Patent Grant
11866662
The present disclosure relates to processes for processing petroleum-based materials and, in particular, processes for cracking hydrocarbon feeds to produce light olefins.
The worldwide increasing demand for light chemical intermediates remains a major challenge for many integrated refineries. In particular, the production of some valuable light olefins, such as ethylene and propylene, has attracted increased attention as pure olefin streams are considered the building blocks for polymer synthesis. The production of light olefins depends on several process variables, such as the feed type, operating conditions, and the type of catalyst. Despite the options available for producing a greater yield of propylene and light olefins, intense research activity in this field is still being conducted.
Light olefins are typically produced through thermal cracking (or steam pyrolysis) of petroleum gases and distillates, such as naphtha, kerosene, or gas oil. Light olefins may also be produced through fluid catalytic cracking processes. Typical hydrocarbon feeds for fluid catalytic cracking processes range from hydrocracked bottoms to heavy feed fractions such as vacuum gas oil and atmospheric residue; however, these hydrocarbon feeds are limited in supply and at least in part, due to limitations of processes used in fluid catalytic cracking processes.
Accordingly, there is an ongoing need for integrated processes which can produce intermediate chemical compounds from hydrocarbon feeds, such as crude oil. The processes of the present disclosure include fractionating a hydrocarbon feed into three streams and contacting the residue stream with one or more hydrotreating catalysts to form a hydrotreated effluent. The processes of the present disclosure further include contacting the hydrotreated effluent and the other streams with an FCC catalyst composition. In particular, the processes of the present disclosure include fractionating the hydrocarbon feed into a light stream, a middle stream, and a residue stream; hydrotreating the residue stream; and introducing the light stream, the middle stream, and the hydrotreated residue streams to a single fluidized catalytic cracking (FCC) reaction zone. The light stream and hydrotreated residue stream are introduced to the single FCC reaction zone upstream of the middle stream, such that the light stream and hydrotreated residue streams experience a greater severity than the middle stream.
According to one embodiment of the present disclosure, a method of processing a hydrocarbon feed includes fractionating the hydrocarbon feed into a light stream, a middle stream, and a residue stream; hydrotreating the residue stream to form a hydrotreated residue stream; and feeding the light stream, middle stream, and the hydrotreated residue stream to a single Fluid Catalytic Cracking (FCC) reaction zone, thereby producing a product stream comprising light olefins. The light stream may comprise hydrocarbons boiling at less than 200° C. The middle stream may comprise hydrocarbons boiling from 200° C. to 540° C. and the residue stream may comprise hydrocarbons boiling at greater than 540° C. The light stream and the hydrotreated residue streams may be exposed to more severe FCC cracking conditions than the middle stream, within the same FCC reaction zone. The single FCC reaction zone may be operated in a down-flow configuration and the FCC may be operated under high severity conditions.
Additional features and advantages of the embodiments of the present disclosure will be set forth in the detailed description that follows and, in part, will be readily apparent to a person of ordinary skill in the art from the detailed description or recognized by practicing the embodiments of the present disclosure.
The following detailed description of the present disclosure may be better understood when read in conjunction with the following drawing in which:
When describing the simplified schematic illustration of
Reference will now be made in greater detail to various aspects, some of which are illustrated in the accompanying drawings.
The present disclosure is directed to processes and catalysts for upgrading hydrocarbon feeds, such as crude oil, through hydrotreating and fluidized catalytic cracking (FCC) to produce greater value chemical products and intermediates, such as but not limited to light olefins, aromatic compounds, and combinations thereof. The processes and FCC catalyst compositions of the present disclosure can enable efficient cracking of feed streams, such as those comprising crude oil, by taking advantage of hydrotreating and the spatial effect within an FCC, such as a down-flow FCC.
As used in the present disclosure, the term “API” refers to the American Petroleum Institute.
As used in the present disclosure, the term “ASTM” refers to the American Society for Testing and Materials
As used in the present disclosure, the term “cracking” refers to a chemical reaction where a molecule having carbon-carbon bonds is broken into more than one molecule by the breaking of one or more of the carbon-carbon bonds; where a compound including a cyclic moiety, such as an aromatic, is converted to a compound that does not include a cyclic moiety; or where a molecule having carbon-carbon double bonds are reduced to carbon-carbon single bonds. As used in the present disclosure, the term “catalytic cracking” refers to cracking conducted in the presence of a catalyst. Some catalysts may have multiple forms of catalytic activity, and calling a catalyst by one particular function does not render that catalyst incapable of being catalytically active for other functionality.
As used in the present disclosure, the term “catalyst” refers to any substance that increases the rate of a specific chemical reaction, such as cracking reactions.
As used in the present disclosure, the term “crude oil” refers to a mixture of petroleum liquids and gases, including impurities, such as sulfur-containing compounds, nitrogen-containing compounds, and metal compounds, extracted directly from a subterranean formation or received from a desalting unit without having any fractions, such as naphtha, separated by distillation.
As used in the present disclosure, the term “naphtha” refers to an intermediate mixture of hydrocarbon-containing materials derived from crude oil refining and having atmospheric boiling points from 36 degrees Celsius (° C.) to 220° C. Naphtha may comprise light naphtha comprising hydrocarbon-containing materials having atmospheric boiling points from 36° C. to 80° C., intermediate naphtha comprising hydrocarbon-containing materials having atmospheric boiling points from 80° C. to 140° C., and heavy naphtha comprising hydrocarbon-containing materials having atmospheric boiling points from 140° C. to 200° C. Naphtha may comprise paraffinic, naphthenic, and aromatic hydrocarbons having from 4 carbon atoms to 11 carbon atoms.
As used in the present disclosure, the term “directly” refers to the passing of materials, such as an effluent, from a first component of the system to a second component of the system without passing the materials through any intervening components or systems operable to change the composition of the materials. Similarly, the term “directly” also refers to the introducing of materials, such as a feed, to a component of the system without passing the materials through any preliminary components operable to change the composition of the materials. Intervening or preliminary components or systems operable to change the composition of the materials can include reactors and separators, but are not generally intended to include heat exchangers, valves, pumps, sensors, or other ancillary components required for operation of a chemical process. Further, combining two streams together upstream of the second component instead of passing each stream to the second component separately is also not considered to be an intervening or preliminary component operable to change the composition of the materials.
As used in the present disclosure, the terms “downstream” and “upstream” refer to the positioning of components or systems relative to a direction of flow of materials through the system. For example, a second component may be considered “downstream” of a first component if materials flowing through the system encounter the first component before encountering the second component. Likewise, the first component may be considered “upstream” of the second component if the materials flowing through the system encounter the first component before encountering the second component.
As used in the present disclosure, the term “effluent” refers to a stream that is passed out of a reactor, a reaction zone, or a separator following a particular reaction or separation. Generally, an effluent has a different composition than the stream that entered the reactor, reaction zone, or separator. It should be understood that when an effluent is passed to another component or system, only a portion of that effluent may be passed. For example, a slipstream may carry some of the effluent away, meaning that only a portion of the effluent may enter the downstream component or system. The terms “reaction effluent” and “reactor effluent” particularly refer to a stream that is passed out of a reactor or reaction zone.
As used in the present disclosure, the term “high-severity conditions” refers to operating conditions of a fluid catalytic cracking system, such as the FCC system, that include temperatures greater than or equal to 580° C., or from 580° C. to 750° C., a catalyst to oil ratio greater than or equal to 1:1, or from 1:1 to 60:1, and a residence time of less than or equal to 60 seconds, or from 0.1 seconds to 60 seconds, each of which conditions may be more severe than typical operating conditions of fluid catalytic cracking systems.
As used in the present disclosure, the term “catalyst to oil ratio” or “CTO weight ratio” refers to the weight ratio of a catalyst to a process stream comprising hydrocarbons.
The term “residence time” refers to the amount of time that reactants are in contact with a catalyst, at reaction conditions, such as at the reaction temperature.
As used in the present disclosure, the term “reactor” refers to any vessel, container, conduit, or the like, in which a chemical reaction, such as catalytic cracking, occurs between one or more reactants optionally in the presence of one or more catalysts. A reactor can include one or a plurality of “reaction zones” disposed within the reactor. The term “reaction zone” refers to a region in a reactor where a particular reaction takes place.
As used in the present disclosure, the terms “separation unit,” and “separator” refer to any separation device(s) that at least partially separates one or more chemical constituents in a mixture from one another. For example, a separation system selectively separates different chemical constituents from one another, forming one or more chemical fractions. Examples of separation systems include, without limitation, distillation columns, fractionators, flash drums, knock-out drums, knock-out pots, centrifuges, filtration devices, traps, scrubbers, expansion devices, membranes, solvent extraction devices, high-pressure separators, low-pressure separators, or combinations of these. The separation processes described in the present disclosure may not completely separate all of one chemical constituent from all of another chemical constituent. Instead, the separation processes described in the present disclosure “at least partially” separate different chemical constituents from one another and, even if not explicitly stated, separation can include only partial separation.
As used herein, the term “light olefins” means olefinic (comprising at least one double bond) hydrocarbons with from 2 to 4 carbon atoms. For example, light olefins may comprise ethylene, propylene, and butylene.
It should further be understood that streams may be named for the components of the stream, and the component for which the stream is named may be the major component of the stream (such as comprising from 50 wt. %, from 70 wt. %, from 90 wt. %, from 95 wt. %, from 99 wt. %, from 99.5 wt. %, or from 99.9 wt. % of the contents of the stream to 100 wt. % of the contents of the stream). It should also be understood that components of a stream are disclosed as passing from one system component to another when a stream comprising that component is disclosed as passing from that system component to another. For example, a disclosed “heavy oil stream” passing to a first system component or from a first system component to a second system component should be understood to equivalently disclose “heavy oil” passing to the first system component or passing from a first system component to a second system component.
The composition of feed streams and processing variables of FCC systems play a significant role in the reaction yields and heat balance within the systems. Conventional FCC systems and processes can require costly refining to produce suitable feed streams. Such additional costly refining can include separating and processing of one or more fractions of a hydrocarbon feedstock before introducing the refined conventional feed into the FCC system. These additional processing steps are energy intensive and reduce the amount of viable feed from an existing hydrocarbon source. Previous systems and methods have been developed to convert crude oil to greater value chemical products and intermediates directly through catalytic cracking to attempt to overcome these limitations, such as by reducing or eliminating the processing steps needed to produce a suitable hydrocarbon feed before introduction into an FCC system. However, contaminants, metals, or both present in heavy hydrocarbon feeds, such as crude oil, can deactivate the catalyst, resulting in decreased yields and increased production costs.
Accordingly, embodiments of the present disclosure are directed to processes for converting crude oil directly to greater value chemical products and intermediates, such as but not limited to olefins and aromatic compounds, through a combination of hydrotreating and FCC using the reaction configurations specified herein.
Referring now to
The Hydrocarbon Feed
The hydrocarbon feed 105 to the present method 100 may be a crude oil, such as a whole crude oil. The “crude oil” may be a raw hydrocarbon which has not been previously processed, such as through one or more of distillation, cracking, hydrotreating, desalting, or dehydration. In embodiments, the crude oil may have undergone at least some processing, such as desalting, solids separation, scrubbing, or combinations of these, but has not been subjected to distillation. For instance, the crude oil may be a de-salted crude oil that has been subjected to a de-salting process. In embodiments, crude oil may not have undergone pretreatment, separation (such as distillation), or other operation that changes the hydrocarbon composition of the crude oil prior to introducing the crude oil to the method 100. As used herein, the “hydrocarbon composition” of the crude oil refers to the composition of the hydrocarbon constituents of the crude oil and does not include entrained non-hydrocarbon solids, salts, water, or other non-hydrocarbon constituents.
The hydrocarbon feed 105, such as a crude oil, may have an American Petroleum Institute (API) gravity of from 25 to 55. For example, the hydrocarbon feed 105 may have an API gravity from 45 to 55, from 50 to 52, from 25 to 35, from 27 to 29, from 30 to 32, from 32 to 34, from 27 to 32, or any subset thereof. The hydrocarbon feed 105 may have a density of greater than 0.8 grams per milliliter (g/ml), greater than 0.82 g/ml, greater than 0.84 g/ml, 0.86 g/ml, 0.88 g/ml, greater than 0.90 g/ml, greater than 0.91 g/ml, from 0.8 g/ml to 1.0 g/ml, from 0.84 to 0.96 g/ml, from 0.86 g/ml to 0.93 g/ml, from 0.88 g/ml to 0.92 g/ml, from 0.9 g/ml to 0.92 g/ml, or any subset thereof, at a temperature of 15 degrees Celsius. According to some embodiments, the hydrocarbon feed 105 may be an Arab heavy crude oil, an Arab medium crude oil, an Arab light crude oil, or an Arab super light crude oil.
The hydrocarbon feed 105 may have an initial boiling point from 30° C. to 50° C. For example, the hydrocarbon feed 105 may have an initial boiling point from 30° C. to 45° C., from 30° C. to 40° C., from 30° C. to 35° C., from 35° C. to 50° C., from 40° C. to 50° C., from 45° C. to 50° C., or any subset thereof. The initial boiling point may be determined according to standard test method ASTM D7169.
The hydrocarbon feed 105 may have an end boiling point (also referred to herein as “EBP” and “FBP”) greater than 720 degrees Celsius. For example, the hydrocarbon feed 105 may have an end boiling point greater than 740° C., greater than 760° C., greater than 780° C., greater than 800° C., greater than 850° C., greater than 900° C., greater than 950° C., or greater than 1000° C. The hydrocarbon feed 105 may have an end boiling point less than 2000° C., less than 1800° C., less than 1600° C., less than 1400° C., less than 1200° C., less than 1000° C., less than 900° C., less than 800° C., less than 750° C., or any subset thereof. The end boiling point may be determined according to standard test method ASTM D7169.
At least 50 weight percent of the hydrocarbon feed 105 may have a boiling point temperature greater than or equal to 300° C. For example, the hydrocarbon feed 105 may have a 50 wt. % boiling point temperature from 300° C. to 500° C., from 300° C. to 475° C., from 300° C. to 450° C., from 300° C. to 425° C., from 300° C. to 400° C., from 300° C. to 375° C., 350° C. to 500° C., from 350° C. to 475° C., from 350° C. to 450° C., from 350° C. to 425° C., from 350° C. to 400° C., from 350° C. to 375° C., 375° C. to 500° C., from 375° C. to 475° C., from 375° C. to 450° C., from 375° C. to 425° C., from 375° C. to 400° C., or any subset thereof. The 50 weight percent boiling temperature may be determined according to standard test method ASTM D7169.
The hydrocarbon feed 105 may have a nitrogen concentration of less than or equal to 5000 parts per million by weight (ppmw). For example, the hydrocarbon feed 105 may have a nitrogen concentration of less than 4500 ppmw, less than 4000 ppmw, less than 3500 ppmw, less than 3000 ppmw, less than 2500 ppmw, less than 2000 ppmw, from 1000 ppmw to 5000 ppmw, from 1000 to 4000 ppmw, from 1000 ppmw to 3000 ppmw, from 1000 ppmw to 2000 ppmw, or any subset thereof. The nitrogen concentration of the hydrocarbon feed 105 may be determined according to standard test method ASTM D4629.
The hydrocarbon feed 105 may have a concentration of paraffin compounds of less than 50 wt. % per unit weight of the hydrocarbon feed 105. For example, the hydrocarbon feed 105 may have a concentration of paraffin compounds of less than or equal to 40 wt. %, less than or equal to 35 wt. %, less than or equal to 30 wt. %, less than or equal to 25 wt. %, less than or equal to 20 wt. %, less than or equal to 15 wt. %, less than or equal to 10 wt. %, or even less than or equal to 5 wt. %, per unit weight of the hydrocarbon feed 105. In embodiments, the hydrocarbon feed 105 may have a concentration of paraffin compounds of from 5 wt. % to less than 50 wt. %, from 5 wt. % to 40 wt. %, from 5 wt. % to 35 wt. %, from 5 wt. % to 30 wt. %, from 5 wt. % to 25 wt. %, from 5 wt. % to 20 wt. %, from 10 wt. % to less than 50 wt. %, from 10 wt. % to 40 wt. %, from 10 wt. % to 35 wt. %, from 10 wt. % to 30 wt. %, from 10 wt. % to 25 wt. %, or even from 10 wt. % to 20 wt. % per unit weight of the hydrocarbon feed 105. The paraffin content of the hydrocarbon feed 105 may be determined according to ASTM 5443.
The hydrocarbon feed 105 may have a concentration of aromatic compounds of greater than or equal to 20 wt. %, per unit weight of the hydrocarbon feed 105. For example, the hydrocarbon feed 105 may have a concentration of aromatic compounds of greater than or equal to 30 wt. %, greater than or equal to 40 wt. %, or even greater than or equal to 50 wt. % per unit weight of the hydrocarbon feed 105, as determined according to ASTM 5443. In embodiments, the hydrocarbon feed 105 may have a concentration of aromatic compounds of from 20 wt. % to 90 wt. %, from 20 wt. % to 80 wt. %, from 20 wt. % to 70 wt. %, from 30 wt. % to 90 wt. %, from 30 wt. % to 80 wt. %, from 30 wt. % to 70 wt. %, from 40 wt. % to 90 wt. %, from 40 wt. % to 80 wt. %, from 40 wt. % to 70 wt. %, from 50 wt. % to 90 wt. %, from 50 wt. % to 80 wt. %, from 50 wt. % to 70 wt. %, or any subset thereof, per unit weight of the hydrocarbon feed 105.
The hydrocarbon feed 105 may have a concentration of naphthenes of greater than or equal to 25 wt. % per unit weight of the hydrocarbon feed 105. For example, the hydrocarbon feed 105 may have a concentration of naphthenes greater than or equal to 27 wt. % per unit weight of the hydrocarbon feed 105, as determined according to ASTM 5443. In embodiments, the hydrocarbon feed 105 can have a concentration of naphthenes of from 25 wt. % to 60 wt. %, from 25 wt. % to 50 wt. %, from 25 wt. % to 40 wt. %, from 25 wt. % to 35 wt. %, from 27 wt. % to 60 wt. %, from 27 wt. % to 50 wt. %, from 27 wt. % to 40 wt. %, from 27 wt. % to 35 wt. %, or any subset thereof per unit weight of the hydrocarbon feed 105.
In some embodiments, the hydrocarbon feed 105 may be a topped crude oil. As used in the present disclosure, the term “topped crude oil” refers to crude oil from which lesser boiling constituents have been removed through distillation, such as constituents having boiling point temperatures less than 180° C. or even less than 160° C. The hydrocarbon feed 105 may comprise, consist of, or consist essentially of a topped crude oil, which has greater than or equal to 95%, greater than or equal to 98%, or even greater than or equal to 99% constituents having boiling point temperatures greater than or equal to 160° C. or greater than or equal to 180° C., depending on the cut point temperature of the topping unit.
Fractionating
Fractionating 110 the hydrocarbon feed 105 to produce the light stream 115 and the residue stream 125 may occur in any separator. For example, the fractionating 110 step may include, without limitation, distillation columns, fractionators, flash drums, knock-out drums, knock-out pots, centrifuges, filtration devices, traps, scrubbers, expansion devices, membranes, solvent extraction devices, high-pressure separators, low-pressure separators, or combinations of these.
The Light Stream
Fractionating 110 the hydrocarbon feed 105 may produce a light stream 115. The light stream 115 may comprise hydrocarbons boiling at less than or equal to 200° C. At least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. %, at least 99 wt. %, or even at least 99.9 wt. % of the hydrocarbons in the light stream 115 may boil at less than or equal to 200° C.
The light stream 115 may comprise at least 50 wt. % of all hydrocarbons with a boiling point of less than or equal to at less than or equal to 200° C., which were originally in the hydrocarbon feed 105. For example, the light stream 115 may comprise at least 75 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. %, or at least 99 wt. % of all hydrocarbons with a boiling point of less than or equal to at less than or equal to 20° C. which were originally in the hydrocarbon feed 105. In some embodiments, the light stream 115 may comprise at least 75 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. %, or at least 99 wt. % of all hydrocarbons with a boiling point of from 25° C. to 200° C., from 35° C. to 200° C., or from 45° C. to 200° C. which were originally in the hydrocarbon feed 105.
The light stream 115 may comprise less than 5 wt. % sulfur, based on the total weight of the light stream 115. For example, the light stream 115 may comprise less than 2.5 wt. %, less than 1 wt. %, less than 0.5 wt. %, less than 0.1 wt. %, or even less than 0.01 wt. % sulfur, based on the total weight of the light stream 115.
The light stream 115 may comprise less than 50 ppm of nitrogen. For example, the light stream 115 may comprise less than 25 ppm, less than 15 ppm, less than 10 ppm, or even less than 5 ppm of nitrogen.
The light stream 115 may comprise less than 5 ppm nickel. For example, the light stream 115 may comprise less than 2.5 ppm, less than 2 ppm, less than 1 ppm, or even less than 0.1 ppm of nickel.
The light stream 115 may comprise less than 5 ppm vanadium. For example, the light stream 115 may comprise less than 2.5 ppm, less than 2 ppm, less than 1 ppm, or even less than 0.1 ppm of vanadium.
The light stream 115 may comprise from 50 wt. % to 99 wt. % of paraffins, based on the total weight of the light stream 115. For example, the light stream 115 may comprise from 60 wt. % to 90 wt. %, from 60 wt. % to 80 wt. %, from 65 wt. % to 75 wt. %, from 70 wt. % to 75 wt. %, or any subset thereof, of paraffins, based on the total weight of the light stream 115.
The light stream 115 may comprise from 1 wt. % to 30 wt. % of naphthenes, based on the total weight of the light stream 115. For example, the light stream 115 may comprise from 5 wt. % to 25 wt. %, from 10 wt. % to 20 wt. %, from 12.5 wt. % to 17.5 wt. %, or any subset thereof, of naphthenes, based on the total weight of the light stream 115.
The light stream 115 may comprise from 1 wt. % to 25 wt. % of aromatics, based on the total weight of the light stream 115. For example, the light stream 115 may comprise from 5 wt. % to 20 wt. %, from 10 wt. % to 15 wt. %, or any subset thereof, of aromatics, based on the total weight of the light stream 115.
The Middle Stream
Fractionating 110 the hydrocarbon feed 105 may produce a middle stream 120. The middle stream 120 may comprise hydrocarbons boiling from 200° C. to 540° C. For example, at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. %, at least 99 wt. %, or even at least 99.9 wt. % of the hydrocarbons in the middle stream 120 may boil from 200° C. to 540° C.
The middle stream 120 may comprise at least 50 wt. % of all hydrocarbons with a boiling point between 200° C. and 540° C., which were originally in the hydrocarbon feed 105. For example, the light stream 115 may comprise at least 75 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. %, or at least 99 wt. % of all hydrocarbons with a boiling point of between 200° C. and 540° C. which were originally in the hydrocarbon feed 105.
The middle stream 120 may comprise less than 5 wt. % sulfur. For example, the light stream 115 may comprise less than 2.5 wt. %, less than 1 wt. %, less than 0.5 wt. %, less than 0.1 wt. %, or even less than 0.01 wt. % sulfur.
The middle stream 120 may comprise less than 50 ppm of nitrogen. For example, the light stream 115 may comprise less than 25 ppm, less than 15 ppm, less than 10 ppm, or even less than 5 ppm of nitrogen.
The middle stream 120 may comprise less than 5 ppm nickel. For example, the light stream 115 may comprise less than 2.5 ppm, less than 2 ppm, less than 1 ppm, or even less than 0.1 ppm of nickel.
The middle stream 120 may comprise less than 5 ppm vanadium. For example, the light stream 115 may comprise less than 2.5 ppm, less than 2 ppm, less than 1 ppm, or even less than 0.1 ppm of vanadium.
The middle stream 120 may comprise from 20 wt. % to 60 wt. % of paraffins, based on the total weight of the middle stream 120. For example, the middle stream 120 may comprise from 25 wt. % to 55 wt. %, from 30 wt. % to 50 wt. %, from 35 wt. % to 50 wt. %, from 40 wt. % to 45 wt. %, or any subset thereof, of paraffins, based on the total weight of the middle stream 120.
The middle stream 120 may comprise from 20 wt. % to 60 wt. % of naphthenes, based on the total weight of the middle stream 120. For example, the middle stream 120 may comprise from 25 wt. % to 55 wt. %, from 30 wt. % to 50 wt. %, from 35 wt. % to 50 wt. %, from 40 wt. % to 45 wt. %, or any subset thereof, of naphthenes, based on the total weight of the middle stream 120.
The middle stream 120 may comprise from 1 wt. % to 30 wt. % of aromatics, based on the total weight of the middle stream 120. For example, the middle stream 120 may comprise from 5 wt. % to 25 wt. %, from 10 wt. % to 20 wt. %, from 12.5 wt. % to 17.5 wt. %, or any subset thereof, of aromatics, based on the total weight of the middle stream 120.
The Residue Stream
Fractionating 110 the hydrocarbon feed 105 may produce a residue stream 125. The residue stream 125 may comprise hydrocarbons boiling at a temperature of at least 540° C. For example, at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. %, at least 99 wt. %, or even at least 99.9 wt. % of the residue stream 125 may comprise hydrocarbons boiling at a temperature of at least 540° C., such as from 540° C. to 1000° C., from 540° C. to 900° C., from 540° C. to 800° C., or any subset thereof.
The residue stream 125 may comprise at least 50 wt. %, at least 75 wt. %, at least 90 wt. %, at least 95 wt. %, at least 99 wt. %, or even at least 99.9 wt. % of all hydrocarbons boiling at a temperature of at least 540° C., which were originally in the hydrocarbon feed 105.
The residue stream 125 may comprise less than 10 wt. % sulfur. For example, the residue stream 125 may comprise less than 7.5 wt. %, less than 5 wt. %, less than 4 wt. %, less than 3 wt. %, less than 2.9 wt. %, less than 2.8 wt. %, less than 2.7 wt. %, less than 2.6 wt. %, less than 2.5 wt. %, from 0.1 to 10 wt. %, from 0.5 to 10 wt. %, from 1 to 10 wt. %, from 2 to 10 wt. %, from 2 to 5 wt. %, from 2 to 3 wt. %, or any subset thereof of sulfur.
The residue stream 125 may comprise less than 7500 ppm of nitrogen. For example, the residue stream 125 may comprise less than 5000 ppm, less than 2500 ppm, less than 1500 ppm, less than 1000 ppm, less than 750 ppm, or less than 600 ppm nitrogen.
The residue stream 125 may comprise less than 500 ppm nickel. For example, the residue stream 125 may comprise less than 250 ppm, less than 10 ppm, less than 50 ppm, less than 25 ppm, less than 20 ppm, less than 15 ppm, less than 10 ppm, less than 5 ppm, less than 2.5 ppm, less than 1 ppm, or even less than 0.1 ppm nickel.
The residue stream 125 may comprise less than 500 ppm vanadium. For example, the residue stream 125 may comprise less than 250 ppm, less than 10 ppm, less than 50 ppm, less than 25 ppm, less than 20 ppm, less than 15 ppm, less than 10 ppm, less than 5 ppm, less than 2.5 ppm, less than 1 ppm, or even less than 0.1 ppm vanadium.
The residue stream 130 may comprise from 40 wt. % to 75 wt. % of naphthenes and aromatics, based on the total weight of the residue stream 130. For example, the residue stream 130 may comprise from 45 wt. % to 70 wt. %, from 50 wt. % to 65 wt. %, from 55. wt. % to 60 wt. %, or any subset thereof, of naphthenes and aromatics, based on the total weight of the residue stream 130.
The residue stream 130 may comprise from 15 wt. % to 55 wt. % of polar aromatics, based on the total weight of the residue stream 130. For example, the residue stream 130 may comprise from 20 wt. % to 50 wt. %, from 25 wt. % to 45 wt. %, from 30 wt. % to 40 wt. %, from 32.5 wt. % to 37.5 wt. %, or any subset thereof, of polar aromatics, based on the total weight of the residue stream 130.
The residue stream 130 may comprise from 1 wt. % to 12 wt. % of saturated hydrocarbons, based on the total weight of the residue stream 130. For example, the residue stream 130 may comprise from 2 wt. % to 10 wt. %, from 4 wt. % to 9 wt. %, from 6 wt. % to 8 wt. %, or any subset thereof, of saturated hydrocarbons, based on the total weight of the residue stream 130.
The Hydrotreater
The residue stream 125 may then be hydrotreated 130. Hydrotreating 130 the residue stream 125 may comprise contacting the residue stream 125 with one or more hydrotreating catalysts in a hydrotreating system. The hydrotreating system may be a single reactor or a series of reactors directly connected. The residue stream 125 may be directly introduced into the hydrotreater after fractionating 110.
The residue stream 125 may be hydrotreated in one or more stages, such as in a three-stage hydrotreater. The multiple stages of the hydrotreater may comprise distinct catalysts in distinct reaction zones. For example, the catalysts may be arranged in distinct beds, the catalysts may be positioned in individual reactors, or the catalysts may be mixed in a single reactor. The residue stream 125 may contact the one or more hydrotreating catalysts in a down flow manner.
Hydrotreating 130 the residue stream 125 may comprise exposing the residue stream 125 to one or more hydrotreating catalysts, such as a hydro-demetallization (also referred to as “HDM”) catalyst, a hydro-desulfurization also referred to as “HDS”) catalyst, and a hydro-dearomatization (also referred to as “HDA”) catalyst. In some embodiments, the one or more hydrotreating catalysts may include hydrodenitrogenation catalysts, hydrodeoxygenation catalysts, or both.
The one or more hydrotreating stages may be arranged in any order. For example, the one or more hydrotreating catalysts may be arranged such that the residue stream 125 first contacts the HDM catalyst, then the HDS catalyst, then the HDA catalyst. Alternately, the one or more hydrotreating stages may be arranged such that the residue stream 125 contacts the HDM, then the HDA, then the HDS; or contacts the HDS, HDA, HDM; or contacts the HDS, then the HDM, then the HDA; or contacts the HDA, then the HDS, then the HDM; or contacts the HDA, then the HDM, then the HDS catalyst. Without being limited by theory, it is believed that having the residue stream 125 contact the HDM and HDS catalysts before the HDA catalysts may prevent or minimize deactivation of the HDA catalysts.
In alternate embodiments, only one or two of the one or more hydrotreating stages and catalysts may be present. The one or more hydrotreating catalysts may be arranged such that the crude oil contacts the HDM then the HDA, or the HDA then the HDM, or the HDS then the HDA, or the HDA then the HDS, or the HDM then the HDS, or the HDS then the HDM catalysts.
In embodiments where the one or more hydrotreating catalysts form a mixed bed, the residue stream 125 may contact the one or more hydrotreating catalysts in a random or simultaneous manner.
The HDM catalyst may include any catalyst suitable for hydrodemetallization. For example, the HDM catalyst may comprise one or more metals from the Groups 5, 6, or 8-10 of the IUPAC periodic table. In some embodiments, the HDM catalyst may comprise molybdenum. The HDM catalyst may further comprise a support material, and the metal may be disposed on the support material. The support material may be gamma-alumina or silica/alumina extrudates, spheres, cylinders, beads, pellets, and combinations thereof. In some embodiments, the HDM catalyst may comprise a gamma-alumina support, with a surface area of from 100 meters squared per gram (m2/g) to 160 m2/g, such as from 100 m2/g to 130 m2/g, or from 130 m2/g to 160 m2/g. In one embodiment, the HDM catalyst may comprise a molybdenum metal catalyst on an alumina support (sometimes referred to as “Mo/Al2O3 catalyst”). It should be understood throughout this disclosure that metals contained in any of the disclosed catalysts may be present as sulfides or oxides, or even other compounds.
In some embodiments, the HDM catalyst may comprise from 0.5 wt. % to 12 wt. % of an oxide or sulfide of molybdenum, such as from 2 wt. % to 10 wt. % or from 3 wt. % to 7 wt. % of an oxide or sulfide of molybdenum, and from 88 wt. % to 99.5 wt. % of alumina, such as from 90 wt. % to 98 wt. % or from 93 wt. % to 97 wt. % of alumina.
The HDM catalyst may have a relatively large pore volume, such as at least 0.8 cubic centimeters per gram (cm3/g) (for example, at least 0.9 cm3/g, or even at least 1.0 cm3/g). The pore size of the HDM catalyst may be predominantly macro-porous (that is, having a pore size of greater than 50 nanometers (nm)). Without being limited by theory, it is believed that this pore structure and volume may provide a large capacity for the uptake of metals, and optionally dopants, on the surfaces of the HDM catalyst. In one embodiment, the HDM catalyst may include a dopant comprising one or more compounds that include elements selected from the group consisting of boron, silicon, halogens, phosphorus, and combinations thereof.
An exemplary HDM catalyst may include KFR-22 from Albemarle Corp.
The HDS catalyst may comprise one or more metals from the Groups 5, 6, or 8-10 of the IUPAC periodic table. The HDS catalyst may comprise one or more metal from Group 6 and one metal from Groups 8-10 of the IUPAC periodic table. Examples of Group 6 metals include molybdenum and tungsten and examples of Group 8-10 metals include nickel and cobalt. The HDS catalyst may further comprise a support material, and the metal may be disposed on the support material. In some embodiments, the HDS catalyst may comprise Mo and Ni on an alumina support (sometimes referred to as a “Mo—Ni/Al2O3 catalyst”). The HDS catalyst may also contain a dopant that is selected from the group consisting of boron, phosphorus, halogens, silicon, and combinations thereof. In one or more embodiments, the HDS catalyst may comprise from 10 wt. % to 18 wt. % of an oxide or sulfide of molybdenum, such as from 11 wt. % to 17 wt. % or from 12 wt. % to 16 wt. % of an oxide or sulfide of molybdenum, from 1 wt. % to 7 wt. % of an oxide or sulfide of nickel, such as from 2 wt. % to 6 wt. % or from 3 wt. % to 5 wt. % of an oxide or sulfide of nickel, and from 75 wt. % to 89 wt. % of alumina such as from 77 wt. % to 87 wt. % or from 79 wt. % to 85 wt. % of alumina.
The HDS catalyst may have a surface area of 140 m2/g to 200 m2/g, such as from 140 m2/g to 170 m2/g or from 170 m2/g to 200 m2/g. The HDS catalyst may have an intermediate pore volume of from 0.5 cm3/g to 0.7 cm3/g, such as 0.6 cm3/g. The HDS catalyst may generally comprise a mesoporous structure having pore sizes in the range of 12 nm to 50 nm.
An exemplary HDS catalyst may include KFR-33 from Albemarle Corp.
The HDA catalyst may comprise one or more metals from Groups 5, 6, 8, 9, or 10 of the IUPAC periodic table. In some embodiments, the HDA catalyst may comprise one or more metals from Groups 5 or 6 of the IUPAC periodic table, and one or more metals from Groups 8, 9, or 10 of the IUPAC periodic table. In some embodiments, the HDA catalyst may comprise molybdenum or tungsten from Group 6 and nickel or cobalt from Groups 8, 9, or 10. The HDA catalyst may further comprise a support material, such as zeolite, and the metal may be disposed on the support material. In one embodiment, the HDA catalyst may comprise tungsten and nickel metal catalyst on a zeolite support that is mesoporous (sometimes referred to as “W—Ni/meso-zeolite catalyst”). In another embodiment, the HDA catalyst may comprise molybdenum and nickel metal catalyst on a zeolite support that is mesoporous (sometimes referred to as “Mo Ni/meso-zeolite catalyst”). The zeolite support material may not be limited to any particular type of zeolite. However, it is contemplated that zeolites such as Y, Beta, AWLZ-15, LZ-45, Y-82, Y-84, LZ-210, LZ-25, Silicalite, or mordenite framework zeolites may be suitable for use in the presently-described HDA catalyst.
The support material (such as a mesoporous zeolite) of the HDA catalyst may be characterized as mesoporous by having average pore size of from 2 nm to 50 nm. Without being bound by theory, it is believed that the relatively large-sized pores (that is, mesoporosity) allow for larger molecules to diffuse inside the zeolite, which is believed to enhance the reaction activity and selectivity of the catalyst. Because of the increased pore size, aromatic-containing molecules can more easily diffuse into the catalyst and aromatic cracking may increase. For example, in some conventional embodiments, the feedstock converted by the hydrotreating catalysts may be vacuum gas oils; light cycle oils from, for example, a fluid catalytic cracking reactor; or coker gas oils from, for example, a coking unit. The molecular sizes in these oils are relatively small compared to those of heavy oils such as crude and atmosphere residue, which may be the feedstock of the present methods and systems. The heavy oils generally are unable to diffuse inside the conventional zeolites and be converted on the active sites located inside the zeolites. Therefore, zeolites with larger pore sizes (that is, mesoporous zeolites) may allow the larger molecules of heavy oils to overcome the diffusion limitation, and may promote the reaction and conversion of the larger molecules of the heavy oils.
In one or more embodiments, the HDA catalyst may comprise from 18 wt. % to 28 wt. % of a sulfide or oxide of tungsten, such as from 20 wt. % to 27 wt. % or from 22 wt. % to 26 wt. % of tungsten or a sulfide or oxide of tungsten, from 2 wt. % to 8 wt. % of an oxide or sulfide of nickel, such as from 3 wt. % to 7 wt. % or from 4 wt. % to 6 wt. % of an oxide or sulfide of nickel, and from 5 wt. % to 40 wt. % of mesoporous zeolite, such as from 10 wt. % to 35 wt. % or from 10 wt. % to 30 wt. % of zeolite. In another embodiment, the HDA catalyst may comprise from 12 wt. % to 18 wt. % of an oxide or sulfide of molybdenum, such as from 13 wt. % to 17 wt. % or from 14 wt. % to 16 wt. % of an oxide or sulfide of molybdenum, from 2 wt. % to 8 wt. % of an oxide or sulfide of nickel, such as from 3 wt. % to 7 wt. % or from 4 wt. % to 6 wt. % of an oxide or sulfide of nickel, and from 5 wt. % to 40 wt. % of mesoporous zeolite, such as from 10 wt. % to 35 wt. % or from 10 wt. % to 30 wt. % of mesoporous zeolite.
It should be understood that some embodiments of the presently-described methods and systems may utilize a HDA catalyst that includes a mesoporous zeolite (that is, having an average pore size of from 2 nm to 50 nm). However, in other embodiments, the average pore size of the zeolite may be less than 2 nm (that is, microporous).
An exemplary HDA catalyst may include KFR-70 from Albemarle Corp.
The residue stream 125 may contact the one or more hydrotreating catalysts at a temperature of at least 300° C., at least 325° C., at least 350° C., at least 375° C., or at least 400° C. The residue stream 125 may contact the one or more hydrotreating catalysts at a temperature of less than 1000° C., less than 800° C., less than 600° C., less than 500° C., or less than 450° C.
The residue stream 125 may contact the one or more hydrotreating catalysts in the presence of hydrogen. For example, the atmosphere in which the residue stream 125 contacts the one or more hydrotreating catalysts may be at least 10 mol. % hydrogen, at least 25 mol. % hydrogen, at least 50 mol. % hydrogen, at least 75 mol. % hydrogen, at least 90 mol. % hydrogen, or even at least 99 mol. % hydrogen.
The residue stream 125 may contact the one or more hydrotreating catalysts at a pressure of at least 75 bar, at least 100 bar, at least 125 bar, or at least 150 bar. For example, the residue stream 125 may contact the one or more hydrotreating catalysts at a hydrogen partial pressure of at least 10 bar, at least 20 bar, at least 30 bar, at least 50 bar, at least 75 bar, at least 100 bar, at least 125 bar, or at least 150 bar.
The residue stream 125 may contact the one or more hydrotreating catalysts at a hydrogen/oil ratio of at least 600. For example, the residue stream 125 may contact the one or more hydrotreating catalysts at a hydrogen/oil ratio of at least 800, at least 1000, at least 1200, from 600 to 1500, from 800 to 1400, from 1100 to 1300, or any subset thereof.
The residue stream 125 may contact the one or more hydrotreating catalysts at a liquid hourly space velocity (LHSV) of greater than 0.1 h−1, greater than 0.2 h−1, greater than 0.25 h−1, greater than 0.28 h−1, less than 0.5 h−1, less than 0.4 h−1, less than 0.35 h−1, less than 0.32 h−1, from 0.1 h−1 to 0.5 h−1, from 0.2 h−1 to 0.4 h−1, from 0.25 h−1 to 0.35 h−1, from 0.28 h−1 to 0.32 h−1, or any subset thereof.
Hydrotreated Residue Stream
Hydrotreating 130 the residue stream 125 may form a hydrotreated residue stream 135.
At least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, or even at least 99 wt. % of the hydrotreated residue stream 135 may have a boiling point temperature of at least 520° C., such as at least 530° C., at least 540° C., at least 550° C., or at least 560° C.
The hydrotreated residue stream 135 may comprise comprises less than 10 wt. % of sulfur, based on the total weight of the hydrotreated residue stream 135. For example, the hydrotreated residue stream 135 may comprise less than 8 wt. %, less than 6 wt. %, less than 4 wt. %, less than 2 wt. %, less than 1 wt. %, less than 0.5 wt. %, less than 0.25 wt. %, or even less than 0.1 wt. % of sulfur, based on the total weight of the hydrotreated residue stream 135.
The hydrotreated residue stream 135 may have a sulfur content of less than 20%, less than 15%, less than 10%, less than 5%, less than 4%, or less than 3%, less than 2%, or even less than 1% of the sulfur content of residue stream 125. The sulfur content may be measured according to standard test method ASTM D-4924.
The hydrotreated residue stream 135 may comprise less than 5000 ppm of nitrogen. For example, the hydrotreated residue stream 135 may comprise less than 2500 ppm, less than 2000 ppm, less than 1500 ppm, less than 1000 ppm, less than 500 ppm, less than 250 ppm, less than 125 ppm, less than 75 ppm, less than 50 ppm, less than 25 ppm, less than 10 ppm, or even less than 1 ppm of nitrogen.
The hydrotreated residue stream 135 may have a nitrogen content of less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 5%, or even less than 1% of the nitrogen content of the residue stream 125. The nitrogen content may be measured according to standard test method ASTM D-4629.
The hydrotreated residue stream 135 may comprise less than 100 ppm of nickel. For example, the hydrotreated residue stream 135 may comprise less than 75 ppm, less than 50 ppm, less than 25 ppm, less than 15 ppm, less than 10 ppm, less than 5 ppm, or even less than 1 ppm of nickel.
The hydrotreated residue stream 135 may have a nickel content of less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 5%, or even less than 1% of the nickel content of the residue stream 125.
The hydrotreated residue stream 135 may comprise less than 100 ppm of vanadium. For example, the hydrotreated residue stream 135 may comprise less than 75 ppm, less than 50 ppm, less than 25 ppm, less than 15 ppm, less than 10 ppm, less than 5 ppm, or even less than 1 ppm of vanadium.
The hydrotreated residue stream 135 may have a vanadium content of less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 5%, or even less than 1% of the vanadium content of the residue stream 125.
The hydrotreated residue stream 135 may have an aromatic content of less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 5%, or even less than 1% of the aromatic content of the residue stream 125.
The hydrotreated residue stream 140 may have a naphthene and aromatic compound concentration of from 20 wt. % to 55 wt. %, based on the total weight of the hydrotreated residue stream 140. For example, the hydrotreated residue stream 140 may have a naphthenes and aromatic compound concentration of from 25 wt. % to 50 wt. %, from 30 wt. % to 45 wt. %, from 35 wt. % to 40 wt. %, or any subset thereof, of naphthenes and aromatic compounds, based on the total weight of the hydrotreated residue stream 140.
The hydrotreated residue stream 140 may have a polar aromatic compound concentration of from 1 wt. % to 6 wt. %, based on the total weight of the hydrotreated residue stream 140. For example, the hydrotreated residue stream 140 may have a polar aromatic compound concentration of from 2 wt. % to 5 wt. %, from 3 wt. % to 4, wt. %, or any subset thereof, based on the total weight of the hydrotreated residue stream 140.
The hydrotreated residue stream 140 may comprise from 40 wt. % to 75 wt. % of saturated hydrocarbons, based on the total weight of the hydrotreated residue stream 140. For example, the hydrotreated residue stream 140 may comprise from 45 wt. % to 70 wt. %, from 50 wt. % to 65 wt. %, from 55 wt. % to 60 wt. %, or any subset thereof, of saturated hydrocarbons, based on the total weight of the hydrotreated residue stream 140.
Spatial Effects of the FCC
The method 100 of processing a hydrocarbon feed 105 may comprise introducing the light stream 115, the middle stream 120, and the hydrotreated residue stream 135 to a single FCC reaction zone 140, thereby producing a product stream 145 comprising light olefins. The light stream 115, the middle stream 120, and the hydrotreated residue stream 135 may be introduced directly into to the single FCC reaction zone 140.
The light stream 115 and the hydrotreated residue stream 135 may experience the same degree of severity in the single FCC reaction zone 140 as one another. For example, the light stream 115 and the hydrotreated residue stream 135 may experience the same or substantially the same degree of severity within the single FCC reaction zone 140 as one another. Degree of severity may refer to peak temperature within the single FCC reaction zone 140, residence time within the single FCC reaction zone 140, or both. For example, the light stream 115 and the hydrotreated residue stream 135 may have a residence time within 30%, within 20%, within 10%, within 5%, within 2.5%, within 1%, or even within 0.1% of one another. The light stream 115 and the hydrotreated residue stream 135 may experience a peak temperature within 10° C., within 5° C., within 2.5° C., within 1° C., or even within 0.1° C. of one another. Exposing the light stream 115 and the hydrotreated residue stream 135 to the same degree of severity within the single FCC reaction zone 140 may be accomplished by combining the light stream 115 and the hydrotreated residue stream 135 before introducing the two streams to the single FCC reaction zone 140.
The light stream 115 and the hydrotreated residue stream 135 may be exposed to more severe FCC cracking conditions than the middle stream 120, in the single FCC reaction zone 140.
Exposing one stream to more severe FCC cracking conditions than another stream may comprise introducing the stream subject to more severe FCC cracking conditions into the single FCC reaction zone upstream of the stream subject to less severe FCC cracking conditions. For example, the light stream 115 and the hydrotreated residue stream 135 may be introduced to the single FCC reaction zone 140 upstream of the middle stream 120. Introducing a first stream upstream of a second stream may mean that the first stream is introduced vertically above the second stream. Without being limited by theory, it is believed that FCC cracking conditions become more severe the closer to the inlet of an FCC, such as a down-flow FCC, a stream is introduced.
The light stream 115 and the hydrotreated residue stream 135 may have a greater residence time in the single FCC reaction zone than the middle stream 120. For example, the light stream 115 and the hydrotreated residue stream 135 may have a residence time in the single FCC reaction zone at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 75%, at least 100%, at least 125%, at least 150%, at least 175%, or at least 200% greater than the residence time of the middle stream 120 in the single FCC reaction zone 140. Specifically, the light stream 115 and the hydrotreated residue stream 135 may each have a residence time in the single FCC reaction zone 140 of at least 0.5 seconds, at least 1 second, at least 2 seconds, from 1 to 2 seconds, from 1 to 3 seconds, or from 2 to 3 seconds. The middle stream 120 may have a residence time in the single FCC reaction zone 140 of less than 1 second, such as from 0.1 to 1 seconds, from 0.25 to 1 seconds, from 0.5 to 1 seconds, from 0.75 to 1 seconds, from 0.1 to 0.75 seconds, from 0.1 to 0.5 seconds, or any subset thereof.
The light stream 115 and the hydrotreated residue stream 135 may be exposed to a greater peak temperature in the single FCC reaction zone 140 than the middle stream 120. For example, the light stream 115 and the hydrotreated residue stream 135 may have a peak temperature in the single FCC reaction zone at least 5° C., at least 10° C., at least 15° C., at least 20° C., at least 25° C., at least 30° C., from 5 to 50° C., from 10 to 45° C., from 15 to 40° C., from 25 to 35° C., or any subset thereof, greater than the peak temperature of the middle stream 120 in the FCC. Specifically, the light stream 115 and the hydrotreated residue stream 135 may have a peak temperature in the single FCC reaction zone of from 650° C. to 720° C., from 650° C. to 700° C., from 655° C. to 695° C., from 660° C. to 690° C., from 665° C. to 685° C., from 670° C. to 680° C., from 660° C. to 700° C., from 670° C. to 700° C., from 670° C. to 720° C., about 675° C. or any subset thereof. The middle stream 120 may have a peak temperature in the single FCC reaction zone of from 640° C. to 670° C., from 650° C. to 670° C., from 655° C. to 665° C., about 660° C., or any subset thereof.
FCC Operating Conditions
In some embodiments, the single FCC reaction zone 140 may be operated in a down-flow manner. Without being limited by theory, it is believed that because reactants and catalysts travel together down a reaction zone in a down-flow FCC, the spatial variation in severity, residence time, and temperature is greater than in an up-flow or FCC.
A down-flow FCC reactor or “downer” is one in which the reactants flow from a catalyst/feed mixing zone downward through the cracking reaction zone to a separation zone. The hydrocarbons are reacted by contact with the FCC catalyst composition in the cracking reaction zone, which causes at least a portion of the hydrocarbons to undergo one or more cracking reactions to form one or more cracking reaction products, such as light olefins. The catalyst, which may have a temperature equal to or greater than the reaction temperature of the cracking reaction zone, may transfer heat to the hydrocarbons, thereby promoting the endothermic cracking reaction.
Steam may be introduced to the top portion of the cracking reaction zone to provide additional heating to the mixture of hydrocarbons and catalyst. Steam may additionally function as a diluent, reducing the partial pressure of hydrocarbons in the FCC reactor. Steam may also prevent secondary reactions, serving to increase selectivity of the cracking reactions.
Upon exit from the FCC reactor, the catalyst may be separated from the hydrocarbons to isolate a spent catalyst. The spent catalyst may then be sent to a regenerator. Regenerated catalyst may have an activity greater than the spent catalyst.
The single FCC reaction zone 140 may be operated under high-severity conditions, otherwise known as an HS-FCC. The single FCC reaction zone 140 may be operated at a peak temperature of greater than or equal to 580° C., a weight ratio of the FCC catalyst composition to the crude oil of from 2:1 to 10:1, and a residence time of from 0.1 seconds to 60 seconds.
The single FCC reaction zone 140 may operate at a peak temperature of greater than or equal to 580° C. For example, the single FCC reaction zone 140 may operate at a peak temperature of greater than 600° C., greater than 620° C., greater than 640° C., greater than 645° C., greater than 660° C., greater than 670° C., from 600 to 700° C., from 600 to 690° C., from 600 to 680° C., from 650 to 700° C., from 650 to 690° C., from 650 to 680° C., from 670 to 700° C., from 670 to 680° C., or any subset thereof. When the reaction temperature is greater than 700° C., the hydrocarbons may undergo increased thermal cracking and decreased catalytic cracking compared to embodiments where the reaction temperature is less than 700° C. Without being limited by theory, it is believed that thermal cracking of the hydrotreated effluent can increase yield of ethylene and decrease yield of other products. Catalytic cracking of the hydrocarbons in the single FCC reaction zone 140 can yield a greater number of desired products, such as light olefins and aromatics.
The weight ratio of the FCC catalyst composition to hydrocarbons in the single FCC reaction zone 140 may be from 2:1 to 10:1, such as from 2:1 to 8:1, from 2:1 to 6:1, from 2:1 to 4:1, from 4:1 to 10:1, from 6:1 to 10:1, or from 8:1 to 10:1. It should be understood that as used in this paragraph, “hydrocarbons” refers to the combined hydrocarbons of the light stream 115 and the hydrotreated residue stream 135.
The fluid catalytic cracking system may be operated with a catalyst-to-oil weight (CTO) ratio from 2:1 to 10:1, where the catalyst-to-oil weight ratio is the weight ratio of the FCC catalyst composition to the weight of hydrocarbons in a unit volume of the reaction mixture comprising the light stream 115, the middle stream 120, the hydrotreated residue stream 135, and the FCC catalyst composition. For example, the single FCC reaction zone 140 can be operated with a catalyst-to-oil weight ratio from 2:1 to 3:1, from 2:1 to 5:1, from 2:1 to 10:1, from 3:1 to 5:1, or from 5:1 to 10:1. Without being bound by theory, it is believed that a catalyst-to-oil weight ratio less than 2:1 may not provide a sufficient amount of catalyst present to catalytically crack the hydrocarbons at an economically high yield. It is believed that a catalyst-to-oil weight ratio greater than 10:1 may not be economically practical for scaling up in commercial applications.
The hydrocarbons may contact the FCC catalyst composition in the single FCC reaction zone 140 with a residence time of from 0.1 to 60 seconds. For example, the hydrocarbons may contact the FCC catalyst composition with a residence time of from 5 to 60 seconds, from 10 to 60 seconds, from 20 to 60 seconds, from 30 to 60 seconds, from 40 to 60 seconds, from 50 to 60 seconds, from 0.1 to 50 seconds, from 0.1 to 40 seconds, from 0.1 to 30 seconds, from 0.1 to 20 seconds, from 0.1 to 10 seconds, from 10 to 50 seconds, from 20 to 40 seconds, or any subset thereof. Without intending to be bound by any particular theory, it is believed that a residence time less than 0.1 seconds may not provide sufficient time for hydrocarbons to be sufficiently cracked by the FCC catalyst composition.
The hydrocarbons may contact the FCC catalyst composition in the presence of steam. For example, the ratio of hydrocarbon to FCC catalyst composition may be steam to hydrocarbons may be from 0:1 to 1:1, such as from 0:1 to 0.75:1, from 0:1 to 0.5:1, from 0:1 to 0.25:1, from 0:1 to 0.1:1, from 0:1 to 0.01:1, or any subset thereof.
The FCC catalyst composition may include one or more of a variety of fluid catalytic cracking catalysts, which may be suitable for use in the single FCC reaction zone 140 operated at high severity conditions. Examples of fluid catalytic cracking catalysts suitable for use as the FCC catalyst composition may include, without limitation, zeolites, silica-alumina catalysts, carbon monoxide burning promoter additives, bottoms cracking additives, light olefin-producing additives, other catalyst additives, or combinations of these components. Zeolites that may be used as at least a portion of the FCC catalyst composition for cracking may include, but are not limited to Y, REY, USY, RE-USY zeolites, or combinations of these. The FCC catalyst composition may also include a shaped selective catalyst additive, such as ZSM-5 zeolite crystal or other pentasil-type catalyst structures, which are often used in other FCC processes to produce light olefins and/or increase FCC gasoline octane. In one or more embodiments, the FCC catalyst composition may include a mixture of a ZSM-5 zeolite crystal and the cracking catalyst zeolite and matrix structure of a conventional FCC cracking catalyst. In one or more embodiments, the FCC catalyst composition may be a mixture of Y and ZSM-5 zeolite catalysts embedded with clay, alumina, and binder.
In one or more embodiments, at least a portion of the FCC catalyst composition may be modified to include one or more rare earth elements (15 elements of the Lanthanide series of the IUPAC Periodic Table plus scandium and yttrium), alkaline earth metals (Group 2 of the IUPAC Periodic Table), transition metals, phosphorus, fluorine, or any combination of these, which may enhance olefin yield. Transition metals may include “an element whose atom has a partially filled d sub-shell, or which can give rise to cations with an incomplete d sub-shell” [IUPAC, Compendium of Chemical Terminology, 2nd ed. (the “Gold Book”) (1997). Online corrected version: (2006—) “transition element” ]. One or more transition metals or metal oxides may also be impregnated onto the catalyst. Metals or metal oxides may include one or more metals from Groups 6-10 of the IUPAC Periodic Table. The metals or metal oxides may include one or more of molybdenum, rhenium, tungsten, or any combination of these. At least a portion of the FCC catalyst composition may be impregnated with tungsten oxide.
The FCC catalyst composition may be formed by a variety of processes. According to one embodiment, the matrix material can be mixed with a fluid such as water to form a slurry, and the zeolites can be separately mixed with a fluid such as water to form a slurry. The matrix material slurry and the zeolite slurry can be combined under stirring. Separately, another slurry can be formed by combining the binder material with a fluid such as water. The binder slurry can then be combined with the slurry containing the zeolites and matrix material to form a final slurry. The final slurry can then be dried, for example by spraying, and then calcined to produce the microparticles of the cracking catalyst.
The FCC catalyst composition can be in the form of shaped microparticles, such as microspheres. As used in the present disclosure, “microparticles” refer to particles having an average particle size of from 0.1 microns and 100 microns. The size of a microparticle refers to the maximum length of a particle from one side to another, measured along the longest distance of the microparticle. For instance, a spherically shaped microparticle has a size equal to its diameter, or a rectangular prism shaped microparticle has a maximum length equal to the hypotenuse stretching from opposite corners. In embodiments, each zeolitic component of the FCC catalyst composition can be included in each catalyst microparticle. However, in other embodiments, microparticles can be mixed, where the microparticles contain only a portion of the FCC catalyst composition. For instance, a mixture of two microparticle types may be included in the FCC catalyst composition, where one type of microparticle includes only ZSM-5, and another type of microparticle includes only the USY zeolite.
The FCC catalyst composition can be contacted with steam prior to use in the single FCC reaction zone 140. The purpose of steam treatment can be to accelerate the hydrothermal aging of the FCC catalyst composition that occurs during operation of the FCC system to obtain an equilibrium catalyst. Not intending to be bound by any particular theory, it is believed that the steam treatment can lead to the removal of aluminum from the framework leading to a decrease in the number of sites where framework hydrolysis can occur under hydrothermal and thermal conditions. This removal of aluminum results in an increased thermal and hydrothermal stability in dealuminated zeolites. The unit cell size can decrease as a result of dealumination, since the smaller SiO4 tetrahedron replaces the larger AlO4− tetrahedron. The acidity of zeolites can also be affected by dealumination through the removal of framework aluminum and the formation of extra-framework aluminum species. Dealumination may affect the acidity of the zeolites by decreasing the total acidity and increasing the acid strength of the zeolite. The total acidity can decrease because of the removal of framework aluminum, which act as Brønsted acid sites. The acid strength of the zeolite may be increased because of the removal of paired acid sites or the removal of the second coordinate next nearest neighbor aluminum. The increase in the acid strength may be caused by the charge density on the proton of the OH group being highest when there is no framework aluminum in the second coordination sphere. In embodiments, the FCC catalyst composition can be contacted with steam at a temperature greater than or equal to 800° C. for a period of 6 hours or greater prior to contacting the hydrocarbons with the FCC catalyst composition.
In embodiments, one or more supplemental feed streams can be combined with the hydrocarbons before introduction of the hydrocarbons to the FCC catalyst. The one or more supplemental feed streams may be added such that they contact the FCC catalyst simultaneously with the hydrocarbons of the light stream 115, middle stream 120, and hydrotreated residue stream 135. The supplemental feed stream may include one or more of vacuum residues, tar sands, bitumen, atmospheric residues, vacuum gas oils, demetallized oils, naphtha streams, or combinations of these.
Product Stream
Fluid catalytic cracking of the light stream 115, the middle stream 120, and the hydrotreated residue stream 135 in the single FCC reaction zone 140 may produce a product stream 145 comprising light olefins. “Light olefins” refers to compounds which include at least one carbon-carbon double bond and from two to four carbon atoms. The product stream 145 may comprise at least 15 wt. %, at least 20 wt. %, at least 25 wt. %, at least 30 wt. %, at least 35 wt. %, at least 40 wt. %, or at least 45 wt. % of light olefins.
The product stream 145 may comprise at least 2 wt. % of C2 olefins, such as ethylene. For example, the product stream 145 may comprise at least 4 wt. %, at least 6 wt. %, at least 8 wt. %, or at least 10 wt. % of C2 olefins.
The product stream 145 may comprise at least 2 wt. % of C3 olefins, such as propylene. For example, the product stream 145 may comprise at least 5 wt. %, at least 10 wt. %, at least 15 wt. %, at least 17 wt. %, or at least 20 wt. % of C3 olefins.
The product stream 145 may comprise at least 2 wt. % of C4 olefins, such as butylene. For example, the product stream 145 may comprise at least 5 wt. %, or at least 9 wt. % of C4 olefins.
The product stream 145 may comprise at least 5 wt. % of gasoline range products. For example, the product stream 145 may comprise at least 10 wt. %, at least 20 wt. %, at least 25 wt. %, or at least 29 wt. % of gasoline range products.
Fluid catalytic cracking of the light stream 115, the middle stream 120, and the hydrotreated residue stream 135 in the single FCC reaction zone 140 may convert the hydrocarbons originally found in the hydrocarbon feed 105 to other products. For example, fluid catalytic cracking of the light stream 115, the middle stream 120, and the hydrotreated residue stream 135 in the single FCC reaction zone 140 may convert at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. %, or even at least 99 wt. % of the hydrocarbons originally in the hydrocarbon feed 105 to other products, such as light olefins.
Fluid catalytic cracking of the light stream 115, the middle stream 120, and the hydrotreated residue stream 135 in the single FCC reaction zone 140 may convert a portion of the hydrocarbons originally found in the hydrocarbon feed 105 to coke. Coke is a solid residue created when oil undergoes severe oxidative and thermal breakdown. Coke may be deposited on the catalyst, the reactor surfaces, or both. In either location, coke may foul the surfaces, impeding reactions. Contacting the above streams with the catalyst may convert less than 10 wt. %, less than 8 wt. %, less than 7 wt. %, less than 6 wt. %, less than 5 wt. %, or less than 4 wt. % of the hydrocarbons originally in the hydrocarbon feed 105 to coke.
The various aspects of the present disclosure will be further clarified by the following examples. The examples are illustrative in nature and should not be understood to limit the subject matter of the present disclosure.
An Arab light crude oil with an API gravity of 33.0 and a sulfur content of 1.6 wt. % was fractionated in a distillation column to form a light stream and a heavy stream. Properties of the feed crude oil stream and the resulting fractions (based on their % composition in crude oil) are given in Table 1 below.
The residue stream from Example 1 was hydrotreated in a three-stage hydrotreater. The reaction conditions were: a weighted average bed temperature of 400° C., a pressure of 150 bar, a liquid hourly space velocity (LHSV) of 0.5 h−1, an H2/oil ratio 1200:1 (v/v), an oil flowrate of 300 ml/h, and an H2 flowrate of 360 L/h.
The first stage of the hydrotreater used a KFR-22 catalyst from Albemarle Co. to accomplish hydro-demetallization (HDM). The second stage of the hydrotreater used a KFR-33 catalyst from Albemarle Co. to accomplish hydro-desulfurization (HDS). The third stage of the hydrotreater used a KFR-70 catalyst from Albemarle Co. to accomplish hydro-dearomatization (HDA). The first, second, and third stages were discrete beds placed atop one another in a single reaction zone. The residue stream flowed downward to the first stage, then to the second stage, and then to the third stage. Properties of this hydrotreated residue stream are shown in Table 2 below.
The respective fractions of Arab light crude were cracked at the conditions presented below. A catalyst with the composition shown in Table 3 below was used in all of the reactions.
An Advanced Cracking Evaluation (ACE) unit was used to simulate a down-flow FCC reaction zone with multiple inlet points. The ACE unit emulates commercial FCC process.
Prior to each experiment, the catalyst is loaded into the reactor and heated to the desired reaction temperature. N2 gas is fed through the feed injector from the bottom to keep catalyst particles fluidized. Once the catalyst bed temperature reaches within ±2° C. of the reaction temperature, the reaction can begin. Feed is then injected for a predetermined time (time-on-stream (TOS)). The desired catalyst-to-feed ratio is obtained by controlling the feed pump. The gaseous product is routed to the liquid receiver, where C5+ hydrocarbons are condensed and the remaining gases are routed to the gas receiver. After catalyst stripping is over, the reactor is heated to 700° C., and nitrogen was replaced with air to regenerate the catalyst. During regeneration, the released gas is routed to a CO2 analyzer. Coke yield is calculated from the flue gas flow rate and CO2 concentration. The above process was repeated for each of Examples 3(A) to 3(C).
The light stream from Example 1 was combined with the hydrotreated residue stream from Example 2 and the combined stream was fed to the ACE unit. To simulate being the first feed introduced into the FCC with the most severe cracking conditions, a time-on-stream (TOS) of 75 seconds and a temperature of 675° C. was used. Fresh catalyst was steamed deactivated at 810° C. for 6 hours to resemble the equilibrium catalyst in the actual process. The steam deactivated catalyst was used in this reaction. It should be understood that TOS directly correlates with residence time.
The middle stream from example 1 was then cracked in the same reactor. To simulate the middle severity, 660° C. and 60 seconds time-on-stream TOS was used. To simulate the single FCC reaction zone, the spent catalyst from Example 3(A) was used without regeneration.
The streams of Examples 3(A) and 3(B) were combined to form a single stream. The single stream simulates the output of processing the two streams in a single FCC reaction zone.
Example 3(Combined) is a weighted average of Examples 3(A) and 3(B). Example 3(A) represented 43 wt. % of the crude oil feed to Example 1. Example 3(B) represented 54 wt. % of the crude oil feed to Example 1.
The same Arab light crude oil used in Example 3 was directly cracked in the same cracking reactor and under the same conditions as was used in Example 3(A), the most severe cracking conditions used. Specifically, the temperature was 675° and the TOS was 75 seconds.
As can be seen in Table 2, the combined yields of total light olefins from the present methods are significantly higher than the yields from the comparative methods. Additionally, each of Examples 3(A)-3(B) and Example 3(Combined) show significantly lower coke formation than the comparative example CE-1.
According to a first aspect of the present disclosure, a method of processing a hydrocarbon feed may comprise fractionating the hydrocarbon feed into a light stream, a middle stream, and a residue stream, hydrotreating the residue stream to form a hydrotreated residue stream; and feeding the light stream, middle stream, and the hydrotreated residue stream to a single Fluid Catalytic Cracking (FCC) reaction zone, thereby producing a product stream comprising light olefins. The light stream may comprise hydrocarbons boiling at less than 200° C. The middle stream may comprise hydrocarbons boiling from 200° C. to 540° C. The residue stream may comprise hydrocarbons boiling at greater than 540° C. The light stream and the hydrotreated residue streams may be exposed to more severe FCC cracking conditions than the middle stream, within the same FCC reaction zone. The single FCC reaction zone may be operated in a down-flow configuration and the single FCC reaction zone may be operated under high severity conditions.
According to a second aspect of the present disclosure, in conjunction with the first aspect, the light stream and the hydrotreated residue streams are combined before entering the single FCC reaction zone.
According to a third aspect of the present disclosure, in conjunction with any of the first or second aspects, the light stream and the hydrotreated residue streams have the same residence times and peak temperatures in the single FCC reaction zone as one another.
According to a fourth aspect of the present disclosure, in conjunction with any of the first through third aspects, the light stream and the hydrotreated residue stream have a greater residence time in the single FCC reaction zone than the middle stream.
According to a fifth aspect of the present disclosure, in conjunction with any of the first through fourth aspects, the light stream and the hydrotreated residue stream have a residence time in the single FCC reaction zone at least 0.5 seconds greater than the residence time of the middle stream.
According to a sixth aspect of the present disclosure, in conjunction with any of the first through fifth aspects, the light stream and the hydrotreated residue stream are exposed to a greater peak temperature in the single FCC reaction zone than the middle stream.
According to a seventh aspect of the present disclosure, in conjunction with any of the first through sixth aspects, the light stream and the hydrotreated residue stream are exposed to a peak temperature at least 10° C. greater than the middle stream, in the single FCC reaction zone.
According to an eighth aspect of the present disclosure, in conjunction with any of the first through seventh aspects, the residue stream is hydrotreated in a three stage hydrotreater.
According to a ninth aspect of the present disclosure, in conjunction with any of the first through eighth aspects, hydrotreating the residue stream comprises exposing the residue stream to a hydro-demetallization catalyst, a hydro-desulfurization catalyst, and a hydro-dearomatization catalyst.
According to a tenth aspect of the present disclosure, in conjunction with any of the first through ninth aspects, hydrotreating the residue stream comprises exposing the residue stream to a hydro-demetallization catalyst, then a hydro-desulfurization catalyst, and then a hydro-dearomatization catalyst.
According to an eleventh aspect of the present disclosure, in conjunction with any of the first through tenth aspects, the hydrocarbon feed is a whole crude oil.
According to a twelfth aspect of the present disclosure, in conjunction with any of the first through eleventh aspects, the hydrocarbon feed has an API gravity of from 25 to 35.
According to a thirteenth aspect of the present disclosure, in conjunction with any of the first through twelfth aspects, the light stream comprises at least 80 wt. % of hydrocarbons boiling at less than 200° C., based on the total weight of hydrocarbons in the light stream.
According to a fourteenth aspect of the present disclosure, in conjunction with any of the first through thirteenth aspects, the light stream comprises at least 90 wt. % of the hydrocarbons initially in the hydrocarbon feed which boil at a temperature of less than 200° C.
According to a fifteenth aspect of the present disclosure, in conjunction with any of the first through fourteenth aspects, the middle stream comprises at least 80 wt. % of hydrocarbons boiling from 200° C. to 540° C., based on the total weight of hydrocarbons in the middle stream.
According to a sixteenth aspect of the present disclosure, in conjunction with any of the first through fifteenth aspects, the middle stream comprises at least 90 wt. % of the hydrocarbons initially in the hydrocarbon feed which boil at a temperature from 200° C. to 540° C.
According to a seventeenth aspect of the present disclosure, in conjunction with any of the first through sixteenth aspects, the residue stream comprises at least 80 wt. % of hydrocarbons boiling at greater than 540° C., based on the total weight of hydrocarbons in the residue stream.
According to an eighteenth aspect of the present disclosure, in conjunction with any of the first through seventeenth aspects, the residue stream comprises at least 90 wt. % of the hydrocarbons initially in the hydrocarbon feed which boil at greater than 540° C.
According to a nineteenth aspect of the present disclosure, in conjunction with any of the first through eighteenth aspects, the product stream comprising light olefins comprises at least 35 wt. % of light olefins, based on the total weight of hydrocarbons in the product stream comprising light olefins.
According to a twentieth aspect of the present disclosure, in conjunction with any of the first through nineteenth aspects, the hydrocarbon feed is a whole crude oil; the residue stream is hydrotreated in a three stage hydrotreater; the light stream and the hydrotreated residue stream have a greater residence time in the single FCC reaction zone than the middle stream; the light stream and the hydrotreated residue stream are exposed to a peak temperature at least 10° C. greater than the middle stream, in the single FCC reaction zone; the light stream comprises at least 99 wt. % of hydrocarbons boiling at less than 200° C., based on the total weight of hydrocarbons in the light stream; the light stream comprises at least 99 wt. % of the hydrocarbons initially in the hydrocarbon feed which boil at a temperature of less than 200° C.; the middle stream comprises at least 99 wt. % of hydrocarbons boiling from 200° C. to 540° C., based on the total weight of hydrocarbons in the middle stream; the middle stream comprises at least 99 wt. % of the hydrocarbons initially in the hydrocarbon feed which boil at a temperature from 200° C. to 540° C.; the residue stream comprises at least 99 wt. % of hydrocarbons boiling at greater than 540° C., based on the total weight of hydrocarbons in the residue stream; and the residue stream comprises at least 99 wt. % of the hydrocarbons initially in the hydrocarbon feed which boil at greater than 540° C.
According to a twenty-first aspect of the present disclosure, in conjunction with any of the first through twenty-fifth aspects, the feed stream is an Arab Heavy, Arab Medium, Arab Light, or Arab Extra Light crude oil.
According to a twenty-second aspect of the present disclosure, in conjunction with any of the first through twenty-first aspects, the single FCC reaction zone operates at a temperature of greater than or equal to 580° C., a weight ratio of the FCC catalyst composition to the crude oil of from 2:1 to 10:1, and a residence time of from 0.1 seconds to 60 seconds,
It is noted that any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure.
It is noted that one or more of the following claims utilize the term “where” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.”
Having described the subject matter of the present disclosure in detail and by reference to specific aspects, it is noted that the various details of such aspects should not be taken to imply that these details are essential components of the aspects. Rather, the claims appended hereto should be taken as the sole representation of the breadth of the present disclosure and the corresponding scope of the various aspects described in this disclosure. Further, it will be apparent that modifications and variations are possible without departing from the scope of the appended claims.
| Number | Name | Date | Kind |
|---|---|---|---|
| 5318695 | Eberly et al. | Jun 1994 | A |
| 7019187 | Powers | Mar 2006 | B2 |
| 9096806 | Abba et al. | Aug 2015 | B2 |
| 9290705 | Bourane et al. | Mar 2016 | B2 |
| 9764314 | Al-Alloush et al. | Sep 2017 | B2 |
| 10889768 | Bourane et al. | Jan 2021 | B2 |
| 10954457 | Al-Herz et al. | Mar 2021 | B2 |
| 11230672 | Al Herz et al. | Jan 2022 | B1 |
| 20050211603 | Guillaume et al. | Sep 2005 | A1 |
| 20080223754 | Subramanian | Sep 2008 | A1 |
| 20110083996 | Shafi et al. | Apr 2011 | A1 |
| 20130248421 | Abba et al. | Sep 2013 | A1 |
| 20140275673 | Long et al. | Sep 2014 | A1 |
| 20160369189 | Ward | Dec 2016 | A1 |
| 20190316047 | Al-Majnouni et al. | Oct 2019 | A1 |
| 20210363433 | Fathi | Nov 2021 | A1 |
| Number | Date | Country |
|---|---|---|
| 1557915 | Dec 2004 | CN |
| 2009073436 | Jun 2009 | WO |
| 2010009077 | Jan 2010 | WO |
| 2010009082 | Jan 2010 | WO |
| 2010009089 | Jan 2010 | WO |
| 2013142563 | Sep 2013 | WO |
| Entry |
|---|
| Chen et al., “Novel Propylene Production Route: Utilizing Hydrotreated Shale Oil as Feedstock via Two-Stage Riser Catgalytic Cracking”, Energy & Fuels, vol. 29, pp. 7190-7195, 2015. |
| Corma et al., “Crude oil to chemicals: light olefins from crude oil”, Catalysis Science & Technology, vol. 7, pp. 12-46, 2017. |
| Usman et al., “Catalytic cracking of crude oil to light olefins and naphtha: Experimental and kinetic modeling”, Chemical Engineering Research and Design, vol. 120, pp. 121-137, 2017. |
