Caseinate. The incredible milk protein

Transcription

1 Caseinate The incredible milk protein

2 Introduction Applications of caseinates This brochure will give you a better understanding of the versatility of caseinates in terms of functional and nutritional properties. We will also discuss their vast application possibilities. Based on our ever expanding experience in caseinate production and application knowledge, DMV has become the leading manufacturer of top quality caseinates. Customers can rely on our products, advice and support and this trustworthiness is based on: The high and constant quality of our caseinates. The high level of process control along the whole production chain (from grass to glass). Our knowledge/expertise on production and application of caseinates. Our goal in working towards long term partnerships with suppliers and customers. In this brochure, we will elaborate further on application possibilities, nutritional properties, functional properties and production and qualitative aspects of caseinates. Historical perspective DMV has a long history in milk processing. More specifically, in manufacturing caseinates. DMV s traditional local and regional dairy co-operatives in the south of the Netherlands started the joint collection and processing of excess quantities of skimmed milk back in the 1930s. Originally, skimmed milk valorisation focussed on manufacturing lactic acid. The production of casein started a bit later. In those days, casein was mainly used for technical applications. Around World War II, production of casein-based imitation wool was an important outlet for DMV s casein. In the 1960s and 70s, casein production was geared to manufacturing food grade caseinates. Application possibilities in processed cheese, processed meat products and other food and nutritional applications were discovered and developed one by one. Caseinates are used in a wide array of food applications. It is almost impossible to list and describe them all in one comprehensive overview. The most important application areas are described below. Dairy products In this segment, caseinates are applied in yoghurt and other fermented products. If milk is transformed into yoghurt by microbial acidification, the casein in the milk is the key structural element of the network structure built up. Adding a limited percentage of caseinate to the milk prior to the fermentation step greatly enhances the firmness of set yoghurt and the viscosity of stirred yoghurt. When a yoghurt producer is legally restricted to utilizing only dairy-based ingredients, the combination of caseinate and selected whey proteins will make it possible for him to tailor the smoothness, thickness and shine of products to customer s wishes. Milk proteins are also added to yoghurt to compensate for the seasonal fluctuation in the protein content of locally available milk. Performance nutrition, nutritional drinks (powder or RTD) and weight management Consumers in this market segment have increased protein needs for different reasons. Body builders need to consume extra protein to increase their muscle mass. Duration sports people need to compensate their protein losses with extra protein consumption. People on a diet can often cut down on carbohydrates and fat consumption. But protein intake, including maintaining the right levels of indispensable amino acids, should not drop under a minimal level. Milk proteins, including caseinates (especially calcium and magnesium caseinates) fit into the protein rich diet applications very well. Especially diets designed for people in sports or actively dieting. Excellent image and flavour characteristics have given caseinates a strong position in this market segment. Caseinates are processed widely in all kinds of performance nutrition and weight management items such as nutrition bars, cookies, shakes, ready-to-drink protein rich beverages and UHT meal replacers. Clinical nutrition People who are hospitalized often need to be tube-fed. This enteral clinical nutrition is a complex but well-balanced mixture of all essential food elements: proteins, fats/oils, carbohydrates, vitamins, minerals and trace elements. All the components must be processed into a nutritious, shelf stable, heat stable, sterile, homogeneous and low viscous product. Caseinates are now being used worldwide in these formulas, simply because they possess the ideal combination of compositional and functional properties: healthy amino acid profile, good emulsifying properties, heat stability, low microbial counts, low lactose, etc. Topping powders, non-dairy creamers, powdered fat concentrates (shortening powders) All the products in this wide group can be described as spray dried emulsions. The manufacturing process starts with a blend of vegetable fat, low molecular weight emulsifiers, carbohydrates and a protein source. Subsequently, this mixture is homogenized under high pressure and spray dried. Skimmed milk (powder) can be used as a protein source. However, since the protein in these products has mainly a technological function as an emulsion stabilizer, caseinate is clearly the more cost-efficient ingredient. Processed cheese/imitation cheese Caseinates are used in processed cheese for their emulsifying and structuring properties. Especially when more matured cheese is used as a cheese base, the emulsifying and creaming properties of the (partially) degraded protein from that cheese can be insufficient and must be augmented with intact casein protein. In imitation cheese, caseinate is used for emulsification and structure formation. By careful selection of the caseinate type, melting and ph-regulating salts and the right processing conditions, tailored imitation cheese structures and melting profiles can be achieved. Calcium caseinate, for example, is a very useful starting material for imitation mozzarella, with its unique filante or melting properties. Optimization of formula and process opens the option of replacing variably available rennet casein. Processed meat, fish and poultry products In a wide range of meat, fish and poultry based products, caseinates are used to stabilize the physical (often emulsion-like) structure during processing and storage. In these processed meat products, caseinate supports the proteins extracted from meat in minimizing weight losses, and fat and water exudation during the smoking and heating processes. Caseinates also have a distinct positive effect on firmness and slicing ease of cooked products. In raw fermented salami type sausages, caseinates exert a strong acidification induced firming effect on product structure and coherence between fat and meat particles. Miscellaneous emulsified liquid foods Examples in this food category include: cream soups, sauces, dressings, coconut milk, cream liquors and liquid toppings. In all these foods, a certain percentage of fat/oil is present in emulsified form. Often the technological challenge is retaining this fat/oil in the product as stable, finely distributed droplets throughout the shelf life of the product. Caseinate is an ideal protein to create and maintain this emulsified state of fat or oil. Caseinates help to assure a very fine fat distribution which is a pre-requisite for a good stability and maximum creaminess (colour and mouthfeel).

3 Health benefits/nutritional functionality Production of caseinate Basic functional properties As indicated, caseinates have found wide application in a range of nutritional applications such as sports nutrition, weight control products, clinical formulas and selected infant foods. In some of these products, technological functionality is very important. But for all of them, nutritional quality is a critical selection criterion in deciding to use caseinate. Amino acid profile Like every other protein in nature, caseinates consist of around 20 different amino acids. These are synthesized by cows according to genetically determined sequences. The availability of and the ratio between the different amino acids are of primary importance for the nutritional value of food proteins. There are several parameters to describe protein quality and a number of them are summarized in table 1. Parameter PER BV AAS PDCAAS Definition Protein Efficiency Ratio Biological Value Amino Acid Score Protein Digestibility Corrected Amino Acid Score Table 1: Biological parameters of protein quality. There is an ongoing debate on the significance of PDCAAS levels higher than 1, which in fact reflects that this protein contains all essential amino acids in a more than sufficient quantity (related to the reference pattern). Non-truncated PDCAAS levels that are clearly higher than 1 signify that the protein is ideally suited for enrichment of low protein foods or replenishment of low quality proteins that contain too low levels of one or more essential amino acids. In table 2 the quality parameters are summarized for various food protein sources. Protein PER BV AAS PDCAAS Egg Cow s milk Casein Whey Soy Wheat Table 2: Nutritional parameters of various food proteins. 1 Digestion speed of caseinates Whey and casein proteins are known to have various digestive properties. After ingestion, proteins are denatured by acid in the stomach and pass into the small intestine where the peptide bonds are hydrolyzed by a variety of enzymes. The resulting mixture of small peptides and amino acids is then transported into the gut cells. Peptides are hydrolyzed within the gut cells and secreted as free amino acids to the bloodstream or further metabolized within the gut. The amino acids in the bloodstream are then available for protein synthesis. The protein digestion rate varies with the type of protein consumed. It is known that the milk proteins whey and casein have different digestion speeds. In acidic conditions, such as in the stomach, casein proteins coagulate. This results in a slower gastric emptying and in a different plasma amino acid pattern compared to whey protein. Protein digestion after intake is reflected in increased plasma amino acid concentrations. The rate at which this increase occurs, determines whether protein sources are considered slow or fast. In figure 1, research results are presented, demonstrating that upon consumption of casein a smaller increase in the circulating levels are observed, but these levels are maintained over a longer period of time (more than 6 hours). 2 The slowdigesting casein protein has a modest effect on protein synthesis, but instead it inhibits whole body protein breakdown. 3, 4 13 C-leucine enrichment (MPE) * Whey Casein Time elapse after administration (minutes) Fig. 1: Speed of amino acid absorption from slow and fast dietary proteins. Appearance of 13 C-leucine in blood plasma after oral administration of 13 C-traced whey protein meal versus 13 C-traced casein meal. The horizontal bars indicate the time frames where the differences between the two meals are significantly different (P<0.05). After Boirie et al (1997). 2 * All caseinates produced by DMV are prepared using only a basis of fresh FrieslandCampina, pasteurized skimmed milk. The whole process is carefully controlled and the time between skimmed milk entering the process and powder ending up in the silo before packaging, is less than an hour. The production of various types of caseinate is presented in figure 2. Skimmed milk Precipitation Acid Acid Casein curd casein-whey Washing/refining Refined curd Alkali: Na Neutrilisation +. K + Ca 2+, Mg 2+ Caseinate solution Drying Roller dried caseinate Spray dried caseinate Fig. 2: General production scheme of various types of caseinate. Our first step is mixing skimmed milk with food grade acid until the iso-electric point (IEP) of the casein fraction of the milk protein is reached. At that ph, the casein proteins coagulate into a curd-like substance that can be separated from the rest of the milk (usually referred to as casein whey or acid whey) by decanting. The collected casein curd still contains too high levels of entrapped lactose and minerals. To purify the protein, the curd is repeatedly rinsed with water and separated again. Subsequently the refined curd - which is still acidic - is transformed into a viscous caseinate solution by concurrent injection of steam and the addition of an alkali. As a neutralization agent, a selection of sodium, calcium, potassium and magnesium hydroxides is used. The viscous caseinate solution obtained, can be either spray dried or roller dried. The physical and functional properties of the different caseinates are mainly determined by the type of alkali applied in the neutralization step and the drying technique used to turn the caseinate solution into a powder. Additional process steps to tailor the application properties can be (in-line) lecithination, agglomeration and (partial) hydrolysis of the protein. In this way, a wide range of caseinate types is produced, all with their own functionality profile and related range of application possibilities. The whole caseinate manufacturing process, from milk supply to storage of bagged caseinates, is monitored using the highest level of quality control and assurance checks. Starting with top quality milk and constant compliance with stringent procedures for production and cleaning practices, ensures that our caseinates can be applied in the most demanding segments of the food industry. Caseinates play various functional roles in food products. DMV s expertise indentifies or develops the right caseinate type for a food product based on the functional requirements of the protein. Although the basic processes for roller dried and spray dried caseinate, and for sodium caseinate and calcium caseinate, are largely the same, the influence of the drying technique and neutralization agent on behaviour and application properties and possibilities, are significant. Functionality profile calcium/magnesium versus sodium/potassium Functionality differences between sodium and calcium caseinate are evident: some of them are highlighted in table 3. In caseinate production, the highly organized micellar structure of the casein fraction in skimmed milk is disintegrated by removing the calcium during the acid precipitation, washing the curd and then adding sodium hydroxide. Therefore sodium caseinate produces a colloidal and somewhat translucent solution of individual, flexible caseinate molecules upon dissolution in water. If in caseinate production, the curd is neutralized with calcium hydroxide however, the natural (sub)micellar structure is restored to a large extent. This is also the reason why a calcium caseinate solution is opaque and low in viscosity. Properties of sodium and calcium caseinate Parameter Sodium Caseinate Calcium Caseinate ph Molecular conformation Random coil in solution Appearance of solution Translucent Opaque Mouthfeel solution Sticky Milk-like 2-5% Dispersibility Slight tendency Good for lumps Solubility Good Good Viscosity (relative) High Low Viscosity (15% at 20 C) Pa.s 0.3 Pa.s Emulsification Very good Good Salt tolerance Very high Limited Heat stability Very high High Micel-like aggregates Table 3: Basic functional differences between sodium caseinate and calcium caseinate.

4 Fresh curd caseinates versus converted caseinates The colloidal conformation of the protein molecules in a sodium caseinate solution is the ideal starting point for the formation of a fine, homogenous and shelf and heat stable emulsion in case fat or oil has to be stabilised. The strong emulsifying properties are also based on the unique and advantageous distribution of hydrophobic and hydrophilic patches along the protein chains. At the moment of emulsion formation and fat droplet encapsulation as occurs in the manufacturing of many multiphase food products the highly flexible caseinate molecules are embedded in the fat/water interface. Through this fat droplet encapsulation, the fat is protected against coalescence and subsequent creaming which translates into (heat) stable emulsion based foods. Calcium caseinate is also a good and strong emulsifier, but the calcium induced aggregated protein conformation results in a thicker protein layer around fat globules in an emulsion. In practical terms, this means that if caseinate is needed mainly for its technical emulsifying functionality and not for a nutritional contribution sodium caseinate is the more efficient choice. This higher efficiency is schematically depicted in figure 3. Calcium caseinate is the preferred choice when good emulsion and heat stability must combine with low viscosity (pleasant to drink) and milky/white appearance. The low viscosity and the milky properties of calcium caseinate are highly valued, especially in applications where higher levels of caseinate must be used to meet nutritional requirements. Fat emulsified by calcium Fat emulsified by sodium Powder characteristics As indicated above, different drying techniques can be use to produce powdered caseinates. Comparing roller dried caseinate with spray dried caseinate produces some typical differences that can determine whether one or the other is chosen. In table 3, the most relevant differences are summarized. The major reasons that food manufacturers prefer to use the slightly more expensive spray dried caseinate, are based on somewhat better flavour characteristics and slightly better heat stability, which can be critical in liquid UHT or retorted products. Especially in sodium caseinate, the perceived quality gap between roller dried and spray dried caseinate has been minimized in time by DMV by continuous optimization of the roller drying process. Comparison of spray dried versus roller dried caseinate Parameter Spray Dried Roller Dried Particle size 100% <500μm 100% <800μm Particle shape Spherical Irregular/angular Occluded air A lot: Little: Tapped bulk density g/L g/L Viscosity 15% sol/20 C 2.5 Pa.s 3.0 Pa.s Dispersibility Relatively poor Somewhat better Dusting Medium Low Free flowing properties Medium to poor Good Flavour More neutral Neutral to slightly more barnyard flavour The manufacturing process for caseinates at DMV is totally geared to the production of so-called fresh curd caseinates. This means only fresh pasteurised FrieslandCampina skimmed milk is used for production of DMV caseinates. In combination with state-of-the-art production facilities and implementation of a demanding QA and QC system, this means that our customer can rely on the quality of our caseinate for whatever functional or nutritional reason they use in their product. In table 5, a number of qualitative features of DMV s caseinate are highlighted. Feature Constant, safe quality Stringent quality control program aimed at top quality High quality packaging material Low contaminant levels, meeting all relevant requirements CCP s in place to control chance of foreign material contamination Total chain control Remarks Microbiologically Chemically Physically Organoleptics Functionality Stringent quality checks by DMV offer customers possibilities of limiting inbound quality control/ release costs. High quality, meeting all requirements and giving the required protection to the caseinate to retain high level quality throughout shelf life. Monitored in milk (by government). Monitored in final product. Sieves and magnets installed. Wood/glass policy: avoid them as much as possible. Milk used in caseinate can be traced back to farm level. and caustic soda to the full dissolution of casein in water by addition of neutralizing agent and subsequent drying. A common piece of equipment for casein conversion is an extruder in which a blend of dried casein, caustic and steam is transformed into a foamy extrudate that is dried and ground into a powder again. Within the group of converted caseinates, quality can be quite variable for two reasons: The method and degree of conversion. The quality of the casein used. E.g. a simple blend of acid casein and caustic might be easy to make. But in the application, the functionality can be insufficient, simply because the casein must first react with the caustic before it goes into solution. It can then exert its emulsifying properties. In e.g. meat product production, the time/temperature is insufficient to achieve this conversion in time. Converted caseinates can also fluctuate in quality because of fluctuation in acid casein quality. If bad casein goes in, no good caseinate can come out. These disadvantages are not applicable to fresh curd caseinates as long as the milk entering the process is of the right quality and the process is run in a constant and consistent way. These last elements are exactly the foundations of DMV s strength in caseinate production and their portfolio. Partnership The best way to learn what DMV in general and caseinate in particular can mean to you, is to get in touch with us. Every single discipline within DMV has people who are ready to help you to: Fig. 3: Schematic picture: a thicker interfacial protein layer is formed during emulsification when aggregated calcium caseinate is used. The properties of potassium caseinate are very similar to sodium caseinate where magnesium caseinate behaves quite similarly to calcium caseinate. Potassium caseinate, which is slightly bitter, is used in applications where sodium levels must be restricted as much as possible. Magnesium caseinate is mainly used in dietary or clinical applications. Magnesium caseinate, like other caseinates, plays roles similar to other caseinates (protein source and emulsifying protein) but at the same time, represents a heat stable and soluble source of nutritionally valuable magnesium. Table 4. Major differences between roller and spray dried caseinate. Dispersing and dissolving caseinates In many applications, caseinates must be dissolved in water or milk as part of the production process or as a step to prepare them for consumption. Especially the greater chance of a lumpy product when dispersing sodium caseinate, requires some attention in industrial processing. However, many tricks and specialized devices have been developed in the various food segments to circumvent these kinds of problems: special high-energy dispersing equipment, pre-mixing with other dry ingredients or pre-blending in the oil phase in emulsion preparation. On the request of customers, DMV s technical sales service team will assist in defining the optimal processing technique and sequence within the constraints of the customer s production possibilities. To obtain really instant properties as required in dry mix nutritional formulas, caseinates are additionally treated with lecithin and/or agglomerated. The fast wetting properties of DMV s instant and/or agglomerated calcium caseinates, instantly creates a nice milkshake-like structure and mouthfeel. GMO free Kosher certified Halal certified Suitable for vegetarians No other allergens than milk protein itself Continuous effort to improve sustainability No GMO ingredients/additives/ processing aids are used. Our caseinates are Circle-U Kosher certified. Our caseinates are HFFIA-certified. Caseinates are considered suitable for a vegetarian diet, but not for a vegan diet. Our caseinates are manufactured in a dedicated factory: no risks of other allergen. FrieslandCampina works to further reduce their CO 2 -footprint and H 2 O-footprint at all stages of milk production and processing. Table 5: The quality of DMV caseinate in a nutshell. The term fresh curd caseinate implies that the process from milk to caseinate is not interrupted by an intermediate drying process as is the case in manufacturing so-called converted caseinates. The raw material for converted casein is acid casein and the conversion process can vary from dry blending of dried acid casein Identify the right caseinate for your application Find the optimum way of working with caseinate Look for more efficient supply Optimize packaging Discuss relevant market developments Investigate what milk proteins can do for you We at DMV are looking forward to working with you. References 1. European Dairy Association, Brussels. Nutritional quality of proteins Boirie Y, Dangin M et al. Slow and fast proteins differently modulate postprandial protein accretion. Proc Natl Acad Sci USA, 1997;94(26): Dangin M, Boirie Y et al. The digestion rate of protein is an independent regulating factof postprandial protein retention. Am J Physiol Endocrinol Metab, 2001;280(2):E Tang JE, Moore DR et al. Ingestion of whey hydrolysate, caseine or soy protein isolate; effects on mixed muscle protein synthesis at rest and following resistance exercise in young men. J Appl Physiol, 2009;107(3):

5 DMV Head Office NCB-Laan 80, P.O. Box 13, 5460 BA Veghel, The Netherlands T F info@dmv.nl North America Office 1285 Rudy Street Onalaska, WI 54650, USA T F david.lee@frieslandcampina.com Copyright DMV, The Netherlands, October 11 Asia Pacific Office Level 3A Quill 9 112, Jalan Semangat Petaling Jaya, Selangor Darul Ehsan, Malaysia T F florian.middelhuis@frieslandcampina.com Iberica Office c/paseo de la Selva 14, Valldoreix (Sant Cugat del Valles), Spain T F Jacques.baijens@frieslandcampina.com Warranty Questions? Technical support? Advice? Call the Caseinate experts The details given in this document are merely intended for information purposes and are in no way legally binding. Consequently we accept no responsibility in the broadest sense of the word for damage that may result from applications based upon this information. Furthermore, this information does not constitute permission to infringe patent and licence rights. DMV is a brand of