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Facts at Your Fingertips

Gu idebo o k January-December 2016

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

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

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
termine which instruments will offer ing, accuracy can be thought of as a ATEX
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
Focusing on the following ten areas fications of resolution (the smallest ISO
can help reduce the time needed to mass change that can be read on a NEMA
research available models and help scale), reproducibility (ability to weigh NTEP
ensure a good value. consistently over time and with differ- UL/CUL
ent operators), linearity (the variance in ETL
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 February 2016 35

Facts At Your Fingertips
Particle-sizing technology selection
Department Editor: Scott Jenkins

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

46 Chemical Engineering 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
H R|

Aldehyde O
Nitrile R—C=N

Ketone O Thioester O

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||

R N R R| R R|

Carboxylic Acid O Sulfone O O


Ether O Thiol R — SH

Ester O Acyl halide O

R| X = Cl, F, Br, I

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 april 2016
Facts At Your Fingertips
Insulating Heat-Transfer-Fluid Piping
Department Editor: Scott Jenkins

eat-transfer-fluid (HTF) system Table 1. Key Properties of Common piping INsulation types
piping is insulated to reduce Insulation type Temperature use range Absorbent? Price
heat loss and prevent worker Fiberglass 0 to 1,000°F (–18 to 538°C) Yes Low
contact with hot surfaces. Insulated Mineral wool 0 to 1,400°F (–18 to 760°C) Yes Low
piping minimizes the effects of chang- Calcium silicate 80 to 1200°F (27 to 650°C) Yes Medium
Cellular glass –450 to 800°F (–268 to 427°C) No Medium
es in ambient temperature to help en-
sure precise control of process tem- most probable explanation is that a fiberglass and so on, may be used.
perature. Proper design of the HTF slow exothermic oxidation reaction On vertical runs of lines of pipe
system and its insulation is required between hydrocarbon-type heating where occasional sources of leaks
to reduce the risk of fire as a result of fluids and the air inside the voids of can develop at flanges and valves,
fluid leakage into insulation. the insulation starts at about 500°F. install protective, tight-fitting caps
Such a reaction is believed to occur below flanges and valves to divert
Types of insulation for the following reasons: any fluid leakage to the outside of
The main insulation materials used • A large heating surface area the insulation.
for HTF system piping are fiberglass, exists within the insulation Install valve stems horizontally to
mineral wool, calcium silicate and • Formation of low-flash-point help avoid stem leakage from enter-
cellular glass. Table 1 lists some im- oxidation products, resulting ing the insulation.
portant properties to consider when from exposure to air On those sections of lines where
choosing insulation. • Temperatures can rise within greater numbers of control valves
Fiberglass and mineral wool are the saturated insulation mass and instrument fittings present high-
fibrous materials produced in simi- due to poor heat dissipation er leakage risk, install cellular glass
lar processes. Thermal conductiv- conditions insulation or metal-shielded insula-
ity is similarly low for both materials. Tests indicate that fiberglass, min- tion to minimize or eliminate any fluid
Calcium silicate insulation is formed eral wool and calcium silicate insula- saturation of the insulation system.
by drying a calcium silicate slurry tions are more subject to this prob- Consult your company’s insulation
in a mold, yielding a material with a lem, since they can absorb large supplier and insurance company for
slightly higher thermal conductiv- amounts of leaking fluid with greater additional suggestions on reducing
ity than fiberglass or mineral wool. surface area of liquid-air contact. fire hazards. n
These three materials have open, air- Cellular glass insulation resists
filled channels, which can wick leak- saturation by heat transfer fluid and, References
ing fluid into the insulation. therefore, may be a safer insulation to 1. “Systems Design Data,” Publication No. 7239193C,
Cellular glass insulation is formed use. Cellular glass normally is more Solutia Inc., subsidiary of Eastman Chemical Co.,
by heating a glass powder mixture, costly for most applications because September 2002.
which melts and expands, leaving of its higher installation cost and its 2. “Liquid Phase Design Guide,” Publication No. TF-04,
5/14, Eastman Chemical Co.
tiny, sealed glass cells throughout the tendency to crack when thermally
3. Controls Southeast Inc., “Insulation,” from www.csiheat.
material. It is impermeable to leaking shocked. Cellular glass is suggested com/csi_university/insulation.aspx, accessed January
fluid and has a thermal conductivity for use around flanges and other ar- 2016.
similar to calcium silicate. eas where leaks are likely to occur,
while lower-cost insulation materials Author
Insulation design may be used for pipe racks and all- The content for this edition of “Facts at Your Fingertips” was
supplied by the Eastman technical support team. If you have
Insulation should be installed to cover welded runs of piping. additional questions or comments, please email Eastman at:
all piping and other exposed surfaces
of the HTF system where heat loss Tips to reduce risk of fire Disclaimer: Although the information and recommenda-
can occur. Free online calculators can Install and maintain a leak-free piping tions set forth herein are presented in good faith, Eastman
be used to determine required insula- system when combustible heat-trans- Chemical Co. and its subsidiar­ies make no representations
or warranties as to the completeness or accuracy thereof.
tion thickness for most processes. fer fluids are being used. Reduce the No representations or warranties, either express or implied,
number of flanges and incorporate or merchantability, fitness for a particular purpose or of
Fire safety adequate flexibility of piping. Use sug- any other nature are made hereunder, and nothing herein
waives any of the seller’s conditions of sale. Eastman and
Fires have occurred in insulation ma- gested piping specifications. If a leak Therminol are trademarks of the Eastman Chemical Co. or
terials that have been soaked with or- develops, remove the insulation and its subsidiaries.
ganic heating fluids at apparent tem- contain and control the HTF until the
peratures of 500 to 600°F, which is leak can be repaired.
Facts At Your Fingertips
well below the autoignition tempera- On horizontal runs of pipe with Sponsored by:
ture of most commercial HTFs. While welded joints and proper flange fit-
the exact mechanism by which such tings, the standard high-temperature
fires occur is not fully understood, the insulation, such as calcium silicate or
38 Chemical Engineering may 2016
Facts At Your Fingertips
Key Reactions for the Petrochemical Industry
Department Editor: Scott Jenkins

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
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
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). \ /
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)
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
to Hydrogen, Methanol and Synthetic Fuels, in “Chemical En- Plants,” John Wiley & Sons, New York, 1977.
ergy Storage,” R. Schloegl (ediitor), De Gruyter, Berlin, 2013.

34 Chemical Engineering june 2016

Facts At Your Fingertips
Industrial Gas Burners
Department Editor: Scott Jenkins

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

istillation is a critical separation TABLE 2.
tool for many applications in Column internals style Fs gpm/ft2 Efficiency ∆P (mmHg)
the chemical process indus- Trays 0.2−1.6 1−20 50−80% 4−10 mmHg / Tray
tries (CPI), and the intelligent design of Random/dumped packing 0.5−2 1−20 HETP 30−40 in. 0.7−1.5 mmHg / ft
a distillation column can have a large Structured packing 0.2−3.5 1−20 HETP 12−30 in. 0.2−0.5 mmHg / ft
impact on eventual process perfor- are shown in Table 2. Column de- Other factors not covered here,
mance and efficiency. This reference signers should use these ranges as such as feed location, exact packing
sheet outlines the design process for a guide to ensure that the appropri- type, control scheme and so on will
distillation columns and defines sev- ate column design and packing have affect the final design of the column.
eral key design factors in this area. been selected. Column design is the art of balanc-
ing these factors to achieve an opti-
Column design process Best practices for factors mized design that can be confidently
Distillation column design is best ac- For the flood ratios, the limit is 100%. built and operated with long-term re-
complished using process simula- A good rule of thumb for new column turn on investment. n
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 References
key design factors shown in Table 1 balancing act — the objective is to 1. Terry Tolliver, retired senior fellow Solutia/Monsanto
starts by sizing the column for maxi- maintain appropriate vapor velocities 2. Kister, H. Z., “Distillation Design,” McGraw-Hill, 1992.
mum superficial vapor velocity (vapor but also allow the ability to turndown 3. Couper, J. R. and others, “Chemical Process Equipment
Selection and Design,” 2nd Ed., Elsevier, Amsterdam,
factor Fs). without having to worry about weep- 2004.
Once a working design is estab- ing or dumping, which can crash the
lished, engineers should check the column outright. Editor’s note: The content for this edition of Facts at your
Fingertips was provided by EPIC Systems, Inc. (St. Louis,
ratio between flowrate (gallons-per- Entrainment ratio relates to physi- Mo.; If you have additional
minute; gpm) and column area (gpm/ cally carrying liquid from one tray to questions or comments, please email Stephen Benbrook:
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- Disclaimer: Although the information and recommen-
reflux ratio, and efficiency ratios are ever possible. The higher the amount dations set forth herein are presented in good faith, EPIC
Systems, Inc. and its subsidiaries make no representations
all within reasonable parameters. of reflux in the column, the larger the or warranties as to the completeness or accuracy thereof.
For basic categories of column in- required column size, but the purer No representations or warranties, either express or implied,
ternals, the appropriate ratio ranges the distillate will be. or merchantability, fitness for a particular purpose or of any
other nature are made hereunder.
Factor What does it measure? When is it applied? Limits and formulas
Flood ratio
Design for 85% for new trays and
Jet flood Accumulation of liquid in the column To all packing types
Downcomer flood Only applies to columns with trays Design for 85% for new trays
Low vapor flow allowing liquid to fall
Weeping point To all columns Less than 50% is acceptable
through the vapor perforations
Entrained liquid carried by the vapor to
Entrainment ratio To any column Less than 10% is acceptable
the tray above
There are many formulas that can be
applied here. In general, the relationship
should be visualized as:
Separation efficiency, based on weeping 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
Facts At Your Fingertips
pH Measurement in Industrial Waters 7.00 pH
Department Editor: Scott Jenkins

etermination of pH is a criti- responds to a ten-fold change in hy- Temperature Reference
compensation electrode
cal and ubiquitous operation drogen ion concentration. In a sample
whenever water is used in the of pure water, it has been determined
chemical process industries (CPI). experimentally that the auto-ionization Glass Reference
This one-page reference provides a of water results in a H+ concentration electrode junction
review of pH chemistry and informa- of 10–7 mol/L, which is equal to the
tion on pH measurement equipment concentration of OH– ions. Because Process
in CPI applications. of this, neutral pH is said to be equal liquid
to 7.0. Values below 7 are acidic,
Chemistry of pH while those above 7 are basic. FIGURE 2. The glass electrode creates a potential
proportional to the pH of the process liquid, while
The quantity pH is a measure of the the reference electrode completes the electrical
acidity or basicity of an aqueous so- pH electrodes circuit and provides a small and stable potential as
lution. It is expressed as the negative Measurement of pH is generally ac- a reference for the pH signal. Electrode tempera-
ture compensation is highly desirable, especially at
logarithm of the activity of hydrogen complished with a pH-sensitive elec- elevated temperatures
ions in solution (pH = – log aH+; where trode. In a glass pH sensor, the glass
aH+ is the activity of hydrogen ions). responds to the acidity level. pH elec- utes the most toward the conductiv-
Effectively, the activity represents trodes consist of an inert glass tube ity of the pH glass.
the concentration of hydrogen ions. with a pH-sensitive glass tip, usually
However, hydrogen ions (that is, free with a bulb-shaped end. The tip con- Reference electrodes
protons) do not exist by themselves tains a fill solution with a known pH. The purpose of the reference elec-
in solution. H+ ions quickly bond with The electrochemical influence of the trode is to create a stable reference
surrounding water molecules, making fill solution compared to the process potential against which the pH sig-
H3O+ (hydronium ion). solution generates a millivolt electri- nal can be measured. Having a con-
Because the pH scale is logarith- cal potential. The glass electrode is stant reference potential is essential
mic, a change of one unit of pH cor- coupled with a reference electrode for high-impedance measurement.
and a temperature-sensing element The typical reference in commercial
(to account for the temperature de- pH sensors uses a potassium chlo-
pendence of pH). ride electrolyte. The consistency of
pH electrodes use specially for- the electrolyte can vary from liquid to
mulated glass capable of generating gel to solid in order to slow down the
electrical potential (voltage) that is migration of process ions inside the
proportional to the pH of the solution reference that come in through the
it is measuring. In a standard pH- reference junction (Figure 2). Depend-
glass electrode, the sensing element ing on the application, the chemistry
is a gel layer with sub-micron thick- of the electrolyte can be changed to
Leached ness on the glass bulb. The potential satisfy specific requirements of the
change is measured in relation to a chemical process. The competitive
reference electrode that is in contact marketplace offers “rebuildable” sen-
with the solution, such that a closed sors with a variety of fill solutions.
electrical loop is created. The reference junction is usually a
Specific formulations of the pH part of a rebuild-kit and is pre-soaked
Process Glass Reference glass are trade secrets for pH-sensor in the corresponding electrolyte solu-
liquid bulk electrolyte
manufacturers. However, it is not a tion. The choice of the materials for
secret that alkali metals render silicate the reference junction can vary from
glass pH-sensitive. The “leached” Teflon to ceramic, to wood. The pur-
layer is formed on the surface of the pose of the reference junction is to
glass membrane once it’s hydrated provide electrical continuity with the
FIGURE 1. A typical bulb of pH-sensitive glass in
a pH sensor is shown at the top and a schematic (Figure 1). The glass electrode must process liquid. It also serves as a
representation of the “leached” layer formation on therefore be kept in an aqueous so- guard to prevent the process liquid
the both sides of the pH-glass is shown below. If lution — once the glass is dehydrat- from penetrating and contaminating
the pH of the reference electrolyte equals that of
process solution, then no potential (E) is generated ed (if the bulb is not immersed or is or poisoning the sensor. n
across the glass. Typically, the reference electrolyte exposed to non-aqueous chemicals)
is buffered to pH 7, so no voltage is generated if the the leached layer disappears and the Editor's note: The pH section was based on information
process liquid has the same acidity as the buffer. If sensor stops working or develops an from several sources, including the International Union on
the process liquid is acidic, then E < 0, and nega- Pure and Applied Chemistry (IUPAC) Goldbook (goldbook.
tive potential is generated. If alkaline, E > 0, and erratic signal. The leached layer is The section on electrodes was adapted from the
positive potential is generated only about 5–10 nm, but it contrib- following article: McMillan G. and Baril, R., pH Measure-
ment and Control, Chem. Eng., August 2010, pp. 32–39.
Facts At Your Fingertips
Agglomeration Processes
Department Editor: Scott Jenkins

gglomeration is a natural phe- time-consuming because the seed
nomenon in which solid par- agglomerates are weakly bonded
ticles stick to each other or to and readily disintegrate back into in-
surfaces. When unwanted, agglom- dividual particles. Eventually, larger
Granule properties affected
eration can cause problems, such aggregates are formed when small include size, bulk density,
as caking, buildup or lumping, but it agglomerates coalesce or individual attrition, dispersion, flowability
is also an important particle-size en- particles adhere to larger agglomer-
largement process widely used in the ates. Once larger agglomerates are
chemical process industries (CPI) to created, growth becomes accelerat-
help overcome challenges, including ed as the increased mass and high-
segregation, difficult flow, low bulk er kinetic energy of agglomerates
density and others. Agglomeration cause them to pick up individual par- Consolidation

can also help control particle-size ticles more rapidly and incorporate FIGURE 1. In wet agglomeration, a wetting step
distribution and reduce potentially them onto their surfaces. The rela- leads to nucleation and particle growth
hazardous aspects of the solids, such tive rates of size enlargement (nucle-
as dust. This one-page reference pro- ation, coalescence and layering) and solid form is made, such as a bri-
vides information on agitation, com- size reduction (attrition and consoli- quette or tablet. Continuous sheets or
pression and sintering methods of dation) establish the final particle size strands may either break down in sub-
agglomeration and their mechanisms. along with the material’s tendency to sequent handling to form a granulated
Agglomeration methods to enlarge wick moisture from its core to outer material, or the material may be further
particulate solids can be broadly layers. The optimal amount of liquid processed through a variety of chop-
broken down into three general cat- added to a powder — the amount ping, spheronizing or forced screening
egories: agglomeration by agitation that gives the resultant agglomer- methods. A key factor in compression
(sometimes referred to as wet ag- ates their greatest integrity and re- agglomeration is the level of force ap-
glomeration or tumble/growth ag- sistance to breakage — is typically plied. Compaction processes range
glomeration; pressure (compaction) 40–90% of its liquid saturation. The from confined compression devices,
agglomeration, and agglomeration liquid saturation is the fraction of to- such as tabletting, briquetting ma-
using heat (sintering). tal void space that can be filled with chines and ram extrusion to uncon-
the liquid. When water (or another fined devices, such as roll presses and
Wet agglomeration liquid) is added to a dry bulk solid, a variety of pellet mills.
Wet agglomeration processes com- liquid bridges will begin to form at
bine powder, liquid (usually water) contact points between particles. Heat sintering
and, if necessary, a binder to impart This is known as the pendular stage In agglomeration using heat (sintering),
shear to form agglomerates. Pro- of saturation. All free moisture is at- atoms and molecules begin to migrate
cessing equipment may include ro- tracted to the interfaces between the across the interface where particles
tating drums, disc or pan agglomera- solid particles by capillary effects, touch each other. This happens at a
tors, pin or ribbon mixers or fluidized and surface tension draws the par- certain elevated temperature, which
beds. Agglomeration can be induced ticles together. As saturation levels is different for various materials. While
by a solvent or slurry atomized onto are increased, the funicular stage is still in solid state, diffused matter forms
the bed of particles, or by the con- eventually reached where all internal bridge-like structures between the sur-
trolled sintering or partial melting of a solid surfaces become surrounded faces, which solidify upon cooling. In
binder component of the feed (Figure by liquid. At this point, the mixture the post-treatment of agglomerates,
1). Next, moist particles join together becomes more fluid-like, tensional this phenomenon produces strong
to form so-called green agglomer- forces disappear, and the agglom- permanent bonds or specific final
ates. Drying or curing takes place in erates become weaker. When the properties in parts that may have been
a final stage. The wet agglomerates powder becomes fully saturated, manufactured by virtually any of the
are created by first forming nuclei that it reaches its capillary state, and at other agglomeration techniques. n
then grow into larger aggregates by higher moisture levels, the system
layering or coalescence. In some cas- begins to behave as a slurry. Editor’s note: Portions of this column have been adapted
from the following articles: Mehos, G. and Kozicki, C., Con-
es, nucleation and aggregate growth sider Wet Agglomeration to Improve Powder Flow, Chem.
take place in two separate pieces of Compaction agglomeration Eng., January 2011, pp. 46–49; and Ennis, B.J., Ag-
equipment that are operated in series. Pressure agglomeration works by ap- glomeration Technology: Mechanisms, Chem. Eng., March
2010, pp. 34–39. Additional references include the follow-
Nucleation gives rise to seed parti- plying external forces to dry particu- ing: Sochon, R.P.J and Salman, A.D., Particle Growth and
cles, which are formed when several late solids to form enlarged particles. Agglomeration Processes, chapter in Chemical Engineering
and Chemical Process Technology, Vol. II, “Encyclopedia of
individual particles adhere to each Continuous sheets of solid material are Life Support Systems;” and Pietsch, W., What is Agglomera-
other. The nucleation stage can be produced, as in roll pressing, or some tion?, Power and Bulk Solids, Feb. 27, 2008.


Facts At Your Fingertips
Sampling for Internal Corrosion
Department Editor: Scott Jenkins

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, FIGURE 1. Weight-loss coupons are installed for a FIGURE 2. Evaluating and monitoring coupons can
period, then weighed to determine corrosion assess micro-pitting on a metal surface
properties of fluids carried, operating
conditions and valid analytical data If the liquid being sampled is com- tubes for water vapor and acid gases:
from proper sampling. This reference posed only of hydrocarbons, no fur- 1. Water vapor
describes considerations for sam- ther testing would be necessary. After 2. Acid gases
pling of internal corrosion. confirming that the sample contains 3. Temperature
water, the pH and temperature of the 4. Pressure
Sampling methods sample should be measured. Next, When sampling for laboratory anal-
Internal corrosion sampling consists the dissolved gases and alkalinity ysis of acid gases, the type of con-
of several overlapping evaluation should be tested. Finally, the sample tainer is important. For CO2 and O2,
methods — some performed with the should have a bacterial dilution series standard carbon-steel cylinders can
system operating normally and others set up. These onsite tests should be be used, but if H2S is to be analyzed,
performed with the equipment operat- performed as quickly and safely as the sample cylinder needs to be lined
ed to facilitate the test method. Widely possible, preferably within 15 min of or treated so that the cylinder itself
used methods for assessing internal taking the sample. Bacteria must be does not react with the H2S and
corrosion include the following: inoculated within 4 h of sampling. corrupt the sample analysis. Also,
• Bacterial analysis when using sample cylinders, the
• Coupons and probes Solids pressure rating should be sufficient
• Deposit analysis The following list for testing solids can to handle the pressure in the system
• Gas samples be used whether the solid material being sampled. Gas sample loca-
• Liquid samples was blown out of the pipeline, ob- tions should be in areas that are rep-
• Inline inspections tained from a pigging run or obtained resentative of the system, and need
These sampling methods can be by separating the pipeline: to be accessible for repeat sampling.
used independently, or in combina- 1. Appearance of the solids Care should be taken to avoid liquids
tion, to determine the extent and sus- 2. pH (water or liquid hydrocarbons) in the
pected causes of internal corrosion. 3. Bacteria density sample cylinder to prevent damage
This information can then help deter- 4. Onsite chemical testing of the analytical equipment.
mine whether mitigating methods are When air is introduced into a pipe,
necessary, as well as whether or not the piping material begins to oxidize, Coupons and probes
the mitigation measures were suc- thus changing the chemistry of the Coupons and probes are also used
cessful. Common potential causes of solid material. So the solid material to measure potential corrosion in
internal corrosion include acid gases should always be visually inspected pipelines. Coupons can be basic
(CO2, H2S), bacterial corrosion, ero- as quickly as possible, before oxida- weight-loss coupons, where a clean
sion corrosion or a combination. tion occurs and changes the appear- known-weight metal coupon is in-
ance of the solid material. Then pH stalled into the pipeline for a period
Liquids testing should be performed, along of time (Figure 1). The coupon is re-
These corrosion tests for liquids are with processing the solid for bacte- moved, cleaned and reweighed, and
prioritized to allow the most accurate rial analysis, as this material can be a a calculation is performed to yield
field analysis: breeding ground for bacteria. Finally, weight loss over time. A more ad-
1. Presence of water any additional onsite chemical testing vanced approach is to use evaluat-
2. pH can be performed. The sample should ing and monitoring coupons, which
3. Temperature then be placed into a container that have a specially prepared smooth
4. Dissolved CO2 minimizes the amount of airspace to surface designed for microscopic
5. Dissolved H2S slow the oxidation of the sample. analysis and used to evaluate micro-
6. Alkalinity pitting (Figure 2). n
7. Bacteria density Gases
The presence-of-water test is per- For gas sampling, the following on- Editor’s note: This edition of “Facts at your Fingertips” was
adapted from the following article: Rine, J., Internal Corro-
formed using a type of litmus paper. site tests can be performed with stain sion Sampling, Chem. Eng., July 2012, pp. 26–29.


Facts At Your Fingertips
Solid-Liquid Separation: Classification, Design and Testing
Department Editor: Scott Jenkins

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-
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
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

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