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The Molecular Separation of Hemp Oil

John F. Hart, Chemtech Services, Inc.

Abstract In today’s  context, it is helpful to define the exact


Molecular Separation methods alternatively meaning  of  “Thin  Film  Distillation.”    Thin  Film  
known as high vacuum, short path distillation, Distillation is accomplished using an apparatus
have been utilized for decades for processing which distributes the chemical compound to be
agricultural oils, including essential oils having distilled into a thin film (typically less than 1.00
similar characteristics to hemp oil. mm thick) across the evaporative surface to
facilitate separation (through boiling) of a
More recently, these separation methods have
specific molecular fraction for subsequent
been employed in the processing of hemp oil for
condensation. Thin film evaporator systems
medicinal and recreational uses to facilitate the
typically include a heating facility to initiate
separation of high value hemp oil fractions, such
boiling and a condenser to re-condense the
as THC and CBD, with minimal thermal
resultant vapors. Vacuum may also be applied,
degradation of the molecules. Molecular
which has the benefit of reducing the observed
Separation methods also allow concentrating of
boiling point of the material to be distilled.
these compounds (>90%) to provide added
value to the resultant fractions. During the middle of the 20th century thin film
and wiped film distillation methods matured into
This paper will review the processes of the high vacuum, short path methods, referred
moderate and high vacuum separation methods to as molecular separation, where separation
and specific results achieved in the processing takes place at vacuum levels below 0.01 mm Hg
of hemp oil products. (or absolute pressure <0.01 mm Hg). There are
a number of different types of molecular
distillation units but the most popular styles are
Concepts and Development of normally defined as: (a) rotary stills; (b)
Molecular Separation centrifugal stills; and (c) wiped film, short path
Molecular Separation generally falls within the stills.
scope of distillation  methods  referred  to  as  “Thin  
Film  Distillation.” Thin film distillation was The wiped film, short path still has proven to be
developed in the early 20th century as scientists the most versatile system and encompasses
discovered that separation (or boiling) of lower applications from laboratory scale (e.g., process
boiling point molecules from higher boiling point rates less than 5 liters per hour) to pilot plant
compounds occurred more quickly when the and commercial scale systems which attain
crude product was dispersed into a thin film. processing rates in excess of 5,000 liters per
This discovery lead to the earliest evaporators hour. This paper will focus primarily on the
known  as  “falling  film  evaporators”  which utilized wiped film, short path distillation unit, its
a heated vertical tube to evaporate low boiling principles of operation and its application to
point products from a film falling down the inside hemp oil products.
diameter of the tube. Vacuum pumps were soon The most important benefits of molecular
applied to the process to accelerate evaporation distillation are basically twofold:
and had the additional benefit of reducing the
 Molecular Distillation allows the distillation of
boiling point of the product being distilled. The
high boiling point products at moderate
falling film evaporator later evolved into the
temperatures through the application of high
wiped film evaporator which utilized a vacuum; and
mechanical wiper system to assure the product
to  be  distilled  was  “wiped”  into  a  uniform  film    The short exposure period to evaporative
thickness. temperatures minimizes the potential for
thermal degradation or isomerization.

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Differentiating Evaporators Figure 2 provides an illustration of the more
common, vertical style, thin film evaporator. At
As suggested previously, the more conventional
this juncture, it is also important to appreciate
thin film evaporators utilize a vertical, heat
the respective merits of each style and its
jacketed tube to initiate boiling, usually under
applicability to different chemical characteristics.
vacuum conditions. The evolution of the short
Consider the following list of evaporator benefits:
path, high vacuum was a direct result of
continued evaporator improvement over Falling Film Evaporator:
 Simplicity, no moving parts
decades in the last century. The relationship
 Temperature: 350°C Maximum
between the short path, wiped film, falling film  Pressure: 1 mm Hg Minimum
within the broader definition of thin film  Film Thickness: very little control
evaporators might be considered as sets within
Wiped Film Evaporator
larger sets as depicted in Figure 1 below.  More Complex with motor & wiper system
Figure 1  Temperature: 350°C Maximum
 Pressure: 1 mm Hg Minimum
Thin Film Evaporators  Film Thickness: good control

Wiped Film – Short Path Evaporator


Wiped Film
Evaporators  More Complex with motor & wiper system
Falling Film
Evaporators &  Temperature: 350°C Maximum
Short Path Degassers  Pressure: 0.001 mm Hg Minimum
Evaporators
 Film Thickness: good control

Figure 2: Evaporator Styles

The FFL Series of Laboratory TFE Systems The RFL Series of Laboratory WFE Systems The KDL Series of Laboratory Short Path
(FFL  signifies  “Falling  Film  Laboratory)  are   (RFL  signifies  “Rolled  Film  Laboratory)  are   Evaporator  Systems  (KDL  signifies  “Knudsen  
typically configured similar to the above typically configured similar to the above Distillator Laboratory) are typically configured
illustration. Generally, the Falling Film illustration. Rollers are used as an alternative similar to the above illustration. Similar to the
Evaporators have no moving parts (like wiper to wiper blades with the added benefit of RFL type evaporator, Rollers are used as an
systems) and rely on a dispersion plate to additional evaporative surface and an agitation alternative to wiper blades with the added
facilitate film formation with continuity. Note effect which facilitates the evaporative benefit of additional evaporative surface and
condenser is external to evaporator. process. Note condenser is external to an agitation effect which facilitates the
evaporator. evaporative process. Note condenser is
internal to evaporator reducing molecular
impedance to high vacuum.

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The Wiped Film, Short Path Evaporator Figure 3 below is typical of several nomographs
distinguishes itself from other styles in that the available online and with a little practice
potential vacuum capability is greater than other generally yield close results. Unfortunately, the
styles of thin film evaporators, and is generally published nomographs as a rule do not extend
considered capable of vacuum (expressed as the chart for vacuum levels below 0.010 mmHg.
absolute pressure) as low as 0.001 mm Hg. However, since most hemp distillations are
This capability is very important in those fields of conducted in the proximity of 0.010 mm Hg the
chemistry where excess temperatures may graphical results are quite reliable.
damage the molecule being distilled (e.g., Figure 3
isomerization or cracking). It is appropriate at
this point to suggest a few definitions which will
introduce some of the nomenclature used in
vacuum distillation. Consider the following
definitions:
Boiling Point (BP) –Webster’s  New  World  Dictionary™  
defines  it  as:  “the  temperature  at  which  a  specified  liquid  
boils; temperature at which the vapor pressure of a
specified liquid equals the atmospheric pressure: water at
sea  level  boils  at  212°F  or  100°C.”

Observed Boiling Point (OBP) – Recognizing that the


pressure condition encountered when boiling chemicals is Distillation System Practical Variables
rarely atmospheric (or 760 mm of mercury) OBP it the
temperature at which a liquid is observed to boil at a The previously discussed definitions have
specific pressure condition. established a basic foundation for approaching
Atmospheric Equivalent Boiling Point (AEBP) – the broader question of what distillation
Unfortunately  Webster  doesn’t  define  this  more  technical   variables should be controlled to assure a
term but simply stated, the AEBP is the atmospheric consistent distillation and derived product.
equivalent temperature (AET) at which a liquid boils when
subjected to specific temperature and pressure conditions
Certainly the operating temperature and
within a distillation unit. The AEBP is a function of the pressure of the evaporator itself is paramount to
observed boiling point at a specific pressure (or vacuum) assure product consistency, but other
condition. components will also contribute to system
Determining the AEBP or AET is a fairly results. A review of Figure 2 suggests that an
complicated mathematical function as suggested integrated, fully functional distillation unit will
in the equation below. have quite a number of vessels and each vessel
AET = (748.1 × A / {[1 / (T + 273.1)] + 0.3861 × A - 0.00051606}) - 273.1
will likely require temperature control. For
Where: AET = Atmospheric Equivalent Temperature, °C
reference, elements of a system may include:
T = Temperature, °C
A = a pressure term, depending on the observed pressure  Feed Tank – Heated
When first solving for A, a large term is derived, here simplified to F
 Variable Speed Feed Pump or Metering Valve
F (large function) = A  Wiper System - Variable Speed Motor
F Simplified function 0.00225  Evaporator Boiling Zone – Heated
Depending on the observed pressure, A takes one of two forms.  Evaporator Residue Zone – Heated
For pressure equal to or greater than 2 torr:  Condenser – Cooling/Heating (internal or external)
A = (5.994295 - 0.972546 * Log10P) / (2663.129 -95.76 * Log10P)
 Cold Trap – Cooling
For pressure less than 2 torr:
 Product Receivers (Residue, Distillate, Cold Trap)
A = (6.761559 - 0.987672 * Log10P) / (3000.538 - 43.00 * Log10P)
 Vacuum Backing Pump
Fortunately, there are a number of online tools  Vacuum Booster Pump
which make calculating the AEBP or AET a lot Note, based upon the above listed elements
easier than solving the above equation. In there are five (5) temperature control zones and
addition, several websites offer a nomograph a two-stage vacuum system designed to deliver
which makes determining the AET even easier. 0.001 mm Hg (for short path evaporator).

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The challenge to product consistency will be the Distillation of Hemp
control of the distillation system variables. The discussion thus far has been related to
Specifically, the most critical variables where equipment aspects associated with the
control is required are: operation of distillation systems capable of
 Product Feed Rate (or Flow Rate)
molecular separation. It is appropriate at this
The best solution is a gear metering pump rated point to consider this equipment within the
for vacuum service and driven by a variable context of how hemp is processed. Moving
speed motor. upstream in the process, the crude hemp oil
 Evaporator Jacket Temperature processed in distillation units is typically derived
A high level of Control of the evaporator
operating temperature is required to assure a
from one or more of the popular extraction
consistent evaporative process. Temperature methods, namely:
variances of no greater than +/- 2°C are
 Super Critical CO2 Extraction
recommended.
 Hydrocarbon Extraction
 Condenser Temperature
 Ethanol Extraction
Somewhat higher tolerances for temperature
control can be applied to the condenser, but All of these popular extraction methods are
variances should be maintained below +/- 5°.
subject to state and local code requirements
 Vacuum Level
System vacuum is typically the most difficult since high pressure or flammable products are
variable to control and frequently the distiller employed, and all of the processes are capable
must adjust his standard operating procedures of producing a good quality of crude extract for
based upon vacuum levels achieved when
subsequent distillation. However, it should be
initiating the distillation. Vacuum control in the
range of 0.10 – 0.001 mm Hg, is particularly noted that the quality of the extract will have an
challenging since variables such as system impact upon the downstream distillation, and
cleanliness or vacuum pump operating fluids impurities such as water or ethanol may
free of contaminants are often hard to control.
preclude obtaining the high vacuum levels
In addition, at these operating levels all seals in
the system must be very tight to minimize the necessary to concentrate THC or CBD as
effect of vacuum leaks. distillate. Further, acid precursors to THC and
CBD, or THCA and CBDA, must be
Failure to control the above indicated variables
decarboxylated prior to conducting high vacuum
will have a detrimental effect on the range of
distillation. Fortunately, the distillation equipment
molecules targeted in the distillation. Practically,
is versatile and it is possible to remove the
when operating distillation equipment, the
undesirable lower boiling point contaminants by
evaporator operating temperature will be
conducting an initial distillation at moderate
determined based upon the system vacuum
vacuum (e.g., 0.10 – 1.0 mm Hg) where the
level which is critical for the distillation of many
distillate will be composed of, for example,
products like hemp. For example, in a molecular
water, ethanol and perhaps some terpenes.
diverse product like hemp oil there are perhaps
Typically, the quantity of distillate is small (e.g.,
two hundred molecules of varying molecular
% Distillate < 5%) and the de-gassed product is
weight with different boiling points. Attempting
collected at the residue receiver. After the low
to distill a crude hemp oil at a less than desirable
boiling point compounds are removed, re-
vacuum level (say absolute pressure > 0.10 mm
distilling the residue product can usually be
Hg) will result in a darker product because, in
accomplished at a higher vacuum level (having
order to evaporate (or distill) all of the target
removed the low boilers) where the target THC
molecules (e.g., THC and CBD), the
and/or CBD compounds are separated as
evaporator’s  operating  temperature  will  have  to  
distillate.
be increased to compensate for poor vacuum
(i.e., target AEBP) causing some contamination It has been the authors experience that
from other products with higher boiling points approximately 50% of the crude hemp extracted
resulting in a darker distillate. oil will require a degassing/decarboxylation
distillation prior to a distillation to concentrate the
THC or CBD compounds.

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Composition and characteristics of Hemp Oil
It is beneficial to consider the chemical
composition of the crude hemp oil and the
respective boiling points (from literature) of
some of the constituents, which may affect the
distillation operating procedure. Figure 4 below
details a number of the compounds which will be
encountered in most hemp species.
Figure 4

Product (acronym) Boiling Point Considering the published boiling points of THC
THC-A 105 °C : 220 °F and CBD, 157°C and 185°C, it would appear
THC 157 °C : 315 °F that the distillation of these two products could
CBN 185 °C : 365 °F
be easily accomplished at atmospheric
CBG NA °C : NA °F
CBC 220 °C : 428 °F
condition. However, the published boiling points
CBD-A NA °C : NA °F may be for a pure substance, and even these
CBD 180 °C : 356 °F boiling points are subject to debate in literature
Linaloon (terpene) 198 °C : 388 °F with  many  sources  listing  the  BP’s  at  much  
ß-Caryophyllene (sesquiterpene) 160 °C : 320 °F
higher values. Practical experience associated
ß-Myrcene (monoterpene) 168 °C : 334 °F
D-Limonene (cyclic terpene) 176 °C : 349 °F
with distilling crude hemp oil suggests the
Humulene (sesquiterpene) 198 °C : 388 °F following:
a-Pinene (monoterpene) 155 °C : 311 °F
 THC and CBD appear to distill at roughly the same
conditions, or AET. Despite the published 23°C
As previously suggested, prior to conducting a difference in the boiling points, it does not appear
high vacuum distillation of crude hemp oil, the practical to separate the two compounds using
acid forms of THC and CBD (THCA & CBDA) high vacuum molecular separation methods.

must be decarboxylated to THC and CBD which  The Atmospheric Equivalent Temperature
is typically accomplished by heating the crude conditions at which the boiling of THC and CBD
compounds begins appears to be less than 400°C
hemp oil (at temperatures > 100°C) for an
(or somewhat below operating conditions of 140°C
extended period thereby removing the CO2 (OBP) at 0.050 mm Hg).
which otherwise would be detrimental to vacuum
levels during distillation. Decarboxylation can be Recognizing that pure or nearly pure THC and
accomplished in both batch and continuous CBD compounds are currently available in the
systems designed for this purpose. general market, it is likely that in the near future
published data will be available suggesting not
Normally, the specific targets of the distillation only  the  BP’s  of  these  compounds, but also
are THC and/or CBD and for reference the partial pressure curves will be available which
following molecular diagrams indicate the may influence future distillation methods.
structure of the THC and CBD compounds.
It is useful at this point to consider some
practical results associated with distillation tests
which will apply to those organizations engaged
in the distillation and processing of hemp oil
derivatives.

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Figure 5 below illustrates pictorially the golden Figure 6
oil distillate product desired by most companies
engaged in processing hemp oil. This product
was obtained in a high vacuum distillation
system under molecular separation conditions.
Figure 5

As indicated previously, the carousels provide


The organization which produced the above an excellent tool for optimizing the distillation
product achieved these results one day after a process. Sampling both distillate and residue
MINI-4 system was assembled with minimal products (using a rotary carousel) from hemp oil
instruction from the supplier. distillation, combined with analysis of the
distillate and residue products, can facilitate the
Recognizing many organizations in the hemp oil complete depletion of the valuable molecules
processing field are distilling a number of (THC and/or CBD) from the feed oil with
different oils (derived from different plant confidence. Utilizing a deep cut initial distillation
species) there is often a practical need for being followed by a second distillation of the D1
able to develop the ideal distillation conditions to Distillate will assure optimum yield and high
maximize yield and purity. It is quite easy to purity of the final (D2) distillate.
equip a laboratory distillation system (or larger
Figure 7
pilot scale system) with multiple collection tube
rotary carousels which allow the collection of
multiple distillate and residue samples at
different atmospheric equivalent temperatures
without having to break vacuum on the system
to remove products. Figure 6 illustrates a
distillation system utilizing a borosilicate glass
evaporator (KDL-6 having 0.06 m2 boiling jacket)
which is equipped with 6-tube rotary carousels
on both residue and distillate discharge nozzles.

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Figure 7 illustrated the results obtained when Figures 8 and 9 exemplify the comment that
using a rotary carousel sampling system for perhaps a two-pass distillation is preferred to
collecting distillate and residue samples from a fully deplete the feed product of CBD
CBD oil distillation conducted over a maximizing the value of the distillation.
temperature (AET) range of 415° - 464°C. The Figure 10 completes the picture in relation to
distillate and residue samples were CBD recovery (from feed product) with
subsequently analyzed for chemical increasingly  higher  AET’s  improving  the  actual  
composition. Although it is difficult to CBD yield (reflected in grams) measured in the
differentiate the color of the distillate, there were final distillate product, again suggesting that a
variations in the translucency and color of the two-pass distillation where the feed material for
distillate  with  the  lower  AET’s  yielding  a  clearer   the second pass is the D1 distillate from the first
product. Further, figures 8-10 illustrate there pass.
were significant variations in the chemical Figure 10
composition of the distillate and residue fractions
removed from the carousels. Hemp Oil Distillate CBD Content
120
Figure 8
100

Actual CBD in Distillate (g)


Hemp Oil Distillate Analysis
45 80
40
60
35
40 Total CBD
% Composition

30
25
20
20
Total CBD 0
15
415 428 439 451 464
10
Atomospheric Equivalent Temperature (°C)
5
0
415 428 439 451 464 Although this document has suggested that
Atomospheric Equivalent Temperature (°C) perhaps a two-pass distillation obtains optimum
results for processing hemp, this comment is
Figure 9 based solely on the fact that most of the
Hemp Oil Residue Analysis distillation systems sold into the hemp oil
25
processing market are considered laboratory
20 scale with processing rated generally not
exceeding 5 liters per hour of feed oil. As this
% Composition

15
industry expands it is expected that many
10 Total CBD processors will prefer to purchase multiple stage
systems (e.g., two or three stage systems)
5
where the products from one stage are pumped
0 into a second (and potentially third) stage for
415 428 439 451 464
further purification and concentrating of the THC
Atomospheric Equivalent Temperature (°C)
and/or CBD distillate. Multiple stage systems are
Based upon the graphical data indicated in quite common in the specialty chemical sector,
Figures 8 and 9, one might draw the conclusion and it is expected that production demand and
that the distillation of the hemp oil achieved price (not to mention Federal and State
optimum results at an AET of 439°C, where the regulations) will dictate if multiple stage units will
%CBD in the distillate was maximized. However, gain popularity in the hemp oil market.
the graphs in fact suggest that at an AET of
439°C there remained a significant fraction of
CBD in the residue product which represented
valuable compound left behind.

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Additional Wiped Film Evaporator (or WFE) Typical System configurations for Short Path
Applications Distillation Systems
Hopefully, the above comments have Although the general principles related to Short
demonstrated the value of molecular separation Path Distillation systems have been discussed
in the hemp oil processing field, but there are and illustrations have been presented to
additional processing areas in this industry facilitate the comprehension of molecular
where more conventional wiped film separation concepts pictures of Short Path
evaporators, with external condensers, Distillation Units may provide a better grasp of
operating at moderate vacuum levels (e.g., 0.5 the technology. Indicated below are a number
to 5.0 mm Hg absolute pressure) will establish of photographs related to Distillation systems
their value. For example, ethanol extraction is devoted to hemp oil processing.
perhaps becoming more commonplace as an Figure 11: MINI-4 Unit
alternative to CO2 or Hydrocarbon extraction.
Further, there are still many producers who
prefer winterization methods applied either
before or after molecular separation distillation
which also utilizes ethanol as the preferred
solution. Based upon current industry practice,
organizations using ethanol are typically using
rotary evaporation techniques to separate the
ethanol from the hemp oil product. Rotary
evaporators have historically been used in many
laboratory applications and the relative simplicity
of the operation of these systems has resulted in
a strong market sector. However, rotary
evaporators have size and processing rate
limitations which limit their growth in the hemp
oil processing sector. In addition, as processing
requirements increase, the rotary evaporator will
have to surmount the inherent safety issues
Figure 12: MINI-5 Unit
associated with processing large quantities of
ethanol.
WFE’s  have  historically  occupied  a  large  
segment of the industrial market related to
processing or stripping flammable solvents from
other constituents. WFE technology is already
being applied in the hemp oil sector in relation to
separating ethanol from hemp oil constituents, in
a fashion which complies with NFPA (National
Fire Protection Association) and subordinate
NEC (National Electrical Code) requirements to
provide for the flammability hazards associated
with processing ethanol solutions. In many
states regulatory agencies are placing more
emphasis on compliance with NFPA standards
associated with handling and processing
flammable liquids and these efforts will likely
expand.

The Molecular Separation of Hemp Oil Page 8 of 9


Figure 13: KDL-6 Unit Figure 15: KDT-6 Unit

Figure 14: KDL-6 Unit w/Controls


Figure 15: KDT-6 w/Controls

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