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Maximizing Heat-Transfer Fluid Longevity

Maximizing Heat-Transfer Fluid Longevity

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F
aced with increased workloadsand time and budget constraintsthat often restrict external train-ing support, many chemical pro-cess operators are forced to get themost out of their heat transfer systemwith less help. This article offers rec-ommendations for how to carry outproactive maintenance on heat-trans-fer fluids, to maximize their useful lifeand minimize problems associatedwith fluid degradation, such as exces-sive downtime for unplanned mainte-nance when the heat transfer systemhas become unsafe or is no longer ableto carry heat in a reliable manner. Itis useful for anyone developing or re-freshing asset-care-management pro-grams related to heat-transfer fluidsand systems.Discussed below are the most com-mon fluid-related problems encoun-tered by heat-transfer systems and a variety of potential solutions. Whileindividual system designs and varia-tions in process and operating condi-tions make each application unique,all heat-transfer fluids share manycommon attributes, making theserecommendations widely applicable.Ultimately, our goal is to educatethose involved with the operationand maintenance of liquid-phaseheat-transfer systems, both large andsmall, that use an organic-based heat-transfer fluid. The organics includechemical aromatics, fluids based onpetroleum derivatives, silicone or gly-col, the polyalphaolefins (PAO; alsoreferred to as API Group IV-basedfluids) and more. A properly designedand operated heat-transfer systemcan be the biggest ally in maintain-ing (and even increasing) productivitywhile reducing overall maintenanceand production costs.
It starts with smart selection
The selection of the heat-transferfluid — whether at the system designphase, or on an ongoing basis aftercommissioning — should not be takenlightly. Fluid selection should not bedictated solely by the purchase priceor any single physical characteristic.Rather, a variety of factors should beconsidered:
•Thepotentialimpactonworkersof
a given fluid, in terms of adequatetraining and protection that mustbe implemented to address hazardsrelated to potential exposure to thefluid, in both its vapor form (inha-lation risk and mist concentration)and liquid form (skin contact). In ad-dition to direct exposure, the choiceof the fluid could impact productiv-ity engendering additional handling and paperwork protocols involving other internal resources within thecompany, such as the health andsafety advisors, medical care per-sonnel, personnel in the receiving department and so forth
•Freightchargesrelatedtodelivery
of fresh product
•Costassociatedwiththepickup,
handling and disposal of the used oiland drums
•Provenfluidperformancebeyond
fresh oil data (for instance, if vendordata is able to demonstrate the re-tention of fresh oil properties aftersome time in service, as demon-strated by extensive oxidation andthermal stability data)
•Canthecurrentsystemaccommo
-date the fluid being considered (interms of compatibility with sealing materials, existence of a properlysized expansion reservoir, suitablematch between the fluid propertiesand the existing hardware, such asthe pump and safety-relief valve)
•Miscibilitywithcurrentheat-trans
-fer fluids if partial (rather than full)changeout is needed
•Documentedsuccessbythevendor
in your type of application
•Levelofliabilitycoverage,service
and expertise the fluid maker anddistributor bring to the table
Feature Report
32
 
ChemiCal engineeringwww.Che.ComDeCember 2009
 
Feature Report
CCCCCCCCCCCCCCCCCCCCCCCCCCHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHH
 
CCCCCCCCCCCCHHHHHHHHHHHHHHHHHHHHHHHHHH
 
CCCCCCCCCCCCCCHHHHHHHHHHHHHHHHHHHHHHHHHHHHHH
 
n
-Hexocosane (C
26
H
54
)COC flash point : 215°C / 419°FMolecular weight : 366.7 grams/mole
n
-Dodecane (C
12
H
26
)COC Flash Point: 71°C / 160°FMolecular weight: 170.34 grams/mole 
Excess Heat
n
-Tetradecane (C
14
H
30
)COC flash point : 99°C / 210°FMolecular weight : 198.4 grams/moleHeavy carbonaceous residues
Maximizing Heat-TransferFluid Longevity
Proper selection, monitoring andmaintenance can protect fluidsand components from damage due tothermal degradation,oxidation damage and contamination
FIGURE 1.
In this example with heat-transer fuid n-hexa-cosane, thermal degradation occurs when excess heatdrives the cracking o a straight-chain hydrocarbon(not shown is the ormation o reactive ree radicals,which have been omitted or clarity)
Gaston Arseneault
Petro-Canada Lubricants, a Suncor Energy business
 
Further discussion of initial fluidselection is beyond the scope of thisarticle, but is covered in Ref. [
1–7 
].Over time, the most commonthreats to the life of heat-trans-fer fluids (and sometimes the en-tire system) include the following:
• Thermal degradation• Oxidative degradation• Process contamination• Contamination by other materials
Each threat is discussed below, along with findings from real case studies,and practical recommendations forhow to deal with these challenges.
Thermal degradaTion
Regardless of the chemistry of theheat-transfer media, thermal degra-dation can occur whenever the heatsource provides more energy than theheat-transfer media can absorb andcarry away at that particular time [
8
].
Figure 1 shows a simple example
of the thermal degradation of a typi-cal petroleum-based heat-transferfluid (
n
-hexacosane) with ISO viscos
-
ity grade 32. In this case, the fluid is
a distribution of molecules of variouslengths, averaging 26 carbons long. As shown in Figure 1, when the en-
ergy submitted to the fluid exceeds the
threshold necessary to start breaking the stable covalent carbon-carbonbonds, the result is the formation of 
shorter hydrocarbons. The example
in Figure 1 shows the scission (crack-ing) of a perfect straight, long-chainalkane into shorter molecules, such
as dodecane (C12) and tetradecane(C14), each having a lower boiling and
flashpoint and viscosity compared to
the starting C26 hydrocarbon.The systematic result of thermal
degradation is a reduction in theoverall fluid viscosity and increased volatility, which increases the risk of leakage and loss through evaporation.
Thermal cracking increases the vapor
pressure, lowers the flashpoint andfire point, and sometimes, reduces au-
toignition temperature (AIT). As thename implies, the AIT is the tempera
-ture at which the fluid vapors are hotenough to ignite spontaneously in ab-sence of an ignition source [
9, 10
]. As shown in Figure 2, the problemworsens if left unaddressed. Reynoldsdiscovered in 1883 [
12, p. 86
], thatlow-viscosity fluids offer the best heattransfer behavior in a forced-convec-tion situation such as a typical heattransfer system. Based on these find-ings, one may think thermal cracking is advantageous from a thermal con-ductivity point of view. However, theresulting drop in viscosity is not nec-essarily favorable.
Safety risks
The concern is that the associated po
-
tential reduction of the AIT of the de
-graded fluid can make the operation of a closed system unsafe if the operat-
ing temperature nears or exceeds the AIT. Moreover, shortened molecules
are not the only species formed during thermal degradation of the fluid.On the other hand, an open system— that is, one in which the heatedfluid is constantly in contact with theatmosphere — is even less forgiving. Any drop in the heat-transfer fluid’sflashpoint and fire point (defined asthe temperature at which the fluidsustains a fire for five seconds in the
 ASTM-D92 Cleveland Open Cup,or COC flashpoint test apparatus)
could jeopardize the entire operation,considering that the fluid was likelychosen, in part, based on its fresh oil,open-cup flashpoint rating (to which asafety margin was likely added).Efforts to determine a definitive re-lationship between a drop in flashpoint
and a drop in AIT have not proven suc
-cessful. Fortunately for users, in manycases where a petroleum-based fluid
exhibits a relatively low flashpoint, wehave seen the AIT remained high, but
this is not always the case.
The performance data shown inTable 1 demonstrate how progressive
thermal degradation leads to steadilydiminishing flashpoint and viscos-
ity of the heat-transfer fluid. The gaschromatography distillation (GCD)
test consists of a simulated distilla-
tion of the fluid in the laboratory. Inthe cited example, the initial distilla
-
tion point (GCD 10%) drops over time,
which again confirms the increasedconcentration of low-boiling compo-nents present in the fluid.
Performance problems
 Another major consequence of thermalcracking is the formation of carbona-ceous residues (Figure 2), which result
from reactions of recombination. To acertain extent, these particles can be
compared to soot that is produced dur-ing fuel combustion in a diesel engine,where it is documented that soot isharder than the metallic componentsof the engine [
13
].
Such unwanted carbon residues are
not only abrasive toward the piping,but they also tend to stubbornly ad-here and harden onto the hot surfacepoints, forming an insulation layer
inside the pipe. This occurrence often
forces the user to increase the heaterset temperature (increasing energyconsumption) to maintain the desiredoperating fluid temperature. As a general rule of thumb, Wheeler[
14
] reports that the widely usedheat-transfer fluids based on poly-
alkylene glycols (PAGs) begin to ex
-perience thermal degradation near
250°C (482°F). Meanwhile, Wheeler
also reports that the thermal degrada-tion of uninhibited polyethylene glycol
results in a mix of five organic acids
[
15
]. The formation of these byproduct
acids leads to increased corrosion overtime in high-temperature systems.Of similar importance is the factthat even systems running at tem-peratures that are considered to be
relatively mild (for example, around149–204°C or 300–400°F), are not ex
-
 
ChemiCal engineeringwww.Che.ComDeCember 2009
33FIGURE 2.
Excessive thermal stress oten results in a breakdown o the heat-transer fuid, and the carbonaceous byproducts can build up on the inside suraceso pipes
 All photos: Petro-Canada Lubricants, a Suncor Energy business
 
Feature Report
34
 
ChemiCal engineeringwww.Che.ComDeCember 2009
empt from the ravages that elevatedtemperatures can bring, in termsof the thermal cracking of the heat-transfer fluid. For example, consider asystem in which the fluid experienceda change in physical properties, com-bined with oil-flow issues (for instance,from a defective pump, a fluid contain-ing solids, or some piping restrictionor pluggage) or a problem with theheater (for instance, the heater coil orelectrical element has baked-on car-bon that acts as an insulation layerforcing a higher energy demand tomaintain the target fluid outlet tem-perature). Such factors can cause arise in the skin-film temperature (thetemperature of the fluid immediatelytouching the heated surface). Any combination of the conditionsmentioned above can cause the skin-film temperature to be significantlyhigher than the temperature of thefluid circulating in the center of theheated pipe (which is called the bulkoil temperature). The larger the gapbetween skin film and bulk oil tem-perature, the more energy the fluidtries to distribute within itself throughturbulence. At some point, the fluid atthe heated surface will receive moreenergy than it can absorb (its heat ca-pacity), carry and release (its thermalconductivity), resulting in thermaldegradation of the fluid.
Minimization strategies
Discussed below are ways to minimizethe thermal degradation of a heat-transfer fluid in open systems.
Use the right fluid for the job.
 
Bychoosing a fluid with a high thermalstability, Guyer and Brownell [
16
]
 
suggest that most problems associ-ated with localized or temporary tem-perature excursion can be prevented. Ashman [
17 
] also emphasizes the im-portance of using a heat-transfer fluidwith a suitable thermal stability forthe application. Hudson, Sahasrana-man
 [6, 7] 
and many others acknowl-edge that petroleum-based fluids of pharmaceutical quality produced by asevere hydrogenation and hydrocrack-ing process (also referred to as “whitemineral oils”) tend to have greaterthermal stability compared to petro-leum base oils that are produced fromother refining methods [
6, 7 
].
Use appropriate venting.
 
 Venting involves the periodic release (from thefluid and the system) of the light, morehighly volatile hydrocarbons that formduring thermal cracking. Venting istypically carried out by circulating some of the hot fluid to the expansionreservoir, so that those molecules witha relatively high vapor pressure cannaturally migrate into the gas phaseabove the fluid. Then, depending onthe system design, the vapors are re-leased directly into the atmosphere orsent to a collection drum or tank, al-though laws governing volatile organiccompounds (VOCs) and other environ-mental trends cause most users tocollect the condensed low-boilers andproperly dispose of them.Fresh fluid needs to be added pe-riodically, to maintain the desiredfluid level (to prevent pump starva-tion and cavitation when the systemcharge contracts after a shutdown). Asa precautionary note, users should re-member that fresh fluid must never beadded directly into the hot oil stream;rather it should be added into the ex-pansion tank or other cool reservoirsconnected to the system
.
 Venting continuously or for extendedperiods is not advised, because the re-sulting rise in the bulk fluid tempera-ture in the expansion tank will accel-erate oxidation (discussed below).We recommend the use of an oil-analysis program to determine therate of generation of low-boilers dur-ing any operation. With proper vent-ing and analysis, users can establishhow often, and for how long, the fluidmust be periodically vented, in orderto safely operate a high temperaturesystem with a fluid that stays in goodcondition (maintaining characteristicsthat are similar to the fresh oil for aslong as possible).
 Adopt proper startup and shut-down procedures.
The successfulstartup of any heat-transfer system isimportant, since the faster the heat-transfer fluid reaches its desired op-erating temperature, the faster thefacility can produce its products andbegin to fulfill orders. This becomeseven more important for systems thatstop and start up regularly.One may say that running the pumpand the heater for a few extra hoursto accommodate a slower, more-gentlestartup is not cost-effective, but formany applications, such an approachpays its own dividends. For instance,by maintaining a more-gradual heat-ing profile at startup, the fluid willbe able to effectively remove heat andreduce the risk of thermal degrada-tion, and minimizing the formationand buildup of baked-on residues. Thenet result will be extended planned-maintenance intervals and greatercomponent life expectancy.Shutdown procedures also impactsystem efficiency and fluid life. Forinstance, Stone [
19
] and others recom-mend maintaining oil circulation after
Table 1.
AnAlysis DAtA showing thermAl DegrADAtion ofthe heAt-trAnsfer fluiD At A meAt-processing fAcility
sada,/dd/fa-, °c(coc)*wa,(Kaf)Va 40 °c,(-k, s)ga aa da(gcD)**10%b,°c90%b,°c%bb335°c
04/04/00 154 660 27.0 327 512 10.4908/10/01155 580 23.2 307 507 14.4006/11/02175 313 22.7 317 490 12.8009/09/02171 51 21.2 201 481 31.9012/09/02161 220 20.5 304 489 16.2003/12/03175 42 19.8 294 490 19.00After startup and shutdown procedure modification of April 200306/11/03169 156 23.0 310 497 15.70New fluidproperties209 35.6382 498 0.80
* COC represents analysis via the ASTM-D92 Cleveland Open Cup (COC) flashpoint testapparatus.** GCD = gas chromatography distillation. The GCD test consists of a simulated distillation of the fluid in the laboratory. Comparison with the fresh-oil boiling curve allows for the detection of lighter and heavier molecules in the fluids.

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