Energy 118 (2017) 77e84

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Energy
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Exergy analysis: A CO2 removal plant using a-MDEA as the solvent

Vafa Feyzi a, Masoud Beheshti a, b, *, Abolfazl Gharibi Kharaji a
a
Department of Chemical Engineering, University of Isfahan, Isfahan, Iran
b
Process Engineering Institute, University of Isfahan, Isfahan, Iran

art i cle i nfo abstract

Article history: An exergy analysis was conducted for CO2 removal process from syngas using methyldiethanolamine activated
Received 3 January 2016
by piperazine (a-MDEA). The process was simulated with Aspen HYSYS and the validation of the results was
Received in revised form
performed using the field data of Fanavaran Petrochemical Company. The process was divided into five separate
16 November 2016
sections. In order to determine the exergy loss, exergy balance equation was established around each section. The results
Accepted 6 December 2016
showed that the highest exergy loss amongst five sections returns to the flasher (contributes 31.5% of total exergy loss);
followed by the absorber column, stripper column, heat recovery section and the pump. In order to decrease the
exergy loss in the process, piperazine concentration in a-MDEA solvent was increased which led to reduction in amine
Keywords:
solvent flow rate. According to the results, the total exergy loss is decreased from 3.25 MW to 2.63 MW. When the
Energy
amine flow rate decreased by 27%, the exergy loss, total energy consumption and the total utilities cost decreased by
Exergy
19%, 18% and 25%, respectively.
CO2 removal
© 2016 Published by Elsevier Ltd.
a-MDEA
Utilities cost

1. Introduction
The carbon monoxide is an important substance in the chemical industry
as secondary feedstock for acetic acid, methanol, phosgene and formic acid
production [1]. Its production process from natural gas is composed of four
steps [2]: the first step is the pre-treatment of raw materials to remove
impurities, such as Sulphur compounds contained in the feedstock; the
second step is the production of raw syngas mainly composed of hydrogen
and carbon monoxide (CO) by steam reforming reactions of feedstock
hydrocarbons; the third step is the separation of carbon dioxide from syngas
and the final step is cryogenic separation.
Considerable amount of carbon dioxide is produced as a by-
product during the methane reforming reaction. First priority in this
condition is to separate the produced carbon dioxide before the cryogenic
system, due to negative impact on cryogenic system and downstream
catalytic processing [2]. There are several and different available
technologies for CO2 removal. Main technologies include: amine processes
[3], hot potassium carbonate [4,5] Phys- ical solvents and Membranes [6].
Generic amines, especially, acti-
vated methyldiethanolamine (a-MDEA) have been used for carbon
* Corresponding author. Department of Chemical Engineering, University of
Isfahan, Isfahan, Iran.
E-mail addresses: masbeh@yahoo.com, m.behshti@eng.ui.ac.ir (M. Beheshti).
dioxide removal in recent decades [7e9]. MDEA is widely used since it
has low vapor pressure which means that it can be used in high
concentration without noticeable evaporation loss. MDEA is highly
resisted toward degradation and is practically non-corrosive [2]. It also has
a very low heat of reaction compared to other alkanolamines. The heat
of reaction is an important parameter since it can cause the largest
operating cost. MDEA, compared to other alkanolamines has a low rate of
reaction with CO2; therefore,
MDEA is often activated by adding primary or secondary amines
and recently piperazine (PZ) as a promoter [10e12].
Recently, some studies investigated the modeling, simulation and
kinetics of CO2 absorption in MDEA and Piperazine solutions [8,13e20].
The study of Afkhamipour and Mofarahi [16] showed that proper
selection of mass transfer and kinetics models have a dominant role in
modeling and simulation of the CO2 capture process by MDEA.
New models are proposed for Aspen Plus rate-based simulation of
absorber column in CO2 capturing by MDEA and piperazine (PZ), where
Eddy diffusivity theory instead of film theory is taken into account [14,20].
Although it is a well-established separation method, the energy
consumption and the costs associated with CO2 separation are substantially
high [40].
Reducing the energy consumption in solvent-based CO2 capture
processes can be addressed through improved solvents and process design
[21]. Many publications are focused on developing new

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0360-5442/© 2016 Published by Elsevier Ltd.
 V. Feyzi
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et al.
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solvents to reduce the energy consumption of the CO2 capture process from a syngas stream while in the other studies [35e45] the feed gas is a flue
[22e27]. Cousins et al. [21] reviewed different flow sheet modifications, gas stream. With the syngas as the feed, due to negative impact on the
which reduced the energy penalty associated with the solvent-based to system and downstream catalytic and cryogenic processing the CO2
capture the CO2 from a high pressure gas stream, either natural gas or content must decrease to less than five ppm, i.e. CO2 recovery is very close
syngas mixtures. It can be appreciated that improvements to the standard to 100% but for a flue gas stream, CO2 content is not completely
process are brought with increased complexity and an increase in the removed. Desiring higher recovery of CO2 requires more energy to be
number of unit oper- ations (which would tend to increase the capital cost).
supplied and more exergy loss is ex- pected. The second difference is
In order to
the type of amine solvent; the amine used in this study is a-MDEA while
increase the energy efficiency and prevent extra costs and energy
in the other studies on amine processes, MEA solvent was used as the
consumption, it is necessary to optimize the process and evaluate the absorption medium.
performance of the whole system by an exergy analysis.
Exergy Analysis is a method of thermodynamic analysis that
commonly is used in the investigated processes, with the aim of 2. Base case
calculating the second thermodynamic law efficiency of the process
As a base case, field data from a CO2 capture plant have been
[28e30]. The thermodynamic performance of a process is best
evaluated by exergy analysis [31,32]. As a process analysis tool, used. This plant is located in Fanavaran petrochemical company,
exergy analysis has the advantage of revealing what makes a pro- cess Mahshahr-Iran, producing about 46000 Nm3/hr. Syngas. Inlet feed stream is
efficient or inefficient. the effluent stream from water gas shift reactors of up-
Clearly the energy consumption in amine processes increases as the CO2 stream plant; this stream contains about 3.5% CO2. Carbon dioxide in the
recovery increases [7]. Different CO2 capturing technolo- gies are feed stream is absorbed by a-MDEA solvent in the absorber column. The
analyzed with exergy method. Atsonios et al. [33,34] per- formed exergitic composition of the feed stream and the amine solvent are illustrated in
analysis for two pre-combustion CO2 capturing schemes, including H2 Tables 1 and 2, respectively.
In this process, methyldiethanolamine (MDEA) have been used as
selective membranes and cryogenic sepa- ration schemes. They
solvent to absorb CO2 from the feed stream. Some amount of
investigated the effects of different process parameters on the exergitic
efficiency through sensitivity analysis. Two other technologies used in piperazine as the activator is added to the water-MDEA solution to enhance
CO2 capturing, investigated with exergy analysis method are the the absorption ability of the solvent.
Absorber column and stripping column are the main process
calcium looping process and the oxyfuel combustion which are
equipment in the CO2 removal process. Both absorber and stripper columns
commonly applied in fossil fuel power plants. Studies performed on
the calcium looping process revealed that most of the exergy loss during are packed bed type. Table 3 shows a summary of the key process
the process returns to the calcination step [35,36]. Several different specification of the absorber and stripper columns.
studies have been performed on the exergy analysis of the oxyfuel We know that the CO2 removal mechanism in amine processes is
combustion for CO2 capture [37e39]. These studies show that the main through chemical reaction between CO2 and amine solvent. The following
exergy losses are located in the boiler, steam generation, steam turbine, reactions may occur during MDEA process for CO2 removal
distilla- tion unit and the compression step. (Kierzkowska and Chacuk, 2010):
Several studies have been done exergy analysis on the process of
CO2 þ R1R2R3N þ H2O 4 (R1R2R3NH)þ þ (HCO3) (1)
CO2 removal from flue gas, using MEA as amine, and have calcu- CO2 þ (OH) (2)
4 (HCO3)-
lated the amounts of exergy loss and exergy efficiency in different
sections of the process [40e45]. These studies revealed that exergy is mainly
(HCO3) þ (OH) 4 (CO3)2 þ H2O (3)
dissipated in the absorption column, the stripping column and the heat
exchangers. Odejobi et al. [43] had investigated the
process for CO2 capture from the exergy viewpoint. They have (R1R2R3NH)þ þ (OH) 4 R1R2R3N þ H2O (4)
studied the effects of several operating parameters on exergy effi- 2H2O 4 (OH) (5)
þ (H3O)þ
ciency and recovery of CO2. Valenti et al. [46] performed an exergy
analysis of the CO2 capturing process using chilled aqueous
R1R2R3N in above equations denotes MDEA, where
ammonia as the adsorption medium, the study revealed that exergy
R1 ¼ R2 ¼ CH2CH2OH and R3 ¼ CH3.
efficiency of this process is more than amine processes. Some studies
The reactions considered between piperazine and CO2 are as follow
performed a comparison between different CO2 capture processes from
(Norouzbahari et al., 2015):
the exergy viewpoint [47,48]. Lara et al. [48] compared the results
of the exergitic analysis of six different CO2 capture technologies to
CO2 þ PZ þ B 4 (PZCOO) þ (BH)þ (6) CO
identify the weakness of any schemes to
reduce inefficiencies, energetic penalties, and hence the opera- þ
2 þ (PZCOO) þ B 4 PZ(COO )2 þ (BH)
tional cost of the systems. Atsonios et al. [47] compared three (7)
carbon capture technologies, the amine scrubbing, the calcium looping þ
where B might be any base present in the solution (PZ, PZH ,
and the oxyfuel combustion in terms of exergy losses, the results revealed
that the calcium looping process is the most effi- cient process with the
lowest exergy penalty. Table 1
In this study, we apply the exergy analysis method in the pro- cess of The composition of the feed stream.
CO2 capture from syngas by a-MDEA amine in order to evaluate the
Component Composition (mole %)
amounts of exergy loss and exergy efficiency in different sections of
the process and reduce exergy loss in the process by proposing some Methane 2.68
H2O 0.34
modifications in operating parameters. There are mainly two differences
N2 0.91
between the process investigated
H2 69.55
in this study and other CO2 removal studies. The first one is the CO2 3.33
difference in the feed gas to process. In this process CO2 is removed CO 23.19
 Table 2 determines where more focusing is needed to improve the system efficiency.
The composition of the amine solvent (a-MDEA). It also help to make an informed design decisions. Exergy (also called
Component Composition (mass %) Availability and Work Potential) is the maximum useful work can be
obtained from a system at a given state and environ- ment; in other words,
MDEA 26.39
Piperazine 3.48
the most work you can get out of a system. In the absence of potential and
H2O 69.72 kinetic energy change during the process, exergy of the stream is
divided into physical exergy and chemical exergy.
Physical exergy, Exph, is the maximum useful work obtained by
Table 3
Key process specification of absorber column and stripper column. passing the unit of mass of each substance from present state (T, P), to the
Parameter Absorber Stripper environmental state (T0, P0) through reversible processes [49,50].
Physical exergy of a stream is determined by the enthalpy and entropy of the
Type of packing FLEXIPAC
stream as Equation (8).
FLEXIPAC Total height of packing(m) 34
19.85
Diameter of column (m) 1.7 15.5 Exph ¼ ½hðT; pÞ hðT0; p0Þ T0½SðT; pÞ SðT0; p0Þ (8)
Packing dimension 250Y 3X
Type of vendor KOCH Chemical exergy is the maximum useful energy which would be attained
KOCH No. of equilibrium stages 36 from the environmental state to the dead state, by means of chemical
11 processes with reactant and products at the environ- mental pressure and
Operating pressure (barg) 15.6 0.5 temperature, when the stream composition is not in chemical equilibrium
with the environment. Standard chemical exergy of various substances is
reported in literature [49]. If standard chemical exergy of all constituents
PZCOO , H2O and OH ). of the stream are available, chemical exergy of the mixture can be
A steady state model of the plant has been developed by using Aspen calculated by Equation (9).
HYSYS (v.8.4) simulator. Calculation type of the simulation is equilibrium,
X X
at which any tray is considered as an equilibrium stage. The selected
Exch ¼ xi 0i þ RT0 xilnxi (9)
property package for this model is DBR-Amine package (v2012.1) which
is a well-established package for amine systems and reasonably predicts
its thermodynamic properties.
The DBR-Amine package considers all the possible reactions be-
i i
tween acid gases and amine solvent. The process flow diagram of
the base case simulation has been illustrated in Fig. 1. 0i is the standard chemical exergy and xi is the molar composition
of component i. So the total exergy of the stream is:
3. Exergy analysis
Ex ¼ Exph þ Exch (10)
Although quantitative evaluation of the energy in a process can be done
Equipment Exergy loss (irreversibility) is calculated by estab- lishing
by the first law of thermodynamics, it is equally important to assign the
the exergy balance around a hypothetical control volume that encircles
quality of energy. The second law of thermodynamics determines the
that equipment.
direction of work or heat; therefore, it cannot indicate the quality of
energy. The exergy analysis integrates the !
first and second laws of thermodynamics in a particular environ- mental X X m_ Ex X T (11)
condition to evaluate the quality of energy, thus this anal- ysis is very I_ m_ iExi k k Q_ W_
þ
important in the optimization of a chemical process. ¼ in out 0
j 1
By applying the exergy analysis method, the amount of ! T j
j
P
Term Q_ j 1 TT
destroyed exergy in each section of the process can be evaluated. It 0
j in equation (11) is the amount of exergy
j

Fig. 1. Process flow diagram of CCP.

transferred to the equipment due to heat exchanges with the heat sources of
the system at temperature Tj. The Exergy efficiency of an equipment in the
process is defined as the ratio of change of exergy in the sinks to the change
of exergy in the sources.
(12)
DExsink
hEx ¼
DExsources

The exergy analysis can be performed when the composition and

the physical properties of all the relevant streams are available, which is why
the Aspen HYSYS program is used. The Szargut et al. [51] method is
applied to calculate the chemical exergy of each stream. Fifteen user
variables and eleven user properties in Aspen HYSYS have been defined
as the reference of partial pressure of components, ambient pressure and
temperature. Visual basic codes are developed to define each user
variable, which is imported to Aspen HYSYS software. These codes are
produced according to the procedure presented by Abdollahi-Demneh et
al. [52]. The data- bank of Aspen HYSYS is used to calculate the
chemical, physical and mixing exergy for each gas and liquid stream in the
process.
Although there is substantial information in the literature, the standard
chemical exergy of MDEA and piperazine in the liquid phase were not
available. Therefore, Visual basic code is defined in User Variable of Aspen
HYSYS. The calculated values for standard chemical exergy of MDEA
and piperazine are 3748.1 kJ/mol and
3116.7 kJ/mol respectively.
The calculated values of standard chemical exergy for other
components presented in the process are compared with the values reported
in literature (Kotas, 1995), Table 4 shows this comparison: Theoretically
different methods were proposed for increasing exergy efficiency in
the CO2 absorption by amine process to
decrease exergy losses. Some of these propositions are as follow:
- Combination of heat and mass transfer in the stripper and absorber
[32,53].
- The use of amines with lower binding energy [54].
- Applying splitting flow on amine stream [55].
- Recovering of the heat available in the syngas stream for
regeneration [41].
- Overhead vapor recompression in the stripping column [41].
4. Results
Field data of the plant for thirteen cases that was operated at
different conditions of feed flow, feed composition, amine flow and amine
composition have been extracted from control room of CCP. These data
were applied to validate the simulation. Relative error was defined for the
temperature of the top and the bottom streams of the absorber and the
stripper columns. The results for relative error in thirteen cases are shown
in Fig. 2. According to the results, all defined relative errors are less than 10.
Therefore, there is a good agreement between simulation and industrial data,
and the simu- lation can be applied to exergy analysis of the mentioned
plant.
Fig. 2. Relative error between simulation result and field data for all thirteen cases.
Table 5
Validation of Aspen HYSYS simulation.
Parameter Field data Aspen HYSYS
Syngas stream flow rate 46149 Nm3/hr 46170 Nm3/hr
Lean amine flow rate 74884 kg/hr 74900 kg/hr
Concentration of CO2 in feed stream 3.33 mol% 3.33 mol%
Concentration of CO2 in Syngas stream 4.7 ppm 4.8 ppm
Concentration of CO2 in CO2 stream 93 mol% 92 mol%
Table 5 compares some key process data from the simulation with the real
field data.
As it mentioned before, the process in the current study is divided
to five sections, including: absorption column, stripping column, heat
recovery section, flasher and pump. Input and output exergy streams of these
sections are shown in Fig. 3.
The choice of the ambient conditions is that defined by Szargut et al.
[51], i.e. the ambient temperature T0 ¼ 298.15 K and pressure P0 ¼ 101.325
kPa. Exergy values of all process streams are shown in Table 6.
Exergy of the streams, exergy efficiency and exergy losses for each
section were calculated from equation (11) and equation (12), these results
are presented in Table 7.
The results show that the section with highest exergy loss is
flasher; this is followed by absorption column, stripping column and
heat recovery section. Net exergy loss of the process is about
3.25 MW. In the flasher section effluent hot stream from the top stage
of the stripper column is cooled by cooling water in exchanger E 102 and
turns to a two phase stream. The vapor and the liquid phases are separated in
flash drum D-2001. Due to finite temper- ature difference between process
stream 5 and cooling water, also low Carnot number for cooling water as
cooling medium in this exchanger (about 0.048), considerable amount of
thermal exergy of stream 5 is destroyed in the flasher section.
One of the main reasons for exergy destruction in chemical
processes is the chemical reactions take occur in the processes [49]. During a
chemical reaction, materials with higher chemical exergy convert to
materials with lower chemical exergy and considerable

Table 4
Standard chemical exergy.
Component Calculated standard chemical exergy (kJ/kmol) standard chemical exergy reported by Kotas (kJ/kmol) CH4

840310 836510
H 2O 116875 11710
H2 238520 238490
O2 3985 3970
CO2 21004 20140
CO 276354 275430
N2 734 720
 Fig. 3. Input and output exergy streams for each section.

Table 6
The exergy values of the streams.

Stream Temperature ( C) Pressure (bar-g) Mass Flow (ton/hr) Physical Exergy (Mj/hr) Chemical Exergy (Mj/hr)

AMINE 37.02 15.6 75 3368.014 654551.4

BFW 126 50 0.159 67.31 70.23
FEED 50 15.8 21.47 2668.2 526935.7
ABSTOP 37.6 15.6 18.38 1883.3 526134.5
ABSBOTT 49.85 15.8 78.25 6560.9 656085.6
2 35 15.6 18.38 1691.8 526080.2
SIN GAS 34.95 15.4 18.36 1968.2 400770.9
SEPLIQ 34.95 15.4 0.0185 0.782 0.882
rich 100.5 15.8 78.25 21427.6 656207.1
5 94.17 0.36 4.795 4133.4 1674.7
4 50 0.36 4.795 427.4 1674.7
CO2 50 0.36 3.243 269 15556.9
16 50 0.36 1.556 1.587 0.134
6 120.8 0.94 75.03 133432.9 655262.3
9 72.1 0.94 75.03 13046.4 655262.3
11 36.5 0.94 75.03 3116.4 654554.2
lean 37.02 15.6 75.03 3368.4 654554.2

Table 7 in the syngas stream. The results are presented in Fig. 4.

Exergy analysis results.
Sections contribution to total Piperazine concentration in a-MDEA solvent is normally in the
Section Exergy Irreversibility exergy loss (%)
efficiency (Mj/hr)

0.33 3152 26.9

Absorber
column 0.42 2933.3 25
Stripper
column 0.87 1934.3 16.5
Heat recovery
section

Flasher 0.41 3690 31.5

Pump 0.93 17.2 0.14
Total 11726.8 100

amount of heat is released. The exergy loss for the absorber column is
relatively high, because of the reactions between CO2 and MDEA solvent
and the heat released in the reactions.
In this study we investigate the effect of the piperazine con-
centration in a-MDEA solvent on the CO2 removal. Simulation re- sults
show that increasing the piperazine concentration increases the absorption
ability of the a-MDEA and reduces the CO2 amount
Fig. 4. Effect of piperazine concentration on the CO2 concentration in syngas stream.
 1.2 The results of the exergy analysis showed that decreasing the amine
flow rate from 75 ton/hr to 54.5 ton/hr. decreases the total
0.97
0.93 0.87 0.91 1 exergy loss to 2.63 MW (see Fig. 6).
Finally, to have a better view on the influence of the modifica- tions, it

Exergy Efficiency
0.8 will be interesting to investigate the change of energy and costs in unit.
0.53 Therefore, in continue total utilities cost and energy consumption of the
0.44 0.42 0.6
0.41 base and modified processes are shown in Table 9.
0.33 0.35 The results indicate that total utilities cost and total energy
0.4
consumption decrease by 25% and 18%, respectively.
0.2

Flasher Heat recovery Stripper 0

section Absorber
5. Discussion
Pump

The simulation of Aspen HYSYS shows that the energy con-

sumption is about 1.3 MJ/kg CO2; this value is in agreement with its
Modified case Base case industrial value. In exergy terms, the total exergy loss is about
0.55 MJ/kg CO2. According to the results, an interesting observation is that
Fig. 5. Comparison of exergy efficiency for the base case and the modified case.
in the pump and heat recovery the exergy losses are rather small, while in the
flasher the loss is substantial. This situation is similar to the study of
Table 8 Geuzebroek et al. [41]. Although the exergy loss of the stripper in this study
Exergy analysis results for the modified plant. (0.14 MJ/kg CO2) is the same of their study, there is a big difference
Exergy efficiency Irreversibility (Mj/hr) between the exergy losses of ab- sorbers. The absorber exergy loss in this
study is 200% smaller than their study. In fact, large exergy loss in certain
Absorber column 0.35 3091
parts of the equip- ment corresponds to a large local driving force.
Stripper column 0.53 1917.7
Heat recovery section 0.91 963.3
Therefore, the driving force of MEA is further than a-MDEA. It corresponds
Flasher 0.44 3520 to the intrinsic properties of MEA as a primary amine and MDEA as a
Pump 0.97 4.8 tertiary amine. Thus, contrast to the Geuzebroek et al. conclusions
[41], it can be concluded that changing the chemical used in the
3690 3520 4000 capture process is effective on the exergy loss. According to the
3152
3091
3500
obtained results, for the same equipment and process the amount of amine
2933.3
flow rate is a very impressive parameter to reduce the exergy loss. Our
3000
investigation indicates when the amine flow rate decreases by 27%, the
Exergy Loss (kj/hr)

2500 exergy loss, total energy consumption and utilities cost decrease by 19%,
1934.3 1917.7
18% and 25%, respectively. Therefore, it may be prudently concluded that
2000
changing the solvent and operation conditions in order to decrease the
963.3 1500 amine flow rate is very effective to reduce the exergy loss, the total
1000 energy con- sumption and consequently the total utilities cost. Due to the
4.8
high amounts of exergy loosed in the stripping column and heat re-
500
17.2 covery section it can be mentioned that one of the main sources of
0
Pump Flasher Heat recovery Stripper Absorber
section exergy destruction in this process is heat transfer through finite
Modified case Base case
temperature difference in heat transferring equipments such as
heat exchangers and reboiler of stripping column. As flow rate of amine is
Fig. 6. Comparison of exergy loss for the base case and the modified case. decreased, amount of required heating in reboiler and amount of heat
transferred between hot and cold steams in heat exchangers decreases,
this fact is the reason for the largest improvement observed in heat
range of 3e5 wt% [56]. This value in the a-MDEA solvent using in recovery section and stripping column.
Fanavaran petrochemical company is about 3.5 wt% and amount of CO2 in
syngas stream is 4.8 ppm (see Fig. 5). 6. Conclusions
By increasing the piperazine concentration from 3.5% to 4.7% the
amine circulation rate decreases from 75 ton/hr. to 54.5 ton/hr, while In this study, we have simulated a CO2 capture plant in CO
CO2 composition in the syngas stream remains at 4.8 ppm. By declining the production unit of Fanavaran Petrochemical Company with Aspen HYSYS
rate of amine circulation the exergy losses in the process decrease due simulator. In this plant, CO2 is removed from a synthesis gas stream by using
to reduce the require power of pump and the reboiler duty in stripping
a-MDEA as the absorption medium. The simulation validation is performed
column. The results of the exergy analysis which was done on the simulation
by comparison of field data from the plant in thirteen different operational
of modified plant are shown in
conditions (such as feed flow, feed composition and composition of amine
Table 8. solvent) with the results from the simulation. This comparison shows
that the simulation can predict the actual data with a reasonably good
Table 9 approximation. Exergy analysis has applied to achieve a clear insight
Total utilities cost and total energy consumption for the base and modified cases. where the actual exergy loss takes place. Exergy analysis result shows that
the flasher had highest rate of exergy loss, it followed by the absorber
Total utilities costs (USD/Yr) Total energy consumption (kw)
column, stripping column and heat recovery section. The main
The base case 2.26Eþ06 7.75Eþ03
The modified case 1.69Eþ06 6.33Eþ03
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