Applied Thermodinamika

in Industry

1
Background
P T

Published meassurements
data

Thermodynamic
Property
• Activity coefficient
Process
(Wilson, NRTL, simulation
UNIQUAC, UNIFAC)
• EoS: virial, vdW, RK,
SRK, PR, Gen.
Corrr.)

3
 MODEL THERMODINAMIKA
PERSAMAAN
UNIT SIZING
KORELASI ENERGY
CODE OPERATION

• Equation of State & Mixing

rules: 100 models Financial
PHYSICAL
• Activity coefficients: 20 Analysis
PROPERTY
Models
• Vapor pressure: 10 models

Thermodynamic
Knowledge
4
 POHON APLIKASI THERMODINAMIKA

Theoritical
vdW Eos Empirical Eos Activity EoS
2000
Coef. PC-Saft
Wong-Sandler
PSRK 1990 UNIFAC
Saft
UNIQUAC
MathIas
Huron-Vidal
Peng-Robinson MBWR 1975
NRTL
Soave ASOG
Wilson

1950
Redlich-Kwong
BWR

Beatie-Bridgemen
Van Laar Meyer
1900 Margules

Van der Waals

Teori Simulasi Eksperimen

5
Pilihan model thermodinamika (Chen and Mathias, 2002)
Chemical systems Primary choice Secondary choice Problem area
Air Separation Peng-Robinson (PR) Corresponding
Soave Redlich-Kwong States
(SRK)
Gas Processing PR, SRK BWRS
Gas Treating Kent-Eisenberg Data, parameters, models
for mixed amine
Electrolyte NRTL
Petrolium Refining BK10, Chao-Seader, Heavy crude
Grayson –Streed, PR, SRK, characterization
Lee-Kessler-Plocker
Petrochemicals-VLE PR, SRK, PSRK NRTL, UNIQUAC, Data, parameters
UNIFAC
Petrochemicals-LLE NRTL, UNIQUAC Data, parameters, models
for VLLE

Chemicals NRTL, UNIQUAC, PSRK UNIFAC Data, parameters

Electrolytes Electrolyte NRTL, Zemaitis Pitzer Data, parameters,

databank, model
polyelectrolytes
Polymer Polymer NRTL, PC-SAFT Sanchez-Lacombe Data, parameters,
EoS, databanks,models for
polar polymer and block
UNIFAC-FV copolymer

7
Hukum I
Jumlah energi total konstan

-DE(lingkungan)
DE(sistim)
Q＋ W+
DEk, DEp,
DU

DE(sistim) + DE(lingkungan) = 0

(DU + DEk + DU )sistim  Q  W = 0

DU + DEk + DEP = Q + W Formulasi matematis HKI
8
Hukum I
Closed system: tidak ada transfer materi dari sistim
ke lingkungan dan sebaliknya (sistim
tidak bergerak)

Sehingga: DEk = 0
DE p = 0

Hukum I untuk closed system:

DU = Q + W

9
 Open system (Steady state)

2
A2, H2,
U2, V2,
Q
1 Ws z
A1, H1, 2
U1, v1,
z1

•
Kontinuitas : m = v1 A1 1 = v2 A2  2 (3)

1 2
Steady state: DH + Dv + gDz = Q + Ws (4)
2
10
Open system (General)

Q W
system
m

Hukum I:
DE(sistim) + DE(lingkungan) = 0
Tiap unit masa mengandung energi:
1 2
U + u + zg
2
Total energi yang dibawa:
 1 2 
m U + u + zg 
 2 
11
 Open system (General)
Energi dalam pada sistim dapat berubah akibat akumulasi
atau kehilangan:
d (mU )
dt
Sehingga:

d (mU )  1 2   1 2   
=  m j U j + u j + z j g  −  mi U i + ui + zi g  + Q + W
 
dt j  2  i  2 

(influent) (effluent)

12
 Open system (General)
Work: ditimbulkan karena dorongan fluida in dan out
(Wf) dan kerja poros karena (Ws)

W = W f + W s

W f =  PjV j m j −  PiVi m i
j i
influent effluent
d (mU )  1   1 
=  m j U j + u 2j + z j g  −  m i U i + ui2 + zi g  + Q +  PjV j m j −  PiVi m i + W s
dt j  2  i  2  j i

Ingat: H  U + PV

d (mU )  1   1 
=  m j  H j + u 2j + z j g  −  m i  H i + ui2 + zi g  + Q + W s
dt j  2  i  2 
13
Hukum I untuk open system (General)

d (mU )  1 2   1 2 
+  m i  H i + ui + zi g  −  m j  H j + u j + z j g  = Q + W s
dt i  2  j  2 
effluent influent

Pada umumnya:
d (mU )
•Steady state: dt = 0
•Satu inlet and outlet: m i = m j = m

 1 2 
m  DH + Du + gDz  = Q + W s Rate energi
 2 
1 2 Rate energi per
DH + Du + gDz = Q + Ws
2 satuan masa
atau mol
14
 PVT behaviour

Diagram PT Diagram PV

P
P

Padat C
C
Pc

Cair

Triple Uap/Gas
point Cair+Uap Tc
T<Tc T>Tc

Tc VL VV
T V

15
•Equation of State (EoS)

f ( P,V , T ) = 0
•Gas ideal (simplest EoS)
-volume individual = 0
PV = RT - no interaction
valid pada tekanan rendah

•Real gas (gas nyata)

Compressibility factor (Z)

PV = ZRT
Untuk gas ideal, Z = 1

16
Virial EoS
B C D
Z = 1+ + + + .........
V V2 V3
Z = 1 + BP + C P 2 + DP 3 + .........
B C
, 3 : 2-body interaction dan 3-body interaction
V V
Truncated Virial EoS
Aplikasi:
B
Z = 1+ Z = 1 + BP • Untuk fasa gas saja
V
• Interaksi antar molekul
signifikan
Z = 1 + BP
• Truncated Virial EoS untuk
1
tekanan rendah
Z
Nilai B telah ditabelkan
untuk berbagai gas
P 17
Ideal gas EoS

Virial EoS
B C D
Z = 1 + + 2 + 3 + .........
V V V
Jika:
P→0 atau V →

Z =1 atau PV = RT

Asumsi tidak ada interaksi antar molekul

Pendekatan yang memadai untuk gas:
pada tekanan yang sangat rendah dan temperatur
sangat tinggi dimana V besar
18
Cubic Equation of State
- penurunan lebih teoritis
- dapat digunakan untuk property gas dan liquid
(aplikasi untuk VLE)

 P 

 2P 
 = 0;  2  = 0
1. Van der Waals EoS (1873)
 V Tc  V Tc
P

C RT a
P= − 2
V −b V
volume
Cair+Uap Tc
T<Tc T>Tc Intermolecular attraction

VL VV
V Jika b=0 dan a/V2=o
27 R 2Tc2 RT Menjadi pers. Gas ideal
a= ;b = c
64 Pc 8Pc
19
Other Cubic EoS

1873-1923, van der Waals

RT a
(vdW) P= − 2
V −b V
1949, Redlich-Kwong (RK) RT a
P= − 12
V − b T (V + b )V
1972, Soave-Redlich- RT a(T )
Kwong (SRK) P= −
V − b V (V + b )

a(T )
1976, Peng-Robinson
RT
(PR) P= − 2
V − b V + 2bV − b 2
20
Fundamental property relations
dU = TdS − PdV U = energi dalam
dH = TdS + VdP H = enthalpy
S = entropy
dA = − PdV − SdT G = Gibbs energy
A = Helmholtz energy
dG = VdP − SdT
Kriteria dari fungsi eksak
Z = Z ( x, y )  M  2Z Pers. Maxwell
  =
 Z   Z   y  x yx  M   N 
dZ =   dx +   dy   =  
 x  y  y  x  N  2Z  y  x  x  y
  =
dZ = Mdx + Ndy  x  y xy

21
Aplikasi pers. Maxwell

U = U ( S ,V )
 U   U   T   P 
dU =   dS +   dV   = − 
 S V  V  S  V  S  S V
dU = TdS − PdV

Dengan cara yang sama:

 T   V  Data Eksperimen
  =  (variabel terukur langsung P, V, T)
 P  S  S  P
 P   S 
  = 
 T V  V T
Properti Thermodinamika
 V   S  H, S, G dll.
  = − 
 T  P  P T
22
Persamaan umum
Enthalpy: Entropy:

  V   dT  V 
dH = C p dT + V − T    dP dS = Cp −  dP
  T  P  T  T  P

EoS EoS

Gas ideal
EoS gas ideal: PV = RT  V  R
  =
 T  P P

dH = C p dT

dT dP
dS = Cp −R
T P

23
Residual Properties

M  M M
R ig

M = the Residual M is the actual Mig = the ideal gas

Molar gas molar value of properties which
properties which any extensive are at the same
are at the same thermodynamic temperature and
temperature and s property: V, pressure.
pressure. U, H, S, G.
 Residual Properties
 GR  V R
From Eq.(6.43), d    dP (const T )
 RT  RT

GR  GR  PV
R
P dP  GR 
     dP   ( Z  1)  (6.45) for ideal gas    0
RT  RT  P 0 0 RT 0 P  RT  P 0

HR P  Z  dP
Eq.(6.45  6.44);  T     (6.46)
RT 0
 T  P P

S R H R GR
From  
RT RT RT

SR P  Z  dP P dP
So,  T      ( Z  1) (const T )  (6.48)
0 T
R  P P 0 P
 Residual Properties
Applied to H and S ; H  H ig  H R S  S ig  S R
Integration of Eq .( 6.23 )and ( 6.24 );
T T
P
H  H 0   C P dT
ig ig ig
S  S 0   C Pig dT  R ln
ig ig

T0 T0 P0
T

Substitution ; H  H 0   C Pig dT  H R
ig
( 6.50 )
T0

T
P
S  S 0   C Pig dT  R ln
ig
 S R ( 6.51 )
T0 P0
 THERMODYNAMIC PROPERTIES OF FLUIDS

PVT EOS:
P

C
RK
SRK
PR
Cair T PRSV H, S, U, G, A dll.
T T
+U
Dll.
c
>
Vap
L
VV < T
Tc V c

+
Cp Heat duty (Q)
Work (W)
Phase Behavior
etc.

24
 Application Case 1
Gas Flow Meter Compensate
In Industry especially PT.Chandra Asri Petrochemical, gas flow meter such as
orifice or venturi type is shown in “mass flow” unit, with the following equation:

Density set as constant value

“Density Design”

𝐴2
𝐾=
2
𝐴
1 − 𝐴2
1
 Application Case 1
Gas Flow Meter Compensate
In actual gas density does not always remain constant as the gas composition,
pressure, temperature change. As the consequence mass flow reading value will
be not actual, it is it is need to "flow compensate" as calibrate with the following
equation:

Get the following data :

1. Gas Composition Select the Calibrate flow
2. Actual Pressure
appropriate EOS reading with Flow
model to calculate Compensate
3. Actual Temperature
density gas equation
4. Density Design
 Application Case 1
Example Problem
Bleed gas flow meter has density design 9.98 kg/m3. Based on observation,
mass flow reading does not represent actual condition, please find actual
condition using various EOS model to define actual gas density:
Parameter Value Unit
Propylene (C3H6) 80 % mol
Propane (C3H8) 15 % mol
Nitrogen (N2) 5 % mol
Pressure 2 kg/cm2
Temperature 40 ℃

Mass Flow Density Actual Actual Mass Flow

EOS Model
Reading (kg/h) (kg/m3) (kg/h)
Peng Robinson (PR)
Redlich Kwong
SRK
Van Der Waals
 Application Case 1
Improvement Design
To improve gas/vapor mass flow reading accuracy using orifice or venturi type
flow meter, online Pressure and Temperature transmitter are installed on
downstream of flow meter. Pressure and Temperature will be inputted to flow
algorithm
 Application Case 2
Steam Depressurization Process
Commonly, Steam produced by boiler in industry was high pressure superheated
steam (HSS). HSS then de-pressurization and de-superheated to produce High
Pressure Steam, Medium Pressure Steam and Low Pressure Steam in saturation
with the following process:
BFW
HSS
BOILER HS
De-Superheated

PCV
BFW

MSS
MS
De-Superheated
PCV
BFW
LSS
LS
De-Superheated
 Application Case 2
Example Problem
Boiler produced HSS at 42 kg/cm2 G and 270 ℃ with capacity 20 T/H, Process
Area requires 20% HS (42 kg/cm2 G), 40% MS (15 kg/cm2 G) and 40% LS (5
kg/cm2 G), please find MSS and LSS temperature and total BFW requirement

? Kg/h BFW 42 kg/cm2 G

HSS saturated
BOILER HS
42 kg/cm2 G De-Superheated
270 ℃
PCV
15 kg/cm2 G BFW ? Kg/h 15 kg/cm2 G
?℃ saturated
MSS
MS
De-Superheated
PCV
BFW 5 kg/cm2 G
? Kg/h saturated
LSS
LS
5 kg/cm2 G De-Superheated
?℃
 Application Case 3
Pressurized Vessel Control
In Industry, liquid transfer from point A to B can be used Pressurized Vessel
with flow control valve instead of Pump. Pressure of Vessel should be
maintained at certain operating pressure to minimize flow disturbance by supply
pressurized Nitrogen:

N2

P vessel
V vessel

Liquid Additive
 Application Case 3
Problem Example
Liquid Additive Vessel with volume 30 m3, maintained at pressure 30 atm and
35 ℃. Please find required N2 flow to maintain the pressure if liquid additive
flow 5 kg/h ( density 900 kg/m3), volume liquid initial at 20 m3?

N2

P 30 atm
V total 30 m3

Liquid Additive
 Application Case 4
Equalizing Pressure Vessel
In Industry, there is equalizing pressure vessel activity before depressurization
through vent valve, this activity will reduce gas vent to flare or recovery area.
Pressure and temperature final can be simulated

PA > PB
Or
PA < PB

Vessel A Vessel B
 Application Case 4
Problem Example
There are two propylene gas vessels has volume 2.5 m3, at the beginning vessel
A pressure was 16.5 kg/cm2 G and temperature 70 ℃, an vessel B Pressure was
1.5 kg/cm2 G and Temperature 70 ℃, what is the final pressure and temperature
of both vessels?

Vessel A Vessel B
2.5 m3 2.5 m3

PAo = 16.5 PBo = 16.5

T=70℃ T=70℃