From: CHEE 4361 Group A / Thursday

Date: 10/05/2020

Subject: Pre-Lab on Virtual Plug Flow Reactor (PFR)

To: Dr. Patrick C. Cirino

Dept. of Chemical & Biomolecular Engineering
University of Houston
Houston, TX 77204

Dear Dr. Cirino,

Enclosed is group A's pre-lab for the laboratory experiment investigating how the gas phase's flow
rates and pressure affect a reaction's parameters. The experiment can be summarized as follows:

This lab's purpose is to study an isothermal packed-bed reactor for a gas-phase catalytic reaction.
Then analyze the data to determine the rate constant k and the adsorption equilibrium KA and KB
by varying the feed-in and reaction conditions (flowrate of A and B, and reactor pressure) and
measuring the effluent gas composition.

Herein we outline the data to be collected, preliminary calculations, and major calculations to be
performed following experimentation and detailed safety analysis.

Each team member contributed approximately the same. Our team has four members, and Jing has
a supporting role every week. She has divided her work fairly with the Team Leader for this week,
Huong Phan.

All of us have studied and obtained EH06, EH05L, and EH26 certificates of General Safety,
Managing Laboratory Waste Spill, and Compressed Gas Cylinder Safety. We are confident that
we understand all potential hazards and appropriate procedures and will proceed in the lab
accordingly.

Sincerely,

JingWangReed HuongPhan
Jing Wang-Reed – Team Leader Huong Phan –Team Leader

UyenTrinh DungNguyen
Uyen Trinh – Technical Lead Dung Nguyen –Secretary/Safety Lead

Enclosure: Virtual Plug Flow Reactor Long Report

Objectives
The goal of this laboratory experiment is to determine the rate constant k and the adsorption
equilibrium constants KA and KB for this gas-phase reaction:

A + B → 2C

We can determine these parameters based on the effluent compositions from an isothermal
packed–bed reactor with constant volume and temperature. The effluent composition values are
dependent on the feed-in conditions by changing the mass flow and pressure controllers.

Experimental Design and Preliminary Calculations

Step-by-Step Procedure

1. This webpage will lead you to the virtual Plug Flow Reaction (PFR) experiment https://virtual-
labs.learncheme.com/catalytic-reactor/#

2. Use your account information to log in. Create an account if you do not have one.

3. A balance of $10000 is provided for a new account, and each measurement costs $250.

4. Click the "startup reactor" button; this cost $125 and waits for the experiment setup to be ready.

5. Each gas's path is represented by a colored line: red for A, blue of B, purple for mixture A, B
and/or C, and green for He. There will be two mass flow controllers and one pressure controller
that you can make an adjustment in this experiment.

6. Click on the mass flow controller to input the feed flow rate of reactant A and/or B from 0.03
- 1.5 mmol.sec-1. A reaction will automatically proceed inside the packed bed reactor.

7. Click on the pressure controller to input the gas mixture's pressure in the range of 0.1 - 1.5
MPa absolute.

8. Wait for the reactor to reach the steady-state and the "sample ready" message to appear on the
status box

9. Click on the six-way valve to deliver the gas mixture sample to the gas chromatography. After
the "result ready" message pops up, we can observe the A, B, and C gas compositions on the
computer screen.

10. Click on the six-way valve to restart the experiment with a new sample.

11. Repeat from step 6 to 10 with new values for the controllers.

12. Use 3 different values for each controller. It will add up to a total of 27 trials
13. Click on the "Data Log" tab to observe all of the operation conditions and result measurements
for further calculations.

14. Log out.

Process Diagram:

Figure 1: Process flow diagram for the catalyst reactor system which follows the isothermal packed bed reactor (PBR) behavior

Preliminary Calculations

The ideal gas law and Dalton's law apply, each component's partial pressure (Pi) is calculated from
its outlet mole fraction (yi) and the total pressure (P) in the reactor:

Pi = Ci ∗ RT

𝐹𝑖
Pi = yi ∗ P = ( )∗𝑃
𝐹𝐴0 + 𝐹𝐵0

Analytical Methods and Instruments

The feed gas flow rates of A and B (mmol.sec-1) can be observed on the mass flow rate controllers.
The gas mixture of A and B are fed to a packed-bed reactor (PBR) where the catalytic reaction
occurred. A pressure controller is used to provide the total pressure of the reactor (MPa). The
outlet gas mixture flows through a column inside the gas chromatography (GC) with Helium as
the carrier gas. The GC task is to separate the different components in the gas mixture and then
delivers each gas component out of the column at different times. A detector placed at the outlet
of GC is used to monitor each component's amount in the mixture, and the result will appear on a
computer screen that is connected to the detector.
Data:
The collected data includes the reactor pressures, temperature, inlet molar flow rates of A and B,
and the outlet mole fractions of A, B, and C. At the beginning of each trial, the feed molar flow
rates and total pressure are modified and recorded. The experiment runs with three different feed
molar flow rates of A, B set points and three different total pressures for each molar flow rate. It
will add up to a total of 27 trials. During each trial, the outlet mole fractions will be recorded in
the data table. Table 1 is an example of how to record the effluent gas compositions, and two more
tables will be added since we are using three different flow rates of A using this format.
Table 1. Raw data of 27 trials obtained from the Data Log of the experiment.

FAo (mmol/s) FBo (mmol/s) P (MPa) T (K) yA yB yC

1.00 0.25 0.50 559 0.708 0.110 0.182
1.00 0.25 1.00 559 0.688 0.083 0.229
1.00 0.25 1.50 559 0.672 0.070 0.258
1.00 0.50 0.50 559 0.540 0.220 0.240
1.00 0.50 1.00 559 0.514 0.165 0.321
1.00 0.50 1.50 559 0.497 0.146 0.357
1.00 0.75 0.50 559 0.436 0.324 0.240
1.00 0.75 1.00 559 0.400 0.263 0.337
1.00 0.75 1.50 559 0.380 0.233 0.387
1.00 1.25 0.50 559 0.328 0.471 0.201
1.00 1.25 1.00 559 0.287 0.419 0.294
1.00 1.25 1.50 559 0.267 0.391 0.342
1.00 1.50 0.50 559 0.301 0.515 0.184
1.00 1.50 1.00 559 0.268 0.462 0.270
1.00 1.50 1.50 559 0.251 0.451 0.298
0.25 0.75 0.50 559 0.098 0.607 0.295
0.25 0.75 1.00 559 0.048 0.556 0.396
0.25 0.75 1.50 559 0.032 0.533 0.435
0.50 0.75 0.50 559 0.241 0.423 0.336
0.50 0.75 1.00 559 0.167 0.352 0.481
0.50 0.75 1.50 559 0.129 0.322 0.549
1.25 0.75 0.50 559 0.531 0.277 0.192
1.25 0.75 1.00 559 0.495 0.236 0.269
1.25 0.75 1.50 559 0.458 0.223 0.319
1.50 0.75 0.50 559 0.577 0.258 0.165
1.50 0.75 1.00 559 0.549 0.218 0.233
1.50 0.75 1.50 559 0.538 0.202 0.260
Major Calculations:
The gas-phase reaction is 𝐴 + 𝐵 → 2𝐶. The rate of disappearance of gas A follows the Langmuir-
Hinshelwood kinetics, and the rate law was found mathematically to be:
dFA kPAPB mmol
−rA = − = (1+K 2 [ cm3s ]
dV APA+KB PB )

The set of ordinary differential equations (ODE) are solved using the 4th order Runge-Kutta
method (5).
kPAnPBn
k1 = (1+ K 2 where n = 0, 1, 2, 3…
A PA+KB PB )

k dV k dV
k(PAn+ 1 )(PBn+ 1 )
2 2
k2 = k dV k dV 2
[1+ KA(PAn+ 1 )+KB (PBn+ 1 )]
2 2

k dV k dV
k(PAn+ 22 )(PBn+ 22 )
k3 = k dV k dV 2
[1+ KA(PAn+ 22 )+KB (PBn+ 22 )]

k(PAn+k3 dV)(PBn+k3 dV)

k 4 = [1+ K 2
A(PAn +k3 dV)+KB (PBn +k3 dV)]

(𝑘1 +2𝑘2 +2𝑘3 +𝑘4)𝑑𝑉

𝑃𝐴𝑛+1 = 𝑃𝐴𝑛 + 6

(𝑘1 +2𝑘2 +2𝑘3 +𝑘4 )𝑑𝑉

𝑃𝐵𝑛+1 = 𝑃𝐵𝑛 + 6

The parameters k, KA, KB, and their 95% confidence intervals are determined by applying the
nonlinear regression to fit the experimental data to the rate expression. In nonlinear regression
analysis, the parameter values are determined at the minimum sum of squares of the differences
between the experimental values and the calculated values for all the data points

The 95% confidence interval for each parameter is defined as (2):

∓ 𝑡𝛼/2 . 𝑠. √𝐶𝑖𝑖

where,

𝑆𝑆𝐸 ∑𝑁
𝑖=1(𝐶𝑖𝑚 −𝐶𝑖𝑐 )
2
𝑠 ≈ √𝑁−𝐾 = √ 𝑁−𝐾

𝐶𝑖𝑖 = [(𝑋 𝑇 𝑋)−1 ]𝑖𝑖 (𝑖 𝑡ℎ 𝑑𝑖𝑎𝑔𝑜𝑛𝑎𝑙 𝑒𝑙𝑒𝑚𝑒𝑛𝑡 𝑜𝑓(𝑋 𝑇 𝑋)−1 )

 = 1 – confidence level
Nomenclature:

Nonlinear regression:

• (XTX)-1: the information matrix for linear regression

• Cic: calculated concentration rate for run i
• Cii: cell in the information matrix
• Cim: measured concertation rate for run i
• K: number of parameters to be determined
• N: number of runs
• s: the estimation of measurement noise
• SSE: the sum of squared of error (residual)
• t/2: appropriate point of T-distribution with N – K degree of freedom

Langmuir isotherm:

• FA0: initial flow rate of A (mmol/sec)

• FB0: initial flow rate of B (mmol/sec)
• Fj: flow rate of species I (mmol/sec)
• KA: adsorption equilibrium constant of A
• KB: adsorption equilibrium constant of B
• P: pressure (MPa)
• PA, PAn: partial pressure of A (MPa)
• PB, PBn: partial pressure of B (MPa)
• Pi: partial pressure of i (MPa)
• T: temperature (K)
• V: volume (cm3)
• vo: volumetric flow rate (cm3/sec)
• yi: the molar fraction of species i

Example calculation:
Data observed:
FAo = 0.5 mmol/sec
FBo = 0.5 mmol/sec
P = 0.10 MPa
T = 592 K
yA = 0.483
yB = 0.466
yC = 0.051
Using gas composition and total pressure to find partial pressure:

PAexp = (0.483) * (0.10) = 0.0483 MPa

 PBexp = (0.466) * (0.10) = 0.0466 MPa
PAo = [ 0.5 / (0.5+0.5)] * (0.10) = 0.05 MPa
PBo = [ 0.5 / (0.5+0.5)] * (0.10) = 0.05 MPa

According to the equation of reaction rate, we have 3 unknown parameters: k, KA, KB

Steps to find the 3 parameters using excel solver

• Choose an initial guess for k, KA, KB

• Use the Runga-Kutta 4th order equation to solve the ODE of the 2nd order rate law
with PAo to find PAcal
• Find the (residual)2 = (PAexp - PAcal)2
• Then sum up all of the residual2 if there are more than one set of data provided
• Use the excel solver to minimize the sum of (residual)2 by changing k, KA, KB
• The values of k, KA, KB are found
• Looking for the 95% confidence interval for those values

Safety Analysis
Reference from: General Laboratory Safety Manual on Blackboard (1).

PPE: Safety is of primary importance for every experiment. To protect against potential laboratory
hazards, long pants, safety glasses, gloves, closed-toe shoes, and laboratory coats must be worn.

Gas Cylinders and Regulators: Accidents involving gas cylinders can cause serious injury or
even death. Slowly turn on the gas valve and slowly increase gas flow. Gas flowing at high pressure
or high velocity can be quite loud. Wear earplugs (provided in the lab) when operating the
compressed gas line that feeds into the cylinder. Be sure to insert the earplugs properly. Avoid
leaks from the cylinder because the gas might be corrosive, flammable, toxic, or unstable.

All students operating a pressure regulator attached to a compressed gas cylinder must have
certification for safety training in the use of compressed gas cylinders. All gas cylinders must be
tightly fastened to a wall or bench, individually. Do not attempt to move any gas cylinders. Avoid
increasing the pressure of the cylinder hastily or over its limit, as the temperature of the cylinder
is proportional to its pressure. If the gas inside the cylinder is flammable, a sudden increase in
temperature could lead to fire hazards.
 Figure 2: Cylinders should be stored individually and in the dark (3).

Figure 3: Not stored in clumps and exposed to sunlight (4).

Tanks and reactors are under high pressure. Prior to running experiments, be sure to understand
how to operate pressure regulators, know the pressure limits of the reactor system, and identify the
pressure relief valve and its operating limits.
 Figure 4: Pressure Regulator

The general operation of the regulator:

1. Make sure the regulator outlet valve (A) is closed (tight clockwise), and the control valve
(B) is open (loose counterclockwise).

2. Open the tank valve slowly (counterclockwise). Watch the tank pressure on the regulator
(C).

3. Slowly turn the regulator control valve (B) until the regulator pressure (D) is at the desired
level.

4. Open the regulator outlet valve (A). You can regulate flow with this valve, but the pressure
depends on the setting of the regulator control valve!

5. Check your system for leaks using a solution of soapy water. If you find leaks and
tightening the connections does not help, ask a TA for assistance.

Electrical Hazards

o Before turning equipment on, check all power cords for any frays and damage, ensure all
electrical connections are secure, and all electrical equipment is Ground Fault Circuit
Interrupter (GFCI) protected.

o Keep the variable voltage controller (Variac) setting as low as possible.

o Avoid spilling any water on or around the variable voltage controller or pumps.
o Be careful because electrical hazards can cause shocks, burns, and electrocution.
o When a person being electrocuted:
Do not touch them!
Turn off the power by unplugging or flipping the circuit breaker – if possible
Use an item made of non-conductive material, for instance, a wooden broom
handle, to pry an electrocuted person away from the point of contact – if
possible
Call 911 immediately.
References
1. Environmental Health and Life Safety (EHLS). General Laboratory Safety Manual.
University of Houston, August 2018
2. Nikolaou, Michael. Numerical and Statistical Methods in Chemical Engineering.
Chemical Engineering Department, University of Houston, Blackboard.
3. Reddy, Palagiri. File: Kitchen –LPG Cooking gas cylinder.JPG
https://commons.wikimedia.org/wiki/File:Kitchen-LPG_cooking_gas_cylinder.JPG
(accessed October 6, 2021).
4. Sagdejev, Ildar. An assorted bundle of gas bottles at Duke University.
https://en.wikipedia.org/wiki/Bottled_gas (accessed October 6, 2021).
5. University of Colorado Boulder. Solving Mass Balance Differential Equations for an
Isothermal Plug Flow Reactor in Excel. https://www.youtube.com/watch?v=Zpb-
gl8HSME (accessed October 6, 2021).