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EP4599031B1 - Huile de pyrolyse à point d'écoulement réduit - Google Patents

Huile de pyrolyse à point d'écoulement réduit

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Publication number
EP4599031B1
EP4599031B1 EP24827749.3A EP24827749A EP4599031B1 EP 4599031 B1 EP4599031 B1 EP 4599031B1 EP 24827749 A EP24827749 A EP 24827749A EP 4599031 B1 EP4599031 B1 EP 4599031B1
Authority
EP
European Patent Office
Prior art keywords
weight
pyrolysis oil
ethylene
plastic
composition
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.)
Active
Application number
EP24827749.3A
Other languages
German (de)
English (en)
Other versions
EP4599031A1 (fr
Inventor
Sofia SIRAK
Claudia Meister
Sachin Subhash WAGH
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.)
Evonik Operations GmbH
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Evonik Operations GmbH
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Publication of EP4599031A1 publication Critical patent/EP4599031A1/fr
Application granted granted Critical
Publication of EP4599031B1 publication Critical patent/EP4599031B1/fr
Active legal-status Critical Current
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/041—Mixtures of base-materials and additives the additives being macromolecular compounds only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/071—Branched chain compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the invention relates to a composition comprising a pyrolysis oil and a polymeric additive for reducing the pour point, viscosity, or both the pour point and viscosity of the pyrolysis oil.
  • the invention further relates to a method of manufacturing said composition, the use of a polymeric additive for reducing the pour point, viscosity, or both the pour point and viscosity of a pyrolysis oil.
  • the invention further relates to a method for transporting or storing a pyrolysis oil.
  • Plastic production continues to grow rapidly, and plastic products remain to be a crucial part of our lives due to the versatility of the material and the low cost associated with plastic production. It is estimated that 250 million tons of plastic per year are either landfilled or dispersed into the environment. It is also predicted that the use of plastic will continue to increase in the future. The increase in plastic production will also be associated with the increase in associated plastic waste, especially with single-use plastic items. The increase in plastic waste has also brought interest in how to effectively recycle or convert plastic waste back into usable materials.
  • plastic waste is by thermochemically converting plastic waste via a pyrolysis process.
  • Pyrolysis is a thermal cracking process that occurs in the absence of oxygen at temperatures above 400°C. The process breaks down polymer chains into smaller chains and molecules. The pyrolysis process can therefore convert plastic waste material into usable products thereby addressing the plastic waste management issues.
  • plastics There are many types of plastics, but the majority of plastic waste is made up of low-density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), polyvinylchloride (PVC), polystyrene (PS), and polyethylene terephthalate (PET). Of those plastics, polyethylene and polypropylene constitute the greatest portion of plastic waste.
  • the pyrolysis provides a final product termed in the art 'pyrolysis oil'.
  • the main products produced from plastic pyrolysis include liquid oil, wax, solid residues, and gas. All such residues are then processed further as part of existing plastic processing plants or steam crackers used in refineries.
  • the conversion of plastic to usable materials is dependent on several factors.
  • the most influential factors are the reactor design, the process temperature, the type of plastic used, and the type of catalyst.
  • the wax residue comprises those pyrolysis products having alkyl chains of 16 or more carbon atoms.
  • the wax residue is a valuable product in the pyrolysis process.
  • the amount of wax residue produced can greatly influence the final pyrolysis oil properties.
  • the main driver in the amount of wax residue produced is the plastic feedstock being introduced into the pyrolysis process.
  • olefinic plastics such as polyethylene and polypropylene are more linear polymers, which therefore break down into waxy linear alkyl chains when converted in the pyrolysis process.
  • Pyrolysis oils produced from polyethylene and polypropylene can yield over 50wt% wax residue depending on the specific pyrolysis oil process conditions.
  • Specific process conditions including catalyst types can also influence oil-to-wax ratio.
  • certain catalysts can be used.
  • conditions such as residence time in the reactor can be influential. For example, 'fast' pyrolysis leads to the production of waxy hydrocarbon mixtures, whereas 'slow' pyrolysis typically produces more oil than wax. ( Materials 2021, 14, 2586 ).
  • waxy chains can also cause a variety of transportation and storage issues.
  • the waxy chains of 12 or more carbon atoms can begin to crystallize as the pyrolysis oil cools to ambient temperature after the pyrolysis process.
  • Pyrolysis oils also typically have a large quantity of paraffins with waxy chains of 16 to more than 40 carbon atoms. These wax chains are most problematic since the melting point is much higher.
  • the wax crystals can then build up and cause an increase in viscosity, making the thicker oil more difficult to pump or move. If there is enough wax residue in the pyrolysis oil, especially in polyolefin pyrolysis oils, then the wax crystals may cause the entire product to solidify at lower temperatures heading towards ambient temperature.
  • wax crystals may also clog equipment such as filters and pipelines, thus increasing servicing costs.
  • high wax amounts can lead to paraffin deposition on pipelines in the production lines. As wax builds up, the efficacy and lifetime of the equipment is decreased.
  • wax is a valuable pyrolysis product, and existing plastic processing plants have been designed and built to use the wax residue.
  • the wax residue made in the pyrolysis process especially from increasingly used olefin feedstocks, is making transportation and storage of the pyrolysis oil more difficult and more expensive.
  • the amount of wax residue varies depending on the plastic feedstock used, and the specific process conditions.
  • polyolefin-based pyrolysis oils produced via current or standard pyrolysis processes tend to produce the most amount of wax, which therefore have the most problems, especially at ambient conditions.
  • the 'pour point' is the lowest temperature at which the pyrolysis oil will still flow, and pyrolysis oils with high wax residue have relatively high pour points (for example, above 50°C), which are usually above standard operating conditions and storage temperatures. This leads to difficulty in processing such pyrolysis oils, as the oil may solidify and become unable to transport.
  • Heat is typically applied to the oil to liquefy it for storage and transportation. This expends heat energy and takes time. Therefore, even slight reductions in the pour point could drastically reduce the amount of heat energy expended and time taken to liquefy or to keep in liquid form the pyrolysis oil for transportation and storage.
  • US2012/0310023A1 discloses that oils obtained in pyrolysis of polyolefin containing plastics mixtures are frequently wax-like semisolid products, and that the use of specific catalysts can result in the production of more light and less waxy products.
  • US2022/081634 discloses the use of a polymeric additive for improving the cold flow properties of a plastic-derived synthetic feedstock composition (see [0008]).
  • the polymer can be an ethylene vinyl acetate (EVA) having a weight-average molecular weight from 800 to 13,000 g/mol, preferably from 900 to 12,000 g/mol (see [0060], [0061] and example 1 of Table 1).
  • EVA ethylene vinyl acetate
  • This document is focused on the treatment of plastic pyrolysis oil with a high wax residue content of alkanes with long carbon chains (high content of waxes having C 16 or longer carbon chains - see e.g. [0048], [0086], [0097], [0115], [00127], as well as the two treated pyrolysis oils of the experimental part [0153]).
  • KR100994244B1 discloses the need to remove the wax from the process and proposes the use of a separation device for wax removal. Therefore, the pyrolysis process will require an additional step to the process.
  • the conventional solutions to reduce viscosity and pour point of pyrolysis oils have been to reduce or eliminate production of the wax by changing the reactor design, adding special catalyst, increasing processing times or having an additional dewaxing process step.
  • those methods help in producing liquid pyrolysis oils with a lower wax content, it creates additional costs, maintenance work, increased processing times, which decrease production efficiency and are thus not good industrially viable solutions.
  • the industry looks for high wax residue content pyrolysis oils for cracking processes, without having the transportation and storage disadvantages.
  • plastic pyrolysis oils strongly depends on the production process, which leads to plastic pyrolysis oils having different wax residue content of alkanes. Therefore, there is still a need to investigate further to find effective and cost-efficient solutions for the treatment of plastic pyrolysis oils from a plastic pyrolysis process in order to keep them liquid, improving the transport and storage of these oils before the cracking process.
  • the present invention is therefore directed to provide a pyrolysis oil with a lower pour point, lower viscosity or both lower pour point and viscosity, as well as other objectives.
  • composition comprising a plastic pyrolysis oil a) and a polymeric additive b) as defined in claim 1.
  • composition of the first aspect of the invention comprising the steps of:
  • a method of transporting or storing a plastic pyrolysis oil a) comprising the step of adding a polymeric additive b) to a pyrolysis oil to form a composition as defined in the first aspect of the invention.
  • Figure 1 is a graph showing the viscosity of pyrolysis oil a) and a composition comprising pyrolysis oil a) with a polymeric additive b) over a temperature range of 40 to 80 °C.
  • the reference number 1 on Figure 1 corresponds to the curve of the untreated pyrolysis oil (Example 1 of Table 5 below), whereas the reference number 2 on Figure 1 corresponds to the curve of the pyrolysis oil composition according to the invention (inventive example 2 of Table 5 below).
  • composition comprising a plastic pyrolysis oil a) and a polymeric additive b), wherein the polymeric additive b) is an ethylene graft polyalkyl(meth)acrylate A) obtainable by grafting onto an ethylene-based copolymer A1), obtainable by polymerizing a monomer composition consisting of ethylene and a compound selected from the group consisting of vinyl esters, acrylates, methacrylates, alpha-olefins or a mixture thereof, based on the total weight of the ethylene-based copolymer A1), a grafting monomer composition A2) comprising alkyl (meth)acrylates of general Formula (I) wherein
  • the polymeric additive b) reduces the pour point of the pyrolysis oil.
  • the polymeric additive may also reduce the viscosity of the pyrolysis oil.
  • the polymeric additive may also reduce both the pour point and the viscosity of the pyrolysis oil.
  • the pour point of a pyrolysis oil a) is reduced by at least 1 °C, more preferably by at least 2 °C, even more preferably by at least 3 °C, most preferably by at least 5 °C, by the addition of the polymeric additive as described herein, when compared to the same pyrolysis oil with no polymeric additive.
  • the reduction in viscosity is preferably of at least 10 %, preferably at least 20 %, even more preferably 30 %, 40 %, 50 %, or 60 % or more, at a temperature from -20 °C to +80 °C, preferably from -10 °C to +50 °C, when the polymeric additive is added to the pyrolysis oil with a wax residue as described herein, when compared to the same pyrolysis oil with no polymeric additive.
  • the polymeric additive b) has a wax inhibition of greater than 1 % relative to the pyrolysis oil a) as determined by the cold finger test measured using CF-15 cold finger device manufactured by PSL with rack temperature set at 5 °C above the Wax Appearance Temperature (WAT) and finger temperature set 20 °C below the WAT for a test period of 24 hours as described in detail in the experimental part of the present invention.
  • the wax inhibition is preferably greater than 5 %, 10 %, 15 %, 25 % or 30 % (measured according to the cold finger test described above and more detail in the experimental part).
  • plastic pyrolysis oil or "pyrolysis oil” as used herein includes any pyrolysis oil produced from the pyrolysis of plastics or plastic waste. Pyrolysis is a thermal cracking process that occurs in the complete or substantial absence of oxygen, at temperatures above 250°C to convert plastic into energy, in the form of solid, liquid and gaseous fuels. The process breaks down polymer chains into smaller chains and molecules.
  • the plastic pyrolysis oil is preferably a plastic waste pyrolysis oil, namely a pyrolysis oil produced from plastic waste.
  • the pyrolysis of plastic waste with a thermal degradation of plastic waste at different temperatures (300-900°C), to produce liquid oil is for example described in Rehan et al., 2017, Int. Biodeterior. Biodegrad. 119, 162-175 .
  • the plastic pyrolysis oil is a plastic pyrolysis oil and/or a plastic waste pyrolysis oil, wherein the plastic and plastic waste are both selected from polyolefins, more preferably polylolefins selected from high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP) and a mixture thereof; polyethylene terephthalate (PET); polyvinyl chloride (PVC); polystyrene (PS); or a mixture thereof.
  • polyolefins more preferably polylolefins selected from high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP) and a mixture thereof
  • PET polyethylene terephthalate
  • PVC polyvinyl chloride
  • PS polystyrene
  • polyolefin pyrolysis oil and "polyolefin waste pyrolysis oil” as used herein defines an oil produced from the pyrolysis of polyolefins or waste polyolefin respectively, wherein the plastic and plastic waste are selected from high-density polyethylene (HDPE), low-density polyethylene (LDPE) and polypropylene (PP).
  • HDPE high-density polyethylene
  • LDPE low-density polyethylene
  • PP polypropylene
  • Pyrolysis oils having a wax content of at least 1 % by weight typically have problems regarding storage and transportation, due to the high pour point and high viscosity of the pyrolysis oil.
  • the terms "wax residue” or “wax content” include that portion of the pyrolysis oil that comprises linear hydrocarbons containing 16 or more carbon atoms.
  • linear hydrocarbons containing 16 or more carbon atoms used herein means "n-paraffin waxes with C 16 or longer carbon chains", namely, "n-paraffin waxes being a mixture of C 16 to C 19 n-paraffin waxes, C 20 to C 29 n-paraffin waxes, C 30 to C 39 n-paraffin waxes, and n-paraffin waxes with C 40 or longer carbon chains".
  • the pyrolysis oil a) of the composition of the present invention has a wax residue of 30 % by weight or less of n-paraffin waxes with C 16 or longer carbon chains, more preferably of 20 % by weight or less, even more preferably of 15 % by weight of less, most preferably of 12 % by weight or less, most preferably of 10 % by weight or less, of n-paraffin waxes with C 16 or longer carbon chains, based on the total weight of the plastic pyrolysis oil a).
  • the pyrolysis oil a) of the composition of the present invention has a wax residue of from 0.01 % by weight to 30 % by weight of n-paraffin waxes with C 16 or longer carbon chains, more preferably from 0.01 % by weight to 30 % by weight, more preferably from 0.01 % by weight to 25 % by weight, even more preferably from 0.01 % by weight to 20 % by weight, even more preferably from 0.01 % by weight to 15 % by weight, most preferably from 0.01 % by weight to 12 % by weight, most preferably from 0.05 % by weight to 10 % by weight of n-paraffin waxes with C 16 or longer carbon chains, based on the total weight of the plastic pyrolysis oil a).
  • the plastic pyrolysis oil a) preferably comprises from 0 % to 30 % by weight of C 16 to C 19 n-paraffin waxes, from 0 % to 30 % by weight of C 20 to C 29 n-paraffin waxes, from 0 % to 30 % by weight of C 30 to C 39 n-paraffin waxes, and from 0 % to 30 % of n-paraffin waxes with C 40 or longer carbon chains, wherein the total wax content of n-paraffin waxes with C 16 or longer carbon chains sums up from 0.01 % by weight to 30 % by weight, based on the total weight of the plastic pyrolysis oil.
  • the plastic pyrolysis oil a) preferably comprises from 0 % to 20 % by weight of C 16 to C 19 n-paraffin waxes, from 0 % to 20 % by weight of C 20 to C 29 n-paraffin waxes, from 0 % to 20 % by weight of C 30 to C 39 n-paraffin waxes, and from 0 % to 20 % of n-paraffin waxes with C 40 or longer carbon chains, wherein the total wax content of n-paraffin waxes with C 16 or longer carbon chains sums up from 0.01 % by weight to 20 % by weight, based on the total weight of the plastic pyrolysis oil.
  • the plastic pyrolysis oil a) preferably comprises from 0 % to 15 % of C 16 to C 19 n-paraffin waxes, from 0 % to 15 % of C 20 to C 29 n-paraffin waxes, from 0 % to 15 % of C 30 to C 39 n-paraffin waxes, and from 0 % to 15 % of n-paraffin waxes with C 40 or longer carbon chains, wherein the total wax content of n-paraffin waxes with C 16 or longer carbon chains sums up from 0.01 % by weight to 15 % by weight, based on the total weight of the plastic pyrolysis oil.
  • the plastic pyrolysis oil a) preferably comprises from 0 % to 12% of C 16 to C 19 n-paraffin waxes, from 0 % to 12 % of C 20 to C 29 n-paraffin waxes, from 0 % to 12 % of C 30 to C 39 n-paraffin waxes, and from 0 % to 12 % of n-paraffin waxes with C 40 or longer carbon chains, wherein the total wax content of n-paraffin waxes with C 16 or longer carbon chains sums up from 0.01 % by weight to 12 % by weight, based on the total weight of the plastic pyrolysis oil.
  • the plastic pyrolysis oil a) preferably comprises from 0 % to 10 % of C 16 to C 19 n-paraffin waxes, from 0 % to 10 % of C 20 to C 29 n-paraffin waxes, from 0 % to 10 % of C 30 to C 39 n-paraffin waxes, and from 0 % to 10 % of n-paraffin waxes with C 40 or longer carbon chains, wherein the total wax content of n-paraffin waxes with C 16 or longer carbon chains sums up from 0.01 % by weight to 10 % by weight, based on the total weight of the plastic pyrolysis oil.
  • the plastic pyrolysis oil a) preferably comprises from 0 % to 10 % of C 16 to C 19 n-paraffin waxes, from 0 % to 10 % of C 20 to C 29 n-paraffin waxes, from 0 % to 10 % of C 30 to C 39 n-paraffin waxes, and from 0 % to 10 % of n-paraffin waxes with C 40 or longer carbon chains, wherein the total wax content of n-paraffin waxes with C 16 or longer carbon chains sums up from 0.01 to 10 % by weight, based on the total weight of the plastic pyrolysis oil.
  • reducing or lowering the pour point or the viscosity or both of a pyrolysis oil makes it easier to transport and store a pyrolysis oil having a wax residue.
  • the present invention obviates the current requirements to modify the reactor, or to modify the reaction process (for example, by the addition of a catalyst) when processing a pyrolysis oil having a wax residue that it is desired to maintain. In this way, current plastic processing plants designed to expect the use of a wax residue pyrolysis oil can continue to operate without redesign.
  • the polymeric additive b) is an ethylene graft polyalkyl(meth)acrylate A) obtainable by grafting onto an ethylene-based copolymer A1), obtainable by polymerizing a monomer composition consisting of ethylene and a compound selected from the group consisting of vinyl esters, acrylates, methacrylates, alpha-olefins or a mixture thereof, based on the total weight of the ethylene-based copolymer A1), a grafting monomer composition A2) comprising alkyl (meth)acrylates of general Formula (I) wherein
  • R 1 is a linear or branched, saturated or unsaturated alkyl group with 7 to 15 carbon atoms.
  • the polymeric additive b) is one polymer A), or a mixture of one or more polymer A).
  • the grafting monomer composition A2) corresponds to the total amount of monomers grafted onto the ethylene-based copolymer A1).
  • the ethylene-based copolymer A1) in the present invention is obtainable by polymerizing a monomer composition consisting of ethylene, and a vinyl ester or a mixture of ethylene monomer and vinyl esters.
  • ester-comprising polymers may be random copolymers, gradient copolymers, block copolymers and/or graft copolymers, more preferably random copolymers.
  • the monomer composition of the ethylene-based copolymer A1) consists of from 55 % to 90 % by weight, preferably from 60 % to 85 % by weight, more preferably from 67 % to 82 % by weight, of ethylene, and from 10 % to 45 % by weight, preferably from 15 % to 40 % by weight, more preferably from 18 % to 33 % by weight, of vinyl ester, based on the total weight of the monomer composition to prepare the ethylene-based copolymer A1).
  • the weight ratio of ethylene-based copolymer A1) to the monomer grafting composition A2) to prepare the ethylene graft polyalkyl(meth)acrylate A), based on the total weight of the ethylene graft polyalkyl(meth)acrylate B), is from 1:1 to 1:10, preferably from 1:1 to 1:8, more preferably from 1:1 to 1:6.
  • the polymeric additive b) further comprises an ethylene-based copolymer B) obtainable by polymerizing a monomer composition consisting of ethylene and a vinyl ester.
  • the monomer composition of the ethylene-based copolymer B) consists of from 55 % to 90 % by weight, preferably from 60 % to 85 % by weight, more preferably from 67% to 82% by weight, of ethylene, and from 10 % to 45 % by weight, preferably from 15 % to 40 % by weight, more preferably from 18 % to 33 % by weight, of a compound selected from the group consisting of vinyl esters, acrylates, methacrylates and alpha-olefins or a mixture thereof, based on the total weight of the monomer composition to prepare the ethylene-based copolymer A1).
  • Suitable vinyl esters derive from fatty acids having linear or branched alkyl groups having 2 to 30 carbon atoms. Examples include vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl laurate and vinyl stearate, and also esters of vinyl alcohol based on branched fatty acids, such as vinyl isobutyrate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl isononanoate, vinyl neononanoate, vinyl neodecanoate, vinyl neoundecanoate and vinyl ester of versatic acids. Particularly preferred vinyl esters are vinyl acetate and vinyl propionate. Most preferred vinyl ester is vinyl acetate.
  • the ethylene-based copolymer A1) or B) consists of ethylene and vinyl acetate.
  • the ethylene-based copolymers A1) and/or B) according to the invention have a weight-average molecular weight (M w ) from 20,000 to 1,000,000 g/mol, preferably from 45,000 to 500,000 g/mol, more preferably from 60,000 to 400,000 g/mol, determined by gel permeation chromatography using poly(methylmethacrylate) calibration standards according to DIN 55672-1 (as described in more detail below).
  • M w weight-average molecular weight
  • the polymeric additive b) comprises an ethylene graft polyalkyl(meth)acrylate A) and an ethylene-based copolymer B), wherein the ethylene-based copolymer B) is from 60 to 95 % by weight and the ethylene graft polyalkyl(meth)acrylate A) is from 5 to 40 % by weight, based on the total amount of the ethylene graft polyalkyl(meth)acrylate A) and the ethylene-based copolymer B).
  • the grafting monomer composition A2) of the ethylene graft polyalkyl(meth)acrylate A) preferably further comprises hydroxy esters of general Formula (II) wherein
  • the grafting monomer composition of the ethylene graft polyalkyl(meth)acrylate A) comprises 0 to 50 % by weight, preferably 0 to 40 % by weight, more preferably 0 to 30 % by weight of hydroxy esters of general Formula (II), based on the total weight of the grafting monomer composition A2).
  • the hydroxy ester of general Formula (II) is 2-hydroxyethyl methacrylate.
  • (meth)acrylate refers to esters of acrylic and methacrylic acid, and to mixtures thereof.
  • alkyl (meth)acrylate refers to esters of (meth)acrylic acid and aliphatic alcohols.
  • the alkyl (meth)acrylates described herein are characterized by the number of carbon atoms in the alkyl chain derived from the alcohol.
  • C 1 to C 30 alkyl (meth)acrylates refers to esters of (meth)acrylic acid and linear or branched alcohols having 1 to 30 carbon atoms.
  • the term encompasses individual (meth)acrylic esters with an alcohol of a particular length, and likewise a mixture of (meth)acrylic esters with alcohols of different lengths.
  • C 1 to C 6 alkyl (meth)acrylates or “C 7 to C 15 alkyl (meth)acrylates” or “C 16 to C 30 alkyl (meth)acrylates” refers to esters of (meth)acrylic acid with linear or branched alkyl chain having 1 to 6 carbon atoms or 7 to 15 carbon atoms or 16 to 30 carbon atoms, respectively.
  • the term encompasses individual (meth)acrylic esters with an alcohol of a particular length, and likewise mixtures of (meth)acrylic esters with alcohols of different lengths.
  • Examples of the C 1 to C 6 alkyl (meth)acrylate monomers where the linear or branched alkyl group contains from 1 to 6 carbon atoms, are methyl methacrylate (MMA), methyl and ethyl acrylate, propyl methacrylate, butyl methacrylate (BMA) and acrylate (BA), isobutyl methacrylate (IBMA), hexyl and cyclohexyl methacrylate, cyclohexyl acrylate and or a mixture thereof.
  • Most preferred C 1 to C 6 alkyl (meth)acrylate monomer is methyl methacrylate, butyl methacrylate or a mixture thereof.
  • Examples of the C 7 to C 15 alkyl (meth)acrylate monomers include (meth)acrylates that derive from saturated alcohols, such as nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, n-dodecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, pentadecyl (meth)acrylate; (meth)acrylates which derive from unsaturated alcohols, for example oleyl (meth)acrylate; cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate having a ring substituent, like tert-butyl
  • Examples of the C 16 to C 30 alkyl (meth)acrylate monomers include (meth)acrylates which derive from saturated alcohols, such as hexadecyl (meth)acrylate, 2-methylhexadecyl (meth)acrylate, heptadecyl (meth)acrylate, 5-isopropylheptadecyl (meth)acrylate, 4-tert-butyloctadecyl (meth)acrylate, 5-ethyloctadecyl (meth)acrylate, 3-isopropyloctadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, cetyleicosyl (meth)acrylate, stearyleicosyl (meth)acrylate, docosyl (meth)acrylate, behenyl (meth)acrylate and/or eicosylt
  • the alkyl (meth)acrylate of general Formula (I) is isodecyl methacrylate.
  • the grafting monomer composition of the ethylene graft polyalkyl(meth)acrylate A) consists of alkyl (meth)acrylates of general Formula (I) and hydroxy esters of general Formula (II). Even more preferably, the grafting monomer composition of the ethylene graft polyalkyl(meth)acrylate A) consists of 2-hydroxethyl methacrylate and isodecyl methacrylate.
  • the polymeric additive b) further comprises a solvent.
  • the solvent is selected from hydrocarbon solvents, mineral oils, diesel fuels of mineral origin, naphthenic solvents, natural vegetable and animal oils, biodiesel fuels, esters, higher alcohols, polyfunctional ether-alcohols or a mixture thereof. More preferably, the hydrocarbon solvents are selected from toluene, benzene and xylene, cyclohexane, heptane, octane, nonane, decane, dodecane, or a mixture thereof. Particularly preferred solvents are isodecanol and diethylene glycol.
  • the polymeric additive b) comprises 0 to 90 % by weight, more preferably 10 to 90 % by weight, even more preferably 20 to 80 % by weight, of a solvent, based on the total amount of the polymeric additive b).
  • the polymers for use in the polymeric additive b) can be obtained by free-radical polymerization and related processes, for example ATRP (Atom Transfer Radical Polymerization), RAFT (Reversible Addition Fragmentation Chain Transfer) or NMP processes (nitroxide-mediated polymerization). More preferably, the polymers in the polymeric additive b) of the invention are prepared by free-radical polymerization.
  • a polymerization initiator is used for this purpose.
  • the usable initiators include the azo initiators widely known in the technical field, such as 2,2'-azo-bis-isobutyronitrile (AIBN), 2,2'-azo-bis-(2-methylbutyronitrile) (AMBN) and 1,1-azobiscyclohexanecarbonitrile, and also peroxy compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide, cyclohe
  • AIBN 2,2'-azo-bis-isobutyronitrile
  • AMBN 2,2'-azo-bis-
  • a chain transfer agent can be used. It is well-known in the art that a good way to control the molecular weight of a polymer chain is to use chain transfer agents during the polymerization synthesis. Chain transfer agents are molecules with a weak chemical bond which facilities the chain transfer reaction. During the chain transfer reaction, the radical of the polymer chain abstracts a hydrogen from the chain transfer agent, resulting in the formation of a new radical on the sulfur atom of the chain transfer agent capable of further propagation.
  • Common chain transfer agents are organic compounds comprising SH groups such as n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, butylthiol glycolate, and octylthiol glycolate.
  • a preferred chain transfer agent is selected from n-dodecyl mercaptan, tert-dodecyl mercaptan or a mixture thereof, most preferably n-dodecyl mercaptan.
  • the monomer mixture to prepare the polymer of the present invention may comprise 0.05 to 7 % by weight, preferably 0.05 to 5 % by weight and more preferably 0.1 to 1 % by weight of initiator based on the total weight of the monomer composition to prepare the polymer.
  • the amount of chain transfer agents to prepare the polymer is in the range of 0 to 5% by weight, preferably 0.01 to 5 % by weight and more preferably 0.05 to 4 % by weight, based on the total weight of the monomer composition.
  • the polymerization may be carried out at standard pressure, reduced pressure or elevated pressure.
  • the polymerization temperature is not critical. Conventionally the polymerization temperature may be in the range of 0 °C to 200 °C, preferably 0 °C to 140 °C, and more preferably 60 °C to 130 °C.
  • the polymerization may be carried out with or without solvent, preferably in a solvent.
  • the solvent is selected from hydrocarbon solvents, mineral oils, diesel fuels of mineral origin, naphthenic solvents, natural vegetable and animal oils, biodiesel fuels, esters, higher alcohols, polyfunctional ether-alcohols or a mixture thereof.
  • the hydrocarbon solvents are selected from toluene, benzene and xylene, cyclohexane, heptane, octane, nonane, decane, dodecane, or a mixture thereof.
  • Particularly preferred solvents are isodecanol and diethylene glycol.
  • the composition comprises polymeric additive b) at a concentration of 0.001 % by weight to 1 % by weight of polymeric additive b), based on the total weight of the pyrolysis oil composition. More preferably, the composition comprises polymeric additive b) at a concentration of 0.005 % by weight to 0.8 % by weight of polymeric additive b), based on the total weight of the pyrolysis oil composition. Even more preferably, the composition comprises polymeric additive b) at a concentration of 0.005 % by weight to 0.5 % by weight of polymeric additive b), based on the total weight of the pyrolysis oil composition.
  • the plastic pyrolysis oil a) is a polyolefin pyrolysis oil, wherein the pyrolysis oil is produced at least partially from the pyrolysis of one or more polyolefins.
  • the pyrolysis oil a polyethylene and/or polypropylene pyrolysis oil, wherein the pyrolysis oil is produced at least partially from the pyrolysis of polyethylene and/or polypropylene.
  • the plastic pyrolysis oil a) comprises 30 % by weight or less, more preferably 20 % by weight or less, even more preferably 15 % by weight or less, even more preferably 12 % by weight or less, most preferably 10 % by weight or less, of n-paraffin waxes with C 16 or longer carbon chains, based on the total weight of the plastic pyrolysis oil a).
  • the plastic pyrolysis oil a) comprises from 0.01 % to 30 % by weight, more preferably from 0.01 % to 20 % by weight, even more preferably from 0.01 % to 15 % by weight, even more preferably from 0.01 % to 12 % by weight, most preferably from 0.05 % to 10 % by weight, of n-paraffin waxes with C 16 or longer carbon chains, based on the total weight of the plastic pyrolysis oil a).
  • the plastic pyrolysis oil a) preferably comprises from 0 % to 30 % by weight of C 16 to C 19 n-paraffin waxes, from 0 % to 30 % by weight of C 20 to C 29 n-paraffin waxes, from 0 % to 30 % by weight of C 30 to C 39 n-paraffin waxes, and from 0 % to 30 % of n-paraffin waxes with C 40 or longer carbon chains, wherein the total wax content of n-paraffin waxes with C 16 or longer carbon chains sums up from 0.01 % by weight to 30 % by weight, based on the total weight of the plastic pyrolysis oil.
  • the plastic pyrolysis oil a) preferably comprises from 0 % to 20 % by weight of C 16 to C 19 n-paraffin waxes, from 0 % to 20 % by weight of C 20 to C 29 n-paraffin waxes, from 0 % to 20 % by weight of C 30 to C 39 n-paraffin waxes, and from 0 % to 20 % of n-paraffin waxes with C 40 or longer carbon chains, wherein the total wax content of n-paraffin waxes with C 16 or longer carbon chains sums up from 0.01 % by weight to 20 % by weight, based on the total weight of the plastic pyrolysis oil.
  • the plastic pyrolysis oil a) preferably comprises from 0 % to 15 % of C 16 to C 19 n-paraffin waxes, from 0 % to 15 % of C 20 to C 29 n-paraffin waxes, from 0 % to 15 % of C 30 to C 39 n-paraffin waxes, and from 0 % to 15 % of n-paraffin waxes with C 40 or longer carbon chains, wherein the total wax content of n-paraffin waxes with C 16 or longer carbon chains sums up from 0.01 % by weight to 15 % by weight, based on the total weight of the plastic pyrolysis oil.
  • the plastic pyrolysis oil a) preferably comprises from 0 % to 12% of C 16 to C 19 n-paraffin waxes, from 0 % to 12 % of C 20 to C 29 n-paraffin waxes, from 0 % to 12 % of C 30 to C 39 n-paraffin waxes, and from 0 % to 12 % of n-paraffin waxes with C 40 or longer carbon chains, wherein the total wax content of n-paraffin waxes with C 16 or longer carbon chains sums up from 0.01 % by weight to 12 % by weight, based on the total weight of the plastic pyrolysis oil.
  • the plastic pyrolysis oil a) preferably comprises from 0 % to 10 % of C 16 to C 19 n-paraffin waxes, from 0 % to 10 % of C 20 to C 29 n-paraffin waxes, from 0 % to 10 % of C 30 to C 39 n-paraffin waxes, and from 0 % to 10 % of n-paraffin waxes with C 40 or longer carbon chains, wherein the total wax content of n-paraffin waxes with C 16 or longer carbon chains sums up from 0.01 % by weight to 10 % by weight, based on the total weight of the plastic pyrolysis oil.
  • plastic pyrolysis oil a) and polymeric additive b) sum up from 90 to 98 % by weight, based on the total weight of the composition.
  • composition according to the invention may further comprise an additive c), wherein the additive c) is any of the group comprising scale inhibitors, corrosion inhibitors, oxygen scavengers, biocides, emulsion breakers, antifoam agents, drag reducing agents, hydrate inhibitors, paraffin dispersants, asphaltene control agents, a pour point depressant other than polymers A) and B), or a mixture thereof.
  • the additive c) is any of the group comprising scale inhibitors, corrosion inhibitors, oxygen scavengers, biocides, emulsion breakers, antifoam agents, drag reducing agents, hydrate inhibitors, paraffin dispersants, asphaltene control agents, a pour point depressant other than polymers A) and B), or a mixture thereof.
  • the amounts of compounds a), b), c) sum up to 90 to 99 % by weight, more preferably sum up to 95 to 98 % by weight, even more preferably sum up to 100 % by weight, based on the total weight of the composition.
  • the invention also provides a method of manufacturing a composition as described above, comprising the steps of:
  • the method for preparing the plastic pyrolysis oil composition according to the invention preferably comprises the step of mixing the pyrolysis oil and the polymeric additive. More preferably, the method comprises the step of mixing for at least 5, 10, 15, 25 or 30 minutes.
  • the method may also comprise a step of heating the pyrolysis oil and the polymeric additive, preferably to at least 40 °C, even more preferably to at least 50 °C, most preferably to at least 60 °C.
  • the method may comprise heating and mixing the pyrolysis oil simultaneously.
  • the method of the present invention is able to reduce the pour point of the pyrolysis oil by at least, or to reduce the viscosity of the pyrolysis oil, or to achieve both, by the addition of the polymeric additive b).
  • the resulting pyrolysis oil is thereby easier to transport and store compared to the pyrolysis oil with no polymeric additive.
  • no modifications to plant design are required to provide a pyrolysis oil having a reduced pour point or viscosity, as this can be achieved by adding the polymeric additive of the present invention after the pyrolysis oil is made.
  • the method comprises the step of providing a plastic feedstock comprising one or more polyolefins and producing the pyrolysis oil at least partially from said feedstock.
  • the polyolefins may be polyethylene and/or polypropylene.
  • the present invention also extends to the use of a polymeric additive as defined herein to reduce the pour point of a plastic pyrolysis oil or to reduce the viscosity of the pyrolysis oil, or both.
  • the pour point of a pyrolysis oil is reduced by at least 1 °C, more preferably by at least 2 °C, even more preferably by at least 3 °C, most preferably by at least 5 °C, by the addition of the polymeric additive as described herein, when compared to the same pyrolysis oil with no polymeric additive.
  • the reduction in viscosity is preferably of at least 10, preferably 20 or 30, even more preferably 40, 50, or 60 % or more, at a temperature from -20° C to +80 °C, preferably from -10° C to +50 °C, when the polymeric additive is added to the pyrolysis oil with a wax residue as described herein, when compared to the same pyrolysis oil with no polymeric additive.
  • the composition according to the invention has a lower pour point and viscosity in comparison to untreated pyrolysis oils.
  • Pyrolysis oils usually solidify making them difficult to transport.
  • pyrolysis oils with lower pour point will remain liquid at lower temperatures, thus making them easier to transport and heat does not need to be applied to the composition before transportation and storage.
  • the present invention also extends to a method for transporting or storing a plastic pyrolysis oil a) comprising the step of adding a polymeric additive b) to the pyrolysis oil a) to form the composition described herein.
  • the plastic pyrolysis oil a) comprises 30 % by weight or less, more preferably 20 % by weight or less, even more preferably 15 % by weight or less, even more preferably 12 % by weight or less, most preferably 10 % by weight or less, of n-paraffin waxes with C 16 or longer carbon chains, based on the total weight of the plastic pyrolysis oil a).
  • the plastic pyrolysis oil a) comprises from 0.01 % to 30 % by weight, more preferably from 0.01 % to 20 % by weight, even more preferably from 0.01 % to 15 % by weight, even more preferably from 0.01 % to 12 % by weight, most preferably from 0.05 % to 10 % by weight, of n-paraffin waxes with C16 or longer carbon chains, based on the total weight of the plastic pyrolysis oil a).
  • the manufacturer or user of the pyrolysis oil can maintain current transportation or storage conditions of wax residue pyrolysis oils (preferably of 30 % by weight or less, more preferably of 20 % by weight or less, more preferably of 15 % by weight or less, more preferably of 12 % by weight or less, most preferably of 10 % by weight or less, of n-paraffin waxes with C 16 or longer carbon chains, based on the total weight of the plastic pyrolysis oil), by using their existing plant design, or possibly lower the transportation or storage conditions of high or higher wax residue pyrolysis oils using existing plant design, i.e. reduced OPEX.
  • the present invention provides a method for transporting or storing a plastic pyrolysis oil a) in liquid form at a temperature in the range -20 °C to +50 °C.
  • the weight-average molecular weights (M w ) and the number-average molecular weights (M n ) of the EVA (polymer B)) and graft base polymer (Polymer A1) are determined by gel permeation chromatography (GPC) using poly(methyl-methacrylate) calibration standards according to DIN 55672-1 using the following measurement conditions: Column: the column set consists of a precolumn and 5 SDV columns as disclosed in Table 1: Table 1 No.
  • SDV 10 ⁇ 8 X50 mm Column 1 SDV LXL 10 ⁇ 8 X 300 mm Column 2 SDV LinL 10 ⁇ 8 X 300 mm Column 3 SDV 100 ⁇ 10 ⁇ 8 X 300 mm Column 4 SDV 100 ⁇ 10 ⁇ 8 X 300 mm Column 5 KF-800D 8 X 100 mm Instruments: Agilent 1100 Series Pump; PSS SECcurity Inline-Degaser; Agilent 1260 Series Autosampler; Agilent 1100 Series RI-Detector; Agilent 1260 Series UV-Detector; Techlab column oven; Oven temperature: 35 °C; Standards: poly(methyl-methacrylate) (so called PMMA) calibration standards; Eluent: tetrahydrofuran (THF); Flow rate: 1 mL/min; Injected volume: 100 ⁇ L; Detection: RI at a temperature of 35 °C and UV at a wavelength of 239 nm.
  • THF poly(methyl-methacrylate)
  • Viscosity was measured using a Discovery HR20 TA instruments rheometer, using a 2° cone and Peltier plate geometry. The shear rate was 10x1/s (or s -1 ). The temperature ramp was 1°C per minute.
  • the flow properties of pyrolysis oil compositions were evaluated by measuring the pour point and by evaluating wax deposition using the cold finger test.
  • Wax content was measured using a Differential Scanning Calorimeter from TA Instruments and analysis via TRIOS software.
  • pour points were measured according to ASTM D97 in 1 °C steps. The test involves cooling the pyrolysis oil composition at a defined cooling rate and measuring the temperature at which the composition can no longer be poured from a vessel.
  • the cold finger test in the present invention was conducted to monitor the wax deposition from a pyrolysis oil, by simulating production conditions.
  • the temperature of the pyrolysis oil composition is higher than the wax appearance temperature (WAT) and the finger temperature is lower than the wax appearance temperature.
  • the cold finger method involves submerging a probe (i.e. the finger) having a certain surface temperature in a pyrolysis oil composition having a defined temperature and determining the amount of wax that is formed on the surface of the finger.
  • the wax appearance temperature of a given pyrolysis oil composition is determined prior to the cold finger test by determining the onset of crystallization by differential scanning calorimetry or similar methods that monitor crystallization.
  • the wax inhibition tests were measured using the CF-15 cold finger device from PSL device with rack temperature set at 64 °C (5 °C above the WAT of an untreated pyrolysis oil, e.g. the Pyrolysis Oil A of Table 4) and finger temperature set at 39 °C (20 °C below the WAT of an untreated pyrolysis oil, e.g. the Pyrolysis Oil A of Table 4) for a test period of 24 hours.
  • the percentage of wax inhibition is determined by determining the weight of the wax collected on the finger when the pyrolysis oil composition is treated with a paraffin inhibitor compared to the same experiment where no paraffin inhibitor is added.
  • the degree of wax inhibition is calculated according to the following equation (1): ([mass of wax measured after x hours in the untreated pyrolysis oil composition] - [mass of wax measured after x hours in the treated pyrolysis oil composition]) / [mass of wax measured after x hours in the untreated pyrolysis oil] x 100%
  • a high degree of wax inhibition calculated according to equation (1) indicates that less wax deposition occurs in the treated pyrolysis oil composition.
  • Table 2 shows the EVA used in the preparation of the polymeric additives.
  • Table 2 Ethylene-vinyl acetate polymers VA content Melt Flow Index M w M n EVA grade [wt%] [kg/mol] [ kg/mol] EVA 12-008 12 008 280 45.1 EVA 18-150 18 150 384 31.5 EVA 28-025 28 25 193 44.5 EVA 33-025 33 25 139 45.9 EVA 28-005 28 5 160 49.7 EVA 28-150 28 150 95 33.7 EVA 33-400 33 400 79 27.3
  • Table 3 shows the composition of some polymeric additives P1 to P5 according to the invention, as well as some comparative polymeric additives P6 to P8.
  • the first step is the synthesis of the EVA-g-PAMA emulsifier.
  • 10 g EVA 18-150 were dissolved in 50 g of isodecanol at 100°C.
  • the solution was cooled down to 90°C and 6.67 g of a monomer mixture of 2-hydroxyethyl methacrylate (HEMA) and isodecyl methacrylate (IDMA) in a ratio of 1:3 and 0.21 g tert-butylper-2-ethylhexanoate were added to the heel.
  • HEMA 2-hydroxyethyl methacrylate
  • IDMA isodecyl methacrylate
  • 33.3 g of the same monomer mixture containing 0.33 g tert-butylper-2-ethylhexanoate were fed into the reaction heel over 210 minutes.
  • the dispersion was created. 16.98 g of the EVA-g-PAMA polymer were added to a mixing vessel, heated to 90°C, and stirred at 200 rpm. As liquid carrier medium C) or solvent, 31.2 g of isodecanol and 21.4 g diethylene glycol were added to the mixing vessel. Finally, 30.4 g EVA 28-025 were charged to vessel and mixed for 5 hours. A milky, white, stable dispersion with a solid content of 38.8wt% was obtained.
  • Table 4 shows the characteristics of some untreated pyrolysis oils, wherein the pyrolysis oils A, B, D and H are polyolefin pyrolysis oils produced from the pyrolysis of polyolefins which include high-density polyethylene, low-density polyethylene and polypropylene.
  • Table 4 Characteristics of untreated plastic pyrolysis oil (namely, before addition of a polymeric additive of the present invention or a comparative polymeric additive) Property Pyrolysis Oil A Pyrolysis Oil B Pyrolysis Oil D Pyrolysis Oil H Pour Point [°C] 51 0 18 -2 Wax Appearance Temperature [°C] 59 48 55 1 Wax Disappearance Temperatu [°C] 71 53 65 10 C 12 -C 15 n-hydrocarbons [wt%] 12.2 0.4 0.8 3.5 C 16 -C 19 n-paraffins [wt%] 1.6 0.9 1.5 2 C 20 -C 29 n-paraffins [wt%] 9.1 0.4 2 3.6 C 30 -C 39 n-paraffins [wt%] 3.6 0.2 3.7 0 >C 39 n-paraffins [wt%] 0.5 0 2.2 0 Total C 16 or greater n-paraffins [wt%] 14.8 1.5 9.4 5.6
  • Example 1 Example 10, Example 19, and Example 27 below correspond to untreated pyrolysis oils before the addition of any polymeric additive b) (Reference examples).
  • Example 2 was prepared by adding 0.1 g of the polymeric additive P1 to 99.9 g of Pyrolysis Oil A. The two components were mixed using an overhead stirred for 30minutes while being heated on a hot plate set to 65°C. Examples 3 to 6, 11 to 18, 20-26, and 28-33 were prepared in the same way as example 2, except that the components and amounts thereof were adjusted according to Table 5, 6, 7 and 8 below.
  • Table 5 Pyrolysis oil compositions according to invention and comparative compositions and pour points and viscosity measurements of said pyrolysis oil compositions in comparison with an untreated pyrolysis oil
  • Table 6 Pyrolysis oil compositions
  • Tables 5, 6, 7 and 8 show that treating a pyrolysis oil with the polymeric additives of the present invention improves the cold temperature performance in comparison to the same untreated pyrolysis oil.
  • Figure 1 is a graph showing the viscosity of pyrolysis oil a) and a composition comprising pyrolysis oil a) with a polymeric additive b) over a temperature range of 40 to 80 °C.
  • the reference number 1 on Figure 1 corresponds to the curve of the untreated pyrolysis oil (Example 1 of Table 5 above), whereas the reference number 2 on Figure 1 corresponds to the curve of the pyrolysis oil composition of inventive example 2 according to Table 5 above.
  • the viscosity plots in Figure 1 show that the polymeric additive lowers the viscosity of the products compared to the untreated pyrolysis oil across a wide temperature range.
  • the untreated pyrolysis oil had a viscosity of approximately 925 cP.
  • the pyrolysis oil including 0.1% by weight of polymeric additive 1 had a viscosity of approximately 13 cP.
  • the untreated pyrolysis oil had a viscosity of approximately 595 cP.
  • the pyrolysis oil including 0.1% by weight of polymeric additive 1 had a viscosity of approximately 6 cP.
  • the untreated pyrolysis oil had a viscosity of approximately 254 cP.
  • the pyrolysis oil including 0.1% by weight of polymeric additive 1 had a viscosity of approximately 4 cP.
  • the untreated pyrolysis oil had a viscosity of approximately 34 cP.
  • the pyrolysis oil including 0.1% by weight of polymeric additive 1 had a viscosity of approximately 3 cP.
  • compositions comprising a pyrolysis oil and treated with a polymeric additive as defined in claim 1 have a much lower viscosity compared to the untreated pyrolysis oil.
  • the polymeric additives of Table 5 drastically reduce the viscosity of the pyrolysis oil, and in some instances by up to 98% at 40-55 °C. These reductions in viscosity of the pyrolysis oils are a great improvement for transporting and pumping the pyrolysis oils.
  • the untreated pyrolysis oils need to be heated in order to be pumped for the transportation, whereas the compositions comprising the pyrolysis oils treated with a polymeric additive according to the invention do not need to be heated anymore and can be directly pumped for transportation.
  • Examples 3 to 6 in Table 5 further demonstrate how compositions comprising pyrolysis oil and treated with a polymeric additive b) as defined in claim 1 achieve a reduction in pour point and viscosity when added to Pyrolysis Oil A. Compared to the untreated oil (Example 1), Examples 3 to 6 achieve a 6 to 12°C reduction in pour point and 22 to 77 % reduction in viscosity. In comparison, the comparative examples 7 to 9 in Table 5 only achieve a 3 °C reduction in pour point and viscosity is undesirably increased by 14 to 41 %.
  • Examples 11 to 15 achieve a reduction in pour point and viscosity when added to Pyrolysis Oil B. Compared to the untreated oil (Example 10), Examples 11 to 15 achieve a 18 to 48 °C reduction in pour point and 7 to 49% reduction in viscosity. In comparison, the comparative examples 16 to 18 in Table 6 only achieve a 12 to 15 °C reduction in pour point and viscosity is undesirably increased by 3 to 41 %.
  • Examples 20 to 23 achieve a reduction in pour point added to Pyrolysis Oil D. Compared to the untreated oil (Example 19), Examples 20 to 23 achieve a 6-9 °C reduction in pour point. In comparison, the comparative examples 24 to 26 in Table 7 cause in increase in pour point of 6-9°C.
  • Examples 28 to 31 achieve a reduction in pour point added to Pyrolysis Oil H. Compared to the untreated oil (Example 27), Examples 28 to 31 achieve a 7 to 10 °C reduction in pour point. In comparison, the comparative examples 32 and 33 in Table 7 do not change the pour point compared to the untreated pyrolysis oil.
  • compositions comprising pyrolysis oil and treated with a polymeric additive b) as defined in claim 1 show improved cold flow improvement, reduced pour point, and reduced viscosity.

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Claims (15)

  1. Composition comprenant une huile de pyrolyse de plastique a) et un additif polymérique b), dans laquelle l'additif polymérique b) est un poly((méth)acrylate d'alkyle) greffé avec de l'éthylène A) pouvant être obtenu par greffage sur un copolymère à base d'éthylène A1), pouvant être obtenu par polymérisation d'une composition de monomères constituée d'éthylène et d'un composé choisi dans le groupe constitué des esters vinyliques, des acrylates, des méthacrylates, des alpha-oléfines ou d'un mélange de ceux-ci, par rapport au poids total du copolymère à base d'éthylène A1),
    une composition de monomères de greffage comprenant des (méth)acrylates d'alkyle A2) de formule générale (I)
    dans laquelle
    R est H ou CH3 et
    R1 est un groupe alkyle linéaire ou ramifié, saturé ou insaturé de 1 à 30 atomes de carbone, de préférence de 7 à 15 atomes de carbone.
  2. Composition selon la revendication 1, dans laquelle la composition de monomères du copolymère à base d'éthylène A1) est constituée
    de 55 % à 90 % en poids, de préférence de 60 % à 85 % en poids, plus préférablement de 67 % à 82 % en poids d'éthylène, et
    de 10 % à 45 % en poids, de préférence de 15 % à 40 % en poids, plus préférablement de 18 % à 33 % en poids, d'un composé choisi dans le groupe constitué des esters vinyliques, des acrylates, des méthacrylates et des alpha-oléfines ou d'un mélange de ceux-ci,
    par rapport au poids total de la composition de monomères pour préparer le copolymère à base d'éthylène A1).
  3. Composition selon la revendication 1 ou 2, dans laquelle le copolymère à base d'éthylène A1) est constitué d'éthylène et d'acétate de vinyle.
  4. Composition selon l'une quelconque des revendications précédentes, dans laquelle le rapport en poids du copolymère à base d'éthylène A1) sur la composition de greffage de monomères A2) pour préparer le poly(méth)acrylate d'alkyle greffé avec de l'éthylène P) est de 1:1 à 1:10, préférablement de 1:1 à 1:8, plus préférablement de 1:1 à 1:6.
  5. Composition selon l'une quelconque des revendications précédentes, dans laquelle l'additif polymérique b) comprend en outre un copolymère à base d'éthylène B) pouvant être obtenu par polymérisation d'une composition de monomères constituée d'éthylène et d'un ester vinylique.
  6. Composition selon l'une quelconque des revendications précédentes, dans laquelle le copolymère à base d'éthylène A1) et/ou le copolymère à base d'éthylène B) a un poids moléculaire moyen en poids de 20 000 à 1 000 000 g/mole, de préférence de 45 000 à 500 000 g/mole, plus préférablement de 60 000 à 400 000 g/mole, déterminé par chromatographie à perméation de gel en utilisant des références d'étalonnage de poly(méthacrylate de méthyle) selon la norme DIN 55672-1.
  7. Composition selon la revendication 6, dans laquelle l'additif polymérique b) comprend un poly(méth)acrylate d'alkyle greffé avec de l'éthylène A) et un copolymère à base d'éthylène B), et dans laquelle le poly(méth)acrylate d'alkyle greffé avec de l'éthylène A) est présent de 5 à 40 % en poids et le copolymère à base d'éthylène B) est présent de 60 à 95 % en poids, par rapport à la quantité totale de l'additif polymérique b).
  8. Composition selon l'une quelconque des revendications précédentes, dans laquelle la composition de monomères de greffage A2) pour préparer le poly(méth)acrylate d'alkyle greffé avec de l'éthylène A) comprend en outre des esters hydroxylés de formule générale (II) dans laquelle
    R est H ou CH3 et
    A est un groupe à base de carbone en C1 à C4 aliphatique, ramifié ou non ramifié.
  9. Composition selon l'une quelconque des revendications précédentes, la composition comprenant de 0,001 à 1 % en poids, de préférence de 0,005 à 0,8 % en poids, plus préférablement de 0,005 à 0,5 % en poids de l'additif polymérique b), par rapport au poids total de la composition.
  10. Composition selon l'une quelconque des revendications précédentes, dans laquelle l'huile de pyrolyse de plastique a) est une huile de pyrolyse de plastique et/ou une huile de pyrolyse de déchets plastiques, dans laquelle le plastique et les déchets plastiques sont choisis parmi des polyoléfines, un poly(téréphtalate d'éthylène), un poly(chlorure de vinyle), un polystyrène ou un mélange de ceux-ci.
  11. Composition selon l'une quelconque des revendications précédentes, dans laquelle l'huile de pyrolyse de plastique a) comprend 30 % en poids ou moins, de préférence 20 % en poids ou moins, plus préférablement 15 % en poids ou moins, encore plus préférablement 12 % en poids ou moins, de cires de n-paraffine comportant des chaînes de carbone au C16 ou plus longues, par rapport au poids total de l'huile de pyrolyse de plastique a).
  12. Composition selon l'une quelconque des revendications précédentes, dans laquelle la composition comprend en outre un additif c), dans laquelle l'additif c) est l'un quelconque du groupe comprenant les inhibiteurs d'incrustations, les inhibiteurs de corrosion, les agents de piégeage d'oxygène, les biocides, les brise-émulsions, les agents antimousse, les agents de réduction de la traînée, les inhibiteurs d'hydrates, les dispersants de paraffine, les agents de régulation des asphaltènes, un agent d'abaissement du point d'écoulement différent des polymères A) et B), ou un de leurs mélanges.
  13. Procédé pour la fabrication d'une composition telle que définie dans l'une quelconque des revendications 1 à 12 comprenant une huile de pyrolyse a) et un additif polymérique b), comprenant les étapes de :
    fourniture d'une matière première de plastique ;
    pyrolyse de la matière première de plastique pour générer l'huile de pyrolyse de plastique a) ;
    préparation de l'additif polymérique b) et
    ajout de l'additif polymérique b) dans l'huile de pyrolyse de plastique a).
  14. Utilisation d'un additif polymérique b) tel que défini dans l'une quelconque des revendications 1 à 12 pour réduire le point d'écoulement d'une huile de pyrolyse de plastique a) ou pour réduire la viscosité de l'huile de pyrolyse, ou les deux.
  15. Procédé de transport et/ou de stockage d'une huile de pyrolyse de plastique a) comprenant l'étape d'ajout d'un additif polymérique b) à l'huile de pyrolyse pour former une composition telle que définie dans l'une quelconque des revendications 1 à 12.
EP24827749.3A 2023-12-21 2024-12-13 Huile de pyrolyse à point d'écoulement réduit Active EP4599031B1 (fr)

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EP23219218 2023-12-21
PCT/EP2024/086140 WO2025132055A1 (fr) 2023-12-21 2024-12-13 Huile de pyrolyse à point d'écoulement réduit

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KR100994244B1 (ko) 2008-04-25 2010-11-12 서울시립대학교 산학협력단 열분해 공정에서 생산되는 왁스 제거용 충격분리 장치
US9200207B2 (en) 2011-05-31 2015-12-01 University Of Central Florida Research Foundation, Inc. Methods of producing liquid hydrocarbon fuels from solid plastic wastes
US10604715B2 (en) * 2013-02-04 2020-03-31 Evonik Operations Gmbh Cold flow improver with broad applicability in mineral diesel, biodiesel and blends thereof
KR20230066548A (ko) 2020-09-14 2023-05-16 에코랍 유에스에이 인코퍼레이티드 플라스틱-유도 합성 공급원료를 위한 저온 흐름 첨가제
WO2023083941A1 (fr) * 2021-11-15 2023-05-19 Evonik Operations Gmbh Dispersions à base d'acétate de vinyle-éthylène appropriées en tant qu'améliorants de point d'écoulement présentant une performance et une stabilité améliorées

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