Purified biomass-based compositions containing ethylene glycol and their use for producing polyesters - Patent Application 20070122990

Abstract

A method for purifying a biomass-based composition comprising ethylene glycol is provided, the method comprising: (a) providing a biomass-based composition comprising water in an amount of at least 0.1% by weight, based on the weight of the biomass-based composition; and (b) contacting the biomass-based composition with a solid acid catalyst and contacting the biomass-based composition with an aldehyde-removing resin to provide a purified biomass-based composition.

Description

[Technical Field]

[0001] The present invention relates to a biomass-based composition comprising ethylene glycol, and methods and uses relating thereto. The present invention also relates to a method for producing polyester using the biomass-based composition. [Background technology]

[0002] Ethylene glycol is an organic polyol with the IUPAC name ethane-1,2-diol. Currently, ethylene glycol is most commonly obtained from fossil fuel sources. One typical method for producing fossil fuel-based ethylene glycol uses ethylene produced from oil. This ethylene is oxidized in the presence of a catalyst to produce ethylene glycol, which is then hydrolyzed to produce ethylene glycol.

[0003] In view of the changing environmental and economic climate, there is a desire to use ethylene glycol obtained from renewable resources such as biomass, e.g., sugars. For example, WO2016001169A1 (Patent Document 1) discloses a method for producing ethylene glycol from sugars, which comprises pyrolysis of the sugars to produce mixed C1-C3 oxygenates (e.g., formaldehyde, glycolaldehyde, glyoxal, acetol, and pyruvaldehyde), which are hydrogenated in the presence of a catalyst to produce a crude ethylene glycol product.

[0004] One of the major industrial uses of ethylene glycol is as a raw material for the production of polyesters. Polyesters have a wide range of applications, including the production of packaging articles (e.g., bottles), textile materials, and electrical appliances. One particularly industrially important polyester is polyethylene terephthalate (PET). A series of patent applications disclose methods for purifying biomass-based crude ethylene glycol products to produce high-purity ethylene glycol (>99 wt% ethylene glycol), which is described as suitable for the production of PET. For example, WO 2015 / 150520 (Patent Document 2) and WO 2022 / 223867 (Patent Document 3) disclose purification methods involving distillation to obtain high-purity ethylene glycol. CN 106866371A (Patent Document 4) discloses a multi-stage crystallization process as a purification method for producing ethylene glycol with a purity ranging from 98.5% to 99.9% from crude ethylene glycol products obtained, for example, from HTHP oxalate hydrogenation. None of these patent applications address problems associated with impurities, nor do they measure the UV transmittance or APHA color of purified ethylene glycol compositions. PET is not actually synthesized, and therefore no indication of PET properties such as CIELAB color is provided.

[0005] Packaging articles are often required to meet strict technical specifications with respect to color properties. The art also expects that ethylene glycol compositions used to manufacture packaging articles have certain technical properties in order to produce packaging articles that meet the required technical specifications. For example, the widely accepted view in the art is that ethylene glycol compositions require high UV transmittance to produce polyester packaging articles that meet the required technical specifications. This can be seen, for example, in Zhang et al., "Identification of impurities affecting commercial ethylene glycol UV transmittance," J Chromatogr A904 (2000) 87-97 (Non-Patent Document 1). The literature addresses the problem of ethylene glycol's low UV transmittance, which makes it unsuitable as a raw material for polyester production. The literature further identifies the presence of several major UV-absorbing impurities, which they propose to remove (but do not describe how) to obtain "polymer-grade" ethylene glycol. The introduction states, "The ethylene glycol used to make polyester should be of very high purity and must meet special UV transmittance specifications, requiring the ethylene glycol to have at least 75%, 95%, and 100% UV transmittance at 220, 275, and 350 nm, respectively. Low UV transmittance at these wavelengths is considered to indicate the presence of undesirable impurities that will degrade the quality of the resulting polyester."

[0006] This assumption regarding UV transmittance is evident in the fact that manufacturers of polyester-grade monoethylene glycol specify minimum UV transmittances at 350, 275, and 220 nm in their product specifications. For example, LyondellBasell (Monoethylene Glycol, Polyester Grade, US Sales Specification Material No. 5017), MEGlobal (Monoethylene Glycol, Polyester Grade, Specific Material 000101232907, Sales Specification Revised January 1, 2019, and Commercial Polyester Grade, Specific Material 000101205133, Sales Specification Revised January 1, 2019), and SABIC (Monoethylene Glycol, Bulk, Technical Data Revised 20220825) all specify minimum UV transmittances of 98% at 350 nm, 90-94% at 275 nm, and 70% at 220 nm.

[0007] Furthermore, a series of patent applications relating to bio-based polyester-grade ethylene glycol use UV transmittance at 350, 275, and 220 nm as the target to be achieved. See, for example, WO2015 / 028156 (Patent Document 5), WO2018 / 089600 (Patent Document 6), WO2018 / 089605 (Patent Document 7), CN101525424A (Patent Document 8), and CN104418997A (Patent Document 9). For example, CN101525424A (Patent Document 10) states that bio-based ethylene glycol suitable for PET production must have a transmittance of more than 50% in the wavelength range from 190 to 350 nm. Also, CN1580020A (Patent Document 11) discloses the purification of crude ethylene glycol product, in which UV absorbance at 220 nm is described as an important characteristic for polyester-grade ethylene glycol. This crude ethylene glycol product is passed through a cation resin to remove metal (iron) ions, and then passed through an aldehyde adsorption resin to produce polyester-grade ethylene glycol. However, there are still no examples of polyesters made from the disclosed polyester-grade ethylene glycol, and they have not measured the UV transmittance or APHA color of the purified ethylene glycol composition, nor have they produced actual PET or measured the CIELAB color of such PET. The above-mentioned continuous setup for purifying ethylene glycol is proposed to avoid metal ions interfering with the aldehyde adsorption resin. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] WO2016001169A1 [Patent Document 2] WO2015 / 150520 [Patent Document 3] WO2022 / 223867 [Patent Document 4] CN106866371A [Patent Document 5] WO2015 / 028156 [Patent Document 6] WO2018 / 089600 [Patent Document 7] WO2018 / 089605 [Patent Document 8] CN101525424A [Patent Document 9] CN104418997A [Patent Document 10] CN101525424A [Patent Document 11] CN1580020A [Patent Document 12] US9,926,247 [Patent Document 13] WO2017 / 216311 [Non-patent literature]

[0009] [Non-Patent Document 1] Zhang et al., “Identification of impurities affecting commercial ethylene glycol UV transmittance”, J Chromatogr A904(2000)87-97 [Non-patent document 2] Schandel et al.,ChemSusChem,2020,13,688-692 Summary of the Invention [Problem to be solved by the invention]

[0010] It would be desirable to provide biomass-based compositions containing ethylene glycol that can be used to produce polyesters and packaging articles that meet the necessary or desired technical specifications of the polyesters and packaging articles. It would also be desirable to provide economically and commercially viable processes for producing such biomass-based compositions and polyesters. [Means for solving the problem]

[0011] According to one aspect of the present invention, there is provided a method for purifying a biomass-based composition comprising ethylene glycol, the method comprising: (a) providing a biomass-based composition comprising water in an amount of at least 0.1 wt. %, based on the weight of the biomass-based composition; and (b) contacting the biomass-based composition with a solid acid catalyst and contacting the biomass-based composition with an aldehyde-removing resin to provide a purified biomass-based composition.

[0012] In one aspect, the solid acid catalyst comprises a sulfonic acid functional group.

[0013] In one aspect, the solid acid catalyst comprises one or more of a resin and a zeolite.

[0014] In one aspect, the aldehyde removal resin comprises one or more of a primary amine functional group, a secondary amine functional group, a tertiary amine functional group, and a quaternary ammonium functional group, and in one aspect, the quaternary ammonium functional group is a quaternary ammonium bisulfite functional group.

[0015] In one aspect, the purified biomass-based composition has a total aldehyde concentration of 50 ppm or less, such as 20 ppm or less, for example 18 ppm or less, for example 15 ppm or less, for example 10 ppm or less, based on the weight of the purified biomass-based composition.

[0016] In one aspect, the biomass-based composition in step (a) has a total aldehyde concentration of 100 ppm or more, such as 200 ppm or more, for example 300 ppm or more, such as 500 ppm or more, for example 1000 ppm or more, based on the weight of the biomass-based composition.

[0017] In one aspect, the solid acid catalyst and the aldehyde removal resin are provided in a common bed.

[0018] In one aspect, the solid acid catalyst is provided in a first bed and the aldehyde removal resin is provided in a second bed, wherein the second bed is downstream from the first bed.

[0019] In one aspect, one or each of contacting the biomass-based composition with the solid acid catalyst and contacting the biomass-based composition with the aldehyde-removing resin is conducted at a temperature of from 10°C to 70°C, e.g., from 35°C to 65°C, e.g., from 40°C to 60°C, e.g., from 45°C to 55°C.

[0020] In one aspect, the method includes contacting the purified biomass-based composition with an aldehyde-removal resin after contacting the biomass-based composition with the solid acid catalyst and contacting the biomass-based composition with the aldehyde-removal resin.

[0021] In one aspect, the purified biomass-based composition is characterized by an APHA color number of less than or equal to 5 mg / LPtCo, as determined according to ASTM D1209-05.

[0022] In one aspect, the purified biomass-based composition is characterized by a post-heat APHA color number of 20 mg / LPtCo or less, as determined according to ASTM D1209-05.

[0023] In one aspect, the method includes, after contacting the biomass-based composition with the solid acid catalyst and contacting the biomass-based composition with the aldehyde-removing resin, subjecting the biomass-based composition to at least one distillation step and / or subjecting the biomass-based composition to at least one melt crystallization step.

[0024] In one aspect, the purified biomass-based composition is subjected to a water removal step (e.g., by distillation), after which the purified biomass-based composition comprises ethylene glycol in an amount of 98% by weight or more, such as 99% by weight or more, such as 99.25% by weight or more, such as 99.5% by weight or more, such as 99.75% by weight or more, for example 99.9% by weight or more, based on the weight of the purified biomass-based composition, and the purified biomass-based composition has a natural upper limit of 100% by weight of ethylene glycol.

[0025] In one aspect, the method includes subjecting the biomass-based composition to at least one distillation step prior to contacting the biomass-based composition with the solid acid catalyst and the aldehyde-removing resin.

[0026] In one aspect, the biomass-based composition is obtained by pyrolytic fragmentation of sugars followed by hydrogenation.

[0027] According to another aspect of the present invention, there is provided a purified biomass-based composition obtainable by a method for purifying a biomass-based composition according to one of the above aspects of the present invention, the purified biomass-based composition being characterized by a post-heat APHA color of less than 20 mg / LPtCo as determined according to ASTM D1209-05 and a UV transmittance of less than 40% at 275 nm as determined according to ASTM method E2193-16.

[0028] According to another aspect of the present invention, there is provided the use of a purified biomass-based composition obtained by the method for purifying a biomass-based composition according to one of the above aspects of the present invention for the production of a polyester, wherein the polyester has the following CIELAB color space value, determined according to ASTM D6290-19: L ≥ 65. * ;-4 to 4 a * ; and b from -4 to 4 * The use is characterized by one or more of the following:

[0029] According to another aspect of the present invention, there is provided a method for producing polyester, comprising contacting a purified biomass-based composition obtained by the method for purifying a biomass-based composition according to one of the above aspects of the present invention with at least one reactant to produce a polyester having the following CIELAB color space value, determined according to ASTM D6290-19: L ≥ 65: * ;-4 to 4 a * ; and b from -4 to 4 * In accordance with the present invention, there is provided a method for producing a polymer characterized by one or more of:

[0030] According to another aspect of the present invention, there is provided a polyester obtainable by a process for producing a polyester according to one of the above aspects of the present invention, which polyester has the following CIELAB color space value, determined according to ASTM D6290-19: L ≥ 65 * ;-4 to 4 a * ; and b from -4 to 4 * The polyester is provided as characterized by one or more of:

[0031] In one aspect, the polyester has the following CIELAB color space parameter values, as determined in accordance with ASTM D6290-19: L ≥ 85. * ;a from -2 to 2 * ; and b from -2 to 2 *In one aspect, the polyester has a CIELAB color space parameter value b of -4 to 4, preferably -2 to 2, as determined according to ASTM D6290-19. * In one aspect, the polyester has a CIELAB color space parameter value a of from −4 to 4, preferably from −2 to 2, as determined according to ASTM D6290-19. * In one aspect, the polyester has a CIELAB color space parameter value L of 65 or greater, preferably 85 or greater, as determined according to ASTM D6290-19. * It is characterized by:

[0032] According to another aspect of the present invention, there is provided a packaging article or preform formed from a polyester according to one of the above aspects of the present invention.

[0033] According to one aspect of the present invention, there is provided a method for purifying a biomass-based composition comprising ethylene glycol, comprising: (a) providing the biomass-based composition comprising water in an amount of at least 0.1 wt. %, based on the weight of the biomass-based composition; and (b) contacting the biomass-based composition with an aldehyde-removing resin to provide a purified biomass-based composition. The method includes:

[0034] In any of the above aspects of the invention, the polyester may comprise polyethylene terephthalate.

[0035] Any feature of any aspect of the invention may be combined with any one or more features of any other aspect of the invention. DETAILED DESCRIPTION OF THE INVENTION

[0036] As described herein, one aspect of the invention is a method for purifying a biomass-based composition comprising ethylene glycol, comprising: (a) providing a biomass-based composition comprising water in an amount of at least 0.1 wt. %, based on the weight of the biomass-based composition; and (b) contacting the biomass-based composition with a solid acid catalyst and contacting the biomass-based composition with an aldehyde-removing resin to provide a purified biomass-based composition. The method includes:

[0037] Ethylene glycol (monoethylene glycol) has many uses, including as an antifreeze and as a monomer for polyester production. The inventors have found that biomass-based compositions containing ethylene glycol may contain small amounts of free aldehydes and acetals, and the presence of these components (e.g., at the ppm level) can lead to discoloration of polyesters formed from the biomass-based compositions. This can be problematic when a final product (e.g., a bottle) with a particular color profile (e.g., reduced color, such as substantially colorless) is desired or required. The inventors have found that treatment of biomass-based compositions containing ethylene glycol with an aldehyde-scavenging resin may not be effective by itself. For example, the inventors have found that biomass-based compositions containing ethylene glycol treated only with an aldehyde-scavenging resin may produce polyesters with an undesirable color profile (e.g., yellowing). Surprisingly, the inventors have found that contacting a biomass-based composition comprising ethylene glycol with a solid acid catalyst and an aldehyde-scavenging resin can provide a biomass-based composition that can be used to produce polyesters having a desirable color profile (e.g., reduced color, such as substantially colorless).

[0038] purification Here, "purify," "purified," and "purification" can be thought of as enriching the composition with ethylene glycol by removing other components from the composition. "Other components" can include impurities, i.e., components present in low concentrations, such as aldehydes or unidentified impurities.

[0039] Biomass-Based Compositions In one aspect, the biomass-based composition has a total carbon content of greater than 0.5 ppt (parts per trillion) as determined by ASTM D6866-22. 14 Has a C content.

[0040] In one aspect, the biomass-based composition is obtained by pyrolytic fragmentation of sugars.

[0041] In one aspect, the biomass-based composition is obtained by hydrogenolysis of sugars.

[0042] The method for purifying a biomass-based composition includes the step (a) of providing a biomass-based composition comprising water in an amount of at least 0.1% by weight, based on the weight of the biomass-based composition.

[0043] In one aspect, the biomass-based composition comprises water in an amount of at least 2% by weight based on the weight of the biomass-based composition. In one aspect, the biomass-based composition comprises water in an amount of at least 5% by weight based on the weight of the biomass-based composition. In one aspect, the biomass-based composition comprises water in an amount of at least 8% by weight based on the weight of the biomass-based composition. In one aspect, the biomass-based composition comprises water in an amount of at least 10% by weight based on the weight of the biomass-based composition. In one aspect, the biomass-based composition comprises water in an amount of at least 15% by weight based on the weight of the biomass-based composition.

[0044] In one aspect, the biomass-based composition comprises water in an amount of 80% by weight or less, based on the weight of the biomass-based composition. In one aspect, the biomass-based composition comprises water in an amount of 70% by weight or less, based on the weight of the biomass-based composition. In one aspect, the biomass-based composition comprises water in an amount of 60% by weight or less, based on the weight of the biomass-based composition. In one aspect, the biomass-based composition comprises water in an amount of 50% by weight or less, based on the weight of the biomass-based composition. In one aspect, the biomass-based composition comprises water in an amount of 40% by weight or less, based on the weight of the biomass-based composition.

[0045] In one aspect, the biomass-based composition comprises water in an amount of 2% to 80% by weight based on the weight of the biomass-based composition. In one aspect, the biomass-based composition comprises water in an amount of 5% to 70% by weight based on the weight of the biomass-based composition. In one aspect, the biomass-based composition comprises water in an amount of 8% to 60% by weight based on the weight of the biomass-based composition. In one aspect, the biomass-based composition comprises water in an amount of 10% to 50% by weight based on the weight of the biomass-based composition. In one aspect, the biomass-based composition comprises water in an amount of 15% to 40% by weight based on the weight of the biomass-based composition.

[0046] In one aspect, the biomass-based composition is obtained by pyrolytic fragmentation of biomass followed by hydrogenation. Alternatively, the biomass-based composition may be obtained by hydrocracking of biomass. Hydrocracking is a chemical reaction similar to hydrolysis, in which hydrogen plays a role similar to that of water. In hydrocracking, bonds (typically in organic molecules) are cleaved while simultaneously adding hydrogen atoms to each of the resulting molecular fragments. In one aspect, the biomass includes one or more of lignocellulose, lignin, sludge, lipids, proteins, and carbohydrates.

[0047] Pyrolytic fragmentation (or pyrolysis) of biomass refers to a process in which a biomass feedstock is subjected to a thermal treatment, leading to the partial decomposition of its constituents to produce pyrolysis products. The pyrolytic fragmentation of glucose and the hydrogenation of the resulting pyrolysis products are known, for example, according to Schandel et al., ChemSusChem, 2020, 13, 688-692 (Non-Patent Document 2), US 9,926,247 (Patent Document 12) and WO 2017 / 216311 (Patent Document 13).

[0048] Biomass includes all types of biogenic materials, i.e., materials produced within the recent past (i.e., the last century) from the sequestration of atmospheric CO2. This includes lignocellulose, lignin, sludge, lipids, proteins, and carbohydrates.

[0049] The carbohydrate category includes polysaccharides, oligosaccharides, and sugars. The polysaccharide category includes long-chain polymers of sugars, such as cellulose, hemicellulose, and starch. The oligosaccharide category includes short-chain polymers of sugars (4-10 monosaccharide units). This category of sugars includes trisaccharides, disaccharides, and monosaccharides. The trisaccharide category includes maltotriose, etc. The disaccharide category includes sucrose, maltose, lactose, and cellobiose, etc. The monosaccharide category includes all monosaccharides in the triose, tetrose, pentose, and hexose categories, and preferred monosaccharides are pentoses and hexoses, more preferably glucose, fructose, mannose, galactose, xylose, and arabinose, or mixtures thereof. Most preferred is glucose as the monosaccharide feedstock. The monosaccharide feedstock may contain up to 5% by weight of di- and trisaccharides relative to the monosaccharide and still be considered a monosaccharide feedstock.

[0050] In one aspect, the biomass-based composition is obtained by pyrolytic fragmentation of carbohydrates followed by hydrogenation. In one aspect, the biomass-based composition is obtained by pyrolytic fragmentation of polysaccharides, oligosaccharides, sugars, and mixtures thereof followed by hydrogenation. In one aspect, the biomass-based composition is obtained by pyrolytic fragmentation of sugars followed by hydrogenation. In one aspect, the biomass-based composition is obtained by pyrolytic fragmentation of polysaccharides, oligosaccharides, trisaccharides, disaccharides, monosaccharides, and mixtures thereof followed by hydrogenation. In one aspect, the biomass-based composition is obtained by pyrolytic fragmentation of disaccharides, monosaccharides, and mixtures thereof followed by hydrogenation. In one aspect, the biomass-based composition is obtained by pyrolytic fragmentation of at least disaccharides followed by hydrogenation. In one aspect, the biomass-based composition is obtained by pyrolytic fragmentation of at least monosaccharides followed by hydrogenation.

[0051] Pyrolytic fragmentation refers to a process in which heat is supplied to a biomass feedstock for a certain amount of time (typically 300-700 °C) to cause its conversion to pyrolysis products (or pyrolytic fragmentation products). Pyrolytic fragmentation does not include conditions or processes in which substantial combustion of the feedstock or gasification into permanent gases is achieved. The heat can be supplied by introducing oxygen or an oxidant to combust a small amount of the feedstock, or heat can be supplied externally, for example, by contacting the feedstock with a hot surface, gas, liquid, or solid to transfer heat. Pyrolytic fragmentation can be carried out in a variety of reactors, including bubbling fluidized-bed reactors, circulating fluidized-bed reactors, ablative reactors, rotating cone reactors, and micro-pyrolyzer units. Heat can be supplied for long periods (slow pyrolysis, >5 minutes), medium periods (normal pyrolysis, 30-300 seconds), and short periods (fast pyrolysis, e.g., less than 30 seconds, typically about 0.5-2 seconds). The pyrolysis fragmentation duration and temperature affect the composition of the pyrolysis products.

[0052] Monosaccharide pyrolysis refers to the conversion of a monosaccharide feedstock (i.e., a monosaccharide feedstock that is substantially free of lignocellulose, lignin, lipids, cellulose, hemicellulose, starch, proteins, oligosaccharides, trisaccharides, and disaccharides) by pyrolysis to a pyrolysis product. Monosaccharide pyrolysis performed with a monosaccharide feedstock containing less than 15% water by weight, based on the weight of the monosaccharide feedstock, is referred to as "dry monosaccharide pyrolysis." Monosaccharide pyrolysis performed on a monosaccharide feedstock containing more than 15% water by weight, based on the weight of the monosaccharide feedstock, is referred to as "wet sugar pyrolysis." The goal of wet monosaccharide pyrolysis can be to convert aqueous monosaccharide feedstock to glycolaldehyde (2-hydroxyacetaldehyde) with the production of other light oxygenates (pyruvaldehyde, acetol, formaldehyde, and glyoxal) and minimal production of other products.

[0053] A monosaccharide feedstock for wet monosaccharide pyrolysis is an aqueous solution of monosaccharides containing more than 15 wt. %, e.g., more than 20 wt. %, more than 30 wt. %, more than 40 wt. %, more than 50 wt. %, more than 60 wt. %, more than 70 wt. %, or more than 80 wt. % water, based on the weight of the monosaccharide feedstock. One example of a monosaccharide feedstock for wet monosaccharide pyrolysis is a feedstock containing 64 wt. % glucose, 1 wt. % maltose (a disaccharide), and 35 wt. % water. Another example of a monosaccharide feedstock for wet monosaccharide pyrolysis is a feedstock containing 32 wt. % glucose, 31 wt. % fructose, 15 wt. % sucrose, and 35.5 wt. % water.

[0054] Monosaccharide feedstocks for dry monosaccharide pyrolysis contain less than 15 wt% water based on the weight of the monosaccharide feedstock. An example of a monosaccharide feedstock for dry monosaccharide pyrolysis is glucose monohydrate (91 wt% monosaccharide and 9 wt% water).

[0055] After pyrolytic fragmentation of the feedstock, the resulting pyrolysis products may be subjected to hydrogenation.

[0056] Hydrogenation refers to a chemical reaction between molecular hydrogen and other compounds or elements, optionally in the presence of a catalytic material and optionally in the presence of a solvent. In this method, glycolaldehyde can be produced from the pyrolytic fragmentation of biomass, e.g., the pyrolysis of sugars, and in this respect, hydrogenation of the pyrolysis product converts glycolaldehyde to ethylene glycol, optionally with the conversion of glyoxal to ethylene glycol, pyruvaldehyde and acetol to propylene glycol, and formaldehyde to methanol, with minimal production of other products. The resulting composition can be referred to as a biomass-based composition.

[0057] Suitable hydrogenation catalysts comprise an active material selected from the group consisting of ruthenium, rhenium, rhodium, iridium, palladium, platinum, copper, and nickel, or a mixture thereof, on a support. The support material is usually made of an inert material. Suitable support materials are carbon, silica, alumina, titania, and zirconia, or a mixture thereof.

[0058] In one aspect, the pyrolysis product is subjected to vapor phase hydrogenation in the presence of hydrogen and a hydrogenation catalyst. When the hydrogenation is vapor phase hydrogenation, the hydrogenation can be carried out at a temperature ranging from 200° C. to 250° C. and a hydrogen partial pressure ranging from 0.5 bar to 5 bar.

[0059] In one aspect, the pyrolysis product is subjected to liquid-phase hydrogenation in the presence of hydrogen and a hydrogenation catalyst. When the hydrogenation is liquid-phase hydrogenation, the hydrogenation can be carried out at a temperature ranging from 60° C. to 120° C. and a hydrogen partial pressure ranging from 20 bar to 200 bar. When the hydrogenation is liquid-phase hydrogenation, the hydrogen partial pressure is the partial pressure in the gas phase above or in which the hydrogenation liquid is dispersed, which is proportional to the concentration of hydrogen in the liquid phase.

[0060] In one aspect, the hydrogenation is carried out in the presence of a solvent selected from the group consisting of water, methanol, ethanol, ethylene glycol, and propylene glycol, or mixtures thereof.

[0061] Prior to hydrogenation, the pyrolysis products may be subjected to operations such as condensation and / or separation.

[0062] In one aspect, the biomass-based composition has a total aldehyde concentration of 100 ppm or greater. In one aspect, the biomass-based composition has a total aldehyde concentration of 200 ppm or greater. In one aspect, the biomass-based composition has a total aldehyde concentration of 300 ppm or greater. In one aspect, the biomass-based composition has a total aldehyde concentration of 500 ppm or greater. In one aspect, the biomass-based composition has a total aldehyde concentration of 1000 ppm or greater. "ppm" may be based on the weight of the biomass-based composition.

[0063] In one aspect, the biomass-based composition has a total aldehyde concentration of 1,000,000 ppm or less. In one aspect, the biomass-based composition has a total aldehyde concentration of 100,000 ppm or less. In one aspect, the biomass-based composition has a total aldehyde concentration of 10,000 ppm or less. In one aspect, the biomass-based composition has a total aldehyde concentration of 8,000 ppm or less. In one aspect, the biomass-based composition has a total aldehyde concentration of 5,000 ppm or less. "ppm" may be based on the weight of the biomass-based composition.

[0064] In one aspect, the biomass-based composition has a total aldehyde concentration of 100 ppm to 1,000,000 ppm. In one aspect, the biomass-based composition has a total aldehyde concentration of 200 ppm to 100,000 ppm. In one aspect, the biomass-based composition has a total aldehyde concentration of 300 ppm to 10,000 ppm. In one aspect, the biomass-based composition has a total aldehyde concentration of 500 ppm to 8,000 ppm. In one aspect, the biomass-based composition has a total aldehyde concentration of 1,000 ppm to 5,000 ppm. "ppm" may be based on the weight of the biomass-based composition.

[0065] Solid acid catalyst and aldehyde removal resin The method for purifying a biomass-based composition includes step (b) contacting the biomass-based composition with a solid acid catalyst and contacting the biomass-based composition with an aldehyde-removing resin to provide a purified biomass-based composition. In this regard, the biomass-based composition may be contacted with the aldehyde-removing resin after the solid acid catalyst. Alternatively, the biomass-based composition may be contacted with the solid acid catalyst and the aldehyde-removing resin simultaneously (e.g., using a mixed bed comprising the solid acid catalyst and the aldehyde-removing resin, which may be referred to as a common-bed configuration).

[0066] In one aspect, the solid acid catalyst is provided in a first bed. This first bed may be provided in a column. In one aspect, the aldehyde removal resin is provided in a second bed. This second bed may be provided in a column. In one aspect, the second bed is downstream of the first bed. The column in which the first bed is provided may be different from the column in which the second bed is provided. The column in which the second bed is provided may be the same column as the column in which the first bed is provided.

[0067] Here, "downstream" (and "upstream") refers to the direction of flow of the biomass composition. For example, operation Y on a biomass-based composition occurring after operation X on the biomass-based composition means that operation Y is downstream of operation X.

[0068] In one aspect, the solid acid catalyst and the aldehyde removal resin are provided in a common bed (mixed bed, common bed configuration). The common bed may be provided in one column. Advantageously, providing the solid acid catalyst and the aldehyde removal resin in one column bed has been found to be particularly effective. Without being bound by theory, it is believed that this arrangement facilitates the removal of aldehyde as it is generated, which promotes continuous aldehyde production.

[0069] One advantage of simultaneously contacting a biomass composition with a solid acid catalyst and an aldehyde-removing resin is that a high degree of aldehyde / ketone and acetal removal can be achieved in a single process. Only free aldehydes and ketones are removed by reaction with the primary amine groups of the amine-containing resin, while the corresponding acetals are not. Acetal hydrolysis is equilibrium-limited, meaning that it is thermodynamically not possible to quantitatively hydrolyze all acetals without removing the corresponding reaction product, the aldehyde or ketone. Furthermore, acetal hydrolysis proceeds at a significant reaction rate only in the presence of an acid catalyst.

[0070] These limitations can be overcome by simultaneous treatment with a solid acid catalyst and an aldehyde-scavenging resin, where the aldehyde-scavenging resin constantly removes free aldehydes or ketones, while the solid acid catalyst continuously catalyzes the hydrolysis of acetals to the corresponding free aldehydes and alcohols. However, a similar effect can be achieved by passing the biomass-based composition through a series of repeating beds of a solid acid catalyst followed by an aldehyde-scavenging resin.

[0071] It is considered within the ability of one skilled in the art to select the operating conditions for the steps of contacting the biomass-based composition with the solid acid catalyst and contacting the biomass-based composition with the aldehyde-removing resin.

[0072] In particular, it is believed to be within the ability of one skilled in the art to select the temperature, pressure, contact time, space velocity, etc. for the steps of contacting the biomass-based composition with the solid acid catalyst and contacting the biomass-based composition with the aldehyde-removing resin.

[0073] In one aspect, one or each of contacting the biomass-based composition with the solid acid catalyst and contacting the biomass-based composition with the aldehyde-removing resin occurs at a temperature of from 10° C. to 70° C. In one aspect, one or each of contacting the biomass-based composition with the solid acid catalyst and contacting the biomass-based composition with the aldehyde-removing resin occurs at a temperature of from 35° C. to 65° C. In one aspect, one or each of contacting the biomass-based composition with the solid acid catalyst and contacting the biomass-based composition with the aldehyde-removing resin occurs at a temperature of from 40° C. to 60° C. In one aspect, one or each of contacting the biomass-based composition with the solid acid catalyst and contacting the biomass-based composition with the aldehyde-removing resin occurs at a temperature of from 45° C. to 55° C.

[0074] solid acid catalyst The solid acid catalyst has an acidic functional group. In one aspect, the acidic functional group is a sulfonic acid functional group.

[0075] In one aspect, the solid acid catalyst comprises an insoluble matrix (or support structure), which may be porous.

[0076] In one aspect, the solid acid catalyst comprises a resin. In one aspect, the solid acid catalyst comprises a crosslinked resin. Non-limiting examples of crosslinked resins or polymers include polystyrene crosslinked with divinylbenzene (styrene-divinylbenzene) and polyacrylic acid crosslinked with divinylbenzene (polyacrylic-divinylbenzene).

[0077] In one aspect, the solid acid catalyst comprises Amberlyst 15. Amberlyst 15 is a strongly acidic styrene-divinylbenzene resin with sulfonic acid functional groups. In one aspect, the solid acid catalyst comprises Amberlyst 131. Amberlyst 131 is a strongly acidic styrene-divinylbenzene resin with sulfonic acid functional groups. Those skilled in the art will appreciate that many types of solid acid catalysts may be used.

[0078] In one aspect, the solid acid catalyst is in the form of particles.

[0079] In one aspect, the solid acid catalyst comprises a zeolite.

[0080] Here, the term "solid" can also include semi-solids such as gels.

[0081] Aldehyde Removal Resin The aldehyde-scavenging resin at least partially removes aldehydes from the biomass-based composition.

[0082] In one aspect, the aldehyde scavenging resin comprises one or more of primary amine functional groups, secondary amine functional groups, tertiary amine functional groups, and quaternary ammonium functional groups, such as quaternary ammonium bisulfite functional groups.

[0083] In one aspect, the aldehyde removal resin comprises an insoluble matrix (or support structure), which may be porous.

[0084] In one aspect, the aldehyde-scavenging resin is a heterogeneous resin. In one aspect, the aldehyde-scavenging resin is a solid or a gel.

[0085] In one aspect, the aldehyde-scavenging resin comprises a crosslinked resin. Non-limiting examples of crosslinked resins or polymers include polystyrene crosslinked with divinylbenzene (styrene-divinylbenzene) and polyacrylic acid crosslinked with divinylbenzene (polyacrylic-divinylbenzene).

[0086] In one aspect, the aldehyde-scavenging resin comprises Purolite A110. In one aspect, the aldehyde-scavenging resin comprises Purolite A830. Purolite A110 is a weakly basic polystyrene-divinylbenzene resin with primary amine functionality. Purolite A830 is a weakly basic polyacrylic-divinylbenzene resin with primary amine functionality.

[0087] In one aspect, the aldehyde-scavenging resin is in granular form.

[0088] Further steps In some aspects, the method of purifying a biomass-based composition includes at least one additional step.

[0089] In one aspect, the method includes, after contacting the biomass-based composition with the solid acid catalyst and the aldehyde-removing resin, further contacting the biomass-based composition with the aldehyde-removing resin. This can be considered a "polishing" step to further aid in the removal of aldehydes from the biomass-based composition. For example, this "polishing" step can be performed after contacting the biomass-based composition with the solid acid catalyst and the aldehyde-removing resin via a common bed configuration or via a separate bed configuration.

[0090] distillation In one aspect, the method of purifying a biomass-based composition includes subjecting the biomass-based composition to at least one distillation step to provide a distillation product, wherein the concentration of ethylene glycol in the distillation product is higher than that in the biomass-based composition.

[0091] In one aspect, the biomass-based composition subjected to the at least one distillation step is aqueous.

[0092] Here, the "distillation product" can be a residue or a fraction. Here, the "residue" (or "bottoms") can be considered to be the liquid fraction that collects at the bottom of a distillation column during distillation. Those skilled in the art will understand that the residue contains components that are less volatile than the components of the fraction. Here, the "fraction" can be considered to be a vapor fraction or a liquid fraction condensed from a vapor or a vapor-liquid mixture that is removed from the distillation column at any point above the bottom of the column during distillation. At least one fraction is collected during distillation, but multiple fractions can also be collected simultaneously from the distillation column. Thus, a "liquid side draw" is a fraction that is not collected from the top of the distillation column.

[0093] In one aspect, the biomass-based composition in step (a) is provided by (I) subjecting the biomass-based composition to at least one distillation step to provide a distillation product, wherein the concentration of ethylene glycol in the distillation product is higher than that in the biomass-based composition. The distillation product may be the biomass-based composition in step (a).

[0094] In one aspect, the method for purifying a biomass-based composition includes (c) subjecting the purified biomass-based composition from step (b) to at least one distillation step to provide a distillation product, wherein the concentration of ethylene glycol in the distillation product is higher than that in the biomass-based composition, and the distillation product is yet another purified biomass-based composition. The distillation step may involve removing water from the diluted composition of step b). This may be accomplished, for example, by evaporation in a rotary evaporator.

[0095] In one aspect, the distillation product comprises ethylene glycol in an amount of 85 wt % or more, such as 90 wt % or more, such as 95 wt % or more, based on the weight of the distillation product.

[0096] In one aspect, the distillation product comprises ethylene glycol in an amount of 99% by weight or less, such as 98% by weight or less, such as 97% by weight or less, based on the weight of the distillation product.

[0097] In one aspect, the at least one distillation step includes a first distillation step comprising feeding the biomass-based composition to a continuous distillation unit to provide a first residue and at least one fraction, wherein one of the first residue and the at least one first fraction is an ethylene glycol-enriched fraction, and the ethylene glycol-enriched fraction can be the distillation product.

[0098] In one aspect, the at least one distillation step includes at least one further distillation step comprising feeding an ethylene glycol-enriched fraction from a preceding distillation step to a continuous distillation unit to provide a further residue and at least one further fraction, wherein one of the further residue and the at least one further fraction is an ethylene glycol-enriched fraction, which can be the distillation product.

[0099] "Enriched" here is relative to the composition from which the distillation was carried out. For example, the ethylene glycol-enriched fraction from the third distillation step is enriched in ethylene glycol compared to the ethylene glycol-enriched fraction from the second distillation step.

[0100] In one aspect, the ethylene glycol-enriched fraction from the first distillation step is also enriched in propylene glycol, and this fraction is referred to as the ethylene glycol- and propylene glycol-enriched fraction from the first distillation step.

[0101] In one aspect, the at least one distillation step includes a second distillation step comprising feeding the ethylene glycol-enriched fraction from the first distillation step to a continuous distillation unit to provide a second residue and at least one second fraction, wherein one of the second residue and the at least one second fraction is an ethylene glycol-enriched fraction, and the ethylene glycol-enriched fraction can be the distillation product.

[0102] In one aspect, the at least one distillation step includes a second distillation step comprising feeding the ethylene glycol-enriched and propylene glycol-enriched fractions from the first distillation step to a sequential distillation unit to provide a second residue and at least one second fraction, wherein one of the second residue and the at least one second fraction is an ethylene glycol-enriched fraction, and the ethylene glycol-enriched fraction can be the distillation product.

[0103] In one aspect, the at least one distillation step includes a third distillation step comprising feeding the ethylene glycol-enriched fraction from the second distillation step to a continuous distillation unit to provide a third residue and at least one third fraction, wherein one of the third residue and the at least one third fraction is an ethylene glycol-enriched fraction, and the ethylene glycol-enriched fraction can be the distillation product.

[0104] In one aspect, the at least one distillation step includes a fourth distillation step comprising feeding the ethylene glycol-enriched fraction from the third distillation step to a continuous distillation unit to provide a fourth residue and at least one fourth fraction, wherein one of the fourth residue and the at least one fourth fraction is an ethylene glycol-enriched fraction, and the ethylene glycol-enriched fraction can be the distillation product.

[0105] In one aspect, at least 80% by weight, such as at least 85% by weight, for example at least 90% by weight, such as at least 92% by weight, for example at least 95% by weight, such as at least 97.5% by weight, for example at least 99% by weight, for example at least 99.5% by weight, based on the weight of the biomass-based composition, of non-ethylene glycol components (i.e., all components that are not ethylene glycol) is removed from the biomass-based composition in the at least one distillation step (in this case, the entire distillation sequence).

[0106] In a given distillation, the split of the feed between the top and bottom of the column is controlled by the feed rate, reflux ratio, energy input to the reboiler, feed preheat, refrigerant supply to the reflux and distillate condensers, pressure, and separating power of the column, and the vapor-liquid equilibrium of the components in the feed.

[0107] Components that are more volatile than ethylene glycol can be condensed and removed as a distillate, and the concentrated ethylene glycol product can be collected as a residue. Alternatively, components that are less volatile than ethylene glycol can be condensed and removed as a residue, and the concentrated ethylene glycol product can be collected as a distillate.

[0108] It is within the knowledge of one skilled in the distillation arts to design the distillation step to provide either an ethylene glycol-enriched bottoms or an ethylene glycol-enriched fraction.

[0109] Melt crystallization In one aspect, the method of purifying a biomass-based composition includes subjecting the distillation product to at least one melt crystallization step to produce crystals and a mother liquor, the crystals providing a purified biomass-based composition, wherein the concentration of ethylene glycol in the purified biomass-based composition is higher than in the distillation product.

[0110] Further Processing Steps An optional further processing step can be used prior to distilling off the water, which involves passing the purified biomass-based composition containing the ethylene glycol composition through a column containing a bed of an aldehyde-removing resin, which can be, for example, Purolite A110, at a temperature of 50° C. This further processing step has been found to further reduce the color of the polyester pellets.

[0111] Refined Biomass-Based Compositions In one aspect, the purified biomass-based composition in step (b) of the method for purifying a biomass-based composition is provided by contacting the biomass-based composition in step (a) of the method for purifying a biomass-based composition with a solid acid catalyst and an aldehyde-removing resin. In one aspect, the purified biomass-based composition in step (b) of the method for purifying a biomass-based composition is provided by the at least one distillation step. In one aspect, the purified biomass-based composition is provided by the at least one melt crystallization step. For example, the purified biomass-based composition in step (b) of the method for purifying a biomass-based composition can be the further purified biomass-based composition from the at least one distillation step or the further purified biomass-based composition from the at least one melt crystallization step. The purified biomass-based composition in step (b) of the method for purifying a biomass-based composition may be hereinafter referred to as the "purified biomass-based composition."

[0112] In one aspect, the purified biomass-based composition has a total aldehyde concentration of 50 ppm or less. In one aspect, the purified biomass-based composition has a total aldehyde concentration of 20 ppm or less. In one aspect, the purified biomass-based composition has a total aldehyde concentration of 18 ppm or less. In one aspect, the purified biomass-based composition has a total aldehyde concentration of 15 ppm or less. In one aspect, the purified biomass-based composition has a total aldehyde concentration of 10 ppm or less. "ppm" may be based on the weight of the purified biomass-based composition.

[0113] In one aspect, the purified biomass-based composition has a total aldehyde concentration of 1 ppm or greater. In one aspect, the purified biomass-based composition has a total aldehyde concentration of 2 ppm or greater. In one aspect, the purified biomass-based composition has a total aldehyde concentration of 5 ppm or greater. In one aspect, the purified biomass-based composition has a total aldehyde concentration of 10 ppm or greater. "ppm" may be based on the weight of the purified biomass-based composition.

[0114] In one aspect, the purified biomass-based composition is characterized by an APHA color number of 10 mg / LPtCo or less (as determined in accordance with ASTM D1209-05). In one aspect, the purified biomass-based composition is characterized by an APHA color number of 9 mg / LPtCo or less (as determined in accordance with ASTM D1209-05). In one aspect, the purified biomass-based composition is characterized by an APHA color number of 8 mg / LPtCo or less (as determined in accordance with ASTM D1209-05). In one aspect, the purified biomass-based composition is characterized by an APHA color number of 7 mg / LPtCo or less (as determined in accordance with ASTM D1209-05). In one aspect, the purified biomass-based composition is characterized by an APHA color number of 6 mg / LPtCo or less (as determined in accordance with ASTM D1209-05). In one aspect, the purified biomass-based composition is characterized by an APHA color number of 5 mg / LPtCo or less (as determined in accordance with ASTM D1209-05).

[0115] The American Public Health Association (APHA) Color Scale, also known as the Hazen Scale or Platinum-Cobalt (PtCo) Scale, is a measure of the color of liquid chemicals. The scale is used to assess the quality of chemicals and other substances, and is a good indicator of the concentration of color-affecting impurities in, for example, ethylene glycol-containing biomass-based compositions.

[0116] Here, the APHA color number is determined in accordance with ASTM D1209-05 at a temperature of 20° C. to 25° C. (room temperature) and atmospheric pressure.

[0117] The APHA color number can also be used to evaluate the thermal stability of liquid chemicals by testing for "APHA color after heating." In the sense of the present invention, this is done by carrying out a heating step, in which the liquid chemical is heated to 200°C for an extended period of time. A period of 2 to 4 hours is suitable in the sense of the present invention. After cooling to room temperature, the APHA color number is determined. The APHA color number can be used as an indicator of the thermal stability of a liquid. A high APHA color number can be an indicator that the substance has degraded or reacted during heating to produce colored impurities.

[0118] Unless otherwise stated herein, APHA color refers to testing of the purified biomass-based composition without a heating step. If a heating step is performed, it is referred to as "post-heat APHA color."

[0119] The inventors have surprisingly found that an ethylene glycol composition may be polymer-grade even if it does not meet industry specifications for UV transmittance at 220 nm, 275 nm, and 350 nm. The inventors have found that an APHA color of less than 5 mg / L PtCO before heating and less than 20 mg / L PtCO after heating are good indicators of whether an ethylene glycol composition may be polymer-grade / suitable for producing colorless PET. An APHA color of less than 15 mg / L after heating is even better.

[0120] Therefore, thermal stability / post-heat AHPA color can be used as an indication of the suitability of a purified biomass-based composition containing ethylene glycol as an ethylene glycol reactant in the synthesis of PET. In one embodiment according to the present invention, a purified biomass-based composition containing ethylene glycol that is considered suitable as a reactant in the synthesis of PET has a post-heat APHA color of less than 20 mg / LPtCo. In one embodiment, a purified biomass-based composition containing ethylene glycol that is considered suitable as a reactant in the synthesis of PET has a post-heat APHA color of less than 15 mg / LPtCo.

[0121] In one aspect, the purified biomass-based composition is characterized by an APHA color number (determined in accordance with ASTM D1209-05) of greater than 0 mg / LPtCo, which may be considered a lower limit for all upper limits set forth herein.

[0122] In one aspect, the purified biomass-based composition comprises ethylene glycol in an amount of 98% or greater by weight, based on the weight of the purified biomass-based composition. In one aspect, the purified biomass-based composition comprises ethylene glycol in an amount of 99% or greater by weight, based on the weight of the purified biomass-based composition. In one aspect, the purified biomass-based composition comprises ethylene glycol in an amount of 99.25% or greater by weight, based on the weight of the purified biomass-based composition. In one aspect, the purified biomass-based composition comprises ethylene glycol in an amount of 99.5% or greater by weight, based on the weight of the purified biomass-based composition.

[0123] In one aspect, the purified biomass-based composition comprises ethylene glycol in an amount of 99.95% by weight or less, based on the weight of the purified biomass-based composition. In one aspect, the purified biomass-based composition comprises ethylene glycol in an amount of 99.9% by weight or less, based on the weight of the purified biomass-based composition. The purified biomass-based composition has an upper limit of 100% by weight of ethylene glycol, based on the weight of the purified biomass-based composition.

[0124] In one aspect, the purified biomass-based composition has a UV transmittance (determined according to ASTM method E2193-16) of less than 40% at 275 nm.

[0125] UV transmittance is used as a simple indicator of the absence of low-level impurities in ethylene glycol that adversely affect color in the resulting PET; i.e., the higher the transmittance, the lower the amount of impurities. Removing low-level impurities from ethylene glycol results in a higher purity ethylene glycol as a result of the impurity removal. It has been widely accepted in the technical field of the present invention that an ethylene glycol composition requires high UV transmittance to be suitable for producing polyesters with acceptable polymer quality. This is particularly true for bottle production, e.g., polyethylene terephthalate bottle production. Purifying biomass-based ethylene glycol to achieve high UV transmittance, even if possible, can be costly and cumbersome (see, for example, WO 2015 / 028156 (Patent Document 5), WO 2018 / 089600 (Patent Document 6), and WO 2018 / 089605 (Patent Document 7)). The inability to achieve biomass-based ethylene glycol that meets UV transmittance specifications in an economical manner has been a major obstacle to achieving more sustainable raw materials for polyester production. The present inventors have surprisingly found that low UV transmittance biomass-based ethylene glycol can be used to produce satisfactory "bottle grade" polyester, even when the biomass-based ethylene glycol does not meet industry specifications for UV transmittance.

[0126] Here, UV transmittance at 275 nm is determined according to ASTM method E2193-16 at temperatures between 20°C and 25°C and atmospheric pressure.

[0127] In one aspect, the purified biomass-based composition has a UV Transmittance at 275 nm (determined according to ASTM Method E2193-16) of 38% or less. In one aspect, the purified biomass-based composition has a UV Transmittance at 275 nm (determined according to ASTM Method E2193-16) of 35% or less. In one aspect, the purified biomass-based composition has a UV Transmittance at 275 nm (determined according to ASTM Method E2193-16) of 32% or less. In one aspect, the purified biomass-based composition has a UV Transmittance at 275 nm (determined according to ASTM Method E2193-16) of 30% or less. In one aspect, the purified biomass-based composition has a UV Transmittance at 275 nm (determined according to ASTM Method E2193-16) of 28% or less. In one aspect, the purified biomass-based composition has a UV Transmittance at 275 nm of 25% or less. In one aspect, the purified biomass-based composition has a UV transmittance at 275 nm (determined according to ASTM method E2193-16) of 22% or less. In one aspect, the purified biomass-based composition has a UV transmittance at 275 nm (determined according to ASTM method E2193-16) of 20% or less.

[0128] In one aspect, the biomass-based composition to be contacted with at least one reactant has a UV Transmittance at 275 nm (determined according to ASTM Method 219) of 0% or greater. In one aspect, the purified biomass-based composition has a UV Transmittance at 275 nm (determined according to ASTM Method E2193-16) of 1% or greater. In one aspect, the purified biomass-based composition has a UV Transmittance at 275 nm (determined according to ASTM Method E2193-16) of 2% or greater. In one aspect, the purified biomass-based composition has a UV Transmittance at 275 nm (determined according to ASTM Method E2193-16) of 5% or greater. In one aspect, the purified biomass-based composition has a UV Transmittance at 275 nm (determined according to ASTM Method E2193-16) of 8% or greater. In one aspect, the purified biomass-based composition has a UV transmittance at 275 nm (determined according to ASTM method E2193-16) of 10% or greater. In one aspect, the purified biomass-based composition has a UV transmittance at 275 nm (determined according to ASTM method E2193-16) of 12% or greater. In one aspect, the purified biomass-based composition has a UV transmittance at 275 nm (determined according to ASTM method E2193-16) of 15% or greater.

[0129] In one aspect, the purified biomass-based composition has a UV transmittance at 275 nm of between 0% and 40% (as determined according to ASTM method E2193-16). In one aspect, the purified biomass-based composition has a UV transmittance at 275 nm of from 1% to 38% (as determined according to ASTM method E2193-16). In one aspect, the purified biomass-based composition has a UV transmittance at 275 nm of from 2% to 38% (as determined according to ASTM method E2193-16). In one aspect, the purified biomass-based composition has a UV transmittance at 275 nm of from 5% to 35% (as determined according to ASTM method E2193-16). In one aspect, the purified biomass-based composition has a UV transmittance at 275 nm of from 10% to 35% (as determined according to ASTM method E2193-16). In one aspect, the purified biomass-based composition has a UV transmittance at 275 nm (determined according to ASTM method E2193-16) of 15% to 35%. In one aspect, the purified biomass-based composition has a UV transmittance at 275 nm (determined according to ASTM method E2193-16) of 20% to 35%.

[0130] In one embodiment according to the present invention, purified biomass-based compositions containing ethylene glycol that are believed to be suitable as reactants in the synthesis of PET have a post-heat APHA color of less than 20 mg / LPtCo. In one embodiment, purified biomass-based compositions containing ethylene glycol that are believed to be suitable as reactants in the synthesis of PET have a post-heat APHA color of less than 15 mg / LPtCo.

[0131] composition In another aspect of the invention, there is provided a purified biomass-based composition obtainable by the method of purifying a biomass-based composition according to an aspect of the invention.

[0132] According to another aspect of the present invention, there is provided a purified biomass-based composition obtainable by the method of purifying a biomass-based composition according to one of the above aspects of the present invention, characterized by a post-heat APHA color of less than 20 mg / LPtCo as determined according to ASTM D1209-05 and a UV transmittance of less than 40% at 275 nm as determined according to ASTM method E2193-16.

[0133] According to another aspect of the present invention, there is provided a purified biomass-based composition obtainable by the method of purifying a biomass-based composition according to one of the above aspects of the present invention, characterized by a post-heat APHA color of less than 15 mg / LPtCo (as determined according to ASTM D1209-05) and a UV transmittance at 275 nm of less than 40% (as determined by ASTM method E2193-16).

[0134] use In another aspect of the present invention, there is provided the use of a purified biomass-based composition obtained by the method of purifying a biomass-based composition according to an aspect of the present invention for producing a polyester.

[0135] The polyester may include polyethylene terephthalate.

[0136] Polyester Manufacturing In another aspect of the present invention, there is provided a method for producing a polyester, comprising contacting a purified biomass-based composition obtained by the method for purifying a biomass-based composition according to an aspect of the present invention with at least one reactant to produce the polyester.

[0137] In one aspect, contacting the purified biomass-based composition obtained by the method of purifying a biomass-based composition with at least one reactant comprises (I) reacting ethylene glycol with the at least one reactant to provide a monomer; and (II) polymerizing the monomer to provide a polyester. However, for the avoidance of doubt, the polyester may be polymerized in any manner suitable to obtain the desired polyester properties.

[0138] In one aspect, the at least one reactant comprises one or more of a diacid, a diester, and an acid anhydride.

[0139] In one aspect, the diacid is a terephthalic acid-based compound, an isophthalic acid-based compound, or a mixture thereof.

[0140] In one aspect, the diacid is a renewable resource, for example, the diacid can be produced via a synthetic route from a biomass-derived feedstock, such as furfural.

[0141] In one aspect, the terephthalic acid-based compound is selected from the group consisting of terephthalic acid, dimethyl terephthalate, or a combination thereof.

[0142] In one aspect, the isophthalic acid-based compound is selected from isophthalic acid, dimethyl isophthalate, or a combination thereof.

[0143] In one aspect, the diacid is selected from naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, succinic acid, glutaric acid, furandicarboxylic acid, adipic acid, azelaic acid, sebacic acid, and combinations thereof.

[0144] In one aspect, the monomer comprises a bis(2-hydroxyethyl) terephthalate monomer.

[0145] The polyester may comprise polyethylene terephthalate. In one aspect, contacting the purified biomass-based composition obtained by the method of purifying a biomass-based composition with at least one reactant comprises (I) reacting ethylene glycol with one or more of a diacid and a diester to provide a bis(2-hydroxyethyl) terephthalate monomer; and (II) polymerizing the monomer to provide a polyester comprising polyethylene terephthalate. In one aspect, step (I) is performed at a temperature of 230°C to 260°C. In one aspect, step (II) is performed at a temperature of 270°C to 300°C. In one aspect, step (II) is performed in the presence of a catalyst. In one aspect, the catalyst is a heterogeneous catalyst. In one aspect, the catalyst is an antimony-containing catalyst, a platinum-containing catalyst, a titanium-containing catalyst, an aluminum-containing catalyst, or a germanium-containing catalyst. In one aspect, the catalyst is antimony(III) oxide. In one aspect, step (II) of the process for producing a polyester is carried out in the presence of a phosphorus-based compound added as a stabilizer.

[0146] The polyester is considered to be polyethylene terephthalate (PET) when the ethylene glycol moiety of the diols in the polyester is greater than 90% and the terephthalic acid moiety of the diacids in the polyester is greater than 90%.

[0147] In one aspect, step (I) of reacting ethylene glycol with at least one reactant to provide a monomer may be carried out in the presence of a small amount of another diol, wherein a small amount is preferably less than 40 mole percent of the total molar amount of diols.

[0148] In one aspect, the other diol is selected from the group consisting of diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,4-pentanediol, 3-methyl-2,4-pentanediol, trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3propanediol, 1,3-hexanediol, 1,4-di(hydroxyethoxy)benzene, 2,2-bis(4-hydroxycyclohexyl)propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis(3hydroxyethoxyphenyl)propane, 2,2-bis(4-hydroxypropoxyphenyl)propane, and cyclohexanedimethanol, or mixtures thereof.

[0149] Polymerization conditions can produce polymer grades with various molecular weights. Polymers with different molecular weights are conventionally described by their intrinsic viscosity (IV) values, as measured by ASTM D792.

[0150] In one aspect, a solid state polymerization (SSP) reaction is further carried out on the polyester at a temperature of 180 to 230°C under an inert or low pressure atmosphere for a period of time to obtain a desired IV. In one aspect, the IV of the polyester after SSP is at least 0.65 dL / g. In one aspect, the IV of the polyester after SSP is at least 0.75 dL / g. In one aspect, the IV of the polyester after SSP is at least 0.85 dL / g. In one aspect, the IV of the polyester after SSP is at least 1.0 dL / g.

[0151] polyester According to another aspect of the present invention, there is provided a polyester obtained by the polyester production method according to one aspect of the present invention.

[0152] In one aspect, the polyester compositions disclosed herein may contain additives in addition to the polyester, which may include, but are not limited to, colorants, ultraviolet (UV) stabilizers, antioxidants, fillers, gas barrier additives, plasticizers, nucleating agents, heat stabilizers, chain extenders, and combinations thereof.

[0153] Additives can be incorporated into the polyester compositions described herein using known methods. For example, additives can be introduced before, during, or after the polymerization step. Additives can also be compounded with the polyester in a subsequent processing or conversion step.

[0154] In one aspect, polyesters according to one or more embodiments and articles thereof can be recycled using conventional recycling methods, such as mechanical and chemical recycling methods, under recycling operating conditions known to those of ordinary skill in the art. In one or more embodiments, packaging articles made using the polyesters disclosed herein are mechanically recycled in the form of chips or granules. Thus, the resulting chips and granules are typically recycled using conventional methods, such as mechanical and chemical recycling methods, under recycling operating conditions known to those of ordinary skill in the art. 14 The resulting chips or granules retain a significant biogenic carbon content, as measurable by Method C and ASTM D6866. The resulting chips or granules could be reprocessed into the same or different polyester-based packaging articles using the processing and manufacturing techniques described herein. Reprocessing can occur simultaneously, but not exclusively, with chips and granules obtained by recycling PET from conventional petrochemical sources (from fossil fuels or non-biobased sources) or conventional polyesters.

[0155] In one aspect, the polyester has an L (determined according to ASTM method D6290-19) of 65 or greater. * In one aspect, the polyester is characterized by a CIELAB color space parameter value of 70 or greater (as determined in accordance with ASTM method D6290-19). *In one aspect, the polyester is characterized by a CIELAB color space parameter value of 75 or greater (as determined in accordance with ASTM method D6290-19). * In one aspect, the polyester is characterized by a CIELAB color space parameter value of 80 or greater (as determined in accordance with ASTM method D6290-19). * In one aspect, the polyester is characterized by a CIELAB color space parameter value of 85 or greater (as determined in accordance with ASTM method D6290-19). * In one aspect, the polyester is characterized by a CIELAB color space parameter value of 90 or greater (as determined in accordance with ASTM method D6290-19). * Characterized by CIELAB color space parameter values.

[0156] Here, the CIELAB color space parameter values ​​are determined in accordance with ASTM D6290-19 at a temperature of 20° C. to 25° C. (room temperature) and atmospheric pressure.

[0157] In one aspect, the polyester has an a of -4 to 4 (as determined according to ASTM method D6290-19). * In one aspect, the polyester is characterized by a CIELAB color space parameter value of -3 to 3 (as determined in accordance with ASTM method D6290-19). * In one aspect, the polyester is characterized by a CIELAB color space parameter value of -2 to 2 (as determined in accordance with ASTM method D6290-19). * Characterized by CIELAB color space parameter values.

[0158] In one aspect, the polyester has a b of -4 to 4 (as determined in accordance with ASTM method D6290-19). * In one aspect, the polyester is characterized by a CIELAB color space parameter value of -3 to 3 (as determined in accordance with ASTM method D6290-19). *In one aspect, the polyester is characterized by a CIELAB color space parameter value of -2 to 2 (as determined in accordance with ASTM method D6290-19). * Characterized by CIELAB color space parameter values.

[0159] The polyester may include polyethylene terephthalate.

[0160] Packaging articles or preforms According to another aspect of the present invention, there is provided a packaging article or preform formed from a polyester according to one of the aspects of the present invention.

[0161] Polyesters according to the present disclosure can be formulated for a range of polymeric articles and products, including, but not limited to, containers, flasks, bottles, vessels, packaging, cups, carpets, clothing, fabrics, string, rope, fiberfills, building materials, furniture, medical applications, films, sheets, laminations, protective packaging, electrical encapsulation, solenoids, smart meters, photovoltaic components, solar junction boxes, automotive parts, wiper arms and gear housings, headlamp retainers, engine covers, connector housings, industrial fibers, 3D printing filaments, transformable articles, and the like.

[0162] As previously mentioned, one application of polyester in one or more embodiments is a film. In particular, polyester film applications can be uniaxially oriented films, biaxially oriented films, multilayer films with other polymeric materials, blown films, and articles, or extrusion coatings. Blow-molded articles can be extrusion blow-molded, stretch blow-molded, or injection blow-molded articles.

[0163] In one or more embodiments, the polyesters can be used to produce polyester fibers from melt spinning and / or drawing, which may include, but are not limited to, drawn textured yarns, partially oriented yarns, polyester staple fibers, fully drawn yarns, spun-drawn yarns, and polyester mesh.

[0164] Manufacturing methods may include, but are not limited to, injection molding, stretch blow molding, lamination, extrusion, thermoforming, melt spinning, and 3D printing.

[0165] In one aspect, the packaging article is a packaging container. In one aspect, the polyester packaging container can be used to package, but is not limited to, food, cosmetics, soft drinks, water, alcoholic beverages, cosmetics, medicines, and edible oils.

[0166] In one aspect, the packaging article is a bottle.

[0167] The polyester may include polyethylene terephthalate.

[0168] Total aldehyde concentration The total aldehyde concentration can be determined by any suitable technique known to those skilled in the art. For example, in one aspect, the total aldehyde concentration is determined using ASTM method E2313-20. The aldehyde can be present as both an acetal and a free aldehyde.

[0169] Ethylene glycol concentration The concentration of ethylene glycol may be determined by any suitable technique known to those of skill in the art. In one aspect, the concentration of ethylene glycol is determined using gas chromatography (GC) with flame ionization detection (FID), also referred to herein as "GC-FID."

[0170] General perspective According to one aspect of the present invention, there is provided a method for purifying a biomass-based composition comprising ethylene glycol, the method comprising: (a) providing a biomass-based composition comprising water in an amount of at least 0.1 wt. %, based on the weight of the biomass-based composition; and (b) contacting the biomass-based composition with a solid acid catalyst and / or contacting the biomass-based composition with an aldehyde-removing resin to provide a purified biomass-based composition. Features of the method for purifying a biomass-based composition according to this general aspect can include any of the features of the method for purifying a biomass-based composition according to any other aspect.

[0171] Any aspect of the present disclosure may be defined relative to any other aspect of the present disclosure. For example, one aspect of the present disclosure may include any of the features of any other aspect of the present disclosure. For example, a feature of one aspect of the present disclosure may be as defined relative to a feature of any other aspect of the present disclosure. [Example]

[0172] Example 1: GC analysis method In all cases, GC analysis was performed on an Agilent 7890A GC equipped with an FID and a PolyARC reactor (PolyARC was obtained from Activated Research Company, 7561 Corporate Avenue, Eden Prairie, MN 55344, USA). The PolyARC reactor converted all analytes to methane before quantification. Helium was used as the carrier and FID makeup gas. Air and H2 were supplied to the PolyARC electronic flow control module and to the FID. Samples were injected without pretreatment. The GC column effluent was sent directly to the inlet of the PolyARC reactor. The reactor effluent was directly connected to the FID. GC conditions: front inlet split: 15:1; inlet temperature: 230 °C; column: DB-624 (60 m × 0.32 mm × 1.8 μm); carrier gas (He): 2 ml / min; injection volume: 0.5 μL. FID conditions: Temperature: 300°C; H2: 1.5 ml / min; Air: 350 ml / min; Make-up (He): 28 ml / min. PolyARC reactor conditions: Temperature: 450°C; H2: 35 ml / min; Air: 2.5 ml / min. The oven starting temperature was 100°C. After injection, the temperature was increased to 125°C at 1.5°C / min and then held for 5 minutes. The temperature was then increased to 260°C at 20°C / min and then held for 10 minutes. Chromatograms were obtained and analyzed as needed. Quantitation was based on peak area unless otherwise noted.

[0173] Example 2 - Biomass-based composition A mixture of C1-C3 oxygenates was obtained by pyrolytic fragmentation of an aqueous sugar (glucose) solution as described in Example 1 of WO 2017 / 216311 (Patent Document 13). A hydrogenated product composition was obtained from the mixture of C1-C3 oxygenates as described in Example 4 of US Pat. No. 9,926,247 (Patent Document 12). The hydrogenated product composition thus obtained was condensed to obtain an aqueous solution of ethylene glycol (a biomass-based composition containing ethylene glycol).

[0174] Example 3 - Distillation An aqueous solution of ethylene glycol provided by Example 2 was distilled to a concentration of 99.7 wt % ethylene glycol based on the weight of the aqueous solution as determined by GC-FID analysis (Example 1).

[0175] The distillation unit used in the experiment was a continuous distillation unit. It included a packed column (50 mm diameter; 4 meters of Sulzer type DX structured packing) with a feed point in the center of the column. The distillation unit reboiler was a wiped-film heat exchanger. The residue was collected as a liquid outlet stream from the wiped-film heat exchanger. At the top of the column, a water-cooled condenser completely condensed the vapors from the column. The condensate was split into two portions according to the reflux ratio, and the reflux fraction was returned to the top of the column as a liquid, while the remainder was collected as a distillate. The liquid side draw was collected through a liquid side draw outlet located 1 meter below the top of the column.

[0176] Distillative purification was carried out as three successive vacuum distillations in series.

[0177] In the first distillation step, an aqueous solution of ethylene glycol was distilled at a pressure of 200 mBar and a reflux ratio of 4. Water and by-products more volatile than propylene glycol were removed as fractions. The residue was enriched in ethylene glycol.

[0178] In the second distillation step, the residue from the first distillation was distilled at a pressure of 200 mBar and a reflux ratio of 20. Propylene glycol and 1,2-butanediol were completely removed as distillate. The residue was enriched in ethylene glycol, which was the distillate product of this distillation.

[0179] In the third distillation step, the residue from the second distillation was distilled at a pressure of 200 mBar and a reflux ratio of 24. The product stream of this distillation, i.e., the fraction containing 99.7% by weight of ethylene glycol, was collected via a liquid side draw. The product stream composition was "Distillation Product." The mass ratio of distillate to feed was 0.13, and the mass ratio of liquid side draw to feed was 0.6.

[0180] Example 4a - Acid Catalyst and Resin Treatment Purification with Dilution (Method of the Invention) The distillation product of Example 3 was subjected to a treatment process, which (1) diluting the distillation product to form a dilute composition, the dilute composition having a water content of approximately 20% by weight, based on the weight of the dilute composition; (2) passing the diluted composition through a column containing a mixed bed of a solid acid catalyst resin (Amberlyst 15) and an aldehyde removal resin (Purolite A110) at a temperature of 50°C; and then (3) removing water from the diluted composition by evaporation on a rotary evaporator; Water was evaporated at a pressure of 70 mBar by immersing the rotating still pot in a heated oil bath at a temperature of 150° C. Distillation was stopped when the water content of the glycol product fraction in the still pot reached 2% by weight.

[0181] This product is referred to as "acid catalyzed and resin treated" product 4a.

[0182] Example 4b - Acid Catalyst and Resin Treatment Purification Without Dilution (Method of the Invention) The distillation product of Example 3 contained approximately 0.3% water by weight and was subjected to a treatment process comprising: (i) passing the distillation product through a column containing a mixed bed of a solid acid catalyst resin (Amberlyst 15) and an aldehyde removal resin (Purolite A110) at a temperature of 50°C; This included:

[0183] This product is referred to as "acid catalyzed and resin treated" product 4b.

[0184] Example 4c - Resin Treatment Purification with Dilution (Comparative Example) The distillation product of Example 3 was subjected to a treatment process, which (1) diluting the distillation product to form a dilute composition, the dilute composition having a water content of approximately 20% by weight, based on the weight of the dilute composition; (2) The diluted composition is passed through a column containing an aldehyde removal resin (Purolite A110) at a temperature of 50°C, and then (3) removing water from the diluted composition by evaporation on a rotary evaporator; Water was evaporated at a pressure of 70 mBar by immersing the rotating still pot in a heated oil bath at a temperature of 150° C. Distillation was stopped when the water content of the glycol product fraction in the still pot reached 2% by weight.

[0185] This product is referred to as "resin treated" product 4c.

[0186] Example 5 - Analysis of "Distillation Product" and "Acid Catalyst and Resin Treatment Product" The distillate product prepared in Example 3 and the catalyst and resin treated products prepared in Examples 4a and 4b were evaluated for parameters related to polyesters (e.g., PET production), including measurement of diethylene glycol concentration (wt%), APHA color (mg / LPtCo), and APHA color (mg / LPtCo) after heating to 200°C for 4 hours.

[0187] The quantification of ethylene glycol is carried out according to Example 1.

[0188] A standard method for determining diethylene glycol concentration is described in ASTM E2409-20a.

[0189] The standard method for determining APHA color is described in ASTM Method D1209-05. APHA color measurements (measurements according to ASTM Method D1209-05) were performed using a mechanical analysis method integrated into a Lovibond PFX-I series spectrocolorimeter. This method is referred to as Pt-Co D1209. APHA color was measured using a 100 mm glass cuvette to hold the sample. Measurements were performed at temperatures between 20°C and 25°C (room temperature) and atmospheric pressure. A standard curve covering the relevant color gamut was prepared by volumetric dilution of commercially available Pt-Co standard solutions (e.g., available from Sigma-Aldrich (Pt-Co / Hazen / APHA Color Reference Standard, Sigma No. 134190 (ASTM Color 100)) with deionized water. The APHA number for a given sample was determined from the standard curve based on the Pt-Co number measured for that sample. That is, a given sample was placed in the colorimeter and tested, and the output Pt-Co number from the colorimeter was used against the standard curve to determine the APHA color number for the given sample.

[0190] Heat treatment of the ethylene glycol samples prior to measurement was accomplished by placing each sample in a glass container and flushing the sample with nitrogen for 15 minutes to remove air. The glass container was sealed and essentially oxygen-free. Each sample in the glass container was heated to 200°C for 4 hours. After cooling, the color of the heat-treated samples was determined using the APHA color method outlined above.

[0191] Table 1 shows the results of the measurements.

[0192] [Table 1]

[0193] As shown in Table 1, products 4a, 4b and 4c have low APHA color, less than 5 mg / L PtCo. However, after heating, APHA color is acceptable only for products 4a and 4b (obtained according to the present invention), being less than 20 mg / L PtCo.

[0194] Example 6 - Polyester Production In each experiment, the distillation product prepared in Example 3 and the catalyst and resin-treated product prepared in Example 4 were used to produce polyester. Each experiment was conducted as a standard batch process. Each experiment involved contacting each product with terephthalic acid to produce a polyester containing polyethylene terephthalate (PET). Isophthalic acid (IPA) was added to each product as a copolymerizable compound at a ratio of 2% based on the total diacid compound. This was done in two steps: (1) contacting terephthalic acid and each product to effect an esterification reaction, during which bis(2-hydroxyethyl) terephthalate was formed, and removing water and volatile by-products; and (2) polymerizing (polycondensing) the bis(2-hydroxyethyl) terephthalate in the presence of an antimony catalyst while continuously removing the released ethylene glycol.

[0195] Step (1) was carried out at atmospheric pressure at temperatures ranging from 150° C. to 260° C. Step (2) was carried out under vacuum (0.01 to 2 mbar) at temperatures ranging from 280° C. to 300° C.

[0196] Step (2) was carried out until the desired level of polymerization was achieved, as determined by measuring intrinsic viscosity, a standard method for determining said intrinsic viscosity being set forth in ASTM Method D4603-18.

[0197] The approximate extent of polycondensation can also be determined indirectly by measuring the torque on the agitator shaft of the mixer in the polymerization reactor. This requires the construction of a standard curve of the relationship between torque and intrinsic viscosity. This method was used to control the duration of polycondensation. Once the desired torque on the agitator shaft was reached, the polymerized material melt was removed from the polymerization vessel and transferred to an ice-water cooling bath to stop the reaction. The intrinsic viscosity values ​​listed in Table 4 are the actual values ​​measured for the polyester product obtained from polycondensation. After cooling, the polymerized material was divided into pellets.

[0198] [Table 2]

[0199] As described here, L * , a * , and b * The parameter values ​​are CIELAB color components. * The value represents the perceived lightness, with 0 being black and 100 being white. * and b * The values ​​represent the four colors of human vision: red, green, blue, and yellow. * The value is an index of yellow. Yellow is b * The closer to 0, the weaker it becomes.

[0200] As shown in Table 2, a * was not substantially affected by the acid catalysis and resin treatment step. In contrast, b * was fairly close to zero. The color of the polyester pellets produced from the distillation product was not acceptable for the production of bottle-grade PET, i.e., PET for the production of water and soft drink bottles. The color of the polyester pellets produced from the acid catalyst and resin-treated product was acceptable for bottle-grade PET production.

[0201] The various embodiments described herein are presented solely for the purpose of aiding in the understanding and teaching of the claimed features. These embodiments are provided only as a representative sample of embodiments and are not intended to be complete and / or exclusive. The advantages, embodiments, examples, functions, features, structures, and / or other aspects described herein should not be construed as limitations on the scope of the invention as defined by the claims or limitations on the equivalents of the claims, and it should be understood that other embodiments may be utilized and changes may be made without departing from the scope of the claimed invention. Various embodiments of the present invention may, where appropriate, comprise, consist of, or consist essentially of any suitable combination of the disclosed elements, components, features, parts, steps, means, etc., other than those specifically described herein. In addition, the present disclosure may include other inventions not currently claimed but that may be claimed in the future.

Claims

1. 1. A method for purifying a biomass-based composition comprising ethylene glycol, comprising: (a) providing a biomass-based composition comprising water in an amount of at least 0.1 wt. % based on the weight of the biomass-based composition; and (b) contacting the biomass-based composition with a solid acid catalyst and contacting the biomass-based composition with an aldehyde-removing resin to provide a purified biomass-based composition; The method comprising:

2. The method of claim 1 , wherein the solid acid catalyst comprises a sulfonic acid functional group.

3. 3. The method of claim 1 or 2, wherein the solid acid catalyst comprises one or more of a resin and a zeolite.

4. 4. The method of claim 1, wherein the aldehyde scavenging resin comprises one or more of primary amine functional groups, secondary amine functional groups, tertiary amine functional groups, and quaternary ammonium functional groups, such as quaternary ammonium bisulfite functional groups.

5. 5. The method of any one of claims 1 to 4, wherein the purified biomass-based composition has a total aldehyde concentration of 50 ppm or less, such as 20 ppm or less, for example 18 ppm or less, such as 15 ppm or less, for example 10 ppm or less, based on the weight of the purified biomass-based composition.

6. 6. The method of any one of claims 1 to 5, wherein the biomass-based composition in step (a) has a total aldehyde concentration of at least 100 ppm, such as at least 200 ppm, for example at least 300 ppm, such as at least 500 ppm, for example at least 1000 ppm, based on the weight of the biomass-based composition.

7. The method of any one of claims 1 to 6, wherein the solid acid catalyst and the aldehyde-scavenging resin are provided in a common bed.

8. 8. The method of any one of claims 1 to 7, wherein the purified biomass-based composition is characterized by an APHA color number of less than or equal to 5 mg / LPtCo, as determined according to ASTM D1209-05.

9. 9. The method of any one of claims 1 to 8, wherein the purified biomass-based composition is characterized by a post-heat APHA color number of 20 mg / LPtCo or less, as determined according to ASTM D1209-05.

10. 10. The method of any one of claims 1 to 9, comprising, after contacting the biomass-based composition with the solid acid catalyst and contacting the biomass-based composition with the aldehyde-removing resin, subjecting the biomass-based composition to at least one distillation step and / or subjecting the biomass-based composition to at least one melt crystallization step.

11. 11. The method of any one of claims 1 to 10, comprising subjecting the biomass-based composition to at least one distillation step prior to contacting the biomass-based composition with the solid acid catalyst and contacting the biomass-based composition with the aldehyde-removing resin.

12. 12. The method of any one of claims 1 to 11, wherein the purified biomass-based composition comprises ethylene glycol in an amount of at least 98% by weight, such as at least 99% by weight, for example at least 99.25% by weight, such as at least 99.5% by weight, for example at least 99.75% by weight, for example at least 99.9% by weight, based on the weight of the purified biomass-based composition.

13. The method according to any one of claims 1 to 12, wherein the biomass-based composition is obtained by pyrolytic fragmentation of sugars followed by hydrogenation.

14. 14. A purified biomass-based composition obtainable by the method of any one of claims 1 to 13, characterized by a post-heat APHA color of less than 20 mg / LPtCo as determined according to ASTM D1209-05 and a UV transmittance of less than 40% at 275 nm as determined by ASTM method E2193-16.

15. The following CIELAB color space values, determined in accordance with ASTM D6290-19: L ≥ 65 ＊ ; a from -4 to 4 ＊ and b from -4 to 4 ＊ 14. Use of a purified biomass-based composition obtained by the method for purifying a biomass-based composition according to any one of claims 1 to 13 for producing a polyester characterized by one or more of the following:

16. 14. A method for producing polyester, comprising contacting a purified biomass-based composition obtained by the method of any one of claims 1 to 13 with at least one reactant to produce a polyester having the following CIELAB color space value, determined according to ASTM D6290-19: L 65 or greater. ＊ ; a from -4 to 4 ＊ and b from -4 to 4 ＊ and producing a polymer characterized by one or more of:

17. The following CIELAB color space values, determined in accordance with ASTM D6290-19: L ≥ 65 ＊ ; a from -4 to 4 ＊ and b from -4 to 4 ＊ 16. A polyester obtained by the process for producing a polyester according to claim 15, characterized by one or more of the following:

18. A packaging article or preform formed from the polyester of claim 17.

19. The method, use, polyester, packaging article or preform according to any one of claims 15 to 18, wherein the polyester comprises polyethylene terephthalate.

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