FR3119398A1 - METHOD FOR PURIFYING A PYROLYSIS OIL FOR USE BY STEAM CRACKING - Google Patents
METHOD FOR PURIFYING A PYROLYSIS OIL FOR USE BY STEAM CRACKING Download PDFInfo
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- FR3119398A1 FR3119398A1 FR2106955A FR2106955A FR3119398A1 FR 3119398 A1 FR3119398 A1 FR 3119398A1 FR 2106955 A FR2106955 A FR 2106955A FR 2106955 A FR2106955 A FR 2106955A FR 3119398 A1 FR3119398 A1 FR 3119398A1
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- pyrolysis
- pyrolysis oil
- waste
- optionally
- process according
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- 238000000197 pyrolysis Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000004230 steam cracking Methods 0.000 title claims description 8
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000002699 waste material Substances 0.000 claims abstract description 16
- 238000000605 extraction Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000011084 recovery Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000004033 plastic Substances 0.000 claims abstract description 10
- 229920003023 plastic Polymers 0.000 claims abstract description 10
- 238000010908 decantation Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000002028 Biomass Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 239000000806 elastomer Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 239000002029 lignocellulosic biomass Substances 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims 9
- 238000000746 purification Methods 0.000 claims 7
- 239000011111 cardboard Substances 0.000 claims 2
- 239000011087 paperboard Substances 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 229920001451 polypropylene glycol Polymers 0.000 claims 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims 1
- 239000002798 polar solvent Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 23
- 239000012263 liquid product Substances 0.000 description 4
- 239000013502 plastic waste Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- -1 alkali metal cation Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/40—Thermal non-catalytic treatment
-
- 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
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one thermal cracking 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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
- C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—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
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
-
- 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
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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
L'invention concerne un procédé de purification d’une huile de pyrolyse issue de la pyrolyse de déchets comprenant des plastiques par extraction liquide/liquide. Cette extraction est réalisée au moyen d’un solvant polaire non miscible avec l’huile de pyrolyse, pour lequel on obtient un taux de récupération supérieur ou égal à 0.95, ce taux de récupération étant défini comme le rapport du volume d’extrait sur le volume de solvant initial, cet extrait étant une phase contenant le solvant, non miscible avec l’huile de pyrolyse, récupérée après agitation puis décantation d’un mélange d’une partie par volume de solvant avec vingt cinq parties par volume de l’huile de pyrolyse à pression atmosphérique et à une température de 20°C.The invention relates to a process for purifying a pyrolysis oil resulting from the pyrolysis of waste comprising plastics by liquid/liquid extraction. This extraction is carried out using a polar solvent immiscible with the pyrolysis oil, for which a recovery rate greater than or equal to 0.95 is obtained, this recovery rate being defined as the ratio of the volume of extract to the volume of initial solvent, this extract being a phase containing the solvent, immiscible with the pyrolysis oil, recovered after stirring then decantation of a mixture of one part by volume of solvent with twenty-five parts by volume of the oil pyrolysis at atmospheric pressure and at a temperature of 20°C.
Description
Domaine de l’inventionField of the invention
L’invention concerne la valorisation d’huiles provenant de la pyrolyse de déchets, en particulier en tant que charge d’un procédé de vapocraquage. Le procédé selon l’invention permet en particulier de purifier l’huile de pyrolyse issue de déchets plastiques de toutes sortes, quelle que soit leur origine. Ces déchets plastiques peuvent contenir en proportions variables d’autres types de déchets comme par exemple la biomasse lignocellulosique et/ou des élastomères.The invention relates to the recovery of oils from the pyrolysis of waste, in particular as feedstock for a steam cracking process. The process according to the invention makes it possible in particular to purify the pyrolysis oil resulting from plastic waste of all kinds, whatever their origin. This plastic waste may contain other types of waste in varying proportions, such as lignocellulosic biomass and/or elastomers.
Art antérieurPrior art
La pyrolyse est une décomposition endothermique en atmosphère réductrice (atmosphère dépourvue en oxygène ou pauvre en oxygène ou atmosphère de gaz inertes) sous l’effet de la chaleur (à partir de 300°C). Ce procédé permet la décomposition de matière organique solide en trois phases : solide (coke de pyrolyse ou char), liquide (constituée de condensables lourds, huiles de pyrolyse ou goudrons ou légers, H2O) et gazeuse (CO, H2, CO2, oléfines et paraffines courtes). Cette matière organique solide peut comprendre des matières plastiques, de la biomasse, des déchets agricoles, des déchets ménagers. Avec l’augmentation du volume des déchets, la pyrolyse permet d’envisager de valoriser ces déchets en les convertissant en produits liquides pouvant ensuite être traités pour produire des produits à haute valeur ajoutée.Pyrolysis is an endothermic decomposition in a reducing atmosphere (atmosphere devoid of oxygen or poor in oxygen or atmosphere of inert gases) under the effect of heat (from 300°C). This process allows the decomposition of solid organic matter into three phases: solid (pyrolysis coke or char), liquid (consisting of heavy condensables, pyrolysis oils or tars or light, H 2 O) and gaseous (CO, H 2 , CO 2 , olefins and short paraffins). This solid organic material can include plastics, biomass, agricultural waste, household waste. With the increase in the volume of waste, pyrolysis makes it possible to consider recovering this waste by converting it into liquid products that can then be treated to produce products with high added value.
Les produits liquides de la pyrolyse, aussi appelés huiles de pyrolyse, peuvent cependant présenter des teneurs élevées en composés indésirables en particulier pour une utilisation en charge d’un traitement de vapocraquage. Ces composés indésirables (ou contaminants) comprennent des hétéroatomes, en particulier oxygène, azote, soufre, mais aussi halogènes et métaux de transition. D’autres composés indésirables comprennent les composés hydrocarbonés insaturés, notamment les aromatiques et les diènes.Liquid pyrolysis products, also called pyrolysis oils, can however have high levels of undesirable compounds, particularly for use in charge of a steam cracking treatment. These undesirable compounds (or contaminants) include heteroatoms, in particular oxygen, nitrogen, sulfur, but also halogens and transition metals. Other undesirable compounds include unsaturated hydrocarbon compounds, including aromatics and dienes.
Le document WO2020/212315 décrit un procédé de récupération des hydrocarbures aliphatiques à partir d’un produit liquide de la pyrolyse de déchets plastiques, notamment d’un mélange de plastiques. Ce produit liquide est soumis à une extraction par un solvant permettant d’obtenir un raffinat à teneur réduite en hydrocarbures aromatiques et /ou en composés polaires par rapport au produit liquide. Ces composés polaires sont des composés organiques contenant des hétéroatomes (N, S, O) ou des sels pouvant comprendre un cation, tel que le cation ammonium, un cation de métal alcalin, un cation d’élément alcalino terreux, un cation d’un métal de transition, et un anion, tel qu’un ion carboxylate, sulfate, phosphate ou halogénure. Le raffinat résultant de l’extraction liquide-liquide subit ensuite à nouveau une extraction par l’eau afin d’éliminer le solvant présent dans le raffinat, ce qui est coûteux en ressources.Document WO2020/212315 describes a process for recovering aliphatic hydrocarbons from a liquid product of the pyrolysis of plastic waste, in particular a mixture of plastics. This liquid product is subjected to extraction with a solvent to obtain a raffinate with a reduced content of aromatic hydrocarbons and/or polar compounds compared to the liquid product. These polar compounds are organic compounds containing heteroatoms (N, S, O) or salts which can comprise a cation, such as the ammonium cation, an alkali metal cation, an alkaline earth element cation, a cation of a transition metal, and an anion, such as a carboxylate, sulfate, phosphate or halide ion. The raffinate resulting from the liquid-liquid extraction then undergoes water extraction again in order to remove the solvent present in the raffinate, which is costly in terms of resources.
Le document WO2020/178599A1 décrit un procédé de valorisation d'une huile de pyrolyse issue de la pyrolyse de plastique ou de caoutchouc, ou d’une combinaison de ceux-ci. L’huile de pyrolyse est traitée avec une solution d’extraction comprenant un solvant organique polaire pour fournir un mélange comprenant un extrait et un raffinat. Le raffinat obtenu par ce procédé d’extraction est une huile de pyrolyse présentant une teneur réduite en composés indésirables tels que résidus solides, oléfines et composés comprenant des hétéroatomes (soufre, azote et halogène). Les composés oxygénés sont considérés comme des composés désirables. La solution de valorisation peut en outre comprendre un fluide hydrocarboné (alcanes ou alcènes, ou mélange des deux) pour favoriser la séparation du raffinat et de l’extrait.Document WO2020/178599A1 describes a method for recovering a pyrolysis oil from the pyrolysis of plastic or rubber, or a combination thereof. The pyrolysis oil is treated with an extraction solution comprising a polar organic solvent to provide a mixture comprising an extract and a raffinate. The raffinate obtained by this extraction process is a pyrolysis oil with a reduced content of undesirable compounds such as solid residues, olefins and compounds comprising heteroatoms (sulphur, nitrogen and halogen). Oxygenated compounds are considered desirable compounds. The upgrading solution may further comprise a hydrocarbon fluid (alkanes or alkenes, or a mixture of the two) to promote the separation of the raffinate and the extract.
Ces documents ne décrivent pas le traitement d’huiles de pyrolyse provenant de la pyrolyse de déchets plastiques en mélange avec d’autres types de déchets.These documents do not describe the treatment of pyrolysis oils from the pyrolysis of plastic waste mixed with other types of waste.
L’invention vise à proposer un procédé de purification d’une huile de pyrolyse permettant de réduire de manière notable la quantité de composés comprenant des hétéroatomes, et tout particulièrement l’oxygène, l’azote, le soufre, les métaux, en particulier les métaux de transition, et les halogénures initialement contenus dans l’huile de pyrolyse. L’invention peut aussi permettre de réduire la quantité de composés hydrocarbonés insaturés initialement contenus dans l’huile de pyrolyse, notamment les composés aromatiques et les dioléfines.The aim of the invention is to propose a method for purifying a pyrolysis oil which makes it possible to significantly reduce the quantity of compounds comprising heteroatoms, and most particularly oxygen, nitrogen, sulfur, metals, in particular transition metals, and the halides initially contained in the pyrolysis oil. The invention can also make it possible to reduce the quantity of unsaturated hydrocarbon compounds initially contained in the pyrolysis oil, in particular aromatic compounds and diolefins.
Un premier objet de l’invention concerne un procédé de purification d’une huile de pyrolyse issue de la pyrolyse de déchets contenant des plastiques, comprenant les étapes suivantes :
- la fourniture d’une huile de pyrolyse contenant des composés hydrocarbonés saturés et insaturés et des composés polaires comprenant au moins un hétéroatome choisi parmi l’oxygène, le soufre, l’azote, un métal de transition, un métal alcalin, un métal alcalino-terreux, un halogène,
- la mise en contact de l’huile de pyrolyse avec un solvant d’extraction polaire non miscible avec l’huile de pyrolyse,
- la récupération d’un extrait et d’un raffinat non miscibles, l’extrait contenant le solvant d’extraction et au moins une partie des composés polaires, et optionnellement au moins une partie des composés hydrocarbonés insaturés, initialement contenus dans l’huile de pyrolyse, le raffinat contenant une huile de pyrolyse traitée à teneur réduite en composés polaires et optionnellement en composés hydrocarbonés insaturés,
dans lequel le solvant d’extraction polaire non miscible avec l’huile de pyrolyse est un solvant pour lequel on obtient un taux de récupération supérieur ou égal à 0,95, ce taux de récupération étant défini comme le rapport du volume d’un extrait sur le volume de solvant initial, et cet extrait est une phase contenant le solvant, non miscible avec l’huile de pyrolyse, récupérée après agitation puis décantation d’un mélange d’une partie par volume de solvant avec vingt cinq parties par volume de l’huile de pyrolyse à pression atmosphérique et à une température de 20°C.A first object of the invention relates to a process for purifying a pyrolysis oil resulting from the pyrolysis of waste containing plastics, comprising the following steps:
- the supply of a pyrolysis oil containing saturated and unsaturated hydrocarbon compounds and polar compounds comprising at least one heteroatom chosen from oxygen, sulfur, nitrogen, a transition metal, an alkali metal, an alkaline metal - earth, a halogen,
- bringing the pyrolysis oil into contact with a polar extraction solvent immiscible with the pyrolysis oil,
- the recovery of an extract and an immiscible raffinate, the extract containing the extraction solvent and at least a part of the polar compounds, and optionally at least a part of the unsaturated hydrocarbon compounds, initially contained in the oil pyrolysis, the raffinate containing a treated pyrolysis oil with a reduced content of polar compounds and optionally of unsaturated hydrocarbon compounds,
in which the polar extraction solvent immiscible with the pyrolysis oil is a solvent for which a recovery rate greater than or equal to 0.95 is obtained, this recovery rate being defined as the ratio of the volume of an extract on the initial volume of solvent, and this extract is a phase containing the solvent, immiscible with the pyrolysis oil, recovered after stirring then decantation of a mixture of one part by volume of solvent with twenty-five parts by volume of pyrolysis oil at atmospheric pressure and at a temperature of 20°C.
Le raffinat obtenu par le procédé selon l’invention est ainsi dépourvu ou quasiment dépourvu de solvant de sorte qu’il n’a pas besoin de subir une autre étape d’extraction avant utilisation.The raffinate obtained by the process according to the invention is thus devoid or almost devoid of solvent so that it does not need to undergo another extraction step before use.
Le procédé selon l’invention permet d’extraire au moins 30%m/m, voire au moins 40%m/m ou au moins 50%m/m de la totalité des composés polaires contenus initialement dans l’huile de pyrolyse, notamment plusieurs composés polaires, en particulier ceux contenant de l’oxygène, du soufre, de l’azote, des halogènes, en particulier chlore, fluor et brome, et des métaux, notamment des métaux de transition, en particulier le fer. Le procédé selon l’invention peut également permettre d’extraire au moins 10%m/m des composés hydrocarbonés insaturés.The process according to the invention makes it possible to extract at least 30% m/m, or even at least 40% m/m or at least 50% m/m of all the polar compounds initially contained in the pyrolysis oil, in particular several polar compounds, in particular those containing oxygen, sulfur, nitrogen, halogens, in particular chlorine, fluorine and bromine, and metals, in particular transition metals, in particular iron. The process according to the invention can also make it possible to extract at least 10% m/m of the unsaturated hydrocarbon compounds.
L’invention a également pour objet un procédé de vapocraquage comprenant une étape de vapocraquage d’un raffinat d’huile de pyrolyse récupéré lors de la mise en œuvre du procédé selon l’invention.The invention also relates to a steam cracking process comprising a steam cracking step of a pyrolysis oil raffinate recovered during the implementation of the process according to the invention.
Ce raffinat d’huile de pyrolyse peut être pur ou dilué, notamment introduit en mélange avec une charge typique de vapocraquage.This pyrolysis oil raffinate can be pure or diluted, in particular introduced as a mixture with a typical steam cracking charge.
Claims (9)
- la fourniture d’une huile de pyrolyse contenant des composés hydrocarbonés saturés et insaturés et des composés polaires comprenant au moins un hétéroatome choisi parmi l’oxygène, le soufre, l’azote, un métal de transition, un métal alcalin, un métal alcalino-terreux, un halogène,
- la mise en contact de l’huile de pyrolyse avec un solvant d’extraction polaire non miscible avec l’huile de pyrolyse,
- la récupération d’un extrait et d’un raffinat non miscibles, l’extrait contenant le solvant d’extraction et au moins une partie des composés polaires, et optionnellement au moins une partie des composés hydrocarbonés insaturés, initialement contenus dans l’huile de pyrolyse, le raffinat contenant une huile de pyrolyse traitée à teneur réduite en composés polaires et optionnellement en composés hydrocarbonés insaturés,
dans lequel le solvant d’extraction polaire non miscible avec l’huile de pyrolyse est un solvant pour lequel on obtient un taux de récupération supérieur ou égal à 0,95, ce taux de récupération étant défini comme le rapport du volume d’un extrait sur un volume de solvant initial, et cet extrait est une phase contenant le solvant, non miscible avec l’huile de pyrolyse, récupérée après agitation puis décantation d’un mélange d’une partie par volume de solvant avec vingt cinq parties par volume de l’huile de pyrolyse à pression atmosphérique et à une température de 20°C.Process for purifying a pyrolysis oil resulting from the pyrolysis of waste containing plastics, comprising:
- the supply of a pyrolysis oil containing saturated and unsaturated hydrocarbon compounds and polar compounds comprising at least one heteroatom chosen from oxygen, sulfur, nitrogen, a transition metal, an alkali metal, an alkaline metal - earth, a halogen,
- bringing the pyrolysis oil into contact with a polar extraction solvent immiscible with the pyrolysis oil,
- the recovery of an extract and an immiscible raffinate, the extract containing the extraction solvent and at least a part of the polar compounds, and optionally at least a part of the unsaturated hydrocarbon compounds, initially contained in the oil pyrolysis, the raffinate containing a treated pyrolysis oil with a reduced content of polar compounds and optionally of unsaturated hydrocarbon compounds,
in which the polar extraction solvent immiscible with the pyrolysis oil is a solvent for which a recovery rate greater than or equal to 0.95 is obtained, this recovery rate being defined as the ratio of the volume of an extract on an initial volume of solvent, and this extract is a phase containing the solvent, immiscible with the pyrolysis oil, recovered after stirring then decantation of a mixture of one part by volume of solvent with twenty-five parts by volume of pyrolysis oil at atmospheric pressure and at a temperature of 20°C.
- une deuxième étape de mise en contact au cours de laquelle le raffinat récupéré est mis en contact avec un nouveau lot du même solvant d’extraction que celui utilisé lors de la première étape de mise en contact mentionnée,
- suivie d’une deuxième étape de récupération d’un deuxième extrait et d’un deuxième raffinat non miscibles,
optionnellement, on réitère n fois ces deux étapes sur le raffinat récupéré lors de l’étape de récupération de l’itération précédente, où n est un entier non nul.Purification process according to any one of claims 1 to 7, comprising:
- a second contacting step during which the recovered raffinate is brought into contact with a new batch of the same extraction solvent as that used during the first contacting step mentioned,
- followed by a second stage of recovery of a second extract and a second immiscible raffinate,
optionally, these two steps are repeated n times on the raffinate recovered during the recovery step of the previous iteration, where n is a non-zero integer.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020237029444A KR20230135671A (en) | 2021-01-29 | 2022-01-24 | Method for refining pyrolysis oil for upgrading by steam-cracking |
| US18/273,928 US20240076558A1 (en) | 2021-01-29 | 2022-01-24 | Method for purifying a pyrolysis oil in order to upgrade it by steam-cracking |
| PCT/FR2022/050125 WO2022162298A1 (en) | 2021-01-29 | 2022-01-24 | Method for purifying a pyrolysis oil in order to upgrade it by steam-cracking |
| EP22704934.3A EP4284896A1 (en) | 2021-01-29 | 2022-01-24 | Method for purifying a pyrolysis oil in order to upgrade it by steam-cracking |
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| FR2100907A FR3119399A1 (en) | 2021-01-29 | 2021-01-29 | METHOD FOR PURIFYING A PYROLYSIS OIL FOR USE BY STEAM CRACKING |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2014236246A1 (en) * | 2013-03-14 | 2015-11-05 | Gtc Technology Us Llc | Separation of impurities during extraction processes |
| WO2020178599A1 (en) | 2019-03-07 | 2020-09-10 | Oxford Sustainable Fuels Limited | Process of upgrading a pyrolysis oil and upgrading solution used therein |
| WO2020212315A1 (en) | 2019-04-18 | 2020-10-22 | Shell Internationale Research Maatschappij B.V. | Recovery of aliphatic hydrocarbons |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2014236246A1 (en) * | 2013-03-14 | 2015-11-05 | Gtc Technology Us Llc | Separation of impurities during extraction processes |
| WO2020178599A1 (en) | 2019-03-07 | 2020-09-10 | Oxford Sustainable Fuels Limited | Process of upgrading a pyrolysis oil and upgrading solution used therein |
| WO2020212315A1 (en) | 2019-04-18 | 2020-10-22 | Shell Internationale Research Maatschappij B.V. | Recovery of aliphatic hydrocarbons |
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| CAS , no. 4394-85-8 |
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