DISTRIBUTIONS OF RESIDENCE TIMES (RTD) FOR CHEMICAL REACTORS © -PART 1- @ e@ By: Mdm. Noor Amirah Abdul HalimTHEORY OF RTD © Definition of Residence Time Distribution (RTD) - Probability distribution function that describes the amount of time that a fluid element could spend inside the reactor o Purpose of RTD Analysis - To characterize the mixing and flow within reactors - To compare the behavior of real reactors to their ideal models Why?.. - For reactors troubleshooting - Estimation of yield for given reaction Future reactor design o The theory of RTD generally begins with 3 assumptions: 1. The reactor is at steady-state, 2. Transports at the inlet and the outlet takes place only by advection 3. The fluid is incompressible (v = constant).Residence Time Distribution (RTD) Function E (t) o The distribution of residence times is represented by an external residence time distribution or an exit age distribution, E(t). The function E(t) has the units of time-1 and is defined such that: ‘The “E Curve [F@d=1 fs, SO tts) o The fraction of the fluid that spends a given duration, (t) inside the reactor is given by the value of B(t)dt. @The Cumulative Distribution Function F(t) o The fraction of the fluid that leaves the reactor with an age less than (t1) is; F(4)=[' E@at Where F (t) is called ‘cumulative distribution’ o Thus, The fraction of the fluid that leaves the reactor with an age greater than (ti) is 1-F(t,)=1 -[ E(t)dt = [oaMean Residence Time tm o The average residence time is given by the first moment of the age distribution: [=O - t, =—2——_ = in tE(dt te [Ewa o For no dispersion/diffusion in the reactor: space time (t) equal to mean residence time (tm) tT=V/v=t,,Variance o2 o The behavior of the function E(¢) also could indicate the degree of dispersion around the mean through the variance (02), o° = [t-t,) Eat (ttn EMEASUREMENT OF RTD o RTD can be determined experimentally by; 1. Injecting an inert chemical/molecule/atom called tracer ,into the reactor at t=0 2. Measure the tracer concentration ,C in the effluent stream as a function of time. Injection Reactor Cult) Detection t=0 The "C" Curveo Properties of tracer : Non reactive species Easily detectable Physical properties similar to reacting mixture Completely soluble in the mixture Not adsorb on the wall or other reactor surface o Common type tracer- Colored an radioactive materials along with inert gases o RTD can be determined by two experimental methods (based on injection method: pulse or step) 1. Pulse experiment 2. Step experimentPulse injection c | —_— Cc The C curve ‘Step response ‘Step injectionPULSE EXPERIMENT o This method required the introduction of a very small volume of concentrated tracer at the inlet of the reactor, .The outlet tracer concentration C (t) is then measured as a function of time. The C curve cA The E curve CH E(t) = a t E(t) > Area = J, c(t)at IX e | C(t) dt 0Example: o From our experiment data of the exit tracer concentration from pulse tracer test t(min) 012 3 4 56 C(mg/m?):000.10.20.30.10 o We can obtain; ‘Area "ty : Area = 0° DB Oba L: 2 oe) ao - ° sa =[3Q2 FEO oa [BO nOpRO 0? [ng Fab DSTEP EXPERIMENT o Ina step experiment, the concentration of tracer at the reactor inlet changes abruptly from 0 to Co. The concentration of tracer at the outlet is measured and normalized to the concentration Co to obtain the non-dimensional cumulative distribution curve F(t) which goes from 0 to 1: Foo 0 Step Input a Ca Cout 7 & r tDISCUSSIONS o The RTD function E(¢) can be determined directly from a pulse input, o The cumulative distribution F(é) can be determined directly from a step input. o Relation of the step- and pulse-responses of a reactor are given by ; " dF F(t)= [ E(idt E(t) = “o The value of the mean residence time (tm) and the variance (02) can also be deduced from the cumulative distribution function F(t): i, =[f ar = [ dF (A) =-fidtl-Fo) = [Fold o =[-1,)°Btodt=[(r-1,)°dEO =[rar@-n =f ll-F()|dt-2EXERCISE 1 The following is an E curve calculated for reactor Y Et) 0 0 2 4 6 minutes 1. What is the maximum value of E shown on this curve? 2. What fraction of the molecules spend between 2 and 2.5 minutes in the reactor 3. What fraction spend between 3.5 and 4 @4.Which curve below corresponds to F(t)? Fw Fy FyEXERCISE 2 The F curves is shown below for a real reactor What is the mean residence time?EXAMPLE The following data were obtained from a tracer test to a reactor. 1) Plot Ct(t). 2) Find E(t). 3) Find the fraction of material that spends between 15 and 20 seconds in the reactor. 4) Find F(t) and, the fraction of material that spends 25 seconds or less in the reactor. 5) Evaluate mean residence time. 6) Evaluate the variance.1. C(t) curve oo 5 6100 15 6200 580 t)o Find E (t) 1. Determine the area of C(t) curve 10 15 20 25 168) 1 mel mg Area =5 (20-10) 5x 102%, + 360-20) 10 fea = 10 Cy en feng Orme fay See2. Construct the E (t) curve lecs>= olis feo jes bol Icx¢maram>):| js fro js fo Ee) (=) fa 0.10 Et) @) °° Q 5 10 15 20 25 30 Ke) For t<10 E(t)=0 For 10 St 20, E@)=E,(t)= 0.10 (t-10) For 205+530, E(t)=E2¢)-0.10 Go-t) For t230, E(t)=0o Fraction of material spend for 15-20 s in reactor FQ) 5 10 15 20 2 30 1) 20 J E(t)dt= A, = Fractional material spending between time 15 and 20 seconds in reactor 3 ff. E(a= Area = (20-15) s (0.05) s +3(20-15) s (0.1-0.05) s* = 0.25 +0.175 = 0.315 37.5% of the material spends between 15 and 20 seconds in the reactoro F(t) and, the fraction of material that spends 25 s or less in the reactor F(25) = area = 0.875 5 15 20 25 30 t@) 87.5% of the material spends less than 25 minutes in the reactor.o Mean residence time (tn) tm = T= Jeeo Variance « ta=t Area= 15 s*2 15: ¢- EQ) 10 05.RTD FOR IDEAL REACTORS o The RTD of a reactor can be used to compare its behavior to that of two ideal reactor models: the PFR and the CSTR (or mixed-flow reactor). o This characteristic is important in order to calculate the performance of a reaction with known kinetics.BATCH & PLUG FLOW REACTORS (PFR) o Inan ideal PFR, there is no mixing and the fluid elements leave in the same order they arrived. o Therefore, fluid entering the reactor at time ¢ will exit the reactor at time t +1, where t is the residence time of the reactor. o The residence time distribution function, E(t) is therefore a dirac delta function (6) at t. o E(t) for PFR is given by: | E(t) = 8(f—T) o Where the dirac delta function (6) at is given as o Assume (x=t) a) = }0 when x #0 [x when x = 0 i B(x) de =1 @PROPERTIES OF DIRAC DELTA 1. S{t-a)=0, tea 2. fF a¢-a)at=1, e>0 3. [°° 7 ()d(t-a) t= F(a),Thus: « Mean residence time: !m = i, tE(t) dt = f, 18(t — 1) dt = Variance: og? = [ (@—v2a¢ — Dat =0 o t 1 E(dt = | a(t — Dat Cumulative distributions: F(t) = | 0CSTR (MIXED FLOW REACTOR) o An ideal CSTR is based on the assumption that the flow at the inlet is completely and instantly mixed into the bulk of the reactor. o The reactor and the outlet fluid have identical, homogeneous compositions at all times. An ideal CSTR has an exponential residence time distribution: o Equation for CSTR E(t) eles Tr t ta =| 1E(t) at = | petdt=t 0 0 [SP eae |” o-netde=e @ o Tt “0PREDICTING CONVERSION AND EXIT CONCENTRATION o The RTD tells us how long the various fluid elements have been in the reactor, but it does not tell us anything about the exchange of matter between the fluid elements. o The length of time each molecule spends in the reactor is all that is needed to predict conversion.TYPE OF MIXING o Macromixing - Produces a distribution of residence times o Micromixing - Describes how molecules of different ages encounter one another in the reactor. 2 types: 1. Complete Segregation : All molecules of the same age group remain together as they travel through the reactor and are not mixed with any other age until they exit the reactor 2. Complete Micromixing Molecules of different age groups are completely mix at the molecular level as soon as they enter the reacCONVERSION (X) o For batch reactor : o For PFR: o For CSTR eC agt 1+kCg ot ka gt 1$kCy gt (xy “ roReactor Modeling Using RTD e¢ 4 ress acre To Ceye Maximum Model Mixedness ModelSEGREGATION MODEL In the segregation model globules behave as batch reactors operated for different times Mean conversion for the segregation model xt) E() The segregation model has mixing at the latest possible point.Xg2XQ0X1 Yo Segregation Model Mixing of different age groups at the ew last possible The farther the molecules travel along the reactor before being removed, the longer their residence time. Each globule exiting the real reactor at different times will have a different conversion. fee, Xe.)MAXIMUM MIXEDNESS MODEL Maximum mixedness: Mixing occurs at the earliest possible point As soon as the fluid enters the reactor, it is completely mixed radially (but not longitudinally) with the other fluid already in the reactor. on 0vgE(AA A+ AR A+AR = mf mayan = vata = mf mayan = vata FOO! eE O)AAIC ao)Continue from previous example: The second order reaction 24—B+C occurs in the liquid phase, The RTD function for the reactor in which it is to be carried out is given by The entering concentration is 2 molar and the specific reaction rate is 0.06 dm?/mol s, 0.10 0.05 E() ©) 5 10 15 20 25 30 " @(a) What is the conversion after 30 seconds in a batch reactor? __kCaot ~ 1+kCa gt 0.06 dm 3/mot es 2 moi fdm* Bos 3.6 ons 14.06 din 3/ino mol fdm? 30s) 4.6 keo73(b) What conversion would be achieved in a PFR with the same mean residence time? __kChot © 1+kCggt ECag = Cos .06 dm 3/tol e snol /dn = 24(c) What conversion would be achieved in a CSTR with the same mean residence time? x (1-xy = Ga 2 x X°-M+1= Cao eC ag =24 fke053](4) What is the conversion predicted by the segregation model? Segregation model R= [Pxe ROH - Jest pePlotting the above data of XE(t) vs. 1) Summary t = 30s Xpatch = 0.78 = 20s Xppe = 0.71 t = 20s Xcsta = 0.53 = 205 Xseg = 0.7