Systems and Methods of Producing Olefins And/Or Aromatics by Low and Medium Severity Aquaprocessing Followed by High Severity Aquaprocessing and Steam Cracking

None.

The present invention generally relates to the production of olefins and/or aromatics. More specifically, the present invention relates to the production of olefins and/or aromatics from crude oil and/or heavy oil by two stages of aquaprocessing, followed by steam cracking.

In the processing of crude oil to produce olefins and aromatics, slurry and ebullated bed hydrocrackers are used for conversion of bottom of the barrel of crude oil (i.e., crude oil fractions with highest boiling points of the crude). Lighter fractions of crude oil in the vacuum gas oil range are independently sent through fixed bed hydrocrackers. Investments in crude to chemicals plants are very high; and this is driven, at least in part, by the high cost of steam crackers and hydrocrackers. High conversion of crude oil streams lends to coke build up in fixed bed hydrocrackers leading to less time on stream. On the other hand, slurry and ebullated bed reactors, which can handle coke, are more costly.

The present inventors have discovered a solution to one or more of the problems described above. The solution, according to embodiments of the invention, involves producing olefins and/or aromatics by aquaprocessing of crude oil and/or heavy ends in two stages, followed by cracking. According to embodiments of the invention, fixed bed hydroprocessing units are less costly than slurry reactors and thus it is advantageous that a majority of the flow goes through the fixed bed hydroprocessing while a sub-stream only goes through the more costly slurry/ebullated bed reactor. In addition to, or as an alternative to, regular crude oil feeds, plastics, plastic pyrolysis oligomers, synthetic crude oil and/or hydrocarbon streams from plastic pyrolysis can be co-processed, in embodiments of the invention. Further, bio oils can be co-processed with, or as an alternative to, crude oil, in embodiments of the invention.

Embodiments of the invention include a method of producing olefins and/or aromatics. The method comprises flowing a hydrocarbon feed into a first aquaprocessing unit having a first catalyst disposed therein and aquaprocessing the hydrocarbon feed in the first aquaprocessing unit to produce a first top stream having a boiling point in a range of up to 200° C. and a first bottom stream that comprises diesel and/or fuel oil and has a boiling point in a range of 305 to 650° C. The aquaprocessing of the hydrocarbon feed comprises contacting the hydrocarbon feed with the first catalyst at a temperature in a range of 280 to 400° C. The method further includes flowing the first bottom stream into a second aquaprocessing unit having a second catalyst disposed therein and aquaprocessing the first bottom stream in the second aquaprocessing unit to produce a second top stream having a boiling point in the range of up to 305° C. and a second bottom stream that comprises one or more of pitch, coke, and fuel oil and has a boiling point in a range of 305 to 650° C. The aquaprocessing of the first bottom stream comprises contacting the first bottom stream with the catalyst at a temperature in a range of 400 to 500° C. The method also includes processing the second top stream in a steam cracking unit to produce olefins and/or aromatics. Aquaprocessing is the hydrocracking of hydrocarbons in the presence of (a) one or more catalysts and (b) a solvent to keep asphaltenes dissolved, at a temperature in the range of 280 to 550° C. and a pressure in the range of 40 to 200 barg. In embodiments of the invention, the aquaprocessing conditions can include a hydrogen to hydrocarbon ratio from 200 to 2000 NL/L of liquid feed and the aquaprocessing can be carried out with or without added steam.

Embodiments of the invention include a system for producing olefins and/or aromatics. The system comprises a first aquaprocessing unit having a first catalyst disposed therein and adapted to contact a hydrocarbon feed with the first catalyst at a temperature in the range of 280 to 400° C. and to produce a first top stream having a boiling point in a range of up to 200° C. and a first bottom stream that comprises diesel and/or fuel oil and that has a boiling point in a range of 305 to 650° C. The system also includes a second aquaprocessing unit that has a second catalyst disposed therein and that is in fluid communication with the first aquaprocessing unit. The second aquaprocessing unit is adapted to contact the first bottom stream with the second catalyst at a temperature in a range of 400 to 500° C. and to produce a second top stream having a boiling point in a range of up to 305° C. and a second bottom stream that comprises one or more of pitch, coke, or fuel oil and that has a boiling point in a range of 305 to 650° C. The system further includes a steam cracking unit in fluid communication with the first aquaprocessing unit and the second aquaprocessing unit. And the steam cracking unit is adapted to produce olefins and/or aromatics from the first top stream and the second top stream.

The following includes definitions of various terms and phrases used throughout this specification.

The terms “about” or “approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment the terms are defined to be within 10%, preferably, within 5%, more preferably, within 1%, and most preferably, within 0.5%.

For the purposes of this disclosure, “X, Y, and/or Z” can be construed as X only, Y only, Z only, or any combination of two or more items X, Y, and Z (e.g., XYZ, XY, XZ, YZ).

The terms “wt. %”, “vol. %” or “mol. %” refer to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or the total moles of material that includes the component. In a non-limiting example, 10 moles of component in 100 moles of the material is 10 mol. % of component.

The term “substantially” and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.

The terms “inhibiting” or “reducing” or “preventing” or “avoiding” or any variation of these terms, when used in the claims and/or the specification, include any measurable decrease or complete inhibition to achieve a desired result.

The term “effective,” as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.

The use of the words “a” or “an” when used in conjunction with the term “comprising,” “including,” “containing,” or “having” in the claims or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”

The words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

The process of the present invention can “comprise,” “consist essentially of,” or “consist of” particular ingredients, components, compositions, etc., disclosed throughout the specification.

The term “primarily,” as that term is used in the specification and/or claims, means greater than any of 50 wt. %, 50 mol. %, and 50 vol. %. For example, “primarily” may include 50.1 wt. % to 100 wt. % and all values and ranges there between, 50.1 mol. % to 100 mol. % and all values and ranges there between, or 50.1 vol. % to 100 vol. % and all values and ranges there between.

Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein.

Embodiments of the invention disclosed herein involves an intensified upgrading process—aquaprocessing—of crude oil heavy ends. And such aquaprocessing can replace multiple convential hydrocrackers in a crude oil to chemicals plant. According to embodiments of this invention, the aquaprocessing is carried out in two stages. The first stage, in embodiments of the invention, is carried out in a first aquaprocessing unit operated at low or medium severity to avoid coking and pressure drop issues that occur in fixed bed units and processes that have a longer time on stream. The heavier product cut from the first stage, according to embodiments of the invention, is converted in the second stage, which is carried out by a second aquaprocessing unit operated under more severe conditions than the first aquaprocessing unit. In embodiments of the invention, the second aquaprocessing unit includes one or more ebullated/slurry reactors and the more severe conditions maximize conversion and avoid pressure drop issues caused by higher conversion. The products from the first aquaprocessing unit and the second aquaprocessing unit are converted in a steam cracking unit to produce to high value chemicals such as olefins and/or aromatics, according to embodiments of the invention.

shows systemfor producing olefins and/or aromatics, according to embodiments of the invention.shows methodfor producing olefins and/or aromatics, according to embodiments of the invention. In embodiments of the invention, methodis implemented using system.

Systems for Producing Olefins and/or Aromatics

shows systemcomprising separation unit(e.g., a flash vessel, distillation column, and/or stripping unit), which, in embodiments of the invention is adapted to separate (a) crude oiland/or (b) first heavy oil stream, which comprises any combination of crude oil, plastics, hydrocarbons from plastics pyrolysis, bio oil, hydrogenated bio oils, oligomers from plastics, synthetic crude oil and pyrolysis oils derived from plastic, bottom cut of crude oil cut, pyrolysis oils, and heavy residues from steam crackers (where (a) and (b) forms combined feed stream) to produce (1) top crude oil cut streamhaving a boiling point in a range of up to 200° C. and (2) bottom crude oil cut stream, having a boiling point greater than 200° C. In embodiments of the invention, separation unitcan comprise one or more of the following: a flash vessel, a distillation column, and/or a stripping unit. According to embodiments of the invention, systemincludes first aquaprocessing unit, which comprises first reactor unitand first separation unit. In embodiments of the invention, first aquaprocessing unitis adapted to receive hydrogen streamand hydrocarbon feed, which comprises, in embodiments of the invention, bottom crude oil cut streamand second heavy oil stream, recycle pyrolysis oil from steam cracker and optionally water. According to embodiments of the invention, first reactor unitis adapted to receive hydrocarbon feedand hydrogen stream. First reactor unit, in embodiments of the invention, comprises a fixed bed reactor, has a first catalyst disposed therein, and is adapted to contact hydrogen streamand hydrocarbon feedwith the first catalyst at a temperature in a range of 280 to 400° C. to produce first reactor unit effluent. In embodiments of the invention, first separation unitcomprises one or more distillation columns and is adapted to receive and separate first reactor unit effluentto produce first top stream, intermediate stream, and first bottom stream. According to embodiments of the invention, first top streamhas a boiling point in a range of up to 200° C., intermediate streamhas a boiling point in a range of 200 to 305° C., and first bottom streamcomprises diesel and/or fuel oil and has a boiling point in a range of 305 to 650° C.

According to embodiments of the invention, systemfurther comprises second aquaprocessing unit, which comprises second reactor unitand second separation unit. According to embodiments of the invention, second reactor unitis in fluid communication with first aquaprocessing unitand is adapted to receive first bottom stream. Second reactor unit, in embodiments of the invention, comprises an ebullated reactor and/or a slurry reactor, has a second catalyst disposed therein, and is adapted to contact first bottom streamwith the second catalyst at a temperature in the range of 400 to 500° C. to produce second reactor unit effluent. In embodiments of the invention, second separation unitcomprises one or more distillation columns and is adapted to receive and separate second reactor unit effluentto produce second top streamand second bottom stream. According to embodiments of the invention, second top streamhas a boiling point in a range of up to 305° C. and second bottom streamcomprises one or more of pitch, coke, or fuel oil and has a boiling point in a range of 305 to 650° C.

System, in embodiments of the invention, includes steam cracking unitis in fluid communication with separation unit, first aquaprocessing unit, and second aquaprocessing unitsuch that top crude oil cut stream, first top stream, intermediate stream, and/or second top streamcan be flowed to steam cracking unitfor processing to produce high value chemicals streamthat comprises olefins and/or aromatics.

Methods for producing olefins and/or aromatics

shows method, in embodiments of the invention, includes block, which involves flowing (a) crude oiland/or (b) first heavy oil stream, comprising any combination of crude oil, plastics, hydrocarbons from plastics pyrolysis, bio oil, hydrogenated bio oils, oligomers from plastics, synthetic crude oil and pyrolysis oils derived from plastic, bottom cut of crude oil cut, pyrolysis oils, and heavy residues from steam crackers (where (a) and (b) forms combined feed stream) to separation unit. And at block, according to embodiments of the invention, separation unitseparates (a) crude oiland/or (b) first heavy oil streamto produce (1) top crude oil cut streamhaving a boiling point in a range of up to 200° C. and (2) bottom crude oil cut stream, having a boiling point greater than 200° C. At block, in embodiments of the invention, methodincludes flowing bottom crude oil cut streamand/or second heavy oil streamto first aquaprocessing unit. In embodiments of the invention, bottom crude oil cut streamand/or second heavy oil streamis combined to form hydrocarbon feed. And in embodiments of the invention, at block, hydrogen streamand hydrocarbon feed, optionally water and recycle pyrolysis oil from steam cracker is flowed to first reactor unit. At block, according to embodiments of the invention, first reactor unit, which comprises a fixed bed reactor and has a first catalyst (e.g., fixed bed hydrocracking commercial catalysts with high activity: a catalyst that comprises one or more of the following: an organometallic compound having one or more of Ni, Mo, Co, W, Zr; NiMo; NiCoMo; NiMoW; alumina; and zeolite) disposed therein, is used to contact hydrocarbon feedand hydrogen stream, optionally water and recycle pyrolysis oil from steam cracker with the first catalyst at a temperature in a range of 280 to 400° C. to produce first reactor unit effluent. In embodiments of the invention, at block, first reactor unit effluentis flowed to first separation unit. And at block, in embodiments of the invention, first separation unit, which can comprise one or more distillation columns, receives and separates first reactor unit effluentto produce first top stream, intermediate stream, and first bottom stream. According to embodiments of the invention, first top streamhas a boiling point in a range of up to 200° C., intermediate streamhas a boiling point in a range of 200 to 305° C., and first bottom streamcomprises diesel and/or fuel oil and has a boiling point in a range of 305 to 650° C.

According to embodiments of the invention, methodfurther comprises, at block, flowing first bottom streaminto second aquaprocessing unit, which comprises second reactor unitand second separation unit. At block, according to embodiments of the invention, second reactor unit, which comprises an ebullated reactor and/or a slurry reactor and has a second catalyst (e.g., fixed bed hydrocracking commercial catalysts with high activity: a catalyst that comprises one or more of the following: an organometallic compound having one or more of Ni, Mo, Co, W, Zr; NiMo; NiCoMo; NiMoW; alumina; and zeolite) disposed therein, is used to contact first bottom streamwith hydrogen, optional water and recycle pyrolysis oil from steam crackers with the second catalyst at a temperature in the range of 400 to 500° C. to produce second reactor unit effluent. In embodiments of the invention, at block, second reactor unit effluentis flowed to second separation unit. And at block, according to embodiments of the invention, second separation unit, which can comprise one or more distillation columns, receives and separates second reactor unit effluentto produce second top streamand second bottom stream. According to embodiments of the invention, second top streamhas a boiling point in the range of up to 305° C. and second bottom streamcomprises one or more of pitch, coke, or fuel oil and has a boiling point in a range of 305 to 650° C.

Method, in embodiments of the invention, includes, at block, flowing top crude oil cut stream, first top stream, intermediate stream, and/or second top streamto steam cracking unit. And at block, embodiments of the invention involve steam cracking unitprocessing top crude oil cut stream, first top stream, intermediate stream, and/or second top streamto produce high value chemicals stream, which comprises olefins and/or aromatics. In embodiments of the invention, the olefins produced at blockincludes ethylene, propylene, butenes, butadienes, and the aromatics include benzene, toluene, xylene, and ethyl benzene.

Although embodiments of the present invention have been described with reference to blocks ofit should be appreciated that operation of the present invention is not limited to the particular blocks and/or the particular order of the blocks illustrated in. Accordingly, embodiments of the invention may provide functionality as described herein using various blocks in a sequence different than that of.

The systems and processes described herein can also include various equipment that is not shown and is known to one of skill in the art of chemical processing. For example, some controllers, piping, computers, valves, pumps, heaters, thermocouples, pressure indicators, mixers, heat exchangers, and the like may not be shown.

In the context of the present invention, at least the following 23 embodiments are disclosed. Embodiment 1 is a method of producing olefins and/or aromatics. The method includes flowing a hydrocarbon feed and hydrogen, along with optional water and recycle pyrolysis oil from steam cracker into a first aquaprocessing unit having a first catalyst disposed therein. The method further includes aquaprocessing the hydrocarbon feed in the first aquaprocessing unit to produce a first top stream having a boiling point in a range of up to 200° C. and a first bottom stream that includes diesel and/or fuel oil and has a boiling point in a range of 305 to 650° C., wherein the aquaprocessing of the hydrocarbon feed includes contacting the hydrocarbon feed and the hydrogen with the first catalyst at a temperature in a range of 280 to 400° C. The method still further includes flowing the first bottom stream into a second aquaprocessing unit having a second catalyst disposed therein. In addition, the method includes aquaprocessing the first bottom stream along with hydrogen, optional water and recycle pyrolysis oil in the second aquaprocessing unit to produce a second top stream having a boiling point in a range of up to 305° C. and a second bottom stream that comprises one or more of pitch, coke, or fuel oil and has a boiling point in a range of 305 to 650° C., wherein the aquaprocessing of the first bottom stream includes contacting the first bottom steam with the second catalyst at a temperature in a range of 400 to 500° C. The method also includes processing the second top stream in a steam cracking unit to produce olefins and/or aromatics. Embodiment 2 is the method of embodiment 1, wherein, within the first aquaprocessing unit, the contacting of the hydrocarbon feed and hydrogen with the first catalyst is carried out in a first reactor unit to produce a first reactor unit effluent, and the method further includes separating the first reactor unit effluent in a first separation unit within the first aquaprocessing unit. Embodiment 3 is the method of embodiment 1, wherein, within the second aquaprocessing unit, the contacting of the first bottom stream with the second catalyst is carried out in a second reactor unit to produce a second reactor unit effluent, and the method further includes separating the second reactor unit effluent in a second separation unit within the second aquaprocessing unit. Embodiment 4 is the method of embodiment 1, wherein the olefins comprise ethylene and/or propylene and the aromatics comprise benzene. Embodiment 5 is the method of embodiment 1, wherein the first aquaprocessing unit includes a fixed bed reactor. Embodiment 6 is the method of embodiment 1, wherein the second aquaprocessing unit includes an ebullated reactor and/or a slurry reactor. Embodiment 7 is the method of embodiment 1, wherein the hydrocarbon feed comprises one or more of the following: crude oil, plastics, oligomers from plastic pyrolysis, synthetic crude oil, bottom crude oil cut, bio oil, and hydrocarbons from plastics pyrolysis. Embodiment 8 is the method of embodiment 7, wherein the hydrocarbon feed comprises a bottom crude oil cut stream and the method further includes distilling crude oil in a separation unit to produce the bottom crude oil cut stream and a top crude oil cut stream having a boiling point in a range of up to 200° C. Embodiment 9 is the method of embodiment 8, further including processing the top crude oil cut stream in the steam cracking unit to produce olefins. Embodiment 10 is the method of embodiment 1, further including processing the first top stream in the steam cracking unit to produce olefins. Embodiment 11 is the method of embodiment 1, further including withdrawing an intermediate stream from the first aquaprocessing unit, the intermediate stream having a boiling point in a range of 200 to 305° C., and processing the intermediate stream in the steam cracking unit to produce olefins. Embodiment 12 is the method of embodiment 1,wherein the first catalyst comprises one or more of: an organometallic compound having one or more of Ni, Mo, Co, W, Zr; NiMo; NiCoMo; NiMoW; alumina and/or zeolite. Embodiment 13 is the method of embodiment 1, wherein the second catalyst comprises particulate hydrocracking catalyst with or without dissolved catalyst.

Embodiment 14 is a system for producing olefins and/or aromatics. The system includes a first aquaprocessing unit having a first catalyst disposed therein and adapted to contact a hydrocarbon feed and hydrogen with the first catalyst at a temperature in a range of 280 to 400° C. and to produce a first top stream having a boiling point in a range of up to 305° C. or less and a first bottom stream that comprises diesel and/or fuel oil and has a boiling point in a range of 305 to 650° C. The system further includes a second aquaprocessing unit having a second catalyst disposed therein and in fluid communication with the first aquaprocessing unit, the second aquaprocessing unit adapted to contact the first bottom stream with the second catalyst at a temperature in a range of 400 to 500° C. and to produce a second top stream having a boiling point in a range of up to 305° C. and a second bottom stream that comprises one or more of pitch, coke, or fuel oil and has a boiling point in a range of 305 to 650° C. The method still further includes a steam cracking unit in fluid communication with the first aquaprocessing unit and the second aquaprocessing unit, the steam cracking unit adapted to produce olefins and/or aromatics from the first top stream and the second top stream. Embodiment 15 is the system of embodiment 14, wherein the first aquaprocessing unit includes a fixed bed reactor. Embodiment 16 is the system of embodiment 14, wherein the second aquaprocessing unit includes an ebullated reactor and/or a slurry reactor. Embodiment 17 to 20 is the system of embodiment 14 further including a separation unit (a flash vessel, a distillation column, and/or a stripping unit) adapted to separate crude oil to produce a bottom crude oil cut stream that is included in the hydrocarbon feed to the first aquaprocessing unit. Embodiment 18 is the system of embodiment 14, wherein the separation unit is a flash vessel in fluid communication with the steam cracking unit and the system is adapted to flow a top crude oil cut stream having a boiling point in a range of up to 200° C. from the separation unitto the steam cracking unit. Embodiment 19 is The system of claim 17, wherein the separation unit is a distillation column in fluid communication with the steam cracking unit and the system is adapted to flow a top crude oil cut stream having a boiling point in a range of up to 220° C. from the distillation column to the steam cracking unit. Embodiment 20 is the system of claim 17, wherein the separation unit is a stripping unit where the top crude oil cut is separated by use of a stripping gas with the stripping gas being hydrogen, saturated gases C1 to C4. The stripping unit is in fluid communication with the steam cracking unit and the system is adapted to flow a top crude oil cut stream having a boiling point in a range of up to 220° C. from the stripping unit to the steam cracking unit. Embodiment 21 is the system of embodiment 14, wherein the first aquaprocessing unit includes one or more distillation columns. Embodiment 22 is the system of embodiment 14, wherein the second aquaprocessing unit includes one or more distillation columns. Embodiment 23 is the system of embodiment 14, wherein pyrolysis oil recycled from steam cracker is preferentially routed to second aquaprocessing unit as compared to first aquaprocessing unit. This is because the second aquaprocessng unit operates at higher severity and conversion over the first unit and as a result, it is required to reduce asphaltene/coke aggregation.

All embodiments described above and herein can be combined in any manner unless expressly excluded.

Although embodiments of the present application and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the embodiments as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the above disclosure, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.