Requirements of the project:
1) Pick one of the following topics as your group project topic;
2) Each project includes 5 questions, you only need to finish at least 2 of them.
3) Write detailed procedures in a word document to explain step by step how you complete
part 2) (report)
4) The report has no page limit
5) If you need some information for your calculation and you can not find it, you can make
assumptions. But you should state any assumptions you make in the report.
6) The report is due on Dec. 1st 2022, should be uploaded to CANVAS!
7) Prepare a presentation based on your report, and record it using webex or other media,
upload the file to CANVAS before Dec. 1st 2022. Everyone in the group should present part
of the talk.
8) On the cover page of the report, please write clearly which topic you choose and list all
group members who contribute to the project. (These who do nothing should not be in the
list)
Project topic 1: Highly Selective Ethane Production from Acetic Acid Hydrodeoxygenation
over Transition Metal Oxide Catalysts (Gas phase reaction in a PBR)
The reaction mechanism is shown in Figure 2 below.
The reaction conditions:
HAc HDO experiments were performed in a fixed-bed reactor with inner diameter of 9.4
mm at 300 oC and 4 MPa. 0.4 g catalyst was firstly diluted by 24 g SiC; and the mixed sample was
loaded in the reactor to improve the reaction-heat transfer. 100 sccm of H2 was used as the ca
ier
gas, a liquid feed of HAc (8 wt. %) was premixed with heptane and was introduced to the reaction
system by a liquid pump (Series I Metering HPLC Pump from Scientific Systems, Inc) at the rate
of 6 mL/hour. The liquid was mixed with hydrogen gas flow before a preheater. The preheater was
held at 200oC. After the passing the preheater, the liquid was vaporized and well mixed with
hydrogen gas, and then went through the fixed bed reactor. The catalysts were stabilized for 3
hours after the feed was introduced.
Assume porosity is the mass ratio of SiC/catalyst. Assume all the steps shown in the figure are
elementary steps. Assume all the k value is 1 (unit based on the actual reaction) for each step.
1) Derive the rate alge
a expression based on the mechanism given in the figure below
(Assume different step to be rate-limiting step).
2) Plot the C2H6 concentration as a function of catalyst weight
3) Plot conversion and overall selectivity of C2H6/other products as a function of catalyst
weight
4) Determine the best operation condition for the system.
5) Plot pressure drop as a function of catalyst weight
Project topic 2: Hydrogen Production from Alcohols Steam Reforming (Gas phase reaction
in a PBR)
The elementary reaction steps are shown below:
2 5 3 2C H OH CH CHO H→ + (1)
3 4CH CHO CH CO→ + (2)
3 3 3 22CH CHO CH COCH CO H→ XXXXXXXXXX)
2 5 4 2C H OH CH H CO→ XXXXXXXXXX)
2 4C H polymers coke→ → (5)
3CH CHO coke→ (6)
3 3CH COCH oligomers coke→ → (7)
4 2CH coke H→ + (8)
2 2 2CO H O CO H+ → + (9)
4 2 2CH H O CO H+ → + (10)
The ethanol steam reforming reactions were performed in a continuous fixed-bed reactor as
shown in Figure 3. The reactor is consisted of a 40 cm long 316 stainless steel tube with 1.27 cm
o.d. and 9.4 mm inner diameter. Catalyst was dispersed on quartz wool which was supported by
SiC. A K-type thermocouple was placed at upstream side of the catalyst bed in a stainless steel
thermowell XXXXXXXXXXcm o.d.). N2 was used as a ca
ier gas and metered by a mass flow controller
from Brooks (model: SLA5850) while premixed ethanol and water were introduced to the system
y an HPLC liquid pump (Series I from Scientific Systems, Inc). All three components were mixed
in a preheater which was controlled at 200 oC before going through the tubular reactor. Vapor
products were cooled by a condenser and drained every hour for GC analysis while gas products
went to an online GC directly with valve injections. Generally, 0.4 g catalyst was tested with a
liquid feed of water premixed with ethanol (wate
ethanol molar ratio = 3:1) at 300 oC.
Assume porosity is the mass ratio of SiC/catalyst. Assume all the steps shown in the figure are
elementary steps. Assume all the k value is 1 (unit based on the actual reaction) for each step.
1) Derive the rate alge
a expression based on the mechanism given in the figure below
(Assume different step to be rate-limiting step).
2) Plot H2 concentration as a function of catalyst weight
3) Plot conversion and overall selectivity of H2/other products as a function of catalyst
weight
4) Determine the best operation condition for the system.
5) Plot pressure drop as a function of catalyst weight
1, filter; 2, mass flow controller; 3, check valve; 4, liquid pump; 5, metering; 6, pre-heater; 7, furnace; 8,
eactor; 9, condenser; 10, separator; 11, three-way valve; 12, back pressure regulator; 13, GC; 14, relief
valve; 15, liquid feed; 16, N2 cylinder; 17, H2 cylinder; 18, vent; PG, pressure gauge; T/C, thermocouple;
PT, pressure transducer; TIC, temperature indicating controller; FIC, flow indicating controller.
Project Topic 3: Selective hydrogenation of C2H2 to C2H4 (Gas phase reaction in a PBR
eactor)
The energy ba
ier for each step was calculated and shown in Figure 1.
The reaction conditions:
The selective hydrogenation of acetylene reactions were performed in a continuous fixed-bed reactor.
Catalyst was stabilized on quartz wool which was supported by SiC XXXXXXXXXXmesh average grain size,
Alfar Aesar). ~50 mg of catalyst was mixed with 500 mg SiC to minimize temperature gradients.
Before reaction, the samples were activated by 10% hydrogen/Argon with a flow rate of 30 mL
min−1 at 220 °C for 1 h and then cooled to reaction temperature (40 °C). The initial pressure of
system is 2 atm. A mixture of acetylene (2%), hydrogen (4%) and ethylene (20%) in a balance of
argon with flow rate of 10 mL min−1 was passed through the reactor and the products were analyzed
with an online gas chromatograph (Agilent, model 6890 with FID) using a HP-PLOT/Q column.
The reactor ID is 9.4mm and the catalyst density can be assumed to be the same as SiC density. The
porosity of the catalyst bed is assumed to be 0.9 (ratio of SiC/catalyst)
Assume all the steps shown in the figure are elementary steps. Assume all the k value is 1 (unit based
on the actual reaction) for each step.
1) Derive the rate alge
a expression based on the mechanism given in the figure below.
2) Plot the C2H4 concentration as a function of catalyst weight
3) Plot conversion and overall selectivity of C2H4/other products as a function of catalyst weight
4) Determine the best operation condition for the system.
5) Plot pressure drop as a function of catalyst weight
Figure 1: Reaction free energy diagram of selective hydrogenation of C2H2 to C2H4 by Pd1-N8.
Project Topic 4: N8 synthesis from N3 precursor (Gas phase reaction in a PFR reactor)
Polymeric nitrogen (PN) is a general family of materials containing all-nitrogen molecules or
clusters. Although it is rare and challenging to synthesize PN members, they are attracting
increasing scientific attention due to their high energy storage capacity and possible use as a
green catalyst. A few theoretical calculations predicted the possible PN phases from N2 gas, but
they all require extremely high pressure and temperature to synthesize. In this work, a practical
way to synthesize N8 polymeric nitrogen from N3
- precursor is elucidated using density
functional theory calculations. The detailed mechanism, 4N3
- → 4N3
* → 2N6 → N12 → N10 + N2
→ N8 (ZEZ) + 2N2, is determined.
1) Derive the rate alge
a expression based on the mechanism given in the figure below.
2) Plot the N8 concentration as a function of reactor volume
3) Plot conversion and overall selectivity of N8/other products as a function of reactor volume
4) Determine the best operation condition for the system.
5) Plot pressure drop as a function of reactor volume
Essentials of Chemical Reaction Engineering
Essentials
of Chemical
Reaction
Engineering
Second Edition
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Essentials
of Chemical
Reaction
Engineering
Second Edition
H. SCOTT FOGLER
Ame and Catherine Vennema Professor of Chemical Engineering
and the Arthur F. Thurnau Professo
The University of Michigan, Ann A
o
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Dedicated to
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vii
Contents
PREFACE xv
ABOUT THE AUTHOR xxxi
CHAPTER 1 MOLE BALANCES 1
1.1 The Rate of Reaction, –rA 4
1.2 The General Mole Balance Equation 8
1.3 Batch Reactors (BRs) 10
1.4 Continuous-Flow Reactors 12
1.4.1 Continuous-Sti
ed Tank Reactor (CSTR) 12
1.4.2 Tubular Reactor 14
1.4.3 Packed-Bed Reactor (PBR) 18
1.5 Industrial Reactors 23
CHAPTER 2 CONVERSION AND REACTOR SIZING 33
2.1 Definition of Conversion 34
2.2 Batch Reactor Design Equations 34
2.3 Design Equations for Flow Reactors 37
2.3.1 CSTR (Also Known as a Backmix Reactor or a Vat) 38
2.3.2 Tubular Flow Reactor (PFR) 38
2.3.3 Packed-Bed Reactor (PBR) 39
2.4 Sizing Continuous-Flow Reactors 40
2.5 Reactors in Series 49
2.5.1 CSTRs in Series 50
2.5.2 PFRs in Series 54
2.5.3 Combinations of CSTRs and PFRs in Series 55
2.5.4 Comparing the CSTR and PFR Reactor Volumes and Reactor
Sequencing 59
viii Contents
2.6 Some Further Definitions 60
2.6.1 Space Time 60
2.6.2 Space Velocity 62
CHAPTER 3 RATE LAWS 71
3.1 Basic Definitions 72
3.1.1 Relative Rates of Reaction 73
3.2 The Rate Law 74
3.2.1 Power Law Models and Elementary Rate Laws 75
3.2.2 Nonelementary Rate Laws 78
3.2.3 Reversible Reactions 82
3.3 The Reaction Rate Constant 85
3.3.1 The Rate Constant k and Its Temperature Dependence 85
3.3.2 Interpretation of the Activation Energy 86
3.3.3 The A
henius Plot 92
3.4 Molecular Simulations 95
3.4.1 Historical Perspective 95
3.4.2 Stochastic Modeling of Reactions 96
3.5 Present Status of Our Approach to Reactor Sizing and Design 99
CHAPTER 4 STOICHIOMETRY 111
4.1 Batch Systems 113
4.1.1 Batch Concentrations for the Generic Reaction, Equation XXXXXXXXXX
4.2 Flow Systems 119
4.2.1 Equations for Concentrations in Flow Systems 120
4.2.2 Liquid-Phase Concentrations 120
4.2.3 Gas-Phase Concentrations 121
4.3 Reversible Reactions and Equili
ium Conversion 132
CHAPTER 5 ISOTHERMAL REACTOR DESIGN: CONVERSION 147
5.1 Design Structure for Isothermal Reactors 148
5.2 Batch Reactors (BRs) 152
5.2.1 Batch Reaction Times 153
5.3 Continuous-Sti
ed Tank Reactors (CSTRs) 160
5