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CHBI 502

REACTION ENGINEERING

CHBI 502

HWs will be distributed after the chapters are covered, deadlines will be posted

NO late submission

MT dates will be determined (mid of the semester) Final exam date will be determined by the registrars office You can contact me anytime through e-mail (okeskin@..) You are wellcome during office hours, you need to ask me if I will be at the office other than these hours. No cheating (HWs, projects, exams)

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Academic dishonesty in the form of cheating, plagiarism, or collusion are serious offenses and are not tolerated at Ko University. University Academic Regulations and the Regulations for Student Disciplinary Matters clearly define the policy and the disciplinary action to be taken in case of academic dishonesty. Failure in academic integrity may lead to suspension and expulsion from the University. Cheating includes, but is not limited to, copying from a classmate or providing answers or information, either written or oral, to others. Plagiarism is borrowing or using someone elses writing or ideas without giving written acknowledgment to the author. This includes copying from a fellow students paper or from a text (whether printed or electronic) without properly citing the source. Collusion is getting unauthorized help from another person or having someone else write a paper or assignment. You can discuss the lecture and reading material, and the general nature nat re of the homework home ork problems, problems with ith anyone. an one Also, Also you o ma may per peruse se all previous ChBI 502 material available anywhere, such as on the web, and in the library accumulated over the years. However, your final solutions should be your own original work. Jointly prepared solutions, and solutions closely resembling those available, are unacceptable.

Textbook

Elements of Chemical Reaction Engineering (4th ed.), H.S. Fogler Prentice Hall, Upper Saddle River, NJ (2005).

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Course Outline, Tentative schedule Review: Chemical Kinetics and Ch1-6, Two-three weeks Chapter 1: Mole Balances Chapter 2: Conversion and Reactor Sizing Chapter 3: Rate Law and Stoichiometry Chapter 4: Isothermal Reactor Design Chapter 5: Collection and Analysis of Rate Data Chapter 6: Multiple Reactions Chapter 7: Reaction Mechanisms, Pathways, Bioreactions and Bioreactors , Two weeks Chapter 8: Steady-State Nonisothermal Reactor Design, Two weeks Chapter 9: Unsteady-state Nonisothermal Reactor Design, One week Chapter 10: Catalysis and Catalytic Reactors, Two weeks Chapter 11: External Diffusion Effects on Heterogeneous Reactions Reactions, One Week Chapter 12: Diffusion and Reaction in Porous Catalysts, Two Weeks Student presentations on projects, One week

Chemical kinetics is the study of chemical rxn rates and reaction mechanisms. Chemical reaction engineering (CRE) combines the study of chemical kinetics with the reactors in which the reactions occur. Objective of the course: Learn how to design equipment for carrying out desirable chemical reactions (what size and what type of equipment) Chemical Kinetics & Reactor Design The reaction system thet operates in the safest and most efficient manner ca t e key ey to t e success of o the t e plant. pa t can be the the Modelling of; Chemical plant Pharmacokinetics Microelectronics Digestive system of an animal

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1. Chemical Identity A chemical species is said to have reacted when it has lost its chemical h i l id identity. tit Th The id identity tit of f a chemical h i l species i i is d determinde t i d by the kind, number, and configuration of that species atoms.

Three ways a chemical species can lose its chemical identity: 1. Decomposition CH3CH3 H2 + H2C = CH2 2 C 2. Combination bi ti 3. Isomerization N2 + O2 2NO C2H5CH = CH2 CH2 = C(CH3)2

2.

Reaction Rate: The reaction rate is the rate at which a species looses its chemical identity per unit volume volume. The rate of a reaction can be expressed as the rate of disappearance of a reactant or as the rate of appearance of a product. Consider species A:

AB p Ap per unit volume rA = the rate of formation of species -rA = the rate of disappearance of species A per unit volume rB = the rate of formation of species B per unit volume

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Example:

AB

If B is being created 0.2 moles per decimeter cubed per second, ie, rB = 0.2 mole/dm3 s Then A is disappearing at the same rate: -rA = 0.2 mole/dm3 s For catalytic reaction, we refer to rA, which is the rate of disappearance of species A on a per mass of catalyst basis.

If continuous dCA/dt = 0

The rate law does not depend on reactor type! -rA is the # of moles of A reacting (disappearing) per unit time per unit volume (mol/dm3 s)

In a reactor, two extreme conditions are considered: 1. No mixing of streams 2. Complete mixing (desirable) Classification of reactions

Ideal mixing (no axial mixing, complete radial mixing)

Steady-state : conditions donot change with time at any point (PFR)

Complete mixing non-steady-state: Uniform composition and temperture at any given instant,

change with time (t) FA0 Stirrer, rpm and design are important

FA

Batch

CSTR)

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Thus,

Batch or continuous Tank or tubular Homogeneous or heterogeneous

Consider species j: rj is the rate of formation of species j per unit volume [e.g. mol/dm3 s] rj is a function of concentration, temperature, pressure, and the type of catalyst (if any) rj is independent of the type of reaction system (batch, plug flow, etc.) rj is an algebraic equation, not a differential equation. We use an algebraic equation to relate the rate of reaction, -rA, to the concentration of reacting species and to the temperature at which the reaction occurs [e.g. rA = k(T) CA2] For example, the algebraic form of the rate law for rA for A (products) may be; a linear function of concentrations:

rA = k C A

2 rA = k C A

rA =

k1 C A 1 + k2 C A

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FA0 FA + rA dV =

0

dN A d dt

[moles / time]

GA = rA V (if all system variables (T, CA, etc.) are spatially uniform throughout system volume)

V1 r1A r2A V2

m m

i 1 =

GiA =

i 1 =

riA Vi

for M subvolumes

G A = rA dV

FA0 FA + rA dV =

dN A dt

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Batch Reactor is used for small-scale operations, for testing new processes, for the manufacture of expensive products, and for the processes that are not easy to convert to continuous. high conversion rates (time spend is longer) high labor cost and & variability of products from batch-to-batch

FA0 = 0

FA = 0

If perfect mixing (no volume change throughout volume)

dN A = rA V dt dN j = rj dV dt

NA NA0 NB1 NA1 NB

t1

t1

dN A = rA V dt dN A dt = rA V

dt =

0

t1

dN A r V N A0 A

N A1

t1 =

dN A r V N A0 A

N A1

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Continuous Stirred Tank Reactor (CSTR) Plug Flow Reactor (PFR) Packed Bed Reactor (PBR)

CSTR

FA0

usually used for liquid-phase rxns usually operated at steady state usually assumed to be perfectly mixed T f(t,V)

FA

V

FA0 FA + rA dV =

0

FA0

dN A dt

dN dt

A

= 0 = rA V

FA

dV

F A 0 F A + rA V = 0

Design eqn for CSTR

V = V =

FA0 FA rA C

A0

FA0 = CA0 v

Molar flow rate

v0 C rA

concentration

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Tubular Reactors consists of a cylindirical pipe and is operated at steady state. Mostly used for gas phase rxns. PFR Derivation: uniform velocity in turbulent flow (no radial variation in velocity, concentration, temperature, reaction rate) IN OUT + GENERATION = ACCUMULATION

FA0 FA + rA dV =

0

dN A dt

Reactants

Products

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FA0

FA V

GA

Fj V + V

G A =

dV = rA V

FA V FA V + V + rA V = 0

Divide by V and rearrange:

FA V + V FA V = rA V

dF A = rA dV V =

FA

FA0

dF A rA

Packed Bed Reactors (PBR) are not homogenous, the fluid-solid heterogenous rxn take place on the surface of the catalyst. Rate (r) is dependent on the mass of catalyst (W). -rA = mol A reacted / (s) (g catalyst) General Balance on W

IN OUT + GENERATION = ACCUMULATION

FA0 FA + rA 'dW =

0

dN A dt

W W W+W

FA(W) FA(W+W)

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Steady State

dN A =0 dt

FA0 FA + rA 'dV =

0 V

dN A dt

dFA = rA ' dW

When pressure drop through the reactor and catalyst decay are neglected, the integral egn can be used to find W:

dFA W= = r ' A FA 0

FA

FA 0

FA

dFA rA '

Batch Reactor Times AB Calculate the time to reduce the number of moles by a factor of 10 (NA = NA0/10) in a batch reactor for the above reaction with

-1 -r rA A = k CA when k = 0.046 min

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Solve :

A dN A dN A t= = r V rA V N A0 A N A0

NA

rA V = k C A V = k t=

N A0

NA V = k N A V

NA

NA =

Therefore, t = 50 minutes

Summary of Chapter 1

Define the rate of chemical reaction. Apply the mole balance equations to a batch reactor, CSTR, PFR, and PBR.

Batch reactor:

concn

CSTR: no spatial variations in the tank, steady state PFR: spatial variations along the reactor reactor, steady state PBR: spatial variations along the reactor, steady state

FA0 FA + rA dV =

0 V

dN A dt

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Reactor

Differential

Algebraic

Integral

Batch

CSTR

PFR

PBR

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Alcohol Stomach VG = 2.4 l Gastrointestinal VG = 2.4 l tG = 2.67 min Liver VL = 2.4 l tL = 2.4 min Central VC = 15.3 l tC = 0.9 min

Perfusion interactions between compartments are shown by arrows. VG, VL, VC, and VM are -tissue water volumes for the gastrointestinal, liver, central and muscle compartments, respectively. VS is the stomach contents volume.

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Chemical Reaction Engineering Chemical reaction engineering is at the heart of virtually every chemical process. It separates the chemical engineer from other engineers. Industries that Draw Heavily on Chemical Reaction Engineering (CRE) are: CPI (Chemical Process Industries) Dow, DuPont, Amoco, Chevron Pharmaceutical Antivenom, Drug Delivery Medicine Pharmacokinetics, Drinking and Driving Microelectronics CVD

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Objectives: Define conversion and space time. Write the mole balances in terms of conversion for a batch reactor, CSTR, PFR, and PBR. Size reactors either alone or in series once given the molar flow rate of A, and the rate of reaction, -rA, as a function of conversion, X.

Conversion: Choose one of the reactants as the basis of calculation and relate the other species involved in the rxn to this basis. Space time: the time necessary to process one reactor volume of fluid based on entrance conditions (holding time or mean residence time)

1. Conversion Consider the general equation

aA A + bB cC C + dD

We will choose A as our basis of calculation.

b c d A+ B C + D a a a

The basis of calculation is most always the limiting reactant. The conversion of species A in a reaction is equal to the number of moles of A reacted per mole of A fed.

Batch

Flow

X=

( N A0 N A ) N A0

X=

(FA0 FA ) FA0

For irreversible reactions, the maximum value of conversion, X, is that for complete conversion, i.e. X = 1.0. For reversible reactions, the maximum value of conversion, X, is the equilibrium conversion, i.e. X = Xe.

= [N A 0 ]

[X ]

[1]

Now the # of moles of A that remain in the reactor after a time t, NA can be expressed in terms of NA0 and X;

[N A ] = [N A 0 ] [N A 0 X ]

N A = N A 0 (1 X )

[2]

dN A = rA V dt dN A = rA V dt

( prefect mixing )

[3]

For batch reactors, we are interested in determining how long to leave the reactants in the reactor to achieve a certain conversion X.

[4]

[5]

1 dN A d ( N A / V0 ) dC A = = V0 dt dt dt dC A = rA dt dt = N A 0 dX rA V

X

From [3]

Constant volume batch reactor From [5] Batch time, t, required to achieve a conversion X.

X

t = N A0

0

dX rA V

As t

Flow Reactor Design Equations: For continuous-flow systems, time usually increases with increasing reactor volume.

FA0 X =

Outlet flow rate

FA0 FA0 X = FA

inlet molar flow rate

F A = F A 0 (1 X ) FA0 = C

A0

v0

volume / time (volumetric flow rate, dm3/s)

moles /volume

For liquid systems, CA0 is usually given in terms of molarity (mol/dm3) For gas systems, CA0 can be calculated using gas laws.

Partial pressure

C A0 =

Entering molar flow rate is

PA 0 y P = A0 0 R T0 R T0

y P FA0 = v0 CA0 = v0 A0 0 R T0

yA0 P0 CA0 R T

= entering mole fraction of A = entering t i total t t l pressure (kP (kPa) ) = entering concn (mol/dm3) = 8.314 kPa dm3 / mol K = T(K)

A+

b c d B C+ D a a a

V =

Substitute for FA

FA0 FA rA

FA = FA 0 FA 0 X V = V = FA 0 ( FA 0 FA 0 X ) rA FA 0 X ( rA ) exit

dFA = FA0 dX

Substitute back:

dFA dX = FA 0 = rA dV dV

V = FA0

0

dX rA

3. Reactor Sizing Given rA as a function of conversion, -rA = f(X), one can size any type of reactor. We do this by constructing a Levenspiel Plot. Here we plot either FA0 / -rA or 1 / -rA as a function of X. For FA0 / -rA vs. X, the volume of a CSTR and the volume of a PFR can be represented as the shaded areas in the Levelspiel Plots shown below:

Levenspiel Plots

rA = k C A = k C A0 (1 X )

Specific rxn rate (function of T) ( ) initial concn

1 1 1 = rA k C A0 1 X

-1/rA

Example: Lets consider the isothermal gas-phase isomerization: AB X 0 0.1 0.2 0.4 0.6 0.7 08 0.8 [T = 500 K] [P = 830 kPa = 8.2 atm] initial charge was pure A -rA(mol/m3s) 0 45 0.45 0.37 0.30 0.195 0.113 0.079 0 05 0.05

Example: Lets consider the isothermal gas-phase isomerization: AB X 0 0.1 0.2 0.4 0.6 0.7 08 0.8 [T = 500 K] [P = 830 kPa = 8.2 atm] initial charge was pure A -rA(mol/m3s) 0 45 0.45 0.37 0.30 0.195 0.113 0.079 0 05 0.05 1 / -rA 2 22 2.22 2.70 3.33 5.13 8.85 12.7 20 0 20.0

Draw -1/rA vs X:

-1/rA

We can use this figure to size flow reactors for different entering molar flow rates. Keep in mind : 1. if a rxn is carried out isothermally, y, the rate is usually greatest at the start of the rxn, when the concn of reactant is greatest. (when x 0 -1/rA is small) 2. As x 1, rA 0 thus 1/-rA & V

An infinite reactor volume is needed to reach complete conversion. For reversible reactions (A B), the max X is the equilibrium conversion Xe. At equilibrium, rA 0. As X Xe, rA 0 thus 1/-rA & V An infinite reactor volume is needed to obtain Xe.

if FA0 = 0.4 mol/s, we can calculate [FA/-rA](m3) Plot FA0/-rA vs X obtain Levenspiel Plot! Example: Calculate volume to achieve 80 % conversion in CSTR.

For instance:

3.6 m3

CSTRs are usually used for liquid-phase rxns.

1.5 m3

4. Numerical Evaluation of Intergrals The integral to calculate the PFR volume can be evaluated using a method such as Simpsons One-Third Rule.

NOTE: The intervals (X) shown in the sketch are not drawn to scale. They should be equal.

Simpsons One-Third Rule is one of the most common numerical methods. It uses three data points. One numerical methods for evaluating integrals are: 1. Trapezoidal Rule (uses two data points) 2. Simpsons Three-Eighths Rule (uses four data points) 3. Five-Point Quadrature Formula

Trapezoidal Rule

f(x) f(x1) A2 f(x0) x0 h A1 x1

x1

x0

f ( x) dx = h [ f ( x ) + f ( x )]

0 1

A1 = f ( x0 ) h A2 = [ f ( x1 ) f ( x0 )] h 2 A = A1 + A2 f ( x1 ) f ( x0 ) = h f ( x0 ) + 2 2 h = [ f ( x0 ) + f ( x1 )] 2

x4

x0

f ( x) dx = 3 ( f

x0

+ 4 f1 + 2 f 2 + 4 f 3 + f 4 ) where

h=

x 4 x0 4

For N+1 points, where N is an integer.

xN

f ( x) dx =

3h ( f 0 + 3 f1 + 3 f 2 + 2 f 3 + 3 f 4 + 3 f 5 + 2 f 6 .....) 8

Example: Consider the liquid phase reaction; A Products which is to take place in a PFR. The following data was obtained in a batch reactor.

X -rA(mol/dm3s)

0 0.01

0.4 0.008

0.8 0.002

If the molar feed of A to the PFR is 2 mol/s, what PFR volume is necessary to achieve 80 % conversion under identical conditions as those under which the batch data was obtained?

10

PFR V = FA0

0

1 dX rA

X

PFR : V = FA0

dX X = FA0 3 r A 0

1 4 1 + + rA ( X = 0) rA ( X 1 ) rA ( X 2 )

PFR : V = FA0

0

0.8

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dX = rA dV

0 .8 0.8

dX F Re arranging : V = FA0 = A0 dX rA 0 rA 0

Lets numerically evaluate the integral with trapezoidal rule

0.8

r

0

FA0

A

dX

f (X ) = f (X ) =

FA 0 rA FA 0 rA

= 0.89

X =0

= 8 .0

X = 0 .8

V=

With five point quadrature V = 2.165 m3

VCSTR > VPFR for the same conversion and rxn conditions. The reason is that CSTR always y operates p at lowest rxn rate. PFR starts at a high g rate, then gradually decreases to the exit rate.

12

Reactors in Series: The exit of one reactor is fed to the next one. Given rA as a function of conversion, one can design any sequence of reactors.

Xi =

Example: Using Levenspiel plots to calculate conversion from known reactor volumes.

Pure A is fed at a volumetric flow rate 1000 dm3/h and at a concentration of 0.005 mol/dm3 to an existing CSTR, which is connected in series to an existing tubular reactor If the volume of the CSTR is 1200 dm3 and the tubular reactor volume is reactor. 600 dm3, what are the intermediate and final conversions that can be achieved with the existing system? The reciprocal rate is plotted in the figure below as a function of conversion for the conditions at which the reaction is to be carried out.

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Solution: By trial and error, we find that a conversion of 0.6 gives the appropriate CSTR volume of 1200 dm3.

Similarly for the PFR, through trial and error, we find that a conversion of 0.8 gives the appropriate PFR volume of 600 dm3.

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Reactor 1: Mole Balance: FA0 FA1 + rA1 V1 = 0

FA0 FA1 X1 = 0.4 -rA1

Reactor 2:

-rA2 FA2 X1 = 0.8

Mole Balance: FA1 FA2 + rA2 V2 = 0 FA2 = FA0 FA0 X2 Combining [4] & [5]:

[4] [5]

V2 =

X = 0.4 X = 0.8

-FA0/rA

X 0.4 0.8

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-FA0/rA

4 X

V PFR = VCSTR ,i

PFRs in Series

FA0 -rA1 FA1 X1 =0.4 -rA2

X2 X

i =1

FA2 X1 = 0.8

X

FA0

0

1 2 dX dX dX = FA0 + FA0 rA 0 rA X 1 rA

The overall conversion of two PFRs in series is the same as one PFR with the same total volume

Reactors in Series: CSTR PFR CSTR Using the data in the table, calculate the reactor volumes V1, V2 and V3 for the CSTR/PFR/CSTR reactors in series sequence along with the corresponding conversion.

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FA 0 X V1 = r A1

at X = X1 = 0.4 the (FA0 / -rA1) = 300 dm3 V1 = (300 dm3) (0.4) = 120 dm3 The volume of the first CSTR is 120 dm3

dX rA = dV FA0

Rearranging and intergrating with limits when V = 0 when V = V2 X = X1 = 0.4 X = X2 = 0.7

0.7 FA0 FA0 = V = dX r r dX A A X1 0.4 X2

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X =

V2 =

X 3

V2 = 0.15 300dm 3 + 4 (370dm 3 ) + 600dm 3 = 119dm 3 3

The volume of last CSTR is 180 dm3

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Summary: CSTR X1 = 0.4 PFR X2 = 0.7 07 CSTR X3 = 0.8 V1 = 120 dm3 V2 = 119 dm3 V3 = 180 dm3

Reactor Sequencing Is there any differences between having a CSTR PFR system & PFR CSTR system? Which arrangement is best?

or

V1 V2 V3 V4

FA0

The choice of reactors depend on ; the Levenspiel plots relative reactor sizes.

X Adiabatic rxns

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Space Time

The space time, tau, is obtained by dividing the reactor volume by the volumetric flow rate entering the reactor:

V v0

Space time is the time necessary to process one volume of reactor fluid at the entrance conditions. This is the time it takes for the amount of fluid that takes up the entire volume of the reactor to either completely enter or completely exit the reactor. It is also called holding time or mean residence time.

Example: v0 = 0.01 m3/s and V = 0.2 m3 = 0.2 m3 / 0.01 m3/s = 20 s It would take 20 s for the fluid at the entrance to move to the exit.

Typical space time for different reactors: Batch : 15 min 20 h (few kg/day 100,000 tons/year 280 tons/day) CSTR : 10 min 4 h Tubular: 0.5s 0 5s 1h (10 to 3 x 106 tons/yr) (50 to 5 x 106 tons/yr)

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SV =

v0 1 = V

instead of using volumetric flow rate at the entrance, you use liquid hourly & gas hourly space velocities (LHSV, GHSV). v0 (for LHSV) is that of a liquid feed rate at 60F or 75F. v0 (for GHSV) is that of the one that measured at STP.

LHSV =

v0 liq V

GHSV =

v0 STP V

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HW (due date: Feb 25): Solve S l th the prpblem bl i in your own way.

http://www.engin.umich.edu/~cre/web_mod/hippo/index.htm

Suggested problems from the web: http://www.engin.umich.edu/~cre/ htt // i i h d / / Additional Homework Problems at each chapter

Example: Consider cell as a reactor. The nutrient corn steep liquor enters the cell of the microorganism Penicillium chrysogenum and is decomposed to form such products as amino acids, RNA and DNA. Write an unsteady mass balance on (a) the corn steep liquor, (b) RNA, and (c) pencillin. Assume the cell is well mixed and that RNA remains inside the cell.

Penicillium chrysogenum

Out Penicillin

Assumption: Penicillin is produced in the stationary state. no cell growth & nutrients are used in making the product.

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Assuming steady state for the rate of production of penicilin in the cells stationary state, dN p =0 dt F Fout F V = in V = out rp rp Similarity, for Corn Steep Liquor with FC = 0

V = FC 0 FC F = C0 rC rC

Summary

Batch Flow

X=

( N A0 N A ) N A0

X=

(FA0 FA ) FA0

For irreversible reactions, the maximum value of conversion, X, is that for complete conversion, i.e. X = 1.0. For reversible reactions, the maximum value of conversion, X, is the equilibrium conversion, i.e. X = Xe.

23

dX N A0 = rA V dt

V=

X

CSTR

V = FA0

0

dX rA

PFR

Reactors in series

Space time

V v0

24

How do we obtain rA = f(X)? We do this in two steps 1. Rate Law Find the rate as a function of concentration, rA = k fn (CA, CB ) 2. Stoichiometry Find the concentration as a function of conversion CA = g(X)

Basic Definitions:

A homogenous rxn is the one that involves only one phase. A heterogeneous rxn involves more than one phase, rxn occurs at the interface between the phases, i.e., solid gas phase. An irreversible rxn proceeds in only one direction A B A reversible rxn can proceed in both directions A B (equilibrium) Molecularity of a rxn is the number of atoms, ions, or molecules involved in a rxn step. The terms unimolecular, bimolecular, and termomolecular refer to rxns involving, respectively, one, two or three atoms interacting in any one rxn step. Unimolecular: radioactive decay Bimolecular: rxns with free radicals Br. + X XBr + Y. Termolecular: rxn pathway following a series of bimolecular rxns.

A rate law describes the behavior of a reaction. The rate of a reaction is a function of temperature (through the rate constant) and concentration. 1. Relative Rates of Reaction aA + bB cC + dD

The reaction : 2A + 3B 5C is carried out in a reactor. If at a particular point, the rate of disappearance of A is 10 mol/dm3s, what are the rates of B and C? The rate of disappearance of A, -rA, is

Rxn Order & Rate Law: Algebraic equation that relates rA to the concentrations of the reactants is called the kinetic expression or rate law. Usually, rate can be written as the product of rxn rate constant and concentrations. In these expressions, usually the limiting reactant is chosen as basis for calculations. -rA = kA(T) fn (CA, CB,..) In reality activities should be used rA = -kA aA aB (ai = i Ci) rA = (-kA A B) CA CB

kA

Power Law and Elementary Rate Laws In general -rA = kA CA CB : order in A : order in B n = + = overall rxn order The unit of rA is always = concentration / time For a rxn with n order: {k} = (concentration)1-n / time Therefore for a zero-, first-, second-, and third-order rxn

zero order ( n = 0) 1st order (n = 1) 2 nd order (n = 2) 3 order (n = 3)

rd

rA = k A ;

{k} = {k} = 1 s

mol dm3 s

rA = k AC A ; rA = k AC A ;

2

{k} =

dm3 mol s

2

rA = k AC A C B ;

Elementary Reactions A reaction follows an elementary rate law if and only if the stoichiometric coefficients are the same as the individual reaction order of each species. For the reaction in the previous example (A + B C + D), the rate law would be: -rA = k CA CB These rate laws can be derived from Collision Theory.

Question What is the reaction rate law for the reaction A + B C if the reaction is elementary? What is rB? What is rC? Calculate the rates of A, B, and C in a CSTR where the concentrations are CA = 1.5 mol/dm3, CB = 9 mol/dm3 and kA = 2 (dm3/mol)() (1/s)

Solution:

A+BC

Then,

For A + B C + D

C C rA = k C A C B C D KC

Elementary

Non Elementary Rate Laws: A large number of homogeneous or heterogeneous rxns do not follow simple rate laws. If the rate law for the non-elementary reaction A + B 2C + D is found to be rA = k CA CB2, then the rxn is said to be 2nd order in A and 1st order in B, and 3rd order overall. For the homogeneous rxn

CO + Cl 2 COCl 2 2 N 2 O 2 N 2 + O2

rCO = k C CO C Cl 2 rN 2O = k C N 2O 1 + k 'C O2

3/ 2

Here, we can speak of reaction orders under certain limiting conditions as at very low concn of O2 (1 >> k CO2)

rN 2O = k N 2O C N 2O

If 1 << k CO2 rN2O

rN 2O =

k N 2O C N 2O k 'CO2

These types are very common for liquid & gas phase rxns on solid catalysts

C6 H 5CH 3 + H 2 catalyst C6 H 6 + CH 4

(toluene: T) (benzene: B) (methane: M)

Specific rxn rate {k} = molT / kg cat s atm2

rT ' =

Per mass of catalyst

k PH 2 PT 1 + K B PB + K T PT

Adsorption constant {KT} = 1 / atm

Example: Gas Phase Catalytic Reactions When studying gas phase catalytic reactions the rate law is developed in terms of partial pressure,

To rewrite the rate law, just use ideal gas law to relate to concentrations CA and CB

The net rate of formation of any species is equal to its rate of formation in the forward reaction plus its rate of formation in the reverse reaction: ratenet = rateforward + ratereverse At equilibrium, ratenet 0 and the rate law must reduce to an equation that is thermodynamically consistent with the equilibrium constant for the reaction. Example: Consider the exothermic, heterogeneous reaction; A+BC At low temperature, the rate law for the disappearance of A is

Recall PA = CA R T

What is the corresponding rate law? If the rate of formation of A for the forward reaction (A + B C) is

then we need to assume a form of the rate law for the reverse reaction that satisfies the equilibrium condition. If we assume the rate law for the reverse reaction (C A + B) is

Then:

and:

Deriving rA: The forward rate is: And the reverse rate law is:

The net rate for species A is the sum of the forward and reverse rate laws:

Solving for Kp: Does this rate law satisfy our requirement at equilibrium. For a rxn at equilibrium

Rate Law for Reversible Reactions Example: Write the rate law for the elementary reaction

Here kfA and krA are the forward and reverse specific reaction rates both defined with respect to A.

(1) (2)

At equilibrium

The equilibrium constant decreases as T increases (exothermic rxns) Ke increases as T increases (endothermic rxns)

10

Reaction Rate Constant, k: k is the specific rxn rate constant given by Arrhenius Equation: k = A eE/RT where, E: activation energy (cal/mol) R: gas constant (cal/mol K) T: temperature (K) A: frequency factor (unit depends on rxn order)

k

T kA T0 k0 A 1013

T

EA (Activation Energy) Molecules need some energy to distort/stretch their bonds so that they break them to form new bonds. The steric & repulsion forces must be overcome as the reacting molecules come close together.

A

2a

C

b+c

B

a+b

C

a+c

11

High energy complex EA-B-C

Energy Barrier

EA + EBC EAB + EC

Rxn Coordinate

The rxn coordinate denotes the energy of the system as a function of progress along the reaction path.

More on Activation Energy The activation energy can be thought of as a barrier to the reaction. One way to view the barrier to a reaction is through the reaction coordinates. These coordinates denote the energy of the system as a function of progress along the reaction path. For the reaction

for the reaction to occur, the reactants must overcome an energy barrier or activation energy EA.

12

Why is there an Activation Energy? (1) the molecules need energy to distort or stretch their bonds in order to break them and to thus form new bonds (2) as the reacting molecules come close together they must overcome both steric and electron repulsion forces in order to react Energy Distribution of reacting molecules In our development of collision theory we assumed all molecules had the same average energy. However, all the molecules dont have the same energy, rather there is distribution of energies where some molecules have more energy than others. The distraction function f(E,T) describes this distribution of the energies of the molecules. The distribution function is read in conjunction with dE f(E, T) dE = fraction of molecules with energies between E and E + dE

13

Increase Temperature

By increasing the temperature we increase the kinetic energy of the reactant molecules which can in turn be transferred to internal energy to increase the stretching and bending of the bonds causing them to be in an activated state, vulnerable to bond breaking and reaction. As the temperature is increased we have greater number of molecules have energies EA and hence the reaction rate will be greater.

14

Activation Energy The activation energy is a measure of how temperature sensitive the reaction is. Reactions with large activation energies are very temperature sensitive.

slope =

ln k 1 ( ) T E slope = R

15

This says if we know the specific rxn rate ko(To) at a temperature To, and we know E, then we can find reaction rate k(T) at any other temperature T for that rxn.

STOICHIOMETRY We shall set up Stoichiometric Tables using A as our basis of calculation in the following reaction. We will use the stoichiometric tables to express the concentration as a function of conversion. We will combine Ci = f(X) with the appropriate rate law to obtain -rA = f(X).

16

where; and

Concentration -- Batch System: Constant Volume Batch: Note: if the reaction occurs in the liquid phase or if a gas phase reaction occurs in a rigid (e.g., steel) batch reactor Then

if

then

17

Example: Write the rate law for the elementary liquid phase reaction 3A + 2B 4C solely in terms of conversion. The feed to the batch reactor is equal molar A and B with CA0 = 2 mol/dm3 and kA= .01 (dm3/mol)41/s. 1) Rate Law: -rA=kCA3CB2 2) Stoichiometry: Species A Liquid phase, v = vo (no volume change)

Species B

What is B? Species A is the limiting reactant because the feed is equal molar in A and B, and two moles of B consumes 3 moles of A.

We now have -rA=f(X) and can size reactors or determine batch reaction times.

18

and

etc.

If the rate of reaction were -rA = kCACB then we would have This gives us -rA = f(X). Consequently, we can use the methods discussed in Chapter 2 to size a large number of reactors, either alone or in series.

19

For Gas Phase Flow Systems: (Variable Volumetric Flow Rate) Combining the compressibility factor equation of state with Z = Z0 with we obtain The total molar flow rate Substituting for FT gives: FT=CTV FTo=CToVo

Example: Calculate For the gas phase reaction 2A + B C the feed is equal molar in A and B. Calculate . Solution A is the limiting reactant

20

etc. Again, these equations give us information about -rA = f(X), which we can use to size reactors. For example if the gas phase reaction has the rate law

then

with

Stoichiometric coefficient

FA = FA0 ( + A X)

21

Calculating the equilibrium conversion for gas phase reaction Consider the following elementary reaction with KC and = 20 dm3/mol and CA0 = 0.2 mol/dm3. Pure A is fed. Calculate the equilibrium conversion, Xe, for both a batch reactor and a flow reactor. Assume constant volume.

Solution At equilibrium

Stoichiometry

Constant Volume V = V0

22

Solving

23

The gas feed consists of 25% toluene and 75% ethylene. Set up a stoichiometric table to determine the concentrations of each of the reacting species and then to write the rate of reaction solely as a function of conversion. Assume the reaction is elementary with kT=250(dm6/mol2s). The entering pressure is 8.2 atm and the entering temperature is 227C and the reaction takes place isothermally with no pressure drop.

24

Basis of Calculation The stoichiometric ratio is one toluene to two ethylene (1/2). However, the feed is one toluene to three ethylene (1/3) and there is not sufficient toluene to consume all the ethylene. Therefore toluene is the limiting reactant and thus the basis of calculation. Entering Concentrations of ethylene and toluene Let A = toluene, B = ethylene, C = ethyl benzene and D = propylene

Ethylene

Since toluene, i.e. A, is the limiting reactant and has a stoichiometric coefficient of 1

Leaving FB

25

P = P0 and T = T0

26

In terms of conversion

27

Summary

We learned to write the rate expression for a given reaction A B or A B Meaning of rate constant, activation energy k= A e {-E/RT}

Summary

1. Batch System Stoichiometric Reactor (similarly for CSTR and PFR!!)

where; and

28

ISOTHERMAL REACTOR DESIGN In Chapter 1 & 2, we discussed balances on batch & flow reactors. In Chapter 3, we discussed rxns. Here, we will combine rxns and reactors. Topics Part 1: Mole Balances in Terms of Conversion 1. Algorithm for Isothermal Reactor Design 2. Applications/Examples of CRE Algorithm 3. Reversible Reactions 4. ODE Solutions to CRE Problems 5. General Guidelines for California Problems 6. PBR with Pressure Drop 7. Engineering Analysis Part 2: Measures Other Than Conversion 1. Measures Other Than Conversion 2. Membrane Reactors 3. Semibatch Reactors

Part 1: Mole Balances in Terms of Conversion 1. Algorithm for Isothermal Reactor Design The algorithm for the pathway of interest can be summarized as: 1. Mole Balance and Design Equation 2. Rate Law 3. Stoichiometry 4. Combine 5. Evaluate The Evaluate Step can be carried out A. Graphically (Plots) B. Numerically (Quadrature Formulas) C. Analytically (Integral tables) D. Using Software Packages

(choose reactor type) (choose rxn type; gas or liq. phase)

The elementary gas phase reaction 2A + B C takes place in a CSTR at constant temperature (500 K) and constant pressure (16.4 atm). The feed is equal molar in A and B. x = 0.9, k= 10dm6/mol2s VCSTR =?

Mole balance Rate Law Stoichiometry gas phase, isothermal (T = T0), no pressure drop (P = P0)

Derivation

Combine

Evaluate

PFR and Batch Reactors Elementary Gas Phase Reaction: 2A + B C PFR Mole Balance Rate Law Stoichiometry gas phase, isothermal (T = T0), no pressure drop (P = P0), CAo=CBo (=1), v=vo(1+X)

Combine

Parameter Evaluation

V=227 dm3

Deriving CA and CB Remember that the reaction is: For a gas phase system:

Batch Reactor Constant Volume, V=Vo and the pressure changes. Mole Balance

Combine

Parameter Evaluation

Scale Up of Liquid Phase Batch Reactor Data to Design of a CSTR: Scale Up a lab experiment to pilot plant operation of full scale production. Find k from experimental data and use it to design a full scale flow reactor. Batch Operation: Liquid phase: (density change is small V = V0) Gas phase with constant volume V = V0.

1 dN A = rA V dt 1 dN A 1 dN A dN A / V0 dC A = = = rA = V dt V0 dt dt dt

Since concn is a measured quantity in liquid phase rxns:

dC A = rA dt

Lets calculate the time necessary to achieve a given conversion X for the irreversible second order rxn: AB

dX N A0 = rA V0 dt 2 rA = k C A C A = C A0 (1 X )

Combine [1], [2] and [3];

dX = k C A0 (1 X ) 2 dt

Rearrange:

dX = k C A0 dt (1 X ) 2

@ t = 0; X = 0; T = T0 (isothermal) k constant

t =

0

1 k C A0

(1 X )

0

dX

t=

1 X k C A0 1 X

It is important to know the reaction time, tR, to achieve a certain conversion. Flow reactors use characteristic rxn times, tR. The time for a total cycle is much longer than tR, as one must account for the time to fill (tF), heat (th) and clean (tC). t = tf + th + tC + tR Design of Continuous Stirred Tank Reactors CSTRs are usually used for liquid phase rxns:

V=

FA0 X v0 C A0 X = ( rA ) exit rA

[1]

Divide by v0:

V C A0 X = v0 rA

[2]

rA = k C A C A = C A0 (1 X )

1 X k 1 X k X= 1+ k

CA =

C A0 1+ k

rxn Damkhler #, Da: a dimensionless # that for a first order rxn

says the degree of conversion that can be achieved in cont. flow reactor.

Da =

Da =

rA0 V k C A0 V = = k C A0 FA0 v0 C A0

2

Da 0.1 Da 10

X=

Da 1 + Da

CSTRs in Series

CA1, X1 CA0 CA2, X2 -rA1 V1 -rA2 V2

For first order rxn (v = v0) The effluent concn of reactant A from the first CSTR is

C A1 =

C A0 1 + 1 k1

where 1 =

V1 v0

V2 =

Solving for CA2:

C A2 =

C A1 C A0 = 1 + 2 k 2 (1 + 2 k 2 )(1 + 1 k1 )

( 1 = 2 = )

C A0 (1 + k ) 2

C A2 =

for n equal sized CSTR system

C An =

C A0 C A0 = n (1 + k ) (1 + Da) n

C A0 (1 X ) = X = 1

C A0 (1 + Da) n

1 1 = 1 n (1 + Da) (1 + k ) n

CSTRs in Parallel: Equal sized reactors are placed in parallel rather than in series:

FA01 FA02 FA03 FA0n

X1

X2

X3

Xn

Xi V = FA0i r Ai

Since Vi = Vj, then Xi = X; -rA1 = -rA2 = ...... = -rA

[1]

V Vi = n FA0 FA0i = n

[2] [3]

V FA0 X i X . = = FA0 r n n r A Ai

[4]

10

Example: 2nd order rxn, v = v0, CA = CA0 (1-X); FA0 X = v0 CA0 X Combine rA = k CA2 and V = FA0 X / -rA

V=

Divide by v0:

FA0 X v0 C A0 X = 2 2 k CA k C A0 (1 X ) 2

V X = v0 k C A0 (1 X ) 2

(1 + 2 k C A0 ) (1 + 2 k C A0 ) 2 (2 k C A0 ) 2 X= 2 k C A0 X= (1 + 2 Da) 1 + 4 Da 2 Da

Since k C A0 = Da for a second order rxn.

is carried out isothermally in a CSTR. Pure A enters at a volumetric flow rate of 25 dm3/s and at a concentration of 0.2 mol/dm3. What CSTR volume is necessary to achieve a 90% conversion when k = 10 dm3/(mol*s)? Mole Balance Rate Law Stoichiometry liquid phase (v = vo)

11

Combine

Evaluate

at X = 0.9,

12

Applying the algorithm to the above reaction occuring in Batch, CSTR, PFR

13

3. Reversible Reaction To determine the conversion or reactor volume for reversible reactions, one must first calculate the maximum conversion that can be achieved at the isothermal reaction temperature, which is the equilibrium conversion. (See Example 3-8 in the text for additional coverage of equilibrium conversion in isothermal reactor design.) Equilibrium Conversion, Xe

Calculate Equilibrium Conversion (Xe) for a Constant Volume System Example: Determine Xe for a PFR with no pressure drop, P = P0 Given that the system is gas phase and isothermal, determine the reactor volume when X = 0.8 Xe

KC = C Ae

C Be 2 C Ae = C A0 (1 X e )

1 C Be = C A0 X e 2

14

Deriving The Equilibrium Constant (KC) and Equilibrium Conversion (Xe) for a Non-Constant Volume System: The reversible reaction:

which takes place in gas phase PFR. Since gas phase reactions almost always involve volume changes, we will have to account for volume changes in our calculations. The equilibrium constant, KC, for this reaction is:

Substituting known values (CA0 = 0.2 mol/dm3 and KC = 100 dm3/mol), and realizing that:

15

Batch Reactor With a Reversible Reaction The following reaction follows an elementary rate law

Initially 77% N2, 15% O2, 8% inerts are fed to a batch reactor where 80% of the equilibrium conversion (Xe = 0.02) is reached in 151 s. What is the specific reaction rate constant k1?

Additional Information

16

17

Tubular Reactors: Gas-phase rxns are usually carried out in tubular reactors where the gas is generally turbulent.

Reactants

Design Eqn:

FA0

dX = rA dV

In the absence of pressure drop or heat exchange, integral form of the design equation is used:

V = FA0

0

dX rA

Pressure Drop in Reactors In liquid-phase rxns, the concn of reactants is not effected by the changes in pressure. However, in gas phase rxns, concn is propotional to total pressure. Pressure Drop & Rate Law Example: Analyze the following second order gas phase reaction that occurs isothermally in a PBR:

Mole Balance Must use the differential form of the mole balance to separate variables:

18

Stoichiometry Isothermal, T = T0

Combine

P = pressure (kPa) Dp = diameter of particle (m) = porosity = volume of void / total bed volume 1 = volume of solid / total V gC = 1 (metric) = viscosity of gas (kg / m s) z = length down the packed bed (m) u = superficial velocity = v0 (volumetric flow) / A2 (cross-area) = gas density (kg/m3) G = u = superficial mass velocity (kg/m2 s)

m = m (st st )

0 v0 = v

0

Ergun, S., 1952. Fluid flow through packed columns. Chemical Engineering Progress 48, pp. 8994.

19

Variable Density

Catalyst Weight

Then

Since

20

Recall that

Notice that

The two expressions are coupled ordinary differential equations. We can solve them simultaneously using an ODE solver such as Polymath. For the special case of isothermal operation and epsilon = 0, we can obtain an analytical solution.

Analytical Solution

2y

dy = dW

y = 1 ( P = P0 ) @ W = 0 y 2 = 1 W

21

Combine

Solve

For gas phase reactions, as the pressure drop increases, the concentration decreases, resulting in a decreased rate of reaction, hence a lower conversion when compared to a reactor without a pressure drop.

22

Pressure Drop in Pipes: Pressure drop for gases flowing through pipes without packing can be neglected. For flow in pipes, P is given by:

dP du 2 f G 2 = G dL dL gD

Where G = u (g/cm3s) = mass velocity is constant along L. u = average velocity of gas, cm/s. f = fanning friction factor f = fnc (Re, pipe roughness

P 4 f G 2 V 1/ 2 = 1 = (1 pV ) P0 0 P0 AC D

Example p 187

23

24

Increasing the particle diameter descreases the pressure drop and increases the rate and conversion.

However, there is a competing effect. The specific reaction rate decreases as the particle size increases, therefore so deos the conversion. k 1/Dp

25

The larger the particle, the more time it takes the reactant to get in and out of the catalyst particle. For a given catalyst weight, there is a greater external surgace area for smaller particles than larger particles. Therefore, there are more entry ways into the catalyst particle.

7. Engineering Analysis - Critical Thinking and Creative Thinking We want to learn how the various parameters (particle diameter, porosity, etc.) affect the pressure drop and hence conversion. We need to know how to respond to "What if" questions, such as: "If we double the particle size, decrease the porosity by a factor of 3, and double the pipe size, what will happen to D P and X?" To answer these questions we need to see how a varies with these parameters

Turbulent Flow

26

Compare Case 1 and Case 2: For example, Case 1 might be our current situation and Case 2 might be the parameters we want to change to.

= constant

Laminar Flow

Part 2: Mole Balances in terms of Concn & Molar Flow Rates In some cases, it is more convenient to deal with number of moles or molar flow rates rather than conversion. Membrane reactors and multiple rxns taking place in gas phase are examples. The main difference in molar flow rates, you have to write the mole balance on each and every species. Membrane reactors can be used to increase conversion when the rxn is thermodynamically limited as well as to increase the selectivity when multiple rxns are occuring. A. Membrane reactors B. Multiple reaction Liquids: Use concentrations, i.e., CA

27

1. For the elementary liquid phase reaction carried out in a CSTR, where V, vo, CAo, k, and Kc are given and the feed is pure A, the combined mole balance, rate laws, and stoichiometry are:

There are two equations, two unknowns, CA and CB Gases: Use Molar Flow Rates, I.E. FI

2. If the above reaction, ,carried out in the gas phase in a PFR, where V, vo,CAo,k, and Kc are given and the feed is pure A, the combined mole balance, rate laws, and stoichiometry yield, for isothermal operation (T=To) and no pressure drop (P=0) are:

28

Microreactors

Are characterized by their high surface area to volume ratios (due to many micro-tubes and channels). Dchannel = 100m, Lch= 2 cm Control of heat and mass transfer resistance!! They are used for highly exothermis rxns, for rxns with toxic or explosive intermediates. ALso,i for the productions of speciality chemicalsi combinatorial chemical screening, chemical sensors.

29

Membrane Reactors

Membrane reactors can be used to achieve conversions greater than the original equilibrium value. These higher conversions are the result of Le Chatelier's Principle; you can remove one of the reaction products and drive the reaction to the right. To accomplish this, a membrane that is permeable to that reaction product, but is impermeable to all other species, is placed around the reacting mixture.

Example: The following reaction is to be carried out isothermally in a membrane reactor with no pressure drop. The membrane is permeable to Product C, but it is impermeable to all other species.

For membrane reactors, we cannot use conversion. We have to work in terms of the molar flow rates FA, FB, FC. Mole Balances

Rate Laws

30

Combine Parameters

Solve

Polymath

3. Semibatch Reactors

Semibatch reactors can be very effective in maximizing selectivity in liquid phase reactions.

kD A+ B D ( product ) kU A+ B U

(undesired )

2

rD = k D C A C B

2

rU = kU C A C B

Selectivity ( D / U ) =

kD C A kU C B

The reactant that starts in the reactor is always the limiting reactant

31

dX rA = dV FA0

2 (1 X ) C A0 X rA = k C A0 + 1 2 ( 1 ) X X K + C

Matlab solution

32

Example: Elementary Irreversible Reaction Consider the following irreversible elementary reaction

-rA = kCACB The combined mole balance, rate law, and stoichiometry may be written in terms of number of moles, conversion, and/or concentrati

Polymath Equations

33

Equilibrium Conversion in Semibatch Reactors with Reversible Reactions Consider the following reversible reaction:

Everything is the same as for the irreversible case, except for the rate law

Where:

34

0.9 0.8 0.7 0.6 conversion 0.5 0.4 0.3 0.2 0.1 0

50

100

150

200

350

400

450

500

35

function f = packedbed(W,x) alpha = 0.0002; k = 10; epsilon = -0.5; FA0=2.5; CA0 = 0.2; f = zeros(2,1); CA = (CA0*(1-x(1))*x(2))/(1 + epsilon*x(1)); ra = k*(CA.^2); f(1) = ra / FA0; f(2) = -alpha*(1 + epsilon*x(1))/(2*x(2)); >> >> >> >> >> >> >> [W x]=ode45('packedbed', [0 1000], [0;1]); plot(W,x(:,1)) xlabel('W, kg') ylabel('X') plot(W,x(:,2)) xlabel('W, kg') ylabel('y')

1.001

0.999

10

20

30

40

50 W , kg

60

70

80

90

100

1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 10 20 30 40 50 W , kg 60 70 80 90 100 X

36

37

P = pressure (kPa) Dp = diameter of particle (m) = porosity = volume of void / total bed volume 1 = volume of solid / total V gC = 1 (metric) = viscosity of gas (kg / m s) z = length down the packed bed (m) u = superficial velocity = v0 (volumetric flow) / A2 (cross-area) = gas density (kg/m3) G = u = superficial mass velocity (kg/m2 s)

m = m (st st )

0 v0 = v

0

Ergun, S., 1952. Fluid flow through packed columns. Chemical Engineering Progress 48, pp. 8994.

For gas phase reactions, as the pressure drop increases, the concentration decreases, resulting in a decreased rate of reaction, hence a lower conversion when compared to a reactor without a pressure drop.

38

Part 2: Mole Balances in terms of Concn & Molar Flow Rates In some cases, it is more convenient to deal with number of moles or molar flow rates rather than conversion. Membrane reactors and multiple rxns taking place in gas phase are examples. Microreactors with multiple reactions

39

There are some basic steps in Analysis of Rate Data 1. Postulate a rate law: a) Power law model for homogeneous rxns:

rA = k C A C B

rA ' =

k PA PB (1 + K A PA + PB ) 2

2. Select reactor type; i.e.; Batch, CSTR, PFR, PBR...... 3. Process your data in term of measured variables (NA, CA or PA) 4. Do simplifications (assumptions), if rA = k CACB and CA>>CB -rA k CB

5. For batch reactors, find reaction order i. Find (- dCA / dt) from CA vs t data. Take ln. Find the order of rxn by ln (- dCA / dt) = ln k + ln CA Find the rate constant, k. ii. Integral Form: dC A = k CA dt Integrate 1 1 t = C A0 ........ k

dC A = k A CA dt slope =

dC ln A dt

dC ln A = ln k A + ln C A dt

kA =

dC ln A dt P

(dC A / dt )P (C AP )

ln C A

We should differentiate the concentration-time data either graphically or numerically. 1. Graphical differentiation 2. Numerical differentiation formula 3. Differentiation of a polynomial fit to the data.

ln C AP

1. Graphical Tabulate (CAi, ti) observations and for each interval calculate Cn = Cn Cn-1 tn = tn tn-1 ti t0 t1 t2 t3 Ci C0 t1 t0 C1 t2 t1 C2 t3 t2 C3 C3 C2 (CA/ t)3 C2 C1 (CA/ t)2 (dCA / dt)2 C1 C0 (CA/ t)1 (dCA / dt)1 t CA CA/ t (dCA / dt)

Plot these values as a histogram Draw a smooth curve Read estimates of (dCA/dt) at t1, t2, ......

x = xn xn-1 y = yn yn-1 Plot these

y n y1 =

i=2

y xi xi

A B C D

y n y1 =

Try to find

xn

x1

dx dx

dy

Numerical Methods If the data points are equally spaced, i.e., t1 t0 = t2 t1 = t time (min) Concn (mol/dm3)

For initial point

t0 CA0

t1 CA1

t2 CA2

........... ...........

3C A0 + 4C A1 C A2 dC A = 2 t dt t0 1 dC A C A( i +1) C A( i 1) = dt 2 t ti

interior point

] ]

End point

1 dC A C A( n 2 ) 4C A( n 1) + C A( n ) = dt tn 2t

Polynomial fit: Fit the concn time data to an nth order polynomial as:

Integral Method We first guess the rxn order and integrate the differential equation used to model the batch system. If the order is correct, the plot of concn time data should be linear. This method is used when rxn order is known but EA and kA are unknown.

Non Linear Regression Non Linear LeastLeast-Square Analysis We want to find the parameter values (alpha, k, E) for which the sum of the squares of the differences, the measured rate (rm), and the calculated rate (rc) is a minimum.

# of parameters to be determined

# of runs

That is we want to be a minimum. For concentration-time data, we can integrate the mole balance equation for -rA = k CAalpha to obtain

dC A = k CA dt k dt = dC A C A k t =

1 1 C A + Const 1 C A0 1

1 1

Const =

C A = 1 C A0

(1 )k t

Vary and k, obtain S2 (or use a search technique) S(, k) is a minimum (optimization methods)

Concentration vs Time Equations for the proposed rate equations can be done by differential or integration method. Ex.: Liquid phase rxn btw trimethylamine(A) and n-propyl bromide (B) was studied by Winkler & Hinshelwood. The results at 139.4oC are shown below. Initial solns of A & B in benzene, 0.2 molal, were mixed and placed in constant temperature bath. After certain times, they were cooled to stop the rxn. Determine the first order and second order specificrates, k1 and k2, asssuming the rxn is irreversible. Use integration & differential methods. Run 1 2 3 4 t, min 13 34 59 120 x (%) 11.2 25.7 36.7 55.2

1st order - rA =

dC A = k1 C A dt dC A 2 nd order - rA = = k2 C A CB dt

Integration Method

[2]

x=

C A0 C A C A0

C A = C A 0 (1 x ) C A =0.1 0.888

If you repeat for four of the runs: Run 1 2 3 4 t, sec 780 2040 3540 7200 k1 x 10-4 (s-1) 1.54 1.46 1.30 1.12 k2 x 10-3 (L/mol s) 1.63 1.70 1.64 1.71 CD 0.0112 0.0257 0.0367 0.0552

1 -ln(CA /CA0)

0.5

800

1600

2400

4800

5600

6400

7200

15 1/CA -1/CA0

10

800

1600

2400

4800

5600

6400

7200

A plot of CD vs t 0.06 0.05 [D] moles/L 0.04 0.03 0.02 0.01 0 0 1000 2000 3000 4000 time, sec 5000 6000 7000 8000

r=

dC A dC D = dt dt

Slopes determined from the curve are given as follows CD 0.0 0.01 0.02 0.03 0.04 0.05 log rA = log k1 + log CA log rA = log k2 + log CA2 = log k2 + 2 log CA CA 0.10 0.09 0.08 0.07 0.06 0.05 r = dCD/dt (105 gmol/L) 1.58 1.38 1.14 0.79 0.64 0.45 (from rA = k1 CA) (from rA = k2 CA2)

1st: log r vs log CA should yield a straight line with a slope of 1.0. 2nd: log r vs log CA should yield a straight line with a slope of 2.0.

log r = -2.76 + 2.0 log CA The data suggest a slope of 2! log k2 = -2.76 k2 = 1.73 x 10-3 L / mol s

log CA

Another Way (Batch Reactor Data) B + A products -rA = kA CACB if and are both unknown, the rxn could be run in an excess of B so that CB remains essentially unchanged

In determining , the rxn is carried (excess of A) - rA = k' 'C B where k' ' =k A C A k A C A0

S 2 = C Am,i C A0

i =1

(1 )k ti

CD

1 / 1

S = C Am,i abs C

2 i =1

1 A0

(1 )k ti

1 / 1

fminsearch

Method of Initial Rates If there is a reverse rxn, it could render the differential method ineffective. In these cases, initial rates could be used for k & . Carry out a series of experiments with different CA0. Determine rA0 for each run. -rA0 = k CA0 ln(-rA0) vs ln(CA0) Instead of doing at different time steps, repeat the rxn.

Method of Half Lives: The half life of a rxn, t, is defined as the ime it takes for the concentration of the reactant to fall to half of its initial value. If you know t, find k & . If there are more than 1 reactant, use method of excess.

rA = k C A

( A products )

dC A = rA = k C A dt C A = C A0 @ t = t1 / 2 CA = 1 C A0 2

@t = 0 t=

1 1 1 1 1 k ( 1) C C A0 A

1

C 1 A0 t= k ( 1) C A t1 / 2

2 1 1 1 = k ( 1) C A0 t1 / n

Similarly

n 1 1 1 = k ( 1) C A0

10

ln t1/ 2 = ln

2 1 + (1 ) ln C A0 ( 1)k

ln t1/ 2

slope = 1

Differential Reactors

ln C A 0

A differential reactor is used to determine the rate of a rxn as a function of either concentration or partial pressure

L FA0 FAe L Conversion is very small in bed CA is constant CA0 (gradientless) Rxn rate is uniform (almost isothermal) FA0 W FAe

Rate of rxn (mass of cat ) = 0 mass of cat FA0 FAe + rA 'w = 0 FA0 FAe + FA0 FAe w v C v C Ae (in terms of conc' n) rA ' = 0 A0 w F x F rA ' = A0 = P (in terms of flow rate) w w v (C C Ae ) v0 (C P ) = rA ' = 0 A0 w w rA ' =

11

Deviations from Ideal Reactors When the mixing criteria of ideal reactors are not satisfied, mathematical expressions for the conservation equations become more difficult.

Deviations from tubular-flow a) Longtidunal mixing due to vortices and turbulence b) Laminar flow (poor radial mixing) c) By-passing in fixed-bed catalytic reactor.

12

Chapter 6 MULTIPLE REACTIONS If there are multiple rxns, use concentrations not conversions.

intermediate

1. Series Reactions

2. Parallel Reactions

Consecutive rxns

4. Independent

Desired & Undesired Rxns We want to get the desired product, D and avoid the formation of undesired one, U.

kD In the parallel rxn A D kU A U

In series

kU kD A D U

D

Cost Total Cost Reactor Cost

Reactor

Low

Efficiency

High

Selectivity and Yield Selectivity tells us how one product is favored over another when multiple rxns take place

S DU =

~

ND NU

tend

Reaction yield = ratio of the rxn rate of a given product to the rxn rate of key reactant A.

Determine the instantaneous selectivity, SD/U, for the liquid phase reactions:

A+B D A+B U 1 A+B U 2 rD = k 1 C A C B

2

rU 1 = k 2 C A C B rU 2 = k 3 C A C B

3

Sketch the selectivity as a function of the concentration of A. Is there an optimum and if so what is it?

SD/U1U 2 = rD k1C A C B k1C A = = rU1 + rU 2 k 2 C A C B + k 3C A 3C B k 2 + k 3C A 2

2

dS *2 * * = 0 = k1 k 2 + k 3C A k1C A 2k 3C A dC A CA =

*

k2 k3

kD A D kU A U

(desired) (undesired )

rD = k D C A

1 2

rU = k U C A

2

If 1 > 2 SD/U =

Case2:

kD CA 1 2 kU

kD 1 k U C A 2 1

SD/U

as C A

If 1 < 2 SD/U =

SD/U

as C A

In Case 1: If gas rxn, we should run it without any inerts and at high pressures to keep CA high. If liquid phase rxn, the diluents should be minimum. CSTR should not be used, batch or plug flow should be used. In Case 2: Dilute the feed with inerts. CSTR should be used, because CA decreases rapidly.

SD/U ~

SD/U

ED > EU

T

SD/U

ED < EU

T

2. Series Reactions

This series reaction could also be written as Reaction (1) Reaction (2)

Species A:

Species B:

at t = 0, CB = 0

When should you stop the reaction to obtain the maximum amount of B? Let's see

Then

And

The Integrating Factor (1) If you only had an expression of the form (2)

things would be much easier, then you could integrate with respect to z and find y(z). (3) then you could manipulate equation (3): (4) where the term in brackets is the left hand side of equation (1). You need du/dz = u f(z). Recall (5)

If you define

, then

(6) This satisfies the condition that du/dz=u f(z). Therefore, and substituting into equation (4), (7)

where the term in brackets is the left hand side of equation (1). CONCLUSION: If your problem is of the form

(which you should be able to evaluate, since you know f(z)), to yield

Derivation

f(t)=k2, so

The constant can be obtained from the intitial condition that at t=0, CB=0;

k1 A+B D k2 A+B U

rD = k 1C A 1 C B

1 2

rU = k 2 C A 2 C B

S D/U =

rD k 1 ( ) ( ) = CA 1 2 CB 1 2 rU k 2

H>>0

We usually want to max SD/U. So the reactors should be designed to max SD/U

B B A A

B A

B D A

B A

H>>0

Algorithm for Solution of Complex Reactions: In combinations of parallel and series rxns, ODE solver packages make life easier. Write the rxns Write the mole balances Net rate laws Stoichiometry Combine & Solve

4. Applications of Algorithm (1) (2) Case 1: PFR Mole Balances dF A A: dV dF B B: dV dF C C: dV dF D D: dV Rate Laws

= rA = rB = rC = rD

NOTE: The specific reaction rate k1A is defined with respect to species A. NOTE: The specific reaction rate k2C is defined with respect to species C.

rA = r1A + r2A

r1A = -k 1A C A C B r1B = 2r1A r1C = -r1A r1A = -k 1A C A C B

2 2

2 2 3 2

rC = k 1A C A C B k 2C C C C A rD = r2D =

r2C 1 3 2 = k 2C C C C A 3 3

Stoichiometry Combine Species A dC A rA = dV v 0 dC A = dV Species B 2 2 3 2 k1A C A C B k 2C C C C A 3 v0 liquid : v = v0 FA = CAv0

dC B rB = dV v 0 dC B 2k1A C A C B = dV v0

2

Evaluate solution using Polymath of MatLab k1A = 0.5 k2C = 2.0 v0 =5.0 @ t=0; V=0, CA0=4, CB0=4, CC0=0, CD0=0

Species C

dC C rC = dV v 0 dCC k1A C A C B k 2C C C C A = dV v0

2 3 2

Vf = 5 dm3

Species D

dC D rD = dV v 0 dC D 1 k 2C C C C A = v0 dV 3

3 2

10

Case 2: CSTR

Species A

We will specify V, CA0, CB0 along with the specific reaction rates kij. This formulation leaves us with four equations and four unknowns (CA, CB, CC and CD)

2 2 3 2 f(C A ) = - V k 1A C A C B + k 2C C C C A + v 0 (C A0 - C A ) 3 f(C B ) = - V 2k 1A C A C B + v 0 (C B0 - C B )

2

f(C C ) = V k 1A C A C B k 2C C C C A v 0 C C

2 3 2

1 3 2 f(C D ) = V k 2C C C C A v 0 C D 3

11

Species A Species B Species C Species D dC A dt dC B dt dC C dt dC C dt = k 1A C A C B

2

2 vC 3 2 k 2C C C C A 0 A 3 V

v0 [C B0 C B ] 2 2 k 1A C A C B V vC 2 3 2 = k 1A C A C B k 2C C C C A 0 C V v0 C D 1 3 2 = k 2C C C C A V 3

FB0

V = V0 +v 0 t

Parameters

k1A = 0.5 v 0 = 1.2 dm 6 mol2 hr k 2C = 2 C B0 = 4 dm 2 mol4 hr

dm 3 hr Initial conditions

mol V0 = 2dm 3 dm 3 C Ai = 4 C Bi = 0 C Ci = 0 C Di = 0

t f = 8 hr

PolyMath Solutions

12

Rate Laws

Net rates

Species A Species B Species C Species D

rA = k 1A C A C B

2

2 3 2 k 2C C C C A 3

2 3 2

rB = r1B = 2 k 1A C A C B

2

rC = k 1A C A C B k 2C C C C A rD = r2D =

r2C 1 3 2 = k 2C C C C A 3 3

Stoichiometry

CA =

13

Combine

P = 0, P = P0 , T =T0 Ci =C T0 Fi FT

Species A

2 2

Species B

Species C Species D

3

FA F T0

FA F T0

C T0 = 0.8

For a CSTR

V= V= V= V=

FT = FD +FC + FB +FA

14

ConcentrationConcentration-Time Trajectories 1. The following concentration-time trajectories were observed in a batch reactor

Solution: Part 1 Choice B is the answer. Choices A and C are incorrect because they show species B eventually consumed, which is clearly not the case

15

Solution: Part 2

(1) B virtually consumed so no more D can be produced in reaction 2. (2) Rates of Consumption of A and Ba are virtually the same. (3) Rate of consumption of B greater than that of A owing to Reaction 2

16

Active Intermediates and Non-elementary Rate Laws: Usually we have seen that rate can be expressed as: -rA = k CA where = 1, 2, 3, 0 However, a large # of rxns, the orders are non-integers Rate laws may also involve a # of elementary rxns and at least one active intermediate. Active intermediate is a high energy molecule that reacts virtually as fast as it is formed.

It is found in small amounts and shown as A*. A + M A* + M The high E is stored in the chemical bonds where high-amplitude oscillations lead to bond ruptures, molecular rearrangement and decomposition Collision Free radicals, unpaired e Ionic intermediates Enzyme-substrat complexes In 1999, Ahmed Zewail got Nobel for fentosecond spectroscopy.

Pseudo-steady-state Hypothesis (PSSH) The PSSH assumes that the net rate of species A* is zero. rA* 0 The reaction has an elementary rate law

However

Mechanism:

Assume that reactions (1) and (2) are elementary reactions, such that

is zero:

if if

[NO 3 *] = [NO 3 *] =

k1 [NO][O 2 ] k2

2 k1 [O 2 ] k3

if k 2 >> rNO2 =

E 2 - (E 1 + E 3 ) RT

k1 k 3 A A [NO] 2 [O 2 ] = 1 3 e k2 A2

[NO] 2 [O 2 ]

if E2 > (E1 + E3) as T increases r decreases. Apparent rxn order at low concns: 2nd order with NO Apparent rxn order at high concns: 1st order with NO

you can say Rxns consist of a) Activation step b) Deactivation step c) Decomposition step

If you have

+ A A*

+ M

Searching for a Mechanism In many cases the rate data are correlated before a mechanism is found. If you have

rP = rP =

2

Steps in Mechanism Search 1. Species having concns appearing in the denominator of the rate law probably collide with the active intermediate A + A* Products 2. If a constant appears in the denominator, one of the rxn steps is probably the spontaneous decomposition of the active intermediate A* Decomposition products 3. Species having concns in the numerator probably produce the active intermediate Reactant A* + Other Products

1. Assume an active intermediate 2. Postulate a mechanism 3. Model each rxn as an elementary rxn 4. Write the rate laws for active intermediates 5. Use PSSH 6. Eliminate intermediate species 7. If the law obeys the experiment, OK. Example 7-1 (pg 384)

Example: Chain rxns will have steps: 1. Initiation : Formation of active intermediate 2. Propagation : Interaction of A* with reactant 3. Termination : deactivation of A* Active Intermediate C2H6 2CH3. Reaction pathways help us to see the inter-connections for multiple rxns. Metabolic pathways are examples.

Enzymatic Rxn Fundamentals Enzymes (E) are proteins with catalytic properties. They act on substrates (S). They increase the rate by 103 to 1017 times! The rxn coordinate for enzyme catalysis: SP

E +S E S P + E

Active intermediate (enzyme substrate complex)

E S

Enzymes are highly specific (1 enzyme 1rxn), remain unchanged and can be used over and over. A typical enzyme will catalyze the rxn of about 1000 substrate molecules every second. Although concn are low, how do they bind specifically, motions are enormously fast at molecular level. It takes a small molecule 0.2 sec to diffuse a distance of 10 m. Active site will be bombarded by about 500,000 random collisions with the substrate molecule per second. They are named by the type of rxn they catalyze (-ase).

E S

E P

E + P

If the enzyme is exposed to extreme T or pH it will denature. (unfolding will make the active site disappear)

E S

E E + S S E P

2O S + E H P+E

k1 E+S E S

(1) (2)

E S E + S

k2 k3

E S+ W P + E (3)

r1S = - k1 (E) (S) r2S = k 2 (E S) r3P = k 3 (E S) (W)

- rS = k1 (E) (S) - k 2 (E S) (*) (from 1)

rES = k1 (E) (S) - k 2 (E S) - k 3 (W) (E S) Using PSSH, rES = 0 (E S) = k1 (E) (S) k 2 +k 3 (W) k1 (E) (S) k 2 + k 3 (W) (**)

(combine 1 with 2 and 3)

Substitute into (*) - rS = k1 (E) (S) - k 2 Rearranging : - rS = k1 k 3 (E) (S) (W) k 2 + k 3 (W)

But still there is (E) : unbound enzyme conc' n, but we can measure total enzyme conc' n : (E t ) = (E) + (E S) Solving for (E) using (**) E= (E t ) (k 2 + k 3 (W)) k 2 +k 3 (W) + k1 (S) k1 k 3 .......... k 2 + .........

Michaelis Menten Eqn: For a given enzyme concn, a sketch of rate of disappearance of the substrate is shown as a function of substrate concn:

-rs

Vmax

Vmax/2

where Vmax is the maximum rate of rxn S for a given total enzyme concn. Km is callad the Michaelis Menten constant, it is the measure of attraction of the enzyme for its substrate (~affinity constant) The Km is equal to substrate concn at which the rate of rxn is equal to one-half of its max rate.

- rs = Vmax (S) K m + (S)

Km

At low substrate conc' n, K m >> (S) - rs = Vmax (S) the rxn is 1st order Km t he rxn is zero order

Product Enzyme Complex: In many rxns, the Enzyme and Product Complex (E-P) is formed directly from the (E-S) complex as:

E +S E S E P E + P Applying PSSH to (E S) and (E P), we obtain : - rs = Vmax (Cs - C p / K c ) Cs + K max +K p C p

Batch Reactor Calculations for Enzyme Rxns: Lets start writing the mole balance on urea in a batch reactor.

Urea + Urease 2NH 3 + CO 2 + Urease - dN urea = -rurea V (1) dt In liq. phase {C V = N} and V is constant - dC urea = -rurea dt (2)

C urea,0

(3)

C urea,0

t=

C urea

C urea

(4)

Integrate t= C C - C urea Km ln urea,0 + urea,0 Vmax C urea Vmax C -X 1 Km + urea,0 ln Vmax Vmax 1 - X (5)

Determine Km and Vmax from batch reactor data using integral method. Divide both sides of (6) by (t Km / Vmax)

C X 1 V 1 ln = max urea,0 t 1- X Km Km t

(7)

where a =

1 1 ln t 1- X

slope = - 1 / Km

1 S0 ln t S

intercept = Vmax / Km

S0 S / t

Effect of temperature on Enzymatic Rxns A very complex issue! If the enzyme did not unfold, the rate would probably follow a Arrhenius temperature dependence. However, at a certain temperature the enzyme will denature and its activity will be lost! Therefore, we will first have an increase and then decrease:

Vmax T

Inhibition of Enzyme Reactions: Temperature, pH and the presence of an inhibitor influences the rates. Even the inhibition of a single (critical) enzyme may be fatal: E.g.: Cyonide will cause the aerobic oxidation to stop when bound to cytochrome oxidase death (the whole pathway will be affected) Asprin inhibits the enzyme used in synthesis of pain-producing reactants Types of Enzyme Inhibition Competitive Uncompetitive Non-competitive E+I ES+I ES+I IE+S Lets look at them individually I E (Inactive) I E S (Inactive) I E S (Inactive) I E S (Inactive)

10

Competitive Inhibition Very important in drug design: I competes with the substrate for the enzyme

E +S E S E P E+I EI

k1 [1] E + S E S k2 [2] E S E+S k3 [3] E S E+P k4 [4] I + E E I (inactive) k5 [5] E I E+I

(1) (2)

Similarly : rE I = 0 = k 4 (E) (I) - k 5 (E I) The enzyme conc' n : E t =E + (E S) + (E I) Combining (1), (2), (3) and (4) : rp = - rs = Vmax S I S + Km 1 + K I k2 + k3 k1 Vma x and K m are unchanged!

Vmax = k 3 E t

and K m =

and K I =

k5 k4

I Say K m ' = K m K m ' > K m (apparent M - M constants) 1 + K I means a larger S is needed for the decomposition of S. To reach it 1 Vmax 2

11

Rearrangin g : I {Lineweave r Burk} 1 + K I As I increases the slope increases and - rS decreases. 1 1 1 Km = + - rS Vmax S Vmax

1 - rS

I2 > I1

Comp. inhibition I1 No I

1 Vmax

1 S

Uncompetitive Inhibition I has no affinity for the enzyme itself but for (E S) complex.

E +S E S E + P + I k2 E S I

12

1 - rS

I 1 + K I

k5 k4

1 S

Slope remains constant, I increases, Intercept increases, -rS decreases.

E +S E S E + P + I KI + I K I'

E I+S E SI

E +S E + I S+ IE

E S I S (inactive) I E S (inactive)

I + E S I E S (inactive) E S P

13

We have:

1 1 = rs Vmax

I 1 Km 1 + K + S V I max

I 1 + K I

1 - rS

I2 > I1

I1

No Inh

1 S

Both the slope and intercept increase as I increases.

Non comp Uncomp Competitive No Inh.

1 - rS

1 S

Substrate Inhibition In some cases, S can act as a inhibitor. If we have uncompetitive substrat inhibition:

S+ E S SE S - rs = Vmax S K m + S + S 2 /K I (1)

14

at low conc' n

K m >> S + S2 / K I

- rs ~ - rs =

Vmax S Km Vmax K I S

-rS -rSmax

Smax = K m K I (from

- drs = 0) dS

Smax

Multiple E and S Systems: We will look at multiple E and multiple S systems in which cyclic regeneration of the activated E occurs. Enzyme Regeneration: Glucose (SR) is oxidized to -gluconolactone (P) by glucose oxidase (E0)

0 SR + O 2 H 2O 2 + P

E0 ER

H2O2 O2

In enzymatic rxns, a second substrate is needed to activate the enzyme. Cofactor / coenzyme bind to the enzyme Unbound enzyme: apo-enzyme Bound enzyme: holo-enzyme

15

Bioreactors A bioreactor is a special reactor that sustains and supports life for cells and tissue cultures. The use of living cells to produce marketable chemical products made the biotechnology a growing industry. Chemicals, agricultural products, food, etc. Some organic chemicals are thought to be produced by living cells instead of petroleum. The advantages are mild rxn conditions, high yields and stereospecific compounds. Bacteria can be modified to be used as chemical factories. In biosynthesis, the cells are called as biomass.

Nutrients

Cell

Products

The chemical rxns are simultaneous in the cell We have i) Nutrient degradation (fueling) rxns, ATP molecules are used to provide energy.

ii) Synthesis of small molecules (like aa, nucleotides) iii) Synthesis of large molecules (like polymerization off aa to form proteins)

Cell Growth & Division The four phases of cell division G1, S, G2 and M The cell division eqn can be written as

More cells + Product Substrate cells Carbon, Nitrogen, Oxygen and Phosphate are some of the substrates.

16

Cell Growth The number of living cells as a function of time can be shown in a batch reactor as:

Lag cell concn

In Phase I : lag phase, there is little increase in cell concn. Cells are adjusting to their new environment, synthesizing enzymes, getting ready to reproduce.

Phase II: exponential growth phase. Cell divide at maximum rate, all of the enzymes pathways are in place. Phase III: Stationary phase: Cells reach a minimum biological place where the one or more of the nutrient are limiting. Phase IV: Death phase: A decrease in live cell concn occurs.

Rate Laws The most commonly used rate expression for Cell + Substrate More cells + Product is the Monod eq.n for exp growth.

rg = C c

Cell Growth Rate (g/dm3s)

= max

rg = max

Cs K s +Cs Cs C c K s +Cs

max : max spec. growth rate Ks : Monod constant (g/dm3) Cs : Substrate (nutrient) concn (g/dm3)

17

rg

Cs

In many systems, product inhibits the growth rate. Wine production is an example, fermentation of glucose to produce ethanol is inhibited by the product ethanol (ethanol kills the yeast)

rg = k obs

max Cc Cs

K s + Cs

where

k obs

Cp = 1 C * p

{Monod Eq.' n}

There are also Tessier & Moser eqns that fit experimental data better. The cell death rate is given by rd = (kd + kt Ct) Cc

Concn of the substance toxic to the cell

rg

I' =

T

I' : fraction of max growth rate Tm : temp. at which max growth occurs.

18

Stoichiometry for cell growth is complex, and chainges with microorganism/ nutrient system, and pH, T, etc. Lets look at the case where one nutrient is limiting: Cell + Subs More cells + Products

y C/S =

Product formation can take place during different phases of the cell growth cycle if it occurs during the exp growth phase:

max C c C s

K s + Cs

The stoichiometric yield coeff btw product & substrate is given by:

y P/S =

Another term is the maintenance utilization term: (to maintain a cells daily activities)

m=

The rate of substrate consumption rsm = m Cc Neglecting the cell maintenance Cc = yc/s [Cs0 Cs]

19

Substrate Utilization

Net rate of Rate Rate = Substrate consumed + consumed to Consumptio n by cells form product rS = y'S/C rg + y'S/P rP

Stoichiometric coeff

if there is production during growth, it is difficult to seperate amount of substrate used in production and growth -rs = ys/c + m Cc The corresponding rate law is rp = rg yp/c growth associated product formation in the grwoth phase.

rp =

(K sn + Csn )

conc'n of a second nutrient which is used for maintenance and production (because the the nutrient is used up for growth)

(k C

p

sn

Cc )

20

Mass Balances

There are two ways that we could account for the growth of microorganisms. Either # of living cells or mass of the living cells. For a CTSR: { called chemostats are the reactors that contain microorganisms}

Cso

Cc Cs

dC c = V0 C VC c + (rg rd )V dt

Substrate Balance

dC S = V0CSO VS C S + rSV dt

For a Batch System:

V = V0 = 0

Cell balance

(divide by V)

dCS dCS = rSV = yS / C ( rg )V mCCV = yS / C ( rg ) mCC dt dt

Substrate

dC s = rsV = mC oV + y s / p ( rp )V dt

21

Product Balance:

dC dt

= r pV = y p / s ( rs )V

Design Equations

For a CSTR

V0 = V

C CO= 0

D= V0 V

is called the dilution rate (a parameter used in bioreactors)

{ D = 1/ T }

CSTR Mass Balance:

dCC = 0 DCC + (rg rd ) dt

{ For Cell } { For Substrate }

dC S = DCSO DCS + rs dt

rg = CC =

( maxCS CC ) (K S + C S )

DCC = rg rd

D (C SO C S ) = rs

If we neglect death rate

divide by Cc V You can control specific growth rate by D!

22

We know

= max

Cs =

Cs Ks + Cs

(Monod Eqn)

Combining

max D

DKs

If a single nutrient is limiting, - cell growth is the only process to substrate consumption. - cell maintanance is neglected. Then;

ys c Cc = yc / s (Cso Cs ) rs = rg

DK s Cc = yc / s Cso max D

wash-out

Assume

rd = 0

rg = Cc

dCc = ( D)Cc dt

if D>

the dilution rate at which wash-out will occur (Cc = 0) is: M C Dmax = max so K s + Cso

23

m c = Cc o

o Cc

V

Subs

= DCc

{Cell

production per unit volume is the mass flow rate of cells out of the reactor}

Cc

DK s ) max D

DCc

Cs

For max D!

You can model runs in living systems. You can find concn-time profiles for medications, toxins, alcohol and drugs in the body! Compartments of body are either a PFR or CSTR. Perfusion rate : Blood flow in/out of organs. unst-st models are used as CSTR liver : PFR(unst-st) The interchange of material btw compartments is primarily through blood flow.

24

Blood 0 flow

C A0

Organ 1

C A1

Organ 2

C A2

1

2

V1

1

2

V2

Organ 3

C A0

C A3

Then the balance eqns on species A in the tissue water volumes of the organs

V1

V2

and

V3

are:

V1

rAi

:matabolism rate of A in organs

25

Energy Balances, Rationale and Overview Calculate the volume necessary to achieve a conversion, X, in a PFR for a firstorder, exothermic reaction carried out adiabatically. For an adiabatic, exothermic reaction the temperature profile might look something like this:

To solve this equation we need to relate X and T. We will use the Energy Balance to relate X and T. For example, for an adiabatic reaction, energy balance can be written in the form

, the

vs. X

2. CSTR with heat exchanger, UA(Ta-T) and large coolant flow rate.

5. Coolant Balance

These are eqns we will use to solve rxn engineering problems with heat changes.

3. Energy Balance

dE = dQ dW

rate of energy added to the system by mass flow

W = Wf + Ws

flow

n

shaft

~

= Fi P V i

i =1 in

+ Fi P V i

i =1 out

+ Ws

Combining with

Hi = Ui + P Vi

n n

dE sys dt

= Q+ W s Fi H i in + Fi H i out

i =1 i =1

(1)

1. 2. 3. 4. 5. 6.

Replace Ei by Ei=Hi-PVi Express Hi in terms of enthalpies of formation and heat capacities Express Fi in terms of either conversion or rates of reaction Define HRX Define CP Manipulate so that the overall energy balance is either in terms of the Equations above 1.A, 1.B, 2, 3A, 3B, or 4 depending on the application

Step 1:

Substitute , and

into equation (1) to obtain the General Energy Balance Equation. General Energy Balance:

We need to put the above equation into a form that we can easily use to relate X and T in order to size reactors. To achieve this goal, we write the molar flow rates in terms of conversion and the enthalpies as a function of temperature. We now will "dissect" both Fi and Hi. Flow Rates, Fi For the generalized reaction:

(2) In general,

Fi = FA0 (i + i X)

where i =

Fi0 FA0

(3)

A = -1 B = -

b a

C =

c a

D =

d a

Then

H

i =1

i0

i =1

H RX

(4) (5)

(6)

i0

i =1 n

(7)

H i = H i (TR ) + H Qi

o

(8)

o TR TR

TM

(9)

H Qi = C pi dT

T1 T o

T2

(10)

H i = H i (TR ) + C pi dT

TR

(11)

Cp = i + i T + i T 2

H i H i0 =

Ti0

C

n

pi

dT = C pi [T - Ti0 ]

(12)

i =1

(13)

H RX = H RX + C p (T - TR )

o

(14)

where H RX =

o

(15)

C p =

d c b C pD + C pC - C pB - C pA a a a

(16)

o i =1

(17)

Adiabatic Operation:

Ws = 0 Q=0

X=

- HRX + Cp (T - TR )

C

i o

pi

(T - Tio )

]

for an exo. rxn why does X increase? This is from E balance, not mole balance.

H RX > C p (T - TR )

o

so X vs T is linear!!!

T=

X - H RX + i C pi To + X C p TR

o

C

i

pi

+ X C p

(19)

FA0

dX = - rA (X, T) dV

(20)

To obtain T, X and concn profiles along the reactor! Use (19) to construct a table of T vs X. Obtain k(T) as a function of X -rA as a function of X. Look at Table 8-2A.

Q = U A (Ta - T) = Ua (Ta - T) V

FA0 To

assume Ws = 0

FAe Te

F H

i

F H

i

V+V

Q+ Fi H i

Fi H i

V + V

=0

(1)

The heat flow to the reactor Q Overall heat transfer coefficient (U) Heat exchange area (A) Difference between ambient temperature (Ta) and reactor temperature (T)

Q = U A (Ta - T) = Ua V (Ta - T)

A 4 = V D

Diameter of reactor

(2)

If V 0

(3) (4)

dFi

dV

H i = C pi dT

(5)

dT dH i = C pi dV dV

(6)

dT Ua (Ta - T) = i H i (-rA ) - Fi C pi 1 4 2 43 dV

H RX

(7)

Rearrange:

Heat generated removed 6 4 7 48 6 Heat 47 48 dT rA H RX Ua (T - Ta) = dV Fi Cpi

(8)

Fi = FA0 ( + i X)

Substitute into (8)

dT Ua (Ta - T) + rA H RX = dV FA0 ( i + i X + C p X )

{for a PFR}

Ua

for a PBR {dW = b dV}

dT = b dW

F C

i

pi

dX - rA = dV FA0

R2 R1

FA0, To

V V + V

Reactants

The fluid will keep the rxn temperature constant for endo/exo thermic rxns You might have A. Co current Flow B. Counter current Flow

10

E in

V

- E out

V + V V

+ Q conduction = 0 + Ua (T - Ta) V = 0

V + V

FA, T

V

FA, T

mc Hc - mc Hc

V + V

mc

Tao

exothermic

dH c dT = Cp a dV dV

Tao

endothermic

Ta2 Ta

FAo, To

T

V V + V

dTa Ua (Ta - T) = dV m c C pc

V=0

V = Vf

At the entrance X = 0; V = 0; Ta = Ta2 At the exit V = Vf; Ta = Tao The soln to the counter-current flow problem to find {T X} is a trial & error procedure. Assume a coolant temp at the entrance (Ta2) Solve ODEs to calculate X, T and Ta as a function of V: Find Ta(V = Vo)

11

Exothermic Rxns:

Xe =

Kc 1 + Kc

Kc =

Kp ( RT )

Energy balance To1 >To Xe Xe1

Xe =

C pi (T - To )

H RXN (T )

if To is changed to To1 Xe as T

To1 Adabatic temperature

To

12

To increase the conversion in an exothermic rxn, use multiple reactors with interstate cooling:

Xe

Xeb

Xe

Optimum Feed Temperature Adiabatic Reactor of fixed size Reversible & Exothermic Rxn

X

T = To -

H rx X C pA ;T

if H rx < 0 as X

2

350

500

600

T, K

As T

Xe

(so the conversion is achieved at the end of the reactor) So there must be an optimum temperature to achieve max X. Curve A: Rxn rate slow, rxn dictated by rate of rxn and reactor volume As T ,r ,X Curve B: Rxn rate very rapid. Virtual equilibrium reached in X dictated by equilibrium conversion

13

Calculate CB

Calculate KC

Calculate -rA 2. Increment X and then repeat calculations. 3. When finished, plot vs. X or use some numerical technique to find V.

14

Consider:

PFR Shaded area is the volume. For an exit conversion of 40% For an exit conversion of 70%

CSTR

15

Looks like the best arrangement is a CSTR with a 40% conversion followed by a PFR up to 70% conversion.

16

At high coolant flow rates the exponential term will be small, so we can expand the exponential term as a Taylor Series, where the terms of second order or greater are neglected, then:

Ta2

Ta:

where

17

R(T): Varying Entering Temperature R(T) Slope = Cpo (1+) Increase To T Vary non-adiabatic parameter : if you increase FA0 (molar flow rate) or decrease heat exch area then will decrease R(T) = = 0 decrease

Ta To

Ua = FA0 C p0 T + Ta Tc = 0 1+

G(T)

High E Low E

G(T)

G(T)

increasing T

X=

k 1+ k

18

Ignition Extinction Curve: The point of intersection of G(T) and R(T) give Tst-st. By plotting Tst-st vs To, we obtain ignition extinction curve.

Upper st-st

As To

Tst-st

Lower st-st

R(T), G(T)

Tc =

T0 + Ta 1+

Tc

T*

Tangency point

Trc = T * - Tc =

Reactor T

R T *2 E

if this diff. is exceeded, transition to the upper st st will occur. At this high temp, it is undesirable or even dangerous.

19

PFR

i =1

dT = dV

F C

j=1 j

i =1 m

i : rxn j : species

pj

Ex:

Rxn 1 :

k1 A B k2 B C

CSTR

Q - W s + FA0

i =1

Q - W s + FA0

i =1

i n

i =1 q

UA(T a - T) + FA0

i =1 i =1

20

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