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API Chemical Synthesis Trends in Reactor Heat Transfer Design
API Chemical Synthesis Trends in Reactor Heat Transfer Design
and advanced
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Introduction Various fluids (and non-fluids) are used to
eat transfer is a fundamental opera- provide heating or cooling. These include steam,
tion in chemical synthesis. This ar- water, water/glycol mixtures, synthetic fluids,
ticle explores basic and advanced con- liquid nitrogen, and electrical heating tape.
cepts, presents some calculations, and The alternatives are compared with guidance
compares different methods for controlling heat given for selecting among them.
transfer systems. Most facilities have heat transfer systems
Functional requirements are discussed for that service multiple reactors. There are sev-
these specific heat transfer requirements: eral ways to configure and control single-fluid
systems. They are compared.
• heating and cooling the reactor
Functional Requirements
• condensing vapors in the overhead system Each part of a reactor system must include the
definition of its heat transfer functional re-
• providing heating and cooling for various quirements. What are the required end-point
reasons such as cooling vacuum pumps, con- temperatures (maximum and minimum)? How
trolling temperature in overheads piping, fast should the temperature change? Is there a
and servicing mixers and pumps specific heating or cooling duty needed? Are
exothermic or endothermic
Figure 1. Simplified
diagram of a VOC reaction conditions ex-
condenser. The liquid pected? Can material so-
nitrogen used to lidify in the reactor over-
condense VOCs is head system? What are the
vaporized in the unit,
environmental emission
and can be used to
blanket the reactors. limits? Consider these and
other questions.
Reactor Functions
Reactors need heating and
cooling for several reasons.
Reactions may proceed best
at specific temperatures,
taking advantage of the re-
lationship between kinetics
and temperature. Tempera-
ture is often used to control
solubility, heating to dis-
solve solid ingredients then
cooling to crystallize prod-
uct in the solution. Exother-
mic or endothermic reac-
tions require cooling or heat-
Figure 2. Temperature and Rate of Heat Transfer in 2000 liter Figure 3. Temperature and Rate of Heat Transfer in 4000-liter
glass-lined reactor with Dowtherm J at -28°C. glass-lined reactor with Syltherm XLT ramped 50°C hotter than
reactor contents.
ing to control isothermal conditions. Boiling for distillation or stabilizers and corrosion inhibitors. The additives are de-
solvent removal demands a heat source. Smaller cooling signed to maximize the service life of the fluid and equip-
needs might be identified for removing heat of mixing or work ment. In addition, the technical support provided by fluid
energy (e.g., pumping). manufacturers justifies the selection of a proprietary product
Temperature ramping is often required. It is very impor- versus generic glycol.
tant to know how fast temperature changes should occur, and Mechanical chillers lose efficiency at low temperatures.
whether the rate of change must be precisely controlled. For Cascade units are available to operate as low as -70°C (-94°F),
example, if a desired reaction occurs at a certain high tem- but a more common limit is around -30°C (-20°F). Lower
perature, but a competing side reaction dominates at lower temperatures are most often obtained using cryogenic gases
temperatures, there would be a desire to raise the reactor such as nitrogen or carbon dioxide.
temperature “as quickly as possible.” Using kinetic data for Modern heat transfer fluids can be used at much lower
the two reactions at the two temperatures, the relationship temperatures. For example, silicone polymer fluids such as
between ramp rate and reaction results could be quantified. polydimethyl siloxane are recommended for use from -100°C
This would be very useful when analyzing heat transfer (-150°F) to 260°C (500°F). Factors to consider when choosing
factors such as jacket area, internal coil, the temperature of fluids and designing systems are given later in this article.
the heat transfer fluid, agitation, etc. Carbon steel is generally avoided for service temperatures
below -45°C (-50°F) because its body-centered crystalline
Reactor Temperature Limits structure becomes brittle.3 Since standard glass-lined carbon
The traditional temperature limits of a glass-lined carbon steel reactors utilize this material, the temperature cannot
steel reactor are -30°C (-20°F) to 230°C (450°F). The reasons be safely reduced. When lower temperatures are needed,
for this range are rooted in the physical capabilities of reactor high-nickel steel can be specified, such as ASTM A645 5% Ni
systems. Scientists would prefer larger envelopes and often alloy. However, it is more common to use a 300 series
express frustration when confronted with these temperature stainless steel in low temperature service.
limitations. Cryogenic temperatures as low as -100°C (- The American Society of Mechanical Engineers’ Boiler
150°F) are encountered in most API facilities.1,2 However, the and Pressure Vessel Code, Section VIII Unfired Pressure
typical plant has only a few reactors equipped to achieve Vessels may be used as a specific guide to the selection of
those low temperatures. materials to be used in low temperature service. Some metals
The lower end of the range is dictated by two factors: 1) the suitable for cryogenic temperatures are stainless steel (300
availability of low temperature cooling sources and 2) the series and other austenitic series), copper, brass, bronze,
behavior of ordinary carbon steel in response to temperature. Monel® (nickel-copper alloy), and aluminum. Non-metal ma-
Traditionally, glycol/water mixtures cooled by mechanical terials that perform satisfactorily in low temperature service
chillers provided cooling. Ethylene glycol is out of favor due are Dacron®, Teflon®, Kel-F® (PCTFE), asbestos impregnated
to its harmful effect on the environment; propylene glycol is with Teflon®, Mylar®, and Nylon. Once the materials are
usually preferred. Concentrations of 60 to 90 volume % glycol selected, the method of joining them must receive careful
in water have a useful lower temperature range of -30°C (- consideration to ensure that the desired performance is
20°F). Allowing for a temperature gradient between the preserved by using the proper soldering, brazing, or welding
jacket and the reactants, this results in a working tempera- techniques and materials.
ture in the reactor of about -25°C (-13°F). New reactors, using the available low temperature heat
Some formulated heat transfer fluids use propylene or transfer fluids, can achieve near-cryogenic temperatures if
ethylene glycol as their primary ingredient, mixed with suitable materials are chosen. These include A203 Grade D
system will operate, and the operating environment. It also 4. Account for diversity. Timelines for each major unit (i.e.,
defines non-functional requirements, constraints, and reactor) are prepared to illustrate the change in heat transfer
deliverables. With an emphasis on required functionality, load as reactions progress. See examples later in this article.
rather than the method of implementing the functions, the Then, an analysis is performed to determine both the average
URS is the basis for determining if the completed system and peak heating and cooling requirements, considering the
meets the user’s needs.6 individual major units independently and together. For in-
stance, if four reactors are included in the project, the diver-
2. Begin developing schematic drawings. A common sity analysis would determine whether peak heating is re-
approach is to start with block diagrams that show the quired simultaneously for all four or only one or two of them.
various heating and cooling loads such as reactors and con-
densers. As details are determined, process flow diagrams 5. Select the heat transfer fluid and distribution scheme.
with heat and material balances are created. The ultimate Heat transfer fluid(s) are selected using criteria listed in
schematic drawing is the Process and Instrumentation Dia- Figure 4, and block diagrams are used to map out a distribu-
gram (P&ID) that illustrates every piece of process equip- tion scheme. Some guidance is given later on selecting be-
ment, pipelines, valves, instruments, and control logic. tween central or local heating and cooling. The distribution
scheme analysis should consider the size of the HTF storage
3. Determine maximum theoretical heat transfer loads. tank (if any), used for a “flywheel” effect, and the flowrates for
Each load is listed (e.g., Reactor 1, Reactor 2, Condenser 1). circulating pumps. If the reactors are not yet specified or
The heating and cooling duties for each are defined and purchased, the design of reactor jackets are reviewed to
quantified. There are usually several different conditions to optimize heat transfer area and pressure drop and ensure
consider; each is listed along with the basis including fre- that heat transfer “zones” are incorporated where necessary.
quency and duration. Calculations are done to compute the
instantaneous loads. 6. Establish the control philosophy. Create Piping and
Instrumentation Diagrams (P&IDs) and at the same time
System Calculations
Important calculations include the heat flux from reactor
jacket, time for heating or cooling a reactor, duty for the Figure 5. Cold central HTF heated locally using electric immersion
overhead condenser, and overall system capacity considering heater.
diversity and heat losses.
Another important consideration is the amount of turbu-
lence in the jacket and in the reactor. The flowrate of fluid
Heat Flux
through the jacket is usually designed to ensure turbulence.
Heating or cooling from a reactor jacket or internal coil is
A pump is often used to circulate fluid through the jacket.
described by the equation:
Another trick is to divide the jacket into parallel zones.
Each type of jacket (annular, dimple, and half-pipe) can be
Q = U A ∆TLM
constructed in independent stacked sections. Half-pipe coils
also can be constructed in multiple interleaved spirals with
Q is the heat flux in watts (Btu/hr)
each of the zones covering the entire reactor sidewall. Zoning
U is the overall heat transfer coefficient, watts/(m2 °C) [Btu/
is done for one of these reasons:
(hr ft2 °F)]
A is the effective heat transfer area, m2 (ft2)
• Different fluids can be used in different zones, preventing
∆TLM is the log-mean temperature difference between jacket
cross contamination. Steam is segregated from chilled
and reactor, °C (°F)
water. Or, heat transfer fluid is kept away from liquid
nitrogen.
Determination of U is somewhat inexact. It depends on many
factors, including the geometry of the reactor, physical prop-
• Pressure drop is managed. High jacket flow may result in
erties of the heat transfer fluid and the reactor fluid, flowrate
excessive pressure drop if the flow path is long. Instead of
through the jacket or coil, and agitation in the reactor.
pumping 100 gpm through a single half-pipe coil, by
Several correlations exist for calculating the film coeffi-
dividing the loop into two zones and putting 50 gpm
cients that are combined into U, the overall heat transfer
through each of two parallel circuits the pressure drop is
coefficient. The correlations are specific to different jacket
cut by about 85%. Or, 100 gpm could be pumped through
types. Some have been published8-10; others are proprietary.
the two parallel loops (total flow rate of 200 gpm), cutting
Low cost software packages are available that do the detailed
pressure drop in half since each of the loops is only half as
calculations. Be aware that the correlations are only approxi-
long as the single loop alternative.
mate; actual results deviate up to 30% from the calculations.
“Typical” heat transfer coefficients are published in many
• Temperature change in the fluid is reduced. With suffi-
handbooks and texts. For instance, Perry’s gives an overall U
cient time, the temperature of the jacket and reactor
of 140 to 370 watts/(m2°C) [25-65 Btu/(hr ft2 °F)] for a glass-
contents equilibrate. It is very easy to approach this
lined carbon steel vessel with heat transfer oil on the jacket
equilibrium in jacketed vessels; dividing the flow to mul-
and organics in the vessel.11 Generalized tables of this type
tiple zones decreases the effect.
should be used with great caution because the actual coeffi-
cients are dependant on a large number of factors that the
• Heat transfer can be localized to a specific portion of the
tables cannot account for. For example, 50% propylene glycol
reactor. This is useful when working with reduced vol-
can be used down to about -20°C (4°F), but the viscosity at that
umes of reactant. It is also helpful if the goal is to maintain
temperature is over 50 cP reducing the overall heat transfer
the reactor contents at a temperature just below boiling.
coefficient to below 50 watts/(m2°C) [9 Btu/(hr ft2 °F)].12
13. Steve, Edward H., “Two circuits are better than one,”
Chemical Engineering, Vol. 109, No 12, November 2002,
page 64.