Process for separating organic products from organic recycle streams

Abstract

Embodiments of the present disclosure generally relate to processes for separating organic products from an organic recycle stream. The processes can be used to form fractions that can be used for further processing. In some embodiments, one or more of the fractions can have a higher concentration of phenol than the concentration of phenol in the separated organic recycle stream. In some embodiments, a fraction can include a phenolic compound, a glycolytic matrix, a curing agent, an accelerator, or a combination thereof. In some embodiments, a fraction can include a phenol oligomer. The separated fractions can be used to form, for example, phenolic resins.

Description

Technical Field

[0001] The embodiments of this disclosure generally relate to a process for separating organic products from an organic circulating stream. Background Technology

[0002] Fiber-reinforced thermosetting composites, such as epoxy and phenolic resin composites, are widely used as structural and lightweight components. After use, these composites are primarily landfilled because they are observed to be non-recyclable. New recycling technologies are beginning to address this problem. In this paper, methods such as high-temperature decomposition, solvent decomposition, thermal decomposition, and catalytic depolymerization are used to separate organic recycling streams (such as oils) from fibers. These organic recycling streams include valuable products such as phenolic compounds, resins, and other organic compounds. However, due to the complexity and high cost of separating valuable organic products from the bulk organic recycling stream, the organic recycling stream is primarily incinerated or used as fuel.

[0003] Therefore, new and improved processes are needed to separate organic products from organic recycling streams. New and improved processes are also needed to generate phenol-rich components from organic recycling streams. Summary of the Invention

[0004] The embodiments of this disclosure generally relate to a process for separating organic products from an organic circulating stream, and more specifically to a process for producing phenol-rich compositions from an organic circulating stream. Unlike conventional techniques, the embodiments described herein enable the removal of phenolic fractions and other organic fractions from resin circulating streams and resin waste streams. Phenolic fractions and other organic fractions can be used to produce, for example, phenolic varnish resins and epoxy resins, as well as other materials.

[0005] In one embodiment, a process is provided, the process comprising (a) contacting a raw material with a first organic solvent and water to form a first aqueous stream containing an organic acid and a first organic stream containing phenol, phenolic compounds, and phenolic oligomers, the raw material having a first concentration of phenol; (b) contacting the first organic stream with an aqueous alkali to form a second aqueous stream containing phenol and phenolic oligomers and a second organic stream containing phenolic compounds; (c) contacting the second aqueous stream with an aqueous acid to form a precipitate containing phenolic oligomers and a third aqueous stream containing phenol; and (d) contacting the third aqueous stream with a second organic solvent to form a composition having a second concentration of phenol greater than the first concentration of phenol.

[0006] In another embodiment, a process is provided comprising contacting a raw material comprising a thermochemical derivative of an epoxy resin composite, a catalytic depolymerization product of an epoxy resin composite, or a combination thereof, with an aprotic solvent and water to form a first aqueous stream comprising an organic acid and a first organic stream comprising phenol, phenolic compounds, and phenolic oligomers, the raw material having a first concentration of phenol. The process further comprises contacting the first organic stream with an aqueous alkali to form a second aqueous stream comprising phenol and phenolic oligomers and a second organic stream comprising phenolic compounds, wherein: the second organic stream further comprises a glycated matrix, a curing agent, an accelerator, or a combination thereof; the aqueous alkali comprises an alkali metal hydroxide; and the second organic stream comprises phenol at a lower concentration than that of the second aqueous stream.

[0007] In one embodiment, a process is provided comprising (a) contacting a raw material comprising a product of solvent decomposition, high-temperature decomposition, thermal decomposition, catalytic depolymerization, or combinations thereof of an epoxy resin composite with a first organic solvent and water to form a first aqueous stream comprising an organic acid and a first organic stream comprising phenol, phenolic compounds, and phenolic oligomers, the raw material having a first concentration of phenol. The process further comprises (b) contacting the first organic stream with an aqueous alkali to form a second aqueous stream comprising phenol and phenolic oligomers and a second organic stream comprising phenolic compounds. The process further comprises (c) contacting the second aqueous stream with an aqueous acid to form a precipitate comprising phenolic oligomers and a third aqueous stream comprising phenol. The process further comprises (d) contacting the third aqueous stream with a second organic solvent to form a composition having a second concentration of phenol greater than the first concentration of phenol.

[0008] In another embodiment, a process is provided comprising (a) contacting a raw material comprising a thermochemical derivative of an epoxy resin composite, a catalytic depolymerization product of an epoxy resin composite, or a combination thereof, with a first aprotic solvent and water to form a first aqueous stream comprising an organic acid and a first organic stream comprising phenol, phenolic compounds, and phenolic oligomers, the raw material having a first concentration of phenol. The process further comprises (b) contacting the first organic stream with an aqueous base to form a second aqueous stream comprising phenol and phenolic oligomers and a second organic stream comprising phenolic compounds, the aqueous base comprising an alkali metal hydroxide, the second organic stream comprising phenol at a lower concentration than the second aqueous stream. The process further comprises (c) contacting the second aqueous stream with an aqueous inorganic acid to form a precipitate comprising phenolic oligomers and a third aqueous stream comprising phenol. The process further comprises (d) contacting the third aqueous stream with a second aprotic solvent to form a composition having a second concentration of phenol greater than the first concentration of phenol.

[0009] In another embodiment, a process for forming a phenolic resin is provided. The process includes contacting a raw material comprising a product of solvent decomposition of an epoxy resin composite, high-temperature decomposition of an epoxy resin composite, thermal decomposition of an epoxy resin composite, catalytic depolymerization of an epoxy resin composite, or combinations thereof, with a first organic solvent and water to form a first aqueous stream comprising an organic acid and a first organic stream comprising phenol, phenolic compounds, and phenolic oligomers, the raw material having a first concentration of phenol. The process further includes contacting the first organic stream with an aqueous alkali to form a second aqueous stream comprising phenol and phenolic oligomers and a second organic stream comprising phenolic compounds. The process further includes contacting the second aqueous stream with an aqueous acid to form a precipitate comprising phenolic oligomers and a third aqueous stream comprising phenol. The process further includes contacting the third aqueous stream with a second organic solvent to form a composition having a second concentration of phenol greater than the first concentration of phenol. The process further includes converting the phenol-rich composition into a phenolic resin.

[0010] In another embodiment, a process is provided for generating a phenol-rich composition. The process includes (a) contacting a feedstock comprising a product of solvent decomposition of an epoxy resin composite, high-temperature decomposition of an epoxy resin composite, thermal decomposition of an epoxy resin composite, catalytic depolymerization of an epoxy resin composite, or combinations thereof, with a first organic solvent and water to obtain a first aqueous stream comprising an organic acid and a first organic stream comprising phenol, phenolic compounds, and phenolic oligomers. The process further includes (b) contacting the first organic stream with an aqueous base to form a second aqueous stream comprising phenol and a second organic stream comprising phenolic compounds. The process further includes (c) contacting the second aqueous stream with an aqueous acid to form a precipitate comprising phenolic oligomers and a third aqueous stream comprising phenol; and (d) contacting the third aqueous stream with a second organic solvent to form a phenol-rich composition.

[0011] In another embodiment, a process is provided for generating a phenol-rich composition. The process includes (a) contacting a raw material comprising a thermochemical derivative of an epoxy resin composite, a catalytic depolymerization product of an epoxy resin composite, or a combination thereof, with a first aprotic solvent and water to obtain a first aqueous stream comprising an organic acid and a first organic stream comprising phenol. The process further includes (b) contacting the first organic stream with an aqueous base to form a second aqueous stream comprising phenol and a second organic stream comprising a phenol compound, the aqueous base comprising an alkali metal hydroxide, and the second organic stream comprising a lower amount of phenol than the second aqueous stream. The process further includes (c) contacting the second aqueous stream with an aqueous inorganic acid to form a precipitate comprising phenol oligomers and a third aqueous stream comprising phenol; and (d) contacting the third aqueous stream with a second aprotic solvent to form a phenol-rich composition.

[0012] In another embodiment, a process for forming a phenolic resin is provided. The process includes contacting a raw material comprising a product of solvent decomposition of an epoxy resin composite, high-temperature decomposition of an epoxy resin composite, thermal decomposition of an epoxy resin composite, catalytic depolymerization of an epoxy resin composite, or combinations thereof, with a first organic solvent and water to obtain a first aqueous stream comprising an organic acid and a first organic stream comprising phenol, phenolic compounds, and phenolic oligomers. The process further includes contacting the first organic stream with an aqueous alkali to form a second aqueous stream comprising phenol and a second organic stream comprising phenolic compounds; contacting the second aqueous stream with an aqueous acid to form a precipitate comprising phenolic oligomers and a third aqueous stream comprising phenol; and contacting the third aqueous stream with a second organic solvent to form a phenol-rich composition. The process further includes converting the phenol-rich composition into a phenolic resin. Attached Figure Description

[0013] To gain a more detailed understanding of the features described above, a more specific description of the disclosure, which has been briefly summarized above, can be obtained by referring to embodiments, some of which are illustrated in the accompanying drawings. However, it should be noted that the drawings illustrate exemplary embodiments only and are therefore not intended to limit the scope of the disclosure, allowing for other equally effective embodiments.

[0014] Figure 1A A flowchart illustrating selected operations of a process for separating products from an organic circulating stream according to at least one embodiment of this disclosure.

[0015] Figure 1B A flowchart illustrating a process for separating products from an organic circulating stream according to at least one embodiment of the present disclosure.

[0016] Figure 2 The image shows the overlap of infrared (IR) spectra of the organic, oligomeric, and phenolic fractions of a high-temperature decomposed oil according to at least one embodiment of this disclosure.

[0017] Figure 3 The diagram shows an overlap of chromatograms of crude high-temperature decomposed oil and separated fractions, as measured by gel permeation chromatography (GPC), according to at least one embodiment of this disclosure.

[0018] Figure 4 The diagram shows an overlap of chromatograms of phenolic varnish resins produced from 20% to 100% recycled material (phenolic fraction) as measured by ultra-high-performance liquid chromatography (UHPLC) according to at least one embodiment of this disclosure.

[0019] The accompanying drawings included herein illustrate various embodiments of the present disclosure. It is contemplated that elements and features of one embodiment may be advantageously incorporated into other embodiments without further description. Detailed Implementation

[0020] Embodiments of this disclosure generally relate to a process for separating organic products from an organic circulating stream. Phenolic-rich compositions can be used to form, for example, phenolic varnish resins. Embodiments of this disclosure can also be used to form fractions or streams containing phenols, phenolic compounds, phenolic oligomers, or combinations thereof, which can be used to form, for example, phenolic varnish resins. Embodiments of this disclosure can also be used to form fractions or streams containing curing agents, accelerators, glycated matrices, advanced resins, or combinations thereof. These curing agents, accelerators, glycated matrices, advanced resins, or combinations thereof can then be used to form, for example, epoxy resins.

[0021] As stated above, prior art cannot address the reuse or recyclability of thermosetting materials present in fiber-reinforced thermosetting composites such as epoxy resin composites and other resin composites. These thermosetting materials are conventionally considered non-recyclable. In contrast, the process described herein enables sustainable recycling of fiber-reinforced thermosetting composites such as epoxy resin composites and other resin composites. In this document, the process of this disclosure enables the extraction of valuable products such as phenols, phenolic compounds, and other organic compounds from solvent decomposition of fiber-reinforced thermosetting composites (solvent decomposition oil), high-temperature decomposition of fiber-reinforced thermosetting composites (high-temperature decomposition oil), thermal decomposition of fiber-reinforced thermosetting composites (thermal decomposition oil), catalytic decomposition of fiber-reinforced thermosetting composites, or any other suitable recycling process. Therefore, the process described herein enables sustainable recycling of fiber-reinforced thermosetting composites such as epoxy resin composites and other resin composites. Furthermore, the process described herein can also mitigate landfill problems associated with fiber-reinforced thermosetting composites. Moreover, the process described herein achieves recyclability so that fiber-reinforced thermosetting composites, such as epoxy resin composites and other resin composites, can be used as a resource rather than left as waste.

[0022] The title is used for convenience only and does not limit the scope of this disclosure. The embodiments described herein can be combined with other embodiments.

[0023] As used herein, "composition" may include components of a composition, reaction products of two or more components of a composition, the balance of remaining starting components, or combinations thereof. The compositions of this disclosure may be prepared by any suitable mixing process.

[0024] As used herein, "phenol-rich composition" means that the relative amount (or concentration) of phenol in the separated composition is greater than the relative amount (or concentration) of phenol in the raw material before separation. For example, if the raw material contained 1% phenol before separation, the composition formed after separation contains more than 1% phenol.

[0025] As used herein, “phenol” refers to compounds of formula (I):

[0026] (I).

[0027] As used herein, “cyclic phenol” refers to a phenol (compound of formula (I)) present in a phenol-rich composition. Cyclic phenols may also be present in other fractions formed by the process described herein.

[0028] As used herein, “phenolic compound” includes compounds represented by formula (II).

[0029] (II).

[0030] The phenolic compound of formula (II) includes at least one hydrogen atom (H) such that z is at least one. In formula (II), R is a group that substitutes for a hydrogen atom on the aromatic ring, and OH is a hydroxyl group that substitutes for a hydrogen atom on the aromatic ring.

[0031] In some embodiments, z is 1 to 4, such as 1, 2, 3, or 4; x is 1 to 4 (such as 1, 2, 3, or 4); y is 1 to 4 (such as 1, 2, 3, or 4); and combinations thereof. The sum of x, y, and z on the aromatic ring of formula (II) is 6. When x is greater than 1, the R groups may be the same or different.

[0032] Each R group in formula (II) can be an unsubstituted hydrocarbon group, a substituted hydrocarbon group, or a functional group containing at least one element from groups 13-17 of the periodic table. When the R group is a functional group containing at least one element from groups 13-17, the R group can be a halogen (F, Cl, Br, or I), O, N, Se, Te, P, As, Sb, S, B, Si, Ge, Sn, Pb, and similar groups, such as C(O)R*, C(C)NR*2, C(O)OR*, NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, SO x (where x=2 or 3), BR*2, SiR*3, GeR*3, SnR*3, PbR*3, and similar groups, wherein R* is independently hydrogen or an unsubstituted hydrocarbon group, or at least one heteroatom is inserted into an unsubstituted hydrocarbon group.

[0033] Each R group in Formula (II) may independently have any suitable number of carbon atoms, such as 1 to 20 carbon atoms, such as 1 to 10 carbon atoms, such as 1 to 5 carbon atoms, such as 1 to 4 carbon atoms. In some embodiments, the number of carbon atoms in each R group of Formula (II) may independently be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. Each of the aforementioned numbers may be preceded by the terms "about," "at least about," "less than about," or "greater than about," and any of the aforementioned numbers may be used alone to describe the range of open ends or in combination to describe the range of closed ends. Each R group in Formula (II) may independently be linear or branched, saturated or unsaturated, cyclic or acyclic, aromatic or non-aromatic. Regarding saturation, each R group in Formula (II) may independently be fully saturated, partially unsaturated, or fully unsaturated.

[0034] In some instances, one or more R groups of formula (II) may be unsubstituted hydrocarbon groups. "Unsubstituted hydrocarbon group" means a group consisting only of hydrogen and carbon atoms. Exemplary, but non-limiting, examples of unsubstituted hydrocarbon groups include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, and tributyl, pentyl, hexyl, heptyl, octyl, ethyl-2-hexyl, isooctyl, nonyl, n-decyl, isodecyl, or isomers thereof; cycloaliphatic groups having 3 to 20 carbon atoms, such as cyclopentyl or cyclohexyl; aromatic groups having 6 to 20 carbon atoms, such as phenyl or naphthyl; or any combination thereof. In some embodiments, one or more R groups of formula (II) may be linear or branched alkenyl groups having 1 to 20 carbon atoms, such as 3 to 10 carbon atoms. The term "alkenyl" refers to a hydrocarbon group having at least one double bond. Exemplary, but non-limiting, examples of alkenyl groups include allyl groups (e.g., -CH2CH=CH2).

[0035] In some embodiments, one or more R groups of formula (II) may be substituted hydrocarbon groups. "Substituted hydrocarbon group" refers to an unsubstituted hydrocarbon group in which at least one hydrogen atom is substituted by at least one heteroatom or a group containing a heteroatom, such as one or more elements of groups 13-17 of the periodic table, such as halogens (F, Cl, Br, or I), O, N, Se, Te, P, As, Sb, S, B, Si, Ge, Sn, Pb, and the like, such as C(O)R*, C(C)NR*2, C(O)OR*, NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, SO x(where x = 2 or 3), BR*2, SiR*3, GeR*3, SnR*3, PbR*3, and the like, wherein R* is independently hydrogen or an unsubstituted hydrocarbon group, or at least one heteroatom is inserted into an unsubstituted hydrocarbon group.

[0036] Exemplary, but non-limiting, examples of substituted hydrocarbon groups include -OR*, wherein an oxygen atom is attached to the ring and wherein R* may comprise 1 to 10 carbon atoms, such as 1 to 5 carbon atoms, such as 2 to 4 carbon atoms. For example, -OR* may be an alkoxy group such as methoxy, ethoxy, propoxy, butoxy, and isomers thereof.

[0037] In some embodiments, each R group in formula (II) is a group that does not react with reactants containing epoxides. For example, and in at least one embodiment, each R group in formula (II) is independently -(C1-C5)alkyl or -O(C1-C5)alkyl.

[0038] In at least one embodiment, the phenolic compound of formula (II) is a monohydric phenol (y is 1).

[0039] In formula (II), and in some embodiments, at least one R group is located on the aromatic ring at an ortho position relative to a hydroxyl group. In some embodiments, the R groups of formula (II) are located on the ring at each ortho position relative to a hydroxyl group.

[0040] As used herein, “phenolic oligomer” means an oligomer of phenol (a compound of formula (I)), an oligomer of a phenolic compound represented by formula (II), or a combination thereof.

[0041] Separation process

[0042] Figure 1A This is a flowchart illustrating selected operations of a process 100 for separating organic products from an organic recycle stream according to at least one embodiment of this disclosure. Process 100 produces a phenol-rich composition. The phenol-rich composition has a higher concentration of phenols compared to the concentration of phenols in the feed organic recycle stream. The phenols obtained from the process are recycled phenols. Figure 1B A flowchart 150 is provided to illustrate an embodiment of a process 100 for producing a phenol-rich composition according to at least one embodiment of the present disclosure.

[0043] During process 100, suitable solvents may be used in various operating phases. Suitable solvents used in one or more operating phases of process 100 include, but are not limited to, aqueous solvents, organic solvents, or combinations thereof. Aqueous solvents may be selected from the group consisting of: water, distilled water, deionized water, ultrapure water, and combinations thereof. Organic solvents may be selected from the group consisting of: halogenated solvents, alcohol solvents, alkyl carbonate solvents, ketone solvents, hydrocarbon solvents, ester solvents, ether solvents, and combinations thereof. Halogenated solvents may be selected from the group consisting of: dichloromethane, chloroform, and combinations thereof. Alcohol solvents may be selected from the group consisting of: ethanol (EtOH), methanol, isopropanol, n-propanol, n-butanol, isobutanol, dibutanol, pentanol (such as n-pentanol, isopentanol, and dipentanol), and combinations thereof. Alkyl carbonate solvents may be selected from the group consisting of: dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and combinations thereof. Ketone solvents may include acetone. Hydrocarbon solvents may be selected from the group consisting of: hexane, pentane, cyclohexane, benzene, toluene, and combinations thereof. Ester solvents may include ethyl acetate. Ether solvents may be selected from the group consisting of: dimethyl ether, diethyl ether, tetrahydrofuran, dipropylene glycol dimethyl ether, methyl tributyl ether, ethylene glycol ether, and combinations thereof. Other solvents such as ethyl acetate, dimethylformamide, acetonitrile, N-methyl-2-pyrrolidone, dimethyl sulfoxide, or combinations thereof may be used. Mixtures of solvents may also be used.

[0044] Process 100 begins at operation 102 by contacting feedstock 155 with a first organic solvent and water to form a first aqueous stream 160 and a first organic stream 165. Feedstock 155 used in operation 102 comprises, is substantially composed of, or is composed of an organic circulating stream. The feedstock has a first concentration of phenol.

[0045] Organic circulating streams may include epoxy resins, phenolic resins, or combinations thereof. Alternatively or additionally, organic circulating streams may include streams used or made during the processing or manufacture of resins, streams used or made during the processing or manufacture of thermosetting materials, streams used or made during the processing or manufacture of fiber-reinforced thermosetting composites, or combinations thereof.

[0046] Alternatively or concurrently, the organic circulating stream may include materials derived from or derived from fiber-reinforced thermosetting composites. As described above, the fiber-reinforced thermosetting composites may be subjected to thermochemical processes, such as high-temperature decomposition, solvent decomposition, thermal decomposition, catalytic depolymerization, or combinations thereof, to separate the organic circulating stream from the fibers. Such organic circulating streams may be products, such as oils, particularly high-temperature decomposition oils, solvent decomposition oils, thermal decomposition oils, catalytic depolymerization oils, or combinations thereof. These oils contain valuable organic compounds such as phenolic compounds, resins, and other organic compounds.

[0047] Accordingly, and in some embodiments, the organic circulating stream may include products from the solvent decomposition of epoxy resin composites, products from the solvent decomposition of phenolic resin composites, products from the high-temperature decomposition of epoxy resin composites, products from the high-temperature decomposition of phenolic resin composites, products from the thermal decomposition of epoxy resin composites, products from the thermal decomposition of phenolic resin composites, products from the catalytic depolymerization of epoxy resin composites, products from the thermal decomposition of phenolic resin composites, or combinations thereof, and products generated from any suitable recycling process of the composite material. These products may be in oil form. Thermal decomposition is typically performed by heating the composite material to form gaseous, liquid, and solid products. Catalytic depolymerization may involve using a transition metal catalyst, such as a ruthenium-based catalyst, to break bonds (such as C(alkyl)-O bonds) in the composite material, thereby forming the product.

[0048] During the solvent decomposition of epoxy resin composites, solvents and acids can be used to separate solvent-decomposed oils from the fibers. Solvents such as acetone, water, ethanol, 2-propanol, or supercritical solvent mixtures can be used herein. Acids such as nitric acid, acetic acid, p-toluenesulfonic acid (p-TsOH), or combinations thereof can be utilized. The products from solvent decomposition depend considerably on the recycling process used and are not intended to be limited to those described herein.

[0049] Exemplary, but non-limiting, examples of products from the solvent decomposition of epoxy resin composites (solvent-decomposed oils) may include, but are not limited to: phenol; aniline; quinoline; 4-(1-methylethyl)phenol; 4-ethylphenol; phenol, 3-(1-methylethyl)-; 2H-1-benzopyran, 3,4-dihydro-; 3-phenoxy-1,2-propanediol; p-hydroxybiphenyl; 2-propanol, 1-phenoxy-3-(phenylamino)-; 1H-indole, 2,5-dimethyl; or combinations thereof. The remaining amount of solvent-decomposed oil may include one or more of the compounds described below for high-temperature decomposition oils, as well as other compounds. Additionally or alternatively, other products of solvent decomposition present in the solvent-decomposed oil may include phenolic compounds, phenolic oligomer glycated matrices, curing agents, accelerators, advanced resins, amine derivatives, phenylamine derivatives, or combinations thereof.

[0050] In some embodiments, the solvent-decomposed oil may include, based on a total weight percentage of the solvent-decomposed oil, from about 2 wt% to about 25 wt%, amounts such as from about 10 wt% to about 17 wt% of phenols, phenolic compounds, and phenolic oligomers, however, other amounts are included. The total weight of the solvent-decomposed oil does not exceed 100 wt%. The remaining amount of the solvent-decomposed oil may include one or more of the compounds described above for the solvent-decomposed oil, as well as other compounds.

[0051] During the high-temperature decomposition of the epoxy resin composite, the composite is heated to approximately 350°C to approximately 500°C in the absence or presence of oxygen in order to form an organic fraction (high-temperature decomposition oil).

[0052] Exemplary, but non-limiting, examples of products from the high-temperature decomposition of epoxy resin composites (high-temperature decomposition oils) may include, but are not limited to: phenol; p-cumenol; 3-isopropylphenol; 4,4'-(1-methylethylidene)bisphenol; toluene; o-cresol; 4-ethylphenol; p-cresol; 4-isopropyl-3-methylphenol; 2-ethylphenol; p-isopropenylphenol; 2-methyl-2-(4'-hydroxyphenyl)pentanone-4; acetone; aniline; m-cresol; benzene; ethylbenzene; styrene; xylene; or combinations thereof. In some embodiments, based on the total weight percentage of the high-temperature decomposition oil, from about 2 wt% to about 30 wt%, amounts of phenol, phenolic compounds, and phenolic oligomers, such as from about 10 wt% to about 22 wt%, but covering other amounts, are included. The total weight of the high-temperature decomposition oil does not exceed 100 wt%. The remaining amount of the high-temperature decomposition oil may include one or more of the compounds described above for solvent-decomposed oils, as well as other compounds. Alternatively, other products of high-temperature decomposition present in high-temperature decomposition oil may include phenolic compounds, phenolic oligomer glycated matrix, curing agents, accelerators, advanced resins, amine derivatives, phenylamine derivatives, or combinations thereof.

[0053] The aforementioned solvent-decomposed oil, high-temperature decomposed oil, thermal decomposed oil, catalytic decomposed oil, their components, or combinations thereof may constitute at least a portion of the raw material 155 of the process described herein.

[0054] The water used for operation 102 may comprise, consist of, or be substantially composed of, tap water, distilled water, deionized water, ultrapure water, or combinations thereof. In some embodiments, the water may include salt. The weight ratio of the raw material to the water used for operation 102 may be from about 1:50 to about 50:1, such as from about 1:35 to about 35:1, such as from about 1:20 to about 20:1, such as from about 1:15 to about 15:1, such as from about 1:10 to about 10:1, such as from about 5:1 to about 1:5, such as from about 3:1 to about 1:3, such as from about 2:1 to about 1:2, such as from about 1.2:1 to about 1:1.2, such as about 1:1, however, encompassing other amounts. Any of the foregoing numbers may be used individually to describe an open-end range or in combination to describe a closed-end range.

[0055] The first organic solvent used for operation 102 may include the organic solvents described above. In some embodiments, the first organic solvent used for operation 102 may comprise, consist substantially of, or consist of a halogenated solvent, an ether solvent, a ketone solvent, an ester solvent, or a combination thereof. In at least one embodiment, the first organic solvent used for operation 102 is selected from the group consisting of halogenated solvents, ether solvents, ketone solvents, ester solvents, and combinations thereof. In some embodiments, the first organic solvent comprises an aprotic solvent. An aprotic solvent is one that does not provide protons (H) to the solution. + Solvents.

[0056] In some embodiments, the first organic solvent used for operation 102 may comprise, consist substantially of, or consist of dichloromethane, chloroform, methyl tert-butyl ether, ethyl acetate, toluene, benzene, hexane, cyclohexane, or combinations thereof. In at least one embodiment, the first organic solvent used for operation 102 is selected from the group consisting of dichloromethane, chloroform, methyl tert-butyl ether, ethyl acetate, toluene, benzene, hexane, cyclohexane, or combinations thereof.

[0057] The weight ratio of raw material 155 to the first organic solvent used in operation 102 may be from about 1:50 to about 50:1, such as from about 1:35 to about 35:1, such as from about 1:20 to about 20:1, such as from about 1:15 to about 15:1, such as from about 1:10 to about 10:1, such as from about 5:1 to about 1:5, such as from about 3:1 to about 1:3, such as from about 2:1 to about 1:2, such as from about 1.2:1 to about 1:1.2, such as about 1:1, however, encompassing other amounts. Any of the foregoing numbers may be used individually to describe the open-end range or in combination to describe the closed-end range.

[0058] During operation 102, raw material 155, water, and the first organic solvent may be fed into the container. The resulting mixture may be mixed, stirred, or otherwise agitated under mixing conditions that effectively form the first aqueous stream 160 and the first organic stream 165. The mixing conditions of operation 102 may include a temperature of about 15°C to about 30°C and an ambient pressure of about 1 atm. Higher temperatures may be used if necessary. However, if higher temperatures are used during mixing, the mixing temperature should be below the boiling point of the water and the first organic solvent.

[0059] The mixing conditions of operation 102 may include stirring, mixing, agitation, or a combination thereof using a suitable device. Suitable devices may include mechanical stirrers such as overhead stirrers, magnetic stirrers (e.g., placing a magnetic stirring bar in a container above a magnetic stirrer), or other suitable devices. For example, a stirrer with blades or propellers may be rotated by receiving rotational power from a stirring motor to stir the components at suitable rotational speeds, such as about 50 rpm to about 1,500 rpm, such as about 75 rpm to about 1,000 rpm, such as about 100 rpm to about 900 rpm, such as about 200 rpm to about 800 rpm, such as about 300 rpm to about 700 rpm, such as about 400 rpm to about 600 rpm, such as about 450 rpm to about 550 rpm, such as about 500 rpm. Any of the foregoing numbers may be used individually to describe an open-end range or in combination to describe a closed-end range. Other rotational speeds are covered and may be selected based on the ability to adequately mix the components. The mixing conditions of operation 102 may include the use of non-reactive gases, such as N2, Ar, or combinations thereof. For example, a non-reactive gas may be introduced into feedstock 155, water, and a first organic solvent to degas the various components or additionally remove unwanted gases such as oxygen from the mixture.

[0060] Mixing, stirring, or agitation may be performed during operation 102 for any suitable period of time, such as about 1 min to about 48 h, such as about 5 min to about 24 h, such as about 30 min to about 10 h, such as about 1 h to about 5 h, such as about 2 h to about 3 h, however covering other periods. Any of the foregoing numbers may be used alone to describe the open-end range or in combination to describe the closed-end range.

[0061] After mixing, the mixture of raw material 155, water, and solvent is separated by a suitable liquid-liquid separation technique, such as decantation, distillation, extraction, extractive distillation, or a combination thereof, and other techniques. Following separation, a first aqueous stream 160 and a first organic stream 165 are obtained. The first aqueous stream 160 may include organic acids such as p-toluenesulfonic acid or hexahydrophthalic acid, and other acids. Depending on, for example, the acid used to form the raw material, any suitable organic acid may be present.

[0062] The first organic stream 165 may include phenolic compounds (including phenols), as well as one or more other organic compounds such as those described above. In some embodiments, the first aqueous stream contains a higher amount of organic acid (e.g., p-toluenesulfonic acid or hexahydrophthalic acid) compared to the amount of organic acid in the first organic stream.

[0063] If desired, the first aqueous stream 160 may undergo operation 102, wherein the first aqueous stream 160 may be contacted with a first organic solvent and the resulting mixture may be separated. After separation, the organic layer may be combined with the first organic stream 165. Subjecting the first aqueous stream 160 to operation 102 may be used to extract any remaining phenols, other organic compounds, or combinations thereof from the first aqueous stream 160. Operation 102 may be performed any suitable number of times, such as 1, 2, 3, 4, or more. The components in the organic layer may be extracted and combined to form the first organic stream 165.

[0064] In some embodiments, and before proceeding to further operations of process 100, solvents such as organic solvents or water may be removed from the first aqueous stream 160, the first organic stream 165, or both. Solvent removal may be accomplished by suitable techniques such as distillation, vacuum distillation, or a combination thereof.

[0065] Process 100 further includes, at operation 104, contacting the first organic stream 165 with an aqueous alkali to form a second aqueous stream 170 and a second organic stream 175.

[0066] The aqueous alkali used for operation 104 may comprise, consist substantially of, or consist of alkali metal hydroxides. Suitable alkali metal hydroxides may include lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), neodymium hydroxide (RbOH), cesium hydroxide (CsOH), or combinations thereof, such as LiOH, NaOH, KOH, or combinations thereof. In some embodiments, the alkali metal hydroxide is selected from the group consisting of LiOH, NaOH, KOH, and combinations thereof.

[0067] An aqueous alkali may be added to the first organic stream 165 until the pH reaches a desired value and is maintained thereto deprotonate the phenols and phenolic compounds, thereby converting them into their corresponding phenol salts. In this document, and in some embodiments, operation 104 may include adding an aqueous alkali to the first organic stream 165 to form a mixture having the desired pH. By converting the phenols and phenolic compounds into their corresponding phenol salts, the compounds become water-soluble, thereby allowing the transfer of the phenols and phenolic compounds to the second aqueous stream 170.

[0068] The suitable pH of the mixture including the aqueous alkali and the first organic stream 165 may be about 9.5 or greater, such as about 9.5 to about 14, such as about 9.5 to about 13, such as about 9.5 to 11, about 10 to about 12, or about 10 to about 11, however, other pH values ​​or ranges are included. Any of the foregoing numbers may be used alone to describe the open-end range or in combination to describe the closed-end range.

[0069] In some embodiments, the aqueous alkali may comprise any suitable concentration of alkali metal hydroxide in the water. The concentration of alkali metal hydroxide in the water may be about 1 wt% or greater, such as about 1 wt% to about 20 wt%, such as about 2 wt% to about 15 wt%, such as about 3 wt% to about 10 wt%, such as about 5 wt% to about 9 wt%, such as about 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, or 8 wt%, however, other values ​​are included. Any of the foregoing numbers may be used individually to describe an open-end range or in combination to describe a closed-end range.

[0070] In some embodiments, the weight ratio of the first organic stream 165 to the aqueous base used in operation 104 may be from about 1:50 to about 50:1, such as from about 1:35 to about 35:1, such as from about 1:20 to about 20:1, such as from about 1:15 to about 15:1, such as from about 1:10 to about 10:1, such as from about 5:1 to about 1:5, such as from about 3:1 to about 1:3, such as from about 2:1 to about 1:2, such as from about 1.2:1 to about 1:1.2, such as about 1:1, however, encompassing other amounts. Any of the foregoing numbers may be used individually to describe the open-end range or in combination to describe the closed-end range.

[0071] During operation 104, the first organic stream 165 and the aqueous base may be fed into the container. The resulting mixture may be mixed, stirred, or otherwise agitated under mixing conditions that effectively form the second aqueous stream 170 and the second organic stream 175. The mixing conditions for operation 104 may include a temperature of about 15°C to about 30°C and an ambient pressure (about 1 atm). Higher temperatures may be used if necessary. However, if higher temperatures are used during mixing, the mixing temperature should be below the boiling point of the water and organic solvent in the mixture.

[0072] The mixing conditions of operation 104 may include stirring, mixing, agitation, or a combination thereof using a suitable device. Suitable devices may include mechanical stirrers such as overhead stirrers, magnetic stirrers (e.g., placing a magnetic stirring bar in a container above a magnetic stirrer), or other suitable devices. For example, a stirrer with blades or propellers may be rotated by receiving rotational power from a stirring motor to stir the components at suitable rotational speeds, such as about 50 rpm to about 1,500 rpm, such as about 75 rpm to about 1,000 rpm, such as about 100 rpm to about 900 rpm, such as about 200 rpm to about 800 rpm, such as about 300 rpm to about 700 rpm, such as about 400 rpm to about 600 rpm, such as about 450 rpm to about 550 rpm, such as about 500 rpm. Any of the foregoing numbers may be used individually to describe an open-end range or in combination to describe a closed-end range. Other rotational speeds are covered and may be selected based on the ability to adequately mix the components. The mixing conditions of operation 104 may include the use of non-reactive gases, such as N2, Ar, or combinations thereof. For example, a non-reactive gas may be introduced into the first organic stream 165 and an aqueous base to degas the various components or additionally remove unwanted gases such as oxygen from the mixture.

[0073] Mixing, stirring, or agitation may be performed during operation 104 for any suitable period of time, such as about 1 min to about 48 h, such as about 5 min to about 24 h, such as about 30 min to about 10 h, such as about 1 h to about 5 h, such as about 2 h to about 3 h, however, other periods are also included. Any of the foregoing numbers may be used alone to describe the open-end range or in combination to describe the closed-end range.

[0074] After mixing, the mixture is separated using suitable liquid-liquid separation techniques, such as decantation, distillation, extraction, extractive distillation, or combinations thereof, and other techniques. Following separation, a second aqueous stream 170 and a second organic stream 175 are obtained.

[0075] The second aqueous stream 170 may include phenols. The second aqueous stream 170 may, where appropriate, include phenolic compounds, other organic compounds, or combinations thereof.

[0076] The second organic stream 175 may include phenolic compounds and, where appropriate, other organic compounds. The second organic stream 175 may also include a matrix for synthesizing epoxy resins. For example, such matrices may include glycinate matrices different from bisphenols. This matrix can be used to replace bisphenols and form epoxy resins. In some embodiments, the glycinate matrix contains bisphenols. Alternatively or additionally, the second organic stream 175 may include curing agents, accelerators, or combinations thereof. Where appropriate, the second organic stream 175 may include advanced resins based on bisphenol A diglycidyl ether, advanced resins based on bisphenol F diglycidyl ether, or combinations thereof. Curing agents, accelerators, glycinate matrices, advanced resins, or combinations thereof can be used to form epoxy resins. Therefore, the second organic stream 175 may include high-value organic compounds. Exemplary, but non-limiting, examples of curing agents present in the second organic stream 175 may particularly include amines, anhydrides, phenolic resins, or combinations thereof. Exemplary, but non-limiting, examples of accelerators present in the second organic stream 175 may particularly include acids, Lewis acids, third amines, phenolic derivatives, or combinations thereof. Exemplary, but non-limiting, examples of the glycated matrix present in the second organic stream 175 may include, in particular, phenolic resins, bisphenols, amine derivatives, or combinations thereof. In at least one embodiment, the second organic stream further comprises a glycated matrix, a curing agent, an accelerator, or a combination thereof.

[0077] The second organic stream 175 may include phenol, depending on the circumstances. In some embodiments, the amount or concentration of phenol contained in the second aqueous stream 170 is greater than the amount or concentration of phenol in the second organic stream 175.

[0078] In some embodiments, the amount of phenol in the second organic stream 175 is lower than the amount of phenol in the second aqueous stream 170. The phenol in the aqueous stream may be in its ionic form. In some embodiments, based on the total weight of the organic compounds present in the second organic stream 175, the amount of phenol in the second organic stream 175 may be about 5 wt% or less, 4 wt% or less, 3 wt% or less, 2.5 wt% or less, 2 wt% or less, 1.5 wt% or less, 1 wt% or less, or 0.5 wt% or less. Any of the foregoing numbers may be used individually to describe an open-end range or in combination to describe a closed-end range. Other amounts of phenol in the second organic stream 175 are also covered.

[0079] The total weight of the organic compounds present in the second organic stream 175 does not exceed 100 wt%. The total weight of the organic compounds in the second organic stream 175 does not include the weight of the first organic solvent. Any of the foregoing numbers may be used alone to describe the open-end range or in combination to describe the closed-end range. The amount of phenols in the second organic stream 175 can be determined by gas chromatography or mass spectrometry as described in the Examples section.

[0080] In some embodiments, the amount or concentration of phenol in the second aqueous stream 170 is greater than the amount or concentration of phenol in the second organic stream 175. In some embodiments, based on the total weight of the organic compounds present in the second aqueous stream 170, the amount of phenol in the second aqueous stream 170 may be about 1 wt% or more, such as about 5 wt% or more, such as about 10 wt% or more, such as 20 wt% or more, such as 30 wt% or more, such as about 50 wt% or more. The total weight of the organic compounds in the second aqueous stream 170 does not include the weight of the first organic solvent (if present).

[0081] The amount of phenol in the second aqueous stream 170 can be determined by gas chromatography-mass spectrometry (GC-MS). In this paper, and prior to GC-MS, the second aqueous stream 170 is extracted with a suitable organic solvent, dried with a suitable drying agent such as sodium sulfate or magnesium sulfate to remove excess solvent, and then diluted with a suitable solvent such as tetrahydrofuran for GC-MS analysis.

[0082] If desired, the second organic stream 175 may undergo operation 104, wherein the second organic stream 175 may be contacted with an aqueous alkali and the resulting mixture may be separated. After separation, the aqueous layer may be combined with the second aqueous stream 170 and the organic layer may be combined with the second organic stream 175. Subjecting the second organic stream 175 to operation 104 may be used to extract any remaining phenols, other organic compounds, or combinations thereof from the second organic stream 175. Operation 104 may be performed any suitable number of times, such as 1, 2, 3, 4, or more. The components in the aqueous layer may be extracted and combined to form the second aqueous stream 170.

[0083] In some embodiments, and before proceeding to further operations of process 100, solvents such as organic solvents or water may be removed from the second aqueous stream 170, the second organic stream 175, or both. Solvent removal may be accomplished by any suitable technique such as distillation, vacuum distillation, or a combination thereof.

[0084] Process 100 further includes, at operation 106, contacting a second aqueous stream 170 with an aqueous acid to form a precipitate 185 and a third aqueous stream 180 containing phenols. The precipitate 185 may include phenol oligomers, other higher molecular weight phenol derivatives, or combinations thereof. The third aqueous stream 180 may, where appropriate, include phenolic compounds and, where appropriate, other organic compounds.

[0085] In some embodiments, the compounds included in the compounds referred to as phenol oligomers and higher molecular weight phenol derivatives may have an average molecular weight that is about two to about four times greater than the average molecular weight of the compounds present in the phenol-rich composition 190, depending on the process used to separate the organic circulating stream from the fiber (e.g., high-temperature decomposition solvent decomposition, thermal decomposition, catalytic depolymerization, or a combination thereof).

[0086] For example, compounds present in the oligomer fraction (corresponding to precipitate 185) may have a weight-average molecular weight (Mi) of about 400 g / mol to about 500 g / mol or about 200 g / mol to about 300 g / mol. w ), and number-average molecular weights (Mi) of about 150 g / mol to about 250 g / mol or about 200 g / mol to about 300 g / mol. n However, other values ​​are also included. In contrast, compounds present in the phenol fraction (corresponding to phenol-rich composition 190) may have an M of about 100 g / mol to about 200 g / mol. w and M from about 75 g / mol to about 150 g / mol or from about 100 g / mol to about 175 g / mol n However, it covers other values.

[0087] The aqueous acid used in operation 106 may comprise, consist of, or be substantially composed of inorganic acids, organic acids, or combinations thereof.

[0088] Any suitable inorganic acid can be used. Exemplary, but non-limiting, examples of inorganic acids suitable for operation 106 may include, in particular, hydrochloric acid (HCl), sulfuric acid (H2SO4), nitric acid (HNO3), phosphoric acid (H3PO4), boric acid (H3BO4), hydrobromic acid (HBr), hydroiodic acid (HI), hydrofluoric acid (HF), perchloric acid (HClO4), and combinations thereof. In some embodiments, the inorganic acid may comprise HCl, H2SO4, HNO3, H3PO4, or combinations thereof. In at least one embodiment, the inorganic acid is selected from the group consisting of HCl, H2SO4, HNO3, H3PO4, and combinations thereof.

[0089] Any suitable organic acid can be used. Organic acids suitable for operation 106 may include carboxylic acids (acids containing one or more -CO2H groups), sulfonic acids (acids containing one or more -SO3H groups), or combinations thereof. Exemplary, but non-limiting, examples of carboxylic acids may include formic acid (HCO2H), acetic acid (CH3CO2H), propionic acid (CH3CH2CO2H), butyric acid (CH3CH2CH2CO2H), lactic acid (CH3CH(OH)CO2H), sorbic acid (CH3(CH)4CO2H), fumaric acid ((CO2H)CH=CHCO2H), malic acid ((CO2H)CH2CH(OH)CO2H), tartaric acid ((CO2H)CH(OH)CH(OH)CO2H), citric acid ((CO2H)CH2C(OH)(CO2H)CH2CO2H), benzoic acid (C6H5CO2H), trifluoroacetic acid (CF3CO2H), trichloroacetic acid (CCl3CO2H), dichloroacetic acid (CHCl2CO2H), fluoroacetic acid (FCH2CO2H), chloroacetic acid (ClCH2CO2H), or combinations thereof. Exemplary, but non-limiting, examples of sulfonic acids may include methanesulfonic acid (CH3SO3H), p-toluenesulfonic acid (CH3C6H4SO3H), trifluoromethanesulfonic acid (CF3SO3H), benzenesulfonic acid (C6H5SO3H), or combinations thereof. Other organic acids may include picric acid ((O2N)3C6H2OH). Other organic acids are covered.

[0090] In at least one embodiment, the organic acid is selected from the group consisting of formic acid, acetic acid, citric acid, oxalic acid, and combinations thereof.

[0091] An aqueous acid may be added to the second aqueous stream 170 until the pH reaches a desired value and is maintained thereon so that phenol salts present in the second aqueous stream can be converted into their corresponding phenols and phenolic compounds. In this document, and in some embodiments, operation 106 may include adding an aqueous acid to the second aqueous stream 170 to form a mixture having the desired pH. At operation 106, higher molecular weight phenolic derivatives and oligomers may precipitate from the mixture.

[0092] The suitable pH value of the mixture comprising the aqueous acid and the second aqueous stream 170 may be about 7.5 or less, such as about 1 to about 7, such as about 1 to about 6.5, such as about 1 to about 5, about 2 to about 4, about 1 to about 3, or about 2 to about 3, however, other pH values ​​or ranges are included. Any of the foregoing numbers may be used individually to describe an open-end range or in combination to describe a closed-end range. In at least one embodiment, the pH value of the mixture comprising the aqueous acid and the second aqueous stream is about 5 or less.

[0093] In some embodiments, the aqueous acid used in operation 106 may have any suitable concentration in water. The concentration of the acid in the water may be about 1 wt% or greater, such as about 1 wt% to about 20 wt%, such as about 2 wt% to about 15 wt%, such as about 3 wt% to about 10 wt%, such as about 5 wt% to about 9 wt%, such as about 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, or 8 wt%, however, other values ​​are included. Any of the foregoing numbers may be used individually to describe the open-end range or in combination to describe the closed-end range.

[0094] In some embodiments, the weight ratio of the second aqueous stream 170 to the aqueous acid used in operation 106 may be from about 1:50 to about 50:1, such as from about 1:35 to about 35:1, such as from about 1:20 to about 20:1, such as from about 1:15 to about 15:1, such as from about 1:10 to about 10:1, such as from about 5:1 to about 1:5, such as from about 3:1 to about 1:3, such as from about 2:1 to about 1:2, such as from about 1.2:1 to about 1:1.2, such as about 1:1, however, encompassing other amounts. Any of the foregoing numbers may be used individually to describe the open-end range or in combination to describe the closed-end range.

[0095] During operation 106, a second aqueous stream 170 and an aqueous acid may be fed into the container. The resulting mixture may be mixed, stirred, or otherwise agitated under conditions that effectively form a precipitate 185 containing phenol oligomers and a third aqueous stream containing phenol. The mixing conditions for operation 106 may include a temperature of about 15°C to about 30°C and an ambient pressure (about 1 atm). Higher temperatures may be used if necessary. However, if higher temperatures are used during mixing, the mixing temperature should be below the boiling point of the water and organic solvent in the mixture.

[0096] The mixing conditions of operation 106 may include stirring, mixing, agitation, or a combination thereof using a suitable device. Suitable devices may include mechanical stirrers such as overhead stirrers, magnetic stirrers (e.g., placing a magnetic stirring bar in a container above a magnetic stirrer), or other suitable devices. For example, a stirrer with blades or propellers may be rotated by receiving rotational power from a stirring motor to stir the components at suitable rotational speeds, such as about 50 rpm to about 1,500 rpm, such as about 75 rpm to about 1,000 rpm, such as about 100 rpm to about 900 rpm, such as about 200 rpm to about 800 rpm, such as about 300 rpm to about 700 rpm, such as about 400 rpm to about 600 rpm, such as about 450 rpm to about 550 rpm, such as about 500 rpm. Any of the foregoing numbers may be used individually to describe an open-end range or in combination to describe a closed-end range. Other rotational speeds are covered and may be selected based on the ability to adequately mix the components. The mixing conditions of operation 106 may include the use of non-reactive gases, such as N2, Ar, or combinations thereof. For example, a non-reactive gas may be introduced into a second aqueous stream 170 and an aqueous acid to degas the various components or additionally remove unwanted gases (e.g., oxygen) from the mixture.

[0097] Mixing, stirring, or agitation may be performed during operation 106 for any suitable period of time, such as about 1 min to about 48 h, such as about 5 min to about 24 h, such as about 30 min to about 10 h, such as about 1 h to about 5 h, such as about 2 h to about 3 h, however covering other periods. Any of the foregoing numbers may be used alone to describe the open-end range or in combination to describe the closed-end range.

[0098] After mixing, the mixture can be subjected to any suitable separation technique, such as solid / liquid techniques including mechanical or gravity separation, such as filtration, vacuum filtration, centrifuges, decanters, decanter-centrifuges, combinations thereof, and other techniques. Separation can be aided by pressing the formed solid filter cake. Separation can be performed once or multiple times. Filtration can be accomplished using a porous surface to draw the filtrate (liquid) from the mixture to one side of the porous surface and retain the matrix source as retentate (solid, precipitate, or filter cake) on the opposite side of the porous surface. For example, the mixture formed at operation 106 can be separated, for example, by filtration to provide a filtrate containing a third aqueous stream 180 and retentate (e.g., precipitate 185).

[0099] The porous surface can be a membrane or glaze made of any suitable material such as ceramic, glass, or other materials. The pore size of the porous membrane can be selected to separate a specific size or range (e.g., weight-average molecular weight or range) of the matrix from the matrix source. The separation process of operation 106 can be performed once or multiple times. After the desired number of separations, the precipitate 185 can be used in conversion processes, such as as a monomer in epoxy resin synthesis or as a comonomer with phenol. The filtrate containing the third aqueous stream 180 can undergo operation 108, as further described below.

[0100] If desired, precipitate 185 may undergo operation 106, wherein precipitate 185 may be contacted with an aqueous acid and the resulting mixture may be separated. After separation, the aqueous layer may be combined with a third aqueous stream 180. Subjecting precipitate 185 to operation 106 may be used to remove any remaining phenols, other organic compounds, or combinations thereof from precipitate 185. Operation 106 may be performed any suitable number of times, such as 1, 2, 3, 4, or more. The components in the aqueous layer may be removed and combined to form the third aqueous stream 180.

[0101] In some embodiments, and before proceeding to further operations of process 100, solvents such as organic solvents or water may be removed from precipitate 185, third aqueous stream 180, or both. Solvent removal may be accomplished by suitable techniques such as distillation, vacuum distillation, or a combination thereof.

[0102] Process 100 further includes, at operation 108, contacting a third aqueous stream 180 with a second organic solvent to form composition 190. Composition 190 may be rich in phenols. Composition 190 has a second concentration of phenols, wherein the second concentration of phenols may be greater than the first concentration of phenols. That is, the concentration of phenols in composition 190 formed by process 100 may be greater than the concentration of phenols in feedstock 155. Operation 108 also produces a fourth aqueous stream 195.

[0103] The phenol-rich composition 190 comprises, is substantially composed of, or is composed of, a phenol, and, where appropriate, one or more additional components. The one or more additional compounds may include phenolic compounds represented by formula (II). In some instances, the one or more additional components may include p-cumenol, 4,4'-(1-methylethylidene)bisphenol, 4-isopropyl-3-methylphenol, a second organic solvent, or a combination thereof.

[0104] The second organic solvent used for operation 108 may include the organic solvents described above. In some embodiments, the second organic solvent used for operation 108 may comprise, consist substantially of, or consist of a halogenated solvent, an ether solvent, a ketone solvent, an ester solvent, or a combination thereof. In at least one embodiment, the second organic solvent used for operation 108 is selected from the group consisting of halogenated solvents, ether solvents, ketone solvents, ester solvents, and combinations thereof. In some embodiments, the second organic solvent comprises an aprotic solvent.

[0105] In some embodiments, the second organic solvent used for operation 108 may comprise, consist substantially of, or consist of dichloromethane, chloroform, methyl tert-butyl ether, ethyl acetate, toluene, benzene, hexane, cyclohexane, or combinations thereof. In at least one embodiment, the second organic solvent used for operation 108 is selected from the group consisting of dichloromethane, chloroform, methyl tert-butyl ether, ethyl acetate, toluene, benzene, hexane, cyclohexane, or combinations thereof.

[0106] In at least one embodiment, each of the first and second organic solvents independently comprises an aprotic solvent. In some embodiments, each of the first and second organic solvents is independently selected from the group consisting of: halogenated solvents, ether solvents, ketone solvents, ester solvents, and combinations thereof. In at least one embodiment, each of the first and second organic solvents is independently selected from the group consisting of: dichloromethane, chloroform, methyl tert-butyl ether, ethyl acetate, toluene, benzene, hexane, cyclohexane, and combinations thereof. In some embodiments, each of the first and second aprotic solvents is independently selected from the group consisting of: dichloromethane, chloroform, methyl tert-butyl ether, ethyl acetate, and combinations thereof.

[0107] The weight ratio of the third aqueous stream 180 to the second organic solvent used in operation 108 may be from about 1:50 to about 50:1, such as from about 1:35 to about 35:1, such as from about 1:20 to about 20:1, such as from about 1:15 to about 15:1, such as from about 1:10 to about 10:1, such as from about 5:1 to about 1:5, such as from about 3:1 to about 1:3, such as from about 2:1 to about 1:2, such as from about 1.2:1 to about 1:1.2, such as about 1:1, however, encompassing other amounts. Any of the foregoing numbers may be used individually to describe the open-end range or in combination to describe the closed-end range.

[0108] During operation 108, a third aqueous stream 180 and a second organic solvent may be fed into the container. The resulting mixture may be mixed, stirred, or otherwise agitated under conditions that effectively form a fourth aqueous stream 195 and a phenol-rich composition 190. The mixing conditions for operation 108 may include a temperature of about 15°C to about 30°C and an ambient pressure (about 1 atm). Higher temperatures may be used if necessary. However, if higher temperatures are used during mixing, the mixing temperature should be below the boiling point of the water and the second organic solvent.

[0109] The mixing conditions of operation 108 may include stirring, mixing, agitation, or a combination thereof using a suitable device. Suitable devices may include mechanical stirrers such as overhead stirrers, magnetic stirrers (e.g., placing a magnetic stirring bar in a container above a magnetic stirrer), or other suitable devices. For example, a stirrer with blades or propellers may be rotated by receiving rotational power from a stirring motor to stir the components at suitable rotational speeds, such as about 50 rpm to about 1,500 rpm, such as about 75 rpm to about 1,000 rpm, such as about 100 rpm to about 900 rpm, such as about 200 rpm to about 800 rpm, such as about 300 rpm to about 700 rpm, such as about 400 rpm to about 600 rpm, such as about 450 rpm to about 550 rpm, such as about 500 rpm. Any of the foregoing numbers may be used individually to describe an open-end range or in combination to describe a closed-end range. Other rotational speeds are covered and may be selected based on the ability to adequately mix the components. The mixing conditions of operation 108 may include the use of non-reactive gases, such as N2, Ar, or combinations thereof. For example, a non-reactive gas may be introduced into a third aqueous stream 180 and a second organic solvent to degas the various components or additionally remove unwanted gases (e.g., oxygen) from the mixture.

[0110] Mixing, stirring, or agitation may be performed during operation 108 for any suitable period of time, such as about 1 min to about 48 h, such as about 5 min to about 24 h, such as about 30 min to about 10 h, such as about 1 h to about 5 h, such as about 2 h to about 3 h, however, other periods are also included. Any of the foregoing numbers may be used alone to describe the open-end range or in combination to describe the closed-end range.

[0111] After mixing, the mixture of the fourth aqueous stream 195 and the second organic solvent is separated using a suitable liquid-liquid separation technique, such as decantation, distillation, extraction, extractive distillation, or combinations thereof, and other techniques. Following separation, the fourth aqueous stream 195 and a phenol-rich composition 190 are obtained. In some embodiments, the fourth aqueous stream 195 may include phenolic compounds, other organic compounds, or combinations thereof, as appropriate.

[0112] If desired, the fourth aqueous stream 195 may undergo operation 108, wherein the fourth aqueous stream 195 may be contacted with a second organic solvent and the resulting mixture may be separated. After separation, the organic layer may be combined with the phenol-rich composition 190. Subjecting the fourth aqueous stream 195 to operation 108 may be used to extract any remaining phenols, other organic compounds, or combinations thereof from the fourth aqueous stream 195. Operation 108 may be performed any suitable number of times, such as 1, 2, 3, 4, or more. The components in the organic layer may be extracted and combined to form the phenol-rich composition 190.

[0113] If necessary, solvents such as organic solvents or water can be removed from the phenol-rich composition 190, the fourth aqueous stream 195, or both. Solvent removal can be accomplished by suitable techniques such as distillation, vacuum distillation, or a combination thereof. The phenols present in the phenol-rich composition 190 can be referred to as "circulating phenols".

[0114] See again Figure 1B The dashed box 172 indicates that the precipitate 185 containing phenolic oligomers and the phenol-rich composition 190 can be used as monomers, comonomers, or both in various conversion processes such as epoxy resin synthesis and phenolic varnish synthesis. When the precipitate 185 containing phenolic oligomers, the phenol-rich composition 190, or a combination thereof are used as comonomers, the other monomer may include phenol (such as non-recycled phenol, e.g., commercial grade phenol).

[0115] Additionally, and as described above, the second organic stream 175 may include phenolic compounds and, where appropriate, other organic compounds. The second organic stream 175 may also include a matrix for synthesizing epoxy resins (such as a glycated matrix different from bisphenol). These matrices can be used to replace bisphenol and for forming epoxy resins. Alternatively or additionally, the second organic stream 175 may include curing agents, accelerators, or combinations thereof. Curing agents, accelerators, and glycated matrices can be used to form epoxy resins. Therefore, the second organic stream 175 may include high-value organic compounds.

[0116] Therefore, embodiments of process 100 can achieve the recycling of phenols, phenolic compounds, curing agents, accelerators, and glycated matrices from raw materials comprising solvent-decomposed oils, high-temperature decomposed oils, or combinations thereof. The phenols, phenolic compounds, curing agents, accelerators, and glycated matrices separated from solvent-decomposed oils and high-temperature decomposed oils can be used in conversion processes such as conversion into phenolic varnish resins, and other applications.

[0117] As stated above, prior art cannot address the reuse or recyclability of thermosetting materials present in fiber-reinforced thermosetting composites (such as epoxy resin composites and other resin composites). These thermosetting materials are conventionally considered non-recyclable. In contrast, the process described herein enables sustainable recycling of fiber-reinforced thermosetting composites such as epoxy resin composites and other resin composites. In this document, the process disclosed herein enables the extraction of valuable products such as phenols, phenolic compounds, and other organic compounds from solvent-decomposed fiber-reinforced thermosetting composites (solvent-decomposed oil), high-temperature decomposed fiber-reinforced thermosetting composites (high-temperature decomposed oil), thermally decomposed fiber-reinforced thermosetting composites (thermal decomposed oil), catalytically decomposed fiber-reinforced thermosetting composites, and other circulating streams. Therefore, the process described herein enables sustainable recycling of fiber-reinforced thermosetting composites such as epoxy resin composites and other resin composites. Furthermore, the process described herein can also mitigate landfill problems associated with fiber-reinforced thermosetting composites.

[0118] Transformation process

[0119] Embodiments of this disclosure also relate to a process for producing phenolic resins (e.g., phenolic varnish resins) from recycled phenols, phenolic compounds, or combinations thereof. Furthermore, recycled phenols refer to phenols obtained from process 100 or flowchart 150, for example, phenols present in phenol-rich composition 190. All phenolic derivatives present in phenol-rich composition 190 are capable of reacting with formaldehyde.

[0120] Cyclic phenols, phenolic compounds, or combinations thereof can be used as monomers or comonomers to form phenolic varnish resins. Alternatively, precipitates 185 containing phenolic oligomers can be used as monomers or comonomers containing phenols to form phenolic varnish resins. Phenolic varnish resins are polymers derived from phenols and formaldehyde. In addition to phenols, cresols present in phenol-rich compositions, such as o-cresol, m-cresol, p-cresol, or combinations thereof, and other phenolic compounds, can be converted into phenolic varnish resins.

[0121] Recycled phenols, phenolic compounds, or combinations thereof can be converted into phenolic varnish resins by any suitable process. Schemes 1 and 2 illustrate exemplary, but non-limiting, general reaction schemes for forming phenolic varnish resins. In Scheme 1, compound (I) is a phenol, compound (V) is a formaldehyde source, and formula (VI-A) is a phenolic varnish resin product. In Scheme 2, compound (II) represents a phenolic compound, compound (V) is a formaldehyde source, and formula (VI-B) is a phenolic varnish resin product. As mentioned above, the phenolic compound of formula (II) can be present in the phenol-rich composition 190.

[0122] Option 1

[0123]

[0124] Option 2

[0125]

[0126] The conversion process typically involves reacting formaldehyde or a formaldehyde source, a catalyst, and a mixture of phenols under reaction conditions to form the reaction product of formula (VI-A). In addition to phenols (compounds of formula (I)), phenolic compounds of formula (II) can be used to prepare the corresponding phenolic varnish resin, as shown in Scheme 2. These phenolic compounds may be present in the phenol-rich composition 190. Although the implementation of the conversion process is described relative to formaldehyde, it is contemplated that other aldehydes and ketones may be used, as further described below with respect to the aldehydes and ketones of formula (VII). Furthermore, although the implementation of the conversion process is described relative to the use of the phenol-rich composition 190, it is contemplated that the precipitate 185 containing phenolic oligomers may be used as a monomer or a comonomer containing phenol to form the phenolic varnish resin.

[0127] In some embodiments, the phenol-rich composition 190 (containing cyclic phenols, phenolic compounds of formula (II), or combinations thereof) can be subjected to conversion conditions that effectively form phenolic varnish resins. In these and other embodiments, non-cyclic phenols, such as commercial-grade phenols, may be added as appropriate. In the conversion process involving the phenol-rich composition 190 and non-cyclic phenols, the weight ratio of composition 190 to non-cyclic phenols can be any suitable weight ratio, such as about 50:1 to about 1:50, such as about 35:1 to about 1:35, such as about 20:1 to about 1:20, such as about 15:1 to about 1:15, such as about 10:1 to about 1:10, such as about 5:1 to about 1:5, such as about 3:1 to about 1:3, such as about 2:1 to about 1:2, however, other amounts are also covered. Any of the foregoing numbers may be used alone to describe the open-end range or in combination to describe the closed-end range. In at least one embodiment, the weight ratio of composition 190 to non-cyclic phenol may be from about 90:10 to about 10:90, such as from about 8:2 to about 2:8, such as from about 7:3 to about 3:7, such as from about 6:4 to about 4:6, such as about 1:1, however, other amounts are also included. Any of the foregoing numbers may be used individually to describe the open-end range or in combination to describe the closed-end range.

[0128] Besides formaldehyde, paraformaldehyde ((CH2O)) n Formaldehyde can be used as a source of formaldehyde. Alternatively, formalin (an aqueous solution of formaldehyde) can be used as a source of formaldehyde. In some embodiments, formaldehyde (or a source of formaldehyde) is introduced into a mixture comprising a phenol (compound of formula (I)), a phenolic compound of formula (II), or a combination thereof. The mixture may also include a solvent, a catalyst, or both, and other components.

[0129] It also includes other aldehydes, as well as ketones, such as those represented by formula (VII):

[0130] (VII)

[0131] In equation (VII), R a and R b Each of these can independently be hydrogen, an unsubstituted hydrocarbon group, a substituted hydrocarbon group, or a functional group containing at least one element from groups 13-17 of the periodic table. R in formula (VII) a and R b Suitable R groups for each of the above may include those described above with respect to formula (II). Exemplary, but non-limiting, examples of unsubstituted hydrocarbon groups include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, and tributyl, pentyl, hexyl, heptyl, octyl, ethyl-2-hexyl, isooctyl, nonyl, n-decyl, isodecyl, or isomers thereof; cycloaliphatic groups having 3 to 20 carbon atoms, such as cyclopentyl or cyclohexyl; aromatic groups having 6 to 20 carbon atoms, such as phenyl or naphthyl; or any combination thereof.

[0132] R in equation (VII) a and R b Each of them may independently have any suitable number of carbon atoms, such as 1 to 20 carbon atoms, such as 1 to 10 carbon atoms, such as 1 to 5 carbon atoms, such as 1 to 4 carbon atoms. In some embodiments, R in formula (VII) a and R b The number of carbon atoms in each of the groups can independently be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. Each of the aforementioned numbers may be preceded by the terms "about," "at least about," "less than about," or "greater than about," and any of the aforementioned numbers may be used individually to describe the open-end range or in combination to describe the closed-end range. The R of the group in formula (VII) a and R b Each of these can independently be linear or branched, saturated or unsaturated, cyclic or acyclic, aromatic or non-aromatic. Regarding saturation, R in equation (VII)... a and R b Each element can be independently classified as fully saturated, partially unsaturated, or completely unsaturated.

[0133] Exemplary, but non-limiting, examples of aldehydes include formaldehyde, acetaldehyde, crotonaldehyde, pentanal, butyraldehyde, 3-methyl-butenal, acrolein, benzaldehyde, furfural, glyoxal, their derivatives, and combinations thereof.

[0134] Exemplary, but non-limiting, examples of ketones include acetone, acetophenone, benzophenone, 2-pentanone (methyl propyl ketone), 3-methyl-2-butanone (methyl isopropyl ketone), 3-hexanone (ethyl propyl ketone), their derivatives, or combinations thereof.

[0135] The total amount of phenol-rich component 190 and non-cyclic phenols (if used) to the amount of formaldehyde used in the conversion reaction is referred to as the phenol / formaldehyde (P / F) weight ratio. The P / F ratio for the conversion process can be from about 1:0.3 to about 1:0.8, such as from about 1:0.4 to about 1:0.6, such as about 1:0.5, however, other ratios are also included. Any of the foregoing numbers may be used individually to describe the open-end range or in combination to describe the closed-end range.

[0136] The catalyst for the conversion process may include any suitable acid or base catalyst, such as Brønsted acids and Brønsted bases. Exemplary, but non-limiting, examples of catalysts include organic acids, inorganic acids, or combinations thereof. Organic acids include, but are not limited to, methanesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, oxalic acid (CAS No. 144-62-7), or combinations thereof. Exemplary, but non-limiting, examples of inorganic acids include, in particular, hydrochloric acid, sulfuric acid, phosphoric acid, or combinations thereof. The acid catalyst may be removed by heating the reaction products containing phenolic varnish resins of formula (VI-A), formula (VI-B), or combinations thereof at high temperatures. For example, oxalic acid decomposes into carbon dioxide at about 160°C or higher, for example, about 165°C or higher. Alternatively or additionally, the acid catalyst may also be removed from the reaction products containing phenolic varnish resins of formula (VI-A), formula (VI-B), or combinations thereof by distillation of the reaction products, neutralization with sodium hydroxide (NaOH), or combinations thereof.

[0137] Exemplary, but non-limiting, examples of alkaline catalysts include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, basic amines, or combinations thereof. The alkaline catalyst used may be an aqueous solution of about 5% to about 50% by weight, such as about 10% to about 40% by weight, such as about 20% to about 30% by weight. Any of the foregoing numbers may be used alone to describe an open-end range or in combination to describe a closed-end range.

[0138] Mixtures comprising phenols (compounds of formula (I)), phenols of formula (II), or combinations thereof may also include one or more solvents. Suitable solvents include organic solvents. Organic solvents may include, but are not limited to, aliphatic hydrocarbons, cyclic aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, ethers, esters, nitriles, or combinations thereof. Exemplary, but non-limiting, examples of organic solvents include tert-butylbenzene (tBB), toluene, ethylbenzene, xylene (one or more of 1,2-xylene, 1,3-xylene, or 1,4-xylene), 1,3,5-trimethylbenzene (also known as mesitylene), decane, monomethyl ethers of diethylene glycol, ethylene glycol monobutyl ether, tetrahydrofuran methanol, ethylene glycol monomethyl ether, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, isomers thereof, or combinations thereof. Other solvents are also included. In some embodiments, the organic solvent includes tert-butylbenzene (tBB), toluene, ethylbenzene, xylene, 1,3,5-trimethylbenzene, isomers thereof, or mixtures thereof.

[0139] In some embodiments, the solvent used to remove or neutralize the catalyst may be selected based on its boiling point. For example, a solvent may be selected to have a boiling point of about 100°C or greater (at 100 kPa (absolute)) to decompose or neutralize the acid or base. As an exemplary, but not limiting, example, a solvent that boils between about 160°C and about 170°C (such as tert-butylbenzene, 1,3,5-trimethylbenzene, or other solvents) may be used with the oxalic acid catalyst, and after the formation of bisphenol, the oxalic acid may be removed from the bisphenol / solvent / oxalic acid mixture at a temperature of about 165°C to about 170°C. Heating at this temperature results in the decomposition and sublimation of the oxalic acid.

[0140] In some instances, the solvent may have a boiling point of about 100°C to about 210°C, such as about 110°C to about 200°C, such as about 120°C to about 190°C, such as about 130°C to about 180°C, such as about 140°C to about 170°C, such as about 150°C to about 160°C, or about 165°C to about 170°C (at 100 kPa (absolute)). Any of the foregoing numbers may be used alone to describe an open-end range or in combination to describe a closed-end range.

[0141] Phenolic varnish resins of formula (VI-A), formula (VI-B), or combinations thereof can be prepared by feeding a phenol-rich component 190, a formaldehyde source, a catalyst, and a solvent into a reactor. As described above, non-recycled phenols can also be utilized. The resulting mixture can be reacted under reaction conditions that effectively form phenolic varnish resins of formula (VI-A), formula (VI-B), or combinations thereof.

[0142] Reaction conditions may include reactor temperatures ranging from about 50°C to about 200°C, such as from about 70°C to about 120°C, such as from about 90°C to about 100°C, but other temperatures are also included. Any of the foregoing numbers may be used individually to describe an open-end range or in combination to describe a closed-end range. Reactor temperature may be the boiling point (or temperature range) of the reaction mixture, or the azeotropic boiling point (or range) of the water-solvent combination. In some instances, using tBB as a solvent under atmospheric conditions, reactor temperatures may be from about 75°C to about 100°C, such as from about 80°C to about 96°C, such as about 96°C. Reactor temperature is the temperature monitored by a temperature probe.

[0143] Reaction conditions may also include reactor pressure, as measured in units of absolute pressure. Reactor pressure may be from about 100 kPa (absolute) to about 450 kPa (absolute), such as from about 105 kPa (absolute) to about 180 kPa (absolute), such as from about 110 kPa (absolute) to about 120 kPa (absolute), however, other pressures are also included. Any of the foregoing numbers may be used individually to describe an open-end range or in combination to describe a closed-end range. In at least one embodiment, the reactor pressure of the reaction conditions may be from about 100 kPa (absolute) to about 180 kPa (absolute), such as from about 100 kPa (absolute) to about 120 kPa (absolute). Any of the foregoing numbers may be used individually to describe an open-end range or in combination to describe a closed-end range. Pressure (or pressure range) may be selected to match the temperature (or temperature range) with respect to a boiling reaction mixture at a pressure ≥100 kPa (absolute) and a temperature ≥96°C.

[0144] Reaction conditions also include the reaction period. The reaction period can be any suitable time period, such as about 0.5 to 20 hours, such as about 1 to about 10 hours, such as about 2 to about 5 hours, however, other time periods are also included. Any of the foregoing numbers may be used alone to describe the range of open ends or in combination to describe the range of closed ends.

[0145] After the reaction is considered complete, water and formaldehyde can be removed from the reaction product comprising the phenolic varnish resin of formula (VI-A), the phenolic varnish resin of formula (VI-B), or a combination thereof. Removal of water and formaldehyde can be performed, for example, by distillation (under suitable conditions) of the reaction product.

[0146] In some embodiments, the removal of water and formaldehyde occurs at a temperature below the boiling point of the solvent. In cases where the solvent is evaporated or distilled away simultaneously with the removal of formaldehyde and water, the solvent can be separated from the aqueous phase in, for example, a phase separator and phase separation vessel in a condenser, and then returned to the reactor containing the reaction products.

[0147] Following the conversion reaction, a reaction product containing phenolic varnish resin of formula (VI-A), phenolic varnish resin of formula (VI-B), or a combination thereof is obtained.

[0148] In some embodiments, the conversion reaction of the phenol-rich composition 190 into a phenolic resin includes forming a mixture comprising the phenol-rich composition, an aldehyde or ketone, and a catalyst; and reacting the mixture to form a phenolic resin.

[0149] In some embodiments, the precipitate 185 comprising phenolic oligomers can be used as a monomer or comonomer (containing phenol) to form a phenolic varnish resin. Alternatively or concurrently, the precipitate 185 comprising phenolic oligomers can be reacted with an epoxy resin in an advanced reaction. In at least one embodiment, a second organic stream 175 (which may include a curing agent, an accelerator, or a combination thereof) can be added to the epoxy resin. In summary, the various fractions obtained from the embodiments described herein comprise valuable products that can be used in a variety of reactions.

[0150] The following examples are provided to offer a complete disclosure and description of how to generate and use embodiments of this disclosure to those skilled in the art, and are not intended to limit the scope of embodiments of this disclosure. Efforts have been made to ensure the accuracy of the figures used, but some experimental errors and biases should be taken into account.

[0151] Example

[0152] Test methods

[0153] Characterization

[0154] Infrared spectroscopy was performed to identify the functional groups present in the various streams of the process described herein. Infrared spectra were obtained using an FTIR spectrometer (Bruker Alpha) equipped with an SB-Diamond attenuated total reflectance spectrometer. Thirty-two scans were run and averaged.

[0155] Gel permeation chromatography was performed to determine the molecular weight distribution of the products in various streams of the process described herein. Gel permeation chromatography chromatograms were obtained using a LaChrom Elite (VWR Hitachi) spectrometer. The setup included a UV-Vis detector (280 nm) and a 1x PLgel Mixed-E column (300 x 7.5 mm inner diameter (ID)). Samples for gel permeation chromatography were diluted in tetrahydrofuran (THF). The sample flow rate was 1 mL / min.

[0156] Gas chromatography-mass spectrometry (GC-MS) was performed to determine the amount of phenol in the second organic stream. GC-MS was performed using an Agilent 8890 GC with an Agilent 5977B mass-selective detector equipped with an HP-5ms ((5%-phenyl)-methylpolysiloxane phase) capillary GC column (30 m length, 0.25 mm ID, 0.25 μm film thickness; part number: 19091S-433UI). Gas chromatography-flame ionization detection (GC-FID) was performed using an Agilent 8890GC equipped with a flame ionization detector and a DB-1 GC column (60 m length, 0.32 mm ID, 1 μm film thickness; part number: 123-1063).

[0157] Ultra-high-performance liquid chromatography (UHPLC) was performed to determine the content of phenols and p-toluenesulfonic acid. UHPLC was also performed after subjecting various fractions to phenolic varnish resin synthesis to determine the presence of phenolic varnish resin products. UHPLC was performed using an ultra-high-performance liquid chromatography-photodiode array (UHPLC-PDA) system. The system consisted of a Waters AcquityUHPLC H-Class equipped with an Acquity UPLC BEH Phenyl column and a PDA detector. A THF / water system was used for sample processing.

[0158] Example 1: An exemplary process for forming phenol-rich compositions

[0159] The separation of phenols and other organic fractions from the recycle stream is performed using the embodiments described herein. Two feedstocks (e.g., feedstock 155) undergo the process described herein. One feedstock contains high-temperature decomposed oil and the other feedstock contains solvent-decomposed oil.

[0160] Add a first organic solvent (dichloromethane, DCM, approximately 50 mL) to the feedstock (approximately 50 g). Then mix the resulting mixture and wash with water (3 x 100 mL) to remove the organic acid, and combine the aqueous layers. The collected fraction comprises a first aqueous stream 160 (containing organic acid) and a first organic stream 165.

[0161] The first organic stream 165 is then washed and mixed with an aqueous alkali (5% sodium hydroxide in water; 3 x 100 mL) to concentrate the alkali-soluble compounds, and the aqueous layers are combined. The collected fraction comprises a second aqueous stream 170 (containing the alkali-soluble compounds) and a second organic stream 175. At this stage, washing and mixing are performed until the aqueous layers become clear.

[0162] Example 1A: Organic fraction

[0163] Before further use, the second organic stream 175 is washed with water (3 x 100 mL), dried over sodium sulfate (Na2SO4), filtered, and the solvent is removed by vacuum. The “organic fraction” in this example corresponds to the second organic stream 175.

[0164] Example 1B: Phenolic fraction

[0165] Hydrochloric acid (HCl, 12 M, 37% of water, 40 mL) is added to the second aqueous stream 170 until a pH of less than about 5 is obtained. A solid residue (e.g., precipitate 185) is formed. Precipitate 185 is filtered and the third aqueous stream 180 is collected.

[0166] The third aqueous stream 180 was mixed and extracted with a second organic solvent (DCM; 3 x 100 mL). The organic layers were combined to form a phenol-rich composition 190.

[0167] Before further use, the phenol-rich composition 190 is dried with Na2SO4, filtered, and the solvent is removed by vacuum. The “phenol fraction” in this example corresponds to the phenol-rich composition 190.

[0168] Example 1C: Oligomeric fraction

[0169] Before further use, the solid residue (e.g., precipitate 185) is dissolved in DCM (50 mL) or acetone (50 mL) and washed with water (3 x 100 mL) or until the aqueous phase becomes clear. The organic layers are combined, dried over Na2SO4, filtered, and the solvent is removed under vacuum. The “oligomeric fraction” in this example corresponds to precipitate 185.

[0170] Table 1-1 shows the main components of the crude solvent decomposition oil (feedstock) and general data for the three separated fractions—organic, oligomeric, and phenolic fractions. The amount of individual components as a percentage of area was determined by GC-FID x GC-MS. Phenols have a retention time of approximately 4.1–4.2 minutes.

[0171] Table 1-1

[0172]

[0173] In summary, the data in Table 1-1 indicate that the process described herein can be used to separate various valuable fractions (e.g., phenolic fractions, oligomeric fractions, and organic fractions) from crude solvent decomposition oil feedstock. For example, and as shown in Table 1-1, the feedstock contains approximately 45% phenol and 55% other compounds. The amount of phenol remains low in the organic fraction (approximately 2%) and the oligomeric fraction (approximately 17%). The phenolic fraction (corresponding to phenol-rich composition 190) contains approximately 85% recycled phenol and other compounds that can be used to form, for example, phenolic varnish resins. Furthermore, the oligomeric fraction (corresponding to precipitate 185) contains phenolic oligomers that can be used to form phenolic varnish resins or react with epoxy resins in advanced reactions, as well as phenolic compounds.

[0174] In some embodiments, the precipitate 185 comprising phenolic oligomers can be used as a monomer or comonomer (containing phenol) to form a phenolic varnish resin. Alternatively or concurrently, the precipitate 185 comprising phenolic oligomers can be reacted with an epoxy resin in an advanced reaction. In at least one embodiment, a second organic stream 175 (which may include a curing agent, an accelerator, or a combination thereof) can be added to the epoxy resin. In summary, the various fractions obtained from the embodiments described herein comprise valuable products that can be used in a variety of reactions and other applications.

[0175] Table 1-2 shows the main components of the crude high-temperature decomposition oil (feedstock) and selected data for the three separated fractions—organic, oligomeric, and phenolic fractions. The amount of individual components as area percentages was determined by GC-FID x GC-MS. Phenols have a retention time of approximately 4.1–4.2 minutes.

[0176] Table 1-2

[0177]

[0178] In summary, the data in Tables 1-2 indicate that the process described herein can be used to separate various valuable fractions (e.g., phenolic fractions, oligomeric fractions, and organic fractions) from crude high-temperature decomposition oil feedstock. For example, the phenolic fraction contains compounds such as 4-isopropylphenol and 4-isopropyl-3-methylphenol, which can be used to form, for example, phenolic varnish resins. Additionally, 4,4'-isopropylidene diol present in the phenolic fraction can be used as a glycinate matrix. The organic fraction (corresponding to the second organic stream 175) contains 2-methyl-2-(4'-hydroxyphenyl)pentanone-4 and 4-isopropyl-3-methylphenol. Each of these compounds can be used to form, for example, phenolic varnish resins. Note that the oily, viscous components of the high-temperature decomposition oil used lead to the accumulation of phenols in the oily oligomeric fraction.

[0179] In summary, the data demonstrate that the separation of organic streams through solvent decomposition and high-temperature decomposition of epoxy resin composites can be achieved using the embodiments of this disclosure.

[0180] Example 2: Infrared Spectroscopy

[0181] The components of oligomeric, phenolic, and organic fractions were studied using infrared (IR) spectroscopy. Figure 2 The overlapping of IR spectra 200 of the oligomer fraction 202, phenol fraction 204, and organic fraction 206, which contain feedstock from high-temperature decomposed oil, is shown. Various functional groups were detected, including those at approximately 3217 cm⁻¹. -1 The hydroxyl (OH) segment, approximately 1595 cm -1 The C=C curve of the aromatic group, and approximately 1226 cm -1 The CH segment. Note that phenol (CH) usually appears as a bimodal signal around the following region.

[0182] In summary, IR spectroscopy indicates that organic fraction 206 is lower in terms of phenols, lower in terms of phenolic oligomers, and lower in terms of higher molecular weight phenolic derivatives. In contrast, approximately 3217 cm⁻¹ -1 Characteristic OH segments and approximately 1226 cm -1 The CH segments are clearly present in the oligomer fraction 202 and the phenol fraction 204.

[0183] Example 3: Gel permeation chromatography

[0184] The composition of organic fractions, oligomeric fractions, phenolic fractions, and the separation of high-temperature decomposed oils and solvent-decomposed oils were studied using gel permeation chromatography (GPC). GPC measurements provide an overview of the molecular weight distribution of individual fractions.

[0185] Analysis of the fractions separated from high-temperature decomposition oil. Figure 3 The image shows the overlap of GPC chromatograms 300 for the crude high-temperature decomposed oil (raw material 302) and the separated fractions (organic fraction 304, oligomer fraction 306, and phenolic fraction 308). Table 2 shows the selected GPC data for the raw high-temperature decomposed oil and fractions. In Table 2, M... n M is the number average molecular weight. w Where M is the weight-average molecular weight, and M z The weight-average molecular weight (Z) is the polydispersity index. PDI refers to the polydispersity index and is defined as the weight-average molecular weight (M). w Divide by the number-average molecular weight (M) n ), (M w / M n ).

[0186]

[0187] The data in Table 2 indicate that the process described herein can be used to separate valuable fractions from crude feedstock. In this paper, the molecular weights of individual fractions of the high-temperature decomposed oil indicate that the oil is clearly separated into fractions of different sizes. The PDI of the oligomeric and phenolic fractions separated from the high-temperature decomposed oil were determined to be close to 1, indicating that these fractions are nearly homogeneous. In summary, the data on the high-temperature decomposed oil fractions indicate that valuable fractions can be separated from the high-temperature decomposed oil feedstock.

[0188] Analysis of fractions separated from solvent-decomposed oils. The composition of the organic, oligomeric, and phenolic fractions separated from solvent-decomposed oils was also studied using GPC. Mi of individual fractions separated from solvent-decomposed oils was also analyzed. w The values ​​are determined in the following order:

[0189] Organic fraction > Oligomeric fraction > Raw materials > Phenolic fraction

[0190] After separating the solvent-decomposed oil, the organic fraction exhibits the highest M value compared to the phenolic and oligomeric fractions. w The value, and the phenol fraction has the lowest M value. w The oligomer fraction has a larger M value than the phenol fraction. w value.

[0191] M of individual fractions separated from solvent-decomposed oil n The values ​​were determined in the following order, with the organic fraction having the highest M value. n The value and the phenol fraction have the lowest M value. n value:

[0192] Organic fraction > Oligomeric fraction > Raw materials > Phenolic fraction

[0193] M of individual fractions separated from solvent-decomposed oil z The values ​​were determined in the following order, with the oligomeric fraction having the highest M value. z The value and the phenol fraction have the lowest M value. z Value (M of raw materials) z uncertain):

[0194] Oligomeric fraction > Organic fraction > Phenolic fraction

[0195] The PDI values ​​of individual fractions from solvent-decomposed oil separation were determined in the following order, with the raw material having the highest PDI value and the phenol fraction having the lowest PDI value:

[0196] Raw materials > Oligomeric fraction > Organic fraction > Phenolic fraction

[0197] Data from the solvent-decomposed oil fraction indicate that valuable fractions can be separated from the solvent-decomposed oil feedstock. GPC chromatograms and data indicate that the embodiments described herein successfully separate the higher molecular weight components in the oligomeric fraction and the lower molecular weight components in the phenolic fraction. The PDI of the phenolic fraction separated from the solvent-decomposed oil was determined to be close to 1, indicating that the phenolic fraction is nearly homogeneous.

[0198] Example 4: Synthesis and Characterization of Phenolic Varnish Resin

[0199] The phenolic varnish resin was formed using the embodiments described herein. The formaldehyde used in the synthesis of the phenolic varnish resin was formalin. Formalin was a 45% formaldehyde solution in water. Oxalic acid was used as a catalyst in the synthesis.

[0200] A general reaction scheme for forming phenolic varnish resins is shown in Scheme 3; however, it should be understood that phenolic compounds of formula (II) can also be used to form phenolic varnish resins, as described in Scheme 2 above. In Scheme 3, A is phenol, B represents a formaldehyde source, and C represents the phenolic varnish resin product. In some instances, n is typically determined to be from about 1 to about 5.

[0201] Option 3

[0202]

[0203] General procedure for synthesizing phenolic varnish resin Phenol (approximately 72.18 g, approximately 0.767 mol, approximately 1.0 equivalent) was placed in a multi-necked flask, mixed, and heated to approximately 95°C. Oxalic acid (approximately 0.345 g, approximately 0.038 mol, approximately 0.005 equivalent) in water (approximately 0.35 mL, approximately 0.005 equivalent) was then added to the flask. Formalin (approximately 25.59 g, approximately 0.383 mol, approximately 0.5 equivalent) was slowly added under reflux over a period of approximately 1 h, and the reaction solution was then stirred under reflux for another 1 h to form a product mixture. Excess phenol was removed by distilling the product mixture under normal pressure, purging the receiver, and then heating under vacuum to approximately 140°C.

[0204] Comparison of phenolic varnish resins The general procedure was followed to form a comparative phenolic varnish resin (Example 406) using 100 wt% pure phenol (commercial grade phenol).

[0205] Exemplary phenolic varnish resin The use of phenolic fractions (phenol-rich components) from the separation processes of high-temperature decomposition oils and solvent decomposition oils in the synthesis of phenolic varnish resins was investigated. General procedures for synthesizing exemplary phenolic varnish resins were followed. In these examples, 20 wt% or 100 wt% of pure phenol was replaced with the phenolic fraction.

[0206] Phenolic varnish resin is produced from the phenolic fraction of oil decomposed at high temperatures. Figure 4 The overlay of UHPLC chromatograms 400 for phenolic varnish resins produced from 20% or 100% recycled materials (phenol fractions) is shown. Examples 402 and 404 refer to phenolic varnish resins prepared from 20% and 100 wt% phenol fractions separated from high-temperature decomposed oils, respectively. Table 3 shows selected GPC data for exemplary phenolic varnish resins (Examples 402 and 404) and comparative phenolic varnish resins (Example 406). In Table 3, "n" refers to a repeating unit in Scheme 3 with a molecular weight of approximately 106 g / mol.

[0207]

[0208] When the comparative phenolic varnish reference (Example 406) is compared with the exemplary phenolic varnish resins (Examples 402 and 404), the exemplary phenolic varnish resins each exhibit a typical molar mass distribution in the low molecular weight range. In summary, the data indicate that the phenolic fraction of high-temperature decomposed oil can be successfully converted into phenolic varnish resins with 20% wt% recycled phenol content (Example 402) and 100 wt% recycled phenol content (Example 404).

[0209] Figure 4 The UHPLC measurements of various phenolic varnish resins shown indicate the formation of phenolic varnish oligomers. This result is particularly evident in the region between 3.6 and 5.2 minutes (dashed box). This region shows the typical distribution of low molecular weight oligomers and the corresponding repeating units "n" (n = 1, 2, 3, 4, and 5). Samples with different "n" correspond to M molecules obtained through molecular weight distribution. n The repeating unit is calculated based on a repeating unit of 106 g / mol (which corresponds exactly to one unit in the polymer backbone).

[0210] Table 3 shows PDI values ​​indicating polymer distribution. For example, a broad distribution in the case of a 100 wt% phenol fraction of a high-temperature decomposition oil (Example 404; PDI of about 4.2) may indicate the possibility of multiple reactions or reactions that do not stop rapidly or react sufficiently. A low PDI (Example 402; PDI of about 1.9) in a 20 wt% phenol fraction of a high-temperature decomposition oil is matched with a phenolic varnish reference (Example 406).

[0211] Furthermore, the 100 wt% phenol fraction of the high-temperature decomposed oil (Example 404) may show a different distribution because it contains a higher proportion of phenolic derivatives compared to all other components. This result indicates that the phenolic varnish resin formed from the 100 wt% phenol fraction of the high-temperature decomposed oil has a higher molecular weight because the monomer used is larger than that of pure phenol (M 94.11 g / mol). wFurthermore, during polymerization, phenolic derivatives (e.g., phenolic compounds and phenolic oligomers) can react in different ways than pure phenol. The use of phenolic fractions separated from high-temperature decomposed oils (Examples 402 and 404) demonstrates that condensation polymerization with formaldehyde to form phenolic varnish resins is feasible even for different compositions of phenolic derivatives (e.g., phenolic compounds and phenolic oligomers).

[0212] Phenolic varnish resins were produced from the phenolic fraction of solvent-decomposed oils. The use of the phenolic fraction (a phenol-rich component) from the separation process of solvent-decomposed oils in the synthesis of phenolic varnish resins was also investigated. General procedures for synthesizing exemplary phenolic varnish resins were followed. In these examples, 20 wt% or 100 wt% of pure phenol was replaced with a phenolic fraction separated from solvent-decomposed oils. Data indicate that the phenolic fraction of solvent-decomposed oils could be successfully converted into phenolic varnish resins with 20% and 100 wt% recycled phenol contents.

[0213] Compared to the comparative phenolic varnish reference (Example 406), the exemplary phenolic varnish resins formed from the phenolic fraction of solvent-decomposed oil exhibit typical molar mass distributions in the low molecular weight range. The use of the phenolic fraction separated from the solvent-decomposed oil (>80 wt% phenol content) can be used to form phenolic varnish resins with low polydispersity and is therefore similar to the known synthesis of pure phenolic varnish resins from phenol and formaldehyde. In summary, the results indicate that the phenolic fraction separated from solvent-decomposed oil can be used to form, for example, phenolic varnish resins.

[0214] The embodiments of this disclosure generally relate to processes for separating organic products from organic recycle streams, and more specifically to processes for producing phenol-rich compositions from organic recycle streams. The embodiments described herein enable the removal of phenolic fractions and other organic fractions from resin recycle streams and resin waste streams. Phenolic fractions and other organic fractions can be used to produce, for example, phenolic varnish resins and epoxy resins, as well as other materials.

[0215] As used herein, without specifying a particular isomer, reference to an R group, alkyl group, substituted alkyl group, hydrocarbon group, or substituted hydrocarbon group (such as butyl) explicitly discloses all isomers (such as n-butyl, isobutyl, dibutyl, and tributyl). For example, reference to an R group having 4 carbon atoms explicitly discloses all its isomers. When a compound is described herein such that, for example, a specific isomer, mirror image isomer, or non-mirror image isomer is not specified in the chemical formula or chemical name, the description is intended to include all isomers and mirror image isomers of the compound described individually or in any combination.

[0216] As will be apparent from the foregoing general description and specific aspects, although the forms of the aspects are shown and described, various modifications may be made without departing from the spirit and scope of this disclosure. Therefore, this disclosure is not intended to be limited thereto. Similarly, the term “comprising” is considered synonymous with the term “including.” Likewise, whenever the transitional phrase “comprising” precedes a component, element, or group of elements, it should be understood that we also consider the same component or group of elements preceded by the transitional phrases “substantially composed of,” “composed of,” “selected from,” or “for,” and vice versa, terms such as “comprising,” “substantially composed of,” and “composed of” also include the product of the combination of elements listed after the term.

[0217] For the purposes of this disclosure, and unless otherwise specified, all numerical values ​​described herein and within the claims are defined by the terms "about" or "approximately," taking into account experimental errors and variations expected by one of ordinary skill in the art. For the sake of brevity, only certain ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to describe a range not explicitly stated, and any lower limit may be combined with any other lower limit to describe a range not explicitly stated, in the same manner, any upper limit may be combined with any other upper limit to describe a range not explicitly stated. For example, describing a numerical range of 1 to 5 includes subranges 1 to 4, 1.5 to 4.5, 1 to 2, and other subranges. As another example, describing a numerical range of 1 to 5, such as 2 to 4, includes subranges 1 to 4 and 2 to 5, and other subranges. Additionally, each point or individual value between its endpoints is included within a range, although not explicitly stated. For example, describing a numerical range of 1 to 5 includes the digits 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, and other digits. Therefore, each point or individual value can serve as its own lower or upper bound in combination with any other point or individual value or any other lower or upper bound, in order to describe a range that is not explicitly stated.

[0218] As used herein, the indefinite article “a (a / a kind)” shall mean “at least one” unless otherwise specified or the context expressly indicates otherwise. For example, an aspect containing “phenolic compound” includes an aspect containing one, two, or more phenolic compounds, unless otherwise specified or the context expressly indicates that only one phenolic compound is included.

[0219] While the foregoing pertains to aspects of the invention, other and further aspects of this disclosure may be designed without departing from its basic scope, which is defined by the following claims.

Claims

1. A process, the process comprising: (a) Contacting a raw material with a first organic solvent and water to form a first aqueous stream containing an organic acid and a first organic stream containing phenol, phenolic compounds, and phenolic oligomers, wherein the raw material has a first concentration of the phenol; (b) Contacting the first organic stream with an aqueous alkali to form a second aqueous stream containing the phenol and the phenol oligomer and a second organic stream containing the phenol compound; (c) Contacting the second aqueous stream with an aqueous acid to form a precipitate containing the phenol oligomer and a third aqueous stream containing the phenol; and (d) Contact the third aqueous stream with the second organic solvent to form a composition having a second concentration of the phenol that is greater than the first concentration of the phenol.

2. The process of claim 1, wherein the raw materials comprise products derived from solvent decomposition of epoxy resin composites, high-temperature decomposition of epoxy resin composites, thermal decomposition of epoxy resin composites, catalytic depolymerization of epoxy resin composites, or combinations thereof.

3. The process of claim 1, wherein the second organic stream further comprises a glycated matrix, a curing agent, an accelerator, or a combination thereof.

4. The process of claim 3, wherein the glycated matrix comprises bisphenol.

5. The process of claim 1, wherein the second organic stream comprises a lower concentration of the phenol than the concentration of the phenol in the second aqueous stream.

6. The process of claim 1, wherein the aqueous acid comprises an inorganic acid, an organic acid, or a combination thereof.

7. The process of claim 6, wherein the inorganic acid is selected from the group consisting of: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and combinations thereof.

8. The process of claim 6, wherein the organic acid is selected from the group consisting of formic acid, acetic acid, citric acid, oxalic acid, and combinations thereof.

9. The process of claim 1, wherein the aqueous alkali comprises an alkali metal hydroxide.

10. The process of claim 9, wherein the alkali metal hydroxide is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, and combinations thereof.

11. The process of claim 1, wherein each of the first organic solvent and the second organic solvent independently comprises an aprotic solvent.

12. The process of claim 1, wherein each of the first organic solvent and the second organic solvent is independently selected from the group consisting of: halogenated solvents, ether solvents, ketone solvents, ester solvents, and combinations thereof.

13. The process of claim 1, wherein each of the first organic solvent and the second organic solvent is independently selected from the group consisting of: dichloromethane, chloroform, methyl tert-butyl ether, ethyl acetate, toluene, benzene, hexane, cyclohexane, and combinations thereof.

14. The process of claim 1, wherein operation (c) further comprises: The aqueous acid is added to the second aqueous stream to form a mixture having a pH of about 5 or less.

15. The process of claim 1, wherein the process further comprises: The composition formed at (d) will be converted into a phenolic resin.

16. The process of claim 15, wherein converting the composition into the phenolic resin comprises: A mixture comprising the composition rich in the phenol, an aldehyde or ketone, and a catalyst is formed; and The mixture is reacted to form the phenolic resin.

17. A process, the process comprising: A raw material comprising a thermochemical derivative of an epoxy resin composite, a catalytic depolymerization product of an epoxy resin composite, or a combination thereof, is contacted with an aprotic solvent and water to form a first aqueous stream comprising an organic acid and a first organic stream comprising phenol, phenolic compounds, and phenolic oligomers, wherein the raw material has a first concentration of the phenol; and The first organic stream is contacted with an aqueous alkali to form a second aqueous stream containing the phenol and the phenol oligomer, and a second organic stream containing the phenol compound, wherein: The second organic stream further comprises a glycated matrix, a curing agent, an accelerator, or a combination thereof; The aqueous alkali comprises an alkali metal hydroxide; and The second organic stream contains a lower concentration of the phenol than the second aqueous stream.

18. The process of claim 17, wherein the alkali metal hydroxide comprises lithium hydroxide, sodium hydroxide, potassium hydroxide, or a combination thereof.

19. The process of claim 17, wherein the thermochemical derivative of the epoxy resin composite material comprises solvent-decomposed oil, high-temperature decomposed oil, or a combination thereof.

20. The process of claim 17, wherein the aprotic solvent is selected from the group consisting of: dichloromethane, chloroform, methyl tributyl ether, ethyl acetate, and combinations thereof.

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