Cross-Metathesis Conversions of Fatty Acid Methyl

Esters to Jet-Eligible Biofuels

Madison Huynh

November 13, 2019

 Abstract

As anthropogenic global warming due to high greenhouse gas emissions threatens

the safety of both human and environmental systems, the necessity of developing sus-
tainable, non-emitting energy has become a pressing issue. Compared to other trans-
portation such as cars and trains, commercial aviation lacks any form of renewable
energy and comprises 12 percent of transportation emissions. This project tests an
oil-to-jet fuel processing pathway from the seeds of Salicornia bigelovii, a noncompet-
itive, easy-to-grow plant. To convert the long hydrocarbon chains of S. bigelovii into
jet-usable fuel, cross-metathesis reactions were performed in which hydrocarbon chains
of an olefin are swapped around the double bond to create varying chain lengths. Using
Hoveyda-Grubbs catalysts, I performed cross-metathesis reactions at low-maintenance
conditions on 1-hexene and the fatty acid methyl esters derived from S. bigelovii ’s
seed oils to generate hydrocarbon chains sufficiently meeting the requirements for
commercial jet fuel. My research found a ratio to maximize reactant conversion by
comparing initial quantities of 1-hexene to fatty acid methyl esters. After analyzing
data via gas chromatography and mass spectrometry, we generated response factors as
well as selectivity, yield, and conversion percentages to quantify the success of these
cross-metathesis reactions and minimize secondary competing reactions. I found that
reactant ratios of R = 4 and R = 2 were best for generating high concentrations of
products. My research presents a carbon-neutral solution for commercial aviation and
found a successful reactant ratio for maximum product generation.

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1 Introduction
In 2018, the Intergovernmental Panel on Climate Change (IPCC) reported a global warm-
ing of 1.5 degrees Celsius. Their research found that 1.0 degrees Celsius of this warming is
anthropogenic, and the majority has occurred during the industrial era. Each decade, an-
thropogenic global warming increases 0.2 degrees Celsius or more, spurring drastic negative
impacts such as the rise of sea levels and failed environmental systems [1]. Upon reaching an
increase of 2.0 degrees Celsius, the scope and magnitude of these impacts will be magnified,
vastly affecting both human and natural systems.
An excess of carbon dioxide (CO2 ) emissions, and other greenhouse gases, increases the
severity of climate change as well as exacerbates the rise of global warming. The hazards
caused by climate change thus far have created multiple observed changes in environmental
systems. Marine heatwaves and change in circulation patterns in the ocean have been caused
by an excess of CO2 and the warming of the planet. Both aquatic and other ecosystems,
including human life, face damage to their environments and loss of natural resources; this
generates the potential for conflicts due to water and food scarcity as well as mass migrations
[1].
Thus, in the status quo, the importance of reducing climate-related risks is growing. The
IPCC has outlined the necessity of decreasing emissions and carbon removal to mitigate these
effects to prevent even more adverse consequences. While other modes of transportation have
commercially used, less-emitting sources, such as cars and trains, commercial aviation has
no such options. Airplane emissions contribute at least four percent globally of all carbon
emissions in the atmosphere [2]. In 2017, the United States consumed 614 million barrels
of kerosene-type jet fuel, and the aviation industry emits 0.6 trillion kg of CO2 per year [3].
This accounts for 12 percent of all transportation emissions, a significant portion of overall
transportation [4]. According to some models, global transportation is expected to grow five
percent each year at least until 2050; therefore, developing sustainable alternatives to jet
fuel will be extremely important for minimizing the carbon impact of the aviation industry
[5].
Photosynthesis intakes CO2 from the atmosphere when plants are grown, creating a
carbon sink. This makes plant matter attractive as a raw material for energy production.
Because photosynthesis will offset CO2 emitted when crop-derived biofuels are burned, bio-
logical feedstocks present a superior strategy for renewable jet production. The entire process
of production and use of plant biofuels would be considered “carbon-neutral,” since the car-
bon absorbed in the process of plant growth compensate for the emissions from burning the
fuels. Figure one shows the process of a biorefinery, starting with the growth of plants.

2
Figure 1: Life-cycle steps of a biorefinery. From plant growth to products, this process is
unique to biofuel development and is significantly different than how crude oil is converted
into usable fuel.

The plants used for energy should ideally not compete with other resources such as
fresh water or consumable food crops, since those take immediate priority over energy [6].
Consequently, halophytes demonstrate a strong possibility as crops for energy usage, since
they can grow in sea water and non-arable soil [7, 8].
Of these halophytes, one standout plant is Salicornia bigelovii, a plant often found growing
along coastlines that offers significant resource potential as a non-competitive saltwater plant
[9]. S. bigelovii is comprised of seeds and the plant itself, both of which can be used as
resources. Because it has a high biomass yield as well as a relatively high percentage of seed
oil (about 30 percent by mass), S. bigelovii mass growth is being tested in several countries
in the Middle East and Central America [10]. Figure 2 depicts the large number of seeds
that S. bigelovii yields, which can be harvested for energy use [11].
In Abu Dhabi, United Arab Emirates, a land sustainability study has been conducted to
determine the success for growth of S. bigelovii, funded by Boeing and the Masdar Institute
[10]. Large quantities of the plant are successfully being grown, and appropriate processes
for the continued growth of these plants are being developed. The location of this study
is especially appropriate because of Abu Dhabi’s status as a transportation, specifically air
travel, hub for many companies and groups.
Many different strategies for processing plant material into usable jet fuels have been de-
veloped. In 2018, a study conducted by the National Renewable Energy Laboratory (NREL)
identified three distinct conversion pathways from crops: oil-to-jet (OTJ), biomass-to-jet

3
Figure 2: Salicornia bigelovii growing in its natural environment. As an annual seed-oil
halophyte, S. bigelovii presents an attractive option as a biologically sustainable energy
source. On each branch of the plant, hundreds of seeds can be found and harvested for
processing [11].

(BTJ), and alcohol-to-jet (ATJ) [12]. However, the NREL discovered that a problem with
several of these pathways was that their required conditions for conversion were extremely
difficult to acquire and maintain, such as high temperature and pressure. Because of these
conditions, the discovered NREL conversion pathways at that time were not viable for scal-
ing into commercial usage, since maintaining such conditions would be costly in a processing
plant.
To address some of these concerns, Wang et. al discovered a process with practically
achievable conditions for conversion of energy crops to jet fuel and other resources. This
study claimed a 75.9 percent conversion of the oils from Amygdalus penduculata into usable
biojet [13]. Through this process, the seed oil triglyceride is separated into three fatty acids
using a lipase. These fatty acids are then reacted with methyl esters to create fatty acid
methyl esters (FAMEs). The three unsaturated FAMEs identified through the separation of
S. bigelovii are methyl oleate (MO), methyl linoleate (ML), and methyl linolenate (MN).
After conversion into FAMEs, the lengths of the hydrocarbon chains are too long to be
used as jet fuel. Figure 3 shows the different types of fuels that are produced in a traditional
distillation column when crude oil is extracted and processed. For jet fuel, only hydrocarbons
with a length between C9 and C16 can be successfully used, and the FAMEs of S. bigelovii
range from C18 and up.
To address this issue, a recent study by Zelin et al. investigated how to convert methyl

4
Figure 3: Schematic of oil-to-jet and biomass-to-jet processing steps. Refining begins with
the grown plant S. bigelovii, which is then separated into its biomass and seeds; each are
processed along their respective paths.

5
Figure 4: Diagram of an oil refinery and separation layers of carbon-chain products. The
separation of products via distillation is the same for a conventional oil refinery and a biore-
finery.

oleate into shorter hydrocarbons using a cross-metathesis reaction with 1-hexene [14]. Both
1-hexene and methyl oleate have double bonds, but methyl oleate is too long to be used
as jet fuel. Thus, second-generation Hoveyda-Grubbs (HG) catalysts, based on Ruthenium,
were used to switch hydrocarbons around the double bond of each molecule. This generates
a range of products from lengths C1 to over C20 , with the majority of products towards the
middle.
My project studied the effect of changing 1-hexene (H) ratios on the generation of prod-
ucts in cross-metathesis reactions with FAMEs, especially investigating methyl linoleate,
which was previously unresearched. By looking into both methyl oleate (MO) and methyl
linoleate (ML), I identified the most common products of these reactions as well which ratios
were best for decreasing competitive secondary self-metathesis reactions. I sought to corrob-
orate and augment the findings of the work done by Zelin et al. by varying ratios of 1-hexene,
as well as testing methyl linoleate instead of methyl oleate, to test which created the most
products of hydrocarbon length C9 to C16 so that they would be usable as jet fuel. I created
my own supported catalyst to maximize its usage, following the outlined procedure of Zelin
et al. [14]. I performed cross-metathesis reactions with ruthenium-based second-generation
Hoveyda-Grubbs catalyst with 1-hexene, methyl oleate, and methyl linoleate. Products were
characterized via gas chromatography-mass spectrometry to identify what was created and
their viability as biologically and environmentally sustainable jet fuel. Throughout this pa-

6
per, the success of the reactions will be defined as the generation of relatively large quantities
of the desired products.

2 Methods and Materials

2.1 Catalyst preparation
The HG catalyst was prepared by impregnating high purity silica resin (pore size 150 Å) with
a solution of catalyst dissolved in cyclohexane (anhydrous, 99.8 %) at standard temperature
and pressure. 500 mg of silica was suspended in 15 mL of cyclohexane, stirred at 510 RPM for
approximately one minute using a magnetic stirrer. To prepare the catalyst solution, 20 mg
of HG was added to 47 mL of cyclohexane, stirred at 510 RPM for approximately 35 minutes,
or until no settled solids were present. Because impregnation does not require a particular
solvent in the final product, the volume of cyclohexane was chosen only as optimal to dissolve
the catalyst. The ratios shown may be scaled to obtain a desired quantity of silica-supported
catalyst.
In previous research that uses silica-supported Grubbs catalysts, it was stated that 3.36
weight percent loading of catalyst onto SiO2 was ideal, assuming that 95 percent of the
catalyst adsorbed onto the silica [15]. We approximated this to 17.6 mg of HG catalyst
being added to the silica solution so that 16.8 mg adsorbed.
To create the ideal assumed loading of catalyst onto silica, 41.3 mL of the HG solution
was titrated onto 15.0 mL of the silica solution dropwise over the span of thirty to thirty-
five minutes. To ensure gradual loading and maximum adsorption, the initial speed of the
magnetic stirrer should be approximately 150 RPM then increased over time to 500 RPM
at the end of titration.
The solution should visibly change color after titration is complete, indicating the com-
plete impregnation of HG catalyst into the silica. After stirring is over, in the vessel used for
mixing the titrated catalyst with the silica, there should be two distinct layers: a completely
transparent, untinted supernatant liquid on top and a thin layer of lightly tinted green pellets
settled on the bottom.
Ultraviolet-visible spectroscopy was performed on the supernatant solution to determine
the weight percent loading. A calibration curve to compare the supernatant solution to was
generated by running pure cyclohexane. The loading percentage was calculated spectroscop-
ically by quantification of the 376 nm absorbance signal of the HG supernatant solution to
detect the concentration of 2nd gen Hoveyda-Grubbs catalyst.
Fourier transform infrared spectroscopy was performed on the prepared solid catalyst to

7
determine the absorbance of HG onto silica. Initially, based on the first FTIR run on the
first day’s catalyst, the peaks were unable to be resolved to match the expected spectrum
[15]. This was likely caused by improper storage of the catalyst before measuring its infrared
spectrum. When testing later batches of prepared catalyst, a small peak at 748 aligning
with the expected spectrum was found, indicating the proper preparation and impregnation
of the catalyst.
The loss of signal as the HG catalyst is added can be used to quantify the percentage of
HG catalyst adsorbed onto silica. Ideally, the loading percentage should be greater than 3%
HG/SiO2 (w/w). The actual loading percentages calculated from our supernatant solution
ranged from 2.91 percent loading to 3.11 percent loading. For the remainder of this experi-
ment, it will be assumed that the loading of HG catalyst on silica is 3.02 percent, the mean
of the supernatant solution’s calculated values.
The impregnated catalyst was filtered using a vacuum filter dual flask apparatus to
remove as much solvent as possible from the cyclohexane. Grade 1 filter paper was placed
inside a ceramic Büchner funnel inside a side-arm flask connected to another side-arm flask
and the wall of the fume hood using rubber filtration hoses. A vacuum was pulled on the
wet HG catalyst for approximately one to two minutes, or until clumps of catalyst broke
into powder using a spatula. After drying, the catalyst-impregnated silica should be a very
light green color, indicating proper adsorption.
The impregnated catalyst was weighed on weighing paper to determine how much HG
catalyst and SiO2 was lost in the process of catalyst preparation. Approximately 500 mg
of prepared HG was generated each time, with approximately 100 mg of SiO2 and catalyst
unused or lost during the titration and drying process. However, this has a negligible effect
on the remainder of the experiment, since less than 500 mg of HG catalyst is used during
each trial.
Each day, a new batch of catalyst was prepared to prevent the catalyst from deactivating
via protein denaturing overnight. Excess prepared catalyst was stored at 4 degrees Celsius
for a short time period after blowing nitrogen (an inert gas) into the vessel, in order to
prevent any decomposition reaction with air.

2.2 Hexene cross-metathesis

Cross-metathesis reactions between fatty acid methyl esters (FAMEs) and 1-hexene were
performed at 30 degrees Celsius and atmospheric pressure. The fatty acid methyl esters
derived from S. bigelovii are methyl oleate, methyl linoleate, and methyl linolenate. This
project focused on methyl oleate, to corroborate the findings of previous papers, and methyl

8
Figure 5: Diagram of cross-metathesis reaction apparatus, including the reaction vessel
(round bottom flask.) Nitrogen flowed through left and right necks of reaction vessel prior
to start of the reaction. Reactants were added through the middle neck of the flask, after
removing the rubber stopper. Products at data collection times were extracted via a needle
through the right rubber septum. A water bath of constant temperature 30.0◦ C using
deionized water in a shallow, wide beaker was maintained using hot plate and thermocouple.
The reaction was mixed using a magnetic stirrer at a constant speed of 300 RPM.

linoleate, which is the most prevalent FAME in S. bigelovii by weight [15]. The reaction was
heated to 30 degrees Celsius to accelerate the process of cross-metathesis while attempting
to minimize evaporation from overheating.
A 25 mL round bottom flask with three necks was used as the reaction vessel. Two of
the necks were the inlet and outlet for inert nitrogen gas flow, covered with a rubber septum
and pierced with a needle. The third neck was used for adding reagents, covered with a
rubber stopper when not in use. Figure 2 depicts the reaction apparatus of the hot plate,
water bath, and round bottom flask.
Nitrogen gas was chosen as the atmosphere for the reaction to prevent any reactions
between the reactants and air, since nitrogen is an inert gas. For approximately five to ten
minutes prior to the start of the reaction, nitrogen was blown through the round bottom
flask, flowing from a nitrogen gas canister through rubber tubing and a needle into the vessel.
The addition of reactants and the removal of products at certain times was performed

9
as quickly as possible to minimize the amount of time when the vessel was uncovered. This
was to prevent any products in the gas phase from escaping via the open neck, or prevent
impurities from the air from contaminating the nitrogen-filled reaction vessel.
The round bottom flask was suspended in a water bath with a system of clamps and
stands on top of a Fisher Scientific Isotemp hot plate and magnetic stirrer. The temperature
of the hot plate was set to 40 degrees Celsius to keep the water at 30 degrees Celsius,
monitored using a thermocouple.
20.0 mL of a stock solution was prepared with a cyclohexane solvent using 0.029 M of the
FAME, and 0.020 M n-dodecane, and varying amounts of 1-hexene. Ratios of R = 2, 4, 5,
and 7 were used to calculate different amounts of 1-hexene, where R is the ratio of 1-hexene
to the FAME. These ratios were tested to determine the optimal ratios for maximum product
creation. By determining relative molarity for R = 2, 4, 5, and 7, the volumes of 1-hexene
were 144 µL, 288 µL, 360 µL, and 504 µL. N-dodecane was chosen as an internal standard
due to its lack of interaction with the reactants. Using an internal standard allowed direct
comparison of relative concentrations to account for any discrepancies or errors in data
collection. 197 µL of the FAME and 90.8 µL of n-dodecane were added to a graduated
cylinder as well as the appropriate volume of 1-hexene. Then, the graduated cylinder was
filled to the 20.0 mL mark with cyclohexane.
100 mg of the impregnated HG catalyst was added to the nitrogen-evacuated round
bottom flask along with a magnetic stirrer. Then, 10 mL of the stock solution was measured
and added to the reaction vessel. The reaction timer was immediately started and the
magnetic stirrer was set to 300 RPM.
The reaction was incubated for 30 minutes at the set constant temperature, 30 degrees
Celsius in the surrounding water bath. Conversion data was taken at specific points: 1, 2,
5, 15, and 30 minutes. Taking more data points would likely have resulted in an overly long
data analysis period in the gas chromatograph mass spectrometer, which was not optimal
since our GC-MS took seven hours to run one trial’s data. Thus, these chosen times provided
us sufficient data for the reactant conversion at various times throughout the reaction period
while optimizing the time spent on data analysis.
At these times, 100 µL of the reaction mixture were removed with a syringe through the
rubber septum, to avoid contamination or loss of products by opening up the vessel entirely.
At 30 minutes, two samples of the reaction mixture were taken to maximize the accuracy of
product concentrations when running samples through the GC-MS and account for any lack
of mixing of products in the final mixture.
Extracted samples were diluted with approximately 1 mL of cyclohexane in the appro-
priate GC-MS vials. The volume of cyclohexane was largely irrelevant due to the presence

10
of the internal standard, n-dodecane, to determine relative product concentrations. The
sample at 0 minutes was prepared by diluting 100 µL of the stock solution with 1 mL of
cyclohexane.

2.3 GC-MS product characterization

The reaction mixture samples taken at time = 1, 2, 5, 15, and 30 minutes were placed into
specialized vials with paper seals so that they could be punctured and extracted when running
gas chromatography mass spectrometry (GC-MS). Our lab’s GC-MS required samples to be
dilute before being analyzed. Thus, as stated previously, approximately 1 mL of cyclohexane
was added to each 100 µL sample.
To not interfere with the GC-MS injection and column process, no solids could be in the
samples. Thus, products were extracted from the side of the vessel intentionally so as not
to take any of the HG catalyst. Additionally, each sample in its vial was allowed to settle,
further preventing any solids from entering the gas chromatography column.
GC-MS was performed on the samples in order to identify products of the cross-metathesis
and self-metathesis reactions. The first phase of this process, gas chromatography, separates
and identifies compounds based on volatility and mass. The second phase, mass spectrome-
try, identifies ions made from shooting electrons at each compound and records their relative
abundances.
The products were identified via a combination of both the gas chromatography and mass
spectrometry results. In the mass spectrum, the largest peak often aligns with the molar
mass of the compound; I used this principle generally to more easily identify each product.
GC-MS was performed at a custom method for organic molecules. The conditions in the
machine were:

Tinjection 250.0◦ C
Tcolumn 80.0◦ C / 220.◦ C
Tionsource 220.0◦ C
Tinterf ace 250.0◦ C

The samples from each trial were analyzed in GC-MS in batches. Before the first sample
and in between each sample, an identical purge method of the column was run. The purge
sample was a vial of pure cyclohexane, at a higher temperature than the normal run. The
purpose of the purge was to prevent contamination of the needle or column between product
analysis of each time interval. By rinsing in cyclohexane and increasing the heat, GC-MS
measurements were made as accurate as possible.

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 The gas chromatograph mass spectrometer method was identical for methyl oleate and
methyl linoleate. This was because the products generated by metathesis reactions of methyl
linoleate are of similar size and possess similar properties to the original methyl oleate reac-
tion.

3 Results and Discussion

3.1 Response factors and yield for hexene and FAMEs
To calculate the consumption of reactants and generation of products relative to the inter-
nal standard (n-dodecane), a response factor was calculated for each methyl oleate/methyl
linoleate and 1-hexene. Because GC-MS results are reported in peak areas and not con-
centrations, a response factor was necessary to identify the relative concentrations of each
product from the metathesis reactions. The formula for the response factor is Response
Factor = AA( IS)C
X CIS
X
.

where AX = area of the compound, CX , is the concentration of the compound, AIS is

the area of the internal standard, and CIS is the concentration of the internal standard.
Response factors were used to quantify concentration of the products with respect to n-
dodecane. Tables 1 and 2 show the conversion percentages of methyl oleate, methyl linoleate,
and 1-hexene based on the initial concentrations of 1-hexene.
After calculating the response factors, yield allowed us to determine the success of
metathesis reactions. Carbon yield relative to the fatty acid methyl ester was derived us-
α ηt
ing the equation ηi = αF AM Ei ηit , where FAME represents either methyl oleate or methyl
F AM E
linoleate and i represents the products of whose yield we sought to calculate. Conversion
was calculated using the equation Conversion Percentage = 1 − RP A30
RP A0
× 100%.

Response Factors: MO Metathesis

Ratio (R) Initial [H] (M) MO Conversion H Conversion
2 0.058 76.6% 39.0%
4 0.116 93.5% 42.1%
5 0.145 81.4% 20.5%
7 0.203 92.3% 22.3%
Table 1. Methyl oleate metathesis reaction products. Conversion percentages assuming a
constant response factor, as previously calculated.

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 Response Factors: ML Metathesis
Ratio (R) Initial [H] (M) ML Conversion H Conversion
2 0.058 97.0% 54.8%
4 0.116 98.1% 40.6%
5 0.145 98.5% 28.2%
7 0.203 99.0% 31.9%
Table 2. Methyl linoleate metathesis reaction products. Conversion percentages assuming a
constant response factor, as previously calculated.

Calibration Curve: MO Metathesis

Ratio (R) Initial [H] (M) MO Conversion H Conversion
2 0.058 76.6% 48.3%
4 0.116 93.5% 44.5%
5 0.145 81.4% 22.4%
7 0.203 92.3% 23.7%
Table 3. Methyl oleate metathesis reaction products. Conversion percentages based on
1-hexene calibration curve.

Calibration Curve: ML Metathesis

Ratio (R) Initial [H] (M) ML Conversion H Conversion
2 0.058 97.0% 68.2%
4 0.116 98.1% 45.4%
5 0.145 98.5% 30.7%
7 0.203 99.0% 33.9%
Table 4. Methyl linoleate metathesis reaction products. Conversion percentages based on
1-hexene calibration curve.

Selectivity
C-M S-MO S-H
100% 7% 34%
88% 4% 66%
94% 3% 40%
87% 3% 45%
Table 5. Ratios of metathesis reaction products. Calculated equilibrium conversions,
methyl oleate conversion percentages, and yield percentages of cross-metathesis and
self-metathesis reactions.

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Figure 6: Concentration versus time for methyl oleate cross-metathesis, R = 2, 4, 5, and
7. Values of concentration were derived from relative peak area, retrieved from GC-MS
measurements. Full names of products can be found in Table 6.

3.2 Methyl oleate cross-metathesis products

The products of methyl oleate can be seen in Figure 6 in the graphs of relative peak area
versus time for R = 2, 4, 5, and 7 respectively. 1DC, 5DC , 9DCE, 5TDC, 9TDE, and
9OD are the products of the reaction that can be used as biojet, since their hydrocarbon
lengths are of the aforementioned appropriate size. Table 6 provides the proper names of
these molecules rather than their acronymous names.
The products in Figure 5 (R = 4) have the highest conversion and relative concentrations
of these jet-eligible products, proving that this reaction was the most successful. The final
concentrations totaled to be higher than the other ratios, and a visual analysis of the graphs

14
Figure 7: Concentration versus time for methyl linoleate cross-metathesis, R = 2, 4, 5, and
7. Values of concentration were derived from relative peak area, retrieved from GC-MS
measurements. Full names of products can be found in Table 6.

also shows that there were higher levels of useful products generated. Thus, R = 4 as a ratio
between 1-hexene and the FAME is optimal for generating the most jet-eligible products.
As seen in Figure 5, higher ratios of 1-hexene were not as successful. In reactions of
1-hexene/FAME ratios R = 5 and R = 7, large amounts of 1-hexene were not reacted, as
seen by less change in the initial versus final levels of 1-hexene in at time = 0 minutes and
time = 30 minutes. Moreover, a visual analysis of the graphs shows that fewer products
were generated.

15
3.3 Methyl linoleate cross-metathesis products
Overall, the reactions of methyl linoleate cross-metathesis with 1-hexene were more successful
than methyl oleate, regardless of the 1-hexene ratios. A visual analysis of Figure 5 shows
the high concentration of many different products that were generated.
When comparing Tables 1 and 2, Table 2 shows the extremely high conversions of methyl
linoleate regardless of the 1-hexene ratios, as well as higher 1-hexene conversion ratios for
lower values of R (R = 2 and R = 4). In particular, ML conversion was 97.0% or higher
for every value of R. In the ML reaction, 1-hexene’s conversion for R = 2 and R = 4 was
nearly double that of R = 5 and R = 7. Table 1 shows significantly lower FAME conversion
percentages for all values of R, and also lower 1-hexene conversion. This further proves that
increasing 1-hexene ratios does not increase the conversion and wastes 1-hexene, since as R
increases, less of the reagent is used.
Because the FAME hydrocarbon chains of methyl linoleate were so long, each section
from either the end of the chain to the double bond or from double bond to double bond
was labeled ”A,” ”B,” or ”C,” and the chain of 1-hexene was labeled ”H.” In Figure 5, the
products of the methyl linoleate cross-metathesis reaction were labeled using this ABCH
naming. Table 6 provides a proper name for each product based on this ABCH label.

16
 MO abbrev. ML abbrev. Species name C after HDO Jet-usable/present?
- B 1,4-pentadiene 5 No
H H 1-hexene 6 No
- BH 1,4-nonadiene 9 Yes
- BC 1,4-decadiene 10 Yes
1DC - 1-decene 10 Yes
5DC HH 5-decene 10 Yes
- CH 5-undecene 11 Yes
- CC 6-dodecene 12 Yes
NDO NDO n-dodecane 12 No
- BBC 1,4,7-tridecatriene 13 Yes
- HBH 5,8-tridecadiene 13 Yes
9DCE A methyl 9-decenoate 10 Yes
5TDC - 5-tetradecene 14 Yes
- CBH 5,8-tridecadiene 14 Yes
- CBC 6,9-pentadecadiene 15 Yes
- HBBH 5,8,11-hexadecatriene 16 Yes
- AB methyl 9,12-tridecadienoate 13 Yes
- CBBH 5,8,11-heptadecatriene 17 No
OCT - 9-octadecene 18 No
9TDE AH methyl tetradecenoate 14 No
- AC methyl 9-pentadecenoate 15 No
- ABB methyl 9,12,15-hexadecatrienoate 16 Yes
- ABH methyl 9,12-heptadecadienoate 17 No
MO - methyl oleate 18 No
- ABC (ML) methyl linoleate 18 No
9OD AA dimethyl 9-octadecen-1,18-dioate 18 No
- C 1-heptene 7 No
- BB 1,4,7-octatriene 8 No
- BBH 1,4,7-dodecatriene 12 Yes

Table 6. Species derived from cross-metathesis reactions. Column of MO abbreviations and

ML abbreviations represent shorthand used in the figure keys of Figures 5 and 6. C after
HDO denotes the length of the hydrocarbon chain, since only C9 to C16 hydrocarbons can
be used as jet fuel. Thus, the final column denotes if the product is jet-eligible, and if so, if
it was present in the reaction.

17
 One issue may be that because methyl linoleate has two double bonds, there is an expo-
nentially larger number of potential products in cross-metathesis and self-metathesis reac-
tions. This results in some extremely long hydrocarbon chains that our GC-MS could not
detect.
Despite this issue, between the methyl linoleate cross-metathesis products, R = 2 and R
= 4 were the most successful of all the reactions. The ratios between the initial concentra-
tion and final concentration of 1-hexene showed that 1-hexene levels decreased significantly
compared to ratios R = 5 and 7. This proves that the higher levels of 1-hexene are not
necessary because the reagent ends up unused after the reaction is over.

3.4 Catalyst deactivation

One potential problem in a mass-scale cross-metathesis reaction is the deactivation of cata-
lyst. After thirty minutes of the reaction, the catalyst no longer is able to be used. It changes
color to a dark brown color, which means it has deactivated. Even if stored properly under
inert conditions, this catalyst cannot be used in future reactions. After examining the used
catalyst under the FTIR, its emission spectrum is entirely different from the original, freshly
prepared catalyst. Thus, after using catalyst one time, it cannot be reused in metathesis
reactions.

4 Conclusions and Future Work

This project revealed that there was an achievable process for convert long-chain FAMEs
into usable biojet fuel that could be potentially scaled for commercial use. By analyzing the
products of Hoyveda-Grubbs cross-metathesis reactions, a fast reaction model was developed
to create theoretically infinitely renewable carbon-neutral fuel for commercial aviation.
My research determined an optimal ratio of 1-hexene to fatty acid methyl esters to
maximize the creation of products that are viable as an alternative jet fuel. This discovery
contradicts those done in previous work, since Zelin et al. claimed that higher levels of
1-hexene would create more products [15]. However, if too much 1-hexene is used, the HG
catalyst will be deactivated and the 1-hexene will be left as the excess reagent. By using
lower ratios of 1-hexene, the ratio of R = 2 and R = 4 optimizes the use of reactants, which
creates a more resource-efficient mechanism since it saves 1-hexene.
Because this project aims to address emissions from the commercial aviation industry,
it is important to note issues with scaling the techniques of this project to the commercial
level. Catalyst deactivation poses an issue for the scaling of this process, since large amounts

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of catalyst would have to be used, then removed from the final products. Ideally, in a
commercial reactor, there would be continuous reactions to maximize the amount of product
created, but the deactivation of catalyst would disrupt that. Potential reactor models could
be a plug-flow reactor or a batch reactor, and research by commercial groups would be able to
investigate this in the future. Additionally, a process for converting deactivated HG catalyst,
either from use in the reaction or from degradation over time, into reusable catalyst would
be necessary to increase the cost-efficiency of this process. This would be an important step
to investigate before commercial adoption.
Moreover, the results of this project are not limited to solely the aviation industry. Cross-
metathesis reactions could be performed with shorter hydrocarbon chains to produce other
biofuel products like gasoline or diesel. This would create, in theory, a renewable source of
carbon-neutral energy that could be infinitely created as long as sufficient amounts of the
catalyst were present. Further research to address this could be done using chemical kinetic
modeling and more study of the Ru-based catalyst itself.
This has significant consequences for climate mitigation efforts, since commercial aviation
makes up a significant portion of greenhouse gas emissions. By creating a carbon-neutral
process for jet fuel production and usage, the growth of the transportation industry will
not have the adverse effects as predicted by climate models since airplanes will be using
alternative, rather than conventional, fuel. Thus, the rate of global warming would slow
rather than accelerate, increasing the amount of time before 2.0 degrees Celsius of warming
is reached; this gives more time for climate adaptation and mitigation efforts in science and
technology to be discovered and take effect.
Future work would focus on the commercial application of these techniques, especially
how to address a mass scaling of these processes. Further research would need to be done
to address the issue of catalyst deactivation before this process is brought to a commercial
level. Moreover, future research would analyze the possibility of eliminating competitive
reactions such as self-metathesis or secondary cross-metathesis reactions to maximize the
yield for biojet-eligible products.

5 References
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Special Report on the impacts of global warming of 1.5C above pre-industrial levels and
related global greenhouse gas emission pathways, in the context of strengthening the global
response to the threat of climate change, sustainable development, and efforts to eradicate
poverty [V. Masson-Delmotte, P. Zhai, H. O. Pörtner, D. Roberts, J. Skea, P.R. Shukla, A.

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Pirani, W. Moufouma-Okia, C. Péan, R. Pidcock, S. Connors, J. B. R. Matthews, Y. Chen,
X. Zhou, M. I. Gomis, E. Lonnoy, T. Maycock, M. Tignor, T. Waterfield (eds.)]. In Press.

[2] McCollum, D. L., Gould, G., Greene, D. L. (2010). Greenhouse gas emissions from
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[3] United States Energy Information Administration. (2018). State Energy Data Sys-
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[4] Air Transport Action Group. (2018). Facts and Figures. https://www.atag.org/facts-
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[5] Deane, P., Shea, R. O., Gallachóir, B. O. (2015). Biofuels for aviation. Insight-E Rapid
Response Energy Brief, (5).

[6] Graham-Rowe, D. (2011). Beyond food versus fuel. Nature, 474(7352), S6.

[7] Lieth, H., Masoom, A. A. (Eds.). (1993). Towards the Rational Use of High Salinity
Tolerant Plants: Vol. 1 Deliberations about High Salinity Tolerant Plants and Ecosystems.
Springer Netherlands.

[8] Sharma, R., Wungrampha, S., Singh, V., Pareek, A., Sharma, M. K. (2016). Halophytes
as bioenergy crops. Frontiers in plant science, 7, 1372.

[9] Anwar, F., Bhanger, M. I., Nasir, M. K. A., Ismail, S. (2002). Analytical characteriza-
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chemistry, 50(15), 4210-4214.

[10] Masdar Institute. (2017). The Seawater Energy and Agriculture System. Sustainable
Bioenergy Research Consortium. 2017. Presentation.

[11] Armitage, A. (2007). Salicornia bigelovii flower.

https://www.flickr.com/photos/annaarmitage/790722292

[12] Al-Yamani, W., Kennedy, S., Sgouridis, S., Yousef, L. F. (2013). A land suitability

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Dhabi, UAE. Arid land research and management, 27(4), 349-360.

[13] Wang, W. C., Tao, L. (2016). Bio-jet fuel conversion technologies. Renewable and
Sustainable Energy Reviews, 53, 801-822.

[14] Wang, M., Chen, M., Fang, Y., Tan, T. (2018). Highly efficient conversion of plant oil
to bio-aviation fuel and valuable chemicals by combination of enzymatic transesterification,
olefin cross-metathesis, and hydrotreating. Biotechnology for biofuels, 11(1), 30.

[15] Zelin, J., Nieres, P. D., Trasarti, A. F., Apesteguı́a, C. R. (2015). Valorisation of
vegetable oils via metathesis reactions on solid catalysts: Cross-metathesis of methyl oleate
with 1-hexene. Applied Catalysis A: General, 502, 410-417.

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