Problem Set 10

CBE 60546 December 5, 2012

Chris Paolucci Advanced Reactions

Problem 1
Reactor Classication: Hydrocarbon Oxidation in a Fixed-Bed reactor. The reactor geometry is modeled by a long thin tube of height 3 m and radius of 0.0127 m. The three reactions of interest are shown alongside gure 1. For this reactor the model we will use is a tubular reactor. From the class notes the hierarchy for this particular model is: 2D (cylindrical coordinates) Non-Isothermal FBR with dispersion Non-Adiabatic The base case is treated as pseudo homogenous, but by adding an eectiveness factor we are incorporating the second phase, making the model a two phase heterogenous one.

A B C A C
k3

k1

k2

Figure 1: Reactor Geometry. Example of modeling temperature along the reactor.

Where A is o-xylene, B is ophthalmic anhydride, and C represents carbon monoxide and and carbon dioxide. The other reactant, O2 , is considered to be in excess, making all three of the above reactions pseudo rst order. I will list the reaction and design equations used by COMSOL here, but please refer to the FixedBed reactor for Catalytic Hydrocarbon Oxidation manual for nomenclature and base values of constants. The rates are given by r1 = b y0 yA0 k1 (1 xA ) r2 = b y0 yA0 k2 xB r3 = b y0 yA0 k3 (1 xA ) ki = Ai eBi /T Since there are 3 components, it is necessary to have two mass balances and an energy balance, since xA = 1 xB xC 1 rB ctot yA0 1 rC (Def f xC + us xC ) = ctot yA0 (ef f T + us g Cp T ) = b [(H1 )rB + (H3 )rC ] (Def f xB + us xB ) = Finally, the boundary conditions for the problem are xB xC (0, z ) = (0, z ) = 0, r r xB xC (R, z ) = (R, z ) = 0, r r T (0, z ) = 0 r T ef f (R, z ) = (T T0 ) r

Problem 2
Problem Statement: Is it correct to describe the terms in the COMSOL notes as mass and heat transfer terms?. Calculations: To have real mass and heat transfer terms it would be necessary to implement a two phase heterogenous model of the FBR, which the base case of this module does not include (we later will add a simplied eectiveness factor though, which accounts for the other phase). Also, the diusional terms in comsol are actually dispersion terms since they occur in one phase, and are lumped together (in the base case Dr = Dz = De f f ). Lastly, the terms described by the design equations in COMSOL are eective averages. Since the base model used is pseudo-homogenous there are only eective mass and heat transfer terms which are described by it, these terms represent volume averages (e.g. D is not a function of r or z).

Problem 3
Problem Statement: Introduce an eectiveness factor. Calculations: For each reaction rate I introduced a rst order non-isothermal eectiveness factor corrected for temperature ( I did not just do so for species B because I do not think it makes sense to consider some rates as eective and others as not since the whole system is assumed two phase by using any eectiveness factor). This factor was dened as follows
1

noniso = iso = 0,iso

ki (T ) Def f

= ki (T0 ) ki (T )

1 R
ki (T0 ) Def f

so iso = 0 ki (T0 ) ki (T )

where 0 = 1 has been assumed. In this way an eectiveness factor for i = 1, 2, 3 was calculated with each i corresponding to the reaction listed in problem 1. These eectiveness factors were then multiplied by their corresponding rates.

Problem 4
Problem Statement: Investigate the eects of varying T0 and Results:

Varying T0
The base case has a feed temperature of 627 K. The inlet temperature was varied around this point from 570 to 700, but at a inlet temperature over 690 K the problem blows up and no solution is reached. It should be noted that the wall temperature, Tw , was held xed at 627 K. The reasons for this will be examined in more detail later. Figures 2-4 show the conversion of each species down the reactor in the z direction. Eects on Conversion

Figure 2: Conversion of A vs. z at varying values

of T0

Figure 4: Conversion of C vs. z at varying values

of T0

Figure 3: Conversion of B vs. z at varying values

of T0 4

To investigate the eects of dispersion in both the r and z dimensions, I make a surface plot of the conversion for each species at the extremum inlet temperatures of 570 K and 690 K.

Figure 5: Conversion of A on r vs. z at T0 = 570

Figure 8: Conversion of A on r vs. z at T0 = 690

Figure 6: Conversion of B on r vs. z at T0 = 570

Figure 9: Conversion of B on r vs. z at T0 = 690

Figure 7: Conversion of C on r vs. z at T0 = 570

Figure 10: Conversion of C on r vs. z at T0 = 690

Figures 5-10 show that there is little eect from radial dispersion at low inlet temperatures, but at larger temperatures the eect starts to become signicant, especially for species C, and high radial 5

concentration gradients will exist in the reactor under those conditions. Lastly I examine the eects of using very low inlet temperatures to get a lower bound for feed inlet temperature

Figure 11: Conversion of A vs. z at various values of T0

Beyond T0 = 550 K the conversion drops o to virtually nothing. Eects on Temperature Next I wanted to look at the eects inlet temperature has on the temperature within the reactor. Plotting T vs. z for various inlet temperatures: Here it starts to become apparent why feed temperatures over 690 do not converge, the Temperature blows up at this point. I wanted to examine the eects of feed temperature around this point.

Figure 12: T vs. z at various values of T0

Figure 13: T vs. z at values of T0 near 690 K

Figure 14: Temperature on r vs. z at T0 = 690

Figures 12, 13, and Figure 1 show how the temperature inside the reactor varies when the inlet temperature is at (or in Figure 12 around) 690 K. There is a hot spot in the reactor where the temperature will increase beyond the bounds of the solution at higher temperatures of the inlet feed than 690 K.

Varying
I vary from 20 W/(m2 K ) to 340. The base case has a heat transfer coecient of 156 W/(m2 K ). First I examine the eects on conversion, then on temperature in the reactor. Using a heat transfer coecient under 20 results in convergence trouble, I will examine why later. Eects on Conversion

Figure 15: Conversion of A vs. z at varying values

of

Figure 17: Conversion of C vs. z at varying values

of

Figure 16: Conversion of B vs. z at varying values

of As seen from Figures 15-17, the behavior becomes erratic at the value of below 20, but otherwise conversion increases with decreasing . To investigate the eects of dispersion in both the r and z dimensions, I make a surface plot of the conversion for species A at the values of =20, 140, 340.

Figure 18: Conversion of A on r vs. z at = 20

Figure 20: Conversion of A on r vs. z at = 340

Figure 19: Conversion of A on r vs. z at = 140

There is not much change between the higher values, but at low values of the conversion occurs more quickly with respect to z . Eects on Temperature Here I look at the full range of values and then narrow in on the trouble range of around = 20. Once again it becomes apparent that the solution blows up because of a hotspot. In this case instead of being caused by high feed temperatures it is caused by a very low heat transfer coecient, which does not allow for the removal of heat at a sucient speed.

Figure 21: T vs. z at varying values of

Figure 22: Temperature on r vs. z at near 20 W/(m2 K )

Analysis
Problem Statement: Summarize the results. Calculations:

Variation of T0
I rst examined the eects of changing inlet temperature from a range of 570 to 690 K on conversion along the z dimension (Figures 2-4). Conversion of A and C increases with increasing inlet temperature, conversion of B does as well up to around 670K. At 690K the conversion of B along the reactor goes down after it passes the hotspot. This solution is an eect of the hot spot I will talk about later. I next looked at conversion along the r and z dimensions at the extremum temperatures of 570 K and 690 K. At the low temperature the eects of radial dispersion are negligible, it is only at the higher temperature of 690 K where we see conversion of all three species (most notably C) changing as a function of R (Figures 5-10). The last thing I examined for conversion was at feed temperatures much lower than the base of 627. From Figure 11 it can be seen that at temperatures lower than 550 K the conversion at the end of the reactor of species A is less than 10%. Next I look at the eects of feed inlet temperature on the temperature within the reactor. Figures 12-14 illustrate that at and near T0 = 690 K there is a hotspot in the reactor where the solution starts to have trouble converging and I get the behavior of conversion of species B as shown in Figure 3. I conclude from these results that the reactor should not be operated with a feed inlet temperature above 670 (possibly even lower depending on the material the tube is made out of). At 690 K the hot spot temperature is around 840K, and incremental increases in feed temperature beyond this point will result in exponentially larger hotspot temperatures. If B is the desired product, one would want to operate at high conversion of A, and low conversion of B. Since both of these increase with temperature there is a tradeo between volume of product and purity of it, and market forces would dictate exactly what inlet temperature to operate at.

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Variation of
I examined the eects of varying the heat transfer coecient from 20-340 W/(m2 K ). First I looked at the eects on conversion of each species (Figures 15-17) as a function of z . I found that conversion of each species increases as decreases, with erratic behavior occurring at a heat transfer coecient of around 20. Figures 18-20 show the conversion of A vs. r and z , and show that there is little eect in the r direction for any value of . I next examined the temperature as a function of z for dierent heat transfer coecients, and looked closely at the = 20 region. I nd that as is lowered a hot spot appears (Figures 21-22). This hot spot is located further down the reactor than the inlet one, but is equally problematic in blowing up the equations. The reactor should be designed in such a way (geometry, material, ow rate) that the heat transfer coecient is at minimum greater than 30 W/(m2 K ).

Conclusions
Intermediate eects could also be found by changing both T0 and simultaneously, and the results shown here indicate that one can be used to compensate for the other. Increasing the inlet temperature while increasing the heat transfer coecient will decrease the hot spot temperature, and vice versa. The upper limits of operable conditions if they are isolated are T0 = 690 K , and = 20 W/(m2 K ). In reality we want to operate at a high conversion of A and low conversion of B, but at a suciently high conversion to make a prot. An economic study would be necessary to further investigate the feasibility of this process.

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