1.

INTRODUCTION
In this project, hydrogenation of carbon monoxide to methanol is searched in terms of
the reaction type, catalysts, and economical aspects. And also the effects of temperature,
catalyst, pressure were discussed.
2.THEORY
2.1. CARBON MONOXIDE
2.1.1. Structure of Carbon Monoxide

Figure 1.1. Structure of carbon monoxide

2.1.2. Physical And Chemical Properties

Carbon monoxide (CO), also called carbonous oxide, is a colorless, odorless and tasteless gas
which is slightly lighter than air. It is highly toxic to humans and animals in higher quantities,
although it is also produced in normal animal metabolism in low quantities, and is thought to
have some normal biological functions.
Property

Carbon Monoxide

Molecular formula:

CO

Molecular weight:

28.01 g/mol

Color:

Colorless

Physical state:

Gas
1

Boiling point:

-191.5C

Melting point:

-205C

Density:

1.145 g/L at 25C and 1 atm

Odor:

Odorless

Solubility:
Water:

2.3 mL/100 mL at 20C

Organic Solvents:

Appreciably soluble in ethyl acetate, chloroform,

acetic acid; freely absorbed by a concentrated
solution of cuprous chloride in hydrochloric acid or
ammonium hydroxide; solubility in methanol and
ethanol about 7 times as great as in water; soluble in
benzene.

Henry's law constant:

57,978.5 atm/mol fraction at 25C

(~1.04 atm-m3/mol)

Auto ignition temperature:

605 C

Flash point:

Flammable gas

Flammability limits:

Upper limit 74.2%; lower limit 12.5%

Conversion factor:

1 ppm=1.16 mg/m3 at 20C and 1 atm

Table 1.1. Properties of carbon monoxide

2.1.3. Major Uses or Sources

Carbon monoxide is an industrial gas that has many applications in bulk chemicals
manufacturing. It is also used in modified atmosphere packaging systems in the US, mainly
with fresh meat products such as beef, pork, and fish to keep them looking fresh. The
technology was first given "generally recognized as safe" (GRAS) status by the U.S. Food
and Drug Administration (FDA) in 2002 for use as a secondary packaging system, and does
not require labeling. In 2004 the FDA approved CO as primary packaging method, declaring
that CO does not mask spoilage odor. Despite this ruling, the process remains controversial
for fears that it masks spoilage. In 2007 a bill was introduced to the United States House of
2

Representatives to label modified atmosphere carbon monoxide packaging as a color additive,

but the bill died in subcommittee. The process is banned in many other countries, including
Canada, Japan, Singapore and the European Union. In biology, carbon monoxide is naturally
produced by the action of heme oxygenase 1 and 2 on the heme from hemoglobin breakdown.
This process produces a certain amount of carboxyhemoglobin in normal persons, even if they
do not breathe any carbon monoxide.

2.2. METHANOL
2.2.1. Structure of Methanol

Figure 2.1. Structure of methanol

2.2.2. History of Methanol

In 1923 the German chemists Alwin Mittasch and Mathias Pier, working for BASF,
developed a means to convert synthesis gas (a mixture of carbon monoxide, carbon dioxide,
and hydrogen) into methanol. A patent was filed Jan 12 1926 (reference no. 1,569,775). This
process used a chromium and manganese oxide catalyst, and required extremely vigorous
conditionspressures ranging from 50 to 220 atm, and temperatures up to 450 C. Modern
methanol production has been made more efficient through use of catalysts (commonly
copper) capable of operating at lower pressures, the modern low pressure methanol (LPM)
was developed by ICI in the late 1960s with the technology now owned by Johnson Matthey
who is a leading licensor of methanol technology.
3

2.2.3. Physical Properties of Methanol

Methanol, also known as methyl alcohol, wood alcohol, wood naphtha or wood spirits, is a
chemical with formula CH3OH (often abbreviated MeOH). It is the simplest alcohol, and is a
light, volatile, colorless, flammable, liquid with a distinctive odor that is very similar to but
slightly sweeter than ethanol (drinking alcohol). At room temperature it is a polar liquid and is
used as an antifreeze, solvent, fuel, and as a denaturant for ethanol. It is also used for
producing biodiesel via transesterification reaction.
Methanol is produced naturally in the anaerobic metabolism of many varieties of bacteria, and
is ubiquitous in the environment. As a result, there is a small fraction of methanol vapor in the
atmosphere. Over the course of several days, atmospheric methanol is oxidized with the help
of sunlight to carbon dioxide and water.
Methanol burns in air forming carbon dioxide and water:
2 CH3OH + 3 O2 2 CO2 + 4 H2O
Property

Methanol

Molecular formula:

CH3OH

Molecular weight:

32.04 g/mol
(C) %37.49, (H) %12.58, (O) %49.94

Color:

Colorless

Physical State:

Liquid

Boiling point:

64.7C

Melting point:

-97C

Flash point:

11C

Density:

0.7915 g/mL at 20C

Water solubility:

Miscible

Vapor density:

1.11

Vapor pressure:

126 mmHg at 25C

Heat of formation

-201.3 MJ/kmol
4

Gibbs free energy

-162.62 MJ/kmol

Heat of vaporization

35278 kJ/kmol

Henrys law constant:

4.55x10-6 atm-m3/mol

Conversion factor:

1 ppm=1.33 mg/m3
1 mg/m3=0.76 ppm

Table 2.1. Properties of methanol

2.2.4. Synthesis of Methanol

There are many ways for production of methanol. The dominant process for manufacturing is
catalytic hydrogenation of carbon dioxide from natural gas in fixed bed system. Most of
methanol is made by hydrogenation design also includes;

A high temperature and a low pressure,

An active and selective catalyst,

A method of supplying the heat of reaction,

The avoidance of side reactions,

A low pressure drop through the catalyst bed,

The highest possible conversion to avoid costly recycle,

Reactor materials suitable for operating conditions,

Conservation of heat and steam,

Good steam factor.

The two major processes currently employed for methanol production use either
high-pressure or low-pressure technology. Each process uses pressurized synthesis gas a
mixture of carbon monoxide, carbon dioxide, and hydrogen that is usually made by steam
reforming of natural gas.
1. In the high-pressure process, the reaction of the components occurs at pressures of about
300 atm.
2. In the low-pressure process, the reaction is catalyzed with a highly selective copper
based compound at pressures of only 50-100 atm.
5

The low-pressure process has replaced the higher pressure route due to lower natural gas
feedstock requirements and significantly lower operating costs.
2.2.5. Methanol Production
The main process of methanol production can be divided into three sections.

Reforming

Compression and Synthesis

Distillation

2.2.5.1. Reforming
The term "steam-hydrocarbon reforming" refers to the endothermic reaction between steam
and methane (or any other alkane) which produces carbon monoxide, carbon dioxide and
hydrogen. The reaction is carried out in a furnace at high temperatures over a nickel catalyst
inside tubes. Fired burners supply heat for the endothermic reaction:
Ni/8000C

CH4 + H2O CO + 3H2

rH = +206 kJ mol-1

Under these conditions, the water gas shift reaction also occurs to a small extent:
Ni/8000C

CO + H2O CO2 + H2

rH = +206 kJ mol-1

Thus the products of the reforming reaction ("synthesis gas") include carbon oxides and
hydrogen as well as unreacted methane, nitrogen, and steam. They leave the furnace at over
800C. Heat is recovered from this stream as it is cooled to 32C.
The recovered heat is used to generate high-pressure steam; heat boiler feed water, and to
supply heat to the distillation section. Some heat, which cannot be recovered, is rejected to
the atmosphere (air coolers) and the cooling water system. After cooling, steam in the
reformed gas is condensed and recycled to water treatment.

2.2.5.2. Compression and Synthesis

The "synthesis gas" from the reformer is then compressed in a centrifugal compressor. A
turbine which draws its power from the high pressure steam system drives this compressor.
Extraction steam from the turbine is used in the reforming reaction and drives other turbines

in the process.

The compressed synthesis gas enters the converter reactor containing copper zinc and catalyst
and the synthesis reaction occurs, according to the equation:
2H2 + CO CH3OH

rH = -92 kJ mol-1

This reaction is highly exothermic and this excess heat is used to heat boiler feed water and
to pre-heat reactant gas.
Since the reaction is exothermic, low temperatures favour conversion to methanol. On the
other hand, the rate of reaction increases with increasing temperature. Pressure will also
affect the position of the equilibrium, with increasing pressure favouring methanol formation.
The final conditions used involve a copper oxide based catalyst at about 5 MPa (50
atmospheres) pressure and about 270C.
As carbon monoxide is used up in the methanol synthesis reaction the water gas shift reaction
reverses producing more carbon monoxide:
H2 + CO2 CO + H2O

rH = +41 kJ mol-1

These reactions combine to produce approximately 40% conversion of carbon oxides to

methanol each pass through the reactor. On leaving the reactor the gas mixture is cooled and
methanol and water condense out. The remaining gas is returned to the circulator, mixed with
incoming compressed synthesis gas and recycled through the methanol converter.
Hence, the overall reactions by which methanol is produced from synthesis gas may be
summarized into the following equation:
Cu-Zn

CO2 + CO + 5H2 2CH3OH + H2O + heat

2.2.5.3. Distillation
The distillation system consists of an extraction column, a refining column, and a recovery
column.
The first step is the removal of the volatile impurities and dissolved gases - these include
carbon dioxide, carbon monoxide, hydrogen, nitrogen, acetone, ethers, esters and volatile
alkanes up to decane - which are carried out in the extraction column. The temperature in this
column is kept as low as possible to prevent significant methanol loss by evaporation.
The bottom of the extraction column provides the feed for the reforming column. The feed is
vaporized and enters the refining column about a third of the way up the column. Methanol
7

is now the most volatile component and it leaves the top of the column with a purity of
99.99%. This is product methanol.

2.2.5.4. Purpose of Methanol Production

The purpose of methanol production is carbon molecules which in raw materials convert in to
methanol at high yield.

As the synthesis pressure increases,

As the molar ratio of carbon monoxide to carbon dioxide increases,

As the inert ratio decreases, which means less waste,

As the rate of feed decreases,

carbon efficiency increases

METHANOL PRODUCTION PROCESS

Feed preparation

Methanol
converter

Natural gas

Seperator

Compressor

vapor

vapor

Cooling
Vapor

Cooler

Demineralisation

Distillation

Rectification
column

Seperator
of
methanol

co

Product: Methanol

Waste Water

Figure 2.2. Methanol production process

2.2.5.5. Other Methods

Although natural gas is the most economical and widely used feedstock for methanol
production, many other feedstocks can be used to produce syngas via steam reforming. Coal
is increasingly being used as a feedstock for methanol production, particularly in China.
In addition, mature technologies available for biomass gasification are being utilized for
methanol production. For instance, woody biomass can be gasified to water gas (a hydrogenrich syngas), by introducing a blast of steam in a blast furnace. The water-gas / syngas can
then be synthesized to methanol using standard methods. The net process is carbon neutral
since the CO2 byproduct is required to produce biomass via photosynthesis.
2 C16H23O11 + 19 H2O + O2 42 H2 + 21 CO + 11 CO2 21 CH3OH + 11 CO2

Figure 2.3. Biomethanol production process

9

2.2.6. Uses of Methanol

Methanol is a common industrial chemical that has been used as an alternative blended liquid
transportation fuel and under consideration for wider use. In the USA its application profile in
2001 was MTBE 37%; formaldehyde 23%; acetic acid 12%; solvents 6%; chloro methanes
6%; methyl methacrylate 3%; miscellaneous, including methylamines, glycol methyl ethers,
dimethyl terephthalate, antifreeze and fuels 17%. In many countries, notably in Asia,
methanol is almost exclusively used to produce the intermediate chemical formaldehyde as
input to urea formaldehyde composite wood adhesive.
World demand for methanol is around 32 million tones per year and increasing modestly by
about 2 to 3% per year but with significant changes in the profile of industry. Since the early
1980s, less-efficient small facilities are being replaced by larger plants using new efficient
low-pressure technologies. The industry has also moved from supplying captive customers,
especially for the production of formaldehyde that typically represents one-half of world
demand and serving primarily the home market, to large globally oriented corporations.
Demand patterns too have been changing such as in Europe where methanol was once
blended into gasoline when its value was around one half that of gasoline, but now
uncompetitive with lower oil prices. Offsetting this was the phasing out of leaded gasoline in
developed countries that required the use of reformulated gasoline as in the US that promoted
the use of MTBE derived from methanol.

10

2.3.CATALYST
There are several types of catalyst named Cr/Zn/Al/Zr fibrous catalyst for hydrogenation of
carbon dioxide to methanol. However the most important is Cu /ZnO.

Figure 3.1. TEM images of the fibrous catalyst

A practical methanol synthesis process greatly requires a high performance catalyst, which
must be highly active and selective for methanol synthesis and also stable for a long period in
a continuous operation. NIRE and RITE have been jointly implicated in the development of
high performance methanol synthesis catalysts since 1990. The authors elucidated the role of
metal oxides contained in Cu/ZnO based ternary catalysts, and then developed Cu/ZnO based
multicomponent catalysts containing two or three metal oxide. The present study is devoted to
optimize the operation conditions for preparing a Cu/ZnO based multicomponent catalyst by
investigating the effects of various preparation conditions on the activity of the catalyst.

11

3. THERMODYNAMIC CALCULATIONS OF THE SYSTEM

3.1. Thermodynamics Properties of The System

CO + 2H2

CH3OH

Carbon
monoxide

Methanol

arjasj

Thermodynamics properties of each component are given below;

Table 3.1. Thermodynamic properties of substances

H0f298 (kj/mol) G0f298 (kj/mol)

PC (bar)

TC (K)

Carbon
monoxide

-110.525

-137.168

34.99

132.9

H2

13.13

33.19

Methanol

-200.66

-161.96

80.97

512.6

The molar heat capacities can be calculated as functions of temperature:

Cp/R = (A+BT+CT2+DT-2) ..(1)

A,B,C and D are constants and given below, T is temperature in Kelvin.

Table 3.2. Constants for heat capacity equation

A

Bx10-3

Cx10-6

D x105

Carbon
monoxide

3.376

0.557

-0.031

H2

3.249

0.422

0.083

Methanol

2.211

12.216

-3.450

12

3.2 Theory of Calculations

dInK/dT= H0/RT2 (Vont Hoff)....(2)

..(3)

G0 = G0f298 Products - G0f298 Reactants ....(4)

G = -RT ln K298 .....(5)
H0 = H0f298 Products - H0f298 Reactants
H

(6)

..(7)

CP = CP Products - CP Reactants .(8)

3.3. Sample Calculations

Using equation (4) and values in Table 4.1, G0 is found as:
G0 = (-161.96)-[(-137.168)+0]
= -24.792 kJ/mol
Using equation (5) K298 is found as:
(-24792 J/mol) = - (8,314 J/mol.K) (298K) ln K298
ln K298 = 10.007
K298 = 2.218 x104
Using equation (8) and values in Table 4.2, CP can be found as:
A = A Products - A Reactants
= (2.211)-[(3.376)+(2*(3.249))]
= -7.663
B = B Products - B Reactants
= (12.216)-[(0.557)+(2*(0.422))]

13

= 10.815 x10-3
C = C Products - C Reactants
= (-3.450)-0
= -3.450 x10-6
D = D Products - D Reactants
= 0-[(-0.031)+(2*(0.083))]
= -0.135 x105
CP = R (A+ BT+ CT2 +DT-2) (J/mol)
Using equation (6) and Table 4.1, H0 can be found as:
H0 = (-200.66)-[(-110.525)+0]
= -90.135 kJ/mol
Using equation (6),

H can be found as:

The equation (3) is obtained from Vant Hoff equation.

T

0+

R(A BT CT

DT 2 )dT

298

= H0+R* (

* (

)+

14

)+

(
)

(
)

)
(

)+

10.007+*

[
]

For T = 273K, putting Cp constants, H0 and R (8.314 j/mol K) into equation above,
Kf was found as below:
InKT=13.20883571 and KT= 545160,6017
Other calculations for different temperatures are done in Excel and given in Appendix.

15

3.4. T-XAe Diagram for the System

We are responsible to draw a graph of mole fractions at equilibrium versus
temperatures. First of all, we draw flow chart for overall system.

Taking basis as 100 mol/s

FA0=30 mol/s
FB0=65 mol/s
FI0=5 mol/s

FC
FI

Table 3.3. Mole percentages of the components in the feed

Initial

After the reaction

Carbon Monoxide (A)

FA0 = 30

FA=FA0 (1-XA)

Hydrogen (B)

FB0 =65

FB=FB0-2FA0XA

Methanol (C)

FC0=0

FC=FC0+FA0XA

Nitrogen (I)

FI0=5

FI=5

FT= FA=FA0 (1-XA)+ FB0-2FA0XA+ FC0+FA0XA+5

=100-60XA

yA = FA / FT
yA = FA0 FA0XA / 100-60XA

yA = (30-30XA / 100-60XA)

yB = FB0-2FA0XA / 100-60XA

yB = (65-60XA / 100-60XA)

yC= FC0+FA0XA / 100-60XA

yC = 30XA / 100-60XA

16

(
(

)
)

(
(
)

(
(

)
(

)
)

(
(

)
)

(
)

)
(

At 273 K and 50 bar, putting Kf = 545160.6017, K = 0.064146 values into the equation
above, XAe was found as 1.00000. Other calculations for different temperatures and pressures
are done in Excel and given in Appendix 10.

17

1.20000

1.00000

0.80000

XAe
50
bar
90
bar
120
bar

0.60000

0.40000

0.20000

0.00000
0

100

200

300

400
T(K)

Figure 4.1. XAe versus T Diagram

18

500

600

700

800

4.ENERGY BALANCE
4.1.Energy Balance Theory
TR

Fc
i

T
pi

dT

T0

inlet

Fic

pi

dT

outlet

0
(H rxn
) FA 0 X A f

TR

d (H )
0
0
c p H rxn H rxn
c p dT H rxn
H rxn c p dT
dT

4.2.Energy and Material Balance:

QR (by the flow) + QR (by the wall) = QG (generated)
Adiabatic system so QR (by the wall) = 0
QR (by the flow) = QG (generated)
TR

Fc
i

pi

dT

T0

inlet

Ficp i dT
Tr

outlet

0
(H rxn
) FA 0 X A f

CO + H2O C2H OH
3
2
(A)

(B)

(C)

For First Reactor:

F A = F A 0 *(1- X A1 )
F B =F B 0 -2 F A 0 * X A1
FC= F A 0 * X A1

TR

Tf

(F A 0 Cp A + F B 0 Cp B + FICpI) dT +

T0

(F A Cp A + F B Cp B +FCCpC + FICpI) dT =

TR

o
(- H rxn
) F A 0 X A1

19

TR

T0

(F A 0 Cp A + F B 0 Cp B + FICPI)dT +

FA0XA1CpC + FICpI

TR

T0

F A 0 (1- X A1 )Cp A +( F B 0 - 2F A 0 X A1 )Cp B +

TR
o
dT=( H rxn
)F A 0

X A1

(F A 0 Cp A + F B 0 Cp B + FBCpI)dT +

F A 0 Cp A + F B 0 Cp B + FICpI + F A 0 X A1 ( CpC-

TR

o
2Cp B - Cp A ) dT = (- H rxn
) F A 0 X A1

T0

(F A 0 Cp A + F B 0 Cp B +FICpI) dT + [F A 0 Cp A + F B 0 Cp B + FICpI +F A 0 X A1 Cp]dT =

TR

o
(- H rxn
) F A 0 X A1

Cp=CpC- 2Cp B - Cp A
T

TR

TR

o
o
( H rxn ) T = H rxn
+ CpdT H rxn
= ( H rxn ) T - CpdT

CpdT = - ( H rxn ) T -

TR

( F A 0 Cp A + F B 0 Cp B + FICpI )dT + F A 0 X A1

T0

CpdT

F A 0 X A1

TR

(F A 0 Cp A +F B 0 Cp B + FICpI )dT + F A 0 X A1

T0

CpdT = -( H rxn ) T F A 0 X A1 +

TR

CpdT F A 0 X A1

TR

(F A 0 Cp A +F B 0 Cp B + FICpI )dT = -( H rxn ) T F A 0 X A1

T0

F A 0 =263.05 mol/sec
F B 0 =574.28 mol/sec
FI =43.84 mol/sec

20

Cp A = 28.0684+(4.614*10-3)T - (0.258*105)T-2
Cp B = 27.012 + (3.509*10-3)T +(0.665*105)T-2
Cp = 18.382+(101.564*10-3)T-(28.863*10-6)T2
C

CpI=27.270+(4.930*10-3)T+(0.333*105)T-2
Cp=-63.71+(0.0899)T+(-28.683*10-6)T2-(107200)T-2
T

(H ) T= H

298

dT

298

(H ) T= 90135 + (-63.71)(T298) + (0.0899)(T2 2982) + (9.561)(T32983)

+(10072000)T-1
T

(F

AO

X A1 =

Cp A FBO CpB FICpI)dT

TO

(H r ) T FA0

From this equation; X A1 was found as 0,19.

For Second Reactor

FA1 = FA0 * (1-XA1)

FA2 = FA0 * (1-XA2)

FB1 = FB0 - 2 (FA0*XA1)

FB2 = FBO 2 (FAO*XA2)

FC1= ( FA0*XA1)

FC2 = (FAO*XA2)

TR

Tf

( FA1 CpA + FB1 CpB + FR1 CpR + FICpI )dT +

T0

( FA2 CpA + FB2 CpB + FR2CpR

TR

o
FICpI dT = (- H rxn
)FA0 (XA2-XA1)

TR

Tf

(FA0(1-XA1) CpA + (FB0- 2FA0XA1) CpB + (FA0XA1) CpR + FICpI) dT +

T0

(FA0(1-XA2)

TR

o
CpA + (FB0-2FA0XA2) CpB + (FA0XA2)CpR + FICpI )dT = (- H rxn
)FA0 (XA2-XA1)

21

TR

Tf

(FA0 CpA + FB0 CPB+ FICpI )dT +

T0

(FA0 XA2 Cp ) dT +

(FAO XA1 Cp) dT +

T0

TR

o
( H rxn
)FA0 (XA2-XA1) = 0

T0

Tf

TR

TR

T0

(FAO CPA + FBO CPB+ FICpI )dT + (FA0 XA2 Cp )dT + (FAO XA1 Cp) dT +
Tf

[( Hrxn)T - CpdT] FAO(XA2-XA1)=0

TR

TR

Tf

( FA0 CpA + FB0 CPB+ FICpI )dT +

T0

FA0 XA2 Cp dT +

Tf

( Hrxn)T FA0XA2 - ( Hrxn)T FAOXA1 -

FA0 XA2 Cp Dt +

FAO XA1 Cp dT =0

T0

TR

FAO XA1 Cp dT +

T0

TR

TR

( FA0 CpA + FB0 CPB+ FICpI )dT + ( Hrxn)T FA0XA2 +

T0

FAOXA1 CpdT +

T0

FAO XA1 Cp dT

- ( Hrxn)T FAOXA1=0

T0

(FA0 CpA + FB0 CPB+ FICpI )dT + ( Hrxn)T FA0XA2 +

T0

FAO XA1 Cp dT +

T0

( Hrxn)T FAOXA1=0
T

-( Hrxn)T FA0(XA2-XA1) =

(FA0 CpA + FB0 CPB+ FICpI )dT + FAOXA1

T0

T0

T f

F
Cp

F
Cp

FICpI

[
F
X

CpdT

]
A0
A1
A0 A B 0 B
T 0

T0
XA2=
+XA1
(H rxn ) T FA0
Tf

From this equation; XA2 was found as 0,32.

22

CpdT

For Third Reactor:

FA2 = FA0 * (1-XA2)

FA3 = FA0 * (1-XA3)

FB2 = FB0 - 2 (FA0*XA2)

FB3 = FBO 2 (FAO*XA3)

FC2= ( FA0*XA2)

FC3 = (FAO*XA3)

TR

Tf

( FA2 CpA + FB2 CpB + FC2 CpC + FICpI )dT +

T0

( FA3 CpA + FB3 CpB + FC3CpC

TR

o
FICpI dT = (- H rxn
)FA0 (XA3-XA2)

TR

Tf

(FA0(1-XA2) CpA + (FB0- 2FA0XA2) CpB + (FA0XA2) CpC + FICpI) dT +

T0

(FA0(1-XA3 CpA

TR

o
+ (FB0-2FA0XA3) CpB + (FA0XA3)CpC+ FICpI )dT = (- H rxn
)FA0 (XA3-XA2)

TR

Tf

(FA0 CpA + FB0 CPB+ FICpI )dT +

T0

(FA0 XA3 Cp ) dT +

(FAO XA2 Cp) dT +

T0

TR

o
( H rxn
)FA0 (XA3-XA2) = 0

T0

Tf

TR

TR

T0

(FAO CPA + FBO CPB+ FICpI )dT + (FA0 XA3 Cp )dT + (FAO XA2 Cp) dT +
Tf

[( Hrxn)T - CpdT] FAO(XA3-XA2)=0

TR

TR

Tf

( FA0 CpA + FB0 CPB+ FICpI )dT +

T0

FA0 XA3 Cp dT +

T0

TR

Tf

( Hrxn)T FA0XA2 - ( Hrxn)T FAOXA3 -

FA0 XA3 Cp Dt +

FAO XA2 Cp dT =0

TR

( FA0 CpA + FB0 CPB+ FICpI )dT + ( Hrxn)T FA0XA2 +

T0

T0

T0

TR

FAO XA2 Cp dT +

FAO XA2 Cp dT

+ ( Hrxn)T FAOXA3=0

T0

23

FAOXA2 CpdT +

(FA0 CpA + FB0 CPB+ FICpI )dT + ( Hrxn)T FA0XA2 +

T0

FAO XA2 Cp dT +

T0

( Hrxn)T FAOXA3=0
T

- ( Hrxn)T FA0(XA3 -XA2) =

(FA0 CpA + FB0 CPB+ FICpI )dT + FAOXA2 CpdT

T0

T0

T f

F
Cp

F
Cp

FICpI

[
F
Xa
2

CpdT

]
A0
A0 A B 0 B

T 0

T0
XA3=
+XA2
(H rxn ) T FA0
Tf

From this equation; XA3 was found as 0,43.

For Fourth Reactor:

FA3 = FA0 * (1-XA3)

FA4 = FA0 * (1-XA4)

FB3 = FB0 - 2 (FA0*XA3)

FB4 = FBO 2 (FAO*XA4)

FR3= ( FA0*XA3)

FR4 = (FAO*XA4)

TR

Tf

( FA3 CpA + FB3 CpB + FR3 CpR + FICpI )dT +

T0

( FA4 CpA + FB4 CpB + FR4CpR

TR

o
FICpI dT = (- H rxn
)FA0 (XA4-XA3)

TR

Tf

(FA0(1-XA3) CpA + (FB0- 2FA0XA3) CpB + (FA0XA3) CpR + FICpI) dT +

T0

(FA0(1-XA4 )CpA

TR

o
+ (FB0-2FA0XA4) CpB + (FA0XA4)CpR + FICpI )dT = (- H rxn
)FA0 (XA4-XA3)

TR

Tf

(FA0 CpA + FB0 CPB+ FICpI )dT +

T0

(FA0 XA4 Cp ) dT +

T0

TR

o
( H rxn
)FA0 (XA4-XA3) = 0

24

(FAO XA3 Cp) dT +

T0

Tf

TR

TR

T0

(FAO CPA + FBO CPB+ FICpI )dT + (FA0 XA4 Cp )dT + (FAO XA3 Cp) dT +
Tf

[( Hrxn)T - CpdT] FAO(XA4-XA3)=0

TR

TR

Tf

( FA0 CpA + FB0 CPB+ FICpI )dT +

T0

FA0 XA4 Cp dT +

Tf

( Hrxn)T FA0XA3 - ( Hrxn)T FAOXA4 -

FA0 XA3 Cp Dt +

FAO XA3 Cp dT =0

T0

TR

FAO XA3 Cp dT +

T0

TR

TR

( FA0 CpA + FB0 CPB+ FICpI )dT + ( Hrxn)T FA0XA23 +

T0

FAOXA3 CpdT +

T0

FAO XA3 Cp dT

+ ( Hrxn)T FAOXA4=0

T0

(FA0 CpA + FB0 CPB+ FICpI )dT + ( Hrxn)T FA0XA3 +

T0

FAO XA3 Cp dT +

T0

( Hrxn)T FAOXA4=0
T

- ( Hrxn)T FA0(XA4 -XA3) =

(FA0 CpA + FB0 CPB+ FICpI )dT + FAOXA3 CpdT

T0

T0

T f

F
Cp

F
Cp

FICpI

[
F
Xa
3

CpdT

]
A0
A0 A B 0 B

T 0

T0
XA4=XA3+
(H rxn ) T FA0
Tf

From this equation; XA4 was found as 0,55.

25

From these calculations, XA versus T graph was plotted.

1.00
0.90
r=0

0.80

-rA=0,1
-rA=0,3

0.70

-rA=0,4
0.60

-rA=1

XA

-rA=10

0.50

Xaf=0,55
adiabatic line1
adiabatic line2

0.40

adiabatic line3
0.30

adiabatic line4
adiabatic line5

0.20

adiabatic line 6
adiabatic line 7

0.10
0.00
450

500

550

600

650

700

Figure 5.1: XA versus T graph

....
Rate Equation For This Reaction:
(

mol (kg cat)-1min-1atm-3 at 250 C

E= 80 kJ mol-1
(

26

1/-rA versus XA graph was plotted.

0.03
0.0275
0.025
0.0225
0.02

1/-rA
0.0175

1/-rA1
1/-rA2

0.015

1/-rA3

0.0125

1/-rA4

0.01
0.0075
0.005
0.0025
0
0

0.05

0.1

0.15

0.2

0.25

0.3 XA 0.35

Figure 6.1: 1/-rA versus XA graph

From this graph reactors were designed as;

Then, from Simpson 1/3 Rule;

V1=9.4794 m3
V2=2.2158 m3

were found.

V3=4.3842 m3
V4=8,319 m3

27

0.4

0.45

0.5

0.55

0.6

5.RESULTS AND DISCUSSION

Firstly, thermodynamic data were used for calculations. These calculations, equilibrium
conversion versus temperature graph was plotted in a pressure range of 50-120 bars. So it was
decided that the reaction is exothermic.
Secondly, plotting the conversion versus temperature graph, adiabatic line equation was
obtained by using energy balance. By intersecting the plotted rate curves, adiabatic line curve
was graphed. The results on rate curve graph (the extensions of the rate curves) are on the
maximum limit for conversion, in other words if we want to extend the arms of the curve, the
results will approach to maximum and sticks to the equilibrium curve and we dont want to
reach equilibrium conditions. For this reason we can not extend the arms of the rate curve for
any reason. Since rate curves were very close to the equilibrium curve and it was showed
variation in very low temperature differences, it was understood that the system was very
sensitive and to get correct results the temperature must be increased by much smaller
amounts. The area 1/-rA-XA of graph was calculated and then by taking the catalyst amount
into account, the volume was calculated.
The catalyst used in this project is not only speed up the reaction, but also starts it.
Therefore, according to operate condition of the catalyst initial temperature was chosen as
450K.
Four reactors were decided to use because of adiabatic lines and XAf values in our graph .
And also three coolers were needed. Therefore our process was highly exothermic. For
instance outlet temperature of first reactor was high so it was prevented to reach high
conversion for second reactor. Inlet temperature of second reactor is lowered by cooler so
higher conversion was approached.
From 1/-rA-XA graph it was decided to use plug flow reactor because after the comparison
of the pug flow reactor and completely stirred tank reactor for this process, reactor was
chosen plug flow reactor instead of volume of completely stirred tank reactor. It was small
because according to adiabatic system was worked. Because of adiabatic process temperature
was always change plug flow reactor was used for all reactors. Volumes were calculated, the
first volume 9.4794 m3 (for per minute), the second volume 2.2158 m3 , the third volume
4.3842 m3, fourth volume 8.319 m3 .

28

Inlet and outlet temperatures, conversions were given at the below table:
Inlet Temperature(K)

Outlet Temperature(K)

Conversion

First Reactor

450

650

0.19

Cooler

650

505

Second Reactor

505

615

0.32

Cooler

615

500

Third Reactor

500

600

0.43

Cooler

600

480

Fourth Reactor

480

580

0.55

6.CONCLUSION
At the beginning investigation for hydrogenation process was made. Then look for
the best catalyst type and depending on literature, Cu/ZnO as a catalyst was chosen. Inlet
temperature and inlet pressure were determined. 550K - 680K temperature range as inlet
temperature, and 100 bar pressure as inlet pressure were chosen. Calculations and depending
on the calculations were made and XAe-T graph was drawn. On the graph the effects of
pressure and temperature were looked. Then inert effects were observed. Continued with rate
curves. Graphs for different constant rate values were drawn. Then, it was continued with
adiabatic lines to decide if the system was adiabatic or not. It was decided to operate the
system in adiabatic conditions. After deciding to use adiabatic system plug flow reactor was
decided to use for reaction. And then this decision number of reactor was designed and found
that using four reactors and three cooler was suitable. Finally, 1/-rA-XA graph was drawn and
depending on this graph volume of the reactors were calculated.

29

7.REFERENCES
1. Perry, R.H., Chilton C.H., Chemical Eng.Hand Book ,6th Ed.,McGraw Hill, 1984
2. Sandler S.I.,Chemical and Engineering Thermodynamics,3rd ed.,John Wiley &
Sons,Inc.,(1999)
3. Alberty, S.,Physical Chemistry,3rd Ed., John Willey & Sons Co., New York, (2001)
4. Kirk-Othmer, Encylopedia of Chemical Technology, 4th Ed., John Willey & Sons,
New York, (1995)
5. Grz ,K.,Kimya Mhendislii Termodinamii. 124-126,Ankara niversitesi Fen
Fakltesi Yaynlar,Ankara (1986)
6. Saito, M., Takeuchi,M., Watanabe, T., Toyr, J., Luo, S., Wu, J., Methanol Synthesis
from CO2 and H2 Over a Cu/ZnO-Based Multicomponent Catalyst,403-408,(1997)
7. Gao, L., Li, H., Chen, B., Jin, H., Lin, R., Hong, H., Proposal of a Natural Gas-Based
Polygeneration System for Power and Methanol Production,206-212,(2008)
8. Xin, A., Yizan, Z., Qiang, Z., Jinfu, W., Methanol Synthesis from CO2
Hydrogenation with a Cu/Zn/Al/Zr Fibrous Catalyst,88-94,(2009)

30

APPENDX 1. Fugacty Calculatons For Carbon Monoxde at 50 bar Pressure

T

Pr

Tr

B0

273
283
293
303
313
323
333
343
353
363
373
383
393
403
413
423
433
443
453
463
473
483
493
503
513
523
533
543
553
563
573
583
593
603
613
623
633
643
653

1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429

2,054
2,129
2,205
2,280
2,355
2,430
2,506
2,581
2,656
2,731
2,807
2,882
2,957
3,032
3,108
3,183
3,258
3,333
3,409
3,484
3,559
3,634
3,710
3,785
3,860
3,935
4,011
4,086
4,161
4,236
4,312
4,387
4,462
4,537
4,612
4,688
4,763
4,838
4,913

0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048

-0,050380452
-0,042919829
-0,036114389
-0,029887074
-0,024172036
-0,018912718
-0,014060304
-0,009572465
-0,005412341
-0,001547704
0,002049732
0,005404885
0,008539776
0,011473933
0,014224725
0,016807645
0,019236553
0,021523879
0,023680798
0,025717385
0,027642739
0,029465098
0,031191938
0,032830053
0,034385633
0,035864326
0,037271297
0,038611273
0,039888592
0,041107239
0,04227088
0,043382895
0,044446402
0,045464283
0,046439202
0,047373632
0,048269864
0,049130026
0,049956098

31

B2
0,130635302
0,13180832
0,13278431
0,133601485
0,134289715
0,134872541
0,135368654
0,135793007
0,136157637
0,1364723
0,136744949
0,136982105
0,137189141
0,137370508
0,137529913
0,137670453
0,13779473
0,137904941
0,138002941
0,13809031
0,138168396
0,13823835
0,138301162
0,138357685
0,138408656
0,138454712
0,138496408
0,138534227
0,138568592
0,138599873
0,138628393
0,138654438
0,138678261
0,138700083
0,138720102
0,138738493
0,138755411
0,138770994
0,138785366

0,969780658
0,975742411
0,980907528
0,985394567
0,989302227
0,992713025
0,995696237
0,998310252
1,000604478
1,002620877
1,004395216
1,005958086
1,00733574
1,008550778
1,009622714
1,010568448
1,011402655
1,012138116
1,012785985
1,013356026
1,013856802
1,014295842
1,014679778
1,015014467
1,015305089
1,015556235
1,01577198
1,015955951
1,016111377
1,01624114
1,016347816
1,01643371
1,016500887
1,016551202
1,016586319
1,016607739
1,016616809
1,016614748
1,016602654

1,016581518
663
673
683
693
703
713
723
733
743
753
763
773

1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429
1,429

4,989
5,064
5,139
5,214
5,290
5,365
5,440
5,515
5,591
5,666
5,741
5,816

0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048

0,050749922
0,051513215
0,05224758
0,052954513
0,053635413
0,054291588
0,054924264
0,055534592
0,056123648
0,056692447
0,057241939
0,057773022

0,138798638
0,138810909
0,138822268
0,138832793
0,138842558
0,138851626
0,138860057
0,138867902
0,13887521
0,138882024
0,138888383
0,138894323

1,01655224
1,01651563
1,016472426
1,016423294
1,01636884
1,016309614
1,016246115
1,016178798
1,016108075
1,016034323
1,015957884

APPENDX 2. Fugacty Calculatons For Hydrogen at 50 bar Pressure

T

Pr

Tr

273
283
293
303
313
323
333
343
353
363
373
383
393
403
413
423
433
443
453
463
473
483
493
503

3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808

8,225
8,527
8,828
9,129
9,431
9,732
10,033
10,334
10,636
10,937
11,238
11,540
11,841
12,142
12,444
12,745
13,046
13,347
13,649
13,950
14,251
14,553
14,854
15,155

w
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216

B0
0,068510152
0,069320641
0,070059953
0,07073646
0,071357316
0,071928664
0,072455809
0,072943347
0,073395284
0,073815121
0,07420593
0,074570418
0,074910979
0,075229732
0,075528566
0,075809163
0,076073028
0,076321513
0,076555831
0,076777076
0,076986238
0,077184211
0,077371807
0,077549764
32

B2
0,138975347
0,138978804
0,13898168
0,138984089
0,138986117
0,138987835
0,138989297
0,138990548
0,138991623
0,13899255
0,138993354
0,138994053
0,138994663
0,138995197
0,138995667
0,138996081
0,138996448
0,138996773
0,138997061
0,138997319
0,138997549
0,138997755
0,13899794
0,138998107

1,017979658
1,017706825
1,017421499
1,017128475
1,016831434
1,0165332
1,016235928
1,015941261
1,015650434
1,01536437
1,015083744
1,014809037
1,014540577
1,014278576
1,014023147
1,013774335
1,013532126
1,013296462
1,013067251
1,012844378
1,012627707
1,012417088
1,012212363
1,012013367

513
523
533
543
553
563
573
583
593
603
613
623
633
643
653
663
673
683
693
703
713
723
733
743
753
763
773

3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808
3,808

15,456
15,758
16,059
16,360
16,662
16,963
17,264
17,566
17,867
18,168
18,469
18,771
19,072
19,373
19,675
19,976
20,277
20,578
20,880
21,181
21,482
21,784
22,085
22,386
22,688
22,989
23,290

-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216

0,077718756
0,077879394
0,078032241
0,07817781
0,078316572
0,07844896
0,078575373
0,078696177
0,078811712
0,07892229
0,079028201
0,079129713
0,079227075
0,07932052
0,07941026
0,079496498
0,079579418
0,079659197
0,079735995
0,079809964
0,079881248
0,079949979
0,080016283
0,080080275
0,080142067
0,080201761
0,080259455

0,138998257
0,138998393
0,138998516
0,138998627
0,138998729
0,138998821
0,138998905
0,138998982
0,138999052
0,138999116
0,138999175
0,138999229
0,138999279
0,138999325
0,138999367
0,138999407
0,138999443
0,138999476
0,138999507
0,138999536
0,138999563
0,138999588
0,138999611
0,138999632
0,138999652
0,138999671
0,138999689

1,011819932
1,011631888
1,011449065
1,011271295
1,011098411
1,01093025
1,010766653
1,010607466
1,010452536
1,010301719
1,010154872
1,010011858
1,009872545
1,009736807
1,00960452
1,009475566
1,009349831
1,009227206
1,009107586
1,00899087
1,008876961
1,008765765
1,008657192
1,008551157
1,008447576
1,008346371
1,008247464

APPENDX 3. Fugacty Calculatons For Methanol at 50 bar Pressure

T

Pr

Tr

273
283
293
303
313
323
333
343
353
363

0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618

0,533
0,552
0,572
0,591
0,611
0,630
0,650
0,669
0,689
0,708

w
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564

B0
-1,073373095
-1,00869147
-0,949690118
-0,895700946
-0,846153086
-0,800556199
-0,758487057
-0,719578686
-0,683511518
-0,650006142
33

B2
-2,286020739
-1,945949525
-1,662999098
-1,426090787
-1,226564937
-1,057597196
-0,913768287
-0,790743756
-0,685033394
-0,593808924

0,064464325
0,094641159
0,129916212
0,169082491
0,210863921
0,25406436
0,297651875
0,340792212
0,382848628
0,423362784

373
383
393
403
413
423
433
443
453
463
473
483
493
503
513
523
533
543
553
563
573
583
593
603
613
623
633
643
653
663
673
683
693
703
713
723
733
743
753
763
773

0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618
0,618

0,728
0,747
0,767
0,786
0,806
0,825
0,845
0,864
0,884
0,903
0,923
0,942
0,962
0,981
1,001
1,020
1,040
1,059
1,079
1,098
1,118
1,137
1,157
1,176
1,196
1,215
1,235
1,254
1,274
1,293
1,313
1,332
1,352
1,371
1,391
1,410
1,430
1,449
1,469
1,488
1,508

0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564

-0,618817322
-0,58972904
-0,562550368
-0,537112006
-0,513263371
-0,490870138
-0,46981215
-0,449981644
-0,431281724
-0,413625057
-0,396932752
-0,381133381
-0,366162141
-0,351960118
-0,338473651
-0,325653772
-0,313455712
-0,301838476
-0,29076446
-0,280199115
-0,270110652
-0,260469776
-0,251249452
-0,242424701
-0,233972405
-0,225871146
-0,218101055
-0,210643679
-0,203481857
-0,196599615
-0,189982063
-0,183615312
-0,177486391
-0,171583172
-0,165894309
-0,160409172
-0,155117796
-0,150010833
-0,1450795
-0,140315544
-0,1357112

34

-0,514764721
-0,446010585
-0,385988588
-0,333408149
-0,287195007
-0,246450871
-0,210421328
-0,17847017
-0,150058754
-0,124729318
-0,102091436
-0,08181096
-0,063600967
-0,047214304
-0,032437427
-0,019085298
-0,006997123
0,003967195
0,013930036
0,022998577
0,031266899
0,038817782
0,045724226
0,052050745
0,057854474
0,06318611
0,068090734
0,072608499
0,076775242
0,080623002
0,08418047
0,087473384
0,090524869
0,093355736
0,09598474
0,098428812
0,100703253
0,102821916
0,104797356
0,106640968
0,108363108

0,462027248
0,498656228
0,533158241
0,565512417
0,595748934
0,623933433
0,650154951
0,674516789
0,697129769
0,718107348
0,737562188
0,755603807
0,772337052
0,787861169
0,802269309
0,815648337
0,828078858
0,839635389
0,85038662
0,860395737
0,869720767
0,878414946
0,88652707
0,894101853
0,901180251
0,907799787
0,913994835
0,9197969
0,925234864
0,930335221
0,935122287
0,939618389
0,943844048
0,947818133
0,95155801
0,955079672
0,958397858
0,961526166
0,964477148
0,967262401
0,969892646

APPENDX 4. Fugacty Calculatons For Carbon Monoxde at 90 bar Pressure

T

Pr

Tr

B0

273
283
293
303
313
323
333
343
353
363
373
383
393
403
413
423
433
443
453
463
473
483
493
503
513
523
533
543
553
563
573
583
593
603
613
623
633
643

2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572

2,054
2,129
2,205
2,280
2,355
2,430
2,506
2,581
2,656
2,731
2,807
2,882
2,957
3,032
3,108
3,183
3,258
3,333
3,409
3,484
3,559
3,634
3,710
3,785
3,860
3,935
4,011
4,086
4,161
4,236
4,312
4,387
4,462
4,537
4,612
4,688
4,763
4,838

0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048

-0,050380452
-0,042919829
-0,036114389
-0,029887074
-0,024172036
-0,018912718
-0,014060304
-0,009572465
-0,005412341
-0,001547704
0,002049732
0,005404885
0,008539776
0,011473933
0,014224725
0,016807645
0,019236553
0,021523879
0,023680798
0,025717385
0,027642739
0,029465098
0,031191938
0,032830053
0,034385633
0,035864326
0,037271297
0,038611273
0,039888592
0,041107239
0,04227088
0,043382895
0,044446402
0,045464283
0,046439202
0,047373632
0,048269864
0,049130026

0,130635302
0,13180832
0,13278431
0,133601485
0,134289715
0,134872541
0,135368654
0,135793007
0,136157637
0,1364723
0,136744949
0,136982105
0,137189141
0,137370508
0,137529913
0,137670453
0,13779473
0,137904941
0,138002941
0,13809031
0,138168396
0,13823835
0,138301162
0,138357685
0,138408656
0,138454712
0,138496408
0,138534227
0,138568592
0,138599873
0,138628393
0,138654438
0,138678261
0,138700083
0,138720102
0,138738493
0,138755411
0,138770994

653

2,572

4,913

0,048

0,049956098

0,138785366

35

B2
0,946268096
0,956763988
0,965898949
0,973865966
0,980827943
0,986922706
0,992267165
0,996960746
1,001088239
1,004722155
1,007924674
1,010749264
1,013242023
1,015442804
1,017386149
1,019102068
1,020616704
1,021952877
1,02313056
1,024167267
1,02507839
1,025877485
1,026576513
1,02718605
1,027715461
1,028173059
1,028566228
1,028901544
1,029184871
1,029421444
1,029615944
1,029772564
1,029895064
1,029986818
1,030050862
1,030089924
1,030106467
1,030102708
1,030080651

663
673
683
693
703
713
723
733
743
753
763
773

2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572
2,572

4,989
5,064
5,139
5,214
5,290
5,365
5,440
5,515
5,591
5,666
5,741
5,816

0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048

0,050749922
0,051513215
0,05224758
0,052954513
0,053635413
0,054291588
0,054924264
0,055534592
0,056123648
0,056692447
0,057241939
0,057773022

0,138798638
0,138810909
0,138822268
0,138832793
0,138842558
0,138851626
0,138860057
0,138867902
0,13887521
0,138882024
0,138888383
0,138894323

1,030042106
1,029988711
1,029921949
1,029843163
1,029753571
1,029654279
1,029546289
1,029430514
1,029307784
1,029178852
1,029044405
1,028905068

APPENDX 5. Fugacty Calculatons For Hydrogen at 90 bar Pressure

T

Pr

Tr

273
283
293
303
313
323
333
343
353
363
373
383
393
403
413
423
433
443
453
463
473
483
493
503

6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855

8,225
8,527
8,828
9,129
9,431
9,732
10,033
10,334
10,636
10,937
11,238
11,540
11,841
12,142
12,444
12,745
13,046
13,347
13,649
13,950
14,251
14,553
14,854
15,155
15,456

w
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216

B0
0,068510152
0,069320641
0,070059953
0,07073646
0,071357316
0,071928664
0,072455809
0,072943347
0,073395284
0,073815121
0,07420593
0,074570418
0,074910979
0,075229732
0,075528566
0,075809163
0,076073028
0,076321513
0,076555831
0,076777076
0,076986238
0,077184211
0,077371807
0,077549764
0,077718756
36

B2
0,138975347
0,138978804
0,13898168
0,138984089
0,138986117
0,138987835
0,138989297
0,138990548
0,138991623
0,13899255
0,138993354
0,138994053
0,138994663
0,138995197
0,138995667
0,138996081
0,138996448
0,138996773
0,138997061
0,138997319
0,138997549
0,138997755
0,13899794
0,138998107
0,138998257

1,032598759
1,032100617
1,031579779
1,031045011
1,030503038
1,029959015
1,029416875
1,028879609
1,028349468
1,027828128
1,027316812
1,026816391
1,026327455
1,02585038
1,02538537
1,024932495
1,024491723
1,024062943
1,023645982
1,023240621
1,022846609
1,022463667
1,022091503
1,021729812
1,021378282

513
523
533
543
553
563
573
583
593
603
613
623
633
643
653
663
673
683
693
703
713
723
733
743
753
763
773

6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855
6,855

15,758
16,059
16,360
16,662
16,963
17,264
17,566
17,867
18,168
18,469
18,771
19,072
19,373
19,675
19,976
20,277
20,578
20,880
21,181
21,482
21,784
22,085
22,386
22,688
22,989
23,290

-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216

0,077879394
0,078032241
0,07817781
0,078316572
0,07844896
0,078575373
0,078696177
0,078811712
0,07892229
0,079028201
0,079129713
0,079227075
0,07932052
0,07941026
0,079496498
0,079579418
0,079659197
0,079735995
0,079809964
0,079881248
0,079949979
0,080016283
0,080080275
0,080142067
0,080201761
0,080259455

0,138998393
0,138998516
0,138998627
0,138998729
0,138998821
0,138998905
0,138998982
0,138999052
0,138999116
0,138999175
0,138999229
0,138999279
0,138999325
0,138999367
0,138999407
0,138999443
0,138999476
0,138999507
0,138999536
0,138999563
0,138999588
0,138999611
0,138999632
0,138999652
0,138999671
0,138999689

1,021036601
1,020704455
1,020381534
1,020067533
1,019762153
1,0194651
1,019176089
1,018894844
1,018621097
1,018354587
1,018095065
1,017842287
1,017596022
1,017356043
1,017122135
1,016894089
1,016671707
1,016454794
1,016243167
1,016036647
1,015835065
1,015638256
1,015446063
1,015258334
1,015074925
1,014895696

APPENDX 6. Fugacty Calculatons For Methanol at 90 bar Pressure

T

Pr

Tr

B0

273
283
293
303
313
323
333
343
353
363

1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112

0,533
0,552
0,572
0,591
0,611
0,630
0,650
0,669
0,689
0,708

0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564

-1,073373095
-1,00869147
-0,949690118
-0,895700946
-0,846153086
-0,800556199
-0,758487057
-0,719578686
-0,683511518
-0,650006142
37

B2
-2,286020739
-1,945949525
-1,662999098
-1,426090787
-1,226564937
-1,057597196
-0,913768287
-0,790743756
-0,685033394
-0,593808924

0,007203535
0,014374966
0,025419541
0,040839194
0,06076334
0,084973576
0,112983796
0,144139824
0,177712778
0,212972943

373
383
393
403
413
423
433
443
453
463
473
483
493
503
513
523
533
543
553
563
573
583
593
603
613
623
633
643
653
663
673
683
693
703
713
723
733
743
753
763
773

1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112
1,112

0,728
0,747
0,767
0,786
0,806
0,825
0,845
0,864
0,884
0,903
0,923
0,942
0,962
0,981
1,001
1,020
1,040
1,059
1,079
1,098
1,118
1,137
1,157
1,176
1,196
1,215
1,235
1,254
1,274
1,293
1,313
1,332
1,352
1,371
1,391
1,410
1,430
1,449
1,469
1,488
1,508

0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564
0,564

-0,618817322
-0,58972904
-0,562550368
-0,537112006
-0,513263371
-0,490870138
-0,46981215
-0,449981644
-0,431281724
-0,413625057
-0,396932752
-0,381133381
-0,366162141
-0,351960118
-0,338473651
-0,325653772
-0,313455712
-0,301838476
-0,29076446
-0,280199115
-0,270110652
-0,260469776
-0,251249452
-0,242424701
-0,233972405
-0,225871146
-0,218101055
-0,210643679
-0,203481857
-0,196599615
-0,189982063
-0,183615312
-0,177486391
-0,171583172
-0,165894309
-0,160409172
-0,155117796
-0,150010833
-0,1450795
-0,140315544
-0,1357112

38

-0,514764721
-0,446010585
-0,385988588
-0,333408149
-0,287195007
-0,246450871
-0,210421328
-0,17847017
-0,150058754
-0,124729318
-0,102091436
-0,08181096
-0,063600967
-0,047214304
-0,032437427
-0,019085298
-0,006997123
0,003967195
0,013930036
0,022998577
0,031266899
0,038817782
0,045724226
0,052050745
0,057854474
0,06318611
0,068090734
0,072608499
0,076775242
0,080623002
0,08418047
0,087473384
0,090524869
0,093355736
0,09598474
0,098428812
0,100703253
0,102821916
0,104797356
0,106640968
0,108363108

0,249240552
0,285915594
0,322491164
0,358555256
0,393785285
0,427938599
0,460841305
0,492376888
0,522475519
0,551104489
0,578259966
0,603960062
0,62823913
0,65114315
0,672726058
0,693046858
0,712167388
0,730150615
0,747059356
0,762955338
0,777898527
0,791946657
0,805154935
0,817575851
0,829259101
0,840251562
0,850597328
0,860337781
0,869511688
0,87815531
0,88630253
0,893984977
0,901232159
0,90807159
0,914528918
0,920628048
0,926391254
0,931839298
0,936991526
0,941865974
0,946479458

APPENDX 7. Fugacty Calculatons For Carbon Monoxde at 120 bar Pressure

T
273
283
293
303
313
323
333
343
353
363
373
383
393
403
413
423
433
443
453
463
473
483
493
503
513
523
533
543
553
563
573
583
593
603
613
623
633
643
653

Pr

Tr

B0

3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430

2,054
2,129
2,205
2,280
2,355
2,430
2,506
2,581
2,656
2,731
2,807
2,882
2,957
3,032
3,108
3,183
3,258
3,333
3,409
3,484
3,559
3,634
3,710
3,785
3,860
3,935
4,011
4,086
4,161
4,236
4,312
4,387
4,462
4,537
4,612
4,688
4,763
4,838
4,913
4,989

0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048

-0,050380452
-0,042919829
-0,036114389
-0,029887074
-0,024172036
-0,018912718
-0,014060304
-0,009572465
-0,005412341
-0,001547704
0,002049732
0,005404885
0,008539776
0,011473933
0,014224725
0,016807645
0,019236553
0,021523879
0,023680798
0,025717385
0,027642739
0,029465098
0,031191938
0,032830053
0,034385633
0,035864326
0,037271297
0,038611273
0,039888592
0,041107239
0,04227088
0,043382895
0,044446402
0,045464283
0,046439202
0,047373632
0,048269864
0,049130026
0,049956098
0,050749922
39

B2
0,130635302
0,13180832
0,13278431
0,133601485
0,134289715
0,134872541
0,135368654
0,135793007
0,136157637
0,1364723
0,136744949
0,136982105
0,137189141
0,137370508
0,137529913
0,137670453
0,13779473
0,137904941
0,138002941
0,13809031
0,138168396
0,13823835
0,138301162
0,138357685
0,138408656
0,138454712
0,138496408
0,138534227
0,138568592
0,138599873
0,138628393
0,138654438
0,138678261
0,138700083
0,138720102
0,138738493
0,138755411
0,138770994
0,138785366
0,138798638

0,928993581
0,94276066
0,954783751
0,965300662
0,9745144
0,98259837
0,989700873
0,995948929
1,001451531
1,006302386
1,010582231
1,014360779
1,017698353
1,020647275
1,023253019
1,025555199
1,0275884
1,029382875
1,030965147
1,032358513
1,033583479
1,034658128
1,035598432
1,036418531
1,037130957
1,037746842
1,038276086
1,038727508
1,039108976
1,039427522
1,039689436
1,039900352
1,040065327
1,0401889
1,040275154
1,040327765
1,040350045
1,040344983
1,040315275
1,040263362

663
673
683
693
703
713
723
733
743
753
763
773

3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430
3,430

5,064
5,139
5,214
5,290
5,365
5,440
5,515
5,591
5,666
5,741
5,816

0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048
0,048

0,051513215
0,05224758
0,052954513
0,053635413
0,054291588
0,054924264
0,055534592
0,056123648
0,056692447
0,057241939
0,057773022

0,138810909
0,138822268
0,138832793
0,138842558
0,138851626
0,138860057
0,138867902
0,13887521
0,138882024
0,138888383
0,138894323

1,040191449
1,040101535
1,039995429
1,039874774
1,039741059
1,039595636
1,039439736
1,039274475
1,039100871
1,038919849
1,038732251

APPENDX 8. Fugacty Calculatons For Hydrogen at 120 bar Pressure

T
273
283
293
303
313
323
333
343
353
363
373
383
393
403
413
423
433
443
453
463
473
483
493
503
513

Pr

Tr

9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139

8,225
8,527
8,828
9,129
9,431
9,732
10,033
10,334
10,636
10,937
11,238
11,540
11,841
12,142
12,444
12,745
13,046
13,347
13,649
13,950
14,251
14,553
14,854
15,155
15,456

w
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216

B0
0,068510152
0,069320641
0,070059953
0,07073646
0,071357316
0,071928664
0,072455809
0,072943347
0,073395284
0,073815121
0,07420593
0,074570418
0,074910979
0,075229732
0,075528566
0,075809163
0,076073028
0,076321513
0,076555831
0,076777076
0,076986238
0,077184211
0,077371807
0,077549764
0,077718756
40

B2
0,138975347
0,138978804
0,13898168
0,138984089
0,138986117
0,138987835
0,138989297
0,138990548
0,138991623
0,13899255
0,138993354
0,138994053
0,138994663
0,138995197
0,138995667
0,138996081
0,138996448
0,138996773
0,138997061
0,138997319
0,138997549
0,138997755
0,13899794
0,138998107
0,138998257

1,043694591
1,043023392
1,042321727
1,04160142
1,040871535
1,040139016
1,039409162
1,038685996
1,037972544
1,037271055
1,036583169
1,035910051
1,035252488
1,034610976
1,033985783
1,033376996
1,032784566
1,032208335
1,031648064
1,031103453
1,030574158
1,030059801
1,02955998
1,029074283
1,028602287

523
533
543
553
563
573
583
593
603
613
623
633
643
653
663
673
683
693
703
713
723
733
743
753
763
773

9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139
9,139

15,758
16,059
16,360
16,662
16,963
17,264
17,566
17,867
18,168
18,469
18,771
19,072
19,373
19,675
19,976
20,277
20,578
20,880
21,181
21,482
21,784
22,085
22,386
22,688
22,989
23,290

-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216
-0,216

0,077879394
0,078032241
0,07817781
0,078316572
0,07844896
0,078575373
0,078696177
0,078811712
0,07892229
0,079028201
0,079129713
0,079227075
0,07932052
0,07941026
0,079496498
0,079579418
0,079659197
0,079735995
0,079809964
0,079881248
0,079949979
0,080016283
0,080080275
0,080142067
0,080201761
0,080259455

0,138998393
0,138998516
0,138998627
0,138998729
0,138998821
0,138998905
0,138998982
0,138999052
0,138999116
0,138999175
0,138999229
0,138999279
0,138999325
0,138999367
0,138999407
0,138999443
0,138999476
0,138999507
0,138999536
0,138999563
0,138999588
0,138999611
0,138999632
0,138999652
0,138999671
0,138999689

1,028143565
1,027697694
1,027264253
1,026842829
1,026433016
1,026034417
1,025646647
1,025269332
1,024902109
1,024544626
1,024196546
1,02385754
1,023527295
1,023205506
1,022891882
1,022586142
1,022288015
1,021997242
1,021713575
1,021436773
1,021166607
1,020902855
1,020645305
1,020393754
1,020148006
1,019907873

APPENDX 9. Fugacty Calculatons For Methanol at 120 bar Pressure

T

B0

B2

Pr

Tr

273

1,482

0,533

0,564

-1,073373095

-2,286020739

0,001395336

283

1,482

0,552

0,564

-1,00869147

-1,945949525

0,003504131

293

1,482

0,572

0,564

-0,949690118

-1,662999098

0,007490539

303

1,482

0,591

0,564

-0,895700946

-1,426090787

0,014090797

313

1,482

0,611

0,564

-0,846153086

-1,226564937

0,023928644

323

1,482

0,630

0,564

-0,800556199

-1,057597196

0,03741282

333

1,482

0,650

0,564

-0,758487057

-0,913768287

0,054691851

343

1,482

0,669

0,564

-0,719578686

-0,790743756

0,075662899

353

1,482

0,689

0,564

-0,683511518

-0,685033394

0,100017198

41

363

1,482

0,708

0,564

-0,650006142

-0,593808924

0,127302009

373

1,482

0,728

0,564

-0,618817322

-0,514764721

0,15698326

383

1,482

0,747

0,564

-0,58972904

-0,446010585

0,18849932

393

1,482

0,767

0,564

-0,562550368

-0,385988588

0,221301868

403

1,482

0,786

0,564

-0,537112006

-0,333408149

0,254883571

413

1,482

0,806

0,564

-0,513263371

-0,287195007

0,288794307

423

1,482

0,825

0,564

-0,490870138

-0,246450871

0,322648469

433

1,482

0,845

0,564

-0,46981215

-0,210421328

0,356125909

443

1,482

0,864

0,564

-0,449981644

-0,17847017

0,388968728

453

1,482

0,884

0,564

-0,431281724

-0,150058754

0,420975628

463

1,482

0,903

0,564

-0,413625057

-0,124729318

0,451995107

473

1,482

0,923

0,564

-0,396932752

-0,102091436

0,481918333

483

1,482

0,942

0,564

-0,381133381

-0,08181096

0,510672242

493

1,482

0,962

0,564

-0,366162141

-0,063600967

0,538213192

503

1,482

0,981

0,564

-0,351960118

-0,047214304

0,564521308

513

1,482

1,001

0,564

-0,338473651

-0,032437427

0,589595574

523

1,482

1,020

0,564

-0,325653772

-0,019085298

0,613449662

533

1,482

1,040

0,564

-0,313455712

-0,006997123

0,636108438

543

1,482

1,059

0,564

-0,301838476

0,003967195

0,657605082

553

1,482

1,079

0,564

-0,29076446

0,013930036

0,677978734

563

1,482

1,098

0,564

-0,280199115

0,022998577

0,697272599

573

1,482

1,118

0,564

-0,270110652

0,031266899

0,715532436

583

1,482

1,137

0,564

-0,260469776

0,038817782

0,732805366

593

1,482

1,157

0,564

-0,251249452

0,045724226

0,749138941

603

1,482

1,176

0,564

-0,242424701

0,052050745

0,764580437

613

1,482

1,196

0,564

-0,233972405

0,057854474

0,779176315

623

1,482

1,215

0,564

-0,225871146

0,06318611

0,792971824

633

1,482

1,235

0,564

-0,218101055

0,068090734

0,806010718

643

1,482

1,254

0,564

-0,210643679

0,072608499

0,818335064

653

1,482

1,274

0,564

-0,203481857

0,076775242

0,829985116

663

1,482

1,293

0,564

-0,196599615

0,080623002

0,840999245

673

1,482

1,313

0,564

-0,189982063

0,08418047

0,851413916

683

1,482

1,332

0,564

-0,183615312

0,087473384

0,861263693

693

1,482

1,352

0,564

-0,177486391

0,090524869

0,870581265

703

1,482

1,371

0,564

-0,171583172

0,093355736

0,879397498

713

1,482

1,391

0,564

-0,165894309

0,09598474

0,887741494

42

723

1,482

1,410

0,564

-0,160409172

0,098428812

0,89564066

733

1,482

1,430

0,564

-0,155117796

0,100703253

0,903120782

743

1,482

1,449

0,564

-0,150010833

0,102821916

0,910206102

753

1,482

1,469

0,564

-0,1450795

0,104797356

0,916919402

763

1,482

1,488

0,564

-0,140315544

0,106640968

0,923282076

773

1,482

1,508

0,564

-0,1357112

0,108363108

0,929314211

APPENDIX 10. XAe Calculations

T
273
283
293
303
313
323
333
343
353
363
373
383
393
403
413
423
433
443
453
463
473
483
493
503
513
523
533
543
553

lnKT
13,20883571
11,81449494
10,50896374
9,283762374
8,131472855
7,04557676
6,020321993
5,05061262
4,131917249
3,260192387
2,43181801
1,643543111
0,892439475
0,175862264
-0,508583745
-1,16307318
-1,789585123
-2,389924802
-2,965742454
-3,51854976
-4,049734237
-4,560571846
-5,052238107
-5,525817883
-5,982314056
-6,422655203
-6,847702434
-7,258255474
-7,655058104

KT

XAe (50 bar)

545160,6017
135197,9037
36642,48863
10761,84593
3399,803297
1147,770633
411,7111423
156,1180763
62,29724785
26,05454922
11,37955142
5,173467244
2,441077342
1,192273829
0,601346636
0,31252426
0,167029452
0,091636574
0,051522202
0,029642393
0,017427005
0,010456078
0,006395005
0,00398261
0,002522981
0,001624338
0,001061893
0,000704336
0,000473642

1,00000
1,00000
1,00000
1,00000
1,00000
0,99999
0,99998
0,99995
0,99985
0,99960
0,99902
0,99773
0,99514
0,99041
0,98268
0,97125
0,95561
0,93531
0,90984
0,87863
0,84101
0,79636
0,74417
0,68430
0,61720
0,54417
0,46764
0,39093
0,31774
43

XAe (90 bar)

1,00000
1,00000
1,00000
1,00000
1,00000
1,00000
1,00000
0,99999
0,99998
0,99994
0,99984
0,99959
0,99904
0,99788
0,99560
0,99153
0,98496
0,97528
0,96207
0,94497
0,92363
0,89764
0,86653
0,82981
0,78703
0,73788
0,68233
0,62081
0,55434

XAe (120 bar)

1,00000
1,00000
1,00000
1,00000
1,00000
1,00000
1,00000
1,00000
0,99999
0,99998
0,99994
0,99985
0,99963
0,99915
0,99813
0,99614
0,99260
0,98684
0,97828
0,96651
0,95121
0,93208
0,90878
0,88093
0,84811
0,80990
0,76596
0,71614
0,66057

563
573
583
593
603
613
623
633
643
653
663
673
683
693
703
713
723
733
743
753
763
773

-8,03880302
-8,410136204
-8,769660835
-9,11794083
-9,455504016
-9,782845019
-10,10042786
-10,40868831
-10,70803607
-10,99885667
-11,28151328
-11,55634832
-11,82368496
-12,08382844
-12,33706734
-12,58367472
-12,82390915
-13,05801566
-13,28622668
-13,50876279
-13,72583353
-13,93763804

0,000322695
0,0002226
0,000155376
0,00010968
7,82576E-05
5,64111E-05
4,1062E-05
3,01692E-05
2,23645E-05
1,67208E-05
1,26038E-05
9,57506E-06
7,3289E-06
5,65015E-06
4,38611E-06
3,42752E-06
2,69555E-06
2,13293E-06
1,69772E-06
1,359E-06
1,09382E-06
8,85036E-07

0,25181
0,19492
0,14826
0,11167
0,08303
0,06171
0,04567
0,03407
0,02549
0,01946
0,01458
0,01102
0,00839
0,00644
0,00497
0,00387
0,00303
0,00239
0,00190
0,00151
0,00121
0,00098

44

0,48473
0,41441
0,34627
0,28302
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