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c/desproj18/reactors 01/02/18

Synthesis and Design CHEN30012, CHEN30022, CHEN30032

CEAS

REACTORS

Vapour Recovery Purge

System

Phase
Feeds Reactor System Separation

Liquid Products
Separation By-products

D.L. Cresswell
01/02/2018 2018
c/desproj18/reactors 01/02/18

DEVELOPMENT OF A "BASE-CASE" DESIGN

The "base-case" design is developed in a series of stages of increasing detail, starting
from the chemist's laboratory data. The process should be costed at each level to keep
the overall profitability under continuous review.

1. INPUT - OUTPUT STRUCTURE

This is the simplest level on which to view the process:

Products
Feeds Process
By-products

Even at this simple level, gross economic calculations are worth doing to determine
if the process has any chance of making money.

2. RECYCLE STRUCTURE

The first level of process detail adds the recycle structure.

Purge

Products
Feeds Reactor System Separation System
By-products

At this level an approximate recycle mass balance can be made. A feel for likely
costs of recycling unconverted reactants should emerge. It may be possible to judge
the process uneconomic, even at this level (eg., large compression costs in the case
of a gaseous recycle stream).

3. REACTOR SYSTEM

The second level examines how the overall process is affected by reactor size and type,
heat effects and equilibrium limitations.

4. SEPARATION SYSTEM

The details of the separation system are added, firstly in terms of "black-boxes".Later,
the details of the liquid separation system and vapour recovery system can be filled out.

Vapour Recovery Purge

System

Phase
Feeds Reactor System Separation

Liquid Products
Separation By-products

INITIAL "BLACK BOX"

02/18 c/desproj18/reactors 01/02/18

SE" DESIGN A CONCRETE EXAMPLE OF THE GENERAL FLOWSHEET

starting STRUCTURE - The Hydrodealkylation of Toluene to Benzene
to keep (presented on Blackboard as "A Case Study")

REACTANT A
(gas) Purge (A+D)
Heat Compressor

Heat

Reactor Cool Flash

rmine

Heat Heat Desired Product (C)

A + D (to Fuel Line)
Recycle of B
REACTANT B
(liquid) Recycle Product Stabiliser
e Column Column Column

Products

By-products Waste
Product (E)

CHEMISTRY
ely Example: A = H2
judge A+B = C+D B = TOLUENE
case 2C = E + A C = BENZENE
D = CH4
E = BIPHENYL
c/mydocuments/desproj18/reactors 01/02/18

REACTORS - HEAT EFFECTS

A Quantitative Indicator - The Maximum Adiabatic Temperature
Change - (delT)max
The question "Are Heat Effects significant in your Reactor ?" requires a Quantitative Indicator.
This is provided by calculating the "Maximum Adiabatic Temperature Change" - (delT)max. This
corresponds to the maximum possible temperature change that can occur if all of the limiting
reactant (A in this case) is completely converted adiabatically. For the reaction A + B <=> C+ D,
this is given by
(delT)max = (-delH).yAo/Cpm
where delH is the Heat of Reaction (eg., kJ/g.mol A), yAo is the mole fraction of A in the feed
and Cpm is the Molar Heat Capacity of the total feed (kJ/g.mol.K).
This calculation assumes 100% conversion of A and ignores possible Equilibrium Limitations.
Note that (delT)max is negative for an Endothermic Reaction (delH > 0) and positive for an
Exothermic Reaction (delH < 0).
The Examples below taken from a selection of well known Industrial Processes show that
(delT)max can run into several hundreds of degrees !
(delH) < 0 (Exothermic Reaction) (delH) > 0 (Endothermic Reaction)
(delT)max (delT)max
(deg. k) (deg. k)
Vinyl Chloride Polymerisation 700 Ethane Cracking
C2H6 = C2H4 + H2 -980
Oxidation Reactions:
eg., o-xylene to phthalic anhydride Steam Reforming
C8H10 + 3O2 = C8H4O3+3H2O 380 CH4 + 2.H2O = CO2 + 4H2 -680
but, in parallel
C8H10 + 10.5O2 = 8CO2+5H2O 1350 ! Dehydrogenation Reactions:
[Lesson: Do not forget the potential for side- Propane to Propene -780
reactions !]
Ammonia Synthesis: Catalytic Reforming:
N2 + 3.H2 = 2.NH3 650 Naphthenes to Aromatics -160
(Thermodynamics comes to our rescue by Paraffins to Naphthenes -30
limiting N2 conversion to be << 100% ) Hydrocracking of Paraffins 75
Shift Conversion Hydrocracking of Naphthenes 112
CO + H2O = CO2 + H2 90
(see "Chemical Reactor Design for Process Plants:Vol.1 Principles and Techniques", Wiley InterScience Publications
(1977) USA.

The overall reactions of Catalytic Reforming are thermally balanced. Heat Effects are not
significant. Catalytic Reforming is carried out in an Adiabatic Reactor, as is the Shift Conversion,
which is moderately exothermic. All the other reactions above have significant Heat Effects and
require more complex reactor configurations - eg., molten Salt-Cooled Multi-Tubular Catalytic
Reactors for Phthalic Anhydride Synthesis, a Series of Adiabatic Fixed Catalyst Beds with
Indirect Interstage Cooling or "Cold Shot" Quenching for Ammonia Synthesis.
For highly Endothermic Reactions such as Ethane Cracking , Steam Reforming and Alkane
Dehydrogenations, Tubular Reactors within Gas-Fired Furnaces are employed or, in the latter
case, a Series of Radial Flow Adiabatic Reactors with Interstage Reheaters.
The potential for "temperature run-away" in Exothermic Reactions necessitates deeper
considerations of both the cooling system and the temperature control system.
c/desproj18/desguide/reactors 01/02/18
SOME REACTOR OPTIONS FOR GAS PHASE SOLID-CATALYSED
REACTIONS
(delT)adiabatic
(deg.K)

A few Industrial Examples NH3 Synthesis N2 + 3.H2 = 2.NH3 +650

Shift Conversion CO + H2O = CO2 + H2 +90
Methanol Dehydration 2.CH3OH = (CH3)2.O + H2O +380
Methane Steam Reforming CH4 + H2O = CO + 3.H2 -680
Propane Dehydrogenation C3H8 = C3H6 + H2 -780

THE INDUSTRIAL "WORKHORSE" - A MULTI-BED QUENCH CONVERTER

(Methanol Synthesis, LT Shift, NH3 Synthesis)
PROS CONS

1. Simple Vessel Structure 1. Numerous control loops

30% Flo w 2. Ease of Catalyst Loading/2. Low grade heat recovery

Unloading
3. Gas to gas mixing
3. Large single reactor
capacity ( > 3000 tons per 4. Pressure drop can be
day in the case of CH3OH) constraining.

4. Simplified heat recovery

240 C
5. Low rate of recycle gas

70% Flo w

270 C

100 C 120 C 120 C He at Re co v e ry

10

8 Equilibrium curve
% CH3OH Locus of Maximum
6 Reaction Rate

2 Re acto r pro file

0
100 200 300 400
T e mp. (C)
c/desproj18/reactors/radialflowreac/reactors 01/02/18
RADIAL FLOW REACTORS - CAN ACHIEVE HIGH
VOLUMETRIC FLOW RATES WITH MINIMUM PRESSURE DROP

(use of small catalyst particles (1 - 2 mm.) mitigates the deleterious

effects of pore diffusion)

There are 4 possible flow configurations for a radial flow fixed bed reactor
(RFFBR). These are illustrated schematically below. The capital prefixes CP
and CF refer to centripetal or centrifugal radial flow, respectively. PROS
1. Low pressure drop.
2. Ease of Catalyst Loading/
Unloading
3. Use of small partices (1-2 mm.)
possible. Mitigates the deleterious
effects of pore diffusion.
CONS
1. Complex vessel structure
2. Unsuitable for metal oxide
catalysts that shrink on reduction.
(a) CP Z Flow (b) CF Z Flow
3. Complex design requires 3xD
Computational Fluid Dynamics

4. Relatively expensive.

(c) CP M Flow (d) CF M Flow

Figure The four possible flow configurations for a radial flow fixed bed reactor.

In the centripetal (CP) reactor the flow is inwards from the outer distributor,
through the catalyst bed to the central collecting pipe, whereas in the centrifugal
(CF) type, the flow is in the opposite sense.The reactors may also be classified
into either Z type or the M (pi) type,depending upon the axial directions of the
flow in the distributing channel and the collecting channel. as indicated above.

Flow uniformity
In a radial flow reactor it is important to maintain a uniform radial flow rate
through the vertical catalyst bed, irrespective of axial position. Kareeri and
co-workers(1) showed from 3xD CFD calculations that the CP M Flow type
is preferred in this sense.
Photographs of full scale reactors and their internals may be found on the Johnsons
Screens web-site (2).

(1) A.A.Kareeri, H.H.Zughbi and H.H.Al-Ali, "Simulation of Flow in a Radial Flow

Fixed Bed Reactor (RFFBR)", www.sintef.no/project/CFD2008/.../31_Kareeri_
Zughbi_Al-Ali.pdf
(2) Internals for Radial Flow Reactors, Johnson Screens , www.johnsonscreens.com
c/desproj18/reactors/radialflowreac/reactors 01/02/18

A CP Z-FLOW RADIAL FLOW REACTOR

Outer screen is an arrangement of scallops with

vertical slots allowing catalyst to flow through
reactor under gravity(if required). V-shape design
retains particles as small as 0.25 mm.diameter
without leading to "plugging".
c/desproj18/steamraising reactor/reactors 01/02/18

A STEAM-RAISING REACTOR

A MU LT I-B ED REACT OR WIT H A STEAM-RAISING REACTOR PROS

IN T ERCOOLIN G B ET WEEN B ED S
Ste am (250 C) 1. Simplified Heat Recovery
Note the Heat Integration ! Fe e d (245 C)
Ste am 2. 27.5 bar steam raising
D rum capability

3. Low rate of recycle gas

240 C
4. Close temperature control
reduces by-products and extends
catalyst life

CONS
1. Low catalyst volume - 1500 - 2000
tpd CH3OH compared with 3000 tpd
for the Multi-Bed reactor

2. Complex construction of a pressure

vessel (tube sheet or pitch arrangement
270 C with large pressure differential)
He at Re co v e ry 265 C
3. Catalyst loading and unloading
140 C requires specialised expertise.
Fe e d (100C) Fe e d (100C)
Pro duct (120 C) 4. Difficulties in maintenance and
inspection.
Pro duct (120 C)
5. Tube vibration necessitates the
T e mp. (C) Locus of T e mp. (C) use of catalyst pellets of enhanced strength
Maxm. Reaction Rate Equilibrium
290 Line 290
280 280
270 270
260 260
250 250
240 240

% Conversion % Conversion
c/mydocuments/desproj18/lurgisteamraiser/reactors 01/02/18
c/mydocuments/desproj18/catalystactivation/reactors 01/02/18

Methanol Synthesis - the Catalyst

Steps in Manufacture:
* Co-precipitate CuNO3 and ZnNO3 by reacting CuCO3 and ZnCO3 with NaNO3.
* Add alumina as a powder to the mixture
* Dry
* Calcine in air
* Sieve to suitable size range
* Pellet to a given density, dictated by required crush strength

Steps in In-Situ Activation

* Load pellets into reactor. Loading procedure is reactor dependent.

Loading is particularly critical for tubular reactors !

* Load each tube individually from a catalyst "sock"

* Measure the pressure drop for each tube (there may be several hundred !)
- it must lie within a narrow interval !

* begin activation by passing a 2% H2/N2 mixture through the reactor in order

to reduce CuO to Cu. This is an exothermic process !
* Control the reduction by measuring the bed temperature rise

* Arrange to collect the water (there is a lot of it - several tonnes!)

* Reduction complete when exotherm has passed through the bed and
H2O generation has ceased.

REACTOR DESIGN MUST ACCOMMODATE CATALYST CHARGING,

ACTIVATION, (REGENERATION, IF APPROPRIATE) AND DISCHARGE.
c/mydocuments/desproj18/porediffusion/reactors 01/02/18

MAJOR CONSIDERATIONS WITH GAS PHASE REACTIONS ARE

* Managing "Catalyst Pore Diffusion" - relevant to both Multi-Bed and Tubular

Reactors.
* Managing Radial Heat Transfer to the "Shell-side" fluid in Tubular Reactors -
particularly critical for exothermic reactions.
* Managing the Bed (or Packed Tube) Pressure Drop.

PORE DIFFUSION :

INTRINSIC RATE (far from equilibrium): Rint = k.Pco.Ph2

Pco,Ph2 in the bulk gas around a pellet (H2 in considerable excess)

R Porous
Catalyst Particle of radius R, density (Rho)p

Effective Diffusivity, De

APPARENT RATE : Rapp = (N).Rint = (N).k.Pco.Ph2 kg.mol/kg.cat.sec

N = Catalyst Effectiveness Factor ,

N= 3/M^2.(M.cothM - 1)

where M= R.[(Rho)p.k.(Rg.T).Ph2/De]^0.5
is usually referred to as the Thiele Modulus.

Targe tte d
ope rating range

Re action is too slow -

incre ase M

Re actio n rate
se v e re ly limite d
by po re diffusio n

RADIAL HEAT TRANSFER

Characterised by

* the Effective Radial Thermal Conductivity - kr,eff

* the inside wall Apparent Heat Transfer Coefficient (hw)
These are both "lumped" parameters, incorporating the combined effects of

Conduction
Conve ction
Radiation (at high te mpe rature s)

The theoretical prediction of kr,eff and hw , as well as recommended empirical

correlations, is dealt with by Dixon et al (1).

(1) Dixon A.G, Cresswell D.L., "Theoretical prediction of effective heat transfer
parameters in packed beds", A.I.Ch.E.Jl. 25 663 (1979).
 c/mydocuments/desproj18/g-l-s- reactors/reactors 01/02/18
GAS-LIQUID REACTIONS INVOLVING A POROUS SOLID CATALYST
Hydrogen Concentration Examples : Hydrogenation of Fats & Oils
Profile Hydrocracking of Heavy Oils
Catalyst Fischer-Tropsch: Syn Gas(CO+2H2) --> Middle Distillate
Ph2 Oxidations
Ph2,i Epoxidations etc.,
A "TRICKLE BED" REACTOR A "BUBBLE COLUMN" REACTOR
Trickle Bed vs. Bubble Column Reactors
Gas Spent Gas Trickle Be ds are more wide ly use d. Bubble
c,i Columns are pre fe rre d unde r the following
conditions:
c
*Operation within the trickle flow regime
Centre Liquid Feed Liquid cannot be achieved due to
Line Product - very low gas flow relative to liquid

- very large liquid residence time required

(1) - channelling due to low bed/catalyst
(2) diameter ratio

- liquid to solid mass transfer is controlling

iq and c,i by Eqns.(1) - (3) it may be shown that Spent Gas The re is more back-mixing in a bubble
column and gas to liquid mass transfe r is
(4) poore r !

tant , given by Liquid Product Gas Liquid Feed

Characteristics
* Cocurrent downward flow of liquid and vapour
*Continuous liquid and vapour phases
n.(5) may be regarded as additive serial
*External catalyst surface only partially wetted by the
liquid
* Catalyst is a fixed bed of particles 2 - 5 mm. diameter
1/Kg.a
Characteristics
* Cocurrent upward flow of liquid and vapour
* Continuous liquid phase, vapour as bubbles dispersed
in the liquid phase
*External catalyst surface fully wetted by the liquid
* Catalyst is a fixed bed of particles 2 - 5 mm. diameter

H/(Kliq.Acat)

H/{k.Acat.(N).Co}
Pulsing/Foaming

(kg.mol/m^2.sec.bar)
2/m^3 reactor volume)
.liq)}
ent (m/sec)
m^3 liq/kg.mol).m/sec} Trickle
L = Supe rficial Mass Ve lo city Flow
/m^3liq) G = Supe rficial Gas Ve lo city
Spray
(6)
nit volume of catalyst (m^2/m^3)

erical particles of diameter dp.

(kg/m^3)
nit Reactor Volume (kg.cat/m^3)
c/mydocuments/desproj18/slurryreactor/reactors 01/02/18
A CONTINUOUS COUNTERCURRENT SLURRY REACTOR SYSTEM

Purge

Recycle
Compressor
Make-up
Catalyst

Fresh Feed
Finishing
Column
Catalyst Feed
Tank

Stage 1 Stage 2

H2 Feed

Product
Catalyst Regeneration Filter

Red Arrows show passage of catalyst as a viscous slurry through the process

CHARACTERISTICS OF SLURRY REACTORS

* Liquid is "Backmixed" ( particularly detrimental if product is a reaction

intermediate) : will also slow down main reaction kinetics

* Catalyst must be separated from liquid

* Pumping of viscous slurries can be expensive and wearing on equipment

* Better temperature control than Trickle Bed or Bubble Column Reactors.

Internal Cooling Coils possible

* An alternative to a fixed-bed gas/solid reactor for highly exothermic reactions.

Liquid is a suitable heat transfer oil. The slurry is not transported and the vessel
contains an internal cooling system.
c/mydocuments/desproj18/g-l-s reactors/reactors 01/02/18

STEPS IN THE REACTION Hy dro g e n Co nce ntratio n

Pro file
Vapour Phase(H2 + N2 + Bulk Vapour Bulk Liquid Cataly st
'Organics) Organic Vapour-Liquid Ph2
H2 transport Equilibrium Ph2,i

Ch2,liq
So lid Cataly st
H2+Org anics
Liquid Phase c,i
H2+Organics
c
Solid-Liquid
Equilibrium Vapour Film Liquid Centre
Film Line

FORMU LAT IN G A RAT E EQU AT ION

Gas-Liquid Mass Transfer Rg-l = Kg.a.(Ph2-Ph2,i) = Kg.a.(Ph2 - H.Ch2,liq) (1)

Liquid-Solid Mass Transfer Rl-s = Kliq.Acat.(Ch2,liq - c,i) (2)

Rate of Chemical Reaction R= k.(N).Acat.Co.c,i kg.mol/m^3.reactor.sec (3)

Since Rg-l = Rl-s = R, eliminating Ch2,liq and c,i by Eqns.(1) - (3) it may be
shown that
R= kapp.Ph2 (4)

where kapp is an apparent 1st order overall rate constant , given by

1/kapp = 1/(Kg.a) + H/Acat.[1/Kliq + 1/{k.(N).Co}] (5)

The three terms making up the right hand side of Eqn.(5) may be regarded as additive
serial resistances making up gas - liquid mass transfer, liquid - solid mass transfer and
chemical reaction. Thus,

Vapour Film Resistance = 1/Kg.a

Liquid Film Resistance = H/(Kliq.Acat)

Solid Catalyst Resistance = H/{k.Acat.(N).Co}

In Eqn.(5) it should be noted that

Kg = Gas Film Mass Transfer Coefficient (kg.mol/m^2.sec.bar)
a= Interfacial Vapour/Liquid Area (m^2/m^3 reactor volume)
H= Henry's Constant {bar/(kg.mol/m^3.liq)}
K liq = Liquid-Solid Mass Transfer Coefficient (m/sec)
k= Intrinsic Reaction Rate Constant {(m^3 liq/kg.mol).m/sec}
N= Catalyst Effectiveness Factor
Co = Concn. of Organic in Liquid (kg.mol/m^3liq)

and Acat = (A/V)s.w/(Rho)s (6)

in which (A/V) = External Surface Area per unit volume of catalyst (m^2/m^3)

= 6/dp for spherical particles of diameter dp.

(Rho)s = Catalyst Particle Dry Density (kg/m^3)
w= Catalyst Mass per unit Reactor Volume (kg.cat/m^3)
EFFICIENT UTILISATION OF EXPENSIVE CATALYST

For Slurry Reactors, the catalyst is in powdered form and the mean dp is of the order of 10 microns.
Despite the low diffusivity in the liquid phase ( <= 10^-9 m^2/sec), the Effectiveness Factor (N) --> 1.
For trickle beds and bubble columns, on the other hand, dp lies in the range 2 - 5 mm. To exploit the
catalyst to the full in these applications (particularly with a precious metal), the catalyst is manufactured
in the form of an eggshell (perhaps 10 microns thick) at the external surface of the inert support. In
this case, too, N -> 1. Then, Eqn.(5) simplifies to

1/kapp = 1/(Kg.a) + H/Acat.[1/Kliq + 1/{k.Co}] (7)

CHARACTERISTICS OF GAS - LIQUID PHASE REACTIONS

* Rate Proportional to Ph2

* Rate Proportional to Organic Concn. (Co) at Low Values: becomes independent of Co

at high values.

* Rate Proportional to Catalyst Concn. (w) at Low Values: becomes independent of w

at high values.

* Rate increases exponentially with T at low values of T: tends to become independent

of T at high values. (shift from chemical rate control to mass transfer rate control)

ESTIMATION OF THE PARAMETERS - (a, Kg, Kl)

A critical review of Heat and Mass Transfer in Cocurrent Gas - Liquid Fixed Bed Reactors with
Recommendations and New Correlations for (a, Kg, Kl) in both Trickle Bed and Bubble Column
Reactors is given in Larachi and co-workers (1)

(1) F.Larachi, L. Belfares, I.Iliuta and B.P.A.Grandjean, " Heat and Mass Transfer in Cocurrent Gas-
Liquid Packed Beds. Analysis, Recommendations, and New Correlations", Ind.Eng.Chem.Res. 2003 42
pp. 222 - 242
c/mydocuments/desproj18/heattransmedia/reactors 01/02/18

CHEMICAL REACTORS AND HEAT TRANSFER MEDIA

Heat Transfer is usually an integral part of Reactor Design. In the case of Adiabatic Reactors, heat transfer is
carried out separately from chemical reactions, involving Feed/Product heat exchange and indirect heating or
cooling between reaction stages. In tubular fixed bed, fluidised bed or slurry reactors, heat transfer and chemical
reactions often occur simultaneously, making their design more complex. The choice of heat transfer fluid is
critical.

MEDIUM TEMP. RANGE PROBLEMS/CONSTRAINTS

(deg. C approx.)

Refrigerants -200 + 30 Mechanical Energy needed.

Low boiling point liquids, often
flammable.

Water, ambient pressure 30 - 100 Cheapest, minimal problems. Good heat transfer
properties

Water, pressurised 100 - 240 Cheap, upper temperature restricted by pressure

Steam

Hot Oil , ambient pressure 150 - 300 Restricted by vapour pressure and decomposition. Leaks cause
Hot Oil , pressurised 200 - 350 process contamination. Good heat transfer properties

Molten Salts, ambient 350 - 500 Difficult technology, Safety of oxidising salts problematic.
pressure.
Combustion Gases 300 - 900 Low Heat Capacity, Expensive recirculation. High losses.

Electricity 700 - 1500 Only way of exceeding flame temperature. Materials of Construction
limiting factors.
c/mydocuments/desproj18/processpressure/reactors 01/02/18

PROCESS PRESSURE
Pressure levels may be determined by a combination of factors, both Thermodynamic and Kinetic.
Ultimately, Plant Pressures may be fixed by Separation Requirements.
However,
(a) Capital Cost increases with Pressure for a Fixed Plant Size.
(b) For Gaseous Systems, Plant Size decreases with Pressure.
Therefore, Optimisation of Pressure (upto 30 bar) !!
(c) Work of initial Gas Compression to Process Pressure increases with Pressure.
(d) Work of Recycling against a fixed deltaP is less at higher pressures.
(e) Gas Compressors are more efficient at medium pressures than at low pressures.

EFFECT OF PRESSURE RANGE ON SYSTEM PARAMETERS

Parameter Pressure (bar)
0 1 10 30 200 500

Volume - Gas decreasing liquid-like

- Liquid no change compression problems

Pumping Costs cheap expensive special

Feed Recirculation expensive easier for fixed delP

Vessel Wall
Thickness constant increasing

Heat Exchange
with Gas poor acceptable good

Liquid B.P's increasing

Physical Props. well - known unknown

Ancill. equipment some problems readily available special designs

Safety problems increase

Leakage inwards minimal increasing