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Converting Spent Coffee Grounds to Biodiesel: A Review of 2016-2017


Unconventional Methods
Mulan Yang
06/24/17, ENGW3315: P2FD, ACS Citation Style, Word Count: 2620

Abstract
Fossil fuels are an unsustainable resource contributing to
climate change, but they are used 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, but the
Biodiesel
In-situ transesterification conventional method for converting SCGs to biodiesel is not
Dimethyl ether extraction suitable for industrial and large scale purposes. Alternatives to
Catalytic hydrotreatment
this method have been proposed, including acid and base
catalyzed in-situ transesterification, catalytic hydrotreatment, and
dimethyl ether extraction. This review examines how each of
these procedures improves the effectiveness or efficiency of
producing biodiesel from SCGs.
Contents
1. Introduction.................................................................................................................................................... 2
2. Increases in Efficiency of a Single Stage .................................................................................................... 3
3. Combining Stages of the Conventional Method....................................................................................... 3
4. Procedures and Operating Conditions ....................................................................................................... 4
5. Large Scale ...................................................................................................................................................... 5
6. Quality of Produced Biodiesel ..................................................................................................................... 6
7. Environmental Concerns ............................................................................................................................. 7
8. Conclusion ...................................................................................................................................................... 7
Acknowledgements............................................................................................................................................ 8
References ........................................................................................................................................................... 8
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1. Introduction
Burning fossil fuels releases greenhouse gases that are changing the Earths climate.1,2 This
unsustainable resource must be replaced with alternative forms of fuel, such as biodiesel. However,
producing biodiesel from food crops requires land and plants that could be used to feed people. In
addition, growing those crops requires energy, water, and other resources that may prevent biodiesel
from being carbon neutral. Growing the feedstock is the most expensive part of the whole process;3
for biodiesel to compete with fossil fuels, an alternative source of oil is needed so that the cost of
biodiesel can be lowered. Researchers have turned to food waste, inedible plant matter that would
otherwise go into landfills, as a possible source for biodiesel. Although usage of food waste as
fertilizer, particle board, or mushroom media has been proposed, these approaches are under used.4
One promising form of food waste from industry is spent coffee grounds (SCGs).3 These are a
plentiful resource, as an estimated 9.34 million tons of coffee was produced from 2016 to 2017.2
Fatty acid methyl esters (FAMEs), the main component of biodiesel, can be extracted from
SCGs,3 but the current method for doing so can be expensive and liable to breaking down in
industry due to the variance in SCGs sizes.2 The conventional method of obtaining FAMEs from
SCGs requires three stages: solvent extraction, esterification, and transesterification (see Figure 1), as
well as drying of the wet SCGs.2 Although this method is high yielding, it is overly time consuming.
Four variations to this procedure are currently being investigated to make the process more feasible
for large scale use. These alternatives are 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 combine multiple stages into one,
but may require pretreatment of the SCGs (see Figure 2).

Fig 1. Conventional method for extraction of oil from SCGs and conversion to biodiesel.2
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Wet SCGs

Drying

Solvent Extraction Liquefied DME In-situ


(Conventional) Extraction Transesterification

Catalytic Transesterification
Hydrotreatment (Conventional)

Coffee Biodiesel

Fig 2. Variations on the conventional method of producing biodiesel from wet SCGs.
2. Increases in Efficiency of a Single Stage
Alternatives have been proposed for the solvent extraction and transesterification stages of
the conventional method.1,5 One study showed that liquefied DME is a more effective extraction
solvent than hexane, which is the most commonly used solvent for extraction.1 A maximum of 16.8
1.0% of oil was recovered from the SCGs. DME has a low boiling point, high affinity for oil, and
partial miscibility with water, all of which make it a highly suitable extraction solvent.1 In addition,
the DME extraction can be performed on wet SCGs1, which saves the time and energy needed to
dry the SCGs in the conventional method.3
Because the oils extracted from SCGs have a very high free fatty acid (FFA) content, they
require treatment before the transesterification step in the conventional method. However, catalytic
hydrotreatment can be used to convert the oils without this pretreatment, saving the costs and
energy that would otherwise have been required. This method resulted in a maximum yield of 13%
based on the dry weight of the initial SCGs.5 Catalytic hydrotreatment also results in bio-
hydrotreated diesel (BHD), which has some advantages over FAMEs.5 These are discussed further
in Section 6.
3. Combining Stages of the Conventional Method
Although improvements for each stage are useful, combining multiple stages saves time and
energy, increasing the efficiency of using SCGs as a feedstock for biofuels. In-situ transesterification
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(also known as direct transesterification) was proposed as an alternative to the conventional method
to lessen the number of steps required to make biodiesel from SCGs.2,4,6 Combining the oil
extraction, esterification, and transesterification steps into one stage makes the process simpler. 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.2 However, when possible, base catalysts are used because they are less
corrosive, require smaller amounts of catalyst, and react faster. A high acidity content is also
undesired for the end biodiesel product, which can be avoided when using a base catalyst and
neutralizing the final reaction mixture with acid.2
4. Procedures and Operating Conditions
The conventional method of producing biodiesel from SCGs is both energy and time
consuming, due to the three stages required to make the end product. The procedures and
operating conditions for the proposed alternative methods should take less time and require less
energy.
The DME extraction procedure aimed to improve the yield from the process, but not the
process itself. Therefore, the procedure is comparable to the conventional method. 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.1
Before catalytic hydrotreatment, the oils from the SCGs were extracted in the conventional
way: using a Soxhlet extractor with hexane as solvent. The resulting oils underwent hydrotreating
reactions in a shaking batch reactor that contained one of two catalysts, NiMo/-Al2O3 or Pd/C.5
Although Pd/C was bought directly, NiMo/-Al2O3 had to be produced using the incipient wetness
impregnation method.5 This could be difficult to produce at a larger scale. However, the Pd/C
catalyst allowed for better hydrocracking and therefore higher biodiesel yield.5 Because Pd/C is
more readily available, catalytic hydrotreatment could still be a potential replacement for the
transesterification step.
Multiple methods were used for acid catalyzed in-situ transesterification of SCGs. In one,
the chosen catalyst was impregnated into the SCGs and then reacted with methanol within a
Soxhlet apparatus.2 In the other, the acid catalyst was combined with other solvents and the SCGs
in a single sealed tube and reacted within a heating bath.4 In both cases, the organic phase was
collected after the reaction mixture was centrifuged and the byproducts were removed.2,4 This
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second method can be used for wet SCGs, whereas other methods dry the SCGs first. Skipping this
pretreatment shortens the time required for the process. Although this stage is fairly complex, the
overall time saved by combining three stages into one makes in-situ transesterification a useful
alternative.
The studies also discerned the optimal conditions for this reaction. A maximum of 17.08
0.70 wt.% of oil was extracted from the dry SCGs at 70 C after running the reaction for 12 h, with
20% of H2SO4 impregnated into the SCGs. This amount of oil equated to 98.61 wt.% of the
possible coffee oil being converted into coffee biodiesel.2 The maximum FAME yield from wet
coffee grounds was found 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. The reaction yielded the most oil when
done at 95 C and with H2SO4 as the catalyst. Although hydrochloric acid, nitric acid, and acetic
acid were also tested, none were as effective as sulfuric acid.4 By comparing how wet and dry SCGs
performed, the study also found that 0-20 wt.% of water present in the SCGs had a negligible effect
on the overall yield.4 Therefore, SCGs may not have to be fully dried before the maximum amount
of oil can be extracted from them. This suggests that, even for processes that traditionally use dry
SCGs, the SCGs would not have to be fully dried to get the best yield.
The method for base catalyzed in-situ transesterification used SCGs from the instant coffee
industry,6 instead of wet SCGs from local coffee shops like the other transesterification study.4 The
procedure 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, none
larger than 1.68 mm. Due to their high FFA level, the SCGs had to be washed with methanol,
filtered, and dried again.6 Sodium hydroxide in methanol was used as the 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 and the glycerol byproduct was removed using a separatory funnel.6 Overall, 77% of the
possible biodiesel could be collected after 3 h.6
The study found that washing the SCGs with methanol can reduce their acidity 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.6 However, SCGs require a lot of
energy to be ground smaller because they tend not to flake. Although doing so would increase the
yield, this may not be possible on a larger scale without significantly increasing the cost and time
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required for SCGs processing. In addition, the smaller particles would be harder to separate out of
the solvent after extraction.6
5. Large Scale
The only procedure tested at a large scale was base-catalyzed in situ transesterification. A
similar methodology allowed the small scale reaction of 30 g to be translated to a large scale reaction
of 4 kg.6 One major 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. After byproducts and excess reagents
were removed, the final refined biodiesel was dried in a hot air oven.6 The average yield for the large
scale reaction was 81.8 1.6%.
6. Quality of Produced Biodiesel
Although the study by Sakuragi et al. was not focused on the final biodiesel product, the oils
that were extracted from the SCGs using liquefied DME were mainly a mixture of saturated and
mono-unsaturated fatty acids. These can be converted into high quality biodiesel.1 However, hexane
extraction is most commonly used because the extracted oil has a more neutral pH than when
diethyl ether or dichloromethane is used for extraction.3 Using DME as the extraction solvent could
result in a higher FFA content in the oils, which could then require more pretreatment before the
transesterification stage.
The final product after catalytic hydrotreatment consisted of straight chain hydrocarbons.5
This is considered a bio-hydrotreated diesel (BHD), which has some advantages over FAMEs, the
product of conventional transesterification processes. FAMEs can have low oxidative stability and
energy content, and cannot be used in isolation in current diesel engines. BHD, if partly isomerized,
does not need to be combined with diesel and can be used by current engines directly.5
Acid catalyzed in-situ transesterification produced biodiesel that satisfied the ASTM
standards for total and free glycerol, kinematic viscosity, and oxidation stability. After the product
was washed with 1% NaOH, it had an acid value of 0.31 mg KOH/g, which also met the ASTM
standard.2 These values indicate that biodiesel produced from this process can be stored and is safe
for engines.
The biodiesel produced from large scale, base catalyzed in-situ transesterification fit the
ASTM standards for moisture content, total glycerin amount, kinematic viscosity, and oxidative
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stability index (OSI), but exceeded standards for cloud point, pour point, and acidity.6 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. This is important because a high OSI value means a decreased chance of the
biodiesel turning into sediment and becoming more acidic and viscous.6 The high acid value of this
biodiesel indicates that 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.6
7. Environmental Concerns
Although the main goal of these studies was to increase the efficiency of producing
biodiesel from SCGs, making the process greener is also important. Using harsh materials that
damage the environment would most likely increase disposal costs and undermine the overall goal
of protecting the environment from the negative effects of fossil fuels.
Overall, the reviewed alternative methods are not less green than the conventional method.
Liquefied DME is an approved green solvent, safe for use in the food industry.1 Solvents used for
in-situ transesterification can be collected and reused.2 This is important because it creates less waste
and uses less energy to obtain more of the solvent. Multiple studies found that the SCGs, even after
being processed for oil, could be used for further purposes. This also helps lower the amount of
waste from this process and results in another valuable product. The coffee ground residue had the
appropriate properties to be mixed with coal into bio-solid fuel for combustion.1 The grounds can
also be used for fertilizer or as fuel pellets.3

8. 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
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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. This review finds that in-situ
transesterification appears to be the most promising new method because it dramatically reduces the
number of steps required for the whole process. However, catalytic hydrotreatment should continue
to be studied because of its superior product, particularly if FAMEs biodiesel cannot meet ASTM
standards.

Acknowledgements
I would like to thank Emily Erhard for peer reviewing this paper and Kelly Scrocco for
reviewing my annotated bibliography.

References
(1) Sakuragi, K.; Li, P.; Otaka, M.; Makino, H. Energies 2016, 9 (2), 106.
(2) Liu, Y.; Tu, Q.; Knothe, G.; Lu, M. Fuel 2017, 199, 157161.
(3) Kondamudi, N.; Mohapatra, S. K.; Misra, M. J. Agric. Food Chem. 2008, 56 (24), 11757
11760.
(4) Park, J.; Kim, B.; Lee, J. W. Bioresour. Technol. 2016, 221, 5560.
(5) Phimsen, S.; Kiatkittipong, W.; Yamada, H.; Tagawa, T.; Kiatkittipong, K.; Laosiripojana,
N.; Assabumrungrat, S. Energy Convers. Manag. 2016, 126, 10281036.
(6) Tuntiwiwattanapun, N.; Monono, E.; Wiesenborn, D.; Tongcumpou, C. Ind. Crops Prod.
2017, 102, 2331.

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