Method for using silica-zirconia catalyst in continuous reactor

Abstract

A method includes contacting an initial composition comprising (i) a triglyceride and (ii) glycidyl, glycidyl ester, or both glycidyl and glycidyl ester with an effective amount of a silica-zirconia catalyst in a continuous reactor. The method can be used to produce a treated composition, such as a treated edible oil, having a reduced (ii) concentration compared to the initial composition.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application No. 63 / 312,328, filed on February 21, 2022, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0003] The present disclosure relates to a method comprising contacting an initial composition comprising (i) triglycerides and (ii) glycidol, glycidyl esters, or both glycidol and glycidyl esters with an effective amount of a silica-zirconia catalyst in a continuous reactor. The method can be used to produce a treated composition, such as a treated edible oil, having a reduced concentration of (ii) compared to the initial composition. Background Art

[0004] Glycidyl esters are known carcinogens and mutagens present in processed edible oils. These thermally generated contaminants are formed at temperatures as low as 200°C; however, much higher temperatures are required to remove the various volatile components in the oil during the deodorization process. After the crude oil has been refined, bleached and deodorized (RBD), additional oil processing is required to reduce the glycidyl ester concentration to acceptable regulatory limits. These reduction methods include a variety of process combinations, including but not limited to, contacting the oil with an enzyme, mixing the oil with acid shear, re-bleaching the oil and / or re-deodorizing at a lower temperature, but for a longer period of time. These known methods are not only inefficient and costly to operate, but also further reduce the quality of the oil and reduce the market price. Summary of the invention

[0005] In one aspect, disclosed herein is a method comprising: contacting an initial composition comprising (i) a triglyceride and (ii) glycidol, a glycidyl ester, or both glycidol and a glycidyl ester in a continuous reactor with an effective amount of a silica-zirconia catalyst to form a treated composition; wherein: the silica-zirconia catalyst comprises porous silica particles impregnated with zirconium oxide; and the concentration of (ii) in the treated composition is less than the concentration of (ii) in the initial composition.

[0006] In some embodiments, the continuous reactor is a packed bed reactor, a rotating bed reactor, a continuous stirred tank reactor (CSTR), a plug flow reactor, or a fluidized bed reactor. In some embodiments, the continuous reactor is a packed bed reactor.

[0007] In some embodiments, the silica-zirconia catalyst comprises particles having a median particle size of about 0.1 μm to about 10,000 μm. In some embodiments, the silica-zirconia catalyst comprises particles having a median particle size of about 50.0 μm to about 400 μm. In some embodiments, the silica-zirconia catalyst comprises particles having a median particle size of about 80.0 μm to about 300 μm.

[0008] In some embodiments, the silica-zirconia catalyst comprises a catalyst having about 50 m 2 / g to about 800m 2 In some embodiments, the silica-zirconia catalyst comprises particles having a BET particle surface area of ​​about 150 m 2 / g to about 450m 2 Particles with a BET particle surface area of ​​1000 μg / g.

[0009] In some embodiments, the silica-zirconia catalyst comprises particles having a pore volume of about 0.1 cc / g to about 3.0 cc / g as measured by the Barrett-Joyner-Halenda (BJH) method. In some embodiments, the silica-zirconia catalyst comprises particles having a pore volume of about 0.5 cc / g to about 2.5 cc / g as measured by the Barrett-Joyner-Halenda (BJH) method. In some embodiments, the silica-zirconia catalyst comprises particles having a pore volume of about 0.8 cc / g to about 2.0 cc / g as measured by the Barrett-Joyner-Halenda (BJH) method.

[0010] In some embodiments, the silica-zirconia catalyst exhibits a pH of about 9 or less than 9. In some embodiments, the silica-zirconia catalyst exhibits a pH of about 1 to about 8. In some embodiments, the silica-zirconia catalyst exhibits a pH of about 2 to about 7. In some embodiments, the silica-zirconia catalyst exhibits a pH of about 3 to about 6.

[0011] In some embodiments, the contacting step occurs at a temperature of about 20° C. to about 250° C. In some embodiments, the contacting step occurs at a temperature of about 30° C. to about 150° C. In some embodiments, the contacting step occurs at a temperature of about 40° C. to about 120° C.

[0012] In some embodiments, the contacting step is performed within about 1 hr. -1 To about 500hr -1In some embodiments, the contacting step occurs at a gravimetric space velocity of about 1 hr. -1 About 120 hours -1 Occurs at a weight airspeed of .

[0013] In some embodiments, the contacting step comprises mixing the initial composition and the silica-zirconia catalyst in a continuous reactor. In some embodiments, the contacting step comprises mixing the initial composition and the silica-zirconia catalyst in a continuous reactor under an inert gas flow or under vacuum. In some embodiments, the inert gas comprises nitrogen, argon, or a combination thereof.

[0014] In some embodiments, the initial composition further comprises an organic solvent. In some embodiments, the organic solvent comprises heptane, hexane, toluene, ether, alcohol or a combination thereof.

[0015] In some embodiments, the initial composition and the treated composition comprise edible oil. In some embodiments, the edible oil is soybean oil, palm oil, corn oil (com 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 a combination thereof. In some embodiments, the edible oil is soybean oil.

[0016] In some embodiments, the glycidyl ester is glycidyl oleate.

[0017] In some embodiments, the silica-zirconia catalyst is present in the continuous reactor at a weight percentage of less than about 2% relative to the amount of the treated composition. In some embodiments, the silica-zirconia catalyst is present in the continuous reactor at a weight percentage of less than about 0.5% relative to the amount of the treated composition. In some embodiments, the silica-zirconia catalyst is present in the continuous reactor at a weight percentage of less than about 0.1% relative to the amount of the treated composition. In some embodiments, the silica-zirconia catalyst is present in the continuous reactor at a weight percentage of less than about 0.05% relative to the amount of the treated composition. In some embodiments, the silica-zirconia catalyst is present in the continuous reactor at a weight percentage of less than about 0.01% relative to the amount of the treated composition.

[0018] In some embodiments, the concentration of (ii) in the treated composition is less than 1.0 ppm. In some embodiments, the concentration of (ii) in the treated composition is less than 0.5 ppm. In some embodiments, the concentration of (ii) in the treated composition is less than 0.2 ppm. In some embodiments, the concentration of (ii) in the treated composition is less than 0.05 ppm.

[0019] In another aspect, disclosed herein is a method of treating an initial edible oil to produce a treated edible oil, comprising the method of any one of the above embodiments, wherein the initial composition and the treated composition are the initial edible oil and the treated edible oil, respectively.

[0020] In some embodiments, the raw edible oil is refined, bleached and / or deodorized (RBD) prior to contacting with the silica-zirconia catalyst.

[0021] In some embodiments, the treated edible oil requires no processing after contacting with the silica-zirconia catalyst.

[0022] In some embodiments, the initial edible oil has an initial free fatty acid content measured as oleic acid content before contacting with the silica-zirconia catalyst, and the method changes the initial free fatty acid content measured by AOCS Official Method Ca 5a-40 by less than about 20%. In some embodiments, the initial edible oil has an initial free fatty acid content measured as oleic acid content before contacting with the silica-zirconia catalyst, and the method changes the initial free fatty acid content measured by AOCS Official Method Ca 5a-40 by less than about 10%.

[0023] In some embodiments, the initial edible oil has an initial p-anisidine value (p-AV) prior to contacting the silica-zirconia catalyst, and the method changes the initial p-anisidine value (p-AV) measured by AOCS Official Method Cd 18-90 by less than 10 units.

[0024] In some embodiments, the initial edible oil has an initial peroxide value (PV) prior to contacting the silica-zirconia catalyst, and the method changes the initial peroxide value measured by AOCS Official Method Cd 8-53 by less than 10 units.

[0025] In some embodiments, the continuous reactor is a packed bed reactor or a CSTR. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 Shown is a comparison of the reaction rate constants (k) for a packed bed process and a batch process using RBD SBO according to Example 1. Both processes used a silica-zirconia catalyst to reduce glycidyl oleate in RBD SBO.

[0027] Figure 2 The catalytic rate constants for the packed bed process using RBD palm oil according to Example 2 are shown. DETAILED DESCRIPTION

[0028] Various embodiments are described below. It should be noted that the specific embodiments are not intended to be exhaustive or limit the broader aspects discussed herein. An aspect described in conjunction with a specific embodiment is not necessarily limited to that embodiment and can be practiced with any other (one or more) embodiments.

[0029] Unless defined otherwise, all technical and scientific terms used herein generally have the same meaning as commonly understood by one of ordinary skill in the art to which this technology belongs.

[0030] It must be noted that as used herein and in the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "an oxide" includes a plurality of such oxides and reference to "the oxide" includes reference to one or more oxides and equivalents thereof known to those skilled in the art, and so forth.

[0031] As used herein, the term "about" modifies, for example, the amount, concentration, volume, process temperature, process time, recovery rate or yield, flow rate, and similar values ​​and ranges thereof of the components in the coated particles and / or compositions used when describing the embodiments of the present disclosure, and refers to the numerical amount variation that may occur, for example, by typical measurement and processing procedures; by inadvertent errors in these procedures; by differences in the components used to implement the method; and similar approximate considerations. The term "about" also includes amounts that differ due to aging of formulations with a specific initial concentration or mixture, and amounts that differ due to mixing or processing formulations with a specific initial concentration or mixture. If the usage of the term is unclear to a person of ordinary skill in the art considering the context in which it is used, "about" will mean a maximum of plus or minus 10% of the specific term. Whether or not modified by the term "about", the attached claims herein include equivalents.

[0032] As used herein, "batch reactor" refers to a closed system in which a reactor is filled with a medium and reactants. The reactants are allowed to react in the reactor for a fixed period of time. No feed is added or product is removed during this period. The reaction product is removed at the end of the reaction. The reactor may have an agitator and an internal heating or cooling system. In some cases, a batch reactor may be operated in a semi-batch mode in which one chemical is charged into the reactor and a second chemical is added slowly.

[0033] As used herein, the term "BET particle surface area" is defined to mean the surface area of ​​a particle as measured by the Brunauer Emmet Teller (BET) nitrogen adsorption method.

[0034] As used herein, "continuous reactor" refers to a reactor characterized by a continuous flow of reactants into the reaction system and a continuous flow of products out of the reaction system (e.g., a packed bed reactor, a rotating bed reactor, a continuously stirred tank reactor (CSTR), a plug flow reactor, or a fluidized bed reactor).

[0035] As used herein, the term "weight space velocity" refers to the mass flow rate (grams / hour) of a composition comprising reactants per unit mass of catalyst (grams) and is given by the following formula:

[0036]

[0037] Among them, m o is the amount of catalyst m used in a given time t (hours) c (g) Mass of oil treated (g).

[0038] As used herein, the term "particle size" refers to the median particle size (D50, which is the volume distribution in size at which 50% by volume of the particles are smaller than this value and 50% by volume of the particles are larger than this value) measured by dynamic light scattering when the particles are slurried in water or an organic solvent (e.g., acetone or ethanol).

[0039] As used herein, the term "pore volume" refers to the median pore volume of a plurality of particles (e.g., the silica-zirconia particles disclosed herein) as measured using the Barrett-Joyner-Halenda (BJH) nitrogen porosimetry method as described in DIN 66134, which is incorporated herein by reference in its entirety.

[0040] In one aspect, a method comprises contacting an initial composition comprising (i) a triglyceride and (ii) glycidol, a glycidyl ester, or both glycidol and glycidyl ester with an effective amount of a silica-zirconia catalyst in a continuous reactor to form a treated composition, wherein the silica-zirconia catalyst comprises porous silica particles impregnated with zirconium oxide; and wherein the concentration of (ii) in the treated composition is lower than the concentration of (ii) in the initial composition. The method according to the present disclosure can be used to reduce the concentration of glycidol, glycidyl ester, or both glycidol and glycidyl ester in the initial composition. The method reduces the concentration of glycidol, glycidyl ester, or both glycidol and glycidyl ester in the initial composition by at least 50% while utilizing relatively low reaction times and temperatures.

[0041] Unexpectedly, it has been found that the use of a silica-zirconia catalyst in a continuous reactor (e.g., a packed bed reactor) improves reaction kinetics and slows down catalyst deactivation of the silica-zirconia catalyst compared to a silica-zirconia catalyst in a batch reactor. In some embodiments, the use of a silica-zirconia catalyst in a continuous reactor increases the reaction constant (k) of the silica-zirconia catalyst by at least about 1% compared to the reaction constant (k) of the silica-zirconia catalyst in the batch process example, when other reaction parameters are consistent with the batch process. This includes about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11% or 12% of the reaction constant increment. In some embodiments, the increment is about 8% to about 12%. Therefore, compared to the silica-zirconia catalyst in the batch reactor, the catalyst life of the silica-zirconia catalyst is increased by using a silica-zirconia catalyst in a continuous reactor, and the total silica-zirconia dosage required to reduce the same amount of total glycidol is reduced.

[0042] Any continuous reactor known to those skilled in the art may be used. Exemplary continuous reactors include, but are not limited to, a packed bed reactor, a rotating bed reactor, a continuous stirred tank reactor (CSTR), a plug flow reactor, or a fluidized bed reactor.

[0043] In some embodiments, the continuous reactor can be a packed bed reactor. A packed bed reactor, also referred to as a fixed bed reactor, can be a cylindrical tube filled with catalyst pellets (e.g., a silica-zirconia catalyst), and reactants (e.g., an initial composition comprising (i) triglycerides and (ii) glycidol, glycidyl esters, or both glycidyl and glycidyl esters) are converted to products as they flow through the bed. The catalyst can be in one or more of a variety of configurations, such as, but not limited to, one large bed, several horizontal beds, several parallel packed tubes, or multiple beds in their own shells. Various configurations can be adjusted according to the need to maintain temperature control within the system. The reactants in a fixed bed reactor can flow downward under gravity.

[0044] In some embodiments, the continuous reactor can be a rotating bed reactor. A rotating bed reactor holds a packed bed in a basket having a central hole. As the basket rotates immersed in the fluid phase, the inertial force generated by the rotating motion forces the fluid outward, thereby generating a circulating flow through the rotating packed bed. Compared to a packed bed reactor, a rotating bed reactor exhibits relatively high mass / heat transfer rates and good fluid mixing.

[0045] In some embodiments, the continuous reactor can be a continuous stirred tank reactor (CSTR). A CSTR is an open system in which materials freely enter or leave the system, which is based on steady-state operation, where the conditions in the reactor do not change over time. Reactants are continuously introduced into the reactor, while products are continuously removed. CSTRs are well mixed, so the contents have relatively uniform properties, such as temperature, density, etc., throughout the process. In addition, the conditions in the reactor exit stream are the same as those in the tank.

[0046] In some embodiments, the continuous reactor can be a fluidized bed reactor. In this type of reactor, a fluid (e.g., an initial liquid composition comprising (i) triglycerides and (ii) glycidol, glycidyl esters, or both glycidol and glycidyl esters) is passed through a solid particulate material (e.g., a silica-zirconia catalyst) at a sufficiently high rate to suspend the solids and make them behave like a fluid. This process is called fluidization, which confers many important advantages to packed bed reactors. A key advantage of using a fluidized bed reactor is the ability to achieve very uniform temperatures in the reactor.

[0047] The silica-zirconia catalyst of the present technology can be formed by a zirconium oxide coating and / or impregnation step, followed by one or more additional steps, such as a drying step, a calcination step, or both. See International Application Publication No. WO202026905, which is incorporated herein by reference in its entirety. The method for preparing a silica-zirconia catalyst suitable for use in the method described herein comprises impregnating porous silica particles with zirconium acetate in acetic acid and 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. Typically, the method for preparing a silica-zirconia catalyst includes an impregnation step that allows the porous silica particles and zirconium acetate to contact for a desired period of time, such as 30 minutes or any desired period of time. After the impregnation step and before the drying step, the method for preparing a silica-zirconia catalyst comprises grinding the impregnated porous silica particles for about 60 minutes. It should be understood that the impregnated porous silica particles may be ground (or milled) for any desired period of time.Zirconium oxide may be impregnated onto at least a portion of the surface of the porous silica particles, and / or at least a portion of the pores of the porous silica particles.

[0048] Suitable porous silica particles that can be used to prepare the silica-zirconia catalysts of the present disclosure include, but are not limited to, silica gel, precipitated silica, fumed silica, and colloidal silica. Suitable porous silica also includes, but is not limited to, ordered mesoporous silica that is prepared by an organic template (e.g., a surfactant) during the silica particle formation process and then subjected to a high temperature treatment to "burn off" the organic matter. Particularly preferred porous silica particles include silica gel or precipitated silica particles. Any commercially available porous silica particles can be used to form the silica-zirconia catalysts of the present disclosure. Commercially available porous silica particles that can be used to form the silica-zirconia catalysts of the present disclosure include, but are not limited to, those available under the trade names Particles purchased from WR Grace (Columbia, MD), such as C807 silica gel particles and MX106 precipitated silica particles, Silica particles and Silica particles. The porous silica particles used to form the silica-zirconia catalyst of the present disclosure include porous silica having a purity of at least about 93.0 wt. % SiO2, 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, at least about 98.0 wt. % SiO2, or up to 100 wt. % SiO2, based on the total weight of the porous silica particles. The porous silica particles used to form the silica-zirconia catalyst of the present disclosure can have a variety of symmetrical, asymmetrical or irregular shapes, including chain-like, rod-like or lath-like. The porous silica particles can have different structures, including amorphous or crystalline, etc. The porous silica particles can include mixtures of particles having different compositions, sizes, shapes or physical structures, or particles that are identical except for different surface treatments. The porosity of the porous silica particles can be intra-particle or inter-particle porosity in the case where smaller particles agglomerate to form larger particles.

[0049] In some embodiments, the silica-zirconia catalysts of the present techniques include at least about 0.01 weight percent (wt. %) zirconium oxide, based on the total weight of the silica-zirconia catalyst. In some embodiments, the silica-zirconia catalysts of the present technology contain about 0.01 wt.% to about 1.0 wt.%, about 1.0 wt.% to about 5.0 wt.%, about 5.0 wt.% to about 10.0 wt.%, about 10.0 wt.% to about 15.0 wt.%, about 15.0 wt.% to about 20.0 wt.%, about 20.0 wt.% to about 25.0 wt.%, about 25.0 wt.% to about 30.0 wt.%, about 30.0 wt.% to about 35.0 wt.%, about 35.0 wt.% to about 40.0 wt.%, about 40.0 wt.% to about 45.0 wt.%, or 45.0 wt.% to about 50.0 wt.% zirconia, based on the total weight of the silica-zirconia catalyst. In some embodiments, the silica-zirconia catalyst of the present technology comprises about 1.5 wt.% to about 14.3 wt.% of zirconium oxide based on the total weight of the silica-zirconia catalyst. In some embodiments, the silica-zirconia catalyst of the present technology comprises about 2.4 wt.% to about 5.0 wt.% of zirconium oxide based on the total weight of the silica-zirconia catalyst. It should be understood that the silica-zirconia catalyst of the present technology can contain any amount of zirconium oxide in the range of about 0.01 wt.% to about 50.0 wt.% (or greater) (or any amount of zirconium oxide range between about 0.01 wt.% and about 50.0 wt.% in increments of 0.01 wt.%, for example, about 0.02 wt.% to about 49.99 wt.%).

[0050] In some embodiments, the silica-zirconia catalyst has a median particle size of about 0.1 μm to about 10,000 μm (or any range of median particle sizes between about 0.1 μm and about 10,000 μm in 0.1 μm increments, such as about 0.2 μm to about 9,999.9 μm). In some embodiments, the silica-zirconia catalysts of the present technology have a median particle size of about 50 μm to about 75 μm, about 75 μm to about 100 μm, about 100 μm to about 125 μm, about 125 μm to about 150 μm, about 150 μm to about 175 μm, about 175 μm to about 200 μm, about 200 μm to about 225 μm, about 225 μm to about 250 μm, about 250 μm to about 275 μm, about 275 μm to about 300 μm, about 300 μm to about 325 μm, about 325 μm to about 350 μm, about 350 μm to about 375 μm, or about 375 μm to about 400 μm. In some embodiments, the silica-zirconia catalysts of the present technology have a median particle size of about 80 μm to about 300 μm.

[0051] In some embodiments, the silica-zirconia catalysts of the present technology may have a 2 / g, at least about 25.0m 2 / g, up to about 2000m 2 / g or more of BET particle surface area. In some embodiments, the silica-zirconia catalyst has a BET particle surface area of ​​about 50 m 2 / g to about 100m 2 / g, about 100m 2 / g to about 150m 2 / g, about 150m 2 / g to about 200m 2 / g, about 200m 2 / g to about 250m 2 / g, about 250m 2 / g to about 300m 2 / g, about 300m 2 / g to about 350m 2 / g, about 350m 2 / g to about 400m 2 / g, about 400m 2 / g to about 450m 2 / g, about 450m 2 / g to about 500m 2 / g, about 500m 2 / g to about 550m 2 / g, about 550m 2 / g to about 600m 2 / g, about 600m2 / g to about 650m 2 / g, about 650m 2 / g to about 700m 2 / g, about 700m 2 / g to about 750m 2 / g or about 750m 2 / g to about 800m 2 / g. However, it should be understood that the silica-zirconia catalyst of the present technology may have a 2 / g to about 2000m 2 / g (or larger) range (or 0.1m 2 / g is in increments of about 10m 2 / g and about 2000m 2 Any range of BET particle surface area values ​​between about 10.1 m / g, for example, about 10.1 m 2 / g to about 1999.9m 2 / g) of any BET particle surface area.

[0052] In some embodiments, the silica-zirconia catalysts of the present techniques may have a pore volume of at least 0.01 cubic centimeter per gram (cc / g) as determined by the Barrett-Joyner-Halenda (BJH) method. In some embodiments, the silica-zirconia catalyst has a relative humidity of about 0.01 cc / g to about 0.1 cc / g, about 0.1 cc / g to about 0.2 cc / g, about 0.2 cc / g to about 0.3 cc / g, about 0.3 cc / g to about 0.4 cc / g, about 0.4 cc / g to about 0.5 cc / g, about 0.5 cc / g to about 0.6 cc / g, about 0.6 cc / g to about 0.7 cc / g, about 0.7 cc / g to about 0.8 cc / g, about 0.8 cc / g to about 0.9 cc / g, about 0.9 cc / g to about 1.0 cc / g, about 1.0 cc / g to about 1.1 cc / g, about 1.1 cc / g to about 1.2 cc / g, about 1.2 cc / g to about 1.3 cc / g, about 1.3 cc / g to about about 1.4cc / g, about 1.4cc / g to about 1.5cc / g, about 1.5cc / g to about 1.6cc / g, about 1.6cc / g to about 1.7cc / g, about 1.7cc / g to about 1.8cc / g, about 1.8cc / g to about 1.9cc / g, about 1.9cc / g to about 2.0cc / g, about 2.0cc / g to about 2.1cc / g, about 2.1cc / g to about 2.2cc In some embodiments, the silica-zirconia catalyst has a pore volume of about 0.1 cc / g to about 2.5 cc / g, about 0.5 cc / g to about 2.5 cc / g, about 0.8 cc / g to about 2.0 cc / g, about 0.1 cc / g to about 2.5 cc / g, about 0.5 cc / g to about 2.5 cc / g, about 0.8 cc / g to about 2.0 cc / g, about 0.6 cc / g to about 2.7 cc / g, about 0.6 cc / g to about 2.8 cc / g, about 0.7 cc / g to about 2.8 cc / g, about 0.8 cc / g to about 2.9 cc / g, or about 0.9 cc / g to about 3.0 cc / g. In some embodiments, the silica-zirconia catalyst has a pore volume of about 0.1 cc / g to about 2.5 cc / g, about 0.5 cc / g to about 2.5 cc / g, or about 0.8 cc / g to about 2.0 cc / g as determined by the Barrett-Joyner-Halenda (BJH) method. However, it should be understood that the silica-zirconia catalysts of the present technology can have a pore volume of about 0.01 cc / g to about 3.00 cc / g (or greater) (or any pore volume range between about 0.01 cc / g and about 3.0 cc / g in increments of 0.01 cc / g, e.g., about 0.02 cc / g to about 2.99 cc / g) as determined by the Barrett-Joyner-Halenda (BJH) method.

[0053] In some embodiments, the silica-zirconia catalyst exhibits a pH of about 9, less than 9, less than 8, less than 7, less than 6, less than 5, less than 4, less than 3, less than 2, or less than 1. In some embodiments, the silica-zirconia catalyst exhibits a pH of about 1 to about 8. In some embodiments, the silica-zirconia catalyst exhibits a pH of about 2 to about 7. In some embodiments, the silica-zirconia catalyst exhibits a pH of about 3 to about 6.

[0054] In some embodiments, the disclosed method comprises contacting an initial composition comprising (i) a triglyceride and (ii) glycidol, a glycidyl ester, or both glycidol and a glycidyl ester with an effective amount of a silica-zirconia catalyst in a continuous reactor at room temperature (e.g., about 20-25° C.), up to about 250° C. In some embodiments, the contacting step is at about 20° C. to about 30° C., about 30° C. to about 40° C., about 40° C. to about 50° C., about 50° C. to about 60° C., about 60° C. to about 70° C., about 70° C. to about 80° C., about 80° C. to about 90° C., about 90° C. to about 100° C., about 100° C. to about 110° C., about 110° C. to about 120° C., about 120° C. to about 130° C., about 130° C. to about 140° C. In some embodiments, the contacting step occurs at a temperature of about 90.0° C., about 140° C. to about 150° C., about 150° C. to about 160° C., about 160° C. to about 170° C., about 170° C. to about 180° C., about 180° C. to about 190° C., about 190° C. to about 200° C., about 200° C. to about 210° C., about 210° C. to about 220° C., about 220° C. to about 230° C., about 230° C. to about 240° C., or about 240° C. to about 250° C. In some embodiments, the contacting step occurs at a temperature of about 90.0° C.

[0055] In some embodiments, the contacting step is performed at about 0.1 hr. -1 To about 500hr -1 In some embodiments, the contacting step occurs at a weight space velocity of about 0.1 hr -1 About 5 hours -1 , about 5 hours -1 About 10 hours -1 , about 10 hours -1 About 20 hours -1 , about 20 hours -1 To about 30 hours -1 , about 30 hours -1 About 40 hours -1 , about 40hr -1 To about 50 hours -1 , about 50hr -1 About 60 hours -1 , about 60hr -1 To about 70 hours-1 , about 70hr -1 About 80 hours -1 , about 80hr -1 To about 90 hours -1 , about 90hr -1 To about 100hr -1 , about 100hr -1 To about 110hr -1 , about 110hr -1 About 120 hours -1 , about 120hr -1 About 180 hours -1 , about 180hr -1 About 240 hours -1 , about 240hr -1 To about 300hr -1 , about 300hr -1 About 360 hours -1 , about 360hr -1 To about 420hr -1 or about 420hr -1 To about 500hr -1 Occurs at a weight airspeed of .

[0056] In some embodiments, the disclosed methods include contacting an initial composition comprising (i) a triglyceride and (ii) glycidol, a glycidyl ester, or both glycidol and a glycidyl ester with an effective amount of a silica-zirconia catalyst in a continuous reactor under a flow of an inert gas or under vacuum (to minimize the oxygen concentration in the atmosphere).

[0057] In some embodiments, the contacting step occurs under vacuum wherein the pressure in the continuous reactor is from about 0.05 bar to about 0.1 bar, from about 0.10 bar to about 0.20 bar, from about 0.20 bar to about 0.30 bar, from about 0.30 bar to about 0.40 bar, from about 0.40 bar to about 0.50 bar, from about 0.50 bar to about 0.60 bar, from about 0.60 bar to about 0.70 bar, from about 0.70 bar to about 0.80 bar, from about 0.80 bar to about 0.90 bar, or from about 0.90 bar to about 0.95 bar.

[0058] In some embodiments, the contacting step occurs under a flow of an inert gas, wherein the inert gas comprises nitrogen, argon, or a combination thereof.

[0059] In some embodiments, the initial composition further comprises an organic solvent. In some embodiments, the organic solvent comprises heptane, hexane, toluene, ether, alcohol or a combination thereof.

[0060] In some embodiments, the initial composition and the treated composition comprise edible oils. Suitable edible 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. In some embodiments, the edible oil is soybean oil.

[0061] In some embodiments, the glycidyl ester is glycidyl oleate.

[0062] In some embodiments, the silica-zirconia catalyst is present in the continuous reactor at a weight percentage of less than about 2% relative to the amount of the treated composition. In some embodiments, the silica-zirconia catalyst is present in the continuous reactor at a weight percentage of less than about 1%, less than about 0.5%, less than about 0.1%, less than about 0.05%, or less than about 0.01% relative to the amount of the treated composition.

[0063] In some embodiments, the concentration of glycidol, glycidyl esters, or both glycidol and glycidyl esters in the treated composition is less than about 1.0 ppm, less than about 0.9 ppm, less than about 0.8 ppm, less than about 0.7 ppm, less than about 0.6 ppm, less than about 0.5 ppm, less than about 0.4 ppm, less than about 0.3 ppm, less than about 0.2 ppm, less than about 0.1 ppm, or less than about 0.05 ppm.

[0064] In another aspect, the present disclosure provides a method for treating an initial edible oil to produce a treated edible oil, comprising the method of any one of the above embodiments, wherein the initial composition and the treated composition are the initial edible oil and the treated edible oil, respectively.

[0065] In some embodiments, the edible oil is refined, bleached, and / or deodorized (RBD) prior to contacting with the silica-zirconia catalyst.

[0066] In some embodiments, the treated edible oil requires no processing after contacting with the silica-zirconia catalyst (i.e., requires no further processing including, but not limited to, contacting the oil with an enzyme, shear mixing the oil with an acid, re-bleaching the oil and / or re-deodorizing the oil at a lower temperature but for a longer period of time, or any combination of the foregoing process steps).

[0067] In some embodiments, the disclosed methods for treating a given initial edible oil are capable of reducing the concentration of glycidol, glycidyl esters, or both glycidol and glycidyl esters in the edible oil to extremely low levels with little effect on (i) the free fatty acid content of the edible oil as measured by AOCS Official Method Ca 5a-40, such as oleic acid content, and / or (ii) the oxidation level of the edible oil as measured by (a) the p-anisidine value of the edible oil as measured, for example, by AOCS Official Method Cd 18-90, (b) the peroxide value of the edible oil as measured, for example, by AOCS Official Method Cd 8-53, or (c) both (a) and (b). AOCS Official Methods Ca 5a-40, 18-90, and 8-53 are incorporated herein by reference in their entirety. The methods described in AOCS Official Methods Ca 5a-40, 18-90, and 8-53 are also well known to those skilled in the art.

[0068] In some embodiments, the method has a negligible change in the free fatty acid (e.g., oleic acid) content of the edible oil as measured by AOCS official method Ca 5a-40. In some embodiments, the initial edible oil has an initial free fatty acid content measured as oleic acid content before contacting with the silica-zirconia catalyst, and the method changes the initial free fatty acid content measured by AOCS official method Ca 5a-40 by less than about 20%, less than about 19%, less than about 18%, less than about 17%, less than about 16%, less than about 15%, less than about 14%, less than about 13%, less than about 12%, less than about 11%, less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, or less than about 1%.

[0069] In some embodiments, the initial edible oil has an initial p-anisidine value (p-AV) prior to contacting the silica-zirconia catalyst, and the method changes the initial p-anisidine value (p-AV) measured by AOCS Official Method Cd 18-90 by less than 10 units, less than 9 units, less than 8 units, less than 7 units, less than 6 units, less than 5 units, less than 4 units, less than 3 units, less than 2 units, or less than 1 unit.

[0070] In some embodiments, the initial edible oil has an initial peroxide value (PV) prior to contacting the silica-zirconia catalyst, and the method changes the initial peroxide value measured by AOCS Official Method Cd 8-53 by less than 10 units, less than 9 units, less than 8 units, less than 7 units, less than 6 units, less than 5 units, less than 4 units, less than 3 units, less than 2 units, or less than 1 unit.

[0071] In some embodiments, the continuous reactor may be a packed bed reactor or a CSTR.

[0072] The present disclosure is further illustrated by the following examples, which should not be interpreted in any way as constituting an imposed limitation on its scope. On the contrary, it will be clearly understood that various other embodiments, modifications and their equivalents that may occur to those skilled in the art after reading the specification herein without departing from the spirit of the present disclosure and / or the scope of the appended claims may be employed.

[0073] Example

[0074] Various embodiments are described below. It should be noted that the specific embodiments are not intended to be exhaustive or limit the broader aspects discussed herein. An aspect described in conjunction with a specific embodiment is not necessarily limited to that embodiment and can be practiced with any other (one or more) embodiments.

[0075] Catalyst Evaluation, Methods and Materials

[0076] Nitrogen pore volume and BET surface area measurements of silica-zirconia particle samples

[0077] The silica-zirconia materials disclosed in the present invention are typical mesoporous materials (pore size 2-50 nm, IUPAC definition), usually showing a type IV isotherm (IUPAC classification). Therefore, nitrogen porosimetry is a suitable method for characterizing them, and the determination of surface area using the BET method and the determination of pore volume from nitrogen adsorption and desorption isotherms using the BJH method are well-established and suitable methods and are used herein. The nitrogen pore volume of the silica-zirconia catalysts was measured using a TriStar Analyzer, Model 3000 and Model II Plus, Micromeritics Instrument Corporation, One Micromeritics Drive, Norcross, Georgia. Prior to analysis, the samples were activated at 400°C for 2 hours in flowing air or nitrogen. At low P / P o = ~0.3 to 0.4 partial pressure, the surface area was calculated from multiple point values ​​of nitrogen volume uptake during the adsorption branch. o =0.967 partial pressure, the adsorption branch of the isotherm stopped, and then the desorption branch of the isotherm was measured. The pore volume was calculated from the desorption branch using the BJH method.

[0078] Total Glycidol Concentration Analysis

[0079] The total glycidol concentration of a given sample was determined using AOCS Official Method Cd 29c-13 (the subject matter of which is incorporated herein by reference in its entirety). 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.

[0080] Reaction rate constants / kinetic analysis

[0081] The reaction rate constants for batch reactors and continuous flow reactors are calculated using the following formula:

[0082]

[0083] Among them, m o is the amount of catalyst m used in a given time t (minutes) c (g) is the mass of the treated oil (g). C0 (ppm) is the concentration of total glycidol in the initial oil, C f (ppm) is the concentration of total glycidol in the treated oil.

[0084] Catalyst synthesis

[0085] The porous silica-zirconia catalyst particles were prepared using the following procedure. The required amount of zirconium acetate was diluted in acetic acid with water and used to impregnate the porous silica particles over the course of 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.

[0086] The resulting silica-zirconia catalyst has a zirconium oxide concentration in the range of 0.01 wt.% to 49.99 wt.%. As discussed further below, in some embodiments, a silica-zirconia catalyst having a zirconium oxide concentration in the range of about 2.00 wt.% to about 20.00 wt.% provides effective results. The final zirconium oxide concentration is determined using ICP elemental trace analysis.

[0087] Twelve silica-zirconia catalyst samples were used to evaluate the reaction kinetics and determine the first-order reaction rate constant. The properties of catalysts A to L are shown in Table 1 below. To determine the reaction rate constant associated with each catalyst, 100 grams of soybean oil spiked with glycidyl oleate was added to a round-bottom flask equipped with an argon stream to displace any oxygen present. The mixing was set to 250 rpm and the oil temperature was raised to 90°C. Once the oil temperature reached 90°C, 2 grams of catalyst were added to the reactor. After 15 minutes, stirring and temperature control were turned off and the catalyst was filtered off. The total glycidol in the initial oil and the final oil was measured. This procedure was repeated for each catalyst listed below (Table 1).

[0088] Table 1. Silica-zirconia catalysts used in this study.

[0089]

[0090] Example 1 - Packed Bed Process Using RBD Soybean Oil Doped with Glycidyl Oleate

[0091] The most active catalyst (Catalyst E in Table 1) was selected for testing in a packed bed process for comparison with a batch process using recycled catalyst.

[0092] Batch Process for RBD Soybean Oil Spiked with Glycidyl Oleate Using Recycled Catalyst

[0093] 2 kg of RBD soybean oil (SBO) was spiked with glycidyl oleate. Spiked SBO (100 grams) was charged into a round bottom flask equipped with an argon flow to displace any oxygen present. Mixing was set to 250 rpm and the oil temperature was raised to 90°C. Once the oil temperature reached 90°C, 2 grams of Catalyst E were added to the reactor. After 15 minutes, stirring and temperature control were turned off and the catalyst was filtered off. The treated oil was analyzed for glycidyl oleate levels. The procedure was repeated 19 more times using 2 grams of Catalyst E recovered from the previous step and 87 grams of fresh spiked SBO.

[0094] Packed bed process using RBD soybean oil doped with glycidyl oleate

[0095] The packed bed reactor was filled with glass wool supplied by Thermo Scientific (Cat. No. 386062500), inert zirconium oxide beads from Bio Spec Products (Cat. No. NC0362415), and 2 grams of Catalyst E. The catalyst bed was heated to 90°C, and then RBD SBO was started to flow through the device at 6.7 g / min to match the conditions of the batch process described above (100 g oil and 2 g catalyst for 15 minutes contact time).

[0096] exist Figure 1 The first order reaction rate constants for the two processes are summarized and compared in Table 2. The data show that when the same amount of catalyst E is used to treat the same amount of spiked SBO, the first order reaction rate constant in the packed bed reactor is higher by more than 8% to more than 12% compared to the batch process using recycled catalyst. As shown in Table 3, this difference is statistically significant with a paired two-sample t-test of P = 0.00046 at a 95% confidence interval well below 0.05. The data also show that the catalyst deactivates more slowly in the packed bed process, meaning that the packed bed process produces a lower total glycidol concentration after treating the same amount of oil, thereby extending the active life of the catalyst. Therefore, the total silica-zirconia dosage requirements in the packed bed process are lower than those required in the recycled batch process.

[0097] Table 2. Rate constants for packed bed process vs. batch process

[0098]

[0099] Table 3. Paired two-sample mean t-test

[0100]

[0101]

[0102] Example 2 - Packed Bed Process Using RBD Palm Oil

[0103] The packed bed reactor was filled with glass wool supplied by Thermo Scientific (Cat. No. 386062500), inert zirconium oxide beads from Bio Spec Products (Cat. No. NC0362415) and 2 grams of Catalyst E. The catalyst bed was heated to 90°C and then RBD palm oil having a total glycidol content of 3.34 ppm was started to flow through the apparatus at 3.4 g / min, corresponding to a weight space velocity of 102 hr -1 The reaction was continued until 5,500 g of palm oil had been treated with the catalyst. The total catalyst dosage was 0.036 wt% (g catalyst / 100 g oil), and although the catalyst deactivated during the test run, the final catalyst activity ( Figure 2 ) is still sufficient to reduce the glycidol level in the oil to below 0.061 ppm.

[0104] The performance of the catalyst was then tested at various space velocities by varying the flow rate of palm oil through the packed bed, with all other conditions remaining constant. Under each set of conditions, 100 g of RBD palm oil was reacted. The results are summarized in Table 4, showing that the catalyst had a room temperature of 100 ℃ and a room temperature of 200 ℃. -1 At an air velocity of 1.3 0.1 g / cm3, the glycidol level in the treated palm oil remained below 1 ppm.

[0105] Table 4. Packed Bed Reactor Performance vs. Weight Space Velocity

[0106]

[0107] Specific Implementation

[0108] Embodiment 1. A method comprising:

[0109] contacting an initial composition comprising (i) a triglyceride and (ii) glycidol, a glycidyl ester, or both glycidol and a glycidyl ester with an effective amount of a silica-zirconia catalyst in a continuous reactor to form a treated composition;

[0110] in:

[0111] The silica-zirconia catalyst comprises porous silica particles impregnated with zirconium oxide; and

[0112] The concentration of (ii) in the treated composition is less than the concentration of (ii) in the initial composition.

[0113] Embodiment 2. The method of Embodiment 1, wherein the continuous reactor is a packed bed reactor, a rotating bed reactor, a continuous stirred tank reactor (CSTR), a plug flow reactor, or a fluidized bed reactor.

[0114] Embodiment 3. The method of Embodiment 1 or Embodiment 2, wherein the continuous reactor is a packed bed reactor.

[0115] Embodiment 4. The method of any of Embodiments 1-3, wherein the silica-zirconia catalyst comprises particles having a median particle size of about 0.1 μm to about 10,000 μm.

[0116] Embodiment 5. The method of any of Embodiments 1-4, wherein the silica-zirconia catalyst comprises particles having a median particle size of about 50.0 μm to about 400 μm.

[0117] Embodiment 6. The method of any of Embodiments 1-5, wherein the silica-zirconia catalyst comprises particles having a median particle size of about 80.0 μm to about 300 μm.

[0118] Embodiment 7. The method of any one of Embodiments 1-6, wherein the silica-zirconia catalyst comprises a catalyst having a 2 / g to about 800m 2 Particles with a BET particle surface area of ​​1000 μg / g.

[0119] Embodiment 8. The method of any one of Embodiments 1-7, wherein the silica-zirconia catalyst comprises a catalyst having a 2 / g to about 450m 2 Particles with a BET particle surface area of ​​1000 μg / g.

[0120] Embodiment 9. The method of any of Embodiments 1-8, wherein the silica-zirconia catalyst comprises particles having a pore volume of about 0.1 cc / g to about 3.0 cc / g as determined by the Barrett-Joyner-Halenda (BJH) method.

[0121] Embodiment 10. The method of any of Embodiments 1-9, wherein the silica-zirconia catalyst comprises particles having a pore volume of about 0.5 cc / g to about 2.5 cc / g as determined by the Barrett-Joyner-Halenda (BJH) method.

[0122] Embodiment 11. The method of any of Embodiments 1-10, wherein the silica-zirconia catalyst comprises particles having a pore volume of about 0.8 cc / g to about 2.0 cc / g as determined by the Barrett-Joyner-Halenda (BJH) method.

[0123] Embodiment 12. The method of any of Embodiments 1-11, wherein the silica-zirconia catalyst exhibits a pH of about 9 or less.

[0124] Embodiment 13. The method of any of Embodiments 1-12, wherein the silica-zirconia catalyst exhibits a pH of about 1 to about 8.

[0125] Embodiment 14. The method of any of Embodiments 1-13, wherein the silica-zirconia catalyst exhibits a pH of about 2 to about 7.

[0126] Embodiment 15. The method of any of Embodiments 1-14, wherein the silica-zirconia catalyst exhibits a pH of about 3 to about 6.

[0127] Embodiment 16. The method of any of Embodiments 1-15, wherein the contacting step occurs at a temperature of about 20°C to about 250°C.

[0128] Embodiment 17. The method of any of Embodiments 1-16, wherein the contacting step occurs at a temperature of about 30°C to about 150°C.

[0129] Embodiment 18. The method of any of Embodiments 1-17, wherein the contacting step occurs at a temperature of about 40°C to about 120°C.

[0130] Embodiment 19. The method of any one of Embodiments 1-18, wherein the contacting step is performed in about 1 hour. -1 To about 500hr -1 Occurs at a weight airspeed of .

[0131] Embodiment 20. The method of any one of Embodiments 1-19, wherein the contacting step is performed in about 1 hour. -1 About 120 hours -1 Occurs at a weight airspeed of .

[0132] Embodiment 21. The method of any of Embodiments 1-20, wherein the contacting step comprises mixing the initial composition and the silica-zirconia catalyst in a continuous reactor.

[0133] Embodiment 22. The method of any one of Embodiments 1-21, wherein the contacting step comprises mixing the initial composition and the silica-zirconia catalyst in a continuous reactor under a flow of an inert gas or under vacuum.

[0134] Embodiment 23. The method of Embodiment 22, wherein the inert gas comprises nitrogen, argon, or a combination thereof.

[0135] Embodiment 24. The method of any one of Embodiments 1-23, wherein the initial composition further comprises an organic solvent.

[0136] Embodiment 25. The method of Embodiment 24, wherein the organic solvent comprises heptane, hexane, toluene, diethyl ether, alcohol or a combination thereof.

[0137] Embodiment 26. The method of any one of Embodiments 1-25, wherein the initial composition and the treated composition comprise edible oil.

[0138] Embodiment 27. The method of embodiment 26, wherein the edible oil is 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 a combination thereof.

[0139] Embodiment 28. The method of any one of Embodiments 26-27, wherein the edible oil is soybean oil.

[0140] Embodiment 29. The method of any one of Embodiments 1-28, wherein the glycidyl ester is glycidyl oleate.

[0141] Embodiment 30. The method of any of Embodiments 1-29, wherein the silica-zirconia catalyst is present in the continuous reactor at a weight percent of less than about 2% relative to the amount of the treated composition.

[0142] Embodiment 31. The method of any of Embodiments 1-30, wherein the silica-zirconia catalyst is present in the continuous reactor at a weight percent of less than about 0.5% relative to the amount of the treated composition.

[0143] Embodiment 32. The method of any of Embodiments 1-31, wherein the silica-zirconia catalyst is present in the continuous reactor at a weight percent of less than about 0.1% relative to the amount of the treated composition.

[0144] Embodiment 33. The method of any of Embodiments 1-32, wherein the silica-zirconia catalyst is present in the continuous reactor at a weight percent of less than about 0.05% relative to the amount of the treated composition.

[0145] Embodiment 34. The method of any of Embodiments 1-33, wherein the silica-zirconia catalyst is present in the continuous reactor at a weight percent of less than about 0.01% relative to the amount of the treated composition.

[0146] Embodiment 35. The method of any one of Embodiments 1-34, wherein the concentration of (ii) in the treated composition is less than 1.0 ppm.

[0147] Embodiment 36. The method of any one of Embodiments 1-35, wherein the concentration of (ii) in the treated composition is less than 0.5 ppm.

[0148] Embodiment 37. The method of any one of Embodiments 1-36, wherein the concentration of (ii) in the treated composition is less than 0.2 ppm.

[0149] Embodiment 38. The method of any one of Embodiments 1-37, wherein the concentration of (ii) in the treated composition is less than 0.05 ppm.

[0150] Embodiment 39. A method of treating an initial edible oil to produce a treated edible oil, comprising the method of any one of embodiments 1-38, wherein the initial composition and the treated composition are the initial edible oil and the treated edible oil, respectively.

[0151] Embodiment 40. The method of Embodiment 39, wherein the initial edible oil is subjected to refining, bleaching and / or deodorization (RBD) treatment prior to contacting with the silica-zirconia catalyst.

[0152] Embodiment 41. The method of Embodiment 39 or Embodiment 40, wherein the treated edible oil requires no processing after contacting with the silica-zirconia catalyst.

[0153] Embodiment 42. The method of any of Embodiments 39-41, wherein the initial edible oil has an initial free fatty acid content measured as oleic acid content prior to contacting with the silica-zirconia catalyst, and wherein the method changes the initial free fatty acid content as measured by AOCS Official Method Ca 5a-40 by less than about 20%.

[0154] Embodiment 43. The method of any of Embodiments 39-42, wherein the initial edible oil has an initial free fatty acid content measured as oleic acid content prior to contacting with the silica-zirconia catalyst, and wherein the method causes the initial free fatty acid content measured by AOCS Official Method Ca 5a-40 to change by less than about 10%.

[0155] Embodiment 44. The method of any of Embodiments 39-43, wherein the initial edible oil has an initial p-anisidine value (p-AV) prior to contacting with the silica-zirconia catalyst, and the method changes the initial p-anisidine value (p-AV) measured by AOCS Official Method Cd 18-90 by less than 10 units.

[0156] Embodiment 45. The method of any of Embodiments 39-44, wherein the initial edible oil has an initial peroxide value (PV) prior to contacting with the silica-zirconia catalyst, and the method changes the initial peroxide value measured by AOCS Official Method Cd 8-53 by less than 10 units.

[0157] Embodiment 46. The method of any one of Embodiments 39-45, wherein the continuous reactor is a packed bed reactor or a CSTR.

[0158] It should be understood that although the above-mentioned silica-zirconia catalysts, methods and uses are described as "comprising" one or more components or steps, the above-mentioned silica-zirconia catalysts, methods and uses may "comprising" or "consisting of" or "consisting essentially of" any of the above-mentioned components or steps of the silica-zirconia catalysts, methods and uses. Therefore, in the case where an open term such as "comprising" is used to describe the present disclosure or a portion thereof, it should be easily understood that (unless otherwise specified) the description of the present disclosure or a portion thereof should also be interpreted as using the term "consisting essentially of" or "consisting of" or variations thereof as described below to describe the present disclosure or a portion thereof.

[0159] As used herein, the terms "comprising," "including," "having," "containing," "characterized by," or any other variations thereof are intended to cover a non-exclusive inclusion of the recited components subject to any otherwise expressly specified limitations. For example, a silica-zirconia catalyst, method, and / or use that "comprising" a list of elements (e.g., components or steps) is not necessarily limited to only those elements (or components or steps), but may also include other elements (or components or steps) not expressly listed or inherent to the silica-zirconia catalyst, method, and / or use.

[0160] As used herein, the transitional phrases "consisting of" and "composed of" exclude any element, step, or component not specified. For example, "consisting of" or "composed of" used in a claim limits the claim to the components, materials, or steps specifically mentioned in the claim, except for impurities normally associated therewith (i.e., impurities within a given component). When the phrase "consisting of" or "composed of" appears in a clause of a claim rather than immediately following a preamble, the phrase "consisting of" or "composed of" is limited only to the elements (or components or steps) set forth in that clause; other elements (or components) are not excluded from the claim as a whole.

[0161] As used herein, the transitional phrases "consisting essentially of and "consisting essentially of" are used to define silica-zirconia catalysts, methods, and / or uses that include materials, steps, features, components, or elements in addition to those literally disclosed, provided that such 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" is a middle ground between "comprising" and "consisting of."

[0162] Although the present invention has been described in a limited number of embodiments, these specific embodiments are not intended to limit the scope of the invention otherwise described and claimed herein. When consulting the exemplary embodiments herein, it may be apparent to those of ordinary skill in the art that further modifications, equivalent forms and variant forms are possible. Unless otherwise indicated, all parts and percentages in the examples and the remainder of the specification are by weight. In addition, any numerical ranges described in the specification or claims, such as numerical ranges representing a specific set of properties, measurement units, conditions, physical states or percentages, are intended to be explicitly incorporated herein by reference or otherwise in a literal sense to include any numerical value falling within such a range, including a subset of any numerical value within the range. For example, whenever a lower limit R is disclosed, L and upper limit R u When a numerical range is specified, any numerical value R falling within the range is specifically disclosed. In particular, the following numerical values ​​R within a certain range are specifically disclosed: R = R L +k(R u -R L), wherein k may be from 1% to 100% in increments of 1%, for example, k is 1%, 2%, 3%, 4%, 5% ... 50%, 51%, 52% ... 95%, 96%, 97%, 98%, 99% or 100%. In addition, any numerical range represented by any two R values ​​as calculated above is also specifically disclosed. Any modifications of the present invention other than those shown and described herein will be apparent to those skilled in the art from the above description and accompanying drawings. Such modifications are intended to fall within the scope of the appended claims.

[0163] All publications, patent applications, issued patents, and other documents mentioned in this specification are incorporated herein by reference, just as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated herein by reference in its entirety. Definitions contained in text incorporated by reference shall not apply if they conflict with definitions in this disclosure.

[0164] Other embodiments are set forth in the following claims.

Claims

1. A method comprising: contacting an initial composition comprising (i) a triglyceride and (ii) glycidol, a glycidyl ester, or both glycidol and a glycidyl ester with an effective amount of a silica-zirconia catalyst in a continuous reactor to form a treated composition; in: The silica-zirconia catalyst comprises porous silica particles impregnated with zirconium oxide; and The concentration of (ii) in the treated composition is less than the concentration of (ii) in the initial composition.

2. The process according to claim 1, wherein the continuous reactor is a packed bed reactor, a rotating bed reactor, a continuous stirred tank reactor (CSTR), a plug flow reactor or a fluidized bed reactor.

3. The process according to claim 1 or 2, wherein the continuous reactor is a packed bed reactor.

4. The method of any one of claims 1-3, wherein the silica-zirconia catalyst comprises particles having a median particle size of about 0.1 μm to about 10,000 μm.

5. The method of any one of claims 1-4, wherein the silica-zirconia catalyst comprises particles having a median particle size of about 50.0 μm to about 400 μm.

6. The method of any one of claims 1-5, wherein the silica-zirconia catalyst comprises particles having a median particle size of about 80.0 μm to about 300 μm.

7. The method according to any one of claims 1 to 6, wherein the silica-zirconia catalyst comprises a catalyst having a 2 / g to about 800m 2 Particles with a BET particle surface area of ​​1000 μg / g.

8. The method according to any one of claims 1 to 7, wherein the silica-zirconia catalyst comprises a catalyst having a 2 / g to about 450m 2 Particles with a BET particle surface area of ​​1000 μg / g.

9. The method of any one of claims 1-8, wherein the silica-zirconia catalyst comprises particles having a pore volume of 0.1 cc / g to about 3.0 cc / g as determined by the Barrett-Joyner-Halenda (BJH) method.

10. The method of any one of claims 1-9, wherein the silica-zirconia catalyst comprises particles having a pore volume of about 0.5 cc / g to about 2.5 cc / g as determined by the Barrett-Joyner-Halenda (BJH) method.

11. The method of any one of claims 1-10, wherein the silica-zirconia catalyst comprises particles having a pore volume of about 0.8 cc / g to about 2.0 cc / g as determined by the Barrett-Joyner-Halenda (BJH) method.

12. The method of any one of claims 1-11, wherein the silica-zirconia catalyst exhibits a pH of about 9 or less.

13. The method of any one of claims 1-12, wherein the silica-zirconia catalyst exhibits a pH of about 1 to about 8.

14. The method of any one of claims 1-13, wherein the silica-zirconia catalyst exhibits a pH of about 2 to about 7.

15. The method of any one of claims 1-14, wherein the silica-zirconia catalyst exhibits a pH of about 3 to about 6.

16. The method of any one of claims 1-15, wherein the contacting step occurs at a temperature of about 20°C to about 250°C.

17. The method of any one of claims 1-16, wherein the contacting step occurs at a temperature of about 30°C to about 150°C.

18. The method of any one of claims 1-17, wherein the contacting step occurs at a temperature of about 40°C to about 120°C.

19. The method of any one of claims 1 to 18, wherein the contacting step is performed over a period of about 1 hour. -1 To about 500hr -1 Occurs at a weight airspeed of .

20. The method of any one of claims 1-19, wherein the contacting step is performed over a period of about 1 hour. -1 About 120 hours -1 Occurs at a weight airspeed of .

21. The method of any one of claims 1-20, wherein the contacting step comprises mixing the initial composition and the silica-zirconia catalyst in a continuous reactor.

22. The method of any one of claims 1 to 21, wherein the contacting step comprises mixing the initial composition and the silica-zirconia catalyst in a continuous reactor under a flow of an inert gas or under vacuum.

23. The method of claim 22, wherein the inert gas comprises nitrogen, argon, or a combination thereof.

24. The method according to any one of claims 1 to 23, wherein the initial composition further comprises an organic solvent.

25. The method of claim 24, wherein the organic solvent comprises heptane, hexane, toluene, ether, alcohol, or a combination thereof.

26. The method of any one of claims 1-25, wherein the initial composition and the treated composition comprise edible oil.

27. The method of claim 26, wherein the edible oil is 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 a combination thereof.

28. The method of any one of claims 26-27, wherein the edible oil is soybean oil.

29. The method of any one of claims 1-28, wherein the glycidyl ester is glycidyl oleate.

30. The method of any one of claims 1-29, wherein the silica-zirconia catalyst is present in the continuous reactor at a weight percent of less than about 2% relative to the amount of the treated composition.

31. The method of any one of claims 1-30, wherein the silica-zirconia catalyst is present in the continuous reactor at a weight percent of less than about 0.5% relative to the amount of the treated composition.

32. The method of any one of claims 1-31, wherein the silica-zirconia catalyst is present in the continuous reactor at a weight percent of less than about 0.1% relative to the amount of the treated composition.

33. The method of any one of claims 1-32, wherein the silica-zirconia catalyst is present in the continuous reactor at a weight percent of less than about 0.05% relative to the amount of the treated composition.

34. The method of any one of claims 1-33, wherein the silica-zirconia catalyst is present in the continuous reactor at a weight percent of less than about 0.01% relative to the amount of the treated composition.

35. The method of any one of claims 1-34, wherein the concentration of (ii) in the treated composition is less than 1.0 ppm.

36. The method of any one of claims 1-35, wherein the concentration of (ii) in the treated composition is less than 0.5 ppm.

37. The method of any one of claims 1-36, wherein the concentration of (ii) in the treated composition is less than 0.2 ppm.

38. The method of any one of claims 1-37, wherein the concentration of (ii) in the treated composition is less than 0.05 ppm.

39. A method of treating a raw edible oil to produce a treated edible oil, comprising the method of any one of claims 1 to 38, wherein the raw composition and the treated composition are the raw edible oil and the treated edible oil, respectively.

40. The method of claim 39, wherein the raw edible oil is subjected to a refining, bleaching and / or deodorizing (RBD) process prior to contacting with the silica-zirconia catalyst.

41. The method of claim 39 or 40, wherein the treated edible oil requires no processing after contacting with the silica-zirconia catalyst.

42. The method of any one of claims 39-41, wherein the initial edible oil has an initial free fatty acid content measured as oleic acid content prior to contacting with the silica-zirconia catalyst, and the method changes the initial free fatty acid content measured by AOCS Official Method Ca 5a-40 by less than about 20%.

43. The method of any one of claims 39-42, wherein the initial edible oil has an initial free fatty acid content measured as oleic acid content prior to contacting with the silica-zirconia catalyst, and the method changes the initial free fatty acid content measured by AOCS Official Method Ca 5a-40 by less than about 10%.

44. The method of any one of claims 39-43, wherein the initial edible oil has an initial p-anisidine value (p-AV) prior to contacting with the silica-zirconia catalyst, and the method changes the initial p-anisidine value (p-AV) measured by AOCS Official Method Cd 18-90 by less than 10 units.

45. The method of any one of claims 39-44, wherein the initial edible oil has an initial peroxide value (PV) prior to contacting with the silica-zirconia catalyst, and the method changes the initial peroxide value measured by AOCS Official Method Cd 8-53 by less than 10 units.

46. ​​The process of any one of claims 39-45, wherein the continuous reactor is a packed bed reactor or a CSTR.

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