Hilb Ers 2015
Hilb Ers 2015
Hilb Ers 2015
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Research Article 1
Tim J. Hilbers*
Green Diesel from Hydrotreated Vegetable
Lisette M. J. Sprakel*
Leon B. J. van den Enk Oil Process Design Study
Bart Zaalberg
Henk van den Berg A systematic approach was applied to study the process of hydrotreating vegetable
Louis G. J. van der Ham oils. During the three phases of conceptual, detailed, and final design, unit opera-
tions were designed and sized. Modeling of the process was performed with Uni-
University of Twente, Faculty Sim Design. Producing green diesel and jet fuel from vegetable oils was found to
of Science and Technology, be technically possible via a flexible process of hydrotreatment. The resulting mass
Enschede, The Netherlands. and energy balances indicated high carbon atom and energy yield. An economic
evaluation proved that the operational expenses mainly depend on the cost of raw
materials. Currently, the margin between crude palm oil and the retail diesel price
is too low to operate an economically viable process. However, production and
utilization of biofuels is required by international regulations.
1 Introduction was 1.9 million barrels per day, which is expected to increase to
6.6 million barrels per day in 2035 [3].
Environmental impact of fossil fuel consumption and govern- Potential processes for diesel from biomass are reviewed by
mental measures to protect the environment increase interest Perego et al. [4]. Biological sources with an appropriate hydro-
in ‘green’ fuels and minimizing the emission of CO2 and other carbon chain length are, e.g., fatty acids in vegetable oils and
greenhouse gases. One of the main issues associated with pro- animal fats. Vegetable oils consist of a mixture of lipids, mainly
duction of biofuels is the energy input in comparison to the triglycerides, i.e., esters of glycerol and un(saturated) fatty
energy content of the product, expressed by the energy return acids. Microalgae also consist of lipids, but the growth of algae
on energy invested (EROI). The ratio should be at least 3:1 to and recovery of lipids is energy-intensive. Transesterification of
cover for infrastructure and transportation, while the ratio is triglycerides with methanol gives a mixture of fatty acid methyl
approximately 1.3:1 for common biofuels [1]. esters (FAME) and glycerol. FAME is usually referred to as
Biofuels can be produced from biomass, particularly second- conventional biodiesel. A promising alternative is hydrotreat-
generation biomass, as it does not compete with food produc- ment of vegetable oils (HVO). The product is a synthetic,
tion. High raw material costs are an issue in making biofuel mostly paraffinic fuel with chemical-physical properties analo-
processes economically attractive. However, proof of technolo- gous to petroleum diesel. Both process and products can be
gy is an increased subject in literature, because international integrated in the existing refinery infrastructure.
regulations require utilization of biofuels in the near future. In This article focuses on the design of a plant for HVO to pro-
the European Union, for example, the 2009/28/EC Renewable duce green diesel. The base case is the conversion of palm oil
Energy Directive (RED) enforces a 20 % target for the energy into 800 000 tons of fuel per year (8000 production hours),
share from renewable sources, of which at least 10 % renew- mainly diesel (C16–C19 alkanes and isomers). Ethical and eco-
ables in the transportation sector. logical matters as well as availability of the raw materials were
In the transportation sector, the most relevant biofuels are not within the scope of this study. Hydrogen is available
bioethanol and renewable diesel. Bioethanol can be blended (1.5 $ kg–1) on site, as this process will be integrated in an exist-
with gasoline and renewable diesel with petroleum diesel. ing refinery. The expanding aviation market also calls for green
Renewable diesel has become industrially more interesting, jet fuel, which can be produced by cracking and isomerization
because the diesel market has been growing since 2000, while of the longer hydrocarbons to enhance the cold flow properties
the gasoline market is in decline [2]. In 2011, the biofuel supply [5]. The objective is to give an unbiased view on the HVO pro-
cess, flexible in both feedstock and final fuel mix.
–
Correspondence: Tim J. Hilbers ([email protected]), 2 HVO versus FAME
Lisette M. J. Sprakel ([email protected]), University of
Twente, Faculty of Science and Technology, Drienerlolaan 5, 7522 ND Biodiesel (FAME) and green diesel (HVO) are not only differ-
Enschede, The Netherlands. ent products, the production also differs. Transesterification
*These authors contributed equally to this paper. into FAME requires methanol and yields the low-value
Chem. Eng. Technol. 2015, 38, No. 00, 1–8 ª 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
’’ These are not the final page numbers!
2 Research Article
by-product glycerol. The HVO process, illustrated in Fig. 1, In the first phase of conceptual design, the scope was defined
consumes hydrogen and yields the valuable by-product pro- in terms of raw materials and product specifications. Deliver-
pane, which can easily be separated, burned, sold or reformed ables for this phase are a list of chemicals, black box calcula-
into hydrogen again. The required methanol and hydrogen are tions, and a functional flow diagram. In this design phase only
commonly produced from approximately the same amount of functions, e.g., separation or reaction, are mentioned. Although
natural gas. However, HVO can handle free fatty acids (FFA) an initial literature study was conducted in this phase, addi-
in the feed, while FAME is limited to 0.5 % FFAs due to un- tional data was required in the next phases.
wanted saponification reactions and catalyst deactivation [4]. The output of the conceptual phase was used to design all
Furthermore, the HVO process is more flexible owing to addi- steps in detail. Alternatives for each function are considered
tional hydrocracking and isomerization. Hydrocracking con- and functions are translated to unit operations. The final stage
trols the chain length of the fuel mixture, whereas isomeriza- of detailed design is process optimization by, e.g., heat integra-
tion enhances cold flow properties being important steps for tion. The process simulator UniSim Design was used to
proper green jet fuel and high-quality diesel. obtain the deliverables of the detailed design phase: a process
In Tab. 1, critical properties of summer diesel and Fisher- flow diagram, a mass and energy balance. The property pack-
Tropsch products (XTL, also synthetic fuel) are compared with age NRTL with the Redlich-Kwong equation of state was
typical HVO and FAME diesel [6]. A high cetane number, low employed.
cloud point, and high heating value of HVO are favorable for The last phase of final design consists of equipment sizing,
HVO. Green diesel also contains hardly any aromatics and evaluation of process economics, an evaluation of the flexibility
minor to no sulfur, depending on the type of catalyst used [4]. of the process, a safety study, and a simple piping & instrumen-
FAME can be blended with regular diesel up to 30 wt % without tation diagram to illustrate process control. Highlights of every
significant engine modifications, though the EN 590 standard phase are discussed in the next sections.
limits blending up to 7 vol %, mainly in light of the cold flow
properties and stability [7].
Currently, three major vendors operate similar processes of 3.1 Phase 1 – Conceptual Design
hydrotreating vegetable oils: Neste Oil (NExBTL) [6], UOP/
Eni-Ecofining [8], and Axens/IFP (Vegan) [4, 9]. The con- The chemistry of hydroprocessing vegetable oils is relatively
ceptual design of each process is similar: pretreatment of (non- simple as illustrated in Fig. 1. Triglycerides are saturated under
edible) vegetable oils, a deoxygenation reactor, a selective hydrogen pressure and converted into free fatty acids and pro-
hydrocracking/isomerization reactor, and product separation pane. Long-chain hydrocarbons, water, carbon monoxide, and
by distillation. Hydrogen is fed to both reactors, producing a carbon dioxide are formed by three simultaneous reactions:
fuel mix, water, CO, and CO2. decarboxylation, decarbonylation, and hydrodeoxygenation
[11, 12]. An advantage of decarboxylation is that no hydrogen
is required, but at the cost of carbon loss in the product.
3 Methods Hydrodeoxygenation is preferred regarding the carbon yield,
but consumes more hydrogen and yields water.
Process synthesis is a procedure of defining alternatives and Two vegetable oils, i.e., palm and Jatropha, and two animal
studying the feasibility of each alternative. A structured fats, i.e., lard and tallow, are potential feedstocks. Each raw
approach consisting of three phases, namely, conceptual, de- material has a different composition of (un)saturated trigly-
tailed, and final, was adopted. In each phase alternatives will cerides that will determine the length of hydrocarbons in the
arise, which are recorded in a hierarchical diagram. If at a cer- products [13]. Simultaneous to the hydrocarbon formation,
tain point an alternative is considered not feasible, another hydrocracking will yield smaller hydrocarbons and a small
option can be selected. After every decision, it is necessary to amount of isomers.
check if the proposed process is still in line with the goal and A preliminary black box calculation was carried out to find
scope [10]. the most promising feedstock. The main driver for the profit-
ability is the narrow margin be-
Table 1. Critical properties of diesel, XTL, HVO, and FAME. tween feedstock (0.75–1.15 $ kg–1)
and retail diesel price (1.10 $ kg–1).
Diesel (summer) XTL HVO (NExBTL) FAME (rape seed) This margin was calculated based
on the costs of raw materials (feed-
CEN Standard EN 590 TS 15940 n/a EN-14214
stock, hydrogen) and revenues
Density (15 °C) [kg m–3] 820–845 765–800 770–790 860–900 from the products (diesel, pro-
pane). Palm oil is most profitable
Cetane number > 51 > 70 75–99 > 51
due to the lower feedstock price.
Higher heating value [MJ kg–1] 43.1 44.1 44.1 37.2
Blending biofuel [vol %] < 7 allowed < 7 allowed < 30 possible < 7 possible
3.1.1 Functional Scheme
Flash point [°C] > 55 > 55 > 61 > 101
Cloud point [°C] > –34 > –34 > –40 n/a
Hydrotreatment of vegetable oil is a
straightforward process (see Fig. 2)
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Research Article 3
Chem. Eng. Technol. 2015, 38, No. 00, 1–8 ª 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
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4 Research Article
ZSM-5 zeolite to enhance surface area, the fast mass transfer, Table 2. Process conditions for unit operations of the hydro-
and easier operation compared to the alternative of a slurry treatment plant.
reactor. The reactor dimensions were calculated based on a res-
idence time of 30 min and a catalyst loading of 20 vol %. Temperature [°C] Pressure [bar] Conversion [%]
The outlet stream of reactor 2 is cooled to 30 °C to remove P1 60–100 1 90 %
hydrogen with a higher purity in the subsequent flash tank
(S2). The feed to the third separation sequence (S3) could be R1 300–350 35 97 %
sent off to a refinery or fractionation column. In this project, S1.1 160 35
three separate distillation columns were designed instead of
one fractionation column for the ease of simulation. All prod- S1.2 150 35
uct streams are cooled to 25 °C, while the heat could be used S1.3 80–470 30
for heat integration. The inlet stream of the final distillation
S1.4 380 35
column is compressed to 5 bar to prevent the liquid petroleum
gas (LPG) gas from reaching subzero temperatures. R2 380 35 100 %
All main unit operations are illustrated in a simplified pro-
S2 30 35
cess flow diagram (PFD) in Fig. 3.
The process conditions of each unit are summarized in S3 30–100 1–5
Tab. 2. To achieve high, up-to-ideal conversion of 100 %, the
temperature is moderate and the pressure is high, in general.
for hydrogen. In terms of carbon efficiency, the HVO process is
less attractive because transesterification of the triglyceride of
3.2.2 Mass Balance oleic acid, as a typical component, to methyl oleate gives a car-
bon yield of 95.0 %. In the HVO process, after hydrotreatment
From the feed of 149 t h–1 of palm oil, 134 t h–1 of refined palm to fully saturated stearic acid (94.7 % yield), hydrogenation
oil was produced. In Fig. 4, the carbon balance of the process reactions decrease the carbon yield further by CO/CO2 losses.
excluding pretreatment is illustrated. Based on refined palm The overall mass yield excluding pretreatment equals 46 %
oil, the total carbon recovery in the main products is 81.1 %. A for diesel (62 t h–1), 25 % for kerosene (34 t h–1), and for 1.7 %
substantial amount of carbon (10.3 %) is converted into pro- naphtha (2.3 t h–1). The total yield of the three main products
pane; 3.7 t h–1 of hydrogen is required for hydrogenation. equals 73 % excluding and 66 % including pretreatment. This is
Steam reforming of this effluent gas stream could produce 80–90 % of the maximum possible yield (82 %) based on the
4.6 t h–1 hydrogen, which would make the process self-sufficient black box calculation.
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Research Article 5
3.2.3 Energy Balance and Heat Integration 3.3 Phase 3 – Final Design
The energy flows in terms of lower heating values (LHV) are 3.3.1 Process Flexibility
shown for the process in Fig. 5. The energy yield is 75 % com-
paring the main products to refined palm oil. The heat of com- Changing the type of feedstock to either lard or Jatropha oil leads
bustion of the products is lower than that of the raw materials, to small changes. The largest differences were observed for Jatro-
caused by exothermic hydrogenation reactions that produce a pha oil. The consumption of hydrogen increased by 12 % (mass-
lot of heat resulting in a lower energy yield in the product. The based) and the production of naphtha by 12 %, whereas the pro-
effluent gas containing propane is responsible for an LHV loss duction of diesel and kerosene grew less significantly; 37 % more
of 13 %, which is a direct loss of LHV in the final products. LPG is produced, the propane-rich effluent gas decreased by
The heat released by the two reactors should be used in the 8.2 %, and the water-phase purge increased by 5.0 %. The differ-
process to save on utilities; therefore, heat integration was ences between palm oil and lard were found to be less extensive:
applied by performing a pinch analysis. All of the 45.5 MW for 3.4 % more naphtha, 10 % more LPG, and 3.1 % less effluent gas.
heating utilities can theoretically be saved and 40 % of the The reaction heat is significantly higher (+21 %) when Jatropha
required 112.6 MW of cooling utilities. Nevertheless, heating oil is used because it contains less saturated triglycerides.
equipment is required to start up the hydrotreatment process. Another important aspect of the project was the flexibility of
Further improvement of heat integration could be achieved by switching the product mix towards more jet fuel instead of die-
integration of reboilers and condensers of different distillation sel. Therefore, cracking was enhanced by increasing the tem-
columns, or increasing cold hydrogen feed to several times the perature of the second reactor. Calculations were performed
stoichiometric requirement. based on the article from Calemma et al. [26] in which hydro-
isomerization and hydrocracking of n-C16 on a Pt/amorphous
SiO2-Al2O3 catalyst was performed. The corresponding annual
revenues are indicated in Fig. 6. The amount of jet fuel can be
Figure 5. Graphical representation of all energy flows in terms of lower heating value (LHV) in megawatts (MW).
Chem. Eng. Technol. 2015, 38, No. 00, 1–8 ª 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
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Research Article 7
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Chem. Eng. Technol. 2015, 38, No. 00, 1–8 ª 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
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