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2nd Year Reactor Design

Reactor Design Project: Methanol Synthesis (I) 2005


2nd Year Chemical Engineering Supervised by Professor. D. Chadwick and Dr. A. Kogelbauer Abstract 1.0 Introduction 1.1 Background Methanol is an important chemical used as the base component to produce formaldehyde and acetic acid. A large amount of Methanol is also used to make Methyl Tertiary Butyl Ether which is an additive used in cleaner burning gasoline. These chemical compounds are then used to make a multitude of useful everyday use products such as laminated wood which has a resin made from methanol, recyclable plastic which uses methanol as a feedstock and many modern clothes and fabrics which use methanol in their production process. 1.2 Problem Statement We have been given the task to design an adiabatic catalytic reactor to produce 300 tonnes per day of methanol. The process used to make the Methanol is of high pressure using syngas (CO/H2) as the feed and an ICI ZnO/Cr2O3 catalyst. Initially we are to use a design incorporating a single catalyst bed. Then after analysing that process we are to investigate an increase in Methanol production by 50% using two adiabatic reactors in series with inter stage cooling. We also know that when the reactors operate at a temperature approaching 700K the side reaction producing Methane and water becomes increasingly important. 2.0 Theory 2.1 Perfect/Ideal Gas For the purposes of the design of the reactor we are assuming that all the gases in the reactor systems are perfect. What this means is that for calculations we can use the Ideal Gas Equation pV = nRT, this equation is normally only applicable for gas at low pressures as was discovered and combined in Charles and Boyles Law however we are using a high pressure system and this assumption will make calculations much simpler. 2.2 Tubular Reactor We are making the assumption that the tubular reactor used in this design project runs with the plug flow assumption. The conditions for plug flow are: (i) Flow rate and Fluid properties are uniform over any cross-section normal to fluid motion (ii) There is negligible axial mixing due to either diffusion or convection

2nd Year Reactor Design

Differential Batch Reactors


Figure 1 Diagram of a PFR showing how differential elements may be considered to be well mixed batch reactors

The plug flow assumption tends to hold at Reynolds numbers greater than 104 as there is good radial mixing and at length divided by the diameter of the reactor is greater than 50 as axial mixing may be neglected. The advantages of the plug flow assumption are that if we take a differential element with boundaries normal to fluid motion it can be taken to be perfectly mixed and that it does not exchange fluid with an element behind or in front of it. Thus it may be considered to act like a differential batch reactor (see fig.1). 2.3 Derivation of Differential Equations Before we could begin to write any programs for the computer we needed to derive four differential equations and calculate these four gradients using our initial reactor parameters. The gradients are dM/d1, dT/d1, dP/d1 and d2/d1. Where M is the catalyst mass, T the temperature, P the total pressure, 1 the extent of reaction 1, 2 the extent of reaction 2. We are using the extent of reaction rather than molar flow rate in our derivations as it reduces problems caused by stoichiometry as we do not have to state what the reaction is in respect to and this in turn makes it much easier to re-evaluate and construct new feed conditions. 2.3.1 Material Balances The basic material balance equation is: Input Output Loss through Reaction = Accumulation So assuming steady state Accumulation = 0 Thus for reaction 1 nCH3OH nCH3OHe r1V = 0 (Eqn. 1) Rearranging:
r1 = dn M dV

(Eqn. 2)

From the definition of extent of reaction:


d1 = dn M M

M = 1

(Eqn. 3)

2nd Year Reactor Design Substituting d1 = dnM into the r1 equation we get.

d V d 1

1 r1

(Eqn. 4)

Thus for reaction 2 nCH4 nCH4e r2V = 0 Rearranging:


r2 = dn Mt dV

(Eqn. 5)

(Eqn. 6)

From the definition of extent of reaction:


dn Mt Mt = 1 (Eqn. 7) Mt Substituting d2 = dnMt into the r2 equation we get. d 2 =
dV d2 = 1 r2

(Eqn. 8)

Thus
d 2 dV d r = 2 = 2 dV d1 d1 r1

(Eqn. 9)

2.3.2 Catalyst Mass Balance From Equation 4 we know that:

d V d 1

1 r1

Thus to get the catalyst mass we multiply through by the catalyst density and convert the units. This gives
dM cat 1 = d1 r1

(Eqn. 10)

2.3.3 Pressure Drop From the data sheet provided we are given the Ergun equation for pressure drop across a reactor.

2nd Year Reactor Design


dP 1.75G 2 (1 ) = d DP 3

(Eqn. 11)

We can then manipulate this equation to give us one of our required gradients. Start by making the Ergun equation in respect to Volume rather than length
dP dP 1 1.75G 2 (1 ) = = (Eqn. 12) dV d A D P 3 A The Ergun equation is in respect to the catalyst volume so we cannot directly introduce our previous derived version of dV/d1 which is for reactor volume however it can be slightly modified to fit.

Vcat = V (1-) Vcat =


M cat

(Eqn. 13)

(Eqn. 14) cat Thus assuming density is constant


1 dV = dM cat cat (1 )

(Eqn. 15)

Then applying Catalyst Mass balance equation


dP dP dM cat dV 1.75G 2 = = 3 d1 dV d1 dM cat r1 AD P cat

(Eqn. 16)

2.3.4 Energy Balance We need to perform an energy balance around the reactor. We have two reactions thus we have two heats of formation.
0 nT H T ,in {nT H T ,out + W } + 1 qdz = 0

(Eqn. 17)

We are then going to make the assumption that the system is at steady state and we will neglect changes in shaft work and both kinetic and potential energy. The PRF will also be treated as adiabatic hence Q = 0. Rearranging:

dT r H r1 r2 H r 2 = 1 (Eqn. 18) dV ni C Pi Next we multiply this value by Eqn. 4 Hence

2nd Year Reactor Design

dT = d 1

H r1

r2 H r 2 r1 ni C Pi

(Eqn. 19)

Hr1 and Hr2 are calculated by following the reaction paths shown below:
298 298 298 H r1 = CO T CpCO + H 2 T CpH 2 + CH 3OH T CpCH 3OH dT + H f 1 (Eqn. 20)

298 298 298 298 H r2 = CO T CpCO + H 2 T CpH 2 + CH 4 T CpCH 4 + H 2O T CpH 2O dT + H f 2 (Eqn. 21)

2.4 Operating Lines Operating line for plug flow reactor is a curve, along which each point represents the achievable extend of reaction at a given temperature. The lower end point of the line is the initial temperature and the higher end point of line corresponds to the maximum achievable extend of reaction under the initial condition. Figure 2 2.5 Equilibrium Curve The main reaction:
CO + 2 H 2 CH 3 OH

(Eqn. 21)

At equilibrium, rate of forward reaction equals the rate of backward reaction. For exothermic reaction, as temperature increases, rate of backward reaction will increases more relative to that of rate of forward reaction. Hence, the equilibrium conversion is lowered, hence extend of reaction. Figure ? 2.6 Optimum Reaction Rate Curve Optimum reaction rate curve is the progression which minimizes the reactor volume (catalyst mass) for a given extend of reaction. For exothermic reversible reactions, two opposing factors are at work when temperature increases. The rate of forward reaction speeds up but the maximum attainable conversion decreases. There is a temperature corresponds to maximum rates and the curve can be plotted as the locus of maximum rates at different temperatures. For exothermic and adiabatic reaction in plug flow reactor, the end point of the operating line should be located between the optimum curve and equilibrium curve. Figure ? T1 should be the optimum outlet temperature. Equilibrium 1 desired Optimum T1 T1 T1

T T0

T0 T0

Figure 2 Best location for the plug flow adiabatic operating line. 2.7 Inter-Stage Cooling 5

2nd Year Reactor Design

T0 P0

Reactor 1

T1 P1 Cooler

T2 P2

Reactor 2

T3 P3

Figure 3 Diagram of an inter stage cooling process with nomenclature of temperature and pressure values

Inter stage cooling is a process used to get the best out of both worlds between reaction rate and reactant conversion. Rate is very much proportional to temperature hence the larger the temperature the larger the rate. However conversion is much less than processes with smaller temperatures, the result of this is that catalyst mass and thus volume has to be much greater. Reactors which deal with reactions at high temperatures and pressures are very expensive so the smaller the volume possible the lower the cost. Costs need to be kept to a minimum when starting a new process as you do not want to be in too much debt before a process has even began producing a product. The cooler allows the temperature during the reaction to drop whilst not affecting pressure or the streams composition so it is an extremely good way of increasing conversion without an increase in overall reactor volume. Due to insufficient information on heat exchanger and insignificant pressure drop, it is also that pressure drop across the cooler is negligible, therefore P1 =P2. It is also assumed that there is no composition change after the cooling. From figure 4, the operating line of the first reactor goes T0 from T1 at the extend of reaction A. If the end point is close to the optimum reaction rate curve, it reaches the maximum reaction rate for the required amount of . Inter-stage cooling device brings T1 back to T2 and the degree of cooling is (T2- T1). The adiabatic operating line from T0-T1 has the same slope as that of from T2 to T3. The second operating line leads to T3, which is closer to the optimum progression line. As the number of inter-stage cooling increases, the final temperature could reach as close as to the optimum progression line. B A A E T5 D T4 C T3 B T2 Cooling A T1 Optimum T T0 Figure 4 Sketch showing how 2 staged adiabatic plug flow reactor can closely approach the optimal temperature progression. Equilibrium Curve

2nd Year Reactor Design

3.0 Simulation Strategy 3.1 Production Requirement From our Design Problem we are required to produce 300 tonnes per day of Methanol. Hence our extent of reaction can be found using a simple equation:
300000 kgday 1 1day = 0.1085 kmols 1 60 60 24 s 17 kgkmol
1

(Eqn. 22)

Second part of the design requires an increase of 50% of production rate using two adiabatic reactors in series. The desired extent of reaction would be 0.16275 kmols-1. 3.2 Single Reactor Operating Lines The aim of the project is to design a reactor size that gives the maximum reaction rate and produces the required amount of Methanol. In general, the size of the reactor depends on many variables including initial temperature, pressure, cross-sectional area, feed rate and catalyst particle diameter. By varying the different variables, the optimum size of reactor could be obtained. The reactor size is related to the mass of catalyst by the following expression using Eqn. 13 and Eqn 14. Vreactor=Mcat/{ ( 1 )} cat Therefore, minimum catalyst mass gives minimum reactor volume as the voidage and density of catalyst are constant. Increasing the particle diameter could increase the surface contact area between the catalyst and reactants, hence the reaction rate. However, particle diameter is fixed as there is insufficient information on different size of catalyst. Feed rate could affect the reaction rate as the initial reaction rate is driven by concentration force. Nevertheless, side reaction in this process may hinder the reaction rate from rising as the reactants are consumed. Therefore, the variables to be varied in this design project are temperature, pressure, crosssectional area and feed rate. By varying one variable, keeping the other variables constant, plot of catalyst mass versus such variable could be made. The value of variable corresponding to the minimum of catalyst should be taken. 3.3 Two reactors in series with inter-stage cooling As shown in 2.7, increases the reactors in series with inter-stage cooling brings the operating line closer to the optimum progression curve. However, the costs of setting up the inter-stage cooling increase correspondingly. Therefore, two reactors are employed in this design project. Nevertheless, end point of the second operating line could reach the optimum temperature curve if the first operating line ends at the position closer enough to the optimum temperature curve. The cross-sectional area and inlet pressure affect would not be varied as the effects of these variables on the operating lines are the same for that of single stage. The optimum cross-sectional area and pressure calculated in 3.2 would be used for as the initial conditions for inter-stage 7

2nd Year Reactor Design cooling design. Thus, inlet temperature and the degree of cooling become the two remaining variables to be considered. The start point of the strategy is to investigate the maximum reaction rate with different initial inlet temperature, T1. This involves trial and errors. As the reaction rates along upper segment of operating lines are calculated in order to obtain the extent of reactions corresponding to the maximum rate for different inlet temperature. Four different values of T0 are chosen as 614K, 618K, 622K and 626K. It is reasonable to test different operating lines on this range, which leads to a smaller size of first stage reactor. It is because the concentration driving force is larger and a large amount of heat would be released in the initial stages of reaction. After obtaining the extent of reactions A at maximum reaction rate of these operating lines (point A on figure 4) , the degree of cooling is varied for different operating lines by moving from point A to point B on constantA line. Then move along the adiabatic path from point B to point C and verify if point C is at the desired final extent of reaction, B. Lastly, a comparison among different total catalyst mass achieved by different operating paths is made. The lowest catalyst mass gives the optimum reactor size. The initial condition of that particular operating path would be the optimum initial condition. 4.0 Results 4.1 Final conditions using the giving initial conditions for single reactor Generally, the optimum reactor size in reactor design is the minimum possible size that could be used for the same amount of production under all the physical constraints including materials availability, feasibility of running at high temperature and pressure and etc. By the maple program, outlet conditions of the single reactor under the given initial conditions are shown as follows: init_con := mass(0) = 0, p(0) = 300, Temp(0) = 610, x2(0) = 0 soln := matrix([[vector([x, Temp(x), mass(x), p(x), x2(x)])], [matrix([[0., 610., 0., 300., 0.], [.1085, 698.049561226478204, 7626.41158487199300, 292.949146341521271, 0.274267908972510239e-2]])]]) T1 P1 Feed Rate Mass of Catalyst 2 698.0 K 292.9 Bar 4.4 7626.4 Kg 0.002742 kmol/s However, this may not be the optimum outlet conditions. Therefore, an investigation to how cross-sectional area, inlet pressure and inlet temperature affect the mass of catalysts is taken.

2nd Year Reactor Design 4.2 Investigation to obtain the optimum initial condition for single reactor
7800 7640 7620 Mass of catalyst (Kg) 7600 7580 7560 7540 7520 7500 7480 7460 0 3 6 9 12 Cross-sectional area (m ^2) Catalyst Mass (Kg) Crosssectional area versus Catalyst mass required 7750 7700 7650 7600 7550 7500 4 4.2 4.4 4.6 4.8 5 5.2 Feed Rate( km ol/s) Catalyst m at ass different feed rate

Figure Mass of catalyst used for 300 tonnes methanol production with different cross-sectional area of reactor As it is shown from the figure, the mass of catalyst required decrease as cross-sectional area of reactor increases. That means the length of the reactor is reduced. It is due to larger surface area for the feed in reactants. The rate of reaction is greater. However, cross-sectional area is restricted by the availability and cost of the material that could withstand the high pressure (300bar). And rate of reduction catalyst mass required decreases as area increases more. Therefore, an reasonable size of area for this high pressure reactor 3m2, which gives cylindrical reactor a radius
8600 8400 Mass Catalytic (Kg) 8200 8000 7800 7600 7400 7200 7000 604 606 608 610 612 614 616 618 Mass Catalytic versus different initial Temperature

Tem perature (K)

of 0.95m given that area =(radius) ) only.

2nd Year Reactor Design

Mass of Catalyst versus different initial pressure


8000

7500

Mass of catalyst (kg)

7000

Mass of Catalyst versus different initial pressure

6500

6000

5500

5000 250 270 290 310 Pressure (bar) 330 350 370

Figure ? Mass Catalytic versus different initial Temperature at cross-sectional area 1m2

630k 640k

620k

610k

600k

590k

580k

Temperature

Figure ? Extend of reaction versus catalyst mass required under different initial temperature From figure ?, it can be seen that even though the catalyst mass decreases when temperature increases beyond 620k, the required production1 could not be reached. Therefore the optimum inlet temperature for the required production lies between 610k and 620k. By varying the feed rate, the minimum catalyst could be obtained at the bottom of the curve, which corresponds to 4.4 kmol/s of feed rate. From the above figure, the initial condition and final conditions for the minimum catalyst mass required are tabulated at table? Table 2 T0 P0 Feed Rate Mass of Catalyst T1 P1 2 614K 350 Bar 4.4 kmol/s 5714 Kg 702.7 K 345.4 Bar 0.00218 kmol/s

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2nd Year Reactor Design

4.3 4.4

Inter-stage cooling using given initial operating line for the first reactor Inter-stage cooling using the

5.0 Discussion 5.1 5.2 5.3 5.4 Initial gradients Optimum initial conditions for single reactor Inter-stage cooling Optimum initial conditions for 2 staged reactors with inter-stage cooling

6.0 Discussion

7.0 Reference -Kandiyoti,Professor R, Chemical Reaction Engineering I, Courses Notes 2004, Imperial College -Octave Levenspiel, Chemical Reaction Engineering, Third edition, John Wiley &Sons

Appendices Appendix 1 - List of Nomenclature used throughout the Report Appendix 2 Calculation of Initial Gradients
d2 r2 = d1 r1

PCO Ph22 PCH 3OH / K km lC o O r1 = 3 kg .ca .h t r ( A + BPCO + CPH 2 + DPCH 3OH )


r2 = 0.5 10 15 exp( 30000 / T ) PCO
km lC o O kg .ca .h t r

K = 10(5332/T -12.831) = 8.13 10-5 bar-2 PCO = 0.30 300 = 90 bar 11

2nd Year Reactor Design PH2 = 0.65 300 = 195 bar PCH3OH = 0.01 300 = 3 bar T = 610 K A = 77.394 K B = 3.172 K C = 0.587 K D = 16.41 K Thus at initial conditions of T = 610 K and P = 300 bar r1 = 0.023 kg .cat .hr r2 = 1.97 10-5 kg .cat .hr Therefore
d 2 = 8.50 10-4 (Dimensionless) d1
km lC o O km lC o O

dM cat 1 = d1 r1

Thus from above


dM cat kg .cat .hr kg .cat .s = 43.147 = 155329.2 d1 km O olC km olCO

dP 1.75G 2 = d1 r1 AD P cat 3

G = 44.86

kg m2s

A = 1m2 DP = 7.04 mm =
PM = 63.18 kg/m3 RT

cat = 1400 kg/m3 = 0.4 (Dimensionless)


dP kmolCO = 137 .870 d1 ms 2 kg .cat .hr

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2nd Year Reactor Design

dT = d 1

H r1

r2 H r 2 r1 ni C Pi

i C Pi = -1.024 1012 JK-1mol-1 n


r1 = H H r 2

The feed conditions to be initially employed in the process are shown in table 1 below:
Table 1 showing all initial given parameters Feed Rate (kmol/s) Feed Compositions (mol %) CO H2 CH3OH CH4 H2O Feed Temperature (K) Feed Pressure (bar) Bed Cross Sectional Area (m2) Second Reactor Inlet Temperature (K) 4.2 30 65 1 3 1 610 300 1 640

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