Hydrogen management

R
efners are currently facing strong competi-
tion, which compels them to lower
operating costs wherever possible and to
utilise all process purge gas and offgas streams.
Stronger environmental regulations and the need
to process heavier crude signifcantly increase
hydrogen demand. The proftability of a refnery
depends on the method by which hydrogen is
produced and how hydrogen-containing gases
are recovered.
The imperative for process optimisation and
cost reduction leads to the application of a
modern hydrogen management system. In the
past, process optimisation and hydrogen recov-
ery could avoid a new hydrogen production plant
(HPP) investment. However, increasing hydro-
gen demand will soon require refneries to invest
in new HPPs, taking into consideration the fact
that most refnery processes involve catalytic
reactions. For this reason, this discussion focuses
on feed purifcation optimisation catalysts for
the hydrogen-producing steam reformer.
Retrospective view
Refneries in the 1970s and early 1980s operated
under quite different conditions than they do
today. The main feedstock was a light and sweet
crude, and this was available in suffcient quan-
tity and easy to handle. As crude oil prices were
low most of the time, investment costs governed
overall production costs. Processes were not
optimised with regard
to operating costs in
order to keep the invest-
ment cost low.
Environmental regula-
tions became more
stringent from the
1980s onwards, with
Axel Dker Sd-Chemie AG
Rainer Basse Uhde GmbH
limitations on sulphur, NOx, VOCs or CO
2
occur-
ring only during the last 20 years. The demand
on the quality of the products was also lower;
petrol and diesel contained lead, sulphur,
aromatics and others. During these times, hydro-
gen demand was quite low and, in case a refnery
operated a hydrogen plant, the process scheme
was simple, as shown in Figure 1.
Investment costs governed hydrogen plant
considerations. The hydrogen plant was a simple
utility unit, which processed natural gas or naph-
tha, depending on the availability, and produced
hydrogen and steam as a by-product. The typical
hydrogen process consists of desulphurisation,
steam reforming, high-temperature CO shift and
hydrogen purifcation. While the steam-reform-
ing process remained in principle the same,
except that the size of the steam reformers
increased signifcantly, the purifcation process
changed from a CO
2
-removal unit, followed by a
methanation unit, to the pressure swing adsorp-
tion (PSA) unit, which can achieve a much purer
hydrogen product and a more effcient hydrogen
plant.
Reneries today
A refnery today operates in a signifcantly differ-
ent environment. Raw material prices are
increasing dramatically. The demand for refnery
products is growing continuously, while the
availability of light and sweet crude is decreas-
www.digitalrening.com/article/1000631 PTQ Q1 2006 1
Several possibilities exist for the recovery of hydrogen from offgases and the
processing of different sources of renery gases through the hydrogen plant
Desu|furisation
Steam
reforming
CO-shift
Hydrogen
purification
Natura|
gas
Hydrogen
product
C
M
Y
CM
MY
CY
CMY
K
SudChemi,fig I S.pdf 8/II/0S ?0.SI.II
Figure 1 Simple hydrogen plant process scheme
ing, so refneries are forced to process more
heavy and sour crude. Also, stronger environ-
mental regulations and higher requirements on
the products are already resulting in a change to
the operating conditions. Due to higher crude oil
and other feedstock prices, operating costs
became more important and refners had to opti-
mise their processes.
These factors force refneries to focus on one
additional refnery product: hydrogen (H). Its
demand has increased signifcantly, and it is
increasingly recognised that hydrogen is a valua-
ble gas that needs special consideration. Utilising
all hydrogen-containing streams is therefore
essential for economical refnery operations.
Increased hydrogen demand
The frst step in meeting the growing demand for
hydrogen was the optimisation of plant processes
and the application of hydrogen management
tools like hydrogen pinch and network optimisa-
tion. This was followed by enhancing the
effciency of existing hydrogen plants and
2 PTQ Q1 2006 www.digitalrening.com/article/1000631
increasing their capacity.
Installation of a pre-reformer or
a reformer, such as a convective
reformer or gas-heated reformer,
operating in parallel to the steam
reformer, adding an LT shift and
raising the PSA effciency are
typical revamp measures.
The latest developments in
processing heavy crude and
producing ultra-low-sulphur fuel
and diesel create a considerably
higher hydrogen demand, which
cannot be covered solely by the
previously described steps. Now,
refneries have no other choice
than to look for new hydrogen
sources, and the most obvious
way is to build a new hydrogen
plant.
The actual new demand drives
the capacity consideration of
new hydrogen plants. Most of
the plants Uhde has built for
refneries during the last several
years are 90 000160 000Nm_/
h. This capacity can easily be
reached by a single-train unit
with a modern top-fred steam
reformer with a single-train PSA unit.
The size of this hydrogen source results in a
changing view of the hydrogen management
system. A large-scale hydrogen plant today is not
the minor supplemental hydrogen supplier it
once was. On the contrary, it is now the major
source of hydrogen, and more often the whole
refnery depends on this source. If it fails, the
whole refnery suffers.
Hydrogen process
A modern hydrogen plant can process not only
natural gas or naphtha, but also other hydrocar-
bons and hydrogen-containing streams. Thus,
refnery planners also consider a modern hydro-
gen plant to be a recovery unit for refnery
offgases and tail gases. When evaluating the
process, three major process steps can be defned
as:
Separation of hydrocarbons into H and C For
this step, a steam reformer or partial oxidation
unit is used, depending on the feedstocks. Steam
reformers will be viewed from the perspective
H
2
product
CO sh|ft
Pressure
sw|ng
adsorpt|on
Off-gas
Refinery
tai|gas
Refinery tai|gas
Export steam
Refinery
tai|gas
Desu|fu-
r|sat|on
Steam
reform|ng
Feed
C
M
Y
CM
MY
CY
CMY
K
SudChemi,fig ? S.pdf 8/II/0S ?0.S0.I
Figure 2 Typical hydrogen plant
2 PTQ Q1 2006 www.digitalrening.com/article/1000631
they still play as the major hydrogen production
unit
Conversion of CO with steam into hydrogen
and CO
2
This conversion takes place in a CO-
shift conversion unit
Hydrogen purifcation Depending on the
required hydrogen purity, CO
2
scrubbing
followed by a methanation unit or a PSA unit
can be used.
The refnery gases sent to a hydrogen plant for
hydrogen recovery or production can be fed into
the plant upstream of each of these process
steps.
The major portion of refnery gases will be fed
into the plant upstream of the reformer (Figure
2). These gases typically contain a higher amount
of hydrocarbons; unfortunately, not only lighter
paraffns, which can be mixed with the main
feed gas, but also olefns and aromatics.
Impurities like halogen compounds, heavy
metals and sulphur do not make their processing
easier.
For special applications, the refnery gas may
be fed into the CO-shift. Such a gas should
contain only a negligible amount of hydrocar-
bons but a high amount of CO, which is to be
converted to CO
2
and H
2
.
Gases already containing a high portion of
hydrogen may be fed directly into the PSA unit.
The hydrogen content should not be less than
60% by volume. Special care needs to be taken if
the gas contains impurities or unsaturated
hydrocarbons. They may require a pre-treatment
or be fed into the steam reformer, even with a
high hydrogen content. Another issue when feed-
ing gas directly into a PSA unit is the increased
PSA offgas. A standard hydrogen plant can use
all PSA offgas as fuel for the steam reformer.
However, due to the additional gas being fed
directly to the PSA unit, the amount of PSA
offgas increases without generating a higher heat
demand in the steam reformer. Depending on
the amount of additional gas and the composi-
tion of this gas, the PSA offgas fow is too high
to be fed completely into the steam reformer fuel
gas system. In this case, an additional consumer
needs to be found. The critical issue is the low
pressure of only 0.20.3 bar gauge, which
requires a compression of the export offgas frst.
The refnery gases normally do not match the
requirements to be fed into the hydrogen plant
without pre-treatment. They need to be
www.digitalrening.com/article/1000631 PTQ Q1 2006 3
compressed frst in case the supply pressure is
below the plant pressure. Unsaturated hydrocar-
bons must be hydrogenated. Impurities will be
removed either by suitable adsorbents like zinc
oxide or promoted zinc oxide catalysts. In case
the sulphur content is higher, a two-stage
removal may be considered. The bulk will be
removed in a stripper and the fnal purity will be
reached over a zinc oxide bed. If the feed gas to
the reformer exceeds a certain content of heavier
hydrocarbons, a pre-reformer needs to be
connected in series to the steam reformer.
Design objectives
A modern hydrogen plant has to process one or
several refnery gases in addition to its major
feedstock, natural gas, LPG or naphtha.
Sometimes, it will even be worth considering the
use of refnery gases as sole feedstock and the
former typical feedstocks as backup only. The
hydrogen yield shall be maximised; ie, all hydro-
gen atoms in the gases fed to a hydrogen plant
shall be recovered as far as technically possible.
As the hydrogen plant is becoming the major
hydrogen supplier for the refnery and the refn-
ery operations depend on this hydrogen, any
disturbance of the hydrogen production due to
unplanned fuctuations, or even a sudden loss of
a refnery gas, must be avoided. The main goal
of the hydrogen plant is to achieve the highest
level of reliability and availability, in addition to
providing a maximum level of fexibility regard-
ing plant load variations and changes in feed gas
fows and composition. These requirements can
be met with an advanced design and integrated
team approach.
The design needs to take into consideration
the aspects of various disciplines. The process
design remains the basic element. However, due
to the refnerys need to operate economically,
the plant controls and possible integration of the
hydrogen plant into an overall advanced control
system is of growing importance. Whereas the
process designer has to develop several operat-
ing cases (sometimes more than 20), he has only
one piece of equipment that must handle all
operating cases. For example, consider three
different feedstocks, one side stream to the PSA
unit, winter and summer cases, mixtures of the
three feedstocks as well as operating only one
feedstock, but each of them with full load and
possibly one or two defned partial load cases.
Nearly all process steps are catalytic reactions,
calling for the early involvement of the catalyst
supplier into the planning team.
A careful analysis of the refnery hydrogen
network is the basis for the hydrogen plant
development that best meets the requirements.
Co-operation between the refnery planner and
hydrogen plant designer in the early design
phase ensures the full potential of the hydrogen
plant can be utilised without asking for the
impossible. For the hydrogen plant designer, it is
essential to have a full understanding of all
aspects and the know-how of all disciplines
available, which are required to design and build
a hydrogen plant and to integrate it into a
complex refnery network.
Catalysts
To add more transparency and clarity to cata-
lysts available for modern refnery hydrogen
network systems, self-explanatory denomina-
tions are used for Sd-Chemie AGs formulations
instead of the C, G and T codes that are
diffcult to note. For example, all the catalysts
needed for the purifcation of hydrocarbon feed-
stocks are available within ActiSorb. ReforMax is
the name of the catalyst family used in all types
of steam reforming, while all hydrotreating cata-
lysts can now be found under HDMax.
A triple-digit code is used to differentiate
among the products in each family. For example,
the catalysts C49 and G-90 LDP are now known
as HDMax 200 and ReforMax 330 LDP respec-
tively (Table 1). Another differentiation is used
in the ActiSorb family, where one or two letters
are added to symbolise the component that is
absorbed (for example, Cl or S).
Simple feed purication
The hydrogen production unit in
a refnery not only provides on-
purpose hydrogen production,
but is also the recycling unit of
many offgases. These gases
normally contain impurities,
which can poison catalysts used
in the steam reformer and shift
section. Removal of all impurities
(for example, desulphurisation)
to the lowest possible level is
therefore the frst priority as
feedstock is introduced through
the series of catalysts in the hydrogen plant.
Classical desulphurisation systems typically
consist of one reactor loaded with a hydrotreat-
ing catalyst (normally CoMo), followed by a
two-reactor system loaded with a zinc oxide
(ZnO) catalyst to absorb the H
2
S. Both ZnO reac-
tors are in series and are interchangable to
achieve optimum purifcation and catalyst life-
time. Sd-Chemie AG has developed a catalytic
system combining these two process steps based
on the ActiSorb G1 catalyst. This is a promoted
ZnO-based catalyst, which hydrogenates all
organic sulphur compounds to H2S. This catalyst
is also formulated to saturate olefns that may be
present in the refnery offgases. In addition, this
high-surface-area ZnO catalyst absorbs all
formed H
2
S. Therefore, all these reactions occur
on this one catalyst in the same reactor. To
achieve the optimum lifetime for ActiSorb G1, it
is recommended that two interchangeable reac-
tors be used in series.
The desulphurisation system using ActiSorb G1
provides refners with capex and opex savings
opportunities. The capex for a new hydrogen
plant can be reduced to one complete reactor,
including all peripheral systems associated with
multiple reactors. Of course, the opex is also
reduced, because only one catalyst system is
required. ActiSorb G1 comprises a higher pick-
up capacity than any other ActiSorb ZnO, so the
lifetime is much higher, meaning the costs per
removed kg of sulphur are much less.
Studies and feld experience show that up to
40% opex can be saved by using ActiSorb G1
compared to standard systems with CoMo/ZnO
catalysts (Figure 3).
4 PTQ Q1 2006 www.digitalrening.com/article/1000631
60
70
80
90
100
110
50 R
n
o
i
t
a
s
i
r
u
f
|
u
s
e
d

f
o

t
s
o
c

e
v
i
t
a
|
e
,

CoMo
ZnO
Cost sav|ngs
Act|Sorb G1
C
M
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CM
MY
CY
CMY
K
SudChemi,fig S.pdf 8/II/0S ?0.S0.44
Figure 3 Performance of ActiSorb G1 relative to CoMo/ZnO catalysts
Trouble-free steam reforming
Close co-operation between the technology
provider for modern steam reformers and the
catalyst manufacturer is required to optimise
each individual design according to the needs of
the respective refnery. The key requirements of
the catalysts, however, are more or less always
the same:
High activity
High stability
Low pressure drop
Resistance to rapid-changing operating
conditions.
The ReforMax 330 LDP is a specially formu-
lated calcium/aluminant, which can withstand
thermo-shocks of over 1000C. This steam-
reforming catalysts ten-hole shape ensures an
always-uniform stress pattern, regardless of the
alignment of the catalyst particle in the reformer
tube. Frequent shutdowns and start-ups of the
reformer do not affect the catalyst. The best
proof of the documented stability of this catalyst
is that after more than 50 shutdowns of a world-
scale hydrogen plant within only two years, the
pressure drop over the reformer tubes increased
only marginally. The catalyst also combines a
high catalytic activity with a low pressure drop.
The steam-reforming catalyst determines
approximately 50% of a steam reformers pres-
sure drop.
With ReforMax 330 LDP, the pressure drop
can be reduced by more than 35% compared to
other commercially available catalysts. Over the
lifetime of the reforming catalyst, this lower
pressure drop accounts for many cost savings in
compressor power while increasing the overall
effciency of the hydrogen plant. The high cata-
lytic activity has a direct impact on reformer
design. The more active the catalyst, the fewer
tubes have to be installed. It goes without saying
that this is a positive contribution to reduce the
capex.
The size of the furnace is basically determined
by the number of reformer tubes, which are
given by the activity of the respective catalyst
and its ability to transfer fast enough a great
amount of heat into the tubes. Using ReforMax
330 LDP, the average heat fux can be as high as
100.000W/m2. This is more than 20% higher
than previous generations of steam-reforming
catalysts. In other words, the reformer can be
built with 20% fewer tubes. As the tubes are the
most expensive part of the reformer, a 20%
reduction in the numbers of tubes again saves
considerable investment costs.
Conclusion
Market globalisation and deregulation press
refners to optimise their processes in order to
reduce costs. The increasing demand for hydro-
gen and rising raw material prices make
hydrogen a valuable product and also an impor-
tant cost factor. The modern hydrogen plant
becomes an integral part of the refnery network
and can no longer be seen as a simple utility unit
at the refnerys periphery. As the refnerys main
hydrogen supplier, reliability of the hydrogen
plant is essential to overall hydrogen manage-
ment and economical refnery operations. The
integration of the hydrogen plant into the refn-
ery network in the early design phase is essential,
requiring the refnery planner, hydrogen plant
designer and catalyst supplier to work as a team.
Only this team approach can ensure develop-
ment of the most cost-effective solution with
respect to overall hydrogen network investment
and operating costs.
Axel Dker has been director of sales and marketing for renery
applications in Europe, Middle East and Africa for Sd-Chemie AG
in Munich, Germany, since 2003. Dker studied at the University
of Munich and holds a PhD degree in chemistry.
Email: axel.dueker@sud-chemie.com
www.digitalrening.com/article/1000631 PTQ Q1 2006 5 4 PTQ Q1 2006 www.digitalrening.com/article/1000631
Application Old designation New name
Hydrogen plants
Hydrodesulphurisation C49 HDMax 200
Desulphurisation G-72D ActiSorb S2
G-1 ActiSorb G1
Steam reforming G-91 LDP ReforMax 210 LDP
G-90 LDP ReforMax 330 LDP
CO conversion G-3C ShiftMax 120
C18 AMT plus ShiftMax 240
Hydrotreating C20-6 HDMax 220
C20-7 HDMax 310
T-2593 HDMax 520
Polygasoline C84-5 PolyMax 845
Traps JCl-3 ActiSorb Cl3
C28 ActiSorb S7
Sd-Chemies catalysts used in refneries
Table 1
Rainer Basse is responsible for the sales of hydrogen and syngas
plants at Uhde GmbH in Dortmund, Germany. Basse studied at
Ruhr-University of Bochum, Germany, and holds a degree in
mechanical engineering and business economics.
Email: rainer.basse@thyssenkrupp.com
6 PTQ Q1 2006 www.digitalrening.com/article/1000631

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