Unit 5

REACTOR MODELING AND DESIGN 9 Hydro treating of oil fractions:

Fundamentals of HDT, Reactor modelling, Catalytic reactors for fuel
processing: Reactor design and fabrication, water gas-shift reactors, modelling
of catalytic deoxygenation of fatty acids: model equations, adsorption
parameter evaluation, particle diffusion and parameter estimation study.
Hydro treating of oil fractions: Fundamentals
of HDT, Reactor modelling
• Catalytic hydrotreating represents a fundamental process in modern petroleum refining operations. It
allows removing hydrocarbon contaminants, such as
• sulfur,
• nitrogen,
• oxygen, and
• metals,
• saturating aromatic rings and olefins, and
• breaking high molecular weight molecules into lighter compounds.
• Due to its flexibility, the process can be employed to upgrade a variety of petroleum streams,
• ranging from naphtha to vacuum residues, or even full-range crude oils.
• Conventional hydrotreating is typically used as a pretreatment step to provide suitable quality feeds for
conversion processes, such as
• reforming,
• catalytic cracking, and
• hydrocracking, and
• also as a finishing step to produce transportation fuels that meet ecological standards.
modelling
• Among all the available hydrotreating reactor technologies, fixed-bed
reactors are the most frequently used in the petroleumindustry.
• In such systems, both gas and liquid flow cocurrently down through a
catalyst bed in trickle-flow regime.
• Modeling and simulation of hydrotreating becomes a challenging task
due to the complex interaction of numerous physical and chemical
processes:
• vapor–liquid equilibrium,
• gas–liquid and liquid–solid mass transfer of reactants and products,
• diffusion inside the catalyst particle,
• vast reaction networks, and
• catalyst deactivation.
Catalytic hydrotreating (HDT)
• the main purpose of the process is to remove impurities such as
• heteroatoms (sulfur, nitrogen, and oxygen) and
• saturate aromatic compounds,
• whereas in the case of heavy oils and residues,
• it also comprises the elimination of metals (nickel and vanadium) and
• conversion of asphaltene molecules.
• Its major applications in current refinery operations can be grouped in the following categories:
• (i) feed pretreatment for conversion processes such as catalytic reforming, catalytic cracking, and
hydrocracking (HCR) and
• (ii) post-HDT of distillates.
• In the first case, generally the objective is to reduce the amount of sulfur, basic nitrogen
compounds, metals, and polynuclear aromatics (PNA), which act as deactivation agents in acid-
catalyzed processes.
• The second group is mainly the finishing step to produce transportation fuels that meet
ecological standards (e.g., ultralow sulfur gasoline and diesel).
Reactors used
• Among all the reactor technologies,
• fixed-bed reactors (FBRs) are still the most widely used in HDT operations due to
their flexibility and relative simplicity .
• Other types of reactors such as moving-bed reactor (MBRs) and ebullated-bed
reactors (EBRs) are also available specifically for upgrading the heaviest fractions,
and their main feature is their capacity for replacing spent catalyst without
interrupting the operation.
• The selection between each type of technology is dictated by catalyst
deactivation, which depends
• The main process variables are pressure, temperature, hydrogen-to-oil
(H2/oil) ratio, and space velocity. Each variable affects the process in
different ways; therefore, the set of operating conditions must be carefully
adjusted to achieve an efficient operation on the nature of the feedstock
Reactions
• hydrodesulfurization (HDS),
• hydrodenitrogenation (HDN),
• hydrodearomatization (HDA),
• hydrodeoxygenation (HDO), and
• hydrodemetallization (HDM).
• Another type of reaction in which high molecular weight compounds are
broken down into lighter molecules is HCR, HCR of asphaltenes, the
process is often referred to as hydrodeasphaltenization (HDAs)
• The chemistry of these reactions can be visualized as a hydrogen
exchange process where hydrogenolysis and hydrogenation mechanisms
consume the externally supplied hydrogen in order to replace
heteroatoms and stabilize unsaturated products .
The HDT process
• Catalytic HDT is a fundamental refining process for the upgrading of a wide
variety of streams, ranging from straight-run naphtha to vacuum residue (VR)
or even heavy and extra-heavy crude oils.
• The HDT process is commonly employed for reducing the contents of
hydrocarbon impurities such as sulfur, nitrogen, oxygen, and aromatics by the
so-called hydrogen addition route. When it is applied to the processing of
heavy feeds, it also has the virtue of bringing down the concentration of
metals (Ni and V) and simultaneously increasing distillate yield at the expense
of the heaviest fractions such as VR and asphaltenes.
• The process has gained significant relevance in the industry due to the
growing demand for transportation fuels and the strict environmental
legislations.
Chemistry
• HDT is a process in which the hydrogen/carbon ratio of the feed is
increased in the presence of a catalyst in a hydrogen- rich
atmosphere.
• HDS, HDN, HDO, and HDM reactions are considered to follow the
hydrogenolysis mechanism, where the carbon–heteroatom bond is
cleaved by a hydrogen molecule.
• Olefin and aromatic molecules are directly hydrogenated without
undergoing any bond cleavage.
• HCR and HDAs reactions, on the other hand, belong to the
acidcatalyzed cracking chemistry incombination with hydrogenation.
Process aspects of HDT
• Process variables
• An accurate selection of the set of operating conditions ensures the best
process performance. The main process variables (temperature, pressure,
space velocity, and H2/oil ratio) are adjusted according to the specific HDT
application.
• Most of these processes are generally carried out in fixed-bed units, with the
exception of ebullated-bed residue HCR.
• Naturally, the severity of the process increases with the heaviness of the
feedstock.
• Distillate HDT is carried out at relatively mild conditions compared to residue
HDT. HCR processes require more severe conditions than HDT and are much
more demanding in terms of hydrogen supply
• Reaction temperature
• Reaction temperature is certainly the most influential process variable. The extent and selectivity of
HDT and HCR reactions are very sensitive to this process parameter because the rate coefficients
increase exponentially with reaction temperature.
• Therefore, reaction temperature is matched to the chemistry of the process in order to achieve the
desired selectivity. Light distillate HDT is performed in a temperature range (320–340 C) that is
sufficient for almost complete HDS and HDN
• Above these temperature levels, there could be degradation of light hydrocarbons as a result of
thermal cracking and unfavorable equilibrium for hydrogenation of aromatics in the case of gas oil
HDT.
• Residues and VGO are more refractory in nature, and therefore, HDT requires higher temperatures,
in which case it is important to operate at higher hydrogen partial pressures to improve the
equilibrium concentration of saturated rings.
• HCR processes are carried out at the highest temperatures because C─C bond scission requires more
energy than HDT reactions.
• Hydrogen partial pressure
• Hydroprocessing units are typically operated in a pressure range of 1–30 MPa.
High pressures are necessary for reducing coke formation on the catalyst
particles, increasing the availability of hydrogen in the liquid phase, increasing
conversion, improving heat transfer, and handling higher volumes of gas [59].
• Hydrogen partial pressure (PH2) is simply the product of multiplying the total
pressure by the hydrogen purity (mol%) of the gas recycle stream. As in the
case of reaction temperature, the required hydrogen partial pressure
increases with the heaviness of the feed and the desired conversion level.
Hydrocrackers are operated at the most elevated hydrogen partial pressures
to attain the highest conversions.
• H2/oil ratio and gas recycle
• H2/oil ratio is a standard measure of the volume of hydrogen
circulating through the reaction system with respect to the volume of
liquid feed. It is defined by the following relationship:

• Gas recycling is required to generate a sufficiently rich hydrogen

environment in the reactor. This ensures keeping hydrogen partial
pressure at appropriate levels and increases the availability of
hydrogen in contact with the catalyst and hydrocarbon molecules. The
recycle rate is established on the basis of process objectives and
economic aspects.
• Space velocity
• Space velocity is a ratio between the hydrocarbon feed rate and the
amount of catalyst loaded in the reactor. It indicates how many
reactor volumes of feed (considering only the volume occupied by the
catalyst) can be processed in a unit of time.
• Space velocity can be established on a volume basis (LHSV) or on a
weight basis (weight hourly space velocity (WHSV)):
Catalytic reactors for fuel processing
• Fuel processing is the conversion of fossil and regenerative fuels to hydrogen-containing gas
mixtures. The chemical conversion is performed in most cases in the gas phase, normally
heterogeneously catalyzed in the presence of a solid catalyst. The first step of the conversion
procedure is named reforming.
• It has been established in large-scale industrial processes for many decades. The industrial
applications most commonly use natural gas as feedstock.
• The product of the natural gas reforming process is synthesis gas, a mixture of carbon
monoxide and hydrogen, which is then used for numerous processes in large-scale chemical
production which are not subject of this section but rather the technology, which provides a
hydrogen-containing gas mixture, named reformate, which is a feed suitable for a fuel cell.
• The fuel cell then converts hydrogen to electrical energy. Depending on the fuel cell type,
removal of carbon monoxide might be required, which is achieved by water-gas shift and
preferential oxidation reactions performed downstream the reformer.
• The reactor types suitable for mobile and decentralized applications are, apart from
conventional fixed-bed reactors, ceramic and metallic monoliths, (microchannel) plate heat
exchangers, and membrane reactors
The basic reactions of fuel processing
• Steam reforming is the gas phase conversion of energy carriers such as hydrocarbons and alcohols described
by the general formula CxHyOz with steam to a mixture of carbon monoxide and hydrogen according to the
following reaction:

• The product mixture of the reaction is named reformate. The reaction is endothermic and thus requires heat
supply
• the reformate usually contains significant amounts of unconverted steam, to a lower extent some
unconverted fuel and carbon dioxide, the latter being formed by the consecutive water–gas shift (WGS)
reaction:

• The WGS reaction increases the hydrogen concentration of the reformate. This reaction is usually fast
enough at the elevated temperatures of hydrocarbon reforming to achieve thermodynamic equilibrium.
Owing to its exothermic character, higher reaction temperatures favor the reverse reaction.
• Partial oxidation is the conversion of fuels under oxygen deficient atmosphere:
Reactor design and fabrication
• Fixed-bed reactors
• Fixed-bed reactors for distributed fuel processing applications are normally
comprised of an insulated stainless steel vessel or tube containing a mesh at the
reactor inlet and outlet respectively, to maintain the catalyst within the reactor.
• When heat has to be removed from or introduced into the catalyst bed, small
tubes are usually introduced into the vessel, which serve as heating or cooling
sources via hot or cold fluid flows.
• The reactor design is then equivalent to that of a shell and tube heat exchanger.
• However, monolithic reactors and plate heat exchangers are more suitable than
fixed beds for the rapid start-up and transient operation requirements of fuel
processors of the smaller scale
Monolithic reactors
• The fabrication of ceramic monoliths is performed mainly via extrusion techniques resulting in
usually elliptic or square shaped monoliths. Cell densities as high as 1600 cells per square inch (cpsi)
are achieved , which corresponds to a channel width of about 500 μm of the mostly rectangular or
hexagonal channels.
• Owing to the low surface area of the monoliths, a catalyst carrier such as alumina or ceria is
deposited onto them usually by wash coating . The ceramic construction material is well compatible
with these carriers, does not migrate into the catalyst coatings, and the precious active metal species
of the catalysts do not migrate into the monolith bodies . The most widely used construction
material for ceramic monolith carriers is cordierite with alumina being an alternative.
• Metallic monoliths have numerous advantages over ceramic honeycombs, such as higher mechanical
stability, lower wall thickness, and higher heat conductivity of the wall material, while the maximum
cell densities are equivalent to those of the ceramic monoliths
• The catalyst coatings in ceramic and metallic monoliths are not always evenly distributed, which
affects the performance of the monoliths concerning flow equipartition and temperature profile,
because the heat conduction is also affected
Microreactors
• Microstructured plate heat exchangers are stacked arrangements with a multitude of parallel
minichannels and high surface- to-volume ratios in the range of 200 m2/m3. The preferred
construction material is stainless steel. Wet chemical etching, initially developed for silicon
micromachining, is suited for mass production of microchannels
• Embossing is an inexpensive technique for manufacturing metal foils highly suitable for mass
production
• Sealing by gaskets increases the thermal mass of the devices considerably, which increases
start-up time demand. Irreversible sealing techniques make typically use of elevated
temperatures for which compatibility to the plate material and its coatings has to be
considered. For chemical reactors, the main issue is the thermal stability of the catalyst coating,
if being filled in or attached before the sealing, which is the current mainly applied method.
Catalyst deactivation may arise from about 300 C to more than 800 C depending on the catalyst
formulation which can pose a serious limit to the applicability of the sealing method.
• (i) spray coating [11], which requires a reduction of the viscosity of the slurry or sol, (ii) flame
spray deposition [20], and (iii) electrophoretic deposition [21]. After the deposition usually
drying and calcinations steps follow, the latter being a heat treatment in air or in other gases for
a defined duration.
Membrane reactors
• MRs combine chemical conversion with a membrane separation step. Within
the scope of fuel processing, MRs are usually either combined with the
reforming step
• Thin metallic membranes may be produced by techniques such as cold rolling
However, the fabrication of thin palladium membranes onto ceramic surfaces
is more complicated and requires methods such as spray pyrolysis chemical
vapor deposition and sputtering, but most frequently electroless plating is
applied .
• Palladium particles are produced from palladium solution containing amine
complexes of palladium in the presence of reducing agents.
• Ceramic surfaces such as α-alumina are first sensitized in acidic tin chloride,
and then palladium is seeded from acidic palladium ammonia chloride .
Water-gas shift reactors – self study