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Unconventional Methods of Converting Spent Coffee Grounds to Biodiesel: A


Review of 2016-2017 Literature
Mulan Yang
05/29/17, ENGW3315: P2D1, ACS Citation Style, Word Count: 2075

Abstract
Fossil fuels are an unsustainable resource contributing to
climate change, but they are utilized for much of the worlds

Keywords electricity production. To address this energy crisis, alternate


Spent coffee grounds (SCGs) sources for biodiesel have been proposed. Spent coffee
Fatty acid methyl esters (FAMEs)
grounds (SCGs) may be a possible feedstock for biodiesel, but
Biodiesel
In-situ transesterification the conventional method for converting SCGs to biodiesel is
Dimethyl ether extraction not suitable for industrial purposes. New methods have been
Catalytic hydrotreatment
proposed, including acid and base catalyzed in-situ
transesterification, catalytic hydrotreatment, and dimethyl ether
extraction. This review examines the procedures and products
of these methods.
Contents
1. Introduction.................................................................................................................................................... 2
2. Dimethyl Ether Extraction .......................................................................................................................... 2
2.1. Methods.......................................................................................................................................... 2
2.2. Results............................................................................................................................................. 3
3. Catalytic Hydrotreatment ............................................................................................................................. 3
3.1. Methods.......................................................................................................................................... 3
3.2. Results............................................................................................................................................. 3
4. in-situ Transesterification............................................................................................................................... 3
4.1. Acid Catalyzed ............................................................................................................................... 4
4.2. Base Catalyzed ............................................................................................................................... 4
4.2.1. Large Scale..................................................................................................................... 5
5. Conclusion ...................................................................................................................................................... 6
Acknowledgements............................................................................................................................................ 6
References ........................................................................................................................................................... 6
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1. Introduction
Burning fossil fuels releases greenhouse gases that are changing the Earths climate. This
unsustainable resource must be replaced with alternative forms of fuel, such as biodiesel. However,
producing biodiesel from food crops prevents that land and plants from being used to feed people.
In addition, growing those crops requires energy, water, and other resources that may prevent
biodiesel from being truly carbon neutral. Researchers have instead turned to food waste as a
possible feedstock for biodiesel because this inedible plant matter would otherwise have gone into
landfills. Although usage of food waste as fertilizer, particle board, or mushroom media has been
proposed, this approach is under used.1 One promising form of food waste from industry is spent
coffee grounds (SCGs), which are plentiful considering the estimated 9.34 million tons of coffee
produced in the 2016/2017.2 From SCGs, fatty acid methyl esters (FAMEs), the main component of
biodiesel, can be extracted.
Previous conventional methods of obtaining FAMEs from SCGs involved multiple steps:
solvent extraction, esterification, and transesterification. 2 This multi-step procedure may be
expensive and liable to breaking down in industry due to the variance in SCGs sizes. New
procedures have been proposed to make this process more efficient. These include dimethyl ether
(DME) extraction, catalyzed hydrotreatment, and acid or base catalyzed in-situ transesterification.
DME may be used in place of hexane as the solvent during the extraction phase. Catalyzed
hydrotreatment can replace the traditional transesterification step. In-situ transesterification can
collapse multiple stages into one, but may require pretreatment of the SCGs.

2. Dimethyl ether extraction


Liquefied DME has been proposed as an alternative to traditional extraction in hexane
because DME is very suited to the extraction conditions. It has a low boiling point, high affinity for
oil, and partial miscibility with water, as well as being biodegradable and a safe solvent for producing
food.3

2.1. Methods
DME extraction was done using an extraction column and a storage container for the
reaction mixture of DME, oil, and water. The extracted oil was filtered. Then, transesterification of
the oil to FAMEs was done using methanol. The reaction took 1 h at 60 C with 1.5 wt.% KOH as
a catalyst. The FAMEs were separated from the rest of the mixture by waiting for the two phases to
separate.3
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2.2. Results
Using this method, a maximum of 16.8 1.0% of oil was recovered. The oils were mainly a
mixture of saturated and mono-unsaturated fatty acids, which can be converted into high quality
biodiesel. The coffee ground residue had the appropriate properties to be mixed with coal for
combustion.3

3. Catalytic hydrotreatment
Because the oils extracted from SCGs have a very high free fatty acid (FFA) content, they
would require treatment before the transesterification step in the conventional method. However,
catalytic hydrotreatment can be done to convert the oils to FAMEs without this pretreatment,
saving the costs and energy that would otherwise have been required. The final product after
hydrotreatment should consist of straight chain hydrocarbons and have a boiling point between that
of gas and diesel.4

3.1. Methods
The oils from the SCGs were extracted in the conventional way: using a Soxhlet extractor
with hexane as solvent. The solvent was then recovered using a rotary evaporator. The resulting oils
underwent hydrotreating reactions in a shaking batch reactor that also contained an activated
catalyst. The two catalysts studied were NiMo/-Al 2O3 and Pd/C.4

3.2. Results
This method resulted in a maximum yield of 13% based on the dry weight of the initial
SCGs. The product consisted mainly of palmitic and stearic acids. The most efficient operating
conditions were 2 h at 400 C. Although the NiMo/-Al 2O3 catalyst was more active, the Pd/C
catalyst allowed for better hydrocracking and therefore higher biodiesel yield. 4

4. In-situ transesterification
In-situ transesterification (also known as direct transesterification) was proposed as an
alternative to the conventional method in hopes of lessening the number of steps required to make
biodiesel from SCGs. This method allows SCGs to be a more economically feasible and
environmentally friendly source of energy. In-situ transesterification is done with an acid catalyst
when the FFA concentration of the material is at least 2.0 mg KOH/g oil. However, when possible
base catalysts are used because they are less corrosive, require smaller amounts of catalyst, and react
faster.2 A high acidity content is also problematic for the end biodiesel product; therefore, it might
be more sensible to use a base catalyst and neutralize the final reaction mixture with acid.
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4.1. Acid catalyzed


There are multiple methods ways in-situ transesterification can be done on SCGs. The
chosen catalyst can be impregnated into the SCGs and then reacted with methanol within a Soxhlet
apparatus,2 or the acid catalyst can be combined with other solvents and the SCGs in a single sealed
tube and reacted within a heating bath.1 In the first case, the methanol can be collected using a
rotary evaporator and the byproducts separated using a separatory funnel and centrifuge. 2 In the
second case, the reaction mixture can be cooled, neutralized using sodium hydroxide, and the
organic phase can be collected after the tube in centrifuged. 1 This second method can be used for
wet SCGs, whereas other methods dry the SCGs first. This lessens the number of steps required and
therefore makes the process more feasible for large scale use.
Two studies done on SCGs from the researchers local coffee shops discerned the optimal
conditions for acid catalyzed in-situ transesterification. The variables examined for effectiveness were
type of acid catalyst, amount of acid impregnation, reaction time, reaction temperature, amount and
type of co-solvents, and moisture content. A study by Liu et al. found that the maximum amount of
oil of 17.08 0.70 wt.% was extracted from the SCGs at 70 C, with 20% of H 2SO4 impregnated
into the SCGs, and after running the reaction for 12 h. This amount of oil equated to 98.61 wt.% of
the possible coffee oil being converted into coffee biodiesel. 2
A study done by Park et al. found the maximum FAME yield to be 16.73 wt.%. The optimal
conditions were 8.33 mL of chloroform per gram of SCGs and a 1:2 chloroform to methanol ratio.
This combination of solvents created a polarity of 0.25, which was most suitable for this process.
The reaction yielded the most oil when done at 95 C and with H 2SO4 as the catalyst. Hydrochloric
acid, nitric acid, and acetic acid were also tested, but each of these acid catalysts had an issue.
Hydrochloric acid required too much water to be added to the reaction mixture, and therefore
would have to be offset. Nitric acid was too strong and overoxidized the products, whereas the
acetic acid was too weak and could not catalyze the reaction to go fast enough. This study also
found that 0-20 wt.% of water present had a negligible effect on the overall yield. 1 Therefore, SCGs
may not have to be fully dried before the maximum amount of oil can be extracted from them. This
indicates that less energy would be needed to extract the biodiesel because the SCGs would not have
to be fully dried first.

4.2. Base catalyzed


The method for this section was taken from Tuntiwiwattanapun et al.s study, which utilized
SCGs from the instant coffee industry, instead of wet SCGs from local coffee shops. 5 The base
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catalyzed in-situ transesterification first required the SCGs to be dried, ground down, and deacidified.
The SCGs were dried by the sun and then by a hot air oven. They were then sieved and separated
into four sizes, with any SCGs greater than 1.68 mm being ground in a Kassel food blender and
sieved again. Due to their high FFA level, the SCGs had to be washed with methanol, filtered, and
dried again.5
Sodium hydroxide in methanol was the chosen alkaline catalyst. The SCGs were combined
with this catalyst within a round bottom flask and mixed for 3 h. The final reaction mixture was
neutralized by H2SO4 and filtered. Any remaining methanol was removed via evaporation. The
glycerol phase of byproducts was removed using a separatory funnel. 5
Washing with methanol can reduce the acidity of the SCGs without losing a significant
amount of oil. Reducing the size of the SCG particles and increasing the reaction temperature
significantly increased the amount of oil collected. However, as SCGs tend not to flake, they would
need to be ground smaller, a process that would require a lot of energy. This may make the process
more difficult for large scale production. In addition, the smaller particles would be harder to
separate out of the solvent after extraction. Overall, 77% of the possible biodiesel could be collected
after 3 h.5

4.2.1. Large scale


A similar methodology allowed the small scale reaction of 30 g to be translated to a large
scale reaction of 4 kg. One large difference between the methods was that the methanol used to
deacidify the SCGs was not removed before in-situ esterification. Instead, the SCGs were combined
with the sodium hydroxide as soon as the correct temperature of 50 C was reached. The reaction
ran for 3 h before the alkaline catalyst was neutralized with sulfuric acid. The reaction mixture was
vacuum filtered and the methanol was evaporated using a Soxhlet unit. The glycerol phase was once
again removed after the products were added to separatory funnels. The hexane solvent was
evaporated off, and the final refined biodiesel further dried in a hot air oven. 5
The average yield for the large scale reaction was 81.8 1.6%. This biodiesel fit the ASTM
requirements for moisture content, total glycerin amount, kinematic viscosity, and OSI, but
exceeded standards for cloud point, pour point, and acidity. 5 This indicates that the biodiesel could
be stored well and that the oils from the SCGs had been converted to FAMEs. However, the cold
flow point indicates that the biodiesel cannot be used in cold climates unless it is mixed with
petroleum. Its OSI value indicates that the in-situ transesterification process produces biodiesel that
is less susceptible to oxidation when stored than the biodiesel made from the conventional method.
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The OSI value may be higher with in-situ transesterification because the reaction is faster and at a
lower temperature. This is important because a high OSI value means a decreased chance of the
biodiesel turning into sediment and becoming more acidic and viscous. 5 The high acid value of this
biodiesel indicates it could corrode an engine. However, the problem may have been due to an
excess of sulfuric acid used to neutralize the catalyst. This problem can be solved by washing the
biodiesel with acidic water instead of using concentrated sulfuric acid. 5

5. Conclusion
Multiple alternatives to the conventional method for converting SCGs to biodiesel have
been proposed. The oil extraction step usually uses hexane, but replacing this solvent with dimethyl
ether allows for a yield of 16.8 1.0%. The traditional transesterification step could be substituted
with catalytic hydrotreatment, which would not require a deacidification step. This substitution
produces a maximum yield of 13%. Acid and base catalyzed in-situ transesterification could shorten
the conventional method into fewer steps, which would be more economically feasible and less
energy intensive. Acid catalyzed in-situ transesterification of SCGs can produce approximately 17.0
wt.% of FAMEs, which is approximately 98 wt.% conversion of the collected oil. Large scale base
catalyzed in-situ transesterification has been attempted with a yield of 81.8 1.6%, which is similar
to that of small scale reactions. Future studies should attempt to adapt these methods so that the
biodiesel products can meet all of the ASTM requirements.

Acknowledgements
I would like to thank Cecelia Musselman for answering my questions about this literature
review. In addition, I would like to thank Emily Erhard for discussing the methods described within
this review with me and Kelly Scrocco for reviewing my annotated bibliography.

References
(1) Park, J.; Kim, B.; Lee, J. W. Bioresour. Technol. 2016, 221, 5560.
(2) Liu, Y.; Tu, Q.; Knothe, G.; Lu, M. Fuel 2017, 199, 157161.
(3) Sakuragi, K.; Li, P.; Otaka, M.; Makino, H. Energies 2016, 9 (2), 106.
(4) Phimsen, S.; Kiatkittipong, W.; Yamada, H.; Tagawa, T.; Kiatkittipong, K.; Laosiripojana, N.;
Assabumrungrat, S. Energy Convers. Manag. 2016, 126, 10281036.
(5) Tuntiwiwattanapun, N.; Monono, E.; Wiesenborn, D.; Tongcumpou, C. Ind. Crops Prod. 2017,
102, 2331.