Facts at Your Fingertips

Gu idebo o k January-December 2016

29215
Table of Contents
Chemical Engineering’s Facts At Your Fingertips package includes a series of twelve condensed,
one-page reference cards that provide useful rules of thumb, common equations and other
practical tips for designing, operating and maintaining chemical process equipment.

The topics covered in 2016 include the following:

Process Hazards Analysis Methods........................................................................................................................................ 3

Weighing Equipment Selection............................................................................................................................................. 4

Particle-Sizing Technology Selection.................................................................................................................................... 5

Organic Chemical Functional Groups................................................................................................................................... 6

Insulating Heat-Transfer-Fluid Piping................................................................................................................................... 7

Key Reactions for the Petrochemical Industry................................................................................................................... 8

Industrial Gas Burners................................................................................................................................................................. 9

Distillation Column Design Factors.....................................................................................................................................10

pH Measurement in Industrial Waters............................................................................................................................... 11

Agglomeration Processes....................................................................................................................................................... 12

Sampling for Internal Corrosion............................................................................................................................................13

Solid-Liquid Separation: Classification, Design and Testing.......................................................................................14

 Facts At Your Fingertips
Process Hazards Analysis Methods
Department Editor: Scott Jenkins
D
ifferent methodologies are
available for conducting the
structured reviews known as
process hazards analyses (PHAs) for
new processes. PHAs are often con-
ducted or moderated by specialists,
with participation by the design team,
representatives of the facility owner,
and experienced process operators.
Each different PHA method is bet-
ter-suited to a specific purpose and
should be applied at different stag-
es of the project development. The
table includes brief descriptions of
some of the most widely used PHA
methods in the chemical process in-
dustries (CPI).
When to use different methods
Different types of PHA studies have
varying impact, depending on the de-
sign phase in which they are applied.
For example, if a consequence analy-
sis is not performed in a conceptual
or pre-FEED (front-end engineering
and design) phase, important plot-
plan considerations can be missed,
such as the need to own more land
to avoid effects on public spaces; or
the fact that the location might have a
different elevation with respect to sea
level than surrounding public places
impacted by a flare plume.
Some other studies, like HAZOP,
cannot be developed without a con-
trol philosophy or piping and instru-
mentation diagrams (P&IDs), and are
performed at the end of the FEED
stage or at the end of the detailed
engineering phase (or for improved
results, at the end of both) to define
and validate the location of pressure
safety valves (PSVs) as well as to
validate other process controls and
instrument safety requirements.
QRA or LOPA evaluations (or both)
are undertaken after the HAZOP study
to validate siting and define safety in-
tegrity levels (SIL), to finally meet the
level required by the plant. n (BLEVE). The results of this study are usually shown on top of the plot plan
Editor’s note: The definitions in the table, and associated
comments, were adapted from the following article: Giar-
dinella, S., Baumeister, A. and Marchetti, M. Engineering for
Plant Safety. Chem. Eng., August 2015, pp. 50–58. An ad-
ditional reference is the following article: Wong, A., Guillard,
P. and Hyatt, N. Getting the Most Out of HAZOP Analysis,
Chem. Eng., August 1, 2004, pp. 55–58.
34
Table: Different PHA methods and Approaches
Method Description
Consequence analysis This method quantitatively assesses the consequences of hazardous material
releases. Release rates are calculated for the worst case and also for alterna-
tive scenarios. Toxicological endpoints are defined, and possible release dura-
tion is determined
Hazard identification HAZID is a preliminary study that is performed in early project stages when
analysis (HAZID) potentially hazardous materials, general process information, initial flow diagram
and plant location are known. HAZID is also generally used later on to perform
other hazard studies and to design the preliminary piping and instrumentation
diagrams (P&IDs)
What-if method The what-if method is a brainstorming technique that uses questions starting
with “What if...,” such as “What if the pump stops running” or “What if the op-
erator opens or closes a certain valve?” For best results, these analyses should
be held by experienced staff to be able to foresee possible failures and identify
design alternatives to avoid them
Hazard and operability The HAZOP technique has been a standard since the 1960s in the chemical,
study (HAZOP) petroleum refining and oil-and-gas industries. It is based on the assumption
that there will be no hazard if the plant is operated within the design param-
eters, and analyzes deviations of the design variables that might lead to unde-
sirable consequences for people, equipment, environment, plant operations or
company image.
If a deviation is plausible, its consequences and probability of occurrence
are then studied by the HAZOP team. Usually an external company is hired to
interact with the operator company and the engineering company to perform
this study. There are at least two methods using matrices to evaluate the risk
(R): one evaluates consequence level (C) times frequency (F) of occurrence;
and the other incorporates exposition (E) as a time value and probability (P)
ranging from practically impossible to almost sure to happen. In this method,
the risk is found by the following equation: R = E × P × C
Layer-of-protection The LOPA method analyzes the probability of failure of independent protection
analysis (LOPA). layers (IPLs) in the event of a scenario previously studied in a quantitative hazard
evaluation like a HAZOP. LOPA is used when a plant uses instrumentation inde-
pendent from operation, safety instrumented systems (SIS) to assure a certain
safety integrity level (SIL). The study uses a fault tree to study the probability of
failure on demand (PFD) and assigns a required SIL to a specific instrumentation
node. For example, in petroleum refineries, most companies will maintain a SIL
equal to or less than 2 (average probability of failure on demand ≥10−3 to <10−2),
and a nuclear plant will tolerate a SIL 4 (average probability of failure on demand
≥10−5 to <10−4)
Fault-tree analysis Fault-tree analysis is a deductive technique that uses Boolean logic symbols (that
is, AND or OR gates) to break down the causes of a top event into basic equip-
ment failures or human errors. The immediate causes of the top event are called
“fault causes.” The resulting fault-tree model displays the logical relationship
between the basic events and the selected top event
Quantitative risk assess- QRA is the systematic development of numerical estimates of the expected
ment (QRA) frequency and consequence of potential accidents based on engineering
evaluation and mathematical techniques. The numerical estimates can vary
from simple values of probability or frequency of an event occurring based on
relevant historical data of the industry or other available data, to very detailed
frequency modeling techniques. The events studied are the release of a haz-
ardous or toxic material, explosions or boiling-liquid expanded-vapor explosion
Failure mode and effects This method evaluates the ways in which equipment fails and the system’s re-
analysis (FMEA) sponse to the failure. The focus of the FMEA is on single equipment failures and
system failures
Chemical Engineering www.chemengonline.com january 2016
Facts At Your Fingertips
Weighing Equipment Selection
Department Editor: Scott Jenkins

T
he number of options available sensitive internal electronics, and also Table 2. Regulations and Standards
for scales and weighing equip- to ensure greater accuracy. Websites
ment can make it difficult to de- 3. Accuracy. In the context of weigh- FM Global www.fmglobal.com
termine which instruments will offer ing, accuracy can be thought of as a ATEX ec.europa.eu/enterprise/atex
HACCP www.fda.gov/food/GuidanceRegula-
the best value and which will meet the combination of several different fac- tion/HACCP/default.htm
application requirements (Table 1). tors, including the quantifiable speci- IEC www.iec.ch
Focusing on the following ten areas fications of resolution (the smallest ISO www.iso.org
can help reduce the time needed to mass change that can be read on a NEMA www.nema.org
research available models and help scale), reproducibility (ability to weigh NTEP www.ncwm.net/ntep
ensure a good value. consistently over time and with differ- UL/CUL www.ul.com
ent operators), linearity (the variance in ETL www.intertek-etlsemko.com
CSA www.csa-international.org
1. Primary use. Identifying the instru- accuracy over the weight values within
ment’s primary use is the first step in the scale’s capacity) and uncertainty
selection. Will the instrument be used of measurement (difference between 7. Features. Additional features can
for weighing solids or liquids? Will the measured weight and true weight due customize the scale for enhanced flex-
device be used at laboratory scale, to environmental variances). ibility, ease of use, functionality, pro-
or larger? Is it needed to weigh large 4. Materials of construction. Basic tection and others. Consider whether
quantities of uniformly sized objects, materials include aluminum alloy, car- your scale would need explosion pro-
such as capsules, tablets or small bon steel, aluminum-coated steel and tection, internal calibration software,
parts? Will the instrument be used for galvanized steel. For these, cleanliness interfacing ability with a computer
weighing moving items on a produc- and corrosion-resistance are not criti- network, wireless connectivity, scale
tion line? Do you need to control con- cal. When higher levels of cleanability readouts that are separated from the
ditions inside a weighing vessel, such and chemical and environmental pro- weighing platform, multi-language
as heating, cooling or mixing? tection are required, AISI-304 and 316 displays, backlit display for dimly lit
2. Capacity. What is the largest possi- stainless steels are possibilities. areas, or other needs.
ble load that a scale would be required 5. Environment. Environmental con- 8. Price. Choosing a scale should
to handle? Do you need overload pro- ditions can affect weighing. Large never be based solely on price, but
tection? What will the overall footprint temperature fluctuations, vibration, the most expensive scale is not nec-
of the scale be and how will the items humidity, magnetic fields, air currents, essarily the best choice.
being weighed fit within the weighing corrosive chemicals and electrical 9. Installation. When installing, it is rec-
area? Would a below-balance setup, interference can all influence weight ommended to place scales in a perma-
where weight is measured via tension measurements, especially at higher nent location and connect to peripheral
instead of compression, work for your resolutions. Consider whether a par- equipment, including a remote display.
application? An unofficial guideline ticular environment would require The resolution and readability should be
recommends use of a balance for specialized padding, protective cov- set, and an initial calibration should be
samples from microgram levels to ap- ers, or more frequent calibrations. performed. For multiple load cells on a
proximately 10 kg, and load cells for 6. Industry regulations. Many indus- large vessel, a corner load test should
those samples from 10 kg to several try-specific regulations exist and may be performed to ensure even weight
metric tons. Try to have the weighed be relevant for some sectors and not distribution. Scales should generally not
quantities lie mostly in the middle of others. Table 2 contains a list of web- be moved from their point of use after
the range of the unit’s specific capac- sites for several of the organizations installation, if possible.
ity to minimize stress or damage to that set standards and regulations. 10. Calibration and service. Regu-
larly scheduled calibration of weighing
Table 1. Instrument categories equipment is necessary, because with
Simple An appropriate vessel is placed on a weighing pan, the scale is tared accordingly, and a solid use, normal stress can cause the ac-
scale or liquid sample is placed into the vessel curacy of a scale to drift slightly. A se-
Counting A small known quantity of pieces is placed on the weighing pan. The scale calculates the av-
scale erage weight of these pieces and stores it in memory. Subsequent unknown quantities of the ries of certified test weights are placed
object are instantly calculated using this average weight no matter how many are placed on on the weighing platform and the re-
the pan. Results can be stored or printed for use in record-keeping and other documentation sults recorded. When displayed results
Check- A checkweigher is the best scale for weighing moving items on a production line, where do not correspond to the test weight,
weigher speed or the need for 100% inspection prohibits manual weighing. The device weighs each
item on the production line according to preset detection limits, ejecting non-compliant items manual or automatic adjustments can
and even sorting items based on programmed user criteria. As each unit is inspected, over- be made to correct the drift. n
filled and underfilled packages are identified and can be quickly rejected
Batch Scales designed for batch weighing incorporate a load cell, connections, valves, relay hard- Editor's note: This column is adapted from the following
weighing ware and process-control software into one integrated system. This system is connected article: Titmas, R. and Carey, S., Weighing Your Options:
systems to and controls one or more feed systems that deliver different ingredients into a common The 10 Most Important Scale Considerations. Chem. Eng.,
receiving vessel at user-defined quantities to blend or create a reaction December 2007, pp. 61–65.

Chemical Engineering www.chemengonline.com February 2016 35

 Facts At Your Fingertips
Particle-sizing technology selection
Department Editor: Scott Jenkins
T
his column summariz-
es the strengths and Technique
limitations of some
widely used industrial parti- Laser diffraction
cle-analysis techniques. Dynamic light scattering
Electrophoretic light scattering
Automated imaging
Sieving Sedimentation
Sieving determines particle- Electrozone sensing
size distributions by mea- Sieving
suring the mass of material
that passes through progressively finer
meshes.The measurement range for
sieving is about 100 µm to 10 mm.
Key advantages. Sieving is a well-
established technology and forms the
original specification for many prod-
ucts. Further, relative to other tech-
niques, it is simple, inexpensive, easy
to use and requires little training.
Limitations. Results are prone to
operator-to-operator variability, and
measurement times are relatively long
(5–10 minutes). The measurement
resolution can be poor, as the num-
ber of size classes are few and wide
(defined by the number of sieves in
the stack), leaving the technique blind
to subtle differences in particles. Mea-
surements become more problematic
for finer particles because they tend
to agglomerate, causing sieve-block-
ing and, possibly measuring agglom-
erates, rather than primary particle
size. Rigorous sieve examination and
maintenance is essential for data in-
tegrity, but is time-intensive.
Most common uses. Uses include
quality assurance (QA) and quality
control (QC) across the solids-han-
dling industries, most often in sectors
where profit margins are tight.
Laser diffraction
Laser diffraction generates particle-
size distributions from measurements
of the angular variation in intensity of
light scattered by a dispersed sample
when it passes through a laser beam.
The measurement range for laser dif-
fraction is about 0.01 µm to 3.5 mm.
Key advantages. Laser diffraction
measurements take less than a min-
ute. Calibration is not necessary, and
with a modern system, routine main-
tenance requirements are minimal.
Full automation reduces manual input
46
Table 1. Characteristics of Particle-Sizing Techniques
Size Shape Zeta Dynamic Rapid Resolution Sampling Wet Dry
potential range
l llll lll ll lll l l
l lll lll ll ll l
l lll lll ll ll l
l l ll ll lll ll l l
l ll l ll ll l
l l ll lll l l
l l l l l l l
to a minimum and at the same time, equipment costs are relatively high.
increases repeatability and reproduc- Most common uses. Uses include
ibility. Laser diffraction reports over product development, QC and pro-
100 class sizes, providing good reso- cess troubleshooting, when size data
lution for detection of particle-size- alone is insufficient, and in the devel-
distribution changes. Robust process opment of particle-sizing methods.
analyzers, for inline and online use,
enable application of the technique Dynamic light scattering
from laboratory to process line, and Dynamic light scattering (DLS) deter-
for automated process control. mines the diffusion speed of particles
Limitations. Samples must be di- moving under Brownian motion from
luted for analysis, which may cause measurements of light scattering in-
particle-size changes (dilution shock). tensity, and converts this to a particle-
The size-distribution calculation as- size distribution using the Stokes-Ein-
sumes the measured particles are stein relationship. The measurement
spherical, so the results can be af- range is about 0.3 nm to 10 µm.
fected by changes in particle shape. Key advantages. DLS is non-inva-
Most common uses. The technique sive, allows complete sample recov-
is used as an alternative to tradi- ery and offers fast, automated, high
tional manual methods in industries throughput analysis. Required sam-
from cement to pharmaceuticals, to ple volumes are very small (as little as
accelerate R&D, enhance product 12µL) and with modern systems that
quality, and to support automated incorporate backscatter technology,
process control. samples can be measured over a
wide range of concentrations. New
Imaging technology for online implementation
Automated imaging technology cap- is an important advance for process
tures images of individual particles, monitoring and automated control.
and uses these to calculate number- Limitations. Light scattering intensity
based particle size and shape distri- scales with particle size to the power
butions. The measurement range is of six, so large particles in a sample
about 0.5 µm to 1 mm. can dominate a result. Although the
Key advantages. Automated im- accessible size range is good, the
aging produces microscope-quality measurement resolution can be poor,
images of thousands of particles in especially when measuring polydis-
a few minutes. The added ability to perse (wide) size distributions.
quantify shape permits the efficient Most common uses. DLS is used in
and robust differentiation of particle R&D, because of its ability to measure
types in a sample, (for example, ag- at the nanoscale using small sample
glomerates from primary particles or volumes, but increasingly for process
contaminants from product particles). monitoring as particle-size specifica-
Compared with microscopy, imaging tions become finer, and for QC. Typical
is faster and less subjective. samples include proteins, polymers,
Limitations. Automated imaging, a emulsions and nanoparticles. n
laboratory technique, is slower than Editor's note: The material for this column was authored
by John Duffy, product marketing manager, Malvern Instru-
techniques like laser diffraction, and ments Ltd., (Malvern, U.K.; www.malvern.com).
Chemical Engineering www.chemengonline.com march 2016
 Facts At Your Fingertips
Organic Chemical Functional Groups
Department Editor: Scott Jenkins

Alkyne R — C = C — R| Sulfide S R and R' represent alkyl groups

R R|

Hydroxyl R — OH Alkene R H
C=C
H R|

Aldehyde O
Nitrile R—C=N
R H

Ketone O Thioester O
R|

R R| R S

Amine R R| R R| H H
N N N Acid anhydride O O

H R|| R R O R|
Secondary Tertiary Primary

Amide O Imine R||

C NH N
R|
R N R R| R R|
R||

Carboxylic Acid O Sulfone O O

S
=
=
R OH R R|

Ether O Thiol R — SH
R R
|

Ester O Acyl halide O

R| X = Cl, F, Br, I
R O R X

C
hemical functional groups are polymers, fragrances and more. presulfiding agents to prevent coke
critical determinants of the Amine. Derivatives of ammonia, formation in ethylene production and
properties and reactivity of amines are important biologically in petroleum refining to presulfide hy-
compounds. The following provides a (amino acids, neurotransmitters), as drodesulfurization catalysts.
review of the structures of common well as in industry. Aniline and etha- Alkene. Alkenes are building blocks
organic functional groups, along with nolamines are important in manufac- for plastics (polyethylene and poly-
some notes and examples. turing dyes, rubber, pharmaceuticals, propylene), among many other uses.
Alkyne. Acetylene is used as a fuel synthetic resins and more. Acid anhydride. Acetic anhydride is
for gas welding and a raw material for Carboxylic acid. Acetic acid, bu- used to prepare acetate esters, while
chemical manufacturing. tyric acid and fatty acids are among the cyclic molecule maleic anhydride,
Hydroxyl. Alcohols and phenols con- the important carboxylic acids. Fatty is widely used in industrial coatings.
tain this functional group, which is ca- acids are key components of many Imine. Imines are used as ligands in
pable of forming hydrogen bonds. soaps and detergents. organic chemistry
Aldehyde. Formaldehyde and ac- Ether. Diethyl ether is used as both a Sulfone. The sulfone sulfolane is used
etaldehyde are important industrial laboratory and industrial solvent and in the manufacturing process for BTX
building blocks used in resins, wood reagent, as well as an engine starting (benzene, toluene and xylenes).
adhesives and others. fluid and in smokeless gunpowder. Thiol. Methyl mercaptan is used as
Ketone. Acetone, cyclohexanone Ester. Esters are used in polymer an odorant to allow the detection of
and methylethyl ketone are impor- manufacturing, and are common in natural gas by smell.
tant ketones, used as solvents or in flavors and fragrances. Thioester. Thioesters appear as inter-
the manufacture of pharmaceuticals, Sulfide. Sulfides have been used as mediates in biochemical reactions. n
36 Chemical Engineering www.chemengonline.com april 2016
 Facts At Your Fingertips
Insulating Heat-Transfer-Fluid Piping
Department Editor: Scott Jenkins
H
eat-transfer-fluid (HTF) system
piping is insulated to reduce
heat loss and prevent worker
contact with hot surfaces. Insulated
piping minimizes the effects of chang-
es in ambient temperature to help en-
sure precise control of process tem-
perature. Proper design of the HTF
system and its insulation is required
to reduce the risk of fire as a result of
fluid leakage into insulation.
Types of insulation
The main insulation materials used
for HTF system piping are fiberglass,
mineral wool, calcium silicate and
cellular glass. Table 1 lists some im-
portant properties to consider when
choosing insulation.
Fiberglass and mineral wool are
fibrous materials produced in simi-
lar processes. Thermal conductiv-
ity is similarly low for both materials.
Calcium silicate insulation is formed
by drying a calcium silicate slurry
in a mold, yielding a material with a
slightly higher thermal conductiv-
ity than fiberglass or mineral wool.
These three materials have open, air-
filled channels, which can wick leak-
ing fluid into the insulation.
Cellular glass insulation is formed
by heating a glass powder mixture,
which melts and expands, leaving
tiny, sealed glass cells throughout the
material. It is impermeable to leaking
fluid and has a thermal conductivity
similar to calcium silicate.
Insulation design
Insulation should be installed to cover
all piping and other exposed surfaces
of the HTF system where heat loss
can occur. Free online calculators can
be used to determine required insula-
tion thickness for most processes.
Fire safety
Fires have occurred in insulation ma-
terials that have been soaked with or-
ganic heating fluids at apparent tem-
peratures of 500 to 600°F, which is
well below the autoignition tempera-
ture of most commercial HTFs. While
the exact mechanism by which such
fires occur is not fully understood, the
38
Table 1. Key Properties of Common piping INsulation types
Insulation type Temperature use range
Fiberglass 0 to 1,000°F (–18 to 538°C)
Mineral wool 0 to 1,400°F (–18 to 760°C)
Calcium silicate 80 to 1200°F (27 to 650°C)
Cellular glass –450 to 800°F (–268 to 427°C)
most probable explanation is that a
slow exothermic oxidation reaction
between hydrocarbon-type heating
fluids and the air inside the voids of
the insulation starts at about 500°F.
Such a reaction is believed to occur
for the following reasons:
• A large heating surface area
exists within the insulation
• Formation of low-flash-point
oxidation products, resulting
from exposure to air
• Temperatures can rise within
the saturated insulation mass
due to poor heat dissipation
conditions
Tests indicate that fiberglass, min-
eral wool and calcium silicate insula-
tions are more subject to this prob-
lem, since they can absorb large
amounts of leaking fluid with greater
surface area of liquid-air contact.
Cellular glass insulation resists
saturation by heat transfer fluid and,
therefore, may be a safer insulation to
use. Cellular glass normally is more
costly for most applications because
of its higher installation cost and its
tendency to crack when thermally
shocked. Cellular glass is suggested
for use around flanges and other ar-
eas where leaks are likely to occur,
while lower-cost insulation materials
may be used for pipe racks and all-
welded runs of piping.
Tips to reduce risk of fire
Install and maintain a leak-free piping
system when combustible heat-trans-
fer fluids are being used. Reduce the
number of flanges and incorporate
adequate flexibility of piping. Use sug-
gested piping specifications. If a leak
develops, remove the insulation and
contain and control the HTF until the
leak can be repaired.
On horizontal runs of pipe with
welded joints and proper flange fit-
tings, the standard high-temperature
insulation, such as calcium silicate or
Chemical Engineering www.chemengonline.com
Absorbent? Price
Yes Low
Yes Low
Yes Medium
No Medium
fiberglass and so on, may be used.
On vertical runs of lines of pipe
where occasional sources of leaks
can develop at flanges and valves,
install protective, tight-fitting caps
below flanges and valves to divert
any fluid leakage to the outside of
the insulation.
Install valve stems horizontally to
help avoid stem leakage from enter-
ing the insulation.
On those sections of lines where
greater numbers of control valves
and instrument fittings present high-
er leakage risk, install cellular glass
insulation or metal-shielded insula-
tion to minimize or eliminate any fluid
saturation of the insulation system.
Consult your company’s insulation
supplier and insurance company for
additional suggestions on reducing
fire hazards. n
References
1. “Systems Design Data,” Publication No. 7239193C,
Solutia Inc., subsidiary of Eastman Chemical Co.,
September 2002.
2. “Liquid Phase Design Guide,” Publication No. TF-04,
5/14, Eastman Chemical Co.
3. Controls Southeast Inc., “Insulation,” from www.csiheat.
com/csi_university/insulation.aspx, accessed January
2016.
Author
The content for this edition of “Facts at Your Fingertips” was
supplied by the Eastman technical support team. If you have
additional questions or comments, please email Eastman at:
team.therminol@eastman.com.
Disclaimer: Although the information and recommenda-
tions set forth herein are presented in good faith, Eastman
Chemical Co. and its subsidiar­ies make no representations
or warranties as to the completeness or accuracy thereof.
No representations or warranties, either express or implied,
or merchantability, fitness for a particular purpose or of
any other nature are made hereunder, and nothing herein
waives any of the seller’s conditions of sale. Eastman and
Therminol are trademarks of the Eastman Chemical Co. or
its subsidiaries.
Facts At Your Fingertips
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may 2016
 Facts At Your Fingertips
Key Reactions for the Petrochemical Industry
Department Editor: Scott Jenkins

A
handful of compounds derived rochemical intermediates include cal routes and reactions required to
from natural gas and crude synthesis gas, ethylene, propylene, manufacture these fundamental pet-
petroleum are converted into butadiene and BTX (benzene, toluene, rochemicals, as well as reactions for
a vast array of industrial petrochemi- xylenes). This one-page reference generating some of their immediate
cals. Starting materials for most pet- provides an overview of the chemi- chemical derivatives.
Petrochemical Starting materials and major products
Petrochemical Potential chemical routes and required reactions Reactions involved in the manufacture of immediate
derivatives
Synthesis gas Methane can be converted to synthesis gas by steam-methane reforming. Syngas is a crucial intermediate resource for the produc-
(syngas, a mixture 2CH4 + 3H2O ⇋ CO + CO2 + 7H2 (reaction occurs at temperatures between 700 tion of hydrogen, methanol and ammonia. For example,
of mainly H2 and and 1,100°C with a nickel-based catalyst) CO2 + 3H2 ⇋ CH3OH + H2O
CO)
The formation of syngas is strongly endothermic and requires high temperatures. Fischer-Tropsch (F-T) synthesis converts syngas into hy-
Steam reforming of natural gas occurs in externally heated tubular reactors. The drocarbons that can then be converted into liquid vehicle
process uses nickel catalysts on a special support that is resistant to the harsh pro- fuels, such as gasoline, diesel and jet fuel, as well as
cess conditions. Waste heat from the oven section is used to preheat gases and to chemicals such as olefins and waxes. A general repre-
produce steam. sentation of the F-T reaction is the following:
(2n + 1) H2 + nCO  CnH(2n+2) + nH2O
Coal, biomass or other hydrocarbons can be converted to syngas via gasification ac-
cording to the following reaction: Product distribution for F-T chemistry includes different-
3C (coal) + O2 + H2O  H2 + 3CO sized alkanes and alkenes, and to a lesser extent,
oxygenated products, such as alcohols. F-T catalysts are
Syngas can also be made via partial oxidation processes, in which a sub-stoichio- either based on cobalt or iron.
metric fuel-air mixture is partially combusted to yield a hydrogen-rich syngas.
Ethylene (C2H4; Ethylene is commercially produced by the steam cracking of a range of hydrocar- Ethanol: C2H4 + H2O (steam)  C2H5OH
H2C=CH2) bons, including ethane from natural gas and naphtha from crude oil. Naphtha is a
name given to petroleum distillates consisting of a mixture of straight-chained and Ethylene oxide (used to make ethylene glycol):
aliphatic hydrocarbons with five to nine carbons. C2H4 + air (O2 source)  C2H4O (in the presence of
Steam cracking is the uncatalyzed thermal decomposition of hydrocarbons at high silver catalyst)
temperatures using steam. In steam cracking, gaseous, saturated hydrocarbons are
broken down into smaller, often unsaturated, hydrocarbons at temperatures from Ethylene dichloride (1,2-dichloroethane; used to make
750–900°C. The partial pressures of the hydrocarbon feeds are kept low to prevent vinyl chloride):
polymerization and condensation reactions from occurring. Steam cracking is generally C2H4 + Cl2  C2H4Cl2 (ferric chloride catalyst)
used to manufacture lighter olefins, such as ethylene and propylene. Steam cracker
feeds can include naphtha, liquefied petroleum gas (LPG), ethane, propane and butane. Polyethylene (used to make plastic resins):
Steam-cracker product distributions can be controlled by changing the composi- C2H4  [–CH2–CH2–]n (using Ziegler-Natta catalyst at
tion of the feed material, the hydrocarbon-to-steam ratio, the cracking temperature pressures of 1,000 to 3,000 bars)
and furnace residence time. Cracking reactions generally take place via free-radical
mechanisms in which alkane carbon-carbon bonds break homolytically, forming Ethylbenzene (used to make styrene)
alkyl radicals, which can abstract hydrogen atoms. For example, in ethane cracking, C2H4 + C6H6  C6H5CH2CH3 (Lewis acids used as
hydrogen abstraction forms ethyl radicals, which undergo a unimolecular, free-radical catalyst)
decomposition to form C–C double bonds.
Initiation: C2H6  ·CH3 + ·CH3
Propagation: ·CH3 + C2H6  ·C2H5 + H· ·C2H5  C2H4 + H·
Termination: ·C2H5 + ·C2H5  C2H4 + C2H6
Propylene (C3H6; A) Steam cracking of naphtha (see above description) Propylene oxide (used to make polyether and polyols) via
H3C–CH=CH2) B) Propane dehydrogenation. Because of an increasing demand for propylene and the hydrochlorination route:
a shift toward ethane cracking over naphtha cracking, a number of “on-purpose” 2C3H6 + Cl2 + H2O  2(H2C–CHCl–CH2OH)
routes to propylene have become more widely used, including propane dehydroge- H2C–CHCl–CH2OH + –OH  H3C–CH–CH2
nation (PDH). \ /
O
C3H8  C3H6 + H2 (in the presence of a Pt-Sn-based catalyst) Polypropylene (used to make plastic resins)
nC3H6  [–CH2–CH–CH2–]n (Ziegler-Natta catalyst)
|
CH3
Butadiene (C4H6; A) Steam cracking of naphtha (see above description) 1,3-butadiene is used for the manufacture of synthetic
H2C=CH–CH=CH2) B) Bio-based butadiene has been commercialized also (using a fermentation route) rubbers and latex
BTX (benzene, A) Steam-cracking of naphtha (see above description) Benzene is used to make ethylbenzene, and then styrene
toluene and xylene B) Catalytic reforming of naphtha. This process uses platinum- or rhenium-based (C6H5CH=CH2), as well as cyclohexane and further pre-
isomers) catalysts. Naphtha reforming dehydrogenates naphthenes, and dehydrogenates and cursors for Nylon
aromatizes paraffins, among other reactions Toluene is used to manufacture toluene diisocyanate (an
intermediate for polyurethane), as well as tri-nitrotoluene
(TNT). It is also used as a component of gasoline, and as
a solvent for sealants, adhesives and others
p-xylene is used to make terephthalic acid, a precursor to
polyesters. o-xylene is used to make phthalic anhydride
Selected resources
Van de Loosdrecht, J. and Niementsverdriet, J. Synthesis Gas Rase, Howard, “Chemical Reactor Design for Process www.syngaschem.com/syngaschem
to Hydrogen, Methanol and Synthetic Fuels, in “Chemical En- Plants,” John Wiley & Sons, New York, 1977. www.chemguide.co.uk
ergy Storage,” R. Schloegl (ediitor), De Gruyter, Berlin, 2013. www.essentialchemistryindustry.org

34 Chemical Engineering www.chemengonline.com june 2016

 Facts At Your Fingertips
Industrial Gas Burners
Department Editor: Scott Jenkins
C
ombustion in industrial burn-
ers is a critical operation in the
chemical process industries
(CPI) for supplying thermal energy
for heat transfer, fluid heating, steam
generation, distillation, endothermic
chemical reactions, metal melting and
others. Burners are mechanical devic-
es utilized for mixing proper quantities
of fuel and air, and also for maintaining
a stable flame inside fired equipment.
Included here are brief descriptions of
key aspects of industrial burner com-
ponents and operation.
Fuel-air mix
Industrial process burners can be
classified in several ways, including
the type of fuel-air mixing involved
(diffusion or premixing).
Raw-gas burners are used for
most applications. In these burners,
the fuel gas passes through orifices
in the gas tip and is injected directly
into the combustion zone, where it
mixes with air. A stabilizer cone is lo-
cated just below the gas to improve
combustion stability. These burners
are suitable for mounting in plenum
chambers (the area where air enters
the burner), and can be used with
preheated combustion air.
Pre-mix burners are those in which
fuel and air are mixed prior to com-
bustion. Pre-mix burners are some-
times used in specialized applica-
tions. In these burners, the kinetic
energy made available by the ex-
pansion of the fuel gas through the
fuel-gas orifice introduces about half
of the combustion air (called primary
air) into the Venturi mixer. This mix-
ture then exits through a large burner
tip, where it is mixed with the balance
of the combustion air (secondary air).
This secondary airflow enters the
burner through the outer, secondary
air register. Premix burners require
less furnace draft than raw-gas burn-
ers. Premix burners can produce a
wide range of flame shapes.
Reducing NOx
Combustion operations frequently
create nitrogen oxides (NOx), spe-
cifically NO and NO2, which must
32
Secondary
combustion
zone
Primary
combustion
zone
Fuel Air Fuel
be highly controlled, as they can be
harmful pollutants. Currently, three
burner configuration methods exist
for reducing nitrogen oxides in burn-
ers: staged air, staged fuel and inter-
nal fluegas recirculation combined
with staged air or staged fuel.
Staged air burners. These types of
burners work by introducing 100% of
the fuel into the burner and only part
of the combustion air (primary air),
thus creating a sub-stoichiometric
flame. This flame has a reduced tem-
perature and therefore inhibits NOx
formation. The flame is completed
with the addition of the secondary
air to complete the combustion pro-
cess. This process allows for greater
control at lower burner loads and
also accommodates a wider range
of fuels.
Staged fuel burners. This burner
method introduces 100% of the
combustion air into the burner and
splits the fuel supply into primary and
secondary volumes (Figure). The pri-
mary fuel mixes with the combustion
air to create a flame. As with staged
air burners, the peak flame tempera-
ture is lower, and NOx formation is
reduced. Secondary fuel is added to
complete the combustion process.
Staged fuel burners provide greater
NOx reduction, as the fuel supply
has a larger effect on NOx forma-
tion. This method is more commonly
used when a consistent fuel supply
is available.
Internal fluegas recirculation burn-
ers. This method combines either
staged air or staged fuel with internal
Chemical Engineering
fluegas recirculation to help reduce
NOx formation. The best results are
obtained where internal fluegas re-
circulation is used to dilute the fuel
gas in a staged fuel burner, creating
a gas with a low calorific value.
Flame size
The size of the burner flame is an im-
portant parameter in controlling the
heat transfer to tubes in the furnace.
The flame size and shape should be
such that the tubes impingement of
the flame upon the tubes they are
heating is avoided.
Maximum flame diameter can be
calculated using Equation (1).
(1)
where:
Df max = Maximum flame dia., ft
Lf = Flame length, ft
SVflame = Specific volume of flame,
ft3/lb
SVfuel + air = Specific volume of fuel
and air mixture, ft3/lb
Vf = Flame propagation velocity, ft/s
Maximum burner length can be
calculated from Equation (2)
(2)
where:
Db = Burner diameter, ft
Vb = Burner exit velocity, ft/s
The diameter of the burner flame
should be evaluated at maximum
burner-flame length.
Burner spacing
Burner spacing is normally 2 to 5 ft, or
sufficient to provide reasonable burn-
er-to-burner clearance, as based on
the maximum burner-flame diameter.
Burner-to-tube clearance must also
be such that minimum clearance is
based on a reasonable distance be-
tween burner outside-flame diameter
and outside diameter of the tubular
heating surfaces. n
Editor's note: The content presented in this column was
adapted from the following articles: Cross, Alan, Fired-Heater
Burner Performance, Chem. Eng., April 2008, pp. 44–47
and Al-Hajji, M.H., Burner Inspection and Maintenance,
Chem. Eng., November 2014, pp. 40–45.
www.chemengonline.com July 2016
 Facts At Your Fingertips
Distillation Column Design Factors
Department Editor: Scott Jenkins

D
istillation is a critical separation
tool for many applications in Column internals style Fs
the chemical process indus- Trays 0.2−1.6
tries (CPI), and the intelligent design of Random/dumped packing 0.5−2
a distillation column can have a large Structured packing 0.2−3.5
impact on eventual process perfor- are shown in Table 2. Column de-
mance and efficiency. This reference signers should use these ranges as
sheet outlines the design process for a guide to ensure that the appropri-
distillation columns and defines sev- ate column design and packing have
eral key design factors in this area. been selected.
Column design process Best practices for factors
Distillation column design is best ac- For the flood ratios, the limit is 100%.
complished using process simula- A good rule of thumb for new column
tion software, such as Aspen HYSYS designs is to keep the limit closer to
or a similar program. Balancing the 85%. Turndown is a vapor-pressure
key design factors shown in Table 1 balancing act — the objective is to
starts by sizing the column for maxi- maintain appropriate vapor velocities
mum superficial vapor velocity (vapor but also allow the ability to turndown
factor Fs). without having to worry about weep-
Once a working design is estab- ing or dumping, which can crash the
lished, engineers should check the column outright.
ratio between flowrate (gallons-per- Entrainment ratio relates to physi-
minute; gpm) and column area (gpm/ cally carrying liquid from one tray to
ft2). The next step should be to en- the one above it with vapor velocity.
sure that flood ratio, weeping point, This ratio should be minimized wher-
reflux ratio, and efficiency ratios are ever possible. The higher the amount
all within reasonable parameters. of reflux in the column, the larger the
For basic categories of column in- required column size, but the purer
ternals, the appropriate ratio ranges the distillate will be.
TABLE 1. DISTILLATION COLUMN DESIGN FACTORS
Factor What does it measure? When is it applied?
Flood ratio
Jet flood Accumulation of liquid in the column
Downcomer flood Only applies to columns with trays
Low vapor flow allowing liquid to fall
Weeping point
through the vapor perforations
Entrained liquid carried by the vapor to
Entrainment ratio
the tray above
Separation efficiency, based on weeping
TABLE 2.
gpm/ft2 Efficiency ∆P (mmHg)
1−20 50−80% 4−10 mmHg / Tray
1−20 HETP 30−40 in. 0.7−1.5 mmHg / ft
1−20 HETP 12−30 in. 0.2−0.5 mmHg / ft
Other factors not covered here,
such as feed location, exact packing
type, control scheme and so on will
affect the final design of the column.
Column design is the art of balanc-
ing these factors to achieve an opti-
mized design that can be confidently
built and operated with long-term re-
turn on investment. n
References
1. Terry Tolliver, retired senior fellow Solutia/Monsanto
2. Kister, H. Z., “Distillation Design,” McGraw-Hill, 1992.
3. Couper, J. R. and others, “Chemical Process Equipment
Selection and Design,” 2nd Ed., Elsevier, Amsterdam,
2004.
Editor’s note: The content for this edition of Facts at your
Fingertips was provided by EPIC Systems, Inc. (St. Louis,
Mo.; www.epicmodularprocess.com). If you have additional
questions or comments, please email Stephen Benbrook:
sbenbrook@epicsysinc.com
Disclaimer: Although the information and recommen-
dations set forth herein are presented in good faith, EPIC
Systems, Inc. and its subsidiaries make no representations
or warranties as to the completeness or accuracy thereof.
No representations or warranties, either express or implied,
or merchantability, fitness for a particular purpose or of any
other nature are made hereunder.
Limits and formulas
Design for 85% for new trays and
To all packing types
packing
Design for 85% for new trays
To all columns Less than 50% is acceptable
To any column Less than 10% is acceptable
There are many formulas that can be
applied here. In general, the relationship
should be visualized as:
Weeping Entrainment
Col. efficiency

Efficiency ratio Most useful for trayed columns

ratio, reflux ratio and vapor rate

Vapor rate

HETP = (Height of packing) ÷ (Number

HETP Height equivalent of a theoretical plate Used for packed columns
of theoretical plates)
Fs = Us × √v
Value used to determine preliminary v = Vapor density lb/ft3
Fs vapor To all columns
column sizing Fs = Vapor F factor
Us = Vapor superficial velocity, ft/s
gal/min per ft2 =
Ratio used to find column area require- (liquid gal/min) ÷ (column area)
Liquid ratio: gpm/ft2 ments and to determine initial equip- To all columns where:
ment sizing gpm = gallons per minute
area = ft2
38 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM AUGUST 2016
 Facts At Your Fingertips
pH Measurement in Industrial Waters
Department Editor: Scott Jenkins
D
etermination of pH is a criti-
cal and ubiquitous operation
whenever water is used in the
chemical process industries (CPI).
This one-page reference provides a
review of pH chemistry and informa-
tion on pH measurement equipment
in CPI applications.
Chemistry of pH
The quantity pH is a measure of the
acidity or basicity of an aqueous so-
lution. It is expressed as the negative
logarithm of the activity of hydrogen
ions in solution (pH = – log aH+; where
aH+ is the activity of hydrogen ions).
Effectively, the activity represents
the concentration of hydrogen ions.
However, hydrogen ions (that is, free
protons) do not exist by themselves
in solution. H+ ions quickly bond with
surrounding water molecules, making
H3O+ (hydronium ion).
Because the pH scale is logarith-
mic, a change of one unit of pH cor-
Leached
layer
Process Glass Reference
liquid bulk electrolyte
FIGURE 1. A typical bulb of pH-sensitive glass in
a pH sensor is shown at the top and a schematic
representation of the “leached” layer formation on
the both sides of the pH-glass is shown below. If
the pH of the reference electrolyte equals that of
process solution, then no potential (E) is generated
across the glass. Typically, the reference electrolyte
is buffered to pH 7, so no voltage is generated if the
process liquid has the same acidity as the buffer. If
the process liquid is acidic, then E < 0, and nega-
tive potential is generated. If alkaline, E > 0, and
positive potential is generated
42
responds to a ten-fold change in hy-
drogen ion concentration. In a sample
of pure water, it has been determined
experimentally that the auto-ionization
of water results in a H+ concentration
of 10–7 mol/L, which is equal to the
concentration of OH– ions. Because
of this, neutral pH is said to be equal
to 7.0. Values below 7 are acidic,
while those above 7 are basic.
pH electrodes
Measurement of pH is generally ac-
complished with a pH-sensitive elec-
trode. In a glass pH sensor, the glass
responds to the acidity level. pH elec-
trodes consist of an inert glass tube
with a pH-sensitive glass tip, usually
with a bulb-shaped end. The tip con-
tains a fill solution with a known pH.
The electrochemical influence of the
fill solution compared to the process
solution generates a millivolt electri-
cal potential. The glass electrode is
coupled with a reference electrode
and a temperature-sensing element
(to account for the temperature de-
pendence of pH).
pH electrodes use specially for-
mulated glass capable of generating
electrical potential (voltage) that is
proportional to the pH of the solution
it is measuring. In a standard pH-
glass electrode, the sensing element
is a gel layer with sub-micron thick-
ness on the glass bulb. The potential
change is measured in relation to a
reference electrode that is in contact
with the solution, such that a closed
electrical loop is created.
Specific formulations of the pH
glass are trade secrets for pH-sensor
manufacturers. However, it is not a
secret that alkali metals render silicate
glass pH-sensitive. The “leached”
layer is formed on the surface of the
glass membrane once it’s hydrated
(Figure 1). The glass electrode must
therefore be kept in an aqueous so-
lution — once the glass is dehydrat-
ed (if the bulb is not immersed or is
exposed to non-aqueous chemicals)
the leached layer disappears and the
sensor stops working or develops an
erratic signal. The leached layer is
only about 5–10 nm, but it contrib-
CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM
7.00 pH
Temperature Reference
compensation electrode
Glass Reference
electrode junction
Process
liquid
FIGURE 2. The glass electrode creates a potential
proportional to the pH of the process liquid, while
the reference electrode completes the electrical
circuit and provides a small and stable potential as
a reference for the pH signal. Electrode tempera-
ture compensation is highly desirable, especially at
elevated temperatures
utes the most toward the conductiv-
ity of the pH glass.
Reference electrodes
The purpose of the reference elec-
trode is to create a stable reference
potential against which the pH sig-
nal can be measured. Having a con-
stant reference potential is essential
for high-impedance measurement.
The typical reference in commercial
pH sensors uses a potassium chlo-
ride electrolyte. The consistency of
the electrolyte can vary from liquid to
gel to solid in order to slow down the
migration of process ions inside the
reference that come in through the
reference junction (Figure 2). Depend-
ing on the application, the chemistry
of the electrolyte can be changed to
satisfy specific requirements of the
chemical process. The competitive
marketplace offers “rebuildable” sen-
sors with a variety of fill solutions.
The reference junction is usually a
part of a rebuild-kit and is pre-soaked
in the corresponding electrolyte solu-
tion. The choice of the materials for
the reference junction can vary from
Teflon to ceramic, to wood. The pur-
pose of the reference junction is to
provide electrical continuity with the
process liquid. It also serves as a
guard to prevent the process liquid
from penetrating and contaminating
or poisoning the sensor. n
Editor's note: The pH section was based on information
from several sources, including the International Union on
Pure and Applied Chemistry (IUPAC) Goldbook (goldbook.
iupac.org). The section on electrodes was adapted from the
following article: McMillan G. and Baril, R., pH Measure-
ment and Control, Chem. Eng., August 2010, pp. 32–39.
SEPTEMBER 2016
 Facts At Your Fingertips
Agglomeration Processes
Department Editor: Scott Jenkins
A
gglomeration is a natural phe-
nomenon in which solid par-
ticles stick to each other or to
surfaces. When unwanted, agglom-
eration can cause problems, such
as caking, buildup or lumping, but it
is also an important particle-size en-
largement process widely used in the
chemical process industries (CPI) to
help overcome challenges, including
segregation, difficult flow, low bulk
density and others. Agglomeration
can also help control particle-size
distribution and reduce potentially
hazardous aspects of the solids, such
as dust. This one-page reference pro-
vides information on agitation, com-
pression and sintering methods of
agglomeration and their mechanisms.
Agglomeration methods to enlarge
particulate solids can be broadly
broken down into three general cat-
egories: agglomeration by agitation
(sometimes referred to as wet ag-
glomeration or tumble/growth ag-
glomeration; pressure (compaction)
agglomeration, and agglomeration
using heat (sintering).
Wet agglomeration
Wet agglomeration processes com-
bine powder, liquid (usually water)
and, if necessary, a binder to impart
shear to form agglomerates. Pro-
cessing equipment may include ro-
tating drums, disc or pan agglomera-
tors, pin or ribbon mixers or fluidized
beds. Agglomeration can be induced
by a solvent or slurry atomized onto
the bed of particles, or by the con-
trolled sintering or partial melting of a
binder component of the feed (Figure
1). Next, moist particles join together
to form so-called green agglomer-
ates. Drying or curing takes place in
a final stage. The wet agglomerates
are created by first forming nuclei that
then grow into larger aggregates by
layering or coalescence. In some cas-
es, nucleation and aggregate growth
take place in two separate pieces of
equipment that are operated in series.
Nucleation gives rise to seed parti-
cles, which are formed when several
individual particles adhere to each
other. The nucleation stage can be
40
time-consuming because the seed
agglomerates are weakly bonded
and readily disintegrate back into in-
dividual particles. Eventually, larger
aggregates are formed when small
agglomerates coalesce or individual
particles adhere to larger agglomer-
ates. Once larger agglomerates are
created, growth becomes accelerat-
ed as the increased mass and high-
er kinetic energy of agglomerates
cause them to pick up individual par-
ticles more rapidly and incorporate
them onto their surfaces. The rela-
tive rates of size enlargement (nucle-
ation, coalescence and layering) and
size reduction (attrition and consoli-
dation) establish the final particle size
along with the material’s tendency to
wick moisture from its core to outer
layers. The optimal amount of liquid
added to a powder — the amount
that gives the resultant agglomer-
ates their greatest integrity and re-
sistance to breakage — is typically
40–90% of its liquid saturation. The
liquid saturation is the fraction of to-
tal void space that can be filled with
the liquid. When water (or another
liquid) is added to a dry bulk solid,
liquid bridges will begin to form at
contact points between particles.
This is known as the pendular stage
of saturation. All free moisture is at-
tracted to the interfaces between the
solid particles by capillary effects,
and surface tension draws the par-
ticles together. As saturation levels
are increased, the funicular stage is
eventually reached where all internal
solid surfaces become surrounded
by liquid. At this point, the mixture
becomes more fluid-like, tensional
forces disappear, and the agglom-
erates become weaker. When the
powder becomes fully saturated,
it reaches its capillary state, and at
higher moisture levels, the system
begins to behave as a slurry.
Compaction agglomeration
Pressure agglomeration works by ap-
plying external forces to dry particu-
late solids to form enlarged particles.
Continuous sheets of solid material are
produced, as in roll pressing, or some
CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM
Growth
Wetting
Granule properties affected
include size, bulk density,
attrition, dispersion, flowability
Breakage
Consolidation
FIGURE 1. In wet agglomeration, a wetting step
leads to nucleation and particle growth
solid form is made, such as a bri-
quette or tablet. Continuous sheets or
strands may either break down in sub-
sequent handling to form a granulated
material, or the material may be further
processed through a variety of chop-
ping, spheronizing or forced screening
methods. A key factor in compression
agglomeration is the level of force ap-
plied. Compaction processes range
from confined compression devices,
such as tabletting, briquetting ma-
chines and ram extrusion to uncon-
fined devices, such as roll presses and
a variety of pellet mills.
Heat sintering
In agglomeration using heat (sintering),
atoms and molecules begin to migrate
across the interface where particles
touch each other. This happens at a
certain elevated temperature, which
is different for various materials. While
still in solid state, diffused matter forms
bridge-like structures between the sur-
faces, which solidify upon cooling. In
the post-treatment of agglomerates,
this phenomenon produces strong
permanent bonds or specific final
properties in parts that may have been
manufactured by virtually any of the
other agglomeration techniques. n
Editor’s note: Portions of this column have been adapted
from the following articles: Mehos, G. and Kozicki, C., Con-
sider Wet Agglomeration to Improve Powder Flow, Chem.
Eng., January 2011, pp. 46–49; and Ennis, B.J., Ag-
glomeration Technology: Mechanisms, Chem. Eng., March
2010, pp. 34–39. Additional references include the follow-
ing: Sochon, R.P.J and Salman, A.D., Particle Growth and
Agglomeration Processes, chapter in Chemical Engineering
and Chemical Process Technology, Vol. II, “Encyclopedia of
Life Support Systems;” and Pietsch, W., What is Agglomera-
tion?, Power and Bulk Solids, Feb. 27, 2008.
OCTOBER 2016
 Facts At Your Fingertips
Sampling for Internal Corrosion
Department Editor: Scott Jenkins
P
roperly selected and executed
sampling techniques are es-
sential for assessing, controlling
and mitigating internal corrosion of
pipes and other assets in the chemi-
cal process industries (CPI). Key data
for evaluating an asset or piping sys-
tem for internal corrosion include the
following: materials of construction,
properties of fluids carried, operating
conditions and valid analytical data
from proper sampling. This reference
describes considerations for sam-
pling of internal corrosion.
Sampling methods
Internal corrosion sampling consists
of several overlapping evaluation
methods — some performed with the
system operating normally and others
performed with the equipment operat-
ed to facilitate the test method. Widely
used methods for assessing internal
corrosion include the following:
• Bacterial analysis
• Coupons and probes
• Deposit analysis
• Gas samples
• Liquid samples
• Inline inspections
These sampling methods can be
used independently, or in combina-
tion, to determine the extent and sus-
pected causes of internal corrosion.
This information can then help deter-
mine whether mitigating methods are
necessary, as well as whether or not
the mitigation measures were suc-
cessful. Common potential causes of
internal corrosion include acid gases
(CO2, H2S), bacterial corrosion, ero-
sion corrosion or a combination.
Liquids
These corrosion tests for liquids are
prioritized to allow the most accurate
field analysis:
1. Presence of water
2. pH
3. Temperature
4. Dissolved CO2
5. Dissolved H2S
6. Alkalinity
7. Bacteria density
The presence-of-water test is per-
formed using a type of litmus paper.
34
FIGURE 1. Weight-loss coupons are installed for a
period, then weighed to determine corrosion
If the liquid being sampled is com-
posed only of hydrocarbons, no fur-
ther testing would be necessary. After
confirming that the sample contains
water, the pH and temperature of the
sample should be measured. Next,
the dissolved gases and alkalinity
should be tested. Finally, the sample
should have a bacterial dilution series
set up. These onsite tests should be
performed as quickly and safely as
possible, preferably within 15 min of
taking the sample. Bacteria must be
inoculated within 4 h of sampling.
Solids
The following list for testing solids can
be used whether the solid material
was blown out of the pipeline, ob-
tained from a pigging run or obtained
by separating the pipeline:
1. Appearance of the solids
2. pH
3. Bacteria density
4. Onsite chemical testing
When air is introduced into a pipe,
the piping material begins to oxidize,
thus changing the chemistry of the
solid material. So the solid material
should always be visually inspected
as quickly as possible, before oxida-
tion occurs and changes the appear-
ance of the solid material. Then pH
testing should be performed, along
with processing the solid for bacte-
rial analysis, as this material can be a
breeding ground for bacteria. Finally,
any additional onsite chemical testing
can be performed. The sample should
then be placed into a container that
minimizes the amount of airspace to
slow the oxidation of the sample.
Gases
For gas sampling, the following on-
site tests can be performed with stain
CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM
FIGURE 2. Evaluating and monitoring coupons can
assess micro-pitting on a metal surface
tubes for water vapor and acid gases:
1. Water vapor
2. Acid gases
3. Temperature
4. Pressure
When sampling for laboratory anal-
ysis of acid gases, the type of con-
tainer is important. For CO2 and O2,
standard carbon-steel cylinders can
be used, but if H2S is to be analyzed,
the sample cylinder needs to be lined
or treated so that the cylinder itself
does not react with the H2S and
corrupt the sample analysis. Also,
when using sample cylinders, the
pressure rating should be sufficient
to handle the pressure in the system
being sampled. Gas sample loca-
tions should be in areas that are rep-
resentative of the system, and need
to be accessible for repeat sampling.
Care should be taken to avoid liquids
(water or liquid hydrocarbons) in the
sample cylinder to prevent damage
of the analytical equipment.
Coupons and probes
Coupons and probes are also used
to measure potential corrosion in
pipelines. Coupons can be basic
weight-loss coupons, where a clean
known-weight metal coupon is in-
stalled into the pipeline for a period
of time (Figure 1). The coupon is re-
moved, cleaned and reweighed, and
a calculation is performed to yield
weight loss over time. A more ad-
vanced approach is to use evaluat-
ing and monitoring coupons, which
have a specially prepared smooth
surface designed for microscopic
analysis and used to evaluate micro-
pitting (Figure 2). n
Editor’s note: This edition of “Facts at your Fingertips” was
adapted from the following article: Rine, J., Internal Corro-
sion Sampling, Chem. Eng., July 2012, pp. 26–29.
NOVEMBER 2016
 Facts At Your Fingertips
Solid-Liquid Separation: Classification, Design and Testing
Department Editor: Scott Jenkins

W
hether to remove solid con- P1 > P2
taminants from a liquid or
separate a solid product P1 P2
from a solvent, solid-liquid (S-L) sepa-
Filtrate
ration is a common unit operation Feed
across the chemical process indus-
tries (CPI). This one-page reference Housing
provides an overview of S-L methods, FIGURE 2. Positive pressure or
Medium
design and testing. vacuum can be used in filtration

Sedimentation versus filtration The driving potential that moves the stantial effect on the level of difficulty
Solid-liquid separation technologies liquid phase, or filtrate, through the of the filtration process, and in turn on
can be classified according to ther- filter medium distinguishes various the appropriate type of filter and op-
mal methods (dryers) or mechanical filtration methods. Separation can erating conditions. For example, par-
methods, where the flow direction of take place using gravity or by impos- ticles that are incompressible (rigid)
the solid and the liquid phases be- ing a pressure gradient (pressure ap- are usually easier to filter than those
comes a differentiating factor. In filtra- plied to filter side, or vacuum applied that are soft and compressible. If the
tion technologies, both phases flow to the filtrate side; Figure 2) particles are slimy or gelatinous, filtra-
in the same direction, while sedimen- tion becomes even more challenging.
tation methods refer to those where Process design
the two phases flow in opposing di- Several issues must be considered in Laboratory testing
rections (Figure 1). A special case, in the design of a new filtration process, Before S-L separation equipment
which the flow directions of the solid or the optimization of an existing one. is selected, the nature and proper-
and liquid phases are at right angles These include the following: ties of materials being filtered should
to each other, is referred to as cross- Feed solids content. Confusion must be determined by laboratory testing.
flow filtration. be avoided by clearly stating whether Knowledge gained through laboratory
In most sedimentation processes, the solids content is expressed on a testing is necessary for specifying fil-
the difference in density between weight or volume basis. Insoluble sol- ter media, filter aids, filter area, cake
the solid and liquid phases is uti- ids content is usually given in volume space needed and cake discharge
lized, but it is also possible to use percent, but not always. technique, a well as for the design of
electric or magnetic fields for sepa- Particle-size distribution. The sol- the S-L separation system.
rating purposes. In some cases, the ids in a slurry are often characterized Laboratory filters must have pres-
natural sedimentation caused by the by average particle size. While this sure-measuring devices to measure
earth’s gravitational field is used to is useful, the size distribution is also the feed and the discharge pres-
this end, for example gravity thick- important. Filters must be designed sures. A sample feed solution is
eners. Natural sedimentation can be to retain the smallest particles that prepared in a container that allows
enhanced by superimposing a cen- need to be removed. The tendency measurement of the volume of the
trifugal field, as is done by cyclones for particles to agglomerate, shifting test batch for filtration. The filtered
and centrifuges. the distribution toward larger sizes, solution (filtrate) is collected in a re-
Filtration uses a filter medium that may also be a factor. ceptacle that allows measurement of
retains the solid phase while allow- Nature of solids. The physical char- the filtrate volume after a measured
ing the liquid phase to flow through. acteristics of the solids have a sub- filtration time. A stopwatch or timer
is used to track the time required for
Sedimentation Filtration
the filtration process from start to
finish. If laboratory testing is not fea-
Driving force of separation = pressure (bars)

Chamber filter press

Driving force of separation = gravitation (g)

Belt filter press

30.0 bar sible at your plant, filter equipment
10,000 g Separator
companies, filter aid suppliers and
Pressure

Centrifuge 15.0 bar

Drum filter
Disc filter 5.0 bar
consultants are available to assist
3,000 g Centrifuge
Dynamic crossflow filter with test work. n
Vacuum Atmospheric

Cyclone Filtration thickener Editor’s note: This edition of “Facts at your Fingertips” was
100 g 1.0 bar
Screen adapted from the following articles: 1) Schmidt, P., Filtration
Centrifuges: An Overview, Chem. Eng., December 2010,
Disc filter pp. 34–38; 2) Gabelman, A., An Overview of Filtration,
1g Gravity thickener
Drum filter Chem. Eng., November 2015, pp. 50–58; and 3) Sent-
Pan filter
0.2 bar manat, J., Clarifying Liquid Filtration, Chem. Eng., October
Belt filter
2011, pp. 38–47.
FIGURE 1. In sedimentation-based processes, the driving force is the earth’s gravity, while either positive
or negative pressure drives filtration processes
36 CHEMICAL ENGINEERING WWW.CHEMENGONLINE.COM DECEMBER 2016