Method for producing higher alcohols from waste plastic pyrolysis oil and higher alcohols obtained therefrom

Abstract

Disclosed is a method for producing higher alcohols from a waste plastic feedstock, the method comprising the steps of: (a) providing a hydrocarbon feedstream comprising a pyrolysis oil feed obtained from the pyrolysis of plastic waste, the pyrolysis oil comprising at least 20 wt. % higher olefins having carbon numbers in the range of C5 to C20, based on the total hydrocarbon content of the pyrolysis oil; (b) contacting the hydrocarbon feedstream with a synthesis gas under hydroformylation conditions in the presence of a hydroformylation catalyst and recovering a hydroformylation product; and (c) subjecting the hydroformylation product to hydrogenation and / or distillation to recover a higher alcohol product.

Description

[Technical Field]

[0001] field This disclosure relates to a method for producing higher alcohols from waste plastic pyrolysis oil and to higher alcohols obtained thereby. [Background technology]

[0002] background Current environmental concerns, particularly those related to fossil fuel extraction and the growing global problem of plastic waste, are driving the chemical industry to seek sustainable feeds and products. In line with these efforts, pyrolysis oils obtained from the thermal decomposition of waste plastics can be a viable alternative or effective addition to conventional fossil fuel-based raw materials. While conventional mechanical plastic recycling processes require thorough sorting and cleaning, the advantage of pyrolysis is its applicability to mixed plastic waste. Liquid plastic pyrolysis products (pyrolysis oils) possess desirable properties that make them suitable as fuels and feeds for producing C2= and C3= monomers for olefin polymers, but they are rarely in a form ready for use as a raw material for higher alcohols. Pyrolysis oils often have limited olefin content and / or contain high levels of contaminants, such as chlorides or metals. U.S. Patent No. 10308896 describes a rather cumbersome method for producing oxo alcohol from waste plastic raw materials, the method comprising pre-fractionating a feedstream containing waste plastic raw materials to produce a first heart-cut paraffin stream, hydrogenating and fractionating this first heart-cut paraffin stream to obtain a second heart-cut paraffin stream, and then dehydrogenating this second heart-cut paraffin stream to form a stream containing olefins which are ultimately hydroformylated to prepare oxo alcohol. Therefore, there is a need to provide an improved method for producing higher alcohols from pyrolysis oil obtained from the thermal decomposition of waste plastics, which can be used alone as feed or in combination with conventional raw materials. [Overview of the project]

[0003] summary In a first embodiment, the present disclosure provides a method for producing higher alcohols from waste plastic raw materials, comprising the steps of: (a) supplying a hydrocarbon feedstream containing a pyrolysis oil feed obtained from the pyrolysis of plastic waste, wherein the pyrolysis oil contains at least 20 wt% of higher olefins having a carbon number in the range of C5 to C20, based on its total hydrocarbon content; (b) contacting the hydrocarbon feedstream with synthesis gas under hydroformylation conditions in the presence of a hydroformylation catalyst to recover a hydroformylation product; and (c) hydrogenating and / or distilling the hydroformylation product to recover a higher alcohol product. In embodiments of the present disclosure, the hydrocarbon feedstream may essentially consist of pyrolysis oil obtained from the pyrolysis of plastic waste. In other embodiments of the present disclosure, the hydrocarbon feedstream may further comprise a conventional feed of higher olefins, which may be a petroleum-based higher olefin feed, such as a higher olefin feed obtained by oligomerization of C3=, C4=, C5= olefins.

[0004] In embodiments of the present disclosure, the pyrolysis oil feed may contain at least 50 wt% linear alphaolefin, more preferably at least 60 wt% linear alphaolefin, based on its total olefin content. In such embodiments, the pyrolysis oil feed is characterized by having an average number of branches per molecule (also known in the art as the branching index) of less than 1, preferably 0.8 or less. In embodiments of the present disclosure, the method may further include, prior to step (b), a step of distilling the pyrolysis oil feed to separate one or more fractions corresponding to any narrow cut range within the range C7-C20, particularly the carbon number ranges C7-C19, C7-C10, C7-C12, C10-C13, C13-C17, C13-C15 and C16-C19. Furthermore, or separately, the method may further include, prior to step (b), one or more steps of selectively reducing a diolefin in a hydrocarbon feedstream, preferably a pyrolysis oil feed, in the presence of a nickel-containing catalyst; contacting a hydrocarbon feedstream, preferably a pyrolysis oil, with an aqueous solution to at least partially remove water-soluble contaminants; and contacting a hydrocarbon feedstream, preferably a pyrolysis oil feed, with one or more adsorbents suitable for at least partially removing one or more contaminants selected from water, metals, chlorides, nitrogen-containing compounds, oxygenates, and phosphorus-containing compounds. In certain embodiments, the step of contacting a hydrocarbon feedstream, preferably a pyrolysis oil feed, with an aqueous solution and / or one or more adsorbents is performed before the selective reduction of the diolefin.

[0005] In a further embodiment, the Disclosure provides compositions comprising a higher alcohol and one or more derivatives of the higher alcohol that can be obtained by the method of the Disclosure. The derivatives may include esters of monocarboxylic acids, dicarboxylic acids, esters of polycarboxylic acids, alkoxylated alcohols, sulfated alcohols, sulfated alkoxylated alcohols, and alcohol etheramines. Alternatively, the derivative may include an ester of a primary alcohol composition with one or more acids. Furthermore, the acid may include one or more of phthalic acid, adipic acid, sebacic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, succinic acid, and trimellitic acid. The drawings below are included to illustrate specific aspects of the disclosure and should not be considered exclusive embodiments. As any person with ordinary skill in the art who benefits from the disclosure will realize, the disclosed subject matter is capable of considerable modifications, alterations, combinations, and equivalents in form and function. [Brief explanation of the drawing]

[0006] [Figure 1] This is an overall flow scheme for removing contaminants from waste plastic pyrolysis oil feed according to the present invention. [Figure 2] This is a labeled GC-MS trace of the low-boiling point pyrolysis oil feed fraction of the present invention. [Figure 3] This is a bar graph showing the area percentage for the low-boiling point pyrolysis oil feed fraction of the present invention. [Figure 4] This is a labeled GC-MS trace of the high-boiling point pyrolysis oil feed of the present invention. [Figure 5] This is a bar graph showing the area percentage for the high-boiling point pyrolysis oil feed fraction of the present invention. [Figure 6] This is the 1H NMR spectrum of the low-boiling point pyrolysis oil feed fraction of the present invention. The inset shows the range of 4.5 to 8.0 ppm, and CDCl3 was used as the solvent indicated by (S) in the spectrum. [Figure 7] This is the 13C{1H} NMR spectrum of the low-boiling point pyrolysis oil feed fraction of the present invention. CDCl3 was used as the solvent, indicated by (S) in the spectrum. [Figure 8] This is the 1H NMR spectrum of the high-boiling point pyrolysis oil feed fraction of the present invention. The inset shows the range of 4.5 to 7.5 ppm, and CDCl3 was used as the solvent indicated by (S) in the spectrum. [Figure 9] This is the 13C{1H} NMR spectrum of the high-boiling point pyrolysis oil feed fraction of the present invention. CDCl3 was used as the solvent indicated by (S) in the spectrum. [Figure 10]This is the 1H NMR spectrum of the hydroformylation product of the low-boiling point pyrolysis oil feed fraction of the present invention. C6D6 was used as the solvent. The gray rectangle indicates the residual diethyl ether from the sodium borohydride workup. [Figure 11] This is the 13C{1H} NMR spectrum of the hydroformylation product of the low-boiling point pyrolysis oil feed fraction of the present invention. C6D6 was used as the solvent. The gray rectangle indicates the residual diethyl ether from the sodium borohydride workup. The inset shows the peaks assigned to the following, magnified in the range of 55-80 ppm: (1) primary alcohol (-CH2-OH); (2) secondary methyl branched alcohol (-CH(CH3)-OH); (3) secondary alkyl branched alcohol (-CH(R)-OH); (4) tertiary alcohol (-C(R)(R*)-OH). [Figure 12] This is the 1H NMR spectrum of the hydroformylation product of the high-boiling point pyrolysis oil feed fraction of the present invention. C6D6 was used as the solvent. The gray rectangle indicates the residual diethyl ether from the sodium borohydride workup. The inset shows a magnified view of the range 3.0–7.5 ppm. [Figure 13] This is the 13C{1H} NMR spectrum of the hydroformylation product of the high-boiling point pyrolysis oil feed fraction of the present invention. C6D6 was used as the solvent. The gray rectangle indicates the residual diethyl ether from the sodium borohydride workup. The inset shows the peaks corresponding to the following, magnified to the range 52-78 ppm: (1) primary alcohol (-CH2-OH); (2) secondary methyl branched alcohol (-CH(CH3)-OH); (3) secondary alkyl branched alcohol (-CH(R)-OH). [Modes for carrying out the invention]

[0007] Detailed explanation The features and advantages of the present invention will become apparent from the following description, which includes examples intended to provide a broad representation of the invention. Various modifications will be apparent to those skilled in the art from this description and from the practice of the invention. It is not intended to limit the scope to the specific forms disclosed, and the present invention includes all modifications, equivalents, and alternatives falling within the scope of the invention defined by the claims. As used herein, the term "plastic" generally refers to a polymeric material (primarily polyethylene, polypropylene or their copolymers) made of at least one organic monomer, either wholly, or in part, which may contain one or more modifications and / or be compounded with one or more additives such as colorants to form a useful material. Plastics include thermosetting as well as thermoplastic polymeric materials. The term "waste plastic" refers to used plastics that are no longer required for their intended purpose. Examples of waste plastics include empty plastic containers, discarded plastic packaging materials, etc.

[0008] The term "hydrocarbon" refers to an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons include, but are not limited to, paraffin, naphthalene, aromatic compounds, and olefins. The term "alkyl" refers to a hydrocarbyl group having no unsaturated carbon-carbon double bonds. Unless otherwise specified herein, the alkyl group may optionally contain heteroatoms or branches. The term "linear alpha olefin (LAO)" refers to an alkene hydrocarbon having a carbon-carbon double bond at the terminal (end) carbon atom of the main carbon chain. Although sometimes a small amount of branched components may be present in a given LAO sample, in most cases, there is no side chain branching in LAO. The terms "branched", "branched hydrocarbon" and "branched" refer to a hydrocarbon or hydrocarbyl group having a straight main carbon chain from which a hydrocarbyl side chain extends. The term "unbranched" refers to a straight-chain hydrocarbon or hydrocarbyl group from which no side chain group extends. Unless otherwise specified, the average number of branches (average branching index) within a particular mixture of olefin oligomers is equal to (0 × % linear olefin + 1 × % mono-branched olefin + 2 × % di-branched olefin + 3 × % tri-branched olefin) / 100, where % linear olefin + % mono-branched olefin + % di-branched olefin + 3 × % tri-branched olefin = 100%. The foregoing percentages are weight percentages (wt.%). For example, a mixture of C8 olefin oligomers containing 10% linear C8 olefin, 30% mono-branched C8 olefin, 50% di-branched C8 olefin, and 10% tri-branched C8 olefin has an average branching index of 1.6. The average branching index may similarly be determined by weighting more highly branched individual olefin oligomers (e.g., having four or more branches).

[0009] This application provides a method for producing higher alcohols from pyrolysis oil obtained by pyrolysis of waste plastics. The method disclosed in this application provides an alternative use for waste plastics that would otherwise likely end up in landfill or the environment. Pyrolysis oil from waste plastics Pyrolysis of waste plastics is well known in the art and may be carried out in a continuous or batch process, with or without a catalyst. Examples of companies carrying out waste plastic pyrolysis include Agilyx Corporation, Recycling Technologies Ltd, Plastic Energy Ltd., and Licella. Non-limiting examples of the process are described in patent applications WO2013 / 070801, WO2014 / 128430, and WO2011 / 123145, the contents of which are hereby incorporated by reference. As described above, the preparation of pyrolysis oil from waste plastics is well known in the art. Thus, the preparation of pyrolysis oil is not necessarily part of the method described in this application. However, in certain embodiments, the preparation of pyrolysis oil from waste plastics may be part of the method. In such embodiments, the method includes the step of preparing pyrolysis oil from waste plastics. The preparation generally involves heating a container containing waste plastics to induce depolymerization of the waste plastics and obtain pyrolysis oil or condensed (liquid) pyrolysis products. In such embodiments, the method of the present application may be an integrated process including the preparation of pyrolysis oil, in which case the pyrolysis oil is used without intermediate storage or transport steps.

[0010] An advantage of pyrolysis is that the process is not limited to a specific type of plastic. Therefore, waste plastics may contain mixtures of different types of plastics, and can still be used in the preparation of pyrolysis oil without the need for sorting. Preferred plastic types include high-density polyethylene, low-density polyethylene, and polypropylene, as well as their polyolefin copolymers. However, other plastic types, such as polyethylene terephthalate (PET), polystyrene, and poly(vinyl chloride) (PVC), may also be present. Polyolefin waste plastics are particularly suitable for pyrolysis, and the pyrolysis oil obtained therefrom is suitable for use as a waste plastic raw material in the production of higher alcohols. The waste plastic raw material can be used as is, or it can be blended with other higher olefin raw materials, such as ordinary higher olefin raw materials obtained by oligomerization of olefins. Depending on the origin and type of waste plastic, the pyrolysis oil obtained therefrom may be used as is, or it may require additional purification to remove contaminants that may adversely affect the hydroformylation catalyst, hydroformylation process, and / or hydroformylation product quality requirements.

[0011] Pyrolysis oil typically contains one or more hydrocarbon materials selected from paraffins, olefins, naphthalenes, and aromatic compounds. The relative amounts of these components may depend on the specific pyrolysis process conditions and the waste plastic material. The boiling point range of the pyrolysis oil may depend on factors such as the pyrolysis conditions and the plastic feed. In some cases, waste plastic pyrolysis oil may be fractionated and / or blended with a typical higher olefin feed having a specific boiling point range to obtain pyrolysis oil having a specific boiling point range. The distillation point may be determined by gas chromatography in accordance with ASTM D2887. As used herein, ordinary higher olefins are produced by oligomerization of propene, butene, or pentene as either a pure feed or a mixture thereof. In the method of the present disclosure, the usual higher olefin feed to the hydroformylation reaction is replaced with or blended with waste plastic pyrolysis oil such that the higher alcohols resulting from the hydroformylation reaction are produced entirely or partially from the waste plastic material.

[0012] Hydrogenation of diolefins In embodiments of this disclosure, the waste plastic pyrolysis oil may contain diolefins, which may affect the hydroformylation catalyst performance. Typically, the diolefin concentration may range from 0.1 to 20 wt% based on the total olefin content. Unless otherwise specified, the content of olefins, paraffins (n-paraffins and isoparaffins), naphthalenes, and aromatic compounds may be determined by vacuum ultraviolet absorption spectroscopy using gas chromatography in accordance with ASTM D8071. Depending on the impurities present in the pyrolysis oil, one or more feed purification steps described in the "Contaminant Removal" section may be performed before hydrogenation of the diolefin to protect the hydrogenation catalyst from deactivation. Selective low-grade diolefin hydrogenation (DIOS) can be used to remove the diolefins. The pyrolysis oil can be hydrogenated before or after blending it with a normal feedstream. The hydrogen treatment step can be carried out using a hydrogen treatment unit that is technically well known. Hydrogen treatment is generally carried out in the presence of a catalyst and under conditions suitable for the desired hydrogenation, as is known to those skilled in the art. Suitable catalysts and process conditions are technically well known. Examples of suitable catalysts include nickel, cobalt, and / or molybdenum-based catalysts, such as nickel (Ni), nickel-molybdenum (NiMo), and cobalt-molybdenum (CoMo) catalysts, which are preferably provided supported on a solid carrier such as alumina.

[0013] Methods for the selective hydrogenation of diolefins are technically well known. U.S. Patent 3,696,160, incorporated herein by reference, discloses the selective hydrogenation of diolefins to corresponding monoolefins using a sulfide-nickel-tungsten catalyst. U.S. Patent 6,118,034, incorporated herein by reference, discloses the selective hydrogenation of diolefins on a nickel-containing precipitate catalyst at temperatures of 40°C to 100°C. U.S. Patent 6,469,223, incorporated herein by reference, discloses the selective hydrogenation of diolefins on a nickel-containing catalyst. Other catalysts and / or process conditions may be used besides those described in U.S. 3,696,160, U.S. 6,118,034, and U.S. 6,469,223. In certain embodiments, low-grade diolefin hydrogenation operates at high LHSV and low temperatures (Table 1). The hydrogen supply rate was set to more than three times the expected stoichiometric consumption to manage exothermic reactions and catalyst deactivation. It was found that increasing the hydrogen supply rate could lead to a decrease in olefin yield due to the percentage of olefins that become saturated and turn into paraffins. The hydrogen supply rate was selected so that diolefin saturation had an acceptable impact on the olefin yield. In certain examples, about 5 to 13% of olefins become saturated and turn into paraffins due to about 60 to 99% diolefin saturation in the DIOS reactor. The hydrogenation reactor has a diameter-to-height ratio of less than 1 so that pyrolysis oil particles can be captured without a noticeable increase in pressure drop. In some cases, the DIOS process may use one or more of the following strategies, namely bypass tubes, modified scale baskets, and bypass reactors, to mitigate significant pressure drops.

[0014] Table 1: Diolefin Hydrogenation Operating Conditions and DIOS Reactor Settings [Table 1]

[0015] Pollutant removal The pyrolysis oil from waste plastics contains various contaminants, such as metals and heteroatomic compounds. As used herein, the term "heteroatomic compound" refers to a molecule containing atomic species other than carbon and hydrogen. Examples of heteroatomic compounds include compounds containing nitrogen, phosphorus, oxygen, or halogens (e.g., chlorine and bromine). These contaminants may adversely affect the DIOS hydrogenation catalyst and / or the subsequent hydroformylation process and equipment. Furthermore, contaminants are undesirable in the resulting higher alcohols. The process described herein not only enables the use of pyrolysis oil from waste plastics supplied to the hydroformylation process, but also allows for the acquisition of high-purity alcohols. Pyrolytic waste plastics may contain polyethylene terephthalate (PET), high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP), and various combinations thereof. The type and concentration of contaminants vary depending on the source of the plastic waste. For example, waste plastic pyrolysis oil produced from HDPE, LDPE, and PP tends to have lower sulfur, oxygen, and nitrogen content, while waste plastic pyrolysis oil produced from PET tends to have a higher aromatic content. Other plastics, such as polyvinyl chloride (PVC), may be present in the waste plastic, but their presence would require additional treatment to remove chlorine. Waste plastics may also contain other materials, such as polyacrylonitrile, polyacrylic acid, and polyvinyl sulfonates, which may introduce undesirable impurities (e.g., nitrogen, oxygen, sulfur). Contaminants can originate from many sources, including residues from additives added to plastics to improve their properties, dirt that accumulates on plastics during handling (use, collection, recycling), or unwanted polymers present in the waste plastics.

[0016] This method applies a broad-spectrum purification procedure that can remove or reduce substantially all contaminants present in the waste plastic pyrolysis oil to acceptable levels. By applying the purification procedure, contamination of one or more of the DIOS hydrogenation catalyst, hydroformylation catalyst, and hydroformylation product is mitigated or avoided. One or more purification steps of the waste plastic pyrolysis oil can be performed before introducing the raw material into the DIOS hydrogenation reactor. Separately or further, one or more purification steps may be applied after the DIOS hydrogenation and hydroformylation processes. The overall flow scheme for contaminant removal (as shown in Figure 1) essentially consists of two steps: i) a water washing step in which a pyrolysis oil feed (4) comes into contact with water (3) in an extraction column / washing tower (5) to remove all water-soluble contaminants; and ii) a series of adsorbents (2), also called a battery of adsorbents, which may include adsorbents with general functionality, such as non-selective adsorbents and / or adsorbents with specific functionality used to remove specific contaminants. Furthermore, the hydrocarbon-rich fraction may be transferred to a settler (6, optional) to remove residual water, and further purified with a series of adsorbents. The series of adsorbents consists of adsorbents with general functionality, such as non-selective adsorbents and / or adsorbents with specific functionality used to remove specific contaminants from pyrolysis oil.

[0017] Each washing step is a liquid-liquid extraction process in which the pyrolysis oil is brought into contact with an aqueous solution to extract water-soluble impurities from the pyrolysis oil. Washing may be carried out using extraction columns or washing towers that are technically well known. Examples of washing towers or columns are described in patent applications EP2338864 and WO93 / 13040, the contents of which are incorporated herein by reference. Non-limiting examples of suitable commercially available liquid-liquid extraction columns include KARR® columns and SCHEIBEL® columns, available from Koch Modular. Washing with water generally yields an aqueous phase (lower stream) containing water-soluble components extracted from the pyrolysis oil and an organic fraction (upper stream) containing hydrocarbon components of the pyrolysis oil. The aqueous phase may be recirculated and brought into further contact with the pyrolysis oil. The aqueous solution generally contains at least 50 wt% water, preferably at least 75 wt% water, and more preferably at least 95 wt% water. In certain embodiments, the aqueous solution has an initial pH between 6 and 8, preferably in the range of about 6.5 and 7.5, and more preferably about 7 (i.e., before contact with the pyrolysis oil). The aqueous solution may be buffered to maintain the pH within this range. In a preferred embodiment, the relative volume of the pyrolysis oil feed to the volume of the aqueous solution used in one or more cleaning steps is in the range of 1:1 to 1:200.

[0018] Furthermore, or separately, the pyrolysis oil is brought into contact with one or more adsorbents suitable for removing one or more contaminants, such as (but not limited to) water, metals, chlorides, nitrogen-containing compounds, oxygenated compounds, and phosphorus-containing compounds. More specifically, the pyrolysis oil feed may pass over one or more adsorbent beds, each containing one or more adsorbents. Each bed may have different adsorbents depending on its adsorption capacity and the detected or predicted level of contaminants, or multiple beds may have the same adsorbent. Depending on the specific contaminants present or expected to be present in the pyrolysis oil feed, one or more adsorbents may be bypassed to avoid unnecessary purification steps. In certain embodiments, information regarding the level of contaminants in the feed can be obtained through in-line monitoring and analysis. The methods described herein are not limited to specific adsorbents. Various adsorbents suitable for the removal of one or more contaminants are technically well known and commercially available. Examples of suitable multipurpose adsorbents include zeolite 13X adsorbents, activated carbon, alumina, and clay. Non-limiting examples of adsorbents suitable for the removal of selected contaminants are provided below.

[0019] Water: Silica gel adsorbent (e.g., Sylobead® silica gel available from WR Grace) and molecular sieves (e.g., AZ-300, GB-620, Molsiv® ADG-401, and Molsiv® HPG-250 adsorbents available from UOP; and F-200 and 4A molecular sieves available from BASF). - Nitrogen compounds: Axsorb® 911 adsorbent, available from Axens. -Mercury: AxTrap® 273 adsorbent available from Axens, Durasorb® HG available from BASF, and Mersorb® available from Selective Adsorption Associates Inc. - Chlorides: AxTrap® 867 adsorbent available from Axens; UOP CLR-204, UOP CLR-300, and UOP CLR-454 available from UOP; Puraspec® Clear® Chloride Guard available from Johnson Matthey; HTG-10 available from Haldor Topsoe; and BASF CL-850. -Silicon: ACT 971 and ACT 981, available from Axens. - Oxygenated materials: Axsorb® 911 adsorbent available from Axens; UOP AZ-300, UOP GB-620, Molsiv® ADG-401, and Molsiv® HPG-250 available from UOP. -Sulfur: Axsorb® 913 adsorbent available from Axens; UOP ADS-120, UOP ADS-130, UOP ADS-280, and UOP SG-731 available from UOP; D-1275E, D1280E, and Prosorb® N available from BASF. - Phosphorus: TK-31 and TK-455 MultiTrap™ catalysts available from Haldor Topsoe.

[0020] In certain embodiments of this disclosure, the entire pyrolysis oil feed may undergo a washing step and / or contact with an adsorbent. In other embodiments, only one fraction (or a portion) of the pyrolysis oil feed may undergo the purification. In certain embodiments, the pyrolysis oil feed may be distilled to obtain fractions having different boiling point ranges. The process may then continue with one or more fractional distillations of interest. In other embodiments, the pyrolysis oil feed may be divided into fractions having the same composition, where some fractions may be purified and others may not. After the purification of one or more fractions, the fractions may be rejoined. By setting the relative volumes of the purified and unpurified fractions, a target level of purification can be achieved.

[0021] Hydroformylation As used herein, hydroformylation, also known as the oxo process, refers to the conversion of olefins to aldehydes via metal-catalyzed carbonyl addition. Hydroformylation can occur by contacting an olefin with synthesis gas ("syngas"), i.e., a mixture of carbon monoxide (CO) and hydrogen (H2), in the presence of a suitable catalyst to form hydroformylation products. More frequently, the aldehydes in the hydroformylation products are converted to alcohols through subsequent reduction, thereby forming primary alcohols having one more carbon atom than the olefin produced. Long-chain primary alcohols formed through hydroformylation and subsequent reduction can find many applications, including, for example, organic solvents, detergents, surfactants, or the alcohol components of ester-based plasticizers for polymers (e.g., PVC). Typical hydroformylation catalysts include group 9 transition metals, such as cobalt or rhodium. Examples of suitable cobalt-containing hydroformylation catalysts include cobalt carbonyl, such as Co2(CO)8, which can be converted to hydridocobalt tetracarbonyl HCo(CO)4 under the high CO / H2 pressures commonly encountered during hydroformylation. A suitable syngas pressure effective for in-situ formation of HCo(CO)4 may be in the range of about 1 MPa to about 30 MPa, and the H2:CO partial pressure ratio may be in the range of about 2:3 to about 3:2, preferably about 1.2:1. A suitable reaction temperature during hydroformylation may be in the range of about room temperature to about 200°C (i.e., about 25°C to about 200°C), or any sub-range therein.

[0022] In embodiments of this disclosure, higher alcohols are produced by a high-pressure cobalt-catalyzed oxo process. Cobalt is supplied to the oxo reactor along with an olefin feed and syngas at a pressure of about 280–300 bar and a temperature of about 160–200°C. Under these conditions, the olefins are hydroformed to aldehydes and several by-products such as acetals and dimers. The hydroformated products are hydrogenated on a copper chromate, NiMo sulfide, or CoMo sulfide catalyst. Typical process conditions include a temperature range of 80–200°C and a pressure of 60–150 bar. After hydrogenation, the product is distilled to remove any unreacted olefins, paraffins, aromatic compounds, and naphthenic compounds (if present), and the alcohol fraction is recovered. A final, gentle hydrogenation may be required to remove trace amounts of aldehydes after distillation. Depending on the boiling point range of the olefins present in the hydroformation feed, a range of higher alcohol products can be obtained.

[0023] Separately, the hydroformylation reaction is carried out in a low-pressure Rh-catalyzed process utilizing technically known process conditions. Examples of Rh-catalyzed hydroformylation processes are described, for example, in Japanese Patent No. EP1004563B1 and Japanese Patent Application Publication No. WO2017 / 080690A1. The present invention describes a method for producing higher alcohols from a hydrocarbon stream consisting essentially of a pyrolysis oil feed obtained from plastic waste, or from a blend of waste plastic pyrolysis oil feed and a conventional feed. In embodiments of the present invention, the pyrolysis oil feed contains at least 20 wt% of higher olefins having a carbon number in the range of C5 to C20, based on its total hydrocarbon content. Advantageously, by supplying a pyrolysis oil feed containing higher olefins, dilution by large amounts of unreactive molecules, which would require further reactors and distillation capacity to produce and recover alcohols, can be avoided.

[0024] In embodiments of the present invention, the pyrolysis oil obtained from waste plastics contains a higher level of linear alphaolefins compared to ordinary petroleum-based raw materials. The pyrolysis oil contained at least 10 wt% linear alphaolefins based on their total olefin content, and in further embodiments, at least 50 wt% linear alphaolefins. In embodiments of the present invention, the olefin contained in the pyrolysis oil is characterized by an average branching number per molecule of less than 1, preferably less than 0.8. Olefin oligomers having an average branching number of about 2.2 or less may exhibit advantageous biodegradability. Advantageously, the higher alcohols produced therefrom also feature a low average branching number, such as an average branching number per molecule of less than 2, which can impart improved biodegradability to derivatives produced from the alcohols.

[0025] In embodiments of the present invention, the hydrocarbon feedstream consists essentially of pyrolysis oil. In further embodiments of the present invention, the hydrocarbon feedstream further comprises a conventional feedstream. Blending a conventional higher olefin feed with a pyrolysis oil allows for adjustment of the average number of branches per molecule of the hydrocarbon feed. In yet another embodiment, the use of relatively low concentrations of pyrolysis oil (e.g., only about 1 wt% or even less) reduces the concentration of certain contaminants in the hydrocarbon feed, thereby reducing the adverse effects of those contaminants on other process steps such as hydroformylation. Using very low concentrations of pyrolysis oil in the hydrocarbon feedstream, particularly less than 1 wt%, can dilute contaminants to such an extent that further processing of the hydrocarbon feedstream is unnecessary. By using only waste plastic pyrolysis raw material sources, or by blending waste plastic pyrolysis raw material sources with conventional petroleum-based raw materials, the processing capacity of an oxo alcohol plant can be increased, thereby improving process efficiency. [Examples]

[0026] To facilitate a better understanding of this disclosure, examples of preferred or representative embodiments are given below. These examples should not be construed as limiting or defining the scope of the invention. Experimental Procedure These tests utilized standard air-sensitive techniques and purification methods. Commercial materials were used either as received or purified according to standard procedures (Anarego, WL; Chair, CL Purification of Laboratory Chemicals; 5th ed.; Elsevier: Oxford, 2003). The CO2(CO)8 pre-catalyst was purchased from Strem Chemicals (Newburyport, MA) and stored at -35°C before use. Unless otherwise specified, operations were performed at ambient temperature (22-28°C). To characterize the pyrolysis oil composition and alcohol composition of the present invention, gas chromatography (GC) and nuclear magnetic resonance (NMR) methods were used. The following two NMR methods were used to characterize branching in the alcohol sample: to determine the average number of branches per molecule 1 For determining H NMR and branching site distribution 13 13C NMR. GC-MS data was obtained using an Agilent 5977 series GC / MSD system. Data analysis was performed using the vendor-supplied MassHunter GC / MS acquisition software in combination with MSD ChemStation and the NIST Mass Spectra Search Program (v2.2; 6 / 2014). Further analysis was performed using OrinPro2019 and Microsoft Excel. 1 H and 13 1H and 13C NMR spectroscopic data were collected using a 400 MHz Bruker NEO NMR spectrometer. 1 H and 13 1H and 13C{1H} chemical shifts were reported in ppm relative to SiMe4 (1H and 13C{1H} δ = 0.0 ppm) using the known chemical shifts of the residual protons or carbons corresponding to the deuterated solvents (i.e., C6D6, CDCl3, etc.) as reported in J. Am. Chem. Soc., (2010), v. 29, pp. 2176-2179. 1 H and 13 13C{1H} δ = 0.0 ppm).

[0027] Characterization of the Pyrolysis Oil Feed The pyrolysis oil feed was derived from polyethylene plastics that were distilled to provide pyrolysis and a wide distillation cut. The waste plastic pyrolysis oil feed was very pale yellow and clear. The pyrolysis oil feed was characterized by GC-MS (Figures 2-5) and NMR spectroscopy (Figures 6-9). An overview of the main components of the mixture is shown in Table 2 (low boiling cut) and Table 3 (high boiling cut). The total linear alpha olefin content measured for the low boiling cut was approximately 73 wt%. The total linear alpha olefin content measured for the high boiling cut was approximately 64 wt%. Consistent with the GC-MS results, NMR spectroscopy ( 1 H and 13 1H and 13C{1H}) confirmed that the feed was composed mainly (i.e., > 50 wt%) of vinyl-terminated olefins. As shown in Figures 6-9, the NMR data suggests, though not limiting, the presence of a considerable number of trace components, including aromatic compounds and dienes. Toluene and trace amounts of xylene were identified at the low boiling point cutoff (93-177°C). The concentration was centered between 6.61 and 6.08 ppm. 1 The 1H NMR spectroscopy shift (Figure 6) is centered around 39.55 ppm. 13 The 13C NMR spectroscopic shift (Figure 7) is consistent with the presence of non-conjugated ("step-dienes"), e.g., 1,4-hexadiene. The presence of these species is a potential concern because they readily isomerize under hydroformylation conditions, yielding conjugated dienes that are known to be catalytic poisons.

[0028] Table 2: Main components identified by GC-MS for low boiling point cutoff: [Table 2]

[0029] Table 3: Main components identified by GC-MS for high boiling point cutoff: [Table 3]

[0030] Hydroformation of pyrolysis oil feed For the hydroformylation of waste plastic pyrolysis oil feed, a high-pressure, 316 SS, continuous stirring, constant-pressure batch autoclave reactor (600 mL) equipped with monitoring, control, and data acquisition capabilities was used. Glass liners were packed inside the reactor. Inside a nitrogen-filled glove box, the solvent, waste plastic feed, and pre-catalyst were introduced into the reactor, whose volume and quantity are indicated in Table 4. The reactor was then sealed under nitrogen (3 psig N2), removed from the glove box, and connected to a reactor system equipped with monitoring, control, heating, stirring, cooling, and process gas supply. The reactor system was then pressurized to 1500 psig (H2 / CO) at room temperature (23°C) and heated to 150°C. The reactor reached process temperature in approximately 20 minutes. Once the process temperature was reached, the batch autoclave was operated in constant pressure mode for 4 hours. At the end of the operation, the process gas supply (singas) was stopped, the unit was depressurized, and purged with nitrogen. After cooling, the reactor was opened, and the liquid hydrocarbon product was filtered through activated basic alumina to remove catalyst ash.

[0031] Table 4. Hydroformylation conditions: [Table 4]

[0032] NaBH4 finish Crude alcohols from each hydroformylation reaction were transferred to a round-bottom flask (500 mL) equipped with a PTFE-coated magnetic stirrer bar. A slightly excess amount of NaBH4 (approximately 17.5 g) was added under a nitrogen atmosphere. This mixture was stirred for 16 hours. The resulting slurry was then mixed with pentane (100 mL). Next, each reaction mixture was transferred to a larger beaker (1 L), and water was slowly added over 1 hour. The reaction mixture was then neutralized to a pH of approximately 6.5 by adding 10% HCl / H2O. As soon as the foaming due to the addition of HCl stopped, each reaction mixture was finished with aqueous solution. Meanwhile, the product was extracted into the organic phase using Et2O (3 × 150 mL). The organic phases were mixed, dried over MgSO4, and filtered. The resulting colorless filtrate was concentrated under rotational evaporation to remove volatile substances (mainly pentane). As shown in Figures 10-13, the crude alcohol product is 1 H and 13Analysis was performed using C{1H} NMR spectroscopy. The estimated yield and conversion rate are shown in Table 5. In both cases, it coincides with alcohol formation. 1 1H NMR spectroscopy revealed a signal, which is consistent with the formation of primary, secondary, and tertiary alcohols, due to a characteristic chemical shift between 62 and 75 ppm. 13 This was verified by 13C NMR spectroscopy. Figures 11 and 13 show the peaks assigned to the following insets: (1) primary alcohol (-CH2-OH); (2) secondary methyl branched alcohol (-CH(CH3)-OH); (3) secondary alkyl branched alcohol (-CH(R)-OH); (4) quaternary alcohol (-C(R)(R * )-OH).

[0033] Table 5: Yield and conversion rate of alcohol [Table 5]

[0034] The conversion rate is expressed as a relative intensity percentage of alcohol content versus residual unsaturated content. The integration range for olefin unsaturated compounds includes vinyl, vinylidene, and internal unsaturated compounds. The integration range for alcohol compounds captures the intensity of the proton at the α-position relative to the -OH functional group. The integration range for olefin unsaturation corresponds to 4.8–5.8 ppm (C6D6). The integration range for estimated alcohol content corresponds to 3.35–4.0 ppm (C6D6). For the estimated conversion rate (% conversion rate), the following formula was used as a function of the integrated alcohol intensity (IAI) and the integrated unsaturation intensity (IUI). % conversion rate=[(IAI) / {(IUI)+(IAI)}]×100

[0035] Hydrogenation Separately or in combination with sodium borohydride reduction, the hydroformylation product may be hydrogenated to convert the remaining olefin content into paraffinic material. Typically, this is carried out by contacting the original (neat) hydroformylation product or a solution thereof with a hydrogenation catalyst containing one or more of the following transition metals: Pd, Pt, Co, Ni, or Mo, in the presence of hydrogen gas. Preferably, these reactions are carried out at a hydrogen pressure of over 100 psig and a temperature of over 50°C. distillation Crude hydroformylation products or product mixtures obtained from either or both hydrogenation and / or sodium borohydride reduction can optionally be distilled. The purpose of distillation is to separate the product alcohol from other molecules in the product mixture by boiling point. The distillation technique may be carried out at atmospheric pressure or under reduced pressure, and low-resolution distillation techniques (i.e., short-path) or high-resolution distillation techniques (i.e., distillation columns, spinning band columns, etc.) may be used.

[0036] Additional Embodiments This disclosure may further include one or more of the following non-limiting embodiments. E1. A method for producing higher alcohols from waste plastic raw materials, comprising: (a) supplying a hydrocarbon feedstream containing a pyrolysis oil feed obtained from the pyrolysis of plastic waste, wherein the pyrolysis oil contains at least 20 wt% of a higher olefin having a carbon number in the range of C5 to C20, based on its total hydrocarbon content; (b) contacting the hydrocarbon feedstream with synthesis gas under hydroformylation conditions in the presence of a hydroformylation catalyst to recover a hydroformylation product; and (c) hydrogenating and / or distilling the hydroformylation product to recover a higher alcohol product. E2. The method according to Embodiment E1, wherein the hydrocarbon feedstream essentially consists of pyrolysis oil obtained from the pyrolysis of plastic waste. E3. The method according to Embodiment E1, wherein the hydrocarbon feedstream further comprises a conventional feed of higher olefins. E4. The method according to Embodiment E3, wherein the normal feed of higher olefins is a petroleum-based higher olefin feed, for example, a higher olefin feed obtained by oligomerization of C3=, C4=, C5= olefins. E5. The method according to any one of Embodiments E1 to E4, wherein the pyrolysis oil feed contains at least 50 wt% linear alphaolefins, more preferably at least 60 wt% linear alphaolefins, based on its total olefin content. E6. The method according to Embodiment E5, characterized in that the pyrolysis oil feed is less than 1, preferably 0.8 or less, and the average number of branches per molecule.

[0037] E7. The method according to any one of embodiments E1 to E6, further comprising the step of subjecting the pyrolysis oil feed to distillation prior to step (b), thereby separating one or more fractions corresponding to any narrow cut range within the range C7 to C20, in particular the carbon number ranges C7 to C19, C7 to C10, C7 to C12, C10 to C13, C13 to C17, C13 to C15 and C16 to C19. E8. The method according to any one of embodiments E1 to E7, further comprising the step of selectively reducing a diolefin in the presence of a nickel-containing catalyst to at least a portion of a hydrocarbon feedstream, preferably a pyrolysis oil feed, prior to step (b). E9. The method according to any one of embodiments E1 to E8, further comprising the step of contacting at least a portion of the hydrocarbon feedstream, preferably the pyrolysis oil feed, with an aqueous solution to remove at least partially water-soluble contaminants prior to step (b). E10. The method according to any one of embodiments E1 to E9, further comprising the step of contacting at least a portion of a hydrocarbon feedstream, preferably a pyrolysis oil feed, with one or more adsorbents suitable for at least partially removing one or more contaminants selected from water, metals, chlorides, nitrogen-containing compounds, oxygenates, and phosphorus-containing compounds, prior to step (b).

[0038] E11. A higher alcohol that can be obtained by the method described in any one of Embodiments E1 to E10. E12. A composition comprising one or more derivatives of the higher alcohols described in Embodiment E11. E13. The composition according to Embodiment E12, wherein the derivative comprises an ester of a monocarboxylic acid, an ester of a dicarboxylic acid, an ester of a polycarboxylic acid, an alkoxylated alcohol, a sulfated alcohol, a sulfated alkoxylated alcohol, and an alcohol etheramine. E14. The composition according to Embodiment E12, wherein the derivative comprises an ester of a primary alcohol composition with one or more acids. E15. The composition according to Embodiment E14, wherein the acid comprises one or more of phthalic acid, adipic acid, sebacic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, succinic acid, and trimellitic acid.

[0039] The disclosures herein are implementable in the absence of any element not specifically disclosed herein and / or any optional element disclosed herein. Compositions and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, but compositions and methods may also “essentially consist of” or “consist of” various components and steps. All numbers and ranges disclosed above may differ slightly. Whenever numerical ranges with lower and upper limits are disclosed, any number and any encompassed range that falls within that range is clearly disclosed. In particular, any range of values ​​disclosed herein (in the form of “about a to about b,” or equally, “about a to b,” or equally, “about ab”) should be understood to indicate any number and range that falls within a broader range of values. All numerical values ​​in the detailed description and claims of this application are modified with “about” or “approximately” with respect to the indicated value, taking into account the experimental errors and variations that a person skilled in the art would expect. Furthermore, terms in the claims have their obvious and ordinary meanings unless the patentee explicitly and clearly defines them to have a different meaning. In addition, the indefinite article "a" or "an" used in the claims is defined in this application as meaning the one or more elements that introduce it.

[0040] Unless otherwise indicated, all numbers used in this specification and related claims to express quantities, properties, etc., of components, such as molecular weight, reaction conditions, etc., should be understood in all cases to be modified with the term “approximately.” Accordingly, unless otherwise indicated, the numerical parameters described in the following specification and the appended claims are approximations that may vary depending on the desired properties to be obtained in embodiments of the present invention. Not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be interpreted using ordinary rounding techniques, taking into account at least the reported number of significant figures. This application provides one or more exemplary embodiments incorporating embodiments of the invention disclosed herein. For the sake of clarity, this application does not describe or illustrate all features of the physical implementation. In developing physical embodiments incorporating embodiments of the present invention, developers should understand that they must make numerous practice-specific decisions to achieve their goals, such as compliance with system-related, business-related, government-related, and other constraints that change from practice to time. While the developers' efforts may be time-consuming, they will still be routine work for those skilled in the art and those who benefit from this disclosure. Accordingly, the present invention is well suited to achieving not only the objectives and advantages described, but also those inherent therein. The present invention can be modified and implemented in different but equivalent forms that will be obvious to those skilled in the art who benefit from the teachings of this application, so the specific embodiments disclosed above are merely illustrative. Furthermore, it is not intended to limit the details of the configuration or design shown herein beyond what is described in the claims below. Accordingly, the specific exemplary embodiments disclosed above may be modified, combined or altered, and all such variations are considered to be within the scope of the present invention. (Note) This disclosure includes the following embodiments. (Embodiment 1) A method for producing higher alcohols from waste plastic raw materials, (a) A step of supplying a hydrocarbon feedstream containing a pyrolysis oil feed obtained from the pyrolysis of plastic waste, wherein the pyrolysis oil contains, based on its total hydrocarbon content, at least 20 wt% of a higher olefin having a carbon number in the range of C5 to C20, (b) The step of contacting the hydrocarbon feedstream with synthesis gas under hydroformylation conditions and in the presence of a hydroformylation catalyst, and recovering the hydroformylation product, (c) A step of recovering a higher alcohol product by hydrogenating and / or distilling the hydroformylation product. The method, including the method described above. (Embodiment 2) The method according to Embodiment 1, wherein the hydrocarbon feedstream essentially consists of pyrolysis oil obtained from the pyrolysis of plastic waste. (Embodiment 3) The method according to Embodiment 1, wherein the hydrocarbon feedstream further includes a conventional feed of higher olefins. (Embodiment 4) The method according to Embodiment 3, wherein the conventional feed of the higher olefin is a petroleum-based higher olefin feed, for example, a higher olefin feed obtained by oligomerization of C3=, C4=, C5= olefins. (Embodiment 5) The method according to any one of Embodiments 1 to 4, wherein the pyrolysis oil feed contains at least 50 wt% linear alphaolefin, more preferably at least 60 wt% linear alphaolefin, based on its total olefin content. (Embodiment 6) The method according to Embodiment 5, characterized in that the pyrolysis oil feed is less than 1, preferably 0.8 or less, and has an average number of branches per molecule. (Embodiment 7) The method according to any one of Embodiments 1 to 6, further comprising the step of distilling the pyrolysis oil feed prior to step (b) to separate one or more fractions corresponding to any narrow cut range within the range C7-C20, in particular the carbon number ranges C7-C19, C7-C10, C7-C12, C10-C13, C13-C17, C13-C15 and C16-C19. (Embodiment 8) The method according to any one of Embodiments 1 to 7, further comprising the step of selectively reducing a diolefin in the presence of a nickel-containing catalyst to at least a portion of the hydrocarbon feedstream, preferably the pyrolysis oil feed, prior to step (b). (Embodiment 9) The method according to any one of Embodiments 1 to 8, further comprising the step of contacting at least a portion of the hydrocarbon feedstream, preferably the pyrolysis oil feed, with an aqueous solution to remove at least partially water-soluble contaminants, prior to step (b). (Embodiment 10) The method according to any one of Embodiments 1 to 9, further comprising the step of contacting at least a portion of the hydrocarbon feedstream, preferably the pyrolysis oil feed, with one or more adsorbents suitable for at least partially removing one or more contaminants selected from water, metals, chlorides, nitrogen-containing compounds, oxygenates, and phosphorus-containing compounds, prior to step (b). (Embodiment 11) A higher alcohol that can be obtained by the method described in any one of Embodiments 1 to 10. (Embodiment 12) A composition comprising one or more derivatives of the higher alcohol described in Embodiment 11. (Embodiment 13) The composition according to Embodiment 12, wherein the derivative comprises a dicarboxylic acid ester, a polycarboxylic acid ester, an alkoxylated alcohol, a sulfated alcohol, a sulfated alkoxylated alcohol, and an alcohol etheramine. (Embodiment 14) The composition according to Embodiment 12, wherein the derivative comprises an ester of a primary alcohol composition with one or more acids. (Embodiment 15) The composition according to Embodiment 14, wherein the acid comprises one or more of phthalic acid, adipic acid, sebacic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, succinic acid, and trimellitic acid.

Claims

1. A method for producing higher alcohols from waste plastic raw materials, (a) A step of supplying a hydrocarbon feedstream comprising a pyrolysis oil feed obtained from the pyrolysis of plastic waste comprising polyethylene, polypropylene, or polyolefin copolymers thereof, wherein the pyrolysis oil comprises, based on its total hydrocarbon content, at least 20 wt% of a higher olefin having a carbon number in the range of C5 to C20, (b) The step of contacting the hydrocarbon feedstream with synthesis gas under hydroformylation conditions and in the presence of a hydroformylation catalyst, and recovering the hydroformylation product, (c) A step of recovering a higher alcohol product by hydrogenating and / or distilling the hydroformylation product. Includes, The method further comprising, prior to step (b), one or more steps of: selectively reducing a diolefin in the presence of a nickel-containing catalyst to at least a portion of the hydrocarbon feedstream; contacting at least a portion of the hydrocarbon feedstream with an aqueous solution to remove at least partially water-soluble contaminants; and contacting at least a portion of the hydrocarbon feedstream with one or more adsorbents suitable for at least partially removing one or more contaminants selected from water, metals, chlorides, nitrogen-containing compounds, oxygenates, and phosphorus-containing compounds.

2. The method according to claim 1, wherein the hydrocarbon feedstream consists of pyrolysis oil obtained from the pyrolysis of plastic waste containing polyethylene, polypropylene, or polyolefin copolymers thereof.

3. The method according to claim 1, wherein the hydrocarbon feedstream further comprises a conventional feed of a higher olefin, and the conventional feed of the higher olefin is a petroleum-based higher olefin feed.

4. The method according to claim 3, wherein the petroleum-based higher olefin feed is a higher olefin feed obtained by oligomerization of C3=, C4=, and C5= olefins.

5. The method according to any one of claims 1 to 4, wherein the pyrolysis oil feed contains at least 50 wt% linear alphaolefins based on its total olefin content.

6. The method according to any one of claims 1 to 5, wherein the pyrolysis oil feed contains at least 60 wt% linear alphaolefins based on its total olefin content.

7. The method according to claim 5 or 6, characterized in that the pyrolysis oil feed has an average number of branches per molecule of less than 1.

8. The method according to claim 5 or 6, characterized in that the pyrolysis oil feed has an average number of branches per molecule of 0.8 or less.

9. The method according to any one of claims 1 to 8, further comprising the step of distilling the pyrolysis oil feed prior to step (b) to separate one or more fractions corresponding to any narrow cut range within the range C7 to C20, in particular the carbon number ranges C7 to C19, C7 to C10, C7 to C12, C10 to C13, C13 to C17, C13 to C15 and C16 to C19.

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