Mô hình hóa, mô phỏng và tối ưu hóa

các quá trình hóa học

Modeling, simulation and optimization for chemical process

Instructor: Hoang Ngoc Ha

Email: [email protected]
Bộ môn QT&TB
Curriculum/syllabi
CuuDuongThanCong.com Seminar group
 Outline
• General introduction
– Structure and operation of chemical
engineering systems
– What is a chemical process?
– Motivation examples
• Part I: Process modeling
• Part II: Computer simulation
• Part III: Optimization of chemical
processes
CuuDuongThanCong.com
 General introduction
• Structure of chemical engineering system

(Copyright © by Prof. Paul Sides at CMU, USA)

CuuDuongThanCong.com
 General introduction
• Conservation laws:
– Give some balance equations such as mass balance (or the molar
number by species), energy balance and momentum equation of the
system under consideration
• Equilibrium thermodynamics
– The extensive variables/intensive variables
– The laws of thermodynamics
• Reaction engineering
– Reaction mechanism
– The rate of a chemical reaction
• Transport processes
– How materials and energy move from one position to another (heat
conductivity, diffusion and convection…)
• Biological processes
– Transform material from one form to another (enzyme process) or
remove pollutants (environmental engineering)

CuuDuongThanCong.com
 General introduction
• References (complements) :

1. Sandler S. I. (1999). Chemical and Engineering

Thermodynamics. Wiley and Sons, 3rd edition.
2. H.B. Callen. Thermodynamics and an introduction to
thermostatics. JohnWiley & Sons Inc, 2nd ed. New York,
1985.
3. De Groot S. R. and P. Mazur (1962) Non-equilibrium
thermodynamics. Dover Pub. Inc., Amsterdam.
4. Vũ Bá Minh. (tập 4) Kỹ thuật phản ứng. NXB ĐHQG Tp. Hồ
Chí Minh, 2004
5. Nguyễn Bin, (tập 5) Các quá trình hóa học. NXB Khoa học
và Kỹ thuật, 2008

CuuDuongThanCong.com
 General introduction
• Conservation laws:
– Give some balance equations such as mass balance (or the molar
number by species), energy balance and momentum equation of the
system under consideration
• Equilibrium thermodynamics
– The extensive variables/intensive variables
– The laws of thermodynamics
• Reaction engineering
– Reaction mechanism
– The rate of a chemical reaction
• Transport processes
– How materials and energy move from one position to another (heat
conductivity, diffusion and convection…)
• Biological processes
– Transform material from one form to another (enzyme process) or
remove pollutants (environmental engineering)

CuuDuongThanCong.com
General introduction

„ Operation of a chemical engineering plant

(Σ)
Dynamical behavior

CuuDuongThanCong.com
Copyright © by T. Marlin
General introduction

„ Oil and gas production plant

CuuDuongThanCong.com
General introduction

„ The system may be

∑
‰ Isolated: There is no transfer of
mass or energy with the
environment

‰ Closed: There may be transfer of

mechanical energy and heat ∑
Open: There is mass transfer with
∑
‰
the environment

CuuDuongThanCong.com
General introduction

Question: determinate physical volume of

the following systems?

Gas

.
QJ
υ A A → υB B A, B

CuuDuongThanCong.com
General introduction
„ What is a chemical process?
‰ Process: A set of actions performed intentionally in order to reach
some result (Longmans Dictionary of Contemporary English)
‰ Processes that involve energy conversion, reaction, separation
and transport are called chemical processes (Prof. Erik Ydstie at
CMU, USA)
‰ Definition: Chemical processes are a special subclass of
processes since their behavior is constrained by a range of
laws and principles which may not apply in other
circumstances (mechanical/electrical systems…)
‰ Properties:

„ Highly nonlinear
„ Complex network
„ May be distributed

CuuDuongThanCong.com
General introduction

„ Chemical processes

‰ Thermal conductivity process

‰ Transport (reaction) process

‰ …

CuuDuongThanCong.com
General introduction

„ Why we need informations about dynamical

behavior?
Process modeling,
computer
‰ Research and development simulation and optimization
Process design
‰

‰ Process control (Σ)

‰ Plant operation
Ordinary Differential Equations
‰ … (ODEs) or Partial Differential
Equations (PDEs) or
Differential and Algebraic
Equations (DAEs)
CuuDuongThanCong.com
Motivation examples

„ Example 1: Gravity-flow tank

F0

The higher the flow rate F̄ , the higher h̄ will be

h

F F

F0 = F0 (t), h = h(t) and F = F (t) Overshoot

F̄0 , h̄ and F̄ : steadystate values

How to understand dynamical behavior to design the

system avoiding « Overshoot »?
CuuDuongThanCong.com
 Motivation examples

„ Example 2: Heat exchanger

Temperature controller

Final control element

Temperature transmitter

Thermocouple

CuuDuongThanCong.com
Motivation examples

„ Example 3: Typical chemical plant and control system

¾Two liquids feeds are pumped into
a reactor
¾They react to form products
¾Reactor effluent is pumped through
a preheater into a distillation

To specify the various pieces

of equipment:
•Fluid mechanics
•Heat transfer
•Chemical kinetics
•Thermodynamics and mass
transfer

CuuDuongThanCong.com
Motivation examples

„ Example 4: Optimization of a silicon process

The silicon reactor

CuuDuongThanCong.com
Motivation examples

„ Example 4: Optimization of a silicon process

CuuDuongThanCong.com
Outline

„ General introduction
‰ Structure and operation of chemical engineering
systems
‰ What is a chemical process?
‰ Motivation examples
„ Part I: Process modeling
„ Part II: Computer simulation
„ Part III: Optimization of chemical processes

CuuDuongThanCong.com
Process modeling

„ Introduction

„ Fundamental laws
‰ Continuity equations

‰ Energy equation

‰ Equations of motion

CuuDuongThanCong.com
Introduction

„ Uses of mathematical models

‰ Can be useful in all phases of chemical engineering, from
research and development to plant operations, and even in
business and economic studies
„ Research and development:
‰ Determinating chemical kinetic mechanisms and parameters from
lab. or pilot-plant reaction data
‰ Exploring the effects of different operating conditions
‰ Adding in scale-up calculations…
„ Design
‰ Exploring the sizing and arrangement of processing equipment
‰ Studying the interactions of various parts…
„ Plant operation
‰ Cheaper, safer and faster
‰ Troubleshooting and processing problems…

CuuDuongThanCong.com
Introduction

„ Scope of course
‰ A deterministic system is a system in which no
randomness is involved in the evolution of states
of the system
‰ A stochastic system is non-deterministic system

Random effects such as noise…

CuuDuongThanCong.com
Introduction

„ Principles of formulation
‰ Basis
„ Fundamental physical and chemical laws such as laws
of conservation of mass, energy and momentum
‰ Assumptions
„ Impose limitations « reasonable » on the model
‰ Mathematical consistency of model
„ Number of variables equals the number of equations
(degrees of freedom)
„ Units of all terms in all equations are consistent

CuuDuongThanCong.com
Introduction

‰ Solution of the model equations

„ Initial and/or boundary conditions
„ Available numerical solution techniques and tools
„ Solutions are physically acceptable…?

‰ Verification
„ The mathematical model is proving that the model
describes the “real-world” situation
‰ Real challenge

CuuDuongThanCong.com
Fundamental laws

„ Continuity equations
‰ Total continuity equations (total mass balance)

‰ Component continuity equations (component balance)

EXERCISE ?
CuuDuongThanCong.com
Fundamental laws

„ Energy balance

EXERCISE ?
CuuDuongThanCong.com
Fundamental laws

„ Equations of motion
³ ´
−
→ d M→
−
v
F = dt

−
→ −
→
Where v = velocity, F = total force and M = mass

„ Pushing in the i direction (i=x,y,z)

³ ´
d M vi
Fi = dt

EXERCISE ?
CuuDuongThanCong.com
Fundamental laws

„ Consider a system with n components

‰ Number of equations obtained from the
fundamental laws
„ n balance equations by species ⎫
⎬ Not independent
„ 1 total mass balance equation ⎭
„ 1 energy balance equation
„ 3 equations of motion (if the system is under
movement)

⇒ n + 1 + (3) equations

CuuDuongThanCong.com
Constitutive equations
Transport equations

Reaction kinetics of
(bio)chemical reaction…

k = k(T, C)

CuuDuongThanCong.com
Other equations

„ As we saw, we need equations that tell us how the

physical properties, primarily density and enthalpy,
change with temperature, pressure, and
composition to rewrite alternative mathematical
models
‰ Equations of state

CuuDuongThanCong.com
Other equations (cont.)

„ In some cases, simplification can be made without

sacrificing much overall accuracy

H = Cp T (liquid)
H = Cp T + λv (vapor)
„ Or more complex, Cp is considered as a function of
temperature
RT
H= Tref
Cp (T )dT

CuuDuongThanCong.com
Other equations (cont.)

„ A polynomial in T is used for Cp

Cp (T ) = A1 + A2 T
„ We obtain
h i
2 T
H = A1 T + A2 T2
Tref
A2 2
= A1 (T − T0 ) + 2 (T − T02 )

CuuDuongThanCong.com
Other equations (cont.)

„ If the mixture is composed of components

(which we know the pure-component
enthalpies) then the total enthalpy can be
averaged P N
j=1 xj hj Mj
H= PN
j=1 xj Mj
xj - mole fraction of jth component

Mj - molecular weight of jth component

hj - pure-component enthalpy of jth component (energy per unit mass)

CuuDuongThanCong.com
Other equations (cont.)

„ Liquid densities can be assumed constant in

many systems
„ Vapor densities usually cannot be considered
invariant in many systems and the PVT
relationship is almost always required.
‰ The simplest and most often used case is the
perfect gas law

nM PM
P V = nRT ⇒ ρv = V
= RT

CuuDuongThanCong.com
Examples of mathematical modeling of
chemical process

(Distributed) Transport reaction systems

De Groot S. R. and P. Mazur (1962) Non-equilibrium thermodynamics. Dover Pub. Inc.,
Amsterdam.

CuuDuongThanCong.com
Examples of mathematical modeling of
chemical process
„ Distributed reaction systems (reactor tubular
for example)

(Σ) V, Ω
Inlet material and/or
energetic flux dV
n chemical species
P Outlet material
k νk Sk = 0 and/or energetic flux

CuuDuongThanCong.com
 Examples of mathematical modeling of
chemical process
„ Mass conservation by species

dmk
R R ∂ρk
Total material flux

d
dt
= dt V
ρk dV = V ∂t
dV
R
Jk = vk ρk ν Mk rv dV
V k
R R
− Ω Jk · dΩ = − V div(Jk )dV Gauss theorem
∂ρk
⇒ ∂t
= −div(Jk ) + νk Mk rv
CuuDuongThanCong.com
Examples of mathematical modeling of
chemical process
P P
∂( k ρk )
∂t
= −div( k Jk )
P P
Jk
ρ= k ρk v= k
ρ
∂ρ v = ρ−1
∂t
= −div(vρ)
∂v →
−
∂t
+ v · ∇v = vdiv(v)
Jck = ρk v Dv
Dt
Jdk = ρk (vk − v) ⇒ Jk = Jdk + Jck
CuuDuongThanCong.com
Examples of mathematical modeling of
chemical process
dU
R ∂ρu R
dt
= V ∂t
dV =− Ω
Ju · dΩ
∂ρu
∂t
= −divJu

Ju = ρuv + pv + Jq = ρ (u + pv) v + Jq
| {z }
=h
P c 0
P d
k hk Jk Jq h J
k k k

CuuDuongThanCong.com
Examples of mathematical modeling of
chemical process
„ Seminar:

‰ Nonisothermal CSTR

‰ Batch reactor

‰ pH systems

‰ Distillation column

CuuDuongThanCong.com
Examples of mathematical modeling of
chemical process
„ Seminar:

‰ Nonisothermal CSTR

‰ Batch reactor

‰ pH systems

‰ Distillation column

CuuDuongThanCong.com
Phương trình dòng
„ Sự vận chuyển trong thiết bị phản ứng của
hỗn hợp phản ứng, bao gồm:
‰ Dòng vật liệu (khối lượng/nồng độ)
‰ Dòng nhiệt năng (năng lượng)
‰ Dòng động lượng (xung)
⇒ Được đặc trưng bởi mật độ dòng Γ (lượng/thể tích)
„ Có dòng đối lưu, dòng dẫn, dòng cấp và
dòng phát sinh
‰ Dòng đối lưu hoặc dòng dẫn có thể tồn tại độc lập hoặc
đồng thời nhưng chỉ trong một pha
‰ Sự vân chuyển xảy ra qua lớp biên của hai pha là dòng
cấp
CuuDuongThanCong.com
Phương trình dòng

„ Các quá trình vận chuyển trong thiết bị

‰ Dòng đối lưu
„ Sự thay đổi vị trí trong không gian của mật độ dòng
được gọi là đối lưu (dòng vận chuyển vĩ mô)
„ Mật độ dòng đối lưu được biểu thị
−
→
j c = Γ−
→
v (lượng/thời gian/diện tích)
‰ Dòng dẫn (khuếch tán)
„ Chuyển động phân tử trong lòng pha khí hoặc pha lỏng
là chuyển động vi mô tạo thành dòng dẫn
−
→ −−→
j d = −DgradC (lượng/thời gian/diện tích)

CuuDuongThanCong.com
Phương trình dòng

„ Các quá trình vận chuyển trong thiết bị (tt)

‰ Dòng cấp
„ Sự vận chuyển của đại lượng đặc trưng từ pha này
sang pha khác gọi là sự cấp
„ Các quá trình xảy ra giữa các pha thường được mô tả
bằng các đại lượng quảng tính
−
→
j = ²f ∆Γ (lượng/thời gian/diện tích)

² - hệ số cấp, f - bề mặt riêng (xét trên một đơn vị thể tích)

∆Γ- động lực
CuuDuongThanCong.com
Phương trình dòng
„ Các quá trình vận chuyển trong thiết bị (tt)
‰ Dòng phát sinh
„ Dòng phát sinh vật chất do phản ứng hóa học
Pm
Gj = i=1 νji ri
„ Dòng phát sinh cuả nhiệt năng do phản ứng hóa học

Gi = (−∆Hi )ri
„ Dòng phát sinh của động lượng do chênh lệch áp suất
‰ Được hình thành do sự thay đổi của áp suất trong hệ, tức
là có tác dụng của xung lực
−−→
G = gradP
CuuDuongThanCong.com
Phương trình dòng

„ Xét trường hợp hệ tổng quát (đồng thể hay

dị thể) có phản ứng hóa học

Inlet material and/or

energetic flux dV
n chemical species
P Outlet material
j νij Sj = 0 and/or energetic flux

CuuDuongThanCong.com
Phương trình dòng

‰ Phương trình cân bằng tổng quát có dạng của

phương trình vi phần riêng phần được
Damköhler thiết lập (1936)
∂Γ −
→ −−→
∂t = −div( v Γ) + div(δ gradΓ) − ²f ∆Γ + G

−
→ −
→ Dòng cấp
Dòng
jc jd phát sinh

Γ = ρ Cj −
→
ρCp T ρ v
CuuDuongThanCong.com
 Phương trình dòng
∂Γ −
→ −−→
∂t = −div( v Γ) + div(δ gradΓ) − ²f ∆Γ + G
„ Viết lại các phương trình cân bằng
∂ρ −
→ ? −−→
∂t = −div( v ρ) + div(D gradρ) − β ? f ∆ρ + G
∂Cj →
− −−→
= −div( v C ) + div(D gradC )
∂t j j
−βj f ∆Cj + Gj
∂ρCp T →
− −−→
∂t = −div( v ρCp T ) + div(αT gradρCp T )
?
−α f ∆ρCp T + G
∂ρ→−v →
− →
− −−→ −→
∂t =
−div( v ◦ ρ v ) + div(ν gradρ v )
→
−
−γf ∆(ρ v ) + G CuuDuongThanCong.com
 Phương trình dòng
∂Γ −
→ −−→
∂t = −div( v Γ) + div(δ gradΓ) − ²f ∆Γ + G
„ Example: xem chương 5, tập 5 (sách Các
quá trình, thiết bị TRONG CÔNG NGHỆ
HÓA CHẤT VÀ THỰC PHẨM, Nguyễn Bin)

‰ Mô hình toán cho hệ khuấy lý tưởng

‰ Chuỗi thiết bị khuấy lý tưởng
‰ Thiết bị khuấy gián đoạn
‰ Thiết bị đẩy lý tưởng
‰ Các bài toán thực tế

CuuDuongThanCong.com
Outline

„ General introduction
‰ Structure and operation of chemical engineering
systems
‰ What is a chemical process?
‰ Motivation examples
„ Part I: Process modeling
„ Part II: Computer simulation
„ Part III: Optimization of chemical processes

Ref.: Burden R. L. and Faires J. D. Numerical analysis.

CuuDuongThanCong.com