Dr. J.

Bezler*
Süd-Chemie AG, Catalytic Technologies, München, Germany

Advanced Hydrogen Production Technology

Upgrade Options and Catalytic Solutions to Meet the Demand for

More Hydrogen in Refineries

5th EMEA Catalyst Technology Conference – 3./4. March 2004

* SÜD-CHEMIE AG
Catalytic Technologies

Lenbachplatz 6 Phone: +49-89-5110-278

80333 Munich Fax: +49-89-5110-516
Germany
e-mail: juergen.bezler@sud-chemie.com

-----------------------------------------------------------------------------------------------------------------

Summary

Future regulations for the limitation of sulfur and aromatics in fuels driven by the
European Auto Oil Programme (AOP II) represent a challenging scenario for the
European refineries. In addition to the need of further investments in order to comply
with these stringent specifications the demand for hydrogen will increase worldwide
in refineries.
Catalytic technologies from Süd-Chemie can be applied to existing hydrogen plants
to maximise throughput and represent a cost-effective way to increase hydrogen
production. Such retrofit options cope with the construction of a new hydrogen plant
with a case-by-case evaluation to determine the best upgrade option for each
particular plant.
This paper describes the advances in the catalytic area to meet the increased
demand for hydrogen in refinery operations.

Page 1
Economic Background

Hydrogen represents an important intermediate both in refining and chemical

industries and is generally accepted to gain importance in future energy production.

Presently the most important use of produced hydrogen is the production of ammonia
and methanol but hydrotreating applications in refineries are becoming more and
more important. Initiated by future fuel specifications refineries will have to produce
new product qualities in accordance to the European Auto Oil Programme (AOP II).
Stringent low sulfur and aromatics fuel has been introduced and the reduction of the
sulfur content to 10 ppm must be reached in the year 2005 in addition to less
aromatics and olefins.

Worldwide the catalytic-process-to-crude-capacity-ratio increased considerably,

reflecting the increase of the conversion level of modern refineries. During the last 5
years catalytic processes like hydrocracking and hydrotreating processes increased
by volume up to 25% indicating the trend for an increased hydrogen demand in
refining.

% Increase of Catalytic Processes since 1997

30
Hydrotreating
25

20 Fluid Catalytic Cracking

15
Hydrocracking
10

5 Naphtha Reforming

0 Crude Destillation Capacity

1998 1999 2000 2001 2002
-5

Figure 1: Catalytic processes in refineries [1]

Page 2
Due to the processing of more heavy and sour crude in refining operations
hydrogenation reactions gain more and more in importance and the hydrogen
demand is increasing dramatically. Since 1991 both in the U.S. and in the European
refineries the total on-purpose hydrogen demand increased significantly in the U.S.
and in the European refinery market [4].

The need for more hydrogen in refinery processes created a market for “buy
hydrogen” and represents a huge economic factor in refinery economics. The
efficiency of hydrogen production is essential for modern refineries [10]. In future the
hydrogen demand will significantly increase and is estimated to grow by 10% per
year through 2008, nearly doubling the market from 61.6m Nm3/day in 2001 to
112.6m Nm3/day in 2008 [5].

The hydrogen demand in refineries [6] is covered from other refinery processes
mainly catalytic reforming. Other sources [11] are recovery from H2 rich off gases or
the production of H2 in the steam reforming process [8].

Hydrogen Hydrogen
Production Consumption

Hydrocracking
Catalytic Reforming
Hydrotreating
Recovery from off-gases Hydrogen
Hydroconversion

H2 Plant
Hydrofinishing

Figure 2: Hydrogen balance and refinery processes [7, 9]

Page 3
Compared to other hydrogen production technologies the steam reforming process
operates with the lowest energy consumption.

Total Energy Consumption

\NatGas Equivalent, Nm3 NG/Nm3 H2
Steam Reforming 0.41
Oxygen Reforming 0.47
Coal Gasification 0.59
Methanol Dissociation 0.88
Water Electrolysis 1.3

Table 1: Economics of hydrogen production [3]

The conversion of more heavy feedstocks requires more hydrogen in refineries.

Following Süd-Chemie`s vision to create performance technology catalytic solutions
are designed for the improvement of refinery operations [12].

Hydrogen
Hydrogen Hydrogen
Production
Production
RFG

Naphtha
Naphtha
HDT
HDT Gasoline
C5/C6-Naphtha Isomerization
Isomerization
TRAP’IT- Cl
TRAP’IT-Cl HH22Off
Off Gas
Gas

HDAr
HDAr Gasoline
Catalytic
Catalytic
HDT
HDT TRAP’IT-S
TRAP’IT-S TRAP’IT- Cl
TRAP’IT-Cl
Naphtha Reforming
Reforming BTX
BTX Clay
Clay BTX
Processing
Processing Treating
Treating

Clay
Clay
HDX
HDX HDS
HDS HDAr
HDAr Kerosene
Kerosene Treating
Treating

HDX
HDX HDS
HDS HDAr
HDAr Diesel
Gas Oil

Olefin
Olefin
C
C44-Olefins
-Olefins Dimerization
Dimerization Gasoline
Saturation
Saturation

HDS
HDT FCC
FCC Sel.
Sel. HDS
HDS Gasoline

Kerosene
HDM
TRAP’IT-M HDX
HDX MHC
MHC/ HC
VGO Diesel

Heavy
Heavy Oil
Oil Sour
Sour Gas
Gas Claus
Claus Unit
Unit Sulphur
Processing
Processing

Tail
Tail Gas
Gas Stack
Stack
Treating
Treating

Figure 3: Süd-Chemie contributes to almost all refinery processes

Page 4
Steam Reforming Process:

Refinery Gas, containing hydrogen is sent to a PSA unit where hydrogen is

extracted. The PSA off-gas is compressed and used as feed in the hydrogen plant,
mixed with natural gas or vaporized naphtha. The gas mixture is preheated and
desulfurized over CoMo catalyst and ZnO, mixed with process steam and sent to the
tubular primary reformer where conversion to equilibrium of methane into hydrogen,
carbon monoxide and carbon dioxide takes place over a nickel catalyst at
temperatures of 850-950ºC. Downstream of the steam reformer the reformed gas is
cooled before entering the shift converter to produce more hydrogen by converting
carbon monoxide into hydrogen. The shift gas is further cooled before entering the
PSA unit and the off-gas of the PSA unit to produce high purity hydrogen [14].

Hydrogen Steam Off Gas

- CH 4
- CO2
- CO
Refinery
Fuel Gas

Natural
Gas

DESULPHURIZATION
DESULPHURIZATION PRIMARY
PRIMARYREFORMER
REFORMER HTS
HTS PSA-UNIT
PSA-UNIT

G-91/G-90
C49 G-72D G-3C
series

CoMo ZnO Ni Fe2O3/Cr2O3 /CuO

Hydrogen
(99.5+% )

Figure 4: Flow sheet of a hydrogen production unit [16]

Page 5
Hydrogen Plant Expansion Options

Since the 1980`s most steam reforming units use pressure swing adsorption
technology to purify the H2 up to 99.9% with higher efficiencies compared to older
plants due to additional export steam credits.

The most important cost factor for hydrogen production based on large steam
reforming plants is energy consumption for feed and fuel. Revamping and
debottlenecking existing hydrogen plants can be the most cost effective way of
meeting increased hydrogen needs. Increasing hydrogen production up to 20% is
possible depending on utility available, flexibility of the refinery, steam production and
design markets. The various options are:

• Installation of pre-reformer reactor

• Increase of the reformer firing rate
• Optimizing of the steam/carbon ratio
• Low temperature shift reactor
• PSA modifications

Süd-Chemie supplies catalysts to the refining industry for more than 50 years.
Innovations by Süd-Chemie in the catalyst area have contributed significantly to the
efficiency of today’s plants. These innovations include introduction of methanation
catalyst, low temperature shift catalyst, promoted high temperature shift catalyst and
shaped reforming catalyst. The innovations were accomplished through extensive
research and development, close contact with our customers, and continuous
improvements in the quality of our catalysts and services. Through these
innovations, Süd-Chemie has maintained its position as one of the leading catalyst
supplier to the industry.

As feedstock flexibility, increased production, and environmental regulations become

more and more important the Süd-Chemie group has once again demonstrated that it
can meet the ever-changing needs of the industry.

Page 6
Catalytic Solutions to Meet the Inreased Hydrogen Demand

1. Increase of Primary Reformer Firing Rate

An increase of the H2 plant throughput by increasing the firing rate of the primary
steam reformer and the feed flow will be followed by an increase of the tube wall
temperatures of primary reformer tubes. Due to the fact that the lifetime of the
catalyst tubes is directly correlated with the tube metal temperature, the lifetime will
be shortened by increasing the firing rate at given wall thickness. A major solution is
to load the primary reformer with high activity steam reformer nickel catalyst to
achieve an optimum conversion of the hydrocarbons in the endothermic steam
reforming reaction with low tube wall temperatures.

Steam Reforming CH4 + H2O ↔ CO + 3H2 ∆H298 = + 49.25 kcal/mole

One aspect of a higher operating rate is high pressure drop across the primary
reformer.

High operating rates have also placed new demands on catalyst activity. In a
primary reformer, gas diffusion into the catalyst pores is important. Therefore, using
catalyst sizes and shapes that expose more outside surface area can enhance the
effective activity of any catalyst formulation.

As operating rates increase, physical demands on the catalyst also increase.

Utilizing existing computer simulation and reformer integration models, Süd-Chemie
developed a number of shapes that appeared to meet the activity and pressure drop
requirements. After evaluation of each shape using finite element analysis to check
the stress patterns the 10-hole LDP (“low differential pressure”) shape has been
developed.

Page 7
Figure 5: G-91/90 LDP 10-Hole catalyst

The advantage of different hole sizes is increased crush strength. With an odd
number of holes in the outer ring, no three holes can be aligned such that a natural
fracture line is established in a radial direction. The particles are domed to ensure
that the surface area on the end of each particle is not blinded from the process gas
due to random packing during loading.

Catalyst Shape Relative Surface Relative Pressure Drop

Area

16 x 16 x 6 mm 1.00 1.00
Raschig Rings
19 x 16 mm LDP 1.48 0.64
10-Hole

Table 2: Comparison of steam reforming catalysts

The pressure drop of the LDP catalyst is only 64% of a 16x16x6 mm Raschig ring
shape. With a loading of G-90LDP pressure drop across a reformer is reduced. This
will increase the suction pressure to the synthesis gas machine; thereby reducing
energy consumption.

The change from a standard catalyst to G-90LDP can also be utilized by increasing
the through-put rate by up to 15%. However, the limiting influence of the air
compressors has to be checked.

Page 8
Computer simulations of the TWT´s of a standard shape steam reforming catalyst
compared to the low differential pressure (“LDP”) shape confirm the lower TWT´s
and are based on the following parameters:

• Field data of operating reformers

• Radiation phenomena
• Reaction kinetics
• Catalyst laboratory testing
• Mathematical techniques
• Computer techniques
• Numerical analysis and convergence schemes

In addition to simulations the plant experience fully supports the superior

performance of the LDP shape in terms of lower TWT`s, lower pressure drop and
saving energy at given flow rate.

2. Optimization of the Steam/Carbon Ratio

The optimization of the S/G ratio can be considered as a stand-alone possibility or

together with other debottlenecking options. As a matter of fact the decreasing of the
S/G ratio will lower the H2 purity in conventional (not PSA based) plants and reduce
the energy available for the CO2 unit. From the catalyst point of view steam reformer
units should operate at S/C ratios in the range of 2.5-3.5, but the formulation of the
catalyst has to be designed to cope with undesired side reactions like carbon
formation [15] and be robust with regard to unforeseen shut-downs during operation
to maintain physical integrity. In numerous applications worldwide Süd-Chemie´s
G-90/G-91 series primary reforming catalysts on calcium aluminate basis proved
superior performance operating at maximum throughput rates. For higher
hydrocarbon feed compositions potassium promoted G-91 catalyst have been
designed to operate without side reactions.

Page 9
 3. Installation of a Low Temperature Shift reactor

The addition of a LTS reactor to the flow scheme of a hydrogen plant represents a
means to increase H2 production without adding more feed. Converting more CO to
CO2 results in an increase H2 recovery of the PSA unit and a lower purge gas fuel to
the primary reformer. Due to the fact that a LTS catalyst can produce impurities like
CH3OH it is of particular importance to operate with a LTS catalyst, which has been
optimised with regard to
• high selectivity
• high activity
• high stability.

The associated problems with by-product formation like methanol production in the
LTS reactor are a loss of H2 yield, CO2 contamination downstream of the LTS unit
and VOC emissions of the plant that are limited by legal authorities.

Methanol formation not only leads to environmental pollution, but also causes other
problems such as: loss of H2 production due to H2 and CO consumption and
contamination of CO2 that can cause problems for downstream users.

One method to reduce the methanol problem involves the installation of a high
pressure condensate stripper. The high pressure overhead is recycled back to the
reformer inlet for methanol destruction. Other energy consuming process involves
condensation of the stripper overhead followed by a pump to inject it into the inlet of
the primary reformer. These modifications represent a significant investment in
process equipment needed to control methanol emissions. The amount of methanol
produced can be influenced by:

• Lowering the LTS inlet temperature

• Increasing the S/G ratio to the LTS reactor
• Lower the plant operating pressure
• Reducing the catalyst volume which decreases contact time
• Catalyst activity loss during ageing

Page 10
None of these alternatives are attractive to most plant operators. Most plants have
been designed to operate at a fixed pressure and S/G ratio to minimize energy
consumption and maximize production. Changes such as those outlined above can
adversely effect both energy consumption and plant rate.

Instead of costly equipment changes or changes in plant operating conditions, a

lower cost alternative may be a more selective C-18 AMT-2 LTS catalyst.

95

90
CO Conversion (%)

85
C18-AMT
80

75

70

65 Competitor

60
0 20 40 60 80
Hours on Stream

Figure 6: Stability of C18-AMT-2 LTS catalysts

The following figures depict the evolution of modern state of the art low temperature
shift catalyst and the significant improvement with regard to selectivity and activity.
The results have been obtained from an extensive worldwide R&D programme on
copper zinc catalytic systems.

Page 11
 MeOH in Condensate (ppm) 2000

1600
C18 AMT
C18-7
Competitor A
1200

800
Competitor B
400
Competitor C
0
C-18 AMT-2
0 1 2 3 4 5 6 7 8

Days on Stream

Figure 7: Selectivity of C18-AMT LTS catalysts

The activity of C18 AMT has been increased by 25% compared to former catalyst
versions and additionally the stability has been improved significantly.

These laboratory results are in full line with catalyst performance in existing plants.
The following operation data demonstrate the improvement of C18 AMT-2 LTS
catalyst in a 50 000 Nm3/h H2 plant with refinery off-gas feed (c(CH3OH) < 5 ppmv
wet gas, C18 AMT-2).

gasphase condensate
200
MeOH content [ppmv]

100

0
Measured C18-7 Measured C18 AMT-2

Figure 8: MeOH by-product formation in a 50000 Nm3/h hydrogen plant

Page 12
 4. Installation of a Pre-Refomer Reactor

The installation of an adiabatic pre reformer represents a possibility to unload the

primary reformer and to operate at an increased feed rate [13]. The heat, which is
required for the endothermic reaction is provided by hot flue gas from the reformer
convection section. In addition the plant can be operated with alternative feed
stocks, e.g. refinery off-gas streams, liquefied petroleum gas, naphtha, C4 cuts).

In summary the advantages after the installation of a pre-reformer are:

● Feed flexibility
● Increased life of reforming catalyst
● Lower heat load on the tubular reformer
● Increased life of tubular reformer tubes
● Increased throughput
● Lower S/C ratio operation

When a pre-reformer is added to an existing plant, the heat load on the tubular
reformer is reduced. This reduces the tube wall temperatures in the tubular reformer.
The amount of reduction depends on the feedstock, S/C ratio and operating
temperature of the pre-reformer.

The following temperature profiles demonstrate the superior performance of the Süd-
Chemie C11-PR pre-reforming catalyst. One striking argument for the high stability
catalyst Süd-Chemie pre-reforming catalyst is the constant conversion operation
during the replacement of 12.0 m3 pre-reforming catalyst after 20 months on stream
and subsequent short loading with 5.6 m3 C11-PR with satisfactory stable plant
operation.

Page 13
 T1_645 R-151 Inlet T1_631 R-151 (9%) T1_632 R-151 (39%)
T1_633 R-151 (69%) T1_634 R-151 (99%)

550
Competitor C-11 PR
520
Bed Temperatures [°C]

490

460

430

400
98
98

99
99

00
0

01
8

99

00
.0
.9

.9
.

l.

.
g.

n.
b.

n.
pr

rz
ai

kt
ov

ez
Ju

Au

Ja
Fe

Ju
M

O
M
A

D
N

Figure 9: Pre-Reformer temperature profile in a syngas plant

Page 14
References:

[1] R. Prada Silvy, World Refining Catalyst Market Update, Oil Gas European Magazin,
p. 108, (2/2003).

[2] A. M. Aitani, S. A. Ali, Hydrogen Management in Modern Refineries, Erdöl, Erdgas

und Kohle, Heft 1, S. 19, (1995).

[3] Chris Spilsbury, Hydrogen Production, Supply and Distribution, Air Products
Hydrogen Production Workshop, University of Glamorgan, (2001).

[4] Nitin M Patel, William F. Baade, Leong Wah Fong (Air Products) Vinay Khurana
(Technip-Coflexip), Creating Value through Hydrogen Management , PTQ Summer,
p. 35, (2003).

[5] David Hunter, Fuel Specs Drive Hydrogen, Chemical Week March 5, (2003).

[6] N. M. Patel, W. F. Baade, L. ,W. Fong, V. Khurana, Creating Value through Hydrogen
Management, PTQ Summer, p. 35, (2003).

[7] R. A. Davis, L. J. Gardodz, N. M. Patel, Refining Hydrogen Management,

Hydrocarbon Engineering, p. 91, September (2001).

[8] J. M. Abrardo, Meeting Hydrogen Demands, Hydrocarbon Engineering, p. 66,

October (1999).

[9] H.-J. Reinhardt, M. Heisel, H.-D. Obermeyer, Use of Industrial Gases in Oil
Refineries, Linde Reports on Science and Technology, p. 9, 62 (2000).

[10] S. Ratan, Enhancing Hydrogen Economics, Hydrocarbon Engineering, p. 47,

February (2003).

[11] N. Hallale, I. Moore, D. Vauk, Hydrogen Optimisation at Minimal Investment, PTQ

Spring, p. 83, (2003).

[12] Süd-Chemie Synthesis Gas Catalyst Conference, Garmisch-Partenkirchen, January

2003.

[13] B. Kandziora, Advanced Hydrogen Technology, Hydrocarbon Engineering, p. 47,

August (2002).

[14] D. Schweer, G. Scholz, M. Heisel, On-site-Versorgung von Erdölraffinerien mit

technischen Gasen, Erdöl, Erdgas und Kohle, Heft 3, S. 115, (2002).

[15] D. L. Trimm, The Formation and Removal of Coke from Nickel Catalyst, Catal. Rev.-
Sci. Eng. 16(2), p. 155, (1977).

[16] G. Bourbonneux, Hydrogen Production in Petroleum Refining – Conversion

Processes (Ed. P. Leprince) Paris, p. 451, (2001).

Page 15