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Introduction to Chemical Reactor Engineering

Problems

c.m. van den bleek a.w. gerritsen

November 2000 (last revised: Sept 17, 2001)

1

Ideal reactors: basics

1 The decomposition of A takes place according to the following reaction equation

A ! 3 B

Experiments were carried out in an ideal, isothermal batch reactor of constant volume. The following concentration profile was measured, starting with 75 vol% A and 25 vol% inert.

8

C A [mol/liter]

6

4

2

0

0
10
20
30
40
time [s]

Starting with the same feed and at the same temperature, an ideal PFR, an ideal CSTR and an ideal batch reactor (but now at constant pressure) are compared.

a For the continuous reactors calculate the space time and for the batch reactor the time at which the reaction has been completed.

b For all three reactors calculate the concentration of A for τ s and t = 15 s, respectively.

c Now sketch C A as a function of τ s and t, respectively for these three reactors and the given reactor in one graph (clearly indicate the scale division on both axes).

To study the liquid phase reaction A ! products, the following experiments have been carried out in a small experimental ideal CSTR:

2

 τ s C A, 0 C A [s] [kmol/m 3 ] [kmol/m 3 ] 44 5 4 52 8 6 58 8 5.5 70 8 7 78 8 5 166 5 3 225 1 0.5 300 2 1 468 5 2
 a Without determining the order of the reaction, calculate the space time needed to convert a feed containing 6 kmol/m 3 A for two-thirds in an ideal PFR. b What will be the space time needed to achieve the same in an ideal CSTR? 3 In a laboratory-scale isothermal ideal CSTR A is converted into B. For every mole of A

one mole of B is formed. A stream of pure A, that has already been converted into B for a small part, is used as the feed of the CSTR: C A,feed = 10 kmol/m 3 and C B,feed /C A,feed = 1/99.

The graph shows the relation measured between space time and feed conversion:

 τ s ξ A [min] [-] 0 0.01 0.030 0.2 0.041 0.4 0.049 0.5 0.062 0.6 0.124 0.8

The table shows some of the measured data.

a Determine the kinetics for this reaction.

b At what space time the maximal rate of disappearance of species A is reached?

c If one has the choice between an ideal PFR and an ideal CSTR, which reactor type will generally be preferred when this process is carried out at a large scale? Why?

4

In

an ideal CSTR the species A, B and C are converted into the products R and S

according to the following reaction scheme:

 + C ! R A with r R = k 1 AC A AC C + C ! S B with r S = k 2 AC B AC C and k 1 = 2.5Ak 2

a If the original reaction mixture consists of equimolar amounts of A, B and C, what will be the fraction of R in the product mixture R and S if the conversion of A is 50%.

b As in a, but now if the conversion of C is 50%.

5 In an ideal CSTR R and S are produced from A according to the following reaction scheme:

A with k 1 = 10 12 e -10800/T s -1

! R

A with k 2 = 10 8 e -7200/T s -1

! S

The temperature of the reactor can only be adjusted to each temperature in the range of 27 to 87 o C .

a Calculate the maximum amount of R that can be produced per mole of A converted.

b What is the space time required to produce 99% of the maximum amount of R?

c At what temperature should the reactor be set in order to obtain a the maximum production of S per mole of A fed, at the same space time as under b?

2

Ideal reactors: in a little more depth

6 The reaction A ! P takes place in a batch reactor with a volume of 2 m 3 . The density does not change. The kinetics of the reaction are: ! r A = kAC A .

a After 10 minutes of reaction (t = t 1 = 10 minutes) 45.12% of the original amount of A in the reaction mixture has been converted. Calculate k and give its dimension. From t = t 1 onwards the reactor is used as an ideal CSTR: a volume flow rate of

φ v m 3 /s pure A is fed to the reactor and a volume flow rate of φ v m 3 /s of reactor fluid is withdrawn from the reactor.

 b Derive the algebraic equation that describes the conversion of A in the reactor for t > t 1 , and which only contains φ v as unknown variable. c What value should φ v have, so that C A remains constant at the value C A (t 1 ) for t > t 1 ? 7 In a CSTR with volume V R m 3 the reaction A ! P takes place without change in density.

The rate of reaction is given by: ! r A = kAC A . At the start-up of the process the reactor is fed from the bottom with a stream of pure A, with

volume flow rate φ v and concentration C A,0 . Because the reactor is drained by overflow it will take some time before the reactor is completely filled and the reactor fluid is also being drawn off. During this filling of the reactor reaction DOES take place.

 a Derive the differential equation that describes the concentration of A in the reactor as a function of time between t = 0, the moment filling of the reactor starts, and t = t 1, the moment the liquid level reaches the brim. Assume that the reactor behaves as an ideal isothermal (batch) reactor and that the values of φ v and C A,0 remain constant. b From this differential equation derive an expression for C A, t1 (the concentration of A in the reactor at time t = t 1 ). The equation must be expressed in terms of k, V , C A and φ v , and must not contain t 1 . c How does C A change after t = t 1 ? Is C A constant or does it change? In case C A changes: does C A increase or decrease? Why? 8 In the seventies, the management of a nitric acid plant producing 500 t/day, has installed a

unit to decolorize its exhaust gas in order to please the people living in the vicinity of the plant. The unit catalytically converts brownish NO 2 into colorless NO. Consequently, a

colorless gas is vented through the stack into the atmosphere. In the atmosphere, however, the NO reacts with oxygen and produces NO 2 again. Usually, mixing of the exhaust gas with the atmosphere is so fast that the amount of newly formed NO 2 remains below the visual

detection limit (approximately 100 ppm), so the failure of this method is not discovered. Sometimes, however, the atmospheric conditions are such that the exhaust gas does not mix with the surroundings but moves away from the chimney as a cone (see sketch).

The radius of the cone is described by:

r = 0.01AX, with X = the distance from the stack [m]. Other data:

− φ v = 1.0A10 5 m 3 /h

the NO level in the exhaust gas leaving the stack is 2000 ppm (by volume)

! r NO

higher than the concentration of NO, the following approximation may be used:

! r NO

the temperature of the exhaust gas is 25 °C

the pressure in the cone is 1 bar

1 kmol of an ideal gas at 0 o C and 1 bar has a volume of 22.7 m 3

the stack has a height of 100 m

the cone can be considered as an ideal PFR.

Assuming the atmospheric conditions are such that the exhaust gas does not mix with its surroundings, calculate the distance at which the failure of the method becomes visible.

= k'AC 2 NO AC O2 , but, as the concentration of oxygen in the stack is very much

= kAC 2 NO with k = 8.0A10 4 m 3 /(kmolAh) (at 25 °C)

9 In an ideal PFR A is converted into products according to a first order irreversible reaction. Because the reaction is strongly exothermic, a reactor is used that consists of a bundle of parallel small-diameter tubes, which are surrounded by a coolant (see scheme). This arrangement enables isothermal operation of the reactor.

coolant

A
products

After some time, a number of tubes become plugged at the outlet. Consequently, these tubes do not longer contribute to normal production. However, some conversion of the reactant will still take place in these tubes, also at steady state, be it only at very small scale.

 a Describe the behavior in a plugged tube by setting up the mass balance for species A and working it out to a differential equation that describes the concentration of A as a function of the distance to the inlet. (The differential equation need not be solved.) A tube has a length of L m and a diameter of d m. The reaction rate constant is k s -1 and the diffusion coefficient is ID m 2 /s. The flow rate of the reactant stream is φ v,0 m 3 /s, and the inlet concentration C A,0 mol/m 3 . Assume that the density does not change. b What are the boundary conditions to solve this differential equation and what is the physical meaning of the boundary condition at the position L? c Which combination of parameters will determine the concentration profile in the tube? Sketch this profile for a number of values of this combination. 10 The exothermic reaction A ! B only takes place in the liquid phase at the boiling point

of the mixture. The reaction is studied in a laboratory, using a glass container of 400 ml,

filled with 270 ml pure A. The container is connected to a cooling element and heated by a flame that produces 600 W of heat (see figure).

As boiling causes violent motion, the temperature and composition may be assumed homogeneous. The amount of liquid in the cooler may be neglected. However, in the return line to the container 30 ml of liquid is always present, of which the composition and temperature are the same as in the glass container. The amount of gas in the container, the cooling element and the lines may be neglected. The glass container, the cooling element and the lines are insulated from the surroundings in such a way that all 600 W produced by the flame are absorbed by the glass container and its content. Removal of heat only takes place by the cooling element. The kinetics of the reaction at 87 °C are: !r A = kAC A with k = 0.111 min -1 . Other data:

Boiling point mixture = boiling point A = boiling point B = 87 °C

The density of the fluid is independent on ξ A and T

The heat of vaporization of the liquid is 360 J/ml, and independent on composition and temperature.

The heat of reaction is 100 kJ per mole of A converted.

The concentration of pure A in the liquid phase is 12 mol/liter.

Determine the volume flow rate φ v,cond returning from the cooling element to the glass container.

11

In a dark room, a balloon is filled with a gas A up to a volume of 1 liter. The pressure in

the balloon then is 2 atmosphere. Subsequently, the balloon is placed under a UV-source. This causes the conversion of A according to:

hv A ! 3 B

Formulate the mass balance of A over the balloon and subsequently determine the volume of the balloon as a function of time. The following statements hold:

 − The gases behave ideally. − The temperature in the balloon is constant. − The balloon can be considered as an ideal batch reactor, for which the volume is directly proportional to the pressure. − The reaction is a first order reaction in A; de reaction rate constant is k s -1 . 12 The closed circuit of the figure below consists of a differential reactor with volume V r ,

a vessel with volume V and a circulation pump. The volume of the pump and the volume of the lines may be neglected. At time t = 0 a certain amount of A is added to the system. Because the reactor is at elevated temperature and the vessel only at room temperature A only reacts in the (isothermal) reactor. The pump recycles the mixture so fast that the reactor behaves as a differential reactor. As the vessel is well mixed, any change in concentration due to the reaction in V r will be adjusted instantaneously in the rest of the system.

In the reactor the reaction A ! R takes places. The reaction is first order in A and has a

reaction rate constant of k s -1 .

a Give the molar balance over the reactor for species A.

b Integrate this molar balance to obtain the concentration of species A as a function of the time. Note: In a differential reactor the change in concentration is small compared to the concentration itself. Consequently, the rate of reaction is independent on the position in the reactor.

13 The kinetics of the gas-phase reaction A + B ! 2 C are studied at laboratory scale in an

ideal PFR. It is already known that the concentration of B does not influence the rate at which

A is converted. Despite high exothermicity of the reaction, it is possible to study the system

isothermally at laboratory scale by choosing correct experimental conditions.

To determine the influence of the concentration of A on the rate of reaction of A the following experiments have been carried out:

 τ s C A [min] [kmol/m 3 ] 0.21 9 0.45 8 1.02 6 3.21 2

The concentration of A in the feed was 10 kmol/m 3 for all experiments.

a Determine the value of the reaction rate constant k from these experiments if the rate of reaction is given by: !r A = kAC A .

In practice, one uses a semi-batch reactor to control the production of heat. At t = 0 the batch

reactor, with a volume of 1 m 3 , only contains B at reaction temperature, with C

/m 3 . All A required for the reaction is fed to the batch reactor as a small, continuous stream of 1 kmol/min starting at t=0. Some additional cooling enables isothermal operation of the system. The operating temperature is exactly the same as the temperature for the kinetics measurements.

B,0

= 10 kmol-

 b Derive the molar balance for species A. c Determine the concentrations of A and B in the system at t = 5 minutes. 14 Two students study the decomposition of P in boiling water under atmospheric

pressure. At these conditions the decomposition reaction is an irreversible reaction with first order kinetics. The students start with 400 ml of a 1.2 M solution of P in water and let the solution boil for 20 minutes in a more or less closed glass vessel. Then the concentration of P in the solution is only 0.441 M. Both students know that the density of the solution is independent on the concentration of P and its decomposition products. They neglect the reactions taking place during heating and cooling of the reaction mixture. They assume (correctly) that the boiling water is ideally stirred. The first student forgets to determine the final volume and assumes that the volume did not change during the experiment. He determines the reaction rate constant k and finds the value

a.

The second student does determine the volume at the end of the experiment. It appears to be 320 ml. The student makes two assumptions:

1. The change in volume is completely caused by the evaporation of water; neither P nor its decomposition products influence the volume.

2. The evaporation took place at a constant rate.

He also determines the reaction rate constant k and finds the value b.

 a What is the value of a? b What is the value of b? c Are the two assumptions above required to determine the value of b? Why? 15 At t = 0 the reactor sketched below contains pure gaseous A at a concentration of 5

kmol/m 3 and a pressure P 0 . The reactor is well-stirred, so the concentration and temperature are the same everywhere in the reactor. From t = 0 on A is converted into B according to:

A ! 3 B.

The reaction is zero order in A. The pressure in the reactor is kept at P 0 by means of an ideal pressure controller that controls valve S, through which part of the reaction mixture is purged.

a

b

Give the mass balance over the reactor for species A.

Integrate the balance to obtain the concentration of A as a function of time.

PC
S

16

flow rate φ v, f , C A = 10 kmol/m 3 ) according to: A ! 2Q. The density of mixtures of A and Q

is independent on their mixing ratio.

The reaction takes place in an ideal CSTR with volume V m 3 . At the usual process conditions

the kinetics of the decomposition are: !r A = kAC A with k = 2 h -1 . Without purification the concentration of A in the product stream would be 2.612 kmol/m 3 ,

which is too high to sell the product directly. Therefore, a separator S is added that separates

A and Q; the pure A is recycled.

Because S has a limited capacity, only the volume flow φ v, 1 is fed to S and separated into

pure A and Q. The second stream leaving the reactor, φ v, 2 , is mixed with the stream of pure Q from separator S. In this way the concentration of A in the product stream has decreased sufficiently to sell it.

If φ v, 1

In a certain plant product Q is made by decomposition of a stream of pure A (volume

= φ v, 2 determine:

C A, 1 , the concentration of A in the stream from the tank to the separation unit C A, 2 , the concentration of A in the stream from the tank to the point of mixing with pure Q C A, p , the concentration of A in the product stream after the mixing point.

17

In an ideal CSTR B is produced from A according to the first order irreversible

reaction: A ! B with k = 2 min -1 . The reactor has a volume of 1 m 3 , the feed has a volume flow rate of 0.5 m 3 /min, with concentration of A of 1 kmol/m 3 . At a certain time the con- centration of A is doubled instantaneously and permanently. Calculate the time at which the concentration of A has approached its new steady-state value to within 4%. Sketch the inlet concentration of A and the concentration of A in the tank as a function of time (both in the same graph).

18 The ideal CSTR (see figure) with volume V m 3 is fed with a stream of pure water; the

volume flow rate is φ v m 3 /s. At time t = 0 valve 1 is closed and valve 2 is opened. This results in the same volume flow φ v , now with a dissolved species A, being fed to the reactor. The

. In the reactor the reaction A ! B takes place. This

reaction is first order in A and has a reaction rate constant of k s -1 .

concentration of A in this stream is C

A,0

 a Formulate the molar balance of species A in the reactor. b Integrate this balance to obtain the concentration of A as a function of time. c Check the final concentration of A at steady-state. 19 In an adiabatic ideal batch reactor with a volume of 1 m 3 B is produced according to the

exothermic gas-phase reaction A ! 3 B. The pressure in the system should not exceed 75 bar in relation to the thickness of the reactor wall. Therefore, an ideal pressure-relief valve has been mounted on the reactor, which lets off when the pressure becomes over 75 bar. Calculate at which temperature the valve starts operating, starting from pure A at a pressure of 25 bar and a temperature of 27 o C. It may be assumed that the temperature of the reactor wall equals the temperature of the gas, which behaves as an ideal gas. The heat capacity of the total system (i.e. reactor + content) is

500 J/K, the enthalpy of reaction H r = - 150 J/mol A. The value of the gas constant R = 8.3310 -2 (liter bar)/(mol K).

20

Six models for a continuous tubular reactor are shown in the figure below. For models

4, 5 and 6 formulate the steady-state molar balance for species A, which is converted into products.

3

Ideal reactors: multiple reactors

21 A cascade of 3 ideal CSTRs, each with a volume of V liter, is fed with φ v liter/s of pure

liquid A (concentration C A,0

(first order kinetics, reaction rate constant k s -1 ). The conversion of the stream leaving the last reactor is ξ 3 at steady state. At a certain moment the second reactor starts to leak. The size of the leakage, φ v, leak , is approximately 0.1Aφ v . Until the leak has been repaired, it is decided to recycle the leaking stream to one of the reactors 1, 2 or 3 using a pump. At steady state these options result in ξ 3,1 , ξ 3,2 and ξ 3,3 , respectively, in the effluent leaving the last reactor. Note:

The height of the liquid level in the tanks does not change. Determine the order in which the conversions ξ 3,1 , ξ 3,2 and ξ 3,3 increase and explain your answer.

mol/liter). In the reactors the decomposition of A takes place

3

22 A substance A decomposes into B and C in the liquid phase according to a first order

reaction with reaction rate constant k 1 s -1 . P also decomposes according to first order kinetics into Q and R. The reaction rate constant is k 2 s -1 . The products B and Q react in the liquid phase according to a reaction that is first order in B and first order in Q. The reaction constant

is k 3 liter/(molAs).

 Thus: A ! B + C P ! Q + R B + Q ! Z

k

k

k

1

2

3

Of the three reaction rate constants it is known that k 1 = 2Ak 2 and k 3 = 3Ak 1 . The density of the liquid phase appears to be independent on the composition of the reaction mixture. It is desired to convert a stream of 2 liter/s pure A (concentration C A,0 mol/liter) and a stream of 3 liter/s pure P (concentration C P,0 ) into Z. There are 3 ideal PFRs available, each with a volume of 30 liters. Only two ways of connecting the reactors will be considered (see figure). Determine which two of the following six assertions are correct and explain your answer:

C

C

A,1

P,1

<

<

C

C

A,2

P,2

C

C

A,1

P,1

=

=

C

C

A,2

P,2

C

C

A,1

P,1

>

>

C

C

A,2

P,2

23 The reaction A ! 2P + Q is used to produce P from a stream of pure A using two

identical ideal CSTRs in series:

It is proposed to change the flow scheme to obtain a higher conversion (the other conditions, such as φ v,0 , C A,O , V, p and T remain unchanged):

First proposal:

Second proposal:

The motivation for these two proposals is that, by recycling, reaction takes place all over again, resulting in a higher conversion.

Third proposal:

Fourth proposal:

The motivation for proposals three and four is that a partial shortcut results in a higher residence time in the reactor, and consequently, to a higher conversion. Which proposal will result in the largest increase in conversion? Why? Does your answer depend on the order of the reaction?

24 To produce Q dimerisation of A can be used. This reaction, 2A ! Q, takes place in the

liquid phase without a change in density. At the usual process conditions the kinetics are:

!r A = kAC A 2 with k = 0.8 m 3 /(kmolAs).

At a certain moment two reactors are available for the partial conversion of a stream of A of

50 liter/s (C

m 3 and an ideal PFR with a volume of 1.875 m 3 . The following alternatives are considered:

= 0.1 kmol/m 3 ) into Q. These reactors are an ideal CSTR with a volume of 7.5

A,0

Give the order in which the conversion increases for the four alternatives (e.g. ξ B < ξ BT = ξ TB < ξ T ) and explain.

25 For the following arrangement of ideal reactors

calculate:

a The volume flow rate at points 2 and 8.

b The concentration of A at points 7 and 13.

Data:

φ v1

= 18 m 3 /s

C A,1 = 10 kmol/m 3

The reaction A ! P with kinetics !r A = 2AC A kmol/(m 3 As)

No change of density due to the reaction.

The streams are divided such that ξ A, 13 is as high as possible.

26

wastewater into the sewer its activity has to be reduced to 0.002 percent of its original value.

It is intended to feed the wastewater to three large underground basins in series before discharging it into the sewer. Circulation in the basins is provided by large mixers. Determine the volume of the basins if the half-life is 10 hours and the basins may be assumed to be ideally mixed.

A plant produces 100 m 3 of radioactive wastewater each hour. Before discharging the

27

For the production of B from A two ideal CSTRs are available, with a volume of 8 and

2 m 3 , respectively. The feed is a stream (4 m 3 /min) of A with a concentration of 8 kmol/m 3 A. The reaction proceeds according to A ! B. The kinetics were measured in a laboratory in a small ideal CSTR at the same temperature. A fractional value is expected for the reaction order. The following observations were made:

 τ s C A,0 C A [min] [kmol/m 3 ] [kmol/m 3 ] 0.15 10 8 0.43 10 6 1.06 10 4 3.36 10 2 9.00 10 1 0.18 5 4 1.26 5 2 4.00 5 1

What is the maximum possible yield of B in the practical situation?

28 The kinetics of the reaction A ! products are studied in a pilot plant consisting of three

ideal CSTRs in series. The operating temperature of each reactor is equal to the temperature

of its feed. Where needed intermediate heat exchanger can be used. The heat of reaction will

be removed completely by a cooling coil that is present in each reactor. The concentration of

A in each reactor is measured. See the sketch for other data. The process is carried out in the

liquid phase.

Data:
− =
2
m 3 /s
φ v,0
= 15
kmol/m 3
− C A,0
3
− V
= 2
m
1
3
− V
= 8
m
2
3
− V
= 8
m
3

!r A

R

= k 4 Ae -Ea/RT AC A

n

= 8.3

kJ/(kmolAK)

Measured values:

C

C

C

A,1

A,2

A,3

= 6.36

= 0.99

= 0.23

kmol/m

kmol/m

kmol/m

3

3

3

a

Determine the order n, the activation energy Ea and the frequency factor k 4 .

Subsequently, it is intended to convert a stream A, with a concentration of 10 kmol/m 3 A and a total molar flow of 50 kmol/s A in an industrial installation that consists of one ideal CSTR. The feed is NOT at reactor temperature but at 300 K. This is also the temperature of the cooling water used to remove the excess heat of reaction. Other data:

b

Calculate the temperature at which the conversion is 90 % and the required reactor

UAA (for cooling of reactor)

H r,A

c p

= 2.0A10 4 kJ/(sAK)

= !1.0A10 5 kJ/kmol = 50 kJ/(kmolAK)

c p and H r,A are independent on temperature and composition

volume.

29

CSTRs in series of volume 4, 10 and 20 liter, respectively. The feed is a stream of pure A of 100 liter/min with concentration C A of 10 mol/liter. The reaction rate equation is: !r A = C A 2 (k = known).

The production of B from A according to reaction A ! B is carried out in three ideal

 a Graphically determine the concentration at the exit of the first, second and third tank, respectively. b Subsequently make a graph of 1/(!r A ) versus C A and in this graph indicate the areas that are a measure of the volumes of the first, second and third tank, respectively. c In the graph of b indicate the area that represents the volume of a PFR yielding the same conversion as the three CSTRs in series. d Estimate the volume of the PFR in c from the area ratios and given tank volumes. Compare this estimated volume with the volume of a PFR that can be calculated from the molar balance for the conversion in a PFR from C A, 0 to C A, 3 (the concentration of A in the third CSTR). 30 Species B is produced from A according to a first order irreversible reaction A ! B.

The system used consists of two CSTRs in parallel, as shown in the figure below. The

volumes of the CSTRs are V 1 and V 2 , respectively, and V 1 > V 2 .

 a Calculate the volume of a CSTR that converts the molar flow φ v,0 AC A,0 to the same degree of conversion ξ A, out if ξ A, 1 = ξ A, 2 . b Determine which of the two reactors V 1 and V 2 has to be in front if the CSTRs are placed in series to yield the highest conversion. c If only the total volume of the two CSTRs is fixed, but the volume of each separate CSTR can be chosen freely, calculate the optimal ratio V 1 / V 2 so that the conversion is as high as possible when the two CSTRs are placed in series. 31 It is planned to make the product R in a reactor system consisting an ideal CSTR and an

ideal PFR in parallel (see figure).

Data:

reaction equation A ! R, with reaction rate constant k = 1 kmol/(m 3 As).

V

V

1

2

= 2

= 3

=

=

m

m

3

3

C A,0

− φ v,0

1 kmol/m 3 10 m 3 /s

Determine into which flows φ v, 1 and φ v, 2 the original flow φ v, 0 has to be divided in order to maximize the total conversion of the system.

32 For the production of P from A two ideal CSTRs with volumes of 3 and 6 m 3 and a

separation column that separates the mixtures of A and P into the pure species are used (see figure).

The kinetics of the reaction are: !r A = kAC A with k = 0.5 min -1 . The feed to the first reactor is

a stream pure A: φ v = 1.5 m 3 /min, C A,0 = 12 kmol/m 3 . A, P and their mixtures may be assumed to have the same density. Determine the concentrations of A and the sizes of the volume flow rates at the following

points:

the exit of the CSTR with a volume of 3 m 3 , the exit of the CSTR with a volume of 6 m 3 , the inlet of the separation column, the exit of the separation column.

33 In a certain process a stream of 6 m 3 /h of pure A and concentration C

kmol/m 3 is converted for 75% into P by a first order irreversible reaction. The densities of A and P are equal. The reactor is a glass vessel with a volume of 3 m 3 equipped with two

stirrers (see figure a). This reactor may be assumed to be ideal. At a certain moment the axis

between the two stirrers breaks, so the lower stirrer stops working. The exit concentration of

A,0

= 20.6

 A increases to 6 kmol/m 3 . Because the reactor is made of glass one can see that the upper part is still well mixed, whereas the lower part of the reactor seems to behave more or less as a

two PFRs (see figure b).

After estimating the volumes it is decided to regard the resulting reactor as shown in figure c:

a combination of an ideal CSTR (volume 2 m 3 ) and two ideal PFRs (each with a volume of 0.5 m 3 ). Check whether the proposed model also leads to the increased exit concentration of

A.

4

Ideal reactors: a financial question

34 It is intended to produce 10 kmol/s of product B from A in a number of CSTRs in

series. Each CSTR has a volume of 0.1 m 3 . Downstream reactor n unreacted reactant A will be separated from the product and recycled to the inlet of the cascade of CSTRs (see figure).

The reaction equation is A ! B with !r A = 2AC A . The feed is pure A and the separation is ideal. What number of tanks, n, is financially most attractive if:

 − yield of B: \$ 40 per kmol B − costs of A: \$ 5 per kmol A − reactor costs: \$ 4 per m 3 and per s − separation costs: \$ 3 per kmol of B to be separated. 35 The government is planning on introducing eco-tax on the emission of carbon

monoxide from motor vehicles, namely for the quantity exceeding 2 g/km. For every gram of carbon monoxide exceeding this limit, 0.002 \$ should be paid for every kilometer. At an average velocity of 50 km/h the emission of current vehicles is 18 g/km higher than the emission standard. However, afterburners are available, which can be mounted between the cylinder and the exhaust, and in which secondary air is used to combust the CO to CO 2 over a

supported platinum catalyst (see scheme).

cylinder

gasoline

afterburner

secondary air

exhaust

air

The costs of these afterburners are entirely determined by the cost of the required catalyst. Currently the cost is \$ 180 per kg. A price-conscious student in chemical reactor engineering wonders, given the high cost of the catalyst, whether it would be sensible to use exactly the amount of catalyst required in his car exhaust to completely comply with the standard. He subsequently calculates whether it would be more attractive to oxidize only part of the CO to CO 2 and pay tax for the remaining part, as far as that exceeds the standard. He assumes a car

usage of 20,000 km/year and for simplification a constant speed of 50 km/h. He further assumes that the reactor can be considered as a homogeneous, isothermal, ideal PFR. Other data:

at a speed of 50 km/h a car produces 800 liter/km of exhaust gas

the secondary combustion air at that speed is 200 liter/km

at these conditions (excess oxygen) the rate of conversion of CO is: r CO = kC CO with k = 39400 h -1

the bulk density of the catalyst is 700 kg/m 3

the life of the catalyst corresponds with 20,000 km; then the catalyst must be completely replaced

the molar mass of CO is 18 g/mol Will the student exceed the standard, and if so, how much eco-tax will he pay each year?

36

rate constant k is 3 h -1 . Besides R a product S is formed, which yields the same amount of money per kmol as A costs per kmol. The kinetics for the formation of S are unknown. After the reactor R and S are separated from each other and from unconverted A. The unconverted A is recycled to the reactor (see figure).

In an ideal CSTR A is converted into R. This reaction is first order in A, the reaction

,
S
A

R

S

Data:

reaction scheme: A ! R A ! S

volume of reactor = 10 m 3

feed φ v,f = 50 m 3 /h

costs of separation = \$4 per kmol A to be separated

cost of A = \$ 2.50 per kmol A

yield of R = \$ 12.50 per kmol R.

Determine the degree of conversion ξ Α for which the plant operates most profitably.

37 In a plant a stream of pure A (φ v = 2 m 3 /s, C A,0 = 0.5 kmol/m 3 ) is available. It is

intended to produce product B according to the first order irreversible liquid phase reaction

A ! B (k = 2

s -1 ).

Because small amounts of the highly undesired product C are formed from B and C can not be separated from B, the selling price of B decreases with increasing conversion in the tubular reactor.

The selling price of B is: \$ 15Aexp(!ξ Α ) per kmol B. The plant is built as shown in the following scheme:

A

ideal PFR
ideal separator

B (+

C)

Data:

the separation is ideal and costs \$ 3 per kmol A to be separated.

the costs of the reactor are \$ 2.50 per m 3 and per second.

the costs of A are \$ 1.50 per kmol.

Graphically determine which reactor volume (approximately) will be installed.

= 1 m 3 /s, C A,0 = 0.5 kmol/m 3 ) into B

according to a second order reaction of which the reaction rate constant has the value 0.5 m 3 /(kmolAs). The proposed reactor is an ideal PFR. The product mixture will be separated into pure B and pure A. The pure A will be recycled to the reactor. Using the following data calculate the reactor volume that is financially most attractive for such a process.

costs A: \$ 0.50 per kmol A

yield B: \$ 40 per kmol B

costs reactor: \$ 2 per (m 3 As)

costs separation: \$ 4 per kmol A to be separated.

38 It is intended to convert a stream of pure A (φ v

What will be the optimal reactor volume if the yield of B is only \$ 0.6 per kmol B?

39 It is intended to make the products B and C from pure A (C A,0 = 4 kmol/m 3 ) according

to the reaction sequence: A ! B ! 2C. All steps are first order, the reaction rate constants are k 1 and k 2 and their values are 3 and 2 h -1 , respectively. The reactions take place in the liquid phase, for which the density may be assumed to be constant. The reaction is carried out in an ideal CSTR. The effluent of the reactor is separated into the pure species B and C in a separation unit. In order for the separation to behave ideally the ratio of the concentrations C and B after the reactor is chosen to be 4 : 1. The stream A leaving the separation unit can not be used further. The following figure shows a schematic of this process:

 a Calculate the concentration of C after the reactor as a function of space time τ s . b Which τ s is used in this process? What are the concentrations of A, B and C in the reactor? c The following financial data are important to the process: − costs \$ 13 per kmol A − yields \$ 20 per kmol C − The price of B depends strongly on the production by the process. If the molar flow of B is expressed in kmol/h the yield of B can, within reasonable limits, be expressed as (40 ! 4Aφ mol,B ) per kmol B. − The costs of the reactor are \$ 4 per (m 3 Ah). − The separation costs \$ 5 per hour. Determine the volume flow rate of A that will render this process most profitable. 40 In a batch reactor B is produced from A by the second order reaction A ! B. The

reaction rate constant is 1 m 3 /(kmolAh). Pure A is used with a concentration of 1 kmol/m 3 .

The time needed for cleaning up, loading etc. is 1 hour. The reactor is in operation all day (24 h/day). One reactor load of A costs \$ 20.000. If all A is converted into B this will yield \$ 30.000. The operating costs of the reactor and the costs for purification of B are negligible compared to the aforementioned costs. Therefore, incomplete conversion reduces the yield proportionally. How many cycles a day will be completed:

 a If one wants to produce as much B as possible in one day? b If one wants to make as much money as possible, while unconverted A can not be reused? c If one wants to make as much money as possible and unconverted A can be reused, but the purification costs of A are negligible? 41 In an ideal PFR (V = 5 m 3 ) B is produced from A (C A,0 = 2 kmol/m 3 ) according to the

reaction: A ! B. This reaction is exothermic (H r,A = -226.810 3 kJ/kmol) and second order in A, with k = 4 kmol/(m 3 h). In order to be able to operate the process isothermally, the reactor has been equipped with a cooling jacket, in which water (40 bar, 250 o C) is converted into steam (40 bar, 250 o C). After the reactor unconverted A is completely separated from B and recycled to the inlet of the reactor (see figure).

Other data:

A

water
40 bar
250
o C
ideal PFR
steam
40 bar
250 o C
S
 − ∆H evaporation, water = 2268 kJ/kg (at 40 bar and 250 o C) − yield steam: \$ 0.01 per kg (at 40 bar and 250 o C) − costs A: \$ 2 per kmol A − yield B: \$ 4 per kmol B − separation cost: \$ 1 per kmol A to be separated − reactor cost: \$ 3 per (m 3 ⋅h)

Calculate what amount of B has to be produced per hour in order to operate the installation as economically attractive as possible.

5

Ideal reactors: no reaction without heat

42 It is intended to produce 800 kg/s B in an ideal CSTR (V = 0.5 m 3 ). A volume flow of

pure A of 2 m 3 /s at 27 o C is available. The reaction proceeds according to: A ! 2B.

The reaction is exothermic, H r,A is !250 kcal/kg, and at 27 o C the reaction rate is 1.0A10 -3 AC A kmol/(m 3 As). In order to achieve the desired production, the process has to be carried out at elevated temperature. Therefore, it is intended to install a heat exchange surface in the tank reactor and use condensing high pressure steam (T = 527 o C) as heating medium. Calculate the heat exchange capacity UAA required if:

Ea

R

− ρ A = ρ B

c p,A = c p,B

You may assume that H r,A , ρ and c p are not a function of temperature and that the temperature at the steam side of the heat exchange surface remains constant at 527 o C.

 = 9.95 kcal/mol = 2A10 -3 kcal/(mol.K) = 800 kg/m 3 = 1.25 kcal/(kgA o C)

43 The solvent ILAP is produced in a small ideal CSTR (V = 20 liters) from a middle

distillate species A. The decomposition reaction is a first order reaction: A ! ILAP + R, with

R being the byproduct of the decomposition. The required heat of reaction is partially

produced by the reaction itself (H

by preheating of the feed (4 m 3 /h, 27 o C) in a heat exchanger. After the reactor the stream is

separated in a distillation column, where 90 % of the produced ILAP is recovered from the product stream. The unreacted A, the remaining ILAP and the byproduct R are used as fuel elsewhere in the plant. The following figure shows a schematic of the process. Determine the heat flow exchanged in the preheater.

= -100 kcal/kg, independent on temperature) and partly

r,A

Data:

net production of ILAP

= 5760 t/year

 − reaction rate constant k = 150 − activation energy Ea = 8 h -1 at 127 o C kcal/mol − gas constant R = 2 cal/(molAK)

densities ρ A, ρ ILAP, ρ R

heat capacities c p,A , c p,ILAP , c p,R

molar mass M ILAP

one year continuous

= 500 kg/m 3 (indep. on T and comp.) = 1 kcal/(kgAK) (indep. on T and comp.) = M R = 8000 h

44 Using of a feed A (φ v,0 = 1 m 3 /s, C

= 4 kmol/m 3 , T = 20 °C) product P is produced in

an ideal CSTR (V = 10 m ). The reaction A ! P (k = 0.9 s -1 ) is exothermic. The reaction temperature is 320 °C. Cooling of the reaction mixture takes place by using a heat transfer surface installed inside the reactor: UAA = 1.2A10 3 kJ/(KAs). Sometimes the feed has a 25% lower concentration of A. With an extra heat exchanger this feed is preheated to 110 o C to maintain the original temperature and conversion (but not C A,out ). Calculate the average temperature of the cooling medium of the reactor, the conversion reached and the amount of heat released per kmol reacted A, if it is further known that the heat capacity (5 kJ/(kgAK)) and density (800 kg/m 3 ) of the mixture are independent on temperature and composition.

A,0

3

45 In an ideal CSTR a first order irreversible exothermic reaction is carried out: A !

products (density is constant).

Data:

 − V = 0.2 m 3 − τ s = 0.2 s − ρ = 1000 kg/m 3 − c p = 3000 J/(kgAK) − ∆H r,A = !281000 J/mol − Ea = 22500 J/mol k − = 1 s -1 (at 27 o C) − = 8.33 R J/(molAK)

Density, heat capacity and reaction enthalpy are independent on temperature and composition.

 a What temperature is needed to reach a conversion of 80%? b What (theoretical) maximum concentration of A in the feed is allowed so that stable operation of the reactor is still possible at this conversion? c If the temperature of the feed stream can only be controlled between 27 and 127 °C, what is the maximum allowable concentration of A in the feed? 46 In an adiabatic ideal batch reactor B is produced from A by the first order irreversible

exothermic reaction A ! B with k = 10e (-1000/T) h -1 , with T expressed in K. At t = 0 the reactor is loaded with pure A and the temperature is 200 o C. The maximum adiabatic temperature rise is 100 o C. The reactor does not absorb any heat. Graphically determine the time required for obtaining a conversion of 40%. What is the temperature in the reactor for this conversion?

47 A small production unit is built for the conversion of raw material A in product B by a

first order irreversible reaction. The reactant stream (pure A, φ v = 5 m 3 /h, T = 20 o C), prior to being fed to the reactor (ideal CSTR, V = 5 m 3 ), is preheated in a feed-effluent heat exchanger with the hot product stream. Subsequently, the product B is separated from unconverted A in a separation step. The unconverted A can not be reused (see figure). The temperature in the reactor is chosen such that 1 kg/s B is produced. To this end, additional heat is supplied by a steam coil inside the reactor. In order to obtain an optimal separation, the feed to the separator must be at 80 o C.

S
steam
A

A

B

Data:

c pA = c pB = 2 kJ/(kgK), independent on T

− ρ A = ρ B = 800 kg/m 3 , independent on T

− ∆H r,A = 100 kJ/kg

The following relation exists between k and T:

5
ln (k) with k [h -1 ]
4
3
2
1
0
1.8
2.0
2.2
2.4

1000/T with T [K]

Calculate:

a The reaction temperature.

b The heat exchange capacity UA of the heat exchanger.

c The amount of heat that has to be supplied by the steam coil.

48

The production of P from A is carried out in an ideal CSTR with a volume of 4 m 3 at a

reaction temperature of 275 o C. The reactor is equipped with a cooling coil with a heat transfer area of 3 m 2 . In order to save cooling water, it was decided to use the cold feed as coolant inside the coil in stead of cooling water. The process scheme is as follows:

The feed flowing through the cooling coil is 2 m 3 /h pure A with a concentration of 50 kmol/m 3 and a temperature of T F o C. For the reaction A ! P the following data are available:

! r A = kAC A with k = 0.5 h -1 at 275 o C, Ea = 40 MJ/(kmol A) and H r,A = - 50 MJ/kmol, independent on temperature. Other data:

− ρ

c p =

R = 8.3 kJ/(kmolAK)

For the calculation of the heat transfer to the cooling coil the following simplified equation may be used:

= 1250 kg/m 3

independent on temperature and composition

10 kJ/(kgAK) independent on temperature and composition

φ heat = UAAA(T reactor - (T 0 +T F )/2), with U = 10 MJ/(m 2 AhAK)

 a What are the values of T 0 and T F at steady state? b Is this steady state stable or unstable with respect to disturbances in the heat flows? c At a certain moment the coil becomes plugged and it is decided to feed the feed stream A directly into the reactor and not use the cooling coil anymore. Qualitatively show how the temperature in the reactor will change in the new situation (T F remains the same). 49 The exothermic decomposition of A into 2B + C takes place in the liquid phase without

change of reaction volume. The reaction is studied in an ideal PFR, which is also ideally insulated from its surroundings: there is no heat loss whatsoever through the wall. Regularly distributed along the length of the tube thermocouples have been placed to study the temperature profile in the reactor. The following results are obtained in one of the experiments:

Location thermocouple [% of length of reactor]

Temperature

[ o C]

 0 100 20 110 40 123 60 137 80 153 100 169

Other data:

= 8.3 J/(molAK)

Ea

C A,0

H r,A , c p and ρ are independent on temperature and composition of the reaction mixture.

φ v

R

V R

10 liter/h

2 liter

k 4

= k 4 Aexp(-Ea/[RT])AC A

= 1.1A10 5

h -1

=

=

-r A

 − ∆H r,A = − 24 kJ/mol − c p = 4 kJ/(kgAK)

= 1.2 kg/liter

ρ

= unknown

= 20 mol/liter

a Determine the conversion ξ a at the outlet of the reactor.

At a certain moment the insulation of the first half of the reactor falls off. From this moment

on heat is transferred to the surroundings (T sur. = 27 o C) and the conversion becomes ξ b .

b Is the conversion ξ b higher, equal to or lower than the original conversion ξ a ? Why? Does

this

answer depend on the value of Ea? Why?

 c Give a well-considered estimation of the value of Ea. 50 At an organic chemistry laboratory you have to carry out a synthesis starting from n-

onsensol using a 3 liters container, a stirrer and a heating plate. The container is insulated from the surroundings. The heating element is only used to bring the n-onsensol (2 kg) to its reaction temperature (500 K). When this temperature has been reached, the heating element is removed and replaced by insulation. Up to 500 K the n-onsensol did not react! The conversion of n-onsensol is an exothermic process (T adiab. = 200 K) and first order in n- onsensol. Within the temperature range considered the following approximation is valid:

k = 1 + 0.001AT h -1 (T expressed in K) The reaction is stopped when 90% of the n-onsensol has been converted. The used container used is made out of teflon, which means that the temperature must not exceed 560 K. To prevent a temperature of over 560 K you have several ice cubes (80 g a piece), which you can throw into the container. You may assume that the ice is at 273 K and that it melts instantaneously and is vaporized from the solution (heat of melting of ice = 335

kJ/kg, c p,water = 4.2 kJ/(kgAK), heat of vaporization of water = 2250 kJ/kg). The heat capacity of the n-onsensol-mixture is 3 kJ/(kgAK), while the container does not absorb any heat.

a How many ice cubes did you need to add to the mixture before the n-onsensol has been converted for 90 %?

b After what time (in minutes) do you have to add the first ice cube at the latest?

c Should you add all the ice cubes at once, or is there a better alternative?

d Why would a pyrex container be preferable for this experiment?

Note:

a
+
bx
bx
ab' a'b
dx =
+
ln(a' b' x)
+
∫ a' b'x
+
b'
(
)
2
b'
dx
1
+
b'x 
= ln   a'
∫ bx
( a b' x
+ +
)(
a'
)
ab'
a' b
a
+
bx
xdx
1
 a
a'
= +
ln a
(
bx
)
ln a'
(
+
b' x
∫ bx
( a )
+ +
)(
a'
b' x
ab'
a' b
b
b'
) 

51

The production of P from pure A takes place according to the first order irreversible gas

phase reaction: A ! P with kinetics ! r A = k 0 exp(!Ea/RT)C A in which

k 0 = 2.010 7 s -1

Ea = 8.310 4 kJ/kmol

R = 8.3 kJ/(kmolK)

The reaction is exothermic, H r,A = 2.010 5 kJ/kmol. In order to control the reaction, a reactor consisting of a bundle of tubes, each with a diameter of 4 cm and a length of 1 m, is used (see figure).

T c
T 0
T c
x
0
L

The bundle is cooled by a cooling medium, which enters the cooling inlet with a temperature T c = 450 K. The heat transfer coefficient U is 0.025 kJ/(m 2 Ks). The flow of the cooling medium is such that heating of the cooling medium can be neglected. The inlet temperature T 0 of the reactant flow is also 450 K for each of the tubes. The tubes can be considered as

ideal PFRs. Per tube 1.2510 -4 kg/s A is fed, with a density of 2.5 kg/m 3 . The molar mass of A is 100 kg/kmol. The heat capacity of both the feed and the products (and their mixtures) is 1.5 kJ/(kgK). H r,A , ρ, and c p are independent on temperature. In the tubes an axial temperature profile will exist.

a Formulate a mass balance and a heat balance for one of the tubes.

b Make the resulting differential equation dimensionless by using the following substitutions:

ξ = (C A,0 C A )/C A,0 ;

t = (T T 0 )/T 0

and

z = x/L

Solving of this set of equations is not possible analytically. Numerically, however, this is no

problem, for instance by dividing the reactor length in 10 slices and calculating t and ∆ξ over each slice, using the initial conditions of that slice and the balance equations above, but then written as differential equations.

c In this way calculate the temperature and the degree of conversion after the first and second slice of a PFR that has been divided in 10 slices.

6

Ideal reactors: with a solid catalyst

52 In a laboratory, research takes place on the heterogeneously catalyzed decomposition of

A. The reaction kinetics of this decomposition appear to be ! r A,s = k s AC A , with k s dependent on the temperature according to the Arrhenius equation. The used catalyst consists of spherical particles with an internal surface area of 62 m 2 /g. During all experiments the decomposition takes place isothermally and in the same reactor. The inlet concentration of A is always 10 mol/m 3 . The diffusion coefficient ID does not depend on temperature. Calculate the value of the effectiveness factor E for each experiment (1-8), using the results listed below.

 Experiment Temp. φ mol A,0 Weight cat. Diam.cat. Conversion [-] [ o C] [mol/h] [g] [mm] [-] 1 127 1 400 8 4.62A10 -4 2 127 1 400 1 ‡ 2 4.62A10 -4 3 127 2 800 8 4.62A10 -4 4 177 10 400 8 2.98A10 -3 5 177 10 400 1 ‡ 2 2.98A10 -3 6 177 20 800 8 2.98A10 -3 7 350 1000 400 8 3.44A10 -2 8 350 2000 800 8 3.44A10 -2

53 The temperature dependence of a first order gas phase reaction is being examined on

two spherical catalysts with different average particle diameter and internal surface area. The catalytic activity per unit internal surface area, k s , the effective diffusion coefficient, ID eff , the

porosity in the catalyst bed, ε bed , and the apparent density of the catalyst particles, ρ p , ARE equal for both catalysts. Furthermore, ID eff is independent on temperature. In a series of isothermal experiments, the following values of the amount of reactant converted per unit mass of catalyst are measured.

 Temp [ o C] 200 250 260 270 280 290 300 350 Catalyst 1 4.325 228.2 434.7 766.9 1241 1853 2607 10690 Catalyst 2 2.161 110 206.6 353.1 552.4 802.7 1113 4536 Rate ratio 2.001 2.074 2.104 2.172 2.247 2.308 2.342 2.357
 a What is the ratio of the particle diameters d p,1 /d p,2 ? b What is the ratio of the specific internal surface areas S v,1 /S v,2 ? 54 Two materials can be used for drying a gas stream of 100 ml/min (at 27 o C and 1 bar)

containing 1 vol% water: mole sieve 5A and γ-Al 2 O 3 . The adsorption of water on these materials can be considered as a surface reaction with reaction kinetics: ! r = kAC

a Determine which drying material results in the lowest water content if the gas stream is fed to an ideal PFR (empty volume 250 ml) filled with one of the drying materials.

b What water content can be achieved?

The following data are known:

 symbol units Mol. sieve Alumina average pore diameter internal surface area particle diameter particle density bed porosity effective diffusion coeff. water in the particles adsorption rate constant d po 5 1040 S m 2 /g 200 200 d p mm 8 2 ρ p kg/m 3 1200 1500 ε bed - m 2 /s 0.6 0.6 ID eff 2.4A10 -8 3.6A10 -6 k s m