100% ethanol basis at maximum ethanol injection rate. Hydrogen and water yields were taken from operations and sample data since they cannot be traced with14C analyses. The negative hydrogen yield results from the ethanol dehydration products reacting with the hydrogen produced from the vacuum gas oil. The14C analysis determined that the ethylene produced from the experimental feedstock comprised up to about 11 wt% biogenic carbon. Table 3 Component14C analysis-based Mass Balance Ultimate (wt%)

[0065] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the present specification and associated claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the incarnations of the present inventions. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claim, each numerical parametershould at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0066] One or more illustrative incarnations incorporating one or more invention elements are presented herein. Not all features of a physical implementation are described or shown in this application for the sake of clarity. It is understood that in the development of a physical embodiment incorporating one or more elements of the present invention, numerous implementation-specific decisions must be made to achieve the developer's goals, such as compliance with system-related, business-related, government-related and other constraints, which vary by implementation and from time to time. While a developer's efforts might be time-consuming, such efforts would be, nevertheless, a routine undertaking for those of ordinary skill in the art and having benefit of this disclosure.

[0067] While compositions and methods are described herein in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of” or “consist of” the various components and steps.

[0068] Therefore, the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular examples and configurations disclosed above are illustrative only, as the present invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative examples disclosed above may be altered, combined, or modified and all such variations are considered within the scope and spirit of the present invention. The invention illustratively disclosed herein suitably may be practiced in the absence of any element that is not specifically disclosed herein and / or any optional element disclosed herein. While compositions and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the compositions and methods can also “consist essentially of” or “consist of” the various components and steps. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearlydefined by the patentee. Moreover, the indefinite articles “a” or “an,” as used in the claims, are defined herein to mean one or more than one of the element that it introduces.

Claims

CLAIMS The invention claimed is:

1. A method comprising: introducing a feedstock comprising a C2-C4bio-alcohol and a petroleum-based hydrocarbon feed into a fluidized catalytic cracking (FCC) reactor containing a catalyst; wherein a concentration of the C2-C4bio-alcohol in the feedstock is about 0.5 wt% to about 99.5 wt%; and wherein the C2-C4bio-alcohol is introduced to a first reaction zone of the FCC reactor and the petroleum-based hydrocarbon feed is introduced to a second reaction zone of the FCC reactor, the first reaction zone being located spatially below the second reaction zone; dehydrating at least a portion of the C2-C4bio-alcohol in the first reaction zone to produce a bio-olefin; cracking at least a portion of the petroleum-based hydrocarbon feed in the second reaction zone to produce a cracking product; and obtaining an FCC product comprising the bio-olefin and the cracking product.

2. The method of claim 1, wherein the first reaction zone has a catalyst / C2-C4bio-alcohol weight ratio of about 5:

300.

3. The method of claim 1, wherein a residence time in the first reaction zone is about 0.5 s to about 30 s.

4. The method of claim 1, wherein the first reaction zone has a temperature of about 850°F to about 1100°F.

5. The method of claim 1, wherein the first reaction zone has a pressure of about 30 psig to about 95 psig.

6. The method of claim 1, wherein a residence time in the second reaction zone is about 0.25 s to about 8 s.

7. The method of claim 1, wherein the second reaction zone has a temperature of about 900°F to about 1300°F.

8. The method of claim 1, wherein the second reaction zone has a pressure of about 10 psig to about 100 psig.

9. The method of claim 1, wherein 90% or more of the FCC product contains biogenic carbon.

10. The method of claim 1, wherein the C2-C4bio-alcohol comprises bio-ethanol.

11. The method of claim 10, wherein the bio-olefin comprises bio-ethylene.

12. The method of claim 1, wherein the bio-olefin comprises bio-ethylene and the FCC product further comprises ethane.

13. The method of claim 12, further comprising: separating the bio-ethylene and the ethane as separate streams from the FCC product; steam cracking the ethane to convert at least a portion of the ethane into ethylene; and combining the ethylene with the bio-ethylene to produce a composite ethylene stream.

14. The method of claim 13, wherein the composite ethylene stream has a biogenic carbon concentration of about 1 wt% to about 50 wt%.

15. The method of claim 13, further comprising: converting the composite ethylene stream into a polyethylene, a linear alpha olefin, or any combination thereof.

16. The method of claim 13, further comprising: converting the composite ethylene stream into a linear alpha olefin; wherein the linear alpha olefin is further converted into a polyalphaolefin.

17. The method of claim 1, wherein the petroleum-based hydrocarbon feed comprises a vacuum gas oil, an atmospheric residue, a vacuum residue, a heavy crude oil, a hydrotreated oil, a coker gas oil, a light cycle oil, a deasphalted oil, or any combination thereof.

18. The method of claim 1, wherein the catalyst comprises a zeolite having an FAU structure.

19. The method of claim 1, wherein the first reaction zone has a lower hydrogen content than the second reaction zone.

20. A method comprising: introducing a feedstock comprising a bio-ethanol and a petroleum-based hydrocarbon feed into a fluidized catalytic cracking (FCC) reactor containing a catalyst comprising an FAU structure; wherein a concentration of the bio-ethanol in the feedstock is about 0.5 wt% to about 99.5 wt%; and wherein the bio-ethanol is introduced to a first reaction zone of the FCC reactor and the petroleum-based hydrocarbon feed is introduced to a second reaction zone of the FCC reactor, the first reaction zone being located spatially below the second reaction zone; wherein the first reaction zone has a catalyst / bio-ethanol weight ratio of about 5:300, a residence time in the first reaction zone is about 0.5 s to about 30 s, the first reaction zone has a temperature of about 850°F to about 1100°F, and the first reaction zone has a pressure of about 30 psig to about 95 psig; wherein a residence time in the second reaction zone is about 0.25 s to about 8 s, the second reaction zone has a temperature of about 900°F to about 1300°F, and the second reaction zone has a pressure of about 10 psig to about 100 psig; dehydrating at least a portion of the bio-ethanol in the first reaction zone to produce bio- ethylene; cracking at least a portion of the petroleum-based hydrocarbon feed in the second reaction zone to produce a cracking product comprising at least some ethane; obtaining an FCC product comprising the bio-ethylene and the cracking product; separating the bio-ethylene and the ethane as separate streams from the FCC product; steam cracking the ethane to convert at least a portion of the ethane into ethylene, and combining the ethylene with the bio-ethylene to produce a composite ethylene stream;wherein the composite ethylene stream has a biogenic carbon concentration of about 1 wt% to about 50 wt%; and optionally, converting the composite ethylene stream into a polyethylene, a linear alpha olefin, or any combination thereof.

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