Reactor Design

Part I
Revised Fa 2015 MVJ, WCM
Previous Contributors: WCP, ADK

Department of Chemical and Materials Engineering

University of Alberta, Edmonton, Canada

ChE 464 (Design I)

Reactor Design Goals

Operability
Control of the operating conditions (T, P, phases)
heat management during conversion.
Provides residence time for the reaction
contact between reacting molecules
Reliability
Maintainability
Safety
Economic viability
Environmental responsibility

The residence time is determined by the kinetics. This topic was discussed in detail in the courses on reactors.

Reaction Kinetics & Design

Molecular reaction rate and required steps determines several
aspects of the reactor design.
Operating
temperature and
pressure range
Phases present
Catalyst
requirements
Residence time
requirements
Energy requirements

One number we care about is the heat

of reaction in this course

Size and type of reactor designed is determined by the reaction.

Figure reference: Ullmans Encyclopaedia of Industrial Chemistry, Ammonia. 2 p.148

Reaction Management & Design

Reaction management is key to reactor design
Heat management
Exothermic reactions may require heat removal (cold stream addition)
Endothermic reactions may require heat (hot stream addition)

Reaction rate management

Reaction is at the molecular level! Molecules must be in the same phase.
Catalyst may be required to effect a reaction step.
Catalyst type and placement in the reactor for selectivity and activity.

Fluid flow and phase management

Mass transfer can be the rate limiting step.

Mixing can maximize diffusion within and between phases.
Maximizing molecular interactions depends on fluid flow management
Fluid dynamics management must consider the bulk and micro flow.

Production Rate Required

Along with residence time, the size of the reactor is determined by
how much product is going to be produced.
Operating ranges are easy to find

The cost of production of a chemical, petroleum or pharmaceutical

commodity product is influenced by the amount produced for a
given capital investment.
A design that maximizes product formation has a greater economic
potential.
The choice between a continuous, semi-batch or a batch reactor is
based on the reaction and tied to the production and reaction rates
Most industrial kinetics are approximated by a simplified
expression over the expected operating range but based on
research to find the optimal/expected operating range!

Overview and
Fundamentals

Nomenclature: Conversion
Terms that are important in defining conversion:
Conversion: Expressed in terms of a reactant (A) or feed
fraction. The fraction of the feed that reacts.
Single pass conversion The percent conversion on a
single pass through the reactor.
aA + bB
rR + sS
XA= Conversion = moles A reacted (product out)
moles of A fed (plant feed)
Single pass conversion = moles of A reacted (reactor outlet)
moles of A to reactor (reactor inlet)
where A is the limiting reactant.

Conversion
Typical flow reactor configuration
Competing Reactions AR, and AS

Feed
A

Reactor

Separator

Recycle Single pass conversion

A

Overall conversion

Product
R&S

Selectivity
Selectivity The fraction of a product (R) or group of
products formed relative to the limiting reagent (A) reacted.
SR = moles A required for R produced with no side reactions
moles A actually reacted
SR = (actual moles R produced) (nsa moles R produced)
(actual moles A reacted) (nsa moles A reacted)
nsa = conditions with no side reactions
Product Selectivity* The fraction of a specific product (R)
or group of products formed relative to the total amount of
products formed (R+S). The sum of product selectivity = 1.
S*R = moles of R produced
moles of all products
*Caution: several alternate definitions of selectivity are in wide use.

Yield
Yield The fraction of a specific product (R) produced from
reactant (A) fed.
YR = moles A required for R produced with no side reactions
moles A actually fed
YR = (actual moles R produced) (nsa moles R formed)
(actual moles A fed)
(nsa moles A reacted)
Y R = SR * X A
%Yield The volume % of a liquid product produced from
liquid feed. Often used in petroleum refining and upgrading.
%Yield = volume of liquid product @60 OF x 100
volume of liquid feed @60 OF

Reactor Design
and Selection

Reactor Selection
What does a reactor look like?
Reactor design optimizes desired product yield.

Different looks to work around patents

Reactor Functions
a) Addition of reagents and removal of products: contains
and retains the catalyst (when applicable)
mixing management (fluid mechanics)
b) Controls the operating conditions (T, P, phases)
heat management (heat transfer)
c) Contact between reacting molecules
mass transfer management (bulk to molecular)
d) Residence time for the material to be converted.
reaction kinetic management
add mix well heat/cool give it time (or speed it up!)

The residence time is determined by the kinetics. This topic was discussed in detail in the courses on reactors.

Reactor Selection
A reactor is complex; to select a reactor type, consider:
Reaction Pathway activation energy, exothermic or
endothermic, mass transfer, kinetics and equilibrium
To determine:
Batch or continuous conversion?
Heat management strategy?
Catalytic, non-catalytic or biological conversion?
Assess and design for the impact of:
Catalyst deactivation rate, lifetime and regeneration.
Phase of the process stream and catalyst.
Physical/mechanical catalyst properties and separation.
Movement of the molecules from bulk phase to reaction site

Continuous or Batch Reactor?

Continuous reaction. Continuous flow of all phases; the
design is time invariant and a steady state approximation can
be used for mass and energy balances. Concentration
of product varies in the reactor, but consistent in space.
Batch reaction. Flow is based on a time dependent process
sequence. The reaction step is contained in a vessel that is
emptied after the reaction process is complete. Concentration
of product is uniform, but varies with time.
Semi-batch reaction. Similar to batch. Continuous flow with
respect to one phase, other phases are contained, or reagents
are added over the course of the reaction.
Continuous or Batch or Semi-batch choices or
requirements will affect the reactor design.

Reactor Heat Management

What is the heat release or required during conversion?
Heat management strategy, e.g. isothermal, adiabatic?
Reactor design options will be different if heating or cooling
are required.

Reactor Catalyst Management

What is the rate of reaction and the activation energy?
Is catalyst required to:
increase the reaction rate?
lower activation energy?
reduce the operating severity?
manage side reactions?
manage a rate limiting step?
Reactor design will be different depending on the type of
catalyst, the phase of the catalyst, the lifecycle and the
recovery of the catalyst.

So you want to make

methanol
Department of Chemical and Materials Engineering
University of Alberta, Edmonton, Canada

What do we need to know?

Chemistry - Methanol
Ullmanns Encyclopedia of Industrial Chemistry
Online at the U of A Library
Main Reactions for Methanol
CO + 2H2 CH3OH
CO2+3H2 CH3OH + H2O
CO and H2 from synthesis gas

Chemistry Synthesis Gas

What is synthesis gas?
Go to Wikipedia understand the terminology
Syngas, or synthesis gas, is a fuel gas mixture consisting
primarily of hydrogen, carbon monoxide, and very often some
carbon dioxide. The name comes from its use as intermediates in
creating synthetic natural gas (SNG)[1] and for producing ammonia
or methanol. Syngas is usually a product of gasification and the
main application is electricity generation. Syngas can be produced
from many sources, including natural gas, coal, biomass, or
virtually any hydrocarbon feedstock, by reaction with steam or
oxygen.

Chemistry Synthesis Gas

Now go to Ullmanns
Search Gasification Understand the reaction
Gas Production, 2. Processes
Assume we will use natural gas as a feedstock:
CH4+H2O CO + 3H2
CO+ H2O CO2 + H2

CO H2

H2

H2

a net C
K3

"

w w
fCO fH2 O
CO H2 O
fCO2 fH2
wCO2 wH2

"!

"

pCO pH2 O
Kw 3&Kp3
pCO2 pH2

Thermodynamics - Methanol

where fi is the fugacity, wi the fugacity coefficient, and pi the partial pressure of the i-th
component.

4.1.2.

Althou
the beg

Main Reactions for Methanol

CO + 2H2 CH3OH -90.77 kJ/mol
CO2+3H2 CH3OH + H2O -49.16
kJ/mol
Both reactions are exothermic
Both reactions decrease the volume (number
of moles)
Methanol formation favored by
increasing pressure (Le Chteliers
principle) and decreasing temperature

Figure 2. Dependence of reaction equilibrium on pressure and temperatu

Dependence of reaction equilibrium on P & T

Catalysts Methanol synthesis

Continuous process for
methanol
Original method: ZnO-Cr2O3
High Pressure Process
25 - 35 MPa & 300 450 C
Not economical last plant closed
in the mid 1980s
Clariant Megamax 800 Catalyst

Current method: Cu-ZnO-Al2O3

Low-Pressure Process
5 10 MPa & 200 - 300 C

Catalyst - Deactivation
Normal catalyst will last 2 5 years
High T will negatively influence
catalyst performance
Sulphur and halides (mainly
chlorine) decrease activity

Reaction Byproducts
Current Low-pressure process has high selectivity
Typically > 99%
Byproducts include higher alcohols, ethers, esters, hydrocarbons
and ketones
Can be used as a high octane fuel additive
Byproducts are kinetically controlled (no thermodynamically)
Care about residence time and temperature

Industrial Methanol Process

Any industrial process will have three main steps
1.Production of synthesis gas
2.Synthesis of methanol
3.Processing of crude methanol

Next Step The Process

Understand the reaction process
Best place to find process information is the Kirk-Othmer
Encyclopedia of Chemical Technology
Search in this Book > Methanol

Read Critically
Always read critically!
From Kirk-Othmer Encyclopedia of Chemical Technology:
Methanol plant reformers typically operate with exit
temperatures within the 8408808 C range: the upper limit
being determined by the tube metallurgy.
Steel melts at about 1370 C
Typographical errors occur in references

Methanol Synthesis Process

METHANOL

Steam
Fuel to reformer
Steam drum

Crude
catchpot

Carbon dioxide (optional)

Cooling

Process steam

Boiler
feedwater

Flue gas
stack

Synthesis gas
compressor
and circulator

Let-down
vessel

Heat
recovery
Combustion
air

Methanol
converter

Reformer
Desulfurization
vessels

Methanol
refining
column
Steam

Cooling

Heat recovery
Lights
removal
column

Feedstock natural gas

Methanol

Fig. 6. Methanol synthesis process flow sheet.

Kirk-Othmer - Methanol

resulting gas streams are combined to give the stoichiometry required by methanol synthesis. Raw gas cleanup is also required to remove contaminants that are

Methanol Synthesis Process

Production of Synthesis Gas

METHANOL

Steam
Fuel to reformer
Steam drum

Crude
catchpot

Carbon dioxide (optional)

Cooling

Process steam

Boiler
feedwater

Flue gas
stack

Synthesis gas
compressor
and circulator

Let-down
vessel

Heat
recovery
Combustion
air

Methanol
converter

Reformer
Desulfurization
vessels

Methanol
refining
column
Steam

Cooling

Heat recovery
Lights
removal
column

Feedstock natural gas

Methanol

Kirk-Othmer - Methanol
Fig. 6. Methanol synthesis process flow sheet.
resulting gas streams are combined to give the stoichiometry required by metha-

Combined Reforming
6

METHANOL
Fuel
Natural
gas

Sulfur
removal

Primary
reformer

Oxygen

Secondary
reformer

Syngas to waste
heat recovery
and compression

Bypass

Fig. 2. Combined reforming.

Kirk-Othmer - Methanol

steam for reforming, and reboil duty for distillation. The overall strategy fo
energy integration is to recover waste heat at the highest levels into the motiv
steam system to satisfy power requirements, and to minimize additional fu

Methanol Synthesis Process

METHANOL
9
Methanol
Synthesis
Steam
Fuel to reformer
Steam drum

Crude
catchpot

Carbon dioxide (optional)

Cooling

Process steam

Boiler
feedwater

Flue gas
stack

Synthesis gas
compressor
and circulator

Let-down
vessel

Heat
recovery
Combustion
air

Methanol
converter

Reformer
Desulfurization
vessels

Methanol
refining
column
Steam

Cooling

Heat recovery
Lights
removal
column

Feedstock natural gas

Methanol

Kirk-Othmer - Methanol Fig. 6. Methanol synthesis process flow sheet.

resulting gas streams are combined to give the stoichiometry required by metha-

Methanol Converter Types

10

METHANOL

Steam
drum

(a)

(b)

(c)

(d)

Fig. 7. Methanol converter types: (a) quench, (b) multiple adiabatic, (c) tube cooled, and
(d) steam
raising.
Methanol
converter
types: (a) Quench, (b) Multiple Adiabatic, (c) tube cooled, (d) steam raising

use are shown in Figure 7. There are a variety of proprietary reactor designs
commercially available from licensors, all of which are either one of these four

Methanol Synthesis Process

METHANOL

Steam
Fuel to reformer
Steam drum

Crude
catchpot

Carbon dioxide (optional)

Cooling

Process steam

Boiler
feedwater

Flue gas
stack

Synthesis gas
compressor
and circulator

Let-down
vessel

Heat
recovery
Combustion
air

Reformer
Desulfurization
vessels

Methanol
refining
column
Steam
Feedstock natural gas

Methanol
converter
Cooling

Heat recovery
Lights
removal
column

Processing of Crude Methanol

Methanol

Fig. 6. Methanol synthesis process flow sheet.

Kirk-Othmer
Methanolare combined to give the stoichiometry required by metharesulting
gas -streams
nol synthesis. Raw gas cleanup is also required to remove contaminants that are
either present in the raw materials or are formed from them.
The high cost of coal handling and preparation and treatment of effluents,

Reaction Rate Data

Search Web of Science for Rate Data
Catalysis Today 197 (2012) 109118

Contents lists available at SciVerse ScienceDirect

Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Effect of the structural and morphological properties of Cu/ZnO catalysts

prepared by citrate method on their activity toward methanol synthesis from
CO2 and H2 under mild reaction conditions
Alejandro Karelovic , Alice Bargibant, Camila Fernndez, Patricio Ruiz
Institute of Condensed Matter and Nanosciences Molecules, Solids and Reactivity (IMCN/MOST), Universit catholique de Louvain, Croix du Sud 2/17, 1348 Louvain-La-Neuve,
Belgium

i n f o
a b s t r a c t
4.2. Kinetic
aspects
The methanol production is enhanced when temperature increases up to 200
225 C (Fig. 3). Above these temperatures, the attainment of thermodynamic
equilibrium for methanol concentration does not permit to increase the
production. That illustrates the fact that these catalysts are well active, and that
an increase in pressure, which increases the methanol concentration at
equilibrium, would certainly enhance the methanol production.

a r t i c l e

Article history:
Received 20 April 2012
Received in revised form 27 July 2012
Accepted 30 July 2012
Available online 29August 2012
Keywords:
CO2 hydrogenation
Methanol synthesis
Low temperature
Cu/ZnO catalysts
Citrate method
Structure-sensitivity
Phases cooperation

Methanol synthesis from CO2 + H2 was studied at mild reaction conditions (140250 C and 7 bar) over
Cu/ZnO catalysts prepared by citrate method. The copper content and calcination temperatures were
varied so as to obtain a wide range in copper particle size (212 nm). Methanol formation rates vary
between 0.84 and 2.98 103 s1 at 180 C. Methanol selectivity can attain 100% at temperatures lower
than 160 C. At higher temperatures, CO formation by reverse water gas shift reaction is highly favored.
The apparent activation energy for methanol formation is in the range 810 kcal/mol, whereas that of
CO formation is much higher (2932 kcal/mol). The methanol formation rates depend linearly on the
amount of exposed copper atoms, whereas for CO formation there is no clear correlation, showing that
special surface sites are responsible for CO formation. The size of copper particles greatly influences the
selectivity to methanol at constant CO2 conversion. Larger particles (1012 nm) are much more selective
than smaller ones (23 nm), this effect is enhanced when CO2 conversion is low. Catalysts prepared by
citrate method are much more active than a reference catalyst prepared by coprecipitation. The activity
of CuO + ZnO catalysts prepared by mechanically mixing of CuO and ZnO present activity comparable
with that of Cu/ZnO catalysts prepared by citrate method, whereas pure copper and ZnO are not active at
these conditions. That strongly suggests that activity is defined by a good contact between Cu0 and ZnO,
whereas the selectivity depends on the morphology of copper nanoparticles.
2012 Elsevier B.V. All rights reserved.

Assume equilibrium conversion Can design the rest of the process without the reactor!!!!
1. Introduction
A significant effort is currently done to diminish CO2 production
and release to the atmosphere. An important challenge resides in
its transformation into value-added products [1]. Due to energetic
and economic reasons, the CO2 hydrogenation to methanol at low
temperature is called to be an important process in the next years,
provided that the hydrogen required is furnished by renewable
sources. Methanol is indeed a common chemical, used mainly as a
feedstock in the industries producing chemicals such as formaldehyde, methyl tert-butyl ether and acetic acid. Moreover, methanol

using CO + CO2 + H2 mixtures in the feed are mainly driven by

reduction of investment costs which are important in the production cost of methanol. The reduction of investment costs obliges to
minimize energy transfer in the different steps of the process (heat
exchangers, heated and cooled reactors, etc.) and also to reduce
the total pressure of the process (gas compressors and pumps).
The reaction is strongly exothermic and requires significantly cooling. Progresses have been made synthesizing more active catalysts
(particularly Cu/ZnO catalysts). The lowering of the reaction temperature improves the selectivity [4].
The desired reaction in the CO -based methanol synthesis is (1)