CN114302943A - Method for producing monoglyceride compositions having a low level of glycidol and monoglyceride compositions produced thereby - Google Patents

Abstract

The present invention relates to a process for producing monoglyceride compositions having a low glycidol content. The invention also relates to a monoglyceride composition obtainable by said process.

Description

Method for producing monoglyceride compositions having a low level of glycidol and monoglyceride compositions produced thereby

Technical Field

The present invention relates to a process for producing monoglyceride compositions having a low glycidol content. The invention also relates to a monoglyceride composition obtainable by said process.

Background

The industrial production of monoglycerides is accompanied by the formation of glycidol and glycidyl esters. These by-products have recently been found to be less desirable. However, attempts to remove glycidol and glycidyl esters from monoglyceride products have not been successful to date. Glycidol and glycidyl esters are produced as a result of processes that occur at elevated temperatures that are commonly used to produce monoglyceride products.

Disclosure of Invention

The present inventors have found that the glycidol and glycidyl ester content of a monoglyceride product can be reduced by using a heat treatment, but the temperature of the heat treatment is lower than the temperature required to produce a monoglyceride. This is highly unexpected as the higher temperature conditions in the production process appear to be responsible for the problem of glycidol.

The present inventors have also found that the content of glycidol and glycidyl ester can be reduced by contacting the monoglyceride product with a solid acidic material, and that this contact can be advantageously used in combination with heat treatment.

Accordingly, one aspect of the present invention relates to a process for producing a monoglyceride-containing product comprising at least 25% w/w monoglyceride and having a low glycidyl equivalent content, which process comprises:

step i) subjecting a first monoglyceride-containing composition (mcc1) comprising at least 25% w/w monoglyceride and at least 1ppm of the total content of glycidyl equivalents to a heat treatment comprising heating the monoglyceride-containing composition to a temperature in the range 90 ℃ to 210 ℃ for a duration sufficient to reduce the total content of glycidyl equivalents by at least 50%,

and/or

Step ii) contacting a second monoglyceride-containing composition (mcc2) comprising at least 25% w/w monoglyceride and a total content of glycidyl equivalents of at least 1ppm with a solid acidic material which is preferably insoluble in monoglycerides.

Another aspect of the invention relates to a monoglyceride-containing product obtainable by the process described herein.

Yet another aspect of the present invention relates to the use of step i) and/or step ii) for the production of a monoglyceride-containing product comprising at least 25% w/w monoglyceride and having a low glycidyl equivalent content; wherein

Step i) comprises heat treating a first monoglyceride-containing composition comprising at least 25% w/w monoglyceride, which heat treatment comprises heating the monoglyceride-containing composition to a temperature in the range 90 ℃ to 210 ℃ for a duration sufficient to reduce the total content of glycidyl equivalents by at least 50%,

and wherein

Step ii) comprises contacting a second monoglyceride-containing composition comprising at least 25% w/w monoglyceride with a solid acidic material which is preferably insoluble in monoglycerides.

Drawings

Figure 1 shows the effect of heat treatment at different temperatures on the glycidol content and the Monoglyceride (MAG) content.

Figure 2 shows the effect of heat treatment at 150 ℃ for different durations on the glycidyl content and MAG content.

Figure 3 shows the effect of different solid acidic materials on the glycidyl content and MAG content.

Figure 4 shows the effect of the amount of solid acidic material Siral 40 on the glycidol content and the Monoglyceride (MAG) content.

Fig. 5 shows the synergy between heat treatment at different temperatures and a solid acidic material (Siral 40).

Detailed Description

One aspect of the present invention relates to a process for producing a monoglyceride-containing product comprising at least 25% w/w monoglyceride and having a low glycidyl equivalent content, the process comprising:

step i) heat treating a first monoglyceride-containing composition (mcc1) comprising at least 25% w/w monoglyceride and a total content of glycidyl equivalents of at least 2ppm, the heat treatment involving heating the monoglyceride-containing composition to a temperature in the range of from 90 ℃ to 210 ℃ for a duration sufficient to reduce the total content of glycidyl equivalents by at least 50%,

and/or

Step ii) contacting a second monoglyceride-containing composition (mcc2) comprising at least 25% w/w monoglyceride and a total content of glycidyl equivalents of at least 1ppm with a solid acidic material which is preferably insoluble in monoglycerides.

In the context of the present invention, the term "monoglyceride-containing product" relates to a composition comprising predominantly partial glycerides, which contain at least 25% w/w monoglyceride.

In the context of the present invention, the term "glycidol" relates to a compound of IUPAC name 2, 3-epoxypropan-1-ol, which contains both an epoxy group and an alcohol group.

In the context of the present invention, the term "glycidyl equivalent" relates to both free glycidol and glycidyl esters. The total content of glycidyl equivalents was determined according to analysis 1.1.

In the context of the present invention, the term "monoglyceride containing product having a low content of glycidyl equivalents" has a content of glycidyl equivalents of at most 10 ppm.

In the context of the present invention, the term "monoglyceride-containing composition" relates to a composition comprising at least 25% w/w monoglyceride and preferably at least 50% w/w glyceride. The monoglyceride-containing composition typically also comprises diglycerides and triglycerides and optionally glycerol.

In the context of the present invention it is,the phrase "Y and/or X" means "Y" or "X" or "Y and X". The phrase "n" according to the same logic₁、n₂、...、n_i-1And/or n_iBy "means" n₁"or" n₂"or_i-1"or" n_i"or component n₁、n₂、...n_i-1And n_iAny combination of (a).

In some preferred embodiments of the invention, the method comprises step i), and optionally further comprises step ii). However, it may also be preferred that the method comprises step i) but not step ii).

In further preferred embodiments of the present invention, the method comprises step ii), and optionally also step i). However, it may also be preferred that the method comprises step ii) but not step i).

In some particularly preferred embodiments of the invention, the method comprises both step i) and step ii), preferably performed as step i) followed by step ii).

Alternatively, but also preferably, where mcc1 and mcc2 are the same composition, steps i) and ii) may be performed simultaneously on the same mcc.

As mentioned above, step i) comprises subjecting a first monoglyceride-containing composition (mcc1) comprising at least 25% w/w monoglyceride and a total content of glycidyl equivalents of at least 2ppm to a heat treatment comprising heating the monoglyceride-containing composition to a temperature in the range of from 90 ℃ to 210 ℃ for a duration sufficient to reduce the total content of glycidyl equivalents by at least 50%.

The heat treatment of step i) preferably comprises heating the first monoglyceride-containing composition to a temperature in the range of from 95 ℃ to 195 ℃, more preferably from 100 ℃ to 180 ℃, even more preferably from 120 ℃ to 170 ℃, and most preferably from 140 ℃ to 160 ℃.

The heat treatment of step i) preferably comprises heating the first monoglyceride-containing composition for a duration sufficient to reduce the total glycidyl equivalent content of mcc1 by at least 60%, more preferably by at least 70%, even more preferably by at least 80%, and most preferably by at least 90%. An even higher level of reduction may be required and thus the heat treatment of step i) preferably comprises heating the first monoglyceride-containing composition for a duration sufficient to reduce the total content of glycidyl equivalents of mcc1 by at least 95%, and more preferably by at least 99%, even more preferably by at least 99.9%.

The heat treatment of step i) is preferably carried out using an inert atmosphere. The inert atmosphere preferably has an oxygen partial pressure that is less than that of atmospheric air (which is typically about 0.2 bar). The inert atmosphere may be obtained, for example, by creating a vacuum and/or by using a suitable inert gas, such as nitrogen, argon or carbon dioxide.

The inert atmosphere may comprise an oxygen partial pressure of at most 0.1 bar, preferably at most 0.05 bar, more preferably at most 0.01 bar, even more preferably at most 0.001 bar, and most preferably at most 0.0001 bar.

The use of an inert atmosphere, for example, helps to avoid the formation of peroxides and other degradation products during processing.

Alternatively or additionally, suitable antioxidants may be added during processing, and may form part of mcc1 to avoid or reduce oxidation.

As mentioned above, step ii) comprises contacting a second monoglyceride-containing composition (mcc2) comprising at least 25% w/w monoglyceride and a total content of glycidyl equivalents of at least 1ppm with a solid acidic material which is preferably insoluble in monoglycerides.

The temperature and contact time of step ii) are preferably selected such that the glycidyl equivalent content of mcc2 is reduced by at least 50%, preferably by at least 70%, even more preferably by at least 80%, and most preferably by at least 90%. An even higher level of reduction may be required and therefore step ii) preferably comprises contacting the second monoglyceride-containing composition with a solid acidic material for a duration sufficient to reduce the total level of glycidyl equivalents of mcc by at least 95%, more preferably at least 99%, and even more preferably at least 99.9%.

If the glycidyl equivalent content is reduced by, for example, 75%, it means that the glycidyl equivalent content after step ii) is 75% lower than the glycidyl equivalent content of mcc 2.

Step ii) is also preferably carried out using an inert atmosphere, especially if combined with a heat treatment.

In the context of the present invention, the term "solid acidic material" is a material that is solid at a temperature of at least 50 ℃, preferably at least 100 ℃, and more preferably at least 210 ℃, and that is also capable of acting as an acid. The solid acidic material may, for example, be a purified acid in solid form. Alternatively, but preferably, the solid acidic material may comprise a matrix material and the surface contains acidic functional groups. The matrix material itself need not be acidic, but is preferably insoluble in the monoglyceride.

Solid acidic materials are well known to the skilled person and are described, for example, in chapters 2 and 3 of "Solid Acid catalysts: From Fundamentals to Applications", h.hattori, y.ono,2015(Hattori 2015), which are incorporated herein by reference for all purposes. It is particularly preferred that the solid acidic material is as defined in Hattori 2015, pages 23 to 36.

In some preferred embodiments of the invention, the solid acidic material is insoluble in monoglycerides.

In the context of the present invention, the term "insoluble in monoglycerides" means that the solid acidic material has a solubility in glycerol monooleate of at most 1g/kg at a temperature of 100 ℃ and atmospheric pressure.

Preferably, the solid acidic material has a solubility in glycerol monooleate at a temperature of 100 ℃ and atmospheric pressure of at most 0.1g/kg, more preferably at most 0.01g/kg, and even more preferably at most 0.001 g/kg.

In some preferred embodiments of the invention, the solid acidic material of step ii) is used in an amount of 0.1 to 10% w/w, more preferably 0.5 to 8% w/w, even more preferably 1 to 6% w/w, and more preferably 2 to 5% w/w, relative to the weight of mcc 2.

The Solid acidic material is preferably characterized as described in chapter 3 of "Solid Acid catalysts: From Fundamentals to Applications", h.hattori, y.ono, 2015.

In some preferred embodiments of the invention, step ii) comprises heating the second monoglyceride-containing composition to a temperature in the range of from 50 ℃ to 180 ℃, more preferably from 60 ℃ to 160 ℃, even more preferably from 70 ℃ to 140 ℃, and most preferably from 80 ℃ to 120 ℃.

Temperatures above 180 ℃ result in an increased degree of monoglyceride reduction, which may, for example, convert two molecules of monoglyceride into one molecule of diglyceride and one molecule of glycerol. Preferably such reduction is avoided or at least reduced, in particular during step ii).

The contact time between the solid acidic material and mcc2 was selected to achieve the desired degree of reduction of glycidyl equivalents. The contact time is preferably at most 24 hours, more preferably at most 12 hours, even more preferably at most 6 hours, and most preferably at most 4 hours. The contact time is preferably in the range of 1 minute to 24 hours, more preferably in the range of 2 minutes to 12 hours, even more preferably in the range of 5 minutes to 6 hours, and most preferably in the range of 10 minutes to 4 hours.

The contact between the solid acidic material and the mcc2 can be performed in a number of different ways. The solid acidic material may, for example, be disposed in a packed column or form part of a stationary phase through which mcc2 flows. Alternatively, the solid acidic material may be dispersed in the form of small particles in mcc2 and contacted with mcc2, the mixture being agitated, for example, by stirring. Once step ii) is complete, the solid acidic material is preferably recovered. The solid acidic material is preferably reused and may need to be regenerated after a period of operation.

It is particularly preferred that the solid acidic material is a heterogeneous acid catalyst which catalyzes the conversion of glycidol and/or glycidyl esters.

The solid acidic material of step ii) is preferably selected from one or more of the following: zeolites, zeotypes, acid clays, metal oxides, mixed metal oxides, sulfate oxides, supported acids, cation exchange resins, and combinations thereof.

For example, the solid acidic material of step ii) comprises, or even preferably consists of: acidic X-or Y-zeolites, mordenite, Zeolite Socony Mobil-5 (ZSM-5), or combinations thereof.

It is particularly preferred that the solid acidic material of step ii) comprises, or even consists of: aluminum phosphates (alpos), Silicoaluminophosphates (SAPOs), or combinations thereof.

In some preferred embodiments of the invention, the solid acidic material of step ii) comprises an acidic bleaching clay, an acidic pillared clay, or a combination thereof.

In some preferred embodiments of the invention, the solid acidic material of step ii) comprises Al₂O₃、ZrO₂Or a combination thereof.

In some preferred embodiments of the invention, the solid acidic material of step ii) comprises, or even consists of: crystalline SiO₂-Al₂O₃Crystalline SiO2-ZrO₂Amorphous SiO₂-Al₂O₃Or a combination thereof.

In some preferred embodiments of the invention, the solid acidic material of step ii) comprises sulfated ZrO₂。

In further preferred embodiments of the present invention, the solid acidic material of step ii) comprises a solid supported on SiO₂Or ZrO₂Trifluoromethanesulfonic acid, sulfuric acid, or sulfonic acid as above.

In some preferred embodiments of the invention, the solid acidic material of step ii) comprises, or even consists of: sulfonated matrices, e.g. sulfonated tetrafluoroethylene based fluoropolymer-copolymers (e.g. NAFION)^tm)。

The first and/or second monoglyceride-containing composition preferably comprises:

-at least 25% w/w monoglyceride,

-at least 1ppm of glycidyl equivalent, and

-glycerol, diglycerides and triglycerides.

In some preferred embodiments of the invention the first and/or second mcc comprises at least 30% w/w, more preferably at least 34% w/w, even more preferably at least 40% and most preferably at least 50% w/w of monoglycerides.

Even higher concentrations of monoglycerides may be preferred, and in some preferred embodiments of the invention the first and/or second mcc comprises at least 80% w/w, more preferably at least 90% w/w, even more preferably at least 95%, and most preferably at least 97% w/w monoglycerides.

In some preferred embodiments of the invention, the first and/or second mcc comprises at most 30% w/w glycerol, more preferably at most 25% w/w, even more preferably at most 15%, and most preferably at most 5% w/w glycerol.

Even less glycerol may be preferred, especially in the content of step ii), thus in some preferred embodiments of the invention the first and/or second mcc comprises at most 5% w/w glycerol, more preferably at most 2% w/w, even more preferably at most 0.5%, and most preferably at most 0.1% w/w.

In some preferred embodiments of the invention the first and/or second mcc comprises at most 30% w/w triglycerides, more preferably at most 20% w/w triglycerides, even more preferably at most 10% w/w triglycerides, and most preferably at most 5% w/w triglycerides.

Even less triglycerides may be required, and thus in some preferred embodiments of the invention the first and/or second mcc comprises at most 4% w/w triglycerides, more preferably at most 2% w/w triglycerides, even more preferably at most 0.5% w/w triglycerides, and most preferably at most 0.1% w/w triglycerides.

In some preferred embodiments of the invention the first and/or second mcc comprises a total amount of monoglycerides and diglycerides of at least 50% w/w, more preferably at least 60% w/w, even more preferably at least 70%, and most preferably at least 80% w/w.

In some preferred embodiments of the invention, the first and/or second mcc has a glycidyl equivalent content of at least 1 ppm. Furthermore, the glycidyl equivalent content of the first and/or second mcc is higher than the glycidyl equivalent content of the monoglyceride containing product, preferably at least 20% higher, more preferably at least 50% higher, even more preferably at least 100% higher, and most preferably at least 200% higher.

In some preferred embodiments of the invention, the first and/or second mcc comprises glycidyl equivalents in an amount of at least 2ppm, more preferably at least 5ppm, even more preferably at least 10ppm, and most preferably at least 15 ppm. Even higher levels of glycidyl equivalents can be achieved, and in some preferred embodiments of the invention, the first and/or second mcc contains glycidyl equivalents in an amount of at least 25ppm, more preferably at least 50ppm, even more preferably at least 100ppm, and most preferably at least 200 ppm.

In some preferred embodiments of the invention, the first and/or second mcc comprises glycidyl equivalents in an amount of 1ppm to 2000ppm, more preferably 5ppm to 1000ppm, even more preferably 10ppm to 800ppm, and most preferably 20ppm to 600 ppm. For example, the first and/or second mcc may preferably contain glycidyl equivalents in an amount of 50ppm to 500ppm, and more preferably 100ppm to 300 ppm.

In some preferred embodiments of the invention, the iodine number of the first and/or second mcc is at least 20, more preferably at least 40, even more preferably at least 60, and most preferably at least 75. For example, it may be preferred that the iodine value of mcc1 is from 20 to 200, more preferably from 40 to 150, even more preferably from 60 to 140, and most preferably from 75 to 120.

In other preferred embodiments of the present invention, the iodine number of the first mcc is less than 20, more preferably at most 15, even more preferably at most 10, and most preferably at most 5.

In some preferred embodiments of the invention, the first and/or second mcc has a peroxide value of at most 10meq/kg, more preferably at most 5meq/kg, even more preferably at most 2meq/kg, and most preferably at most 1 meq/kg. It is furthermore preferred that the raw material used for the preparation of mcc likewise has a low peroxide value of preferably at most 10meq/kg, more preferably at most 5meq/kg, even preferably at most 2meq/kg, and most preferably at most 1 meq/kg.

It is particularly preferred that the method of the invention comprises the steps of:

a) contacting glycerol with a diglyceride and/or triglyceride under conditions sufficient to provide a reaction mixture comprising:

-at least 25% w/w monoglyceride,

-at least 1% w/w glycerol,

di-and/or tri-glycerides, and

-at least 1ppm of glycidyl equivalent,

b) subjecting the composition derived from the reaction mixture of step a) to distillation to remove an amount of glycerol, thereby providing a glycerol-enriched first distillate and a monoglyceride-enriched first distillation residue,

c) optionally, subjecting the first distillation residue to distillation to further enrich the monoglycerides, thereby providing a monoglyceride-enriched second distillate and a diglyceride-depleted second distillation residue,

d) optionally, further purifying the first distillation residue and/or the second distillate,

and recovering the first distillation residue of step b), the second distillate of step c) or the further purified composition of step d) as a monoglyceride-containing product,

and wherein the first and/or second monoglyceride-containing composition is a composition derived from step a), b), c) or d).

In the context of the present invention, the term "composition" derived from a "previous composition comprises at least a significant part of the monoglycerides of the previous composition and preferably has a weight ratio between monoglycerides and diglycerides which is substantially the same as, or even higher than, the previous composition.

A "composition" derived from a "previous composition preferably comprises at least 50% w/w monoglyceride of a previous composition, more preferably at least 70% w/w, even more preferably at least 90% w/w, and most preferably at least 95% w/w monoglyceride of a previous composition.

In a preferred embodiment of the invention, a "composition" derived from a "prior composition is the prior composition itself or a monoglyceride concentrate thereof.

In the context of the present invention, the term "monoglyceride concentrate" of a previous composition relates to a composition prepared by processing a previous composition to comprise a higher absolute concentration of monoglycerides than the previous composition. Such methods for concentrating monoglycerides are well known to the skilled person and include, for example, phase separation.

In some preferred embodiments of the present invention, the composition derived from the reaction mixture of step a) is obtained by removing at least some glycerol from the reaction mixture of step a), preferably by separation of a liquid glycerol phase.

As noted above, step a) comprises contacting glycerol with a diglyceride and/or triglyceride under conditions sufficient to provide a reaction mixture comprising:

-at least 25% w/w monoglyceride,

-at least 1% w/w glycerol,

di-and/or tri-glycerides, and

-at least 1ppm of glycidyl equivalent.

The processes for producing monoglycerides are well known to those skilled in the art and the contacting of step a) is typically carried out at a temperature in the range of from 220 ℃ to 300 ℃, and more preferably in the range of from 250 ℃ to 300 ℃. The contacting is generally carried out in the presence of a suitable catalyst and under pressure to assist in the formation of the monoglyceride.

In some preferred embodiments of the invention, the reaction mixture of step a) further comprises one or more of:

a reaction mixture comprising:

-10% w/w to 50% w/w of diglycerides,

-1% w/w to 30% w/w triglycerides, and

-0% w/w to 10% w/w free fatty acids.

In some preferred embodiments of the invention, the reaction mixture of step a) comprises:

-25% w/w to 60% w/w monoglyceride,

-10% w/w to 50% w/w of diglycerides,

-1% w/w to 30% w/w triglycerides,

-1% w/w to 25% w/w glycerol,

-0% w/w to 10% w/w free fatty acids, and

-at least 1ppm of glycidyl equivalent.

The reaction mixture of step a) preferably comprises glycidyl equivalents in an amount of at least 5ppm, more preferably at least 10ppm, even more preferably at least 15ppm, and most preferably at least 20 ppm.

Even higher levels of glycidyl equivalents can be achieved and in some preferred embodiments of the invention the reaction mixture of step a) comprises glycidyl equivalents in an amount of at least 50ppm, more preferably at least 100ppm, even more preferably at least 150ppm, and most preferably at least 200 ppm.

In some preferred embodiments of the invention, the reaction mixture of step a) comprises glycidyl equivalents in an amount of from 1ppm to 2000ppm, more preferably from 5ppm to 1000ppm, even more preferably from 10ppm to 800ppm, and most preferably from 20ppm to 600 ppm. For example, the reaction mixture of step a) may preferably comprise glycidyl equivalents in an amount of 50ppm to 500ppm, and more preferably 100ppm to 300 ppm.

In some preferred embodiments of the invention, the total amount of mono-and diglycerides of the reaction mixture of step a) is at least 50% w/w, more preferably at least 60% w/w, even more preferably at least 70% w/w, and most preferably at least 80% w/w.

In some preferred embodiments of the invention, the iodine number of the reaction mixture of step a) is at least 20, more preferably at least 40, even more preferably at least 60, and most preferably at least 75. For example, it may be preferred that the iodine number of the reaction mixture of step a) is from 20 to 200, more preferably from 40 to 150, even more preferably from 60 to 140, and most preferably from 75 to 120.

In other further preferred embodiments of the present invention, the iodine value of the reaction mixture of step a) is less than 20, more preferably at most 15, even more preferably at most 10, and most preferably at most 5.

In some preferred embodiments of the invention, the peroxide number of the reaction mixture of step a) is at most 10meq/kg, more preferably at most 5meq/kg, even more preferably at most 2meq/kg, and most preferably at most 1 meq/kg. It is furthermore preferred that the starting materials used for the preparation of the reaction mixture of step a) likewise have a low peroxide value of preferably at most 10meq/kg, more preferably at most 5meq/kg, even preferably at most 2meq/kg, and most preferably at most 1 meq/kg.

As mentioned above, step b) comprises subjecting the composition derived from the reaction mixture of step a) to distillation to remove an amount of glycerol, thereby providing a glycerol-enriched first distillate and a monoglyceride-enriched first distillation residue.

In some preferred embodiments of the invention, the composition of the reaction mixture derived from step a) distilled in step b) comprises:

-25% w/w to 80% w/w monoglyceride,

-10% w/w to 50% w/w of diglycerides,

-1% w/w to 30% w/w triglycerides,

-1% w/w to 25% w/w glycerol,

-0% w/w to 10% w/w free fatty acids, and

-at least 1ppm of glycidyl equivalent.

The distillation of step b) may for example involve a continuous tray, thin layer, packed column or short path distillation. Suitable temperatures and pressures are preferably in the range from 100 ℃ to 210 ℃ and from 0.001 mbar to 50 mbar, more preferably in the range from 110 ℃ to 190 ℃ and from 0.01 mbar to 20 mbar, even more preferably in the range from 120 ℃ to 170 ℃ and from 0.1 mbar to 10 mbar. Superheated steam may be used, for example, to increase removal of glycerol on a tray or packed distillation column.

As mentioned above, the process of the invention may optionally comprise a step c) of subjecting the first distillation residue to distillation to further enrich the monoglycerides, thereby providing a monoglyceride-enriched second distillate and a diglyceride-depleted second distillation residue.

Thus, in some preferred embodiments of the invention, the process of the invention comprises a step c) of subjecting the first distillation residue to distillation to further enrich the monoglycerides, thereby providing a monoglyceride-enriched second distillate and a diglyceride-depleted second distillation residue.

However, in other preferred embodiments of the present invention, the method does not comprise step c).

The distillation of step c) can for example be carried out as a continuous short path distillation using temperatures and pressures in the range of 150 ℃ to 250 ℃ and 0.0001 mbar to 10 mbar, preferably 160 ℃ to 230 ℃ and 0.001 mbar to 1 mbar, even more preferably 170 ℃ to 220 ℃ and 0.001 mbar to 0.1 mbar.

As mentioned above, the process of the present invention optionally comprises d) further purifying the first distillation residue and/or the second distillate.

Thus, in some preferred embodiments of the present invention, the method of the present invention comprises step d). However, in other preferred embodiments of the present invention, the method does not comprise step d).

Further purification may, for example, involve stripping on a packed or tray distillation column, bleaching with an adsorptive bleaching agent (e.g., bleaching earth) and/or a reductive bleaching agent (e.g., hydrogen peroxide, sodium borohydride, or sodium hypophosphite).

In some preferred embodiments of the invention, the method comprises at least step i), and step i) is performed during or before step b).

In some preferred embodiments of the invention, the process comprises at least step i) and step c), and step i) is performed before the distillation of step c).

In some preferred embodiments of the invention, the process comprises at least step i) and step d), and step i) is performed before further purification of step d).

In some preferred embodiments of the invention, the process of the invention comprises at least step ii), and step ii) is performed after step b), and preferably after step c) and/or d) if step c) and/or d) forms part of the process.

The inventors have found that it is advantageous to carry out step ii) on a composition having a relatively low concentration of glycerol. It is therefore preferred that the glycerol content of the mcc2 is at most 10% w/w, more preferably at most 5% w/w, even more preferably at most 1% w/w, and most preferably at most 0.5% w/w.

If not used directly after production, the monoglyceride-containing product is preferably packaged in a suitable container. The suitable container may be, for example, a bulk shipping container in a truck, an intermediate bulk container, a drum, a tank, a bag, or a box. If a bin is used, it preferably has a polymeric liner that is in contact internally with the monoglyceride-containing product. If the monoglyceride-containing product is transferred to a bulk transport container in a truck, it is generally preferred to maintain the monoglyceride-containing product at a temperature sufficient to keep it liquid during storage and transport.

Another aspect of the invention relates to a monoglyceride-containing product, e.g. obtainable according to the process described herein.

The monoglyceride-containing product preferably comprises:

-at least 80% w/w monoglyceride,

up to 1ppm of glycidyl equivalent, and

-optionally, glycerol, diglycerides and triglycerides.

In some preferred embodiments of the invention, the monoglyceride-containing product comprises at least 50% w/w, more preferably at least 60% w/w, even more preferably at least 70%, and most preferably at least 75% w/w monoglyceride.

Even higher concentrations of monoglycerides may be preferred, and in some preferred embodiments of the invention, the monoglyceride-containing product comprises at least 80% w/w, more preferably at least 90% w/w, even more preferably at least 95%, and most preferably at least 97% w/w monoglycerides.

In some preferred embodiments of the invention, the monoglyceride-containing product comprises at most 5% w/w glycerol, more preferably at most 2% w/w glycerol, even more preferably at most 0.5% w/w glycerol, and most preferably at most 0.1% w/w glycerol.

In some preferred embodiments of the invention, the monoglyceride-containing product comprises a total amount of water of at most 2% w/w, more preferably at most 1% w/w, even more preferably at most 0.3%, and most preferably at most 0.1% w/w.

In some preferred embodiments of the invention, the monoglyceride-containing product comprises at most 5% w/w triglycerides, more preferably at most 2% w/w triglycerides, even more preferably at most 0.5% w/w triglycerides, and most preferably at most 0.1% w/w triglycerides.

In some preferred embodiments of the invention, the monoglyceride-containing product comprises at least 70% w/w, more preferably at least 60% w/w, even more preferably at least 70%, and most preferably at least 80% w/w of the total amount of monoglycerides and diglycerides.

Even higher concentrations of monoglycerides may be preferred, and in some preferred embodiments of the invention, the monoglyceride-containing product comprises at least 80% w/w monoglyceride, more preferably at least 90% w/w, even more preferably at least 95%, and most preferably at least 97% w/w of the total amount of monoglycerides and diglycerides.

In some preferred embodiments of the invention, the glycidyl equivalent content of the monoglyceride-containing product is at most 10ppm, more preferably at most 5ppm, even more preferably at most 1ppm, and most preferably at most 0.5 ppm.

The inventors have demonstrated that the present invention makes it possible to achieve even lower glycidyl equivalent contents, and in some preferred embodiments of the invention, the glycidyl equivalent content of the monoglyceride-containing product is at most 0.3ppm, more preferably at most 0.1ppm, even more preferably at most 0.05ppm, and most preferably at most 0.02 ppm.

In some preferred embodiments of the invention, the iodine value of the monoglyceride-containing product is at least 20, more preferably at least 40, even more preferably at least 60, and most preferably at least 75. For example, it may be preferred that the iodine value of the monoglyceride-containing product is from 20 to 200, more preferably from 40 to 150, even more preferably from 60 to 140, and most preferably from 75 to 120.

In other preferred embodiments of the present invention, the iodine value of the monoglyceride-containing product is less than 20, more preferably at most 15, even more preferably at most 10, and most preferably at most 5.

In some preferred embodiments of the invention, the peroxide number of the monoglyceride-containing product is at most 10meq/kg, more preferably at most 5meq/kg, even more preferably at most 2meq/kg, and most preferably at most 1 meq/kg.

The present inventors have found that the present invention is particularly useful for producing monoglyceride containing products having a high monoglyceride content, a low equivalent glycidyl content.

Thus, in some particularly preferred embodiments of the invention, the monoglyceride-containing product comprises:

-at least 90% w/w monoglyceride, more preferably 95% w/w monoglyceride, and even more preferably at least 97% w/w monoglyceride, and

-a content of glycidyl equivalents of at most 10ppm, more preferably at most 5ppm, even more preferably at most 1ppm, and most preferably at most 0.5 ppm.

The present inventors have also found that the present invention is particularly useful for producing monoglyceride containing products having a high monoglyceride content, a low equivalent glycidyl content and a low peroxide value. This is even more evident when producing monoglyceride containing products with high unsaturation which are more prone to peroxide formation.

Thus, in some particularly preferred embodiments of the invention, the monoglyceride-containing product comprises:

-at least 90% w/w monoglyceride, more preferably 95% w/w monoglyceride, and even more preferably at least 97% w/w monoglyceride,

-glycidyl equivalents of at most 10ppm, more preferably at most 5ppm, even more preferably at most 1ppm, and most preferably at most 0.5ppm,

and has:

-a peroxide value of at most 10meq/kg, more preferably at most 5meq/kg, even preferably at most 2meq/kg, and most preferably at most 1 meq/kg.

In other preferred embodiments of the present invention, the monoglyceride-containing product comprises:

-at least 90% w/w monoglyceride, more preferably 95% w/w monoglyceride, and even more preferably at least 97% w/w monoglyceride,

a content of glycidyl equivalents of at most 10ppm, more preferably at most 5ppm, even more preferably at most 1ppm, and most preferably at most 0.5ppm,

and has:

a peroxide value of at most 10meq/kg, more preferably at most 5meq/kg, even preferably at most 2meq/kg, and most preferably at most 1meq/kg,

an iodine number of at least 20, more preferably at least 40, even preferably at least 60, and most preferably at least 75.

Yet another aspect of the present invention relates to the use of step i) and/or step ii) for the production of a monoglyceride-containing product comprising at least 25% w/w monoglyceride and having a low glycidyl equivalent content; wherein

Step i) comprises heat treating a first monoglyceride-containing composition comprising at least 25% w/w monoglyceride, which heat treatment involves heating the monoglyceride-containing composition to a temperature in the range 90 ℃ to 210 ℃, preferably for a duration sufficient to reduce the total content of glycidyl equivalents by at least 50%, and wherein

Step ii) comprises contacting a second monoglyceride-containing composition comprising at least 25% w/w monoglyceride with a solid acidic material which is preferably insoluble in monoglycerides.

The above uses are preferably used to reduce the level of glycidyl equivalents in mcc and thus in the final monoglyceride containing product.

The invention has been described above with reference to specific embodiments and aspects. However, other embodiments than the above described are equally possible within the scope of the invention. The various features and steps of the various embodiments and aspects of the present invention may be combined in other ways than those described herein, unless expressly stated otherwise.

Examples

Analysis 1.1: determination of the content of glycidyl equivalents

The content of glycidyl equivalents was determined according to AOCS Official Method Cd 29b-13, re-approved in 2017.

Analysis 1.2: determination of the amounts of mono-, di-, tri-, free glycerol and free fatty acids

The amounts of mono-glycerides (MAG), di-glycerides (DAG), Triglycerides (TAG), free glycerol and Free Fatty Acids (FFA) were determined according to AOCS office Method Cd 11b-91, re-approved in 2009.

Analysis 1.3: determination of peroxide number

The peroxide value of the sample was determined according to AOCS Official Method Cd 8 b-90. Peroxide value in units meq H₂O₂Provided as a/kg sample.

Analysis 1.4: determination of iodine value

Iodine Value (IV) of the sample was determined according to AOAC office Method 993.20. Iodine value is expressed as grams of iodine absorbed by a test portion of 100g following the specified procedure.

Analysis 1.5: determination of Lovibond color

Lovibond color was measured according to AOCS Cc 13 j-97. The samples were measured in a cuvette of 25.4mm (1 inch) cell path length.

Example 1: conventional method for producing monoglycerides and diglycerides

Conventional monoglyceride-containing products are produced using steps a), b), c) and d).

a) 90g of glycerol, 210g of high-oleic sunflower oil (iodine number 80) and 0.75g of NaOH(s) were placed in a three-neck round-bottom flask and stirred. The reaction mixture was heated to 250 ℃ at 500 mbar for 60 minutes after the reaction temperature was reached. The hot reaction mixture was rapidly cooled to 80 ℃ in an ice/water bath. 0.72g H was added with stirring₃PO₄(85% aqueous solution), and the precipitate formed was removed by filtration. The reaction mixture was analyzed for composition and total glycidol content.

b) The reaction mixture from step a) was allowed to separate in a separatory funnel for 60 minutes in a heating box at 80 ℃. The lower glycerol phase was removed and discarded and the upper glycerol ester phase was collected and analyzed for composition and total glycidyl content.

c) The product from step b) was distilled at 130 ℃ and 0.3 mbar pressure on a UIC KDL 5 short path vacuum distillation apparatus and the product was collected as residue. The product was analyzed for composition and total glycidol content.

d) The product from step c) was distilled at 170 ℃ and 0.001 mbar pressure on a UIC KDL 5 short path vacuum distillation apparatus and the product was collected as distillate. The product was analyzed for composition and glycidyl equivalent content.

The results are summarized below:

example 2: effect of heat treatment at different temperatures

In N₂The product prepared as described in example 1b) was then heated to 110 ℃, 150 ℃, 180 ℃, 210 ℃, 230 ℃ and 250 ℃ for 10 minutes and then rapidly cooled to 25 ℃. The product was analyzed for composition and glycidyl equivalent content. The results are summarized below and shown in fig. 1:

and (4) conclusion:

the most effective temperature for glycidol reduction is about 180 ℃. It was furthermore observed that the MAG content decreased when operating in the temperature range of 180 ℃ to 250 ℃.

Example 3: heat treatment at 140 ℃ for different durations

In N₂The product prepared as described in example 1d) was heated to 140 ℃ and heated under N₂Samples were taken at 0 hours, 4 hours, 8 hours and 12 hours and then rapidly cooled to 25 ℃. The product was analyzed for composition and glycidyl equivalent content. The results are summarized below and shown in fig. 2:

and (4) conclusion:

after 8 hours, the glycidol was significantly reduced, however the MAG content was reduced from 98.1% to 95.2%, which reduced the quality of the finished product.

Example 4: glycidol reduction effect of different solid acidic materials

The product from example 1d) was heated to 110 ℃ and 1% or 2% of a heterogeneous catalyst was added, under N₂The mixture was then stirred at 110 ℃ for 10 minutes. The catalyst was removed by filtration and the reaction mixture was rapidly cooled to 25 ℃. The product was analyzed for composition and glycidyl equivalent content.

The results are summarized below and shown in fig. 3:

and (4) conclusion:

the glycidol reduction was accelerated by the addition of various acidic catalysts, however the MAG content decreased at different rates depending on the type of acidic catalyst used.

Example 5: effect of concentration of solid acidic Material on glycidol removal

Heating the product from example 1d) to 110 ℃ and adding 0.25%, 0.50% or 1.00% Siral 40, and reacting in N₂The mixture was then stirred at 110 ℃ for 10 minutes. The catalyst was removed by filtration and the reaction mixture was rapidly cooled to 25 ℃. The product was analyzed for composition and glycidyl equivalent content. The results are summarized below and shown in fig. 4:

and (4) conclusion:

the reduction in glycidol increases significantly with higher amounts of Siral 40, but only very limited degradation of MAG was observed.

Example 6: synergistic effect between heat treatment in low-glycerol environment and solid acidic material

The product from example 1d) was heated to 110 ℃, 150 ℃ or 180 ℃ and 1.00% Siral 40 was added, in N₂The mixture was then stirred at 110 deg.C, 150 deg.C or 180 deg.C for 10 minutes. The catalyst was removed by filtration and the reaction mixture was rapidly cooled to 25 ℃. A reference experiment was performed for each temperature using exactly the same procedure without addition of catalyst. The product was analyzed for composition, total Lovibond color and glycidyl equivalent content. The results are summarized below:

and (4) conclusion:

this example shows that the degradation of glycidol is accelerated at 110 ℃ to 180 ℃ and that the degradation of MAG is reduced by the addition of Siral 40. Furthermore, the Lovibond red and yellow colors were reduced at 150 ℃ and 180 ℃ by the addition of Siral 40.

Example 7: heat treatment before and after distillation

1) The product was prepared as described in steps a) and b) of example 1 and was prepared under N₂A sample of the product of step b) -was taken off and then rapidly cooled to 25 ℃. Samples were analyzed for glycidol.

2) In N₂The product from step 1) was then heated to 150 ℃ for a duration of 60 minutes. In N₂Samples were taken down and then rapidly cooled to 25 ℃. Samples were analyzed for glycidol.

3) The product of step 2) was distilled as described in steps c) and d) of example 1. In N₂A sample of the resulting product was removed and then rapidly cooled to 25 ℃. Samples were analyzed for glycidol.

4) In N₂The product from step 3) is heated to 100 ℃. In N₂Samples were taken at 240 min, 480 min, 720 min and 1440 min and then rapidly cooled to 25 ℃. The product was analyzed for composition and glycidyl equivalent content. The results are summarized below.

And (4) conclusion:

the present inventors have found that it is beneficial to apply heat treatment at various stages in the monoglyceride production process.

Example 8: heat treatment before distillation, followed by treatment with solid acidic material

1) The product was prepared as described in steps a) and b) of example 1 and was prepared under N₂A sample of the product of step b) -was taken off and then rapidly cooled to 25 ℃. Samples were analyzed for glycidol.

2) In N₂The product from step 1) was then heated to 150 ℃ for a duration of 60 minutes. In N₂Samples were taken down and then rapidly cooled to 25 ℃. Samples were analyzed for glycidol.

3) The product of step 2) was distilled as described in steps c) and d) of example 1. In N₂A sample of the product of step d) was taken off and then rapidly cooled to 25 ℃. Samples were analyzed for glycidol.

4) Heating the product from step 3) to 150 ℃ and adding 1 w/w% Siral 40, and adding N₂The mixture was then stirred at 150 ℃ for 10 minutes. Subsequently the Siral 40 was removed by filtration and the reaction mixture was rapidly cooled to 25 ℃. The product was analyzed for glycidyl equivalent content.

And (4) conclusion:

the inventors have found that it is beneficial to apply a heat treatment before distillation and then a treatment with SIRAL 40 after distillation.

Example 9 Mass production-steamingHeat treatment before distillation

A series of experiments were conducted in an industrial monoglyceride/monoglyceride-diglyceride production facility to demonstrate the method of the present invention on a large scale. An overview of the process setup is shown in fig. 6.

The heat treatment unit is inserted after decanting the glycerol, as this is expected to provide the best product quality of the finished product. The heat treatment is carried out as a continuous process using a tundish which can accommodate an amount of intermediate product corresponding to 2 hours flowing to the distillation apparatus. The tank was of a standard non-agitated stainless steel type with a protective nitrogen atmosphere. The intermediate product resulting from the decantation is heated by a plate heat exchanger and fed to the top of the tank onto the inner side wall of the tank to minimize mixing with the product in the tank. The product is pumped out of the bottom of the tank and pumped to the normal distillation process. The heat treatment time was adjusted by controlling the amount in the tank using an inlet pump and an outlet pump. The quantity in the tank is measured by a standard radar level sensor. Or a load cell may be used. The optimum heat treatment conditions in the apparatus are about 110 minutes to 130 minutes at about 150 ℃ to 160 ℃.

The following typical results were obtained based on the average of 3 independent experiments performed with each monoglyceride-containing composition.

And (4) conclusion: the present inventors have demonstrated that the heat treatment process can be applied to monoglyceride compositions based on a variety of raw materials, and that it can be carried out on a large scale.

EXAMPLE 10 Mass production-Heat treatment after distillation

A series of experiments were conducted in an industrial monoglyceride/monoglyceride-diglyceride production facility to demonstrate the method of the present invention on a large scale. An overview of the process setup is shown in fig. 7.

A heat treatment unit was inserted after the distillation unit to demonstrate the possibility of removing glycidol from the distilled monoglyceride product. The heat treatment is operated as a continuous process using a tundish which can hold an amount of intermediate product equivalent to 2 hours flowing to the distillation apparatus. The tank was of a standard non-agitated stainless steel type with a protective nitrogen atmosphere. The distilled product is heated by a plate heat exchanger and fed to the top of the tank onto the inside wall of the tank to minimize mixing with the product in the tank. The product was pumped out of the bottom of the tank prior to analysis. The heat treatment time was adjusted by controlling the amount in the tank using an inlet pump and an outlet pump. In the following examples, the heat treatment involved a reaction time of 2 hours and a heat treatment temperature of 155 ℃.

The following typical results were obtained based on the average of 2 independent experiments performed with each monoglyceride-containing composition.

And (4) conclusion: the present inventors have demonstrated that the heat treatment process can be applied to distilled monoglyceride compositions based on a variety of raw materials, and that it can be carried out on a large scale 32.

Claims (34)

1. A process for producing a monoglyceride-containing product comprising at least 25% w/w monoglyceride and having a low glycidyl equivalent content, which process comprises:

step i) heat treating a first monoglyceride-containing composition comprising at least 25% w/w monoglyceride and a total glycidyl equivalent content of at least 2ppm, the heat treatment comprising heating the first monoglyceride-containing composition to a temperature in the range of from 90 ℃ to 210 ℃ for a duration sufficient to reduce the total glycidyl equivalent content by at least 50%, and/or

Step ii) contacting a second monoglyceride-containing composition comprising at least 25% w/w monoglyceride and a total content of glycidyl equivalents of at least 1ppm with a solid acidic material.

2. The process according to any one of the preceding claims, wherein the heat treatment of step i) comprises heating the first monoglyceride-containing composition to a temperature in the range of from 95 ℃ to 195 ℃, more preferably from 100 ℃ to 180 ℃, even more preferably from 120 ℃ to 170 ℃, and most preferably from 140 ℃ to 160 ℃.

3. The method according to any one of the preceding claims, wherein the heat treatment of step i) comprises heating the first monoglyceride-containing composition for a duration sufficient to reduce the total glycidyl equivalent content by at least 70%, more preferably at least 80%, and most preferably at least 90%.

4. The method according to any of the preceding claims, wherein the heat treatment of step i) and/or step ii) is performed with an inert atmosphere.

5. The process according to any of the preceding claims, wherein the solid acidic material of step ii) is used in an amount of 0.1 to 10 w/w% relative to the weight of the second monoglyceride-containing composition.

6. The process according to any one of the preceding claims, wherein the solid acidic material of step ii) provides a pH of at most 5 when 10g of the solid acidic material is mixed in 100ml demineralized water at 25 ℃ and allowed to equilibrate for 10 minutes; more preferably a pH of at most 4, even more preferably a pH of at most 3, and most preferably a pH of at most 2.

7. The process according to any preceding claims, wherein step ii) comprises heating the second monoglyceride-containing composition to a temperature in the range of from 50 ℃ to 180 ℃, more preferably from 60 ℃ to 160 ℃, even more preferably from 70 ℃ to 140 ℃, and most preferably from 80 ℃ to 120 ℃.

8. A method according to any one of the preceding claims, wherein the solid acidic material of step ii) is selected from one or more of the following: zeolites, zeotypes, acid clays, metal oxides, mixed metal oxides, sulfated oxides, supported acids, and cation exchange resins, and combinations thereof.

9. The method according to any one of the preceding claims, wherein the first and/or second monoglyceride-containing composition comprises:

-at least 25% w/w monoglyceride,

-at least 1ppm of glycidyl equivalent, and

-glycerol, diglycerides and triglycerides.

10. The method according to any of the preceding claims, wherein the first and/or second monoglyceride-containing composition comprises at least 30% w/w, more preferably at least 34% w/w, even more preferably at least 40%, and most preferably at least 50% w/w monoglyceride.

11. The method according to any of the preceding claims, wherein the first and/or second monoglyceride-containing composition comprises at most 30% w/w, more preferably at most 25% w/w, even more preferably at most 15%, and most preferably at most 5% w/w glycerol.

12. The method according to any of the preceding claims, wherein the first and/or second monoglyceride-containing composition comprises at most 30% w/w triglycerides, more preferably at most 20% w/w triglycerides, even more preferably at most 10% w/w triglycerides, and most preferably at most 5% w/w triglycerides.

13. The method according to any of the preceding claims, wherein the first and/or second monoglyceride-containing composition comprises a total amount of monoglycerides and diglycerides of at least 50% w/w, more preferably at least 60% w/w, even more preferably at least 70%, and most preferably at least 80% w/w.

14. The method according to any one of the preceding claims, wherein the first and/or second monoglyceride-containing composition comprises glycidyl equivalents in an amount of at least 5ppm, more preferably at least 10ppm, even more preferably at least 15ppm, and most preferably at least 20 ppm.

15. The method according to any one of the preceding claims, comprising step i).

16. The method according to any of the preceding claims, comprising step ii).

17. The method according to any of the preceding claims, comprising both steps i) and ii).

18. The method according to any one of the preceding claims, comprising both steps i) and ii), and wherein step i) is performed before step ii).

19. The process according to any one of the preceding claims, wherein the monoglyceride-containing product is packaged in a suitable container, including a bulk transport container in a truck, an intermediate bulk container, a drum, a tank, a bag, a bin with a polymeric liner.

20. The method according to any of the preceding claims, further comprising the step of:

a) contacting glycerol with a diglyceride and/or triglyceride under conditions sufficient to provide a reaction mixture comprising:

-at least 25% w/w monoglyceride,

-at least 1% w/w glycerol,

di-and/or tri-glycerides, and

-at least 1ppm of glycidyl equivalent,

b) subjecting the composition of the reaction mixture derived from step a) to distillation to remove an amount of glycerol, thereby providing a first distillate enriched in glycerol and a first distillation residue enriched in monoglycerides,

c) optionally subjecting the first distillation residue to distillation to further enrich the monoglycerides, thereby providing a monoglyceride-enriched second distillate and a diglyceride-depleted second distillation residue,

d) optionally, further purifying the first distillation residue and/or the second distillate,

and recovering the first distillation residue of step b), the second distillate of step c) or the further purified composition of step d) as the monoglyceride-containing product,

and wherein the first and/or second monoglyceride-containing composition is a composition derived from step a), b), c) or d).

21. The process according to any one of the preceding claims, wherein the reaction mixture of step a) comprises:

-25% w/w to 60% w/w monoglyceride,

-10% w/w to 50% w/w of diglycerides,

-1% w/w to 30% w/w triglycerides,

-1% w/w to 25% w/w glycerol,

-0% w/w to 10% w/w free fatty acids, and

-at least 1ppm of glycidyl equivalent.

22. The process according to any of the preceding claims, wherein the reaction mixture of step a) comprises glycidyl equivalents in an amount of at least 5ppm, more preferably at least 10ppm, even more preferably at least 15ppm, and most preferably at least 20 ppm.

23. The process according to any of the preceding claims, wherein the total amount of mono-and diglycerides of the reaction mixture of step a) is at least 50% w/w, more preferably at least 60% w/w, even more preferably at least 70% w/w, and most preferably at least 80% w/w.

24. The process according to any one of the preceding claims, wherein the composition provided in step b) derived from the reaction mixture of step a) comprises:

-25% w/w to 80% w/w monoglyceride,

-10% w/w to 50% w/w of diglycerides,

-1% w/w to 30% w/w triglycerides,

-1% w/w to 25% w/w glycerol,

-0% w/w to 10% w/w free fatty acids, and

-at least 1ppm of glycidyl equivalent.

25. The method according to any of the preceding claims, comprising at least step i), and wherein step i) is performed during or before step b).

26. The process according to any one of the preceding claims, comprising at least step i) and step c), and wherein step i) is carried out before the distillation of step c).

27. The method according to any of the preceding claims, comprising at least step ii), and wherein step ii) is performed after step b), and if steps c) and/or d) form part of the method, step ii) is also preferably performed after steps c) and/or d).

28. The process according to any of the preceding claims, wherein the glycidyl equivalent content of the monoglyceride-containing product is at most 10ppm, more preferably at most 5ppm, even more preferably at most 1ppm, and most preferably at most 0.5 ppm.

29. A process according to any one of the preceding claims, wherein the iodine value of the monoglyceride-containing product is at least 20, more preferably at least 40, even more preferably at least 60, and most preferably at least 75.

30. The process according to any of the preceding claims, wherein the monoglyceride-containing product has a peroxide value of at most 10meq/kg, more preferably at most 5meq/kg, even preferably at most 2meq/kg, and most preferably at most 1 meq/kg.

31. A monoglyceride-containing product obtainable according to claim 1 and preferably obtainable according to one or more of claims 2 to 30.

32. The monoglyceride-containing product according to claim 31, comprising:

-at least 90% w/w monoglyceride, more preferably 95% w/w monoglyceride, even more preferably at least 97% w/w monoglyceride,

-glycidyl equivalents of at most 10ppm, more preferably at most 5ppm, even more preferably at most 1ppm, and most preferably at most 0.5ppm,

and has:

-a peroxide value of at most 10meq/kg, more preferably at most 5meq/kg, even preferably at most 2meq/kg, and most preferably at most 1 meq/kg.

33. The monoglyceride-containing product according to claim 32, further having an iodine value of at least 20, more preferably at least 40, even preferably at least 60, and most preferably at least 75.

34. Use of step i) and/or step ii) for the production of a monoglyceride-containing product comprising at least 25% w/w monoglyceride and having a low glycidyl equivalent content; wherein

Step i) comprises heat treating a first monoglyceride-containing composition comprising at least 25% w/w monoglyceride, which heat treatment comprises heating the monoglyceride-containing composition to a temperature in the range 90 ℃ to 210 ℃ for a duration sufficient to reduce the total content of glycidyl equivalents by at least 50%,

and wherein

Step ii) comprises contacting a second monoglyceride-containing composition comprising at least 25% w/w monoglyceride with a solid acidic material.

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