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Re-printed from | HydrocarbonEngineering | June 2011
 Robert Absil,
Intertek, USA,
examines the
impact of
hydrogen
in trickle
bed reactor
operation.

D
uring the design stage or during operations, a plant
operator may consider changing the treat gas rate and/or
hydrogen partial pressure in the hydrotreater reactor to
reduce costs. Since these are major process changes, a risk
analysis has to be done. Risk assessments are important when
implementing new technology in a process plant or refinery to
avoid potentially costly consequences. In order to implement this
process change, the plant operator should consider following a
step by step outline, which includes identification of each
potential technical risk; examination of the fundamentals
associated with each risk using in house literature or patent data;
assessment of semi qualification of each risk; mitigation of risk
by installing protection layers, such as pilot testing.1
Trickle bed reactor operation
Trickle bed reactors are the ‘workhorses’ of the refining,
chemical and petrochemical industries. They are constituted by a
three phase reactor, within which liquid and gas flow
concurrently down the catalyst bed, with the liquid flowing as a
thin film over the catalyst particles. Recycled hydrogen and
make up hydrogen are introduced into the reactor, both with
varying degrees of purity. The total hydrogen consumption
consists primarily of chemical hydrogen consumption, which
occurs as a result of reaction. Additional contributions include
dissolution in product effluent (approximately 10 - 20 ft3/bbl)2
and leakage losses (approximately 10 ft3/bbl).3 The chemical

Re-printed from June 2011| HydrocarbonEngineering |

 hydrogen consumption is specific to the process. The separator
configuration determines the amount of light ends adsorbed in
the liquid effluent, while the hydrogen recycle stream recovered
in the separator section is optionally scrubbed to remove the
hydrogen sulfide. The scrubbed hydrogen is then combined with
make up hydrogen and compressed to the desired inlet pressure.
The recycled hydrogen is approximately three to five times in
excess of the make up hydrogen.4
The role of hydrogen: chemical kinetics
Hydrogen is used in the trickle bed reactor operations because it
is a reactant in a large number of processes, including
hydrotreating, hydrodesulfurisation, hydrodenitrification,
hydrodeoxygenation and olefin/aromatic hydrogenation. A
hydrogen term, typically the hydrogen concentration at the
catalyst surface, is also incorporated in the rate equations that
model the kinetic reactions taking place on the catalyst surface.
In the absence of mass transfer limitations, the hydrogen
concentration at the catalyst surface is determined using only the
hydrogen partial pressure and Henry’s constant.5 The hydrogen
partial pressures must be calculated at the reactor inlet and
outlet. These have been reported to differ by as much as
100 - 500 psi when hydrotreating and/or hydrocracking a
feedstock, or when a large pressure drop exists across the
reactor. The outlet hydrogen partial pressure is considered more
important because it better reflects average reaction conditions
throughout the bed: it is a function of total pressure and vapour
phase composition.3 Additionally, accurate determination of
hydrogen partial pressures is important due to its particular
impact on kinetics. Gas oil consists of sulfur compounds with a
wide range of reactivities,6, 7 while in ultra low sulfur diesel
(ULSD) production the least reactive sulfur compounds are
converted in the lower section of the reactor at the lower
hydrogen partial pressures.
As a result of the substantially reduced bed length, the
pressure drop will be significantly smaller in bench scale or pilot
plant reactors than in a commercial reactor. Consequently, the
impact of the pressure drop across the reactor on the hydrogen
partial pressure will not be taken into account if pilot plant testing
is conducted at inlet hydrogen partial pressures, although loading
pilot plant reactors with inert, non-porous diluent to increase
wetting efficiency will increase the pressure drop. Therefore,
calculations are necessary prior to estimating the hydrogen
partial pressures at the inlet and outlet of the commercial reactor.
Consideration must be given to pressure drop increases during
the run, due to reactor plugging. If particulates cannot be
eliminated at source, than they must be dealt with (for example,
by using feed filters).1
Three mechanisms operating in hydrodesulfurisation
processes include:7
 Hydrogenolysis or direct desulfurisation.
 Hydrogenation followed by hydrogenolysis.
 Isomerisation of sterically hindered dimethyl substituted
dibenzothiophenes.
The hydrogen sulfide generated reduces the hydrogen
partial pressure at the reactor outlet. Furthermore, hydrogen
sulfide can have an inhibiting effect on hydrodesulfurisation
activity. 6, 7 CoMo/Al2O3 catalysts convert sulfur compounds via
direct desulfurisation, while NiMo/Al2O3 catalysts exhibit a
higher selectivity to the hydrogenation route. NiMo/Al2O3
Re-printed from | HydrocarbonEngineering | June 2011
catalysts are preferred over CoMo/Al2O3 catalysts if inhibitors
can be removed, since NiMo/Al2O3 catalysts are more
susceptible to hydrogen sulfide inhibition than CoMo/Al2O3
catalysts. The isomerisation reactions occur with an acidic
function and convert sterically hindered
dimethyldibenzothiophenes to more reactive
dimethyldibenzothiophenes. The inhibition effect results in a
loss of activity at a given temperature.7 While referring to
catalysts developed in the 1970s, McCulloch and Roeder
estimated that 'each vol.% S (all else held constant) reduces
desulfurisation activity by something like 3 – 5%, which means
3 – 5% higher catalyst loading is required to offset this effect.
Therefore, a weighted average H 2S vapour phase of 8 – 9%
would require roughly 30 – 40% more catalyst to do the same
job as compared to 0% H2S in vapour phase (admittedly a
hypothetical case).' 3 As a result, the inhibiting effect on
hydrodesulfurisation performance has to be taken into account.
Scrubbing the recycle stream to remove hydrogen sulfide can
reduce H 2S inhibition, but can also increase hydrogen partial
pressure.
The role of treat gas: fluid dynamics
In trickle bed reactors, the fluid dynamics and chemical kinetics
are interconnected. Reactor scale liquid maldistribution due to
poor liquid distribution at the inlet of the reactor, or due to
anisotropic sections in the bed, is assumed to be absent. The
fluid dynamic properties include wetting efficiency, liquid holdup,
pressure drop, mass and heat transport coefficients. Specifically,
treat gas pressure and flow rates have been shown to impact
these parameters. The wetting efficiency is defined here as the
fraction of the total external surface area of the catalyst that is
wetted by the liquid feed. When the liquid flow rate rises, the
liquid hold up follows because more liquid is covering the
particles and the pressure drop increases; likewise, the wetting
efficiency also increases. Due to the reduced length of pilot plant
reactors (in comparison with commercial reactors) and operation
of the same liquid hourly space velocity and with the same
particle size, the liquid velocities in the pilot plant reactors are
substantially smaller, causing wetting efficiency problems. This
has been remedied by using inert, nonporous diluents when
loading the pilot plant reactors.8
In the trickle flow regime, there is very little interaction
between the treat gas and the liquid. Treat gas composition
consists of hydrogen and inerts (for example, methane) and other
impurities (such as hydrogen sulfide). Beyond the threshold of
treat gas velocity ranging from 1 - 2 cm/sec, substantial
interaction occurs between the gas and the liquid at the
gas/liquid interface, causing the pressure drop to increase across
the bed and the liquid holdup to decrease with increasing treat
gas rate. The wetting efficiency increases due to improved
spreading of the liquid holdup over the external catalyst area with
increased treat gas flow.8
An increase in gas density, due to either a pressure increase
or an introduction of a higher molecular weight gas component
such as methane in the treat gas, produces a higher gas/liquid
interaction and results in an increased pressure drop and a
decreased liquid holdup and an improvement in wetting
efficiency. When the high pressure momentum transfer through
the gas/liquid interface becomes large enough, gas is entrained
into the liquid, forming tiny bubbles, leading with increased gas
density to enhanced gas/liquid surface area and gas side and
liquid side mass transfer coefficients. The impact of these
changes on reactor performance will depend on whether mass
and heat transport limitations are present.8
Drivers increasing hydrogen demand
The main drivers that lead to a higher hydrogen demand in
refineries include the use of heavier (lower API, higher sulfur)
crude oil, more stringent environmental regulations (lower sulfur
products) and increased upgrading in the future to meet low
sulfur marine fuel demand. The presence of increased sulfur
content results in higher hydrogen consumption when meeting
product sulfur specifications. Furthermore, hydrogen consumption
is substantially higher than required for just
hydrodesulphurisation because of aromatic hydrogenation
reactions at higher hydrotreating severities.9 MARPOL Annex VI
amendments requiring SOx emissions within the emission control
areas (ECA) will limit marine fuels at 1% sulfur until 2015 and
less than 0.1% sulfur after 2015.10 Due to the high cost and
technical difficulties associated with onboard scrubbing and low
sulfur fuel oil production, ships may switch to marine diesel.11
Conclusion
The demand for hydrogen in refineries will continue to increase,
emphasising the need for effective hydrogen management
programs at refineries and chemical plants. These hydrogen
management programs are focused on minimising the costs
associated with hydrogen usage and should use risk analysis to
assess the impact of the proposed changes on the operations.
The role of hydrogen in trickle bed hydrotreating operations has
been briefly reviewed and demonstrates the complexity of this
type of analysis and the risks when changing the hydrogen partial
pressure and/or the treat gas rate.
References
1. ABSIL, R.P., Petroleum Technology Quarterly, Q1 2011,
101 -109.
2. K AES, G.L., Refinery Process Modeling, The Athens Printing
Company, Athens, Georgia, 2008, 251 - 265.
3. McCULLOCH, D.C., and ROEDER, R.A., Hydrocarbon
Processing 1976, February, 81 - 86.
4. TURNER, J., and REISDORF, M., Hydrocarbon Processing 2004,
March, 61 - 70.
5. KORSTEN, H., and HOFFMANN, U., AIChE J., 1996, 42(5),
1350 - 1360.
6. KALLINIKOS, L.E., JESS, A., PAPAYANNAKOS, N.G., Journal of
Catal. 2010, 269, 169 - 178.
7. STANISLAUS, A., MARAFI, A., and RANA, M.S., Catal. Today
2010, 153, 1 - 68.
8. Al-Dahhan, M.H., Larachi, F., Dudukovic, M.P. and Laurent, A.,
Ind, Eng. Chem. Res. 1997, 36, 3292 - 3314.
9. LEE, C.K., McGOVERN, S., MAGALHAES, C. da SILVA, L.E.,
OSOWSKI, C.A, 2008, Oct 13, http://www.ogj.com/index/article-
display/342288/articles/oil-gas-journal/ volume-106/issue-38/
processing/study-compares-methods-that-measure-hydrogen-
use-in-diesel-hydrotreaters.html.
10. VAUTRIAN, J., 2008, Nov 24, http://www.ogj.com/index/article-
display/346119/articles/oil-gas-journal/volume-106/issue-44/
processing/a-new-regs-require-lower-bunker-fuel-sulfur-levels.
html.
11. WALDRON, M., IEA, Oil & Gas Markets 2010, Energy Statistics
Working Group, 01 Dec 2010.

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Re-printed from June 2011| HydrocarbonEngineering |