WO2017085737A1

WO2017085737A1 - A natural based monoglyceride with improved odor and flavor

Info

Publication number: WO2017085737A1
Application number: PCT/IN2016/000274
Authority: WO
Inventors: Prakash Damodar KAMAT
Original assignee: Fine Research & Development Centre Pvt Ltd
Priority date: 2015-11-19
Filing date: 2016-11-17
Publication date: 2017-05-26

Abstract

The subject-matter relates to a monoacylglyceride and a catalyst-free process of production of said monoacylglyceride by transesterfication of natural oils/fats with glycerole at temperatures between 230°C- 260°C under a high pressure nitrogen atmosphere. The resulting product contains 40-50% by weight of monoacylglyceride, 30-45% by weight of diacylglyceride and 5-30% by weight of triacylglyceride and can be further enriched in monoacylglyceride by distillation. It is intended for use as emulsifier for food, cosmetics or polymers.

Description

A NATURAL BASED MONOGLYCERIDE WITH IMPROVED ODOR AND FLAVOR

The present invention relates to natural based monoglyceride with improved odor and flavor and its process of preparation. Background of the invention

Great Britain Patent number 763474 suggests preparation of glycerylmonostearate by heating a mixture of the fatty acid and glycerol with or without a catalyst to high temperature.

Journal of the American Oil Chemists Society Vol.59, No.lO published in October 1982 a technical news feature (pg 795 -802A) on Glycerolysis of Fats and Methyl Esters-Status, Review and critique by Norman O.V. Sonnt AG. The paper discloses that the reaction between a fat and glycerol will take place without a catalyst present but the rate is reasonably rapid only near 287°C, or prohibitively too high for practical commercial operations. Fat glycerolyses may be carried out with sodium or potassium hydroxide as catalyst for industrial scale, in order to reduce cycle time. Grun disclosed that fats such as palm oil and tallow could be interchanged with glycerol in the presence of tin catalyst. The present invention provides monoglyceride with improved odor and flavor at lower temperatures without catalyst.

United States Patent number 3083216 (assigned to M/S Colgate -Palmolive Company) exemplifies use of 1000 parts of glycerine per part of tallow for the preparation of high purity glycerylmonostearte (90%) at 280°C under a nitrogen atmosphere in the presence of catalyst, caustic soda. The present invention prepares monoglyceride with lower parts of glycerine yielding colorless monoglyceride with controlled free glycerine and low acid value. Further, it will encompass an additional process step for deactivating the caustic soda. The addition of catalyst like caustic soda could impart color to the monoglyceride. The use of caustic soda could also contaminate monoglyceride with soap.

l United States Patent number 3160646 (assigned to M/S Henkel & Cie G.m.b.H ) claims use of 50 mol % of glycerol with fatty acid esters at 260-300°C to prepare high content of monoglycerides. The present invention provides monoglyceride with improved odor and flavor from vegetable oils and/or fats with lower parts of glycerine yielding monoglyceride with controlled free glycerine.

A two-stage procedure for the high-yield manufacture of monoglycerides for use as emulsifying agents from triglycerides and glycerol using lipase is described in European published patent application number 445692A2. However, processes with lipases are not commercially viable and longer hours of processing.

Prior art suggests preparation of monoglycerides by reacting glycerol with fatty acid radical in the presence of catalyst. The disadvantages in the use of catalyst is that at the end of the reaction the catalyst needs to be destroyed or removed as they could cause reversion, and furthermore contribute in the case of food emulsifiers to problems of soapy taste, color stability and occasionally when the product is used at higher temperature to foaming problems.

The process of the present invention will be conducted in the absence of catalyst and hence will be economical with less number of unit operations. Further the product will be free of catalyst associated contaminants.

Object of the invention

The object of the present invention provides a natural based monoglyceride with improved odor, flavor and color.

Yet another object is a commercially feasible non-catalytic process for the preparation of a natural based monoglyceride with improved odor, flavor and color.

Summary of the invention

A natural based monoglyceride with improved odor and flavor.

A natural based monoglyceride with improved odor and flavor and wherein the natural based monoglyceride comprises 40 to 50% by weight monoglyceride, 30 to 45% by weight diglyceride and 5 to 30% by weight triglyceride.

A non-catalytic process for the preparation of natural based monoglyceride with improved odor and flavor comprising reacting unsaturated and/or saturated vegetable oils and/or fats with glycerine at a temperature of about 230°C to 260°C under nitrogen atmosphere of about 1 to 10 kg/cm²; wherein the mole ratio of fatty acyl groups in said unsaturated and/or saturated vegetable oils and/or fats to total glyceryl is about 1:4.

A 90% natural based monoglyceride prepared by a non-catalytic process comprising reacting unsaturated and/or saturated vegetable oils and/or fats with glycerine at a temperature of about 23Q°C to 260°C under nitrogen atmosphere of about 1 to 10 kg/cm²; wherein the mole ratio of fatty acyl groups in said unsaturated and/or saturated vegetable oils and/or fats to total glyceryl is about 1:4; further comprising short path distillation. Description of the invention

Monoglycerides are used in many industries as additives. Some of the industries are food, cosmetics and polymers. For uses in foods, cosmetics and polymers for the food packaging industry the end users demand additional properties such as the additive should be free of odor, flavor and color.

The present invention provides a natural based monoglyceride with improved odor, flavor and color. According to one embodiment of the present invention is a natural based monoglyceride with improved odor and flavor.

The fatty acyl group in the monoglyceride may be with 8 to 22 carbon atoms. The natural based monoglyceride with improved odor and flavor of the present invention comprises 40% to 50% by weight monoglyceride, 30 to 45% by weight diglyceride and 5 to 30% by weight triglyceride.

The natural based monoglyceride with improved odor and flavor of the present invention has color ranging from 0.4 to 0.6 G.

The natural based monoglyceride with improved odor and flavor of the present invention has an acid value of 1.2 to 1.5. The natural based monoglyceride with improved odor and flavor of the present invention is free of soap i.e. metal salt of fatty acid such as sodium or potassium salt of fatty acid. The natural based monoglyceride with improved odor and flavor is used in the preparation of natural emulsifiers for foods and cosmetics as it is free from catalysts, partially hydrogenated oils, inorganic materials and organic impurities.

The natural based monoglyceride with improved odor and flavor is also used in polymers.

According to another embodiment of the present invention is a non-catalytic process for the preparation of natural based monoglyceride with improved odor and flavor comprising reacting unsaturated and/or saturated vegetable oils and/or fats with glycerine at a temperature of about 230°C to 260°C under nitrogen atmosphere of about 1 to 10 kg/cm²; wherein the mole ratio of fatty acyl groups in said unsaturated and/or saturated vegetable oils and/or fats to total glyceryl is about 1:4.

The fatty acyl group in the monoglyceride and vegetable oils and/or fats may be with 8 to 22 carbon atoms.

The term non-catalytic process referred to herein is process in the absence of catalyst selected from organic, inorganic compound such as alkali metal hydroxide or metal salts and the like; enzyme such as lipase and the like; acid catalyst and their mixtures. The term conventional process herein describes a catalytic process which has additional process steps such as neutralization of catalyst followed by filtration resulting in loss in yield of about 3 to 5%.

Also, normally neutralization of catalyst is carried out by using phosphoric acid which results in phosphate salts having varying degree of solubility. This results in minor amount of phosphate impurities in the monoglyceride leading to mal taste of the monoglyceride such as glycerol monostearate (GMS). The purification/intensification of the mono/di glyceride by distillation leaves residue of about 50% which is further recycled to obtain the crude product. The residue with small amount of phosphate impurity results in color formation reducing the possible number of recycles. The natural based monoglyceride with improved odor and flavor prepared by the non- catalytic process will comprise 40% to 50% by weight monoglyceride, 30 to 45% by weight diglyceride and 5 to 30% by weight triglyceride.

The natural based monoglyceride with improved odor and flavor prepared by the process of the present invention has color ranging from 0.4 to 0.6 G.

The natural based monoglyceride with improved odor and flavor prepared by the process of the present invention has an acid value of 1.2 to 1.5. The natural based monoglyceride with improved odor and flavor prepared by the process of the present invention is free of soap i.e. metal salt of fatty acid such as sodium or potassium salt of fatty acid.

The natural based monoglyceride with improved odor and flavor is used in the preparation of natural emulsifiers for foods and cosmetics as it is free from catalysts, partially hydrogenated oils, inorganic materials and organic impurities.

The natural based monoglyceride with improved odor and flavor is also used in polymers. According to yet another embodiment is a natural based monoglyceride comprising 90% monoglyceride. The natural based monoglyceride with improved odor and flavor comprising 40 to 50% by weight monoglyceride, 30 to 45% by weight diglyceride and 5 to 30% by weight triglyceride prepared by the non-catalytic process comprising reacting unsaturated and/or saturated vegetable oils and/or fats with glycerine at a temperature of about 230°C to 260°C under nitrogen atmosphere of about 1 to 10 kg/cm² ; wherein the mole ratio of fatty acyl groups in said unsaturated and/or saturated vegetable oils and/or fats to total glyceryl is about 1:4; may be further purified as per known methods such as disclosed in United States Patent number 3160646 to prepare at least 90% monoglyceride.

The natural based monoglyceride comprising 90% monoglyceride prepared by the process of the present invention has glycerine of about 0.3 to 0.4% by weight. The natural based monoglyceride comprising 90% monoglyceride is used in the preparation of natural emulsifiers for foods and cosmetics as it is free from catalysts, partially hydrogenated oils, inorganic materials and organic impurities.

The natural based monoglyceride comprising 90% monoglyceride is also used in polymers.

The following examples illustrate preferred embodiments in accordance with the present invention without limiting the scope of the invention.

EXAMPLES

Test Methods

Mono, di, triglyceride and free glycerine by HPLC method developed in house using GPC KF- 801 column.

Color determination by AOCS Cc 13j-97

Acid Value AOCS Cd 31-63

Soap content AOCS Ccl7-79

EXAMPLE 1

Procedure:

• Glycerine and HPS is charged into a pressure reactor, stirred and heated.

· The reactor is purged with nitrogen and pressurized upto 2.0 kg/cm2 nitrogen pressure.

• The reactor is heated to 170-180°C, nitrogen released and fresh nitrogen filled to 5.0 kg/cm2 pressure and reaction continued.

• Heating is continued at 240°C and 5.0kg/cm2 pressure until monoglyceride content is 45% minimum.

· The reaction mixture is cooled to 120°C, and excess glycerine separated.

• The reaction mixture is filtered and subjected to short path distillation.

Yield of Product: Actual / (Expected) : 1450g (1465g) Results

Example Raw Material Reaction Conditions

Yield

Oil Glycerine Temp Press gm

Time g(mol) I.V. /C18 g(mol) °C kg/cm² (hr)

2 HPS 1.0 310(3.36) 240 10 1422 10

1156 (1.40) C18:0 - 24%

RBD Palm

3 Stearin 206 (2.24) 240 Ambient

820 (1.0) C18:0 - 39% 11

RBD Palm

4 Stearin 30.0 791 (8.60) 245 Ambient 4

3200 (3.8415) C16-61.8 3871

C18:0-4.97

C18:l- 24.45

AV= 35

5 Cannola oil 123

878 (1.0) C18=1.97 206 (2.24) 240 8 1051 9

C18:l= 62

C18:2=18

C18:3=7

6 HPS 0.9

294

1200(1.425) C18:0-39 (3.192) 245 Ambient

1402 10

Analytical Results

EXAMPLE 7 : Comparison of color and acid value of monoglyceride obtained by the process of the present invention versus conventional catalysed process

The table above demonstrates the advantage of the process of the present invention over the conventional process for the preparation of monoglyceride with regards to the number of residue recycles and the color of the product.

Example 8 : Comparison of odor of monoglyceride obtained by the process of the present invention versus conventional catalysed process

Internal test panel of 6 members was constituted and two samples were given for testing odor. The panel members graded the samples on the basis of their perception as follows: 1: No detectable odour

2: Mild Odour

3: Strong odour Findings of the Internal test panel :

*: Average of the Six Panelists' Value.

Results : The odor of the GMS obtained by the process of the present invention was superior to the GMS obtained by the conventional, catalysed process. Example 9 : Comparison of free soap in monoglyceride obtained by the process of the present invention versus conventional catalysed process

Claims

1. A natural based monoglyceride with improved odor and flavor.

2. A natural based monoglyceride with improved odor and flavor and wherein the natural based monoglyceride comprises 40 to 50% by weight monoglyceride, 30 to 45% by weight diglyceride and 5 to 30% by weight triglyceride.

3. A natural based monoglyceride with improved odor and flavor as claimed in claim 1 or 2 and wherein its color ranges from 0.4 to 0.6 G.

4. A natural based monoglyceride with improved odor and flavor as claimed in claim 1 or 2 with an acid value 1.2 to 1.5.

5. A natural based monoglyceride with improved odor and flavor as claimed in claim 1 or 2 free of soap.

6. A natural based monoglyceride with improved odor and flavor as claimed in claim 1 to 5 prepared from unsaturated and/or saturated vegetable oils and/or fats and glycerine wherein the fatty acyl group is with 8 to 22 carbon atoms.

7. A non-catalytic process for the preparation of natural based monoglyceride with improved odor and flavor comprising reacting unsaturated and/or saturated vegetable oils and/or fats with glycerine at a temperature of about 230°C to 260°C under nitrogen atmosphere of about 1 to 10 kg/cm²; wherein the mole ratio of fatty acyl groups in said unsaturated and/or saturated vegetable oils and/or fats to total glyceryl is about 1:4.

8. A non-catalytic process for the preparation of natural based monoglyceride with improved odor and flavor comprising reacting unsaturated and/or saturated vegetable oils and/or fats with glycerine at a temperature of about 230°C to 260°C under nitrogen atmosphere of about 1 to 10 kg/cm²; wherein the mole ratio of fatty acyl groups in said unsaturated and/or saturated vegetable oils and/or fats to total glyceryl is about 1:4 and the fatty acyl group is with 8 to 22 C atoms.

9. A non-catalytic process for the preparation of natural based monoglyceride with improved odor and flavor as claimed in claim 7 or 8 wherein the natural based monoglyceride comprises 40 to 50% by weight monoglyceride, 30 to 45% by weight diglyceride and 5 to 30% by weight triglyceride.

10. A non-catalytic process for the preparation of natural based monoglyceride with improved odor and flavor as claimed in claim 9 wherein the color of the natural based monoglyceride ranges from 0.4 to 0.6 G.

11. A non-catalytic process for the preparation of natural based monoglyceride with improved odor and flavor as claimed in claim 9 wherein the natural based monoglyceride has an acid value ranging from 1.2 to 1.5.

12. A non-catalytic process for the preparation of natural based monoglyceride with improved odor and flavor as claimed in claim 9 wherein the natural based monoglyceride is free of soap.

13. A non-catalytic process for the preparation of natural based monoglyceride with improved odor and flavor as claimed in claim 9 further comprising short path distillation to obtain at least 90% by weight natural based monoglyceride.

14. A non-catalytic process for the preparation of natural based monoglyceride with improved odor and flavor as claimed in claim 13 wherein the natural based monoglyceride has free glycerine between 0.3 to 0.4% by weight.

15. A 90% natural based monoglyceride as obtained from process as claimed in claim 13.

16. A 90% natural based monoglyceride as obtained from process as claimed in claim 13 with free glycerine between 0.3 to 0.4% by weight.

17. A natural based monoglyceride as claimed in claims 1 to 5 and 15 to 16 for use in the preparation of natural emulsifiers for foods and cosmetics.

18. A natural based monoglyceride as claimed in claims 1 to 5 and 15 to 16 as additives in polymers.