Simulation of Biodiesel

Production Using Reactive

Distillation (RD)
A comparative study of the advantages of RD on
efficiency in biodiesel production
Max Levy
Dept. of Chemical Engineering
University of Florida
April 24, 2013

Presented to the Department of

Chemical Engineering in partial
fulfillment of the requirements for a
Bachelor of Science degree with Honors

Table of Contents
Abstract ......................................................................................................................................................... 2
Introduction & Background .......................................................................................................................... 3
Biodiesel Production in the Future ........................................................................................................... 3
Reactive Distillation .................................................................................................................................. 4
Experimental Methods ................................................................................................................................. 6
Simulation 1: Conventional Methods (No RD) .......................................................................................... 7
Simulation 2: Production with RD ............................................................................................................. 8
Experimental Results and Discussion.......................................................................................................... 10
Comparison of Products.......................................................................................................................... 10
Comparison of Reaction/Separation Schemes ....................................................................................... 11
Energy ................................................................................................................................................. 11
Materials ............................................................................................................................................. 12
Conclusion ................................................................................................................................................... 14
Works Cited ................................................................................................................................................. 15

Abstract
This study aims to investigate how the production of biodiesel can be improved by
introducing a reactive distillation column into the production scheme. Biodiesel is a fuel
developed as an alternative to traditional gasoline or petrodiesel fuels for the
transportation sector. The energy balance regarding its production is generally much
more positive than for other fuels, such as ethanol. However, in many nations, the
production of biodiesel delivers a narrow profit margin. That being said, there is room to
improve the production process for this fuel. Reactive distillation (RD), a relatively novel
unit operation, can allow for greater production-level efficiency. It involves the
combination of a reactor and distillation column in one multi-stage vessel. Integrating
the reaction and separation processes can allow for better results in terms of
conversion, selectivity, and purity, thereby reducing total cost. By creating and a
juxtaposing two different Aspen HYSYS simulations of biodiesel productionwith and
without RDconclusions could be drawn. It was found that implementing reactive
distillation in the scheme allowed for drastically lowered capital and material costs,
thereby improving the production process.

Introduction & Background

Biodiesel Production in the Future
For all of the 21st century, energy has been a pressing global issue. Biodiesel is
often mentioned in debates regarding future large-scale energy sources. Compared to
current gasoline and diesel fuels, biodiesel offers a cleaner, more sustainable solution
as a transportation fuel1. For years, biodiesel has been applicable in the transportation
sector as a viable energy source. The fuel can be used at 100% purity, or blended with
regular diesel fuel (petrodiesel). Engine modifications are only necessary when using
high compositions of biodiesel.

+ 3 3 +
(Figure 1)

The reaction in Figure 1 shows how biodiesel is formed from raw materials. The
triglycerides necessary for reaction are obtained many different ways in industry. For
one, triglycerides are found in high concentrations in virgin oils, vegetable oils, and fats.
Oftentimes, a facility may use discarded cooking oils as feedstock for the reaction. This
green solution allows for minimized cost of raw materials. Reaction of this feedstock
with an excess of methanol (typically 6:1 molar ratio), yields biodiesel (a methyl-ester)
and an undesired side-product of glycerol.
While the production of biodiesel is more efficient with respect to energy
consumption than other fuel options1, the profit margin is small. Efforts have been made
on the national, state, and local levels to incentivize biodiesel production in light of this.
In the United States, a program was implemented to provide tax credits for biofuel
production. Each gallon produced resulted in a $1 tax credit when made from virgin oils,
and $0.50 for recycled feedstock2. However, this subsidy program expired in 2010, thus
diminishing the incentive for biodiesel production.
Much of the cost of the fuel stems from the processing necessary for large-scale
continuous production. While the reaction and product separation steps are not as
arduous as some, research has been done to investigate methods for increased
efficiency. In many cases, changes were made to conditions such as temperature,
pressure, and catalyst selection leading to more optimal results. Other researchers,
however, have looked to a more dramatic change in the process that can reduce both
operating and capital costs: using reactive distillation3.

Reactive Distillation
Although the process was patented in the 1920s, reactive distillation or
catalytic distillationhas only been used in industry for three decades. It is a unit
operation that simultaneous reacts and separates key reactants and products in one
column. The main benefit of reactive distillation (RD), when compared to conventional
methods, is the increased control over the contents of the vessel. This increased control
translates into numerous benefits that can be obtained in a variety of processes, such
as biodiesel production.
Generally speaking, it is found that reactive distillation is especially beneficial for
processes involving equilibrium-limited reactions with difficult separations. Using
reactive distillation allows for the constant removal of product from reaction zones,
thereby pulling chemical equilibrium to the right. In addition, difficult separations can be
overcome by reacting through azeotropic compositions and distillation boundaries4.
Along with biofuel production, reactive distillation offers an efficient solution to
many inefficient chemical processes. The most cited example of reactive distillation in
industry is for the production of methyl acetate at Eastman Company5. In this case,
application of reactive distillation and its added capabilities allowed for a dramatic
reduction in capital and operating costs. Figures 2 and 3 below depict two PFDs for the
same process- production of high purity methyl acetate. The figure on the left was
proposed as a complicated method to deal with the difficult separations encountered in
the process. Alternatively, a PFD was proposed to achieve the same purity through
reactive distillation, and is shown on the right. Reactive distillation was subsequently
implemented, as the fiscal benefits were apparent.

(Figures 2 and 3, not to scale)6

This application of RD to methyl acetate is not an isolated incident. The benefits

that make RD an attractive operation can be obtained in a variety of processes. The
majority of reactive distillations advantages revolve around its control over the
reaction(s) occurring. Such control can lead to higher conversion, selectivity, and
efficiency, all at lower total cost.

(Figure 4)4

The above figure shows how reactive distillation compares to conventional

processes with regards to the established principles of Green Engineering4. Many of the
principles show that reactive distillation is a more sustainable solution than conventional
methods. However some drawbacks appear, mostly due to the complexity of operation.
For example, the first principle is Inherent, not circumstantial. This refers to whether a
process is inherently safer, easier to operate or control than conventional methods. This
is a weak point for reactive distillation, due to the complexity of the system and its
specialized equipment.
Principle 4 sheds light on the majority of the strengths of RD for many reasons
that go hand-in-hand with principle 5. Output-pulled, not input-pushed can refer to a
situation illustrated by Le Chatelier's principle which states that reaction equilibrium can
be driven to the right in one of two ways. One method is to add an excess of reactant to
push equilibrium to the right. The more efficient method, however, is to pull
equilibrium by removing products constantly as they form. Having said that, reactive

distillation allows for the stage-by-stage control necessary to efficiently drive equilibrium
to the right.
This control is especially relevant in the case of biodiesel production.
Conventionally, a 100% excess of methanol (6:1 molar ratio alcohol/oil) is used to drive
equilibrium to the right for high conversion7. In certain cases, a 42:1 molar ratio8 is used
to obtain product. These inefficient methods contribute directly to high material costs.
Additionally, having to separate and recycle the methanol back into the system in such
large quantities adds operating costs through energy consumption. Implementing
reactive distillation in this process allows for a cited reduction in methanol excess to
achieve the same conversion9. As a result of the reduction in methanol and greater
overall control, selectivity is also increased. Therefore, implementing reactive distillation
in large-scale production has the potential to result in dramatic increases in overall
efficiency. To attain a high-level estimate of the widespread change, simulation data for
the two cases can be compared.

Experimental Methods
In order to explore the effect of RD on biodiesel production in greater detail, the
following comparative study assesses two HYSYS simulations on several levels. By
judging overall energy consumption and high-level capital costs, more can be
understood regarding this process and its room for improvement via reactive distillation.
Modeling reactive distillation is no easy feat. Due to the potential complexity of
systems involved, high power software is necessary. Most of the complexity of the
modeling arises from the physical and chemical constraints that must be satisfied. Many
conventional unit operations deal with these constraints independently. However in
reactive distillation, they must often be dealt with simultaneously. In most cases,
differential equations representing mass transfer, phase and chemical equillibria, and
reaction kinetics must all be solved simultaneously. For this reason, reactive distillation
is often seen as unfavorable compared to processes that are easier to design and
control.

(Figure 5)

While accuracy of the software was very important for the sake of this study,
exact precision was not. The software selectedAspen HYSYS V7.3was chosen
based on its accuracy for modeling conventional systems, and option for reactive
distillation. There are certainly limitations to the accuracy of the softwares ability to
model an RD system. In order to counteract the expected inaccuracies, some of the
data were benchmarked with cited experimental data9.
The first step of building a HYSYS model of a process requires the selection of
components and a fluid package. The key components for the reaction (in both cases)
were methanol, glycerol, water, vegetable oil, and biodiesel. The first three can be
selected by these common names, but the oil and fuel could vary. Vegetable oils and
cooking oils are made up of two components: triglycerides and free fatty acids.
Rapeseed oil, or canola oil, generally consists of triolein (triglyceride) and oleic acid
(FFA) among other components. For the sake of simplicity, the feedstock was modeled
as a mixture (95-5 by mass of triolein and oleic acid. The biodiesel that forms from
these components was selected as m-oleate, a mono-alkyl ester. The General NRTL
fluid package was then chosen for the organic liquids. No catalysts were selected or
needed in the scope of this study.

+ +
For both simulationswith and without RDthe same feedstock composition
was used. A stream of 95 wt. % triglyceride was chosen based on standards of low fatty
acid content in canola oil.

Simulation 1: Conventional Methods (No RD)

The feedstock outlined above was brought to continuous reactor (modeled as a
Conversion Reactor in HYSYS) at 4 atm and 50 degrees C. There, a feed stream of
methanol was also brought in at standard conditions. As cited in past studies, the
quantity of methanol fed was set as a fixed ratio of triglyceride fed (6:1), a 100% excess.

This was important to simulate actual conditions in spite of the ideal reaction conversion
in HYSYS.

(Figure 6)
The reaction proceeds at a specified conversion rate of 97%. And the product
splits into a liquid and vapor phase. The vapor phase, consisting of mostly methanol
and water, is cooled to 70 degrees and sent to a distillation column to purify the
methanol for recycle. The water, and some methanol, are then discarded.
The liquid phase product of the reaction is subsequently cooled to 30 degrees
and decanted into two liquid phases to remove glycerol from the biodiesel. The light
liquid, theoretically consisting of mostly biodiesel, can then be sent to a liquid-liquid
extraction column. After contacting with water to remove impurities, the raffinate is sent
to a heater before having oil and water waste removed in consecutive separators.
Theoretically, the light liquid coming from the final decanter would consist of high purity
biodiesel.
Lastly, the adjust function of HYSYS was used to find the feed flow that would
correspond to desired biodiesel capacity (10 million gallons annual).
Unit Operation
Reactor
Distillation Column
Decanter/Separator
LLE Column
Total

Amount in Model
1
1
3
1
6
(Table 1)

Simulation 2: Production with RD

The feedstock for Simulation 2 is the same as that of conventional methods with
respect to the oil. However, the amount of methanol needed for reaction is altered.
According to experimental data collected during literature review, optimal conversion

occurs with a methanol excess of 33% (as opposed to 100%). This excess corresponds
to a 4:1 molar ratio with the triglycerides fed. Again, the accuracy of this excess was not
necessary to drive equilibrium in HYSYS, but was necessary to accurately model
subsequent separations.

(Figure 7)
Using the capabilities of HYSYS, a model for biodiesel production with reactive
distillation could only be created with great caution. Two streams (methanol and oil) are
fed to a ten-stage distillation column in HYSYS and converged with specified
parameters but no reaction.
After several failed attempts at immediately introducing the reaction at full
conversion, a more gradual approach was formulated. With the oil and methanol
entering at trays 1 and 9, respectively, a dummy stream of low flow was introduced.
This dummy stream consisted of reaction productglycerol and m-oleate. After
converging the column with all the components present, the reaction could then be
introduced.
First, the reaction package containing the relevant reactions was selected, but
only at tray 1 and with 1% conversion. After convergence of the column, the reaction
was then expanded gradually tray-by-tray until it spanned from the condenser to the
reboiler. Conversion rate was subsequently increased gradually to convergence.
HYSYS automatically assumed that at chemical equilibrium was reached at each of the
ten trays. In order to effectively remedy this situation, the specified reaction conversion
was adjusted to reflect an effective conversion of 97%.
In this simulation, the parameters of the column were selected to result in a
distillate product of only water and methanol. This mixture is cooled and decanted to
obtain a high-purity methanol stream for recycle. The bottoms product consisting of the
remaining organics is heated to separate oil waste, and then cooled and decanted once
more. Theoretically, the resulting light-liquid would consist of high-purity biodiesel (moleate).

Unit Operation
Reactor
Distillation Column
Decanter/Separator
LLE Column
Total

Amount in Model
0.5
0.5
3
0
4
(Table 2)

Experimental Results and Discussion

Once both simulations were completed and fully converged and optimized, a
plethora of data became available for comparison. Many aspects of each simulation
were important to consider when contrasting the models. Properties of the final product
were analyzed to determine the more optimal fuel. In addition, high-level capital cost
estimate could be performed to assess the feasibility of each design. Operating costs
could also be evaluated by comparing energy estimates as well as the big picture for
raw materials. While the main goal of this study is to compare the biodiesel production
between both methods, it was also valuable to analyze how the product compares to
industry standards.

Comparison of Products
Arguably the most important evaluation to make in this study is the comparison of
the biodiesel products created in the simulations. Of all the properties available for
assessment, the ones selected were as follows: composition, density, and viscosity.
The importance of composition is evident when discussing purity. A high mass fraction
of alkyl ester (m-oleate) would indicate highly pure biodiesel. Minimizing impurities such
as glycerol, water, triglycerides, and methanol is also crucial. If the density of a biodiesel
is too high or low, the fuel injection in an engine will not function properly and may
cause damage10. Viscosity also plays a big role in the application of the product.
Standards are generally set to require the fuel to be viscous enough to lubricate without
being too viscous to flow12. It is important to note that the built-in HYSYS value for the
viscosity of m-oleate was benchmarked against experimental data13 and found to be
significantly higher. The following table compares the biodiesel produced in each
simulation to each other, as well as United States standards

Final Product Property

Alkyl-Ester %(mass)
Density (kg/m3) 15 C
Viscosity* (mm2/s) 40 C
Glycerol %
Methanol %
Total glyceride %
Water %
Acceptable Fuel

Fuel
Fuel Produced
Produced
With RD
Without RD
98.93%
98.99%
881.0
881.1
7.0*
7.0*
0%
.03%
~0%
~0%
0.95%
0.85%
0.02%
0%
Yes
Yes
(Table 3)

Fuel Standards11
(USA and Global)
96.5% min
860 - 900
1.9 6.0
0.24% max
0.2% max
1.2% max
0.05% max
---

According to the table above, the fuels created by both models satisfy the
standards set by the United States and other nations. As previously mentioned, the high
viscosity arises from an error in the built-in HYSYS m-oleate viscosity. Because this
value is overestimated, so too is the estimation of product viscosity.
When comparing the products formed by the two models, not much difference is
apparent. The model that utilized reactive distillation was effective in creating a slightly
more pure product with less oil. The model without reactive distillation produced a
biofuel of comparable purity, slightly higher oil content, but no glycerol.

Comparison of Reaction/Separation Schemes

While both simulations seemed to produce biofuels of nearly equal quality, their
respective schemes were unmistakably different. As highlighted in the Methods section,
Simulation 1 (without RD) required 6 total unit operations for effective production.
Simulation 2 (with RD) required only 4 unit operations to achieve the comparable quality
of product. This contrast sheds light on a dramatic reduction in capital costs, as well as
operating costs, obtained by the implementation of reactive distillation.

Energy
Another essential aspect for comparison between the two simulations is the
energy requirements. Many strides were made to optimize the quality of product in both
schemes. However heat integration and optimization was not performed on either of the
simulations. There is undoubtedly room for energy optimization in both of the schemes,
as several heaters were used. However, for the purposes of this study, a more general
approach to evaluating the energy differences was sufficient.
Both schemes involved two pathways after the reactor/RD column: biodiesel
purification, methanol purification. As mentioned, Scheme 1 required a distillation
column to purify the methanol for recycle. This distillation column operates at a higher
temperature than the decanter used in Scheme 2. While this means that less cooling is
necessary in Scheme 1, the flow is twice as high thus increasing the total duty. The

energy difference in this portion is likely not as significant as in other parts of the
models.
For purification of the biodiesel, only two unit operations (decanters) were
needed after the RD column, as opposed to the four operations (including LLE) in
Scheme 1. In order to obtain optimal results from the liquid-liquid extraction, an L/V ratio
of almost 3 was needed, thus requiring more water. However the steepest energy costs
were incurred for the separation of oil from biodiesel (necessary to meet fuel standards).
In Scheme 1, a decanter feed stream would be heated from 30 to 385 C. The same
temperature (385 C) was obtained in Scheme 2 from a RD product at 290 C. Therefore,
while Scheme 1 saw significantly higher energy costs in downstream separation, while
Scheme 2 required less energy after reaction and distillation in the RD column.

Materials
In addition to a lessened load on capital and energy, Simulation 2 also
demonstrates savings on material costs. From the start, the scheme without reactive
distillation requires more methanol, as determined by experimental data. While this
initial investment in more raw materials adds more cost to the conventional scheme,
effective recycle would minimize the losses. However, as table 4 shows, this opportunity
is not fully seized. While Scheme 2 uses 33% less methanol, the amount recovered and
available for recycle is nearly the same as in Scheme 1. Given prices found on the ICIS
webpage, this amounts to a multi-million dollar difference in raw material cost (Table 4).
In addition to this annual difference is the separation costs associated with the methanol
recycle. In scheme 1, obtaining high purity methanol at a considerable flow rate requires
a distillation column, as opposed to the decanter used in scheme 2.

Methanol needed for

desired production (kg/hr.)
Methanol available for
recycle after reaction
(kg/hr.)
Methanol annual cost
At $0.96/lb. (ICIS)

Scheme 1 (No RD)

1229

Scheme 2 (RD)
817.9

184.3

177.7

~$19,000,000+

~$11,700,000+

(Table 4)
Similarly, a difference in material costs was also observed by analyzing the
amount of unrecoverable biodiesel that is lost in separation. While great efforts were
employed to keep these values at a minimum, binary interactions rendered certain
separations unfavorable, resulting in product loss. Tables 5 and 6 detail the extent of
these losses in the respective schemes.

Scheme 1
(No RD)
Decanter 1
LLE
Decanter 2
Decanter 3
Total Loss
Total
Produced

Amount of
m-Oleate
(kg/hr.)
0.9232
0.0027
20.7759
0.1616
21.8634
5802

(Table 5: Product Losses without RD)

Scheme 2 (RD)

Decanter 1
Decanter 2
Total Loss
Total Produced

Amount of
m-Oleate
(kg/hr.)
16.111
0.0131
16.1241
5826

(Table 6: Product Losses with RD)

Conclusion
Much data could be analyzed from the simulations created. Both models, with
and without reactive distillation, effectively showed that quality fuel can be produced
with just a few unit operations. The product of both simulations was consistent with both
experimental data, and federal standards on fuel quality. When the models were
compared to each other, many differences stood out. To achieve nearly identical
products, the number and type of unit operations was dramatically reduced by
implementing reactive distillation. High-level capital cost analysis implies that a biodiesel
production facility that uses RD would be cheaper to build. A broad-scope energy
analysis shows many differences. While the downstream separation operations require
more energy when reactive distillation is not implemented, the RD column requires
significant energy input to the reboiler and condenser. This implies that more research
can be done to accurately assess the impact of RD on overall duty. Differences in
material costs are much more conclusive. Requiring less methanol from the start, the
RD set-up allowed for more efficient methanol recycle. This led to a dramatic reduction
in material losses. As expected, the reactive distillation column allowed for the difficult
separations to be overcome upstream. This not only lowered downstream separation
costs, but also resulted in less product losses.
Taking into consideration the effect of implementing a reactive distillation column
in the design of a biodiesel production facility, a positive conclusion can be drawn.
Significant reductions in capital and material costs with RD result in an expected
reduction in total plant costs. These savings are crucial for biodiesel production, as the
innate profit margin is not yet high enough for widespread appeal. Implementation is
often an obstacle, as the technology is more complex to design and operate. Also, more
work can be done to quantify the energy impact. But the material and capital savings go
a long way. In conclusion, this study has shown that utilizing reactive distillation
technology in biodiesel production will likely lead to increased overall efficiency, as well
as higher profit margins that are so vital in that industry.

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