LABORATORY MANUAL

REACTION ENGINEERING LAB

Chemical Engineering Department Universiti Teknologi PETRONAS Bandar Sri Iskandar 31750 TRONOH Perak Darul Ridzuan

Written and compiled by: Nurhayati Mellon (2006) Revised: January 2012

TABLE OF CONTENT

GENERAL SAFETY IN THE LABORATORY ............................................................... 3 COLLECTION AND ANALYSIS OF RATE DATA .......................................................... 8 DISTRIBUTION OF RESIDENCE TIME FOR CHEMICAL REACTORS ................................... 14 EXPERIMENT 1: BATCH LIQUID REACTOR ............................................................ 23 EXPERIMENT 2: CSTR WITH HOT WATER CIRCULATOR ............................................ 32 EXPERIMENT 3: CSTR IN SERIES ...................................................................... 39 EXPERIMENT 4: CSTR DYNAMICS ..................................................................... 45 EXPERIMENT 5: PACKED BED REACTOR ............................................................. 52

GENERAL SAFETY IN THE LABORATORY

GENERAL SAFETY IN THE LABORATORY This chapter contains a brief account of some aspects of safety, which are especially relevant to the School of Chemical Engineering. It is to serve as a guide and not as a comprehensive manual on safety. A collection of literature on laboratory hazards is maintained in the library. The safety legislation places the responsibility to work safely firmly on each and every individual. Every staff/student has, at all time, a duty to care for the Health and Safety of himself/herself and of all other people who may be affected by his/her actions. Responsibility cannot be delegated. Everyone must observe all safety precautions. The provision or acquisition of information concerning hazards, before they are encountered and the development of sound practical techniques are the main ways in which standards can be improved. Protective clothing: Laboratory coats (or other protective clothing) and covered shoes MUST be worn at all times. Skin, baju kurung, jubah and shorts are not allowed to be worn in the laboratory. Rubber gloves should be worn handling corrosive materials, and heatproof gauntlets when discharging any equipment involving on heat. Foot-Ware: 1. Stout shoes or boot should be worn in the plant/laboratory. 2. Soft-shoes, uncovered shoes, sandals, and slippers are not permitted. 3. 'Totector' boots MUST be used during lifting and winching operations. During such operations ALL personnel must wear helmets. Other personal protection equipment: 1. Googles, full face visor, gloves, resporators, earplugs and ear muffs are available and must be used whenever necessary 2. When working in a laboratory, either safety spectacles or an eye shield MUST normally be worn especially when handling chemical or hazardous equipment. 3. When performing any operation involving hazard to eyes, e.g. handling acid or alkali, use either full visor or work in fume hood.
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4. If there is any doubt concerning personnel safety and protection, Safety Officer/ Programme Chairman/lecturer should be consulted.

Electricity: 1. Very large amount of electricity is consumed during unit operations experiments. Sometimes the floor may be wet. Care is therefore essential 2. Always switch off power before removing plugs from sockets. All personnel working in the laboratory must know where to switch off all main power supplies in an emergency Cables And Hoses: 1. Cables must be suspended and not lying on the floor. All cables and hoses should be routed to avoid walkways. Pipes carrying steam can cause contact burns and scalding at outlets. Broken Glass: 1. This should dispose off in the glass bin, NOT in the usual waste bin. Breakage should also be reported to the technician in charge of the equipment. Heavy Machinery And Lathes: 1. Operation of these machines is only allowed under the supervision of a Workshop Technician. Suitable operating procedures are laid down for these machines and adequate guards are fitted. Never use the machine when the guards are not in place. 2. Always obey the set instructions and use whatever special protective clothing and equipment are specified. Instruction sheets: 1. Any appropriate instruction sheets should be studied before starting the experiment. Particular attention should be given to the recommended precautions, start up procedure and sequence of operation.

2. Equipment should be left in safe condition and electrically isolated at the end of any working period and should not be left operating when unattended. (Unless the procedure given below is complied with) 3. Water supplies should be isolated or disconnected when the equipment is not in use. 4. There should be no eating or reading of newspapers in the laboratory. 5. Smoking is strictly prohibited in all laboratories. Toxic substances: 1. Almost every chemical is poisonous to some extent. A recently published estimate suggests that between 1% and 2% off all common laboratory chemicals are carcinogenic. Therefore one must adopt a double edged approach to the handling of all chemicals. 2. A safe and reliable laboratory techniques must be cultivated. 3. Additionally must learn to recognize special toxic hazards and carry out advance planning to deal with them. Normally a poison may enter the body through the nose, mouth or skin. Some techniques for avoidance are: 1. Do not smoke, eat or drink in laboratories. Do not use mouth pipetting techniques, always use the pipette pump. Try not to allow chemicals to come contact with the hands. Always wash thoroughly at the end of the period of laboratory work, and during the work if necessary. 2. Use a fume cupboard or glove box whenever handling materials that can gives toxic fumes, dusts or aerosol. Where necessary use a respirator. Remember that homogenisers, centrifuges and other dissolution techniques produce aerosols. Notice that spillage of mercury represent long-term sources of a volatile and cumulative poison. 3. Broken glassware represents a common way for unintentional injection of chemicals. Handle broken glass and other sharp objects with caution. Chemicals can also enter the body through breaks in the skin. Therefore use plasters or gloves whenever such risks are present. 4. Many liquids readily pass through the skin. Some such as aniline are poisonous in themselves, other such as dimethysulphoxide will dissolve and carry through material which had been on the skin surface. You must always aim to avoid or contain spillage. If they do occur, spillage must be cleared up immediately, avoid skin contact. Rubber gloves under certain circumstances may be used to hold chemicals against the skin. Therefore:
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1. Learn the various emergency procedures 2. Know the location of the nearest telephone; fire alarm, fire fighting equipment, first aid box and eye wash station. Ensure that all these appliances are maintained in a satisfactory state 3. Know the location of the main control valve, stopcocks and switches. 4. Use all appropriate protective devices. Eye protection must always be used when chemical substances or apparatus are handled 5. Ensure that adequate warning notices are always given and that warning notices, which no longer apply removed. 6. Ensure that all equipment intended to run unattended for long periods example overnight is safely and securely assembled, a bears a notice showing the date and clearly stating the emergency close down procedure. 7. Avoid smoking and eating in laboratories 8. Do not wear laboratory coats in place where people eat or drink 9. Ensure that all hazardous materials are properly stored and in the minimum quantities consistent with the work being undertaken. 10. Report to the Programme Chairman/lecturer or technician on any accidents involving personal injury and incidents that might have had serious consequences. Accident report forms are available. 11. Treat all aspects of safety as matters of paramount importance.

Thus the basic equation for any health risk (Farmer, 1989) is: HAZARD x EXPOSURE = RISK To minimise risk, both hazard and exposure must be kept to a minimum, and this needs a proper formulated safety measures. Safety means abiding the well-laid rules, failing which will result in the unwanted problems and disaster. The rules and regulation itself do not guarantee safety without the full co-operation from all the members of any organisations. Realisation and appreciation of the chemical hazards should be the main concern to us as the quality of environment is in question which determine the survival of the future generation. Emergency Evacuation Plan In the event of evacuation, the alarm will ring continuously. Please follow the evacuation procedure; as follows: 1. Leave by the nearest safe exit. Proceed in calm.
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2. Proceed to your assigned Emergency Assembly Area (EAA). 3. Please leave all personal belonging. 4. Choose another exit route if you detect or sense a hazard. 5. Be ready to provide management or emergency response personnel with information they need for documentation. Security Officers are located at every building to control the situation. 6. Return to the building only after you are told it is safe to do so

COLLECTION AND ANALYSIS OF RATE DATA

INTRODUCTION In order to successfully design a chemical reactor for industrial scale application, the designer needs to know the rate law for the reaction as well as how the change in temperature, pressure and concentration affects the conversion, selectivity and yield of the reaction. These data are obtained through laboratory scale experiment. Usually the studies on rate analysis are done using either batch reactor or differential reactor due to the ease of mole balance analysis. Batch reactor is usually used for homogeneous system whereas differential reactor is usually used for heterogeneous systems. For batch reactor, experimental data are taken during the transient operation. For differential reactor, the experimental data are taken during the steady state operation. There are several techniques available to analyse experimental data and the suitability of each method depends on the type of reaction or experimental condition involved. Among the techniques are: 1. Differential method of analysis 2. Integral method of analysis 3. Methods of initial rates 4. Method of half lives Only two techniques will be discussed in detailed in this section. These are the differential and integral method of analysis. THE ALGORITHM FOR DATA ANALYSIS Generally, there are 5 steps involved in analysing rate law and rate law parameter (Fogler, 2006): 1. Postulate the rate law. For homogeneous reaction, the rate law is most probably presented by the power law models:
rA = kC , rA = kC CB A A

For heterogeneous reaction, the rate law is most probably presented by the LangmuirHinshelwood model:

' rA =

kPA kPA ' , rA = 1 + K A PA (1 + K A PA + K B PB )2

2. Select the reactor type used for the experiment and the corresponding mole balance equation. For example: a. If a batch reactor is used, then the appropriate equation that represents the mole balance equation for reaction A P is:

rA =

dC A dt

b. If a differential reactor is used, then the appropriate equation that represents the mole balance equation for reaction A P is:

rA =

C p vo FP = W W

3. Process your data in terms of the measured variables. For example, if the data that is measured in the lab experiment is in terms of product concentration, but the mole balance equation is in terms of the reactant concentration, then it is necessary to change the mole balance equation in terms of the measure variables from lab experiment. This is to reduce error during analysis. 4. Look for any simplifications. For example, if the reaction involved two reactants, in which one reactant presents in excess, then take the concentration to be constant. For gas phase reaction, if the reaction takes place in large amount of inert such that the mole fraction of the reactant is small, then take the expansion factor, 0. 5. Analyse the data using suitable techniques to find the rate law, i.e. reaction order, reaction rate constant, adsorption constant (for solid catalysed reaction) etc. This is where the techniques for data analysis are used. Only two techniques will be discussed here. Refer to any Reaction Engineering textbook for any other techniques.

DIFFERENTIAL METHOD OF ANALYSIS In this method, the data are analysed in their differential forms. One advantage of using this method is that there is no need to guess the initial value of reaction order as seen in the integral method of analysis later. Differential method is less accurate than integral method although this method indicates clearly bad data. However, this method is valid and best used for data that are presumed to differentiate smoothly. Consider a liquid phase reaction A was recorded. P, takes place isothermally in a batch reactor.

Assume that during the reaction, the data on concentration change with respect to time Therefore, the measured variable in this case is the concentration of reactant with respect to time. The mole balance equation and the rate law is given below:

Mole balance:

rA =

dC A dt

Rate law:

rA = kC A

Combining these two equation gives:

dC A = k AC A dt

The easiest way to analyse the above equation and evaluate the value of reaction rate constant, k and reaction order, , is to transform the above equation into a straight line equation in which both the parameter k and can be obtained graphically. Taking the natural logarithm on both side gives:

dC ln A = ln k A + ln C A dt
Plotting a graph of ln(-dCA/dt) vs. ln CA will give a straight line with as the slope of the graph as given in the next figure:

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ln (-dCA/dt)

ln (-dCA/dt)

= slope

k = (-dCA/dt)/(CA)

ln CA (a)

ln CA (b)

Figure 1: Differential method to determine the reaction order

Three methods are available to evaluate the derivative (-dCA/dt). These are: 1. Graphical differentiation method 2. Numerical differentiation formulas 3. Differentiation of a polynomical fit to the data Graphical differentiation method This method involves plotting -CA/t as a funtion of t and then using equal area differentiation to obtain -dCA/dt. The procedure are outline below: 1. Tabulate the (yi,xi) data as shown in Table below. Table 1: Graphical differentiation data xi x1 x2 x3 yi y1 x2 x1 y2 x3 x2 y3 y3 y2 (y/x)3 (dy/dx)3 y2 y1 (y/x)2 (dy/dx)2

y/x

dy/dx (dy/dx)1

2. For each interval, calculate xn = xn xn-1 and yn = yn yn-1. 3. Calculate yn/xn as an estimate of the average slope in an interval xn-1 to xn 4. Plot these value as a histogram versus xi. 5. Draw a smooth curve that best represents the area under the histogram. 6. Estimate the value of (dy/dx) from the curve.

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y/x
(dy/dx)2

(dy/dx)4

x1

x2

x3

x4

xi

Figure 2: Equal area differentiation

Numerical differentiation method This method can be used when the data points of the independent variable are equally spaced, e.g. t1-t0 = t2-t1 = t. The three point differentiation formulas are given below:

Initial point:

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

Interior point:

((

) (

))

Final point:

1 dC A (C A(n2 ) 4C A(n1) + 3C A(n ) ) = dt tn 2 t

Polynomial Fit This method requires the use of computer software packages that are able to fit data into nth order polynomial:

C A = a0 + a1t + a 2 t 2 + ......... + a n t n

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Once the data is fitted to the right polynomial equation and the value of constants ai (where i=0, 1, 2, 3n) are known, the equation is then differentiated with respect to time:

dC A = a1 + 2 a 2 t + 3a 3 t 2 + ......... + na n t n 1 dt
INTEGRAL METHOD OF ANALYSIS This method requires an initial guess of the reaction order prior to integration of the differential equation used to represents the mole balance and reaction rate. If the guess is correct, the appropriate plot of the concentration-time data should be linear. This method is usually used to evaluate the reaction rate constant at different temperature for cases where the reaction order is already known in order to find the activation energy of a reaction. Assume a liquid phase reaction, A P takes place isothermally in a batch reactor.

Mole balance:

rA =

dC A dt

Rate law:

rA = kC A

Assuming the reaction is elementary gives an initial guess of reaction order, = 1. After combining and integrating the above equation with the limit of CA=CA0 at t=0, the resulting equation is shown below:

ln

C A0 = kt CA

Therefore, a plot of ln(CA/CA0) vs. t should gives a straight line through the origin for the initial assumption of reaction order = 1 to be correct. Otherwise, the initial assumption is incorrect and the whole process needs to be repeated with different initial guess of reaction order.

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DISTRIBUTION OF RESIDENCE TIME FOR CHEMICAL REACTORS

INTRODUCTION Reactor design and operation are the heart of almost all chemical producing plant and plays an important role in determining the success or failure of a chemical plant. The ability of the engineer in charge in choosing the most efficient method of operation for the reactor is vital in ensuring the reactor is always operated in the most optimised manner. However, since real reactors are subject to non-ideality, their design equation and charaterisation is different than those of ideal reactors. Understanding non-steady behaviour of real reactor is necessary for the design and operation of the reactor. What is resident time distribution (RTD)? Residence time distribution (RTD) refers to the characteristic of the mixing that occurs in a chemical reactor. Real reactors are subject to non-ideal flow pattern. For example, in tubular reactor, by assuming that the flow inside the reactor is of plug flow type and no axial mixing exists, the design equation of the tubular reactor was simplified to those of plug flow reactor (PFR). However, the actual flow inside a real tubular reactor, especially if packings are used inside the reactor, is no longer of plug flow type and some degree of axial mixing does exist inside the reactor. Hence, the mixing characteristic of real reactors will be different than ideal reactors and this is reflected in the RTD of the reactor. In short, information on RTD for a given reactor yields distinctive clues to the type of mixing occurring within the reactor. What is the use of RTD? RTD is mainly used to account for the non-ideality inside a reactor. Non-ideality inside a reactor leads to the existence of dead zone, stagnant zone and actual conversion that is less than those predicted by ideal reactors. On the microscale level, the analyst will be able to predict the conversion inside a non-ideal reactor should the reactor is to be used for some other reaction How does one measures RTD? The RTD is determined experimentally by injection an inert chemical, molecule, or atom, called a tracer, into the reactor at some time t = 0 and then measuring the tracer concentration, C, in the effluent stream as a function of time. A tracer should be non reactive, easily detectable, have physical properties similar to those of the reacting mixture and completely soluble in the mixture. It should not adsorb on the walls or other surfaces in the reactor. The two most used methods of injection are pulse input and step input.
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Pulse input. In this method, a known conce s entration of tracer is injec cted into the feedstream for a short period of time. The outlet co d T oncentration of the tracer is then mea r asured as a function of f time. The effluent concentrati time cur ion rve, as shown in Figure 1, is called the C-curve. n e esidence time distribution function, or known as th E(t) describes the amou of time e n r he unt The re differ rent fluid elem ment spend in the reactor in a quantitative manner It is define as: r r. e

E( t ) =

C( t )
0

C( t )dt

ntegral in the denominato is the area under the C curve. e or The in

Figure 1 Co oncentration-time curves in RTD analy ysis.

15

An alternative way of interpreting the residence-time function is in its integral form: Fraction of material leaving the reactor that has resided in the reactor for times between t1 and t2

t2

= E (t )dt
t1

Since the fraction of all the material that has resided for a time t in the reactor between t = 0 and t = is 1; therefore,

E (t )dt = 1
0

Large inaccuracies in the analysis arise when the concentration-time curve has a long tail. To reduce this inaccuracies, the analyst may extrapolate the tail and analytically continue the calculation. The tail of the curve may sometimes be approximated as an exponential decay. The inaccuracies introduced by this assumption are very likely to be much less than those resulting from either truncation or numerical imprecision in this region. Step input This method requires a continuous flow of tracer to the reactor during the whole experiment. The effluent concentration at exit of the reactor is monitored and the experiment is completed when the effluent concentration reach a steady state value. This method is easier to carry out compared to pulse input and it is not necessary to know the total amount of tracer that goes into the reactor during the experiment. However, it might be difficult to maintain a constant tracer concentration and flow into the reactor, especially if the experiment runs for a long period of time since large amount of tracer will be required. This method should be avoided if the cost of the tracer is very expensive. The E(t) function of step input is define as:

E (t ) =

d dt

C (t ) C0 step

(15)

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Chara acteristics of RTD Figure 5 illustrates typical RTD resulting fr e s Ds rom different reactor situa t ations. Figure 5 (a) and e (b) co orrespond to nearly ideal PFRs and C l CSTRs respect tively. In Figure 5 (c) one observes e that a principal peak occurs a a time sm at maller than th space tim he me

=V v

(i.e., early (

exit o fluid) and also that flu exits at a time greate than space of uid er e-time, . Th curve is his representative of the RTD for a packed-be reactor with channeling and dead zones. One ed g z scena ario by which this situation might occur is shown in Figure 5 (d). Figure 5 (e) shows the n . RTD f the CSTR i Figure 5 (f which has dead zones a bypassing The dead z for in f), and g. zone serves to red duce the effe ective reactor volume indi icating that t active rea the actor volume is smaller e than e expected.

Figur re5. (a) RTD for near plu D ug-flow react tor; (b) RTD for near per rfectly mixed CSTR; (c) d RTD for packed-be reactor w f ed with dead zon and chann nes neling; (e) ta reactor w ank with shortcircui iting flow (by ypass); (f) CST with dead zone. TR d

17

Cumu ulative distrib bution functio on Cumu ulative distrib bution functio or also kn on, nown as F(t) i define as the normalised response is to a p particular input. This is de efine as: frac ction of efflue ent which h been in re has eactor for l less than time t e

E (t )dt =
0

= F (t )

Althou not as fa ugh avourable as E(t), this F(t is sometim used to m t) mes model chemic reactor cal and to analyse non o n-ideality insi a reactor. An example of F(t) curv is given in Figure 6. ide e ve

re tive distribut tion curve, F F(t). Here: 80 [F(t)] of th molecules spend 40 0% he s Figur 6. Cumulat min. o less in the reactor, and 20% of the m or e d molecules [1 F(t)] spend longer than 40 min. in d the re eactor. moment - Me Residence Time ean e First m Mean residence tim is also kn me nown as the f first moment The mean residence ti t. ime, tm for any re eactor is the same as its a average reside ence time or space time, regardless of its RTD. It is define as: d

tm =

tE (t )dt
0

E (t )dt
0

tC (t )dt t C t = tE (t )dt = = C t C (t )dt

0
i i

m, e f lows us to cal lculate the For a close system knowing the mean residence time of a reactor all volum of reactor provided tha the value o volumetric flow rate is k me at of known.

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Second moment variance Second moment, or variance, is also known as the square of the standard deviation and is taken about the mean. This moment represents the distribution, or the spread of the data about its mean. The greater the value, the greater is the distribution of the data.

Variance is define as:

2 = (t t m ) 2 E (t )dt
0

Third moment - skewness The third moment is also taken about the mean and is related to the skewness of the data. This represents extend of skewness of data distribution about the mean i.e. whether the data is skewed in one direction or another with reference to the mean. It is define as:

s3 =

3/ 2

(t t
0

) 3 E (t )dt

(21)

In terms of RTD analysis, these three moments are sufficient for RTD characterisation. Models are useful for representing flow in real vessel, for scale up, and for diagnosing poor flow. There are different kinds of models depending on whether flow is close to plug, mixed, or somewhere in between. The chart from Figure 7 points out which model should be used to represent a given setup if it is uncertain.

19

Fi igure 7 Map showing whic flow mode should be used in any s s ch els situation.

Figure 8. The sprea e ading of trace according to the disper er rsion model. ose pulse of tracer is introduced into the fluid enterin a reactor. The pulse ng Suppo an ideal p spreads as it pass through t ses the vessel, a and to chara acterize the s spreading ac ccording to rsion model F Figure 8), we assume a diffusion-like process superimposed on plug flow. e disper We ca this disper all rsion or longitudinal dispe ersion to dist tinguish it fro molecular diffusion. om r The dispersion coe d efficient D (m2/s) represen this spread m nt ding process. Thus id r large D means rapi spreading of the tracer curve small D means slow spreading w D = 0 means no spr reading, henc plug flow ce

Also

D characterizing the spread in the who vessel. g d ole is the dimensionless group c uL
D D s ispersion num mber and as a vessel di as an ud uL uL let as the Pecl number D

nspiel [2} sug ggested calli ing Leven

intens (degree) of axial dispe sity ersion. (Note it is not reco e ommended to call the reciprocal of thi group o is

define as ed

uL ence rests in the use of D in place of D (molecula diffusion ar . The differe D

coeffi icient) hence these group have comple e, p etely differen meanings.) nt In dim mensionless f form where z = (ut + x ) and = t/ = tu/L, the basic d )/L differential equat tion representing this disp persion model is l

C D 2 C C = uL z 2 z
20

(24)

where the vessel dispersion number is the parameter that measures the extent of axial dispersion. Thus

D 0 uL
D uL

negligible dispersion, hence plug flow

large dispersion, hence mixed flow

The dispersion model usually represents quite satisfactory flow that deviates not too greatly from plug flow, thus real packed bed and tubes. Case D/uL < 0.01. When an idealized pulse is imposed fitting the dispersion model for small extents of dispersion, D/uL < 0.01, results in the following family of equations:

E = E =

(1 ) 2 exp 4 (D / uL) 4(D / uL) 1

(25)

E=

( L ut ) 2 u3 exp 4DL 4DL / u V L = v u DL 3 U

(26)

tm = =

(27)

2 =

2 D = 2 2 uL

or

2 = 2

(28)

Case D/uL > 0.01, closed vessel/open vessel. For the large deviations from plug flow, D/uL > 0.01, here the pulse response is broad and it passes the measurement point slowly enough that it changes shape it spreads as it being measured. This gives a nonsymmetrical E curve. An additional complication enters the picture for large D/uL : what happens right at the entrance and exit of the vessel strongly affects the shape of the tracer curve as well as the relationship between the parameters of the curve and D/uL .

21

Let us consider two types of boundary conditions: either the flow is undisturbed as it passes the entrance and exit boundaries (we call it open boundary conditions), or you have plug flow outside the vessel up to the boundaries we call this the closed boundary conditions). In all cases D/uL is evaluated from the parameters of the trace curves; however each curve has its own mathematics. Closed vessel. For the closed vessel situation an analytical expression for the E curve is not available. However the curve can be constructed by numerical methods, or its mean and variance can be evaluated exactly as

2 V D D 2 uL / D tm = = , = 2 = 2 2 1 e v uL uL
2

(29)

Open vessel (00). This represents a convenient and commonly used experimental device, a section of long pipe, a fixed-bed tubular reactor, etc. It also happens to be the only physical situation (besides small D/uL ) where the analytical expression for the E curve is not too complex:

E, 00 =

(1 ) 2 1 exp 4 (D / uL) 4(D / uL) ( L ut ) 2 u exp 4 Dt 4Dt

(30)

E00 =

(31)

t m,00 =

V v

D 1 + 2 uL
2

(32)

=
2

2 00 2 tm

D D =2 + 8 uL uL

(33)

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EXPERIMENT 1: BATCH LIQUID REACTOR

INTRODUCTION In the majority of industrial chemical processes, a reactor is the key equipment in which raw materials undergo a chemical change to form desired products. This reactor is usually used for small-scale operation, for the manufacture of expensive products or for processes that cannot be carried out under continuous process. Although batch reactor has the capability of giving high conversion, it has its own drawback in terms of high labour cost, variation in product quality from batch to batch and difficulty in terms of large scale production. The unit comes complete with a glass reactor, constant temperature water circulating unit, temperature and conductivity monitoring systems, and Data Acquisition System. Student shall be able to conduct the well-known saponification reaction between ethyl acetate and sodium hydroxide. Objectives: 1. To evaluate the rate equation needed to design a production scale reactor by studying the saponification reaction of ethyl acetate and sodium hydroxide to form sodium acetate in a batch reactor. SUMMARY OF THEORY In batch reactions, there are no feed or exit streams and therefore the equation is simplified into:

Rate of A Rate of A loss within reactor = accumulated due to chemical within the reaction reactor

(1)

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The rate of reaction of component A is defined as:

( rA ) =

1 dN A V dt by reaction

moles of A produced by reaction unit unit volume time

(2)

By this definition, if A is a reaction product, the rate is positive; whereas if it is a reactant, which is consumed, the rate is negative. Rearranging equation (2),

(-rA ) V

= N A0

dX A dt

(3)

The saponification reaction between ethyl acetate and sodium hydroxide proceed as follow: NaOH + H3COOC2H5 CH3COONa + C2H5OH Ethyl Alcohol

Sodium Hydroxide + Ethyl Acetate

Sodium Acetate +

This reaction can be considered as an elementary reaction. METHODOLOGY The unit consists of the followings: a. Reactor The reactor consists of a glass vessel with top and bottom plate made of stainless steel. The reactor is vacuum insulated by an outer glass jacket. The reactor comes with a cooling coil, a 1.0 kW heater, a temperature sensor and stirrer system. b. Feed Inlet System (Liquid Reactions) For each liquid reactant, a 20-L feed tank, a pump, a needle valve and a flow meter are provided. Each reactant is pumped from the feed tank to the appropriate inlet port at the reactor top plate.
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c.

Water Bath The water bath system consists of a 25-L tank, 2x2.0kW cartridge heaters, temperature sensor and controller, and a circulation pump.

d.

Product/ Waste Tank A 50-L rectangular tank made of stainless steel is provided for collecting the product or waste before being discharged.

e.

Control Panel The control panel consists of all the necessary electrical components for controlling the operations of the unit. Components mounted on the panel door are all labeled for convenience. The control panel also houses the necessary modules for data acquisition system.

f.

Data Acquisition System The Data Acquisition System consists of a personal computer, ADC modules and instrumentations for measuring the process parameters. A flowmeter with 0 to 5 VDC output signal is supplied for each feed stream. A temperature sensor and temperature transmitter with 4 to 20 mA output signal are provided to measure the reaction temperature. A conductivity sensor with controller are provided for monitoring the reaction conversion. All analog signals from the sensors will be converted by the ADC modules into digital signals before being sent to the personal computer for display and manipulation. Figure 1 shows the process diagram for Batch Liquid Reactor.

25

cooling H2O in cooling H2O out

FEED TANK T2 (20-L) FT2

vent

SP1 FT1 V1 M

TI4 V2
V4

Vacuum Gauge
V10

FEED TANK T1 (20-L) TI3

V3

LS2

to vacuum pump

LS1

drain

V6 PUMP P2

V14 3-L CAPACITY REACTOR VESSEL (Vacuum Jacketted) PUMP P1

V5

drain

26

LS3

TIC2 V7
V8

TT2

WATER BATH T3 (25-L) TIC1 TT1 V12 V9 PUMP P3 WASTE TANK T4 (50-L)
drain

CT1 V11
sampling

drain

V13

Figure 1: Batch Liquid Reactor

EXPERIMENTAL PROCEDURES The main objective of the experiment is to evaluate the rate equation needed to design a production scale reactor by studying the saponification reaction of ethyl acetate and sodium hydroxide to form sodium acetate in a batch reactor. following sub-objective should be fulfilled: 1. 2. 3. Preparing the calibration curve for conversion vs. conductivity and preparing reactants. Study the effect of inadequate mixing to the saponification reaction. Obtain the concentration and conversion profile of the reaction between Ethyl Acetate and Sodium Hydroxide in a batch reactor in order to evaluate the reaction rate constant and reaction order. 4. 5. Study the effect of temperature on batch saponification reaction of Ethyl Acetate and Sodium Hydroxide in order to obtain the activation energy. Study the effect of inadequate mixing to the saponification reaction. To achieve this, the

A process flow diagram of the reactor is shown in Figure 1. This reactor has a total volume of approximately 3 litres. A scale is provided to determine the reactor volume. a) Preparation of the calibration curve for Conversion vs. Conductivity: 1. Prepare the following solutions and determine the conductivity values for each of them. Conductivity [mS/cm]

Conversion [%] 0.00 0.25 0.50 0.75 1.00

Solutions 1-L of 0.05M NaOH 1-L of 0.075M NaOH + 1-L of 0.025M Sodium Acetate 1-L of 0.05M NaOH + 1-L of 0.05M Sodium Acetate 1-L of 0.025M NaOH + 1-L of 0.075M Sodium Acetate 1-L of 0.05M Sodium Acetate

2. Determine the slope and y-axis intercept from the plot of conversion vs. conductivity.
27

b)

Reactants Preparation 1. Prepare 1 litre of 0.25 M standard HCl and 1 litre of 0.1 M standard NaOH. 2. Prepare 0.1 M NaOH solution in feed tank T1 and 0.1 M Ethyl acetate in feed tank T2. 3. Confirm the concentration of your 0.1 M NaOH solution by titrating a small amount of it with standard 0.25 M HCl using phenolphthalein as indicator. 4. Ensure the concentration of the ethyl acetate solution using the following procedure: First, add 0.1 M NaOH solution to a sample of ethyl acetate solution such that the 0.1 M NaOH solution is in excess to ensure all of the ethyl acetate reacted. Let this mixture react overnight. On the following day, determine the amount of unreacted NaOH by direct titration with standard 0.25 M HCl. Record the ethyl acetate real concentration.

CHECKPOINT: 1. Which of the four species involved in the saponification reaction above responsible for the conductivity reading? What is the justification for your answer? 2. What is meant by kinetic operating regime? 3. What is meant by elementary reaction? 4. Discuss in your group what will be the vital information that you need to get from the experiment for your data analysis later. EXPERIMENT A: THE EFFECT OF STIRRER SPEED ON SAPONIFICATION REACTION Objective: 1. To study the effect of stirrer speed on saponification reaction and hence to obtain the kinetic operating regime. Procedure: 1. To begin a batch reaction experiment, switch on pump P2 and start pumping 1 litre of the 0.1 M ethyl acetate into the reactor. Stop pump P2. 2. Switch on pump P1 and start pumping 1 litre of the 0.1 M NaOH into the reactor as quickly as possible. Stop pump P1 and close valve V1 simultaneously when the reaction volume reaches 2 litres. Switch on the stirrer and set the speed at about 200 rpm.
28

Immediately start the timer and click the START button on SOLDAS data acquisition systems. 3. Record the conductivity values at 1-minute interval for 30 minutes. 4. Switch off all switches when you are finished with the experiment. Drain off all liquid from the reactor 5. Repeat the procedure above but use a different stirring speed 400 rpm, 600 rpm, 800 rpm, 1000 rpm. All other conditions are the same. (e.g. initial concentration and temperature) Task: 1. Plot the concentration time data for all your experiment and analyse the initial rate of reaction for all experiment. Can you suggest where is the kinetic operating regime? You have to complete this analysis before you proceed to the next experiment. EXPERIMENT B: BATCH SAPONIFICATION REACTION OF ETHYL ACETATE AND SODIUM HYDROXIDE Objective: 1. To find the reaction order and rate constant for saponification reaction between ethyl acetate and sodium hydroxide. Procedure: 1. To begin a batch reaction experiment, switch on pump P2 and start pumping 1 litre of the 0.1 M Ethyl acetate into the reactor. Stop pump P2. 2. Switch on pump P1 and start pumping 1 litre of the 0.1 M NaOH into the reactor as quickly as possible. Stop pump P1 and close valve V1 simultaneously when the reaction volume reaches 2 litres. Switch on the stirrer and set the speed as per your result in Experiment A. Remember that you must operate in the kinetic regime. 3. Immediately start the timer and click the START button on SOLDAS data acquisition systems. 4. Record the conductivity values at 1-minute interval in an appropriate table. 5. Switch off all switches when you are finished with the experiment. Drain off all liquid from the reactor

29

Task: 1. Determine the order of the reaction, n, and the rate constant, k, for the saponification reaction based on the data obtained in experiment above. 2. Does the order of reaction and the rate constant, k, obtained from experiment the same as reported in literature?

EXPERIMENT C: EFFECT OF TEMPERATURE ON BATCH SAPONIFICATION REACTION OF ETHYL ACETATE AND SODIUM HYDROXIDE Objective: 1. To study the effect of temperature on saponification reaction between ethyl acetate and sodium hydroxide. 2. To evaluate the activation energy for the reaction. Pre-heat Procedure: 1. 2. 3. Fill up the water bath tank T3 with tap water. Switch on heaters H2 and H3 and set the bath temperature on the temperature controller TIC2 to about 2C less the desired reaction temperature. When the bath temperature is reached, open valve V8 and switch on pump P3. Allow the feed temperature in both tanks to increase until bath temperature is reached. In the meantime, close valves V3 and V6 and run pumps P1 and P2 to stir the feeds. 4. Increase the water bath temperature accordingly for different reaction temperature as required in the experiment. Procedure: 1. Follow the feed pre-heating procedure above. 2. To begin a batch reaction experiment, switch on pump P2 and start pumping 1 litre of the 0.1 M Ethyl acetate into the reactor. Stop pump P2. 6. Set the reaction temperature on TIC1 to 40C and run the cooling water. Switch on pump P1 and start pumping 1 litre of the 0.1 M NaOH into the reactor at the highest possible flow rate. Stop pump P1 and close valve V1 simultaneously when the reaction volume reaches 2 litres. Switch on heater H1. Switch on the stirrer and set the speed so that the reactor operate in the kinetic regime as per your result in Experiment A. Immediately start the timer and click the START button on SOLDAS data acquisition systems. 3. Record the conductivity values at 1 minute interval in an appropriate table. 4. When the conductivity reading seems to remain constant, stop the experiment. 5. Drain off the reactor content. Repeat the experiment for reaction temperatures of 30 and 40C.
30

6. Switch off all switches when you are finished with the experiment. Drain off all liquid from the reactor. Task: 1. Discuss on the effect of temperature on the reaction rate, k. 2. Determine the activation energy, E, from the plot ln k vs. 1/T. 3. What is meant by activation energy? What is its significant? SAFETY & MAINTENANCE 1. After each experiment, drain off any liquids from the reactor and make sure that the reactor and tubings are cleaned properly. Flush with de-ionized water as necessary. Note: NaOH and Ethyl acetate are corrosive and they may damage the tubings and the rig in the long run. 2. Dispose all liquids immediately after each experiment. Do not leave any reactants or product in the tank over a long period of time. 3. Wipe off any spillage from the unit immediately.

SAFETY PRECAUTIONS 1. Always observe all safety precautions in laboratory. 2. Always wear protective clothing, shoes, helmet and goggles throughout the laboratory session. 3. Always run the experiment after fully understand the equipment and procedures. 4. Always plug in all cables into appropriate sockets before switching on the main power on the control panel. Inspect all cables for any damage to avoid electrical shock. Replace if necessary. 5. DO NOT switch on the heater unless it is fully submerged in the liquid. Always maintain liquid level above the height of the heater to avoid damage to the heater. 6. Make sure that the stirrer assembly is secured properly. Avoid excessive load to the electrical motor to prevent damage. 7. Inspect the unit, including tubings and fittings, periodically for leakage and worn out. Leakage might cause damage to equipments by corrosive chemical in the long run.

31

EXPERIMENT 2: CSTR WITH HOT WATER CIRCULATOR

INTRODUCTION The continuous stirred tank reactor (CSTR) is particularly suitable for liquid phase reactions and is widely used in the chemicals industry. Advantages include consistent product quality, straightforward automatic control and low manpower requirements. In developing the design equation for an ideal CSTR, it is assume that the reactor operates at steady state and the reactor is perfectly mixed. Therefore, the temperature, concentration and reaction inside the reactor are independent of position and time. In other word, every variable is the same anywhere inside the reactor and the concentration and temperature at reactor exit is identical to those inside the reactor. Ideally, due to the perfect mixing assumptions, the concentration and temperature of reactant will immediately be the same as the concentration and temperature of mixture inside the reactor. However, due to non-ideality of real reactors, the concentration and temperature will need an adjustment time before it reach a steady state value. Objectives: 1. To evaluate the rate equation needed to design a production scale reactor by studying the saponification reaction of ethyl acetate and sodium hydroxide to form sodium acetate in a CSTR. 2. To determine the effect of inadequate mixing on the reaction rate SUMMARY OF THEORY The saponification reaction between ethyl acetate and sodium hydroxide proceed as follow: NaOH + H3COOC2H5 CH3COONa + C2H5OH Ethyl Alcohol

Sodium Hydroxide + Ethyl Acetate

Sodium Acetate +

This reaction can be considered as an elementary reaction. The reaction carried out in a Continuous Stirred Tank Reactor eventually reaches steady state when a certain amount of conversion of the starting reagents has taken place. The

32

steady state conditions will vary depending on concentration of reagents, flowrates, volume of reactor and temperature of reaction. Applying the general mole balance equation to a CSTR:

Fio Fi + ri dV =

dN i dt

Assuming that the reactor operates at steady state (therefore, no accumulation) and that the reactor is perfectly mixed (no spatial variations in the rate of reactions), the equation is simplified to the design equation of CSTR, which will be used in this experiment:

V =

Fio Fi ri

33

cooling H2O in cooling H2O out

FEED TANK T2 (20-L) FT2

vent

SP1 FT1 V1 M

TI4 V2
V4

Vacuum Gauge
V10

FEED TANK T1 (20-L) TI3

V3

LS2

to vacuum pump

LS1

drain

V6 PUMP P2

V14 PUMP P1 3-L CAPACITY REACTOR VESSEL (Vacuum Jacketted)

V5

drain

34

LS3

TIC2 V7
V8

TT2

WATER BATH T3 (25-L) TIC1 TT1 V12 V9 PUMP P3 WASTE TANK T4 (50-L)
drain

CT1 V11
sampling

drain

V13

Figure 1: The schematic diagram of continuous stirred tank reactor( hot water circulation)

CHECKPOINT 1. Which species is responsible for the conductivity value recorder during the experiment? What will be the trend of the conductivity value during the experiment? 2. What is meant by elementary reaction? 3. Discuss in your group what will be the vital information that you need to obtain from the experiment in order to achieve the objective of the experiment. How will you perform your analysis to find the reaction order and rate constant? METHODOLOGY Preparation of the calibration curve for Conversion vs. Conductivity: 3. Prepare the following solutions and determine the conductivity values for each of them. Conductivity [mS/cm]

Conversion [%] 0.00 0.25 0.50 0.75 1.00

Solutions 1-L of 0.05M NaOH 1-L of 0.075M NaOH + 1-L of 0.025M Sodium Acetate 1-L of 0.05M NaOH + 1-L of 0.05M Sodium Acetate 1-L of 0.025M NaOH + 1-L of 0.075M Sodium Acetate 1-L of 0.05M Sodium Acetate

4. Determine the slope and y-axis intercept from the plot of conversion vs. conductivity. b) Reactants Preparation 5. Prepare 1 litre of 0.25 M standard HCl and 1 litre of 0.1 M standard NaOH. 6. Prepare 0.1 M NaOH solution in feed tank T1 and 0.1 M Ethyl acetate in feed tank T2. 7. Confirm the concentration of your 0.1 M NaOH solution by titrating a small amount of it with standard 0.25 M HCl using phenolphthalein as indicator.
35

8. Ensure the concentration of the ethyl acetate solution using the following procedure: First, add 0.1 M NaOH solution to a sample of ethyl acetate solution such that the 0.1 M NaOH solution is in excess to ensure all of the ethyl acetate reacted. Let this mixture react overnight. On the following day, determine the amount of unreacted NaOH by direct titration with standard 0.25 M HCl. Record the ethyl acetate real concentration.

EXPERIMENT A: INVESTIGATION OF SAPONIFICATION REACTION IN A CSTR Objective: 1. To find the reaction order and the reaction rate constant in continuos stirred tank reactor (hot water circulation) Procedure: 1. Make up 5.0 litre batches of 0.1M sodium hydroxide and 0.1M ethyl acetate. 2. Remove the lids of the reagent vessels and carefully fill with the reagents to a level approximately 50mm from the top. Refit the lids. 3. Adjust the set point of the temperature controller to 30C. 4. Collection of conductivity data will be from the start of experiment until a steady state condition is reached in the reactor and this takes approximately 30 minutes. It is advisable to set the data collection period to, say, 45 minutes. 5. Using the calibration graph for each of the feed pumps, set the pump speed control to give 40 ml/min flowrate. 6. Set the agitator speed controller to 7.0.Switch on both feed pumps and the agitator motor, and start the data logger program (or begin taking readings if no computer is being used). After a few minutes the temperature sensor tip will be covered (about 25mm of liquid in reactor) Switch on the hot water circulator. 7. Repeat the experiment using different value of initial concentration of NaOH and ethyl acetate, while maintaining the reaction temperature at 30oC. (suggested: 0.05M and 0.15M)

36

Task: 1. Evaluate the value of rate constant and reaction order for the above reaction. Use the appropriate equations and tools for data analysis.

EXPERIMENT B: EFFECT OF TEMPERATURE ON BATCH SAPONIFICATION REACTION OF ETHYL ACETATE AND SODIUM HYDROXIDE Objective: 1. To study the effect of temperature on saponification reaction between ethyl acetate and sodium hydroxide. 2. To evaluate the activation energy for the reaction. Procedure: 1. Repeat Experiment A at another two temperatures (e.g. 35oC and 40oC). Use one value of concentration only. Task: 1. Evaluate the activation energy for the above reaction. EXPERIMENT C: EFFECT OF INADEQUATE MIXING ON REACTION RATE Objective: 1. To determine the effect of inadequate mixing on the reaction rate

Procedure 1. Repeat Experiment A after removing the baffles from the reactor. This is achieved by removing the conductivity and temperature probes then removing the lid of the reactor. The baffle arrangement simply lifts out. Note: Seek the help from technician or lab demonstrator for this experiment. Repeat the experiment with baffles removed and no stirring action. Three sets of data will be obtained: a. b. c. Stirred reactor with baffle (see Experiment A) Stirred reactor, no baffle Un-stirred reactor, no baffle
37

Task: 1. Comment on the results obtained. How did removal of the baffle affect the reaction rate? What effect does stirring have on the reaction rate?

SAFETY & MAINTENANCE 1. After each experiment, drain off any liquids from the reactor and make sure that the reactor and tubings are cleaned properly. Flush with de-ionized water as necessary. Note: NaOH and Ethyl acetate are corrosive and they may damage the tubings and the rig in the long run. 2. Dispose all liquids immediately after each experiment. Do not leave any reactants or product in the tank over a long period of time. 3. Wipe off any spillage from the unit immediately. IMPORTANT: It is essential when handling these chemicals to wear protective clothing, gloves and safety spectacles. SAFETY PRECAUTIONS 1. Always observe all safety precautions in laboratory. 2. Always wear protective clothing, shoes, helmet and goggles throughout the laboratory session. 3. Always run the experiment after fully understood the equipment and procedures. 4. Always plug in all cables into appropriate sockets before switching on the main power on the control panel. Inspect all cables for any damage to avoid electrical shock. Replace if necessary. 5. DO NOT switch on the heater unless it is fully submerged in the liquid. Always maintain liquid level above the height of the heater to avoid damage to the heater. 6. Make sure that the stirrer assembly is secured properly. Avoid excessive load to the electrical motor to prevent damage. 7. Inspect the unit, including tubings and fittings, periodically for leakage and worn out. Leakage might cause damage to equipments by corrosive chemical in the long run.

38

EXPERIMENT 3: CSTR IN SERIES

INTRODUCTION In CSTR in series, two CSTR are connected together in series arrangement, i.e. the exit of the first CSTR becomes the feed to the second CSTR. This arrangement allows higher conversion to be achieved from the CSTR. The basic principle is still the same as single CSTR although the equation used in the analysis will be slightly different. The concept of Damkohler number, Da, which is dimensionless number, allows us to find a quick estimate on the degree of conversion that can be achieved in a CSTR. Objectives: 1. To find the reaction rate constant in a Continuous Stirred Tank Reactor in series. 2. To determine the order of chemical reactions for series reactor. 3. To study the dynamics behaviour of CSTR in series. SUMMARY OF THEORY Damkohler number, Da, is define as the ratio of the rate of reaction A to the rate pf convective transport of A at the entrance of the reactor:

Da =

rA0V FA0

(1)

The value of Damkohler number gives an idea on the conversion inside a reactor. Usually, Da = 0.1 gives a conversion of less than 10% and Da = 10 gives a conversion of greater than 90%. The design equation of CSTR in series also differs slightly from single CSTR. If a first order reaction takes place in 2 CSTR in series, the effluent concentration from the first reactor is given by:

C A1 =

C A0 1 + 1 k1

(2)

where 1 = V1/0. Mole balance on reactor 2 then gives:

C A2 =

C A0 C A1 = 1 + 2 k 2 (1 + 2 k 2 )(1 + 1 k1 )
39

(3)

Therefore, for n reactors in series (all individual reactors has the same volume):

C An =

(1 + k )

C A0

, X = 1

(1 + k )n

(4)

Using this as our basis, we can now predict the conversion in nth reactor for CSTR in series provided the value of Da and residence time of the reactor are known. The saponification reaction between ethyl acetate and sodium hydroxide proceed as follow: NaOH + H3COOC2H5 CH3COONa + C2H5OH Ethyl Alcohol

Sodium Hydroxide + Ethyl Acetate

Sodium Acetate +

This reaction can be considered as an elementary reaction.

Figure 1: The schematic diagram of continuous stirred tank reactor in series

40

CHECKPOINT 1. Develop an equation to relate the conversion at the outlet of nth reactor with Da for second order reaction. 2. What is the equation for Da for second order reaction? METHODOLOGY a) Preparation of the calibration curve for Conversion vs. Conductivity: 1. Prepare the following solutions and determine the conductivity values for each of them. Conductivity [mS/cm]

Conversion [%] 0.00 0.25 0.50 0.75 1.00

Solutions 1-L of 0.05M NaOH 1-L of 0.075M NaOH + 1-L of 0.025M Sodium Acetate 1-L of 0.05M NaOH + 1-L of 0.05M Sodium Acetate 1-L of 0.025M NaOH + 1-L of 0.075M Sodium Acetate 1-L of 0.05M Sodium Acetate

2.

Determine the slope and y-axis intercept from the plot of conversion vs. conductivity.

b)

Reactants Preparation 1. Prepare 1 litre of 0.25 M standard HCl and 1 litre of 0.1 M standard NaOH. 2. Prepare 0.1 M NaOH solution in feed tank T1 and 0.1 M Ethyl acetate in feed tank T2. 3. Confirm the concentration of your 0.1 M NaOH solution by titrating a small amount of it with standard 0.25 M HCl using phenolphthalein as indicator.

41

EXPERIMENT A: INVESTIGATION OF SAPONIFICATION REACTION IN CSTR IN SERIES Objective: 1. To investigate the effect of residence time on the exit conversion of the reactor. Procedure: 1. Make up 5.0 litre batches of 0.05M sodium hydroxide and 0.05M ethyl acetate. 2. Remove the lids of the reagent vessels and carefully fill with the reagents to a level approximately 50mm from the top. Refit the lids. 3. Adjust the set point of the temperature controller to 30C. 4. Collection of conductivity data will be until a steady state condition is reached in the reactor and this takes approximately 45 minutes 5. Set the sampling rate of the software to 30 seconds and set the time period to be 60 minutes. 6. Set the pump speed control to give 60ml/min flowrate. 7. Switch on both feed pumps, and start sampling the data 8. Repeat the experiment twice using different value of flow rate. Task: 1. Plot graph that shows the variation of Damkohler number vs. conversion and number of tank in series. Give your comment. 2. By means of Levenspiel plot, can you comment on the similarity of CSTR in series to those of PFR? Note: You will need the value of k and n for the saponification reaction between ethyl acetate and sodium hydroxide in this experiment. Refer to previous experiment done. EXPERIMENT B: INVESTIGATION OF DYNAMIC BEHAVIOUR OF CSTR IN SERIES Objective: 1. To investigate the dynamic behaviour of CSTR in series by introducing both step change and pulse change input. Procedure: 1. Make up 5.0 litres of a solution of 0.1M sodium hydroxide and fill one of the feed vessels to approximately 50.0mm from the top of the vessel. Fill the other feed vessel with demineralised water. 2. Start the reactor stirrer and set to a speed of '7.0' on the speed adjust dial. The experiment can be carried out at room temperature.
42

3. Start the water feed pump and set the speed control to maximum in order to fill the reactor to the overflow as quickly as possible. When all reactors are full, stop the water feed pump. 4. For step change input, start the sodium hydroxide feed pump and set to 50 ml/min. Maintain the sodium hydroxide feed pump until steady state is achieved. 5. At this point start taking readings of conductivity at regular intervals manually or, if using the Data Logger (CEX-303 IFD), initiate the program. 6. Repeat all above steps (1-3), but limit the sodium hydroxide input to 3 minutes. This is pulse input. Task: 1. Discuss the different behaviour obtained for CSTR in series when step and pulse change input is introduced to the reactor. 2. What is the purpose of studying the dynamic behaviour of reactor? SAFETY & MAINTENANCE 1. After each experiment, drain off any liquids from the reactor and make sure that the reactor and tubings are cleaned properly. Flush with de-ionized water as necessary. Note: NaOH and Ethyl acetate are corrosive and they may damage the tubings and the rig in the long run. 2. Dispose all liquids immediately after each experiment. Do not leave any reactants or product in the tank over a long period of time. 3. Wipe off any spillage from the unit immediately. IMPORTANT: It is essential when handling these chemicals to wear protective clothing, gloves and safety spectacles. SAFETY PRECAUTIONS 1. Always observe all safety precautions in laboratory. 2. Always wear protective clothing, shoes, helmet and goggles throughout the laboratory session. 3. Always run the experiment after fully understood the equipment and procedures. 4. Always plug in all cables into appropriate sockets before switching on the main power on the control panel. Inspect all cables for any damage to avoid electrical shock. Replace if necessary.
43

5. DO NOT switch on the heater unless it is fully submerged in the liquid. Always maintain liquid level above the height of the heater to avoid damage to the heater. 6. Make sure that the stirrer assembly is secured properly. Avoid excessive load to the electrical motor to prevent damage. 7. Inspect the unit, including tubings and fittings, periodically for leakage and worn out. Leakage might cause damage to equipments by corrosive chemical in the long run.

44

EXPERIMENT 4: CSTR DYNAMICS

INTRODUCTION In the majority of industrial chemical processes, a reactor is the key item of equipment in which raw materials undergo a chemical change to form desired products. The design and operation of chemical reactors is thus crucial to the whole success of the industrial operation. Reactors can take a widely varying form, depending on the nature of the feed materials and the products. Understanding non-steady behaviour of process equipment is necessary for the design and operation of automatic control systems. One particular type of process equipment is the continuous stirred tank reactor. In this reactor, it is important to determine the system response to a change in concentration. This response of concentration versus time is an indication of the ideality of the system. The CSTR Dynamics (Model BP 107) has been designed to follow the dynamics of the simplest classic case of a well-mixed, multi-staged process operation. The unit comes with three stirred tank reactors connected in series complete with sump tanks and circulation pumps. Instruments are provided for the measurement of conductivity in each reactor. Students may select either step change input or impulse input to the reactor and will continuously monitor the responses in each reactor at a suitable interval. Objective: The Objective of this study is to determine the transient behaviour of continuous Stirredtank in series. SUMMARY OF THEORY METHODOLOGY The unit consists of the followings: 1. Reactors Three reactors made of borosilicate glass, each having approximately 2 liters capacity. Each reactor is fitted with variable speed stirrer mounted on the top plate. Temperature and conductivity sensors are provided for each reactor. Flows between vessels are by gravity. Overflow tubes are provided for the 2nd and 3rd reactor.

45

2. Stirrer System Variable speed stirrer system with digital display consisting of a motor and a shaft with impellers made of stainless steel. Speed adjustments by means of a speed controller knob on each stirrer. 3. Feed Tanks Two 15-L cylindrical tanks made of stainless steels are provided with the unit. Each tank has a feed pump to transfer the liquid from feed tank to the reactors. Each tank is fitted with a level switch to protect the pumps from dry run. 4. Waste Tank A rectangular 50-L waste tank made of stainless steel is provided at the bottom of the equipment. 5. Dead Time Coil Material Volume : : 3/8 stainless steel tubing approx. 200 ml

6. Instrumentations Flowmeter: Range : Output : Display : Conductivity Meter: Sensor Range Output Display : : : 0 to 200 mS/cm 4 (CT1, CT2, CT3, CT4) 4 to 20 mA conductivity controller with digital display for each sensor mounted on the control panel Temperature Sensor: No. of Sensors : Sensor type : 3 (TT1, TT2, TT3) RTD No. of Sensors : 0 to 500 ml/min 0 to 5 VDC LCD digital display

7. Data Acquisition System The Data Acquisition System consists of a personal computer, ADC modules and instrumentations for measuring the process parameters. A flowmeter with 0 to 5 VDC output signal is supplied for feed flowrate measurement. Conductivity sensors with controller are provided for monitoring the tracer concentration in each reactor. All
46

analog signals from the sensors will be converted by the ADC modules into digital signals before being sent to the personal computer for display and manipulation.

47

EXPERIMENTAL PROCEDURES Experiment A: The Effect of Step Change Input In this experiment a step-change input would be introduced and the progression of the tracer will be monitored via the conductivity measurements in all the three reactors and after the dead time coil. 1. 2. 3. 4. 5. Fill up the feed tank T1 with deionised water. Prepare about 10-L of 0.025M sodium chloride solution in feed tank T2. Set the 3-way valve V3 position towards pump P1. Close valve V6. Open valve V5. Switch on Pump P1 to initially fill up all three reactors with deionised water. Record each reactor volume. Adjust needle valve V4 to obtain a flowrate of approximately 150 ml/min on flowmeter FT1. Make sure that no air bubbles are trapped in the piping. Note: It is important to maintain the liquid level in each reactor. Adjust the flowrate if

necessary. 6. 7. 8. 9. 10. 11. 12. 13. 14. Switch on stirrers 1, 2 and 3. Set the stirrer speed to approximately 200 rpm. Continue pumping the de-ionized water until all conductivity readings (CT1, CT2, CT3) are stable at low values. Record these conductivity values at time t0. Switch off pump P1. Quickly set the 3-way valve V3 position towards pump P2. Switch on pump P2 and start the timer simultaneously. Record all conductivity values (CT1, CT2, CT3) at a suitable interval in an appropriate table. Continue recording the conductivity values until all readings are almost constant. Switch off pump P2. Close valve V4. Drain all liquids in each reactor by opening valves V11, V12, and V13. Repeat the experiment with the stirrer speed is set at approximately 300 rpm.

Plot the graph of E (t) vs t for each reactor and discuss the trend across the three reactors. Note: For operations with SOLDAS Data Acquisition System, refer to the DAS operating procedure. In step 9, click the START button. Conductivity values will be recorded automatically and a table will be generated.

48

Experiment B: The Effect of Pulse Input In this experiment a pulse input would be introduced and the progression of the tracer will be monitored via the conductivity measurements in all the three reactors and after the dead time coil. 1. 2. 3. 4. 5. Note: 6. 7. 8. 9. 10. Fill up feed tank T1 with deionised water. Prepare about 10-L of 0.025M sodium chloride solution in feed tank T2. Set the three-way valve V3 position towards pump P1. Close valve V6. Open valve V5. Switch on Pump P1 to fill up all three reactors with deionised water. Record each reactor volume. Adjust needle valve V4 to obtain a flowrate of approximately 150 ml/min on flowmeter FT1. Make sure that no air bubbles are trapped in the piping. It is important to maintain the liquid level in each reactor. Adjust the flowrate if necessary. Switch on stirrers 1, 2 and 3. Set the stirrer speed to approximately 200 rpm. Continue pumping the deionised water until all conductivity readings (CT1, CT2, CT3) are stable at low values. Record these conductivity values at time t0. Switch off pump P1. Quickly set the 3-way valve V3 position towards pump P2. Switch on pump P2 and start the timer simultaneously. Let pump P2 to operate for 2 minutes, and then switch off pump P2. Quickly switch the 3-way valve V3 position back towards pump P1. Switch on pump P1 and let it run till the end of experiment. 11. 12. 13. 14. 15. 15. Record all conductivity values (CT1, CT2, CT3) at a suitable interval in an appropriate table. Continue recording the conductivity values until all readings are almost constant. Switch off pump P1. Close valve V4. Drain all liquids in reactors by opening valves V11, V12 and V13. Repeat the experiment with the stirrer speed is set at approximately 300 rpm. Plot the graph of E (t) vs t for each reactor and discuss the trend across the three reactors Note: For operations with SOLDAS Data Acquisition System, refer to the DAS operating procedure. In step 9, click the START button. Conductivity values will be recorded automatically and a table will be generated.

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Experiment C: The Investigation on Dead Time Coil In this experiment the modeling of real (non-ideal) reactor can be accomplished by assembling the CSTR and dead time coil in parallel. A pulse input would be introduced in such a way that a fraction of it passes through the coil. This is analogous to the existing of a stagnation zone in a real reactor. Then, the progression of the tracer will be monitored via the conductivity measurements at the exit. 1. 2. 3. 4. 5. 6. Note: 7. 8. 9. 10. 11. Fill up feed tank T1 with de-ionized water. Prepare about 10-L of 0.025M sodium chloride solution in feed tank T2. Set the three-way valve V3 position towards pump P1. Open valves V6 and V10. Close valves V5 and V15. Switch on Pump P1 and allow the liquid to flow slowly through the coil for few minutes to bleed off any air trapped. Close valve V10. Open valve V15. Adjust needle valve V4 to obtain a flowrate of approximately 150 ml/min on flowmeter FT1. Make sure that no air bubbles are trapped in the piping. It is important to maintain the liquid level in reactor R3. Adjust the flowrate if necessary. Switch on stirrer 3. Set the stirrer speed to approximately 200 rpm. Continue pumping the de-ionized water until conductivity reading (CT3) is stable at low values. Record this conductivity value at time t0. Switch off pump P1. Quickly set the 3-way valve V3 position towards pump P2. Switch on pump P2 and start the timer simultaneously. Let pump P2 to operate for 2 minutes, and then switch off pump P2. Quickly switch the 3-way valve V3 position back towards pump P1. Switch on pump P1 and let it run till the end of experiment. 12. 13. 14. Record conductivity value (CT3) at a suitable interval (e.g. 30 sec) in an appropriate table. Continue recording the conductivity value until readings are almost constant. Repeat the experiment (steps 5 to 13) but this time allow the liquid to partially flow through the dead time coil. This is done by adjusting valve V15 to get the right flow while valve V10 remains open. 15. 16. Stop the experiment and drain all liquids in reactors by opening valves V11, V12 and V13. Plot the graph of E (t) vs t for each reactor and discuss the trend across the three reactors

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Note: For operations with SOLDAS Data Acquisition System, refer to the DAS operating procedure. In step 10, click the START button. Conductivity values will be recorded automatically and a table will be generated. 4. REFERENCES 1. Levenspiel, O., Chemical Reaction Engineering, John Wiley, 1972. 2. Fogler, H.S., Elements of Chemical Reaction Engineering, 3rd Edition, Prentice Hall PTR, 1999. 3. Smith, J.M., Chemical Engineering Kinetics, McGraw Hill, 1981. 4. Astarita, G., Mass Transfer with Chemical Reaction, Elsevier, 1967.

MAINTENANCE 1. After each experiment, drain off any liquids from the reactor and make sure that the reactor and tubings are cleaned properly. Flush the system with de-ionized water until no traces of salt are detected. 2. 3. Dispose all liquids immediately after each experiment. Do not leave any solution or waste in the tanks over a long period of time. Wipe off any spillage from the unit immediately.

SAFETY PRECAUTIONS 1. 2. 3. 4. Always observe all safety precautions in laboratory. Always wear protective clothing, shoes, helmet and goggles throughout the laboratory session. Always run the experiment after fully understand the equipment and procedures. Always plug in all cables into appropriate sockets before switching on the main power on the control panel. Inspect all cables for any damage to avoid electrical shock. Replace if necessary. 5. 6. Make sure that the stirrer assembly is secured properly. Avoid excessive load to the electrical motor to prevent damage. Inspect the unit, including tubings and fittings, periodically for leakage and worn out. Leakage might cause damage to equipments by corrosive chemical in the long run.

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EXPERIMENT 5: PACKED BED REACTOR

INTRODUCTION In the majority of industrial chemical processes, a reactor is the key item of equipment in which raw materials undergo a chemical change to form desired products. The design and operation of chemical reactors is thus crucial to the whole success of the industrial operation. Reactors can take a widely varying form, depending on the nature of the feed materials and the products. Understanding non-steady behaviour of process equipment is necessary for the design and operation of automatic control systems. One particular type of process equipment is the tubular reactor. In this reactor, it is important to determine the system response to a change in concentration. This response of concentration versus time is an indication of the ideality of the system. The RTD in Packed Bed has been designed for students experiment on residence time distribution (RTD) in a tubular reactor. The unit consists of mainly a vertical glass column packed with glass Raschig rings. Sump tanks and circulation pumps are provided as well as instruments to measure concentration of the tracer passing through the column. Students may select either step change input or impulse input to the reactor and will continuously monitor the responses in the reactor at a suitable interval. Objective: 1. To determine the effect of liquid (L) and gas (G) feed rates on the mean residence time and degree (intensity) of liquid-phase axial dispersion. SUMMARY OF THEORY METHODOLOGY The unit consists of the followings: 1. Reactor A column made of borosilicate glass packed with 8 x 8mm Raschig rings. Column OD: 100 mm; ID: 82 mm; Height: 1,500 mm. Top and bottom caps made of stainless steel fitted with appropriate inlet and outlet ports. A differential pressure tapping is also provided on both caps. 2. Feed Tank 20-L cylindrical tank made of stainless steel comes with a circulation pump. The tank is fitted with a level switch to protect the pump from dry run.

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3. Dosing Tank 20-L cylindrical tank made of stainless steels a metering pump. 4. Waste Tank 50-L rectangular tank made of stainless steel. 5. Instrumentations Air Flowmeters: Range : Output : Display : Liquid Flowmeter: Range : Output : Display : Conductivity Meter: Sensor Range Output Display : : : 0 to 200 mS/cm 2 (CT1, CT2) 4 to 20 mA conductivity controller with digital display for each sensor mounted on the control panel 6. Data Acquisition System The Data Acquisition System consists of a personal computer, ADC modules and instrumentations for measuring the process parameters. A flowmeter with 0 to 5 VDC output signal is supplied for feed flowrate measurement. Conductivity sensors with controller are provided for monitoring the tracer concentration in each reactor. All analog signals from the sensors will be converted by the ADC modules into digital signals before being sent to the personal computer for display and manipulation. No. of Sensors : 0 to 5 LPM 0 to 5 VDC LCD digital display 0 to 50 LPM; 0 to 200 LPM 0 to 5 VDC LCD digital display

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Figure 1. Process Diagram for RTD Studies in Tubular Reactor (BP 112).

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EXPERIMENTAL PROCEDURES General Start-Up Procedure 1. Perform a quick inspection to make sure that the equipment is in proper working condition. 2. Check that all valves are initially closed. 3. Open valve V13 to fill up the feed tank T1 with de-ionized water. 4. Prepare 10 liter of 0.2M NaCl solution in dosing tank T2. Record the conductivity reading for this solution. 5. Flush the system with de-ionized water until no traces of salt is detected. 6. Switch on the main power on the control panel. Note: For operations with SOLDAS Data Acquisition System, switch on the computer and run the Data Acquisitions System (DAS) software. Refer to DAS operating procedure. 7. Ensure the compressed air supply is on. Set the pressure regulator to about 2 bar. 8. The equipment is now ready to be run.

Operating modes: There are two modes of operations: 1. Counter-current mode: The liquid stream is flowing downward from top of the column while the gas stream is flowing upward from bottom of the column. The pulse or step input tracer is injected at the top of the column. 2. Co-current mode: Both the liquid and gas streams are flowing upward from bottom of the column. The pulse or step input tracer is injected at the bottom of the column. Experiment A: The effect of step change input Objective: input. A. Counter-current Mode Procedures: 1. Perform the general start-up procedure.
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To study the dynamic behaviour of packed bed reactor due to step change

2. Set the valves appropriately for counter-current mode: 3. Valves V3, V5 and V10 remain closed. 4. Open valve V1 and switch on pump P1. Fill up the column with de-ionized water to packing height. Note: The water level must be maintained throughout the experiment. Use valve V4 to adjust the level if necessary. 5. Adjust valve V1 to obtain a liquid flowrate of 500 ml/min. 6. Open valve V6. Open valve V8 to obtain a gas flow rate of 1.0 L min-1. 7. Observe the conductivity reading of CT1 and let it stabilizes at low value. 8. Switch on dosing pump P2. Open valve V14 and bleed off any air trapped in the tubing. 9. Close valve V14. Open valve V9 and start timer simultaneously. Click the start button for SOLDAS data acquisition systems.Record conductivity reading CT1 at 1 min interval. 10. Continue recording until conductivity reading is constant. 11. Repeat the experiment with gas flow rate of 2.0 L min-1. Ensure that the system is flushed with de-ionized water until no traces of salt is detected. 12. Stop the experiment and drain out all liquid from the system. B. Co-current Mode Procedures: 1. Perform the general start-up procedure. 2. Set the valves appropriately for co-current mode: 3. Valves V2, V4 and V9 remain closed. Open valves V3 and V5. 4. Switch on pump P1. Open and adjust valve V1 to obtain a liquid flowrate of 500 ml/min. 5. Open valve V6. Open valve V8 to obtain a gas flowrate of 1 Lmin-1. 6. Observe the conductivity reading of CT2 and let it stabilizes at low value. 7. Switch on dosing pump P2. Open valve V15 and bleed off any air trapped in the tubing. 8. Close valve V15. Open valve V10 and start timer simultaneously. Click the start button for SOLDAS data acquisition systems. Record conductivity reading CT2 at 1 min interval. 9. Continue recording until conductivity reading is constant. 10. Repeat the experiment with gas flow rate of 2.0 L min-1. Ensure that the system is flushed with de-ionized water until no traces of salt is detected. 11. Stop the experiment and drain out all liquid from the system.
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Experiment B: The effect of pulse input. Objective: To study the dynamic behaviour of packed bed reactor due to pulse change input. A. Counter-current Mode Procedures: 1. Perform the general start-up procedure. 2. Set the valves appropriately for counter-current mode: 3. Valves V3, V5 and V10 remain closed. 4. Open valve V1 and switch on pump P1. Fill up the column with de-ionized water to packing height. Note: The water level must be maintained throughout the experiment. Use valve V4 to adjust the level if necessary. 5. Adjust valve V1 to obtain a liquid flowrate of 500 ml/min. 6. Open valve V6. Open valve V8 to obtain a gas flowrate of 1.0 L min-1. 7. Observe the conductivity reading of CT1 and let it stabilizes at low value. 8. Switch on dosing pump P2. Open valve V14 and bleed off any air trapped in the tubing. 9. Close valve V14. Open valve V9 and start timer simultaneously. Click the start button for SOLDAS data acquisition systems.Record conductivity reading CT1 at 1 min interval. 10. Let dosing pump P2 run for 2 minutes. Close valve V9 and stop pump P2. 11. Continue recording until conductivity reading is constant. 12. Repeat the experiment with gas flow rate of 2.0 L min-1. Ensure that the system is flushed with de-ionized water until no traces of salt is detected. 13. Stop the experiment and drain out all liquid from the system. B. Co-current Mode Procedures: 1. Perform the general start-up procedure. 2. Set the valves appropriately for co-current mode: 3. Valves V2, V4 and V9 remain closed. Open valves V3 and V5. 4. Switch on pump P1. Open and adjust valve V1 to obtain a liquid flowrate of 500 ml/min.
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5. Open valve V6. Open valve V8 to obtain a gas flowrate of 10 6. Observe the conductivity reading of CT2 and let it stabilizes at low value. 7. Switch on dosing pump P2. Open valve V15 and bleed off any air trapped in the tubing. 8. Close valve V15. Open valve V10 and start timer simultaneously. Click the start button for SOLDAS data acquisition systems. Record conductivity reading CT1 at 1 min interval. 9. Let dosing pump P2 run for 2 minutes. Close valve V10 and stop pump P2. 10. Continue recording until conductivity reading is constant. 11. Stop the experiment and drain out all liquid from the system. Task: For all experiment above, carry out the following task: 1. Obtain the E(t) curve 2. Determine the mean residence time, tm, of the system. 3. Determine the variance, 2, and the skewness, s3, of the system. 4. Does your system have negligible dispersion or large dispersion? (Hint: Give your comment based on the value of the dimensionless group, D/uL) 5. Are there any dead zones in your reactor at the chosen operating condition? 6. What are the effect of different gas flow rate on the residence time distribution? MAINTENANCE 1. After each experiment, drain off any liquids from the reactor and make sure that the reactor and tubings are cleaned properly. Flush the system with de-ionized water until no traces of salt are detected. 2. Dispose all liquids immediately after each experiment. Do not leave any solution or waste in the tanks over a long period of time. 3. Wipe off any spillage from the unit immediately. SAFETY PRECAUTIONS 1. Always observe all safety precautions in laboratory. 2. Always wear protective clothing, shoes, helmet and goggles throughout the laboratory session. 3. Always run the experiment after fully understand the equipment and procedures.

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4. Always plug in all cables into appropriate sockets before switching on the main power on the control panel. Inspect all cables for any damage to avoid electrical shock. Replace if necessary. 5. Inspect the unit, including tubings and fittings, periodically for leakage and worn out.

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