WO2024069624A1 - Procédé de recyclage de déchets plastiques et produits de haute valeur ainsi fabriqués - Google Patents

Procédé de recyclage de déchets plastiques et produits de haute valeur ainsi fabriqués Download PDF

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Publication number
WO2024069624A1
WO2024069624A1 PCT/IL2023/051015 IL2023051015W WO2024069624A1 WO 2024069624 A1 WO2024069624 A1 WO 2024069624A1 IL 2023051015 W IL2023051015 W IL 2023051015W WO 2024069624 A1 WO2024069624 A1 WO 2024069624A1
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WIPO (PCT)
Prior art keywords
paraffinic
product
stream
ppm
aromatic compounds
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PCT/IL2023/051015
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English (en)
Inventor
Daria FRĄCZAK
Justyna Odrobińska
Antonina DRABIK
Krzysztof BACHTA
Marcin Stec
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Clariter IP
Cohn De Vries Stadler & Co.
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Publication of WO2024069624A1 publication Critical patent/WO2024069624A1/fr

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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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/302—Viscosity
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/16—Residues
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/18—Solvents

Definitions

  • the present disclosure concerns a process for recycling of plastic waste by means of thermal cracking, and high value products, such as solvents, oils and waxes, manufactured thereby.
  • polyolefins A major component in municipal and industrial waste are polyolefins, which are used for a variety of domestic products, mainly packaging, as well as for agricultural needs such as greenhouses and irrigation tubing. Since only some of the polyolefin waste is recycled into new polyolefin products, it would be beneficial to provide a recycling process that enables obtaining high valuable products from additional polyolefin plastic waste.
  • the present disclosure provides an industrial recycling process of polyolefin waste for obtaining high value products, such as solvents, oils and waxes at a high degree of purity.
  • the products produced by processes of this disclosure have low aromatic content, typically below 3000 ppm (e.g. below 2000 ppm (0.2 wt%)), and meet FDA requirements, as well as the requirements of cosmetology.
  • high value byproducts are also produced, which can be used as fuel due to their high calorific value or as additives/modifiers for bituminous and asphalt masses.
  • thermocracking step mainly due to the broad range of intermediates produced during the thermocracking step and the ensuing hydrotreating process, which is configured for treating the thermocracking product as a whole, prior to separation into distinct hydrocarbon fractions.
  • the process of disclosure hence, enables obtaining a wide variety of products having a low aromatics and low impurities content from the same polyolefin feedstock in an integrated process.
  • a process for obtaining paraffinic products having an aromatic compounds content of at most about 3000 ppm from a mixture of polyolefins comprising:
  • paraffinic products comprising:
  • thermocracking a waste polyolefins mixture in a melt state in a thermolysis reactor to obtain a hydrocarbons vapor stream under conditions comprising (i) pressure of at most 1 barg, (ii) temperature ranging between about 320°C and about 450°C, (iii) absence of oxygen, and (iv) residence time of the mixture in the thermolysis reactor of between about 2 and about 40 hours;
  • paraffinic products comprising:
  • the C6-C20 paraffinic product, the C14-C32 paraffinic product, and/or the C20-C70 paraffinic product have an aromatic compounds content of at most about 2000 ppm.
  • each of the C6-C20 paraffinic product, the C14-C32 paraffinic product, or the C20-C70 paraffinic product has an aromatic compounds content of at most about 2000 ppm.
  • polyolefins or poly(alkenes) means to denote linear, branched, crosslinked or block polymers which consist of or are produced from olefinic monomers.
  • the polyolefins are typically obtained from plastic waste (e.g. sorted plastic waste), with or without virgin or unprocessed polyolefins.
  • the mixture of polyolefins comprises polyethylene and polypropylene.
  • the polyolefins mixture comprises polyethylene in an amount ranging between 10 wt% and 90 wt%, and polypropylene in an amount ranging between 10 wt% and 90 wt%.
  • the polyolefins mixture consists essentially of polyethylenes.
  • the polyolefin mixture consists essentially of polypropylenes.
  • the polyolefins mixture comprises up-to 10wt% of polystyrene. According to some embodiments, the polyolefins mixture comprises upto 5wt% of polystyrene.
  • the polyolefins mixture comprises up-to 5wt% non-polyolefinic polymers other than polystyrene (e.g. polyvinylchloride, polyethylene terephthalate, acrylonitrile butadiene styrene, nylon, polyurethanes, etc. ⁇ .
  • polystyrene e.g. polyvinylchloride, polyethylene terephthalate, acrylonitrile butadiene styrene, nylon, polyurethanes, etc. ⁇ .
  • the process comprises a pre-step before step (a), or pretreating the feedstock.
  • the pretreatment of the feedstock can comprise one or more steps of separating the polyolefins from the waste, washing the waste with water, dewatering the waste, shredding the waste, and removing contaminants and/or substances of concern from the waste.
  • the polyolefin mixture is fed into the thermocracking reactor at step (a) in a melt state.
  • the melting of the polyolefin mixture is obtained by extrusion.
  • step (a) of the process the molten mixture is thermocracked into smaller hydrocarbon molecules.
  • Thermocracking or thermal cracking means to denote decomposition of polymeric materials by means of temperature. Unlike the typical thermal process used for treating plastic waste, in the thermocracking process decomposition is carried out under inert atmospheric conditions, reducing the amount of undesired coke and promoting random scission mechanism that generates a heterogeneous mixture of paraffins, olefins and aromatics in a wide range of chain lengths.
  • thermocracking is carried out under conditions of: (i) pressure of at most 1 barg, (ii) temperature ranging between about 320°C and about 450°C, (iii) absence of oxygen, and (iv) residence time of the mixture in the thermolysis reactor of between about 2 and about 40 hours.
  • thermolysis reactor In the process of this disclosure, a combination of conditions permits obtaining high yield of hydrocarbon vapor products out of the polyolefin mixture, with minimal formation of coke.
  • the temperature in the thermolysis reactor is maintained at a range of 320°C- 450°C, which is lower than typical plastic waste processing processes. According to some embodiments, the temperature in the thermolysis reactor is between about 350°C and about 420°C. While in typical waste treatment processes higher temperatures are utilized, promoting formation of low molecular weight volatile products, the relatively low temperatures utilized in step (a) of the present process permit obtaining a wide range of condensable hydrocarbons chain lengths to enable a wide range of final products (as will be described further below). Low temperatures also minimize secondary reactions in terms of formation of aromatics, as well as degradation/cracking of wax components.
  • Pressure within the thermolysis reactor is maintained as to not to exceed about 1 barg, according to some embodiments not exceeding about 0.5 barg.
  • the inventors have found that as the boiling point of the cracking products are decreased under high pressure, pressures above 1 barg will cause heavy hydrocarbons (which are desired products in the process described herein) to pyrolyze instead of vaporize at given operation temperature. Hence, under pressurized cracking, more energy is required for further hydrocarbon cracking and the average molecular weight of gas product decreases.
  • maintaining the pressure at maximum 1 barg preferably at most about 0.5 barg, permits obtaining energetical efficiency on the one hand and a desired profile of cracking products on the other hand.
  • the residence time in the thermolysis reactor is defined as the average amount of time that the mixture spends in the thermolysis reactor.
  • the inventors have found that in the process of the present disclosure, long residence time will result in formation of light fractions and shorter residence times will produce mainly heavy fractions, a residence time of between about 2 and about 40 hours in step (a) achieves a balance of thermolysis products between light, medium and heavy fractions that can be further processed to various high value products, as will be described below.
  • Longer residence time also reduces the amounts of olefins, enabling secondary hydrogenation of double bonds in the thermolysis reactor, ensuring lower hydrogen consumption in the hydrotreatment unit and lower exothermal effect in the hydrotreating (making the process safer and easier to control).
  • the residence time ranges between about 2 and about 30 hours. According to other embodiments, the residence time ranges between about 3 and about 20 hours. According to some other embodiments, the residence time ranges between about 3 and about 10 hours. According to yet other embodiments, the residence time ranges between about 4 and about 6 hours.
  • the process comprises treating the mixture at step (a) in one or more thermolysis reactors arranged in parallel.
  • thermolysis reactor can be a batch reactor, semi-batch reactor, continuous flow reactor (CFR), auger reactor or combinations thereof.
  • thermocracking is carried out under a flow of nitrogen or other stripping agents, like light hydrocarbon stream, for continuous removal of undesired volatiles from the reactor.
  • the thermolysis reactor comprises a heated circulation loop defined between a circulation outlet of the reactor and a circulation inlet of the reactor, for circulating a portion of the mixture therethrough during thermocracking.
  • the circulation loop is designed to continuously circulate a portion of the mixture in-and-out of the thermolysis reactor.
  • the viscosity of the process fluid i.e. the melt at its partially thermocracked form
  • continuous circulation of a portion of the content of the thermolysis reactor through the heated circulation loop permits better control over the temperature of the melt, while also permitting exposing small portions of the melt (i.e. the circulated portion) to a higher temperature than that maintained in the reactor for short periods of time (during passage through the loop) to enable proper heating of the mixture, while also minimizing formation of undesired coke due to the short residence time in the loop.
  • the temperature in the circulation loop is between about 400°C and about 450°C.
  • the portion of mixture within the circulation loop during thermocracking is between about 2 and about 50 % of the thermolysis reactor’s volume. According to other embodiments, the portion of mixture within the circulation loop during thermocracking is between about 2 and about 30 % of the thermolysis reactor’s volume.
  • step (a) further comprises removal of solid residues from the thermolysis reactor.
  • the solids removed from the thermolysis reactor can be further treated and disposed or further utilized.
  • the solids (or as sometimes called “reactor bottoms”) can be used as fuel due to their high calorific value (typically 36-47 MJ/kg), e.g. in waste incineration plants or cement plants.
  • the solids can also be used as cement or bitumen asphalt additives or as a binder for ores.
  • thermocracking step produces a broad distribution of saturated and unsaturated hydrocarbon thermolysis products in vapor form.
  • step (b) volatile C1-C5 compounds are removed from the hydrocarbons vapor stream, and the remainder of hydrocarbons stream, typically comprising C6-C70 hydrocarbons, is quenched to obtain a condensate stream.
  • the condensate stream is also referred to herein as pyrolysis oil.
  • the non-condensable gases/vapors (C1-C5) are separated and can be utilized for energy recovery. In the processes of this disclosure, the non-condensable gases constitute about 5-15%wt of the total feed to the reactors.
  • the temperature during quenching at step (b) of the process ranges between about 150°C and about 250°C.
  • the condensate is then treated, at step (c), as a whole in a main catalytic hydrotreatment unit to obtain a hydrotreated stream of the condensate.
  • Hydrotreatment refers to reducing of double bonds and aromatic bonds in the hydrocarbons of the condensate stream.
  • hydrotreating conditions applied in this process also permit fast removal of heteroatoms and non-hydrocarbon compounds by turning these into volatile compounds (for example sulfur-organic compounds as hydrogen sulfide, nitrogen containing compounds as ammonia, and oxygen-containing compounds as water).
  • volatile compounds for example sulfur-organic compounds as hydrogen sulfide, nitrogen containing compounds as ammonia, and oxygen-containing compounds as water.
  • the purpose of the main hydrotreatment is to treat all hydrocarbons of the condensate stream with hydrogen (H2). This process step also reduces the Bromine number of the treated stream to below 0.5 gBr2/100g.
  • hydrotreating of the complete condensate stream is essential to provide proper product quality, as well as to prevent unwanted polymerization reactions from unsaturated components further downstream of the process.
  • the hydrotreatment of the entire hydrocarbon condensate does not necessitate flushing between fractions (as no separate fractions are treated), also preventing contamination due to treatment of different fractions in the same hydrotreater.
  • hydrotreatment of the entire condensate prior to separation removes resin-creating components (mainly reactive diolefins or olefins like styrene from PS), enabling to maintain long operations of the distillation columns.
  • the main catalytic hydrotreatment unit is operated at step (c) is carried out under conditions comprising temperature of between about 250°C and about 340°C, pressure of at least about 45 barg, and a hydrogen to condensate stream ratio of at least about 150 Nm 3 /m 3 (normal cubic meter / cubic meter).
  • the condensate stream is heated to operating temperature of minimum 250°C.
  • the temperature at any time in the reactor is maintained as high as possible but not above 340°C, as the inventors have found that, in the conditions of the process disclosed herein, aromatics' hydrogenation/saturation is not effective above 340°C.
  • the hydrogenation reaction of unsaturated components is exothermic, and the heat generated is primarily influenced by the composition of the feed. Higher PP concentration in the feed generates more unsaturated compounds which will be hydrogenated in this reactor.
  • the temperatures are controlled by H2/HC ratio and the inlet temperature. Any heat input into the process is carefully controlled at maximum temperatures to avoid the further cracking of the hydrocarbons and the formation of coke residue. Further control of the temperature can be obtained by introduction of cold hydrogen between the catalytic beds for quenching.
  • the difference between inlet temperature of the condensate stream and the temperature in the main catalytic hydrotreatment unit is at most 50°C.
  • main hydrotreating is carried out under pressure ranging between 60 barg and 200 barg.
  • the feed liquid hourly space velocity which is a ratio of liquid feed volume flowing within an hour to the catalyst volume, ranges between 0.5 h' 1 and 2.0 h’ 1 .
  • LHSV feed liquid hourly space velocity
  • the main hydrotreatment stage is a catalytic process at high temperatures and high pressures.
  • the catalytic reaction takes place on a fixed catalyst bed at the presence of a high-volume ratio of hydrogen.
  • the catalyst in the main hydrotreatment step can be selected from alumina, silica, zeolite, noble-earth metals (cobalt, molybdenum, nickel, tungsten, platinum, zirconium and others), as well as alloys of metals.
  • the main catalytic hydrotreatment utilizes at least one Ni-Mo catalyst.
  • Catalysts are typically sensitive to poisons (for example by arsenic, vanadium, silicon, nickel but also other metals and halogenates).
  • the catalysts are typically prone to silicon poisoning, which may at times be present in the source material (and hence may be present to some extent in the condensate stream).
  • the condensate stream can be fed into the main hydrotreatment reactor through at least one guard bed.
  • the condensate stream of step (b) is passed through at least one guard bed reactor comprising at least one guard bed catalyst prior to introduction into step (c).
  • the temperature in the at least one guard bed reactor is between about 290°C and 340°C.
  • the hydrogen to condensate stream ratio in the at least one guard bed reactor is about 150 Nm 3 /m 3 .
  • the condensate stream is passed through one or more traps to remove contaminants from the condensate stream before feeding into the main hydrotreatment reactor.
  • the traps may be for metals, silicon, halogenates, phosphorous, etc.
  • the one or more traps comprise iron oxide, iron exchange resin, clays, silica gel, alkaline or alkaline earth metal oxide, active aluminum oxide, active carbon, molecular sieves, high porosity nickel molybdenum (NiMo), cobalt molybdenum (CoMo) catalysts, or any combination thereof.
  • the traps can be operated with or without hydrogen coverage.
  • the hydrotreated stream is separated into product streams at step (d) of the process.
  • the hydrotreated stream is separated into 3 main streams, typically according to the hydrocarbons molecular weight and boiling temperature: (i) a C6-C20 product stream having a boiling temperature of between about 60°C and about 330°C, (ii) a C14-C32 product stream having a boiling temperature of between about 300°C and about 450°C, and (iii) a C20-C70 product stream having an initial boiling temperature of at least about 350°C.
  • the main streams comprise: (i) a C6-C18 product stream having a boiling temperature of between about 100°C and about 300°C, (ii) a C14-C24 product stream having a boiling temperature of between about 300°C and about 380°C, and (iii) a C22-C70 product stream having an initial boiling temperature of at least about 380°C.
  • Each of the streams (i)-(iii) is then separately treated, at step (e) to obtain the final paraffinic products.
  • the product streams are treated in step (e) as follows:
  • the C20-C70 product stream can be bleached to improve color and quality of the paraffinic product.
  • the bleaching agent can be at least one of natural bleaching earths, acid-activated bleaching earths, activated carbon (e.g. for removal of polyaromatic hydrocarbons as well as a wide range of specific pollutants), synthetic amorphous silica (e.g. for selective removal of phosphatides, trace metals and soaps), etc.
  • the C6-C20 stream is, in some embodiments, first catalytically hydrotreated, and then distilled in at least one solvent distillation column to obtain a C6- C20 paraffinic product, typically a solvent, having an aromatic compounds content of at most about 3000 ppm, preferably at most 2000 ppm.
  • the catalytic hydrotreatment of the C6-C20 product stream in step (e) mainly aims at further reducing the aromatics content of the light fraction.
  • Low boiling aromatics are especially unwanted in solvents (being the C6-C20 product) as they may present health hazards.
  • the concentration of aromatics in the C6-C20 stream can vary directly with the presence of various contaminants (e.g. polystyrene) in the polyolefin feed mixture, and may not all be treated to the desired level in the main hydrotreating step.
  • the catalytic hydrotreatment of the C6-C20 product stream in step (e) is carried out under conditions comprising temperature of between about 170°C and about 300°C, pressure of at least 45 barg, and hydrogen to condensate stream ratio of at least 150 Nm 3 /m 3 (normal cubic meter / cubic meter). These conditions are not only aiming at significant conversion of aromatics, but also at avoiding overheating, which may cause undesired side reactions.
  • the C6-C20 product stream is treated by one or more distillation stages in order to obtain a C6-C20 paraffinic product with an aromatic compounds content of at most about 3000 ppm, preferably at most 2000 ppm.
  • the C6- C20 paraffinic products are typically solvents having a boiling temperature of between about 100°C and about 360°C.
  • Various solvents, having different boiling temperature ranges within this broad range, can be obtained by varying the parameters of the distillation column and/or by utilizing two or more consecutively arranged solvent distillation columns.
  • the C14-C32 product stream is catalytically hydrotreating at step (e), followed by distillation in at least one oil distillation column to obtain a C 14-C32 paraffinic product having an aromatic compounds content of at most about 3000 ppm, preferably at most 2000 ppm.
  • the purpose of hydrotreating the C14-C32 product stream is mainly to isomerize linear paraffins of this hydrocarbons fraction into branched paraffins, in order to obtain an oil product with an improved cloud point of below -10°C and the pour point of the oil of below -20°C.
  • the cloud point and pour point are an indication of linear waxes present in the oil, which are unwanted in oil products.
  • Another purpose of the hydrotreatment of the C14-C32 product stream is to mildly hydrocrack long chain hydrocarbons into shorter-chain hydrocarbons, effectively dewaxing the C14-C32 product.
  • catalytically hydrotreating said C14-C32 product stream in step (e) comprising hydrotreating the C14-C32 product stream under conditions comprising a temperature of between about 310°C and about 360°C, pressure of at least 25 barg, and a hydrogen to C14-C32 product stream ratio of at least 150 Nm 3 /m 3 .
  • catalytically hydrotreating said C14-C32 product stream in step (e) is carried out in two consecutive hydrotreatment steps: step (el) comprising hydrotreating the C14-C32 product stream under conditions comprising a temperature of between about 310°C and about 360°C, pressure of at least 30 barg, and a hydrogen to C14-C32 product stream ratio of at least 150 Nm 3 /m 3 ; followed by: step (e2) comprising hydrotreating the product of step (el) under conditions comprising a temperature of between about 170°C and about 300°C, pressure of at least 25 barg, and a hydrogen to C14-C32 product stream ratio of at least 150 Nm 3 /m 3 .
  • step (el) the C14-C32 product stream is isomerized, while in step (e2), the isomerized stream is further treated to convert the remainder of unsaturated hydrocarbons into saturated hydrocarbons, thereby further reducing aromatics content in the resulting oil product.
  • Step (e2) also improves the color of the oil according to the Saybolt color scale.
  • the process comprises dewaxing (mild hydrocracking) the C14-C32 product stream, for removal of hydrocarbons which readily solidify (i.e. waxes). Removal of wax is typically required for the production of lubricating oil which will remain fluid over a broad range of temperatures.
  • the catalytic dewaxing process comprises passing the C14-C32 product stream through a catalyst in which the active hydrocracking sites are accessible only to the paraffin molecules, and selectively hydrocracks waxy molecules to short-chain products, leaving valuable lube oil components unchanged.
  • the C14-C32 product stream is treated by one or more distillation stages in order to obtain a C14-C32 paraffinic product with an aromatic compounds content of at most 2000 ppm.
  • the C14-C32 paraffinic products are typically oils, that comprise at least 50 wt% C14-C32 iso-paraffinic compounds, preferably at least about 95 wt% C14-C32 iso-paraffinic compounds and have kinematic viscosity ranging between 5.00 mm 2 /s and 15.00 mm 2 /s, as measured according to ISO 3104 at 40°C.
  • the oils obtained after distillation typically have a boiling temperature of between about 320°C and about 420°C.
  • C20-C70 product stream is distilled at step (e) in a wax distillation column to obtain the C20-C70 paraffinic product.
  • the C20-C70 paraffinic product is a wax, typically comprising at least 95 wt% C20-C70 normal paraffinic compounds (determined by GC/MS), with an oil content of between about 10 wt% and 60 wt%, and no more than about 3000 ppm aromatic compounds.
  • the waxes obtained after distillation typically have a boiling temperature of at least 350°C.
  • the C20-C70 paraffinic product comprises up to about 85 wt% iso-paraffins and up to about 60 wt% of n-paraffins (determined according to ASTM D5442), and no more than about 3000 ppm aromatic compounds.
  • Wax distillation can be carried out by one or more distillation steps. According to some embodiments, the distillation products of each distillation step are blended at predetermined ratios to obtain the wax product.
  • the paraffinic products produced by the process of this disclosure are characterized by low aromatics content, i.e. below about 3000 ppm, preferably below 2000 ppm.
  • the paraffinic products are also characterized by low sulfur content (typically below 10 ppm), low nitrogen content, low chlorine content, controlled paraffins ratios, etc.
  • the paraffinic products produced by the process of this disclosure meet the FDA requirements for amount of Polycyclic Aromatic Hydrocarbons (PAHs).
  • PAHs Polycyclic Aromatic Hydrocarbons
  • the oil and solvent products meet the requirements of U.S. FDA qualitative test, 21CRF ⁇ 178.3620 within the range of the limits in the ultraviolet absorbance at specific wavelengths: 280-289nm A ⁇ 4.0, 290- 299nm A ⁇ 3.3, 300-329nm A ⁇ 2.3, 330-360nm A ⁇ 0.8 (test method ASTM D2269-99).
  • the wax products meet the requirements of FDA 21 CRF ⁇ 172.886, for maximum ultraviolet absorbance limits for a specific path length: 280-289nm A ⁇ 0.15, 290-299 nm A ⁇ 0.12, 300-359nm A ⁇ 0.08, 360-400nm A ⁇ 0.02.
  • a paraffinic solvent having a boiling range of at most about 100°C, an initial boiling point of at least about 85°C, and final boiling point of in the range of between about 150°C and about 360°C
  • the fluid comprises normal paraffinic compounds in the range of between about 15 wt% and 65wt%, isoparaffinic compounds in the range of between about 30 wt% and about 75 wt%, cy clo-paraffinic compounds in the range of between about 0 wt% and about 35wt%, and no more than about 3000 ppm of aromatic compounds.
  • the paraffinic solvent comprises no more than about 2000 ppm of aromatic compounds.
  • the paraffinic solvent is obtained by the process described herein.
  • the paraffinic solvent comprises C6-C20 paraffinic hydrocarbons. According to other embodiments, the paraffinic solvent consists essentially of paraffinic C6-C20 hydrocarbons.
  • the percent ratio between the n-paraffins and iso-paraffins i.e. percent n-paraffins to percent iso-paraffins
  • the percent ratio between the n-paraffins and iso-paraffins ranges between about 1 : 1.2 and about 1 :2.5.
  • the percent ratio between the n-paraffins and iso-paraffins in the C6-C20 paraffinic product ranges between about 1 : 1.5 and about 1 :4.5.
  • the percent ratio between the n-paraffins and iso-paraffins in the C6-C20 paraffinic product ranges between about 1 : 1.2 and about 1 :4.5.
  • the paraffinic solvent comprises less than 3 ppm of each of sulfur, chloride and nitrogen.
  • the paraffinic solvent has an initial boiling point ranging between about 85°C and about 110°C, final boiling point of in the range of between 155°C and 180°C, and kinematic viscosity ranging between 0.70 mm 2 /s and 0.90 mm 2 /s (as measured according to ASTM D445 at 25°C).
  • the paraffinic solvent has an initial boiling point ranging between about 135°C and about 160°C, final boiling point of in the range of between 185°C and 220°C, and kinematic viscosity ranging between 1.00 mm 2 /s and 1.40 mm 2 /s (as measured according to ASTM D445 at 25°C).
  • the paraffinic solvent has an initial boiling point ranging between about 170°C and about 195°C, final boiling point of in the range of between 235°C and 250°C, and kinematic viscosity ranging between 1.60 mm 2 /s and 1.90 mm 2 /s (as measured according to ASTM D445 at 25°C).
  • the paraffinic solvent has an initial boiling point ranging between about 190°C and about 210°C, final boiling point of in the range of between 245°C and 270°C, and kinematic viscosity ranging between 1.80 mm 2 /s and 2.40 mm 2 /s (as measured according to ASTM D445 at 25°C).
  • the paraffinic solvent has an initial boiling point ranging between about 205°C and about 245°C, final boiling point of in the range of between 270°C and 290°C, and kinematic viscosity ranging between 1.95 mm 2 /s and 3.10 mm 2 /s (as measured according to ASTM D445 at 25°C).
  • the paraffinic solvent has an initial boiling point ranging between about 240°C and about 280°C, final boiling point of in the range of between 335°C and 360°C, and kinematic viscosity ranging between 5.50 mm 2 /s and 7.20 mm 2 /s (as measured according to ASTM D445 at 25°C).
  • the paraffinic solvent has an initial boiling point ranging between about 240°C and about 260°C, final boiling point of in the range of between 310°C and 330°C, and kinematic viscosity ranging between 3.30 mm 2 /s and 4.70 mm 2 /s (as measured according to ASTM D445 at 25°C).
  • paraffinic solvent as disclosed herein for use in cosmetic products, paints, printing ink, plasticizers, degreasers, textile manufacturing, explosive manufacturing, cleaning products manufacturing, self-starting barbecue brickettes, solvent extraction (copper and others), road solvents, and wood preservatives (resins for timber and foundry applications).
  • a paraffinic solvent as disclosed herein for use as solvent in surfactant production or as in pesticides compositions are provided.
  • an article of manufacture comprising at least one paraffinic solvent as disclosed herein, said article of manufacture being selected from a cosmetic product, a paint, a plasticizer, a degreaser, a cleaning product, an explosive product, a printing ink, a self-starting barbecue brickette, an extraction/leaching solution, a road solvent, wood preservatives, and pesticide compositions.
  • a paraffinic oil comprising at least 50 wt% C14-C32 iso-paraffinic compounds, preferably at least 95 wt% C14-C32 iso-paraffinic compounds and having kinematic viscosity ranging between 5.00 mm 2 /s and 15.00 mm 2 /s, as measured according to ASTM D445 at 25°C, the fluid comprising no more than about 3000 ppm of aromatic compounds.
  • the paraffinic oil comprises no more than about 2000 ppm of aromatic compounds.
  • the paraffinic oil is obtained by the process described herein.
  • the paraffinic oil has an initial boiling point of at least about 300°C, and final boiling point of at least about 380°C.
  • the paraffinic oil has a boiling temperature of between about 300°C and about 380°C.
  • the paraffinic oil has a boiling temperature of between about 320°C and about 420°C.
  • paraffinic oil as disclosed herein, for use in food processing, cosmetics, pharmaceutical formulations, energy storage devices, agricultural products, as base oils, metal working fluid, and biodiesel substitute.
  • an article of manufacture comprising at least one paraffinic oil as disclosed herein, the article of manufacture being selected from a food processing product, a cosmetic product, a pharmaceutical product, an energy storage device, an agricultural product, a base oil, a metal working fluid, and biodiesel substitute.
  • a paraffinic wax comprising at least 95 wt% C20-C70 normal paraffinic compounds (determined by GC/MS), an oil content of between about 10 wt% and 60 wt%, and no more than about 3000 ppm aromatic compounds.
  • a paraffinic wax comprising at least 85 wt% C20-C70 paraffinic compounds, said C20-C70 paraffinic compounds comprising up to about 85 wt% C20-C70 iso-paraffins and up to about 60 wt% of C20-C70 n-paraffins (determined according to ASTM D5442), and no more than 3000 ppm aromatic compounds.
  • the paraffinic wax comprises no more than about 2000 ppm of aromatic compounds.
  • the paraffinic wax has a needle penetration (at 25°C, ASTM D1321) of at least 100, congealing point of 40-60°C (ASTM D938), and kinematic viscosity of 3-5.5 mm 2 /s (at 100°C, ISO 3104).
  • the paraffinic wax has a needle penetration (at 25°C, ASTM D1321) of 70-105, congealing point of 50-65°C (ASTM D938), and kinematic viscosity of 4.5-7.5 mm 2 /s (at 100°C, ISO 3104).
  • the paraffinic wax has a needle penetration (at 25°C, ASTM D1321) of 60-95, congealing point of 60-80°C (ASTM D938), and kinematic viscosity of 7.5-10 mm 2 /s (at 100°C, ISO 3104).
  • the paraffinic wax has a needle penetration (at 25°C, ASTM D1321) of 70-155, congealing point of 50-70°C (ASTM D938), and kinematic viscosity of 4.5-8.0 mm 2 /s (at 100°C, ISO 3104).
  • the paraffinic wax has a needle penetration (at 25°C, ASTM D1321) of 60-120, congealing point of 55-80°C (ASTM D938), and kinematic viscosity of 7-10 mm 2 /s (at 100°C, ISO 3104).
  • the paraffinic wax is obtained by the process disclosed herein.
  • PAHs polycyclic aromatic hydrocarbons
  • paraffinic wax as disclosed herein, for use in shoe polish, floor polish, candles, tissue-paper softening, manufacture of wax paper and paper packages, matches, pesticide traps, tire manufacturing, anti-ozonate formulations, lubricating aids, fertilizers, anti-caking aids, agricultural products, fruit and/or vegetable coating, hydrophobic coatings, concrete curing, cosmetics, hot melt adhesives (for food), mining, road applications (road resins markings, bitumen extender), fatty acids derivatives, PVC stabilizers, and wax emulsions.
  • an article of manufacture comprising a paraffinic wax as disclosed herein, the article of manufacture being selected from a shoe polish, a floor polish, a candle, a tissue-paper softening formulation, wax paper, waxed paper packages, matches, a pesticide trap, a tire, an anti-ozonate formulation, a lubricating aid, a fertilizer, an anti-caking aid, an agricultural product, a fruit and/or vegetable coating, a hydrophobic coating, a concrete curing agent, a cosmetic product, a hot melt adhesive, a PVC stabilizer and a wax emulsion.
  • thermocracking residue having a total solids, namely coke/carbon and ash content of at least 30 wt%, and a calorific value of at least 30 MJ /kg.
  • the solid product comprises at most 0.5 wt% sulfur, at most 0.5 wt% nitrogen, at most 0.3 wt% chlorine, and/or at most 0.01 ppm mercury.
  • the solid product comprises between about 5 and 15 wt% hydrogen.
  • the solid product comprises between about 30 and 95 wt% volatile components.
  • a manufacturing facility for processing polyolefin waste into paraffinic products having an aromatic compounds content of at most 2000 ppm comprising:
  • thermolysis reactor for receiving a mixture of polyolefins in a melt state, and thermocracking said mixture to obtain a hydrocarbons vapor stream, the thermolysis reactor being configured for operation under conditions comprising (i) pressure of at most
  • thermolysis reactor 1 barg, (ii) temperature ranging between about 320°C and about 450°C, (iii) absence of oxygen, and (iv) residence time of the mixture in the thermolysis reactor of between about
  • thermolysis reactor a quenching column in fluid communication with said thermolysis reactor and configured for receiving the hydrocarbons vapor stream, removing volatile C1-C5 volatile compounds therefrom, quenching the remainder of the hydrocarbons vapor stream to obtain a condensate stream;
  • the one or more treating units of the facility comprise at least one catalytic hydrotreating unit, for hydrotreating said C6-C20 product stream, and at least one solvent distillation column for distilling the C6-C20 product stream after hydrotreating to obtain a C6-C20 paraffinic product having an aromatic compounds content of at most about 3000 ppm, preferably at most about 2000 ppm.
  • the one or more treating units of the facility comprise at least one catalytic hydrotreating unit for hydrotreating said C14-C32 product stream, and at least one oil distillation column for distilling the C14-C32 product stream after hydrotreating to obtain a C 14-C32 paraffinic product having an aromatic compounds content of at most 3000 ppm.
  • the facility comprises a catalytic hydrotreating unit for treating said C14-C32 product stream under conditions comprising a temperature of between about 320°C and about 360°C, pressure of at least 25 barg, and a hydrogen to C14-C32 product stream ratio of at least 150 Nm 3 /m 3 .
  • the facility comprises two catalytic hydrotreating units, arranged in sequence, for treating said C14-C32 product stream: a first catalytic hydrotreating unit for hydrotreating the C14-C32 product stream under conditions comprising a temperature of between about 310°C and about 360°C, pressure of at least 25 barg, and a hydrogen to C14-C32 product stream ratio of at least 150 Nm 3 /m 3 ; followed by a second catalytic hydrotreating unit for hydrotreating the product received from the first catalytic hydrotreating unit under conditions comprising a temperature of between about 170°C and about 300°C, pressure of at least 25 barg, and a hydrogen to C14-C32 product stream ratio of at least 150 Nm 3 /m 3 .
  • the one or more treating units of the facility comprise at least one wax distillation column for distilling said C20-C70 product stream to obtain a C20-C70 paraffinic product having an aromatic compounds content of at most 3000 ppm.
  • the facility further comprises at least one extruder for obtaining said melt of polyolefins before introduction into the thermolysis reactor.
  • the thermolysis reactor comprises a heated circulation loop defined between a circulation outlet of the reactor and a circulation inlet of the reactor, for circulating a portion of the mixture therethrough during thermocracking.
  • the facility further comprises at least one guard bed reactor comprising at least one guard bed catalyst, located between the quenching column and the main hydro treatment unit, and configured for receiving condensate stream from the quenching column and treating the condensate stream therein to remove contaminants therefrom prior to hydrotreating.
  • at least one guard bed reactor comprising at least one guard bed catalyst, located between the quenching column and the main hydro treatment unit, and configured for receiving condensate stream from the quenching column and treating the condensate stream therein to remove contaminants therefrom prior to hydrotreating.
  • the facility comprises at least one contaminants’ trap, located between the quenching column and the main hydro treatment unit, and configured for receiving condensate stream from the quenching column and removing one or more contaminants from the condensate stream prior to hydrotreating.
  • the term about is meant to encompass deviation of ⁇ 10% from the specifically mentioned value of a parameter, such as temperature, pressure, concentration, etc.
  • a numerical range is indicated herein, it is meant to include any cited numeral (fractional or integral) within the indicated range.
  • the phrases ranging/ranges between a first indicate number and a second indicate number and “ranging/ranges from” a first indicate number "to” a second indicate number are used herein interchangeably and are meant to include the first and second indicated numbers and all the fractional and integral numerals therebetween.
  • the phrase consists essentially of means to denote a composition or mixture which comprises at least 98wt% of a single component.
  • Ppm means to denote parts per million.
  • ...at least one... as applied to any component of the product or process should be read to encompass one, two, three, four, five, or even more different occurrences of said component in a product or process disclosed herein.
  • the processes of the present disclosure involve numerous process steps which may or may not be associated with other common physical-chemical processes so as to achieve the desired purity and form of each product. Unless otherwise indicated, such process steps, if present, may be set in different sequences without affecting the workability of the process and its efficacy in achieving the desired end result. As a person skilled in the art would appreciate, a sequence of steps may be employed and changed depending on various economical aspects, material availability, raw materials, environmental considerations, etc.
  • Fig i is a schematic representation of an exemplary process and facility according to an embodiment of this disclosure.
  • FIG. 1 Shown in Fig. 1 is an exemplary process and facility for carrying out the process according to an embodiment of this disclosure.
  • the following acronyms are utilized:
  • Fig. 1 shown is an exemplary process and facility for carrying out the process according to this disclosure.
  • the process shown in Fig. 1 is first fed with a feedstock comprising, and at times consisting of, a polyolefin mixture.
  • the Mixture is prepared in the Mixed Solid Waste (MSW) Preparation Unit, and transferred into the Feed Preparation Unit (FPU), which typically comprises at least one dryer and one extruder for drying, blending and melting the polyolefins feedstock.
  • MSW Mixed Solid Waste
  • FPU Feed Preparation Unit
  • the melt mixture is fed into the thermocracking reactor (CSTR), in which thermocracking of the mixture takes place, decomposing the long polyolefin chains into shorter hydrocarbon molecules. Solids are continuously removed from the CSTR, while a portion of the mixture is circulated through a forced circulation loop. In the circulation loop, the portion of the mixture is circulated back into the CSTR via a heater (HT). Such circulation facilitates better control over the overall temperature of the mixture, and enables heating portions of the mixture that are circulated through the loop to a higher temperature than that of the CSTR.
  • CSTR thermocracking reactor
  • HT heater
  • Thermocracking is carried out under conditions comprising (i) pressure of at most 1 barg, preferably at most 0.5 barg (ii) temperature ranging between about 320°C and about 450°C, preferably between about 350°C and 420°C (iii) absence of oxygen, and (iv) residence time of the mixture in the thermolysis reactor of between 2 and 40 hours, preferably between about 4 and about 6 hours.
  • pressure of at most 1 barg preferably at most 0.5 barg
  • temperature ranging between about 320°C and about 450°C, preferably between about 350°C and 420°C
  • iii) absence of oxygen preferably between about 3 and about 6 hours.
  • residence time of the mixture in the thermolysis reactor of between 2 and 40 hours, preferably between about 4 and about 6 hours.
  • Such conditions are optimal in the process of this disclosure for obtaining a broad range of hydrocarbon fractions, which are utilized in the process to produce a wide range of final products from a single thermocracking step.
  • such conditions
  • thermolysis products exit the CSTR as a hydrocarbons vapor stream, and are quenched in a quenching column.
  • condensable gaseous hydrocarbons C6 ⁇
  • lighter products C1-C5
  • the condensate stream is then transferred into the Main Hydrotreatment Unit (MHT), in which catalytic hydrotreating takes place for reducing the content of aromatic and olefinic hydrocarbons in the stream by hydrogenating the multiple bonds in nonsaturated hydrocarbons.
  • MHT Main Hydrotreatment Unit
  • the hydrotreating conditions applied in this process also permit fast removal of heteroatoms and nonhydrocarbon compounds by turning these into volatile compounds (for example sulfurorganic compounds as hydrogen sulfide, nitrogen containing compounds as ammonia, and oxygen-containing compounds as water).
  • volatile compounds for example sulfurorganic compounds as hydrogen sulfide, nitrogen containing compounds as ammonia, and oxygen-containing compounds as water.
  • thermocracking products enables to obtain a broad range of hydrocarbons in a single hydrotreatment step, together with efficient reduction in olefins and aromatics content. This enables obtaining a broad range of products with careful control over the aromatics content from a uniform and integral manufacturing process.
  • the MHT in a process according to this disclosure is operated under conditions comprising temperature of between about 250°C and about 340°C, pressure of at least 45 barg, and a hydrogen to condensate stream ratio of at least 150 Nm 3 /m 3 (normal cubic meter / cubic meter).
  • conditions comprising temperature of between about 250°C and about 340°C, pressure of at least 45 barg, and a hydrogen to condensate stream ratio of at least 150 Nm 3 /m 3 (normal cubic meter / cubic meter).
  • the condensate stream can be fed into the MHT via at least one Guard Bed (GB), which typically comprises at least one guard bed catalyst for removing undesired contaminants. Further (or alternatively), the condensate stream can be passed through one or more traps (not shown) for removing contaminants from the condensate stream before feeding into the MHT, for example removing metals, silicon, halogenates, phosphorous, etc. from the stream.
  • GB Guard Bed
  • the condensate stream can be passed through one or more traps (not shown) for removing contaminants from the condensate stream before feeding into the MHT, for example removing metals, silicon, halogenates, phosphorous, etc. from the stream.
  • the hydrotreated stream can be treated in a Light Ends Stabilizer column (LES) for removing further C1-C5 gaseous hydrotreatment products that may be contained in the hydrotreated stream, and from there the C6 ⁇ hydrotreated stream is fed into a Main Fractionation Column (MFC) for separation into fractions, typically based on boiling temperature and molecular weight.
  • LES Light Ends Stabilizer column
  • MFC Main Fractionation Column
  • the MFC which can be for example a tray or packed type column, is typically operated under atmospheric pressure and heated to about 330°C.
  • Three main product streams are obtained from the MFC: (i) a C6-C20 product stream having a boiling temperature of between about 60°C and about 330°C, (ii) a C14-C32 product stream having a boiling temperature of between about 300°C and about 450°C, and (iii) a C20-C70 product stream having a boiling temperature of at least about 350°C.
  • Each of these product streams is then treated in one or more treatment steps in order to obtain the final paraffinic products.
  • the C6-C20 stream is first catalytically hydrotreated in the Aromatics Hydrotreatment unit (AHT) to further reduce the aromatics content of the light fraction. Low boiling aromatics are especially unwanted in solvents as they may present health hazards.
  • AHT Aromatics Hydrotreatment unit
  • the stream is then distilled in at least one Solvent Distillation column (SD) to obtain a C6-C20 paraffinic product, i.e. the solvent, that has an aromatic compounds content of at most 3000 ppm, preferably at most 2000 ppm.
  • SD Solvent Distillation column
  • the catalytic hydrotreatment in the AHT can be carried out under conditions comprising a temperature of between about 170°C and about 300°C, pressure of at least 45 barg, and hydrogen to condensate stream ratio of at least 150 Nm 3 /m 3 (normal cubic meter / cubic meter). These conditions do not only aim at significant conversion of aromatics, but also at avoiding overheating, which may cause undesired side reactions.
  • the SD can contain a plurality of distillation stages carried out in sequence, out of each stage a different solvent fraction can be isolated as a separate solvent product depending on its boiling temperatures.
  • various solvents having different boiling temperature ranges can be obtained by varying the parameters of the distillation column and/or by utilizing two or more solvent distillation columns consecutively arranged.
  • the C14-C32 product stream is also catalytically hydrotreated.
  • the C14-C32 product stream is first catalytically hydrotreated in an Isomerization Hydrotreating Unit (IHT), then in a Finishing Hydrotreatment Unit (FHT), and then distilled in one or more Oil Distillation columns (OD), to obtain a C14-C32 paraffinic oil product having an aromatic compounds content of at most 3000 ppm, preferably at most 2000 ppm.
  • the C14-C32 is an isoparaffinic oil.
  • the purpose of the IHT is mainly to isomerize linear paraffins of this hydrocarbons fraction into branched paraffins in order to obtain an oil product with an improved cloud point of below -10°C and the pour point of the oil of below -20°C, while the purpose of the FHT is to convert the remainder of unsaturated hydrocarbons into saturated hydrocarbons, thereby further reducing the aromatics content in the resulting oil product.
  • IHT can be carried out under conditions comprising a temperature of between about 310°C and about 360°C, pressure of at least 25 barg, and a hydrogen to C14-C32 product stream ratio of at least 150 Nm 3 /m 3 .
  • FHT is typically carried out under conditions comprising a temperature of between about 170°C and about 300°C, pressure of at least 25 barg, and a hydrogen to C14-C32 product stream ratio of at least 150 Nm 3 /m 3 .
  • a C14-C32 paraffinic oil product is obtained with an aromatic compounds content of at most 2000 ppm, that comprise at least 50 wt% C14- C32 iso-paraffinic compounds, preferably at least 95 wt% C18-C27 iso-paraffinic compounds and kinematic viscosity ranging between 5.00 mm 2 /s and 15.00 mm 2 /s, as measured according to ASTM D445 at 25°C.
  • the oils obtained after distillation typically have a boiling temperature of between about 300°C and about 380°C.
  • the C20-C70 product stream is distilled in one or more Wax Distillation columns (WD).
  • WD Wax Distillation columns
  • two wax distillation columns are utilized, WD1 and WD2 arranged in a series.
  • the resulting wax product from WD1 and WD2 can be stand-alone wax products, however these can also be mixed in a Waxes Blending Mixer (WMB) to obtain the paraffinic wax product.
  • WMB Waxes Blending Mixer
  • Tables 1-1 and 1-2 below show the composition of the various streams during a process according to this disclosure, starting from different waste polyolefins feedstock.
  • Table 1-1 group compositions during process (wt%), feedstock of PE/PP 70:30, 5% PS
  • Table 1-2 group compositions during process (wt%), feedstock of PE/PP 30:70, 5% PS
  • Tables 2-1 and 2-2 provide analytical data for various paraffinic solvents obtained by a process of this disclosure, from different waste polyolefin feedstocks. Tables 2-3 to 2-5 show the chemical composition of various solvent fractions obtained for different feedstocks. Table 2-4 provides additional paraffinic solvent products obtained by a process according to another embodiment of this disclosure. Table 2-1: analytical results for paraffinic solvents, feedstock PE/PP
  • Table 2-4 gomposition (wt%) of different solvent fractions, feedstock PE/PP 70/30
  • Table 2-5 analytical results for additional paraffinic solvents
  • Table 3 provides analytical data for paraffinic oil products obtained by a process of this disclosure.
  • Tables 4-1 and 4-2 provides analytical data for paraffinic waxes obtained by a process of this disclosure.
  • Table 4-1 analytical results for paraffinic waxes, feedstock PE/PP
  • Table 4-2 analytical results for paraffinic waxes, feedstock PE/PP + 5wt% PS
  • Table 5 provides analytical data for a solid product, i.e. dried reactor bottoms, obtained by a process of this disclosure.

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Abstract

La divulgation concerne des procédés de recyclage de déchets plastiques au moyen d'un craquage thermique dans des conditions définies combinées à des traitements d'hydrogénation catalytique pour obtenir divers produits paraffiniques à valeur élevée avec un degré élevé de pureté et une teneur réduite en composés aromatiques. La divulgation concerne également des produits paraffiniques de haute pureté produits par le procédé, tels que des solvants, des huiles et des cires ayant une teneur en composés aromatiques d'au plus 3000 ppm.
PCT/IL2023/051015 2022-09-28 2023-09-19 Procédé de recyclage de déchets plastiques et produits de haute valeur ainsi fabriqués WO2024069624A1 (fr)

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WO2010049824A2 (fr) 2008-10-31 2010-05-06 Bl Laboratories Sp. Z O.O. Appareil et procédé pour réaliser la thermolyse de déchets plastiques de manière continue
WO2010106399A2 (fr) 2009-03-14 2010-09-23 Bl Laboratories Sp. Z O.O. Appareil pour réaliser la thermolyse de déchets plastiques et procédé de thermolyse en continu
WO2010116211A1 (fr) 2009-04-08 2010-10-14 Bl Laboratories Sp.Z.O.O. Appareil pour la thermolyse de déchets de matières plastiques et procédé pour la thermolyse de déchets de matières plastiques
WO2010136850A1 (fr) 2009-05-25 2010-12-02 Clariter Poland Sp. Zo. O. Procédé de production de produits hydrocarbonés de grande valeur à partir de déchets plastiques et appareil permettant de mettre en œuvre ledit procédé
WO2012072842A1 (fr) * 2010-12-03 2012-06-07 Consejo Superior De Investigaciones Científicas (Csic) Procédé et installation pour le traitement de pneumatiques hors d'usage
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US20220073826A1 (en) * 2019-01-24 2022-03-10 Sabic Global Technologies B.V. Process for the preparation of polyethylenes from waste plastic feedstocks

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WO2010049824A2 (fr) 2008-10-31 2010-05-06 Bl Laboratories Sp. Z O.O. Appareil et procédé pour réaliser la thermolyse de déchets plastiques de manière continue
WO2010106399A2 (fr) 2009-03-14 2010-09-23 Bl Laboratories Sp. Z O.O. Appareil pour réaliser la thermolyse de déchets plastiques et procédé de thermolyse en continu
WO2010116211A1 (fr) 2009-04-08 2010-10-14 Bl Laboratories Sp.Z.O.O. Appareil pour la thermolyse de déchets de matières plastiques et procédé pour la thermolyse de déchets de matières plastiques
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