WO2016142805A1 - Procédé de déchloration de flux d'hydrocarbures et huiles de pyrolyse - Google Patents

Procédé de déchloration de flux d'hydrocarbures et huiles de pyrolyse Download PDF

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Publication number
WO2016142805A1
WO2016142805A1 PCT/IB2016/051133 IB2016051133W WO2016142805A1 WO 2016142805 A1 WO2016142805 A1 WO 2016142805A1 IB 2016051133 W IB2016051133 W IB 2016051133W WO 2016142805 A1 WO2016142805 A1 WO 2016142805A1
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Prior art keywords
hydrocarbon stream
treated
stream
total weight
hydrocarbon
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PCT/IB2016/051133
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English (en)
Inventor
Ravichander Narayanaswamy
Krishna Kumar Ramamurthy
Alexander Stanislaus
Mohammad JAVEED
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Sabic Global Technologies, B.V.
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Priority to US15/085,278 priority Critical patent/US20160264880A1/en
Publication of WO2016142805A1 publication Critical patent/WO2016142805A1/fr

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Classifications

    • 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
    • C10G45/06—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 containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—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 containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • 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
    • 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
    • C10G9/36—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 with 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

Definitions

  • This disclosure relates the treatment of hydrocarbon streams via processes which include dechlorination.
  • Waste plastics contain polyvinylchloride (PVC).
  • PVC polyvinylchloride
  • pyrolysis oils are off -spec for use as a feedstock for steam crackers because steam cracker feed specifications require chloride levels less than 3 ppm and olefin content less than 1 wt%.
  • a process for dechlorination of a hydrocarbon stream comprising contacting the hydrocarbon stream with a hydroprocessing catalyst in the presence of hydrogen to yield a hydrocarbon product, wherein the hydrocarbon stream comprises one or more chloride compounds in a concentration of 5 ppm or more based on a total weight of the hydrocarbon stream, and recovering a treated hydrocarbon stream from the hydrocarbon product, wherein the treated hydrocarbon stream comprises the one or more chloride compounds in a concentration of less than 5 ppm based on a total weight of the treated hydrocarbon stream.
  • Figure 1 illustrates a hydroprocessing system which dechlorinates chloride compounds, and in embodiments, additionally hydrogenates olefins contained in a hydrocarbon stream to levels suitable for introduction to a steam cracker.
  • Figure 2 is a graph of a staged catalyst sulphiding protocol, showing temperature versus time.
  • Embodiments of a process for dechlorination of a hydrocarbon stream which include contacting the hydrocarbon stream with a hydroprocessing catalyst in the presence of hydrogen to yield a hydrocarbon product.
  • Embodiments of the process include recovering a treated hydrocarbon stream from the hydrocarbon product, where the treated hydrocarbon stream has a reduced concentration of chloride compounds compared to the concentration of chloride compounds in the hydrocarbon feed stream.
  • Figure 1 illustrates a hydroprocessing system 100 which dechlorinates chloride compounds, and in embodiments, additionally hydrogenates olefins contained in a hydrocarbon stream 1 to levels suitable for introduction to a steam cracker 30.
  • the system 100 includes a hydroprocessing reactor 10, a separator 20, and a steam cracker 30.
  • the hydrocarbon stream 1 feeds to the hydroprocessing reactor 10, and the reaction product effluent flows from the hydroprocessing reactor 10 in the hydrocarbon product stream 2 to the separator 20.
  • a treated product (e.g., in gas or liquid form) is recovered from the hydrocarbon product stream 2 and flows from the separator 20 via treated hydrocarbon stream 4, with one or more sulphur- containing gases and/or chlorine-containing gases flowing from the separator 20 in stream 3.
  • a second hydroprocessing reactor and a second separator may be placed in between separator 20 and treated hydrocarbon stream 4.
  • the treated product flowing from the separator 20, in such embodiments, may contain residual sulphur, and the second hydroprocessing reactor/second separator combination may treat the treated product flowing from the separator 20 to completely remove the sulphur such that a second treated product flowing in the treated hydrocarbon stream 4 from the second separator contains less than 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.1 ppmw S based on total weight of the treated hydrocarbon stream 4.
  • the treated product in the treated hydrocarbon stream 4 may flow directly (e.g., without any separations or fractionations of the treated hydrocarbon stream 4) or via blended hydrocarbon stream 4' (e.g., without any separations or fractionations of the treated hydrocarbon stream 4 and blended hydrocarbon stream 4') to a steam cracker 30, from which high value products flow in stream 6.
  • the hydrocarbon stream 1 generally includes one or more hydrocarbons and one or more chloride compounds. In embodiments, the hydrocarbon stream 1 may additionally include one or more sulphides, hydrogen, or combinations thereof.
  • the hydrocarbon stream 1 is generally in a liquid phase.
  • a hydrogen (H 2 ) stream can be added to hydrocarbon stream 1 before entering the hydroprocessing reactor 10.
  • a H 2 stream is additionally added in between various catalyst beds in a multi-bed arrangement in the hydroprocessing reactor 10 to enrich the reactor environment with H 2 .
  • the hydrocarbon stream 1 may be a stream from an upstream process, such as a pyrolysis process, which contains one or more chloride compounds, and optionally, also one or more sulphides, for example, from the pyrolysis of waste plastics.
  • the hydrocarbon stream 1 may be doped with the one or more sulphides, via a doping stream 7.
  • Examples of the one or more hydrocarbons which may be included in the hydrocarbon stream 1 include paraffins (n-paraffin, i-paraffin, or both), olefins, naphthenes, aromatic hydrocarbons, or combinations thereof.
  • the group of hydrocarbons may be collectively referred to as a PONA feed (paraffin, olefin, naphthene, aromatics) or PIONA feed (n-paraffin, i-paraffin, olefin, naphthene, aromatics).
  • a particular embodiment of the hydrocarbon stream 1 is a plastic pyrolysis oil, discussed in more detail below.
  • any paraffin may be included in the hydrocarbon stream 1.
  • paraffins which may be included in the hydrocarbon stream 1 include, but are not limited to, Ci to C 22 n-paraffins and i-paraffins.
  • the concentration of paraffins in the hydrocarbon stream 1 may be less than 10 wt% based on the total weight of the hydrocarbon stream 1.
  • the concentration of paraffins in the hydrocarbon stream 1 may be 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, or more based on the total weight of the hydrocarbon stream 1.
  • embodiments include paraffins of carbon numbers up to 22, the disclosure is not limited to carbon number 22 as an upper end-point of the suitable range of paraffins, and the paraffins can include higher carbon numbers, e.g., 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, and higher.
  • any olefin may be included in the hydrocarbon stream 1.
  • olefins which may be included in hydrocarbon stream 1 include, but are not limited to, C2 to C10 olefins and combinations thereof.
  • the concentration of olefins in the hydrocarbon stream 1 may be less than 10 wt% based on the total weight of the hydrocarbon stream 1.
  • the concentration of olefins in the hydrocarbon stream 1 may be 10 wt%, 20 wt%, 30 wt%, 40 wt% or more based on the total weight of the hydrocarbon stream 1.
  • embodiments include olefins of carbon numbers up to 10, the disclosure is not limited to carbon number 10 as an upper end-point of the suitable range of olefins, and the olefins can include higher carbon numbers, e.g., 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, and higher.
  • the hydrocarbon stream 1 comprises no olefins.
  • Any naphthene may be included in the hydrocarbon stream 1.
  • naphthenes include, but are not limited to, cyclopentane, cyclohexane, cycloheptane, and cyclooctane.
  • the concentration of naphthenes in the hydrocarbon stream 1 may be less than 10 wt% based on the total weight of the hydrocarbon stream 1.
  • the concentration of naphthenes in the hydrocarbon stream 1 may be 10 wt%, 20 wt%, 30 wt%, 40 wt% or more based on the total weight of the hydrocarbon stream 1.
  • While embodiments include naphthenes of carbon numbers up to 8, the disclosure is not limited to carbon number 8 as an upper end-point of the suitable range of naphthenes, and the naphthenes can include higher carbon numbers, e.g., 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, and higher.
  • Aromatic hydrocarbons suitable for use in the hydrocarbon stream 1 include, but are not limited to, benzene, toluene, xylenes, ethyl benzene, or combinations thereof.
  • the concentration of aromatic hydrocarbons in the hydrocarbon stream 1 may be less than 10 wt% based on the total weight of the hydrocarbon stream 1.
  • the concentration of aromatic hydrocarbons in the hydrocarbon stream 1 may be 10 wt%, 20 wt%, 30 wt%, 40 wt% or more based on the total weight of the hydrocarbon stream 1.
  • aromatic hydrocarbons of carbon numbers up to 8 the disclosure is not limited to carbon number 8 as an upper end-point of the suitable range of aromatic hydrocarbons, and the aromatic hydrocarbons can include higher carbon numbers, e.g., 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, and higher. In an embodiment, the aromatic hydrocarbons carbon number is as high as 22.
  • the hydrocarbon stream 1 comprises no aromatic hydrocarbons.
  • Chloride compounds which may be included in the hydrocarbon stream 1 include, but are not limited to, aliphatic chlorine-containing hydrocarbons, aromatic chlorine-containing hydrocarbons, and other chlorine -containing hydrocarbons.
  • Examples of chlorine-containing hydrocarbons include, but are not limited to, 1-chlorohexane (CgH 13 Cl), 2-chloropentane (CsHnCl), 3-chloro-3-methyl pentane (CgH 13 Cl), (2- chloroethyl) benzene (CgHgCl), chlorobenzene (CgH 5 Cl), or combinations thereof.
  • the concentration of chloride compounds in the hydrocarbon stream 1 may be 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10 ppm, 15 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1,000 ppm, 1,100 ppm, 1,200 ppm, 1,300 ppm, 1,400 ppm, 1,500 ppm, 1,600 ppm, 1,700 ppm, 1,800 ppm, 1,900 ppm, 2,000 ppm or more based on the total weight of the hydrocarbon stream 1.
  • Sulphides which may be included in the hydrocarbon stream 1 include sulphur-containing compounds.
  • a sulphiding agent such as dimethyl disulphide (C 2 H 6 S 2 ), dimethyl sulphide (C 2 3 ⁇ 4S), mercaptans (R-SH), carbon disulphide (CS 2 ), hydrogen sulphide (H 2 S), or combinations thereof may be used as the sulphide in the hydrocarbon stream 1.
  • one or more sulphides e.g., dimethyl disulphide (C 2 H 6 S 2 ), dimethyl sulphide (C 2 3 ⁇ 4S), mercaptans (R-SH), carbon disulphide (CS 2 ), hydrogen sulphide (H 2 S), or combinations thereof
  • the hydrocarbon stream 1 e.g., the hydrocarbon stream 1 is "doped" with one or more sulphides
  • doping stream 7 e.g., the hydrocarbon stream 1 is "doped" with one or more sulphides
  • the one or more sulphides are added to the hydrocarbon stream 1 in an amount such that a sulphur content of the hydrocarbon stream 1, after sulphide addition, is about 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt% or more based on the total weight of the hydrocarbon stream 1.
  • the doping stream 7 may include components tailored for doping such as hexadecane and dimethyl disulphide; alternatively, the doping stream 7 may be a heavier oil (e.g., naphtha, diesel, or both) which already contains sulphide compounds (or to which sulphides are doped to achieve the sulphur content disclosed herein) and which is blended with the hydrocarbon stream 1 to achieve the sulphur content described above.
  • a heavier oil e.g., naphtha, diesel, or both
  • sulphide compounds or to which sulphides are doped to achieve the sulphur content disclosed herein
  • one or more sulphides are present in the hydrocarbon stream as a result of upstream processing from which the hydrocarbon stream 1 flows.
  • the hydrocarbon stream 1 may contain one or more sulphides in an amount such that a sulphur content of the hydrocarbon stream 1, without sulphide doping, is about 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt% or more based on the total weight of the hydrocarbon stream 1.
  • the hydrocarbon stream 1 may contain one or more sulphides in an amount insufficient for sulphiding (e.g., less than 5,000, 4,000, 3,000, 2,000, 1,000, 900, 800, 700, 600, 500, 400, 300, 200, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 5, or 1 ppm) the hydroprocessing catalyst contained in the hydroprocessing reactor 10 (the catalyst is discussed in more detail below), and doping stream 7 is utilized to raise the concentration of the one or more sulphides in the hydrocarbon stream 1 to such that a sulphur content of the hydrocarbon stream 1, after sulphide addition, is about 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt% or more based on the total weight of the hydrocarbon stream 1.
  • the hydroprocessing catalyst contained in the hydroprocessing reactor 10 the catalyst
  • the sulphur content of the hydrocarbon stream 1, after sulphide addition using doping stream 7, is up to about 3 wt% based on the total weight of the hydrocarbon stream 1.
  • the sulphur content of the hydrocarbon stream 1, without sulphide addition using doping stream 7, is up to about 3 wt% based on the total weight of the hydrocarbon stream 1.
  • the hydrocarbon stream 1 may be one or more plastic pyrolysis oils which contain any of the paraffins, i-paraffins, olefins, naphthenes, aromatic hydrocarbons, chloride compounds, sulphides, or combinations thereof as disclosed herein.
  • the one or more plastic pyrolysis oils may be obtained from pyrolysis of waste plastics (for example, from a high severity process as disclosed in U.S. Patent No. 8,895,790, which is incorporated by reference in its entirety, or from any low temperature severity pyrolysis process known in the art with the aid of this disclosure).
  • Other streams which may comprise at least a portion of the hydrocarbon stream 1 include a reformate stream from catalytic naphtha reformer, tire pyrolysis oil, and any other chloride containing hydrocarbon stream.
  • the hydrocarbon stream 1 may be one or more pyrolysis oils as described above which is blended with a heavier oil (e.g., a naphtha or diesel, via doping stream 7).
  • a heavier oil e.g., a naphtha or diesel
  • blending the treated hydrocarbon stream 4 with a non-chlorinated stream 5 as described for embodiments below may additionally occur; alternatively, the subsequent blending may not occur.
  • the hydroprocessing reactor 10 is configured to dechlorinate, and in some embodiments, additionally hydrogenate components of the hydrocarbon stream 1 fed to the hydroprocessing reactor 10.
  • the hydrocarbon stream 1 is contacted with the hydroprocessing catalyst in the presence of hydrogen to yield a hydrocarbon product in stream 2. It is contemplated the hydrocarbon stream 1 may be contacted with the hydroprocessing catalyst in upward flow, downward flow, radial flow, or combinations thereof, with or without a staged addition of hydrocarbon stream 1, doping stream 7, a H 2 stream, or combinations thereof. It is further contemplated the components of the hydrocarbon stream 1 may be in the liquid phase, a liquid-vapor phase, or a vapor phase while in the hydroprocessing reactor 10.
  • the hydroprocessing reactor 10 may facilitate any reaction of the components of the hydrocarbon stream 1 in the presence of, or with, hydrogen. Reactions may occur as the addition of hydrogen atoms to double bonds of unsaturated molecules (e.g., olefins, aromatic compounds), resulting in saturated molecules (e.g., paraffins, i-paraffins, naphthenes). Additionally or alternatively, reactions in the hydroprocessing reactor 10 may cause a rupture of a bond of an organic compound, with a subsequent reaction and/or replacement of a heteroatom with hydrogen.
  • unsaturated molecules e.g., olefins, aromatic compounds
  • saturated molecules e.g., paraffins, i-paraffins, naphthenes
  • Examples of reactions which may occur in the hydroprocessing reactor 10 include, but are not limited to, the hydrogenation of olefins, removal of heteroatoms from heteroatom-containing hydrocarbons (e.g., dechlorination), conversion of one or more aromatics to one or more cycloparaffins, isomerization of one or more normal paraffins to one or more i- paraffins, selective ring opening of one or more cycloparaffins to one or more i-paraffins, or combinations thereof.
  • the hydroprocessing reactor 10 may be any vessel configured to contain the hydroprocessing catalyst disclosed herein.
  • the vessel may be configured for gas phase, liquid phase, vapor- liquid phase, or slurry phase operation.
  • the hydroprocessing reactor 10 may include one or more beds of the hydroprocessing catalyst in fixed bed, fluidized bed, moving bed, ebullated bed, slurry bed, or combinations thereof, configuration.
  • the hydroprocessing reactor 10 may be operated adiabatically, isothermally, nonadiabatically, non-isothermally, or combinations thereof.
  • the reactions of this disclosure may be carried out in a single stage or in multiple stages.
  • the hydroprocessing reactor 10 can be two reactor vessels fluidly connected in series, each having one or more catalyst beds of the hydroprocessing catalyst.
  • two or more stages for hydroprocessing may be contained in a single reactor vessel.
  • the first stage may dechlorinate and hydrogenate components of the hydrocarbon stream 1 to yield a first hydrocarbon product having a first level of chloride compounds and olefins.
  • the first hydrocarbon product may flow from the first stage to the second stage, where other components of the first hydrocarbon product are dechlorinated and hydrogenated to yield a second hydrocarbon product stream (stream 2 in Figure 1) having a second level of chloride compounds and olefins.
  • the second hydrocarbon product stream may then be treated as described herein for stream 2.
  • the hydroprocessing reactor 10 may comprise one or more vessels.
  • the sulphur present in the hydrocarbon stream 1 is removed as H 2 S to provide a reduced level of sulphur acceptable for downstream processing in steam crackers and refinery units.
  • hydrogen may feed to the hydroprocessing reactor 10 in stream 8.
  • the rate of hydrogen addition to the hydroprocessing reactor 10 is generally sufficient to achieve the hydrogen-to- hydrocarbon ratios disclosed herein.
  • the disclosed hydroprocessing reactor 10 may operate at various process conditions. For example, contacting the hydrocarbon stream 1 with the hydroprocessing catalyst in the presence of hydrogen may occur in the hydroprocessing reactor 10 at a temperature of 100 °C to 450 °C; alternatively, 100 °C to 350 °C; or alternatively, 260 °C to 350 °C. Contacting the hydrocarbon stream 1 with the hydroprocessmg catalyst in the presence of hydrogen may occur in the hydroprocessing reactor 10 at a pressure of 1 barg to 200 barg; or alternatively, 20 barg to 60 barg.
  • Contacting the hydrocarbon stream 1 with the hydroprocessing catalyst in the presence of hydrogen may occur in the hydroprocessing reactor 10 at a weight hourly space velocity (WHSV) of between 0.1 hr -1 to 10 hr 1 ; or alternatively, 1 hr -1 to 3 hr 1 .
  • WHSV weight hourly space velocity
  • Contacting the hydrocarbon stream 1 with the hydroprocessing catalyst in the presence of hydrogen may occur in the hydroprocessing reactor 10 at a hydrogen-to-hydrocarbon (H 2 /HC) flow ratio of 10 to 3,000 NL /L; or alternatively, 200 to 800 NL/L.
  • H 2 /HC hydrogen-to-hydrocarbon
  • dechlorination using the hydroprocessing catalyst as described herein is performed in the hydroprocessing reactor 10 without the use of chlorine sorbents, without addition of Na 2 C0 3 in an effective amount to function as a dechlorinating agent, or both.
  • the hydroprocessing catalyst may be any catalyst used for hydrogenation (e.g., saturation) of olefins and aromatic hydrocarbons (e.g., a commercially available hydrotreating catalyst).
  • the hydroprocessing catalyst is a cobalt and molybdenum catalyst (Co-Mo catalyst) on an alumina support.
  • the hydroprocessing catalyst is a nickel and molybdenum catalyst (Ni-Mo catalyst) on an alumina support or tungsten and molybdenum catalyst (W-Mo catalyst) on an alumina support.
  • catalyst embodiments may include platinum and palladium catalyst (Pt-Pd catalyst) on an alumina support, nickel sulphides suitable for slurry processing, molybdenum sulphides suitable for slurry processing, nickel and molybdenum sulphides, or combinations thereof.
  • Pt-Pd catalyst platinum and palladium catalyst
  • the hydroprocessing catalyst is activated and/or the activity is maintained by sulphiding the hydroprocessing catalyst.
  • the hydroprocessing catalyst may be sulphided (i.e., activated) and/or sulphiding (i.e., maintaining of the catalyst activity) of the hydroprocessing catalyst may be performed (e.g., maintaining the hydroprocessing catalyst in sulphided form is accomplished) by continuously contacting the hydrocarbon stream 1 containing one or more sulphides with the hydroprocessing catalyst.
  • the one or more sulphides may be included in the hydrocarbon stream 1 in an amount such that the sulphur content of the hydrocarbon stream 1 is about 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt% based on the total weight of the hydrocarbon stream 1.
  • the sulphur content of the hydrocarbon stream 1 is up to about 3 wt% based on the total weight of the hydrocarbon stream 1.
  • the hydroprocessing catalyst may be sulphided (i.e., activated) by contacting a catalyst activating stream 9 containing one or more sulphides with the hydroprocessing catalyst for a period of time (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9 or more hours) sufficient to activate the hydroprocessing catalyst (before contacting the hydrocarbon stream 1 with the hydroprocessing catalyst).
  • the catalyst activating stream 9 may include a hydrocarbon carrier for the one or more sulphides, such as hexadecane.
  • the one or more sulphides may be included in the catalyst activating stream 9 in an amount such that the sulphur content of the catalyst activating stream 9 is about 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt% or more based on the total weight of the catalyst activating stream 9.
  • the sulphur content of the catalyst activating stream 9 is up to about 3 wt% based on the total weight of the catalyst activating stream 9.
  • flow of the catalyst activating stream 9 may be discontinued, and sulphiding (i.e., maintaining catalyst activity) of the hydroprocessing catalyst may be maintained (e.g., maintaining the hydroprocessing catalyst in sulphided form is accomplished) by continuously contacting the hydrocarbon stream 1 containing one or more sulphides with the hydroprocessing catalyst.
  • the one or more sulphides may be included in the hydrocarbon stream 1 in an amount such that the sulphur content of the hydrocarbon stream 1 is about 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt% based on the total weight of the hydrocarbon stream 1.
  • the sulphur content of the hydrocarbon stream 1 is up to about 3 wt% based on the total weight of the hydrocarbon stream 1.
  • catalyst activity is also maintained by chloriding the hydroprocessing catalyst.
  • the hydroprocessing catalyst is chlorided using the one or more chloride compounds provided to the hydroprocessing catalyst by the hydrocarbon stream 1.
  • the one or more chloride compounds which contribute to acidification of the hydroprocessing catalyst may be included in the hydrocarbon stream 1 in concentrations disclosed herein.
  • the hydrocarbon product stream 2 may contain one or more olefins in a concentration of less than 1 wt% based on the total weight of the hydrocarbon product stream 2. It is also contemplated that the concentration of aromatic hydrocarbons in the hydrocarbon product stream 2 is less than the concentration of aromatic hydrocarbons in the hydrocarbon stream 1 due to hydrogenation of at least a portion of the aromatic hydrocarbons in the hydroprocessing reactor 10. For example, aromatic hydrocarbons may be present in the hydrocarbon product stream 2 in a concentration of less than 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 wt% based on the total weight of the hydrocarbon product stream 2.
  • the reaction product flows as effluent from the hydroprocessing reactor 10 in the hydrocarbon product stream 2 to the separator 20.
  • Separator 20 may be any vessel which can recover a treated hydrocarbon stream 4 from the hydrocarbon product 2 which is fed to the separator 20.
  • the treated hydrocarbon stream 4 may be recovered by separating a treated product (e.g., liquid product or gas product) from sulphur and chlorine-containing gas in the separator 20, and by flowing the treated product in the treated hydrocarbon stream 4 from the separator 20.
  • a treated product e.g., liquid product or gas product
  • the separator 20 is a condenser which operates at conditions which condense a portion of the hydrocarbon product stream 2 into the treated product (e.g., liquid product or treated liquid product) while leaving sulphur and chlorine-containing compounds in the gas phase.
  • the treated liquid product flows from the separator 20 in treated hydrocarbon stream 4, and the sulphur and chlorine- containing gas flows from the separator 20 via stream 3.
  • the separator 20 is a scrubbing unit containing a caustic solution (e.g., a solution of sodium hydroxide in water) which removes (e.g., via reaction, adsorption, absorption, or combinations thereof) sulphur and chlorine -containing gases from the hydrocarbon product stream 2 to yield the treated product (e.g., gas product or treated gas product) which flows from the separator 20 via treated hydrocarbon stream 4 while the sulphur and chlorine-containing compounds in the gas phase flow from the separator 20 via stream 3.
  • a caustic solution e.g., a solution of sodium hydroxide in water
  • the separator 20 is a condenser in communication with a scrubbing unit containing a caustic solution.
  • the condenser may operate at conditions which condense a portion of the hydrocarbon product stream 2 into the mid-treated product (e.g., liquid product or treated liquid product) while leaving sulphur and chlorine-containing compounds in the gas phase.
  • the mid-treated liquid product flows from the condenser and experiences a pressure reduction (e.g., via a valve or other pressure reducing device known in the art with the aid of this disclosure) which creates an effluent gas which flows from the scrubbing unit, leaving the treated product flowing in treated hydrocarbon stream 4.
  • Sulphur and chlorine -containing compounds flow from the separator 20 in stream 3.
  • the treated hydrocarbon stream 4 includes one or more chloride compounds in a concentration of less than 5 ppm, 4 ppm, 3 ppm, 2 ppm, 1 ppm, or 0.5 ppm based on a total weight of the treated hydrocarbon stream 4.
  • the one or more chloride compounds in the treated hydrocarbon stream 4 may be the same as some or all of the one or more chloride compounds in the hydrocarbon stream 1; alternatively, it is contemplated that only some of the one or more chloride compounds in the treated hydrocarbon stream 4 are the same as only some of the one or more chloride compounds in the hydrocarbon stream 1; alternatively, it is contemplated that none of the one or more chloride compounds in the treated hydrocarbon stream 4 are the same as the one or more chloride compounds in the hydrocarbon stream 1.
  • the treated hydrocarbon stream 4 includes the one or more olefins in a concentration which is less than a concentration of the one or more olefins in the hydrocarbon stream 1 due to hydrogenation of at least a portion of the one or more olefins from the hydrocarbon stream 1 while the hydrocarbon stream 1 is contacted with the hydroprocessing catalyst in the hydroprocessing reactor 10.
  • the one or more olefins are present in the treated hydrocarbon stream 4 in a concentration of less than 1 wt% based on the total weight of the treated hydrocarbon stream 4.
  • the treated hydrocarbon stream 4 includes one or more paraffins, and the concentration of the one or more olefins is less than 1 wt% based on the total weight of the treated hydrocarbon stream 4.
  • the treated hydrocarbon stream 4 may be fed directly to the steam cracker 30.
  • the treated hydrocarbon stream 4 may be blended with a non-chlorinated hydrocarbon stream 5 to yield a blended hydrocarbon stream 4' (streams 4' and 5 having dashed lines to denote the alternative embodiment) having a concentration of one or more chlorides which is less than 3 ppm based on a total weight of the blended hydrocarbon stream 4'.
  • the blended hydrocarbon stream 4' may be fed to the steam cracker 30.
  • Steam cracker 30 generally has feed specification requirements. First, the steam cracker 30 requires the concentration of chloride compounds in the feed to the steam cracker 30 to be less than 3 ppm. Second, the steam cracker 30 requires the concentration of olefins in a stream fed to the steam cracker 30 to be less than 1 wt%. The steam cracker 30 cracks molecules or cleaves at elevated temperatures carbon- carbon bonds of the components in the treated hydrocarbon stream 4 or blended hydrocarbon stream 4' in the presence of steam to yield high value products such as ethylene, propylene, butene, butadiene, aromatic compounds, or combinations thereof. The high value products may flow from the steam cracker 30 via stream 6.
  • dechlorination can occur over the operating temperature ranges disclosed herein for the hydroprocessing reactor 10, including operating temperatures in the low-end of the temperature ranges disclosed herein. Removal of chloride compounds to less than 1 ppm occurs at temperatures below 350 °C. Moreover, achieving sub-ppm chloride compound concentrations is possible with initial chloride content in the hydrocarbon stream 1 of 1,000 ppm or more. Moreover still, removal of chloride compounds is effective for different types and classes of chlorides present in the hydrocarbon stream 1. When the hydroprocessing reaction is conducted at temperatures at or above 350 °C, it has been found that the treated hydrocarbon product contains 3ppm or higher chloride content. In such cases, the treated hydrocarbon product stream can be blended as described herein with a non-chlorinated stream 5 in such proportions to make the combined blended hydrocarbon stream 4' meet the steam cracker feed specifications.
  • Operation at low temperatures also has an added advantage of corrosion mitigation of the reactor metallurgy.
  • corrosion rates start to increase at reactor temperatures over 300 °C. It has been found that the efficiency of dechlorination according to the disclosed embodiments is good at reactor temperatures below 350 °C, and the dechlorination process works with a sulphided Co-Mo catalyst on an alumina support even as low as 260 °C, with the chlorides in the treated product being less than 1 ppm.
  • the metallurgy corrosion issue is mitigated and longer equipment life is possible while achieving dechlorination to levels desirable for feed to steam cracker 30.
  • the disclosed embodiments also demonstrate olefins in the hydrocarbon product are reduced typically to less than 1 wt% of the treated hydrocarbon stream 4 from a feed olefin concentration of 20 wt% or more in the hydrocarbon stream 1.
  • the disclosed processes achieve the requirements of chloride content and olefin content of the feed for a steam cracker 30.
  • Examples 1 to 5 were conducted in a fixed bed reactor located inside a 3 -zone split-tube furnace.
  • the reactor internal diameter was 13.8 mm and had concentrically located bed thermowell of 3 mm outer diameter.
  • the reactor was 48.6 cm long.
  • Commercial hydroprocessing catalyst of Co-Mo on alumina (8 g bone dry weight) was broken along the length to particles of 1.5 mm long and diluted with SiC in the ratio of 60 % SiC to 40 % catalyst to give a mean particle diameter of 0.34 mm. This was done to avoid slip through of the chlorides due to wall slip or channeling in the small diameter reactor.
  • Preheating bed and post-catalyst inert beds was provided in the form of 1 mm glass beads.
  • the catalyst bed temperature was controlled to isothermal by varying the controlled furnace zone skin temperatures.
  • the hydroprocessing catalyst was sulphided using 3 wt% S in hexadecane (S was introduced as dimethyl disulphide).
  • Liquid feed i.e., the hydrocarbon stream
  • H 2 gas was fed using a mass flow controller.
  • the reactor effluent gases i.e., hydrocarbon product
  • the reactor effluent gases were cooled to condense out the liquids (i.e., the treated hydrocarbon stream in the form of a liquid product) under pressure while allowing non-condensed gases (e.g., containing chloride(s), chlorine, hydrogen sulphide, or combinations thereof) to separate.
  • non-condensed gases e.g., containing chloride(s), chlorine, hydrogen sulphide, or combinations thereof
  • Example 1 a feed was prepared by mixing plastic pyrolysis oil (36.3 g) with n-hexadecane (240 g), and then adding dimethyl disulphide (the sulphide) and 1-chlorohexane (the chloride compound) to give a sulphur content of 2.34 wt% and 836 ppm chloride in the feed.
  • This feed was used as a hydrocarbon stream which was contacted with the sulphided hydroprocessing catalyst in the packed bed reactor as mentioned above in the presence of H 2 under several operating conditions as provided in the table below:
  • Example 1 demonstrates it is possible to dechlorinate a hydrocarbon stream containing plastic pyrolysis oil and having chloride compounds from a chloride content of more than 800 ppm chlorides to less than 5 ppm in the liquid product.
  • the chloride content of the liquid product i.e., the treated hydrocarbon stream
  • Example 1 demonstrates removal of chloride compounds to chloride contents less than 3 ppm, and even sub-ppm levels.
  • Example 2 a feed was prepared by adding dimethyl disulphide (the sulphide) and 2- chloropentane, 3 -chloro-3 -methyl pentane, 1-chlorohexane, (2-chloroethyl) benzene, and chlorobenzene (the chloride compounds) to n-hexadecane to give a sulphur content of 2wt% in the mixture and a chloride content of 1,095 ppm in the mixture. Each of the chloride compounds contributed approximately 220 ppm to the feed mixture.
  • This feed was used as a hydrocarbon stream which was contacted with the hydroprocessing catalyst in the packed bed reactor as mentioned above in the presence of H 2 at 300 °C reactor bed temperature, 40 barg reactor pressure, 414 NL/L H 2 /HC flow ratio, and 0.92 hr "1 weight hourly space velocity (WHSV).
  • the chloride content of the liquid product i.e., treated hydrocarbon stream was 0.23 ppm.
  • Example 2 demonstrates it is possible to dechlorinate a hydrocarbon stream containing no olefins and chloride compounds from a chloride content of about 1,100 ppm chlorides to the sub-ppm level in the in the liquid product.
  • EXAMPLE 3
  • Example 3 a hydrocarbon feed mixture was prepared to contain 30 wt% n-hexadecane, 10 wt% i-octane, 20 wt% 1-decene, 20 wt% cyclohexane, and 20 wt% ethyl benzene. To this the organic chlorides mentioned in Example 2 above were added along with dimethyl disulphide to give 205 ppm organic chlorides and 2 wt% S in the mixture.
  • This feed was used as a hydrocarbon stream which was contacted with the hydroprocessing catalyst in the packed bed reactor as mentioned above in the presence of H 2 at conditions of 300 °C reactor temperature, 60 barg reactor pressure, 0.92 hr "1 WHSV and 414 NL/L H 2 /HC flow ratio.
  • the liquid product (analyzed in DHA) contained 0.183 wt% olefins and 0.11 ppmw chlorides.
  • Example 3 demonstrates removal of olefins from a hydrocarbon stream such that the liquid product has less than 1 wt% olefin content needed in a steam cracker feed.
  • Example 4 a hydrocarbon feed mixture was prepared to contain 30 wt% n-hexadecane, 10 wt% i-octane, 20 wt% 1-decene, 20 wt% cyclohexane, and 20 wt% ethyl benzene. To this the organic chlorides mentioned in Example 2 above were added along with dimethyl disulphide to give 205 ppm organic chlorides and 2 wt% S in the mixture.
  • This feed was used as a hydrocarbon stream which was contacted with the hydroprocessing catalyst in the packed bed reactor as mentioned above in the presence of H 2 at conditions of 260 °C reactor temperature, 60 barg reactor pressure, 0.92 hr "1 WHSV and 414 NL/L H 2 /HC flow ratio.
  • the liquid product i.e., the treated hydrocarbon stream
  • Example 4 demonstrates the effective removal of chloride compounds from a hydrocarbon stream at very low temperatures.
  • Example 5 a hydrocarbon feed mixture was prepared to contain 30 wt% n-hexadecane, 10 wt% i-octane, 20 wt% 1-decene, 20 wt% cyclohexane, and 20 wt% ethyl benzene. To this the organic chlorides mentioned in Example 2 above were added along with dimethyl disulphide to give 205 ppm organic chlorides and 2 wt% S in the mixture.
  • This feed was used as a hydrocarbon stream which was contacted with the hydroprocessing catalyst in the packed bed reactor as mentioned above in the presence of H 2 at conditions of 300 °C reactor temperature, 20 barg reactor pressure, 0.92 hr "1 WHSV and 414 NL/L H 2 /HC flow ratio.
  • the liquid product i.e., the treated hydrocarbon stream
  • Example 5 demonstrates the effective removal of chloride compounds from a hydrocarbon stream at low operating pressures.
  • Example 6 demonstrates a process for sulphiding a hydroprocessing catalyst. The particular steps of the process are shown in Figure 2. The time of 0 hours (zero time) in Figure 2 corresponds to a time after the hydroprocessing catalyst is introduced into the hydroprocessing reactor.
  • the hydroprocessing reactor (having previously been loaded with the hydroprocessing catalyst) was purged with hydrogen for 30 to 60 minutes at a set operating pressure (e.g., 40 to 60 barg).
  • the set operating pressure was maintained by venting the reactor when the pressure of the reactor during hydrogen purging increased above the set operating pressure (e.g., due to a hydrogen source pressure greater than the set operating pressure).
  • the sulphiding feed was then introduced into the reactor using a high pressure pump against the set reactor pressure at a weight hourly space velocity (WHSV) of 3 hr "1 (on bone-dry catalyst basis).
  • the sulphiding feed (e.g., for use in doping stream 7 of Figure 1) was prepared by mixing n-hexadecane with dimethyl disulphide in appropriate quantity to give 3 wt% sulphur based on total weight of the sulphiding feed.
  • n-hexadecane is used for the sulphiding feed.
  • straight -run naphtha, diesel, or vacuum gas oils can also be used.
  • Figure 2 indicates the hydroprocessing catalyst was soaked with a sulphiding feed without a flow of hydrogen in the reactor and at ambient temperature for a period of 3 hours (ending at time 3.5 hours after zero time in Figure 2).
  • Catalyst soaking provides for complete wetting of the hydroprocessing catalyst; however, soaking is optional. Liquid was drained from the bottom of a downstream gas liquid separator.
  • the hydroprocessing reactor bed temperature was raised to 250 °C at a rate of 30 °C per hour with a flow of H 2 at a ratio of 200NL H 2 /L liquid feed. As shown in Figure 2, the temperature was increased from a time of 3.5 hours to a time of 10.8 hours after zero time.
  • the hydroprocessing reactor bed temperature was then held at 250 °C for a period of 8 hours. As shown in Figure 2, the temperature was held from a time of 10.8 hours to a time of 18.8 hours after zero time.
  • the bed temperature was further increased to 320 °C to 350 °C at a rate of 20 °C per hour without any temperature overshoot at the final temperature. As shown in Figure 2, the temperature was increased from a time of 18.8 hours to a time of 22.3 hours after zero time. [0077]
  • the hydroprocessing reactor bed temperature was then maintained at 320 °C to 350 °C for a period of 8 hours. As shown in Figure 2, the temperature was maintained at 320 °C to 350 °C from a time of 22.3 hours to a time of 30.0 hours after zero time.
  • a first embodiment which is a process for dechlorination of a hydrocarbon stream comprising:
  • hydrocarbon stream comprises one or more chloride compounds in a concentration of 5 ppm or more based on a total weight of the hydrocarbon stream;
  • the treated hydrocarbon stream comprises the one or more chloride compounds in a concentration of less than 5 ppm based on a total weight of the treated hydrocarbon stream.
  • a second embodiment which is the process of the first embodiment, wherein the treated hydrocarbon stream comprises the one or more chloride compounds in a concentration of less than 1 ppm based on the total weight of the treated hydrocarbon stream.
  • a third embodiment which is the process of any one of the first through the second embodiments, wherein the hydrocarbon stream comprises the one or more chloride compounds in a concentration of greater than 200 ppm based on a total weight of the hydrocarbon stream.
  • a fourth embodiment which is the process of any one of the first through the third embodiments, wherein the hydrocarbon stream further comprises one or more olefins, wherein the treated hydrocarbon stream further comprises the one or more olefins in a concentration of less than 1 wt% based on the total weight of the treated hydrocarbon stream.
  • a fifth embodiment which is the process of the fourth embodiment, wherein the one or more olefins are present in the hydrocarbon stream in a concentration of 20 wt% or more based on the total weight of the hydrocarbon stream.
  • a sixth embodiment which is the process of any one of the fourth through the fifth embodiments, wherein the concentration of the one or more olefins in the treated hydrocarbon stream is less than the concentration of the one or more olefins in the hydrocarbon stream due to hydrogenation of at least a portion of the one or more olefins from the hydrocarbon stream during the step of contacting.
  • a seventh embodiment which is the process of any one of the first through the sixth embodiments, wherein the hydrocarbon stream is one or more of a plastic pyrolysis oil and a tire pyrolysis oil.
  • An eighth embodiment which is the process of any one of the first through the seventh embodiments, wherein the hydrocarbon stream further comprises paraffins.
  • a ninth embodiment which is the process of the eighth embodiment, wherein the hydrocarbon stream further comprises one or more olefins, wherein the treated hydrocarbon stream further comprises the paraffins and the one or more olefins, wherein the one or more olefins of the treated hydrocarbon stream are present in a concentration of less than 1 wt% based on the total weight of the treated hydrocarbon stream.
  • a tenth embodiment which is the process of any one of the first through third and eighth embodiments, wherein the hydrocarbon stream comprises no olefins.
  • An eleventh embodiment which is the process of any one of the first through the tenth embodiments, further comprising:
  • a twelfth embodiment which is the process of the eleventh embodiment, wherein the one or more sulphides are added to the hydrocarbon stream in an amount such that a sulphur content in the hydrocarbon stream is about 0.5 wt% to about 5 wt% based on the total weight of the hydrocarbon stream.
  • a thirteenth embodiment which is the process of any one of the first through the twelfth embodiments, wherein the hydrocarbon stream further comprises one or more sulphides.
  • a fourteenth embodiment which is the process of the thirteen embodiment, wherein the one or more sulphides of the hydrocarbon stream are present in an amount such that a sulphur content of the hydrocarbon stream is about 0.5 wt% to about 5 wt% based on the total weight of the hydrocarbon stream.
  • a fifteenth embodiment which is the process of any one of the first through the fourteenth embodiments, wherein the hydroprocessing catalyst comprises cobalt and molybdenum on an alumina support, nickel and molybdenum on an alumina support, or nickel and molybdenum sulphides.
  • a sixteenth embodiment which is the process of any one of the first through the fifteenth embodiments, wherein contacting the hydrocarbon stream with the hydroprocessing catalyst comprises: contacting one or more sulphides contained in or added to the hydrocarbon stream with the hydroprocessing catalyst.
  • a seventeenth embodiment which is the process of the sixteenth embodiment, wherein the one or more sulphides are contained in or added to the hydrocarbon stream in an amount such that a sulphur content of the hydrocarbon stream is about 2 wt% based on the total weight of the hydrocarbon stream.
  • An eighteenth embodiment which is the process of any one of the first through the seventeenth embodiments, wherein the step of contacting is performed at a temperature of 100 °C to 450 °C.
  • a nineteenth embodiment which is the process of any one of the first through the eighteenth embodiments, wherein the step of contacting is performed at a temperature of 100 °C to 350 °C.
  • a twentieth embodiment which is the process of any one of the first through the nineteenth embodiments, wherein the step of contacting is performed at a temperature of 260 °C to 350 °C.
  • a twenty-first embodiment which is the process of any one of the first through the twentieth embodiments, wherein the hydrocarbon stream is in a liquid phase.
  • a twenty-second embodiment which is the process of any one of the first through the twenty-first embodiments, wherein the step of contacting is performed at a weight hourly space velocity of 0.1 to 10 hr 1 .
  • a twenty-third embodiment which is the process of any one of the first through the twenty- second embodiments, wherein the step of contacting is performed at a hydrogen to hydrocarbon ratio of 10 to 3,000 NL/L.
  • a twenty-fourth embodiment which is the process of any one of the first through the twenty- third embodiments, wherein the step of contacting is performed at a pressure of 1 to 200 barg.
  • a twenty-fifth embodiment which is the process of any one of the first through the twenty- fourth embodiments, wherein the treated hydrocarbon stream comprises the one or more chloride compounds in a concentration of less than 3 ppm based on a total weight of the treated hydrocarbon, the process further comprising:
  • a twenty-sixth embodiment which is the process of any one of the first through the twenty- fifth embodiments, further comprising:
  • a twenty-seventh embodiment which is the process of any one of the first through the twenty-sixth embodiments, wherein recovering a treated hydrocarbon stream from the hydrocarbon product comprises:
  • a twenty-eighth embodiment which is the process of any one of the first through the twenty- seventh embodiments, wherein no hydrogen halides and no halogenated organic compounds are recycled to the hydroprocessing reactor.
  • a twenty-ninth embodiment which is the process of any one of the first through the twenty- eighth embodiments, wherein the step of contacting is performed without use of chlorine sorbents.
  • a thirtieth embodiment which is the process of any one of the first through the twenty-ninth embodiments, wherein the step of contacting is performed without the presence of Na 2 C0 3 in an effective amount to function as a dechlorinating agent.
  • a thirty-first embodiment which is the process of any one of the first through the thirtieth embodiments, wherein the hydroprocessing reactor is configured to operate in the slurry phase.
  • a thirty-second embodiment which is the process of any one of the first through the thirty- first embodiments, wherein the step of contacting includes simultaneous dechlorination and hydrogenation of the hydrocarbon stream such that the treated hydrocarbon stream comprises the one or more chloride compounds in a concentration less than 1 ppm and one or more olefins in a concentration less than 1 wt% based on the total weight of the treated hydrocarbon stream.
  • a thirty-third embodiment which is the process of any one of the first through the thirty- second embodiments, wherein the hydroprocessing catalyst is sulphided.
  • a thirty-fourth embodiment which is the process of any one of the first through the thirty- third embodiments, wherein the one or more chloride compounds include chlorine-containing hydrocarbons.
  • a thirty-fifth embodiment which is the process of the thirty-fourth embodiment, wherein the chlorine-containing hydrocarbons include aliphatic chlorine-containing hydrocarbons, aromatic chlorine- containing hydrocarbons, other hydrocarbons containing chlorides, or a combination of any of aliphatic chlorine-containing hydrocarbons, aromatic chlorine-containing hydrocarbons, and other hydrocarbons containing chlorides.
  • a thirty-sixth embodiment which is the process of any one of the thirty-fourth through the thirty-fifth embodiments, wherein the chlorine-containing hydrocarbons include 1-chlorohexane, 2- chloropentane, 3-chloro-3-methyl pentane, (2-chloroethyl) benzene, chlorobenzene, or combinations thereof.

Abstract

L'invention concerne un procédé de déchloration d'un flux d'hydrocarbures, comprenant la mise en contact du flux d'hydrocarbures avec un catalyseur d'hydrotraitement en présence d'hydrogène pour obtenir un produit hydrocarboné qui satisfait aux exigences de l'unité de craquage à vapeur en termes de teneur en chlorure, et dans d'autres modes de réalisation, aux exigences en termes de teneur en oléfines.
PCT/IB2016/051133 2015-03-10 2016-03-01 Procédé de déchloration de flux d'hydrocarbures et huiles de pyrolyse WO2016142805A1 (fr)

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