Novel Food Ingredient Development Using Supercritical

Particle Formation Techniques

Feral Temelli
Department of Agricultural, Food and Nutritional Science, University of Alberta,
Edmonton, Alberta T6G 2P5, Canada
feral.temelli@ualberta.ca

ABSTRACT
Numerous techniques have been developed for particle formation, encapsulation,
impregnation and drying using supercritical carbon dioxide (SC-CO2), demonstrating the
flexibility in such technologies while offering advantages in terms of the control of particle
size, size distribution and morphology that cannot be matched by conventional technologies.
In various techniques, CO2 serves as a solvent, co-solvent, anti-solvent or solute, resulting in
the formation of particles or assist in the atomization of the liquid phase to facilitate drying.
Even though the majority of these techniques have been developed targeting pharmaceutical
applications, in particular for controlled release drug delivery systems, similar approaches are
being extended for the delivery of food-related bioactives. A variety of food ingredients based
on proteins, lipids, carbohydrates and minor components have been processed using SC-CO2
technologies and characterized in terms of their properties and functionality. For example,
lipid-based particles, including liposomes and solid lipid particles have been loaded with
hydrophobic (lutein) and hydrophilic (vitamin B2 and anthocyanins) bioactives. It is
important to better understand the relationships between product functionality and processing
parameters so that optimal processes can be designed to produce ingredients with maximum
functionality and bioavailability. Considering the growing demand for functional food
ingredients with health benefits, ingredients produced using SC-CO2 particle formation
technologies show great potential for further development, targeting food and natural health
product applications.

INTRODUCTION
With the tremendous developments in nanotechnology, its applications for food
ingredients have been receiving growing interest, targeting specific functionalities. The results
of a survey performed by Yada et al. [1] to identify engineered nanomaterials that are used as
food ingredients demonstrate the extent of food and dietary supplement products marketed as
containing nanomaterials around the globe. In this survey, three categories of ingredients were
identified: emulsions, dispersions, and their water-soluble powdered preparations (including
lipid-based structures); solid encapsulates (solid structures containing an active material); and
metallic or other inorganic particles [1]. Despite some concerns related to the fate of many of
these engineered nanomaterials within the food matrix and within the gastrointestinal tract
after consumption, such ingredients are a reality in the marketplace. The technologies used in
the production of these ingredients were not identified in the survey [1] but the critical fluid
technologies have a major role to play in this growing trend due to the advantages they offer.

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 Numerous particle formation techniques using pressurized fluids have been developed
mainly over the past two decades. The main motivation behind this development has been the
fact that particles with controlled properties can be obtained, which is not possible with
conventional techniques. Tuneability of the parameters involved in supercritical processes,
such as temperature, pressure, nozzle diameter and depressurization rate, allows the control of
particle size, particle size distribution and morphology. Also, the capability to process at
relatively low temperatures allows handling of heat-sensitive materials, which can be easily
degraded when subjected to some traditional operations. Avoiding the use of organic solvents
or efficient removal of such solvents when included in the process is another major advantage
of using supercritical fluids for the formation of particles.
A plethora of supercritical fluid-based techniques developed, as listed in Table 1,
together with the range of acronyms attributed to each has unfortunately led to some
confusion, especially in cases where there are relatively minor differences between them and
this trend seems to be continuing. In fact, this situation reflects the flexibility offered by the
supercritical fluids and the ease with which modifications can be made to reach a target. Each
one of these processes has its own complexities and requires a good knowledge of the
thermodynamic behavior, fluid dynamics, mass transfer and nucleation-growth kinetics to be
able to design and control the product properties.

FOOD INGREDIENTS
Numerous supercritical carbon dioxide (SC-CO2)-based techniques (Table 1) have
been reported in the literature for particle formation, encapsulation and drying. In general, the
particle formation techniques are classified into four categories, depending on the function of
SC-CO2 as a solvent, co-solvent, solute or anti-solvent. In addition, the use of SC-CO2 for
drying of aqueous solutions has opened up new opportunities for various ingredient
applications. Several reviews, focusing on the different particle formation techniques, reflect
the level of interest and activity in this field [2-8].
The majority of the applications of these techniques has been in the area of
pharmaceuticals, targeting various drug delivery systems. In comparison, food-related
applications and natural materials-based ingredients for use in other applications, such as
natural health products, cosmetics and personal care products have been more limited but
certainly growing rapidly due to the great potential. These ingredients may be single
component or multi-component composite systems. Micronization of single component
ingredients, resulting in micro- or nano-sized particles, leads to a large specific surface area,
which can significantly increase bioavailability. On the other hand, composite systems refer to
micro/nano spheres or capsules where an active component is coated with a shell material to
protect it from external factors like oxygen, pH, heat, light etc. and minimize its degradation.
Encapsulation of liquid ingredients to powder form leads to ease of handling and
incorporation into powder formulations with uniform distribution even at low concentrations.
Release rate of the bioactive in the core can be controlled by changing the specifics of the
shell material, including its thickness and thus controlled/targeted delivery systems can be
designed for various bioactives. It is also possible to mask undesirable taste (i.e. bitterness) of
some components. Furthermore, reactive species can be isolated by encapsulation.
Polysaccharides and proteins are commonly used as coating materials for food ingredients.
These concepts, which have been critical for the success of many drugs, have become
mainstream in the food, natural health products and cosmetic industries for the delivery of
various nutrients and bioactives.

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Table 1. Plethora of techniques used for particle formation, encapsulation, impregnation and drying

Particle formation techniques

CO2 as a solvent RESS: rapid expansion of supercritical solutions
RESS-N: rapid expansion of supercritical solutions with a non-solvent
CSS: crystallization from supercritical solutions
SSI: supercritical solvent impregnation
SFEE*: supercritical fluid extraction and expansion
CO2 as a co-solvent DELOS: depressurization of an expanded liquid organic solution
DELOS-SUSP: depressurization of an expanded liquid organic solution –
suspension
CO2 as an anti- SAS: supercritical anti-solvent
solvent GAS: gas anti-solvent
GASP: gas anti-solvent precipitation
GASC: gas anti-solvent crystallization
GASR: gas anti-solvent recrystallization
PCA: precipitation with a compressed fluid anti-solvent
ASES: aerosol solvent extraction system
SEDS: solution enhanced dispersion of solids
SEDS-PA: solution enhanced dispersion of solids with prefilming
atomization
SFEE*: supercritical fluid extraction of emulsions
SAE: supercritical anti-solvent extraction
CO2 as a solute PGSS: particles from gas saturated solutions
scMM: supercritical melt micronization
SC-CO2-assisted drying
CO2 for drying PGSS-drying: particles from gas saturated solutions - drying
CO2 for atomization CAN-BD: carbon dioxide assisted nebulization with a bubble dryer
SAA: supercritical assisted atomization
SEA: supercritical enhanced atomization
SAA-HCM: supercritical assisted atomization with hydrodynamic cavitation
mixer
Use of gas-expanded PGX: pressurized gas-expanded liquid drying
liquids ELAS: expanded liquid anti-solvent
Aerogels Drying of alcogels using SC-CO2
Powders CPF: concentrated powder form
*Note that SFEE has been used to describe two different processes.

Traditional techniques for the encapsulation of bioactives include spray drying,

coacervation, extrusion, gelation using polymers such as alginates and fluidized bed.
Depending on the specific attributes of the targeted bioactive, some concerns associated with
these traditional techniques are the use of high temperatures or organic solvents that can lead
to degradation and loss of biological activity, difficulties in controlling particle characteristics
and low encapsulation efficiencies and yields. Therefore, the advantages offered by the
supercritical technologies are immense and the potential for processing of ingredients
targeting food and natural health products is huge.
The food ingredient-related applications of SC-CO2-based particle technologies can be
classified as lipid-, protein-, carbohydrate- and minor component-based ingredients obtained
using the different techniques listed in Table 1, encompassing both single component and
composite systems for bioactives. Lipid-based ingredients involve solid lipid particles and
liposomes. Solid lipid particles have been formed used palmitic and stearic acids, β-sitosterol,
soy lecithin, mono- and tristearin, hydrogenated canola oil and palm oil, milk fat and cocoa

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butter. Formation of liposomes from soy lecithin or pure phospholipids involved the use of
solvents in some cases but recent developments avoid the use of organic solvents and
surfactants [9]. Protein-based ingredients involved bovine serum albumin, gelatin, lysozyme,
casein, whey protein isolate and zein. Carbohydrate-based particles have been produced using
sugars, oligo- and polysaccharides. Aerogels have been prepared from polysaccharides like
agar, alginate, chitin, chitosan, carrageenan, β-glucan and starch using SC-CO2 drying. Minor
components such as antioxidants, carotenoids and essential oils have also been processed with
or without the addition of coating materials. For example, Solid lipid particles were loaded
with mint essential oil [10] and vitamin B2 [11], while liposomes were loaded with
anthocyanin [12] and lutein using SC-CO2 processes.
Proper characterization of the particles/ingredients obtained in terms of their physico-
chemical properties and both physical and physiological functionality is of utmost
importance. A range of particle morphologies can be obtained using the different SC-CO2
techniques, including porous structures, solid and hollow spheres, irregularly shaped particles,
sponges, needles and fibers among others, which can be evaluated using different microscopy
methods. Understanding the crystalline vs amorphous nature of the particles is also essential.
In composite materials where a bioactive may be impregnated or encapsulated in a
biopolymer, it is essential to determine the bioactive loading and encapsulation efficiency of
this delivery vehicle. Bioavailability of a bioactive compound ingested as part of a food
matrix depends on the fraction that reaches the targeted site in a biologically active form.
Different micronization techniques employing supercritical fluids that not only increase
surface area but also impact morphology and crystallinity definitely improve bioavailability of
various bioactives. In addition, it is possible to design controlled and/or targeted delivery
vehicles. The challenge is to better understand the relationships and to better link the product
functionality to processing parameters. Thus, the goal should be to generate particles/powders
of specific targeted functionality by choosing the appropriate supercritical process and by
controlling the processing parameters.

SUMMARY AND PERSPECTIVES

Taking advantage of the flexibility offered by the unique properties of SC-CO2, a
plethora of techniques has been developed for particle formation, micronization,
encapsulation and drying of various ingredients. A large number of patents have been issued
for the different processes [2]. Numerous abbreviations have been adopted to describe these
techniques even though the differences between them are quite subtle in many cases. It even
got to the point of using the same abbreviation for two different processes (for example, SFFE
being used for ‘supercritical fluid extraction of emulsions’ and ‘supercritical fluid extraction
and expansion’), which makes it confusing to distinguish between different processes.
The supercritical technology offers many advantages, especially for the treatment of
bioactive components sensitive to heat and oxygen. The requirements for enhanced
functionality and performance of various ingredients in the food and natural health products
sectors are getting more difficult to meet with conventional technologies and the supercritical
technology has a big role to play for the design and development of functional ingredients.
The high product quality can outweigh the technical challenges associated with these
supercritical processes and the investment cost associated with them. In addition, it is possible
to integrate particle formation or encapsulation step with the SC-CO2 extraction operation all
under CO2 environment. With so many different processing options, the product
characteristics can vary immensely, ranging from amorphous spheres or fibers to crystals and
encapsulated powders. Thus, a decision tree as suggested by Gomes et al. [6] would be
beneficial to choose between the various process options, depending on the targeted
functionality.

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 A wide range of processing possibilities have been evaluated in lab scale, targeting
lipid-, protein-, carbohydrate-, and minor component-based ingredients. Depending on the
specific nature and chemistry of the components different supercritical techniques have been
developed and processing parameters have been investigated. Product characteristics,
including particle size, size distribution, bulk density, morphology and crystallinity, vary
depending on process and equipment parameters such as pre- and post-expansion temperature
and pressure, CO2-to-feed ratio, size and type of nozzle used etc. Thus, optimizations have to
be done on a case-by-case basis. For some of the applications, process simulations, cost
analysis and pilot scale testing have been performed.
Despite all the developments, scale up to industrial production is still associated with
numerous challenges. Atomization would require larger and multiple nozzles that can be
operated without clogging. Particle recovery is a major challenge (potentially causing caking
and blocking of filters) that ideally needs to be done in a continuous manner while avoiding
agglomeration. Multiple vessels may be needed to establish a semi-continuous operation to
allow harvesting of particles from one vessel at a time in a sequential manner. Some of the
processes employ organic solvents, which jeopardizes one of the major advantages of the SC-
CO2 technology. When absolutely necessary, as in the case of drying operations, ethanol is the
preferred solvent for food ingredients that needs to be removed from the product. Thus, it is
critical to have a good understanding of the phase behavior of the ternary system water-
ethanol-CO2 under different conditions and to maximize the recycling of ethanol and CO2. It
is also worthwhile to note that the impact of the presence of other components in the system
on this phase equilibria is lacking. Similarly, understanding the phase equilibria for various
other multicomponent ingredient systems is still a challenge. In addition, when coating
materials are employed for encapsulation purposes, it is important to take advantage of the
fact that SC-CO2 leads to the modification of the physical properties of the polymeric coating
materials, such as reduction of melting or glass transition temperatures and viscosity due to
swelling or plasticization. Interactions between the coating material, bioactive and CO2
impact how the bioactive is impregnated or released from the matrix; however, our
understanding of such interactions is limited. Enhancing our knowledge of the fundamentals
of these processes to overcome the various challenges requires further research.
Based on the fundamental understanding, some of the applications developed in lab
scale have moved on to pilot scale and even industrial scale production [3, 8]. For example, a
plant with a production capacity of 200 kg powder per hour has been operating in Harbin,
China since 2007 for deoiling of lecithin [3, 8]. The relatively lower investment and operating
costs of PGSS led to its success at industrial scale [8]. An industrial scale PGSS plant with a
capacity of 300 kg/h has been in operation in Germany since 2008 [3]. CPF ingredients are
already on the market, as powder ingredients with standardized level of various extracts of
herbs and spices (rosemary, pepper, ginger, cinnamon etc.) [3]. In 2012, Unilever has
launched the “Cool Blending” technology, which utilizes solid lipid particles micronized
using SC-CO2 in spreads and margarines (www.unilever.com). In the meantime, Ceapro Inc.
(Edmonton, AB, Canada) (www.ceapro.com) is scaling up the PGX technology for drying of
high molecular biopolymers and impregnating them with bioactives. The key point in this
success is demonstrating the superior quality of these products as well as the favorable
economics. Considering the wide range of concepts tested at lab scale to produce ingredients
of unique functionalities, close collaboration between the research and industry communities
are taking some of them to commercial scale and we can look forward to more next
generation products in the near future. In addition, expansion of the existing supercritical
extraction plants by adding particle formation/encapsulation units would open new
opportunities and expansion of their product lines, which in turn may lead to new food and
natural health product applications.

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ACKNOWLEDGEMENTS
The financial support of the Natural Sciences and Engineering Research Council of Canada
(NSERC) is gratefully acknowledged.

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