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CHEMICAL REACTION ENGINEERING II

CHE 416

CHEMICAL KINETICS AND REACTION DESIGN:


Motivation for understanding chemical kinetics and reaction design: This is what makes us chemical engineers the reactor is the central feature of most chemical processes. Even if separation costs dominate, the reactor often determines the separation costs. Chemical reactions are ubiquitous in nature and industry.

COURSE OUTLINE:CHE416
IDEAL REACTORS ASSUMPTIONS (IDEAL VS. REAL) MATERIAL BALANCE / PERFORMANCE OR DESIGN EQUATIONS COMPARISON OF IDEAL REACTORS NONISOTHERMAL OPERATION ENERGY BALANCE EQUATION APPLICATION TO DESIGN

OUTLINE:CHE416 CONTD.
REAL VERSUS IDEAL REACTORS SOURCE OF DEVIATIONS RESIDENCE TIME DSTRIBUTION RTD FUNCTIONS CONVERSIONS-1ST ORDER RXNS REACTOR MODELS

ATTENTIVE IN CLASS
RE-READ NOTES PRACTICE SOLVING QUESTIONS YOURSELF ASK QUESTIONS TO BE SURE YOU UNDERSTAND BE READY FOR WEEKLY TESTS

WHY IDEAL REACTORS?


Represent distinct extremes of mixing (100% in BR and CSTR; 0% in axial direction for PFR) Ideal reactors simpler to analyse [well defined flow pattern of fluid in reactors] More complex real reactors can be examined in terms of ideal reactors For new designs ideal reactors help determine type of mixing that leads to better results

WHY IDEAL REACTORS? Contd.


estimate the size of the required reactor syst. Gives insight into: the operation of the real reactors Effect of parameters on results most important factors to control Hence powerful models for chemical reaction systems much to gain from a study of ideal reactors.

IDEAL REACTOR MODELS


Based on assumptions about mixing patterns within them One of the assumptions represent the best way of contacting the reactants Easy to treat mathematically Insights obtained are significant for real reactors-type of mixing, important design parameters, better control

Ideal reactor types


1. batch reactor (BR) 100% mixing 2. Continuously(operated) stirred tank reactor (CSTR) 3. plug flow reactor (PFR)

Batch Reactor (BR)


operates in a discontinuous way reactants and any other substances (catalyst, solvent etc.) are loaded into the reactor at beginning Contents subjected to perfect mixing (and left to react) for a certain period. The resultant mixture is then discharged.

Batch reactor: homogenous reaction mixture

Batch Reactor (BR)2


operates in unsteady mode with respect to time at any position Composition at any point in reactor changes continuously wrt time 1st order reaction: CA=CA0e-kt operates in steady mode wrt space. No variation from point to point because of perfect mixing at any point in time

CA VS t,

CA VS t,p Fig
1

Advantages/Disadvantages of BR
is simple, needs little supporting equipments, high flexibility-high conversions through as high reaction time as desired ideal for small-scale experiments (kinetics studies).

Advantages/Disadvantages of BR2
Industrially, a single unit may be used for the manufacture of relatively small amounts of material (drugs, dyes, cosmetic articles)-not dedicated unit Disadvantages are idle periods (for loading, unloading, cleaning, heating etc).

Design equation of BR
Obtained from the law of conservation of matter. Written for any component in the system [ reactant, product, inert] Written in terms of limiting reactant ,A Written for the whole volume of reactor because of uniform conditions within it

Control volume/element of volume


Reactions occur in a localized region of space Control volume is any region of space that has a finite volume with boundaries that clearly separate the region from the rest of the universe. real or abstract ,macrosized Chosen according to the dictates of the analysis that we are undertaking

Law of conservation of mass


a

Balance after t>0


Rate in=0 no inflow after charging Rate out=0 no outflow after charging Rate of disappearance by reaction=V(-rA) Rate of accumulation=dNA/dt =dNA0(1-XA)/dt = -NA0dXA/dt t=REACTION TIME

Substituting in equation 0-0-V(-rA)=-NA0dXA/dt Integrating between: t=0, XA=0

dt N A0
0 X Ae

X Ae

dX A V (rA )

t N A0

dX A V (rA )

For constant volume reaction mixture

t C A0

X Ae

dX A V (rA )

This gives the time for a conversion of XA=XAe as a function of the: rate law and the initial concentration of A

Reaction time, t, is the natural performance measure for a BR


Integral =area under the curve of [1/(-rA ) ] vs.XA. It may be evaluated 1.Analytically 2.Graphically 3.Numerically( minimum of 5 points considered sufficient)

f(x)

1 2 3

a=0

x=(a+b)/2

b=XAe

CONTINUOUS STIRRED TANK REACTOR (CSTR)


Continuous refers to the inflow and outflow of materials. Hence CFSTR Name misses the essence of the idealization completely ideality arises from assumption that the reactor is perfectly mixed and hence homogeneous Continuous perfectly mixed reactor(=CPMR) is an even better name

CSTR: Homogeneous reaction


mixture, constant inflow & outflow

CSTR contd2.
mixing so perfect that concentration and temperature are spatially uniform within whole of reactor and correspond to those of the exit stream; operates in a steady mode wrt. time [at all times, Ci is same at any point] operates in a steady mode wrt. space Ci .is same at all points at any t]

Design equation: CSTR


element of volume=total reactor Rate in=FA0 Rate out=FAe Rate of disappearance by reaction =V(-rA) Rate of accumulation =0 (steady state) FA0 - FAe- V(-rA)=0

CSTR
reactants *

contd.

continuously fed into the

reactor products continuously drawn from reactor Also called vat, backmix reactor, mixed flow reactor 100% back mixing

Term In Square Brackets =area of The Rectangle1/(-ra) By Xae


Rearranging to obtain the space time,

VCSTR=[FA0/(-rA)] x XAe

Space time and space velocity


= time required to process one reactor volume of feed measured at specified conditions, usually feed conditions = V/vo = (reactor volume)/(volumetric feed rate =space time Space velocity=1/space time gas hourly Space velocity GHSV liquid hourly Space velocity=LHSV

APPLICATION OF CSTR. For continuous production


WHEN INTENSE MIXING IS REQUIRED CAN BE USED ALONE OR AS part OF BATTERY of CSTRs EASY TO MAINTAIN GOOD TEMPERATURE CONTROL CONVERSION OF REACTANT PER VOLUME IS LOWEST OF THE FLOW REACTORS. LARGE VOLUME IS REQUIRED MOST LIQUID PHASE REACTIONS

Plug/Piston/ slug flow reactor [PFR] Continuous Tubular Reactors (CTRs). Plug flow Tubular Reactors (PFTR)
FLUID Flows orderly
No Element Of Fluid Mixing With Or Overtaking Any Other Element Ahead Or Behind. May Be Lateral Mixing, No Diffusion Along The Flow Path (0% Of Backmixing).

Plug flow Tubular Reactors (PFTR)


CONTINUOUS OPERATION reactants continuously fed into the reactor products continuously drawn from reactor operates in a steady mode wrt. time [at all times, Ci is same at a given point] Spatial variation in composition and temperature from entrance to exit of reactor

PFR or PFTR or CTRs


Variation in composition and temperature along the length of reactor The PFR model works well for many fluids: liquids, gases, and slurries. turbulent flow and axial diffusion cause a degree of mixing in the axial direction in real reactors PFR model is appropriate when these effects are sufficiently small that they can be ignored.

Design equation2

DESIGN EQUATION: PFR


element of volume is a section of tube of volume V, small enough for the rate of reaction within it to be considered uniform. Rate IN(moles / time) =FA Rate out(moles / time) =FA + FA Rate of disappearance by reaction = V(-rA) Rate of accumulation =0 (steady state) Substituting in balance equation

FA-(FA+FA)-(-rA)V=0
-FA=(-rA)V FA/V=-(-rA) As V0 In terms of XA, dV =FA0 [dXA/(-rA)] Integrating,

From : FA= FA0(1- XA) Separating variables and integrating

Applications: PFR
Large-scale reactions Homogeneous or heterogeneous reactions Continuous production Most gas phase reactions Relatively Easy to maintain(no moving parts) Highest conversion per volume Difficult to control temperature within the reactor, hence hot spots for exothermic rxns As one long tube or as a tube bank

Actual residence time and space time


THE actual time a fluid element resides in the reactor will be equal to the space time only if: 1. There is no change in the number of moles during the reaction 2. There is no change in temperature 3. There is no change in pressure 4. = vo(1+XAA) [T /T0][P 0 /P]

Actual residence time:PFR


the time to traverse and element of volume dV, is dtr From differential form of the design equation Substituting for dV from above,

tr=Actual residence time of fluid in reactor,

Actual residence time: PFR contd.


Integrating

SYSTEM OF REACTORS CSTR in a series


CSTR in series: nth reactor IN OUT-DISAPPEARANCE BY REACTION=0

CSTRs in a series
FA0 CA0 FA2; CA2

FA1;

CA1

2 1

CA3

nth CSTR in a series

1/(-rA) [XA2-XA1)/(-rA2) 1/(-rA3)

[XA3-XA2)/(-rA3)

[XA1-XA0)/(-rA1)
1/(-rA2) 1/(-rA1)

XA

XA0

XA1

XA2

XA3

SIZE COMPARISON OF IDEAL REACTORS: for single reactions


Kind of reactors affects the Size of reactor affects and selectivity

BR vs. PFR
*

CA0= NA0/V for BR ;

CA0= FA0/0 for PFR

PFR vs. CSTR


For any conversion and for all positive reaction orders, the CSTR is always larger than the PFR: VCSTR / VPFR > 1.

For any conversion, the ratio of volumes : VCSTR/VPFR increases with the reaction order. For any positive reaction order, the ratio of volumes VCSTR/VPFR increases with the conversion

Size comparison of single reactors: autocatalytic reactions


(1/rA) - A curve, a comparison of areas will show which reactor is superior for a given job

positive nth order, the rate is maximum at high CA it slows progressively as the reactant is consumed

in autocatalytic reactions, the rate at the start is low (little product is present), it increases to a maximum as product is formed and then it drops again as reactant is consumed.

Size comparison of multi-reactor systems Instead of a single reactor


Reactors of the same or different types,

different or equal size , arranged in


series or in parallel, can be used.

PFR in se vs. A single P

XA0

XA1

XA2 XA3

Design for parallel reactions A D; rD =k1CA1 ; A U; rU =k2CA2

Summary of ideal reactor systems: general rules


a single, piston flow reactor will give higher conversion and better selectivity than a CSTR. combinations of isothermal reactors provide intermediate levels of performance compared with single reactors that have the same total volume and flow rate. parallel reactor system has an extra degree of freedom compared with a series system. A parallel reactor system at the same.T, total V and flowrate has no performance advantages compared with a single reactor When heat must be transferred to or from the reactants, identical small reactors in parallel may be preferred because the desired operating temperature is easier to achieve.

Summary of ideal reactor systems: general rules


A single, PFR will give higher conversion and better selectivity than a CSTR. combinations of isothermal reactors provide intermediate levels of performance compared with single reactors that have the same total volume and flow rate.

GENERAL RULES CONTD1.


A parallel reactor system has an extra degree of freedom compared with a series system. A parallel reactor system at the same T, total V and flowrate has no performance advantages compared with a single reactor

GENERAL RULES CONTD2


When significant amounts of heat must be transferred to or from the reactants, identical small reactors in parallel may be preferred because the desired operating temperature is easier to achieve. Autocatalytic reactions are exceptions to both these statements.

N equal-size CSTR in series; 1st order constant density reaction


At constant reaction T,

Same results as a single PFR with same Several CSTRs in series approaches performance of a single PFR with same total V