People`s democratic republic of Algeria

Ministry of higher education and scientific research

Polytechnic high school of Constantine

Department of process engineer

PROBLEM 1

By : HASSAINE Abdelhak

Academic year :2023/2024

Problem 1 :
The hydrogenolysis of low-weight paraffins takes place in a tubular flow reactor.
Determination of the reaction rate constants :
z
FAz FAz + dFA

dv

The Kinetic of the propane reaction may be assumed to be first order .

The stoichiometry of the main reaction may be considered to be of the form :

H2 +C3H8 CH4 + C2H6

B+A C+D
MB/A : 𝒊𝒏𝒑𝒖𝒕 + 𝒈𝒆𝒏𝒆𝒓𝒂𝒕𝒆𝒅 = 𝒐𝒖𝒕𝒑𝒖𝒕 + 𝒄𝒐𝒏𝒔𝒖𝒎𝒑𝒕𝒊𝒐𝒏 +
𝒂𝒄𝒄𝒖𝒎𝒖𝒍𝒂𝒕𝒊𝒐𝒏
A is a reactive 𝒈𝒆𝒏𝒆𝒓𝒂𝒕𝒆𝒅 = 0

Steady-state system 𝒂𝒄𝒄𝒖𝒎𝒖𝒍𝒂𝒕𝒊𝒐𝒏 = 0

𝒊𝒏𝒑𝒖𝒕 = 𝒐𝒖𝒕𝒑𝒖𝒕 + 𝒄𝒐𝒏𝒔𝒖𝒎𝒑𝒕𝒊𝒐𝒏
𝒊𝒏𝒑𝒖𝒕 = 𝑭𝑨𝒛
𝒐𝒖𝒕𝒑𝒖𝒕 = 𝑭𝑨𝒛 + 𝒅𝐅𝐀
𝒄𝒐𝒏𝒔𝒖𝒎𝒑𝒕𝒊𝒐𝒏 = ( −𝒓𝑨𝒔 ) ∗ 𝒅𝑽
FAz = FAz + dFA + (−𝑟𝐴𝑠 ) ∗ 𝑑 𝑉

−𝑑FA = (−𝑟𝐴𝑠 ) ∗ 𝑑 𝑉
Where −𝑟𝐴𝑠 = 𝑘 ∗ 𝐶𝐴𝑠 ∗ 𝐶𝐵𝑠 , Feed ratio B/A = 2 , Reactor pressure = 7.0 MPa
FA = FAe * ( 1- XA )
dFA = - FAe *dXA
Where (−𝑟𝐴𝑠 ) = 𝐾 ∗ CA * CB
FAe *dXA = 𝐾 ∗ CA * CB * dV
Where V = Q*t , dV=Q*dt
 ts XA
∫0 𝑑ts= FAe * ∫0 𝑑 XA /(Qs*( 𝐾 *CA * CB))

Where Q=Qe*(1+α’*XA) , α’= -yA*δσ/ σA=0 , F/Q=C , FBe= 2* FAe , CBe= 2* CAe ,
FB=FBe-[(σi/ σA)*FAe*XA] , CB=CAe*(2-XA)
FA=FAe-[(σi/ σA)*FAe*XA] , CA=CAe*(1-XA)
XA
tS = FAe *∫0 𝑑XA /(Qe*( 𝐾 * CAe*(1-XA) * CAe*(2-XA)))
XA
tS = FAe *∫0 𝑑XA /(Qe*( 𝐾 * CAe*(1-XA) * CAe*(2-XA)))
XA
tS = ∫0 𝑑XA /( 𝐾 * CAe*(2-XA)*(1-XA)) , CAe=?

ideal gas law:

P*V= n*R*T , CAe= PAe / R*T , PAe=?
Feed ratio :
PBe/ PAe =2 , PT= PAe+ PBe , PAe= PT/3=7/3=2.33MPa
XA
K= R*T*∫0 𝑑XA /( tS * PAe*(1-XA)* (2-XA))
XA
∫0 𝑑 XA /(1-XA)* (2-XA)=A/(1-XA) +B/(2-XA)
XA
∫0 𝑑 XA /(1-XA)* (2-XA)= [A*(2-XA)+B*(1-XA)]/ (1-XA)* (2-XA)

A=1 , B=-1
K=(R*T*3*Ln[(1-0.5*XA)/(1-XA)])/ts*pT)
A.N
R=8.314 j/mol*K ,
T(K) Space time (s) Fraction Constant (K) (s- Constant (Km)
1
propane ) (s-1)
converted
811 42 0.018 6.3*10-7
811 98 0.037 5.18*10-7 Km=7.342*10-7
811 171 0.11 16.8*10-7
866 40 0.26 1.35*10-5
866 81 0.427 1.48*10-5 Km=1.257*10-5
866 147 0.635 2.3*10-5

Determination the activation energy of the reaction :

Where

law of Arrhenius: K=A*𝑒 (−Ea / R∗T)

 A: The total number of well-oriented shocks per second between reactants.

𝒆(−𝐄𝐚 / 𝐑∗𝐓) : between 0 and 1, is the probability for a well-oriented shock.

K: The number of successful shocks.
Linear regression:
I plotted the graph of ln k versus 1/T

Ln(K)=Ln A-(Ea/R)*1/T

Ln(K) 1/T
-14.12 1.23*10-3
-11.28 1.15*10-3

Ln(K)=1/T
0
1.15*10-3 1.23*10-3
-2

-4

-6

-8

-10

-12

-14
y = -2.84x - 8.44
-16 R² = 1

Ln(K)=Ln A-(Ea/R)*1/T

Y=-2.84x-8.44
Ea/R=2.84, Ln(A)=-8.44, R=8.314 J/mol*K
Ea=2.84*8.314 , A=EXP(-8.44)
Ea=23.61J/mol
A=0.000216s-1
The activation energy of the reaction :
Ea=23.61 J/mol

Noticed:
We notice that the activation energy is positive therefore the reaction is endothermic.