Chemical Reactors

Vasile Lavric, Professor

Chemical Engineering
Department

June 5, 2008 FILS – Chemical Reactors 1

Preparatory Notions Revisited
 Chemical Reactors
BIBLIOGRAPHY

1. Octave Levenspiel, Chemical Reaction Engineering, Third

Edition, John Wiley & Sons, New York, 1999

2. Ronald W. Missen, Charles A. Mims, Bradley A. Saville,

Introduction to Chemical Reaction Engineering and Kinetics,
John Wiley & Sons, New York, 1999

3. E. Bruce Nauman, Chemical Reactor Design, Optimization, and

Scale-up, McGraw-Hill, New York, 2002

4. Lanny D. Schmidt, The Engineering of Chemical Reactions,

Oxford University Press, New York, 1998

June 5, 2008 FILS – Chemical Reactors 2

Preparatory Notions Revisited
 Chemical Reactors
BIBLIOGRAPHY (Cont.)

5. Holland, C.D., Anthony, R.G., Fundamentals of Reaction Engineering,

Prentice-Hall Inc., Englewood Cliffs, 1979.
6. Froment, G.F., Bischoff, K.B., Chemical Reactor Analysis and Design, John
Wiley & Sons, New York, 1979.
7. Lee, H.H., Heterogeneous Reactor Design, Butterworth Publishers, Boston,
1985.
8. Levenspiel, O., The Chemical Reactor Omnibook+, OSU Book Stores Inc.,
Corvallis, 1984.
9. Danckwerts, P.V., Gas-Liquid Reactions, McGraw-Hill, New York, 1970.
10. Denbigh, K.G., Turner, J.R., The Chemical Reactor Theory - an Introduction,
2nd edition, Cambridge Univ. Press, 1971.
11. Hill, C.G. jr., An Introduction to Chemical Kinetics and Reactor Design, John
Wiley & Sons, New York, 1977.
12. Tarhan, M.O., Catalytic Reactor Design, McGraw-Hill, New York, 1983
13. Lavric, V., Chemical Reactors, 1996 (UPB lithography)

June 5, 2008 FILS – Chemical Reactors 3

Preparatory Notions Revisited
 Chemical Reactors
Examination
Written test – multiple choices, five variants to select from; free access to all
documentation

The rules of grading:

A) no answer checked, Zero points;
B) all answers checked, Zero points; g  pg
C) for the rest, the following formula applies: P 
b 1
where g stands for the number of good answers checked, pg stands for the
weight fraction of the answer g and b stands for bad answers checked.

Examples:
3 1
C.1 in all, three good answers (⅓ weight each), all checked: P  3  1 since no
0 1
bad answer is checked;
2 1
C.2 two good answers and one bad: P  3 1
11 3
C.3 no good answer and one bad answer: Zero
June 5, 2008 FILS – Chemical Reactors 4
Preparatory Notions Revisited
 Chemical Reactors
Outline of the Course:

1. Introductory notions revisited

2. Flow through chemical reactors – characterization and

influence

3. Homogeneous isothermal reactors – ideal and real

flow

4. Thermal behavior of chemical reactors

June 5, 2008 FILS – Chemical Reactors 5

Preparatory Notions Revisited
 Chemical Reactors
Definition:
The Chemical Reactor is the confined space where a
chemical process develops, resulting in transformation of
reactants in others (products),
some species (reactants) products under strict
observation of the mass conservation laws.

The Hybrid Chemical Reactor, ensures in situ separation of

the valuable product or intermediate, not only lowering the
overall production costs, but increasing the process rate due
to higher chemical driven forces.

Every industrial chemical process aims towards economically

fabricating a desired product from a variety of starting materials
through a succession of treatment steps, which can be abstracted in
a general processing flowsheet.

June 5, 2008 FILS – Chemical Reactors 6

Preparatory Notions Revisited
 Chemical Reactors
The flowsheet of a typical chemical process

Pre-chemical
processing physi- Chemical processing
Row materials cal treatment stages
steps

Post-chemical
processing
physical treat-
Products
ment steps

June 5, 2008 FILS – Chemical Reactors 7

Preparatory Notions Revisited
 Chemical Reactors
Design of the chemical Reality
reactor - many alternatives The process to be known
and studied
can be proposed for a process.
Optimum solution – concerns Abstraction
not just the chemical reactor.
One design may have low
Physical Model
chemical reactor cost, but the
The “reality” as we
materials leaving the unit may are able to grasp
be such that their treatment
requires much higher costs.
Simplifying Boundary Improvement
The economics of the over-all Assumptions Conditions
process must be considered

Mathematical Model
The “reality” as we Predictions not suffi-
ciently close to reality
are able to predict it
June 5, 2008 FILS – Chemical Reactors 8
Preparatory Notions Revisited
 Chemical Reactors
Information used in chemical reactor modeling

Stoichiome Momentum Heat Mass

try & Ki- transport transport transport
netics

Chemical
Reactor
Modeling

Thermo- Phases Balance Automation

dynamics flow equations & Control

June 5, 2008 FILS – Chemical Reactors 9

Preparatory Notions Revisited
 Chemical Reactors
Classification of chemical reactions useful in reactor modeling

Non-catalytic Catalytic

Most gas-phase reactions Most liquid-phase reactions

Homo-
Reactions in colloidal systems
geneous Fast reactions such as burning
of a flame Enzyme and microbial reactions
Burning of coal Ammonia synthesis
Roasting of ores Oxidation of ammonia to produce
Attack of solids by acids nitric acid
Hetero-
geneous Gas-liquid absorption with
Cracking of crude oil
reaction
Reduction of iron ore to
Oxidation of SO2 to SO3
iron and steel
June 5, 2008 FILS – Chemical Reactors 10
Preparatory Notions Revisited
 Chemical Reactors
Classification of chemical reactions by stoichiometry
• single
• multiple
• series A 
k1
 R 
k2
S

• parallel
A 
k1
R
• competitive A 
k2
S
A 
k1
R
• side – by – side B 
k2
S
A  B 
k1
R
• mixed R  B 
k2
S

• polymerization
June 5, 2008 FILS – Chemical Reactors 11
Preparatory Notions Revisited
 Elementary vs. Non-elementary
Reactions

Elementary reactions - individual reaction steps that are

caused by collisions of molecules

• mono, bi and tri-molecular processes

• the rate equation corresponds to a stoichiometric equation

• when no correspondence between stoichiometry and rate

exists, the reaction is sad to be non-elementary.

June 5, 2008 FILS – Chemical Reactors 12

Preparatory Notions Revisited
 Elements of systematic
stoichiometry
• chemical species are denoted by Aj, where j=1,,S with S being the number
of all chemical species involved in the chemical process;
• stoichiometric coefficients are denoted by j, for a single reactions and ij for
multiple reactions, with i=1,,R, where R stands for the total number of
chemical reactions between the S chemical species;
• the stoichiometric coefficients for products are positive, while for reactants
are negative, to show the progression of the chemical process

S
Single reactions 
j 1
j Aj  0

  A0   rank  
R  S 
Multiple reactions    i j Aj   0
i 1  j 1 

June 5, 2008 FILS – Chemical Reactors 13

Preparatory Notions Revisited
 Measuring the progress of the
chemical process
Measuring the progress of a chemical process - quantifying the degree of
participation of a molecular species in this chemical process
• intensive units - normalized value, independent of the starting point
• extensive units/variables – their values will depend upon the initial quantity
of each and every species participating at the chemical process

As intensive variable, the conversion is the widest used;

As extensive variable, the degree of advancement or the reaction extent are the
widest used.

The rule of thumb advocates that, for a single reaction chemical process,
conversion is the appropriate measure of transformation, while the degree of
advancement should be used for all other cases.

June 5, 2008 FILS – Chemical Reactors 14

Preparatory Notions Revisited
 Measuring the progress of the
chemical process
The conversion Limiting reactant
Single reaction chemical process
S

 j Aj  0  qQ  s S
kd
a A  b B   
kr
j 1

The degree of transformation for each reactant species is given by

the fractional conversions

N A0  N A N B0  N B XB 
b N A0
XA  ; XB  XA
N A0 N B0 a NB0
 q 
N A  N A0 1  X A  NQ  N A0  M QA  X A  N Aj 0
 a  M jA 
 b   s  N A0
N B  N A0  M BA  X A  N S  N A0  M SA  X A 
 a   a 
June 5, 2008 FILS – Chemical Reactors 15
Preparatory Notions Revisited
 Measuring the progress of the
chemical process
The degree of advancement / The extent S
Single reaction chemical process 
j 1
j Aj  0

N Aj  N Aj 0
 ; j  1, 2, , S N Aj  N Aj 0   j
j
R  S 
Multiple reaction chemical process    i j Aj   0
i 1  j 1 
i 
 N Aj  N Aj 0 ;
i
i  1, 2, , R N Aj  N Aj 0   ij  i
R

 ij i 1

S R
NT  N 0   ij  i
j 1 i 1

June 5, 2008 FILS – Chemical Reactors 16

Preparatory Notions Revisited
Composition of the chemical mixture
N Aj
Molar concentration C Aj 
V
Single reaction chemical process – constant volume
 j 
C Aj  C A0  M jA  X A 
 a 
Single reaction chemical process – variable volume
 j  j
N A0  M jA  X A  M jA  X A
C Aj   a   C A0 a
V0 1   A  x A  1  A  X A
 N X 0  N X 1
 A A
for gas phase reactions
V X A 0
V X A 1
 N X A 0
A  
V X A 0   X A 1   X A 0
  X 1
for liquid phase reactions
 A

June 5, 2008 FILS – Chemical Reactors 17

Preparatory Notions Revisited
Composition of the chemical mixture
N Aj
Molar fraction y Aj 
NT
Single reaction chemical process

 j  j
N A0  M jA  X A  M jA  X A
y Aj  S  a   a
 j  S
 j 
 N A0  M jA  X A   jA
M  X A
j 1  a  j 1  a 
Multiple reaction chemical process
R R
N A j 0   ij  i y Aj 0   ij  M i
y Aj  S
i 1
R
 S
i 1
R
N 0   ij  i 1   ij  M i
j 1 i 1 j 1 i 1

June 5, 2008 FILS – Chemical Reactors 18

Preparatory Notions Revisited
 Thermodynamics
Thermodynamics
• the heat liberated or absorbed during the chemical process

S
C p   j  C p , Aj
j 1

• the maximum possible extent of reaction

S
G   j  GA0 j   RT ln K
0

j 1

June 5, 2008 FILS – Chemical Reactors 19

Preparatory Notions Revisited
 Chemical kinetics
Chemical kinetics
• concerned with the rates and mechanisms of chemical reactions;
• search for the factors that influence the rate of reaction;
• tool for: gaining insight into the reacting systems nature, understanding how
chemical bonds are made/broken, and estimating their energies and stability;
• the mode of reaction of compounds provides clues to their structure;
• the basis for important theories in combustion and dissolution;
• permit satisfactory design of equipments to effect the reactions on a technical
scale
• in polymerization processes: the stoichiometry and kinetics are complex. A
polymer is always a mixture of macromolecules having different chain lengths -
statistics can be used, to simplify the mathematical treatment, lumping the infinite
number of conservation equations (polymers and/or free radicals) into an easier
mathematical model, focused on several characteristics of the molecular mass
distribution, like mean, dispersion and symmetry;
June 5, 2008 FILS – Chemical Reactors 20
Preparatory Notions Revisited
 Chemical kinetics
Definition of reaction rate

1 dN Aj moles of Aj which modify during chemical process

rAj  
V dt  volume of fluid    time 
V can be replaced by A (aria), W (mass of catalyst),
Vw (volume of catalyst), Vr (volume of \reactor)

 volume   mass of   surface   volume   volume 

  rAj    rA j    rAj    rAj    rAj
 of fluid   solid   of solid   of solid   of reactor 
For complex reactions - the equivalent reaction rate for every reaction

1 1  dN Aj  1 d i
ri      , i  1, 2, , R
V  ij  dt
 i V dt
June 5, 2008 FILS – Chemical Reactors 21
Preparatory Notions Revisited
 Chemical kinetics
The change in moles of any species is, for a single reaction

dN Aj
 V  j  r  V  rA j
dt

The change in moles of any species is, for multiple reactions

dN Aj R dN Aj  R
     ij  V  ri  V  rAj
dt 
i 1  dt i i 1

June 5, 2008 FILS – Chemical Reactors 22

Preparatory Notions Revisited
 Chemical kinetics
Equilibrium of Elementary Reversible Reactions


kd
A  B   Q  S , KC
kr

rforward  kd C ACB rreverse  kr CQ CS

Equilibrium rS , forward  rS ,reverse  0

k d C R CS
KC  
k r C AC B

Molecularity and Order of Reaction Homework

Temperature dependent term of a rate equation Homework

June 5, 2008 FILS – Chemical Reactors 23

Preparatory Notions Revisited
 Chemical Processes Kinetics

Searching for a mechanism (Lavric, 1996)

homework

June 5, 2008 FILS – Chemical Reactors 24

Preparatory Notions Revisited