WO2017089938A1 - Methods for generating c2-c3 and aliphatic hydrocarbons - Google Patents

Methods for generating c2-c3 and aliphatic hydrocarbons Download PDF

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Publication number
WO2017089938A1
WO2017089938A1 PCT/IB2016/056972 IB2016056972W WO2017089938A1 WO 2017089938 A1 WO2017089938 A1 WO 2017089938A1 IB 2016056972 W IB2016056972 W IB 2016056972W WO 2017089938 A1 WO2017089938 A1 WO 2017089938A1
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Prior art keywords
hydrocarbons
hydrogenation
catalyst
reaction chamber
converting
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PCT/IB2016/056972
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French (fr)
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Aghaddin Mamedov
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Sabic Global Technologies B.V.
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/14—Inorganic carriers the catalyst containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals

Definitions

  • the presently disclosed subject matter relates to methods for producing C2-C3 hydrocarbon streams.
  • Olefins refer to any unsaturated hydrocarbon chain that contains at least one carbon-carbon double bond.
  • Light olefins in particular ethylene and propylene, are used in the production of plastics and petrochemicals. Olefins are produced via certain processes, including the conversion of methanol to olefins (MTO), the conversion of syngas to olefins, and most commonly steam cracking. During such methods, productivity of olefin production can be less than optimal due to the large amount of heavy hydrocarbons i.e., C4- C10 hydrocarbons that are produced as by-products.
  • the C4-C10 hydrocarbons that are produced as by-products may be converted into light hydrocarbon cracking feed. This can be done via hydrogenolysis/hydrocracking, where hydrogen is added to the heavy hydrocarbons to lyse carbon-carbon bonds and convert them to lighter hydrocarbons.
  • U.S. Patent No. 4,140,621 discloses a method of converting C4-C7 hydrocarbons into C2-C3 hydrocarbons via hydrogenolysis in the presence of an alumina carrier catalyst, where the hydrogenolysis reaction is conducted separately from the hydrogenation of olefinic hydrocarbon feed.
  • U.S. Patent No. 4,247,386 discloses a method of converting C5+ hydrocarbons to C2-C3 hydrocarbons via hydrocracking in the presence of a palladium catalyst.
  • G.B. Patent No. 1,016,033 discloses a method of converting C2-C7 hydrocarbons into methane in the presence of a Pt/Al 2 0 3 catalyst.
  • the presently disclosed subject matter provides methods for producing C2-C3 hydrocarbons from C4-C10 hydrocarbon streams.
  • the presently disclosed subject matter provides methods for producing C2-C3 hydrocarbons and for producing aliphatic hydrocarbons from the C2-C3 hydrocarbons.
  • an example method can include using hydrogenolysis to convert C4-C10 hydrocarbons to C2-C3 cracking feed, while simultaneously using hydrogenation to convert olefinic fragments to lower molecular weight aliphatic hydrocarbons.
  • a method for producing C2-C3 hydrocarbon feedstock from C4-C10 hydrocarbons can include using a single reaction chamber that uses one or more hydrogenolytic catalyst and one or more hydrogenation catalyst. The method can further include feeding C4-C10 hydrocarbons and C2-C3 olefin fragments to the reaction chamber. The method can further include converting the C4-C10 hydrocarbons to C2-C3 hydrocarbons via hydrogenolysis.
  • the method can further include converting the C2-C3 olefin fragments to light aliphatic hydrocarbons via hydrogenation.
  • the hydrogenolysis and hydrogenation reactions can occur concurrently.
  • the hydrogenolysis and hydrogenation reactions can take place at a temperature of at least about 550 °C.
  • the one or more hydrogenolytic catalyst can be different than the one or more hydrogenation catalyst.
  • the reaction can take place in a fixed bed adiabatic reactor.
  • an exemplary method can include a single reaction chamber that uses one or more hydrogenolytic catalyst and one or more hydrogenation catalyst.
  • the method can further include feeding C4-C10 by-product hydrocarbons and C2- C3 olefin fragments to the reaction chamber.
  • the method can further include converting the C4-C10 hydrocarbons to a C2-C3 hydrocarbon feedstock via hydrogenolysis.
  • the method can further include converting the C2-C3 olefin fragments to light aliphatic hydrocarbons feedstock via hydrogenation.
  • the method can further include directing the C2-C3 hydrocarbon feedstock and light aliphatic hydrocarbons feedstock back to the naphtha steam cracking process.
  • the hydrogenolysis and hydrogenation reactions can occur concurrently. In certain embodiments, the hydrogenolysis and hydrogenation reactions can take place at a temperature between about 550 °C and about 600 °C. In certain embodiments, the one or more hydrogenolytic catalysts can be different than the one or more hydrogenation catalysts. In certain embodiments, the reaction can take place in a fixed bed adiabatic reactor.
  • the method can further include converting any C0 2 which may exist as a by- product of the olefins production process to hydrocarbons via hydrogenation.
  • FIG. 1 is a schematic diagram depicting an exemplary method in accordance with one non-limiting embodiment of the disclosed subject matter.
  • FIG. 2 is a schematic diagram depicting an exemplary method in accordance with one non-limiting embodiment of the disclosed subject matter.
  • the presently disclosed subject matter provides methods for producing C2-C3 hydrocarbon feedstock from C4-C10 hydrocarbons.
  • the methods of the present disclosure can be used to produce hydrocarbon feedstock that can be recycled in a naphtha steam cracking process.
  • FIG. 1 is a schematic representation of a non-limiting exemplary method according to the disclosed subject matter.
  • the method 100 can include providing a reaction chamber with one or more hydrogenolytic catalysts, and one or more hydrogenation catalysts, 101.
  • the method 100 can further include feeding C4-C10 hydrocarbons and C2-C3 olefin fragments to a reaction chamber, 102.
  • the method can further include hydrogenolysis of a C4-C10 hydrocarbon stream to produce C2-C3 hydrocarbons in the presence of one or more hydrogenolytic catalysts, 103.
  • the hydrogenolysis of the C4-C10 hydrocarbon stream can include the following reaction:
  • C4-C10 hydrocarbons such as, but not limited to octane, can be added to hydrogen to produce ethane and/or propane.
  • the method can further include hydrogenation of olefin fragments to low molecular weight aliphatic hydrocarbons in the presence of one or more hydrogenation catalysts, 104.
  • the hydrogenolytic catalyst and the hydrogenation catalyst can be within the same reaction chamber.
  • the hydrogenolysis process, 103, and hydrogenation process, 104 can occur concomitantly.
  • the hydrogenation can occur at the same conditions as the hydrogenolysis reaction and within the same reaction chamber as the hydrogenolysis reaction.
  • the reaction can take place in a conventional fixed bed adiabatic reactor.
  • the temperature of the hydrogenolysis of the C4-C10 hydrocarbon feed stream to C2-C3 hydrocarbons can be about 500 °C to about 650 °C, e.g., 550 °C to about 600 °C.
  • the one or more hydrogenolytic catalysts can be different from the one or more hydrogenation catalysts.
  • the hydrogenolytic catalyst can include Pt based on a support.
  • the catalyst support can be alumina.
  • the hydrogenation catalyst can include a Mo based catalyst.
  • the hydrogenation catalyst can be MoS 2 .
  • the C4-C10 hydrocarbon feedstream may be a byproduct of olefins production processes.
  • the C4- C10 hydrocarbon feedstream can be a by-product of naphtha cracking.
  • the C4- C10 hydrocarbon feed stream can be a by-product of a methanol to olefins process or a syngas to olefins process.
  • the C4-C10 hydrocarbon stream can contain butane, pentane, hexane, heptane, octane, xylene, benzene, toluene, butylene, and propylene, as well as H 2 0, C0 2 .
  • the C2-C3 hydrocarbons that can be produced by hydrogenolysis of the C4-C10 hydrocarbon stream can include ethane, propane, ethylene and/or propylene.
  • FIG. 2 is a schematic representation of a non-limiting exemplary method according to the disclosed subject matter.
  • the method 200 can include a method of efficiently producing olefins during a naphtha steam cracking process where the amount of naphtha cracking feed consumed is lowered.
  • the method 200 can include providing a reaction chamber the includes one or more hydrogenolytic catalyst and one or more hydrogenation catalyst, 201.
  • the one or more hydrogenolytic catalysts can be different from the one or more hydrogenation catalysts.
  • the hydrogenolytic catalyst can include Pt based on a support.
  • the catalyst support can be alumina.
  • the hydrogenation catalyst can include a Mo based catalyst.
  • the hydrogenation catalyst can be MoS 2 .
  • the method 200 can further include feeding a C4-C10 hydrocarbon feedstream and a C2-C3 olefins stream to a reaction chamber, 202.
  • the C4-C10 hydrocarbon feedstream may be a by-product of olefins production processes.
  • the C4-C10 hydrocarbon feedstream can be a by-product of naphtha cracking.
  • the C4-C10 hydrocarbon feed stream can be a by-product of a methanol to olefins process or a syngas to olefins process.
  • the C4-C10 hydrocarbon stream can contain butane, pentane, hexane, heptane, octane, xylene, benzene, toluene, butylene, and propylene, as well as H 2 0, C0 2 .
  • the method 200 can further include converting the C4- C10 hydrocarbon feedstream to a C2-C3 hydrocarbon feedstock via hydrogenolysis, i.e., hydrocracking, 203.
  • the temperature of the hydrogenolysis of the C4-C10 hydrocarbon feed stream can be about 550 °C to about 600 °C.
  • the method 200 can further include converting the C2- C3 olefin fragments to a C2-C3 aliphatic hydrocarbon feedstock via hydrogenation, 204.
  • the hydrogenolysis of C4-C10 hydrocarbons to C2-C3 hydrocarbons and the hydrogenation of olefin fragments to low molecular aliphatic hydrocarbons can occur concurrently in the single reaction chamber.
  • the reaction can take place in a conventional fixed bed adiabatic reactor.
  • the method 200 can further include directing the C2-C3 hydrocarbon feedstock and low molecular aliphatic feedstock back to the naphtha steam cracking process, 205.
  • the methods 100 and 200 can further include converting C0 2 which may exist as a by-product of the olefins production process to hydrocarbons via hydrogenation.
  • the hydrogenation of by-product CO 2 can include the following reaction:
  • the term “about” or “approximately” means within an acceptable error range for the particular value as determined by one of ordinary skill in the art, which will depend in part on how the value is measured or determined, i.e., the limitations of the measurement system. For example, “about” can mean a range of up to 20%, up to 10%, up to 5% and/or up to 1% of a given value.

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Abstract

The presently disclosed subject matter provides methods of producing C2-C3 hydrocarbon feedstock from C4-C10 hydrocarbons. In a non-limiting embodiment, the method can include using hydrogenolysis to convert C4-C10 hydrocarbons to C2-C3 cracking feed, while simultaneously using hydrogenation to convert olefinic fragments to lower molecular weight aliphatic hydrocarbons.

Description

METHODS FOR GENERATING C2-C3 AND ALIPHATIC HYDROCARBONS
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to and the benefit of U.S. Provisional Application No. 62/259,132, filed November 24, 2015. The contents of the referenced application are incorporated into the present application by reference.
FIELD
[0002] The presently disclosed subject matter relates to methods for producing C2-C3 hydrocarbon streams.
BACKGROUND
[0003] Olefins, or alkenes, refer to any unsaturated hydrocarbon chain that contains at least one carbon-carbon double bond. Light olefins, in particular ethylene and propylene, are used in the production of plastics and petrochemicals. Olefins are produced via certain processes, including the conversion of methanol to olefins (MTO), the conversion of syngas to olefins, and most commonly steam cracking. During such methods, productivity of olefin production can be less than optimal due to the large amount of heavy hydrocarbons i.e., C4- C10 hydrocarbons that are produced as by-products. In order to increase efficiency of olefins production, the C4-C10 hydrocarbons that are produced as by-products may be converted into light hydrocarbon cracking feed. This can be done via hydrogenolysis/hydrocracking, where hydrogen is added to the heavy hydrocarbons to lyse carbon-carbon bonds and convert them to lighter hydrocarbons.
[0004] Certain methods for converting heavy hydrocarbons to lighter hydrocarbons via hydrogenolysis exist in the art. U.S. Patent No. 4,140,621 discloses a method of converting C4-C7 hydrocarbons into C2-C3 hydrocarbons via hydrogenolysis in the presence of an alumina carrier catalyst, where the hydrogenolysis reaction is conducted separately from the hydrogenation of olefinic hydrocarbon feed. U.S. Patent No. 4,247,386 discloses a method of converting C5+ hydrocarbons to C2-C3 hydrocarbons via hydrocracking in the presence of a palladium catalyst. G.B. Patent No. 1,016,033 discloses a method of converting C2-C7 hydrocarbons into methane in the presence of a Pt/Al203 catalyst.
[0005] There is a need for methods for converting C4-C10 hydrocarbons to C2-C3 cracking feed while simultaneously hydrogenating olefin fragments to lower molecular weight aliphatic hydrocarbons in a single reaction.
SUMMARY OF THE DISCLOSED SUBJECT MATTER
[0006] The presently disclosed subject matter provides methods for producing C2-C3 hydrocarbons from C4-C10 hydrocarbon streams. In particular, the presently disclosed subject matter provides methods for producing C2-C3 hydrocarbons and for producing aliphatic hydrocarbons from the C2-C3 hydrocarbons.
[0007] In certain embodiments, an example method can include using hydrogenolysis to convert C4-C10 hydrocarbons to C2-C3 cracking feed, while simultaneously using hydrogenation to convert olefinic fragments to lower molecular weight aliphatic hydrocarbons. For example, and not by way of limitation, a method for producing C2-C3 hydrocarbon feedstock from C4-C10 hydrocarbons can include using a single reaction chamber that uses one or more hydrogenolytic catalyst and one or more hydrogenation catalyst. The method can further include feeding C4-C10 hydrocarbons and C2-C3 olefin fragments to the reaction chamber. The method can further include converting the C4-C10 hydrocarbons to C2-C3 hydrocarbons via hydrogenolysis. The method can further include converting the C2-C3 olefin fragments to light aliphatic hydrocarbons via hydrogenation. In certain embodiments, the hydrogenolysis and hydrogenation reactions can occur concurrently. In certain embodiments, the hydrogenolysis and hydrogenation reactions can take place at a temperature of at least about 550 °C. In certain embodiments, the one or more hydrogenolytic catalyst can be different than the one or more hydrogenation catalyst. In certain embodiments, the reaction can take place in a fixed bed adiabatic reactor.
[0008] The presently disclosed subject matter further provides methods for efficiently producing olefins during a naphtha steam cracking process by consuming less naphtha cracking feed. In certain embodiments, an exemplary method can include a single reaction chamber that uses one or more hydrogenolytic catalyst and one or more hydrogenation catalyst. The method can further include feeding C4-C10 by-product hydrocarbons and C2- C3 olefin fragments to the reaction chamber. The method can further include converting the C4-C10 hydrocarbons to a C2-C3 hydrocarbon feedstock via hydrogenolysis. The method can further include converting the C2-C3 olefin fragments to light aliphatic hydrocarbons feedstock via hydrogenation. The method can further include directing the C2-C3 hydrocarbon feedstock and light aliphatic hydrocarbons feedstock back to the naphtha steam cracking process.
[0009] In certain embodiments, the hydrogenolysis and hydrogenation reactions can occur concurrently. In certain embodiments, the hydrogenolysis and hydrogenation reactions can take place at a temperature between about 550 °C and about 600 °C. In certain embodiments, the one or more hydrogenolytic catalysts can be different than the one or more hydrogenation catalysts. In certain embodiments, the reaction can take place in a fixed bed adiabatic reactor.
[0010] The method can further include converting any C02 which may exist as a by- product of the olefins production process to hydrocarbons via hydrogenation.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a schematic diagram depicting an exemplary method in accordance with one non-limiting embodiment of the disclosed subject matter.
[0012] FIG. 2 is a schematic diagram depicting an exemplary method in accordance with one non-limiting embodiment of the disclosed subject matter. DETAILED DESCRIPTION
[0013] The presently disclosed subject matter provides methods for producing C2-C3 hydrocarbon feedstock from C4-C10 hydrocarbons. In certain embodiments, the methods of the present disclosure can be used to produce hydrocarbon feedstock that can be recycled in a naphtha steam cracking process.
[0014] For the purpose of illustration and not limitation, FIG. 1 is a schematic representation of a non-limiting exemplary method according to the disclosed subject matter. In certain embodiments, the method 100 can include providing a reaction chamber with one or more hydrogenolytic catalysts, and one or more hydrogenation catalysts, 101. The method 100 can further include feeding C4-C10 hydrocarbons and C2-C3 olefin fragments to a reaction chamber, 102. The method can further include hydrogenolysis of a C4-C10 hydrocarbon stream to produce C2-C3 hydrocarbons in the presence of one or more hydrogenolytic catalysts, 103. For example, and not by way of limitation, the hydrogenolysis of the C4-C10 hydrocarbon stream can include the following reaction:
C8Hi8 + 2H2→ C2H6 + 2C3H8 [Formula 1 ]
As shown in Formula 1, during the hydrogenolysis process, C4-C10 hydrocarbons such as, but not limited to octane, can be added to hydrogen to produce ethane and/or propane.
[0015] The method can further include hydrogenation of olefin fragments to low molecular weight aliphatic hydrocarbons in the presence of one or more hydrogenation catalysts, 104. In certain embodiments, the hydrogenolytic catalyst and the hydrogenation catalyst can be within the same reaction chamber. In certain embodiments, the hydrogenolysis process, 103, and hydrogenation process, 104, can occur concomitantly. For example, and not by way of limitation, the hydrogenation can occur at the same conditions as the hydrogenolysis reaction and within the same reaction chamber as the hydrogenolysis reaction. In certain embodiments, the reaction can take place in a conventional fixed bed adiabatic reactor.
[0016] In certain embodiments, the temperature of the hydrogenolysis of the C4-C10 hydrocarbon feed stream to C2-C3 hydrocarbons can be about 500 °C to about 650 °C, e.g., 550 °C to about 600 °C.
[0017] In certain embodiments, the one or more hydrogenolytic catalysts can be different from the one or more hydrogenation catalysts. In certain embodiments, the hydrogenolytic catalyst can include Pt based on a support. For example, and not by way of limitation, the catalyst support can be alumina. In certain embodiments, the hydrogenation catalyst can include a Mo based catalyst. For example, and not by way of limitation, the hydrogenation catalyst can be MoS2.
[0018] In certain embodiments, the C4-C10 hydrocarbon feedstream may be a byproduct of olefins production processes. For example and not by way of limitation, the C4- C10 hydrocarbon feedstream can be a by-product of naphtha cracking. Alternatively, the C4- C10 hydrocarbon feed stream can be a by-product of a methanol to olefins process or a syngas to olefins process. For example, and not by way of limitation, the C4-C10 hydrocarbon stream can contain butane, pentane, hexane, heptane, octane, xylene, benzene, toluene, butylene, and propylene, as well as H20, C02 .
[0019] For example, and not by way of limitation, the C2-C3 hydrocarbons that can be produced by hydrogenolysis of the C4-C10 hydrocarbon stream can include ethane, propane, ethylene and/or propylene.
[0020] For the purpose of illustration and not limitation, FIG. 2 is a schematic representation of a non-limiting exemplary method according to the disclosed subject matter. In certain embodiments, the method 200 can include a method of efficiently producing olefins during a naphtha steam cracking process where the amount of naphtha cracking feed consumed is lowered. In certain embodiments, the method 200 can include providing a reaction chamber the includes one or more hydrogenolytic catalyst and one or more hydrogenation catalyst, 201.
[0021] In certain embodiments, the one or more hydrogenolytic catalysts can be different from the one or more hydrogenation catalysts. In certain embodiments, the hydrogenolytic catalyst can include Pt based on a support. For example, and not by way of limitation, the catalyst support can be alumina. In certain embodiments, the hydrogenation catalyst can include a Mo based catalyst. For example, and not by way of limitation, the hydrogenation catalyst can be MoS2.
[0022] In certain embodiments, the method 200 can further include feeding a C4-C10 hydrocarbon feedstream and a C2-C3 olefins stream to a reaction chamber, 202. In certain embodiments, the C4-C10 hydrocarbon feedstream may be a by-product of olefins production processes. For example and not by way of limitation, the C4-C10 hydrocarbon feedstream can be a by-product of naphtha cracking. Alternatively, the C4-C10 hydrocarbon feed stream can be a by-product of a methanol to olefins process or a syngas to olefins process. For example, and not by way of limitation, the C4-C10 hydrocarbon stream can contain butane, pentane, hexane, heptane, octane, xylene, benzene, toluene, butylene, and propylene, as well as H20, C02. In certain embodiments, the method 200 can further include converting the C4- C10 hydrocarbon feedstream to a C2-C3 hydrocarbon feedstock via hydrogenolysis, i.e., hydrocracking, 203. In certain embodiments, the temperature of the hydrogenolysis of the C4-C10 hydrocarbon feed stream can be about 550 °C to about 600 °C.
[0023] In certain embodiments, the method 200 can further include converting the C2- C3 olefin fragments to a C2-C3 aliphatic hydrocarbon feedstock via hydrogenation, 204.
[0024] In certain embodiments, the hydrogenolysis of C4-C10 hydrocarbons to C2-C3 hydrocarbons and the hydrogenation of olefin fragments to low molecular aliphatic hydrocarbons can occur concurrently in the single reaction chamber. In certain embodiments, the reaction can take place in a conventional fixed bed adiabatic reactor.
[0025] In certain embodiments, the method 200 can further include directing the C2-C3 hydrocarbon feedstock and low molecular aliphatic feedstock back to the naphtha steam cracking process, 205.
[0026] In certain embodiments, the methods 100 and 200 can further include converting C02 which may exist as a by-product of the olefins production process to hydrocarbons via hydrogenation. For example and not by way of limitation, the hydrogenation of by-product CO2 can include the following reaction:
C02 + 3H2→ CH3OH + H20 [Formula 2]
[0027] As used herein, the term "about" or "approximately" means within an acceptable error range for the particular value as determined by one of ordinary skill in the art, which will depend in part on how the value is measured or determined, i.e., the limitations of the measurement system. For example, "about" can mean a range of up to 20%, up to 10%, up to 5% and/or up to 1% of a given value.
[0028] In addition to the various embodiments depicted and claimed, the disclosed subject matter is also directed to other embodiments having other combinations of the features disclosed and claimed herein. As such, the particular features presented herein can be combined with each other in other manners within the scope of the disclosed subject matter such that the disclosed subject matter includes any suitable combination of the features disclosed herein. The foregoing description of specific embodiments of the disclosed subject matter has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosed subject matter to those embodiments disclosed.
[0029] It will be apparent to those skilled in the art that various modifications and variations can be made in the systems and methods of the disclosed subject matter without departing from the spirit or scope of the disclosed subject matter. Thus, it is intended that the disclosed subject matter include modifications and variations that are within the scope of the appended claims and their equivalents.
[0030] Various patents and patent applications are cited herein, the contents of which are hereby incorporated by reference herein in their entireties.

Claims

1. A method of producing C2-C3 hydrocarbon feedstock using a single reaction chamber that comprises at least one hydrogenolytic catalyst and at least one hydrogenation catalyst, comprising:
(a) feeding C4-C10 hydrocarbons and olefin fragments to the reaction chamber;
(b) converting the C4-C10 hydrocarbons to C2-C3 hydrocarbons by hydrogenolysis in the reaction chamber; and
(c) converting the olefin fragments to low molecular aliphatic hydrocarbons by hydrogenation in the reaction chamber, wherein
the hydrogenolysis and hydrogenation reactions occur concurrently at a temperature of at least 550 °C.
2. The method of claim 1, wherein the at least one hydrogenolytic catalyst comprises a catalyst that is different from the at least one hydrogenation catalyst.
3. The method of claim 2 , wherein the hydrogenolytic catalyst is Pt/Al203.
4. The method of claim 2, wherein the hydrogenation catalyst is MoS2.
5. The method of claim 2, wherein the reaction takes place in a fixed bed reactor.
6. The method of claim 2, further comprising:
(a) converting any C02 that is present in the by-product C4-C10 hydrocarbon stream to hydrocarbons by hydrogenation.
7. The method of claim 1 , wherein the hydrogenolytic catalyst comprises Pt/Al203.
8. The method of claim 7, further comprising:
(a) converting any C02 that is present in the by-product C4-C10 hydrocarbon stream to hydrocarbons by hydrogenation.
9. The method of claim 1, wherein the hydrogenation catalyst comprises MoS2.
10. The method of claim 1, wherein the single reaction chamber comprises a chamber within a fixed bed reactor.
11. The method of claim 1, wherein the C4-C10 hydrocarbons comprise butane, pentane, hexane, heptane, octane, xylene, benzene, toluene, butyl ene, and propylene.
12. The method of claim 1, wherein the C2-C3 hydrocarbons comprise ethane, propane, ethylene and/or propylene.
13. The method of claim 1, further comprising:
(a) converting C02 that is present in the C4-C10 hydrocarbon stream to hydrocarbons by hydrogenation.
14. A method of efficiently producing olefins during a naphtha cracking process by consuming less naphtha cracking feed by using a single reaction chamber that comprises at least one hydrogenolytic catalyst and at least one hydrogenation catalyst, comprising:
(a) feeding by-product C4-C10 hydrocarbons and olefin fragments to the reaction chamber;
(b) converting the C4-C10 hydrocarbons to a C2-C3 hydrocarbon feedstock by hydrogenolysis in the reaction chamber;
(c) converting the olefin fragments to a low molecular aliphatic hydrocarbon feedstock by hydrogenation in the reaction chamber; and
(d) directing the feedstocks back to the naphtha cracking process, wherein the hydrogenolysis and hydrogenation reactions are occurring concurrently at a temperature between about 500 °C to about 600 °C and the at least one hydrogenolytic catalyst is different from the at least one hydrogenation catalyst.
15. A method of efficiently producing olefins during a naphtha cracking process by consuming less naphtha cracking feed, comprising: (a) providing a single reaction chamber that comprises the hydrogenolytic catalyst Pt/Al203 and the hydrogenation catalyst MoS2;
(b) feeding by-product C4-C10 hydrocarbons and olefin fragments to the reaction chamber;
(c) converting the C4-C10 hydrocarbons to a C2-C3 hydrocarbon feedstock by hydrogenolysis;
(d) converting the olefin fragments to a low molecular aliphatic hydrocarbon feedstock by hydrogenation; and
(e) directing the feedstocks back to the naphtha cracking process, wherein the hydrogenolysis and hydrogenation reactions are occurring concurrently in a fixed bed reactor at a temperature between about 500 °C to about 600 °C.
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