Paper Number:

MB04-304

Process Modeling Approach for Evaluating the Economic

Feasibility of Biodiesel Production

1,2
Dhruv Tapasvi, 1Dennis Wiesenborn and 2Cole Gustafson
1
Department of Agricultural and Biosystems Engineering
2
Department of Agribusiness and Applied Economics
North Dakota State University
Fargo, ND 58105

Written for presentation at the

2004 North Central ASAE/CSAE Conference
Sponsored by the Manitoba Section of CSAE
Winnipeg, Manitoba, Canada
September 24-25, 2004

Abstract.
A biodiesel process model was developed by incorporating the process-engineering
principles of mass and energy balances and with the help of spreadsheets and other software
tools. The basis of the model is a production facility that uses a continuous
transesterification process with two stirred tank reactors, methanol as alcohol and sodium
methoxide as catalyst. The model quantifies all the inputs and outputs in the biodiesel
production process. It can be used to compare various vegetable oils used for biodiesel
production in terms of process inputs and outputs and it can be correlated to the economic
cost data for performing various biodiesel economic feasibility studies.

Keywords.

Biodiesel, process model, spreadsheet, glycerol refining, methanol recovery, ester washing

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Introduction
Numerous factors have pushed energy from biomass into the forefront of policy

and industry discussions. Large harvests of traditional crops, low farm prices,

dependence on foreign energy sources and environmental problems due to

combustion of fossil fuels have increased interest in renewable energy sources such

as biodiesel.

Biodiesel is a diesel-fuel replacement produced from domestic renewable

resources such as vegetable oils, animal fats and recyclable cooking oils. Chemically,

biodiesel is defined as the mono-alkyl esters of long-chain fatty acids derived from

lipid sources. The demand for biodiesel is constantly on the increase as more persons

are becoming aware of its potential to address the above issues. In order to meet the

anticipated demand, more biodiesel production plants have to be set-up in the near

future. The foremost step for setting-up a biodiesel production plant in a particular

region is the evaluation of economic feasibility of biodiesel production. The economic

feasibility study must be based on authentic and reliable production data.

Various process engineering principles, such as mass and energy balances,

can be utilized to collect the production data by analyzing the biodiesel production

process in terms of the various inputs, outputs and their compositions. Such

information is, in turn, needed for quantifying utility requirements and sizing

equipment. Thus, performing the mass and energy balance analysis of the full process

is a key step towards obtaining economic cost data for performing the economic

feasibility studies.

Efforts have been reported to quantify the biodiesel production process

(Sheehan et al., 1998; Kleber, M. 2004), but no clear and transparent approach has
1
been utilized to illustrate the detailed inputs and outputs involved in the process. Many

economic feasibility study groups have applied the so-called “black box” approach by

listing the data for various inputs and outputs of biodiesel production collected from

private consultancy firms. Such approaches leave the readers with little understanding

of the underlying calculations, and no basis for determining whether advances in

process technology were taken into consideration. In order to resolve the above

issues and in effort to provide a complete understanding of the biodiesel production, a

detailed biodiesel process model is needed.

Such a process-modeling approach has been utilized extensively by chemical

and food process industries for detailed design and feasibility evaluation of a

production plant. One excellent example of a process model was shown by Fryer et

al., 1997 by modeling a cheese manufacturing plant using spreadsheets. The basic

idea of development of a biodiesel process model on spreadsheets came heavily from

the idea behind this cheese model.

The objectives of this present study include:

Objective 1: Selection of the biodiesel production process based on comprehensive

literature survey and by visiting current biodiesel production plants.

Objective 2: Developing a biodiesel process model based on the selected process by

incorporating the process-engineering principles of mass and energy balances and

with the help of computer spreadsheets and other software tools. This includes

specifying user-inputs in the model, referenced assumptions made for mass and

energy balance equations and the detailed calculations performed for quantifying

various biodiesel process inputs and outputs.

2
Biodiesel production process description

The continuous base-catalyzed process was selected for the process model

development (Figure 1), based on a detailed literature review for biodiesel production

(Freedman et al., 1984; Freedman et al., 1996; Noureddini et al., 1997; Darnoko et al.,

2000; Van Gerpen et al., 2003; Sheehan et al., 1998) and by visiting current biodiesel

production plants. This is the most widely used biodiesel process in the European

Union and US. The biodiesel production process was divided into four main sections:

(a) Crude oil degumming, refining and drying: The crude oil is subjected to acid

degumming for removing hydratable and non-hydratable phosphatides followed by

alkali refining for removing the free fatty acids. Crude oil (1) is heated to 70oC in the

heater (A). Phosphoric acid (2) is added to the heated crude oil in the mixing tank (B)

for converting the non-hydratable phosphatides to water-soluble phosphatidic acid.

Soft water (4) is added to the mixing tank for the formation of gums from the

hydratable phosphatides. The mixing tank outstream (5) is centrifuged (C) to separate

the oil from the gums-water mix (6). Using a separator (D), the gums (7) are removed

from water (8). The degummed oil (9) is sent to a refining tank (E) for alkali refining.

Sodium hydroxide solution is added for converting the free fatty acids (FFA) present in

the degummed oil to oil-insoluble soaps. Proper mixing is ensured for the reaction.

This is followed by the addition of wash water for dissolving the soaps, which results in

the formation of soapstock that is removed from the oil using a centrifuge (F). The

resulting centrifuge outstream (14) goes to a vacuum oil dryer (G) to remove the

3
 CRUDE OIL DEGUMMING REFINING
10 11 15
3 4
Crude oil
G
B E
1 2 5 9 12 14 16 H 17 Refined oil
A C F
6
7 D 13

8
28
TRANSESTERIFICATION ESTER WASHING
18 19 23 24 M 34
29
N P
17 I 20 22 K 25 27 31 O 33 35 Biodiesel
J L

21 26 30 32

METHANOL RECOVERY

36 37 T 40 U 42 Recycled Methanol
R S
Q 38 39

41
43 47
45
GLYCEROL REFINING
V 44 W 46 48
X Glycerol

Figure 1. Continuous base-catalyzed biodiesel production process

A, heater; B, mixing tank; C, centrifuge; D, gums/water separator; E, refining tank; F,

centrifuge; G, vacuum oil dryer; H, surge tank; I, continuous stirred tank reactor (CSTR)
1; J, decanter 1; K, CSTR 2; L, decanter 2; M, heater; N, wash columns; O, settler tank;
P, vacuum ester dryer; Q, collecting tank; R, heater; S, glycerol-alcohol stripper; T,
distillation column; U, condenser; V, glycerol hold tank; W, acidulation reactor; X,
decanter. (Continued next page)

4
(Continued Figure 1).
1, crude oil; 2, heated crude oil; 3, phosphoric acid; 4, soft water; 5, mixing tank outstream; 6,
gums-water mix; 7, gums; 8, water; 9, degummed oil; 10, NaOH solution; 11, wash water; 12,
refining tank outstream; 13, soapstock; 14, refined oil; 15, water vapor; 16, hot oil; 17, dried
refined oil; 18, sodium methoxide; 19, methanol; 20, CSTR 1 outstream; 21, glycerol phase;
22, ester phase; 23, sodium methoxide; 24, methanol; 25, CSTR 2 outstream; 26, glycerol
phase; 27, ester phase; 28, wash water; 29, heated wash water; 30, waste stream; 31, washed
esters; 32, aqueous phase; 33, esters; 34, water vapor; 35, biodiesel; 36, glycerol/aqueous
phase; 37, heater outstream; 38, super heated steam; 39, saturated methanol vapors and
saturated steam; 40, methanol vapor; 41, distillation column bottoms; 42, recycled methanol;
43, hot glycerol solution; 44, glycerine; 45, HCl solution; 46, acidulation reactor outstream;
47, waste; 48, product glycerol.

remaining water in the oil. The dried degummed and refined oil is sent to a surge tank

for cooling.

(b) Transesterification reaction: The refined oil stream (17) enters the CSTR 1 (I)

maintained at 65oC. Typically 100% excess methanol is added to the reactor along

with the suitable amounts of the catalyst sodium methoxide. Transesterification

reaction between triglycerides and methanol takes place in the presence of catalyst

sodium methoxide to form methyl esters i.e. biodiesel and glycerol, a co-product. Also,

the remaining trace amount of free fatty acids in the refined oil reacts with sodium

methoxide to form soaps and methanol. The reaction products (20) are separated

using decanter 1 (J) into a glycerol phase (glycerol, methanol, sodium methoxide,

soaps) and ester phase (methyl esters, unreacted oil, methanol, soaps). Further, the

ester phase (22) enters the CSTR 2 (K) and the glycerol phase goes to a collecting

tank (Q). A similar process occurs in CSTR 2 (K) and decanter 2 (L), typically using

100% excess methanol, based upon the unreacted triglyceride present. The ester

phase from decanter 2 (L) goes to the ester-washing section and the glycerol phase

enters the collecting tank (Q).

5
(c) Ester washing: Impurities in the ester phase (27), such as methanol, soaps and

free glycerol have to be separated from the methyl esters. This is done by washing the

ester phase (27) by warm water (29) in wash columns. The resultant waste stream

(30) is sent to the collecting tank (Q) and the washed ester stream (31) to a settler

tank (O). The remaining aqueous phase is separated from the methyl esters in the

settler tank (O). Finally, the ester stream (33) is vacuum dried to remove any trace

amounts of moisture in the vacuum ester dryer (P).

(d) Methanol recovery and glycerol refining: Streams 21, 26, 30 and 32 are

combined in the collecting tank (Q). The resulting stream (36) is heated to the normal

boiling point of methanol (65oC) in the heater (R). The methanol is stripped from the

heated stream (37) using super heated steam (38) in the glycerol-alcohol stripper (S).

The saturated methanol vapors and the steam are fed into a distillation column to

recover pure methanol vapors as distillate (40). The methanol vapors (40) are

condensed in a condenser (U) and are recycled back (42) to the CSTRs. Bottoms (41)

of the distillation column contain the glycerol, condensed steam and other impurities.

The hot glycerol solution (44) from the bottom of the stripper (S) is sent to a glycerol

hold tank (V). The crude glycerol (44) from this hold tank is mixed with proper amounts

of HCl solution in the acidulation reactor (W). Catalyst sodium methoxide in the stream

(44) reacts with HCl to form methanol and NaCl and the soaps present in this stream

react with HCl to form free fatty acids and NaCl in the acidulation reactor (W). Using a

decanter (X), product glycerol (48) is separated from the free fatty acids and other

impurities such as unreacted oil (47).

6
Biodiesel process model development

User-specified inputs

Following are the user-specified input parameters required by the spreadsheet model:

(a) Desired transesterification reaction efficiency. Default value is 98%.

(b) Amount of crude oil to be processed per day (kg/s).

(c) Methanol/triglyceride mole ratio. Default value is 6 (100% excess methanol of

that required by the reaction stoichiometry).

Mass balance assumptions

(a) Degumming/refining section

i. Mixing tank (B): Heated crude oil (2) is mixed with 0.1% percent of 0.85wt%

phosphoric acid aqueous solution (3) (Hernandez et al., 1996) followed by the

addition of soft wash water (4) equal to 75% of the phosphatide content in the

crude oil (1) (Erickson., 1995).

ii. Centrifuge (C): All phosphatide in the form of gums, all unreacted phosphoric

acid and 99.5% of the stream 4 is recovered in stream 6 (Sheehan et al., 1998).

iii. Refining tank (E): 9.5 wt% NaOH aqueous solution equal to 113% excess of that

required for stoichiometric conversion of free fatty acids present in stream 9 is

added. Wash water in the form of soft water equal to 15% of the mass flow rate

of stream 9 is added (Sheehan et al., 1998). 99% of the free fatty acids are

converted to soaps by reaction with NaOH.

iv. Stream 13: contains soaps formed from the reaction of free fatty acids and NaOH

in the form of soapstock, triglycerides equal to 2.5 times the amount of free fatty

acid loss, unsaponifiable matter attached to triglycerides, in the same proportion

7
 as present in the original oil (0.015:1), and 99.5% of the stream 11 (Sheehan et

al., 1998).

v. Vacuum oil dryer (G): 100% of the water removal from stream 14 is achieved.

(b) Transesterification section

i. CSTR 1 (I): sodium methoxide catalyst (18) equal to 1% of the stream 17 (Myron

Danzer, personal communication. 2004.) is added in the form of a 10% solution

in methanol. Methanol is added based upon the methanol: TG ratio being input.

85% transesterification reaction efficiency is assumed (Van Gerpen et al., 2003).

Also, all the free fatty acids in the oil react with the catalyst to form soap and

methanol.

ii. Stream 21: contains 60% of the total methanol in stream 20, all glycerol and

sodium methoxide in stream 20, and 10% of the total amount of soaps present in

stream 20 formed from the reaction between free fatty acids and sodium

methoxide in the CSTR 1 (I) (Van Gerpen et al., 2003).

iii. CSTR 2 (K): sodium methoxide catalyst equal to 1% of the triglyceride left

unreacted in the stream 22 is added in the form of a 10% solution in methanol

(Myron Danzer. personal communication. 2004). Methanol is added based upon

the methanol: TG ratio being input. Calculations are based upon the total

transesterification reaction efficiency being input by the user.

iv. Stream 26: contains 60% of the total methanol in stream 20, 10% of the total

amount of soaps in stream 25, and all the glycerol and sodium methoxide in

stream 25 (Van Gerpen et al., 2003).

8
(c) Ester washing section

i. Stream 28: It is equal to the 20% of the methyl esters amount in stream 27

(Sheehan et al., 1998).

ii. Stream 30: Contains 90% of the stream 28 and 100% of the methanol and soaps

contained in stream 27. No ester is lost (Sheehan et al., 1998).

iii. Stream 33: Only 0.5% of the stream 28 is remaining (Sheehan et al., 1998).

iv. Vacuum ester dryer (P): 100% moisture removal.

(d) Methanol recovery and glycerol refining section

i. Glycerol-alcohol stripper (S): Super-heated steam is at 1 bar pressure and 180oC

(Myron Danzer. personal communication. 2004).

ii. Stream 39: 100% recovery of the saturated methanol vapors and saturated

steam.

iii. Methanol recovery distillation column (T): Stream 40 contains methanol vapors

with 0.05% moisture level and stream 41 contains less than 0.5% methanol

(Sheehan et al., 1998).

iv. Stream 45: 10% aqueous HCl solution equal to 50% mass flow rate of the

glycerine stream 44 (Sheehan et al., 1998).

v. Acidulation reactor (X): Sodium methoxide reacts with HCl to form methanol and

NaCl. Soaps react with HCl to form free fatty acids and NaCl.

vi. Stream 48: Product glycerol solution is obtained from the acidulation decanter.

9
Sample mass balance calculations

Mass balance calculations involve the use of the basic conservation of mass equation,

which states that the total mass of the components in a process has to be conserved.

Mass balance equations were applied to each individual unit for identifying the

components in each stream in the whole production process with the assumption that

no net depletion or accumulation occurred and all mass was accounted for in Fig. 1

flows.

Centrifuge: Refer to Unit C in Fig. 1. Stream 5 (mixing tank outstream) is separated

into stream 6 (gums-water mix) and stream 9 (degummed oil).

Overall mass balance equation is represented by M5 = M6 + M9. Component balances

include

(a) Water (w) balance: M5w = M6w + M9w,

(b) Triglyceride (t) balance: M5t = M6t + M9t, and

(c) Gums (gu) balance: M5gu = M6gu + M9gu.

where

Mi is the mass flow rate (Kg/s) of any stream i and Mij is the mass flow rate of any

component j in stream i (Kg/s).

Continuous stirred tank reactor (CSTR) 1: Refer to Unit I in Fig. 1. Stream 17

(refined oil) is mixed with stream 18 (catalyst sodium methoxide) and stream 19

(methanol). Following two reactions take place to yield the stream 20 (CSTR 1

outstream).

10
 1. Reaction a: Transesterification reaction between triglyceride and methanol

to produce methyl esters known as biodiesel and glycerol in the presence of

catalyst sodium methoxide. Reaction efficiency is user-defined.

CH2COOR1 CH2OH

CHCOOR2 + 3 CH3OH 3 RCOOCH3 + CHOH

CH2COOR3 CH2OH

(Triglyceride) (Methanol) (Methyl esters) (Glycerol)

2. Reaction b: Reaction between free fatty acids (FFA) in the refined oil with

sodium methoxide to produce soaps and methanol. Reaction efficiency is

assumed to be 100% (transesterification section assumption i).

RCOOH + NaOCH3 RCOONa + CH30H

(FFA) (Sodium methoxide) (Soaps) (Methanol)

Overall mass balance equation:

M17 + M18 + M19 = M20 (1)

Components balances:

Triglyceride (t):

M20t = M17t - [(Reaction a efficiency/100)*(M17t)] (2)

Methyl esters (me):

M20me = {[(M.Wme*3)/(M.Wt)]*[(Reaction a efficiency/100)*(M17t)]} (3)

Glycerol (g):

M20g = {[(M.Wg)/(M.Wt)]*[(Reaction a efficiency/100)*(M17t)]} (4)

Free fatty acids (f):

M20f = M17f - [(Reaction b efficiency/100)*(M17f)] (5)

11
Methanol (m):

M20m = [M18m + M19m]

- [(M.Wm*3)/(M.Wt)]*[(Reaction a efficiency/100)*(M17t)]

- {[(M.Wm)/(M.Wf)]*[(Reaction b efficiency/100)*(M17f)]}

(6)

Sodium methoxide (sm):

M20sm = M18sm - {[(M.Wsm)/(M.Wf)]*[(Reaction b efficiency/100)*(M17f)]} (7)

Soaps (s):

M20s = {[(M.Ws)/(M.Wf)]*[(Reaction b efficiency/100)*(M17f)]} (7)

where

Mi is the mass flow rate (Kg/s) of any stream i, Mij is the mass flow rate of any

component j in stream I (Kg/s) and M.Wj be the molecular weight of component i.

Mass flow rates of all other components remain the same.

Super-heated steam (su) calculations in glycerol-alcohol stripper: Refer to Unit S

in Fig. 1. Stream 38 (Super-heated steam) is required to vaporize all the water and

methanol from glycerol present in stream 37. Stream 39 contains the saturated

methanol vapors, water vapor and saturated steam vapors. Stream 44 is crude

glycerol solution with some impurities (sodium methoxide and soaps).

M38su = {[(M37w)*(Cpw)*( tw)] + [(M37w)*(Lw)] +[(M37m)*(Cpm)*( tm)] +

[(M37m)*( Lw)]}/(Hsu - Hsa) (8)

where

Cpw, Cpm are the specific heats of water and methanol respectively,

12
 tw, tm are the temperature differences required for water and methanol to reach

their respective normal boiling points,

Lw, Lw are the latent heats of vaporization of water and methanol respectively and,

Hsu and Hsa are the enthalpies of super-heated steam and saturated steam

respectively.

Discussion

Figure 2 shows the basic structure of the model as seen from a portion of the

spreadsheet screen. The specified user inputs of the desired transesterification

efficiency, crude oil to be processed and methanol: triglyceride ratio is given at the top

left hand side of the screen. This portion of the spreadsheet lists only 10 from a total of

48 streams identified in the actual model whereas all the components in the various

streams have been shown.

An example of the various process inputs and outputs identified by this model

have been illustrated in Table 1 by choosing an arbitrary basis of 100 kg/hr crude oil

entering the production plant. All the calculations change according to the specified

inputs. It provides the reader with a clear understanding of how the amounts of various

process inputs and outputs are inter-related. As the model has been based upon the

compositional data of vegetable oils, it can be used for comparisons between different

vegetable oils used for biodiesel production in terms of various process inputs and

outputs. Table 1 also shows an example of this type of comparison between soybean

oil and canola oil.

13
Figure 2: Screen view of the first 10 screens in the biodiesel process model
spreadsheet

14
Table 1: Biodiesel process inputs and outputs provided by the model with
basis of 100 Kg/hr crude oil processed

Soybean oil (Kg/hr)1 Canola oil

(Kg/hr)2

Process Inputs
Crude oil (1) 100.00 100.00
Methanol (19 + 24) 13.84 14.31
Sodium methoxide (18 + 23) 10.84 10.98
NaOH (9.5 wt% aqueous 14.93 14.86
soln.)(10)
HCl (10% aqueous soln.) (45) 6.24 6.12
Process water (4 + 11 + 28) 34.69 34.49

Process Outputs
Biodiesel (35) 92.81 94.04
Methanol recycled (42) 13.36 13.70
Glycerol (48) 10.28 10.53
Waste (6 + 13 + 41 + 47) 55.57 54.05
1
Composition: 96.0% triglycerides, 0.5% free fatty acids, 2.0% phosphatides, and
1.5% others (unsaponifiable matter) (Erickson.1995).
2
Composition: 97.25% triglycerides, 0.5% free fatty acids, 1.25% phosphatides, and
1.0% others (unsaponifiable matter) (Gunstone.2002).

Conclusion

The present biodiesel production model was developed for analyzing the

biodiesel production and ultimately designing its production unit. The model can be

utilized in performing economic feasibility studies of biodiesel production in different

regions simply by linking it to the economic cost data. This paper deals mainly with the

mass balances calculations including the super-heated steam calculations in the

15
glycerol-alcohol stripper (S) that were necessary for satisfying the conservation of

mass principle. A separate spreadsheet has been included in the model that deals

with the energy balance calculations based on the conservation of energy principle

(energy is conserved here similar to mass conservation principle) for calculating the

process steam requirements of the biodiesel production process but is out of the

scope for the present paper. Once a particular capacity of the biodiesel production

unit has been selected (say 15 million gallons per year), the model can also be utilized

in the process equipment design of the various equipments involved in the production

process based on the various stream mass flow rates and the desired process

conditions, ultimately leading to the detailed biodiesel process plant design.

References

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Cooperative.
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yields of fatty esters from transesterified vegetable oils. Journal of American Oil
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