US20170327750A1 - Internal heat generating material coupled hydrocarbon cracking - Google Patents

Internal heat generating material coupled hydrocarbon cracking Download PDF

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Publication number
US20170327750A1
US20170327750A1 US15/584,598 US201715584598A US2017327750A1 US 20170327750 A1 US20170327750 A1 US 20170327750A1 US 201715584598 A US201715584598 A US 201715584598A US 2017327750 A1 US2017327750 A1 US 2017327750A1
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cracking
stream
reactor
hydrocarbon feed
hgm
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Hussein Mohammed Al Yami
Miao SUN
Ola Ali
Wei Xu
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Saudi Arabian Oil Co
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Saudi Arabian Oil Co
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Assigned to SAUDI ARABIAN OIL COMPANY reassignment SAUDI ARABIAN OIL COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AL YAMI, HUSSAIN MOHAMMED, ALI, Ola, SUN, Miao, XU, WEI
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    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/10—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with stationary catalyst bed
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/16—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "moving bed" method
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/20—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert heated gases or vapours
    • 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/22—Higher olefins

Definitions

  • Embodiments of the present disclosure generally relate to processing of hydrocarbons, and specifically relate to a method of cracking a hydrocarbon feed with a heat generating material coupled hydrocarbon cracking process.
  • Hydrocarbon cracking is a highly endothermic process.
  • the temperature of the reactor housing drops as the cracking reaction is initiated, because the activation of the endothermic cracking process consumes heat faster than the reactor adds additional heat. Adding the additional heat to maintain the reactor temperature adds significant costs to hydrocarbon cracking operations.
  • current steam-cracking processes operate at 800-1000° C., consuming as much as 40% of the energy used by the entire petrochemical industry.
  • Specific energy consumption is about 4500-5000 kcal/kg of ethylene for the most up-to-date steam-crackers. Overall, about 70% of production costs in typical ethane- or naphtha-based olefin plants are due to energy consumption.
  • Embodiments of the present disclosure are directed to methods of cracking a hydrocarbon feed using exothermic heat generating materials (HGM) to fuel the energy requirements of endothermic hydrocarbon cracking processes.
  • HGM heat generating materials
  • the methods and systems of the present disclosure have industrial applicability, specifically in the oil and gas industries due to the high energy costs traditionally required for hydrocarbon cracking.
  • the HGMs of the present disclosure are added to help the hydrocarbon cracking process become energy neutral or approach energy neutrality, thereby reducing the overall energy costs associated with hydrocarbon cracking.
  • a method of cracking a hydrocarbon feed includes vaporizing a hydrocarbon feed and vaporizing a heat generating material (HGM) stream comprising at least one aldehyde or ketone. Further, the method includes introducing the vaporized hydrocarbon feed and the vaporized heat generating material stream to a cracking reactor. Finally, the method also includes cracking the hydrocarbon feed to produce a cracking product, where the cracking product comprises C 1 -C 4 hydrocarbons and C 5 + hydrocarbons.
  • HGM heat generating material
  • the cracking product may include ethylene, propylene, butenes, benzene, toluene, xylenes, ethylbenzene, H 2 , methane, ethane, LPG, naphtha, gasoline, and gas oils.
  • a method of cracking a hydrocarbon feed includes vaporizing a hydrocarbon feed and vaporizing a heat generating material (HGM) stream comprising at least one aldehyde or ketone. Further, the method includes heating the vaporized hydrocarbon feed and vaporized HGM stream to a pre-reaction temperature of at least 100° C. and introducing the vaporized hydrocarbon feed and the vaporized heat generating material stream to a cracking reactor. Finally, the method also includes cracking the hydrocarbon feed to produce a cracking product, where the cracking product comprises C 1 -C 4 hydrocarbons and C 5 + hydrocarbons.
  • HGM heat generating material
  • the cracking product may include ethylene, propylene, butenes, benzene, toluene, xylenes, ethylbenzene, H 2 , methane, ethane, LPG, naphtha, gasoline, and gas oils.
  • a method of cracking a hydrocarbon feed includes introducing a hydrocarbon feed and a heat generating material (HGM) stream comprising at least one aldehyde or ketone to a cracking reactor. The method further includes vaporizing the hydrocarbon feed and the heat generating material stream within the cracking reactor. Finally, the method also includes cracking the hydrocarbon feed to produce a cracking product, where the cracking product comprises C 1 -C 4 hydrocarbons and C 5 + hydrocarbons.
  • HGM heat generating material
  • the cracking product may include ethylene, propylene, butenes, benzene, toluene, xylenes, ethylbenzene, H 2 , methane, ethane, LPG, naphtha, gasoline, and gas oils.
  • FIG. 1 is a schematic illustration of a lab-scale reactor system for operation in accordance with one or more embodiments of the present disclosure.
  • FIG. 2 is a temperature profile of the catalyst bed temperature with and without the heat generating material feed at a reaction temperature of 560° C.
  • FIG. 3 is a temperature profile of the catalyst bed temperature with and without the heat generating material feed at a reaction temperature of 584° C.
  • hydrocarbons cracking is an endothermic process.
  • the traditionally endothermic cracking process can become thermally neutral or approach thermal neutrality.
  • the HGMs generate exothermic heat when included in the hydrocarbon cracking processes of the present disclosure. This exothermic heat may provide additional heat needed for the endothermic hydrocarbon cracking process.
  • the HGM may also act as a diluent to prevent coking while also acting as an oxidant to promote hydrocarbon cracking.
  • the hydrocarbon cracking system of FIG. 1 is a laboratory set-up provided for the present discussion, which follows; however, it should be understood that the present systems and methods encompass other configurations including large-scale and industrial process schemes.
  • a laboratory scale hydrocarbon cracking system 100 for cracking a hydrocarbon feed 4 is shown. Specifically, the hydrocarbon cracking system 100 performs catalytic hydrocarbon cracking of a hydrocarbon feed 4 in the presence of a heat generating material (HGM) stream 2 .
  • HGM heat generating material
  • the hydrocarbon feed 4 may refer to any hydrocarbon source derived from petroleum, coal liquid, or biomaterials.
  • Example hydrocarbon sources include whole range crude oil, distilled crude oil, residue oil, topped crude oil, liquefied petroleum gas (LPG), naphtha, gas oil, product streams from oil refineries, product streams from steam cracking processes, liquefied coals, liquid products recovered from oil or tar sands, bitumen, oil shale, biomass hydrocarbons, and the like.
  • LPG liquefied petroleum gas
  • the hydrocarbon feed 4 may include n-hexane, naphtha, mixed butenes, ethylene, and their combinations.
  • the HGM stream 2 may include various components utilized to generate exothermic heat which may be used in the cracking process.
  • the HGM comprises at least one aldehyde or ketone.
  • the aldehyde is a formaldehyde.
  • formaldehyde is gaseous at room temperature, it is typically distributed as 37% by mass dissolved in water. This mixture is commonly known as 100% formalin.
  • methanol may be added to the formalin to prevent oxidation and polymerization.
  • formaldehyde with methanol performs well as an HGM, because it was surprisingly found that the predictable side reactions, such as the conversion of formaldehyde to CO and H 2 are inhibited by the simultaneous additions of hydrocarbons.
  • additional HGM stream 2 components beyond a ketone or aldehyde, such as formaldehyde may include one or more additional aldehydes, additional ketones, or alcohols.
  • additional aldehydes, ketones, alcohols, or their combinations helps promote or hinder selectivity to certain reaction products. For example, as the ratio of additional aldehydes, ketones, or alcohols to formaldehyde or other aldehyde is varied the reactions products may shift toward or away from light olefins.
  • the formalin 37 weight % formaldehyde in water
  • the formalin 37 weight % formaldehyde in water
  • the HGM 2 may comprise 5 to 37 weight % formaldehyde, or 10 to 37 weight % formaldehyde, or 20 to 37 weight % formaldehyde, or 25 to 37 weight % formaldehyde.
  • Components of the HGM stream 2 may be obtained from renewable sources. Specifically, components such as aldehydes, ketones, and alcohols may be obtained from a fermentation process of biomass or syngas processes.
  • the hydrocarbon cracking system 100 may comprise a reactor system having at least one catalyst bed reactor 10 , and optionally, additional reactors and units.
  • these additional optional units may include a preheater reactor 12 connected to the at least one catalyst bed reactor 10 and additional heaters or heat exchangers 18 .
  • the hydrocarbon cracking system 100 may also comprise a reactor system without a catalyst bed reactor.
  • a hydrocarbon cracking system 100 utilizing thermal cracking without a catalyst is envisioned.
  • the catalyst bed reactor 10 may include a solid acid catalyst bed 14 disposed in the catalyst bed reactor 10 .
  • the operation of the catalyst bed reactor 10 results in the cracking of the hydrocarbon feed 4 to produce a cracking product 40 , where the cracking product 40 comprises light C 1 -C 4 hydrocarbons, such as ethylene and propylene, and heavy C 5 + hydrocarbons.
  • the cracking product 40 may include ethylene, propylene, butenes, benzene, toluene, xylenes, ethylbenzene, H2, methane, ethane, LPG, naphtha, gasoline, and gas oils.
  • the particular combination of products in the cracking product 40 depends on the constituents of the feed to the catalyst bed reactor 10 .
  • Adding the HGM stream 2 to the catalyst bed reactor 10 reduces or eliminates the additional heat energy input requirements in the catalyst bed reactor 10 .
  • the HGM stream 2 undergoes an exothermic reaction in the catalyst bed reactor 10 which offsets the endothermic cracking process yielding a thermally neutral overall hydrocarbon cracking operation. Varying the make-up, the flow rate, or both the make-up and the flow rate of the HGM stream 2 may yield an overall hydrocarbon cracking operation that is thermally negative to thermally neutral to thermally positive.
  • the solid acid catalyst bed 14 of the catalyst bed reactor 10 may include an aluminosilicate zeolite, a silicate (for example, silicalites), or a titanosilicate.
  • the solid acid catalyst is an aluminosilicate zeolite having a Mordenite Framework Inverted (MFI) structure.
  • MFI structured aluminosilicate zeolite catalyst may be a ZSM-5 catalyst.
  • the ZSM-5 catalyst may be an H-ZSM-5 catalyst where at least a portion of the ZSM-5 catalyst ion exchange sites are occupied by H+ ions.
  • the aluminosilicate zeolite catalyst for example, the H-ZSM-5 catalyst, may have a Si/Al molar ratio of at least 10. In further embodiments, aluminosilicate zeolite catalyst may have a Si/Al molar ratio of at least 30, or at least 35, or at least 40. Additionally, the aluminosilicate zeolite catalyst may also include one or more additional components used to modify the structure and performance of the aluminosilicate zeolite catalyst. Specifically, aluminosilicate zeolite catalyst may include phosphorus, boron, nickel, iron, tungsten, other metals, or combinations thereof.
  • the aluminosilicate zeolite catalysts may comprise 0-10% by weight additional components, 1-8% by weight additional components, or 1-5% by weight additional components.
  • these additional components may be wet impregnated in the ZSM-5 followed by drying and calcination.
  • the aluminosilicate zeolite catalysts may contain mesoporous structures.
  • the catalyst may be sized to have a diameter of 25 to 2,500 micrometers ( ⁇ m). In further embodiments, the catalyst may have a diameter of 400 to 1200 ⁇ m, 425 to 800 ⁇ m, 800 to 1000 ⁇ m, or 50 to 100 ⁇ m.
  • the minimum size of the catalyst particles depends on the reactor design to prevent passage of catalyst particles through the filter with reaction products.
  • the catalyst bed reactor 10 may be a fixed-bed reactor, a fluidized bed reactor, a slurry reactor, or a moving bed reactor. In a specific embodiment, the catalyst bed reactor 10 is a fixed-bed reactor. In some embodiments with a fixed bed reactor, the residence time of the combined hydrocarbon feed 4 and the heat generating material stream 2 in the catalyst bed reactor 10 is in the range of 0.05 seconds to hour. For example, the residence time may approach 1 hour for diesel hydrotreating a liquid feed and is generally in the range of 0.1 to 5 seconds in an FCC application. As such, in various embodiments, the residence time in the catalyst bed reactor 10 is 0.1 seconds to 5 seconds or 5 minutes to 1 hour.
  • the desired residence time in a fixed bed reactor of the combined hydrocarbon feed 4 and the heat generating material stream 2 for optimal hydrocarbon cracking is dependent on operating temperature and composition of both the solid acid catalyst bed 14 , the hydrocarbon feed 4 , and the heat generating material stream 2 .
  • the bed voidage which represents the volume fraction occupied by voids, is between 0.2 and 1.0. In further embodiments, the bed voidage is between 0.3 and 0.8.
  • the catalyst bed reactor 10 may have an operating temperature of 250 to 850° C. In further embodiments, the catalyst bed reactor 10 has an operating temperature of 450 to 650° C., or 540 to 560° C., or 575 to 595° C. Without being limited to theory, the addition of the HGM 2 is believed to improve the catalyst life of the solid acid catalyst bed 14 .
  • the HGM 2 acts as a diluent and oxygenates the hydrocarbon feed to prevent coking.
  • the solid acid catalyst bed 14 may be preheated in a gas flow containing heated nitrogen 6 and oxygen at sufficient flow rate to heat the solid acid catalyst bed 14 .
  • the oxygen may be provided as air.
  • the preheated gas flow is heated from 250 to 650° C., or from 475 to 525° C., or from 490 to 510° C. in various embodiments.
  • the method further may include preheating the hydrocarbon feed 4 upstream of the catalyst bed reactor 10 .
  • This preheating of the hydrocarbon feed 4 may be achieved in a preheater reactor 12 .
  • the hydrocarbon fed 4 may be heated in the presence of nitrogen 6 .
  • the preheater reactor 12 may raise the temperature of the hydrocarbon feed 4 being supplied to the catalyst bed reactor 10 to a pre-reaction temperature of at least 100° C.
  • the hydrocarbon feed 4 is typically heated to a pre-reaction temperature of 200-300° C. This range of the pre-reaction temperature is maintained low enough to prevent thermal cracking in the preheater reactor 12 before the catalyst bed reactor 10 .
  • the hydrocarbon cracking system 100 may also optionally include at least one hydrocarbon preheater 18 disposed upstream of the preheater reactor 12 .
  • the hydrocarbon preheater or preheaters 18 raises the temperature of the hydrocarbon feed being supplied to the at least one preheater reactor 12 .
  • the preheaters 18 may include a heat exchanger or a similar heater device familiar to one of ordinary skill in the art.
  • the hydrocarbon cracking system 100 may also include at least one heat generating material preheater 16 disposed upstream of the catalyst bed reactor 10 .
  • the heat generating material preheater 16 raises the temperature of the heat generating material stream 2 being supplied to the at least one catalyst bed reactor 10 .
  • the heat generating material preheater 16 raises the temperature of the heat generating material stream 2 to a pre-reaction temperature of at least 100° C.
  • the maximum pre-reaction temperature of the heat generating material stream 2 is limited by the cracking temperature of the heat generating material stream 2 so that thermal cracking of the heat generating material stream 2 does not occur before the catalyst bed reactor 10 .
  • the hydrocarbon cracking system 100 also may also include other heating components as shown.
  • the hydrocarbon cracking system 100 may include a reactor oven 20 , or a hot box 22 surrounding the catalyst bed reactor 10 , the preheater reactor 12 , the heat generating material preheater 16 , and the hydrocarbon preheater 18 .
  • the reactor oven 20 may help maintain the temperature of the catalyst bed reactor 10 and the preheater reactor 12 .
  • the hot box 22 serves to retain heat around the catalyst bed reactor 10 , the preheater reactor 12 , the heat generating material preheater 16 , and the hydrocarbon preheater 18 so as to reduce thermal losses.
  • the hydrocarbon preheater 19 , the preheater reactor 12 , and the heat generating material preheater 16 may also be combined into a single preheater to raise the temperature of both the hydrocarbon feed 4 and the heat generating material stream 2 before entering the catalyst bed reactor 10 .
  • the hydrocarbon feed 4 and the heat generating material stream 2 are heated until the hydrocarbon feed 4 and heat generating material stream 2 are respectively vaporized.
  • the hydrocarbon feed 4 and the heat generating material stream 2 may be mixed together and vaporized concurrently in a single feed preheater.
  • the hydrocarbon feed 4 and the heat generating material stream 2 may be independently vaporized with separate feed preheaters before being combined and fed to a cracking reactor.
  • heated steam or other diluent may be injected into the vaporized hydrocarbon feed 4 , the vaporized heat generating material stream 2 , or a combined vaporized stream of the hydrocarbon feed 4 and the heat generating material stream 2 before being fed into the cracking reactor.
  • Providing a diluent to the feed to the cracking reactor spaces the molecules of the hydrocarbon feed 4 out.
  • formalin 37 weight % formaldehyde in water
  • the addition of steam or other diluent may be unnecessary as formalin comprises water which is converted to steam during vaporization of the heat generating material stream 2 .
  • vaporization of the hydrocarbon feed 4 and heat generating material stream 2 may be achieved inside the cracking reactor and not prior to injection into the reactor.
  • balancing the amounts of the heat generating materials stream 2 and the hydrocarbon feed 4 may facilitate a thermally neutral cracking process.
  • the HGM stream 2 and the hydrocarbon feed 4 are fed to the catalyst bed reactor 10 at a weight ratio of 1:10 to 10:1.
  • the heat generating material stream 2 and the hydrocarbon feed 4 are fed to the catalyst bed reactor 10 at a ratio of 1:6 to 6:1, 1:3, to 3:1, or 1:2 to 2:1.
  • the heat generating material stream 2 and the hydrocarbon feed 4 are fed to the catalyst bed reactor 10 at a ratio of 2:3 to 3:2.
  • the cracking product 40 may comprise a variety of light C 1 -C 4 hydrocarbons and heavy C 5+ hydrocarbons.
  • the cracking product 40 specifically comprises propylene, butenes such as 2-trans-butene, n-butene, iso-butene and 2-cis-butene, C 5 olefins, aromatics, methane, ethane, propane, butanes, and pentane.
  • the constituents of the cracking product 40 are dependent upon the components of the hydrocarbon feed 4 and the heat generating material stream 2 .
  • formaldehyde not only provides heat to offset the endothermic cracking process, but also is an effective reactant to produce light olefins.
  • the hydrocarbon cracking system 100 may also include a condenser and at least one liquid/gas separator 24 .
  • the liquid/gas separator 24 which may include a flash drum or the like.
  • the cracking product 40 is fed to a condenser upon exiting the cracking reactor where the temperature of the gaseous cracking product 40 is reduced and is partially condensed.
  • the partially condensed feed is subsequently fed to the liquid/gas separator 24 where the liquid and gas phases are separated.
  • the light hydrocarbon stream 42 may be separated as gas phase light hydrocarbons, while the liquid phase heavy hydrocarbon stream 44 are separately discharged from the liquid/gas separator 24 .
  • the hydrocarbon cracking system 100 may include multi-product distillation columns.
  • Industrial scale separation utilizing distillation columns, stripping columns, or extraction columns and other methods and processes for handling and separating product streams are known to one having skill in the art and may be equally utilized.
  • the light hydrocarbon stream 42 may be cooled and collected as a liquid hydrocarbon product.
  • propylene and ethylene may be separated via a distillation, extractive distillation or membrane separation methodology.
  • the rate of total flow of the HGM stream 2 , hydrocarbon feed 4 , and steam or other diluents supplied to the hydrocarbon cracking system 100 is adjusted to control the space velocity of the reaction.
  • the weight hourly space velocity (WHSV) is defined as the flow of reactants, for example, in grams/hour (g/hr), divided by weight the catalyst weight, for example, in grams (g).
  • the flow of reactants includes the total flow of the HGM stream 2 , hydrocarbon feed 4 , and steam or other diluents.
  • the weight hourly space velocity of the reaction is 0.01 to 100 hours ⁇ 1 (h ⁇ 1 ).
  • the weight hourly space velocity of the reaction is 1 to 8 hours ⁇ 1 , 2 to 4 hours ⁇ 1 , or 2.8 to 3.4 h ⁇ 1 .
  • Ethylene and propylene are two of the main petrochemical building blocks used in various applications, for example, the production of plastics and synthetic fibers.
  • ethylene is extensively used to manufacture polyethylene, ethylene chloride and ethylene oxide which are very useful for the packaging, plastic processing, construction and textile industries.
  • propylene is commonly used to make polypropylene, but it is also a basic product necessary to produce propylene oxide, acrylic acid and many other chemical derivatives.
  • Plastic processing, the packaging industry, the furnishing sector, and the automotive industry are frequent users of propylene and its derivatives. Thus, increasing yields of light olefins such as ethylene and propylene to supply the numerous industrial users is desirable.
  • the reactants selected from n-hexane, naphtha, and formaldehyde (37% solution stabilized in 13.88% of methanol) were introduced into the reactor to start the reaction
  • the products from the catalytic reaction were analyzed by an online gas chromatograph equipped with an Agilent HP-Al/KCl (50 m ⁇ 0.53 mm ID, 15 ⁇ m) column and detected by a Flame Ionization Detector (FID) detector.
  • FID Flame Ionization Detector
  • N 2 , CH 4 , C 2 H 6 , C 2 H 4 , C 3 H 8 , C 3 H 6 , n-C 4 H 10 , i-C 4 H 10 , 1-C 4 H 8 , 2-cis-C 4 H 8 , 2-trans-C 4 H 8 , i-C 4 H 8 , n-C 5 H 12 , and n-C 5 H 6 were used as calibration standards. All the lines and valves between the exit of the fixed bed flow reactor and the gas chromatographs were heated to 105° C. to prevent condensation of heavier hydrocarbons.
  • Liquid products were collected separately using a low pressure liquid/gas separator.
  • the organic part, if any, was separated from water and its compositions were analyzed by gas chromatography mass spectroscopy (GCMS) to identify the products and followed by gas chromatography (GC) to determine their concentrations.
  • GCMS gas chromatography mass spectroscopy
  • the conversion of hexane was determined as a weight percentage.
  • the conversion is defined as the percentage of the weight of hexane converted into final products.
  • the equation for the conversion of hexane is provided as equation (1) with W i being the weight of hexane injected and W f being the weight of unreacted hexane detected by GC.
  • WHSV weight hourly space velocity
  • the normal reaction time was 35 minutes.
  • the catalyst bed was purged with high purity nitrogen at a flowrate of 0.2 liters/min for 30 minutes to flush away all reaction products and hydrocarbons before introducing air. Introduction of air is delayed as it may be a combustion hazard in the presence of hydrocarbons and reaction products.
  • the catalyst was regenerated using an air flow rate of 0.154 lit/min for 1 hour or until the temperature stabilized. After that the catalyst bed was flushed with nitrogen again for 30 minutes to remove combustion products
  • Tests were run with hexane as the hydrocarbon feed 4 in combination with formaldehyde as the heat generating material stream 2 to demonstrate the effect of the heat generating material. Each test was run for 35 minutes. Table 1 details various cracking process parameters for the cracking product 40 when formaldehyde is present and when formaldehyde is not present. The coupling of the hexane and formaldehyde results in an increased C 6 conversion, ethylene yield, and propylene yield.
  • Table 2 provided as follows, details various cracking process parameters for the cracking product 40 when formaldehyde is present and the residence time is varied. Each test was run for 35 minutes. An increased residence time results in an increased C 6 conversion.
  • FIG. 2 demonstrates that when hexane and the heat generating material are provided at a 2:1 ratio the resulting drop in temperature of the solid acid catalyst bed 14 is reduced.
  • the temperature bed of the solid acid catalyst bed 14 drops very vast when introducing the hexane feed and a controller then responds by increasing the wall temperature of the catalyst bed reactor 10 .
  • the wall temperature doesn't increase as fast as the temperature drops in the catalyst bed reactor 10 from the endothermic reaction.
  • FIG. 3 demonstrates that when hexane and the heat generating material are provided at a 1:2 ratio the resulting drop in temperature of the solid acid catalyst bed 14 is eliminated.
  • the greater percentage of heat generating material relative to hexane (hydrocarbon) results in the solid acid catalyst bed 14 temperature immediately rising.
  • the temperature of the solid acid catalyst bed 14 immediately drops before slowly starting to increase after a period of time.
  • the solid acid catalyst in the solid acid catalyst bed did not exhibit decay after 35 minutes of operation in the illustrative examples.
  • the disclosure provides a method of cracking a hydrocarbon feed.
  • the method comprises introducing a hydrocarbon feed to a cracking reactor, introducing a heat generating material (HGM) stream comprising at least one aldehyde or ketone to the cracking reactor, vaporizing the hydrocarbon feed and the HGM stream, and cracking the hydrocarbon feed to produce a cracking product.
  • the cracking product comprises C 1 -C 4 hydrocarbons and C 5 + hydrocarbons.
  • the disclosure provides the method of the first aspect, in which the hydrocarbon feed and HGM stream are vaporized subsequent to introduction to the cracking reactor.
  • the disclosure provides the method of the first aspect, in which the hydrocarbon feed and HGM stream are vaporized prior to introduction to the cracking reactor.
  • the disclosure provides the method of any of the first through third aspects, in which the HGM stream comprises ketone.
  • the disclosure provides the method of any of the first through fourth aspects, in which the HGM stream comprises an aldehyde.
  • the disclosure provides the method of the fifth aspect, in which the aldehyde is formaldehyde dissolved in water.
  • the disclosure provides the method of the sixth aspect, in which the formaldehyde dissolved in water is stabilized with an organic solvent.
  • the disclosure provides the method of the seventh aspect, in which the organic solvent is methanol.
  • the disclosure provides the method of any of the first through eighth aspects, in which the HGM stream further comprises an alcohol, an additional ketone, or an additional aldehyde.
  • the disclosure provides the method of any of the first through ninth aspects, in which the cracking product comprises ethylene, propylene, butenes, benzene, toluene, xylenes, ethylbenzene, H 2 , methane, ethane, LPG, naphtha, gasoline, and gas oils.
  • the disclosure provides the method of any of the first through tenth aspects, in which the cracking reactor is at least one catalyst bed reactor.
  • the disclosure provides the method of the eleventh aspect, in which the catalyst bed reactor includes a solid acid catalyst bed disposed in the catalyst bed reactor and the catalyst bed reactor is at a reaction temperature of 250 to 850° C.
  • the disclosure provides the method of the eleventh or twelfth aspects, in which the catalyst bed reactor comprises a fluidized bed reactor, a fixed-bed reactor, a slurry reactor, or a moving bed reactor.
  • the disclosure provides the method of the eleventh or twelfth aspects, in which the catalyst bed reactor is a fixed bed reactor.
  • the disclosure provides the method of any of the twelfth through fourteenth aspects, in which the solid acid catalyst is a ZSM-5 catalyst.
  • the disclosure provides the method of the fifteenth aspect, in which the ZSM-5 catalyst has a Si/Al molar ratio of at least 10.
  • the disclosure provides the method of the fifteenth aspect, in which the ZSM-5 catalyst has a Si/Al molar ratio of at least 30.
  • the disclosure provides the method of the fifteenth aspect, in which the ZSM-5 catalyst comprises phosphorus, boron, nickel, iron, tungsten, or combinations thereof.
  • the disclosure provides the method of any of the first through eighteenth aspects, in which the HGM stream and the hydrocarbon feed stream are fed at a weight ratio of 1:10 to 10:1.
  • the disclosure provides the method of any of the first through nineteenth aspects, in which the hydrocarbon feed stream comprises non-fractioned or fractioned crude oil, hexane, naphtha, mixed butenes, ethylene, and combinations thereof.

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