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
  • 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
  • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
  • C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
• • 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
  • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
  • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
  • C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
• • 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

Definitions

• the present invention relates to a process for purifying a pyrolysis oil and a unit for carrying out said process.
• the present invention further relates to a purified pyrolysis oil obtainable or obtained by said process.
• the pyrolysis is a thermal degradation of waste material 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 and tires are 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 pyrolysis oil obtained from these materials if not purified can damage by corrosion for example during storage or cracking. Therefore, a high quality pyrolysis oil is preferred as feedstock to prevent corrosion problems in downstream refinery processes.
• US 2021/0277324 A1 discloses the purification of a pyrolysis oil by treating the oil with sodium hydroxide at a temperature of 240 °C.
• WO 2014/165859 A1 discloses a method for purifying a pyrolysis oil by reducing contaminants content such as acids, metals.
• WO 2020/178599 A1 discloses a process for upgrading a pyrolysis oil comprising washing with water the pyrolysis oil, followed by washing the pyrolysis oil with an alkane and treating the obtained organic phase with an upgrading solution comprising polar organic solvent.
• the present invention relates to a process for purifying a pyrolysis oil, the process comprising:
• 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 F0 may consist of pyrolysis oil.
• the pyrolysis oil to be purified can have any oxygen content.
• the pyrolysis oil according to (i) has a total acid number (TAN) in the range of from 0.5 to 60 mg KOH/g(FO), more preferably 1 to 40 mg KOH/g(FO), preferably in the range of from 3 to 20 mg KOH/g(F0), determined as described in Reference Example 3.
• TAN total acid number
• the pyrolysis oil according to (i) has an oxygen content in the range of from 0 to 15 g(O)/100g(F0), more preferably in the range of from 0.5 to 10 g(O)/100g(F0), more preferably in the range of from 0.5 to 5 g(O)/100g(F0), more preferably in the range of from 0.5 to 2 g(O)/100g(F0), determined as described in Reference Example 4.
• the pyrolysis oil according to (i) 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 300 wppm, determined as described in Reference Example 1.1.
• 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 1.2.
• the pyrolysis oil according to (i) 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 2.
• the pyrolysis oil according to (i) has an iron content in the range of from 1 to 100 wppm (ppm by weight), preferably from 10 to 50 wppm, determined as described in Reference Example 6.
• the pyrolysis oil according to (i) has a zinc content in the range of from 1 to 100 wppm (ppm by weight), preferably from 1 to 50 wppm, determined as described in Reference Example 6.
• the pyrolysis oil according to (i) has a tin content in the range of from 1 to 100 wppm (ppm by weight), preferably from 1 to 50 wppm, determined as described in Reference Example 6.
• the pyrolysis oil provided in (i) is obtained from the pyrolysis of waste material, the waste material being plastic waste material or tire waste material or biomass waste.
• (i) comprises
• (i.1) removing a pyrolysis oil from a storage tank or a truck.
• (ii.2) comprises
• (ii.2) comprises
• (ii.2) comprises
• the extraction unit UM1 is one or more of a stirred vessel, a mixing pump and a static mixer, more preferably a stirred vessel.
• bringing in contact preferably mixing, according to (ii.2) is performed at a temperature T1 in the range of from 10 to 95 °C, more preferably in the range of from 15 to 85 °C, more preferably in the range of from 20 to 80 °C.
• bringing in contact, more preferably mixing, according to (ii.2) is performed at a pressure p1 in the range of from 0.8 to 1 .2 bar(abs), more preferably in the range of from 0.9 to 1.1 bar(abs). More preferably, when T1 ⁇ 95 °C, bringing in contact, more preferably mixing, according to (ii.2) is performed at a pressure p1 in the range of from 0.8 to 1.2 bar(abs), more preferably in the range of from 0.9 to 1 .1 bar(abs), more preferably at about 1 bar(abs).
• bringing in contact, more preferably mixing, according to (ii.2) is performed at a pressure p1 in the range of from 0.5 to 5 bar(abs), more preferably in the range of from 0.7 to 3 bar(abs), more preferably in the range of from 0.9 to 2 bar(abs).
• the pressure p1 is in the range of from 1 to 16 bar(abs).
• the base B is one or more of an alkali metal compound, an alkaline earth metal compound (e.g. alkaline earth metal oxide and/or hydroxide such as calcium hydroxide) and ammonia.
• B is an alkali metal compound being one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate, more preferably one or more of potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate, more preferably one or more of potassium hydroxide and sodium hydroxide, more preferably potassium hydroxide or sodium hydroxide, more preferably potassium hydroxide.
• the base B is one or more of a potassium compound, more preferably one or more of potassium hydroxide, potassium bicarbonate and potassium carbonate, more preferably potassium hydroxide or potassium carbonate, more preferably potassium hydroxide.
• water used in (ii) is demineralized water.
• the weight ratio of water to F0 is in the range of from 0.05:1 to 2:1 , more preferably in the range of from 0.1 :1 to 1.5:1 , more preferably in the range of from 0.1 :1 to 1.2:1 , more preferably in the range of from 0.1 :1 to 0.5:1 , more preferably in the range of from 0.2:1 to 0.5:1 , more preferably in the range of from 0.25:1 to 0.5:1 , more preferably in the range of from 0.3:1 to 0.5:1.
• the liquid-liquid separation unit US1 is one or more of a hydrocyclone, a settler tank and a centrifuge, more preferably a decanter, a hydrocyclone, a settler tank or a centrifuge, more preferably a settler tank.
• UM1 and US1 are two distinct units.
• the separation in US1 according to (ii.3) is performed at a temperature in the range of from 10 to 95 °C, more preferably in the range of from 15 to 85 °C, more preferably in the range of from 20 to 80 °C.
• the process further comprises passing M1 into a solid-liquid separation unit SLS1 for removing solids, if any, in M1.
• the solid-liquid separation unit SLS1 is one or more of a filter and a centrifuge.
• the solid-liquid-separation can be performed with a filter using a differential pressure as driving force or with a centrifuge working with centrifugal force to separate liquid and solids.
• a filter means often a discontinuous solid-liquid-separation, where the pressure difference is increasing with increasing filtration time.
• the solids After a certain amount of pressure difference or filtration time, the solids have to be removed from the filter via a backflush by a fluid or gas or a mixture of both (e.g. disposal filter, backflush filter) or by an automatic system (e.g. automatic cleaning filter) or rotating or vibrating (e.g. pressure leaf filter, candle filter, filter press).
• a second parallel filter is started operation until a certain pressure difference or filtration time is reached, where the solid emptied filter will be in operation again.
• the filtration can be performed with disposal filter (e.g. bag filter, filter with filter sheets or membranes), where the solids are removed by back flushing or the solids remain on the filter cloth, which lead to a substitution of the filter after a certain pressure difference or operational time.
• disposal filter e.g. bag filter, filter with filter sheets or membranes
• the filtration can be supported by the use of a filter aid to improve the filtration behavior. That can lead to a potential usage of a continuous filter (e.g. belt filter, drum filter).
• Centrifuges can be used for a discontinuous solid-liquid-separation or continuous solid-liquid- separation depending on the centrifuge type.
• Centrifuges e.g. decanter centrifuge, separator centrifuge
• 2 phase solid-liquid
• 3 phase-system of two liquid phases and solids to separate the solids from the liquid or liquids and the liquid from the liquid.
• a separator centrifuge the solids have to be released after the centrifuge loaded to a maximum of solids (discontinuous) compared to a decanter centrifuge, where the solids are continuously separated and removed.
• the centrifugation can be supported by the use of flocculants to improve the centrifugation behavior.
• the process further comprises passing the stream FA(1) comprising PA(1) obtained according to (ii.3) in a separation unit LISA1 , preferably a settler tank, obtaining an aqueous stream SA1 comprising water.
• a separation unit LISA1 preferably a settler tank
• the process further comprises one or more purification treatment step for purifying SA1.
• the process further comprises recycling SA1 , more preferably purified SA1 (water), in UM1.
• F A (1) consists of water.
• the process further comprises recycling at least a portion of water comprised in FA(1) obtained according to (ii.3) into UM1.
• the process further comprises, after (ii) and prior to (iii), an acidic treatment.
• the acidic treatment may comprise adding one or more acidic component to F1.
• (ii) of the process of the present invention further comprises one or more subsequent extraction in ZE.
• the process further comprises, when crud is formed at the interphase of PA(1) and Po(1) in US1 , purging said crud from US1.
• US1 comprises a means for purging the optional crud formed at the interphase of P A (1) and P o (1).
• the purged crud is subjected to one or more purification treatments.
• the crud can be treated with a filter and/or a centrifuge.
• (iii) preferably comprises
• the present invention relates to a process for purifying a pyrolysis oil, the process comprising:
• the washing unit UM2 is one or more of a stirred vessel, a mixing pump and a static mixer, more preferably a stirred vessel.
• the weight ratio of water to F1 is in the range of from 0.05:1 to 2:1 , more preferably in the range of from 0.1 :1 to 1.5:1, more preferably in the range of from 0.1 :1 to 1.2:1 , more preferably in the range of from 0.1:1 to 0.5:1.
• the weight ratio of water to F1 is in the range of from 0.05:1 to 2:1 , more preferably in the range of from 0.1 :1 to 1.5:1 , more preferably in the range of from 0.1 : 1 to 1.2: 1 , more preferably in the range of from 0.1:1 to 0.5: 1.
• T2 is in the range of from 15 to 85 °C, more preferably in the range of from 20 to 80 °C.
• T1 ⁇ T2 Preferably 0.75 T1 ⁇ T2 ⁇ 1.25 T1 , more preferably 0.90 T1 ⁇ T2 ⁇ 1.1 T1.
• water used in (iii) is demineralized water.
• the liquid-liquid separation unit US2 is one or more of a hydrocyclone, a settler tank, and a centrifuge, more preferably a hydrocyclone, a settler tank or a centrifuge, more preferably a settler tank or centrifuge.
• UM2 and US2 are two distinct units.
• the separation in US2 according to (iii.3) is performed at a temperature in the range of from 10 to 85 °C, more preferably in the range of from 15 to 85 °C, more preferably in the range of from 20 to 80 °C.
• the process further comprises passing M2 into a solid-liquid separation unit SLS2 for removing solids, if any, in M2.
• the solid-liquid separation unit SLS2 is one or more of a filter and a centrifuge.
• the solid-liquid-separation can be performed with a filter using a differential pressure as driving force or with a centrifuge working with centrifugal force to separate liquid and solids.
• a filter means often a discontinuous solid-liquid-separation, where the pressure difference is increasing with increasing filtration time.
• the solids After a certain amount of pressure difference or filtration time, the solids have to be removed from the filter via a backflush by a fluid or gas or a mixture of both (e.g. disposal filter, backflush filter) or by an automatic system (e.g. automatic cleaning filter) or rotating or vibrating (e.g. pressure leaf filter, candle filter, filter press).
• a second parallel filter is started operation until a certain pressure difference or filtration time is reached, where the solid emptied filter will be in operation again.
• the filtration can be performed with disposal filter (e.g. bag filter, filter with filter sheets or membranes), where the solids are removed by back flushing or the solids remain on the filter cloth, which lead to a substitution of the filter after a certain pressure difference or operational time.
• disposal filter e.g. bag filter, filter with filter sheets or membranes
• the filtration can be supported by the use of a filter aid to improve the filtration behavior. That can lead to a potential usage of a continuous filter (e.g. belt filter, drum filter).
• Centrifuges can be used for a discontinuous solid-liquid-separation or continuous solid-liquid- separation depending on the centrifuge type.
• Centrifuges e.g. decanter centrifuge, separator centrifuge
• 2 phase solid-liquid
• 3 phase-system of two liquid phases and solids to separate the solids from the liquid or liquids and the liquid from the liquid.
• a separator centrifuge the solids have to be released after the centrifuge loaded to a maximum of solids (discontinuous) compared to a decanter centrifuge, where the solids are continuously separated and removed.
• the centrifugation can be supported by the use of flocculants to improve the centrifugation behavior.
• the process further comprises, when crud is formed at the interphase of PA(2) and Po(2) in US2, purging said crud from US2.
• (iii) preferably comprises (iii.T) introducing F1 into an extraction column UM+US comprised in Zw; (iii.2’) introducing water into UM+IIS;
• the present invention relates to a process for purifying a pyrolysis oil, the process comprising:
• the weight ratio of water to F1 is in the range of from 0.05:1 to 2:1 , more preferably in the range of from 0.1 :1 to 1.5:1, more preferably in the range of from 0.1 :1 to 1.2:1 , more preferably in the range of from 0.1:1 to 0.5:1.
• T2’ is in the range of from 15 to 85 °C, more preferably in the range of from 20 to 80 °C.
• 0.75 T1 ⁇ T2’ ⁇ 1 .25 T1 Preferably 0.90 T1 ⁇ T2’ ⁇ 1.1 T1 .
• (iii) is performed at a pressure p2 in the range of from 0.75 to 1 .25 bar(abs), more preferably in the range of from 0.9 to 1.1 bar(abs), more preferably at about 1 bar(abs).
• FA(2) consists of water.
• the process further comprising recycling at least a portion of water comprised in FA(2) obtained according to (iii.3) in (ii.2) and/or (iii.2); or recycling at least a portion of water comprised in FA(2) obtained according to (iii.3’) in (ii.2) and/or (iii.2’).
• recycling at least a portion of water comprised in FA(2) obtained according to (iii.3) in (ii.2) and/or (iii.2) comprises passing the at least portion of water comprised in FA(2) obtained according to (iii.3) into UM1 and/or UM2.
• recycling at least a portion of water comprised in FA(2) obtained according to (iii.3’) in (ii.2) and/or (iii.2’) comprises passing the at least portion of water comprised in FA(2) obtained according to (iii.3’) into UM1 and/or UM+IIS.
• water used in (iii) is demineralized water.
• no base is added in (iii), the base being one or more of an alkali metal compound (such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate more preferably one or more of potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate), an alkaline earth metal compound and ammonia.
• an alkali metal compound such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate more preferably one or more of potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate
• an alkaline earth metal compound and ammonia such as potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate
• the stream F2 comprising the purified pyrolysis oil obtained according to (iii) has a total acid number (TAN) which is lower than the TAN of the pyrolysis oil provided in (i).
• TAN total acid number
• the stream F2 comprising the purified pyrolysis oil obtained according to (iii) has a TAN in the range of from 0 to 20 mg KOH/g(F2), more preferably in the range of from 0 to 10 mg KOH/g(F2), more preferably in the range of from 0 to 4 mg KOH/g(F2), determined as described in Reference Example 3.
• the stream F2 comprising the purified pyrolysis oil obtained according to (iii) has an oxygen content equal to or lower than, more preferably lower than, the oxygen content of the pyrolysis oil provided in (i).
• the stream F2 comprising the purified pyrolysis oil has an oxygen content in the range of from 0 to 2 g(0)/100g(F2), determined as described in Reference Example 4.
• the stream F2 comprising the purified pyrolysis oil obtained according to (iii) has a reduced iron content compared to the pyrolysis oil provided in (i).
• the reduction of the iron (Fe) content in F2 compared to the pyrolysis oil provided in (i) can be in the range of from 1 to 100%, or in the range of from 5 to 95%, or in the range of from 40 to 90%.
• the stream F2 comprising the purified pyrolysis oil obtained according to (iii) has a reduced total chlorine content and/or chloride content compared to the pyrolysis oil provided in (i).
• the reduction of the total chlorine content and/or chloride content in F2 compared to the pyrolysis oil provided in (i) can be in the range of from 1 to 100%, or in the range of from 1 to 80% or in the range of from 10 to 50%.
• the stream F2 comprising the purified pyrolysis oil obtained according to (iii) has a reduced tin (Sn) content compared to the pyrolysis oil provided in (i).
• the reduction of the tin content in F2 compared to the pyrolysis oil provided in (i) can be in the range of from 1 to 100%, or in the range of from 5 to 80%, or in the range of from 20 to 80%.
• the stream F2 comprising the purified pyrolysis oil obtained according to (iii) has a reduced zinc (Zn) content compared to the pyrolysis oil provided in (i).
• the reduction of the zinc content in F2 compared to the pyrolysis oil provided in (i) can be in the range of from 1 to 100%, or in the range of from 5 to 80%, or in the range of from 20 to 80%.
• the stream F2 comprising the purified pyrolysis oil obtained according to (iii) has a nitrogen content lower to the nitrogen content of the pyrolysis oil provided in (i). It is conceivable according to the present invention that the stream F2 comprising the purified pyrolysis oil obtained according to (iii) has a sulfur content lower to the sulfur content of the pyrolysis oil provided in (i).
• F2 consist of the purified pyrolysis oil.
• the process of the present invention further comprises one or more subsequent washing in Zw.
• the process further comprises
• pH of P A (3) ⁇ pH of P A (2).
• pH of PA(4) ⁇ pH of PA(2).
• pH of PA(4) ⁇ pH of PA(3). More preferably, pH of PA(4) ⁇ pH of PA(3) ⁇ pH of PA(2) ⁇ pH of P A (1).
• the process further comprises recycling at least a portion of FA(4) into UM2 and/or UM3 (if present).
• FA(4) consists of water.
• UM4 is one or more of a stirred vessel, a mixing pump and a static mixer, more preferably a stirred vessel.
• the weight ratio of water to the at least portion of F2, more preferably F2, or the at least portion of F3, more preferably F3, is in the range of from 0.05:1 to 2:1 , more preferably in the range of from 0.1 :1 to 1.5:1 , more preferably in the range of from 0.1 :1 to 1.2:1 , more preferably in the range of from 0.1 :1 to 0.5: 1.
• T4 is in the range of from 15 to 85 °C, more preferably in the range of from 20 to 80 °C.
• T1 ⁇ T4 Preferably 0.75 T1 ⁇ T4 ⁇ 1.25 T1 , more preferably 0.90 T1 ⁇ T4 ⁇ 1.1 T1.
• the liquid-liquid separation unit US4 is one or more of a hydrocyclone, a settler tank, and a centrifuge, more preferably a hydrocyclone, a settler tank or a centrifuge, more preferably a settler tank or centrifuge.
• UM4 and US4 are two distinct units.
• the separation in US4 according to (iv.4) is performed at a temperature in the range of from 10 to 85 °C, more preferably in the range of from 15 to 85 °C, more preferably in the range of from 20 to 80 °C.
• the process further comprises passing M4 in a solid-liquid separation unit SLS4 for removing solids, if any, in M4.
• the solid-liquid separation unit SLS4 is one or more of a filter and a centrifuge.
• the solid-liquid-separation can be performed with a filter using a differential pressure as driving force or with a centrifuge working with centrifugal force to separate liquid and solids.
• a filter means often a discontinuous solid-liquid-separation, where the pressure difference is increasing with increasing filtration time.
• the solids After a certain amount of pressure difference or filtration time, the solids have to be removed from the filter via a backflush by a fluid or gas or a mixture of both (e.g. disposal filter, backflush filter) or by an automatic system (e.g. automatic cleaning filter) or rotating or vibrating (e.g. pressure leaf filter, candle filter, filter press).
• a second parallel filter is started operation until a certain pressure difference or filtration time is reached, where the solid emptied filter will be in operation again.
• the filtration can be performed with disposal filter (e.g. bag filter, filter with filter sheets or membranes), where the solids are removed by back flushing or the solids remain on the filter cloth, which lead to a substitution of the filter after a certain pressure difference or operational time.
• disposal filter e.g. bag filter, filter with filter sheets or membranes
• the filtration can be supported by the use of a filter aid to improve the filtration behavior. That can lead to a potential usage of a continuous filter (e.g. belt filter, drum filter).
• Centrifuges can be used for a discontinuous solid-liquid-separation or continuous solid-liquid- separation depending on the centrifuge type.
• Centrifuges e.g. decanter centrifuge, separator centrifuge
• 2 phase solid-liquid
• 3 phase-system of two liquid phases and solids to separate the solids from the liquid or liquids and the liquid from the liquid.
• a separator centrifuge the solids have to be released after the centrifuge loaded to a maximum of solids (discontinuous) compared to a decanter centrifuge, where the solids are continuously separated and removed.
• the centrifugation can be supported by the use of flocculants to improve the centrifugation behavior.
• the process further comprises recycling at least a portion of FA(3) into UM2.
• FA(3) consists of water.
• UM3, if present, is one or more of a stirred vessel, a mixing pump and a static mixer, more preferably a stirred vessel.
• the weight ratio of water to the at least portion of F2, more preferably F2 is in the range of from 0.05: 1 to 2: 1 , more preferably in the range of from 0.1 : 1 to 1 .5: 1 , more preferably in the range of from 0.1 :1 to 1.2:1 , more preferably in the range of from 0.1 :1 to 0.5:1.
• T3 is in the range of from 15 to 85 °C, more preferably in the range of from 20 to 80 °C.
• T1 ⁇ T3 ⁇ 1.25 T1 Preferably 0.90 T1 ⁇ T3 ⁇ 1.1 T1.
• the liquid-liquid separation unit US3 is one or more of a hydrocyclone, a settler tank and a centrifuge, more preferably a hydrocyclone, a settler tank or a centrifuge, more preferably a settler tank or centrifuge.
• UM3 and US3 are two distinct units.
• the separation in US3 according to (iv.1 ) is performed at a temperature in the range of from 10 to 85 °C, more preferably in the range of from 15 to 85 °C, more preferably in the range of from 20 to 80 °C.
• the process further comprises passing M3 in a solid-liquid separation unit SLS3 for removing solids, if any, in M3.
• the solid-liquid separation unit SLS3 is one or more of a filter and a centrifuge.
• water used in (iv) is demineralized water.
• no base is added in (iv), the base being one or more of an alkali metal compound (such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate more preferably one or more of potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate), an alkaline earth metal compound and ammonia.
• an alkali metal compound such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate more preferably one or more of potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate
• an alkaline earth metal compound and ammonia such as potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate
• (iv) is performed at a pressure p3 in the range of from 0.75 to 1 .25 bar(abs), more preferably in the range of from 0.9 to 1.1 bar(abs), more preferably at about 1 bar(abs).
• the process further comprises
• the storage unit SU is a storage tank, more preferably a storage tank made of one or more of steel and stainless steel, more preferably carbon steel and stainless steel.
• the process of the present invention further comprises one or more of a dechlorination step, a hydrogenation step, a hydroprocessing step, a steam cracking step, a hydrocracking step, an adsorption step, a distillation step, a stripping step, and an aqueous extraction step.
• the process of the present invention is a continuous or semi-continuous process.
• the process of the present invention consists of (i), (ii), (iii) and optionally (iv) and optionally (v).
• the present invention further relates to a unit for carrying out the process for purifying a pyrolysis oil according to the present invention, the unit comprising at least one extraction zone ZE comprising an extraction unit UM1 and a liquid-liquid separation unit US1 , UM1 being located upstream of US1 ; an inlet means for introducing F0 into ZE; an outlet means for removing F1 from ZE; an inlet means for introducing F0 into UM1 ; an outlet means for removing M1 from UM1 ; an inlet means for introducing M1 into US1 ; an outlet means from removing F1 from US1 ; at least one washing zone Zw, located downstream of ZE, an inlet means for introducing F1 into Zw; an outlet means for removing F2 from Zw.
• US1 comprises a means for purging the optional crud formed at the interphase of PA(1) and P o (1).
• Zw comprises a washing unit UM2; a liquid-liquid separation unit US2, UM2 being located upstream of US2; an inlet means for introducing F1 into UM2; an inlet means for introducing water into UM2; an outlet means for removing M2 from UM2; an inlet means for introducing M2 into US2; an outlet means from removing F2 from US2.
• Zw further comprises a washing unit UM4, preferably a mixing unit, and a liquid-liquid separation unit US4, UM4 being located downstream of US2 and US4 being located downstream of UM4.
• Zw further comprises a washing unit UM3, preferably a mixing unit, and a liquid-liquid separation unit US3, UM3 being located downstream of US2 and upstream of UM4, US3 being located downstream of UM3 and upstream of UM4.
• Zw comprises an extraction column UM+IIS; an inlet means for introducing F1 into UM+IIS; an inlet means for introducing water into UM+IIS; an outlet means from removing F2 from UM+IIS.
• the unit further comprises one or more of a storage tank, a cracking zone, a dechlorination zone, an hydrogenation zone, a hydroprocessing zone, a stripping zone and a distillation zone.
• the present invention further relates to a purified pyrolysis oil, obtainable or obtained by a process according to the present invention.
• the purified pyrolysis oil of the present invention has a total acid number (TAN) in the range of from 0 to 20 mg KOH/g(oil), more preferably in the range of from 0 to 10 mg KOH/g(oil), more preferably in the range of from 0 to 4 mg KOH/g(oil), more preferably in the range of from 0 to 1 mg KOH/g(oil), more preferably from 0 to less than 1 mg KOH/g(oil), determined as described in Reference Example 3.
• TAN total acid number
• the purified pyrolysis oil of the present invention has an oxygen content in the range of from 0 to 2 g(O)/1 OOg(oil), determined as described in Reference Example 4.
• the present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated.
• every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to "The process of any one of embodiments 1 , 2, 3 and 4".
• the following set of embodiments represents a suitably structured part of the general description directed to preferred aspects of the present invention, and, thus, suitably supports, but does not represent the claims of the present invention.
• a process for purifying a pyrolysis oil comprising:
• 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 300 wppm, determined as described in Reference Example 1.1 ; 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 1.2.
• B is one or more of an alkali metal compound, an alkaline earth metal compound and ammonia
• B is an alkali metal compound being one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate, more preferably one or more of potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate, more preferably one or more of potassium hydroxide and sodium hydroxide, more preferably potassium hydroxide or sodium hydroxide, more preferably potassium hydroxide.
• liquid-liquid separation unit US1 is one or more of a hydrocyclone, a settler tank and a centrifuge, preferably a decanter, a hydrocyclone, a settler tank or a centrifuge, more preferably a settler tank.
• the washing unit UM2 is one or more of a stirred vessel, a mixing pump and a static mixer, more preferably a stirred vessel.
• the weight ratio of water to F1 is in the range of from 0.05:1 to 2:1 , preferably in the range of from 0.1 :1 to 1.5:1, more preferably in the range of from 0.1 :1 to 1.2:1 , more preferably in the range of from 0.1:1 to 0.5:1 or more preferably in the range of from 0.8:1 to 1.2:1.
• liquid-liquid separation unit US2 is one or more of a hydrocyclone, a settler tank, and a centrifuge, preferably a hydrocyclone, a settler tank or a centrifuge, more preferably a settler tank or centrifuge.
• the weight ratio of water to F1 is in the range of from 0.05:1 to 2:1, preferably in the range of from 0.1 :1 to 1.5:1 , more preferably in the range of from 0.1 :1 to 1.2:1 , more preferably in the range of from 0.1:1 to 0.5:1 or more preferably in the range of from 0.8:1 to 1.2:1.
• a unit for carrying out the process for purifying a pyrolysis oil according to any one of embodiments 1 to 40 comprising at least one extraction zone ZE comprising an extraction unit UM1 and a liquid-liquid separation unit US1 , UM1 being located upstream of US1 ; an inlet means for introducing F0 into ZE; an outlet means for removing F1 from ZE; an inlet means for introducing F0 into UM1; an outlet means for removing M1 from UM1; an inlet means for introducing M1 into US1; an outlet means from removing F1 from US1; at least one washing zone Zw, located downstream of ZE, an inlet means for introducing F1 into Zw; an outlet means for removing F2 from Zw.
• US1 comprises a means for purging the optional crud formed at the interphase of PA(1) and Po(1).
• Zw comprises a washing unit UM2; a liquid-liquid separation unit US2, UM2 being located upstream of US2; an inlet means for introducing F1 into UM2; an inlet means for introducing water into UM2; an outlet means for removing M2 from UM2; an inlet means for introducing M2 into US2; an outlet means from removing F2 from US2.
• Zw further comprises a washing unit UM4, preferably a mixing unit, and a liquid-liquid separation unit US4, UM4 being located downstream of US2 and US4 being located downstream of UM4; wherein optionally Zw further comprises a washing unit UM3, preferably a mixing unit, and a liquid-liquid separation unit US3, UM3 being located downstream of US2 and upstream of UM4, US3 being located downstream of UM3 and upstream of UM4.
• the unit of any one of embodiments 41 to 45 further comprising one or more of a storage tank, a cracking zone, an adsorption zone, a dechlorination zone, an hydrogenation zone, a hydroprocessing zone, a stripping zone and a distillation zone. 47.
• Process comprising the step: using the unit according to any one of embodiments 41 to 46 to obtain a purified pyrolysis oil, monomer, polymer or polymer product.
• Process preferably comprising the steps according to any one of embodiments 1 to 40, comprising the further step: converting the stream F2 obtainable or obtained by the process according to any one of embodiments 1 to 40 or a chemical material obtainable by or obtained by the process according to any one of embodiments 1 to 40 to obtain a monomer, polymer or polymer product.
• polymer or polymer product is a granulate, strand, rod, plate, pipe, foil, layer, film, sheet, fiber, filament, coating, extruded and/or molded article, soft foam, half-rigid foam and/or rigid foam.
• the monomer is a di- or polyol; preferably butandiol; aldehyde; preferably formaldehyde; di- or polyisocyanate; preferably methylene diphenyl diisocyanate (MDI), polymeric methylene diphenyl diisocyanate (pMDI), toluene diisocyanate (TDI), hexamethylenediisocyanate (HDI) or isophoronediisocyanate (IPDI); amide; preferably caprolactam; alkene; preferably styrene, ethene and norbornene; alkyne, (di)ester; preferably methyl methacrylate; mono or diacid; preferably adipic acid or terephthalic acid; diamine; preferably hexamethylenediamine, nonanediamine, or sulfones; preferably 4,4
• polymer is and/or the polymer product comprises polyamide (PA); preferably PA 6 and PA 66; polyisocyanate polyaddition product; preferably polyurethane (Pll), thermoplastic polyurethane (TPU), polyurea or polyisocyanurate (PIR); low-density polyethylene (LDPE), high-density polyethylene (HDPE), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinyl acetate (PVA), polystyrene (PS), poly acrylonitrile butadiene styrene (ABS), poly styrene acrylonitrile (SAN), poly acrylate styrene acrylonitrile (ASA), polytetrafluoroethylene (Teflon), thermoplastic polyurethanes (TPU), poly(methyl acrylate) (PMA), poly(methyl methacrylate)
• the polymer and/or the polymer product is/are or is/are a part of: a part of a car, preferably cylinder head cover, engine cover, housing for charge air cooler, charge air cooler flap, intake pipe, intake manifold, connector, gear wheel, fan wheel, cooling water box, housing or housing part for heat exchanger, coolant cooler, charge air cooler, thermostat, water pump, radiator, fastening part or part of battery system for electromobility, dashboard, steering column switch, seat, headrest, center console, transmission component, door module, car exterior for A, B, C or D pillar cover, spoiler, door handle, exterior mirror, windscreen wiper, windscreen wiper protection housing, decorative grill, cover strip, roof rail, window frame, sunroof frame, antenna panel, headlight and taillight, engine cover, cylinder head cover, intake manifold, airbag, or cushion; a cloth, preferably shirt, trousers, pullover, boot, shoe, shoe sole, tight or jacket;
• a purified pyrolysis oil obtainable or obtained by a process according to any one of embodiments 1 to 40.
• the term “crud” refers to an electrostatic-, solid- or surface active stabilized layer, containing aqueous and organic phases, that most commonly accumulates at the aqueous/organic interface in the settlers of solvent-extraction processes as well known in the art.
• X is a chemical element and A, B and C are concrete elements such as Li, Na, and K, or X is a temperature and A, B and C are concrete temperatures such as 10 °C, 20 °C, and 30 °C.
• X is one or more of A and B” disclosing that X is either A, or B, or A and B, or to more specific realizations of said feature, e.g. “X is one or more of A, B, C and D”, disclosing that X is either A, or B, or C, or D, or A and B, or A and C, or A and D, or B and C, or B and D, or C and D, or A and B and C, or A and B and D, or B and C and D, or A and B and C and D, or A and B and C and D, or A and B and C and D, or A and B and C and D, or A and B and C and D.
• the converting steps to obtain the monomer, polymer or polymer product may comprise one or more synthesis steps and can be performed by conventional synthesis and technics well known to a person skilled in the art.
• the person skilled in the art to perform the converting step is from the technical field(s) pyrolysis, gasification, remonomerization, depolymerization and/or synthesis and/or production of monomers, polymers and polymer compounds, and its further processing (e.g. extrusion, injection molding). Examples of the steps of the conversion are described in “Industrial Organic Chemistry”, 3.
• 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 total acid number was determined by titration with KOH according to ASTM D3242.
• the sample (1 - 10 mg) is pyrolyzed/reduced in a reductive gas atmosphere on a soot contact, the oxygen was converted hereby to carbon monoxide (CO).
• the carbon monoxide is detected and quantified via IR spectrometry.
• the analyzer used is elementar analyzer model rapid OXY cube®.
• Two corrosion coupons of steel material 1. 0425 (DIN EN 10028-2) are stored in the tested pyrolysis oil at 60°C and under nitrogen atmosphere. Every 7 days the samples are washed with water, xylene and water again, dried and weighed. The medium is exchanged with fresh pyrolysis oil and the samples are put back. After 4 cycles (28 days) the average linear corrosion rate* is calculated and the coupons were examined.
• the surfaces of the corrosion coupons are examined in accordance to DIN 50905 using a binocular microscope at 10-20x magnification to detect various corrosion phenomena, frequency, extent and distribution of localized corrosion as well as discoloration of the coupon surface, scale formation or corrosion products. The depth of localized corrosion, e.g. shallow pit corrosion, is measured by optical focusing with light microscopy.
• Example 1 Process for purifying a pyrolysis oil according to the present invention
• TAN total acid number
• the pH of the aqueous phase of the mixture was adjusted to 10 with 10 % NaOH (1.1) or KOH (1.2 and 1 .3).
• the obtained mixture was mixed for 15 min.
• For the mixture with NaOH the mixture was transferred to a centrifuge.
• For the mixtures with KOH said mixtures were settled for 5 (1.2) and 7 (1.3) minutes in the glass vessel of 1.3 L.
• the aqueous phase was thus separated after settling from the organic (oil) phase.
• the organic phase was analyzed.
• demineralized water was further added to the organic phase for removing remaining salts /caustic (entrainment).
• the obtained mixture water/organic (oil) phase was introduced into a settler (liquid/liquid separation unit).
• the aqueous phase was separated after settling from the organic phase, said washed organic phase was analyzed. Different settling durations were applied depending on the sample, for 1.1 , it was 8 min; for 1.2 it was 6 min and for 1.3 it was 2.5 min. The results are listed in Table 1 below.
• the pyrolysis oil prior the purification treatment according to the present invention was corrosive. The local corrosion and pitting corrosion are not acceptable.
• the pyrolysis oil purified according to the present invention with NaOH reduces greatly the corrosion: reduction of the average linear corrosion vl of more than 99% and only sporadic rust spots (superficial). There is thus no pitting corrosion or local corrosion as opposed to the comparative example which demonstrates a clear improvement.
• Said purified pyrolysis oil does not affect the technical stability of the steel material (vl of less than 0.1 mm/y in combination with no pitting or localized corrosion).
• the pyrolysis oil purified according to the present invention with KOH reduces greatly the corrosion: reduction of the average linear corrosion vl of about 80% and only sporadic rust spots (superficial). There is thus no pitting corrosion or local corrosion as opposed to the comparative example which demonstrates a clear improvement. Said purified pyrolysis oil does not affect the technical stability of the steel material.
• v demineralized water/ organic phase
• Corrosion tests were performed as described in Reference Example 5 with the pyrolysis oil F0 (cf. Table 2 above) and with the purified pyrolysis oil obtained not according to the present invention (different pH). The results are detailed in Table 6 below.
• the pyrolysis oil purified not according to the present invention with KOH at pH 7 reduces the average linear corrosion vl.
• the pyrolysis oil is more corrosive than the purified pyrolysis oils obtained according to the process of the present invention (cf. Tables 3 and 4 above). Even if vl has been reduced, the presence of local corrosion and pitting corrosion is not acceptable.
• Example 2 Process for purifying a pyrolysis oil according to the present invention
• TAN total acid number
• the pH of the aqueous phase of the mixture was adjusted to 10 with 25 % NaOH
• the obtained mixture was mixed for 15 min.
• the mixture was transferred to a centrifuge.
• the aqueous phase was thus separated after settling from the organic (oil) phase.
• the organic phase was analyzed.
• demineralized water was further added to the organic phase for removing remaining salts /caustic (entrainment).
• the obtained mixture water/organic (oil) phase was introduced into a settler (liquid/liquid separation unit).
• the aqueous phase was separated after settling from the organic phase, said washed organic phase was analyzed. The results are listed in Table 7 below.
• the extraction permits to purify the pyrolysis oil by reducing its TAN as well as the Fe-, Sn- and Zn-contents.
• the mixture was shook.
• the pH of the aqueous phase of the mixture was of pH 4.3.
• the obtained mixture water / organic phase (oil) was introduced into a centrifuge. The aqueous phase was thus separated from the organic (oil) phase.
• demineralized water was further added to the organic phase for a second washing step.
• the obtained mixture water/or- ganic phase (oil) was introduced into a centrifuge.
• the aqueous phase was separated after from the organic phase.
• a third washing step was performed and the aqueous phase was separated with a centrifuge from the organic phase, said washed organic phase was analyzed. The results are listed in Table 3 below.
• pyrolysis oils (each of them having a total acid number (TAN) of about 8.5 mg KOH/g, a total chlorine content of 24 wppm, a chloride content ⁇ 5 wppm, a nitrogen content of 0.5 wt.-% based on the weight of the pyrolysis oil and an oxygen content of 1 wt.-% based on the weight of the pyrolysis oil, a density of 916 kg/m 3 and a viscosity of 6.4 mPas) have been extracted with NaOH or KOH in centrifuge glasses under the conditions detailed in Table 9. After the extraction, phase separation of these oils have been observed (cf. Table 9).
• TAN total acid number
• NaOH sodium salts of fatty acids
• potassium soaps potassium salt of fatty acids
• FIG. 1 is a schematic representation of a unit for carrying out the process for purifying a pyrolysis oil according to embodiments of the invention.
• the unit comprises an extraction zone ZE comprising an extraction unit UM1 and a liquid-liquid separation unit US1 , US1 being located downstream of UM1 , and a washing zone Zw, downstream of ZE, comprising a washing unit UM2 and a liquid-liquid separation unit US2, US2 being located downstream of UM2.
• the stream F0 comprising a pyrolysis oil is introduced into UM1 together with water and a base B.
• F0, water and B are brought in contact in UM1 at a temperature in the range of from 10 to 200 °C, preferably in the range of from 10 to 95 °C.
• a mixture M1 is removed from UM1 , said mixture comprising an aqueous phase PA(1) and an organic phase Po(1), the pH of the aqueous phase PA(1) of M1 being in the range of from 7.5 to 11.
• M1 is introduced into US1.
• a stream FA(1) comprising PA(1) and a stream F1 comprising the extracted pyrolysis oil (P o (1)) are obtained and removed from US1 and ZE.
• F1 is introduced into UM2 together with water. F1 and water are brought in contact at a temperature in the range of from 10 to 95 °C.
• a mixture M2 is obtained, said mixture comprising an aqueous phase PA(2) and an organic phase Po(2), the pH of the aqueous phase PA(2) of M2 being in the range of from 7.5 to 11 , pH of PA(2) ⁇ pH of PA(1).
• M2 is then introduced into US2.
• a stream F2 comprising the purified pyrolysis oil is obtained.
• a further stream FA(2) comprising PA(2) is also obtained.
• F2 can then be stored or transferred for further treatment(s).
• FA(1), aqueous stream, and/or FA(2), aqueous stream are recycled (not shown) in UM1 and/or UM2.
• a purge not shown
• FIG. 2 is a schematic representation of a unit for carrying out the process for purifying a pyrolysis oil according to embodiments of the invention.
• the unit comprises an extraction zone ZE comprising an extraction unit UM1 , a solid-liquid separation unit SLS1 and a liquid-liquid separation unit US1 , SLS1 being located downstream of UM1 and US1 being located downstream of SLS1 , and a washing zone Zw, downstream of ZE, comprising a washing unit UM2, a solid-liquid separation unit SLS2 and a liquidliquid separation unit US2, SLS2 being located downstream of UM2 and US2 being located downstream of SLS2.
• the process is as defined in Figure 1 , except that M1 prior to be introduced into US1 is passed through SLS1 to remove solids if any and that M2 prior to be introduced into US2 is passed through SLS2 to remove solids if any.
• FIG 3 is a schematic representation of a unit for carrying out the process for purifying a pyrolysis oil according to embodiments of the invention.
• the unit comprises an extraction zone ZE comprising an extraction unit UM1 and a liquid-liquid separation unit US1 , US1 being located downstream of UM1 , and a washing zone Zw, downstream of ZE, comprising a washing unit UM2 combined to a liquid-liquid separation unit US2.
• ZE optionally comprises a solid-liquid separation unit SLS1, located downstream of UM1 and upstream of US1.
• the stream F0 comprising a pyrolysis oil is introduced into UM1 together with water and a base B.
• F0, water and B are brought in contact in UM1 at a temperature in the range of from 10 to 200 °C, preferably in the range of from 10 to 95 °C.
• a mixture M1 is removed from UM1, said mixture comprising an aqueous phase PA(1 ) and an organic phase Po(1), the pH of the aqueous phase PA(1 ) of M1 being in the range of from 7.5 to 11.
• M1 is introduced into US1. If SLS1 is present, M1 is passed through SLS1 prior to be introduced into US1.
• a stream FA(1) comprising PA(1 ) and a stream F1 comprising the extracted pyrolysis oil are obtained and removed from US1 and ZE. Further, F1 is introduced into the combined UM2/US2 being an extraction column.
• Water is also introduced into said column and brought in contact with F1 at a temperature in the range of from 10 to 95 °C, the phases of M2 are separated in the column, the pH of the aqueous phase PA(2) of M2 being in the range of from 7.5 to 11, pH of PA(2) ⁇ pH of PA(1 ).
• a stream F2 comprising the purified pyrolysis oil is obtained (removed at the top of the column).
• a further stream FA(2) comprising PA(2) is also obtained (removed at the opposite of the column, namely the bottom).
• F2 can then be stored or transferred for further treatment(s).
• FA(2), aqueous stream is recycled (not shown) in UM1 and/or Zw.
• FIG. 4 is a schematic representation of a unit for carrying out the process for purifying a pyrolysis oil according to embodiments of the invention.
• the unit comprises an extraction zone ZE comprising an extraction unit UM1 , an optional solid-liquid separation unit SLS1 and a liquid-liquid separation unit US1, SLS1 being located downstream of UM1 and US1 being located downstream of SLS1, and a washing zone Zw, downstream of ZE, comprising a washing unit UM2, an optional solid-liquid separation unit SLS2 and a liquid-liquid separation unit US2, SLS2 being located downstream of UM2 and US2 being located downstream of SLS2.
• Zw of the unit further comprises a washing unit UM4, an optional solid-liquid separation unit SLS4 and a liquid-liquid separation unit US4, SLS4 being located downstream of UM4 and US4 being located downstream of SLS4.
• F2 is introduced into UM4 together with water. F2 and water are brought in contact at a temperature in the range of from 10 to 95 °C.
• a mixture M4 is obtained, said mixture comprising an aqueous phase PA(4) and an organic phase Po(4), the pH of the aqueous phase PA(4) of M4 being in the range of from 7.5 to 11 , pH of PA(4) ⁇ pH of PA(1 ).
• M4 is then introduced into US4, and optionally passed through LISL4 prior to be introduced into US4.
• a stream F4 comprising the purified pyrolysis oil is obtained.
• a further stream FA(4) comprising PA(4) is also obtained. F4 can then be stored or transferred for further treatment(s).
• FA(4), aqueous stream is recycled (not shown) in UM2.
• Zw of the unit further comprises a washing unit UM3 and a liquid-liquid separation unit US3, it can further comprises a solid-liquid separation unit SL3, SLS3 if present being located downstream of UM3 and US3 being located downstream of SLS3.
• F2 is introduced into UM3 (not UM4) together with water.
• F2 and water are brought in contact at a temperature in the range of from 10 to 95 °C.
• a mixture M3 is obtained, said mixture comprising an aqueous phase PA(3) and an organic phase Po(3), the pH of the aqueous phase PA(3) of M3 being in the range of from 7.5 to 11 , pH of PA(3) ⁇ pH of PA(1 ).
• M3 is then introduced into US3, and optionally passed through LISL3 prior to be introduced into US3.
• a stream F3 comprising the purified pyrolysis oil is obtained.
• a further stream FA(3) comprising PA(3) is also obtained.
• F3 is then introduced into UM4 together with water. F3 and water are brought in contact at a temperature in the range of from 10 to 95 °C.
• a mixture M4 is obtained, said mixture comprising an aqueous phase PA(4) and an organic phase Po(4), the pH of the aqueous phase PA(4) of M4 being in the range of from 7.5 to 11 , pH of PA(4) ⁇ pH of PA(1 ).
• M4 is then introduced into US4, and optionally passed through LISL4 prior to be introduced into US4.
• a stream F4 comprising the purified pyrolysis oil is obtained.
• a further stream FA(4) comprising PA(4) is also obtained.
• F4 can then be stored or transferred for further treatment(s).
• FA(4), aqueous stream is recycled (not shown) in UM2 and/or UM3.
• FA(3), aqueous stream is recycled (not shown) in UM2.
• FA(2), aqueous stream is recycled (not shown) in UM1.

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=90719232

Family Applications (1)

Country Status (5)

Family Cites Families (24)

• 2024
  • 2024-04-12 EP EP24716831.3A patent/EP4695348A1/de active Pending
  • 2024-04-12 WO PCT/EP2024/060026 patent/WO2024213732A1/en not_active Ceased
  • 2024-04-12 KR KR1020257037561A patent/KR20250172945A/ko active Pending
  • 2024-04-12 CN CN202480025011.7A patent/CN120958106A/zh active Pending
  • 2024-04-12 JP JP2025559711A patent/JP2026512896A/ja active Pending

Also Published As

Similar Documents

Legal Events