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Department Editor: Rebekkah Marshall

Preventing
Runaway
Reactions
general considerations [1]
A process is considered to be thermally
safe only if the reactions can easily be
controlled, and if the raw material, the
products, the intermediates and the re-
action masses are thermally stable under
the considered process conditions. Check
into the process equipment, its design, its
sequence of operation and the control
strategies. In addition to the engineer-
ing aspects, get detailed information on
thermodynamic and kinetic properties
of the substances involved, such as the
reaction rates or heat-release rates as
a function of process conditions. Deter-
mine the physical and chemical proper-
ties, as well.
Understanding of thermal-hazard po-
tential requires knowledge of various
skills and disciplines [3]. These include:
Operating mode: The mode of opera-
tion is an important factor. For instance,
a batch reaction, where all the reactants
are charged initially, is more difficult to
control than a semi-batch operation in
which one of the reactants is charged
progressively as the reaction proceeds
(for more, see Design Options).
Engineering: Design and layout of the
plant and equipment and its built-in con-
trols impact the entire process. The ca-
pacity of the heating or cooling system
is important in this context. Process en-
gineering is used to understand the con-
trol of the chemical processes on a plant
scale. It determines which equipment
should be used and how the chemical
processes should be performed. In ad-
dition, take into account technical failure
of equipment, human errors (deviations
from operating instructions), unclear
operating instructions, interruption of
energy supply, and external influences,
such as frost or rain (for more, see De-
sign Options).
Chemistry: The nature of the process and
the behavior of products must be known,
not only under reaction conditions, but
also in case of unexpected deviations
(for example, side reactions, instability
of intermediates). Chemistry is used to
gain information regarding the reaction
pathways that the materials in question
follow.
Physical chemistry and reaction kinetics:
The thermophysical properties of the reac-
tion masses and the kinetics of the chemi-
cal reaction are of primary importance.
Physical chemistry is used to describe the
reaction pathways quantitatively.
data collection
The following data are especially rel-
evant in avoiding runaway reactions:
Physical and chemical properties, ig-
nition and burning behavior, electro-
static properties, explosion behavior
and properties, and drying, milling,
and toxicological properties
Interactions among the chemicals
Interactions between the chemicals
and the materials of construction
Thermal data for reactions and de-
composition reactions
Cooling-failure scenarios
design options [2]
If a reaction is has the potential for
runaway, the following design changes
should be considered:
Batch to continuous. Batch reactors
require a larger inventory of reac-
tants than continuous reactors do, so
the potential for runaway in continu-
ous systems is less by comparison
Batch to semi-batch. In a semi-batch
reaction, one or more of the reactants
is added over a period of time. There-
fore, in the event of a temperature or
pressure excursion, the feed can be
switched off, thereby minimizing the
chemical energy stored up for a sub-
sequent exothermic release
Continuous, well-mixed reactors to
plug flow designs. Plug-flow reactors
require comparatively smaller volumes
and therefore smaller (less dangerous)
inventories for the same conversion
Reduction of reaction inventory via
increased temperature or pressure,
changing catalyst or better mix-
ing. A very small reactor operating
at a high temperature and pressure
may be inherently safer than one
operating as less extreme conditions
because it contains a much lower in-
ventory [3]. Note that while extreme
conditions often result in improved
reaction rates, they also present their
own safety challenges. Meanwhile, a
compromise solution employing mod-
erate pressure and temperature and
medium inventory may combine the
worst features of the extremes [3].
Less-hazardous solvent
Externally heated or cooled to inter-
nally heated or cooled
thermal stability
criteria [1, 4]
As a guideline, three levels are sufficient
to characterize the severity and prob-
ability of a runaway reaction, as shown
in the Table.
Defining high, meDium
anD low risk [1]
Severity Probability
High T
ad
>

200K TMR
ad
< 8 h
Medium 50K < T
ad
<

200K 8 h < TMR
ad
<
24 h
Low T
ad
<

50K and
the boiling point
cannot be sur-
passed
TMR
ad
> 24 h
adiabatic temperature rise
The adiabatic temperature rise is calculated
by dividing the energy of reaction by
the specific heat capacity as shown in
Equation (1).
T
ad
= 1,000Q
r
/C
p
(1)
where:
T
ad
= adiabatic temperature rise, K
Q
r
= energy of reaction, kJ/kg
C
p
= heat capacity, J/(kg)(K)
time to maximum rate (tmr)
TMR
ad
(the time to maximum rate, adiabatic) is
a semiquantitative indicator of the probability
of a runaway reaction. Equation (2), defining
TMR
ad
in hours, is derived for zero-order
reaction kinetics:
TMR
ad
= C
p
RT
o
2
/3,600q
o
E
a
(2)
where:
R = gas constant, 8.314 J/molK
T
o
= absolute initial temperature, K
q
o
= specific heat output at To, W/kg
E
a
= activation energy, J/mol
The TMR value provides operating personnel
with a measure of response time. Knowledge
of the TMR allows decisions to be based on
an understanding of the time-frame available
for corrective measures in case heat transfer
is lost during processing.
References
1. Venugopal, Bob, Avoiding Runaway Reac-
tions, Chem. Eng., June 2002, pp. 5458.
2. Smith, Robin, Chemical Process Design,
McGraw-Hill, New York, 1995.
3. Kletz, T. A., Cheaper, Safer Plants,
IChemE Hazard Workshop, 2d., IChemE,
Rugby, U.K., 1984.
4. Gygax, R., Reaction Engineering Safety,
Chem. Eng. Sci., 43, 8, pp. 175971, Au-
gust 1998.
Department Editor: Rebekkah Marshall
Hazardous Area
Classifcation
Guidelines by location
Over the years, hazardous area clas-
sification requirements for the U.S.
have evolved around a single area-clas-
sification system known as the Class/
Division system. Today, the system
addresses establishment of boundaries
of hazardous areas and the equipment
and wiring used in them. Meanwhile,
European countries, as well as some
other countries around the world, have
developed their own area classification
systems to address hazardous locations
safety issues. This independent develop-
ment has resulted in systems for these
countries or groups of countries based
on the International Electrotechnical
Commission (IEC) Zone system, with de-
viations to meet each countrys national
codes. While other countries do accept
and use the Division system (most nota-
bly Canada and Mexico), the majority
of the worlds hazardous locations are
classified using the concepts of the IEC
Zone system. The U.S. National Electri-
cal Code (NEC; NFPA 70) also recog-
nizes the Zone system and allows its
use in the U.S. under article 505 of the
NEC. ATEX requires the use of IEC-type
hazardous area classifications.
defininG hazardous areas
A hazardous area is designated as any
location in which a combustible material
is or may be present in the atmosphere
in sufficient concentration to produce an
ignitable mixture. The North American
method identifies these areas by Class,
Division and Group or optionally by
Class, Zone and Group, while the IEC
and CENELEC designate these areas by
Gas/Dust, Zone and Group. The likeli-
hood that the explosive atmospheres are
present when the equipment is operating
are designated in Tables 1, 2 and 5.
equipment selection
For equipment selection purposes, haz-
ardous area classifications also consider:
The maximum surface temperature of
the equipment under normal operat-
ing conditions (see the Temperature
Code designations in Table 3)
The ignition-related properties of
the explosive atmosphere (see the
Group designations in Table 4)
The protection method(s) used by
the equipment to prevent ignition of
the surrounding atmosphere (see the
Protection Method designations in
Table 6)
Acknowledgement and references
We would like to thank Vladimir Stetsovsky of Chilworth
Technology, Inc. for his contributions to this page
1. National Electrical Code-2005-NFPA 70, National
Fire Protection Association.
2. NFPA 497-2004, Recommended Practice for the
Classification of Flammable Liquids, Gases, or
Vapors and of Hazardous (Classified) Locations for
Electrical Installations in Chemical Process Areas.
3. NFPA 499-2004, Recommended Practice for the
Classification of Combustible Dusts and of Hazard-
ous (Classified) Locations for Electrical Installations
in Chemical Process Areas.
4. IEC 60079-10-2002 Electrical apparatus for explo-
sive gas atmospheres Part 10: Classification of
hazardous areas.
5. IEC 61241-3-2005 Electrical apparatus for use in
the presence of combustible dust Part 3: Classifi-
cation of areas where combustible dusts are or may
be present.
Table 3. Temperature Codes
The Temperature class defines the maximum
surface temperature of the device. Ratings are
given with reference to 40C ambient
T1 450C T3A 180C
T2 300C T3B 165C
T2A 280C T3C 160C
T2B 260C T4 135C
T2C 230C T4A 120C
T2D 215C T5 100C
T3 200C T6 85C
The additional temperature classifications high-
lighted above are for USA and Canada only
Table 4. Gas and Dust Groups
Hazardous locations are grouped according to their ignition
properties
Typical
gas
IEC gas
group
North Ameri-
can group
Minimum ignition
energy
Acetylene IIC A 20J
Hydrogen IIC + H
2
B 20J
Ethylene IIB C 60J
Propane IIA D 100J
*Methane I
Metal dust E
Coal dust F
Grain dust G
Fibers
*Mining application under jurisdiction of U.S. Mine Safety and
Health Administration (MSHA)
Table 2. Relationship Between Divisions and Zones
North America Europe
Division
method
Zone
method IEC standard
Ignitable mixture present
continuously (long periods) Division
1
Zone
0
Zone 0
(Zone 20-Dust)
Ignitable mixture present
intermittently
Zone
1
Zone 1
(Zone 21-Dust)
Ignitable mixture is not
normally present
Division
2
Zone
2
Zone 2
(Zone 22-Dust)
Table 5. Information Required For Establishing
Extent of Hazardous Area
Gas/Vapors Dust
Flash point
Flammability limits
Auto-ignition temperature
Minimum ignition energy,
MIC or MESG for equipment
selection purposes
Gas/Vapor group
Vapor/Gas density
Area ventilation conditions
Location of gas/vapor release
points. Frequency and rate of
release
A/B classification
Minimum explosible dust
concentration
Minimum ignition energy
Minimum ignition tempera-
ture (cloud/layer)
Electrical resistivity
Dust group
Area ventilation conditions
Location of dust release
points. Frequency and rate of
release
Table 6. Types of Protection for Electri-
cal Equipment (IEC/ATEX and NEC)
Technique
IEC
Des-
cription
Permitted
Zone
Permit-
ted Di-
vision
Oil immersion Ex o 1 & 2
Pressurization Ex p 1 & 2 1 & 2
Powder filling Ex q 1 & 2
Flameproof Ex d 1 & 2
Explosion Proof 1 & 2
Increased safety
Intrinsic safety Ex ia 0,1 & 2 1 & 2
Intrinsic safety Ex ib 1 & 2
Encapsulation Ex m 1 & 2
Special protection Ex s 0,1 & 2
Nonincendive 2
Nonsparking Ex nA 2
Enclosed break Ex nC 2
Energy limited Ex nL 2
Simplified
pressurization
Ex nP 2
Restricted
breathing
Ex nR 2
Table 7. Types of Ignition Protection for Mechanical Equipment (ATEX)
Method Description
To ensure that ignition sources cannot arise Construction safety c, Inherent safety g,
To ensure that ignition sources cannot become active Control of ignition sources b
To prevent the explosive atmosphere from reaching
the ignition source
Inert liquid immersion k, Inert gas pressuriza-
tion p, Flow restricting enclosure fr
To contain the explosion and prevent flame propagation Flame proof enclosures d, Flame arresters
Table 1. Hazardous Areas*
North America IEC (Europe)
Class Division Zones
Class I Gas or
vapor
Class II Dust
Class III Fiber
or flying (no group
designation)
Division 1: Pres-
ent or likely to be
present in normal
operation
Division 2: Not
present in normal
operation, could
be present in ab-
normal operation
Gas/Vapor
or Dust
Zone 0 (Gas) /
Zone 20 (Dust)
Zone 1 (Gas) /
Zone 21 (Dust)
Zone 2 (Gas) /
Zone 22 (Dust)
An area in which an explosive atmosphere is
continually present or present for long
periods or frequently
An area in which an explosive atmosphere is
likely to occur in normal operation
An area in which an explosive atmosphere is
not likely to occur in normal operations and,
if it does occur, will exist for only a short time
* This table represents a corrected version from that in the original printing
Department Editor: Rita L. D'Aquino
Solvent Selection
Methodology
A STEPWISE ProcEdurE
Organic solvents have been used in many industries for centu-
ries, but the methods and tools to select optimal solvents while
minimizing their adverse environmental, health, safety and op-
erational concerns are still evolving. The appropriate selection
of solvents depends to a large extent on the application more
specifcally on what needs to be dissolved, and under what
conditions. This article presents a four-step approach to solvent
selection based upon Ref. 1*, where the reader will fnd a list of
additional resources on this topic.
Identify the challenge and solvent characteristics.
The frst two steps are: 1) identifying the actual problem and
technology or unit operation required to solve it; and 2) defning
the requirements that must be met by the solvent, using criteria
related to its physical and chemical properties (e.g., pure-solvent
properties, such as normal boiling point, the Hildebrand solubility
parameter at 300 K, the Hansen solubility parameters; solvent-
solute properties, such as the solubility of the solute as a function
of the composition of the mixture; and functional constraints, such
as solute loss in solute).
Obtain reliable values of solvent properties and
narrow down selection. There are several alternatives for this
third step. For example, one can measure the required properties,
use a database of properties of chemicals (or solvents), or, use
property models to estimate them. For solvent-selection problems
not involving chemical reactions, the pattern of the desired
solvent is established through analysis of the solute, application
type, and other constraints.
Once this is established, a database of known solvents can
be used to identify the solvents that match the necessary pattern
(Table 1). On the other hand, when chemical reactions are
involved, the approach is based on transition-state theory and
requires consideration of the solvation energies of the reactants,
products and transition states, and thus, knowledge of the reac-
tion mechanism.
When the crucial values have been found, the solvent search
could be such that frst, solvent-pure properties are used, followed
by solvent-EHS, then solvent-solute, and fnally solvent-function.
Narrow down the list by removing the compounds that do not
match desired properties.
A protocol derived by Britest Ltd. (www.britest.co.uk) seeks to
use mechanistic principles to guide solvent selection (Figure). The
objective is to follow the arrows according to the problem defni-
tion and a search criterion until an end-point is reached, thereby
obtaining the characteristics of the candidate solvents. These
characteristics are used to identify the group to which the solvents
belong using solvents database (see Table 2). The corresponding
group-types are evaluated and a fnal selection is made.
Verify selection. The fourth step is to verify that the solvent
works as expected by performing a computational validation
by simulation. Experimental validation of a solvent candidate is
required at all stages of process development.
Table 2. Well-known solvents together with their related properties
Solvent Name Molecule type Group type Charge NBP NMP Sol. Par.
(K) (K)
1-Methyl-2-pyrrolidinone Amide 1 NE/EPD 475.15 249.15 23.16
Acetonitrile Nitrile 1 E/NPG 354.75 229.35 24.05
Dimethyl sulphoxide S-oxide 1 E/NPG 462.15 291.65 26.75
Dimethyl formamide Amide 1 NE/NPG 426.15 212.75 23.95
Dimethylacetamide Amide 1 NE/NPG 438.15 253.15 22.35
Diisopropyl ether Ether 2 NE/EPD 341.65 181.35 14.45
Dimethyl ether Ether 2 NE/EPD 248.35 131.65 15.12
Methyl tertbutyl ether Ether 2 NE/EPD 328.35 164.55 15.07
Tetrahydrofuran Ether 2 NE/EPD 338.15 164.85 18.97
Chlorobenzene Chloride 3 NE/P 632.35 404.9 19.35
m-xylene (also o-; p-) Aromatic HC 3 NE/P 412.27 225.3 18.05
Toluene Aromatic HC 3 NE/P 383.95 178.25 18.32
Acetic acid Acid 4 PG 391.05 289.81 19.01
Propionic acid Acid 4 E/PG 414.25 252.45 19.41
Sulfuric acid Acid 4 E/PG 610
ordered
283.46 28.41
Propanol Alcohol 5 E/N 370.35 147.05 24.45
Ethanol Alcohol 5 E/N 351.35 159.05 26.13
Butanol Alcohol 5 E/N 390.81 183.85 23.35
Ethylene glycol Alcohol 5 E/N 470.45 260.15 33.7
Dichloromethane Chloride 6 NE/EPD 313.15 178.05 20.37
Heptane Alkane 7 NE/I 371.65 182.55 15.2
Hexane Alkane 7 NE/I 341.85 177.85 14.9
Pentane Alkane 7 NE/I 309.22 143.42 14.4
Methanol Alcohol 4, 5 E/N 337.85 175.47 29.59
Water Aqueous 4, 5 E/N 373.15 273.15 47.81
NE = non-electrolytic solvent; E = electrolytic solvent; P = polarizable; EPD = electron-pair
donor; I = inert; PG = protogenic (proton donor); N= neutral (donor & acceptor); NPG =
non-protogenic (proton acceptor); NBP = normal boiling point; NMP = normal melting point;
Sol. Par. = Hildebrand solubility parameter at 300 K (MPa
1/2
)
Table 1. Some well-known databases and solvent selection tools
Databases Address and comments
ChemFinder Searchable data and hyperlink index: http://chemfnder.cambridgesoft.com
Solvents Databases Solvent substitution data systems at http://es.epa.gov/ssds/ssds.html;
Handbook of Solvents from www.chemtec.org/cd/ct_23.html; and
SOLVDB at http://solvdb.ncms.org/index.html
NIST Webbook
DIPPR and
TAPP
Source of physical and chemical data at http://webbook.nist.gov
www.aiche.org/TechnicalSocieties/DIPPR/About/Mission.aspx; and
www.chempute.com/tapp.htm
CAPEC Database Pure as well as mixture properties data, including solvent-solute database:
www.capec.kt.dtu.dk/Software/ICAS-and-its-Tools
Selection Tools Address and comments
SMSwin A specialized software for property estimation and solvent classifcation:
www.capec.kt.dtu.dk/documents/software/SMSWIN.htm
NRTL-SAC and
eNRTL-SAC
Activity coeffcient method based on segment contributions. Predictive based
on a small set of solubility data. Useful for crystallization solvent selection
and extends to LLE and VLE: www.aspentech.com
Stability, solubility of reactants, products
Single phase or solid-liquid
Homogeous catalysis
by Pt group complexes
Moderate polarity
DPA ethers,
aromatics
Dipolar
aprotic
Fast, low temp,
but recovery
difficult
Slow, high-
temperature,
easy recovery
Aromatic
hydrocarbon
(xylene)
High polarity
Water, carboxylic
acids, inorganic
acids, lower
alcohols
Condensation SN1/E1 SN2/E2
Substrate/product hydroxyl sensitive
No
Yes
Water,
alcohols
Dipolar aprotic
ethers
Consider
solvation
Two-phase or liquid-liquid
(polar phase is water)
Water, immiscible solvent
Choose polarity
based on substrate
and reagent
solubility. May need
phase-transfer catalyst
Group 7 Group 5 Group 2 Group 4 Group 3 Group 1 Group 3
Group 6 Group 1 Group 2
Group 3 Group 1
*Reference: 1. Gani, R., et al., A Modern Approach to Solvent Selection, Chem. Eng., Vol. 113, No. 3, pp. 3043, Mar. 2006. Author E-mail: rag@kt.dtu.dk
Department Editor: Rita L. D'Aquino
T
he formation of crystals requires the birth of
new particles, also called nucleation, and
the growth of these particles to the fnal
product size. The driving force for both rates is
the degree of supersaturation, or the numerical
difference between the concentration of solute in
the supersaturated solution in which nucleation
and growth occurs vs. concentration of solute in
a solution that is theoretically in equilibrium with
the crystals.
In a batch crystallizer, the crystal size
distribution (CSD) is controlled by frst seeding
the initially supersaturated batch with a known
number and size distribution of crystals, and
then controlling the rate of evaporation or
cooling (i.e., rate of energy transfer) so as to
achieve a level of supersaturation that supports
adequate crystal growth and an acceptable
rate of nucleation. The relationship between
supersaturation and growth is linear, but that
between nucleation and growth is raised to a
power that is usually greater than one, making
it diffcult to grow large crystals when nucleation
is occurring. The following procedure describes
how to achieve the optimal growth rate:
1. Screen the seeds at the beginning of the ex-
periment to determine the cumulative number
of crystals that are greater than a given size
N. Estimate N
Li,
the number of crystals of a
given size (L
av
) obtained from the screening:

(1)

N
W
L k
L
i
av v c
i
=

3



The parameters are defned in the table
of nomenclature. To convert from m to ft,
multiply by 3.28 x 10
6
.
2. Continue to measure the number and size
of crystals as the cooling or evaporation
program is in progress. Prepare an inverse
cumulative plot of the number of crystals
greater than a given size vs. size of the
crystal (Figure 1). The crystal growth rate de-
pends on the energy transfer rate, so modify
the rate of energy transfer until a desirable
product is obtained.
3. Repeat the frst two steps at intervals
throughout the batch cycle and plot the
results as shown in Figure 1. The family of
curves resulting from data plotted under the
selected conditions indicates that the number
of crystals is not increasing with time. Thus,
no additional nucleation is occurring yet.
4. Proceed to collect crystal samples, an-
ticipating the onset of nucleation. Figure
2 indicates that the number of crystals is
signifcantly increasing with time. In this
fgure, t
1
(not to be confused with t
1
in Figure
1) represents the start of this new set of batch
dynamics. It is safe to assume that signifcant
nucleation is now occurring and that the rate
of energy transfer is too high.
5. By taking the slope of the curve represent-
ing the estimated number of nuclei present
at the measured point in time (N
ti
) vs. time
(t
i
), one can determine the nucleation rate.
Using your representation of Figure 3, create
a dashed, horizontal line across the lower
portion of the graph depicting the selected,
cumulative number of crystals (N
i
), and their
sizes (L
1
L
4
) over time (t
1
t
4
).
6. For a selected cumulative number of crystals
(N
i

), plot the crystal size (L) vs. time (t), as


demonstrated in Figure 3. The slopes repre-
sent the crystal growth rate (G). If the level of
supersaturation changes during the run, the
growth rate also changes. Non-parallel lines
would indicate that the larger crystals are
growing at a faster rate, due to a reduced
diffusional resistance [layer] at the crystal
surface. With larger particles, the resistance
layer may be smaller, allowing the solute to
more readily reach the crystal surface and
incorporate itself into the lattice. These fac-
tors collectively contribute to the accelerated
growth rate of the larger particles. Parallel
lines indicate that the growth rate is not
dependent on crystal size.
7. Increase the rate of cooling or evaporation
until additional nucleation occurs, upon
which you can safely assume that the growth
rate is too high.
8. Develop a seeding and evaporation profle
that will yield a growth rate that is lower than
the value found in Step 6.
When determining the growth rate, keep in
mind the difference in mixing characteristics
between a laboratory-scale vessel and a com-
mercial confguration. A small tank generally
offers a higher relative pumping capacity,
shorter blend time, and higher average shear
rates within a narrower range.
UsefUl observations
Most processors will agree that when it
comes to crystals, the larger, the better. Large
crystals are easier to handle in downstream
operations, such as washing, centrifugation
and drying.
As previously mentioned, it is desirable for
the seeds size distribution to refect a nar-
row cut of particles. In this cut, the weight
of crystals with sizes fner than Ls should be
minimal because these tiny particles add
enormously to the number of crystals that
compete for supersaturation and growth.
Studies show that milled seeds may not grow
as well as unmilled seeds. Furthermore, not
all crystals of a given size grow at the same
constant rate. This is sometimes attributed to
the differences in the surface characteristics
of particles that have equal dimensions.
Fines destruction in a batch system can
greatly reduce the effects of secondary nucle-
ation on the CSD, and signifcantly increase
crystal size while narrowing the CSD.
In practice, not all additional nucleation can
be suppressed. Crystallizations carried out at
low levels of supersaturation near the meta-
stable zone (i.e., the conditions under which
crystals grow, but do not typically nucleate)
will display some secondary nucleation, due
to crystal-crystal interactions and contact
between the crystals and the impeller. Nev-
ertheless, the mean crystal size, shape and
distribution are dramatically improved when
seeding is followed by a programmed rate of
energy transfer.
Reference: Genck, W., Better Growth in Batch Crystal-
lizers, Chem. Eng., Vol. 106, No. 8, pp. 9095, Aug.
2000. E-mail: genckintl@aol.com
/
h
n
u
m
b
e
r

o
f

c
r
y
s
t
a
I
s

I
a
r
g
e
r

t
h
a
n
-
Size, - (Mm)
-h = smallest measurable size
/h
1
U
1
-
1
-
2
-
3
U
2
U
3
U
4
-h
/
h

n
u
m
b
e
r

o
f

c
r
y
s
t
a
l
s

l
a
r
g
e
r

t
h
a
n

-
-h = smallest measurable size
/U
1
/U
2
/U
3
/U
4
U
1
U
2
U
3
U
4
-h
4
J
[
F

-
( =
/h
1
/h
2
/h
3
U
1
U
2
U
3
U
4
Time, U (min)
E-
EU
Controlling
Crystal Growth
NomeNclature
A Crystalsurfacearea,ft
2
B Nucleationrate,(numberofnuclei)/
ft
3
/s
G Crystalgrowthrate,m/s
k
v
Crystal-volumeshapefactor,
dimensionless
L Crystalsize,m
L Smallest-measurablesize,m
L
av
Sizeofcrystalfraction,m
L
f
Finalsizeofcrystal,m
L
s
Seedsize,m
N Numberofseeds
N
i
Constant,cumulativenumber
ofcrystalsincrystallizer
N
Li
Numberofcrystalsofagivensize,
L
av
N
ti
Numberofcrystalnucleiatanytime
S Rateofsupersaturation
S* Maximumallowablesupersatura-
tion,lb/ft
3
solvent
t, t
i
, t
f
Time,h
W
i
Weightofcrystalsonscreen

c
Crystaldensity,lb/ft
3
FiGure 1. FiGure 2. FiGure 3.
Department Editor: Rita L. D'Aquino
AchievabIe combustibIes in ash, %
Unit heat output,10
6
Btu/h
Average fueI cost, $/10
6
Btu
F
u
e
I

s
a
v
i
n
g
s
,

$
1
,
0
0
0
/
y
r
5
10
15
20
50
CombustibIes in ash, %
320
240
160
80
0
6.00 4.00 3.00 2.50 2.00
1.50
1.00
0.50
40 30 20 10
10 25 50 10 100
150
200
300
400
0
B
C
A
FIGURE 1. This nomograph is used to
estimate annual cost savings from reducing
combustible losses due to unburned carbon
This article has been drawn from the work of Wayne Turner and Steve Doty, Boilers and Fired
Systems, Energy Management Handbook, 6th Ed., Ch. 5, The Fairmont Press, Lilburn, Ga., 2006.
Fuel Selection
Considerations
T
he selection and application of fuels to various
combustors are complex. Most existing units have
limited fexibility in their ability to fre alternative
fuels. New units must be carefully planned to assure
the lowest frst costs without jeopardizing the future
capability to switch to a different fuel.
Natural gas
Natural gas has traditionally been the most attrac-
tive fuel type for combustors because of the limited
need for fuel-handling equipment (e.g., pipelines,
metering, a liquid-knockout drum, and appropriate
controls) and the freedom from pollution-control
equipment. Drawbacks include rising fuel costs, in-
adequate gas supplies and lower boiler efficiencies
that result from firing natural gas, particularly when
compared to the firing efficiencies of oil or coal.
Fuel oil
Fuel oils are graded as No. 1, No. 2, No. 4, No.
5 (light), No. 5 (heavy), and No. 6. Distillates are
Nos. 1 and 2, and residual oils are Nos. 4, 5, and
6. Oils are classifed according to their physical
characteristics by the American Society for Testing
and Materials (ASTM) per Standard D-396. No.
2 oil is suitable for industrial use and for home
heating. The primary advantage of using a distillate
oil rather than a residual oil is that it is easier to
handle, requiring no heating to transport and no
temperature control to lower the viscosity for proper
atomization and combustion. However, consider-
able purchase cost penalties exist between residual
and distillate.
Distillates can be divided into two classes:
straight-run, which is produced from crude oil by
heating it and then condensing the vapors; and
cracked, which involves refning at a high tempera-
ture and pressure, or refning with catalysts to pro-
duce the required oil from heavier crudes. Cracked
oils contain substantially more aromatic and olefnic
hydrocarbons, which are more diffcult to burn
than the paraffnic and naphthenic hydrocarbons
obtained from the straight-run process. Sometimes
a cracked distillate, called industrial No. 2, is used
in fuel-burning installations of medium size (small
package boiler or ceramic kilns, for example).
Because of the viscosity range permitted by
ASTM, No. 4 and No. 5 oil can be produced in
a variety of ways: blending of No. 2 and No.
6, mixing refnery by-products, utilization of off-
specifcation products, and so on. Because of the
potential variations in characteristics, it is important
to monitor combustion performance routinely to
obtain optimum results. Burner modifcations may
be required to switch from, say, a No. 4 blend to a
No. 4 distillate.
Light (or cold) and heavy (or hot) No. 5 fuel oil
are distinguished primarily by their viscosity rang-
es: 150 to 300 SUS (Saybolt Universal Seconds) at
100F and 350 to 750 SUS at 100F, respectively.
The (No.) classes normally delineate the need for
preheating for proper atomization.
The No. 6 fuel oil is also referred to as residual,
Bunker C, and reduced- or vacuum bottoms. Because
of its high viscosity, 900 to 9,000 SUS at 100F, it
can only be used in systems designed with heated
storage and a high enough temperature (to achieve
proper viscosity) at the burner for atomization.
Notable fuel oil properties include the following:
1) Viscosity indicates the time required in seconds
for 60 cm
3
of oil to fow through a standard-size
orifce at a specifc temperature. In the U.S., it is
normally determined with a Saybolt viscosimeter,
which comes in Universal and Furol variants. The
differences between them are the orifce size and
the sample temperature. Thus, when stating an oils
viscosity, the type of instrument and temperature
must also be stated. The Universal has the small-
est opening and is used for lighter oils. 2) The
fash point is the temperature at which oil vapors
are ignited by an external fame. As heating
continues above this point, suffcient vapors are
driven off to produce continuous combustion. The
fash point is also an indication of the maximum
temperature for safe handling. Distillate oils have
fash points of 145200F; heavier oils have
fash points up to 250F. 3) The pour point is the
lowest temperature at which an oil fows under
standard conditions, and is roughly 5F above
the solidifcation temperature. Knowledge of the
pour point helps determine the need for heated
storage, the storage temperature, and the need
for heating and pour-point depressant.
Coal
The selection of coal as fuel involves higher
capital investments because of the need for
handling equipment, coal preparation (crush-
ing, conveying, pulverizing, etc.) and storage;
ash handling and storage; pollution-abatement
equipment; and maintenance. The operating
cost savings at current (2007) fuel prices of coal
over oil or gas justifes a great portion, if not
all, of the signifcantly higher capital invest-
ments required for coal.
Coal-fred steam generators and vessels
inherently suffer effciency losses due to a failure
to burn all the available fuel. The unburned fuel
is the remaining carbon in the leftover ash. The
nomograph (Figure 1) may be used to assess
how a reduction in unburned carbon translates
into energy and cost savings. A sample calcula-
tion follows.
Example: The system is a coal-fred steam
generator with a continuous rating of 145,000
lb/h; average (avg.) boiler load = 125,000 lb/h;
existing combustibles in ash = 40% (measured);
obtainable combustibles in ash = 5%; actual oper-
ating time = 8,500 h/yr; design-unit heat output =
150 10
6
Btu/h; avg. heat output = 129 10
6

Btu/h; avg. fuel cost = $1.50/10
6
Btu.
Analysis: In Figure 1A, the percent of existing
combustibles (measured) are shown on the
horizontal axis. The curves above it represent the
proposed improvement in percent of unburned
carbon in ash. From the coordinates in Figure
1A draw a horizontal line to the curve in Figure
1B that represents the design-unit heat output.
Drop the line to the appropriate fuel-cost curve in
Figure 1C. Extend the line from that point to the
left to obtain the corresponding annual fuel sav-
ings, assuming continuous operation at full boiler
design output. To calculate actual annual fuel
savings, a correction factor (CF) is required that
considers actual boiler load and actual run time:
Actual savings, $ = Savings from chart x CF
where CF = operating avg. heat output/design
heat output [(actual operating h/yr)/(8,760
h/yr)]
Savings for this example =
$210,000/yr [(129 10
6
Btu/h)/(150 10
6

Btu/h)] [(8,500 h/yr)/(8,760 h/yr)]
= $175,200/yr.
Note: If the heat output of the unit or the average
fuel cost exceeds the limit of the fgures, use half
of the particular value and double the savings
obtained from Figure 1C.
It is probable that pulverized-coal-fred instal-
lations suffer from high UCL whenever any of
the following are experienced: a change in the
raw-fuel quality from the original design basis;
deterioration of the fuel burners, burner throats,
or burner swirl plates or impellers; increased
frequency of soot blowing to maintain heat-transfer
surface cleanliness; a noted increase in stack gas
opacity; uneven flame patterns characterized by a
particularly bright spot in one section of the flame
and a notably dark spot in another; CO formation
as determined from a flue-gas analysis; frequent
smoking observed in the combustion zone;
increases in refuse quantities in collection devices;
neglect of critical pulverizer internals and classifier
assemblies; a high incidence of coal hang-up in
the distribution piping to the burners; and frequent
manipulation of the air/coal primary and second-
ary air registers.
Techniques used successfully to reduce high
UCL and/or high-excess-air operation include:
modifying or replacing the pulverizer internals to
increase the coal fneness; installing additional or
new combustion controls to maintain consistent
burner performance; purchasing new coal feeders
that are compatible with and responsive to unit
demand fuctuations; calibrating air fow and
metering devices to ensure correct air/coal mixtures
and velocities at the burner throats; installing
turning vanes or air foils in the secondary air-supply
duct or air plenum to ensure even distribution and
proper air/fuel mixing at each burner; replacing
worn and abraded burner impeller plates; installing
new classifers to ensure that proper coal fnes
reach the burners for combustion; rerouting or
modifying air/coal distribution piping to avoid
coal hang-up; increasing the air/coal mixture
temperature exiting the pulverizers to ensure good
ignition without coking; and cleaning deposits from
burner throats.
Department Editor: Rita L. D'Aquino
Materials of
Construction
Low-temperature
appLications [1]
One key engineering consideration is the
choice of materials of construction for frigid
applications. Nickel-chromium (Ni-Cr) type
stainless steels are notably versatile at low or
cryogenic temperatures. They offer a combi-
nation of high impact strength (IS) and corro-
sion resistance. In the austenitic phase, with
face-centered-cubic crystals, the combination
of Cr and Ni in the material improves IS and
toughness down to temperatures as low as
250C. For good IS at temperatures down
to 45C, C-Mn-Si steels are recommended.
The most preferred grades are fine-grained
steels of pressure-vessel quality, such as ASTM
A 516 and ASTM A 537 (in all grades). For
temperatures between 45 and 100C (for
example, for liquid-ethylene storage), steels
containing 2.59% Ni are useful. Between
150 and 250C, the Ni-Cr austenitic steels
(300 series, of 18/8 varieties), are highly
recommended. In the nonferrous category,
Al has excellent properties for temperatures
as low as 250C. Also attractive are Cu and
some of its alloys, which can withstand tem-
peratures down to 195C.
chemicaL resistance
CPVC [2]. Many nonmetals do not have the
tensile strength to meet the pressure require-
ments of various process applications, espe-
cially at elevated temperatures. But years of
testing and actual field performance prove
that chlorinated polyvinyl chloride (CPVC)
systems can be pressure rated for operation
as high as 200F. CPVCs high heat-distor-
tion temperature and resistance to corrosion
make it suitable for applications such as
metal processing, pulp and paper, and in-
dustrial wastewater treatment, where harsh
and corrosive chemicals are commonly used
(see Figure 1). Another advantage of CPVC
is that it is lighter than metal, and therefore
less expensive to install, from both a mate-
rial cost and labor perspective. CPVC is not
recommended where aromatic solvents and
esters are present in high concentrations.
FRP pipe [3]. Composite fiberglass-rein-
forced plastic (FRP) pipe has been replac-
ing conventional pipe material, such as
steel and concrete, in numerous applica-
tions because of its corrosion resistance,
low design weight (25% of concrete pipe
and 10% of steel pipe), high fatigue en-
durance, and adaptability to numerous
composite blends (Table 5, Ref. 3) and
manufacturing methods. FRP pipe may
be divided into two broad categories:
gravity pipe (dia. from 8 to 144 in.) and
pressure pipe (dia. from 1 to 16 in.). It is
not unusual to see FRP pressure pipe han-
dling pressures as high as 2,0005,000
psi during chemical processing, with the
higher-pressure pipe at the lower end of
the diameter scale.
heat transfer
properties [4]
Metals, including specialty materials, are
the best choice in terms of good heat trans-
fer. In the lined category, glass is used ex-
tensively for process equipment where good
heat transfer is required. Lined materials,
however, often have the problem of uneven
thermal expansion, which may weaken the
bonding of the lining in due course. While
fluoropolymers have excellent compatibility
with various chemicals and special surface
and physical chemistries, they are gener-
ally not used for reaction vessels because
of their poor heat-transfer properties. Ther-
mal conductivities for various materials are
listed in the Table, and typical applications
are shown in Figure 2.
THERMAL CONDUCTIVITY OF VARIOUS
MATERIALS OF CONSTRUCTION [4]
Material Thermal conduc-
tivity, W/(m)(K)
Carbon Steel (CS) 60.59
SS 304 40.71
SS 316 14.23
SS 316 L 14.23
Hastelloy B
2
9.12
Hastelloy C
2
10.21
Tantalum
2
57.5
Titanium
2
21.67
Zirconium
2
20.77
Graphite 121.15
Hexoloy 125.65
Glass
1
1.00
Lead 35.30
Inconel
2
12.00
CPVC 0.14
PTFE (Polytetra-
fluoroethylene)
1
0.25
PFA (Perfluoro-
alkoxy resin)
1
0.19
ETFE (Ethylene
tetrafluoroethylene)
1
0.24
PVDF (Polyvinylidene
fluoride)
1
0.23
ECTFE (Ethylene chlo-
rotrifluoroethylene)
1
0.16
1. Common choice for lining material
2. Exotic metals
Excellent
Good
Fair
Poor
Weak acids
Weak bases
Salts
Strong acids
Aliphatics
Strong bases
Strong oxidants
Halogens
Aromatic solvents
Esters and ketones
Figure 1. CPVC offers resistance to a
variety of harsh chemicals
Exotic 300
250
200
150
100
50
0
-50
-100
T
e
m
p
e
r
a
t
u
r
e
,

C
Exotic Exotic
Exotic
Fluoropolymer,
glass lined,
exotic
Fluoropolymer,
glass lined,
exotic
Glass lined,*
exotic
Glass lined,*
exotic
Exotic
Exotic Exotic
Exotic
Exotic
Exotic
Application:
Typical
equipment:
Tanks,
vessels
Pipelines,
valves,
owmeters
Mixers
Reactors
Storage Transport Agitation (Agitation +
heat transfer)
Exotic Exotic Exotic
Figure 2. When looking beyond steel for materials of construction, it is impor-
tant to consider the intended application and temperature range. Exotic (specialty)
metals (see Table) are shown here to serve well in all applications. Another mate-
rial, equally suited to a specific requirement, however, may be chosen as the more
cost-effective option
References
1. Nalli, K., Materials of Construction For Low-Tem-
perature and Cryogenic Processes, Chem. Eng.
July 2006, pp. 4447.
2. Newby, R. and Knight, M., Specifying CPVC In
Chemical Process Environments, Chem. Eng., Oc-
tober 2006, pp. 3438.
3. Beckwith, S., and Greenwood, M., Dont Over-
look Composite FRP Pipe, Chem. Eng., May
2006, pp. 42-48.
4. Robert, J., Selecting Materials of Construction,
Chem. Eng., September 2005, pp. 6062.
Department Editor: Rebekkah Marshall
Heat Transfer
Fluids and Systems
STARTUP
1. Verifycontrolandsafetysystems:Itisvitallyim-
portant to verify all control and safety systems
arecalibratedandreadyforoperationandare
functioningproperly
2.Checkforleakage
3.Remove moisture from the system, using dry,
compressedairorothersuitablemeans.Fillthe
systemwithheattransferfluid
4.Systemfilling
a. Fillthesystemtodesiredlevelavoidingany
unnecessaryaerationofthefluid
b. Openallvalves,thenstartthemaincircula-
tionpumpinaccordancewiththemanufac-
turers recommendations. Allow for thermal
expansion of fluid in determining the cold
chargelevel
c. Circulate the heat transfer fluid through the
systemforabout3to4hourstoeliminateair
pockets, and to assure complete system fill
beforefiringtheheater
5. Starttheheater
a. Bringthesystemuptotemperatureslowlyto
help prevent thermal shock to heater tubes,
tube/heater joints and refractory materials;
and allow operators to check the function-
ing of instruments and controls. The slow
heat-up will also allow moisture trapped in
allsectionsofthesystemtoescapeasvapor.
Inertgasshouldsweeptheexpansiontankto
removenoncondensablesandresidualmois-
turetoasafelocation.Holdthetemperature
stableabove100C(212F)untilnosigns
of moisture remain (knocking or rattling of
pipes,nomoisturefromvents,andsoon)
b. Bring the system to operating temperature,
puttheusersonline,andplacetheexpan-
sion-tankinertingsystemintooperation
c.Thefluidshouldgenerallybeanalyzedwithin
24hofplantstartupandannuallythereafter
d.Checkandcleanstartupstrainersasneeded
The system should be heated and cooled for at
least two cycles with the filter in place since the
resultingexpansionandcontractionwillloosenmill
scale. Reinsulate any surfaces left bare for leak-
checkingpurposes.
OPERATIONS
Heaters: Proper fluid-heater operation will help
ensurelonglifeofthefluid.Commonheaterprob-
lems include flame impingement, excessive heat
flux,controlovershoot,lowfluidflow,andinterlock
malfunctions.
Piping and pumps: Aleak-freesystemwillhelpto
ensuresafeandreliableoperation.Somekeyfea-
turesofaleak-freedesignareasfollows:
Maintainvalvesandpumppackingandseals
Avoid the use of threaded fittings (welded or
flangedconnectionsarepreferred)
Realignpumpsandretorqueflangesoncesys-
temachievesoperatingtemperatureafterinitial
systemstartup
Confirmwithyourfluidsupplierwhattheproper
elastomersare.Notallelastomersarecompat-
iblewithallheattransferfluids
FLUID ANALYSIS
Fluid testing helps detect system malfunction, fluid contamination, moisture, thermal
degradation, as well as other factors that impact system performance (see Table). For
systemsoperatingnearthefluidsmaximumtemperature,annualanalysisissuggested.
Possible actions
1. Filtration: Small diameter particles sus-
pended in heat transfer fluid can be ef-
fectivelyremovedviafiltration.Filterswith
100-mmorlessnominal-particle-removal
ratings should be considered for initial
system treatment. Continuous filtration
through10-mmratedfilterscanmaintain
systemcleanliness
2. Venting: Iflowboilerconcentrationand/
ormoistureisallowedtoreachexcessive
levelsinthefluid,problemssuchaspump
cavitation,increasedsystempressureand
flash-pointdepressioncanoccur.Intermit-
tent,controlledventingtoasafelocation
isacommonsolutiontominimizethepo-
tential for problems caused by excessive
lowboilerormoistureconcentration
3. Inerting: Aneffectivemethodofminimiz-
ing fluid oxidation is to blanket the ex-
pansiontankwithaclean,dry,inertgas,
suchasnitrogen,CO
2
,ornaturalgas
4. Dilution/replacement: Canbeusedtore-
movesomefraction(orall)ofthefluidand
replace with virgin fluid to maintain fluid
propertieswithinnormalranges.Caution
is advised when using reclaimed fluid,
which can return degradation products
and/orcontaminantsintothesystem
5. Cleaning: If a system flush is necessary,
several different methods are available.
Specialty-engineered, heat-transfer flush
fluids may be used to remove sludge or
tar from piping/equipment. Hard car-
bondepositsonheatersurfaces(coke)
generally require the use of mechanical
cleaning techniques like sand or bead
Test result Potential effects Possible cause Possible
actions*
Viscosity
increase
Poor heat-transfer rate, de-
posits, high vapor pressure,
pump cavitation
Contamination
Thermal degradation
Fluid oxidation
4, 5
4, 5
3, 4
Total acid
number
increase
System corrosion,
deposits
Severe oxidation
Acidic contamination
3, 4
4, 5
Moisture
increase
Corrosion, excess system
pressure, pump cavitation,
mechanical knocking
System leaks
Residual moisture in
new or cleaned unit
Unprotected vent or
storage
2
2
2, 3
Insoluble
solids
increase
Poor heat transfer, wear of
pump seals, plugging in
narrow passages
Contamination
Dirt
Corrosion
Oxidation
Thermal stress
1, 4, 5
1, 4
1, 3, 5
1, 3
1, 4
Low- and
high-boiler
increase**
Pump cavitation, poor heat
transfer, excess system
pressure, deposits
Low boilers
High boilers
Contamination
2
4
4, 5
* For detailed guidance on actions, please consult with your fluid engineering specialist.
** For an excellent discussion on low and high boilers, please consult Ref. [4].
blasting,wirebrushing,orhigh-pressure
waterjetting.Forprocesscontamination,
consult with your fluid supplier for sug-
gestedcleaningmethods
SHUTDOWN
Preventoverheatingoffluidduetoresidual
heatintheheater.
1. Shutoffburnercompletelywiththecircu-
lating pump still operating. Continue to
runthepumpatfullcapacitytodissipate
residualheatintheheater
2. Whentheheaterhascooledtothemanu-
facturersrecommendedlowtemperature,
shutoffthecirculatingpumpandswitch
offrequiredheaterelectricalcontrols
3.Caution must be exercised during shut-
downtoensurethatnoareainthesys-
tempipingistotallyandcompletelyiso-
lated. This will prevent a vacuum from
forming,whichcoulddamage(implode)
equipment
4. Operateheattracing,ifneeded
References and further reading
1.Gamble, C.E., Cost Management in Heat
TransferSystems,Chem. Eng. Prog.,July2006
pp.2226.
2. Gamble,C.E.,CleaningOrganicHeatTransfer
FluidSystems,Process Heating,Oct.2002.
3. Beain, others, Properly Clean Out Your Or-
ganicHeatTransferFluidSystem,Chem. Eng.
Prog.,May2001.
4. Spurlin,others,DefiningThermalStability,Pro-
cess Heating,Nov.2000.
5. LiquidPhaseDesignGuide,Pub#7239128C,
Solutia,Inc.,1999.
Facts at Your Fingertips SponSored by
Department Editor: Kate Torzewski
Pristine
Processing
Equipment
P
rocesses in the pharmaceutical, biotechnology, food and semiconductor industries must
meet a high set of standards to ensure high product purity. Equipment criteria specifc to
high-purity processes are established to minimize contamination and maintain prod-
uct integrity. In designing a pristine process, material and equipment style are of upmost
importance. Bacteria is the main cause of contamination and is prone to growing in the dead
cavities of equipment created by sharp corners, crevices, seams and rough surfaces. Another
source of contamination is leaking, which allows undesirable chemicals to compromise the
quality of the process ingredients, by causing contamination, rusting and particle generation.
MATERIALS OF CONSTRUCTION
Many factors must be taken into consideration when selecting materials of construction for
use in pristine process applications where high-purity and sanitation are paramount. All sur-
faces should be constructed of a smooth material that will not corrode, generate particles
or harbor dead cavities. These criteria can be met with three standard materials: 316L
stainless steel (SS), polyvinylidene fuoride (PVDF) and polytetrafuoroethylene (PTFE). The
advantages and disadvantages of these materials are summarized below to facilitate the
material selection process for a given application with consideration of chemical compat-
ibility, cost, and temperature stability.
Valves
Valves should not harbor contaminants and
must be easy to clean. By these criteria,
diaphragm and pinch valves are excellent
choices for ultrapure processes, as they
have smooth, gently curved surfaces that
will not harbor contaminants. Ball check,
full-port plug and full-port ball valves are
good choices as well, while butterfy, spring
check, gate and swing check valves are all
unacceptable, since contamination can col-
lect in the corners that are essential to their
design. Though several valves are appropri-
ate for pristine processes, certain valves
are better suited for particular applications.
Diaphragm valves are the most widely used
in high-purity systems for their resistance
to contamination and ability to be used as
a control valve. Ball and plug valves, on
the other hand, are less costly and are not
limited by temperature and pressure. Also,
in applications using sterile steam and
freeze-drying, ball valves are preferred over
diaphragm valves because they eliminate
the risk of catastrophic seat failure.
Seals
As with all pristine processing equipment,
high-purity seals should not have any
cavities where contaminants can breed. By
choosing a seal with gland rings that do not
need to be threaded or ported, the areas
where bacteria can breed are minimized. In
choosing a seal material, it is important to
fnd a compound that will not swell, crack,
pit or fake, thus reducing seal failure and
contamination. To ensure the success of
seals, furoelastomers are a top choice in
pristine processing applications for their ex-
cellent thermal stability, chemical resistance
and mechanical durability.
Piping
The surface of piping, as well as any wet-
ted equipment parts, should have a very
smooth surface. When 316 SS is being
used, electropolishing is a good method
for achieving an ultra-smooth fnish. Joining
methods should minimize crevices and dead
cavities, and all materials should be free of
biological degradable substances, leachable
substances, and glues and solvents that may
migrate into the product stream.
References
1. Smith, B., What Makes a Pump for High-Purity
Fluids?, Chem. Eng., pp. 8789, April 2002.
2. Schmidt, M., Selecting Clean Valves, Chem.
Eng., pp. 107111, June 2001.
3. Wulf, B., Pristine Processing: Designing Sanitary
Systems, Chem. Eng., pp. 7679, Nov. 1996.
4. Weeks, D. T. and Bennett, T., Specifying Equip-
ment for High-Purity Process Flow, Chem. Eng.,
pp. 2730, Aug. 2006.
EQUIPMENT STYLE SELECTION
Critical factors in high-purity equipment selection include cleanability, cost, fow capabili-
ties and product compatibility. With these considerations in mind, criteria useful for choos-
ing pumps, valves, seals and piping are described in this section.
Pumps
A fundamental requirement of pristine processing pumps is the ability to clean a pump in
place without disassembly. Pump seals, gaskets and internal surfaces should eliminate the
buildup of material and should clean out easily during wash cycles. The most common pump
styles for high-purity processes are centrifugal, lobe-style and peristaltic pumps, which are
outlined below.
MATERIALS OF CONSTRUCTION
Material Advantages Disadvantages
Stainless
Steel
Mechanical strength
Functions at 121C
(steam-sterilization temperature)
Vulnerability to corrosion by
certain chemicals, which
increases with temperature
PVDF
Chemically inert
Resistant to corrosion and leaching
Durable and long-lasting
Retains circumferential strength
Functions only intermittently
at 121C
PTFE
The most chemically inert plastic
Resistant to corrosion and leaching
Avoids leaching
Suitable for coating equipment
Complex shapes are
diffcult to form
PUMPS
Pump
style
Advantages Disadvantages
Applications best
suited for this style
Centrifugal
Low cost
Easy cleanability
Effciency and fow de-
crease with increasing
pressure and volume
Handling low-
viscosity products
Handling high fowrates
(401,500 gal/min)
Peristaltics
Low cost
Easy cleanability
No mechanical
seals
Non-damaging to
delicate products
The need for hoses may
cause issues in elastomeric
compatibility, temperature
and pressure limitations,
and a need to change
hose regularly
Small, batch-oriented
applications
Laboratory or pilot-
scale plants
Rotary
Lobes
Higher pressure
and fow
capabilities
Unaffected by
pressure variations
High cost
Large, continuous
duty applications
Steaming and high
pressure applications
Department Editor: Kate Torzewski
Pump Selection
and Specifcation
PUMP SELECTION
I
n choosing a pump, it is important to match a pumps capabili-
ties with system requirements and the characteristics of the liquid
being processed. These factors include the inlet conditions,
required fowrate, differential pressure and liquid characteristics.
Generally, the quality of the liquid should remain unchanged after
passage through a pump. Therefore, material compatibility, viscos-
ity, shear sensitivity and the presence of particulate matter in a
liquid are important considerations in pump selection.
Most engineering applications employ either centrifugal or
positive displacement (PD) pumps for fuid handling. These pumps
function in very different ways, so pump selection should be based
on the unique conditions of a process.
Centrifugal pumps
The most widely used pump in the chemical process industries for
liquid transfer is the centrifugal pump. Available in a wide range of
sizes and capacities, these pumps are suitable for a wide range of
applications. Advantages of the centrifugal style include: simplic-
ity, low initial cost, uniform fow, small footprint, low maintenance
expense and quiet operation.
Positive displacement pumps
Though engineers may be frst inclined to install centrifugal pumps,
many applications dictate the need for PD pumps. Because of their
mechanical design and ability to create fow from a pressure input,
PD pumps provide a high effciency under most conditions, thus
reducing energy use and operation costs.
Choosing centrifugal versus positive displacement
These two main pump styles respond very differently to various
operating conditions, so it is essential to evaluate the requirements
of a process prior to choosing an appropriate pump. Table 1 il-
lustrates the mechanical differences between these pumps, as well
as the effects of pressure, viscosity and inlet conditions on fowrate
and pump effciency.
Range of operation
Pump styles range far beyond simply PD and centrifugal pumps.
PD pumps encompass many specifc styles, including a variety of
reciprocating, rotary and blow-cover pumps. Likewise, centrifugal
pumps encompass radial, mixed, and axial fow styles, which all
belong to a greater category of kinetic pumps.
A simple way to narrow down pump styles is to determine the
required capacity that your pump must handle. Based upon a
required capacity in gal/min. and a pressure in lb
f
/in.
2
, the pump
coverage chart below can help engineers focus their selection to a
just a few pump styles.
PUMP SPECIfICaTIONS
Based on the application in which a pump will be used, the pump
type, and service and operating conditions, the specifcations of a
pump can be determined.
Casting connection: Volute casing effciently converts velocity en-
ergy impacted to the liquid from the impeller into pressure energy.
A casing with guide vanes reduce loses and improve effciency
over a wide range of capacities, and are best for multistage high-
head pumps
Impeller details: Closed-type impellers are most effcient. Open-
type impellers are best for viscous liquids, liquids containing solid
matter, and general purposes
Sealings: Rotating shafts must have proper sealing methods to
prevent leakage without affecting process effciency negatively.
Seals can be grouped into the categories of noncontacting seals
and mechanical face seals. Noncontacting seals are often used
for gas service in high-speed rotating equipment. Mechanical face
seals provide excellent sealing for high leakage protection
Bearings: Factors to take into consideration while choosing a
bearing type include shaft-speed range, maximum tolerable shaft
misalignment, critical-speed analysis, loading of compressor
impellers, and more. Bearing styles include: cylindrical bore; cy-
lindrical bore with dammed groove; lemon bore; three lobe; offset
halves; tilting pad; plain washer; and taper land
Materials: Pump material is often stainless steel. Material should
be chosen to reduce costs and maintain personnel safety while
avoiding materials that will react with the process liquid to create
corrosion, erosion or liquid contamination
References
1. Perrys Chemical Engineers Handbook, 7th ed. New York: McGraw
Hill, 1997.
2. Petersen, J. and Jacoby, Rodger. Selecting a Positive Displacement Pump,
Chem. Eng. August 2007, pp. 4246.
PumP ComParison Chart
Centrifugal
Pump
Positive displacement
pump
Mechanics
The pump imparts a
velocity to the liquid,
resulting in a pressure
at the outlet.
Pressure is created
and flow results
The pump captures
confined amounts of
liquid and transfers
them from the suction
to discharge port.
Flow is created and
pressure results
Performance
Flow varies with
changing pressure
Flow is constant with
changing pressure
Viscosity
Efficiency decreases
with increasing viscosity
Efficiency increases with
increasing viscosity
Efficiency
Efficiency peaks at the
best-of-efficiency point.
At higher or
lower pressures,
efficiency decreases
Efficiency increases
with increasing pressure
Inlet
conditions
Liquid must be in the
pump to create a pres-
sure differential. A dry
pump will not prime on
its own
Negative pressure is
created at the inlet port.
A dry pump will prime
on its own
100
5
2
2 5 10 1 2 5 100
Capacity, gaI/min
2 5 1,000 2
10
100
1,000
10,000
510,000
1,000
5
2
H
e
a
d
,

f
t

o
f

I
i
q
u
i
d
P
r
e
s
s
u
r
e
,

I
b
f
/
i
n
2
10,000
5
2
10
Metering - pIunger
Metering - diaphragm
Screw
Regenerative
CentrifugaI -singIe stage, singIe suction
CentrifugaI -muItistage
CentrifugaI -doubIe suction
Gear Direct-acting steam
MuIticyIinder AxiaI fIow
Adapted from Perrys Chemical Engineers Handbook
Department Editor: Kate Torzewski
Avoiding
Seal Failure
S
eals are assemblies of elements that prevent
the passage of a solid, liquid, gas or vapor
from one system to another. When a seal
allows leakage of material, failure has occurred.
This guide provides an overview of common seal
types and a discussion of seal failure to aid in
choosing the most effective seal and avoiding
future failure.
seal types
Seals types can be classifed within two broad
categories: static and dynamic. Static seals have
no relative motion between mating surfaces, while
dynamic seals do have relative motion between
a moving surface and a stationary surface. Seals
do not have to ft into one category or the other;
rather, seal types can fall anywhere on a spectrum
between static and dynamic, and few seals are
strictly one type or the other. Table 1 describes the
applications and requirements of several common
seal types.
seal failure
Seal failure is caused by a wide variety of circumstances, including improper in-
stallation and environmental factors such as temperature, pressure, fuid incompat-
ibilities, time and human factors.
Most causes of failure can be described as mechanical diffculties or system
operations problems. Examples of mechanical diffculties include strain on the
seal face caused by improper installation and vibration caused by improper net
positive suction head. Meanwhile, system operating problems can include condi-
tions that are outside of a pumps best performance envelope, such as upsets, dry
running, and pressure or temperature fuctuations. Changes in the fuid being pro-
cessed can cause problems as well, especially with fuids that fash or carbonize.
Common visual indicators of failure include short cuts, V-shaped notches in the
seal, skinned surface in localized areas, or thin, peeled-away area on the seal.
Table 2 describes causes of some of the most prevalent types of seal failure with
recommended methods of action.
In some cases, the cause of failure may be diffcult to determine due to the com-
plexity of the seal construction. These unique failure modes can result in faking or
peeling of the seal face, corrosion, faking or pitting of the carbon faces, degrada-
tion of the elastomer energizer seals, and spring or bellows breakage. It is likely
that these rapid degradations are a result of contamination, which can be avoided
with careful installation or using pre-assembled, cartridge-type mechanical seals.
References
1. Ashby, D. M. Diagnos-
ing Common Causes of
Sealing Failure, Chem.
Eng. June 2005, pp.
4145.
2. Netzel, J., Volden,
D., Crane, J. Suitable
Seals Lower the Cost
of Ownership, Chem.
Eng. December 1998,
pp. 9296.
TABLE 1. COMPARISON OF COMMON SEAL TYPES
Type Applications Periodic
Adjustment
Required?
Moving
friction
Tolerances
required (mov-
ing seals)
Gland
adapters
required?
Space
require-
ments
Static Dynamic
O-ring X X No Medium Close No Small
T-seal X X No Medium Fairly close No Small
U-packing X No Low Close No Small
V-packing X Yes Medium Fairly close Yes Small
Cup-type pack-
ing
X No Medium Close Yes Medium
Flat gasket X Yes No Large
Compression or
jam packing
X X Yes High Fairly close Yes Large
TABLE 2. SOLUTIONS TO COMMON CAUSES OF SEAL FAILURE
Failure type Definition Causes Solutions
Compression
set
A lost of resiliency caused by the
failure of a seal to rebound after it has
been deformed for some period of
time. The seal will exhibit a fattened
surface corresponding to the contours
of the mating hardware
Exposure to excessive tempera-
ture or incompatible fuids
Excessive deformation of the
elastomer at installation
An incompletely vulcanized seal
Choose proper defection for the seal
Choose appropriate elastomer mate-
rial for the application in terms of
thermal stability and compression set
resistance
Nibbling and
extrusion
A seal starts to appear to be torn
away in little pieces until it loses its
overall shape and fows into whatever
void area is available
Excessive clearance gaps
Improper seal material
Excessive volume-to-void ratio
Inconsistent clearance gaps
Increase bulk hardness of the sealing
element
Decrease clearance gaps
Redesign volume-to-void ratio
Add anti-extrusion devices
Spiral failure A seal rolls within its gland, resulting
in cuts or marks that spiral around the
circumference of the seal
Applications where a seal is
used in a slow, reciprocating
fashion
Irregular surface over the mating
parts causing the seal to grip to
certain contact points
Use an elastomer with a higher bulk
hardness
For male-type installation, increase the
installed stretch on the seal
Specify a smoother, more uniform fn-
ish on mating hardware
Change the type of seal to a lip-type
confguration
Explosive
decompres-
sion
Seal exhibits blisters, fssure, pock
marks or pits, both externally and
internally
Gas entrapment within the
elastomer during high-pres-
sure cycling, followed by rapid
depressurization
Use an elastomer material that is more
resilient to explosive decompression
Use polymeric or metal seals if
0possible
Wear Smooth burnishing of a sealing
surface
Relative motion of the seal
against the mating surface
Use a harder material
Use a polymeric solution