Enzymatic Interesterification Method for Producing Cocoa

Butter Alternatives (CBAs)

Basri Omac4/07/2016

Outline

• Introduction• Cocoa butter• Cocoa butter Alternatives• Modification methods for the production of cocoa butter

alternatives• Conclusion

Introduction

• Chocolates has a wide variety and found in common places

• The ingredients of chocolate – Cocoa, cocoa butter, milk, sugar, lecithine

(emulsifier) and flavoring agents• An increasing demand for chocolate and

chocolate-type products

Schematic representation of the structure of chocolate

Talbot, 2012

Compositional Limitations on Some Codex Chocolate Descriptions

Talbot, 2012

Cocoa butter

• Special characteristics of cocoa butter– Cocoa butter (fat obtained from the mature bean of Theobroma

cacao) consists of mainly 23-30% palmitic acid, 32-37% stearic acid, and 30-37% oleic acid (in the form of SOS, POS, POP)

– The melting point of it is between 32 and 36oC– In spite of low melting point, it is hard and brittle at normal

temperature– Help to prevent `fat bloom`

• It is also responsible for the gloss, texture.• Price of cocoa butter is depending on fluctuating cocoa bean

prices• To be needed cocoa butter alternatives (CBAs)

Jahurul et al., 2013

Cocoa Butter Alternatives (CBAs)• To be divided into three main groups according to their functionality and

similarity to cocoa butter.– The cocoa butter equivalents (CBEs)

• Nonlauric fats with similar physicochemical characteristics as cocoa butter and are hence compatible with cocoa butter in every amount without changing the properties of cocoa butter

– The cocoa butter replacers (CBRs)• Nonlauric fats include fractions of hydrogenated oils • Possesing good flavor, odour, and colour properties and do not need tempering

– The cocoa butter substitutes (CBSs)• They contain a large amount (45-55%) of lauric acid and considerable amount (15-20%)

of myristic acid• Produced from palm kernel and/or coconut oil by means of fractionation and/or

hydrogenation • Because of the presence of lauric and myristic acid, they have a sharp melting profile

giving a good mouth feel to the compound chocolates

Gregersen et al., 2015

Classification of Cocoa Butter Alternatives

Verstringe et al., 2012

Modification Methods for the Production of CBAs

• Why do we need modification of oils and fats?– The specific fatty acid profile and their distribution on the glycerol

backbone in natural oils and fats affect their functional properties like crystallization and melting behavior

• Several methods were developed– Hydrogenation– Fractionation– Interesterification

• To modify the physical and chemical properties of natural oils and fats for extending their applicability.

• Commercial CBAs may be produced by combination of different processing steps such as interesterification and fractionation

1. Hydrogenation

• An old method in the oils and fats industries• Can be used in the formation of CBAs• However, high cost because of high

temperature and pressure• And the use of this method has been recently

reduced because partial hydrogenation may cause to form trans-fatty acids.

Abigor et al., 2003

2. Fractionation

• used in the production of CBAs to obtain fractions with properties compatible with cocoa butter or to obtain fractions that can be used for the formulation of CBAs

• Involving a fractional crystallization followed by a separation between the liquid olein fraction and the crystallized stearin fraction.

• Mostly solvent fractionation are utilized.• However, the operation cost for it can not be economical• This method is mainly used to separate the desired

composition from fat obtained by another modification method

Abigor et al., 2003; Calliauw et al., 2005

3. Interesterification

• an important method resulting in the redistribution of the fatty acids along the glycerol backbone

• refers to the reaction of triacylglycerols within or between the molecules or with other acyl donors or alcohol moieties, forming new esters by an interchange of fatty acid groups.

• Based on the catalysis, this method is divided into chemical and enzymatic interesterification

• Increasing trend to reduce/ exclude trans fatty acids because of stricter legislation and consumer organisations

Abigor et al., 2003; Verstringe et al., 2012

3.1 Chemical Interesterification

• Chemical interesterification has been used to modify oils and fats into functional products for many decades.

• It leads to a random distribution of fatty acids on the glycerol backbone.

• Nevertheless, the chemical interesterification requires high temperature and pressure which degrade the oils and fats and introduce impurities

• Loss of valuable minor-components (tocopherols)• High oil losses (up to 10 %)• Risky operation because of catalyst

Farfan et al., 2015

Chemical Interesterification Catalysts

3.2 Enzymatic Interesterification

• can be recently conducted in specific or nonspecific conditions based on the regioselectivity of the used enzyme

• used to modify functional properties including the crystallization and melting behavior of natural oils and fats by playing the specific fatty acid profile and their distribution on the glycerol backbone

• achieved under milder conditions leading to fewer side reactions, less post-treatment and in consequences less oil losses.

• The demand of this method increases because of increasing trend to avoid chemicals in food processing

• Lower capital investment cost compare to chemical process• Different varieties of lipases are used in industries because of their

regiospecificity and stereospecifity in production of specific structures.

Verstringe et al., 2012

Investment and operating cost

Types of Enzymatic Interesterification

• Nonspecific enzymatic interesterification (ester-ester exchange) method can be used for the production of commodity fats to modify the overall melting properties, increasing compatibility within the solid phase and enhancing the plasticity of the final product.

• Specific enzymatic interesterification (acidolysis or ester-ester exchange) may be used to produce tailor-made products as cocoa butter equivalents, anti-bloom agents, breast milk substitutes, and low calorie fats.

Positional specificity of lipases on TAGs

Conclusion

• Cocoa butter alternatives can be produced by using several modification methods.

• Enzymatic interesterification can be crucial method to be used for the production of CBAs because of its advantages:– Simple, clean, and safe– Cost effective when running continuously– No side reactions

References• Abigor, R. D., Marmer, W. N., Foglia, T. A., Jones, K. C., DiCiccio, R. J., Ashby, R., and Uadia, P. O. 2003.

Production of cocoa butter-like fats by the lipase-catalyzed interesterification of palm oil and hydrogenated soybean oil. Journal of the American Oil Chemists Society, 80(12):1193-1196.

• Calliauw, G., Foubert, I., De Greyt, W., Dijckmans, P., Kellens, M., and Dewettinck, K. 2005. Production of cocoa butter substitutes via two-stage static fractionation of palm kernel oil. Journal of the American Oil Chemists Society 82(11), 783–789.

• Farfan, M., Alvarez, A., Garate, A., and Bouchon, P. 2015. Comparison of chemical and enzymatic iteresterification of fully hydrogenated soybean oil and walnut oil to produce a fat base with adequate nutritional and physical characteristics. Food Technology and Biotechnology, 53(3):361-365.

• Gregersen, S. B., Povey, M. J. W., Kidmose, U., Andersen, M. D., Hammershaj, M., and Wiking, L. 2015. Identification of important mechanical and properties and acoustic parameters for sensory quality of cocoa butter alternatives. Food Research International, 76(3):637-644.

• Jahurul, M. H. A., Zaidul, I. S. M., Norulaini, N. A. N., Sahena, F., Jinap, S., Azmir, J., Sharif, K. M., and Mohd Omar, A. K. 2013. Cocoa butter fats and possibilities of substitution in food products concerning cocoa varieties, alternative sources, extraction methods, composition, amd characteristics. Journal of Food Engineering, 117(4):467-476.

• Talbot, G. 2012.Chocolate and cocoa butter-structure and composition. Cocoa Butter and Related Compounds 1 st Ed. Edited by Nissim Garti and Neil R. Widlak, AOCS Press, Urbana, IL, USA.

• Verstringe, S., De Clecq, N., Nguyen, T. M., Kadivar, S., and Dewettinck, K. 2012. Enzymatic and other modification techniques to produce cocoa butter alternatives. Cocoa Butter and Related Compounds 1 st Ed. Edited by Nissim Garti and Neil R. Widlak, AOCS Press, Urbana, IL, USA.