Faculty of Chemical Engineering

Hydrogenation of hydrocarbon by trickle bed reactor

Prepared by: Tolaz Yasin

Supervised by: Dr.Arkan Jasim Hadi

Octobor 2020

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Discription of Reactor Design
Reactor Design is the study of chemical reaction rates and reaction mechanisms. The study of
chemical reaction engineering (CRE) combines the study of chemical kinetics with the reactors
in which the reactions occur.Chemical kinetics and reactor design are at the heart of producing
almost all industrial chemicals. It is primarily a knowledge of chemical kinetics and reactor
design that distinguishes the chemical engineer from other engineers. The selection of a reaction
system that operates in the safest and most efficient manner can be the key to the economic
success or failure of n chemical plant.

reactor design uses in many industries and there are many type of reactor, for example
Continuous stirred-tank reactors are most generally used in industrial processing, primarily in
homogeneous liquid-phase flow reactions, CSTRs are also used in the pharmaceutical industry
as a loop reactor. another application of CSTR s that contain the use of a biological catalyst to
make products. In a fermenter, microbes catalyze a reaction which impart much larger molecules
into smaller molecules for example ethanol, methanol, or other hydrocarbons. Vapor product can
be clear away from the top of a unit without separation, or liquid product can be clear away from
the bottom, filtering out and recycling the microbial media.

a chemical reactor deals with multiple aspects of chemical engineering. Chemical engineers
design reactors to maximize net present value for the given reaction. Designers ensure that the
reaction proceeds with the highest efficiency towards the desired output product, producing the
highest yield of product while requiring the least amount of money to purchase and operate.
Normal operating expenses include energy input, energy removal, raw material costs, labor, etc.

There are a couple main basic vessel types:

- A tank

- A pipe or tubular reactor (laminar flow reactor(LFR))

Both types can be used as continuous reactors or batch reactors. Most commonly, reactors are
run at steady-state, but can also be operated in a transient state. When a reactor is first brought
back into operation (after maintenance or inoperation) it would be considered to be in a transient
state, where key process variables change with time. Both types of reactors may also
accommodate one or more solids (reagents, catalyst, or inert materials), but the reagents and
products are typically liquids and gases.

There are three main basic models used to estimate the most important process variables of
different chemical reactors:

- Batch Reactor

- Continuous Stirred-Tank Reactor (CSTR)

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- Plug Flow Reactor (PFR)

Key process variables include

- Residence time (τ) , Volume (V) , Temperature (T) , Pressure (P) , Concentrations of chemical
species (C1,C2, C3,... Cn) ,Heat transfer coefficients (h, U) Chemical reactions occurring in a
reactor may be exothermic, meaning giving off heat, or endothermic, meaning absorbing heat. A
chemical reactor vessel may have a cooling or heating jacket or cooling or heating coils (tubes).

Introduction
Hydrogenation process is a well-known method to have been used in refinery over many
decades. It has the advantage of converting various hydrocarbons to most valuable ones, ranging
from dealkylation of aromatics, opening of naphthenic rings, hydrocracking of paraffin chains,
removal of hetro-atoms and saturation of carbon-carbon bonds (see Scheme 1).10 For instance,
hydrogenation reaction can proceed through the addition of adsorbed hydrogen molecule on
catalyst surface to the unsaturated bonded atom to form a corresponding saturated alkane.11–14
It also has the advantage to open up an unsaturated ring and removal of hetro-atoms into any
hydrocarbon formed molecules.

Scheme 1: Typical hydrogenation units and products for fuel range blending

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hydrogenation reaction in petroleum industry
The hydrogenation reactions of hydrocarbon feedstocks are extensively carried out in petroleum
refineries. The practice usually employs the use of metallic/ acidic catalysts at elevated
temperature and hydrogen pressure conditions. The hydrogenation process in refinery constitutes
versatile activities of a number of important reactions, which includes the removal of hetro-atoms
such as sulphur, nitrogen and metals, saturation of olefins and aromatic, opening of naphthenic
rings, and to improve the H/C ratio in hydrocarbon range fuels. The main primary objectives are
as follows:

1. Removal of sulphur from gasoline blending components to meet the recent clean fuel
specifications and downstream processes.

2. Removal of sulphur from diesels and kerosene for heavy engines and home heating,
respectively.

3. Conversion of kerosene to jet fuel through mild aromatic saturation.

4. Removal of hetro-atoms for efficient catalyst activity in FCC.

5. Hydrocarbon rings opening and saturation of olefins into paraffin which couldcould further be
converted into iso-paraffins for cetane/octane improvement.

Scheme 2:a generic form of hydrogenation reactions in refinery

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Hydrogenation of Unsaturated C4-C8 to Alkanes
The hydrogenation reaction involved the addition of absorbed hydrogen on the catalyst surface to
the unsaturated hydrocarbon in the feed and producing the corresponding paraffin. A simple
generic mechanism is outlined in Scheme 3 below.

Scheme 3: Illustrative mechanism for hydrogenation of hydrocrabons.

Hydrogenation of hydrocarbon is exothermic and produces a significant amount heat. However,

alkynes are thermodynamically less stable than the respective alkene due to the nature of their
bonding and strongly adsorb catalyst surfaces. Highly unsaturated hydrocarbons are sometimes
hydrogenated into corresponding olefin depending on demands. Producing the desired alkene
rather than the alkane, however, in catalytic hydrogenation, may be difficult because there are
significant numbers of hydrogenation catalysts effective in promoting the addition of hydrogen
but fewer are selective in that aspect. Hydrogenation of unsaturated bonds is considered a very
important catalytic technique in refinery operations. Ideally, hydrogenation can be performed at
low temperature of ~100°C or below and relatively low hydrogen pressure of typically 10–15 bar
in a catalyst system system constituting constituting noble metal such as Pt, Pd, Rh and Ru.
However, catalyst metals such as Ni, Co, Sn and Mo, etc., required a high temperature and high
hydrogen pressure but are cheaper and more accessible.

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Trickle bed reactor
The trickle bed reactor (TBR) is a three phase reactor commonly used in industrial applications,
such as petroleum, petrochemical and chemical processes, waste water treatment, and
biochemical and electrochemical processes. Hydrogenation, oxidation and des- ulfurization are
among the most common reactions used in a trickle read reactor. Generally, achieving high
conversion requires high operating temperature to favor catalytic activity, and high operat- ing
pressure to improve gas solubility and mass and heat transfer rates, to handle gas volumes from
high operating temperature at lower capital cost and to slow down the catalyst deactivation .
Commercial trickle bed reactors are usually operated under steady state mode (constant feed
rates) under trickle flow regime (low gas and liquid flow rates), which means that the interaction
between gas and liquid is rather poor]. Therefore, the gas-liquid mass trans- fer rate is low. At
this condition, it is likely that catalyst particles in the reactor are not completely wet by the
liquid.

scheme 4:trickle bed reactor

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TBR with Co-current Gas-Liquid Downflow
A TBR consists of a column that may be very high (above 10 to 30 m), equipped with one or
various fixed beds of solid catalysts, throughout which gas and liquid move in co-current
downflow. (Figure 5_a) shows the typical film flow texture found during a trickle- flow regime.
In this mode, gas is the continuous phase and liquid holdup is lower. This operation is the one
most used in practice, since there are less severe limitations in throughput than in countercurrent
operation.for gas-limited reactions (high liquid reactant flux to the catalyst particle, low gas
reactant flux to the particle), especially at partially wetted conditions, a downflow reactor is
preferred, as it facilitates transport of the gaseous reactant to the catalyst. In contrast to
commercial TBR, in the case of bench-scale TBR operating at equivalent space velocity, the
liquid velocity and the catalyst bed length have important effects on the performance of the
reactor.

TBR with Countercurrent Gas-Liquid Flow

TBRs operating in countercurrent gas-liquid flow (Figure 5_b) provide an opportunity for
selective removal of by-products that may act as inhibitors (e.g., in hydrodesulfurization, where
hydrogen sulfide may have an inhibitory effect). The introduction of FBRs with countercurrent
flow in a number of refining operations is probably either via redesign of existing reactors or by
introduction of new technology. As mentioned earlier, the goal is not an improvement in reactant
(hydrogen) mass transfer, which is not rate limiting, but enhanced removal of inhibitory
byproducts or in situ product separation. That is why countercurrent flow will become more
prominent in the future for processes that suffer from byproduct catalyst inhibition.

A catalytic PBR with countercurrent mode is a suitable alternative to TBRs for reactions
conducted over catalysts with a very large surface area-to-volume ratio. However, the main
problem of the countercurrent reactor for commercial application is due to hardware limitations.
There is therefore a need to develop improved hardware configurations that allow countercurrent
contacting of gas and liquid in the presence of small catalyst particles.

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 scheme _5 type of trickle bed reactor

Scheme_6 reactant concentration profile

C Ai = concentration of A in liquid at the interface, kmol/m3 C A(g)=bulk gas concentration

C Ab = bulk liquid concentration of A, kmol/m3 C Ai(g)= concentration of A at
interface

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Experimental hydrogenation reaction and controlling
Catalysts and Reactants. The catalyst was a commercial Shell NiO-MoO3 on γ-alumina
supplied as 1/16 in. extrudates crushed and sieved to 360-500 μm particles. Textural properties
were determined by nitrogen adsorption methods em- ploying a Micromeritics ASAP 2000
analyzer and fol- lowing standard procedures.The liquid feed for the hydrogenation runs
consisted of 20 wt % of a light fraction of anthracene oil dissolved in toluene (purity >99.5%).
Anthracene oil was supplied by NalonChem (Asturias, Spain).

Equipment and Reaction Experiments. The hy- drogenation reactions were carried out in a
cocurrent downflow high-pressure trickle-bed reactor. The ex- perimental system used in this
investigation is shown inFigure7. Thereactorwasastainlesssteeltubeof9 mm i.d. and 450 mm
length placed inside an electrically heated furnace. Five thermocouples measured the temperature
at different reactor heights. The temper- ature of the reaction zone, located in the center of the
bed, was kept constant at the desired value. The hydrogen gas flow rate was controlled by a
Brooks 5850TR/X-5879E mass flowmeter and controller. The liquid feed was supplied by a
Kontron LC T-414 pump. The pressure inside the reactor line was maintained by a Tescom back-
pressure regulator. The reactor effluent flowed into a 1000 mL stainless steel cylinder acting as a
gas liquid separator and a reservoir for liquid reaction product. A two-valve system allowed
periodical with- drawal of liquid samples to the analytical equipment. The catalyst was sulfided
in situ before use by passing a mixture of 10% of H2S in H2 at 673 K over it during 4 h at a flow
of 30 cm3(NTP)/min. An additional 1 wt % CS2 was added to the liquid mixture to maintain the
catalyst in the sulfided form. A total amount of 2.4 g of catalyst was introduced in the central
zone of the reactor diluted with low-area inert alumina (Jansen) of the same granulometry. The
reactor was also filled with alumina both above and below the reaction zone, the length of which
was 40 mm.The hydrogenation reactions were carried out at 573K and a total pressure of 9.8
MPa.

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Figure 7. Flow diagram of the trickle-bed hydrogenation unit: (1) hydrogen buffer; (2) filter; (3)
mass flowmeter and controller; (4) feed pump; (5) pulse damper; (6) reactor; (7) rupture disk;
(8) gas-liquid separator; (9) graphic recorder.

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REFERENCES

1. M. H. Al-Dahhn, F. Larachi, M. P. Dudukovic and A. Laurent, Ind

2. Boitiaux, J. P. et al. (1987). Liquid phase hydrogenation of unsaturated hydrocarbons on
palladium, platinum and rhodium catalysts. Part I: Kinetic study of 1-butene, 1,3butadiene
and 1-butyne hydrogenation on platinum. Appl. Catal., 32, 145–168,
3. Al-Dahhan, M.; Dudukovic, M. P. Pressure Drop and Liquid Holdup in High Pressure
Trickle-Bed Reactors. Chem. Eng. Sci. 1994, 49, 5681.
4. Al-Dahhan, M.; Dudukovic, M. P. Catalyst Wetting Efficiency in Trickle-Bed Reactors at
High Pressure. Chem. Eng. Sci. 1995, 50, 2377.
5. Baldi, G. Design and Scale-up of Trickle-Bed Reactors. Solid-Liquid Contacting
Effectiveness. In Multiphase Chemical Reactors, Vol. II: Design Methods Rodrigues, A.
E., Calo, J. M., and Sweed, N. M., Eds.; NATO Advanced Study Institute Series E52;
Sijthoff and Noordhoff: Alphen aan den Rijn, The Netherlands, 1980; pp 323-341.

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