Вы находитесь на странице: 1из 8

According to Shirazi et al.

(2007), the reaction rate for the hydrogenation process can be


determined as follows:
 Letting A be the hydrogen reactant, M be cyclopentene, T be the product, s denoting the
active site of catalyst, 𝜃1 the active site occupied by cyclopentene and 𝜃2 the active site
occupied by the product
Hence, the equations can be written as:
1. Adsorption M + s ↔ 𝑀. 𝑠 (K1 , K-1) -r1 = K1CM (1- 𝜃1 − 𝜃2 )
2. Reaction 3A2 + M.s → T.s + 2H2O (K2) -r2 = K2 𝜃1 CA
3. Desorption T.s ↔ T + s (K3 , K-3) -r3 = K3 𝜃1 – K-3 (1- 𝜃1 − 𝜃2 )
By assuming equilibrium condition for reaction 1 and 3 (r1 and r3 = 0) and solving the above
equation, the rate equation can be written as:

Computer Simulation
Polymath can be used to simulate the above process in order to facilitate the task of determining
the rate law and the kinetics of the reaction:
The preceeding elementary hydrogenation reaction cab be represented as:
A+B↔C
The concentrations of each species can be written as:

Performing mole balances on each species and combining them with the concentrations equations:
Hence the following ODE equations and appropriate explicit equations can be used to generate
the
polymath report:
 Differential equations
𝑑𝐹𝑎
= 𝑟𝑎
𝑑𝑉
𝑑𝐹𝑏 𝐹
= −𝑟𝑎 . −𝐾𝑐 ∗ 𝐶𝑇𝑜 ( 𝐹𝐵 )
𝑑𝑉 𝑇

𝑑𝐹𝑐
= −𝑟𝑎
𝑑𝑉
The explicit equations can be for instances the values being attributed to the different constants
incolvedin the reaction: Kc, FT , CTo .
The liquid phase production of methyl bromide from an aqueous solution of methyl amine
and bromide cyanide

The production of methyl bromide occurs through an irreversible liquid phase reaction that follows
an elementary rate law. The reaction between aqueous solutions of bromide cyanide and
methylamine is carried out in a semi batch reactor which is operated at isothermal conditions. The
reactants are input simultaneously which lead to the formation of methyl bromide and cyanamide.
The desired product methyl bromide being more volatile than the undesired one (cyanamide), is
vaporized and continuously removed.

In so doing, the equilibrium is shifted towards the right, causing an increase in the final conversion
above that which would be achieved if methyl bromide was not withdrawn. Furthermore upon
withdrawal of methyl bromide, the reactant becomes more concentrated which results in an
increase in the rate of reaction and a decrease in the processing time.

FOGLER (2010, p. 188) states that closed form analytical solutions to the differential equations
coming from the mole balance of these reaction types can be acquired only for the reactions of
zero and first order. He also added that ordinary differential equation solvers should be applied for
the rest.

Considering that the liquid phase production of methyl bromide is a second order reaction, ODE
solvers are used for the simulation.

Determination of concentration of bromine cyanide and methyl bromide and the rate of reaction as
a function of time

Reactant

Let A: Concentration of aqueous bromine cyanide

Let B: Concentration of aqueous methyl amine


Product

Let C: Concentration of methyl bromine

Let D: Concentration of cyanamide

Assumption

Concentration of aqueous methyl amine (B), CBo = 0.025 mol/dm3

Flow rate of aqueous methyl amine (B), v0 = 0.05 dm3/s

Concentration of aqueous bromine cyanide (A), CAo = 0.05 mol/dm3

The specific reaction rate constant, k = 2.2 dm3/s.mol

Hence, it can be written that:

Since it is a single step reaction , the rate law is given by :

−𝑟𝑎 = 𝑘𝐶𝐴 𝐶𝐵

𝑑𝐶𝐴 𝑣
= −𝑘𝐶𝐴 𝐶𝐵 − ( 𝑜 ) 𝐶𝐵
𝑑𝑡 𝑉

𝑑𝐶𝐴 𝑣𝑜
= −𝑘𝐶𝐴 𝐶𝐵 + ( ) (𝐶𝐵𝑜 − 𝐶𝐵 )
𝑑𝑡 𝑉

Since

𝑉 = 𝑉𝑜 + 𝑣𝑜 𝑡

Similarly for the products C and D,


𝑑𝑁𝐶
= 𝑟𝑐 𝑉 = 𝑟𝑎 𝑉
𝑑𝑡

𝑑𝑁𝐶 𝑑(𝐶𝐶 𝑉) 𝑑(𝐶𝐶 ) 𝑑𝑉 𝑑(𝐶𝐶 )


= =𝑉 + 𝐶𝐶 =𝑉 + 𝑣𝑜 𝐶𝐶
𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡

Therefore ,

𝑑𝐶𝐶 𝑣𝑜 𝐶𝑐
= 𝑘𝐶𝐴 𝐶𝐵 −
𝑑𝑡 𝑉

and also ,

𝑑𝐶𝐷 𝑣𝑜 𝐶𝐷
= 𝑘𝐶𝐴 𝐶𝐵 −
𝑑𝑡 𝑉

In order to calculate conversion, X

Since

𝑁𝐴𝑜 −𝑁𝐴
𝑋=
𝑁𝐴0

Then

𝐶𝐴𝑜 𝑉𝑜 −𝐶𝐴 𝑉
𝑋=
𝐶𝐴0 𝑉𝑜

The equations derived above can be straightforwardly solved by making the use of software for
ODE solver, such as Polymath. When using an ordinary differential equation (ODE) solver such
as Polymath or MATLAB, it is usually easier to leave the mole balances, rate laws, and
concentrations as separate equations rather than combining them into a single equation to obtain
an analytical solution. Writing the equations separately leaves it to the computer to combine them
and produce a solution. This is shown by the graphs generated below.
ODE report – Polymath Program

Differential equations as entered by the user.

[1] d(Ca)/d(t) = - k*Ca*Cb - vo*Ca/V

[2] d(Cb)/d(t) = - k*Ca*Cb + vo*(Cbo – Cb)/V

[3] d(Cc)/d(t) = - k*Ca*Cb - vo*Cc/V

[4] d(Cd)/d(t) = - k*Ca*Cb - vo*Cd/V

The following explicit equations and values are entered by the user, in order to generate a graph.

[1] k = 2.2

[2] vo = 0.05

[3] Cbo = 0.025

[4] Vo = 5

[5] Cao = 0.05

[6] rate = k*Ca*Cb

[7] V = Vo + vo*t

[8] X = (Cao*Vo – Ca*V)/(Cao*Vo)

The concentrations of bromine cyanide (A) and methyl amine are shown as a function of time in
figure 1, and the rate is illustrated in figure 2.
Figure 1 Polymath output: Concentration-time trajectories (Source: Fogler, n.d.)

Figure 2 Reaction - rate time trajectory Fogler, n.d.)


References

 FOGLER.S.H., 2010. Essentials of Chemical Reaction Engineering. [online] Available from:


http://www.chegg.com/homework-help/asked-explore-example-problems-chapter-learn-effects-
varyin-chapter-6-problem-2qp-solution-9780132317160-exc
[Accessed 21 February 2017]

 SHIRAZI.L & HADIPOUR.A., 2007. Determination of the kinetic parameters and Modeling of
the reactor for hydrogenation of M-nitrotoluene in a multi phase slurry reactor. Petroleum and
Coal. [online] 46 (3). Available from:
http://www.vurup.sk/sites/vurup.sk/archivedsite/www.vurup.sk/pc/vol49_2007/issue3/pdf/pc_3_2
007_shirazi.pdf
[Accessed 26 February 2017]

 Polymath-software.com. (n.d.). Reasons for using polymath. [online] Available at:


http://www.polymath-software.com/top10/index.htm
[Accessed 21 February 2017]

Вам также может понравиться