Pyrolysis oil having reduced pour point and / or viscosity

Abstract

The present invention relates to a composition comprising pyrolysis oil and a polymer additive for reducing the pour point, the viscosity, or both the pour point and the viscosity of the pyrolysis oil. The present invention further relates to a method of manufacturing said composition, the use of a polymer additive for reducing the pour point, the viscosity, or both the pour point and the viscosity of the pyrolysis oil. The present invention further relates to a method of transporting or storing pyrolysis oil.

Description

Technical Field

[0001] This invention relates to compositions comprising pyrolysis oil and polymeric additives for reducing the pour point, viscosity, or both of the pyrolysis oil. The invention further relates to methods of manufacturing said compositions, and the use of the polymeric additives for reducing the pour point, viscosity, or both of the pyrolysis oil. The invention further relates to methods of transporting or storing pyrolysis oil. Background Technology

[0002] Plastic production continues to grow rapidly, and plastic products remain a significant part of our lives due to the material's versatility and the low costs associated with its production. It is estimated that 250 million tons of plastic end up in landfills or dispersed into the environment each year. Plastic use is also projected to continue increasing in the future. This increase in plastic production will also be linked to an increase in associated plastic waste, particularly from single-use plastic products. The increase in plastic waste has also sparked interest in how to effectively recycle or convert plastic waste back into usable materials.

[0003] One effective way to manage plastic waste is through thermochemical conversion via pyrolysis. Pyrolysis is a thermal decomposition process that occurs at temperatures above 400°C in the absence of oxygen. This process breaks down polymer chains into smaller chains and molecules. Therefore, pyrolysis can transform plastic waste materials into usable products, thereby addressing the issue of plastic waste management. While there are many types of plastics, most plastic waste is made from low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), and polyethylene terephthalate (PET). Of these plastics, polyethylene and polypropylene constitute the largest portion of plastic waste. Pyrolysis provides a final product known in the art as “pyrolysis oil.” The main products generated from the pyrolysis of plastics include liquid oil, wax, solid residues, and gases. All these residues are then further processed as part of a steam cracker used in existing plastic processing plants or oil refineries.

[0004] In pyrolysis processes, the conversion of plastics into usable materials (such as oils, gases, and waxes) depends on several factors. The most influential factors are reactor design, process temperature, type of plastic used, and type of catalyst.

[0005] Wax residues comprise those pyrolysis products with alkyl chains having 16 or more carbon atoms. Wax residues are valuable products of the pyrolysis process. The amount of wax residue produced can significantly influence the properties of the final pyrolysis oil. The primary driver of the amount of wax residue produced is the plastic feedstock introduced into the pyrolysis process. For example, olefin plastics such as polyethylene and polypropylene are more linear polymers, and therefore decompose into waxy linear alkyl chains during the pyrolysis process. Depending on the specific pyrolysis oil process conditions, pyrolysis oil produced from polyethylene and polypropylene can generate more than 50% by weight of wax residue.

[0006] Specific process conditions, including catalyst type, can also affect the oil / wax ratio. Certain catalysts can be used to obtain a lower wax residue content in the final product. Furthermore, conditions such as residence time in the reactor can also have an effect. For example, “rapid” pyrolysis results in a mixture of waxy hydrocarbons, while “slow” pyrolysis typically produces more oil than wax (Materials 2021, 14, 2586).

[0007] However, waxy chains can also cause various transportation and storage problems. As pyrolysis oil cools to ambient temperature after the pyrolysis process, waxy chains with 12 or more carbon atoms may begin to crystallize. Pyrolysis oils often also contain a significant amount of alkanes with waxy chains of 16 to more than 40 carbon atoms. These wax chains are the most problematic because they have much higher melting points. Wax crystals can then accumulate and cause an increase in viscosity, making the thicker oil more difficult to pump or move. If sufficient wax residue is present in pyrolysis oil, especially in polyolefin pyrolysis oils, wax crystals can cause the entire product to solidify at lower temperatures close to ambient temperature. Once solidified, expensive heating must be used to melt the product in order to move or process it further. Wax crystals can also clog equipment such as filters and pipes, thereby increasing maintenance costs. Finally, high wax levels can cause paraffin deposits on pipes in the production line. As wax accumulates, the efficiency and lifespan of the equipment are reduced.

[0008] Nevertheless, wax is a valuable pyrolysis product, and existing plastics processing plants have been designed and built to utilize wax residues. However, wax residues produced during pyrolysis, especially those from increasingly used olefin feedstocks, are making the transportation and storage of pyrolysis oils more difficult and expensive.

[0009] As mentioned earlier, the amount of wax residue varies depending on the plastic raw materials used and the specific process conditions. Furthermore, polyolefin-based pyrolysis oils produced through current or standard pyrolysis processes tend to produce the largest amounts of wax, thus posing the most problems, especially under environmental conditions. The "pour point" is the lowest temperature at which a pyrolysis oil will still flow, and pyrolysis oils with high wax residues have relatively high pour points (e.g., above 50°C), typically higher than standard operating conditions and storage temperatures. This makes such pyrolysis oils difficult to process, as they may solidify and become untransportable. Heat is typically applied to the oil to liquefy it for storage and transport. This consumes thermal energy and takes time. Therefore, even a slight decrease in the pour point can significantly reduce the amount of thermal energy consumed and the time spent liquefying or maintaining the pyrolysis oil in liquid form for transport and storage.

[0010] One solution for lowering the pour point of pyrolysis oil is to modify process conditions or catalyst type to produce pyrolysis oil with a lower pour point. However, this requires expensive catalysts, longer process runs, or specialized reactors. Increasing process time or modifying the reactor also increases costs or reduces overall efficiency. Furthermore, valuable wax products are no longer produced in the same quantities and are therefore unavailable for subsequent processing as intended for the desired wax products. Other solutions have been implemented to separate the wax by introducing a dewaxing step and reprocessing the oil to break it down into smaller molecules. However, these solutions also increase costs and reduce the efficiency of the method.

[0011] US2012 / 0310023A1 discloses that the oil obtained from the pyrolysis of polyolefins containing plastic mixtures is often a waxy semi-solid product, and that the use of certain catalysts can lead to the production of lighter and less waxy products.

[0012] Lee et al., in Journal of Analytical and Applied Pyrolysis 94 (2012) 209–214, explained that a large portion of plastic waste composed of polyethylene is converted into waxy oils. Waxy oils can be problematic, as they can cause plant operation disruptions, ranging from pipe blockages to shorter instrument lifespans. Therefore, there is a need to upgrade pyrolysis technologies to produce high-quality oils. The authors demonstrated the effectiveness of zeolite catalysts in the catalytic upgrade of the pyrolysis process.

[0013] Hakeem et al. described the problem of high wax content in pyrolysis oils in Applied Petrochemical Research (2018) 8:203–210, and proposed that catalysis can also be used to reduce the wax content in the final product and upgrade the oil to a lower wax quality to improve the final properties.

[0014] KR100994244B1 discloses the need to remove wax from the process and proposes the use of a separation device to remove wax. Therefore, the pyrolysis process will require additional steps.

[0015] US2022 / 081634 discloses the use of polymer additives for improving the cold flow properties of plastic-derived synthetic raw material compositions (see

[0008] ). In the disclosed polymer additives, the polymer can be a copolymer of an α-olefin monomer and an olefinically unsaturated carboxylic acid monomer or a derivative thereof, such as a maleic anhydride monomer, with a weight-average molecular weight ranging from 20,000 to 70,000 g / mol (see

[0070] ,

[0076] and Example 3 in Table 1). This document focuses on treating plastic pyrolysis oils with high wax residue content (which is alkanes with long carbon chains) (high content of C...). 16 Waxes with longer carbon chains – see, for example,

[0048] ,

[0086] ,

[0097] ,

[0115] ,

[00127] , and the two types of treated pyrolysis oils in Experimental Section

[0153] .

[0016] WO2023 / 183460 discloses compositions comprising pyrolysis oil and an additive composition, said additive composition comprising (a) one or more nitrogen-containing antioxidants; and optionally, (b) a copolymer comprising maleic anhydride-derived units and α-olefin-derived units; and / or (c) a reaction product of a carboxylic acid and a polyamine. It also relates to a method for improving the oxidative stability of a composition by adding the above-described additive composition to a composition comprising pyrolysis oil (see abstract). The optional copolymer comprising maleic anhydride-derived units and α-olefin-derived units preferably has a number average molecular weight of 1,000 to 50,000 g / mol, more preferably 8,000 to 17,000 g / mol (polymer C on pages 12-14 and Table 1, which has an M of 15,000 g / mol). n ).

[0017] Jin et al., in Chinese Journal of Chemical Engineering 26 (2018) 400–406, explained how reactor design can help influence the wax content in the final pyrolysis oil products. The authors compared falling film reactors with other reactor types to improve the liquid / wax ratio. They showed that the liquid / wax ratio in a vertical falling film pyrolysis reactor was slightly higher than that achieved in a tubular reactor, equal to that in a rotary kiln reactor, and slightly lower than that in a fluidized bed.

[0018] Therefore, as illustrated above, conventional solutions for reducing the viscosity and pour point of pyrolysis oils have involved reducing or eliminating wax production by altering reactor design, adding special catalysts, increasing processing time, or providing additional dewaxing steps. While these methods contribute to the production of liquid pyrolysis oils with lower wax content, they incur additional costs, maintenance, and processing time, which reduces production efficiency and thus are not industrially viable solutions. Furthermore, industry seeks pyrolysis oils with high wax residue content for use in cracking processes without the disadvantages of transportation and storage.

[0019] However, the properties of plastic pyrolysis oils are highly dependent on the production method, resulting in varying alkane wax residue contents. Therefore, further research is needed to find effective and cost-efficient solutions for treating plastic pyrolysis oils from plastic pyrolysis processes, keeping them in a liquid state to improve their transport and storage prior to the pyrolysis process. Summary of the Invention

[0020] Therefore, the present invention relates to providing pyrolysis oils having a lower pour point, lower viscosity, or both lower pour point and viscosity, as well as other purposes. Invention Overview

[0022] According to a first aspect of the invention, a composition is provided comprising plastic pyrolysis oil a) and polymer additive b) to reduce the pour point, viscosity, or both of the pyrolysis oil.

[0023] According to a second aspect of the present invention, a method for manufacturing the composition of the first aspect of the present invention is provided, comprising the following steps:

[0024] Provide plastic raw materials;

[0025] The plastic raw material is pyrolyzed to generate plastic pyrolysis oil a);

[0026] Preparation of polymer additives as described herein (b); and

[0027] Add polymer additive b) to the pyrolysis oil a).

[0028] According to a third aspect of the invention, the use of polymer additive b) as described herein for reducing the pour point of plastic pyrolysis oil a) or reducing the viscosity of the pyrolysis oil, or both, is provided.

[0029] According to a fourth aspect of the invention, a method for transporting or storing plastic pyrolysis oil a) is provided, comprising the step of adding a polymer additive b) to the pyrolysis oil to form a composition of the first aspect of the invention. Invention Details

[0031] According to the present invention, a composition is provided comprising plastic pyrolysis oil a) and a polymer additive b), wherein the polymer additive b) is a copolymer P prepared by polymerizing a monomer composition, the monomer composition comprising

[0032] i) Based on the total weight of copolymer P), 10 to 70% by weight of monomers selected from alkyl maleic acid esters of formula (I), maleimide compounds of formula (II), or mixtures thereof.

[0033] (I)

[0034] (II)

[0035] In formulas (I) and (II), R'' is a straight-chain or branched alkyl group having 10 to 40 carbon atoms, preferably 10 to 30 carbon atoms, more preferably 12 to 30 carbon atoms, and even more preferably 18 to 22 carbon atoms.

[0036] and

[0037] ii) Based on the total weight of copolymer P), 30 to 90% by weight of nonfunctionalized α-olefins of formula (III) or mixtures thereof,

[0038] (III)

[0039] Wherein R2 is a straight-chain alkyl group having 8 to 40 carbon atoms, preferably 10 to 40 carbon atoms, more preferably 15 to 35 carbon atoms, and even more preferably 20 to 32 carbon atoms.

[0040] Based on the total weight of plastic pyrolysis oil a), said plastic pyrolysis oil a) contains 12% by weight or less of C 16 Or longer-chain alkane waxes with positive carbon chains.

[0041] Polymer additive b) lowers the pour point of the pyrolysis oil. This polymer additive also lowers the viscosity of the pyrolysis oil. This polymer additive can lower both the pour point and viscosity of the pyrolysis oil.

[0042] Preferably, compared with the same pyrolysis oil without polymer additives, the pour point of 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, and most preferably by at least 5°C by adding polymer additives as described herein.

[0043] Compared to the same pyrolysis oil without polymer additives, when polymer additives are added to pyrolysis oils with wax residues as described herein, the viscosity reduction is preferably at least 10%, preferably at least 20%, and even more preferably 30%, 40%, 50%, or 60% or more at temperatures ranging from -20°C to +80°C, preferably from -10°C to +50°C.

[0044] As described in detail in the Experimental Section of this invention, the polymer additive b) exhibits a wax inhibition of greater than 1% relative to the pyrolysis oil a) by using a CF-15 cold fingering apparatus manufactured by PSL, measured during a 24-hour cold fingering test at a rack temperature set 5°C higher than the wax appearance temperature (WAT) and a fingering temperature set 20°C lower than the WAT. The wax inhibition is preferably greater than 5%, 10%, 15%, 25%, or 30% (measured according to the cold fingering test described above and in more detail in the Experimental Section).

[0045] Plastic pyrolysis oil a)

[0046] As used herein, the terms "plastic pyrolysis oil" or "pyrolysis oil" include any pyrolysis oil produced from the pyrolysis of plastics or plastic waste. Pyrolysis is a thermal cracking process that occurs at temperatures above 250°C in the complete or substantially absence of oxygen to convert plastics into energy in the form of solid, liquid, and gaseous fuels. This process breaks down polymer chains into smaller chains and molecules.

[0047] The preferred pyrolysis oil for plastics is pyrolysis oil from plastic waste, i.e., pyrolysis oil produced from plastic waste. For example, Rehan et al., 2017, Int. Biodeterior. Biodegrad. 119, 162–175, describe the production of liquid oil from the pyrolysis of plastic waste at different temperatures (300–900 °C).

[0048] Preferably, the plastic pyrolysis oil is plastic pyrolysis oil and / or plastic waste pyrolysis oil, wherein the plastic and plastic waste are both selected from polyolefins, more preferably from polyolefins such as high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP) and mixtures thereof; polyethylene terephthalate (PET); polyvinyl chloride (PVC); polystyrene (PS); or mixtures thereof.

[0049] As used herein, the terms “polyolefin pyrolysis oil” and “polyolefin waste pyrolysis oil” are defined as oils produced from the pyrolysis of polyolefins or waste polyolefins, wherein the plastics and plastic waste are selected from high-density polyethylene (HDPE), low-density polyethylene (LDPE), and polypropylene (PP).

[0050] Due to the high pour point and high viscosity of pyrolysis oils, those with a wax content of at least 1% by weight typically present storage and transportation problems. The terms "wax residue" or "wax content" include portions of pyrolysis oils containing straight-chain hydrocarbons with 16 or more carbon atoms.

[0051] In the context of this invention, the term "straight-chain hydrocarbon containing 16 or more carbon atoms" as used herein refers to "a hydrocarbon having C..." 16 "or longer chain alkane waxes", that is, "n-chain alkane waxes are C..." 16 To C 19 n-chain alkane waxes, C 20 To C 29 n-chain alkane waxes, C 30 To C 39 n-chain alkane waxes and those with C 40 "or a mixture of positive-chain alkane waxes with longer carbon chains."

[0052] The pyrolysis oil of the compositions of the present invention a) has 12% by weight or less of C 16 Or longer-chain alkane waxes, preferably 0.01% to 12% by weight of C 16 Or longer-chain alkane waxes, more preferably 0.05% to 12% by weight of C 16 Wax residues of or longer-chain positive-chain alkane waxes. Based on the total weight of plastic pyrolysis oil a), the pyrolysis oil a) of the compositions of the present invention may also preferably have 10% by weight or less of C 16 Or longer carbon chain alkane waxes, more preferably 0.01% to 10% by weight of C 16 Or longer carbon chain alkane waxes, more preferably 0.05% to 10% by weight of C 16 Wax residues of positive-chain alkane waxes with longer carbon chains.

[0053] According to a preferred embodiment of the invention, based on the total weight of the plastic pyrolysis oil, the plastic pyrolysis oil a) preferably contains 0% to 12% C by weight. 16 To C 19 n-Alkane waxes, 0% to 12% C 20 To C 29 n-Alkane waxes, 0% to 12% C 30 To C 39 n-Alkane waxes and 0% to 12% by weight of C 40 Or longer carbon chain alkane waxes, wherein the carbon chain has C 16 The total wax content of or longer-chain positive-chain alkane waxes is 12% by weight or less.

[0054] According to a preferred embodiment of the invention, based on the total weight of the plastic pyrolysis oil, the plastic pyrolysis oil a) preferably contains 0% to 12% C by weight. 16 To C 19 n-Alkane waxes, 0% to 12% C 20 To C 29 n-Alkane waxes, 0% to 12% C 30 To C 39 n-Alkane waxes and 0% to 12% by weight of C 40 Or longer carbon chain alkane waxes, wherein the carbon chain has C 16 The total wax content of or longer-chain positive-chain alkane waxes is 0.01 to 12 by weight.

[0055] According to another preferred embodiment of the invention, based on the total weight of the plastic pyrolysis oil, the plastic pyrolysis oil a) preferably contains 0% to 10% by weight of C. 16 To C 19 n-Alkane waxes, 0% to 10% C 20 To C 29 n-Alkane waxes, 0% to 10% C 30 To C 39 n-Alkane waxes and 0% to 10% by weight of C 40 Or longer carbon chain alkane waxes, wherein the carbon chain has C 16 The total wax content of or longer-chain positive-chain alkane waxes is 10% by weight or less.

[0056] According to another preferred embodiment of the invention, based on the total weight of the plastic pyrolysis oil, the plastic pyrolysis oil a) preferably contains 0% to 10% by weight of C. 16 To C 19 n-Alkane waxes, 0% to 10% C 20 To C 29 n-Alkane waxes, 0% to 10% C 30 To C 39 n-Alkane waxes and 0% to 10% by weight of C 40 Or longer carbon chain alkane waxes, wherein the carbon chain has C 16 The total wax content of or longer-chain positive-chain alkane waxes is 0.01 to 10% by weight.

[0057] Advantageously, reducing or lowering the pour point or viscosity of the pyrolysis oil, or both, makes it easier to transport and store pyrolysis oil with wax residues. In this way, the present invention eliminates the current requirement to modify the reactor or reaction process (e.g., by adding a catalyst) when processing pyrolysis oil with desired wax residues. In this way, plastic processing equipment currently designed to use pyrolysis oil with wax residues can continue to operate without redesign.

[0058] polymer additives b)

[0059] Polymer additive b) is a copolymer P prepared by polymerizing a monomer composition, said monomer composition comprising

[0060] i) Based on the total weight of copolymer P), 10 to 70% by weight of monomers selected from alkyl maleic acid esters of formula (I), maleimide compounds of formula (II), or mixtures thereof.

[0061] (I)

[0062] (II)

[0063] In formulas (I) and (II), R'' is a straight-chain or branched alkyl group having 10 to 40 carbon atoms; and

[0064] ii) Based on the total weight of copolymer P), 30 to 90% by weight of one or more nonfunctionalized α-olefins of formula (III),

[0065] (III)

[0066] R2 is a straight-chain alkyl group having 8 to 40 carbon atoms, preferably 10 to 40 carbon atoms, more preferably 15 to 35 carbon atoms, and even more preferably 20 to 32 carbon atoms.

[0067] According to the present invention, polymer additive b) is a polymer P), or a mixture of one or more polymers P).

[0068] In the context of this invention, the monomer composition corresponds to the total amount of monomers used to prepare copolymer P.

[0069] In a preferred embodiment, polymer additive b) is copolymer P prepared by polymerizing a monomer composition, said monomer composition comprising

[0070] i) Based on the total weight of the copolymer, 10 to 70% of the maleic acid alkyl ester compound of formula (I), and

[0071] ii) 30 to 90% by weight of one or more nonfunctionalized α-olefins of formula (III) based on the total weight of copolymer P).

[0072] Preferably, R in formulas (I) and (II) ’’ It is a straight-chain or branched alkyl group having 10 to 40 carbon atoms, more preferably 12 to 30 carbon atoms, and even more preferably 18 to 22 carbon atoms.

[0073] Preferably, R2 in formula (III) is a straight-chain alkyl group having 10 to 40 carbon atoms, more preferably 10 to 35 carbon atoms, and even more preferably 10 to 32 carbon atoms.

[0074] Based on the total weight of copolymer P), the content of alkyl maleate i) in copolymer P is preferably 20 to 50% by weight, more preferably 25 to 40% by weight.

[0075] Based on the total weight of copolymer P), the content of α-olefin ii) in copolymer P is preferably 50 to 80% by weight, more preferably 60 to 75% by weight.

[0076] In one embodiment, polymer additive b) is obtained by making a mixture containing maleic acid C 18 -C 22 Alkyl esters and C 20 -C 32 Polymers prepared by polymerization of monomer compositions of nonfunctionalized α-olefins.

[0077] In another embodiment, polymer additive b) is obtained by making a mixture containing maleic acid C 18 -C 22 Alkyl esters and C 20 -C 24 Polymers prepared by polymerization of monomer compositions of nonfunctionalized α-olefins.

[0078] In a further embodiment, polymer additive b) is obtained by making a mixture containing maleic acid C 18 -C 22 Alkyl esters and C 10 -C 18 Polymers prepared by polymerization of monomer compositions of nonfunctionalized α-olefins.

[0079] A copolymer is a polymer formed by linking two or more different types of monomers in a polymer chain.

[0080] According to the present invention, polymer additive b) is a polymer P), or a mixture of one or more polymers P). Preferably, polymer additive b) comprises one or more copolymers P), more preferably selected from copolymers P containing maleic acid C. 18 -C22 Alkyl esters and C 20 -C 32 Polymers prepared by polymerization of monomer compositions of nonfunctionalized α-olefins, by using maleic acid C 18 -C 22 Alkyl esters and C 20 -C 24 Polymers prepared by polymerization of monomer compositions of nonfunctionalized α-olefins, by using maleic acid C 18 -C 22 Alkyl esters and C 10 -C 18 Polymers prepared by polymerization of monomer compositions of nonfunctionalized α-olefins or mixtures thereof.

[0081] As used herein, the term "maleic ester" refers to an ester of maleic acid. The term "alkyl maleate" refers to an ester of maleic acid and an aliphatic alcohol. Alkyl maleates as described herein are characterized by the number of carbon atoms in the alkyl chain derived from the alcohol.

[0082] For example, the term "maleic acid C" 18 -C 22 "Alkyl ester" refers to an ester of maleic acid and a straight-chain or branched alcohol having 18 to 22 carbon atoms. This term includes individual maleic esters of alcohols with a specific length, as well as mixtures of maleic esters of alcohols with different lengths. Similarly, the term "maleic acid C" refers to... 20 -C 24 "Alkyl ester" refers to an ester of maleic acid with a straight-chain or branched alkyl chain having 20 to 24 carbon atoms. The term includes individual maleic esters of alcohols with a specific length, as well as mixtures of maleic esters of alcohols with different lengths.

[0083] α-Alkenes are compounds composed of hydrogen and carbon, containing one or more pairs of carbon atoms linked by double bonds. As used herein, the term C1-C... 40 Olefins, C 10 -C 18 Alkenes or C 20 -C 32 Alkenes are alkenes that contain straight-chain, branched or cyclic residues having 1 to 40 carbon atoms, 10 to 18 carbon atoms or 20 to 32 carbon atoms, respectively.

[0084] As an optional component, the monomer composition used to prepare copolymer P may contain additional monomers (iii) derived from one or more comonomers or mixtures thereof.

[0085] Preferably, these comonomers iii) are selected from:

[0086] Hydroxyalkyl methacrylates, preferably selected from the following hydroxyalkyl methacrylates: 3-hydroxypropyl methacrylate, 3,4-dihydroxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,5-dimethyl-1,6-hexanediol methacrylate, and 1,10-decanediol methacrylate.

[0087] Aminoalkyl methacrylates and aminoalkyl (meth)acrylamides, preferably selected from the following aminoalkyl methacrylates and aminoalkyl (meth)acrylamides: N-(3-dimethylaminopropyl)methacrylamide, 3-diethylaminopentyl (meth)acrylate, and 3-dibutylaminohexadecyl (meth)acrylate.

[0088] Nitriles of (meth)acrylic acid and other nitrogen-containing (meth)acrylates, preferably selected from the following nitriles of (meth)acrylic acid and other nitrogen-containing (meth)acrylates: N-(methacryloyloxyethyl)diisobutyl ketone imine, N-(methacryloyloxyethyl)bishexadecyl-ketone imine, (meth)acryloylaminoacetonitrile, 2-methacryloyloxyethyl methyl cyanamide, and (meth)acrylate cyanomethyl ester.

[0089] Aryl methacrylates, such as benzyl methacrylate or phenyl methacrylate, wherein the acryloyl residues may be unsubstituted or substituted up to four times in each case;

[0090] Carbonyl-containing (meth)acrylates, preferably selected from the following carbonyl-containing (meth)acrylates: 2-carboxyethyl (meth)acrylate, carboxymethyl (meth)acrylate, N-(methacryloyloxy)-formamide, acetone (meth)acrylate, N-methacryloyl-2-pyrrolidone, N-(2-methacryloyloxyoxyethyl)-2-pyrrolidone, N-(3-methacryloyloxypropyl)-2-pyrrolidone, N-(2-methacryloyloxypentadecanyl)-2-pyrrolidone, N-(3-methacryloyloxyheptadecyl)-2-pyrrolidone;

[0091] The (meth)acrylates of ether alcohols are preferably selected from the following (meth)acrylates of ether alcohols: tetrahydrofurfuryl (meth)acrylate, methoxyethoxyethyl (meth)acrylate, 1-butoxypropyl (meth)acrylate, cyclohexyloxyethyl (meth)acrylate, propoxyethoxyethyl (meth)acrylate, benzyloxyethyl (meth)acrylate, furfuryl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-ethoxy-2-ethoxyethyl (meth)acrylate, 2-methoxy-2-ethoxypropyl (meth)acrylate, ethoxylated (meth)acrylate, 1-ethoxybutyl (meth)acrylate, methoxyethyl (meth)acrylate, 2-ethoxy-2-ethoxy-2-ethoxyethyl (meth)acrylate, and esters of (meth)acrylate and methoxy polyethylene glycol;

[0092] The (meth)acrylate of halogenated alcohols is preferably selected from the following (meth)acrylates of halogenated alcohols: 2,3-dibromopropyl (meth)acrylate, 4-bromophenyl (meth)acrylate, 1,3-dichloro-2-propyl (meth)acrylate, 2-bromoethyl (meth)acrylate, 2-iodoethyl (meth)acrylate, and chloromethyl (meth)acrylate.

[0093] Ethylene oxide (meth)acrylate, preferably selected from the following ethylene oxide (meth)acrylates: 2,3-epoxybutyl methacrylate, 3,4-epoxybutyl methacrylate, 10,11-epoxyundecyl methacrylate, 2,3-epoxycyclohexyl methacrylate, ethylene oxide (meth)acrylates such as 10,11-epoxyhexadecyl methacrylate, glycidyl methacrylate;

[0094] Phosphorus-, boron-, and / or silicon-containing (meth)acrylates, preferably selected from the following phosphorus-, boron-, and / or silicon-containing (meth)acrylates: 2-(dimethylphospho)propyl (meth)acrylate, 2-(ethylphosphito)propyl (meth)acrylate, 2-dimethylphosphonomethyl (meth)acrylate, dimethylphosphonoethyl (meth)acrylate, diethylmethacryloylphosphonate, dipropylmethacryloylphosphate, 2-(dibutylphosphono)ethyl (meth)acrylate, 2,3-butylenemethacryloylethyl borate, methyldiethoxymethacryloylethoxysilane, and diethylphosphate (meth)acrylate.

[0095] The sulfur-containing (meth)acrylate is preferably selected from the following sulfur-containing (meth)acrylates: ethyl thionyl ethyl (meth)acrylate, 4-cyanothiobutyl (meth)acrylate, ethyl sulfonyl ethyl (meth)acrylate, cyanothiomethyl (meth)acrylate, methyl thionyl methyl (meth)acrylate, and bis(methacryloyloxyethyl)sulfur.

[0096] Heterocyclic (meth)acrylates, preferably selected from the following heterocyclic (meth)acrylates: 2-(1-imidazolyl)ethyl (meth)acrylate, (meth)acrylate Zolpidemyl ethyl ester, N-methacryloylmorpholine and 2-(4-morpholino)ethyl acrylate;

[0097] Maleic acid and maleic acid derivatives, preferably maleic acid monoesters and diesters, maleic anhydride, methylmaleic anhydride, maleimide, and methylmaleimide;

[0098] Fumaric acid and its derivatives, preferably monoesters and diesters of fumaric acid;

[0099] Vinyl halides, preferably selected from vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride;

[0100] Vinyl ester, preferably vinyl acetate;

[0101] The aryl-containing vinyl monomers are preferably selected from the following aryl-containing vinyl monomers: styrene, substituted styrene having alkyl substituents in the side chain, such as α-methylstyrene and α-ethylstyrene, substituted styrene having alkyl substituents on the ring, such as vinyltoluene and p-methylstyrene, and halogenated styrene, such as monochlorostyrene, dichlorostyrene, tribromostyrene and tetrabromostyrene.

[0102] Heterocyclic vinyl compounds, preferably selected from the following heterocyclic vinyl compounds: 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazole and hydrogenated vinylthiazole, vinyl... azole and hydrogenated vinyl azole;

[0103] Vinyl and isoprene ethers;

[0104] Methacrylic acid and acrylic acid,

[0105] Or a mixture thereof.

[0106] In one implementation, comonomer iii) is styrene.

[0107] As used herein, the term "(meth)acrylate" refers to an ester of acrylic acid and methacrylic acid, and mixtures thereof. The term "(meth)acrylate alkyl ester" refers to an ester of (meth)acrylic acid and an aliphatic alcohol. Alkyl methacrylates as described herein are characterized by the number of carbon atoms in the alkyl chain derived from the alcohol.

[0108] The proportion of comonomers in the monomer composition can vary depending on the use and performance of the polymer additive b). Preferably, the content of comonomer iii) in the monomer composition used to prepare copolymer P) is in the range of 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0.1 to 15% by weight, based on the total weight of the monomer composition.

[0109] Preferably, based on the total weight of the monomer composition, the total amount of monomers and comonomers is 95 to 100% by weight, more preferably 100% by weight.

[0110] Preferably, the weight-average molecular weight of polymer additive b) is 8,000 to 600,000 g / mol, more preferably 8,000 to 300,000 g / mol, even more preferably 8,000 to 100,000 g / mol, and most preferably 10,000 to 50,000 g / mol, determined by gel permeation chromatography using poly(methyl methacrylate) calibration standards according to DIN 55672-1 (described in more detail below).

[0111] Preparation method of polymer additive b)

[0112] The preparation of olefin-maleic acid ester copolymers and olefin-maleic acid imide derivative copolymers is well known in the art and described in the literature, for example in US10738138B2 and US4192930.

[0113] Olefin-maleic ester copolymers: These polymers comprise combinations of one or more olefins and esters of maleic acid or maleic acid derivatives (such as citralic acid, nadic acid). Such polymers can be manufactured by copolymerizing an unsaturated ester of maleic anhydride (or its derivative) with one or more α-olefins or by reacting an alcohol (the structural moiety with a hydroxyl group) with a copolymer formed from maleic anhydride (or its derivative) and one or more α-olefins.

[0114] "R" represents an alkyl group derived from an alcohol or a structural moiety containing a hydroxyl group from the ester used to produce maleic anhydride. Depending on the esterification conversion, the "R" group may appear once or twice in the maleic anhydride derivative moiety of the polymer.

[0115] The term alkyl maleate refers to an ester of maleic acid or a maleic acid derivative. The structure is represented by formula (I).

[0116] "Malic acid C" 18 -C 22 "Alkyl ester" refers to an ester of maleic acid or a maleic acid derivative, wherein the alkyl chain length is 18-22 carbon atoms. Esterification of maleic anhydride can be partial or complete, and R in formula (I) ’’ It is a straight-chain or branched alkyl group having 18 to 22 carbon atoms.

[0117] Olefin-maleic acid imide derivative copolymers: These polymers are combinations of one or more olefins and N-alkyl, N-aryl, or N-alkylaryl maleimides or maleimide derivatives. Such polymers can be produced by copolymerizing unsaturated imides with one or more α-olefins or by reacting amines with copolymers formed from maleic anhydrides (or their derivatives) and one or more α-olefins.

[0118] The term "alkylmaleimide" refers to a derivative resulting from the reaction of maleic anhydride with an ammonia or amine derivative. The structure is represented by formula (II).

[0119] “C 18 -C 22 "alkylmaleimide" refers to a derivative resulting from the reaction of maleic anhydride with an ammonia or amine derivative. The imidization of maleic anhydride can be partial or complete, and R in formula (II) ’’ It is a straight-chain or branched alkyl group having 18 to 22 carbon atoms.

[0120] The polymer of polymer additive b) can be obtained by free radical polymerization and related methods, such as ATRP (atom transfer radical polymerization), RAFT (reversible addition-fragmentation chain transfer), or NMP (nitrogen oxide radical controlled polymerization). More preferably, the polymer b) of the present invention is prepared by free radical polymerization.

[0121] Conventional free radical polymerization is specifically described in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition. Typically, polymerization initiators are used for this purpose. Available initiators include azo initiators well-known in the art, such as 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2-methylbutyronitrile) (AMBN), and 1,1-azobiscyclohexanenitrile, as well as peroxides, such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauroyl peroxide, tert-butyl peroxypentanoate, tert-butyl peroxy-2-ethylhexanoate, tert-pentyl peroxy-2-ethylhexanoate, ketone peroxide, tert-butyl peroctanoate, methyl isobutyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide, tert-butyl perbenzoate, and isopropyl peroxide. The preferred initiator for preparing polymer additive b) is tert-butyl peroxy-2-ethylhexanoate, 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, dicumyl peroxide, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, cumyl hydroperoxide, tert-butyl hydroperoxide, bis(4-tert-butylcyclohexyl) peroxydicarbonate, or mixtures of two or more of the above compounds with each other, as well as mixtures of the above compounds with unmentioned but equally radical-forming compounds. Tert-butyl peroxy-2-ethylhexanoate is a preferred initiator for preparing polymer additive b).

[0122] In addition, chain transfer agents can be used. It is well known in the art that a good way to control the molecular weight of polymer chains is to use chain transfer agents during the polymerization process. Chain transfer agents are molecules with weak chemical bonds that promote chain transfer reactions. During the chain transfer reaction, the free radicals of the polymer chain abstract hydrogen from the chain transfer agent, resulting in the formation of new free radicals on the sulfur atoms of the chain transfer agent that can further grow. Common chain transfer agents are organic compounds containing SH groups, such as n-butylthiol, n-octylthiol, n-dodecylthiol, tert-dodecylthiol, butylthiol glycolate, and octylthiol glycolate. Preferred chain transfer agents are selected from n-dodecylthiol, tert-dodecylthiol, or mixtures thereof, with n-dodecylthiol being the most preferred.

[0123] Preferably, based on the total weight of the monomer composition used to prepare polymer additive b), the monomer mixture used to prepare polymer additive b) of the present invention may contain 0.05 to 7% by weight, preferably 0.05 to 5% by weight, more preferably 0.1 to 1% by weight of an initiator. Based on the total weight of the monomer composition, the amount of chain transfer agent used to prepare polymer additive b) is in the range of 0 to 5% by weight, preferably 0.01 to 5% by weight, more preferably 0.05 to 4% by weight.

[0124] The polymerization can be carried out under standard pressure, reduced pressure, or increased pressure. The polymerization temperature is not critical. Conventionally, the polymerization temperature can range from 0°C to 200°C, preferably from 0°C to 140°C, and more preferably from 60°C to 130°C.

[0125] The polymerization may or may not be carried out with a solvent. The term "solvent" is to be interpreted broadly herein. The polymerization is preferably carried out in nonpolar solvents. These include hydrocarbon solvents, such as aromatic solvents like toluene, benzene, and xylene, saturated hydrocarbons such as cyclohexane, heptane, octane, nonane, decane, and dodecane, which may also be in branched form, or mixtures thereof, such as naphtha. These solvents can be used alone or as mixtures. Particularly preferred solvents are mineral oils, mineral-derived diesel fuels, cycloalkane solvents, natural vegetable and animal oils, biodiesel fuels, and synthetic oils (e.g., ester oils, such as dinonyl adipate) or mixtures thereof.

[0126] The plastic pyrolysis oil composition according to the present invention

[0127] Preferably, based on the total weight of the pyrolysis oil composition, the composition contains polymer additive b at a concentration of 0.001 wt% to 1 wt%. More preferably, based on the total weight of the pyrolysis oil composition, the composition contains polymer additive b at a concentration of 0.005 wt% to 0.8 wt%. Even more preferably, based on the total weight of the pyrolysis oil composition, the composition contains polymer additive b at a concentration of 0.005 wt% to 0.5 wt%.

[0128] In a particular embodiment, the plastic pyrolysis oil is a polyolefin pyrolysis oil, wherein the pyrolysis oil is at least partially generated by the pyrolysis of one or more polyolefins. Optionally, the pyrolysis oil is a polyethylene and / or polypropylene pyrolysis oil, wherein the pyrolysis oil is at least partially generated by the pyrolysis of polyethylene and / or polypropylene.

[0129] Preferably, the pyrolysis oil a) and polymer additive b) together account for 90 to 98% by weight based on the total weight of the pyrolysis oil composition.

[0130] The composition according to the invention may further comprise additive c), wherein additive c) is any one of the following: scale inhibitor, corrosion inhibitor, oxygen scavenger, biocide, demulsifier, defoamer, drag reducer, hydrate inhibitor, paraffin dispersant, asphaltenes control agent, pour point depressant different from copolymer P), or a mixture thereof.

[0131] Preferably, based on the total weight of the composition, the total amount of compounds a), b), and c) is 90 to 99 by weight, more preferably 95 to 98 by weight, and even more preferably 100 by weight.

[0132] Any specific embodiment or preferred aspect of the polymer additives b), polymer P), and pyrolysis oil a) listed herein is applicable to the plastic pyrolysis oil composition according to the invention.

[0133] Preparation of the plastic pyrolysis oil composition according to the present invention

[0134] The present invention also provides a method for manufacturing the composition as described above, comprising the following steps:

[0135] Provide plastic raw materials;

[0136] The plastic raw material is pyrolyzed to generate plastic pyrolysis oil a);

[0137] Preparation of polymer additives b); and

[0138] Add polymer additive b) to the plastic pyrolysis oil a).

[0139] The method for preparing the plastic pyrolysis oil composition according to the invention preferably includes the step of mixing the pyrolysis oil and polymer additives. More preferably, the method includes the step of mixing for at least 5, 10, 15, 25 or 30 minutes.

[0140] The method may further include the step of heating the pyrolysis oil and polymer additives, preferably to at least 40°C, more preferably to at least 50°C, and most preferably to at least 60°C. The method may include simultaneously heating and mixing the pyrolysis oil.

[0141] The method of the present invention can reduce the pour point of pyrolysis oil, or reduce the viscosity of pyrolysis oil, or both. This makes the resulting pyrolysis oil easier to transport and store compared to pyrolysis oil without polymer additives. Furthermore, no modifications to the apparatus design are required to provide pyrolysis oil with a reduced pour point or viscosity, as this can be achieved by adding the polymer additives of the present invention after the pyrolysis oil is prepared.

[0142] In a particular embodiment, the method includes the steps of providing a plastic raw material comprising one or more polyolefins and producing pyrolysis oil from said raw material in at least a portion. The polyolefin may be polyethylene and / or polypropylene.

[0143] Uses of polymer additives b)

[0144] The invention is also extended to the use of polymer additives as defined herein for reducing the pour point of plastic pyrolysis oil or reducing the viscosity of pyrolysis oil, or both.

[0145] Preferably, compared with the same pyrolysis oil without polymer additives, the pour point of the pyrolysis oil is reduced by at least 1°C, more preferably by at least 2°C, even more preferably by at least 3°C, and most preferably by at least 5°C by adding polymer additives as described herein.

[0146] Compared to the same pyrolysis oil without polymer additives, when polymer additives are added to pyrolysis oils with wax residues as described herein, the viscosity reduction is preferably at least 10%, preferably 20% or 30%, and more preferably 40%, 50% or 60% or more, at a temperature of 0 to 80°C, preferably 40°C, 45°C or 50°C or at a temperature of 40 to 50°C.

[0147] Methods for transporting or storing plastic pyrolysis oil

[0148] Advantageously, as illustrated in the experimental section, the compositions according to the invention have lower pour points and viscosities compared to untreated pyrolysis oils. Pyrolysis oils typically solidify, making them difficult to transport. In contrast, pyrolysis oils with lower pour points remain liquid at lower temperatures, thus making them easier to transport and eliminating the need to apply heat to the composition before transport and storage.

[0149] The invention also extends to a method for transporting or storing plastic pyrolysis oil a), comprising the step of adding a polymer additive b) to the pyrolysis oil to form the composition described herein.

[0150] By reducing the content of C by 12% or less by weight 16 The pour point of pyrolysis oil containing wax residues of longer-chain positive-chain alkane waxes, or by lowering the viscosity of such pyrolysis oil, or by both, can be maintained by using their existing equipment designs for pyrolysis oils containing 12% or less of C-type waxes based on plastic pyrolysis oil. 16 The transport or storage conditions of pyrolysis oil with a total wax content of or longer-chain positive-chain alkane waxes, or the possibility of using existing equipment designs to reduce the transport or storage conditions of pyrolysis oil with high or relatively high wax residues, i.e., reducing OPEX.

[0151] The present invention provides a method for transporting and / or storing liquid form of plastic pyrolysis oil (a) at temperatures ranging from -20°C to +50°C.

[0152] In the context of this invention, all the details provided above regarding the composition, pyrolysis oil, and polymer additives also apply to the method according to the invention. Detailed Implementation

[0153] Experimental Section

[0154] The invention is further illustrated in detail below with reference to embodiments and comparative examples, but is not intended to limit the scope of the invention.

[0155] method

[0156] In this invention, the weight-average molecular weight (M) of the copolymer (polymer additive b) is... w ) and number-average molecular weight (M n The following measurements were performed using poly(methyl methacrylate) calibration standards, according to DIN 55672-1, by gel permeation chromatography (GPC):

[0157] column: The column assembly consists of a front column as disclosed in Table 1 and 5 SDV columns:

[0158] Table 1

[0159]

[0160] instrument: Agilent 1100 Series pumps; PSS SECcurity in-line degasser; Agilent 1260 Series autosamplers; Agilent 1100 Series RI detectors; Agilent 1260 Series UV detectors; Techlab column ovens;

[0161] Oven temperature: 35℃;

[0162] Standard sample: Poly(methyl methacrylate) (so-called PMMA) calibration standard;

[0163] Eluent: Tetrahydrofuran (THF);

[0164] flow: 1 mL / min;

[0165] Injection volume: 100 μL;

[0166] Detection: RI at 35°C and UV at 239 nm.

[0167] Viscosity was measured using a Discovery HR20 TA Instruments rheometer with a 2° cone and Peltier plate geometry. The shear rate was 10 x 1 / s (or s). -1 The temperature ramp is 1℃ / minute.

[0168] The wax content was measured using a differential scanning calorimeter from TA Instruments and analysis via TRIOS software.

[0169] The determination of waxes was performed using an Agilent 6890 series high-temperature gas chromatograph.

[0170] Pour point is measured in 1°C increments according to ASTM D97. This 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 the container.

[0171] Preparation of polymer additives

[0172] Polymer additives OMAC1, OMAC2, OMAC3, OMAC5 and OMAC6 were prepared according to Example 1 (steps 1 and 2b) in US10,738,138, using the monomer weight ratios shown in Table 2 below.

[0173] The polymer additive OMAC4 was prepared according to Example 1 (steps 1 and 2a) in US10,738,138, using the monomer weight ratios shown in Table 2 below.

[0174] Table 2: Monomer composition, polymer content, and weight-average molecular weight of different polymer additives (b) used in the pyrolysis oil according to the present invention.

[0175]

[0176] After polymerization, the solvent is not removed, so the resulting polymer is mixed with the polymer oil. For the reproducibility of the examples, the polymer content of the polymer additives is provided in Table 2.

[0177] Untreated pyrolysis oil :

[0178] Table 3 below shows the characteristics of some untreated pyrolysis oils, where pyrolysis oils A, B, D and G are polyolefin pyrolysis oils produced from the pyrolysis of polyolefins including high-density polyethylene, low-density polyethylene and polypropylene.

[0179] Table 3 The characteristics of untreated plastic pyrolysis oil (i.e., before the addition of the polymer additive of the present invention or the comparative polymer additive).

[0180]

[0181] Preparation of the composition according to the present invention

[0182] Examples 1, 8, 15 and 22 are plastic pyrolysis oils (untreated pyrolysis oils) before the addition of any polymer additives according to the present invention.

[0183] Example 2 was prepared by adding 0.1 g of OMAC1 to 99.9 g of pyrolysis oil A. The two components were mixed for 30 minutes using a top-mounted stirrer while heating on a hot plate set to 65°C.

[0184] Other compositions Examples 3-7, 9-14, 16-21 and 23-28 were prepared in a manner similar to that of Example 2 using the polymer additives and amounts shown in Tables 4-7 below.

[0185] Table 4 Comparative pyrolysis oil compositions compared to untreated pyrolysis oil A

[0186]

[0187] n / a: Not applicable (baseline), nm: Not measured

[0188] Table 5 The pyrolysis oil composition according to the present invention compared with untreated pyrolysis oil B.

[0189]

[0190] n / a: Not applicable (baseline), nm: Not measured

[0191] Table 6 The pyrolysis oil composition according to the present invention compared with untreated pyrolysis oil D.

[0192]

[0193] n / a: Not applicable (baseline), nm: Not measured

[0194] Table 7 The pyrolysis oil composition according to the invention compared with untreated pyrolysis oil G

[0195]

[0196] n / a: Not applicable (baseline), nm: Not measured

[0197] result

[0198] Table 4 shows that adding OMAC copolymers to C with a content greater than 14% by weight... 16 In pyrolysis oils with higher n-chain alkane content, an undesirable increase in viscosity was observed. Examples 2-7 show that the viscosity of pyrolysis oil A treated with OMAC copolymer increased significantly from 6% to 547%. This substantial increase in viscosity makes the handling and transportation of the oil much more difficult.

[0199] Conversely, when the OMAC polymer of the present invention is combined with C having 12% by weight or less 16 When combined with pyrolysis oils containing higher levels of n-alkane content, it advantageously achieves both a reduction in viscosity and a reduction in pour point compared to the same pyrolysis oil without polymer additives. This is the ideal result, where the treated pyrolysis oil will flow at a lower temperature (lower pour point) and have a lower viscosity to improve operational performance.

[0200] Similarly, Examples 9-14 demonstrate how the OMAC copolymer achieves this reduction in pour point and viscosity when added to pyrolysis oil B. Compared to the untreated oil (Example 8), Examples 9-14 exhibit a pour point 39-48°C lower and a viscosity reduction of 29-77%.

[0201] Examples 16-21 also demonstrate how the OMAC copolymer achieves this reduction in pour point and viscosity when added to pyrolysis oil D. Compared to the untreated oil (Example 15), Examples 16-21 exhibit a pour point 6-15°C lower and a viscosity reduction of 77-99%.

[0202] Examples 23-28 demonstrate how the OMAC copolymer achieves this reduction in pour point and viscosity when added to pyrolysis oil G. Compared to the untreated oil (Example 22), Examples 23-28 exhibit a pour point 6-36°C lower and a viscosity reduction of >95%.

[0203] It has been shown that OMAC copolymers, especially those derived from plastic pyrolysis processes with 12% or less C, are effective. 16 It is most effective in treating plastic pyrolysis oils with higher or higher n-chain alkane content. Experimental data confirm that adding OMAC copolymers to C4 ... 16 How to effectively keep plastic pyrolysis oils with higher n-chain alkane content in liquid form by effectively lowering their pour point and / or viscosity, thereby improving the transport and storage of these oils prior to the pyrolysis process.

Claims

1. A composition comprising plastic pyrolysis oil a) and a polymer additive b), wherein the polymer additive b) is a copolymer P prepared by polymerizing a monomer composition, the monomer composition comprising i) Based on the total weight of the copolymer, 10 to 70% by weight of monomers selected from alkyl maleic acid esters of formula (I), maleimide compounds of formula (II), or mixtures thereof, (I) (II) In equations (I) and (II), R ’’ It is a straight-chain or branched alkyl group having 10 to 40 carbon atoms, preferably 10 to 30 carbon atoms, more preferably 12 to 30 carbon atoms, and even more preferably 18 to 22 carbon atoms; and ii) Based on the total weight of the copolymer, 30 to 90% by weight of a nonfunctionalized α-olefin of formula (III) or a mixture thereof, (III) Wherein R2 is a straight-chain alkyl group having 8 to 40 carbon atoms, preferably 10 to 40 carbon atoms, more preferably 15 to 35 carbon atoms, and even more preferably 20 to 32 carbon atoms. Based on the total weight of the plastic pyrolysis oil a), the plastic pyrolysis oil a) contains 12% by weight or less of C 16 Or longer-chain alkane waxes with positive carbon chains.

2. The composition according to claim 1, wherein the polymer additive b) is a copolymer P prepared by polymerizing a monomer composition, the monomer composition comprising i) Based on the total weight of the copolymer, 10 to 70% of the alkyl maleate compound of formula (I), and ii) 30 to 90% by weight of the nonfunctionalized α-olefin of formula (III) based on the total weight of the copolymer P).

3. The composition according to claim 1 or 2, wherein, based on the total weight of the copolymer P), the monomer composition of the copolymer P contains 20 to 50% by weight, preferably 25 to 40% by weight, of an alkyl maleic acid ester compound of formula (I).

4. The composition according to any one of the preceding claims, wherein, based on the total weight of the copolymer P), the monomer composition of the copolymer P contains 50 to 80% by weight, preferably 60 to 75% by weight, of a nonfunctionalized α-olefin of formula (III).

5. The composition according to any one of the preceding claims, wherein the copolymer P) is selected by comprising maleic acid C 18 -C 22 Alkyl esters and C 20 -C 32 Polymers prepared by polymerization of monomer compositions of nonfunctionalized α-olefins, or by polymerization of monomer compositions containing maleic acid C 18 -C 22 Alkyl esters and C 20 -C 24 Polymers prepared by polymerization of monomer compositions of nonfunctionalized α-olefins, or by polymerization of monomer compositions containing maleic acid C 18 -C 22 Alkyl esters and C 10 -C 18 Polymers prepared by polymerization of monomer compositions of nonfunctionalized α-olefins, or mixtures thereof.

6. The composition according to any one of the preceding claims, wherein the monomer composition for preparing the copolymer P further comprises monomer iii), which is selected from: Hydroxyalkyl methacrylates, preferably selected from the following hydroxyalkyl methacrylates: 3-hydroxypropyl methacrylate, 3,4-dihydroxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,5-dimethyl-1,6-hexanediol methacrylate, and 1,10-decanediol methacrylate. Aminoalkyl methacrylates and aminoalkyl (meth)acrylamides, preferably selected from the following aminoalkyl methacrylates and aminoalkyl (meth)acrylamides: N-(3-dimethylaminopropyl)methacrylamide, 3-diethylaminopentyl (meth)acrylate, and 3-dibutylaminohexadecyl (meth)acrylate. Nitriles of (meth)acrylic acid and other nitrogen-containing (meth)acrylates, preferably selected from the following nitriles of (meth)acrylic acid and other nitrogen-containing (meth)acrylates: N-(methacryloyloxyethyl)diisobutyl ketone imine, N-(methacryloyloxyethyl)bishexadecyl-ketone imine, (meth)acryloylaminoacetonitrile, 2-methacryloyloxyethyl methyl cyanamide, and (meth)acrylate cyanomethyl ester. Aryl methacrylates, such as benzyl methacrylate or phenyl methacrylate, wherein the acryloyl residues may be unsubstituted or substituted up to four times in each case; Carbonyl-containing (meth)acrylates, preferably selected from the following carbonyl-containing (meth)acrylates: 2-carboxyethyl (meth)acrylate, carboxymethyl (meth)acrylate, N-(methacryloyloxy)-formamide, acetone (meth)acrylate, N-methacryloyl-2-pyrrolidone, N-(2-methacryloyloxyoxyethyl)-2-pyrrolidone, N-(3-methacryloyloxypropyl)-2-pyrrolidone, N-(2-methacryloyloxypentadecanyl)-2-pyrrolidone, N-(3-methacryloyloxyheptadecyl)-2-pyrrolidone; The (meth)acrylate of ether alcohols is preferably selected from the following (meth)acrylates of ether alcohols: tetrahydrofurfuryl (meth)acrylate, methoxyethoxyethyl (meth)acrylate, 1-butoxypropyl (meth)acrylate, cyclohexyloxyethyl (meth)acrylate, propoxyethoxyethyl (meth)acrylate, benzyloxyethyl (meth)acrylate, furfuryl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-ethoxy-2-ethoxyethyl (meth)acrylate, 2-methoxy-2-ethoxypropyl (meth)acrylate, ethoxylated (meth)acrylate, 1-ethoxybutyl (meth)acrylate, methoxyethyl (meth)acrylate, 2-ethoxy-2-ethoxy-2-ethoxyethyl (meth)acrylate, and esters of (meth)acrylate and methoxy polyethylene glycol; The (meth)acrylate of halogenated alcohols is preferably selected from the following (meth)acrylates of halogenated alcohols: 2,3-dibromopropyl (meth)acrylate, 4-bromophenyl (meth)acrylate, 1,3-dichloro-2-propyl (meth)acrylate, 2-bromoethyl (meth)acrylate, 2-iodoethyl (meth)acrylate, and chloromethyl (meth)acrylate. Ethylene oxide (meth)acrylate, preferably selected from the following ethylene oxide (meth)acrylates: 2,3-epoxybutyl methacrylate, 3,4-epoxybutyl methacrylate, 10,11-epoxyundecyl methacrylate, 2,3-epoxycyclohexyl methacrylate, ethylene oxide (meth)acrylates such as 10,11-epoxyhexadecyl methacrylate, glycidyl methacrylate; Phosphorus-, boron-, and / or silicon-containing (meth)acrylates, preferably selected from the following phosphorus-, boron-, and / or silicon-containing (meth)acrylates: 2-(dimethyl phosphate)propyl (meth)acrylate, 2-(ethyl phosphite)propyl (meth)acrylate, 2-dimethylphosphonomethyl (meth)acrylate, dimethylphosphonoethyl (meth)acrylate, diethylmethacryloylphosphonate, dipropylmethacryloyl phosphate, 2-(dibutylphosphonoethyl)acrylate, 2,3-butylenemethacryloyl ethyl borate, methyldiethoxymethacryloylethoxysilane, and diethyl phosphate (meth)acrylate. The sulfur-containing (meth)acrylate is preferably selected from the following sulfur-containing (meth)acrylates: ethyl thionyl ethyl (meth)acrylate, 4-cyanothiobutyl (meth)acrylate, ethyl sulfonyl ethyl (meth)acrylate, cyanothiomethyl (meth)acrylate, methyl thionyl methyl (meth)acrylate, and bis(methacryloyloxyethyl)sulfur. Heterocyclic (meth)acrylates, preferably selected from the following heterocyclic (meth)acrylates: 2-(1-imidazolyl)ethyl (meth)acrylate, (meth)acrylate Zolpidemyl ethyl ester, N-methacryloylmorpholine and 2-(4-morpholino)ethyl acrylate; Maleic acid and maleic acid derivatives, preferably maleic acid monoesters and diesters, maleic anhydride, methylmaleic anhydride, maleimide, and methylmaleimide; Fumaric acid and its derivatives, preferably monoesters and diesters of fumaric acid; Vinyl halides, preferably selected from vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride; Vinyl ester, preferably vinyl acetate; The aryl-containing vinyl monomers are preferably selected from the following aryl-containing vinyl monomers: styrene, substituted styrene having alkyl substituents in the side chain, such as α-methylstyrene and α-ethylstyrene, substituted styrene having alkyl substituents on the ring, such as vinyltoluene and p-methylstyrene, and halogenated styrene, such as monochlorostyrene, dichlorostyrene, tribromostyrene and tetrabromostyrene. Heterocyclic vinyl compounds, preferably selected from the following heterocyclic vinyl compounds: 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxetane, vinylfuran, vinylthiophene, vinylthiocyclopentane, vinylthiazole and hydrogenated vinylthiazole, vinyl... azole and hydrogenated vinyl azole; Vinyl and isoprene ethers; Methacrylic acid and acrylic acid, Or a mixture thereof.

7. The composition according to any one of the preceding claims, wherein, based on the total weight of the composition, the composition comprises 0.001 to 1% by weight, preferably 0.005 to 0.8% by weight, more preferably 0.005 to 0.5% by weight of polymer additive b).

8. The composition according to any one of the preceding claims, wherein the weight-average molecular weight of the copolymer (P) is 8,000 to 600,000 g / mol, preferably 8,000 to 300,000 g / mol, more preferably 8,000 to 100,000 g / mol, and most preferably 10,000 to 50,000 g / mol, as determined by gel permeation chromatography using a poly(methyl methacrylate) calibration standard according to DIN 55672-1.

9. The composition according to any one of the preceding claims, wherein the plastic pyrolysis oil a) is plastic pyrolysis oil and / or plastic waste pyrolysis oil, wherein the plastic and plastic waste are selected from polyolefins, polyethylene terephthalate, polyvinyl chloride, polystyrene, or mixtures thereof.

10. The composition of claim 9, wherein, based on the total weight of the plastic pyrolysis oil, the plastic pyrolysis oil a) contains 0% to 12% C 16 To C 19 n-Chain alkane waxes, 0% to 12% C 20 To C 29 n-Chain alkane waxes, 0% to 12% C 30 To C 39 n-chain alkane waxes and 0% to 12% of C 40 Or longer carbon chain alkane waxes, wherein the carbon chain has C 16 The total wax content of or longer-chain positive-chain alkane waxes is 12% by weight or less.

11. The composition according to any one of the preceding claims, wherein the composition further comprises additive c), wherein additive c) is any one of: scale inhibitor, corrosion inhibitor, oxygen scavenger, biocide, demulsifier, defoamer, drag reducer, hydrate inhibitor, paraffin dispersant, asphaltenes control agent, pour point depressant other than copolymer P, or a mixture thereof.

12. The composition according to any one of the preceding claims, wherein the polymer additive b) lowers the pour point of the pyrolysis oil a) by at least 1°C, or wherein the polymer additive b) lowers the viscosity of the pyrolysis oil a) by at least 10% at a temperature of -20°C to +80°C, or both.

13. A method for manufacturing the composition according to any one of claims 1 to 12, comprising the following steps: Provide plastic raw materials; The plastic raw material is pyrolyzed to generate plastic pyrolysis oil a); Preparation of polymer additives (b); and Add the polymer additive b) to the plastic pyrolysis oil a).

14. The use of polymer additive b) according to any one of claims 1 to 12 for reducing the pour point of plastic pyrolysis oil a) or reducing the viscosity of plastic pyrolysis oil a) or both.

15. A method for transporting or storing plastic pyrolysis oil a), comprising the step of adding a polymer additive b) to said plastic pyrolysis oil a) to form a composition according to any one of claims 1 to 12.

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