A GUIDE TO EXTRACTION WITH CARBON DIOXIDE

INTRODUCTION
The purpose of an extraction is to bring one or more compounds of interest into solution. Behind the choice of solvent, extraction
parameters, and extraction type, are a multitude of complex and interwoven principles. Carbon dioxide (CO2) is well-known as a gas at
ambient conditions. When its pressure and temperature are altered to form a liquid or supercritical fluid, CO2 becomes an excellent solvent
for the solutes derived from botanical material. The present work aims to provide a guided tour through the process of extraction using
CO2 as a solvent, furthering the reader’s understanding of where key steps take place.

EXTRACTION WITH CARBON DIOXIDE

STORAGE
The process begins with the CO2 reservoir (Figure 1, i). This is the reservoir that will supply the system with solvent during operation. CO2
can be stored as either a low-pressure gas, a high-pressure gas or a liquid. The type of storage selected will influence the steps required to
move the solvent through the system.

DISTRIBUTION
Drawing from the solvent reservoir, a pump (Figure 1, ii) will pressurize and deliver CO2 to the extraction chamber(s). Different systems will
employ different style pumps. Dual acting positive displacement pumps and diaphragm pumps are those most commonly used in the
extraction industry.

DUAL ACTING POSITIVE DISPLACEMENT PUMPS

Dual acting positive displacement pumps (Figure 2) have the ability to deliver an uninterrupted flow of solvent to the extraction system. The
pump’s hydraulic cylinder applies force, in turn, to two oppositely-directed pistons. Liquid enters the available space ahead of one piston as
force is applied to the other to deliver a volume of solvent (Figure 2, i). At the completion of this stroke, force is applied to the opposite piston,
now primed with a volume of solvent ready for delivery (Figure 2, ii). In this fashion, dual acting positive displacement pumps eliminate the
interruption in solvent output (that is, they eliminate the downstroke), making them the favoured option for efficient and continuous solvent
delivery. Their design is also very robust, offering advantages in increased reliability and in minimized downtime for maintenance.
DIAPHRAGM PUMPS
Solvent enters diaphragm pumps on their downstroke (Figure 3, i) and is delivered on their output stroke (Figure 3, ii). Though many variations
on their design are available, solvent delivery is thus in pulses: the system will experience an interruption in solvent flow at each downstroke
as the pump is primed with a new volume of solvent for delivery. Diaphragm pumps also generally have smaller displacements (that is, pump
strokes provide a lesser fluctuation in internal volume) and operate at higher frequencies (that is, they move through comparatively more
cycles per timespan of operation). Given their style of solvent delivery, these characteristics mean increased ware and system pulsation. This
style of pump is also known to be less robust and more unreliable, inviting increased downtime for maintenance and component failure.

As the CO2 reaches the pump, it must be in either high-pressure-gas or liquid state. Only liquid and supercritical phases have adequate
solvent power to be of use in extraction. As such, one or the other will be required in the extraction chamber for the process of bringing
solutes into solution to begin. Thus, if a high-pressure gas is delivered to the chamber, enough additional pressure must be built up therein
to produce a liquid or supercritical fluid. If the solvent is pumped as a liquid, no change of phase is required, however, an operator may
wish to adjust fluid temperature, including in selection of supercritical phase, before the solvent reaches the extraction chamber.

PHASES AND EFFICIENCY

The phase of the solvent as it is acted upon by a system’s solvent-delivery pump can appreciably affect the extraction machinery’s mechanical
efficiency. Liquids are effectively non-compressible, meaning the force applied by the pump is used to very efficiently deliver solvent to the
system. In comparison, an appreciable quantity of the work applied to a volume of gas will be given off as thermal energy as the gas is
compressed. Thus, when acting on a volume of gaseous solvent, a meaningful amount of the output stroke’s energy is converted to heat. This
can additionally limit the equipment’s suitability for use in low-temperature extractions.
Delivering solvent as a liquid incorporates a further efficiency increase as a result of solvent density. The density, that is, the number of
particles per unit volume, of gases even under high pressure is much lower than that of liquids. This means that two identical pumps, one
primed with a volume of gaseous CO2, the other with an identical volume of liquid CO2, do not contain the same amount of solvent: the
pump filled with liquid CO2 contains many more solvent molecules than does the pump filled with gaseous CO2. Put another way, fewer
pump strokes are required to deliver a given amount of solvent when it is pumped as a liquid.

STATES OF MATTER AND SOLVENT POWER

A solute is considered to have been brought into solution once it is able to intermolecularly interact with a surrounding sphere of solvent
molecules. This molecular arrangement is termed a solvation sphere (a hydration sphere when the solvent is water). To form one, three
conditions must be met. First, the solute and solvent must be appropriately matched in terms of solubility. Second, enough solvent
molecules must be present to surround the solute and, third, the solute and solvent molecules must be moving slowly enough to be able
to appreciably interact with one another. The presence or lack of adequate solvent molecules at conditions allowing or prohibiting
interactions between molecules can be summarized as the solvent power.
As mentioned above, the density of gases is very low, even at higher pressures. Furthermore, molecules in the gaseous phase are travelling
at very high speeds, too quickly to allow for appreciable interaction with one another or other molecules. Their pace of travel does mean
gaseous CO2 molecules will penetrate the feedstock matrix very quickly (that is, they have high diffusivity), however, they are too energetic
and few in number to have much solvent power once they arrive.
In contrast, liquids have very high density and much lower diffusivity. Their lessened rate of molecular movement allows for appreciable
intermolecular interactions. These interactions help hold the molecules in close proximity, helping to provide their density and give rise
to liquids’ lessened diffusivities. Overall, liquids have excellent solvent power.
Supercritical fluids occupy a broad phase niche between liquids and gases. Their densities vary across a wide range of values and are very
tuneable, that is, large changes in density result with only small changes in pressure and/or temperature, near their critical points (the
minimum temperature and pressure that must be concurrently attained to achieve the supercritical phase). Supercritical fluids can be
thought of as bringing diffusivity more towards that of a gas, yet with solvent power more toward that of a liquid.

PHASE MANAGEMENT (OPTIONAL)

Temperature adjustments, including where they induce a phase change, can be made using a phase management system (Figure 1, iii). To adjust
solvent temperature, flow is directed through one or more heat-exchange bath(s) or vessel(s). Designs tend to include a coiled or otherwise-folded
solvent flow path within the bath(s) or vessel(s). This serves to maximize the surface area over which energy exchange can occur.
To reduce solvent temperature, cold heat transfer fluid is circulated through the interior volume of the vessel(s), absorbing heat from the solvent
through the flow path piping. To heat the solvent, hot heat transfer fluid is circulated in identical fashion, transferring its heat through to the CO2.
Heat can also be transferred to the solvent using a phase management system featuring heating bands in direct contact with the flow path.
Of note, temperature may also be increased by heating the extraction vessel. Heat will also result from compressing gas to liquid or
supercritical fluid phases within the extraction chamber.

EXTRACTION
Extraction (Figure 1, iv) begins the moment CO2 at conditions suitable for dissolving the targeted solute(s) is brought into contact with the
feedstock matrix. For this solubility match to occur, the solvent must provide an attractive environment with adequate push and pull
factors to encourage solute(s) into solution.

SOLUBILITY
A solubility match between a solvent and a solute is centered predominantly around polarity, that is, the distribution of electron density
across a molecule. Polarity is dictated by the presence or absence of electronegative atoms in a molecule, as well as how they are arranged
across its structure. If the distribution is very even and/or balanced by a plane of symmetry through a molecule, it will fall towards the non-
polar end of the polarity spectrum. The more imbalance in electronic distribution a structure possesses, the more polar it will be. The
closer the polarities of the solute and solvent, the better suited the solvent will be as an environment for that solute. In other words, like
dissolves like. The predominantly non-polar solutes found in botanical material are well-matched to CO2, a non-polar solvent.
To be present in the solvent environment, a solute must diffuse from its position in the feedstock matrix. Physical phenomena particularly
relevant in assisting this process are chemical potential and the solute’s volatility.
Chemical potential can be thought of as a how far away, energetically-speaking, a system is from equilibrium. In terms of bringing solutes
into solution, the largest drive for diffusion of a molecule is found where a 100-percent concentration of that molecule exists adjacent to
a zero concentration. Chemical potential will decrease as the concentrations even out. The situation attains its lowest chemical potential
as concentration reaches the equilibrium value. Taking advantage of chemical potential is thus a process of maintaining a low solute
concentration in the solvent and a solute concentration gradient between feedstock and solvent environments.
If chemical potential is thought of as a factor pulling solutes into solution, then volatility is a push factor. Recalling the above discussion
of phases of matter, as molecular movement increases, there is a point at which a molecule’s kinetic energy overcomes all intermolecular
attractions with the environment around it, allowing it to take to the vapour phase. Solutes can be pushed across this boundary, and thus
toward leaving their position in the feedstock matrix, by increasing temperature (and thus the energy of movement of the solute
molecules). Of note, the temperature required is unique to each substance; those substances that become volatile at lower temperatures
are termed volatiles, while those requiring more heat forcing are described as non-volatile.
Once the extraction vessel is filled with solvent at the selected temperature and to the desired pressure, the operator will begin either a
static or dynamic extraction. In the context of extractions, static and dynamic refer to movement of the solvent. In a static extraction, the
vessel is filled with solvent and left to soak. This volume of solvent remains until either a new static extraction of the material is initiated,
a dynamic extraction of the material is initiated, or the extraction is culminated.
In a dynamic extraction, the solvent is constantly renewed. This means the feedstock material is exposed to an ever-refreshed volume of
CO2 passing through the extraction vessel in circulation through the system. The extraction continues until either a volume of solvent is
isolated in the extraction chamber (initiating a static extraction), or the extraction is concluded.
An extraction will only be productive as long as the solvent remains unsaturated, there is impetus for solutes to diffuse into solution and
the solvent continues to be a more attractive environment to the solute(s) than the native plant matrix. Figure 4 examines this visually.
Both parts i and ii depict a number of solute molecules diffusing into a volume of solvent. In part i, there is only impetus for a small number
of additional solute molecules to diffuse into solution where so many are already present. In part ii, the solvent is much less saturated,
providing the drive for many more solute molecules to move into solution.
In a static extraction, the same volume of solvent remains in contact with the feedstock. As the extraction progresses, the solvent becomes
increasingly laden with solutes molecules, decreasing the impetus for additional solute molecules to be brought into solution. Dynamic
extractions maintain a lower degree of saturation and larger concentration gradient by continuously renewing the solvent in contact with
the plant matrix. This helps drive diffusion of the solute(s) into solution.
SEPARATION
In a successful extraction, the solvent leaving the extraction chamber will be laden with solute(s) of interest. Now coaxed away from the
feedstock material, the solute(s) must be isolated from the solvent. Separation (Figure 1, v) is carried out in one or more separation
vessel(s). Where multiple vessels are used, arrangements can be in series, in parallel, or both.
Separation is achieved by inducing a density drop. Solute dissolution will occur as density is lowered adequately to remove the solvent
power required to maintain a given solute molecule in solution. This point differs for different solutes, largely based on their molecular
weight. That is, more solvent molecules are required to surround a structure of larger size, and less solvent molecules are readily available
at lower densities. Solutes dropping out of solution collect at the bottom of the separation vessel(s) ready for removal.

SEPARATION IN SERIES AND IN PARALLEL

In-series and in-parallel separation arrangements differ in the solvent pathway through the vessels. For arrangements in series, flow moves
through individual vessels one at a time in succession. That is, the solvent will enter and then exit the first vessel before entering and exiting the
next vessel. At least two vessels are required to create a series but there is no particular maximum number of vessels that can be incorporated.
For arrangements in parallel, flow is split into two or more pathways, entering parallel vessels concurrently. That is, a division in the flow
path leads part of the solvent through one vessel and part through another; an individual branch of the flow path can never pass through
both of two vessels in a parallel arrangement (for then these two vessels would be arranged in series). There is no particular upper limit to
the number of vessels that can be arranged in parallel, and flow through the parallel branches need not be evenly split.
Various extraction system designs will make use of different separation vessel layouts. Of note, the equipment need not be only one of in-
series or in-parallel: some designs may incorporate a parallel arrangement of two or more separation series. Overall, a number of benefits
are available in choosing equipment with multi-vessel configurations.
Where equipment configurations allow, one or more flow branch(es) of a parallel arrangement can remain in-use while maintenance or
cleaning is performed on another. Additionally, flow may be individually directed through different parallel branches at different stages
of an extraction. This allows solutes extracted at different conditions to be allocate to different branches and thus vessels.
Vessels in series can be used to create a separation cascade. Successive density drops in each new vessel decrease the CO2’s solvent power
in stepwise fashion, preferentially condensing groups of solutes into individual vessels for collection. Of note, because the most delicate
compounds are also generally the most soluble, they are the very last fraction to precipitate out of the CO2 stream.
Both of in-parallel and in-series arrangements can also be used to increase the throughput potential of a system by providing additional
volume and vessel surface area.
Of note, where equipment allows solvent conditions to be modified over the course of an extraction, fractional extraction can also be used to
separate the elution of solute groups without the need for multiple separation vessels arranged in series. Conditions of the solvent entering
the extraction chamber are tuned to successively target the elution of specific groups of compounds (based on their solubilities). These are
then collected in the separation vessel(s) as individual fractions over the course of the extraction. As above, the most delicate compounds are
most soluble, and so must be targeted first. Further, each new group of compounds must be extracted at the gentlest possible solvent
conditions to minimize extraction of further solute groups. In this fashion, fractionation is achieved with minimal risk of solute decomposition.
In an open system, separation marks the final step in the process. The CO2 is released to atmosphere upon leaving the separation stream.
Costs can be conserved by choosing a design that instead uses a closed system. In a closed design, the same volume of solvent is circulated
through the system and returned to storage (Figure 1, vi) to be used anew for further loops through the equipment; recycling the solvent
may require additional process steps.
RECYCLING (OPTIONAL)
Some closed-loop systems incorporate one or more filtration vessel(s) as a final step in the separation portion of the flow path. These
vessel(s) are designed to remove moisture and any remaining particulate or vaporized plant components from the solvent stream before
it returns to storage.
As the CO2 leaves the filter vessel(s), it must be returned to storage conditions before rejoining the solvent reservoir. If storage conditions
require the CO2 undergoes a density increase, two options exist. A heat exchanger can cool the CO2, increasing its density; where cooling
is adequate, formation of a liquid results. The density of a gas can also be increased through compression. Compression in adequate
amounts can also be used to produce a liquid, however, this process generates appreciable heat and is considered inefficient.
Once the CO2 has been returned to the reservoir, the loop through the system is complete and the solvent is ready to be used anew for
further trips through the extraction system.

CONCLUSION
From storage to distribution, phase management to extraction and separation to recycling, this concludes a tour through CO2 extraction
systems. For more information and to organise to tour CO2 extraction equipment in person, please contact Vitalis Extraction Technology.