Use of a silica-zirconia catalyst in a process for reducing glycidol, glycidyl esters, or both glycidol and glycidyl esters

Abstract

To provide an effective method for reducing exothermic pollutants such as glycidyl esters from a triglyceride-containing composition such as an edible oil, and to provide a catalyst to be used.SOLUTION: A method for reducing the amount of (i) glycidol, (ii) glycidyl esters, or (iii) both glycidol and glycidyl esters in a composition comprising triglycerides, the method comprising: A method of contacting a composition comprising triglycerides with an effective amount of a particulate silica-zirconia catalyst to reduce the amount of said (i), (ii) or (iii) in the composition, wherein the silica-zirconia catalyst comprises porous silica particles impregnated with zirconia, wherein the amount of said (i), (ii) or (iii) is reduced without affecting other components of the composition comprising triglycerides.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to the use of a silica-zirconia catalyst in a process for reducing glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition. The present invention also relates to a silica-zirconia catalyst and a method for making the silica-zirconia catalyst. [Background technology]

[0002] Glycidyl esters are known carcinogens and mutagens found in processed edible oils. These pyrogenic contaminants are formed at temperatures as low as 200°C. However, much higher temperatures are required to remove various volatile components from the oil during the deodorization process. Once crude oil has been refined, bleached, and deodorized (RBD), additional oil treatment is required to reduce glycidyl ester concentrations to acceptable regulatory limits. These reduction methods include, but are not limited to, a wide variety of process combinations, such as contacting the oil with enzymes, shear-mixing the oil with acid, re-bleaching the oil, and / or re-running the deodorization at lower temperatures but for extended periods of time. These known methods are not only inefficient and expensive to operate, but also further degrade oil quality and reduce market value.

[0003] There remains a need in the art for effective methods for reducing pyrogenic contaminants, such as glycidyl esters, from triglyceride-containing compositions, such as edible oils. Summary of the Invention

[0004] The present invention addresses the aforementioned need in the art by discovering a method for reducing glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition, which provides an effective, environmentally friendly method without the drawbacks of known methods. The method of the present invention advantageously (1) requires much lower processing temperatures, (2) requires shorter processing times, (3) does not increase the free fatty acid content of the edible oil, and (4) does not result in any significant oxidation, as measured by p-anisidine and / or peroxide values, of the treated triglyceride-containing composition (e.g., the treated edible oil).

[0005] Thus, the present invention provides a method for reducing the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition. In some embodiments, the method for reducing the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition comprises contacting the triglyceride-containing composition with an effective amount of a silica-zirconia catalyst to reduce the amount of (i) glycidol, (ii) glycidyl esters, or (iii) both glycidol and glycidyl esters in the composition, wherein the amount of (i) glycidol, (ii) glycidyl esters, or (iii) both glycidol and glycidyl esters is reduced without affecting other components of the composition, including the triglyceride (i.e., without increasing the free fatty acid content of the triglyceride-containing composition and without significant oxidation of the triglyceride-containing composition, as measured by the p-anisidine and / or peroxide values ​​of the treated triglyceride-containing composition).

[0006] In some embodiments, the present methods advantageously involve relatively short reaction times (e.g., 60 minutes or less) and relatively low reaction temperatures (e.g., typically from room temperature up to about 100°C). The method may further include heating the triglyceride-containing composition and the silica-zirconia particles using the disclosed silica-zirconia catalyst to more effectively reduce glycidol, glycidyl esters, or both glycidol and glycidyl esters. Unexpectedly, it has been found that the introduction of an effective amount of the disclosed silica-zirconia catalyst particles results in excellent catalytic activity in reducing glycidol, glycidyl esters, or both glycidol and glycidyl esters present in a triglyceride-containing composition (e.g., edible oil).

[0007] In some desirable embodiments, the methods for reducing glycidol, glycidyl esters, or both glycidol and glycidyl esters in triglyceride-containing edible oils desirably provide edible oils having low levels of glycidyl esters, i.e., less than 0.2 ppm, with little or no change in (i) the initial free fatty acid content of the edible oil (as measured by its oleic acid content), or (ii) the initial lipid oxidation level of the edible oil as measured by (a) the p-anisidine value of the edible oil as measured by American Oil Chemists' Society (AOCS) Official Method Cd 18-90, (b) the peroxide value of the edible oil as measured by AOCS Official Method Cd 8-53, or (c) both (a) and (b).

[0008] The present invention further relates to silica-zirconia catalysts suitable for use in the disclosed methods for reducing glycidol, glycidyl esters, or both glycidol and glycidyl esters in triglyceride-containing compositions. The silica-zirconia catalyst comprises porous silica particles impregnated with zirconia. In some embodiments, the zirconia is impregnated on at least a portion of the surface of the porous silica particles. In some embodiments, the zirconia is impregnated within at least a portion of the pores of the porous silica particles. In some embodiments, the zirconia is impregnated such that it is substantially disposed within the pores of the porous silica particles. Typically, the silica-zirconia particulate catalyst comprises at least 0.01 weight percent (wt%) zirconia, based on the total weight of the silica-zirconia particles. More typically, the silica-zirconia particulate catalyst comprises from about 1.0 wt% to about 50.0 wt% zirconia, based on the total weight of the catalyst.

[0009] The present invention further relates to a method for making the silica-zirconia microparticle catalyst disclosed herein. In some embodiments, the method for making the silica-zirconia catalyst includes impregnating porous silica particles with zirconium acetate in aqueous acetic acid, drying the impregnated porous silica particles for a time and at a temperature sufficient to dry the impregnated porous silica particles, i.e., at about 80°C to about 150°C for about 1 hour to about 4 hours, and calcining the dried zirconia-impregnated porous silica particles at a temperature in the range of about 400°C to about 1000°C for about 2 hours to about 8 hours.

[0010] The present invention further relates to a composition comprising (i) a triglyceride-containing composition and (ii) a silica-zirconia microparticle catalyst disclosed herein. In some embodiments, the composition comprises (i) an oil and (ii) a silica-zirconia catalyst disclosed herein. The composition may further comprise glycidol, glycidyl esters, or both glycidol and glycidyl esters (i.e., the composition before being subjected to the methods disclosed herein to reduce the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters), or may have minimal or negligible amounts of glycidol, glycidyl esters, or both glycidol and glycidyl esters (i.e., the composition after being subjected to the methods disclosed herein to reduce the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters). In some desirable embodiments, the triglyceride-containing composition is an oil, particularly an edible oil such as soybean oil or palm oil.

[0011] These and other features and advantages of the present invention will become apparent after a review of the following detailed description of the disclosed embodiments and the appended claims. DETAILED DESCRIPTION OF THE INVENTION

[0012] In order to promote an understanding of the principles of the invention, a description of specific embodiments of the invention follows, and specific language is used to describe the specific embodiments. It is understood, however, that no limitation of the scope of the invention is intended by the use of specific language. Alterations, further modifications, and further applications of the principles of the invention as contemplated are generally contemplated as would normally occur to one skilled in the art to which the invention pertains.

[0013] It should be noted that, as used in this specification and the appended claims, the singular forms "a," "and," and "the" include plural referents unless the context clearly dictates otherwise. So, for example, a reference to "an oxide" includes a plurality of such oxides, a reference to "the oxide" includes a reference to one or more oxides and equivalents thereof known to those skilled in the art, and so forth.

[0014] For example, when used in describing embodiments of the present disclosure, "about" to modify amounts, concentrations, volumes, process temperatures, process times, recovery or yield, flow rates, and similar values ​​and ranges of ingredients in coated particles and / or compositions refers to variations in numerical quantities that may occur, for example, through typical measuring and handling procedures, through inadvertent errors in these procedures, through differences in ingredients used to carry out these methods, and through considerations of approximation. The term "about" also encompasses amounts that vary with aging of formulations having particular initial concentrations or mixtures, as well as amounts that vary with mixing or processing of formulations having particular initial concentrations or mixtures. The appended claims, whether modified by the term "about," include equivalents.

[0015] As used herein, the term "triglyceride-containing composition" (also referred to herein as "composition comprising triglycerides") is preferably any liquid containing one or more triglycerides, and optionally one or more additional composition components. In some embodiments of the present invention, glycidol, glycidyl esters, or both glycidol and glycidyl esters are present in an edible oil, such as soybean oil.

[0016] As used herein, the term "crystalline" refers to a solid material whose constituent atoms, molecules, or ions are arranged in an orderly pattern extending in all three directions, as can be measured by X-ray diffraction or differential scanning calorimetry. As used herein, the term "amorphous" refers to a solid material whose constituent atoms, molecules, or ions are arranged in a random, unordered pattern extending in all three directions, as can be measured by X-ray diffraction or differential scanning calorimetry.

[0017] As used herein, the term "BET particle surface area" is defined to mean the particle surface area as measured by the Brunauer Emmet Teller (BET) nitrogen adsorption method.

[0018] As used herein, the phrase "total pore volume" refers to the average pore volume of a plurality of particles (e.g., silica-zirconia particles disclosed herein) as determined using Barrett-Joyner Halenda (BJH) nitrogen porosimetry as described in DIN 66134.

[0019] As used herein, the phrase "particle size" refers to the amount of water or acetone or ethanol in the particles. This refers to the average particle size (D50, the volume distribution where 50 volume percent of the particles are smaller than this number and 50 volume percent are larger than this number) when slurried in an organic solvent such as alcohol, as measured by dynamic light scattering. How to use silica-zirconia catalyst

[0020] The present invention relates to a method for reducing the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition. The method may, for example, include contacting the triglyceride-containing composition with an effective amount of a silica-zirconia catalyst for a time and temperature sufficient to reduce the amount of glycidol, glycidyl esters, or both. The method may further include mixing the triglyceride-containing composition and the silica-zirconia catalyst with an inert gas under vacuum or, optionally, with heating. The method typically reduces the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters by at least 50 weight percent (wt%) in a given triglyceride-containing composition while utilizing relatively low reaction times and temperatures. For example, the reaction time and temperature may be as little as 60 minutes, with a reaction temperature below about 100°C.

[0021] In some embodiments, the disclosed methods for reducing the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition include contacting the triglyceride-containing composition with an effective amount of a catalyst at room temperature, although other temperatures can be used (e.g., preferably from room temperature, about 20-25°C, up to about 90.0°C).

[0022] Typically, the heating step, when used in the disclosed methods, involves heating the triglyceride-containing composition and silica-zirconia catalyst to a temperature of at least about 40.0° C. In some embodiments, the heating step, when used in the disclosed methods, involves heating the triglyceride-containing composition and silica-zirconia catalyst to a temperature of about 90.0° C. Typically, the heating step involves heating the triglyceride-containing composition and silica-zirconia catalyst to a temperature of about 20.0° C. to about 90.0° C. (or any temperature range between about 20.0° C. and about 90.0° C. in 0.1° C. increments, e.g., about 20.1° C. to about 89.9° C.).

[0023] Regardless of the maximum temperature reached during any heating step (e.g., about 90.0°C), the heating step, if used, desirably comprises heating the triglyceride-containing composition and silica-zirconia catalyst to a temperature of about 90.0°C and maintaining the temperature for at least 10.0 minutes. In some embodiments, the heating step comprises heating the triglyceride-containing composition and silica-zirconia catalyst to a maximum temperature (e.g., about 90.0°C) and maintaining the maximum temperature for about 30.0 minutes. It should be understood that in the disclosed methods, the maximum temperature (e.g., about 90.0°C) of any heating step can be maintained at the maximum temperature (e.g., about 90.0°C) for any desired time, for example, from about 5.0 minutes to about 60.0 minutes (or in 0.1 minute increments within any range of minutes between about 5.0 minutes and about 60.0 minutes, e.g., from about 5.1 minutes to about 59.9 minutes).

[0024] Desirably, the heating step, when used in the disclosed method, comprises heating the triglyceride-containing composition and silica-zirconia catalyst (i) under a flow of inert gas (i.e., under an inert gas blanket), (ii) under a vacuum, or (iii) both (i) under a flow of inert gas and (ii) under a vacuum. Typically, the inert gas, when used, comprises nitrogen, argon, carbon dioxide, or any combination thereof.

[0025] Glycidol, glycidyl esters, or glycidol in triglyceride-containing compositions The disclosed method for reducing the amount of both glycidyl esters and glycidyl esters comprises a triglyceride-containing composition comprising (i) a triglyceride-based oil, (ii) an organic solvent capable of dissolving triglycerides, or (iii) both a triglyceride-based oil and an organic solvent capable of dissolving triglycerides. Suitable oils include, but are not limited to, soybean oil, palm oil, corn oil, canola oil, rapeseed oil, fish oil, algae oil, sunflower oil, olive oil, vegetable oil, plant-derived oil, animal-derived oil, microbial-derived oil, or any combination thereof. Suitable organic solvents include, but are not limited to, heptane, hexane, toluene, diethyl ether, alcohol, or any combination thereof.

[0026] In some desired embodiments, the disclosed methods for reducing glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition are particularly useful when the triglyceride-containing composition includes an edible oil, such as soybean oil or palm oil.

[0027] Typically, the disclosed methods for reducing glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition include using an effective amount of silica-zirconia catalyst of at least about 0.01 wt.% silica-zirconia catalyst, based on the total weight of the silica-zirconia catalyst and the triglyceride-containing composition. In some embodiments, the amount of silica-zirconia catalyst used in the disclosed methods is from about 0.5 wt.% to about 10.0 wt.% silica-zirconia catalyst, based on the total weight of the silica-zirconia catalyst and the triglyceride-containing composition. In other embodiments, the amount of silica-zirconia catalyst used in the disclosed methods is from about 1.0 wt.% to about 3.0 wt.% silica-zirconia catalyst, based on the total weight of the silica-zirconia catalyst and the triglyceride-containing composition. However, it should be understood that any amount of silica-zirconia catalyst, for example, from about 0.5 wt. % to about 10.0 wt. % of the silica-zirconia catalyst (or any range of weight percent from about 0.5 wt. % to about 10.0 wt. % in 0.1 wt. % increments, e.g., from about 0.6 wt. % to about 9.9 wt. %), based on the total weight of the silica-zirconia catalyst and the triglyceride-containing composition, can be used in the disclosed methods for reducing the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition.

[0028] It has been unexpectedly found that the disclosed methods for reducing the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition can reduce the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in the triglyceride-containing composition to a level of less than about 10.0 parts per million (ppm) of glycidol, glycidyl esters, or both glycidol and glycidyl esters in the triglyceride-containing composition. In some embodiments, the disclosed methods can reduce the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in the triglyceride-containing composition to a level of less than about 5.0 ppm of glycidol, glycidyl esters, or both glycidol and glycidyl esters in the triglyceride-containing composition. In other embodiments, the disclosed methods can reduce the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition to a level of less than about 1.0 ppm of glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition. In other embodiments, the disclosed methods can reduce the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition to a level of less than about 0.5 ppm of glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition. In yet other embodiments, the disclosed methods can reduce the amount of glycidol, glycidyl esters, or glycidol and glycidyl esters in a triglyceride-containing composition. The amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters can be reduced to a level of less than about 0.2 ppm of glycidol, glycidyl esters, or both glycidol and glycidyl esters in the triglyceride-containing composition.

[0029] Unexpectedly, it has been found that the disclosed method for reducing the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition can reduce the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition by at least 50 weight percent (wt%) within the above reaction parameters (i.e., reaction temperatures from room temperature to less than about 100°C, and / or reaction times up to about 60 minutes). In some embodiments, the method reduces the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition by at least 80.00 wt%. In some embodiments, the disclosed methods can reduce the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition by up to about 99.99 wt.% (or any range of weight percent between about 50.00 wt.% and 99.99 wt.% in 0.01 wt.% increments, e.g., about 50.01 wt.% to 99.98 wt.%) within the above reaction parameters (i.e., reaction temperatures from room temperature to less than about 100°C, and / or reaction times of up to about 60 minutes).

[0030] Additionally, and unexpectedly, the disclosed methods for reducing glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition, as described above, can reduce the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in a given triglyceride-containing composition to extremely low levels without adversely affecting the free fatty acid content of the given triglyceride-containing composition. In some embodiments, a given triglyceride-containing composition (e.g., soybean oil or palm oil) has a free fatty acid content prior to contact with the silica-zirconia catalyst of the present invention, and in particular, the disclosed methods comprising contacting a triglyceride-containing composition (e.g., soybean oil or palm oil) with a silica-zirconia catalyst result in only a slight change in the free fatty acid content (i.e., as oleic acid) of the triglyceride-containing composition, as measured by AOCS Official Method Ca 5a-40.

[0031] In some desirable embodiments of the present invention, the method for reducing glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition includes a method for producing an edible oil having a level of glycidol and / or glycidyl esters of less than 0.2 ppm with little or no change in (i) the free fatty acid content of the edible oil (i.e., as oleic acid), or (ii) the oxidation level of the edible oil as measured by (a) the p-anisidine value of the edible oil, e.g., as determined by AOCS Official Method Cd 18-90, (b) the peroxide value of the edible oil, e.g., as determined by AOCS Official Method Cd 8-53, or (c) both (a) and (b).

[0032] In some embodiments, the disclosed methods of producing edible oils (e.g., having glycidol and / or glycidyl ester levels of less than 0.2 ppm) change the initial free fatty acid content (i.e., measured as oleic acid content) of the edible oil by less than about 20%. In other embodiments, the disclosed methods of producing edible oils (e.g., having glycidol and / or glycidyl ester levels of less than 0.2 ppm) change the initial free fatty acid content (i.e., measured as oleic acid content) of the edible oil by less than about 10%.

[0033] As described in AOCS Official Method Cd 18-90, the entire subject matter of which is incorporated herein, the lipid oxidation level of a given edible oil is determined by the p-amino acid content of the edible oil. The p-anisidine value of edible oils can be measured. The processing of edible oils can result in a series of undesirable chemical reactions involving oxygen that degrade the quality of the edible oil. These undesirable oxidation reactions can produce primary oxidation products, such as peroxides, dienes, and free fatty acids, as well as secondary products, such as carbonyls, aldehydes, and trienes. The p-anisidine value of edible oils measures the amount of aldehydes in the edible oil.

[0034] In some embodiments, the disclosed methods of producing edible oils having levels of glycidyl esters of less than 0.2 ppm change the initial p-anisidine value of the edible oil by less than about 10.0 units. In some embodiments, the disclosed methods of producing edible oils having levels of glycidyl esters of less than 0.2 ppm change the initial p-anisidine value of the edible oil by less than about 1.0 unit. In some embodiments, the disclosed methods of producing edible oils having levels of glycidyl esters of less than 0.2 ppm change the initial p-anisidine value of the edible oil by less than about 0.2 units.

[0035] The oxidation level of a given edible oil can also be measured by the peroxide value of the edible oil as determined by AOCS Official Method Cd 8-53. As set forth in AOCS Official Method Cd 8-53, the subject matter of which is incorporated herein in its entirety, the peroxide value provides a measure of the amount of peroxides in a given edible oil.

[0036] In some embodiments, the disclosed methods for producing edible oils having levels of glycidyl esters of less than 0.2 ppm change the initial peroxide value of the edible oil by less than about 10.0 units. In other embodiments, the methods for producing edible oils having levels of glycidyl esters of less than 0.2 ppm change the initial peroxide value of the edible oil by less than about 7.0 units. In other embodiments, the methods for producing edible oils having levels of glycidyl esters of less than 0.2 ppm change the initial peroxide value of the edible oil by less than about 2.0 units.

[0037] Typically, edible oils are subjected to a refined, bleached, and deodorized (RBD) process. In conventional methods of producing edible oils, after RBD processing, the edible oil is subjected to further processing before use. Further processing of conventionally prepared edible oils (i.e., not processed using the methods described herein) includes, but is not limited to, contacting the oil with enzymes, shear-mixing the oil with acid, re-bleaching the oil, and / or re-running the deodorization at a lower temperature for an extended period of time, or any combination of the aforementioned process steps. However, edible oils that are subjected to RBD processing and subsequently processed using the methods described herein to produce edible oils having levels of glycidol and / or glycidyl esters of less than 0.2 ppm typically do not require further processing before use (i.e., do not require further processing, including, but not limited to, contacting the oil with enzymes, shear-mixing the oil with acid, re-bleaching the oil, and / or re-running the deodorization at a lower temperature for an extended period of time, or any combination of the aforementioned process steps). Silica-Zirconia Catalysts Used in the Processes Described Herein

[0038] The silica-zirconia catalyst used in the methods described herein comprises porous silica particles impregnated with zirconia. As described above, in some embodiments, the zirconia is impregnated onto at least a portion of the surface of the porous silica particles. In some embodiments, the zirconia is impregnated within at least a portion of the pores of the porous silica particles. In some embodiments, the zirconia is impregnated such that it is substantially disposed within the pores of the porous silica particles.

[0039] Suitable porous silica particles useful in preparing the silica-zirconia catalyst of the present invention include, but are not limited to, silica gel, precipitated silica, fumed silica, and colloidal silica. Suitable porous silica also includes those containing organotins during the formation of the silica particles. Particularly preferred porous silica particles include, but are not limited to, ordered mesoporous silica prepared through plating (e.g., surfactants) followed by high-temperature treatment to "burn out" the organic matter. Particularly preferred porous silica particles include silica gel or precipitated silica particles.

[0040] Any commercially available porous silica particles may be used to form the silica-zirconia catalyst of the present invention. Commercially available porous silica particles useful for forming the silica-zirconia catalyst of the present invention include, but are not limited to, SYLOID®, SYLOBLOC® silica particles, such as SYLOID® C807 silica gel particles and SYLOID® MX106 precipitated silica particles, and particles available from W.R. Grace (Columbia, MD) under the tradename DARACLAR® silica particles.

[0041] The porous silica particles used to form the silica-zirconia catalyst of the present invention comprise porous silica having a purity of at least about 93.0 wt.% SiO2, or at least about 93.5 wt.% SiO2, at least about 94.0 wt.% SiO2, at least about 95.0 wt.% SiO2, at least about 96.0 wt.% SiO2, at least about 97.0 wt.% SiO2, or at least about 98.0 wt.% SiO2 and up to 100 wt.% SiO2, based on the total weight of the porous silica particles.

[0042] The porous silica particles used to form the silica-zirconia catalyst of the present invention can have a variety of different symmetrical, asymmetrical, or irregular shapes, including chain-like, rod-like, or clapper-like. The porous silica particles can have different structures, including amorphous or crystalline. In a preferred embodiment, the porous silica particles are amorphous. The porous silica particles can include a mixture of particles having different compositions, sizes, shapes, or physical structures, or particles that may be identical except for different surface treatments. The porosity of the porous silica particles can be intra- or inter-particle, where smaller particles aggregate to form larger particles.

[0043] Typically, the silica-zirconia catalyst (and, independently, the porous silica particles used to form the silica-zirconia particles) has an average particle size of about 0.1 microns (μm) to about 10,000 μm (or in 0.1 μm increments anywhere in the range of average particle size from about 0.1 μm to about 10,000 μm, e.g., about 0.2 μm to about 9,999.9 μm). In some embodiments, the silica-zirconia particles used in the methods described herein (and, independently, the porous silica particles used to form the silica-zirconia particles) have an average particle size of about 80.0 μm to about 400 μm. In some embodiments, the silica-zirconia particles used in the methods described herein (and, independently, the porous silica particles used to form the silica-zirconia particles) have an average particle size of about 100.0 μm to about 200 μm.

[0044] The silica-zirconia catalysts used in the processes described herein (and independently, the porous silica particles used to form the silica-zirconia catalyst) typically have a pore volume of at least 0.01 cubic centimeters per gram (cc / g), as determined by the Barrett-Joyner Halenda (BJH) method. More typically, the silica-zirconia catalysts (and independently, the porous silica particles used to form the silica-zirconia catalyst) have a pore volume of at least 0.5 cc / g, as determined by the Barrett-Joyner Halenda (BJH) method. In some embodiments, the silica-zirconia catalysts (and independently, the porous silica particles used to form the silica-zirconia catalyst) have a pore volume of from about 0.5 cc / g to about 3.0 cc / g or more, as determined by the Barrett-Joyner Halenda (BJH) method. However, the silica-zirconia catalysts used in the processes described herein (and independently, the porous silica particles used to form the silica-zirconia catalyst) may have a pore volume of at least 0.01 cubic centimeters per gram (cc / g), as determined by the Barrett-Joyner Halenda (BJH) method. It should be understood that the porous silica particles (as used herein) can have a pore volume, as measured by the Barrett-Joyner-Halenda (BJH) method, of from about 0.01 cc / g to about 3.00 cc / g (or greater) (or any range of pore volume from about 0.01 cc / g to about 3.0 cc / g in increments of 0.01 cc / g, e.g., from about 0.02 cc / g to about 2.99 cc / g).

[0045] The silica-zirconia catalysts used in the methods described herein (and independently, the porous silica particles used to form the silica-zirconia catalysts) may also have an average pore size of at least 0.1 nanometers (nm), as measured by a mercury intrusion testing procedure using an Autopore IV 9520, available from Micromeritics Instrument Corp. Typically, the silica-zirconia catalysts used in the methods described herein (and independently, the porous silica particles used to form the silica-zirconia catalysts) have an average pore size of from about 1.0 nm to about 1,000.0 nm. In some embodiments, the silica-zirconia catalysts used in the methods described herein (and independently, the porous silica particles used to form the silica-zirconia catalysts) have an average pore size of from about 1.0 nm to about 100.0 nm. In other embodiments, the silica-zirconia catalysts used in the methods described herein (and independently, the porous silica particles used to form the silica-zirconia catalysts) have an average pore size of from about 2.0 nm to about 50.0 nm. However, it will be understood that the silica-zirconia catalysts used in the methods described herein (and independently, the porous silica particles used to form the silica-zirconia catalysts) may have average pore diameters of from about 0.1 nm to about 1,000.0 nm (or larger) (or any range of average pore diameters from about 0.1 nm to about 1,000.0 nm in 0.1 nm increments, e.g., from about 0.2 nm to about 999.9 nm).

[0046] The silica-zirconia catalysts used in the processes described herein (and independently, the porous silica particles used to form the silica-zirconia catalysts) also have a surface area of ​​at least about 10 m 2 / g~about 2000m 2 Typically, the silica-zirconia catalysts used in the processes described herein (and independently, the porous silica particles used to form the silica-zirconia catalysts) may have a BET particle surface area of ​​at least about 25.0 m / g or more. 2In some embodiments, the silica-zirconia catalyst (and independently, the porous silica particles used to form the silica-zirconia catalyst) has a BET particle surface area of ​​at least about 50 m / g. 2 / g~about 800m 2 / g. However, the silica-zirconia catalysts used in the methods described herein (and independently, the porous silica particles used to form the silica-zirconia catalysts) have a BET particle surface area of ​​about 10 m 2 / g~about 2000m 2 Any BET particle surface area in the range of 10 m / g or more (or about 10 m 2 / g~about 2000m 2 / g for 0.1m 2 / g increments, for example, approximately 10.1m 2 / g ~ approx. 1999.9m 2 It should be understood that the particle size may have any range of BET particle surface area values ​​(e.g., 1000 nm / g).

[0047] The silica-zirconia catalysts used in the processes described herein (and independently, the porous silica particles used to form the silica-zirconia catalysts) may also be subjected to size reduction. Any known particle size reduction method may be used, including, but not limited to, grinding, such as ball milling or grinding in a pestle and mortar.

[0048] The silica-zirconia catalysts used in the processes described herein (and independently, the porous silica particles used to form the silica-zirconia catalysts) may comprise (i) any of the porous silica particles described above in combination with (ii) zirconia. As noted above, the zirconia may be impregnated onto at least a portion of the particle surface of the porous silica particles, or (ii) impregnated within at least a portion of the pores of the porous silica particles; The zirconia may be (iii) impregnated on at least a portion of the surface of the porous silica particles and within at least a portion of the pores of the porous silica particles, or (iv) substantially within the pores of the porous silica particles. In one embodiment, the zirconia is disposed substantially within the pores of the silica particles.

[0049] Typically, the silica-zirconia catalysts used in the processes described herein contain at least about 0.01 weight percent (wt%) zirconia, based on the total weight of the silica-zirconia catalyst. In some embodiments, the silica-zirconia catalysts used in the processes described herein contain from about 1.0 wt% to about 50.0 wt% zirconia, based on the total weight of the silica-zirconia catalyst. In some desirable embodiments, the silica-zirconia catalysts used in the processes described herein contain from about 1.5 wt% to about 14.3 wt% zirconia, based on the total weight of the silica-zirconia catalyst. In other desirable embodiments, the silica-zirconia catalysts used in the processes described herein contain from about 2.4 wt% to about 5.0 wt% zirconia, based on the total weight of the silica-zirconia catalyst. However, it should be understood that the silica-zirconia catalyst used in the processes described herein may contain any amount of zirconia ranging from about 0.01 wt. % to about 50.0 wt. % (or more) (or in 0.01 wt. % increments within any range of amounts of zirconia from about 0.01 wt. % to about 50.0 wt. %, e.g., from about 0.02 wt. % to about 49.99 wt. %, based on the total weight of the silica-zirconia catalyst).

[0050] In some embodiments, the silica-zirconia catalyst of the present invention has (i) an average particle size of from about 80.0 μm to about 400 μm, (ii) a pore volume of from about 0.5 cc / g to about 3.0 cc / g or more, as determined by the Barrett-Joyner Halenda (BJH) method, (iii) an average pore diameter of from about 1.0 nm to about 100.0 nm, and (iv) a pore volume of at least about 50.0 m 2 / g~about 800m 2 / g BET particle surface area, and (v) about 1.0 wt. % to about 50.0 wt. % zirconia, based on the total weight of the silica-zirconia catalyst.

[0051] In some embodiments, the silica-zirconia catalyst of the present invention (i) has an average particle size of from about 100.0 μm to about 200 μm, (ii) has a pore volume of from about 1.0 cc / g to about 2.0 cc / g as determined by the Barrett-Joyner Halenda (BJH) method, (iii) has an average pore diameter of from about 15.0 nm to about 30.0 nm, and (iv) has a pore volume of at least about 75.0 m 2 / g~about 400m 2 / g BET particle surface area, and (v) about 2.5 wt. % to about 15.0 wt. % zirconia, based on the total weight of the silica-zirconia catalyst. Methods for making silica-zirconia catalysts for use in the methods described herein

[0052] The silica-zirconia catalysts used in the methods described herein may be formed by a zirconia coating and / or impregnation step, followed by one or more additional steps, such as a drying step, a calcination step, or both. In some embodiments, a method for making silica-zirconia catalysts suitable for use in the methods described herein includes impregnating porous silica particles with zirconium acetate in aqueous acetic acid, drying the impregnated porous silica particles at about 105° C. for about 2 hours, and calcining the dried impregnated porous silica particles at about 500° C. for about 4 hours.

[0053] Typically, the method for making a silica-zirconia catalyst includes an impregnation step in which porous silica particles are contacted with zirconium acetate for a desired period of time. In some embodiments, the impregnation step involves contacting the porous silica particles with zirconium acetate for about 30 minutes. However, it should be understood that the impregnation step may involve contacting the porous silica particles with zirconium acetate for any desired period of time.

[0054] In some desired embodiments, the method of making the silica-zirconia catalyst includes milling the impregnated porous silica particles for about 60 minutes after the impregnation step and before the drying step, It should be understood that the impregnated porous silica particles can be milled (or ground) for any desired period of time. Compositions used and prepared in the methods described herein

[0055] The present invention further relates to a triglyceride-containing composition comprising the silica-zirconia catalyst described herein. As mentioned above, typically, a given triglyceride-containing composition (i.e., before or after the above-described method for reducing the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in the triglyceride-containing composition and / or the method for producing an edible oil, and before removal of the silica-zirconia catalyst) contains the silica-zirconia catalyst described herein in an amount greater than about 0.01 wt.%, typically from about 0.50 wt.% to about 10.0 wt.% (or any range of weight percent from about 0.50 wt.% to about 10.00 wt.% in 0.01 wt.% increments, e.g., from about 1.00 wt.% to about 3.00 wt.%), based on the total weight of the silica-zirconia catalyst and triglyceride-containing composition. As mentioned above, in some desirable embodiments, the triglyceride-containing composition of the present invention comprises a silica-zirconia catalyst described herein in an oil (e.g., an edible oil such as soybean oil or palm oil) or an organic solvent (e.g., a triglyceride-dissolving solvent such as toluene) (i.e., before or after the above-described method for reducing the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in the triglyceride-containing composition and / or the method for producing the edible oil, and before removal of the silica-zirconia catalyst). In some desirable embodiments, the triglyceride-containing composition of the present invention comprises a silica-zirconia catalyst described herein in an edible oil (e.g., soybean oil or palm oil) (i.e., before or after the above-described method for reducing the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in the triglyceride-containing composition and / or the method for producing the edible oil, and before removal of the silica-zirconia catalyst).

[0056] The present invention further relates to the oil- and triglyceride-containing compositions obtained from the above-described methods for reducing the amount of glycidol, glycidyl esters, or both glycidol and glycidyl esters in a triglyceride-containing composition, either before or after removal of the silica-zirconia catalyst, and / or the methods for producing edible oils. In some desirable embodiments, the disclosed methods are used to produce edible oils.

[0057] Although the above silica-zirconia catalysts, methods, and uses are described as "comprising" one or more components or steps, it should be understood that the above silica-zirconia catalysts, methods, and uses can "comprise," "consists of," or "consist essentially of" any of the above components or steps of the silica-zirconia catalysts, methods, and uses. As a result, the present invention Where the invention or portions thereof are described in open-ended terms such as "comprising," the description or portions thereof may also (unless otherwise specified) be accompanied by the terms "consisting essentially of" or "consisting of" or "consisting of" or "consisting of," as set forth below. It should be readily understood that these variations should be construed as describing the present invention or a portion thereof.

[0058] As used herein, the terms "comprises," "comprising," "includes," "including," "having," "having," "containing," "containing," "characterized by," or any other variation thereof, are intended to include a non-exclusive inclusion of the listed components, subject to any limitation expressly indicated to the contrary. For example, a silica-zirconia catalyst "comprises" a series of elements (e.g., components or steps). The method and / or use do not necessarily relate to only these elements (or components or steps). It is not limited and may include other elements (or components or steps) not expressly listed or inherent in the silica-zirconia catalyst, method, and / or use.

[0059] As used herein, the transitional phrases "consists of" and "consist of" "(consisting of)" excludes any element, step, or component not specified. For example, the use of "consists of" and "consisting of" in a claim limits the claim to the components, materials, or steps specifically recited in the claim, excluding impurities normally associated therewith (i.e., impurities within a given component). When appearing within a clause in the body of a claim rather than immediately following a clause, the phrase "consist of" or "consisting of" shall not include the elements (or components or The scope of the claims is limited to only certain elements (or steps). No other elements (or components) are excluded from the scope of the claims as a whole.

[0060] As used herein, the transitional phrase "consists essentially of" "Consisting essentially of" and "consisting essentially of" are used to describe a literal disclosure. "Consisting essentially of" is used to define a silica-zirconia catalyst, method, and / or use that includes materials, steps, features, components, or elements in addition to those listed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term "consisting essentially of" lies in the intermediate range between "comprising" and "consisting of."

[0061] The present invention is further illustrated by the following examples, which should not be construed as imposing limitations on its scope in any way. On the contrary, it should be clearly understood that various other embodiments, modifications, and equivalents thereof may be relied upon, which may suggest themselves to those skilled in the art upon reading the description herein without departing from the spirit of the invention and / or the scope of the appended claims. [Example]

[0062] The following examples describe (i) a process according to the present invention for preparing a silica-zirconia catalyst, and (ii) the evaluation of the silica-zirconia catalyst in reducing glycidol, glycidyl esters, or both glycidol and glycidyl esters in various triglyceride-containing compositions. Nitrogen pore volume and BET surface area measurements of silica-zirconia particle samples

[0063] The nitrogen pore volume of the silica-zirconia catalyst was measured using an Autosorb® iQ analyzer available from Quantachrome Instrument (Boynton Beach, FL). Each sample was degassed for 4 hours at 65°C (i.e., below the melting temperature of the wax, which is approximately 80°C). Nitrogen adsorption / desorption isotherms were measured at 77K, increasing the nitrogen pressure from 0.01% atmosphere to 0.998% atmosphere, and then decreasing it from 0.998% atmosphere to 0.025% atmosphere, respectively. The pore volume was calculated using the AsiQwin™ version 5.0 program based on the BJH theory. See, for example, Barrett et al., The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms, J. Am. Chem Soc. 1951, 73(1), pp. 373-380; BET surface area can also be determined using the Brunauer Emmet Teller method (Brunauer, et al., "Adsorption of Gases in Multimolecular Layers". J. Am. Chem Soc. 1938, 60(2):309-319), both of which subject matter are incorporated herein by reference in their entireties. To be incorporated. Total glycidol concentration analysis

[0064] The total glycidol concentration of a given sample is determined using AOCS Official Method Cd 29c-13, the entire subject matter of which is incorporated herein by reference. This method determines the concentration of the sum of (i) total free glycidol and (ii) bound glycidol (i.e., glycidyl esters) present in a given sample. Catalyst synthesis

[0065] Porous silica-zirconia catalyst particles were prepared using the following procedure: The desired amount of zirconium acetate was diluted with aqueous acetic acid and impregnated onto porous silica particles for 30 minutes, followed by grinding for an additional hour. The material was then dried at 105°C for 2 hours and then calcined at 500°C for 4 hours.

[0066] The resulting silica-zirconia catalysts had zirconia concentrations ranging from 0.01 wt. % to 49.99 wt. %. As described further below, in some embodiments, silica-zirconia catalysts having zirconia concentrations ranging from about 2.00 wt. % to about 20.00 wt. % provided effective results. The final zirconia concentration was determined using ICP elemental microanalysis.

[0067] Four sample silica-zirconia catalysts, Catalysts A through D, were prepared using the synthesis procedures described herein, and their properties are shown in Table 1 below. [Table 1] Reaction procedure

[0068] Each oil / solvent was charged to a round-bottom flask and glycidol and / or glycidyl ester (e.g., glycidyl oleate) was added. The overhead mixer was set to 250 rpm. The reactor was flushed with inert gas, and then an initial sample was taken for GC / MS analysis. After the desired catalytic amount of silica-zirconia catalyst was added, the temperature was increased to the desired set point. After the desired time, a final sample was taken and then filtered through a filter disc to remove solid catalyst before analysis.

[0069] The reaction temperature is not limited, but is preferably about 45°C to about 90°C. For the edible oil industry, maintaining the temperature below 90°C helps prevent oxidation of the oil while allowing sufficient time for the reduction of glycidol and glycidyl esters. Similarly, the reaction time is not limited, but is preferably less than 2 hours to minimize residence time in the refiner. Example 1 - Control Experiment

[0070] The above reaction procedure was used in the following examples. Soybean oil with glycidyl oleate was mixed and heated under argon to a maximum temperature of 90° C. The total glycidol concentration in the reaction mixture was measured over a 30 minute period, as shown in Table 2 below. [Table 2]

[0071] As shown in Table 2, if no catalyst is added to the reaction mixture, there is no reduction in glycidol / glycidyl oleate. Example 2 - Effect of Dosing Silica-Zirconia Catalyst in the Reaction Mixture

[0072] The above catalyst synthesis and reaction procedures were used in the following examples. Catalyst A of the present invention was added to soybean oil spiked with glycidyl oleate at 0.5, 1.0, 1.5, and 2.0 wt. %, based on the total weight of the silica-zirconia catalyst and soybean oil. The reaction mixture was mixed and heated to a maximum temperature of 90° C. under argon. The concentration of total glycidol in the reaction mixture was measured before and after 30 minutes, as shown in Table 3 below. [Table 3] Limit of quantitation (LOQ) = 0.20 ppm

[0073] As shown in Table 3, a dosage of 0.5 wt% silica-zirconia catalyst significantly reduces glycidol / glycidyl oleate within 30 minutes at 90° C. Similarly, increasing the dosage of silica-zirconia catalyst improves the reduction of glycidol / glycidyl oleate in the reaction mixture over time. Example 3 - Effect on Zirconia Concentration and Total Glycidol Reduction

[0074] The catalyst synthesis and reaction procedures described above were used in the following examples. Catalysts A, B, C, and D of the present invention were added to soybean oil spiked with glycidyl oleate. 2.0 wt. % of silica / zirconia catalyst was used, based on the total weight of catalyst and soybean oil. The reaction mixture was mixed and heated to a maximum temperature of 90°C under argon. The concentration of total glycidol in the reaction mixture was measured before and after 30 minutes, as shown in Table 4 below. [Table 4]

[0075] As shown in Table 4, increasing the concentration of zirconia on the silica base significantly improves the glycidol / glycidyl oleate reduction in the reaction mixture. Example 4 - Reaction Temperature and Effect on Total Glycidol Reduction

[0076] The catalyst synthesis and reaction procedures described above were used in the following examples. Catalyst A of the present invention was added to soybean oil spiked with glycidyl oleate. 2.0 wt. % of silica / zirconia catalyst was used, based on the total weight of catalyst and soybean oil. The reaction mixture was mixed and heated under argon to a maximum temperature of 23°C (no heat), 45°C, and 90°C. The concentration of total glycidol in the reaction mixture was measured before and after 7 hours, 2 hours, and 30 minutes, respectively, as shown in Table 5 below. [Table 5]

[0077] As shown in Table 5, this catalytic reaction proceeds without any additional heat. Heating the mixture accelerates the reaction in a truly catalytic manner, but excess heat can cause more glycidol / glycidyl oleate to form. For example, in edible oil refining, it has previously been shown that glycidyl esters are formed during the deodorization process at temperatures above 200°C. Example 5 - Total Glycidol Reduction in Soybean Oil at 45°C and Effect on Oxidation

[0078] The catalyst synthesis and reaction procedures described above were used in the following examples. Catalyst A of the present invention was added to soybean oil spiked with glycidyl oleate. 2.0 wt. % of silica / zirconia catalyst was used, based on the total weight of catalyst and soybean oil. The reaction mixture was mixed and heated to a maximum temperature of 45°C under argon. The free fatty acid concentration (FFA%), p-anisidine value (p-AV), total glycidol concentration, and peroxide value (PV) in the reaction mixture were measured over a two-hour period, as shown in Table 6 below. [Table 6]

[0079] As shown in Table 6, the free fatty acid concentration and p-anisidine values ​​remained unchanged, while the peroxide and total glycidol concentrations decreased over the 2 hour reaction period, demonstrating that no significant decomposition occurs during this glycidol / glycidyl ester reduction reaction. Example 6 - Total glycodol reduction in palm oil at 90°C and effect on oxidation

[0080] The catalyst synthesis and reaction procedures described above were used in the following examples. Catalyst A of the present invention was added to palm oil spiked with glycidyl oleate. 2.0 wt. % of silica / zirconia catalyst was used, based on the total weight of catalyst and palm oil. The reaction mixture was mixed and heated to a maximum temperature of 90°C under argon. The free fatty acid concentration, p-anisidine (p-AV) value, peroxide value (PV), and total glycidol concentration in the reaction mixture were measured over a 30-minute period, as shown in Table 7 below. [Table 7]

[0081] As shown in Table 7, the free fatty acid concentration and p-anisidine values ​​did not change significantly, while the peroxide values ​​and total glycidol content decreased over the 30-minute reaction period, with the final total glycidol content being less than measurable. Palm oil is easily oxidized upon heating, which explains the slight but significant increase in p-AV. Simply lowering the reaction temperature prevents the formation of secondary oxidation products. Example 7 - Effect of matrix / solvent on glycodol reduction

[0082] The catalyst synthesis and reaction procedures described above were used in the following examples. Catalyst A of the present invention was added to a reaction matrix spiked with free glycidol. 2.0 wt. % of silica / zirconia catalyst was used, based on the total weight of catalyst and matrix / solvent. The reaction mixture was mixed and heated to a maximum temperature of 90°C under argon. The concentration of total glycidol in the reaction mixture was measured over a 30-minute period, as shown in Table 8 below. [Table 8]

[0083] As shown in Table 8, the reaction proceeds in both edible oil and organic solvent matrices to reduce free glycidol in addition to glycidyl esters. Comparative Example 8 - Use of a Commercial Silica / Zirconia Catalyst

[0084] The reaction procedure described above and commercially available nonporous silica / zirconia particles purchased through Fisher Scientific were used in the following examples. One sample of 0.1 mm silica / zirconia beads was manufactured by Bio Spec Products (catalog number: NC0362415), and another sample of 0.1 mm silica / zirconia beads was manufactured by Research Products International Corp. (catalog number: 50212145). The commercially available silica / zirconia particles were added to soybean oil spiked with glycidyl oleate. 2.0 wt. % of the silica / zirconia particles were used, based on the total weight of the particles and soybean oil. The reaction mixture was mixed and heated to a maximum temperature of 90°C under argon. The p-anisidine (p-AV) value, peroxide value (PV), and total glycidol concentration in the reaction mixture were measured before and after 30 minutes, as shown in Table 9 below. [Table 9]

[0085] As shown in Table 9, commercially available non-porous silica / zirconia particles do not effectively reduce total glycidol in a given reaction mixture compared to the inventive silica / zirconia catalysts described herein. In contrast to the inventive silica / zirconia catalysts disclosed herein, these commercially available silica / zirconia particles are non-porous and have a lower surface area.

[0086] While the present invention has been described with respect to a limited number of embodiments, these specific embodiments are not intended to limit the scope of the invention as described and claimed elsewhere herein. Further modifications, equivalents, and variations are possible and will be apparent to those skilled in the art upon review of the exemplary embodiments herein. All parts and percentages in the examples, as well as in the remainder of the specification, are by weight unless otherwise specified. Furthermore, any range of numbers recited in the specification or claims, such as those representing a particular set of properties, units of measure, conditions, physical states, or percentages, is intended to be expressly incorporated herein by reference or otherwise set forth, including any numbers contained within such ranges, and any subset of numbers within any range so recited. For example, a lower limit R L Whenever a numerical range with an upper limit Ru is disclosed, any number R that falls within the range is specifically disclosed. In particular, the following numbers R within the range are specifically disclosed: R = R L +k(Ru-R L ), where k is a variable ranging from 1% to 100%, in 1% increments; for example, k is 1%, 2%, 3%, 4%, 5%, ... 50%, 51%, 52%, ... 95%, 96%, 97%, 98%, 99%, or 100%. Additionally, any numerical range represented by any two values ​​of R, as calculated above, is also specifically disclosed. Any modifications of the present invention, in addition to those shown and described herein, will become apparent to those skilled in the art from the foregoing description and accompanying drawings. Such modifications are intended to fall within the scope of the appended claims. All publications cited herein are incorporated by reference in their entirety.

Claims

1. 1. A method for reducing the amount of (i) glycidol, (ii) glycidyl ester, or (iii) both glycidol and glycidyl ester in a composition comprising triglycerides, comprising: contacting the composition comprising the triglycerides with an effective amount of a particulate silica-zirconia catalyst to reduce the amount of (i) glycidol, (ii) glycidyl esters, or (iii) both glycidol and glycidyl esters in the composition, wherein the silica-zirconia catalyst comprises porous silica particles impregnated with zirconia; A method wherein the amount of (i) glycidol, (ii) glycidyl ester, or (iii) both glycidol and glycidyl ester is reduced without affecting other components of the composition, including the triglycerides.

2. 10. The method of claim 1, wherein the silica-zirconia catalyst comprises zirconia disposed on at least a portion of the surface of the porous silica particles.

3. The method of claim 1 or 2, wherein the silica-zirconia catalyst comprises zirconia disposed within at least a portion of the pores of the porous silica particles.

4. The method of any one of claims 1 to 3, wherein the silica-zirconia catalyst comprises zirconia disposed substantially within the pores of the porous silica particles.

5. The method of any one of claims 1 to 4, wherein the silica-zirconia catalyst comprises particles having an average particle size of from about 0.1 microns (µm) to about 10,000 µm.

6. The method of any one of claims 1 to 5, wherein the silica-zirconia catalyst comprises particles having an average particle size of about 80.0 µm to about 400 µm.

7. 7. The method of any one of claims 1 to 6, wherein the silica-zirconia catalyst comprises particles having a pore volume of at least 0.01 cubic centimeters per gram (cc / g) as determined by the Barrett-Joyner Halenda (BJH) method.

8. The method of any one of claims 1 to 7, wherein the silica-zirconia catalyst comprises particles having a pore volume of at least 0.5 cc / g as determined by the Barrett-Joyner Halenda (BJH) method.

9. 9. The method of any one of claims 1 to 8, wherein the silica-zirconia catalyst comprises particles having a pore volume, as determined by the Barrett-Joyner Halenda (BJH) method, of from about 0.5 cc / g to about 3.0 cc / g or more.

10. 10. The method of any one of claims 1 to 9, wherein the silica-zirconia catalyst comprises particles having an average pore size of at least 0.1 nanometers (nm) to about 1,000 nm, as determined by mercury intrusion testing procedure using an Autopore IV 9520 available from Micromeritics Instrument Corp.

11. The method of any one of claims 1 to 10, wherein the silica-zirconia catalyst comprises particles having an average pore size of from about 1.0 nm to about 100.0 nm.

12. The silica-zirconia catalyst has an average pore diameter of about 2.0 nm to about 50.0 nm. The method of any one of claims 1 to 11, comprising particles comprising:

13. The silica-zirconia catalyst is at least about 10 m ２ / g~Maximum approx. 2000m ２ 13. The method of any one of claims 1 to 12, comprising particles having a BET particle surface area of ​​1 / g or more.

14. The silica-zirconia catalyst is at least about 25.0 m ２ 14. The method of any one of claims 1 to 13, comprising particles having a BET particle surface area of ​​1 / g.

15. The silica-zirconia catalyst is at least about 50.0 m ２ / g ~ approx. 800m ２ 15. The method of any one of claims 1 to 14, comprising particles having a BET particle surface area of ​​1 / g.

16. The method of any one of claims 1 to 15, wherein the porous silica particles comprise silica gel, precipitated silica, or fumed silica particles.

17. 17. The method of any one of claims 1 to 16, wherein the silica-zirconia catalyst comprises particles comprising at least 0.01 weight percent (wt%) zirconia, based on the total weight of the silica-zirconia catalyst.

18. 18. The method of any one of claims 1 to 17, wherein the silica-zirconia catalyst comprises particles comprising from about 1.0 wt. % to about 50.0 wt. % zirconia, based on the total weight of the silica-zirconia catalyst.

19. 19. The method of any one of claims 1 to 18, wherein the silica-zirconia catalyst comprises particles comprising about 1.5 wt% to about 15.0 wt% zirconia, based on the total weight of the silica-zirconia catalyst.

20. The silica-zirconia catalyst is impregnating porous silica particles with a soluble zirconium compound in water; drying the impregnated porous silica particles at about 105° C. for about 2 hours; and calcining the dried impregnated porous silica particles at about 500° C. for about 4 hours.

20. The method according to any one of claims 1 to 19.

21. 21. The method of claim 20, wherein the impregnation step contacts the porous silica particles with the soluble zirconium compound for about 30 minutes.

22. The method comprises:

22. The method of claim 20 or 21, further comprising milling the impregnated porous silica particles for about 60 minutes after the impregnation step and before the drying step.

23. 23. The method of any one of claims 1 to 22, further comprising mixing the composition comprising the triglyceride and the silica-zirconia catalyst.

24. The method of any one of claims 1 to 23, wherein the contacting step is carried out at room temperature.

25. 25. The method of claim 23 or 24, wherein the mixing step is performed at room temperature.

26. 26. The method of any one of claims 1 to 25, further comprising heating the composition comprising the triglyceride and the silica-zirconia catalyst to a temperature of at least 40.0°C.

27. 27. The method of any one of claims 1 to 26, further comprising heating the composition comprising the triglyceride and the silica-zirconia catalyst to a temperature of about 90.0°C.

28. The heating step heating the composition comprising the triglyceride and the silica-zirconia catalyst to a maximum temperature; and maintaining the maximum temperature for at least 10.0 minutes.

29. The heating step heating the composition comprising the triglyceride and the silica-zirconia catalyst to a maximum temperature; maintaining said maximum temperature for about 30.0 minutes; The method of any one of claims 26 to 28, comprising:

30. 30. The method of any one of claims 26 to 29, wherein the heating step and the mixing step are performed simultaneously.

31. The contacting step 31. The method of any one of claims 1 to 30, comprising mixing the composition comprising the triglyceride and the silica-zirconia catalyst under a flow of inert gas.

32. 32. The method of claim 31 , wherein the inert gas comprises nitrogen, argon, carbon dioxide, or any combination thereof.

33. The contacting step 33. The method of any one of claims 1 to 32, comprising mixing the composition comprising the triglyceride and the silica-zirconia catalyst under vacuum.

34. 34. The method of any one of claims 1 to 33, wherein the composition comprising the triglyceride comprises (i) an oil, (ii) an organic solvent, or (iii) both an oil and an organic solvent.

35. 35. The method of any one of claims 1 to 34, wherein the composition comprising the triglyceride comprises an edible oil.

36. 36. The method of any one of claims 1 to 35, wherein the composition comprising the triglyceride comprises (i) a triglyceride-based oil, (ii) an organic solvent capable of dissolving a triglyceride, or (iii) both a triglyceride-based oil and an organic solvent capable of dissolving a triglyceride.

37. 37. The method of any one of claims 1 to 36, wherein the composition comprising the triglyceride comprises soybean oil, palm oil, corn oil, canola oil, rapeseed oil, fish oil, algal oil, sunflower oil, olive oil, vegetable oil, plant-derived oil, animal-derived oil, microbial-derived oil, or any combination thereof.

38. 38. The method of any one of claims 1 to 37, wherein the composition comprising the triglyceride comprises soybean oil.

39. 35. The method of claim 1, wherein the composition comprising the triglyceride comprises heptane, hexane, toluene, diethyl ether, alcohol, or any combination thereof.

1. The method according to claim 1.

40. 40. The method of any one of claims 1 to 39, wherein the glycidyl ester in the composition comprising a triglyceride comprises glycidyl oleate.

41. 41. The method of any one of claims 1 to 40, wherein the amount of the silica-zirconia catalyst comprises at least about 0.01 wt.% of the silica-zirconia catalyst, based on the total weight of the composition comprising the silica-zirconia catalyst and the triglyceride.

42. 42. The method of any one of claims 1 to 41, wherein the amount of the silica-zirconia catalyst comprises from about 0.5 wt. % to about 10.0 wt. % of the silica-zirconia catalyst, based on the total weight of the composition comprising the silica-zirconia catalyst and the triglyceride.

43. 43. The method of any one of claims 1 to 42, wherein the amount of the silica-zirconia catalyst comprises from about 1.0 wt % to about 3.0 wt % of the silica-zirconia catalyst, based on the total weight of the composition comprising the silica-zirconia catalyst and the triglyceride.

44. 44. The method of any one of claims 1 to 43, wherein the method reduces the amount of (i) glycidol, (ii) glycidyl esters, or (iii) both glycidol and glycidyl esters to a level of less than 10.0 parts per million (ppm) of (i) glycidol, (ii) glycidyl esters, or (iii) both glycidol and glycidyl esters in the composition comprising the triglyceride.

45. 45. The method of any one of claims 1 to 44, wherein the method reduces the amount of (i) glycidol, (ii) glycidyl esters, or (iii) both glycidol and glycidyl esters to a level of less than 5.0 ppm of (i) glycidol, (ii) glycidyl esters, or (iii) both glycidol and glycidyl esters in the composition comprising the triglyceride.

46. 46. ​​The method of any one of claims 1 to 45, wherein the method reduces the amount of (i) glycidol, (ii) glycidyl esters, or (iii) both glycidol and glycidyl esters to a level of less than 1.0 ppm of (i) glycidol, (ii) glycidyl esters, or (iii) both glycidol and glycidyl esters in the composition comprising the triglyceride.

47. 47. The method of any one of claims 1 to 46, wherein the method reduces the amount of (i) glycidol, (ii) glycidyl esters, or (iii) both glycidol and glycidyl esters to a level of less than 0.5 ppm of (i) glycidol, (ii) glycidyl esters, or (iii) both glycidol and glycidyl esters in the composition comprising the triglyceride.

48. 48. The method of any one of claims 1 to 47, wherein the method reduces the amount of (i) glycidol, (ii) glycidyl esters, or (iii) both glycidol and glycidyl esters to a level of less than 0.2 ppm of (i) glycidol, (ii) glycidyl esters, or (iii) both glycidol and glycidyl esters in the composition comprising the triglyceride.

49. 49. The method of claim 1, wherein the method reduces the amount of (i) glycidol, (ii) glycidyl ester, or (iii) both glycidol and glycidyl ester in the composition comprising the triglyceride by at least 50 weight percent (wt%). The method described.

50. 50. The method of any one of claims 1 to 49, wherein the method reduces the amount of (i) glycidol, (ii) glycidyl esters, or (iii) both glycidol and glycidyl esters in the composition comprising the triglyceride by at least 80.00 wt.%.

51. 51. The method of any one of claims 1 to 50, wherein the method reduces the amount of (i) glycidol, (ii) glycidyl esters, or (iii) both glycidol and glycidyl esters in the composition comprising triglycerides by up to 99.99% by weight.

52. A method for producing an edible oil, comprising the method of any one of claims 35 to 51.

53. 53. The method of claim 52, wherein the edible oil is subjected to a refine bleach deodorization (RBD) process before contacting with the silica-zirconia catalyst as described in any one of claims 35 to 51.

54. 54. The method of claim 53, wherein the edible oil produced does not require further processing before use.

55. 55. The method of any one of claims 35 to 54, wherein the method results in a level of total free and bound glycidol (i.e., glycidol and glycidyl esters) of less than 0.2 ppm.

56. 56. The method of any one of claims 35-55, wherein the edible oil has an initial free fatty acid content measured as the content of oleic acid, and the method alters the initial free fatty acid content as measured by AOCS Official Method Ca 5a-40 by less than about 20%.

57. 57. The method of any one of claims 35 to 56, wherein the edible oil has an initial free fatty acid content measured as the content of oleic acid, and the method alters the initial free fatty acid content as measured by AOCS Official Method Ca 5a-40 by less than about 10%.

58. 58. The method of any one of claims 35 to 57, wherein the edible oil has an initial p-anisidine value (p-AV) and the method changes the initial p-anisidine value (p-AV) by less than 10 units as measured by AOCS Official Method Cd 18-90.

59. 59. The method of any one of claims 35 to 58, wherein the edible oil has an initial peroxide value (PV) and the method changes the initial peroxide value by less than 10 units as measured by AOCS Official Method Cd 8-53.

60. 60. The silica-zirconia catalyst used in the method of any one of claims 1 to 59.

61. The silica-zirconia catalyst has (i) an average particle size of about 80.0 μm to about 400 μm, (ii) a pore volume of about 0.5 cc / g to about 3.0 cc / g or more as determined by the Barrett-Joyner-Halenda (BJH) method, (iii) an average pore diameter of about 1.0 nm to about 100.0 nm, and (iv) an average pore size of at least about 50.0 m. ２ / g ~ approx. 800m ２ 61. The method of claim 60, comprising particles having a BET particle surface area of ​​1.0 to 50.0 wt. % zirconia based on the total weight of the silica-zirconia catalyst. The silica-zirconia catalyst described herein.

62. The silica-zirconia catalyst has (i) an average particle size of from about 100.0 μm to about 200 μm, (ii) a pore volume of from about 1.0 cc / g to about 2.0 cc / g as determined by the Barrett-Joyner Halenda (BJH) method, (iii) an average pore diameter of from about 15.0 nm to about 30.0 nm, and (iv) a pore size of at least about 75.0 m. ２ / g ~ approx. 400m ２ 62. The silica-zirconia catalyst of claim 60 or 61, comprising particles having a BET particle surface area of ​​1000 nm to 1500 nm / g, and (v) from about 2.5 wt. % to about 15.0 wt. % zirconia, based on the total weight of the silica-zirconia catalyst.

63. 63. The silica-zirconia catalyst of any one of claims 60 to 62, wherein the silica-zirconia catalyst comprises porous silica particles impregnated with zirconia.

64. 64. The silica-zirconia catalyst according to any one of claims 60 to 63, wherein the silica-zirconia catalyst comprises zirconia on at least a portion of the surface of the porous silica particles.

65. 65. The silica-zirconia catalyst of any one of claims 60 to 64, wherein the silica-zirconia catalyst comprises zirconia disposed within at least some of the pores of the porous silica particles.

66. 66. The silica-zirconia catalyst of any one of claims 60 to 65, wherein the silica-zirconia catalyst comprises zirconia disposed substantially within the pores of the porous silica particles.

67. The silica-zirconia catalyst is impregnating porous silica particles with a soluble zirconium compound in water; drying the impregnated porous silica particles at about 105°C for about 2 hours; calcining the dried impregnated porous silica particles at about 500°C for about 4 hours; 67. The silica-zirconia catalyst of any one of claims 60 to 66, comprising particles formed by:

68. 68. An oil comprising the silica-zirconia catalyst used in the method of any one of claims 1 to 59 or as claimed in any one of claims 60 to 67.

69. An edible oil used in a method according to any one of claims 1 to 59 or comprising a silica-zirconia catalyst according to any one of claims 60 to 67.

70. 60. An oil obtainable from the method of any one of claims 1 to 59.

71. 60. An edible oil obtainable from the method of any one of claims 1 to 59.

72. 72. The edible oil of claim 71, wherein the edible oil comprises soybean oil, palm oil, corn oil, canola oil, rapeseed oil, fish oil, algal oil, sunflower oil, olive oil, vegetable oil, plant-derived oil, animal-derived oil, microbial-derived oil, or any combination thereof.

73. 73. The edible oil of claim 71 or 72, wherein the edible oil comprises soybean oil or palm oil.

74. 68. An oil having a reduced content of (i) glycidol, (ii) glycidyl esters, or (iii) both glycidol and glycidyl esters, said oil having been treated with the silica-zirconia catalyst of any one of claims 60 to 67.

75. 75. The oil of claim 74, wherein the oil is an edible oil.

76. 76. The edible oil of any one of claims 69, 71-73, and 75, wherein the edible oil is a deodorized oil that has been subjected to a refinery bleaching and deodorization (RBD) process prior to contacting with the silica-zirconia catalyst as described in the method of any one of claims 35-51.

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