Dehydroaromatization Reactor(PBR-100)

Brief Summary

According to Fayzullaev (2017). The process of forming aromatics such as benzene is commonly
done through Catalytic Hydrocracking and reforming of oil fractions, however due to the increasing
supply of oil as fuel and increasing supply of aromatics other viable methods to obtain aromatics is
through Dehydroaromatization Reaction of light gases. The raw material used is Purified Natural Gas
(mostly Methane) is fed to a Packed Bed Reactor at T=800 C and P=0.3 bar, In dehydroaromatization
reaction of methane the catalyst(MoO3x·(ZrO2·ZnO2)z/bentonite) synthesized based on bentonite using
ammonium bicarbonate and hexamethylenediamine with highest activity. The reaction is a complex
(non-conventional) kinetic reaction. Equation 1 and 2 are the chemical reaction shown below

There are 5 key steps for the dehydroaromatization reaction to occur:

i.) Diffusion of reactants to the catalyst

bed
Initiation

ii.) Adsorption of the reactants

iii.) Chemical Reaction

Propagation

iv.) Desorption of Product

Termination

v.) Diffusion of Product

𝟔𝑪𝑯𝟒 (𝒈) → 𝑪𝟔 𝑯𝟔 (𝒈) + 𝟗𝑯𝟐 (𝒈) (Eqn 1)

𝑪𝑯𝟒 (𝒈) → 𝑪(𝒔) + 𝟐𝑯𝟐 (𝒈) (Eqn 2)

The main steps to be undertaken for the propagation mechanism of the catalyst and the gas is
methane⟶olefines⟶aromatic hydrocarbons which is shown on Figure 1

Figure 1 Propagation Mechanism of Olefins

The reaction of catalytic aromatization of

methane and coking process of the catalyst
active centers could be expressed by the
following scheme and a part of them blocks the
catalytic centers, the other part reduces active
phases of metal clusters and is basically
localized on external surface of a catalyst. As a
result total conversion of methane decreases
and formation speed of aromatic hydrocarbons
increase.

Retrieved from : 10.1021/acs.iecr.6b02701

Kinetic Data
Where, fi is the fugacity of component i;
𝒇𝑪 𝑯 𝒇𝟗𝑯 KR1 and KR2 is the equilibrium
𝒌𝟏 𝒇𝟔𝑪𝑯𝟒 (𝟏 − 𝟔 𝟔 𝟔 𝟐 ) constant of reactions 1 and 2,
𝑲𝑹𝟏 𝒇𝑪𝑯𝟒
𝒓𝟏 = 𝟔 respectively, which can be calculated
(𝟏 + 𝑲𝑪𝑯𝟒 𝒇𝑪𝑯𝟒 + 𝑲𝑯𝟐 𝒇𝑯𝟐 + 𝑲𝑪𝟔𝑯𝟔 𝒇𝑪𝟔𝑯𝟔 ) from thermodynamic data ;
k1 and k2 are the rate constants of
𝒇𝟐𝑯𝟐 Reactions 1 and 2, respectively;
𝒌𝟐 𝒇𝑪𝑯𝟒 (𝟏 − )
𝑲𝑹𝟐 𝒇𝑪𝑯𝟒 Ki is the adsorption equilibrium
𝒓𝟐 = 𝟔 constant of component i. The
(𝟏 + 𝑲𝑪𝑯𝟒 𝒇𝑪𝑯𝟒 + 𝑲𝑯𝟐 𝒇𝑯𝟐 + 𝑲𝑪𝟔𝑯𝟔 𝒇𝑪𝟔𝑯𝟔 ) following kinetic parameters are
used for the present simulations.
−𝟐. 𝟎𝟗𝟎𝟗 × 𝟏𝟎𝟓 𝟏
𝒌𝟏 = 𝟖. 𝟏𝟐𝟖𝟑 × 𝟏𝟎−𝟑 𝐞𝐱𝐩 ( (
𝑹 𝑻

𝟏
− ))
𝟗𝟒𝟑. 𝟏𝟓𝑲

−𝟐. 𝟎𝟗𝟎𝟗 × 𝟏𝟎𝟓 𝟏 𝟏

𝒌𝟐 = 𝟐. 𝟑𝟐𝟓𝟐 × 𝟏𝟎−𝟑 𝐞𝐱𝐩 ( ( − ))
𝑹 𝑻 𝟗𝟒𝟑. 𝟏𝟓𝑲

𝟏 𝟏
𝑲𝑪𝑯𝟒 = 𝐞𝐱𝐩 (−𝟏. 𝟏𝟗𝟔𝟑 − 𝟏. 𝟑𝟐𝟎𝟗 × 𝟏𝟎𝟐 ( − ))
𝑻 𝟗𝟒𝟑. 𝟏𝟓

𝟏 𝟏
𝑲𝑯𝟐 = 𝐞𝐱𝐩 (𝟏. 𝟔𝟕𝟑𝟔 + 𝟏. 𝟓𝟕𝟗𝟔 × 𝟏𝟎𝟑 ( − ))
𝑻 𝟗𝟒𝟑. 𝟏𝟓

𝟏 𝟏
𝑲𝑪𝟔𝑯𝟔 = 𝐞𝐱𝐩 (−𝟗. 𝟎𝟗 + 𝟏. 𝟏𝟕𝟕 × 𝟏𝟎𝟓 ( − ))
𝑻 𝟗𝟒𝟑. 𝟏𝟓

[𝑪𝟔 𝑯𝟔 ][𝑯𝟐 ]𝟗
𝑲 𝑹𝟏 =
[𝑪𝑯𝟒 ]𝟔

[𝑯𝟐 ]𝟐
𝑲 𝑹𝟐 =
[𝑪𝑯𝟒 ]

When T=800 oC and 0.3 bar

𝒌𝟏 = 𝟎. 𝟐𝟎𝟓𝟓

𝒌𝟐 = 𝟎. 𝟎𝟏𝟓𝟎𝟕
 𝑲𝑪𝑯𝟒 = 𝟎. 𝟑𝟎𝟕𝟓

𝑲𝑪𝑯𝟒 = 𝟒. 𝟓𝟑𝟓

𝑲𝑪𝟔𝑯𝟔 = 𝟑. 𝟎𝟔𝟖 × 𝟏𝟎−𝟏𝟏

At equilibrium,

𝑲𝑹𝟏 = 𝟑. 𝟐𝟒𝟐 × 𝟏𝟎−𝟑

𝑲𝑹𝟐 = 𝟐. 𝟎𝟒𝟖 × 𝟏𝟎−𝟑

According to ASPEN PLUS Property Table, the fugacity coefficient at T=800oC of the following are

𝒇𝑪𝑯𝟒 = 𝟎. 𝟎𝟏𝟔𝑷𝑫

𝒇𝑯𝟐 = 𝟎. 𝟎𝟎𝟐𝑷𝑫

𝒇𝑪𝟔𝑯𝟔 = 𝟎. 𝟔𝟕𝟓𝑷𝑫

Using the rate experimental equations above,

𝒎𝒐𝒍
𝒓𝟏 = 𝟒. 𝟔𝟐𝟕 × 𝟏𝟎 − 𝟒
𝒉𝒓

𝒎𝒐𝒍
𝒓𝟐 = 𝟕. 𝟏𝟑𝟐𝟏𝟗 × 𝟏𝟎 − 𝟓
𝒉𝒓

Reaction Rates

𝑹𝑪𝑯𝟒 = −𝟔𝒓𝟏 − 𝒓𝟐

𝑹𝑪𝟔𝑯𝟔 = 𝒓𝟏

𝑹𝑯𝟐 = 𝟗𝒓𝟏 + 𝟐𝒓𝟐

𝒎𝒐𝒍
𝑹𝑪𝑯𝟒 = −𝟐. 𝟖𝟒𝟕𝟓𝟐𝟏𝟗 × 𝟏𝟎−𝟑
𝒉𝒓

𝒎𝒐𝒍
𝑹𝑪𝟔𝑯𝟔 = 𝟒. 𝟔𝟐𝟕 × 𝟏𝟎−𝟒
𝒉𝒓

𝒎𝒐𝒍
𝑹𝑯𝟐 = 𝟒. 𝟑𝟎𝟔𝟗𝟒 × 𝟏𝟎−𝟑
𝒉𝒓
Weight of catalyst,

FA0 (from ASPEN PLUS) = 2539.7 kmol/hr CH4

𝒎𝒐𝒍
-ra = r1= 𝟒. 𝟔𝟐𝟕 × 𝟏𝟎 − 𝟒
𝒉𝒓

𝑿
𝒅𝑿𝒂
𝑾𝒄𝒂𝒕𝒂𝒍𝒚𝒔𝒕 = 𝑭𝑨𝟎 ∫
𝟎 −𝒓𝒂

𝟎.𝟗𝟗
𝒅𝑿𝒂
𝑾𝒄𝒂𝒕𝒂𝒍𝒚𝒔𝒕 = 𝟐𝟓𝟑𝟗. 𝟕 × 𝟏𝟎𝟑 ∫
𝟎 𝟐. 𝟖𝟒𝟕𝟐𝟓𝟏𝟗 × 𝟏𝟎−𝟑

𝑾 = 𝟖𝟖𝟑. 𝟎𝟔𝟑 × 𝟏𝟎𝟔 kg

Volume of Reactor,

ρ catalyst = 3.625 kg/mL Fayzullae et al (2017),

𝟏
𝑽𝒓𝒆𝒂𝒄𝒕𝒐𝒓 = (𝑾𝒄𝒂𝒕𝒂𝒍𝒚𝒔𝒕 ) ( )
𝝆𝒄𝒂𝒕𝒂𝒍𝒚𝒔𝒕

𝒎𝑳
𝑽𝒓𝒆𝒂𝒄𝒕𝒐𝒓 = (𝟖𝟖𝟑. 𝟎𝟔𝟑 × 𝟏𝟎𝟔 𝐤𝐠) ( )
𝟑. 𝟔𝟐𝟓 𝒌𝒈

𝑽𝒓𝒆𝒂𝒄𝒕𝒐𝒓 = 𝟐𝟒𝟔. 𝟎𝟖 𝒎𝟑

Number of Tubes

Based on trial and error, assume L=12 m and D 0.4064 m

𝝅
𝑽𝒓𝒆𝒂𝒄𝒕𝒐𝒓 = 𝒏 ( 𝑫𝟐 ) (𝑳)
𝟒
𝝅
𝟐𝟒𝟔. 𝟎𝟖 𝒎𝟑 = 𝒏 ( ) (𝟎. 𝟒𝟎𝟔𝟒 𝒎)𝟐 (𝟏𝟐 𝒎)
𝟒

𝒏 = 𝟏𝟕𝟗. 𝟖𝟕 𝒕𝒖𝒃𝒆𝒔

Residence Time,

Given v0 = 156.166054218774 m3/hr and V = 246.08 m3

𝑽
𝝉=
𝒗𝟎
 𝟐𝟒𝟔. 𝟎𝟖 𝒎𝟑
𝝉=
𝒎𝟑
𝟏𝟓𝟔. 𝟏𝟔𝟔
𝒉𝒓

𝝉 = 𝟏. 𝟓𝟖 𝒉𝒓𝒔

Heat Transfer

𝟔𝑪𝑯𝟒 (𝒈) → 𝑪𝟔 𝑯𝟔 (𝒈) + 𝟗𝑯𝟐 (𝒈) (Eqn 1)

𝑪𝑯𝟒 (𝒈) → 𝑪(𝒔) + 𝟐𝑯𝟐 (𝒈) (Eqn 2)

based on Himmelblau (2008),

Reactants n a b x 102 c x105 D x 10 9

CH4 (if T in K) 19.87 5.021 1.268 -11
CH4(if T in K) 34.31 5.469 0.3661 -11

𝑪𝟎𝑷 = 𝒂 + 𝒃(𝑻) + 𝒄(𝑻)𝟐 + 𝒅(𝑻)𝟑

𝑪𝟎𝑷 = 𝒂 + 𝒃(𝑻) + 𝒄(𝑻)−𝟐

𝑻
𝑸 = 𝒏∫ 𝑪𝟎𝒑 𝒅𝑻
𝟐𝟓𝒐 𝑪

𝒌𝒎𝒐𝒍 𝑻
𝑸 = 𝟐𝟓𝟑𝟗. 𝟕 ∫ 𝟑𝟒. 𝟑𝟏 + 𝟓. 𝟒𝟔𝟗 × 𝟏𝟎−𝟐 𝑻 + 𝟎. 𝟑𝟔𝟔𝟏 × 𝟏𝟎−𝟓 𝑻𝟐 + (−𝟏𝟏. 𝟎 × 𝟏𝟎−𝟗 )𝑻𝟑 𝒅𝑻
𝒉𝒓 𝟐𝟓𝒐 𝑪

𝒌𝑱
𝑸 = 𝟏𝟏𝟎. 𝟔𝟔𝟕 × 𝟏𝟎𝟔
𝒉𝒓

Heat Transfer Coefficient from Towler et al (2013)

 Fluid density, ρ 0.05998799 kg/m3
Superficial velocity, u 0.38049 m/s
Effective particle diameter 0.00075 m
Fluid viscosity 0.03 cP

𝐤𝐠 𝐦
𝒉𝒊 𝒅𝒕 (𝟎. 𝟎𝟓𝟗𝟗𝟖𝟕𝟗𝟗 𝟑 ) (𝟎. 𝟑𝟖𝟎𝟒𝟗 𝐬 ) (𝟎. 𝟎𝟎𝟎𝟕𝟓 𝐦) 𝟔(𝟎.𝟎𝟎𝟎𝟕𝟓)
𝐦
= 𝟎. 𝟖𝟏𝟑 𝐞− 𝟎.𝟑𝟖𝟏
𝝀𝒇 𝒌𝒈
𝟎. 𝟎𝟑 ∗ 𝟏𝟎−𝟐 𝟐
𝒎 −𝒔

𝒉𝒊 𝒅𝒕
= 𝟎. 𝟎𝟒𝟓𝟖𝟒𝟔𝟕 /𝒎𝟑
𝝀𝒇

Diffusivities from Towler et al (2013)

 Temperature 1073.15 K
MMair 29 kg/kmole
MMCH4 16.042 kg/kmole
P,bar 0.3 bar
vCH4 24.42
vair 20.1

𝟎.𝟓
𝟏 𝟏
𝟏𝟎−𝟕 (𝟏𝟎𝟕𝟑. 𝟏𝟓)𝟏.𝟕𝟓 (𝟐𝟗 + 𝟏𝟔. 𝟎𝟒𝟐)
𝑫𝒗 = 𝟏. 𝟎𝟏𝟑 ×
𝟏 𝟏 𝟐
𝟎. 𝟑 [(𝟐𝟒. 𝟒𝟐)𝟑 + (𝟐𝟎. 𝟏)𝟑 ]

𝒎𝟐
𝑫𝒗 = 𝟑. 𝟕𝟔𝟐𝟓𝟓 × 𝟏𝟎−𝟑
𝒔

ASPEN PLUS v 8.8 SIMULATION

 Storage Tank Sketch
Item Number PFR-100
Measurement Metric
Service Dehydro-
aromatization
Reactor
Operating Conditions
Pressure (bar) 0.3
Temperature (K) 1073.15
Design Conditions
Pressure (bar) 1.0
Temperature (K) 1083.15
Metallurgy
Material of Carbon Steel
Construction
Joint Efficiency 0.85
Max. Allowable 12 900
Stress (psia)
Corrosion 3.8
Allowance (mm)
Specifications for Construction
Geometry/Position Plug Flow
Tubes
Foundation Vertical
Type of Roof Flat Ends
Bottom Support Concrete
Capacity (cu. m) 246.08
Tube Specifications
Inside Tube 0.1023
diameter (m)
Outside Tube 6.416
Diameter (m)
Total Number of 235
Tubes
Tube Thickness (m) 4.7752e-2
Tube Insulation Steel Wool