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PROCESS MODELLING
Process modeling is done using process simulators. Although far from reality,
process simulators are used to mimic real processes. Equipped with advanced com-
putation techniques, comprehensive thermodynamic packages and large component
libraries, process simulators today provide reliable information of process design and
operations. In this work, both cases are modeled using Aspen Plus. Basic steps to
process modeling and simulation using process simulators include defining chemical
components, selecting thermodynamic model and method, designing process flow-
sheet by choosing proper operating units, determining plant capacity and setting
up input parameters. Detailed descriptions of each step will be discussed in the
preceding chapter.
Table 1.1 below shows the chemical compounds used in the simulation work.
Simulating an actual content of vegetable oil is complex because of its mixture of
oils with fat content. In this work, rapeseed oil is used as the feedstock. Since oleic
acid is a major fatty acid in rapeseed oil with a composition of 64,4% Ma and Hanna
(1999), triolein is chosen to represent rapeseed oil. Methyl oleate is taken as the
resulting biodiesel product. In real application, however, new vegetable oil actually
contains 0,05 wt% FFA Myint and El-Halwagi (2009), but this is not considered in
this work. Catalysts in biodiesel production that can be used are various as discussed
before. Today most large scale plants prefers base-catalyst. For that reason, sodium
hydroxide is chosen as the catalyst and softwater (contain 37% hydrochloric acid) is
used to neutralize any remaining catalyst.
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2
In biodiesel production, both methanol and glycerol are highly polar compo-
nents. Therefore, both NRTL and UNIQUAC models are recommended for predict-
ing the activity coefficients of the components in a liquid phase Zhang et al. (2003).
In this simulation, NRTL is used as the main thermodynamic method. For the
modeling of decanter and mixer, the Redlich-Kwong-Soave (RKS) thermodynamic
properties are used following the approach by Myint and El-Halwagi Myint and
El-Halwagi (2009). Electrolyte chemistry is not modeled in detail here and because
sodium hydroxide and softwater are both electrolyte chemistry they are modeled
using physical property data for water, but with their correct molecular weight.
Most of the compounds properties are available in the Aspen Plus component li-
brary. Nevertheless, some of them have to be estimated. For example, coefficients
for the extended antoine vapor pressure equation for the adjusted sodium hydroxide
and softwater are estimated using Aspen Properties and their results are inserted
into the flowsheet. In another example, although triolein is in the Aspen chemical
database, some of the properties such as coefficients for ideal gas heat capacity equa-
tion, Watson heat of vaporization equation coefficients and OMEGA value have to
be estimated using Aspen Properties for the model to converge properly.
The simulated capacity of both cases is 8000 ton/yr with oil feed input of
1050 kg/hr. The biodiesel purity of more than 99.6 wt% is assumed according to
the ASTM specification. Additionally, to optimize the plant profitability, glycerol
is further refined to meet the pharmaceutical standard of more than 92 wt%. Since
the economic feasibility of the biodiesel industry is much more affected by plant
capacity, vegetable oil price, and price of biodiesel, it requires government subsidy
for positive net profit Zhang et al. (2007). In this work, the total biodiesel selling
3
The modelling for Case 1 is based on the work of several researchers West
et al. (2008); Myint and El-Halwagi (2009); Zhang et al. (2003). The flowsheet con-
figuration is shown in Figure 1.1a. The reaction is carried out with a 100% excess of
methanol to oil or 6:1 molar ratio with 1 wt% sodium hydroxide based on oil. The
catalyst and methanol feed flowrates are 10 kg/hr and 110 kg/hr, respectively. The
reaction yield is assumed 95%, the temperature is set at 60o C, and the pressure is
at 1 bar. The reaction product then enters a methanol recovery unit with 6 theo-
retical stages and the reflux ratio of 0,05. The distillation column is kept below the
atmospheric pressure in order to maintain the bottom product temperature under
250o C, which will prevent a decomposition of biodiesel and glycerol. The bottom
product is then sent to a water washing column. It is mixed with 10 kg/hr water
before being settled down in a decanter to separate the main products, i.e., biodiesel
and glycerol. Based on the component density, the upper part which contains 97%
biodiesel is sent to a biodiesel purification column. Using six theoretical stages with
a reflux ratio of 2 and being operated under vacuum to maintain product temper-
ature below 250o C, biodiesel is further purified to meet the product specifications
of 99,6wt%. The bottom stream of the decanter contains 82% glycerol and the rest
is a mixture of methanol, water and sodium hydroxide. To further purify glycerol,
the stream is first passed to a catalyst neutralization reactor. Phosphoric acid at
8,33 kg/hr is added to neutralize the sodium hydroxide. The output stream is then
sent to a filter to separate the solid sodium phosphate salt. The liquid stream is
then sent to a glycerol purification column. Using four theoretical stages, at the
reflux ratio of 1 and being operated under vacuum, the bottom product stream is
able to achieve glycerol purification of above 92wt%. The summary of the main
unit operation specifications for Case 1 is listed in Table 1.2 and Table 1.3 gives the
simulation results of the input and output streams. Full results of each stream can
be viewed in Appendix B.
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(a)
(b)
Figure 1.1: Biodiesel process flowsheet (a) alkali-based (b) supercritical methanol
5
Neutralization reactor
Reactor type CSTR (Stoichiometric) N/A
Temperature, o C 30
Pressure, bar 1
H3 PO4 flowrate, kg/hr 8,33
Conversion, % 100
Volume, m3 0.40
8
9
Figure A.1: Case 1: Process flowsheet for the alkali-catalyzed process (Case 1).
Figure A.2: Case 1: Process flowsheet for the supercritical methanol process (Case
2).
Table A.1: Simulation results: Case 1.
Stream 1 2 3 5 6 7 8 9 10 11 12 13
Temperature C 31,7 60 60 176 32,8 32,9 176,1 30 29,8 30 30 30
Pressure bar 1 1 1 0,3 0,25 1 1 1 1 1 1 1
Vapor Frac 0 0 0 0 0 0 0 0 0 0 0 0
Mole Flow kmol/hr 8,329 1,186 9,515 4,869 4,646 4,646 4,869 4,869 5,424 1,918 3,506 2,003
Mass Flow kg/hr 268,863 1050 1318,863 1170 148,863 148,863 1170 1170 1180 122,883 1057,117 131,213
Volume Flow cum/hr 0,323 1,171 1,561 1,504 0,19 0,19 1,504 1,336 1,353 0,097 1,239 0,097
Enthalpy MMkcal/hr -0,476 -0,516 -1,055 -0,724 -0,264 -0,264 -0,724 -0,81 -0,848 -0,233 -0,618 -0,258
Mass Flow kg/hr
TG 0,005 1050 52,5 52,496 0,005 0,005 52,496 52,496 52,496 0,004 52,492 0,004
MEOH 258,858 0 150,567 1,709 148,858 148,858 1,709 1,709 1,709 0,778 0,93 0,778
NAOH 10 0 10 10 0 0 10 10 10 10 0 0
GLY 0 0 103,749 103,749 0 0 103,749 103,749 103,749 102,546 1,203 102,546
FAME 0 0 1002,046 1002,046 0 0 1002,046 1002,046 1002,046 0 1002,047 0
H2O 0 0 0 0 0 0 0 0 10 9,555 0,445 14,059
H3PO4 0 0 0 0 0 0 0 0 0 0 0 0,163
NA3PO4 0 0 0 0 0 0 0 0 0 0 0 13,662
Mass Frac
TG 0 1 0,04 0,045 0 0 0,045 0,045 0,044 0 0,05 0
MEOH 0,963 0 0,114 0,001 1 1 0,001 0,001 0,001 0,006 0,001 0,006
NAOH 0,037 0 0,008 0,009 0 0 0,009 0,009 0,008 0,081 0 0
GLY 0 0 0,079 0,089 0 0 0,089 0,089 0,088 0,835 0,001 0,782
FAME 0 0 0,76 0,856 0 0 0,856 0,856 0,849 0 0,948 0
H2O 0 0 0 0 0 0 0 0 0,008 0,078 0 0,107
H3PO4 0 0 0 0 0 0 0 0 0 0 0 0,001
NA3PO4 0 0 0 0 0 0 0 0 0 0 0 0,104
Mole Flow kmol/hr
TG 0 1,186 0,059 0,059 0 0 0,059 0,059 0,059 0 0,059 0
MEOH 8,079 0 4,699 0,053 4,646 4,646 0,053 0,053 0,053 0,024 0,029 0,024
NAOH 0,25 0 0,25 0,25 0 0 0,25 0,25 0,25 0,25 0 0
GLY 0 0 1,127 1,127 0 0 1,127 1,127 1,127 1,113 0,013 1,113
FAME 0 0 3,38 3,38 0 0 3,38 3,38 3,38 0 3,38 0
H2O 0 0 0 0 0 0 0 0 0,555 0,53 0,025 0,78
H3PO4 0 0 0 0 0 0 0 0 0 0 0 0,002
NA3PO4 0 0 0 0 0 0 0 0 0 0 0 0,083
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Table A.2: Simulation results: Case 1 (cont.).
Stream 14 INPUT1 INPUT2 INPUT3 INPUT4 INPUT5 OUTPUT1 OUTPUT2 OUTPUT3 OUTPUT4 PROD1 PROD2
Temperature C 60,5 30 30 30 30 30 194 329,7 60,5 71,1 194 221,9
Pressure bar 1 1 1 1 1 1 0,15 0,2 1 0,4 0,15 0,5
Vapor Frac 0 0 0 0 0 0 1 0 0 0 0 0
Mole Flow kmol/hr 1,92 1,186 0,25 3,433 0,555 0,085 0,034 0,072 0,083 0,751 3,399 1,169
Mass Flow kg/hr 117,55 1050 10 110 10 8,33 1,467 55,07 13,662 13,995 1000,58 103,556
Volume Flow cum/hr 0,096 1,159 0,005 0,14 0,01 0,002 8,92 0,076 0 0,015 1,339 0,094
Enthalpy MMkcal/hr -0,23 -0,528 -0,017 -0,195 -0,038 -0,006 -0,002 -0,02 -0,028 -0,05 -0,501 -0,169
Mass Flow kg/hr
TG 0,004 1050 0 0 0 0 0,002 50,501 0 0 1,989 0,004
MEOH 0,778 0 0 110 0 0 0,66 0 0 0,778 0,271 0
NAOH 0 0 10 0 0 0 0 0 0 0 0 0
GLY 102,546 0 0 0 0 0 0,004 0 0 0,006 1,2 102,54
FAME 0 0 0 0 0 0 0,589 4,569 0 0 996,889 0
H2O 14,059 0 0 0 10 0 0,213 0 0 13,059 0,232 1
H3PO4 0,163 0 0 0 0 8,33 0 0 0 0,151 0 0,012
NA3PO4 0 0 0 0 0 0 0 0 13,662 0 0 0
Mass Frac
TG 0 1 0 0 0 0 0,001 0,917 0 0 0,002 0
MEOH 0,007 0 0 1 0 0 0,45 0 0 0,056 0 0
NAOH 0 0 1 0 0 0 0 0 0 0 0 0
GLY 0,872 0 0 0 0 0 0,003 0 0 0 0,001 0,99
FAME 0 0 0 0 0 0 0,401 0,083 0 0 0,996 0
H2O 0,12 0 0 0 1 0 0,145 0 0 0,933 0 0,01
H3PO4 0,001 0 0 0 0 1 0 0 0 0,011 0 0
NA3PO4 0 0 0 0 0 0 0 0 1 0 0 0
Mole Flow kmol/hr
TG 0 1,186 0 0 0 0 0 0,057 0 0 0,002 0
MEOH 0,024 0 0 3,433 0 0 0,021 0 0 0,024 0,008 0
NAOH 0 0 0,25 0 0 0 0 0 0 0 0 0
GLY 1,113 0 0 0 0 0 0 0 0 0 0,013 1,113
FAME 0 0 0 0 0 0 0,002 0,015 0 0 3,362 0
H2O 0,78 0 0 0 0,555 0 0,012 0 0 0,725 0,013 0,056
H3PO4 0,002 0 0 0 0 0,085 0 0 0 0,002 0 0
NA3PO4 0 0 0 0 0 0 0 0 0,083 0 0 0
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Table A.3: Simulation results: Case 1 (cont.).
Utility ID: COL1-EC COL1-ER COL2-EC COL2-ER COL3-EC COL3-ER HEX1-E HEX2-E P1-E P2-E
Utility type: WATER STEAM WATER STEAM WATER STEAM STEAM WATER ELECTRICITY ELECTRICITY
$/hr 0,971564 1,459847 1,233631 116,0738 0,057165 6,883366 0,136188 0,320941 0,00083 0,006132
kg/hr 14500,95 214,6834 18412,4 6975,587 853,2066 413,6638 22,39927 4790,164
Gcal/hr 0,043359 0,110439 0,330291 0,42548 0,015305 0,025232 0,011987 0,085928 1,15E-05 8,50E-05
kcal/kg -2,99005 514,425 -17,9385 60,99552 -17,9385 60,99552 535,1658 -17,9385
$/kg 6,70E-05 0,0068 6,70E-05 0,01664 6,70E-05 0,01664 0,00608 6,70E-05
$/kWhr 0,062 0,062
C 27 160 27 400 27
C 47 125 47 300 47
bar 1 5 1 41 1
bar 0,9 4,9 0,9 40,9 0,9
Inlet vapor fraction: 0 1 0 1 0
Outlet vapor fraction: 0 0 0 1 0
kcal/kg -3789,79 -3155,89 -3789,79 -3049,75 -3789,79
kcal/kg -3769,81 -3691,38 -3769,81 -3110,67 -3769,81
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Bibliography
Lim, Y., Lee, H., Lee, Y., Han, C., 2009. Design and economic analysis of the process
for biodiesel fuel production from transesterificated rapeseed oil using supercritical
methanol. Ind. Eng. Chem. Res. 48, 53705378.
Ma, F., Hanna, M. A., 1999. Biodiesel production: A review. Bioresource Technology
70, 115.
Myint, L., El-Halwagi, M., 2009. Process analysis and optimization of biodiesel
production from soybean oil. Clean Tech. Environ Policy (doi:10.1007/s10098-
008-0156-5).
van Kasteren, J., Nisworo, A., 2007. A process model to estimate the cost of indus-
trial scale biodiesel production from waste cooking oil by supercritical transester-
ification. Resources Conservation and Recycling 50, 442458.
West, A., Posarac, D., Ellis, N., 2008. Assessment of four biodiesel production pro-
cesses using hysys.plant. Bioresource Technology 9 (99), 65876601.
Zhang, Y., Dub, M. A., McLean, D. D., Kates, M., 2003. Biodiesel production from
waste cooking oil: 1. process design and technological assessment. Bioresource
Technology 89, 116.
Zhang, Y., Dub, M. A., McLean, D. D., Kates, M., 2007. Biodiesel production from
waste cooking oil: 2. economic assessment and sensitivity analysis. Bioresource
Technology 90, 229240.
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