US20130197285A1 - Integrated hydrotreating and steam pyrolysis process for direct processing of a crude oil - Google Patents

Integrated hydrotreating and steam pyrolysis process for direct processing of a crude oil Download PDF

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US20130197285A1
US20130197285A1 US13/751,946 US201313751946A US2013197285A1 US 20130197285 A1 US20130197285 A1 US 20130197285A1 US 201313751946 A US201313751946 A US 201313751946A US 2013197285 A1 US2013197285 A1 US 2013197285A1
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product stream
mixed product
hydrogen
zone
liquid
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Raheel Shafi
Julio HASSELMEYER
Abdennour Bourane
Ibrahim A. ABBA
Abdul Rahman Zafer AKHRAS
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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: HASSELMEYER, Julio, ABBA, IBRAHIM A., AKHRAS, ABDUL RAHMAN ZAFER, BOURANE, ABDENNOUR, SHAFI, RAHEEL
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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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
    • 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
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • 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
    • C10G47/22—Non-catalytic cracking in the presence of hydrogen
    • 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
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/16—Preventing or removing incrustation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/0042—Degasification of liquids modifying the liquid flow
    • B01D19/0052—Degasification of liquids modifying the liquid flow in rotating vessels, vessels containing movable parts or in which centrifugal movement is caused
    • B01D19/0057—Degasification of liquids modifying the liquid flow in rotating vessels, vessels containing movable parts or in which centrifugal movement is caused the centrifugal movement being caused by a vortex, e.g. using a cyclone, or by a tangential inlet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B01D2257/7025—Methane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B01D53/526—Mixtures of hydrogen sulfide and carbon dioxide
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/308—Gravity, density, e.g. API
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4075—Limiting deterioration of equipment
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/42—Hydrogen of special source or of special composition
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80—Additives
    • C10G2300/805—Water
    • C10G2300/807—Steam
    • 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
    • C10G2400/30—Aromatics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane

Definitions

  • the present invention relates to an integrated hydrotreating and steam pyrolysis process for direct processing of a crude oil to produce petrochemicals such as olefins and aromatics.
  • the lower olefins i.e., ethylene, propylene, butylene and butadiene
  • aromatics i.e., benzene, toluene and xylene
  • Thermal cracking, or steam pyrolysis is a major type of process for forming these materials, typically in the presence of steam, and in the absence of oxygen.
  • Feedstocks for steam pyrolysis can include petroleum gases and distillates such as naphtha, kerosene and gas oil. The availability of these feedstocks is usually limited and requires costly and energy-intensive process steps in a crude oil refinery.
  • BMCI Bureau of Mines Correlation Index
  • BMCI 87552/VAPB+473.5*(sp. gr.) ⁇ 456.8 (1)
  • VAPB Volume Average Boiling Point in degrees Rankine
  • BMCI ethylene yields are expected to increase. Therefore, highly paraffinic or low aromatic feeds are usually preferred for steam pyrolysis to obtain higher yields of desired olefins and to avoid higher undesirable products and coke formation in the reactor coil section.
  • the system and process herein provides a steam pyrolysis zone integrated with a hydroprocessing zone to permit direct processing of crude oil feedstocks to produce petrochemicals including olefins and aromatics.
  • An integrated hydrotreating and steam pyrolysis process for the direct processing of a crude oil is provided to produce olefinic and aromatic petrochemicals.
  • Crude oil and hydrogen are charged to a hydroprocessing zone operating under conditions effective to produce a hydroprocessed effluent reduced having a reduced content of contaminants, an increased paraffinicity, reduced Bureau of Mines Correlation Index, and an increased American Petroleum Institute gravity.
  • Hydroprocessed effluent is thermally cracked in the presence of steam to produce a mixed product stream, which is separated.
  • Hydrogen from the mixed product stream is purified and recycled to the hydroprocessing zone, and olefins and aromatics are recovered from the separated mixed product stream.
  • crude oil is to be understood to include whole crude oil from conventional sources, crude oil that has undergone some pre-treatment.
  • crude oil will also be understood to include that which has been subjected to water-oil separation; and/or gas-oil separation; and/or desalting; and/or stabilization.
  • FIG. 1 is a process flow diagram of an embodiment of an integrated process described herein.
  • FIG. 2A-2C are schematic illustrations in perspective, top and side views of a vapor-liquid separation device used in certain embodiments of a steam pyrolysis unit in the integrated process described herein.
  • FIG. 1 A process flow diagram including an integrated hydroprocessing and steam pyrolysis process and system is shown in FIG. 1 .
  • the integrated system generally includes a selective catalytic hydroprocessing zone, an optional separation zone 20 , a steam pyrolysis zone 30 and a product separation zone.
  • Selective hydroprocessing zone includes a hydroprocessing reaction zone 4 having an inlet for receiving a mixture of crude oil feed 1 and hydrogen 2 recycled from the steam pyrolysis product stream, and make-up hydrogen as necessary. Hydroprocessing reaction zone 4 further includes an outlet for discharging a hydroprocessed effluent 5 .
  • Reactor effluents 5 from the hydroprocessing reactor(s) are cooled in a heat exchanger (not shown) and sent to a high pressure separator 6 .
  • the separator tops 7 are cleaned in an amine unit 12 and a resulting hydrogen rich gas stream 13 is passed to a recycling compressor 14 to be used as a recycle gas 15 in the hydroprocessing reactor.
  • a bottoms stream 8 from the high pressure separator 6 which is in a substantially liquid phase, is cooled and introduced to a low pressure cold separator 9 in which it is separated into a gas stream and a liquid stream 10 .
  • Gases from low pressure cold separator includes hydrogen, H 2 S, NH 3 and any light hydrocarbons such as C 1 -C 4 hydrocarbons.
  • stream gas stream 11 which includes hydrogen, H 2 S, NH 3 and any light hydrocarbons such as C 1 -C 4 hydrocarbons, with steam cracker products 44 . All or a portion of liquid stream 10 serves as the feed to the steam pyrolysis zone 30
  • an optional separation zone 20 (as indicated with dashed lines in FIG. 1 ) is employed to remove heavy ends of the bottoms stream 10 from low pressure separator 9 , i.e., the liquid phase hydroprocessing zone effluents.
  • Separation zone 20 generally includes an inlet receiving liquid stream 10 , an outlet for discharging a light fraction 22 comprising light components and an outlet for discharging a heavy fraction 21 comprising heavy components, which can be combined with pyrolysis fuel oil from product separation zone 70 .
  • separation zone 20 includes one or more flash vessels.
  • separation zone 20 includes, or consists essentially of (i.e., operates in the absence of a flash zone), a cyclonic phase separation device, or other separation device based on physical or mechanical separation of vapors and liquids.
  • a vapor-liquid separation device is illustrated by, and with reference to, FIGS. 2A-2C .
  • a similar arrangement of a vapor-liquid separation device is also described in U.S. Patent Publication Number 2011/0247500 which is incorporated by reference in its entirety herein.
  • the cut point can be adjusted based on vaporization temperature and the fluid velocity of the material entering the device, for example, to remove a fraction in the range of vacuum residue.
  • Steam pyrolysis zone 30 generally comprises a convection section 32 and a pyrolysis section 34 that can operate based on steam pyrolysis unit operations known in the art, i.e., charging the thermal cracking feed to the convection section in the presence of steam.
  • a vapor-liquid separation section 36 is included between sections 32 and 34 .
  • Vapor-liquid separation section 36 through which the heated steam cracking feed from convection section 32 passes, can be a separation device based on physical or mechanical separation of vapors and liquids.
  • a vapor-liquid separation device is illustrated by, and with reference to FIGS. 2A-2C .
  • a similar arrangement of a vapor-liquid separation device is also described in U.S. Patent Publication Number 2011/0247500 which is incorporated by reference in its entirety herein.
  • vapor and liquid flow through in a cyclonic geometry whereby the device operates isothermally and at very low residence time.
  • vapor is swirled in a circular pattern to create forces where heavier droplets and liquid are captured and channeled through to a liquid outlet as fuel oil 38 , for instance, which is added to a pyrolysis fuel oil blend, and vapor is channeled through a vapor outlet as the charge 37 to the pyrolysis section 34 .
  • the vaporization temperature and fluid velocity are varied to adjust the approximate temperature cutoff point, for instance in certain embodiments compatible with the residue fuel oil blend, e.g., about 540° C.
  • a quenching zone 40 includes an inlet in fluid communication with the outlet of steam pyrolysis zone 30 , an inlet for admitting a quenching solution 42 , an outlet for discharging an intermediate quenched mixed product stream 44 and an outlet for discharging quenching solution 46 .
  • an intermediate quenched mixed product stream 44 is converted into intermediate product stream 65 and hydrogen 62 , which is purified in the present process and used as recycle hydrogen stream 2 in the hydroprocessing reaction zone 4 .
  • Intermediate product stream 65 is generally fractioned into end-products and residue in separation zone 70 , which can one or multiple separation units such as plural fractionation towers including de-ethanizer, de-propanizer and de-butanizer towers, for example as is known to one of ordinary skill in the art.
  • suitable apparatus are described in “Ethylene,” Ullmann's Encyclopedia of Industrial Chemistry, Volume 12, Pages 531-581, in particular FIG. 24 , FIG. 25 and FIG. 26 , which is incorporated herein by reference.
  • product separation zone 70 includes an inlet in fluid communication with the product stream 65 and plural product outlets 73 - 78 , including an outlet 78 for discharging methane, an outlet 77 for discharging ethylene, an outlet 76 for discharging propylene, an outlet 75 for discharging butadiene, an outlet 74 for discharging mixed butylenes, and an outlet 73 for discharging pyrolysis gasoline. Additionally an outlet is provided for discharging pyrolysis fuel oil 71 .
  • one or both of the heavy fraction 21 from flash zone 20 and the fuel oil portion 38 from vapor-liquid separation section 36 are combined with pyrolysis fuel oil 71 and can be withdrawn as a pyrolysis fuel oil blend 72 , e.g., a low sulfur fuel oil blend to be further processed in an off-site refinery.
  • a pyrolysis fuel oil blend 72 e.g., a low sulfur fuel oil blend to be further processed in an off-site refinery.
  • hydroprocessing reaction zone 4 includes one or more unit operations as described in commonly owned United States Patent Publication Number 2011/0083996 and in PCT Patent Application Publication Numbers WO2010/009077, WO2010/009082, WO2010/009089 and WO2009/073436, all of which are incorporated by reference herein in their entireties.
  • a hydroprocessing zone can include one or more beds containing an effective amount of hydrodemetallization catalyst, and one or more beds containing an effective amount of hydroprocessing catalyst having hydrodearomatization, hydrodenitrogenation, hydrodesulfurization and/or hydrocracking functions.
  • hydroprocessing reaction zone 4 includes more than two catalyst beds.
  • hydroprocessing reaction zone 4 includes plural reaction vessels each containing one or more catalyst beds, e.g., of different function.
  • Hydroprocessing reaction zone 4 operates under parameters effective to hydrodemetallize, hydrodearomatize, hydrodenitrogenate, hydrodesulfurize and/or hydrocrack the crude oil feedstock.
  • hydroprocessing is carried out using the following conditions: operating temperature in the range of from 300° C. to 450° C.; operating pressure in the range of from 30 bars to 180 bars; and a liquid hour space velocity in the range of from 0.1 h ⁇ 1 to 10 h ⁇ 1 .
  • operating temperature in the range of from 300° C. to 450° C.
  • operating pressure in the range of from 30 bars to 180 bars
  • a liquid hour space velocity in the range of from 0.1 h ⁇ 1 to 10 h ⁇ 1 .
  • advantages are demonstrated, for instance, as compared to the same hydroprocessing unit operation employed for atmospheric residue. For instance, at a start or run temperature in the range of 370° C.
  • the deactivation rate is around 1 T/month. In contrast, if residue were to be processed, the deactivation rate would be closer to about 3 T/month to 4 T/month.
  • the treatment of atmospheric residue typically employs pressure of around 200 bars whereas the present process in which crude oil is treated can operate at a pressure as low as 100 bars. Additionally to achieve the high level of saturation required for the increase in the hydrogen content of the feed, this process can be operated at a high throughput when compared to atmospheric residue.
  • the LHSV can be as high as 0.5 while that for atmospheric residue is typically 0.25.
  • Deactivation at low throughput (0.25 hr ⁇ 1 ) is 4.2 T/month and deactivation at higher throughput (0.5 hr ⁇ 1 ) is 2.0 T/month.
  • the opposite is observed. This can be attributed to the washing effect of the catalyst.
  • Reactor effluents 5 from the hydroprocessing zone 4 are cooled in an exchanger (not shown) and sent to a high pressure cold or hot separator 6 .
  • Separator tops 7 are cleaned in an amine unit 12 and the resulting hydrogen rich gas stream 13 is passed to a recycling compressor 14 to be used as a recycle gas 15 in the hydroprocessing reaction zone 4 .
  • Separator bottoms 8 from the high pressure separator 6 which are in a substantially liquid phase, are cooled and then introduced to a low pressure cold separator 9 .
  • Remaining gases, stream 11 including hydrogen, H 2 S, NH 3 and any light hydrocarbons, which can include C 1 -C 4 hydrocarbons, can be conventionally purged from the low pressure cold separator and sent for further processing, such as flare processing or fuel gas processing.
  • hydrogen is recovered by combining stream 11 (as indicated by dashed lines) with the cracking gas, stream 44 , from the steam cracker products.
  • the bottoms 10 from the low pressure separator 9 are optionally sent to separation zone 20 or passed directly to steam pyrolysis zone 30 .
  • the hydroprocessed effluent 10 contains a reduced content of contaminants (i.e., metals, sulfur and nitrogen), an increased paraffinicity, reduced BMCI, and an increased American Petroleum Institute (API) gravity.
  • the hydroprocessed effluent 10 is optionally conveyed to separation zone 20 to remove heavy ends as bottoms stream 21 and provide the remaining lighter cut as pyrolysis feed 22 .
  • hydrotreated effluent 10 serves as the pyrolysis feedstream without separation of bottoms.
  • the pyrolysis feedstream e.g. having an initial boiling point corresponding to that of the feed and a final boiling point in the range of about 370° C. to about 600° C.
  • the pyrolysis feedstream is conveyed to the inlet of a convection section 32 in the presence of an effective amount of steam, e.g., admitted via a steam inlet.
  • the mixture is heated to a predetermined temperature, e.g., using one or more waste heat streams or other suitable heating arrangement.
  • the heated mixture of the pyrolysis feedstream and additional steam is passed to the pyrolysis section 34 to produce a mixed product stream 39 .
  • the heated mixture of from section 32 is passed through a vapor-liquid separation section 36 in which a portion 38 is rejected as a fuel oil component suitable for blending with pyrolysis fuel oil 71 .
  • the steam pyrolysis zone 30 operates under parameters effective to crack fraction 22 (or effluent 10 in embodiments in which separation zone 20 is not employed) into the desired products including ethylene, propylene, butadiene, mixed butenes and pyrolysis gasoline.
  • steam cracking in the pyrolysis section is carried out using the following conditions: a temperature in the range of from 400° C. to 900° C. in the convection section and in the pyrolysis section; a steam-to-hydrocarbon ratio in the convection section in the range of from 0.3:1 to 2:1; and a residence time in the convection section and in the pyrolysis section in the range of from 0.05 seconds to 2 seconds.
  • the vapor-liquid separation section 36 includes one or a plurality of vapor liquid separation devices 80 as shown in FIGS. 2A-2C .
  • the vapor liquid separation device 80 is economical to operate and maintenance free since it does not require power or chemical supplies.
  • device 80 comprises three ports including an inlet port for receiving a vapor-liquid mixture, a vapor outlet port and a liquid outlet port for discharging and the collection of the separated vapor and liquid, respectively.
  • Device 80 operates based on a combination of phenomena including conversion of the linear velocity of the incoming mixture into a rotational velocity by the global flow pre-rotational section, a controlled centrifugal effect to pre-separate the vapor from liquid (residue), and a cyclonic effect to promote separation of vapor from the liquid (residue).
  • device 80 includes a pre-rotational section 88 , a controlled cyclonic vertical section 90 and a liquid collector/settling section 92 .
  • the pre-rotational section 88 includes a controlled pre-rotational element between cross-section (S 1 ) and cross-section (S 2 ), and a connection element to the controlled cyclonic vertical section 90 and located between cross-section (S 2 ) and cross-section (S 3 ).
  • the vapor liquid mixture coming from inlet 82 having a diameter (D 1 ) enters the apparatus tangentially at the cross-section (S 1 ).
  • the area of the entry section (S 1 ) for the incoming flow is at least 10% of the area of the inlet 82 according to the following equation:
  • the pre-rotational element 88 defines a curvilinear flow path, and is characterized by constant, decreasing or increasing cross-section from the inlet cross-section S 1 to the outlet cross-section S 2 .
  • the ratio between outlet cross-section from controlled pre-rotational element (S 2 ) and the inlet cross-section (S 1 ) is in certain embodiments in the range of 0.7 ⁇ S 2 /S 1 ⁇ 1.4.
  • the rotational velocity of the mixture is dependent on the radius of curvature (R 1 ) of the center-line of the pre-rotational element 88 where the center-line is defined as a curvilinear line joining all the center points of successive cross-sectional surfaces of the pre-rotational element 88 .
  • the radius of curvature (R 1 ) is in the range of 2 ⁇ R 1 /D 1 ⁇ 6 with opening angle in the range of 150° ⁇ R 1 ⁇ 250°.
  • the cross-sectional shape at the inlet section S 1 although depicted as generally square, can be a rectangle, a rounded rectangle, a circle, an oval, or other rectilinear, curvilinear or a combination of the aforementioned shapes.
  • the shape of the cross-section along the curvilinear path of the pre-rotational element 38 through which the fluid passes progressively changes, for instance, from a generally square shape to a rectangular shape.
  • the progressively changing cross-section of element 88 into a rectangular shape advantageously maximizes the opening area, thus allowing the gas to separate from the liquid mixture at an early stage and to attain a uniform velocity profile and minimize shear stresses in the fluid flow.
  • connection element includes an opening region that is open and connected to, or integral with, an inlet in the controlled cyclonic vertical section 90 .
  • the fluid flow enters the controlled cyclonic vertical section 90 at a high rotational velocity to generate the cyclonic effect.
  • the ratio between connection element outlet cross-section (S 3 ) and inlet cross-section (S 2 ) in certain embodiments is in the range of 2 ⁇ S 3 /S 1 ⁇ 5.
  • the mixture at a high rotational velocity enters the cyclonic vertical section 90 .
  • Kinetic energy is decreased and the vapor separates from the liquid under the cyclonic effect.
  • Cyclones form in the upper level 90 a and the lower level 90 b of the cyclonic vertical section 90 .
  • the mixture is characterized by a high concentration of vapor
  • the mixture is characterized by a high concentration of liquid.
  • the internal diameter D 2 of the cyclonic vertical section 90 is within the range of 2 ⁇ D 2 /D 1 ⁇ 5 and can be constant along its height, the length (LU) of the upper portion 90 a is in the range of 1.2 ⁇ LU/D 2 ⁇ 3, and the length (LL) of the lower portion 90 b is in the range of 2 ⁇ LL/D 2 ⁇ 5.
  • the end of the cyclonic vertical section 90 proximate vapor outlet 84 is connected to a partially open release riser and connected to the pyrolysis section of the steam pyrolysis unit.
  • the diameter (DV) of the partially open release is in certain embodiments in the range of 0.05 ⁇ DV/D 2 ⁇ 0.4.
  • a large volume fraction of the vapor therein exits device 80 from the outlet 84 through the partially open release pipe with a diameter DV.
  • the liquid phase e.g., residue
  • the liquid phase with a low or non-existent vapor concentration exits through a bottom portion of the cyclonic vertical section 90 having a cross-sectional area S 4 , and is collected in the liquid collector and settling pipe 92 .
  • connection area between the cyclonic vertical section 90 and the liquid collector and settling pipe 92 has an angle in certain embodiment of 90°.
  • the internal diameter of the liquid collector and settling pipe 92 is in the range of 2 ⁇ D 3 /D 1 ⁇ 4 and is constant across the pipe length, and the length (LH) of the liquid collector and settling pipe 92 is in the range of 1.2 ⁇ LH/D 3 ⁇ 5.
  • the liquid with low vapor volume fraction is removed from the apparatus through pipe 86 having a diameter of DL, which in certain embodiments is in the range of 0.05 ⁇ DL/D 3 ⁇ 0.4 and located at the bottom or proximate the bottom of the settling pipe
  • apparatus 80 can be formed as a monolithic structure, e.g., it can be cast or molded, or it can be assembled from separate parts, e.g., by welding or otherwise attaching separate components together which may or may not correspond precisely to the members and portions described herein.
  • Mixed product stream 39 is passed to the inlet of quenching zone 40 with a quenching solution 42 (e.g., water and/or pyrolysis fuel oil) introduced via a separate inlet to produce an intermediate quenched mixed product stream 44 having a reduced temperature, e.g., of about 300° C., and spent quenching solution 46 is discharged.
  • the gas mixture effluent 39 from the cracker is typically a mixture of hydrogen, methane, hydrocarbons, carbon dioxide and hydrogen sulfide.
  • mixture 44 is compressed in a multi-stage compressor zone 51 , typically in 4-6 stages to produce a compressed gas mixture 52 .
  • the compressed gas mixture 52 is treated in a caustic treatment unit 53 to produce a gas mixture 54 depleted of hydrogen sulfide and carbon dioxide.
  • the gas mixture 54 is further compressed in a compressor zone 55 , and the resulting cracked gas 56 typically undergoes a cryogenic treatment in unit 57 to be dehydrated, and is further dried by use of molecular sieves.
  • the cold cracked gas stream 58 from unit 57 is passed to a de-methanizer tower 59 , from which an overhead stream 60 is produced containing hydrogen and methane from the cracked gas stream.
  • the bottoms stream 65 from de-methanizer tower 59 is then sent for further processing in product separation zone 70 , comprising fractionation towers including de-ethanizer, de-propanizer and de-butanizer towers. Process configurations with a different sequence of de-methanizer, de-ethanizer, de-propanizer and de-butanizer can also be employed.
  • hydrogen 62 having a purity of typically 80-95 vol % is obtained.
  • Recovery methods in unit 61 include cryogenic recovery (e.g., at a temperature of about ⁇ 157° C.).
  • Hydrogen stream 62 is then passed to a hydrogen purification unit 64 , such as a pressure swing adsorption (PSA) unit to obtain a hydrogen stream 2 having a purity of 99.9%+, or a membrane separation units to obtain a hydrogen stream 2 with a purity of about 95%.
  • PSA pressure swing adsorption
  • the purified hydrogen stream 2 is then recycled back to serve as a major portion of the requisite hydrogen for the hydroprocessing zone.
  • methane stream 63 can optionally be recycled to the steam cracker to be used as fuel for burners and/or heaters.
  • the bottoms stream 65 from de-methanizer tower 59 is conveyed to the inlet of product separation zone 70 to be separated into methane, ethylene, propylene, butadiene, mixed butylenes and pyrolysis gasoline discharged via outlets 78 , 77 , 76 , 75 , 74 and 73 , respectively.
  • Pyrolysis gasoline generally includes C5-C9 hydrocarbons, and benzene, toluene and xylenes can be extracted from this cut.
  • one or both of the unvaporized heavy liquid fraction 21 from flash zone 20 and the rejected portion 38 from vapor-liquid separation section 36 are combined with pyrolysis fuel oil 71 (e.g., materials boiling at a temperature higher than the boiling point of the lowest boiling C10 compound, known as a “C10+” stream) and the mixed stream can be withdrawn as a pyrolysis fuel oil blend 72 , e.g., a low sulfur fuel oil blend to be further processed in an off-site refinery.
  • pyrolysis fuel oil 71 e.g., materials boiling at a temperature higher than the boiling point of the lowest boiling C10 compound, known as a “C10+” stream
  • selective hydroprocessing or hydrotreating processes can increase the paraffin content (or decrease the BMCI) of a feedstock by saturation followed by mild hydrocracking of aromatics, especially polyaromatics.
  • contaminants such as metals, sulfur and nitrogen can be removed by passing the feedstock through a series of layered catalysts that perform the catalytic functions of demetallization, desulfurization and/or denitrogenation.
  • the sequence of catalysts to perform hydrodemetallization (HDM) and hydrodesulfurization (HDS) is as follows:
  • a comparative example was conducted as shown in Tables 1 and 2 below. Atmospheric residue was used as a feedstock to a hydroprocessing unit. A virgin crude oil was distillated to produce a light naphtha fraction, a heavy naphtha fraction, a kerosene fraction, a diesel fraction and an atmospheric residue fraction boiling above 370° C. The atmospheric residue fraction was hydrotreated to produce a hydrotreated effluent containing a light naphtha fraction, a heavy naphtha fraction, a kerosene fraction, a diesel fraction, an atmospheric residue fraction boiling above 370° C. and a vacuum residue fraction boiling above 540° C.
  • the hydrotreated effluent excluding the vacuum residue fraction was passed to a steam pyrolysis reactor to produce ethylene.
  • the ethylene yield was 6.5 wt % from the virgin crude oil, or 21.6 wt % from the feed to steam pyrolysis.
  • a whole crude oil feedstock was processed according to the process described with respect to FIG. 1 .
  • a hydrotreated effluent was produced containing a light naphtha fraction, a heavy naphtha fraction, a kerosene fraction, a diesel fraction, a gas oil fraction boiling between 370° C. and 540° C., and a vacuum residue fraction boiling above 540° C.
  • the hydrotreated effluent excluding the vacuum residue fraction was passed to a steam pyrolysis reactor to produce ethylene.
  • the ethylene yield was 19.1 wt % based on the mass of the whole crude oil feed, or 23.3 wt % based on the mass of the feed to the steam pyrolysis zone.
  • the ethylene yield in this process based on whole crude oil as a feedstock was about three times the yield of a process using atmospheric residue as a feed to the steam pyrolysis zone.
  • the hydrogen content of the feed to the steam pyrolysis zone is enriched for high yield of olefins
  • coke precursors are significantly removed from the initial whole crude oil which allows a decreased coke formation in the radiant coil;
  • hydrogen produced from the steam cracking zone is recycled to the hydroprocessing zone to minimize the demand for fresh hydrogen.
  • the integrated systems described herein only require fresh hydrogen to initiate the operation. Once the reaction reaches the equilibrium, the hydrogen purification system can provide enough high purity hydrogen to maintain the operation of the entire system.

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CN107118801A (zh) 2017-09-01
WO2013112965A1 (en) 2013-08-01
KR102118616B1 (ko) 2020-06-03
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EP2807236B1 (en) 2020-12-09
EP2807236A1 (en) 2014-12-03
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