Reactor Design

Reactor design is a key part in gasification systems, and gasifiers can be fixed or
fluidized beds, updraft or downdraft, and may include staged introduction of either
fuel or oxidant.

From: Waste to Energy Conversion Technology, 2013

Related terms:

Reactor, Pyrolysis, Nuclear Energy, Nuclear Reactors, Biomass, Catalyst, Neutrons,

Temperature, Feedstocks

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Learn more about Reactor Design

26th European Symposium on Comput-

er Aided Process Engineering
Nicolas M. Kaiser, ... Kai Sundmacher, in Computer Aided Chemical Engineering,
2016

Abstract
Reactor design approaches often do not allow designing entirely innovative reactors
and considering the impact of uncertainties during the design procedure. Therefore
a probabilistic design framework is proposed in this work. Its advantages are exem-
plified on the reactor design task for the hydroformylation of 1-dodecene in a ther-
momorphic solvent system. It is illustrated how different types of uncertainties are
included and how their impact on the performance and the predictive power of the
performance can be quantified. Therefore two reactor concepts, namely a PFTR and
a cascade of CSTRs, are compared. The results indicate that the spatially controlled
PFTR shows higher performance than the CSTR cascade but has a lower predictive
power of the performance. There are operation points at which the approximation
by the CSTR cascade is preferable since it is less sensitive to uncertainties.
> Read full chapter

Introduction to liquid metal cooled re-

actors
F. Roelofs, in Thermal Hydraulics Aspects of Liquid Metal Cooled Nuclear Reactors,
2019

1.2 Liquid metal reactor design

Nuclear reactor design is highly multidisciplinary. In each reactor, disciplines like
fuel and material science, reactor physics, thermal hydraulics, and structural me-
chanics interact. This makes nuclear engineering one of the most demanding
professions. There may be only a few people who have a thorough understand-
ing covering all these disciplines. Most engineers specialize in one or two of the
disciplines allowing them to obtain a deep understanding. Designing a reactor
and performing safety assessments of reactors therefore remain a team effort and
strongly depend on the interaction between people and the integration by the few
engineers having a basic understanding of all involved disciplines. This book puts the
focus on the specialized topic of liquid-metal thermal hydraulics for advanced (fast)
nuclear reactors, a discipline that is essential for liquid-metal fast reactor design and
the subsequent safety assessment of the design and the reactor as built.

> Read full chapter

Gas-To-Liquids (GTL)
Xiuli Wang, Michael Economides, in Advanced Natural Gas Engineering, 2009

Fischer-Tropsch reactors
Reactor design for Fischer-Tropsch synthesis has significant effects on product
composition (by influencing the chain growth probability ), operability, safety,
and economics. Although different designs are provided by various companies, the
following three reactor categories can be identified, namely fixed-bed, circulating
and entrained fluidized-bed, and slurry reactors (Figure 7-19).
Figure 7-19. Types of Fischer-Tropsch reactors (Spath and Dayton, 2003)

Fixed-bed reactors
Fixed-bed reactors consist of a bundle of a few thousand long narrow tubes sitting
vertically inside a vessel. Each tube contains catalyst particles (about 2-3 mm in
diameter). The vessel also acts as heat exchanger to remove the Fischer-Tropsch
reaction heat by generating steam on the outer side of the tubes.

Fixed-bed reactors are simple, flexible, and easy to scale up. However, they have a
number of disadvantages:

• High cost.

• Multiple reactors in parallel are required for larger plants.

• To avoid high pressure drop in the reactor tubes, large catalyst particles are
needed resulting in low effectiveness factor (low catalyst activity per unit mass,
resulting from difficulty of reactants to diffuse into the core of a catalyst
particle).
• Low heat transfer from the catalyst bed and temperature variation in the tubes.
This results in (a) difficulty in controlling product composition due to
variability of the chain growth probability ; (b) hot spots in the catalyst bed
that may lead to catalyst sintering and reactor instability; and (c) low conversion
(35-40%) necessary to avoid excessive temperatures (in this case, unreacted
feed may be recycled).

Packed-bed reactors were originally used by Fischer and Tropsch and by Sasol. They
remain an option for relatively small GTL plants.
Circulating and entrained fluidized-bed reactors
Circulating fluidized-bed reactors address the heat removal problems that affect
fixed-bed reactors. Heat is removed through internal cooling coils that make steam
in the reaction section (in Figure 7-19), where small catalyst particles (100 μm)
circulate with the feed. The products of the reaction and the catalyst circulate from
the reaction section to the separation section (right) where products are removed.

Fluidized-bed reactors have a number of advantages:

• Better heat removal results in isothermal operation with better product con-
trol.
• Smaller catalyst particles result in higher effectiveness factor.

• Small unit size.

• Because of circulation, fresh catalyst can be added and deactivated catalyst

removed.

However, fluidized-bed reactors also have a number of disadvantages:

• Complex design and difficult scale-up. More recent designs using an

entrained fluidized-bed have resulted in increased capacity, and lower com-
plexity, size, cost, and catalyst consumption.
• Catalyst agglomeration caused by liquid product sticking to the particles. To
avoid this, the operating temperature can be maintained above the dew points
of the products, which may inadvertently force the value of to be low (with
products only suitable for gasoline and chemicals markets).

A comparison of fixed-bed and circulating-bed reactors is shown in Table 7-11.

Table 7-11. Comparison of Fixed and Circulating-Bed Selectivities

Process variable Fixed bed Circulating bed

Temperature, °C 180-250 330-350
0.95 0.85
Product Selectivities (% carbon basis)

CH4 4 7
C2-C4 alkenes 4 24
C2-C4 alkanes 4 6
Gasoline (naphtha) 18 36
Middle distillate (diesel) 19 12
Waxes 48 9

Slurry reactors
Another way to alleviate the poor heat transfer problem of packed-bed reactors is
the use of slurry reactors. The slurry is a mix of catalyst particles (10–200 μm) and
product oil at about 35% in a reactor (in Figure 7-19). Reaction heat is removed
by internal cooling coils that generate steam. Part of the slurry is taken out of the
reactor where the oil is removed at a filter, and catalyst particles are separated and
recycled.

Slurry reactors have the following advantages:

• They are suitable for large-scale designs.

• Temperature control is effective, resulting in high conversion and high values

for (0.95–0.98).
• Pressure drop is low.

• Catalyst can be replenished after separation at the filter.

• Units are compact, easy to scale up, and less expensive than packed-bed
designs.

Slurry reactors have the following disadvantages, which will be likely overcome in the
future:

• High viscosity of slurries.

• Catalyst particle settling and attrition.

• Low mass transfer in the liquid.

• Filtration difficulties.

> Read full chapter

Developing Commercial Process Flow

Sheets
Joe M. Bonem, in Chemical Projects Scale Up, 2018

Either reactor design (PFA or CSTR) may also include the use of a diluent such as
hexane or, in the case of a gas fluid bed, nitrogen. The utilization of a diluent has
the following advantages:

• It dilutes the incoming reactants mitigating the chance of reactor hot spots.

• It provides a limited “heat sink,” that is, in the case of a loss of temperature
control in the reactor, the diluent provides a means to absorb some of the
excess heat.
• If the product “C” or “E” in the reactions described by Eqs. (3.1) and (3.2) is a
solid, it mitigates the risk of the material in the reactor becoming too viscous.
• It reduces the reactor vapor pressure in a liquid reactor if either the reactants
or product has a high vapor pressure.

> Read full chapter

Cooling and Thermal Concepts

Malcolm Joyce, in Nuclear Engineering, 2018

7.6.3 Gaseous Coolants

For reactor designs where the coolant and moderator are not the same unified
volume of substance, in contrast to the case of light water reactors, there are a
number of important coolant options to be considered. The requirements of a
separate, dedicated coolant contrast significantly with the properties of a combined
water-based coolant/moderator, because sympathetic moderation properties are no
longer required of the coolant. Hence, the requirement for coolants for these reactor
designs is often for them to exhibit low cross sections for both neutron scattering
and absorption. This often turns a reactor designer's attention to coolants that are in
the gaseous phase under typical reactor operating conditions.

There is an important historical context behind the development of gaseous reactor

coolants. When it was necessary to remove nuclear fuel frequently from reactor
cores to extract nuclear materials from it and because of the burn-up limitations of
early metallic fuel materials, solid-phase moderators such as graphite were selected
because they offered the flexibility to do this while a reactor was operating. This was
much more convenient than the process of shutting a reactor down, waiting for
the decay heat to subside, depressurising the system and removing pressure vessel
components to get inside. However, this resulted in reactor cores that are much
larger than most water-moderated alternatives. Routing liquid coolants throughout
such a core can be sophisticated, as demonstrated by perhaps the most extreme
exponent of such a system; the Soviet RBMK reactor design (discussed further in
Chapter 10).

Gaseous coolants offer a convenient alternative in such cases where, assuming the
gas in question is cheap and abundant, the perfusion of the gas throughout the
system can be achieved more easily and cost effectively. One further advantage of
gaseous coolants, at the time reactor designs were at the height of their technical
development in the 20th century, is that the heated gaseous outlet substituted almost
directly in conventional boiler plants (albeit at lower temperatures) for the hot flue
gases usually derived from fossil-fuel plants. This enabled established boiler designs
to be used as the basis for early gas-cooled reactor steam generators.

Several requirements of reactor coolants are common to both liquids and gases:
nonflammability, chemical stability, low susceptibility to neutron activation and
good thermophysical properties (particularly high heat capacity and thermal con-
ductivity). The lower density of gases usually requires that higher flow rates are
necessary, relative to liquid phase coolants, to achieve similar heat transfer rates.
Gaseous coolants are, by definition, already vaporised and consequently it is not
possible to lose a high-capacity condensate from the system as a result of vapor-
isation as is the case with most liquid coolants, particularly water. This effectively
removes the upper temperature limit in terms of Carnot efficiency associated with
the critical point, so removing an important constraint in terms of thermodynamic
efficiency. Naturally, there are other engineering constraints to be considered
at higher operating temperatures, such as fuel-clad integrity and the action of the
high-temperature gas on reactor componentry, and so on. Nevertheless gas-cooled
nuclear reactors generally have higher thermodynamic efficiencies than their wa-
ter-cooled counterparts principally because of their higher operating temperatures.

The move away from the use of reactors for both power and nuclear materials
production has largely removed the imperative to refuel on-load. Rather, the eco-
nomic focus for power reactor operation has moved towards higher burn-up with
longer periods between fuel loading and shorter refuelling outages to optimise
the proportion of time spent at power. This has led to the widespread adoption of
light-water reactor technology throughout the world with gas-cooled reactors falling
out of favour. The UK remains a significant exponent of the gas-cooled technology
today. However, a central theme of several future reactor designs currently under
consideration is a drive to achieve higher thermodynamic efficiencies. One route
to this goal is to use gaseous coolants to increase outlet temperatures significantly
beyond current levels. Gaseous coolants may offer several further advantages in the
future that are not being exploited widely at present and these will be discussed in
further detail in Chapter 11. For example, the absence of significant moderation
lends the use of gaseous coolants to some fast reactor concepts.

The characteristically high upfront cost of nuclear plant and strong competition
from natural gas with regard to cost of electricity generation are causing research
attention to turn to the direct use of the heat generated by fission reactors [7]. This is
in contrast to continuing to employ downstream electricity generation systems and
incurring the conversion efficiency penalties that they introduce. An important
application of this approach might be, for example, in the production of bulk
chemical products used as the feedstock in pharmaceuticals production. The outlet
gas stream from the reactor would be used as the source of process heat to drive the
chemical processes directly. Used in this way, a reactor plant could replace an on-site,
fossil-fuelled plant offering a combination of power and heat with the advantages
of being low-carbon and rarely needing to be refuelled (if at all in the context of
small modular reactor designs). A further advantage of gaseous coolants is that,
in contrast with reactor designs that use the combination of graphite moderation
and light-water coolant, gas-cooled reactors lack the additional moderation that
can result in relatively high moderator-to-fuel ratios. This can result in operational
instability in the event of nucleation in a liquid coolant, as will be discussed in
Chapter 8 and also in Chapter 14. This represents an important design benefit,
particularly in terms of passive safety requirements associated with unexpected
changes in reactor power.

7.6.3.1 Carbon dioxide

Of the few options for gaseous reactor coolants that exist, given the caveats discussed
above, carbon dioxide is perhaps the most common in use today albeit now being
in decline in favour of light water. While several countries explored gas-cooled
reactors with carbon dioxide in the 1960s and 1970s, the most common design
is the Advanced Gas-cooled Reactor (AGR) using low-enriched uranium dioxide
fuel, carbon dioxide coolant and a graphite moderator. These reactors replaced the
previous generation of carbon-dioxide-cooled reactors in the UK that were based on
metal fuel of natural enrichment (Magnox) clad in magnesium alloy. Both designs
will be discussed further in Chapter 10.

With reference to Table 7.1, carbon dioxide has a significantly lower specific heat
capacity and density relative to those of water, as might be expected given its
gaseous state. While it has a lower dynamic flow rate in comparison to light water
systems (for example, the Sizewell B pressurised water reactor in Table 7.1), the
volumetric flow rate is approximately sixfold the flow rate of water-cooled plant (i.e.
PWR with the comparison based on an AGR). Carbon-dioxide-cooled reactors usually
require dedicated gas production facilities on site and gas circulators to achieve such
flow rates. The latter are used effectively in place of the primary coolant pumps in
water-cooled reactors.

To exploit the benefits of the vapour-phase Rankine cycle described earlier in this
chapter, nuclear reactors cooled with carbon dioxide are almost always used in a
dual-cycle, indirect configurations. The gas constitutes the primary coolant and light
water is almost always used in the secondary, due to its abundance and the other
beneficial attributes described earlier. The interface between the two sides of the
coolant system is the reactor boiler. Typically, several boilers are configured per
reactor core. While being relatively unreactive, at high temperatures carbon dioxide
can react with graphite and some steels. The main source of induced radioactivity
in carbon dioxide is that of trace impurities of 13C (1.11% abundance and not
radioactive) that becomes 14C as a result of neutron activation; 14C is a relatively
long-lived − emitter [8].

7.6.3.2 Helium
Helium has also been considered for use as a reactor coolant [9,10]. It satisfies most
of the requirements specified above and, as a noble gas, it has the benefit of being
chemically unreactive. Further, as reflected in the differences in its thermophysical
properties and flow characteristics, it offers a heat transfer performance that is
superior to carbon dioxide. This is usually reflected by it requiring reduced pumping
power. However, for mainstream use in gas-cooled reactors the important parame-
ter that has prevented its widespread use thus far has been its cost as compared to
the relative abundance and availability of carbon dioxide.

For future reactor design developments, where the emphasis is on raising operating
temperatures to achieve better thermodynamic efficiencies, helium is featured
in several possibilities. It offers greater chemical stability at higher temperatures
(~ 850°C) than carbon dioxide in addition to its heat transfer advantages. Helium
also offers the potential for direct, single-loop reactor circuit designs mated to
a helium-drive turbine and the supply of process heat, as described above. It is
indicated in theoretical analyses, however, that the potential exists for impurities to
be released into the coolant from in-core components and materials, predominantly
graphite, at such extreme temperatures. These will have to be removed from the
helium in these systems [11].

> Read full chapter

Production of biofuels via hydrother-

mal conversion
P. Biller, A.B. Ross, in Handbook of Biofuels Production (Second Edition), 2016

17.3.1 Hydrothermal carbonization

The reactor design in hydrothermal processing can be either batch or continuous.
Continuous reactors require feeding systems that operate under pressure and in-
clude either slurry-based pumps or lock and hopper systems for larger particles. The
use of larger particles usually requires more severe reaction conditions to achieve
similar carbonization to smaller particles. The feedstock may require pretreatment
to reduce the particle size and/or to remove contaminants such as stone, metal, or
plastic. The uniform feed is fed into the hydrothermal reactor where it is processed
typically for several hours depending on the reactor design. The slurry is then typi-
cally mechanically dewatered and dried. The hydrochar can be pelletized depending
on final use. The process water is either treated to remove nutrients, recycled or
both. A general process layout for HTC is summarized in Fig. 17.5.

Figure 17.5. Schematic layout of an HTC process.

The process water is considered a waste product but advancements have recently
been made in treating this stream by anaerobic digestion resulting in enhanced
biogas yields (Fettig, 2010; Danso-Boateng et al., 2015; Reza et al., 2014a,b). The
process water from HTC contains high levels of TOC and therefore linking to AD
can produce significant levels of biogas. Levels of biological methane potential
range from 0.5 to 1 L/g TOC (Wirth and Mumme, 2014; Oliveira et al., 2013). Some
challenges remain, such as reducing inhibition to methanogens but integration has
clear advantages and the integration of HTC with AD shows particular promise.

It is generally considered that for continuous operation, the process waters will
need to be recycled to minimize water usage (Uddin et al., 2014). During HTC, the
soluble organics in the water phase are both being produced and adsorbed although
there is evidence that the production dominates (Uddin et al., 2014), which means
it will continue to increase on multiple cycling. The level of inorganics will also
increase leading to a build-up of inorganics in the reactor (Uddin et al., 2014). This
may cause problems with salt corrosion and may require additional measures to
precipitate salts with possible recovery of nutrients. Recycling of process water can
be considered for each of the hydrothermal process routes and in HTC it has been
shown to increase the HTC yields of the hydrochar (Uddin et al., 2014).

> Read full chapter

Regulating Bioelectrochemical CO2 Se-

questration for Platform Chemicals
Production
Sai Kishore Butti, ... S. Venkata Mohan, in Microbial Electrochemical Technology,
2019
5.5.3.3 Reactor Architecture and Counter Electrodes
The reactor design and the counter electrode (CE) material have been the regulatory
factors for improving the productivity in BES. The product synthesis in BES from
inorganic carbon source is dependent on the electrochemical power developed in
BES and the extracellular electron transfer mechanisms involved, which are a func-
tion of anodic electrolyte, anode material, reactor design, interelectrode distance,
and scale of operation. Development of potent pure culture microbial catalysts for
understanding the electron transfer mechanisms have been successfully developed
and optimized in most of the studies. The current knowledge on the reactor design
and CEs influencing CO2 sequestration has remained fragmented and requires
development of good materials and designs. An overview of the various reactor
designs currently being developed for CO2 sequestration in BES are elaborated
below (Fig. 5.5.4). A detailed and thorough comparison between state-of-the-art sin-
gle-reactor and two-reactor systems in terms of energetic efficiency, productivity,
long-term stability, and costs would provide valuable information to develop BES
into a technology.

Figure 5.5.4. Critical factors acting as key regulators during bioelectrochemical CO2

sequestration in a bioelectrochemical system.

5.5.3.3.1 Single-Reactor BES Systems

BES reactors are often configured into a single-reactor system comprising two
chambers having an anode and a cathode setup, where both the electrodes are
operated at a potential difference. In the domain of CO2 biosequestration, the
primary part is the cathodic chamber, in which specific biocatalysts are enriched to
accept electrons from the cathode to reduce CO2. Protons and electrons that are
required for this process are evolved from the oxidation reactions at the anode.
Electrons flow via the closed circuit from the anode to the cathode, and protons
migrate usually through the proton exchange membrane toward the cathode. This
type of reactor arrangement is beneficial as it provides efficient contact between the
biocatalyst and the cathode lowering the electrical energy losses by enabling either
microbially induced acceleration of electron mediators or through DET. An externally
applied potential is generally required to drive the CO2 reduction reactions in these
reactors as the anodic chamber is either photocatalyzed or electrocatalyzed water
oxidation that generates the electrons and protons necessary for the biocathodic
CO2 reduction. The limiting factor that influences the cathodic CO2 reduction is the
migration of O2 generated during water oxidation to cathodes. The incorporation
of proton exchange membrane (PEM) limits O2 diffusion into the cathodic chamber
and prevents energy losses due to abiotic O2 electron reduction. Because PEMs are
expensive and difficult to scale up, membrane-less single-chamber reactors have
been adopted, in which the cathode and the anode are positioned to limit cathode
exposure to oxygen, and the use of a salt bridge has been developed. It provides the
possibility to use the in situ potential to extract negatively charged products such as
acetate, n-butyrate, and caproate from CO2.

5.5.3.3.2 Two-Reactor BES Systems

The BES systems driven by a biological oxidation reaction at the anode plays the
role of reducing power source in the two-chamber BES. These kinds of systems
employ two reactors with specific function of generating reducing equivalents and
CO2 bioreduction. The initial production of reduction shuttles such as Fe2+, NH4+,
and H2 are produced in the first reactor and autotrophic bacteria for the microbial
conversion of CO2 in the second reactor. The main benefit of two-reactor systems
is that highly specialized and productive bioelectrochemical cells could be used to
provide redox mediators at a high rate to the subsequent bioreactor, ensuring that
the electron source is not a limiting factor. It requires less external electrical energy
but simultaneously provides sufficient voltage to compensate for the electrode
overpotentials associated with bioelectrochemical CO2 reduction.

5.5.3.3.3 Photo-BES Systems

In the photo-BES systems, the anodic chamber or the source of reducing power or
electrons is derived from the light energy derived from the sun. The major catalysts
usually employed are the photoelectric material in the case of an abiotic anode and
photobacteria in a biotic anode, which require light exposure to provide energy for
the reduction of CO2. In a recent study, a photo-BES reactor was designed with
Methanosarcina sp. as the microbial catalyst for methane production from CO2 and
H2, where H2 was generated photo-electrochemically. In the case of photoelectric
anodes, the potential required for water splitting is provided by applied external
potential and light capture with an inorganic photocathode comprising TiO2 coated
with a nickel–molybdenum alloy to catalyze hydrogen evolution. Reactors contain an
abiotic photo anode or biotic photo anode capable of driving methane production
by Methanosarcina or acetate production by Sporomusa sp. However, the efficiency
of solar fuel cells is low, and most of the studies are in the proof-of-concept
stages or laboratory scale. Further optimization is essentially needed in this domain,
which could open new horizons in the development of semiartificial photosynthesis,
making this technology significantly viable and energetically efficient for the
biotechnological production of commodity chemicals.

> Read full chapter

Proceedings of the 8th International

Conference on Foundations of Com-
puter-Aided Process Design
Richard C. Pattison, Michael Baldea, in Computer Aided Chemical Engineering,
2014

2 Segmented Catalyst Macromorphology

Conventional reactor designs address the issue of longitudinally moderating heat
generation by judiciously distributing the fuel feed, or using multiple external heat
exchangers. These ideas are difficult to implement directly at the small scales
of CPRs, but can be emulated by a segmented combustion catalyst configuration
(Figure 1), consisting of alternating catalytically active and inactive sections (Pattison
et al., 2013).

Figure 1. Autothermal CPR with PCM layer and segmented catalytic combustion
segments.

While the segmented macromorphology can successfully modulate the rate of heat
release in the combustion channel, it is not a feedback control mechanism per se.
Clearly, the lengths of active and inactive sections cannot be adjusted online, and
must be fixed at the construction stage. Their optimal lengths can be determined via
a steady- state optimization. In (Pattison et al., 2013), we proposed formulating this
calculation as a least squares tracking problem at the nominal, steady-state reactor
capacity, where a parameterized temperature profile that leads to high reactor
conversion is optimized simultaneously with the catalyst layer configuration that
ensures that this distributed temperature target is closely tracked. The parameter-
ized profile for each channel includes a “preheating zone” where the temperature
gradually increases, and a common middle, constant-temperature “plateau” that
constitutes the main reaction zone.

> Read full chapter

Radioactive waste management in nu-

clear decommissioning projects
L. Valencia, in Nuclear Decommissioning, 2012

15.10 Future trends

New reactor designs, especially in the USA, are based on mobile treatment facilities
for evaporation, drying of sludge, and supercompaction. Such facilities can help
to reduce cost-intensive processes on each site. Appropriately equipped tracks are
coupled to the on-site waste-storage tanks and vessels, the waste is treated and
qualified disposal waste packages are produced, before the facility moves on to the
next site. Such procedures could also be useful for decommissioning activities, and
would contribute to sustainable financing and simplification of waste-management
processes.

The interim storage of spent fuel on site usually occurs in countries where fuel-re-
processing facilities are not available; for example the USA, Germany and Lithuania.
This also avoids transporting spent fuel over long distances. As the operation of a
high-level waste repository is not envisaged in the near future in these countries,
on-site storage of spent fuel will represent a viable and preferred alternative. The
storage of spent fuel either on site or in centralized storage facilities is essential
for the future use of nuclear power and also for future decommissioning projects.
As explained in 15.2, storage solutions can be found outdoors, as in the USA and
Lithuania; or indoors, as in Germany and Sweden.

> Read full chapter

Fouling During Hydrotreating
James G. Speight PhD, DSc, in Fouling in Refineries, 2015

12.2.3.1 Downflow Fixed-Bed Reactor

The reactor design commonly used in HDS of distillates is the fixed-bed reactor de-
sign in which the feedstock enters at the top of the reactor and the product leaves at
the bottom of the reactor (Figure 12.3). The catalyst remains in a stationary position
(fixed-bed) with hydrogen and petroleum feedstock passing in a downflow direction
through the catalyst bed. The HDS reaction is exothermic and the temperature rises
from the inlet to the outlet of each catalyst bed. With a high-hydrogen consumption
and subsequent large temperature rise, the reaction mixture can be quenched with
cold recycled gas at intermediate points in the reactor system. This is achieved by
dividing the catalyst charge into a series of catalyst beds and the effluent from each
catalyst bed is quenched to the inlet temperature of the next catalyst bed.

The extent of desulfurization is controlled by raising the inlet temperature to each

catalyst bed to maintain constant catalyst activity over the course of the process.
Fixed-bed reactors are mathematically modeled as plug-flow reactors with very little
back-mixing in the catalyst beds. The first catalyst bed is poisoned with vanadium
and nickel at the inlet to the bed and may be a cheaper catalyst (guard bed). As the
catalyst is poisoned in front of the bed, the temperature exotherm moves down
the bed and the activity of the entire catalyst charge declines thus requiring a raise
in the reactor temperature over the course of the process sequence. After catalyst
regeneration, the reactors are opened and inspected, and the high-metal content
catalyst layer at the inlet to the first bed may be discarded and replaced with fresh
catalyst. The catalyst loses activity after a series of regenerations and, consequently,
after a series of regenerations it is necessary to replace the complete catalyst charge.
In the case of very high-metal content feedstocks (such as residua), it is often
necessary to replace the entire catalyst charge rather than to regenerate it. This is due
to the fact that the metal contaminants cannot be removed by economical means
during rapid regeneration and the metals have been reported to interfere with the
combustion of carbon and sulfur, catalyzing the conversion of sulfur dioxide (SO2)
to sulfate (SO42 −) that has a permanent poisoning effect on the catalyst.

Fixed-bed HDS units are generally used for distillate HDS and may also be used
for residuum HDS, but require special precautions in processing. The residuum
must undergo two-stage electrostatic desalting so that salt deposits do not plug the
inlet to the first catalyst bed and the residuum must be low in vanadium and nickel
 content to avoid plugging the beds with metal deposits. Hence the need for a guard
bed in residuum HDS reactors.

During the operation of a fixed-bed reactor, contaminants entering with fresh feed
are filtered out and fill the voids between catalyst particles in the bed. The buildup
of contaminants in the bed can result in the channeling of reactants through the
bed and reducing the HDS efficiency. As the flow pattern becomes distorted or
restricted the pressure drop throughout the catalyst bed increases. If the pressure
drop becomes high enough physical damage to the reactor internals can result.
When high-pressure drops are observed throughout any portion of the reactor, the
unit is shutdown and the catalyst bed is skimmed and refilled.

With fixed-bed reactors, a balance must be reached between reaction rate and
pressure drop across the catalyst bed. As catalyst particle size is decreased, the
desulfurization reaction rate increases but so does the pressure drop across the
catalyst bed. Expanded-bed reactors do not have this limitation and small 1/32 inch
(0.8 mm) extrudate catalysts or fine catalysts may be used without increasing the
pressure drop.

> Read full chapter

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