EP4212604A1 - Compositions stabilisées comportant des oléfines - Google Patents

Compositions stabilisées comportant des oléfines Download PDF

Info

Publication number
EP4212604A1
EP4212604A1 EP22305030.3A EP22305030A EP4212604A1 EP 4212604 A1 EP4212604 A1 EP 4212604A1 EP 22305030 A EP22305030 A EP 22305030A EP 4212604 A1 EP4212604 A1 EP 4212604A1
Authority
EP
European Patent Office
Prior art keywords
plastic
composition
gums
pyrolysis
oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22305030.3A
Other languages
German (de)
English (en)
Inventor
Alexandrine CHOFFAT
Jean-Pierre Thoret-Bauchet
Thierry Guerin
Cindy Adam
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Totalenergies One Tech
Original Assignee
Totalenergies One Tech
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Totalenergies One Tech filed Critical Totalenergies One Tech
Priority to EP22305030.3A priority Critical patent/EP4212604A1/fr
Priority to PCT/EP2022/086919 priority patent/WO2023134977A1/fr
Publication of EP4212604A1 publication Critical patent/EP4212604A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
    • 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

Definitions

  • the present invention relates to stabilised compositions comprising hydrocarbon stream resulting from the pyrolysis of plastic wastes.
  • the present invention pertains to novel compositions for inhibiting polymerization in industrial plant of hydrocarbon streams obtained from pyrolysis of plastic waste, which contain reactive hydrocarbons and potentially oxygenates, thereby preventing fouling in processing equipment and storage tanks.
  • Pyrolysis transforms plastics, and most of their additives and contaminants, into gaseous chemicals while most of the non-volatile contaminants or additives end up in the solid by-product; chars or ashes.
  • any kind of plastic waste can be converted, although some pre-sorting of non-organic waste is desired and purification of the output material is necessary as several hetero-elements (i.e. presently referred to as elements different of carbon, hydrogen or oxygen) may be volatilized.
  • Plastic waste is a complex and heterogeneous material, due to several factors.
  • plastic as material refers to numerous different polymers with different chemical properties that need to be separated from each other prior to recycling.
  • the main polymers found in plastic from municipal solid waste are polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP) and polystyrene (PS).
  • Other polymers essentially include polyurethanes, polyamides (PA), polycarbonates, polyethers and polyesters other than PET.
  • PET polyethylene terephthalate
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • Other polymers essentially include polyurethanes, polyamides (PA), polycarbonates, polyethers and polyesters other than PET.
  • PA polyamides
  • PET polycarbonates
  • polyethers polyethers
  • polyesters other than PET.
  • additives such as functional additives (stabilizers, antistatic agents, flame retardants, plasticizers, lubricants, slipping agents, curing agents, foaming agents, biocides, antioxidants etc.), dyes and pigments, fillers (e.g. glass fibers, talcum, carbon fibers, carbon nanotubes), commonly used in plastic packaging as well as additives such as flame retardants, frequently used in plastic for electronics.
  • functional additives stabilizers, antistatic agents, flame retardants, plasticizers, lubricants, slipping agents, curing agents, foaming agents, biocides, antioxidants etc.
  • dyes and pigments e.g. glass fibers, talcum, carbon fibers, carbon nanotubes
  • fillers e.g. glass fibers, talcum, carbon fibers, carbon nanotubes
  • metal compounds are purposely added during plastic production (often as oxides, carbonates, acids, etc.).
  • Beside additives containing hetero elements other than metals are used in making plastics, for instance halogen
  • Silicone polymers which are silicon containing organic materials, are often used in plastic formulations. Thanks to their surface characteristics, applications for silicones range from silicone rubbers, used as sealants for joints, to silicone surfactants for cosmetic products while they are increasingly used in the plastics sector, as process enhancing additives (processing aids), and for the modification of polymers.
  • the used plastic waste can have been contaminated during lifespan by remains of liquids with which they were in contact (beverages, personal-care products, etc.) and of food that can also introduce contamination of the plastic.
  • some plastic waste may be present in the form of partially decomposed waste, such as partly burnt plastic.
  • pyrolysis plastic oils may also contain oxygenates such as aldehydes or ketones.
  • Pyrolysis of plastic waste allows producing naphtha, ethylene, propylene and aromatics but, as previously mentioned, those products are polluted by many hetero elements originating from the waste plastic itself.
  • significant concentration of silicon and of organic silicon can be found in pyrolysis plastic oils.
  • many prior art processes were focused on the removal of chlorine compounds, other impurities in the pyrolysis plastic oil simply forbid the direct use of pyrolysis plastic oil in other processes such as steam cracking.
  • steam crackers are very sensitive to the presence of olefins or dienes in the feed and to the presence of silicon or of organic silicon compounds.
  • oxygenates present in pyrolysis plastic oil are capable to be converted to peroxides and so enhance polymer and gums formation.
  • the presence of olefins and oxygenates may result in undesirable polymerisation during storage, transport from the production place to further treatment place as well as during purification and further processing treatments.
  • purification operations are often carried out at elevated temperatures which can increase the rate of undesired polymerization.
  • Polymerization such as thermal polymerization, during hydrocarbon processing treatments, results not only in product loss, but also in loss of production efficiency caused by the formation of fouling deposits and their deposition on process equipment, particularly on the heat transfer surfaces of the processing equipment.
  • the processing may include, for example, preheating, hydrogenation, fractionation, extraction, hydrocracking, vapocracking, fluid catalytic cracking, and the like of hydrocarbon streams to remove, concentrate, or have added thereto the unsaturated hydrocarbons prior to storage or use. These deposits decrease the thermal efficiency of the equipment and decrease the separation efficiency of the distillation towers.
  • operating modifications to reduce the rate of fouling can result in reduced production capacity. The excessive build-up of such deposits can cause plugging in tower plates, transfer tubes, and process lines, which could result in unplanned shutdowns.
  • Undesirable polymerization may also cause operational problems such as increase in fluid viscosity, temperature, restricted flow in pipelines, and blocking of filters. In heat requiring operations, such deposition adversely affects heat transfer efficiency.
  • compositions produced from pyrolysis of waste plastic is difficult to forecast due to the complexity of such compositions.
  • analysis by gas chromatography of pyrolysis plastic oil only allows identification of 25 to 45wt% of the compounds containing oxygen and azote.
  • undesirable polymerisation is generally monitored by measuring the gum content.
  • the present invention is a composition stabilized against premature polymerization comprising:
  • At least one additive capable to reduce gums formation or buildup and at least one dispersant agent are present.
  • the additive capable to reduce gums formation or buildup is an antipolymerant such as a stable free radical or a precursor thereof, such as hydroxylamines.
  • the antipolymerant can be a stable nitroxide free radical and/or a hydroxylamine substituted with at least one alkyl, aryl or alkylaryl group.
  • the additive capable to reduce gums formation or buildup is selected among the unhindered phenols, the hindered phenols, the aminophenols, the phenylenediamines and mixtures thereof.
  • said at least one additive which is a dispersant agent is selected from products of reaction between a phenol substituted with a C9-110 hydrocarbon chain, an aldehyde and an amine or polyamine or ammonia, from alkenyl succinimides or mixtures thereof.
  • the present invention also concerns a process for preparing a composition stabilized against premature polymerization, comprising :
  • the present invention also concerns a process for the processing of a composition stabilized against premature polymerization, comprising :
  • the composition is stabilized against premature polymerization without being contacted with, and/or without any use of, a solid removal material that requires a further separation step.
  • the present invention does not require the use/presence of solid material suitable for removing oxygen, metals, phosphorous, halogens and/or nitrogen contained in pyrolysis plastic oil, whatever the form of oxygen, metals, phosphorous, halogens and/or nitrogen.
  • Such solid removal materials include silica gel, alumina, promoted alumina, inorganic materials such as clay, pillared clay, apatite, hydroxyapatite, alkaline or alkaline earth metal oxide, calcined alumina, boehmite, bayerite, hydrotalcite, spinel, acid-exchanged clay, molecular sieves (which are alkaline or alkaline earth metal containing alumino-silicate sieves 3A, 4A, 5A or 13X).
  • inorganic materials such as clay, pillared clay, apatite, hydroxyapatite, alkaline or alkaline earth metal oxide, calcined alumina, boehmite, bayerite, hydrotalcite, spinel, acid-exchanged clay, molecular sieves (which are alkaline or alkaline earth metal containing alumino-silicate sieves 3A, 4A, 5A or 13X).
  • alkane or “alkanes” as used herein describe acyclic branched or unbranched hydrocarbons having the general formula C n H 2n+2 , and therefore consisting entirely of hydrogen atoms and saturated carbon atoms; see e.g. IUPAC. Compendium of Chemical Terminology, 2nd ed. (1997 ).
  • alkanes accordingly describes unbranched alkanes ("normal-paraffins” or “n-paraffins” or “n-alkanes” or “paraffins”) and branched alkanes ("iso-paraffins” or “iso-alkanes”) but excludes naphthenes (cycloalkanes). They are sometimes referred to by the symbol "HC-".
  • olefin olefins
  • alkene alkenes
  • alkyne or “alkynes” as used herein relate to an unsaturated hydrocarbon compound containing at least one carbon-carbon triple bond.
  • hydrocarbon refers to the alkanes (saturated hydrocarbons), cycloalkanes, aromatics and unsaturated hydrocarbons alone or in combination.
  • C # alcohols As used herein, the terms “C # alcohols”, “C # alkenes”, or “C # hydrocarbons”, wherein “ # " is a positive integer, is meant to describe respectively all alcohols, alkenes or hydrocarbons having # carbon atoms. Moreover, the term “C # + alcohols”, “C # + alkenes”, or “C # + hydrocarbons”, is meant to describe all alcohol molecules, alkene molecules or hydrocarbons molecules having # or more carbon atoms. Accordingly, the expression “C 5 + alcohols” is meant to describe a mixture of alcohols having 5 or more carbon atoms.
  • silicon As used herein, the terms "silicon”, “metals”, “phosphorous”, “halogens”, “nitrogen” and “oxygen” refer to their respective chemical elements contained in the stream to be purified.
  • Weight hourly space velocity is defined as the hourly weight of flow per unit weight of catalyst and liquid hourly space velocity (LHSV) is defined as the hourly volume of flow per unit of volume of catalyst.
  • conversion means the mole fraction (i.e., percent) of a reactant converted to a product or products.
  • selectivity refers to the percent of converted reactant that went to a specified product.
  • wt% refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component.
  • 10 grams of component within 100 grams of the material is 10 wt% of components.
  • wtppm or “ppm” each equally refer to “parts per million” and are given based on weight. For instance, “100 ppm” shall mean 100 ppm by weight. Similarly, the term “wtppb” or “ppb” refers to "parts per billion” and are given based on weight.
  • naphtha refers to the general definition used in the oil and gas industry. Naphtha refers to a hydrocarbon originating from crude oil distillation having a boiling range from 15 to 250°C as measured by ASTM D2887. Naphtha contains substantially no olefin as the hydrocarbons originates from crude oil. It is generally considered that a naphtha has carbon number between C3 and C11, although the carbon number can reach in some case C15. It is also generally admitted that the density of naphtha ranges from 0.65 to 0.77 g/mL.
  • gas oil refers to the general definition used in the oil and gas industry. It refers to a hydrocarbon originating from crude oil distillation having a boiling range from 210 to 360°C as measured by ASTM D86. Gas oil contains substantially no olefin as the hydrocarbons originates from crude oil. It is generally considered that a gas oil has carbon number between C12 and C20, although the carbon number can reach in some case C25. It is also generally admitted that the density of gas oil ranges from 0.82 to 0.86 g/mL, wherein commercial specification limits density to 0.86 g/mL according to ASTM D1298 (ISO 3675, IP 160).
  • LPG refers to the general definition used in the oil and gas industry. It refers to a hydrocarbon essentially comprised of C3 (propane) with some C4 isomers; n-butane and isobutene.
  • pyrolysis plastic oil refers to the liquid products obtained once waste plastic or plastic waste have been thermally pyrolyzed.
  • the pyrolysis process shall be understood as an unselective thermal cracking process.
  • the plastic to be pyrolyzed can be of any type.
  • the plastic to be pyrolyzed can be polyethylene, polypropylene, polystyrene, polyester, polyamide, polycarbonate, etc.
  • These pyrolysis plastic oils contain paraffins, i-paraffins (iso-paraffins), dienes, alkynes, olefins, naphthenes, and aromatic components.
  • Pyrolysis plastic oil may also contain impurities such as organic chlorides, oxygenated and/or silylated organic compounds, organic silicon compounds, metals, salts, phosphorous, sulfur and nitrogen compounds.
  • the plastic used for generating pyrolysis plastic oil is a waste plastic, irrespective of its origin or nature.
  • the composition of the pyrolysis plastic oil is dependent on the type of plastic that is pyrolyzed. Pyrolysis plastic oil is mainly (especially over 80wt%, most often over 90wt%) constituted of hydrocarbons having from 1 to 150 carbon atoms and impurities.
  • the term "Diene Value” (DV) or "Maleic Anhydride Value” (MAV) is a measure of the conjugated double bonds (dienes) in the oil.
  • MAV Maleic Anhydride Value
  • one mole of Maleic anhydride corresponds to 1 mole of conjugated double bond and the result corresponds to the amount of maleic anhydride in milligrams that will react with 1 gram of oil.
  • One known method to quantify dienes is the UOP 326-17: Diene Value by Maleic Anhydride Addition Reaction.
  • bromine number corresponds to the amount of reacted bromine in grams by 100 grams of sample. The number indicates the quantity of olefins in a sample. It is determined in grams of Br 2 per 100 grams of sample (gBr 2 /100g) and can be measured according to ASTM D1159-07R17 method.
  • boiling point refers to boiling point generally used in the oil and gas industry. Boiling point is measured at atmospheric pressure. The initial boiling point is defined as the temperature value when the first bubble of vapor is formed. The final boiling point is the highest temperature that can be reached during a standard distillation. At this temperature, no more vapor can be driven over into the condensing units. The determination of the initial and final boiling points is known in the art. Depending on the boiling range of the mixture, various standardized methods can be used, such as ASTM D2887-19ae2 relating to the boiling range distribution of petroleum fractions by gas chromatography. For compositions containing heavier hydrocarbons ASTM D7169-05 may alternatively be used. Boiling range of distillates is advantageously measured using ASTM D7500, D86 or D1160.
  • the concentration of metals in the matrix of hydrocarbon can be determined by any method known in the art. Relevant characterization methods include XRF or ICP-AES methods. Those skilled in the art know which method is the most adapted to each metal measurement and to which hydrocarbon matrix. Features, structures, characteristics or embodiments may be combined in any suitable manner, as would be apparent to a person skilled in the art from this disclosure, in one or more embodiments.
  • Potential gums » inform on the tendency of a fuel to form gum and deposits under accelerated aging conditions. They give an indication on the stability of a fuel during its storage. Potential gums can be determined by means of method ASTM D873-12(2018).
  • the hydrocarbon stream has a diene value of at least 0.5 g I 2 /100 g, preferably at least 1 g I 2 /100 g, as measured according to UOP 326, a bromine number of at least 5 g Br 2 / 100g as measured according to ASTM D1159.
  • the hydrocarbon stream contains at least 2 wt% of plastic pyrolysis oil.
  • said hydrocarbon stream contains at least 25 wt % of pyrolysis plastic oil, preferably at least 50 wt% more preferably 75 wt %, even more preferably at least 90 wt % of pyrolysis plastic oil. It is also possible to use pure pyrolysis plastic oil, and this is the most preferred embodiment. In the latter case, the hydrocarbon stream is only consisting of pyrolysis plastic oil.
  • Contaminants contained in plastic pyrolysis oil may comprise constituents which are not boiling below 700°C, preferably not below 600°C, such as gums in the form of plastic oligomers and residues of pyrolysis of plastic, optionally metals and optionally solids.
  • the plastic pyrolysis oil is originating from the stream of pyrolyzed waste plastic for which the C1 to C4 hydrocarbons have been removed and/or the components having a boiling point higher than 350°C have been removed and/or preferably further converted in a steam cracker, and/or a FCC, or a hydrocracking unit, a coker or a visbreaker or blended in crude oil or crude oil cut to be further refined.
  • the other component of said hydrocarbon stream may include any diluent miscible with the pyrolysis plastic oil.
  • diluent preferably has a diene value of at most 0.5 g I 2 /100 g as measured according to UOP 326-17, a bromine number of at most 5 g Br 2 / 100g as measured according to ASTM D1159.
  • the diluent according to the invention is preferably selected from a naphtha and/or a paraffinic solvent and/or a diesel or a straight run gasoil, containing at most 1 wt% of sulfur, preferably at most 0.1 wt% of sulfur, and/or a hydrocarbon stream having a boiling range between 50°C and 150°C or a boiling range between 150°C and 250°C or a boiling range between 200°C and 350°C, having preferably a bromine number of at most 5 gBr 2 /100g, and/or a diene value of at most 0.5 gI 2 /100g or any combination thereof.
  • an antipolymerant such as a stable free radicals or a precursor thereof, such as a hydroxylamine compound.
  • stable free radical (or precursor thereof under conditions which produce the stable free radical in situ) as defined may be used in the present invention.
  • the stable free radicals suitable for use in this invention may be selected from, but are not limited to, the following groups of chemicals: nitroxides (e.g., di-tert butylnitroxide), hindered phenoxys (e.g., galvinoxyl), hydrazyls (e.g., diphenylpicrylhydrazyl), and stabilized hydrocarbon radicals (e.g., triphenylmethyl), as well as polyradicals, preferably biradicals of these types.
  • certain precursors that produce stable free radicals in situ may be selected from the following groups: nitrones, nitrosos, thioketones, benzoquinones, amines and hydroxylamines.
  • the stable free radical may be a stable nitroxide and may be substituted with at least one alkyl, aryl or alkylaryl group.
  • the hydroxylamine may be substituted with at least one alkyl, aryl or alkylaryl group.
  • the stable nitroxide free radical or the hydroxylamine may be substituted with a straight or branched chain alkyl of 1 to 20 carbon atoms, a straight or branched chain alkyl of 1 to 20 carbon atoms which is substituted by one to three aryl groups, an aryl of 6 to 12 carbon atoms, or an aryl of 6 to 12 carbon atoms which is substituted by one to three alkyl groups of 1 to 6 carbon atoms.
  • hydroxylamines substituted with at least one alkyl, aryl or alkylaryl group include, but are not necessarily limited to N-ethylhydroxylamine (EHA); N,N'-diethylhydroxylamine (DEHA); N-ethyl N-methylhydroxylamine (EMHA); N-isopropylhydroxylamine (IPHA); N,N' dibutylhydroxylamine (DBHA); N-amylhydroxylamine (AHA); N-phenylhydroxylamine (PHA); and the like and mixtures thereof.
  • EHA N-ethylhydroxylamine
  • DEHA N,N'-diethylhydroxylamine
  • EMHA N-ethyl N-methylhydroxylamine
  • IPHA N-isopropylhydroxylamine
  • DBHA N,N' dibutylhydroxylamine
  • AHA N-amylhydroxylamine
  • PHA N-phenylhydroxylamine
  • a stable nitroxide free radical that can be used in this invention is a nitroxide having the formula (I) shown below or an amine precursor thereof.
  • R1, R2, R3 and R4 are alkyl groups or heteroatom substituted alkyl groups and no hydrogen is bound to the remaining valences on the carbon atoms bound to the nitrogen.
  • the alkyl (or heteroatom substituted) groups R1-R4 may be the same or different, and preferably contain 1 to 15 carbon atoms.
  • R1-R4 are methyl, ethyl, or propyl groups.
  • the heteroatom substituents may include, halogen, oxygen, sulfur, nitrogen and the like.
  • R5 and R6 are halogen, cyano,-COOR wherein R is alkyl or aryl, --CONH2, --S--C6H5, --S--COCH3,-OCOC2H5, carbonyl, alkenyl where the double bond is not conjugated with the nitroxide moiety or alkyl of 1 to 15 carbon atoms, R5 and R6 may also form a ring of 4 or 5 carbon atoms and up to two heteroatoms, such as O, N or S by R5 and R6 together.
  • R5 and R6 examples of suitable compounds having the structure above and in which R5 and R6 form part of the ring are pyrrolidin-1-oxys, piperidinyl-1-oxys, the morpholines and piperazines.
  • Particular examples wherein the R5 and R6 above form part of a ring are 4-hydroxy-2,2,6,6-tetramethyl-piperindino-1-oxy, 2,2,6,6-tetramethyl-piperidino-1-oxy, 4-oxo-2,2,6,6-tetramethyl-piperidino-1-oxy and pyrrolin-1-oxyl.
  • Suitable R5 and R6 groups are methyl, ethyl, and propyl groups.
  • a specific example of a suitable compound where R1-R6 are alkyl groups is di-tert-butylnitroxide.
  • the preferred carbonyl containing nitroxides are those wherein the R5 and R6 form a ring structure with the nitrogen, preferably a six number ring, for example, 4-oxo-2,2,6,6-tetramethylpiperidino-1-oxy.
  • Examples of nitroxides that can be used in the present invention are the 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (also referred as 4 OH Tempo), the 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl (also referred as 4 NH Tempo), and 4 butoxy Tempo, or their amine precursors.
  • additives capable to reduce gums formation or buildup one can also cite the unhindered phenols, the hindered phenols, the aminophenols, the phenylenediamines.
  • the aminophenol may be selected from the compounds given by the following formula (II):
  • R1 is selected from hydrogen, a C1-C20 alkyl group, C6-C12 aryl group, or OR', with R' being a H, an C1-C20 alkyl or a C6-C12 aryl group.
  • R2 is selected from an C1-C20 alkyl, a phenyl group, or OR', with R' having the same meaning as before.
  • Non-exclusive examples of such compounds are 2-aminophenol (2 AP), 3-hydroxy-2-aminophenol, 2-amino-naphthalen-1 -ol, 3-amino-naphthalen-2-ol, 1-amino-naphthalen-2-ol, 2-amino-tert-butyl-phenol, and 2-amino-4-methylphenol.
  • Suitable hindered or unhindered phenols may include, but are not necessarily limited to, 4-tert butylcatechol (TBC); tert-butyl hydroquinone (TBHQ); 2,6-di-tert-butyl-4-methoxyphenol (DTBMP); 2,4 di-tert-butylphenol; 2,5-di-tert-butylphenol; 2,6-di tertbutylphenol; 2,4, tri-tert-butylphenol; butylated hydroxyltoluene (BHT, also known as 2,6 di-tert-butyl-paracresol and 2,6 di-tert-butyl methylphenol); 2,6 di-tert-butyl-4-nonylphenol; 2,6-di-tert-butyl-4-sec-butylphenol; 2-butyl-4-methylphenol; 2-tert-butyl-4-methoxyphenol (also known as butylated hydroxyanisole or BHA); 2, di-tert
  • the phenylenediamines of this invention have at least one N-H group and are advantageously of the following formula (III): wherein R1, R2, and R3 are the same or different and are hydrogen, straight or branched chain alkyl of 1 to 20 carbon atoms, straight or branched chain alkyl of 1 to 20 carbon atoms which is substituted by one to three aryl groups, aryl of 6 to 12 carbon atoms, or aryl of 6 to 12 carbon atoms which is substituted by one to three alkyl groups of 1 to 6 carbon atoms.
  • Suitable examples of phenylenediamines include N-phenyl-N'-methyl-1,4-phenylediamine, N-phenyl-N'-ethyl-1,4-phenylediamine, N-phenyl-N'-n-propyl-1,4-phenylediamine, N-phenyl-N'-isopropyl-1,4-phenylediamine (NIPP PPDA), N-phenyl-N'-n-butyl-1,4-phenylediamine, N-phenyl-N'-iso-butyl-1,4-phenylediamine, N-phenyl-N'-sec-butyl-1,4-phenylediamine, N-phenyl-N'-t-butyl-1,4-phenylediamine, N-phenyl-N'-n-pentyl-1,4-phenylediamine, N-phenyl-N'-n-hexyl-1,4-phenyled
  • the additive capable to reduce gums formation or buildup is selected among the unhindered phenols, the hindered phenols, the aminophenols, the phenylenediamines, and mixtures thereof.
  • the additive capable to reduce gums formation or buildup is selected among the unhindered phenols, the hindered phenols, aminophenols and mixtures thereof. In another most preferred embodiment, the additive capable to reduce gums formation or buildup is selected among phenylenediamines.
  • suitable additives include 4-tert butylcatechol (TBC); 2,6-di tertbutylphenol; butylated hydroxyltoluene (BHT), tocopherols including alpha-, beta-, gamma-, delta-tocopherol, phenylenediamines, in particular those of the above list, and mixtures thereof.
  • TBC 4-tert butylcatechol
  • BHT butylated hydroxyltoluene
  • tocopherols including alpha-, beta-, gamma-, delta-tocopherol, phenylenediamines, in particular those of the above list, and mixtures thereof.
  • additive which is a dispersant agent
  • such additive is a dispersant/detergent capable to prevent the agglomeration of insoluble compounds, formed during oxidation reactions. Such additive does not reduce the gum content.
  • the dispersant/detergent agent used in the present invention may be selected from:
  • the alkyl phenols can be prepared by an alkylation reaction between a phenol and an olefin or a polyolefin such as polyisobutylene or polypropylene.
  • the aldehyde used can contain from 1 to 10 carbon atoms, generally formaldehyde or paraformaldehyde.
  • the amine used can be an amine or a polyamine including the alkanolamines having one or more hydroxyl groups.
  • the amines used are generally selected from ethanolamine, diethanolamines, methylamine, dimethylamine, ethylenediamine, dimethylaminopropylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and/or 2-(2-aminoethylamino)ethanol.
  • This dispersant can be prepared by a Mannich reaction by reacting an alkylphenol, an aldehyde and an amine as described in patent U.S. Pat. No.5,697,988 .
  • other dispersants such as:
  • the dispersant/detergent agent used in the present invention may be selected from the above compounds (ii) and (v).
  • Such preferred dispersant/detergent agent(s) may be added to the above described additive(s) capable to reduce gums formation or buildup and more particularly to the preferred additive(s)..
  • the stabilized composition it is of use in industrial processes for plastic recycling in which hydrocarbon streams is handled or manipulated other than the intentional polymerization of the olefin.
  • Such processes include but are not limited to hydrocarbon cracking processes, preheating, distillation, hydrogenation, extraction, etc.
  • the proportion of b) with reference to a) can be up to 5000wppm, advantageously up to 3000 wppm, in particular from 50 to 5000 wppm, preferably from 50 to 3000 wppm, most preferably from 300 to 1500wppm, or within any of these limits.
  • the proportion of c) with reference to a) can be up to 5000wppm, advantageously up to 3000 wppm, in particular from 50 to 5000 wppm, preferably from 50 to 3000 wppm, most preferably from 300 to 1500wppm, or within any of these limits.
  • the additives of this invention may also be used with other additives known to prevent fouling such as metal deactivators, corrosion inhibitors and the like.
  • the stabilizer combination of this invention may be applied at any point in an industrial plant stream or process where it is effective.
  • Step (a) for providing a hydrocarbon stream as defined above may comprise :
  • step (b) said at least one additive capable to reduce gums formation or buildup is added to said at least one plastic pyrolysis oil provided by step (i), prior to step (iii).
  • the additives are added to the pyrolysis plastic oil immediately after the pyrolysis of the plastic waste.
  • step (c) said at least one additive is added to said at least one plastic pyrolysis oil provided by step (i), prior to step (iii), preferably immediately after the pyrolysis of the plastic waste.
  • steps (b) and (c) are performed simultaneously, preferably immediately after the pyrolysis of the plastic waste.
  • the additives can be introduced as pure or as a dilute solution in a hydrocarbon or equivalent and/or they can be introduced simultaneously or separately.
  • the additives may be diluted in hydrocarbons, for example C6-C20 aromatic hydrocarbons substituted or not, including toluene, benzene, naphthalene, substituted or not, and their mixtures, heavy aromatic naphtha, a middle distillate (boiling range 180-360°C) such as a jet fuel or a diesel, or in polar solvents, in particular alcohols such as glycols, ethanol, or water.
  • hydrocarbons for example C6-C20 aromatic hydrocarbons substituted or not, including toluene, benzene, naphthalene, substituted or not, and their mixtures, heavy aromatic naphtha, a middle distillate (boiling range 180-360°C) such as a jet fuel or a diesel, or in polar solvents, in particular alcohols such as glycols, ethanol
  • the stabilized composition described in the present invention or obtained by the process of the present invention may be used as such or further processed alone or in combination with another feedstock such as naphtha, gasoil or any crude oil refining product. It may for example be fractionated according to distillation temperature ranges, to feed a steam cracker, a FCC, a hydrocracker, a catalytic hydrogenation unit or a pool of fuels or combustibles such as naphtha, gas oil, heavy fuel oil and/or for the preparation of lubricants.
  • the process for the processing of a composition stabilized against premature polymerization uses a stabilized composition as described in the present invention and in particular obtained by the process for preparing a composition stabilized against premature polymerization of the invention.
  • additives contained in the stabilized composition may present a two high boiling point to be used in a further processing step and/or may be detrimental to the further processing.
  • step (a) it may be preferable to reduce, or completely remove, some or all of the additives by submitting the stabilized composition provided in step (a) to an evaporation step (b) under operating conditions efficient to obtain a composition containing a reduced amount of additives.
  • evaporation may be performed at temperatures and pressure efficient to obtain a gaseous hydrocarbon stream having a final boiling point of at most 650°C, preferably of at most 500°C, more preferably of at most 380°C, and optionally a residue.
  • Such evaporation is optionally performed in presence of steam.
  • the stabilized composition in the evaporation step, may be heated using steam, at a temperature which is high enough to avoid condensation of steam when direct mixing is envisioned, since steam condensation could lead to hammering issues.
  • Non-vaporized products are removed in a separation section to produce the gaseous hydrocarbon stream.
  • the stabilized composition may be heated using a hot oil, which is collected in admixture with the non-vaporized products and may be recycled.
  • the evaporation step may be performed using a flash drum, a kettle, a single or double wall thin film evaporator, a falling film evaporator or a combination of at least two of them.
  • Such evaporation step (b) may be particularly useful before processing the stabilized composition in a steam cracker.
  • the gaseous hydrocarbon stream obtained from evaporation step (b) is then submitted to the further processing step (c).
  • the stabilized composition provided in step (a) or the composition containing a reduced amount of additives provided in step (b) may, prior to step (c), be mixed with naphtha, gasoil or any crude oil refining product to have a pyrolysis plastic oil concentration ranging from 0.01 wt% to at most 90 wt%; preferably 0.1 wt% to 75 wt% even more preferably 1 wt% to 50 wt% or within any of these limits.
EP22305030.3A 2022-01-13 2022-01-13 Compositions stabilisées comportant des oléfines Pending EP4212604A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP22305030.3A EP4212604A1 (fr) 2022-01-13 2022-01-13 Compositions stabilisées comportant des oléfines
PCT/EP2022/086919 WO2023134977A1 (fr) 2022-01-13 2022-12-20 Traitement de compositions stabilisées comprenant des oléfines

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP22305030.3A EP4212604A1 (fr) 2022-01-13 2022-01-13 Compositions stabilisées comportant des oléfines

Publications (1)

Publication Number Publication Date
EP4212604A1 true EP4212604A1 (fr) 2023-07-19

Family

ID=79831156

Family Applications (1)

Application Number Title Priority Date Filing Date
EP22305030.3A Pending EP4212604A1 (fr) 2022-01-13 2022-01-13 Compositions stabilisées comportant des oléfines

Country Status (2)

Country Link
EP (1) EP4212604A1 (fr)
WO (1) WO2023134977A1 (fr)

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3219666A (en) 1959-03-30 1965-11-23 Derivatives of succinic acids and nitrogen compounds
US3329658A (en) 1962-05-14 1967-07-04 Monsanto Co Dispersency oil additives
US3565804A (en) 1965-08-23 1971-02-23 Chevron Res Lubricating oil additives
US3702300A (en) 1968-12-20 1972-11-07 Lubrizol Corp Lubricant containing nitrogen-containing ester
US5697988A (en) 1991-11-18 1997-12-16 Ethyl Corporation Fuel compositions
WO2002088055A1 (fr) * 2001-04-30 2002-11-07 Baker Hughes Incorporated Inhibition de la croissance polymere en flocon
EP1884556A2 (fr) 2006-08-04 2008-02-06 Infineum International Limited Améliorations de compositions de carburant diesel
EP1887074A1 (fr) 2006-08-04 2008-02-13 Infineum International Limited Procédé et utilisation pour la prévention de dépôts d'injecteur de carburant
WO2009040582A1 (fr) 2007-09-27 2009-04-02 Innospec Limited Compositions de combustible
US20090282731A1 (en) 2008-05-13 2009-11-19 Afton Chemical Corporation Fuel additives to maintain optimum injector performance
US20100162617A1 (en) * 2008-12-29 2010-07-01 Fina Technology, Inc. Stabilization of Pygas for Storage
WO2010097624A1 (fr) 2009-02-25 2010-09-02 Innospec Limited Procédés et utilisations relatifs à des compositions pour carburant
WO2010132259A1 (fr) 2009-05-15 2010-11-18 The Lubrizol Corporation Sels d'amide et/ou d'ester d'ammonium quaternaire
WO2011134923A1 (fr) 2010-04-27 2011-11-03 Basf Se Terpolymère quaternisé
WO2013119941A1 (fr) * 2012-02-09 2013-08-15 Ullom William Appareil de pyrolyse à définition de zones destiné à la conversion de déchets de polymère
DE202015009755U1 (de) * 2015-01-19 2020-02-06 Bluealp Innovations B.V. Anlage zum Überführen von Kunststoffabfällen in einen Brennstoff mit Eigenschaften von Diesel/Heizöl

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3342735A (en) 1965-04-23 1967-09-19 Texaco Inc Alkenyl succinic anhydride-amine-ps reaction product
US3567623A (en) * 1969-02-10 1971-03-02 Betz Laboratories Antifoulant agents for petroleum hydrocarbons
US4639259A (en) 1985-10-09 1987-01-27 Kaiser Aluminum & Chemical Corporation Promoted scavenger for purifying HCl-contaminated gases
US4762537A (en) 1985-11-07 1988-08-09 Aluminum Company Of America Adsorbent for HCl comprising alumina and acid-treated Y zeolite
US4775458A (en) * 1986-12-18 1988-10-04 Betz Laboratories, Inc. Multifunctional antifoulant compositions and methods of use thereof
US5316998A (en) 1992-05-05 1994-05-31 Discovery Chemicals, Inc. HCl adsorbent and method for making and using same
WO2018156914A1 (fr) * 2017-02-27 2018-08-30 Ecolab USA, Inc. Formulation anti-encrassement pour compresseurs

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3219666A (en) 1959-03-30 1965-11-23 Derivatives of succinic acids and nitrogen compounds
US3329658A (en) 1962-05-14 1967-07-04 Monsanto Co Dispersency oil additives
US3565804A (en) 1965-08-23 1971-02-23 Chevron Res Lubricating oil additives
US3702300A (en) 1968-12-20 1972-11-07 Lubrizol Corp Lubricant containing nitrogen-containing ester
US5697988A (en) 1991-11-18 1997-12-16 Ethyl Corporation Fuel compositions
WO2002088055A1 (fr) * 2001-04-30 2002-11-07 Baker Hughes Incorporated Inhibition de la croissance polymere en flocon
EP1884556A2 (fr) 2006-08-04 2008-02-06 Infineum International Limited Améliorations de compositions de carburant diesel
EP1887074A1 (fr) 2006-08-04 2008-02-13 Infineum International Limited Procédé et utilisation pour la prévention de dépôts d'injecteur de carburant
WO2009040582A1 (fr) 2007-09-27 2009-04-02 Innospec Limited Compositions de combustible
US20090282731A1 (en) 2008-05-13 2009-11-19 Afton Chemical Corporation Fuel additives to maintain optimum injector performance
US20100162617A1 (en) * 2008-12-29 2010-07-01 Fina Technology, Inc. Stabilization of Pygas for Storage
WO2010097624A1 (fr) 2009-02-25 2010-09-02 Innospec Limited Procédés et utilisations relatifs à des compositions pour carburant
WO2010132259A1 (fr) 2009-05-15 2010-11-18 The Lubrizol Corporation Sels d'amide et/ou d'ester d'ammonium quaternaire
WO2011134923A1 (fr) 2010-04-27 2011-11-03 Basf Se Terpolymère quaternisé
WO2013119941A1 (fr) * 2012-02-09 2013-08-15 Ullom William Appareil de pyrolyse à définition de zones destiné à la conversion de déchets de polymère
DE202015009755U1 (de) * 2015-01-19 2020-02-06 Bluealp Innovations B.V. Anlage zum Überführen von Kunststoffabfällen in einen Brennstoff mit Eigenschaften von Diesel/Heizöl

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
IUPAC: "Compendium of Chemical Terminology", 1997
KIRKOTHMER: "Encyclopedia of Chemical Technology", vol. 5, 1950, INTERSCIENCE PUBLISHERS, article "Ethylene Amines", pages: 898 - 905

Also Published As

Publication number Publication date
WO2023134977A1 (fr) 2023-07-20

Similar Documents

Publication Publication Date Title
JPH09183993A (ja) アルキルフェノールとアルデヒドとの縮合生成物、およびそれらの誘導体
KR101264932B1 (ko) 폴리이소부테닐페놀의 제조 방법
WO1995020637A2 (fr) Compositions huileuses-aqueuses d'hydrocarbures, de combustibles et d'additifs
KR20210030392A (ko) 니트록사이드 억제제, 퀴논 메티드 지연제 및 아민 안정화제를 포함하는 단량체 중합 억제용 조성물
EP2125919B1 (fr) Anti-encrassement amélioré pour équipement de traitement d'hydrocarbures
CN1291967A (zh) 聚合防止性组合物,聚合防止剂和防止聚合的方法
US5171420A (en) Method for controlling fouling deposit formation in a liquid hydrocarbonaceous medium
JP6095131B2 (ja) 液状炭化水素の加工の際の汚染の低減方法
TWI826485B (zh) 作為乙烯系單體之防垢劑之含氧胺及醌甲基化物之組合物
US20100081727A1 (en) Process for preparing ene adducts
KR20230153399A (ko) 플라스틱-유도된 합성 공급원료를 위한 안정제 첨가제
EP4212604A1 (fr) Compositions stabilisées comportant des oléfines
US5342505A (en) Use of polyalkenyl succinimides-glycidol reaction products as antifoulants in hydrocarbon process media
WO2010108857A1 (fr) Compositions stabilisées comprenant des oléfines
KR20220004676A (ko) 산소화 아미노페놀 화합물 및 단량체 중합 방지 방법
EP1689792A1 (fr) Compose hydroxyaromatique alkyle issu de polyisobutylenes classique et a vinylidene eleve et compostions et procedes associes
EP0632121B1 (fr) Inhibiteur d'incrustation pour procédés pétrochimiques
US5194142A (en) Method for controlling fouling deposit formation in a liquid hydrocarbonaceous medium
CA3009069A1 (fr) Procede de dispersion de sous-produits formes dans des systemes de dilution a la vapeur
CA2503534C (fr) Dispersant anti-salissure
US5292425A (en) Use of the reaction products of polyalkenylsuccinimides, triazoles, and aldehydes as anti foulants in hydrocarbon process media
CN109563419B (zh) 在工艺水中抑制聚合的方法
CA2067853A1 (fr) Methode servant a reduire la formation de depots dans un medium hydrocarbone liquide
KR20190091450A (ko) 석유 공정 스트림을 위한 항파울링 조성물
TW202348992A (zh) 用於化學回收之塑膠原料的氧化穩定性測試方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20240111

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR