Catalytic Conversion of Algal Oil into Green Diesel

Research proposal by
Zachary Karmiol
University of Nevada Reno
Materials Science Undergraduate
Mentor: Prof. Hongfei Lin
Abstract: This project is to design heterogeneous catalysts which will convert algal oil, lipids
extracted from algae, to green diesel, a drop-in replacement of its petroleum counterpart. The
proposed hydrothermal process uses sub-critical water as a co-solvent in the presence of a
heterogeneous catalyst. This process is more environmentally friendly than the current method
of converting lipids to biodiesel through transesterification. The catalysts will be multifunctional,
making use of hydrocracking and decarboxylation to refine the algal oil.
Introduction: As fossil fuels dwindle on earth, shifting societys dependence away from
petroleum to renewable biomass resources is generally viewed as an important contributor not
only to reduce detrimental impact on the climate change but also to increase the robustness of
our energy production and national energy security.[1] Compared to other biomass feedstock,
microalgae can be a suitable alternative feedstock for next generation biofuels because certain
species contain high amounts of oil, which could be extracted, processed and refined into
transportation fuels.[2-4]Algae have fast growth rate, permit the use of non-arable land and nonpotable water, and do not displace food crops cultures.[5,6] The algal oil extracted from algae is
currently used for the production of ester-based biodiesel fuels by transesterification of lipids,
which requires a non-recoverable homogenous alkaline catalyst and the addition of methanol
mainly produced from fossil fuels.[6,7] This process is unsustainable, creates environmental
risks, and results in low quality diesel. In order to integrate with the existing infrastructures but
to reduce fossil fuel consumption, it is necessary to produce hydrocarbons from algal oil. Nonester green diesel is pure hydrocarbons that are indistinguishable from their petroleum
counterparts. Benefits of non-ester fuels may include (i) higher energy density, (ii) excellent
combustion quality, (iii) good low-temperature properties, and (iv) superior thermal stability,
storage stability, and materials compatibility.[8] In this proposal, a one stage hydrothermal
catalytic process will be used to produce green diesel using lipids from algal biomass as the
feedstock. This process has the advantages of reducing the cost, time, energy, material needed,
and environmental risks associated with producing ester-based fuels from algal lipids. The
essential part of this process is to design and develop a multifunctional heterogeneous catalyst
actively converting lipids to hydrocarbons.
Objectives:
Design and Synthesize multifunctional catalysts for converting lipids to hydrocarbons.
Determine which catalysts are most effective in activity, selectivity, and stability.
Optimizing catalysts and operation conditions to minimize hydrogen use.
Gain experience and knowledge in materials synthesis, as well as their application in
renewable fuels.

Research Hypothesis: Lipids can be converted to green diesel through multiple steps.[9] We
have demonstrated that a lipid sample can be converted to free fatty acids, using the proposed
hydrothermal treatment. Further converting fatty acids to hydrocarbons cannot be completed
without catalysts under hydrothermal conditions. To develop a one-pot process of converting
lipids to hydrocarbons, it is necessary to develop catalysts which remain active in hydrothermal
environment to allow this process to function in an environmentally friendly way. We aim to
design a multifunctional catalyst in combination of solid acid and metal, which are capable of
decarboxylation and hydrocracking.[10]
Research Plans: This project will focus on designing, synthesizing, and evaluating
multifunctional catalysts for green diesel production using the lipid portion of algae as the
feedstock. The synthesis of the catalysts includes multiple methods such as impregnation, codeposition, and ion exchange. As-prepared catalysts will be tested with key merit comparison on
their activity, selectivity, and stability. Analysis of the catalyst as well as the green diesel
product will enable us to determine which catalyst is preferable based on the aforementioned
criteria. Characterization of surface intermediates on the catalyst will be conducted to elucidate
reaction pathways which will be used for further optimization of designed catalysts. The
candidates of solid acid materials include zeolite, alumina, and zirconia. Besides the acidic
functions, these are also the supports of metals. The candidates of metal catalysts must have
high activity of hydrogenation for this application. Therefore, common hydrogenation metal
catalysts in petroleum refining industry including nickel, cobalt, ruthenium, platinum, palladium,
as well as bimetallic alloys.

Timetable:
2/7

3/29

5/18

7/7

8/26

10/15

12/4

1/23

3/13

5/2

Catalyst Testing
Catalytic Synthesis
Kinetic Studies
Chemical Analysis
Catalyst Characterization
Process Optimization

Plans for Dissemination of Results: The results from our research will be shared within the
Chemical and Materials Engineering Departments of UNR. We will also present at the weekly
seminars for Chemical Engineering students in order to guide other undergraduates into research
of their own.
Qualifications: I have studied social impacts of science and technology as well as engineering,
thus an understanding of the work in a larger context. Finishing my junior year, having
completed courses covering the broad fields applied in this research. I have spent the past two
semesters in in lab under Dr. Lin doing research, thus my time will be spent actually applying
what I have already learned rather than being trained.

References:
[1]

A.J. Ragauskas, C.K. Williams, B.H. Davison, G. Britovsek, J. Cairney, C. a Eckert, W.J. Frederick, J.P.
Hallett, D.J. Leak, C.L. Liotta, J.R. Mielenz, R. Murphy, R. Templer, and T. Tschaplinski, The path
forward for biofuels and biomaterials., Science, vol. 311, Jan. 2006, pp. 484-9.

[2]

L. Brennan and P. Owende, Biofuels from microalgaeA review of technologies for production,
processing, and extractions of biofuels and co-products, Renewable and Sustainable Energy Reviews, vol.
14, Feb. 2010, pp. 557-577.

[3]

T.M. Mata, A. a Martins, and N.S. Caetano, Microalgae for biodiesel production and other applications: A
review, Renewable and Sustainable Energy Reviews, vol. 14, Jan. 2010, pp. 217-232.

[4]

J. Ferrell and V. Reed, National Algal Biofuels Technology Roadmap, 2010.

[5]

L. Gouveia and A.C. Oliveira, Microalgae as a raw material for biofuels production., Journal of industrial
microbiology & biotechnology, vol. 36, Feb. 2009, pp. 269-74.

[6]

H.C. Bold, The Cultivation of Algae, Botanical Review, vol. 8, 1942, pp. 69-138.

[7]

A. Demirbas, Production of Biodiesel from Algae Oils, Energy Sources, Part A: Recovery, Utilization,
and Environmental Effects, vol. 31, Jan. 2009, pp. 163-168.

[8]

L. Li, E. Coppola, J. Rine, J.L. Miller, and D. Walker, Catalytic Hydrothermal Conversion of Triglycerides
to Non-ester Biofuels, Energy & Fuels, vol. 24, Feb. 2010, pp. 1305-1315.

[9]

N.H. Tran, J.R. Bartlett, G.S.K. Kannangara, a S. Milev, H. Volk, and M. a Wilson, Catalytic upgrading of
biorefinery oil from micro-algae, Fuel, vol. 89, Feb. 2010, pp. 265-274.

[10]

J.O. Olusola, M.M. Adediran, A.K. Oluseyi, and U.L. Ajao, Processing of triglycerides to diesel range
hydrocarbon fuels: easily practicable small scall approach, Energy & Environment, vol. 20, 2009, pp. 13251342.

Budget:
Chemicals
Item

Supplier

Item Number

Cost

5% Pd on C
5% Pt on C
KOH
H2SO4
5% Ru on C
Raney-Ni
Pd2(NO3)2
CeO2
ZrO2
Zeolite
Ni on SiO2-Al2O3

Sigma
Sigma
Sigma
Sigma
Sigma
Sigma
Sigma
Sigma
Sigma
Sigma
Sigma

205680-10G
205931-10G
221473-500G

208779-100G

72.4
100.5
30.2
55.1
159.5
67
204
32.9
33.1
36.8
54.1

320501-500ML

206180-25G
221678-100G
76070-5G
211575-100G
230693-100G
96096-100G

Lab Equipment
Heterogenous Pd Kit 1

Sigma

659967-1KT

193

pH meter

Fischer Sci

13-301-01

154.42

Total
Chemicals: $845.60
+

Equipment: $347.42
$1,193.20