CROSS REFERENCE TO RELATED APPLICATIONS

[0001] None.

BACKGROUND OF THE INVENTION

A. Field of the Invention

[0002] 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 aquaprocessing, followed by steam cracking.

B. Description of Related Art

[0003] In the processing of crude oil to produce olefins and/or aromatics, multiple hydrocrackers are used for upgrading crude oil heavy ends; and steam crackers are used to maximize ethylene production. The economics of this type of processing is negatively affected by high capex, low ethylene to propylene ratio (the E/P ratio), and methane loss. 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 in hydrocrackers and subsequent maximizing of the E/P ratio in steam crackers leads to lower carbon efficiency as more methane gets produced. For crude to chemical processing plants to be viable, the economics and chemical yields of such plants have to be improved.

SUMMARY OF THE INVENTION

[0004] 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 high severity aquaprocessing of crude oil and/or heavy ends, followed by cracking at low severity. In addition, or as an alternative to, to regular crude oil feeds, plastics, plastic pyrolysis oligomers, synthetic crude oil or hydrocarbon streams from plastic pyrolysis can be co-processed. Further, bio oils can be co-processed with, or as an alternative to, crude oil in embodiments of the invention. [0005] Embodiments of the invention include a method of producing olefins and/or aromatics. The method includes flowing a hydrocarbon feed and hydrogen into an aquaprocessing unit having a catalyst disposed therein and aquaprocessing the hydrocarbon feed in the aquaprocessing unit to produce a first stream comprising gas having a boiling point in a range of up to 200 °C, a second stream having a boiling point in a range of 200 to 350 °C, and a third stream that comprises one or more of pitch, coke, or fuel oil and has a boiling point in s range of 350 to 650 °C. The aquaprocessing of the hydrocarbon feed comprises contacting the hydrocarbon feed and the hydrogen with the catalyst at a temperature in a range of 400 to 500 °C. The method further includes flowing the first stream and the second stream to a steam cracking unit; and processing the first stream and the second stream in the steam cracking unit to produce olefins and/or aromatics. The olefins include ethylene and propylene and the steam cracking unit is operated such that a mass ratio of propylene to ethylene (P/E) is 0.6 to 0.68. 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.

[0006] Embodiments of the invention include a system for producing olefins and/or aromatics. The system for producing olefins and/or aromatics includes an aquaprocessing unit having a catalyst disposed therein and adapted to contact a hydrocarbon feed and hydrogen with the catalyst at a temperature in a range of 400 to 500 °C to produce a first stream comprising gas having a boiling point in a range of up to 200 °C, a second stream having a boiling point in a range of 200 to 350 °C, and a third stream that comprises one or more of pitch, coke, or fuel oil and has a boiling point in a range of 350 to 650 °C. The system further includes a steam cracking unit in fluid communication with the aquaprocessing unit, wherein the steam cracking unit is adapted to produce olefins and/or aromatics from the first stream and the second stream.

[0007] The following includes definitions of various terms and phrases used throughout this specification. [0008] 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%.

[0009] 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).

[0010] 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.

[0011] The term “substantially” and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.

[0012] 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.

[0013] The term “effective,” as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result.

[0014] 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.”

[0015] 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. [0016] The process of the present invention can “comprise,” “consist essentially of,” or “consist of’ particular ingredients, components, compositions, etc., disclosed throughout the specification.

[0017] 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.

[0018] 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.

BRIEF DESCRIPTION OF THE DRAWINGS

[0019] For a more complete understanding, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:

[0020] FIG. 1 shows a system for producing olefins and/or aromatics, according to embodiments of the invention; and

[0021] FIG. 2 shows a method of producing olefins and/or aromatics, according to embodiments of the invention. DETAILED DESCRIPTION OF THE INVENTION

[0022] 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 the invention, the aquaprocessing unit is operated at high severity for maximum conversion to low boiler steam cracker feedstock and then operating the steam cracker at lower severity and for improved chemical yields. The products from the high severity aquaprocessing and low severity steam cracking produces high value chemicals such as olefins and/or aromatics, according to embodiments of the invention.

[0023] FIG. 1 shows system 10 for producing olefins and/or aromatics, according to embodiments of the invention. FIG. 2 shows method 20 for producing olefins and/or aromatics, according to embodiments of the invention. In embodiments of the invention, method 20 is implemented by system 10.

Systems for producing olefins and/or aromatics

[0024] FIG. 1 shows system 10 comprising separation unit 103 (e.g., a flash vessel, distillation column, and/or stripping unit), which, in embodiments of the invention is adapted to separate (a) crude oil 100 and/or (b) first heavy oil stream 101, which comprises a flash vessel, distillation column, and/or stripping unit (where (a) and (b) forms combined stream 102) to produce (1) top crude oil cut stream 104 having a boiling point in a range of up to 200 °C and (2) bottom crude oil cut stream 105 having a boiling point greater than 200 °C. According to embodiments of the invention, system 10 includes aquaprocessing unit 109, which comprises reactor unit 110 and separation unit 112. In embodiments of the invention, aquaprocessing unit 109 is adapted to receive hydrogen stream 107 and hydrocarbon feed 108 with or without water, which comprises, in embodiments of the invention, bottom crude oil cut stream 105 and second heavy oil stream 106. According to embodiments of the invention, reactor unit 110 is adapted to receive hydrocarbon feed 108 and hydrogen stream 107. Reactor unit 110, in embodiments of the invention, comprises a fixed bed reactor, has a catalyst disposed therein, and is adapted to contact hydrogen stream 107 and hydrocarbon feed 108 with the catalyst at a temperature in a range of 400 to 500 °C to produce first reactor unit effluent 111. In embodiments of the invention, separation unit 112 comprises one or more distillation columns and is adapted to receive and separate reactor unit effluent 111 to produce first stream 113, second stream 114, and third stream 115. According to embodiments of the invention, first stream 113 has a boiling point in a range of up to 200 °C, second stream 114 has a boiling point in a range of 200 to 350 °C, and third stream

115 comprises pitch/coke/fuel oil and has a boiling point in a range of 350 to 650 °C.

[0025] System 10, in embodiments of the invention, includes steam cracking unit 116 in fluid communication with separation unit 103 and aquaprocessing unit 109 such that top crude oil cut stream 104, first stream 113 and/or second stream 114 can be flowed to steam cracking unit

116 for processing to produce high value chemicals stream 117, which comprises olefins and/or aromatics.

Methods for producing olefins and/or aromatics

[0026] FIG. 2 shows method 20, in embodiments of the invention, includes block 200, which involves flowing (a) crude oil 100 and/or (b) first heavy oil stream 101, 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 to separation unit 103. And at block 201, according to embodiments of the invention, separation unit 103 separates (a) crude oil 100 and/or (b) first heavy oil stream 101 (where (a) and (b) forms combined stream 102) to produce (1) top crude oil cut stream 104 having a boiling point in a range of up to 200 °C and (2) bottom crude oil cut stream 105 having a boiling point greater than 200 °C. At block 202, in embodiments of the invention, method 20 includes flowing bottom crude oil cut stream 105 and/or second heavy oil stream 106 to aquaprocessing unit 109. In embodiments of the invention, bottom crude oil cut stream 105 and/or second heavy oil stream 106 is combined to form hydrocarbon feed 108 with or without water. And hydrogen stream 107 and hydrocarbon feed 108, at block 203, in embodiments of the invention, is flowed to reactor unit 110. At block 204, according to embodiments of the invention, reactor unit 110, which comprises one or more of: a fixed bed reactor, ebullated reactor, and slurry reactor and has a catalyst (e.g., 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/or zeolite) disposed therein, is used to contact hydrocarbon feed 108 and hydrogen stream 107 with the catalyst at a temperature in the range of 400 to 500 °C to produce reactor unit effluent 111. In embodiments of the invention, at block 205, reactor unit effluent I l l is flowed to separation unit 112. And at block 206, in embodiments of the invention, separation unit 112, which can comprise one or more distillation columns, receives and separates reactor unit effluent 111 to produce first stream 113, second stream 114, and third stream 115. According to embodiments of the invention, first stream 113 is a gas and has a boiling point in a range of up to 200 °C, second stream 114 has a boiling point in a range of 200 to 350 °C and third stream 115 comprises pitch coke and/or fuel oil and has a boiling point in a range of 350 to 650 °C.

[0027] Method 20, in embodiments of the invention, includes, at block 207, flowing top crude oil cut stream 104, first stream 113, and/or second stream 114 to steam cracking unit 116. And at block 208, embodiments of the invention involve steam cracking unit 116 processing top crude oil cut stream 104, first stream 113 and/or second stream 114 to produce high value chemicals stream 117, which comprises olefins and/or aromatics. In embodiments of the invention, the olefins produced at block 208 includes ethylene and propylene and the aromatics include benzene. According to embodiments of the invention, the processing at block 208 involves operating steam cracking unit 116 to produce propylene and ethylene such that a mass ratio of propylene to ethylene (P/E) is 0.6 to 0.68. According to embodiments of the invention, the operating conditions that provide a mass ratio of propylene to ethylene (P/E) is 0.6 to 0.68 includes a temperature in the range of 750 to 900 °C, a pressure in the range of <1 atm to 3 atmg.

[0028] Although embodiments of the present invention have been described with reference to blocks of FIG. 2 it 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 FIG. 2. Accordingly, embodiments of the invention may provide functionality as described herein using various blocks in a sequence different than that of FIG. 2.

[0029] 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. [0030] In the context of the present invention, at least the following 14 embodiments are disclosed. Embodiment 1 is a method of producing olefins and/or aromatics. The method includes flowing a hydrocarbon feed and hydrogen into an aquaprocessing unit having a catalyst disposed therein. The method further includes aquaprocessing the hydrocarbon feed in the aquaprocessing unit to produce a first stream comprising gas having a boiling point in a range of up to 200 °C, a second stream having a boiling point in a range of 200 to 350 °C, and a third stream that comprises one or more of pitch, coke, or fuel oil and has a boiling point in a range of 350 to 650 °C, wherein the aquaprocessing of the hydrocarbon feed includes contacting the hydrocarbon feed and the hydrogen with the catalyst at a temperature in a range of 400 to 500 °C. The method still further includes flowing the first stream and the second stream to a steam cracking unit. In addition, the method includes processing the first stream and the second stream in the steam cracking unit to produce olefins and/or aromatics, wherein the olefins include ethylene and propylene, wherein the steam cracking unit is operated such that a mass ratio of propylene to ethylene (P/E) is 0.6 to 0.68. Embodiment 2 is the method of embodiment 1, wherein, within the aquaprocessing unit, the contacting of the hydrocarbon feed and the hydrogen with the catalyst is carried out in a reactor unit to produce a reactor unit effluent, and the method further includes separating the reactor unit effluent in a separation unit within the aquaprocessing unit. Embodiment 3 is the method of embodiment 1, wherein operating conditions of the steam cracking unit include a temperature of 750 to 900 °C and a pressure of <1 atm to 3 atmg. Embodiment 4 is the method of embodiment 1, wherein the aquaprocessing unit includes one or more of: a fixed bed reactor, an ebullated reactor, or a slurry reactor. Embodiment 5 is the method of embodiment 1, wherein the hydrocarbon feed comprises one or more of the following with or without water: crude oil, plastics, oligomers from plastic pyrolysis, synthetic crude oil, bottom crude oil cut, bio oil, and hydrocarbons from plastics pyrolysis. Embodiment 6 is the method of embodiment 5, wherein the hydrocarbon feed comprises a bottom crude oil cut stream and the method further includes separating 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 7 is the method of embodiment 6, further including processing the top crude oil cut stream in the steam cracking unit to produce olefins and/or aromatics. Embodiment 8 is the method of embodiment 1, wherein the catalyst 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. [0031] Embodiment 9 is a system for producing olefins and/or aromatics. The system includes an aquaprocessing unit having a catalyst disposed therein and adapted to contact a hydrocarbon feed and hydrogen with the catalyst at a temperature in a range of 400 to 500 °C to produce a first stream comprising gas having a boiling point in a range of up to 200 °C, a second stream having a boiling point in a range of 200 to 350 °C, and a third stream that comprises one or more of pitch, coke, or fuel oil and has a boiling point in a range of 350 to 650 °C. The method further includes a steam cracking unit in fluid communication with the aquaprocessing unit, the steam cracking unit adapted to produce olefins and/or aromatics from the first stream and the second stream. Embodiment 10 is the system of embodiment 9, wherein the aquaprocessing unit includes one or more of: a fixed bed reactor, an ebullated reactor, or a slurry reactor. Embodiment 11 is the system of embodiment 9 further including a separation unit adapted to separate crude oil to produce at least a portion of a bottom crude oil cut stream that is included in the hydrocarbon feed to the aquaprocessing unit. Embodiment 12 is the system of embodiment 9, wherein the separation 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 200 °C from the separation unit to the steam cracking unit. Embodiment 13 is the system of embodiment 9, wherein the aquaprocessing unit is adapted to produce diesel. Embodiment 14 is the system of embodiment 9, wherein the aquaprocessing unit includes one or more distillation columns.

[0032] All embodiments described above and herein can be combined in any manner unless expressly excluded.

[0033] 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.