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
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
  • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
  • C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a 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
  • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
  • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
• • 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
• • 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
• • 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
  • C10G45/10—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 platinum group metals or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • 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
  • C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
  • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
  • C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, 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
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
  • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
  • C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/44—Hydrogenation of the aromatic hydrocarbons
  • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
  • C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, 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
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/44—Hydrogenation of the aromatic hydrocarbons
  • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
  • C10G45/52—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing platinum group metals or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/44—Hydrogenation of the aromatic hydrocarbons
  • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
  • C10G45/54—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
  • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
  • C10G65/06—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a selective hydrogenation of the diolefins
• • 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
  • C10G2300/1003—Waste materials
• • 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
• • 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
  • C10G2300/4006—Temperature
• • 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
  • C10G2300/70—Catalyst aspects
• • 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
  • C10G2300/70—Catalyst aspects
  • C10G2300/708—Coking aspect, coke content and composition of deposits

Definitions

• the present invention relates to a process for purifying a pyrolysis oil comprising a hydrogenation step prior to a dehalogenation step, a production unit for carrying out said process and a purified pyrolysis oil obtained or obtainable by said process.
• the pyrolysis is a thermal degradation of plastic waste in an inert atmosphere and yields value added products such as pyrolysis gas, liquid pyrolysis oil and char (residue), wherein pyrolysis oil is the major product.
• the pyrolysis gas and char can be used as fuel for generating heat, e.g. for reactor heating purposes.
• the pyrolysis oil can be used as source for syngas production and/or processed into chemical feedstock such as ethylene, propylene, C4 cuts, etc. for example in a (steam) cracker.
• the plastic waste is mixed plastic waste composed of different types of polymers.
• the polymers are often composed of carbon and hydrogen in combination with other elements such as chlorine, bromine, fluorine, sulfur, oxygen and nitrogen that complicate recycling efforts.
• the elements other than carbon and hydrogen may be harmful during the further processing of the crude pyrolysis oil, since they may deactivate or poison catalysts used in the further processing of the pyrolysis oil.
• halogen-containing compounds can damage the cracker by corrosion in that they release hydrogen halide.
• Sulfur-containing compounds can deactivate or poison catalysts used in the cracker, or can contaminate the cracker products. Nitrogen containing impurities may also poison downstream catalysts.
• Plastic waste typically contains heteroatom containing additives such as stabilizers and plasticizers that have been incorporated to improve the performance of the polymers.
• additives also often comprise nitrogen, halogen and sulfur containing compounds and heavy metals.
• waste engine oils, transformer oils, hydraulic oils and machine oils may contain heavy metal abrasion. The heavy metals are often toxic and the quality of the pyrolysis oil is reduced by the presence of heavy metal impurities.
• plastic waste often may be uncleaned plastics with residue that may also contain elements other carbon and hydrogen. Therefore, the reduction of the nitrogen, sulfur, halogen content in the pyrolysis oil as well as the heavy-metal content is essential for any profit-generating processing of the pyrolysis oil.
• a high quality pyrolysis oil rich in carbon and hydrogen and low in elements other than carbon and hydrogen is preferred as feedstock to prevent catalyst deactivation and corrosion problems in downstream refinery processes.
• WO 2017/083018 A1 discloses a process for reducing chloride content of a hydrocarbon feed stream. Further, FR 3 103 822 discloses a process for treating pyrolysis oil for subsequent steam cracking, said process comprises a hydrogenation step prior to a hydroprocessing step. However, there is still a need to provide improved process for purifying pyrolysis oil obtained from plastic waste.
• the process of the present invention permits to reduce the diene content as well as chlorine, nitrogen and sulfur contents, such reduced amounts being particularly adapted for subsequent steam cracking. Further, it was surprisingly found that the process of the present invention was an economic process providing high value purified pyrolysis oils.
• dehalogenation of pyrolysis oil may turn out to be an essential step to sustain steady reactor downstream operation.
• a reason for the instability is believed to be the formation of ammonium halide such as ammonium chloride which may desublimate upon lowering the temperature of the effluent of a hydroprocessing step.
• nitrogen is typically present in larger amounts in the pyrolysis oil feed than halogene such as chlorine, and can only be removed via hydroprocessing and then is present as ammonia, it is believed to be essential to lower the halogen content upstream of a hydroprocessing step, thus avoiding desublimation of ammonium halide and and reducing its absolute content.
• HCI corrosive attack of technical equipment
• Ammonium chloride itself may cause corrosion, too.
• catalytic and/or adsorbent performance suffers from increased contents of dienes and/or conjugated aromatic olefins.
• Their oligomerization respective polymerization is believed to be caused by increased temperature and/or radical forming compounds as e.g. peroxides or other impurities as acids or metal salts acting such as lewis acids. It was found that such oligo- or polymerization can coke the catalyst and/or the adsorbent or block their pore system reducing accessibility of reactants to the catalyst and/or adsorbent.
• the present invention relates to a process for purifying a pyrolysis oil, the process comprising:
• dehalogenation as used in the context of the present invention generally comprises “dechlorination”, “debromination” as well as “defluorination”. According to the present invention, the term “dehalogenation” preferably comprises “dechlorination”. If, e.g., the pyrolysis oil to be subjected to the process according to the present invention does not contain brominated organic compounds and fluorinated organic compounds, but only chlorinated compounds as halogenated organic compounds, the term “dehalogenation” would be directed to “dechlorination”, and the process of the invention would a process for purifying a pyrolysis oil, the process comprising:
• step (iii) subjecting the stream S1 obtained from (ii) to dechlorination in at least one dechlorination zone Z2 downstream of Z1 , obtaining a stream S2 being depleted, compared to S1 , in the one or more chlorinated organic compounds; wherein a preferred step (iii) would comprise
• the pyrolysis oil comprised in SO can be a non-treated crude pyrolysis oil.
• the pyrolysis oil comprised in SO can be a suitably pretreated crude pyrolysis oil.
• suitable pretreatment procedures are non-hydrogenation methods and include, but are not restricted to, distillation, dilution, precipitation, filtration, and extraction.
• the said crude pyrolysis oil can be subjected to one suitable pretreatment procedure, or to two or more suitable pretreatment procedures.
• the pretreatment is, for example, a distillation, it is possible to enrich the pyrolysis oil with respect to at least one of the one or more organic compounds comprising conjugated double bonds, or with respect to at least one of the one or more halogenated organic compounds, or with respect to at least one of the one or more organic compounds comprising conjugated double bonds and at least one of the one or more halogenated organic compounds.
• the pretreatment is, for example, a dilution, it is possible to add one or more alkanes. By doing so, it may be possible to precipitate one or more asphaltenes from the mixture resulting from dilution which may then be removed by filtration.
• the pretreatment is, for example, an extraction, it is possible to use an aqueous extraction medium, such as an acidic aqueous extraction medium or a basic extraction medium.
• from 1 to 100 weight-% or from 5 to 100 weight-% or from 10 to 100 weight-% or from 20 to 100 weight-% or from 30 to 100 weight-% or from 40 to 100 weight-% or from 50 to 100 weight-% or from 60 to 100 weight-% or from 70 to 100 weight-% or from 80 to 100 weight- % or from 90 to 100 weight-% of SO may consist of pyrolysis oil.
• the pyrolysis oil according to (i) comprises the one or more organic compounds comprising conjugated double bonds in a total amount in the range of from 0.1 to 75 g(l2)/100 g, more preferably from 0.4 to 60 g(l2)/100 g, more preferably from 1 to 30 g(l2)/100 g of the pyrolysis oil, determined as described in Reference Example 1.
• the one or more organic compounds comprising conjugated double bonds comprise one or more organic compounds according to formula (I)
• R 1 , R 2 , R 3 , R 4 , R 5 are, independently of each other, H, alkyl having from 1 to 6 carbon atoms, alkenyl having from 1 to 6 carbon atoms, or aryl having from 5 to 10 carbon atoms, more preferably H.
• R 6 and R 7 are, independently of each other, H, alkyl having from 1 to 6 carbon atoms, alkenyl having from 1 to 6 carbon atoms, or aryl having from 5 to 10 carbon atoms, more preferably H.
• the one or more organic compounds according to formula (I) comprise one or more of butadiene, isoprene, dienes having 5 or 6 carbon atoms, styrene, methyl styrene, indene, substituted styrene, substituted indene, and 3-methyl-2-butenal, more preferably comprise one or more of butadiene, isoprene, dienes having 5 or 6 carbon atoms, styrene, methyl styrene, indene, and 3-methyl-2-butenal.
• organic compounds according to formula (I) it is preferred that they comprise styrene.
• the pyrolysis oil according to (i) has a styrene content in the range of from 0.2 to 30 Area%, more preferably in the range of from 1 to 20 Area%, determined as described in Reference Example 8.
• any halogenated organic compounds can be comprised in the pyrolysis oil comprised in SO provided in (i).
• the one or more halogenated organic compounds comprise one or more of mono-, oligo- or polyhalogenated aromatic compounds, alkyl halides and alkenyl halides.
• the pyrolysis oil to be purified can have any chlorine content. It is however preferred that the pyrolysis oil has a total chlorine content in the range of from 30 to 3,000 wppm (ppm by weight), more preferably from 30 to 500 wppm, more preferably from 30 to 200 wppm, determined as described in Reference Example 2.1 .
• the pyrolysis oil to be purified can have any chloride content. It is however preferred that the pyrolysis oil has a chloride content of at most 100 wppm, more preferably in the range of from 0 to 30 wppm, determined as described in Reference Example 2.2.
• the pyrolysis oil to be purified can have any nitrogen content. It is however preferred that the pyrolysis oil has a nitrogen content in the range of from 50 to 20,000 wppm (ppm by weight), more preferably from 50 to 5,000 wppm, more preferably from 100 to 4,000 wppm, determined as described in Reference Example 3.
• the pyrolysis oil to be purified can have any sulfur content. It is however preferred that the pyrolysis oil has a sulfur content in the range of from 50 to 30,000 ppm by weight (wppm), preferably from 50 to 5,000 wppm, more preferably from 100 to 3,000 wppm, determined as described in Reference Example 4.
• wppm ppm by weight
• the pyrolysis oil is preferably obtained from plastic waste.
• the “plastic waste” to be pyrolyzed typically is mixed or pre-sorted plastic waste.
• the pyrolysis oil to be purified can typically comprise a solid phase and a liquid phase, wherein the liquid phase includes an organic phase and an aqueous phase.
• a weight ratio between the aqueous phase and the organic phase in the liquid phase of the pyrolysis oil can be in the range of from 0.01 :1 to 3.2:1 , preferably in the range of from 0.05:1 to 3:1.
• the stream SO is preferably a liquid stream. It is conceivable that the pyrolysis oil is at least partially in the form of a wax which, prior to be subjected to the process of the present invention, is suitably liquefied.
• the stream SO subjected to hydrogenation in (ii) has preferably a temperature in the range of from 60 to 250 °C, more preferably from 80 to 220 °C, more preferably from 100 to 200 °C.
• any heterogeneous hydrogenation catalyst can be used as far as it permits to hydrogenate (pre-hydrogenation) according to (ii) the stream SO comprising the pyrolysis oil to be purified prior to the dehalogenation according to (iii).
• the heterogeneous hydrogenation catalyst according to (ii) comprises an element of the groups 8 to 12, more preferably 8 to 10, more preferably 9 and 10, of the periodic table of elements, more preferably an element selected from the group consisting of Ni, Pd and Co, more preferably from the group consisting of Ni and Pd.
• the heterogeneous hydrogenation catalyst according to (ii) further comprises a support material for said element of the groups 8 to 12 of the periodic table of elements, wherein the support material is preferably selected from the group consisting of an oxidic material and carbon, wherein the oxidic material is more preferably one or more of alumina, silica, magnesia, zirconia, titania, a zeolitic material, a silica-alumina phosphate (SAPO) material, zinc oxide, sodium oxide, mixed silica-alumina, zeolite and calcium oxide, more preferably alumina.
• SAPO silica-alumina phosphate
• said catalyst comprises Ni, more preferably in an amount, calculated as NiO, in the range of from 0.5 to 70 weight-%, more preferably from 0.75 to 45 weight-%, more preferably from 1 to 20 weight-%, based on the total weight of the hydrogenation catalyst.
• the heterogeneous hydrogenation catalyst according to (ii) further comprises an element of the group 6 of the periodic table of elements, wherein the element of the group 6 is more preferably one or more of Mo and W, more preferably Mo.
• the heterogeneous hydrogenation catalyst according to (ii) comprises from 1 to 40 weight-%, more preferably from 2 to 35 weight-%, more preferably from 3 to 30 weight-% of an oxide of said element of the group 6, more preferably Mo oxide or W oxide, based on the total weight of the hydrogenation catalyst.
• the heterogeneous hydrogenation catalyst according to (ii) comprises Ni and Mo supported on a support material, more preferably a support material as defined in in the foregoing. More preferably, the hydrogenation catalyst comprises Ni and Mo supported on alumina.
• said catalyst comprises Pd, more preferably in an amount, calculated as elemental Pd, in the range of from 0.01 to 5 weight-%, more preferably from 0.1 to 1 weight-%, more preferably from 0.15 to 0.8 weight-%, based on the total weight of the catalyst.
• the heterogeneous hydrogenation catalyst according to (ii) further comprises a promoter, the promoter more preferably being one or more of an element of the groups 10 and 11 of the periodic table of elements, preferably one or more of Cu, Au, Ag, and Pt, more preferably one or more of Ag and Pt, more preferably Ag.
• the atomic ratio of the element of groups 8 to 12 of the periodic table, more preferably Pd, relative to the promoter is in the range of from 0.1 :1 to 10:1 , more preferably from 2:1 to 7:1 , more preferably from 2.5:1 to 6:1.
• the heterogeneous hydrogenation catalyst according to (ii) comprises Pd supported on a support material, preferably a support material as defined in the foregoing, wherein the support material is more preferably alumina or carbon, more preferably alumina.
• the heterogeneous hydrogenation catalyst according to (ii) preferably is in the form of extrudates, pellets, rings, spherical particles or spheres, more preferably spherical particles or extrudates.
• (ii) comprises
• the gas stream GO has a temperature in the range of 100 to 250 °C, more preferably from 120 to 220 °C, more preferably from 140 to 200 °C.
• the gas stream GO is introduced at a pressure in the range of from 10 to 100 bar(abs), more preferably from 15 to 90 bar(abs), more preferably from 20 to 80 bar(abs), more preferably in the range of from 20 to 55 bar(abs).
• from 70 to 100 weight-%, more preferably from 80 to 100 weight-%, more preferably from 90 to 100 weight-%, of the gas stream GO consists of H2. Further conceivable ranges are from 92 to 100 weight-% or from 94 to 100 weight-% or from 96 to 100 weight-% or from 98 to 100 weight-%.
• GO is preferably introduced continuously or semi-continuously, more preferably continuously into Z1 .
• SO is preferably introduced semi-continuously or continuously, more preferably continuously, into Z1.
• GO is introduced into Z1 according to (ii.1) for a period At prior to introducing SO into Z1 according to (ii.2).
• the hydrogenation catalyst comprises Ni
• the hydrogenation catalyst comprises Pd
• it may be preferred that it is activated under flow of hydrogen (GHSV 1000/h) at 50 to 130 °C (1 K/min), for example for 6 to 24 h such as 12 h, preferably at atmospheric condition.
• hydrogen can be diluted by nitrogen to avoid excess temperature.
• GO is preferably brought in contact with the heterogeneous hydrogenation catalyst comprised in Z1 , wherein GO has a temperature in the range of 50 to 250 °C, more preferably from 120 to 220 °C, more preferably from 140 to 200 °C.
• the liquid hourly space velocity is preferably in the range of from 0.2 to 10 m 3 /(m 3 h), more preferably in the range of from 0.3 to 5 m 3 /(m 3 h), more preferably in the range of from 0.5 to 2 m 3 /(m 3 h), wherein the LHSV is defined as the volume flow of SO through Z1 (in m 3 /h) per volume of heterogeneous hydrogenation catalyst comprised in Z1 (in m 3 ).
• the present invention it is possible to recycle a portion of S1 , S1 ’, obtained from (ii) and removed from Z1 , back to Z1 as part of the starting material subjected to hydrogenation.
• the stream SO is subjected to hydrogenation, but also the additional stream ST.
• its LHSV in Z1 relative to the LHSV of SO, LHSV(S1 ’):LHSV(S0), corresponding to the recycle ratio, is preferably in the range of from 1 :1 to 20:1 , such as from 1 :1 to 5:1 or from 5:1 to 10:1 or from 10:1 to 15:1 or from 15:1 to 20:1.
• ST can be admixed with SO at every suitable position in the process, preferably upstream of Z1 . If a portion of S1 is recycled, the remaining portion of S1 is referred to herein as the stream S1 which is subjected to dehalogenation according to (iii).
• the process further comprises
• GO GO
• its hourly space velocity, GHSV, in Z1 , relative to the GHSV of GO, LHSV(G0”):LHSV(G0), corresponding to the recycle ratio is preferably in the range of from 1 :1 to 20:1 , such as from 1 :1 to 5:1 or from 5:1 to 10:1 or from 10:1 to 15:1 or from 15:1 to 20:1.
• the reaction zone Z1 is comprised in a continuous stirred tank reactor (CSTR) or a fixed bed reactor, more preferably in a fixed bed reactor, wherein the fixed bed reactor is more preferably a trickle bed reactor.
• CSTR continuous stirred tank reactor
• fixed bed reactor is more preferably a trickle bed reactor.
• reaction zones Z1 are preferably employed which are arranged serially and/or in parallel, wherein more preferably, one single reaction zone Z1 is employed according to (ii).
• the stream S1 obtained from (ii), and subjected to dehalogenation in (iii), comprises a reduced amount of the one or more organic compounds comprising conjugated double bonds of from 50 to 100%, more preferably from 70 to 100 %, more preferably from 75 to 100 %, compared to SO.
• the total amount of the one or more organic compounds comprising conjugated double bonds is determined as described in Reference Example 1.
• the stream S1 obtained from (ii) and subjected to dehalogenation in (iii) comprises the one or more organic compounds comprising conjugated double bonds in a total amount in the range of from 0 to 3 g(l2)/100 g, preferably from 0 to 2 g(l2)/100g, more preferably from 0 to 1 g(l2)/100 g, more preferably from 0 to 0.25 g(l2)/100 g, more preferably from 0 to 0.1 g(l2)/100 g of the stream S1 , determined as described in Reference Example 1 .
• the stream S1 obtained from (ii), and subjected to dehalogenation in (iii), comprises a reduced styrene amount from 50 to 100%, more preferably from 70 to 100 %, more preferably from 75 to 100 %, compared to SO.
• the styrene amount is determined as described in Reference Example 8.
• the stream S1 obtained from (ii) and subjected to dehalogenation in (iii) has a styrene content in the range of from 0 to 1 .5 Area%, more preferably in the range of from 0 to 0.1 Area%, determined as described in Reference Example 8.
• the stream S1 subjected to dehalogenation in (iii) has a temperature in the range of from 150 to 450°C, more preferably from 200 to 400°C, more preferably from 250 to 350 °C.
• the dehalogenation zone Z2 according to (iii) comprises, more preferably consists of an adsorption zone, more preferably comprising a heterogeneous adsorbent material suitable for adsorbing halide comprised in at least one of the one or more halogenated organic compounds, preferably comprised all of the one or more halogenated organic compounds.
• any heterogeneous adsorbent material can be used according to (iii) as far as it permits to adsorb halide comprised in at least one of the one or more halogenated organic compounds.
• the heterogeneous adsorbent material according to (iii) comprises one or more of a carbon-containing adsorbent material and an aluminum- containing adsorbent material, more preferably an aluminum-containing adsorbent material.
• the carbon-containing adsorbent material is preferably a carbon-containing molecular sieve, more preferably activated charcoal.
• the aluminum-containing adsorbent material is preferably an alumina, an aluminum-containing molecular sieve, a silicoaluminophosphate, a silica- alumina hydrate or a hydrotalcite.
• the aluminum-containing molecular sieve is preferably an aluminosilicate, more preferably having a molar ratio of Si: Al, calculated as SiC ⁇ AhOs, in the range of from 2:1 to 10:1 , more preferably from 2:1 to 4:1.
• the silica-alumina hydrate preferably has weight ratio AhO3:SiO2 in the range of from 1 :1 to 10:1 , more preferably from 1 :1 to 2:1.
• the hydrotalcite is preferably an aluminum and magnesium containing hydrotalcite, more preferably an aluminum-magnesium hydroxycarbonate, preferably having a MgOAhOs weight ratio in the range of from 63:37 to 70:30.
• the heterogeneous adsorbent material comprises an hydrotalcite as defined in the foregoing.
• heterogeneous adsorbent material according to (iii) comprises an element of the groups 1 , 2, 11 and 12.
• the aluminosilicate mentioned above contains one or more of potassium oxide, sodium oxide, magnesium oxide and calcium oxide.
• the heterogeneous adsorbent material according to (iii) comprises particles characterized by a particle size distribution having a D50 value in the range of from 1 to 6,500 micrometers, more preferably from 2 to 2,000 micrometers, more preferably from 8 to 500 micrometers, more preferably from 10 to 50 micrometers or from 3 to 9 micrometers, the D50 particle size being determined as described in Reference Example 5.
• the heterogeneous adsorbent material being an hydrotalcite defined in the foregoing comprises particles characterized by a particle size distribution having a D50 value in the range of from 3 to 9 micrometers, the D50 particle size being determined as described in Reference Example 5.
• the heterogeneous adsorbent material according to (iii) has preferably an average pore volume in the range of from 0.1 to 5 ml/g, more preferably in the range of from 0.15 to 2 ml/g, the average pore volume being determined as described in Reference Example 6.
• the heterogeneous adsorbent material according to (iii) has a BET specific surface area in the range of from 50 to 1 ,000 m 2 /g, more preferably in the range of from 100 to 900 m 2 /g, more preferably in the range of from 150 to 600 m 2 /g, the BET specific surface area being determined as described in reference Example 7.
• the adsorbent material can be suitably regenerated, if so desired.
• (ill) comprises (111.1 ) introducing a gas stream G1 into Z2 preferably being an adsorption zone, more preferably a gas stream comprising one or more of hydrogen and nitrogen, more preferably hydrogen;
• the gas stream G1 has a temperature in the range of 250 to 500°C, more preferably in the range of from 300 to 400 °C.
• the gas stream G1 is introduced at a pressure in the range of from 1 to 100 bar(abs), more preferably in the range of from 5 to 80 bar(abs), more preferably in the range of from 10 to 50 bar(abs).
• the liquid hourly space velocity is in the range of from 0.2 to 10 m 3 /(m 3 h), more preferably in the range of from 0.3 to 5 m 3 /(m 3 h), more preferably in the range of from 0.5 to 2 m 3 /(m 3 h), wherein the LHSV is defined as the volume flow of S1 through Z2 (in m 3 /h) per volume of adsorbent material comprised in Z2 (in m 3 ).
• from 90 to 100 weight-%, more preferably from 95 to 100 weight-%, more preferably from 98 to 100 weight-%, of the gas stream G1 consists of H2.
• preferably from 90 to 100 weight-%, more preferably from 95 to 100 weight-%, more preferably from 98 to 100 weight-%, of the gas stream G1 consists of nitrogen.
• G1 is preferably introduced continuously or semi-continuously, more preferably continuously, into Z2 and wherein according to (iii.2) S1 is introduced continuously or semi- continuously, more preferably continuously, into Z2.
• the adsorption zone Z2 is comprised in a continuous stirred tank reactor (CSTR) or a fixed bed reactor, more preferably in a fixed bed reactor, more preferably a trickle bed reactor, the reactor preferably comprising an adsorption bed comprising the heterogeneous adsorbent material.
• CSTR continuous stirred tank reactor
• a fixed bed reactor more preferably a trickle bed reactor
• the reactor preferably comprising an adsorption bed comprising the heterogeneous adsorbent material.
• reaction zones Z2 are preferably employed which are arranged serially and/or in parallel or one single reaction zone Z2 is preferably employed according to (iii), more preferably one single reaction zone Z2 is employed according to (iii).
• the stream S2 obtained from (iii) has a reduced total chlorine content of from 50 to 100 %, preferably 60 to 100 %, more preferably from 75 to 100%, compared to SO and S1 .
• the stream S2 obtained from (iii) has a total chlorine content in the range of from 0 to 200 wppm (ppm by weight), more preferably from 0 to 160 wppm, more preferably from 0 to 130 wppm, determined as described in Reference Example 2.1.
• the stream S2 obtained from (iii) has a chloride content of at most 40 wppm (ppm by weight), more preferably from 0 to 30 wppm, more preferably from 0 to 20 wppm, more preferably from 0 to 1 wppm, determined as described in Reference Example 2.2.
• the stream S2 obtained from (iii) comprises the one or more organic compounds comprising conjugated double bonds in a total amount in the range of 0 to 3 g(l2)/100 g, more preferably from 0 to 2 g(l2)/100 g, more preferably from 0 to 1 g(l2)/100 g, more preferably from 0 to 0.25 g(l2)/100 g, more preferably from 0 to 0.1 g(l2)/100 g of the stream S2, determined as described in Reference Example 1 .
• the stream S2 obtained from (iii) has a nitrogen content in the range of from 50 to 20,000 ppm by weight wppm, more preferably from 50 to 5,000 wppm, more preferably from 100 to 4,000 wppm, determined as described in Reference Example 3.
• the stream S2 obtained from (iii) has a sulfur content in the range of from 50 to 30,000 ppm by weight (wppm), more preferably from 50 to 5,000 wppm, more preferably from 100 to 3,000 wppm, determined as described in Reference Example 4.
• the stream S2 has a chlorine content, a nitrogen content, a sulfur content and a total amount of the one or more organic compounds comprising conjugated double bonds as defined in the foregoing.
• the dehalogenation zone Z2 according to (iii) comprises, more preferably is a catalytic zone, the catalytic zone more preferably comprising a heterogeneous dehalogenation catalyst, said catalyst preferably comprising one or more catalytically active elements of groups 8 to 12 of the periodic system of elements.
• (iii) preferably comprises
• the stream S2 obtained from (iii), prior to being subjected to hydroprocessing according to (iv) as defined in the following, is subjected to extraction, more preferably using an aqueous extraction medium, obtaining a stream S2 being depleted in one or more dissolved halides comprised in S2 obtained from the dehalogenation zone Z2, said halides more preferably comprising one or more halides of N-containing organic compounds.
• the process of the present invention preferably further comprises, after (iii),
• any heterogeneous hydroprocessing catalyst can be used as far as it permits to obtain a stream S3.
• the heterogeneous hydroprocessing catalyst according to (iv) comprises an element of the groups 8 to 10, more preferably 9 and 10 of the periodic table of elements, more preferably an element selected from the group consisting of Ni and Co, wherein the hydroprocessing catalyst more preferably comprises Ni.
• the heterogeneous hydroprocessing catalyst according to (iv) comprises Ni in an amount, calculated as NiO, in the range of from 0.5 to 10 weight-%, more preferably in the range of from 1 to 6 weight-%, based on the weight of the hydroprocessing catalyst.
• the heterogeneous hydroprocessing catalyst according to (iv) further comprises a support for the element of the groups 8 to 10 of the periodic table of elements, wherein the support preferably is an oxidic material.
• the oxidic material is one or more of alumina, silica, magnesia, zirconia, zinc oxide, calcium oxide, mixed silica-alumina, zeolite, Mo-doped alumina and titania, more preferably alumina, zeolite and silica-alumina, more preferably alumina.
• the heterogeneous hydroprocessing catalyst according to (iv) further comprises an element of the group 6 of the periodic table of elements, wherein the element of the group 6 is more preferably one or more of Mo and W.
• the hydroprocessing catalyst comprises in the range of from 1 to 40 weight-%, more preferably from 3 to 30 weight-%, of an oxide of said element of the group 6, more preferably Mo oxide or W oxide, based on the weight of the hydroprocessing catalyst.
• the heterogeneous hydroprocessing catalyst according to (iv) comprises Ni and Mo on a support, more preferably a support as defined in in the foregoing, wherein the hydroprocessing catalyst more preferably comprises Ni and Mo on alumina.
• the hydroprocessing catalyst in particular the hydroprocessing catalyst comprising Ni, may comprise from 0.1 to 5 weight-%, preferably from 0.1 to 4 weight-%, more preferably from 0.1 to 3 weight phosphorus, calculated as P2Osand based on the total weight of the catalyst.
• (iv) comprises
• the gas stream G2 has a temperature in the range of 250 to 550°C, more preferably in the range of from 300 to 450 °C, more preferably in the range of from 325 to 400 °C.
• the gas stream G2 is introduced at a pressure in the range of from 20 to 150 bar (abs), more preferably in the range of from 30 to 90 bar(abs), more preferably in the range of from 40 to 80 bar(abs), more preferably in the range of from 45 to 60 bar(abs).
• the liquid hourly space velocity is in the range of from 0.1 to 10 m 3 /(m 3 h), more preferably in the range of from 0.15 to 5 m 3 /(m 3 h), more preferably in the range of from 0.2 to 2 m 3 /(m 3 h), wherein the LHSV is defined as the volume flow of S2 through Z3 (in m 3 /h) per volume of heterogeneous hydroprocessing catalyst comprised in Z3 (in m 3 ).
• G2 may preferably be recycled from the stream obtained from hydroprocessing.
• from 50 to 100 weight-%, more preferably from 70 to 100 weight-%, more preferably from 90 to 100 weight-%, of the gas stream G2 consists of H2. Further conceivable ranges are from 92 to 100 weight-% or from 94 to 100 weight-% or from 96 to 100 weight-% or from 98 to 100 weight-%.
• G2 is preferably introduced continuously or semi-continuously, more preferably continuously, into Z3.
• S2 is preferably introduced continuously or semi-continuously, more preferably continuously, into Z3.
• (iv) comprises
• the gas stream G2 has a temperature in the range of 250 to 550°C, more preferably in the range of from 300 to 450 °C, more preferably in the range of from 325 to 400 °C.
• the gas stream G2 is introduced at a pressure in the range of from 20 to 150 bar(abs), more preferably in the range of from 30 to 90 bar(abs), more preferably in the range of from 40 to 80 bar(abs), more preferably in the range of from 45 to 60 bar(abs).
• from 50 to 100 weight-%, more preferably from 70 to 100 weight-%, more preferably from 90 to 100 weight-%, of the gas stream G2 consists of H2. Further conceivable ranges are from 92 to 100 weight-% or from 94 to 100 weight-% or from 96 to 100 weight-% or from 98 to 100 weight-%.
• the liquid hourly space velocity is in the range of from 0.1 to 10 IT 1 , preferably in the range of from 0.1 to 5 IT 1 , more preferably in the range of from 0.2 to 2 IT 1 , wherein the LHSV is defined as the volume flow of S2 or Sp(i) through Z3 (in m 3 /h) per volume of heterogeneous hydroprocessing catalyst comprised in Z3 (in m 3 ).
• G2 is preferably introduced continuously or semi-continuously, more preferably continuously, into Z3.
• S2 is preferably introduced continuously or semi-continuously, more preferably continuously, into Z3.
• from 50 to 100 weight-%, more preferably from 70 to 100 weight-%, more preferably from 90 to 100 weight-%, of the gas stream F(i) consists of H2. Further conceivable ranges are from 92 to 100 weight-% or from 94 to 100 weight-% or from 96 to 100 weight-% or from 98 to 100 weight-%.
• the gas stream F(i) is introduced at a pressure in the range of from 20 to 150 bar(abs), more preferably in the range of from 30 to 90 bar(abs), more preferably in the range of from 40 to 80 bar(abs), more preferably in the range of from 45 to 60 bar(abs).
• the n serially coupled catalyst beds B(i) are fixed catalyst beds.
• reaction zone Z3 is comprised in a reactor comprising one catalyst bed, wherein the catalyst bed comprises a heterogeneous hydroprocessing catalyst.
• reaction zone Z3 is preferably comprised in a continuous stirred tank reactor (CSTR) or a fixed bed reactor, more preferably in a fixed bed reactor, more preferably a trickle bed reactor.
• CSTR continuous stirred tank reactor
• fixed bed reactor more preferably in a fixed bed reactor, more preferably a trickle bed reactor.
• the stream S3 obtained from (iii) has a reduced total chlorine content of from 90 to 100 %, more preferably of from 95 to 100 %, more preferably of from 99 to 100%, more preferably of from 99.5 to 100%, compared to SO and S1 .
• the stream S3 obtained from (iv) has a total chlorine content in the range of from 0 to 50 wppm (ppm by weight), more preferably from 0 to 30 wppm, more preferably from 0 to 20 wppm, more preferably from 0 to 10 wppm, more preferably from 0 to 5 wppm, more preferably from 0 to 2 wppm, determined as described in Reference Example 2.1.
• the stream S3 obtained from (iv) has a chloride content in the range of from at most 40 wppm (ppm by weight), preferably from 0 to 30 wppm, more preferably from 0 to 20 wppm, more preferably from 0 to 1 wppm, determined as described in Reference Example 2.2.
• the stream S3 obtained from (iii) has a reduced nitrogen content of from 80 to 100 %, more preferably of from 85 to 100 %, more preferably of from 90 to 100%, compared to SO, S1 and S2.
• the stream S3 obtained from (iv), more preferably after removing dissolved NH3, has a nitrogen content in the range of from 0 to 200 ppm by weight (wppm), more preferably in the range of from 0 to 100 wppm, more preferably from 0 to 50 wppm, more preferably from 0 to 10 wppm, determined as described in Reference Example 3.
• the stream S3 obtained from (iii) has a reduced sulfur content of from 80 to 100 %, more preferably of from 85 to 100 %, more preferably of from 90 to 100%, compared to SO, S1 and S2.
• the stream S3 obtained from (iv), more preferably after removing dissolved H2S has a sulfur content in the range of from 0 to 200 ppm by weight (wppm), more preferably from 0 to 100 wppm, more preferably from 0 to 50 wppm, determined as described in Reference Example 4.
• the stream S3 obtained from (iii) comprises the one or more organic compounds comprising conjugated double bonds in a total amount in the range of 0 to 3 g(l2)/100 g, more preferably from 0 to 2 g(l2)/100 g, more preferably from 0 to 1 g(l2)/100 g, more preferably from 0 to 0.25 g(l2)/100 g, more preferably from 0 to 0.1 g(l2)/100 g of the stream S3 obtained from
• the stream S3 has a chlorine content, a nitrogen content, a sulfur content and a total amount of the one or more organic compounds comprising conjugated double bonds as defined in the foregoing.
• the stream S3 obtained from (iv), preferably prior to being subjected to (v) as defined in the following, is depleted in one or more nitrogen-containing compounds and sulfur- containing compounds compared to S2.
• polymers comprised in plastic waste may contain oxygen. Such oxygen is preferably removed in the above-described hydroprocessing step.
• the process of the present invention preferably further comprises, after (iii), or (iv) as defined in the foregoing,
• the process of the present invention is a continuous or semi-continuous process, more preferably a continuous process.
• the process of the present invention consists of (i), (ii), (iii), more preferably of (i), (ii), (iii) and (iv), more preferably of (i), (ii), (iii), (iv) and (v).
• the present invention further relates to a production unit for carrying out the process for purifying a pyrolysis oil according to the present invention, the unit comprising at least one reaction zone Z1 , Z1 comprising a heterogeneous hydrogenation catalyst; an inlet means for introducing SO into Z1 ; an outlet means for removing S1 from Z1 ; at least one dehalogenation zone Z2, Z2 preferably comprising a heterogeneous adsorption material or a heterogenous dehalogenation catalyst; an inlet means for introducing S1 into Z2; an outlet means for removing S2 from Z2; wherein Z1 is located upstream of Z2.
• the production unit further comprises an extraction zone to remove halides, more preferably comprising one or more halides of N-containing organic compounds, said extraction zone more preferably being arranged downstream of Z2.
• the production unit further comprises at least one reaction zone Z3, Z3 comprising a heterogeneous hydroprocessing catalyst; an inlet means for introducing S2 into Z3; an outlet means for removing S3 from Z3; wherein Z2 is located upstream of Z3.
• reaction zone Z3, Z3 comprising a heterogeneous hydroprocessing catalyst
• the present invention further relates to a purified pyrolysis oil, obtainable or obtained by a process according to the present invention comprising (i), (ii) and (iii), or (i), (ii), (iii) and (iv).
• the purified pyrolysis oil has preferably a chlorine content and a total amount of the one or more organic compounds comprising conjugated double bonds as defined in the foregoing for the stream S2, more preferably a chlorine content, a nitrogen content a sulfur content and a total amount of the one or more organic compounds comprising conjugated double bonds as defined in the foregoing for the stream S2.
• the purified pyrolysis oil has preferably a chlorine content, a nitrogen content a sulfur content and a total amount of the one or more organic compounds comprising conjugated double bonds as defined in the foregoing for the stream S3.
• the purified pyrolysis oil has a total chlorine content in the range of from 0 to 50 wppm (ppm by weight), more preferably from 0 to 30 wppm, more preferably from 0 to 20 wppm, more preferably from 0 to 10 wppm, more preferably from 0 to 5 wppm, more preferably from 0 to 2 wppm, determined as described in Reference Example 2.1 .
• the purified pyrolysis oil has a chloride content in the range of from at most 40 wppm (ppm by weight), preferably from 0 to 30 wppm, more preferably from 0 to 20 wppm, more preferably from 0 to 1 wppm, determined as described in Reference Example 2.2.
• the purified pyrolysis oil has a nitrogen content in the range of from 0 to 200 ppm by weight (wppm), more preferably in the range of from 0 to 100 wppm, more preferably from 0 to 50 wppm, more preferably from 0 to 10 wppm, determined as described in Reference Example 3.
• wppm ppm by weight
• the purified pyrolysis oil has a sulfur content in the range of from 0 to 200 ppm by weight (wppm), more preferably from 0 to 100 wppm, more preferably from 0 to 50 wppm, determined as described in Reference Example 4.
• the purified pyrolysis oil comprises the one or more organic compounds comprising conjugated double bonds in a total amount in the range of 0 to 3 g(l2)/100 g, more preferably from 0 to 2 g(l2)/100 g of the purified pyrolysis oil, determined as described in Reference Example 1.
• a process for purifying a pyrolysis oil comprising:
• the pyrolysis oil according to (i) comprises the one or more organic compounds comprising conjugated double bonds in a total amount in the range of from 0.1 to 75 g(l2)/100 g, preferably from 0.4 to 60 g(l2)/100 g, more preferably from 1 to 30 g(l2)/100 g of the pyrolysis oil, determined as described in Reference Example 1 .
• the one or more halogenated organic compounds comprise one or more of mono- oligo- or polyhalogenated aromatic compounds, alkylhalides and alkenylhalides.
• the pyrolysis oil according to (i) has a total chlorine content in the range of from 30 to 3,000 wppm (ppm by weight), preferably from 30 to 500 wppm, more preferably from 30 to 200 wppm, determined as described in Reference Example 2.1 ; wherein the pyrolysis oil according to (i) has a chloride content of at most 40 wppm, more preferably in the range of from 0 to 30 wppm, determined as described in Reference Example 2.2.
• any one of embodiments 1 to 9 wherein the pyrolysis oil according to (i) has a nitrogen content in the range of from 50 to 20,000 wppm (ppm by weight), preferably from 50 to 5,000 wppm, more preferably from 100 to 4,000 wppm, determined as described in Reference Example 3.
• the process of any one of embodiments 1 to 10 wherein the pyrolysis oil according to (i) has a sulfur content in the range of from 50 to 30,000 ppm by weight (wppm), preferably from 50 to 5,000 wppm, more preferably from 100 to 3,000 wppm, determined as described in Reference Example 4.
• the process of any one of embodiments 1 to 11 wherein the pyrolysis oil is obtained from plastic waste.
• any one of embodiments 1 to 12, wherein the stream SO is a liquid stream.
• the process of any one of embodiments 1 to 13, wherein the stream SO subjected to hydrogenation in (ii) has a temperature in the range of from 60 to 250 °C, preferably from 80 to 220 °C, more preferably from 100 to 200 °C.
• the process of any one of embodiments 1 to 14, wherein the heterogeneous hydrogenation catalyst according to (ii) comprises an element of the groups 8 to 12, preferably 8 to 10, more preferably 9 and 10, of the periodic table of elements, preferably an element selected from the group consisting of Ni, Pd and Co, more preferably from the group consisting of Ni and Pd.
• the heterogeneous hydrogenation catalyst according to (ii) further comprises a support material for said element of the groups 8 to 12 of the periodic table of elements, wherein the support material is preferably selected from the group consisting of an oxidic material and carbon, wherein the oxidic material is preferably one or more of alumina, silica, magnesia, zirconia, titania, a zeolitic material, a sili- ca-alumina phosphate (SAPO) material, zinc oxide, sodium oxide, mixed silica-alumina, zeolite and calcium oxide, more preferably alumina.
• SAPO sili- ca-alumina phosphate
• heterogeneous hydrogenation catalyst according to (ii) comprises Ni, preferably in an amount, calculated as NiO, in the range of from 0.5 to 70 weight-%, more preferably from 0.75 to 45 weight-%, more preferably from 1 to 20 weight-%, based on the total weight of the hydrogenation catalyst.
• the heterogeneous hydrogenation catalyst used in (ii) further comprises an element of the group 6 of the periodic table of elements, wherein the element of the group 6 is preferably one or more of Mo and W, more preferably Mo; wherein the hydrogenation catalyst preferably comprises from 1 to 40 weight-%, more preferably from 2 to 35 weight-%, more preferably from 3 to 30 weight-% of said element of the group 6, based on the total weight of the hydrogenation catalyst.
• the heterogeneous hydrogenation catalyst according to (ii) comprises Ni and Mo supported on a support material, preferably a support material as defined in embodiment 16, wherein the hydrogenation catalyst preferably comprises Ni and Mo supported on alumina.
• the heterogeneous hydrogenation catalyst according to (ii) comprises Pd, preferably in an amount, calculated as elemental Pd, in the range of from 0.01 to 5 weight-%, preferably from 0.1 to 1 weight-%, more preferably from 0.15 to 0.8 weight-%, based on the total weight of the catalyst.
• the heterogeneous hydrogenation catalyst according to (ii) further comprises a promoter, the promoter preferably being one or more of an element of the groups 10 and 11 of the periodic table of elements, preferably one or more of Cu, Au, Ag, and Pt, more preferably one or more of Ag and Pt, more preferably Ag.
• the process of embodiment 21 wherein the atomic ratio of the element of groups 8 to 12 of the periodic table, preferably Pd, relative to the promoter is in the range of from 0.1 :1 to 10:1 , preferably from 2:1 to 7:1 , more preferably from 2.5:1 to 6:1.
• the heterogeneous hydrogenation catalyst according to (ii) comprises Pd supported on a support material, preferably a support material as defined in embodiment 16, wherein the support material is preferably alumina or carbon, more preferably alumina.
• liquid hourly space velocity is in the range of from 0.2 to 10 m 3 /(m 3 h), preferably in the range of from 0.3 to 5 m 3 /(m 3 h), more preferably in the range of from 0.5 to 2 m 3 /(m 3 h), wherein the LHSV is defined as the volume flow of SO through Z1 (in m 3 /h) per volume of heterogeneous hydrogenation catalyst comprised in Z1 (in m 3 ).
• reaction zone Z1 is comprised in a continuous stirred tank reactor (CSTR) or a fixed bed reactor, preferably in a fixed bed reactor, wherein the fixed bed reactor is preferably a trickle bed reactor.
• CSTR continuous stirred tank reactor
• fixed bed reactor preferably a trickle bed reactor.
• the stream S1 obtained from (ii) and subjected to dehalogenation in (iii) comprises the one or more organic compounds comprising conjugated double bonds in a total amount in the range of from 0 to 3 g(l2)/100 g, preferably from 0 to 2 g(l2)/100g, more preferably from 0 to 1 g(l2)/100 g, more preferably from 0 to 0.25 g(l2)/100 g, more preferably from 0 to 0.1 g(l2)/100 g of the stream S1 , determined as described in Reference Example 1.
• any one of embodiments 1 to 35 wherein the stream S1 subjected to dehalogenation in (iii) has a temperature in the range of from 150 to 450°C, preferably from 200 to 400°C, more preferably from 250 to 350 °C.
• the heterogeneous adsorbent material according to (iii) comprises one or more of a carbon-containing adsorbent material and an alumi- num-containing adsorbent material, preferably an aluminum-containing adsorbent material; wherein the carbon-containing adsorbent material is preferably a carbon-containing molecular sieve, more preferably activated charcoal; wherein the aluminum-containing adsorbent material is preferably an alumina, an aluminum-containing molecular sieve, a silicoaluminophosphate, a silica-alumina hydrate or a hydrotalcite; wherein the aluminum-containing molecular sieve is preferably an alumina, an aluminosilicate, preferably having a molar ratio of Si:AI, calculated as SiC ⁇ AhOs, in the range of from 2:1 to 10:1 , more preferably from 2:1 to 4:1 ; wherein the silica-alumina hydrate preferably has weight ratio Ah
• the heterogeneous adsorbent material according to (iii) comprises particles characterized by a particle size distribution having a D50 value in the range of from 1 to 6,500 micrometers, preferably from 2 to 2,000 micrometers, more preferably from 8 to 500 micrometers, more preferably from 10 to 50 micrometers or from 3 to 9 micrometers, the D50 particle size being determined as described in Reference Example 5.
• the heterogeneous adsorbent material according to (iii) has a BET specific surface area in the range of from 50 to 1 ,000 m 2 /g, preferably in the range of from 100 to 900 m 2 /g, more preferably in the range of from 150 to 600 m 2 /g, the BET specific surface area being determined as described in reference Example 7.
• liquid hourly space velocity is in the range of from 0.2 to 10 IT 1 , preferably in the range of from 0.3 to 5 IT 1 , more preferably in the range of from 0.5 to 2 IT 1 .
• the stream S2 obtained from (iii) comprises the one or more organic compounds comprising conjugated double bonds in a total amount in the range of 0 to 3 g(l2)/100 g, preferably from 0 to 2 g(l2)/100 g, more preferably from 0 to 1 g(l2)/100 g, more preferably from 0 to 0.25 g(l2)/100 g, more preferably from 0 to 0.1 g(l2)/100 g of the stream S2, determined as described in Reference Example 1.
• dehalogenation zone Z2 comprises, preferably is a catalytic zone, preferably comprising a hetero- geneous dehalogenation catalyst, said catalyst comprising one or more catalytically active elements of groups 8 to 12 of the periodic system of elements.
• the heterogeneous hydroprocessing catalyst used in (iv) comprises an element of the groups 8 to 10, preferably 9 and 10 of the periodic table of elements, preferably an element selected from the group consisting of Ni and Co, wherein the hydroprocessing catalyst more preferably comprises Ni; wherein the heterogeneous hydroprocessing catalyst according to (iv) more preferably comprises Ni in an amount, calculated as NiO, in the range of from 0.5 to 10 weight-%, more preferably in the range of from 1 to 6 weight-%, based on the weight of the hydroprocessing catalyst.
• the heterogeneous hydroprocessing catalyst according to (iv) further comprises a support for the element of the groups 8 to 10 of the periodic table of elements, wherein the support preferably is an oxidic material; wherein the oxidic material preferably is one or more of alumina, silica, magnesia, zirconia, zinc oxide, calcium oxide, mixed silica-alumina, zeolite, Mo-doped alumina and titania, more preferably alumina, zeolite and silica-alumina, more preferably alumina.
• heterogeneous hydroprocessing catalyst according to (iv) further comprises an element of the group 6 of the periodic table of elements, wherein the element of the group 6 is preferably one or more of Mo and W; wherein the hydroprocessing catalyst preferably comprises in the range of from 1 to 40 weight-%, more preferably from 3 to 30 weight-%, of an oxide of said element of the group 6, preferably Mo oxide or W oxide, based on the weight of the hydroprocessing catalyst.
• heterogeneous hydroprocessing catalyst according to (iv) comprises Ni and Mo on a support, preferably a support as defined in embodiment 53, wherein the hydroprocessing catalyst preferably comprises Ni and Mo on alumina.
• liquid hourly space velocity is in the range of from 0.1 to 10 IT 1 , preferably in the range of from 0.1 to 5 IT 1 , more preferably in the range of from 0.2 to 2 IT 1 .
• liquid hourly space velocity is in the range of from 0.1 to 10 IT 1 , preferably in the range of from 0.1 to 5 IT 1 , more preferably in the range of from 0.2 to 2 IT 1 .
• reaction zone Z3 is comprised in a continuous stirred tank reactor (CSTR) or a fixed bed reactor, preferably in a fixed bed reactor, more preferably a trickle bed reactor.
• CSTR continuous stirred tank reactor
• fixed bed reactor preferably in a fixed bed reactor, more preferably a trickle bed reactor.
• (iv) preferably after removing dissolved H2S, has a sulfur content in the range of from 0 to 200 ppm by weight (wppm), preferably from 0 to 100 wppm, more preferably from 0 to 50 wppm, determined as described in Reference Example 4.
• wppm ppm by weight
• the stream S3 obtained from (iii) comprises the one or more organic compounds comprising conjugated double bonds in a total amount in the range of 0 to 3 g(l2)/100 g, preferably from 0 to 2 g(l2)/100 g, more preferably from 0 to 1 g(l2)/100 g, more preferably from 0 to 0.25 g(l2)/100 g, more preferably from 0 to 0.1 g(l2)/100 g of the stream S3 obtained from (iv), determined as described in Reference Example 1.
• a production unit for carrying out the process for purifying a pyrolysis oil comprising at least one reaction zone Z1 , Z1 comprising a heterogeneous hydrogenation catalyst; an inlet means for introducing SO into Z1 ; an outlet means for removing S1 from Z1 ; at least one dehalogenation zone zone Z2, Z2 preferably comprising a heterogeneous adsorption material or a heterogenous dehalogenation catalyst; an inlet means for introducing S1 into Z2; an outlet means for removing S2 from Z2; wherein Z1 is located upstream of Z2; and preferably an extraction zone to remove halides, preferably comprising one or more halides of N-containing organic compounds, said extraction zone preferably being arranged downstream of Z2.
• the production unit of embodiment 85 further comprising at least one reaction zone Z3, Z3 comprising a heterogeneous hydroprocessing catalyst; an inlet means for introducing S2 into Z3; an outlet means for removing S3 from Z3; wherein Z2 is located upstream of Z3.
• a purified pyrolysis oil obtainable or obtained by a process according to any one of embodiments 1 to 53 or according to any one of embodiments 54 to 81 .
• Reference Example 1 Measurement of the total amount of the one or more organic compounds comprising conjugated double bonds
• the diene content is determined by UOP326-17.
• dienes are reacted with maleic anhydride (MA) and the consumption of MA is determined (by titration of the remainder MA). It can be expressed as g(l2)/100g(sample) or alternatively as g(MA)/100g(sample).
• the unit can be interconverted by multiplying the MA-value (MAV) by a factor 2.59 to obtain the value expressed with g(l2)/100g(sample) corresponding to the molar weight of I2 and MA. Accordingly, 1wt% Styrene or 0.52 wt.-% Butadiene correspond to 0.94g(MA)/100g or 2.43g(l2)/100g.
• Reference Example 2 .1 Measurement of total chlorine content (wppm)
• the sample is filtered with a 0.45pm syringe filter before analysis.
• the chlorine content is determined by combustion of the respective sample at 1050°C. Resulting combustion gases, i.e., hydrogen chloride, are led into a cell in which coulometric titration is performed.
• the sample is filtered with a 0.45pm syringe filter before analysis.
• the chloride content is determined by ion chromatography.
• Apparatus Ion chromatograph 850 Professional (Metrohm) (Pre column: Metrosep A Supp4/5 S-Guard and Analytical column: Metrosep A Supp 5 250/4; Flow: 0.7 mL/min; Column temperature: 30°C; Detector temperature: 40°C; Inject volume: 25 pL; Suppressor MSM HC Rotor A).
• Sample preparation 0.2 g - 0.4 g of the sample were weighed and dissolved in 10 mL toluene. For analyte extraction, 10 mL deionized water were added. After centrifugation, the aqueous phase was extracted and analyzed. Samples with a concentration below the limit value of the method were spiked with 20 pg/L chloride standard solution (corresponding to a limit value of 1 mg/kg chloride in the sample) to check the recovery rate.
• the nitrogen content is determined by combustion of the respective sample at 1000°C. NO contained in resulting combustion gases reacts with ozone so that NO2* is formed. Relaxation of excited nitrogen species is detected by chemiluminescence detectors according to ASTM D4629 (N). Calibration range is from 0.5 wppm to 50 wppm. Samples with higher concentrations are diluted with xylene to be in calibration range.
• the sulfur content is determined by combustion of the respective sample at 1000°C.
• UV fluorescence detectors Sulfur dioxide which is contained in resulting combustion gases is excited by UV (ultraviolet) light. Light which is emitted during relaxation is detected by UV fluorescence detectors according to ASTM D5453 (S). Calibration range is from 0.5 wppm to 50 wppm. Samples with higher concentrations are diluted with xylene to be in calibration range.
• the D50 particle size was determined by optical methods or by an air sieve, for example by various instruments, namely, Cilas Granulometer 1064 supplied by Quantachrome, Malvern Mastersizer or Heilstrahlsieb (air sieve) supplied by Alpine.
• Cilas Granulometer 1064 supplied by Quantachrome
• Malvern Mastersizer or Heilstrahlsieb (air sieve) supplied by Alpine.
• Reference Example 6 Determination of the average pore volume
• Pore volume can be derived from BET measurements (for micro and mesopores) or alternatively Hg porosimetry (for macropores). The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms JACS 1951 (73) 373-380 E.P. Barret, L.G. Joyner, P.P. Halenda.
• the BET surface area of the adsorbent material is measured by using an instrument supplied by Quantachrome (Nova series) or by Micromeritics (Gemini series).
• Quantachrome Nova series
• Micromeritics Micromeritics
• GC method with a nonpolar, 100% dimethylpolysiloxane phase column and FID-detector.
• Final column temperature and inlet temperature are 330°C and 320°C, respectively.
• Integrated area signal of Styrene as ratio of all integrated peaks times 100% is Area%. Area% roughly correlates with wt.%.
• the total acid number was determined by titration with KOH according to ASTM D3242.
• adsorbents bed corundum (WSK F46; commercial corundum) is filled from 55 to 80cm. In this corundum zone the feed is preheated to the reaction temperature whereas in the lower corundum filled zone the product stream is cooled from the reactor temperature down to the trace heating temperature.
• Example 1 Process for purifying a pyrolysis oil according to the present invention
• a feed stream SO comprising a pyrolysis oil having a MAV of 9.01 g(l2)/100g , a styrene content of 6.1 Area% determined by GC, a total chlorine content of 560 wppm, a chloride content of 1 wppm, a nitrogen content of about 3260 wppm, a sulfur content of about 2630 wppm, a total acid number (TAN) of 3.69 mg(KOH/g(feed) and a density of 0.8653 g/ml was subjected to hydrogenation in a reactor comprising an activated Pd-catalyst (Catalyst E-157 SDU 1/8” commercially available from BASF: 0.7wt.-%Pd on 1/8” alumina beads) with H2 at 50 bar and at a temperature of 195 °C.
• Catalyst E-157 SDU 1/8 commercially available from BASF: 0.7wt.-%Pd on 1/8” alumina beads
• the resultant feed stream S1 had a MAV reduced by about 80% to 1.75 g(l2)/100g and the styrene content was reduced to 1 .1 Area% (> 80% conversion), the N- and S-contents were not changed compared to SO. Also, the chlorine content was basically unaltered (cf. Table 1).
• the stream S1 was then subjected to dechlorination in a reactor comprising a Cl-adsorbent (hydrotalcite: aluminum-magnesium hydroxycarbonate powder having a MgO:Al2O3 weight ratio of 70:30) in the presence of H2 at 350 °C and at a pressure of 50 bar.
• adsorbent was compacted, then crushed and sieved to an average particle size of 500-1000 micrometers. Further, it was calcined at 450°C for 5h in air and equilibrated in ambient air overnight.
• LHSV liquid hourly space velocity
• the stream S2 was further washed with an equivalent volume of water and analyzed (see Table 2.2). The N-, S-contents were not changed compared to S1.
• the resultant feed stream S3 had in average a total chlorine content of below 2 wppm, a chloride content of below 1 wppm (see Table 2.3) and also greatly reduced N- and S-contents of from 3264 wppm up to about 31 wppm for N content and of from 2630 wppm up to about 47 wppm for S content (see Table 3).
• Comparative Example 1 Process for purifying a pyrolysis oil not according to the present invention (representative of FR 3 107 530)
• a feed stream SO comprising a pyrolysis oil as the one in Example 1 was subjected to hydrogenation in a reactor comprising an activated Pd-catalyst (Catalyst E-157 SDU 1/8” commercially available from BASF: 0.7 wt.-%Pd on 1/8” alumina beads) with H2 at 50 bar and at a tempera- ture of 195 °C.
• the resultant feed stream S1 had a MAV reduced by about 80% to 1.75 g(l2)/100g and the styrene content was reduced to 1.1 Area% (> 80% conversion), the N-, S- contents were not changed compared to SO, i.e. the N-content was of about 3260 wppm and the S-content was of about 2630 wppm.
• the chlorine and chloride contents are in Table 4.
• the tube was exchanged as explained in the following. Indeed, to enable access to the downstream section, the system was depressurized and purged with nitrogen. A 1 m long thin tubing heated to 40°C (as the complete following downstream section) with 1 ,5mm ID was located after the transfer line from the reactor (180°C, 4mm ID) and before the gas/liquid separator. This tube was exchanged. This change of tube permitted to decrease the pressure drop across the reactor system substantially so that it was not noticeable anymore.
• the pressure drop of the reactor is externally determined with 100mln(N2)/min at ambient outlet pressure. Resulting values are given in Table 6.
• the aforementioned process (representative of FR 3 107 530) which does not comprise a dechlorination step between the hydrogenation and hydroprocessing steps presents high pressure drop increase rates during the reaction course which do not allow stable operation unless water is injected downstream which causes serious corrosion issues.
• increased pressure drop of the reactors after the reaction (210 mbar vs. 71 mbar with the inventive process; cf. Table 6) was observed. Therefore, the process of the present invention presents a great improvement compared to this known process in view of more stable operation regarding increasing pressure drop and thus allowing increased TOS, which permits to obtain an improved oil production in terms of stability and duration.
• Example 2 As opposed to Example 1 , the process was started with a dechlorination step.
• a feed stream SO comprising a pyrolysis oil as the one in Example 1 was subjected to dechlorination in a reactor comprising a Cl-adsorbent (hydrotalcite: aluminum-magnesium hydroxycarbonate powder having a MgdAhOs weight ratio of 70:30) in the presence of H2 at 350 °C and at a pressure of 50 bar.
• the adsorbent was compacted, then crushed and sieved to an average particle size of 500-1000 micrometers. Further, it was calcined at 450°C for 5h in air and equilibrated in ambient air overnight.
• LHSV liquid hourly space velocity
• Figure 1 is the analysis by XRD of the solid obtained in Comp. Ex. 1 contained in the tube . Reflexes of crystalline NH4CI are marked with asterisks.
• Figure 2 a is a picture of the corundum of the preheating zone for Comparative Example 2 (black powder).
• b. is a picture of the corundum of the preheating zone for Example 1 (powder lighter than in a.).

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