Method for using silica-zirconia catalyst in a continuous reactor

Abstract

The method includes contacting an initial composition including (i) triglycerides and (ii) glycidol, a glycidyl ester, or both glycidol and glycidyl esters with an effective amount of a silica-zirconia catalyst in a continuous reactor. The method is useful for producing a treated composition, such as a treated edible oil, having a reduced concentration of (ii) compared to the initial composition.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 312,328, filed February 21, 2022, the contents of which are incorporated by reference in their entirety herein.

[0002]

[0002] The present disclosure is directed to a process that includes contacting an initial composition comprising (i) triglycerides, and (ii) glycidol, a glycidyl ester, or both glycidol and glycidyl esters, with an effective amount of a silica-zirconia catalyst in a continuous reactor. The process is useful for producing a treated composition, such as a treated edible oil, having a reduced concentration of (ii) compared to the initial composition. [Background technology]

[0003]

[0003] Glycidyl esters are known carcinogens and mutagens found 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 various volatile components from the oil during the deodorization process. After the crude oil is 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 wide variety of process combinations including, but not limited to, contacting the oil with enzymes, shear mixing the oil with acids, rebleaching the oil, and / or rerunning 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 deteriorate the quality of the oil, lowering its market price. Summary of the Invention [Means for solving the problem]

[0004] In one aspect, disclosed herein is a process comprising the steps of contacting in a continuous reactor an initial composition comprising (i) triglycerides, and (ii) glycidol, a glycidyl ester, or both glycidol and glycidyl esters, with an effective amount of a silica-zirconia catalyst to form a treated composition; the silica-zirconia catalyst comprises porous silica particles impregnated with zirconia; and the concentration of (ii) in the treated composition is lower than the concentration of (ii) in the initial composition.

[0005] 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.

[0006] 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.

[0007] In some embodiments, the silica-zirconia catalyst is about 50 ml 2 / g to about 800m 2 In some embodiments, the silica-zirconia catalyst comprises particles having a BET particle surface area of ​​up to about 150 m 2 / g to about 450m 2 / g.

[0008] 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 determined 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 determined 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 determined by the Barrett-Joyner-Halenda (BJH) method.

[0009] In some embodiments, the silica-zirconia catalyst exhibits a pH of about 9 or less. 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.

[0010] In some embodiments, the contacting step is performed at a temperature of about 20° C. to about 250° C. In some embodiments, the contacting step is performed at a temperature of about 30° C. to about 150° C. In some embodiments, the contacting step is performed at a temperature of about 40° C. to about 120° C.

[0011] In some embodiments, the contacting step is for about 1 hour. -1 ~About 500 hours -1 In some embodiments, the contacting step is carried out for about 1 hour. -1 ~ approx. 120 hours -1 This is done at a weight hourly space velocity of 1000 rpm.

[0012] 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.

[0013]

[0013] In some embodiments, the initial composition further comprises an organic solvent, hi some embodiments, the organic solvent comprises heptane, hexane, toluene, diethyl ether, an alcohol, or a combination thereof.

[0014] In some embodiments, the initial and treated compositions include an edible oil. In some embodiments, the edible oil is soybean oil, palm oil, corn oil, canola oil, rapeseed oil, fish oil, algae oil, sunflower oil, olive oil, vegetable oil, vegetable derived oil, animal derived oil, microbial derived oil, or a combination thereof. In some embodiments, the edible oil is soybean oil.

[0015]

[0015] In some embodiments, the glycidyl ester is glycidyl oleate.

[0016] In some embodiments, the silica-zirconia catalyst is present in the continuous reactor at a weight percent of less than about 2% based on the amount of the treated composition. In some embodiments, the silica-zirconia catalyst is present in the continuous reactor at a weight percent of less than about 0.5% based on the amount of the treated composition. In some embodiments, the silica-zirconia catalyst is present in the continuous reactor at a weight percent of less than about 0.1% based on the amount of the treated composition. In some embodiments, the silica-zirconia catalyst is present in the continuous reactor at a weight percent of less than about 0.05% based on the amount of the treated composition. In some embodiments, the silica-zirconia catalyst is present in the continuous reactor at a weight percent of less than about 0.01% based on the amount of the treated composition.

[0016]

[0017] 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.

[0017]

[0018] 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 and treated compositions are initial and treated edible oils, respectively.

[0018]

[0019] In some embodiments, the initial edible oil is subjected to a refining, bleaching and / or deodorizing (RBD) process prior to contact with the silica-zirconia catalyst.

[0020] In some embodiments, the treated edible oil does not require any processing after contact with the silica-zirconia catalyst.

[0019]

[0021] In some embodiments, the initial edible oil has an initial free fatty acid content measured as the percentage of oleic acid before contact 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 the percentage of oleic acid before contact 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%.

[0020]

[0022] In some embodiments, the initial edible oil has an initial p-anisidine value (p-AV) prior to contact with the silica-zirconia catalyst, and the process changes the initial p-anisidine value (p-AV) by less than 10 units as measured by AOCS Official Method Cd 18-90.

[0021]

[0023] In some embodiments, the initial edible oil has an initial peroxide value (PV) prior to contact with the silica-zirconia catalyst, and the method changes the initial peroxide value by less than 10 units as measured by AOCS Official Method Cd 8-53.

[0022]

[0024] In some embodiments, the continuous reactor is a packed bed reactor or a CSTR. [Brief description of the drawings]

[0023] [Figure 1]

[0025] 1 is a graph showing a comparison of reaction rate constants (k) for packed bed and batch processes using RBD SBO according to Example 1. Both processes used silica-zirconia catalyst for the reduction of glycidol oleate in the RBD SBO. [Diagram 2]

[0026] FIG. 1 is a graph showing catalytic rate constants for a packed bed process using RBD palm oil according to Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024]

[0027] Various embodiments are described below. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein. An aspect described in connection with a specific embodiment is not necessarily limited to that embodiment and can be implemented with any other embodiment(s).

[0025]

[0028] 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.

[0026]

[0029] It must 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 "an oxide" includes a reference to one or more oxides and equivalents thereof known to those skilled in the art, and so forth.

[0027]

[0030] As used herein, the term "about" modifies, for example, amounts, concentrations, volumes, process temperatures, process times, recovery or yields, flow rates, and similar values ​​and ranges thereof of ingredients in coated particles and / or compositions used to describe embodiments of the present disclosure, and refers to variations in 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 the method, and through approximation considerations. The term "about" also encompasses amounts that vary with age of a formulation or mixture containing a particular initial concentration, as well as amounts that vary with mixing or processing of a formulation or mixture containing a particular initial concentration. If there are uses of a term that are not clear to one of ordinary skill in the art, "about" means up to ±10% of the particular term, given the context in which it is used. Whether modified by the term "about," the claims appended hereto include equivalents.

[0028]

[0031] As used herein, a "batch reactor" refers to a closed system in which the reactor is filled with a medium and reactants. The reactants are allowed to react in the reactor for a period of time. No feedstock is added or product is withdrawn during this time. 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 to the reactor and a second chemical is added at a delay.

[0029]

[0032] 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.

[0030]

[0033] As used herein, "continuous reactor" refers to a reactor characterized by a continuous flow of reactants to and products from the reaction system (e.g., a packed bed reactor, a rotating bed reactor, a continuous stirred tank reactor (CSTR), a plug flow reactor, or a fluidized bed reactor).

[0031]

[0034] As used herein, the term "weight hourly space velocity" is defined by the following formula:

[0032]

number

[0033] [In the formula, m o is the mass of catalyst, m, over a given time, t (hours). c (g) is the mass of oil treated with This refers to the mass flow rate of a composition containing reactant (grams / hour) per mass of catalyst (grams) given by:

[0034]

[0035] As used herein, the term "particle size" refers to the median particle size (D50, i.e., the volume distribution where 50 volume percent of the particles are smaller than this number and 50 volume percent of the particles are larger than this number) measured by dynamic light scattering when the particles are slurried in water or in an organic solvent such as acetone or ethanol.

[0035]

[0036] As used herein, the term "pore volume" refers to the median pore volume of a plurality of particles (e.g., silica-zirconia particles disclosed herein) as determined using the Barrett-Joyner-Halenda (BJH) nitrogen porosimetry method as described in DIN 66134, the entirety of which is incorporated herein by reference.

[0036]

[0037] In one aspect, the method includes 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 to form a treated composition; the silica-zirconia catalyst comprises porous silica particles impregnated with zirconia; and 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 is useful for reducing the concentration of glycidol, glycidyl esters, or both glycidol and glycidyl esters in the initial composition. The method reduces the concentration of glycidol, glycidyl esters, or both glycidol and glycidyl esters in the initial composition by at least 50% while utilizing a relatively short reaction time and low temperature.

[0037]

[0038] 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 delays catalytic deactivation of the silica-zirconia catalyst compared to the use of the silica-zirconia catalyst in a batch reactor. In some embodiments, with other reaction parameters consistent with the batch process, the use of the silica-zirconia catalyst in a continuous reactor increases the reaction constant (k) of the silica-zirconia catalyst by at least about 1% compared to that of the example batch process. This includes an increase in the reaction constant of about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11% or 12%. In some embodiments, the increase is about 8% to about 12%. As a result, the catalyst life of the silica-zirconia catalyst is increased, and the overall silica-zirconia dosage required to reduce the same amount of total glycidol is reduced by the use of the silica-zirconia catalyst in a continuous reactor compared to the use of the silica-zirconia catalyst in a batch reactor.

[0038]

[0039] 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.

[0039]

[0040] In some embodiments, the continuous reactor may be a packed bed reactor. A packed bed reactor is also known as a fixed bed reactor and may be a cylindrical tube packed with catalyst pellets (e.g., silica-zirconia catalyst) along with reactants (e.g., an initial composition containing (i) triglycerides and (ii) glycidol, glycidyl esters, or both glycidol and glycidyl esters) that undergo conversion to products while flowing through the bed. The catalyst may 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 a shell per se. The various configurations may be adapted according to the need to maintain temperature control in the system. The flow of reactants in a fixed bed reactor may be downward under gravity.

[0040]

[0041] In some embodiments, the continuous reactor may be a rotating bed reactor. A rotating bed reactor holds a central hole and a fixed packed bed in a basket. When immersed in a fluid phase and the basket is spinning, the inertial force created by the spinning motion pushes the fluid outwards, thereby creating a circulating flow through the rotating packed bed. Rotating bed reactors exhibit relatively fast mass / heat transfer and good fluid mixing compared to packed bed reactors.

[0041]

[0042] In some embodiments, the continuous reactor may be a continuous stirred tank reactor (CSTR). A CSTR is an open system in which materials freely enter and exit the system, which operates on a steady-state basis, with reactor conditions not changing over time. Reactants are continuously introduced into the reactor while products are continuously removed. CSTRs are well mixed, and therefore the contents have relatively homogenous properties throughout, such as temperature, density, etc. Also, the conditions of the reactor outlet stream are the same as those inside the vessel.

[0042]

[0043] In some embodiments, the continuous reactor may be a fluidized bed reactor. In this type of reactor, a fluid (e.g., an initial composition containing (i) triglycerides and (ii) glycidol, glycidyl esters, or both glycidol and glycidyl esters) is passed through a solid granular material (e.g., a silica-zirconia catalyst) at a sufficiently high velocity to suspend the solid and make it behave as if it were a fluid. This process is known as fluidization and offers many important advantages over packed bed reactors. One important advantage of using a fluidized bed reactor is the ability to achieve a very uniform temperature in the reactor.

[0043]

[0044] The silica-zirconia catalyst of the present technology may be formed by one or more additional steps, such as coating and / or impregnating zirconia, followed by drying, calcining, or both. See International Publication No. 202026905, the entirety of which is incorporated herein by reference. A method for making a silica-zirconia catalyst suitable for use in the methods described herein includes impregnating porous silica particles with zirconium acetate in acetic acid containing 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 making a silica-zirconia catalyst includes an impregnation step in which the porous silica particles are in contact with zirconium acetate for a desired time, for example, 30 minutes or any desired time. The method for making a silica-zirconia catalyst includes grinding 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 may be milled (or ground) for any desired period of time. The zirconia may be impregnated into at least a portion of the surface of the porous silica particles and / or into at least a portion of the pores of the porous silica particles.

[0044]

[0045] Suitable porous silica particles useful for preparing the silica-zirconia catalyst 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 prepared via organic templates (e.g., surfactants) during the formation of silica particles, followed by high-temperature treatment to "burn out" the organics. Particularly preferred porous silica particles include silica gel or precipitated silica particles. Any commercially available porous silica particles may be used to form the silica-zirconia catalyst of the present disclosure. Commercially available porous silica particles useful for forming the silica-zirconia catalyst of the present disclosure 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 WRGrace (Columbia, MD) under the trade name DARACLAR® 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%, at least about 93.5 wt%, at least about 94.0 wt%, at least about 95.0 wt%, at least about 96.0 wt%, at least about 97.0 wt%, at least about 98.0 wt%, 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 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, etc. The porous silica particles can include a mixture of particles with different compositions, sizes, shapes, or physical structures, or particles that may be identical except for different surface treatments. When smaller particles aggregate to form larger particles, the porosity of the porous silica particles can be intraparticle or interparticle.

[0045]

[0046] In some embodiments, the silica-zirconia catalyst of the present technology comprises 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 catalyst of the present technology comprises 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% zirconia 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% zirconia based on the total weight of the silica-zirconia catalyst. It is understood that the silica-zirconia catalyst of the present technology may comprise any amount of zirconia in the range of about 0.01 wt% to about 50.0 wt% (or more) (or any range of amounts of zirconia between about 0.01 wt% and about 50.0 wt%, in 0.01 wt% increments based on the total weight of the silica-zirconia catalyst, e.g., about 0.02 wt% to about 49.99 wt%).

[0046]

[0047] 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 size 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 catalyst of the present technology has 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 catalyst of the present technology has a median particle size of about 80 μm to about 300 μm.

[0047]

[0048] In some embodiments, the silica-zirconia catalyst of the present technology has a viscosity of at least about 10 m 2 / g, at least about 25.0m 2 / g, maximum approximately 2000m 2 In some embodiments, the silica-zirconia catalyst has a BET particle surface area of ​​about 50 m 2 / g~about 100m 2 / g, about 100m 2 / g~about 150m 2 / g, approx. 150m 2 / g~about 200m 2 / g, approx. 200m 2 / g ~ approx. 250m 2 / g, approx. 250m 2 / g~about 300m 2 / g, approx. 300m 2 / g ~ approx. 350m 2 / g, approx. 350m 2 / g~about 400m 2 / g, approx. 400m 2 / g ~ approx. 450m 2 / g, approx. 450m 2 / g~about 500m 2 / g, approx. 500m 2 / g ~ approx. 550m 2 / g, approx. 550m 2 / g~about 600m 2 / g, approx. 600m 2 / g~about 650m 2 / g, approx. 650m 2 / g~about 700m 2 / g, approx. 700m 2 / g ~ approx. 750m 2 / g, or about 750m 2 / g~about 800m 2 / g. However, the silica-zirconia catalyst of the present technology has a BET particle surface area of ​​about 10 m 2 / g to about 2000m 2 Any BET particle surface area in the range of 10 m / g or more (or about 10 m 2 / g to about 2000m 2 BET particle surface area values ​​in any range between 0.1 m / g 2 / g increments, for example, about 10.1m 2 / g~approx. 1999.9m 2 / g).

[0048]

[0049] In some embodiments, the silica-zirconia catalyst of the present technology 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. In some embodiments, the silica-zirconia catalyst may have a pore volume of at least 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, or about 0.4 cc / g to about 0.5 cc / g as determined by the Barrett-Joyner-Halenda (BJH) method. , about 0.5cc / g to about 0.6cc / g, about 0.6cc / g to about 0.7cc / g, about 0.7cc / g to about 0.8cc / g, about 0.8cc / g to about 0.9cc / g, about 0.9 cc / g ~ approx. 1.0cc / g, approx. 1.0cc / g ~ approx. 1.1cc / g, approx. 1.1cc / g ~ approx. 1.2cc / g, approx. 1.2cc / g ~ approx. 1.3cc / g, approx. 1.3cc / g ~ Approximately 1.4cc / g, approximately 1.4cc / g~approximately 1.5cc / g, approximately 1.5cc / g~approximately 1.6cc / g, approximately 1.6cc / g~approximately 1.7cc / g, approximately 1.7cc / g~approximately 1.8c c / 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 / g, about The pore volume is about 2.2cc / g to about 2.3cc / g, about 2.3cc / g to about 2.4cc / g, about 2.4cc / g to about 2.5cc / g, about 2.5cc / g to about 2.6cc / g, about 2.6cc / g to about 2.7cc / g, about 2.7cc / g to about 2.8cc / g, about 2.8cc / g to about 2.9cc / g, or about 2.9cc / g to about 3.0cc / g. In some embodiments, the silica-zirconia catalyst has a pore volume of about 0.1cc / g to about 2.5cc / g, about 0.5cc / g to about 2.5cc / g, or about 0.8cc / g to about 2.0cc / g, as determined by the Barrett-Joyner-Halenda (BJH) method.However, it should be understood that the silica-zirconia catalyst of the present technology may have a pore volume of from about 0.01 cc / g to about 3.00 cc / g (or more) as determined by the Barrett-Joyner-Halenda (BJH) method (or any range of pore volumes between about 0.01 cc / g and 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).

[0049]

[0050] 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.

[0050]

[0051] In some embodiments, the method of the present disclosure includes 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 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., about 140° C. to about 20 ... The contacting step is carried out at a temperature of about 140° C., about 140° C. to about 150° C., 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 is carried out at a temperature of about 90.0° C.

[0051]

[0052] In some embodiments, the contacting step is for about 0.1 hours. -1 ~About 500 hours -1 In some embodiments, the contacting step is performed for about 0.1 hours. -1 ~ approx. 5 hours -1 , about 5 hours -1 ~ approx. 10 hours -1 , about 10 hours -1 ~ approx. 20 hours -1 , about 20 hours -1 ~ approx. 30 hours -1 , about 30 hours -1 ~ approx. 40 hours -1 , about 40 hours -1 ~ approx. 50 hours -1 , about 50 hours -1 ~ approx. 60 hours -1 , about 60 hours -1 ~ approx. 70 hours -1 , about 70 hours -1 ~ approx. 80 hours -1 , about 80 hours -1 ~ approx. 90 hours -1 , about 90 hours -1 ~ approx. 100 hours -1 , about 100 hours -1 ~ approx. 110 hours -1 , about 110 hours -1 ~ approx. 120 hours -1 , about 120 hours -1 ~ approx. 180 hours -1 , about 180 hours -1 ~ approx. 240 hours -1 , about 240 hours -1 ~About 300 hours -1 , about 300 hours -1 ~About 360 hours -1 , about 360 hours -1 ~ approx. 420 hours -1 , or about 420 hours -1 ~About 500 hours -1 This is done at a weight hourly space velocity of 1000 rpm.

[0052]

[0053] In some embodiments, the method of the present disclosure comprises contacting in a continuous reactor under flowing inert gas or under vacuum to minimize atmospheric oxygen concentration an initial composition comprising (i) triglyceride and (ii) glycidol, glycidyl ester, or both glycidol and glycidyl ester with an effective amount of a silica-zirconia catalyst.

[0053]

[0054] In some embodiments, the contacting step is carried out under vacuum and 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.

[0054]

[0055] In some embodiments, the contacting step is carried out under a flow of inert gas, where the inert gas comprises nitrogen, argon, or a combination thereof.

[0056] In some embodiments, the initial composition further comprises an organic solvent, hi some embodiments, the organic solvent comprises heptane, hexane, toluene, diethyl ether, an alcohol, or a combination thereof.

[0055]

[0057] In some embodiments, the initial and processed compositions include edible oil.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, vegetable-derived oil, animal-derived oil, microbial-derived oil, or combinations thereof.In some embodiments, the edible oil is soybean oil.

[0056]

[0058] In some embodiments, the glycidyl ester is glycidyl oleate.

[0059] In some embodiments, the silica-zirconia catalyst is present in the continuous reactor at a weight percent of less than about 2% based on the amount of treated composition, hi some embodiments, the silica-zirconia catalyst is present in the continuous reactor at a weight percent 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% based on the amount of treated composition.

[0057]

[0060] 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.

[0058]

[0061] In another aspect, the disclosure provides 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 and treated compositions are initial and treated edible oils, respectively.

[0059]

[0062] In some embodiments, the edible oil is subjected to a refining, bleaching and / or deodorizing (RBD) process prior to contact with the silica-zirconia catalyst.

[0063] In some embodiments, the treated edible oil does not require any processing after contact with the silica-zirconia catalyst (i.e., no further processing is required, 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-running the deodorization at a lower temperature but for an extended period of time, or any combination of the process steps mentioned).

[0060]

[0064] In some embodiments, the disclosed method of treating a given initial edible oil is capable of reducing the concentration of glycidol, glycidyl esters, or both glycidol and glycidyl esters in the edible oil to very low levels that have little effect on (i) the free fatty acid content, e.g., oleic acid content, of the edible oil, as measured, for example, by AOCS Official Method Ca 5a-40, and / or (ii) (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) the oxidation level of the edible oil, as measured, for example, by both (a) and (b). AOCS Official Methods Ca 5a-40, 18-90, and 8-53 are incorporated herein by reference in their entireties. Additionally, the methods described in AOCS Official Methods Ca 5a-40, 18-90, and 8-53 are well known to those skilled in the art.

[0061]

[0065] In some embodiments, the method results in negligible change in the free fatty acid content (e.g., oleic acid) 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 the content of oleic acid prior to contact with the silica-zirconia catalyst, and the method changes the initial free fatty acid content as 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%.

[0062]

[0066] In some embodiments, the initial edible oil has an initial p-anisidine value (p-AV) prior to contact with the silica-zirconia catalyst, and the process changes the initial p-anisidine value (p-AV) 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 as measured by AOCS Official Method Cd 18-90.

[0063]

[0067] In some embodiments, the initial edible oil has an initial peroxide value (PV) prior to contact with the silica-zirconia catalyst, and the method changes the initial peroxide value 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 as measured by AOCS Official Method Cd 8-53.

[0064]

[0068] In some embodiments, the continuous reactor may be a packed bed reactor or a CSTR.

[0069] The present disclosure is further illustrated by the following examples, which should not be construed as limiting its scope in any way. On the contrary, it should be clearly understood that various other embodiments, modifications, and equivalents thereof can be relied upon, which may themselves suggest themselves to those skilled in the art upon reading the description herein, without departing from the spirit of the present disclosure and / or the scope of the appended claims. EXAMPLES

[0065]

[0070] Various embodiments are described below. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein. An aspect described in connection with a specific embodiment is not necessarily limited to that embodiment and can be implemented with any other embodiment(s).

[0066]

[0071] Catalyst evaluation, methods and materials

[0072] Nitrogen pore volume and BET surface area measurements of silica-zirconia particle samples

[0073] The silica-zirconia materials of the present disclosure are typical mesoporous materials (pore size 2-50 nm, IUPAC definition) that usually exhibit type IV isotherms (IUPAC classification). Therefore, nitrogen porosimetry is a preferred method for its characterization, and the determination of surface area using the BET method and pore volume using the BJH method from nitrogen adsorption-desorption isotherms are well-established and preferred methods and are used herein. The nitrogen pore volumes of the silica-zirconia catalysts were measured using a TriStar Analyzer, Model 3000 and Model II Plus, Micromeritics Instrument Corporation (One Micromeritics Drive, Norcross, Georgia). Samples were activated in flowing air or nitrogen at a temperature of 400° C. for 2 hours prior to analysis. Surface areas were measured using the P / P o The adsorption branch of the isotherm was calculated from the multipoint values ​​of the nitrogen volume taken up during the adsorption branch at low partial pressures of P / P o = 0.967 and then the descending branch of the isotherm was measured. The pore volume was calculated from the desorption branch using the BJH method.

[0067]

[0074] Total glycidol concentration analysis

[0075] 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, which determines the concentration of the sum of (i) total free glycidol and (ii) bound glycidol (i.e., glycidyl esters) present in a given sample.

[0068]

[0076] Reaction rate constants / kinetic analysis

[0077] The reaction rate constants for batch and continuous flow reactors are calculated using the following equation:

[0069]

number

[0070] [In the formula, m o is the mass of a given catalyst, m c where C is the mass of oil (g) treated with glycidol (g) for a given time, t (min), C0 (ppm) is the concentration of total glycidol in the initial oil, and C f (ppm) is the concentration of total glycidol in the treated oil] It was calculated by:

[0071]

[0078] Catalyst synthesis

[0079] 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 into the porous silica particles for 30 minutes, then ground for an additional hour. The material was then dried at 105°C for 2 hours and then calcined at 500°C for 4 hours.

[0072]

[0080] The resulting silica-zirconia catalyst had a zirconia concentration ranging from 0.01% to 49.99% by weight. As described further below, in some embodiments, silica-zirconia catalysts having zirconia concentrations ranging from about 2.00% to about 20.00% by weight have provided effective results. The final zirconia concentration was determined using ICP elemental microanalysis.

[0073]

[0081] The reaction kinetics was evaluated using 12 silica-zirconia catalyst samples to determine first order reaction rate constants. Table 1 below shows the properties of Catalyst A through Catalyst L. To determine the reaction rate constants associated with each catalyst, 100 g of soybean oil loaded with glycidyl oleate was added to a round bottom flask equipped with an argon flow to displace any oxygen present. Mixing was set at 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, the stirring and temperature control were stopped and the catalyst was filtered off. The total glycidol in the initial and final oils was measured. This procedure was repeated for each type of catalyst listed below. (Table 1).

[0074]

[0082]

[0075] [Table 1]

[0076] Example 1

[0083] Packed-bed process using RBD soybean oil loaded with glycidol oleate.

[0084] The catalyst with the highest activity (Catalyst E in Table 1) was selected for testing in a packed bed process compared to a batch process with recycled catalyst.

[0077]

[0085] Batch processing of RBD soybean oil loaded with glycidol oleate using recycled catalyst

[0086] 2 kg of RBD soybean oil (SBO) was loaded with glycidol oleate. Loaded SBO (100 g) was charged into a round bottom flask equipped with an argon flow to displace any oxygen present. Mixing was set at 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, the stirring and temperature control were stopped and the catalyst was filtered off. The processed oil was analyzed for glycidol oleate levels. The procedure was repeated 19 more times with 2 grams of catalyst E recovered from the previous step and 87 g of freshly loaded SBO.

[0078]

[0087] Packed-bed process using RBD soybean oil loaded with glycidol oleate.

[0088] A packed bed reactor was loaded with glass wool provided by Thermo Scientific (catalog number: 386062500), inert zirconia beads from Bio Spec Products (catalog number: NC0362415), and 2 grams of catalyst E. The catalyst bed was heated to 90° C. and then the RBD SBO flow was started by the instrument at 6.7 g / min to match the conditions for the batch process described above (100 g oil and 2 g catalyst, 15 min contact time).

[0079]

[0089] The first-order reaction rate constants for both processes are summarized and compared in FIG. 1 and Table 2. The data show that when processing the same amount of loaded SBO with the same amount of catalyst E, the first-order reaction rate constants are 8% to 12% higher in the packed bed reactor compared to the batch process using the reused catalyst. This difference is statistically significant, as shown in Table 3 by P=0.00046, well below 0.05 in the t-test for paired two samples with 95% confidence interval. The data also suggest that catalyst deactivation is slower in the packed bed process, which means that the packed bed process gives a lower total glycidol concentration after processing the same amount of oil, and therefore the active life of the catalyst is extended. The overall silica-zirconia dosage requirement is therefore lower in the packed bed process compared to that in the reused batch process.

[0080]

[0090]

[0081] [Table 2]

[0082]

[0091]

[0083] [Table 3]

[0084] Example 2

[0092] Packed bed process using RBD palm oil.

[0093] A packed bed reactor was packed with glass wool provided by Thermo Scientific (catalog number: 386062500), inert zirconia beads from Bio Spec Products (catalog number: NC0362415), and 2 grams of catalyst E. The catalyst bed was heated to 90° C. and then an RBD palm oil stream with a total glycidol content of 3.34 ppm was added to the packed bed for 102 hours. -1The flow rate was started by the instrument at 3.4 g / min, corresponding to a weight hourly space velocity of 1000 ppm. The reaction was continued until 5,500 g of palm oil had been processed with the catalyst. The overall catalyst dosage was 0.036 wt% (g catalyst / 100 g oil), and although the catalyst was deactivated over the extended test run, the final catalyst activity (Figure 2) was still sufficient to reduce the glycidol level in the oil to less than 0.061 ppm.

[0085]

[0094] The catalyst performance was then tested at various space velocities by varying the flow rate of palm oil through the packed bed, while all other conditions were kept the same. 100 g of RBD palm oil was reacted under each set of conditions. The results are summarized in Table 4, and the glycidol level in the processed palm oil increased after 420 hours. -1 It was shown that the residual concentration was less than 1 ppm even at high space velocities.

[0086] [Table 4]

[0087]

[0095] Certain embodiments

[0096] Embodiment 1. A method comprising the steps of contacting in a continuous reactor an initial composition comprising (i) triglycerides, and (ii) glycidol, a glycidyl ester, or both glycidol and glycidyl esters, with an effective amount of a silica-zirconia catalyst to form a treated composition; the silica-zirconia catalyst comprises porous silica particles impregnated with zirconia; The method wherein the concentration of (ii) in the treated composition is lower than the concentration of (ii) in the initial composition.

[0088]

[0097] 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.

[0098] Embodiment 3. The method of embodiment 1 or 2, wherein the continuous reactor is a packed bed reactor.

[0089]

[0099]

[0023] Embodiment 4. The method of any one of embodiments 1 to 3, wherein the silica-zirconia catalyst comprises particles having a median particle size of about 0.1 μm to about 10,000 μm.

[0100] Embodiment 5. The method of any one of embodiments 1 to 4, wherein the silica-zirconia catalyst comprises particles having a median particle size of about 50.0 μm to about 400 μm.

[0090]

[0101]

[0023] Embodiment 6. The method of any one of embodiments 1 to 5, wherein the silica-zirconia catalyst comprises particles having a median particle size of about 80.0 μm to about 300 μm.

[0102]

[0023] Embodiment 7. The silica-zirconia catalyst is about 50 m 2 / g to about 800m 2 7. The method of any one of the preceding claims, comprising particles having a BET particle surface area of ​​up to 1 / g.

[0091]

[0103] 8. The silica-zirconia catalyst is about 150 m 2 / g to about 450m 2 8. The method of any one of the preceding claims, comprising particles having a BET particle surface area of ​​up to 1 / g.

[0092]

[0104] Embodiment 9. The method of any one of embodiments 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 0.1 cc / g to about 3.0 cc / g.

[0093]

[0105]

[0023] Embodiment 10. The method of any one of embodiments 1 to 9, 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 2.5 cc / g.

[0094]

[0106]

[0031] Embodiment 11. The method of any one of embodiments 1 to 10, wherein the silica-zirconia catalyst comprises particles having a pore volume, as determined by the Barrett-Joyner-Halenda (BJH) method, of from about 0.8 cc / g to about 2.0 cc / g.

[0095]

[0107] Embodiment 12. The method of any one of embodiments 1 to 11, wherein the silica-zirconia catalyst exhibits a pH of about 9 or less.

[0108] Embodiment 13. The method of any one of embodiments 1 to 12, wherein the silica-zirconia catalyst exhibits a pH of about 1 to about 8.

[0096]

[0109] Embodiment 14. The method of any one of embodiments 1 to 13, wherein the silica-zirconia catalyst exhibits a pH of about 2 to about 7.

[0110] Embodiment 15. The method of any one of embodiments 1 to 14, wherein the silica-zirconia catalyst exhibits a pH of about 3 to about 6.

[0097]

[0111] Embodiment 16. The method of any one of embodiments 1 to 15, wherein the contacting step is carried out at a temperature of about 20° C. to about 250° C.

[0112] Embodiment 17. The method of any one of embodiments 1 to 16, wherein the contacting step is carried out at a temperature of about 30° C. to about 150° C.

[0098]

[0113] Embodiment 18. The method of any one of embodiments 1 to 17, wherein the contacting step is carried out at a temperature of about 40° C. to about 120° C.

[0114] Embodiment 19. The contacting step lasts for about 1 hour. -1 ~About 500 hours -1 19. The method of any one of the preceding embodiments, wherein the process is carried out at a weight hourly space velocity of

[0099]

[0115] Embodiment 20. The contacting step lasts for about 1 hour. -1 ~ approx. 120 hours-1 20. The method of any one of the preceding claims, wherein the process is carried out at a weight hourly space velocity of

[0116] Embodiment 21. The method of any one of the preceding embodiments, wherein the contacting step comprises mixing the initial composition and the silica-zirconia catalyst in the continuous reactor.

[0100]

[0117] Embodiment 22. The method of any one of the preceding embodiments, wherein the contacting step comprises mixing the initial composition and the silica-zirconia catalyst in the continuous reactor under flowing inert gas or under vacuum.

[0101]

[0118] Embodiment 23. The method of embodiment 22, wherein the inert gas comprises nitrogen, argon, or a combination thereof.

[0119] Embodiment 24. The method of any one of embodiments 1 to 23, wherein the initial composition further comprises an organic solvent.

[0102]

[0120] Embodiment 25. The method of embodiment 24, wherein the organic solvent comprises heptane, hexane, toluene, diethyl ether, an alcohol, or a combination thereof.

[0121] Embodiment 26. The method of any one of embodiments 1 to 25, wherein the initial and processed compositions comprise an edible oil.

[0103]

[0122] 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, vegetable-derived oil, animal-derived oil, microbial-derived oil, or a combination thereof.

[0104]

[0123] Embodiment 28. The method of embodiment 26 or 27, wherein the edible oil is soybean oil.

[0124] Embodiment 29. The method of any one of embodiments 1 to 28, wherein the glycidyl ester is glycidyl oleate.

[0105]

[0125] Embodiment 30. The method of any one of the preceding embodiments, wherein the silica-zirconia catalyst is present in the continuous reactor in a weight percent of less than about 2% based on the amount of the treated composition.

[0106]

[0126] Embodiment 31. The method of any one of embodiments 1 to 30, wherein the silica-zirconia catalyst is present in the continuous reactor in a weight percent of less than about 0.5% based on the amount of the treated composition.

[0107]

[0127] Embodiment 32. The method of any one of the preceding embodiments, wherein the silica-zirconia catalyst is present in the continuous reactor in a weight percent of less than about 0.1% based on the amount of the treated composition.

[0108]

[0128] Embodiment 33. The method of any one of embodiments 1 to 32, wherein the silica-zirconia catalyst is present in the continuous reactor in a weight percent of less than about 0.05% based on the amount of the treated composition.

[0109]

[0129] Embodiment 34. The method of any one of embodiments 1 to 33, wherein the silica-zirconia catalyst is present in the continuous reactor in a weight percent of less than about 0.01% based on the amount of the treated composition.

[0110]

[0130] Embodiment 35. The method of any one of embodiments 1 to 34, wherein the concentration of (ii) in the treated composition is less than 1.0 ppm.

[0131] Embodiment 36. The method of any one of the preceding embodiments, wherein the concentration of (ii) in the treated composition is less than 0.5 ppm.

[0111]

[0132] Embodiment 37. The method of any one of embodiments 1 to 36, wherein the concentration of (ii) in the treated composition is less than 0.2 ppm.

[0133] Embodiment 38. The method of any one of embodiments 1 to 37, wherein the concentration of (ii) in the treated composition is less than 0.05 ppm.

[0112]

[0134] Embodiment 39. A method for treating an initial edible oil to produce a treated edible oil, comprising the method of any one of embodiments 1 to 38, wherein the initial and treated compositions are initial and treated edible oils, respectively.

[0113]

[0135] Embodiment 40. The method of embodiment 39, wherein the initial edible oil is subjected to a refining, bleaching and / or deodorizing (RBD) treatment prior to contact with the silica-zirconia catalyst.

[0136] Embodiment 41. The method of embodiment 39 or 40, wherein the treated edible oil does not require processing after contact with the silica-zirconia catalyst.

[0114]

[0137] Embodiment 42. The method of any one of embodiments 39 to 41, wherein the initial edible oil has an initial free fatty acid content, measured as the content of oleic acid, prior to contact with the silica-zirconia catalyst, and the method changes the initial free fatty acid content, as measured by AOCS Official Method Ca 5a-40, by less than about 20%.

[0115]

[0138] Embodiment 43. The method of any one of embodiments 39 to 42, wherein the initial edible oil has an initial free fatty acid content, measured as the content of oleic acid, prior to contact with the silica-zirconia catalyst, and the method changes the initial free fatty acid content, as measured by AOCS Official Method Ca 5a-40, by less than about 10%.

[0116]

[0139] Embodiment 44. The method of any one of embodiments 39 to 43, wherein the initial edible oil has an initial p-anisidine value (p-AV) prior to contact with the silica-zirconia catalyst, 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.

[0117]

[0140] Embodiment 45. The method of any one of embodiments 39 to 44, wherein the initial edible oil has an initial peroxide value (PV) prior to contact with the silica-zirconia catalyst, and the method changes the initial peroxide value by less than 10 units as measured by AOCS Official Method Cd 8-53.

[0118]

[0141] Embodiment 46. The method of any one of embodiments 39 to 45, wherein the continuous reactor is a packed bed reactor or a CSTR.

[0142] 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, when the present disclosure or portions thereof are described in open-ended terms such as "comprising," it should be readily understood that the description of the present disclosure or portions thereof should also be construed as describing the present disclosure or portions thereof using the terms "consisting essentially of" or "consisting of," or variations thereof, as described below (unless otherwise specified).

[0119]

[0143] As used herein, the terms "comprises," "comprising," "includes," "including," "having," "having," "containing," "characterized by," or any other variation thereof, are intended to include a non-exclusive inclusion of the recited elements, subject to any limitations expressly indicated to the contrary. For example, a silica-zirconia catalyst, method, and / or use that "comprises" a list of elements (e.g., elements or steps) is not necessarily limited to only those elements (or elements or steps) and may include other elements (or elements or steps) not expressly listed or inherent to the silica-zirconia catalyst, method, and / or use.

[0120]

[0144] As used herein, the transitional phrases "consists of" and "consisting of" exclude any elements, steps, or components not specified. For example, "consists of" or "consisting of" used in a claim limits the claim to those components, materials, or steps specifically recited in the claim, excluding impurities normally associated therewith (i.e., impurities in a given component). When the phrase "consist of" or "consisting of" appears in a clause in the body of a claim rather than immediately following a preamble, the phrase "consist of" or "consisting of" limits only the elements (or components or steps) recited in that clause. Other elements (or components) are not excluded from the scope of the claim as a whole.

[0121]

[0145] As used herein, the transitional phrases "consists 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 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 middle ground between "comprises" and "consisting of."

[0122]

[0146] Although the present invention has been described with 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 one of ordinary skill in the art upon review of the exemplary embodiments herein. All parts and percentages in the examples and the remainder of the specification are by weight unless otherwise specified. Furthermore, any range of numbers recited in this specification or claims, such as those representing a particular set of properties, units of measurement, conditions, physical states, or percentages, is intended to be literally and explicitly incorporated herein by reference or otherwise indicating, including any numbers contained within such ranges, as well as any subset of numbers within any range so recited. For example, a lower limit R L and upper limit R u Whenever a numerical range having a value of R is disclosed, any number R falling within the range is specifically disclosed. In particular, the following numbers R falling within the range are specifically disclosed: R = R L +k(R u -R L) where k can be from 1% to 100% in 1% increments, e.g., 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 specifically disclosed. Any modifications of the present invention, in addition to those shown and described herein, will become apparent to one skilled in the art from the foregoing description and accompanying drawings. Such modifications are intended to be included within the scope of the appended claims.

[0123]

[0147] All publications, patent applications, issued patents, and other documents mentioned herein are incorporated by reference herein to the same extent as if each individual publication, patent application, issued patent publication, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions contained within the text that are incorporated by reference are excluded to the extent that they conflict with definitions in this disclosure.

[0124]

[0148] Other embodiments are set forth in the following claims.

Claims

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

2. 10. The process of 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. 10. The process of claim 1, wherein the continuous reactor is a packed bed reactor.

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

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

7. The silica-zirconia catalyst is about 50 m ２ / g to about 800m ２ 10. The method of claim 1, comprising particles having a BET particle surface area of ​​up to 1000 nm / g.

8. The silica-zirconia catalyst was approximately 150 m ２ / g to about 450m ２ 10. The method of claim 1, comprising particles having a BET particle surface area of ​​up to 1000 nm / g.

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

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

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

12. 10. The method of claim 1, wherein the silica-zirconia catalyst exhibits a pH of about 9 or less.

13. The method of claim 1, wherein the silica-zirconia catalyst exhibits a pH of from about 1 to about 8.

14. The method of claim 1, wherein the silica-zirconia catalyst exhibits a pH of from about 2 to about 7.

15. The method of claim 1, wherein the silica-zirconia catalyst exhibits a pH of from about 3 to about 6.

16. 10. The method of claim 1, wherein the contacting step is carried out at a temperature of from about 20°C to about 250°C.

17. 10. The method of claim 1, wherein the contacting step is carried out at a temperature of from about 30°C to about 150°C.

18. 10. The method of claim 1, wherein the contacting step is carried out at a temperature of from about 40°C to about 120°C.

19. The contacting step lasts for about 1 hour. －１ ~ Approximately 500 hours －１ 10. The process of claim 1, wherein the process is carried out at a weight hourly space velocity of

20. The contacting step lasts for about 1 hour. －１ ~ Approximately 120 hours －１ 10. The process of claim 1, wherein the process is carried out at a weight hourly space velocity of

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

22. 10. The method of claim 1, wherein the contacting step comprises mixing the initial composition and the silica-zirconia catalyst in a continuous reactor under a flow of inert gas or under vacuum.

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

24. The method of claim 1 , wherein the initial composition further comprises an organic solvent.

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

26. The method of claim 1 , wherein the initial and treated compositions comprise an edible oil.

27. 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. 27. The method of claim 26, wherein the edible oil is soybean oil.

29. 2. The method of claim 1, wherein the glycidyl ester is glycidyl oleate.

30. 10. The method of claim 1, wherein the silica-zirconia catalyst is present in the continuous reactor in a weight percent of less than about 2% based on the amount of treated composition.

31. 10. The method of claim 1, wherein the silica-zirconia catalyst is present in the continuous reactor in a weight percent of less than about 0.5% based on the amount of treated composition.

32. 10. The method of claim 1, wherein the silica-zirconia catalyst is present in the continuous reactor in a weight percent of less than about 0.1% based on the amount of treated composition.

33. 10. The method of claim 1, wherein the silica-zirconia catalyst is present in the continuous reactor in a weight percent of less than about 0.05% based on the amount of treated composition.

34. 10. The method of claim 1, wherein the silica-zirconia catalyst is present in the continuous reactor in a weight percent of less than about 0.01% based on the amount of treated composition.

35. 10. The method of claim 1, wherein the concentration of (ii) in the treated composition is less than 1.0 ppm.

36. 10. The method of claim 1, wherein the concentration of (ii) in the treated composition is less than 0.5 ppm.

37. 10. The method of claim 1, wherein the concentration of (ii) in the treated composition is less than 0.2 ppm.

38. 10. The method of claim 1, wherein the concentration of (ii) in the treated composition is less than 0.05 ppm.

39. 39. A method for treating an initial edible oil to produce a treated edible oil, comprising the method of any one of claims 1 to 38, wherein the initial and treated compositions are initial and treated edible oils, respectively.

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

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

42. 40. The method of claim 39, wherein the initial edible oil has an initial free fatty acid content measured as the content of oleic acid before contact with the silica-zirconia catalyst, and wherein said method changes the initial free fatty acid content as measured by AOCS Official Method Ca 5a-40 by less than about 20%.

43. 40. The method of claim 39, wherein the initial edible oil has an initial free fatty acid content measured as the content of oleic acid before contact with the silica-zirconia catalyst, and wherein said method changes the initial free fatty acid content as measured by AOCS Official Method Ca 5a-40 by less than about 10%.

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

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

46. 40. The process of claim 39, wherein the continuous reactor is a packed bed reactor or a CSTR.

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