Annual Meeting

March 19-21, 2006

Grand America Hotel
Salt Lake City, UT

AM-06-27 Integrated Hydrogen Solutions: Combining

Hydrogen Recovery and Optimized Steam
Reforming

Presented By:

James D. Fleshman
Senior Principal Engineer
Foster Wheeler USA
Corporation
Houston, TX

Mario Campi
Process Manager
Foster Wheeler
Milan, Italy

National Petrochemical & Refiners Association 1899 L Street, NW 202.457.0480 voice

Suite 1000 202.429.7726 fax
Washington, DC www.npra.org
20036.3896
Introduction

The design of a hydrogen supply system involves much more than specifying a plant to
produce a particular amount of hydrogen. In order to remain competitive in today’s
economy, it is necessary to optimize how hydrogen is produced, recovered and
compressed, particularly for a complex refinery.

Tighter regulations on sulfur content of transportation fuels continue to require additional

hydrogen capacity for hydroprocessing, while at the same time the regulations on
aromatic content of gasoline limit catalytic reformer throughput and byproduct hydrogen
production. The trend towards the processing of heavier crudes and the more
widespread use of residue conversion technologies further aggravates the hydrogen
shortfall. As a consequence the demand for hydrogen continues to increase.

This article addresses the methods for meeting these challenges and focuses on an
innovative, cost-effective solution developed by Foster Wheeler for the NIS Pancevo
Refinery in Serbia.

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Hydrogen Management

The most economic solution to a hydrogen supply problem is to make best use of
existing resources. Adding a new unit to supply the entire shortfall without
optimization is rarely the low cost solution.

Developing an optimum supply scheme requires an evaluation of the hydrogen

demand, the configuration of the existing system, and available options for
increasing capacity. Foster Wheeler applies a proven approach to hydrogen
management, which addresses:
• The current refinery balance
• Hydrogen recovery from various refinery offgases
• Upgrading or revamping options for existing hydrogen production units.
• Additional new capacity
• Purchasing hydrogen over-the-fence

The final evaluation also factors in capital and operating cost, as well as
operability and reliability of supply.

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Hydrogen Balance

When analyzing hydrogen resources in refinery complexes, Foster Wheeler uses

a hydrogen pinch technique to identify the best opportunities for offgas re-use
and purification and to quantify the minimum size of any new hydrogen
production facilities that may be required. The pinch technique aims to develop
the optimal hydrogen recovery scheme based on capital cost, operating cost, and
constructability. Key elements of the pinch analysis are:

• Confirmation of existing network headers

• Compression requirements
• Potential for re-use of offgases containing hydrogen
• Potential application for hydrogen purification
• Cost analysis

Revamp Opportunities

There are a number of options for upgrading existing hydrogen production units.
Depending on the age of the unit, new technologies are available in virtually all
areas of the plant. These include improved alloys for reformer catalyst tubes,
improved catalysts, and more efficient CO2 removal solutions or Pressure Swing
Adsorption (PSA) adsorbent.

Increased throughput can also generally be achieved by additions to the plant

such as a pre-reformer or post-reformer, or a LT shift converter.

An increase in capacity also requires changes to the remainder of the system,

including gas cooling and hydraulics, and at some point additional capacity
becomes prohibitively expensive. Other solutions for consideration involve
sharing of hydrogen supplies with neighboring facilities or an over-the-fence
supply from an industrial gas supplier. Once these options have been

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 exhausted, and a new hydrogen production unit identified, the new facilities need
to be integrated into the existing system.

Integrated Offgas Utilization

Because of economics, there has been an increased focus on the best way to
integrate available hydrogen-rich refinery offgas streams into hydrogen
generation capacity. Aside from the actual hydrogen balance, it is necessary to
consider purification, compression, and the impact on the refinery fuel balance.

Hydrogen expansion projects generally include offgas purification by PSA in

order to meet purity specifications. A new hydrogen plant will typically include a
Steam Methane Reformer (SMR), also with purification by PSA. In that case
there are typically three PSA configurations to be considered when developing an
integrated hydrogen supply system:

• Combine refinery offgas (ROG) with SMR gas upstream of a common PSA.
• Combine the ROG with feedstock upstream of the SMR.
• Send the ROG to a dedicated hydrocarbon based PSA unit where tail gas is
recompressed for either fuel export or utilized as reformer feed.

The first configuration, use of a common PSA unit, often appears the simplest
and can at least theoretically offer a cost-effective solution. There are, however,
a number of adsorbent and fuel balance problems with this configuration, which
limit its application.

The impurities present in SMR gas – CO2, CO and N2 – require a different set of
PSA adsorbents than are required by the hydrocarbons present in ROG. A PSA
unit with mixed feedstock requires adsorbents to remove both sets of impurities.
In that case there is a risk that the heavier hydrocarbons from the refinery gas
will reach the adsorbents for SMR gas and be permanently adsorbed, damaging

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 the bed and reducing its capacity. This makes the combined system very
sensitive to the flow and to the composition of the ROG, and puts the system at
risk of permanent damage if the flow or composition of the ROG varies.

This results in the following constraints on the combined PSA system, which
limits it usefulness:
- The ratio of ROG to SMR gas needs to be kept constant for optimum bed
usage without risk of bed contamination.
- If the SMR is shutdown, the PSA operation on ROG alone may result in
adsorbent contamination by heavy hydrocarbons moving too high in the bed.
- In many cases the offgas stream often contains less H2 and significantly
higher concentrations of heavy hydrocarbons than originally predicted. This
is difficult to foresee and can lead to irreversible adsorbent de-activation if it
goes undetected and adequate measures are not taken to adjust the PSA
cycle time.
- Because of the heavier hydrocarbons, the combined PSA tail gas has a much
higher calorific value, which is often in excess of the steam reformer fuel
requirements. A tail gas compressor is then required to route the excess gas
into the fuel gas network. Moreover, the excess tail gas contains CO2 from
the SMR, which can upset the refinery fuel system.

If the amount of ROG is small, it may still be feasible to combine SMR and refinery gas
in a single PSA unit. However, as the quantity of hydrogen contained in the ROG
increases, it becomes more practical to either use the ROG as SMR feedstock, which
eliminates the tail gas problem, or to install a separate PSA to purify the ROG streams.

Where separate PSA units are used, tail gas from the SMR PSA is returned to the
SMR as a dedicated fuel stream, while tail gas from the ROG PSA unit can be
compressed and used in the refinery fuel system.

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Case History – NIS Pancevo

Foster Wheeler recently had the opportunity to review various integration options at
the NIS Pancevo refinery in Serbia.

NIS-Petrol has two refineries in Serbia: one in Pancevo and the other in Novi Sad,
with a total installed capacity of 5 million metric tons/annum (MMTPA). The
Pancevo refinery is undergoing a development program aimed at:
• Production of gasoline and diesel in accordance with European standards (EU
2010+)
• Meeting domestic and European environmental protection standards
• Increasing conversion
• Generating export products
• Energy optimization
• Increasing and securing refinery profitability

Key refinery units in the development include a Continuous Catalytic Reformer

(CCR), Mild Hydrocracker (MHC), Naphtha and Diesel Hydrotreater (DHT) plus
support units including a new hydrogen plant.

The hydrogen demand for the new units was 64,000 Nm3/h of high purity hydrogen.
Two hydrogen-rich offgas streams were available, one from the CCR unit and a
purge stream from the new MHC/DHT unit. Table 1 shows the composition of the
CCR and MHC/DHT offgas streams. The hydrogen recovered from these two
streams was to be supplemented with ”on purpose” hydrogen produced in a new
SMR. Natural gas was available as primary feed to the SMR with LPG available as
supplemental feed.

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 Table 1
Hydrogen-Rich ROG Stream Properties

CCR Offgas MHC/DHT Offgas

Component
Volume % Volume %
H2 94.93 73.95
Methane 1.52 13.17
Ethane 1.41 5.36
Propane 0.99 3.73
Butanes 0.56 2.26
Naphtha 0.59 1.11
H2S 0.00 0.01
H2O 0.00 0.41
Total 100.00 100.00

Flow, kg-mols/Hr 1,057.8 340.0

Pressure, bar-g 18 20
Temperature, °C 38 45

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The hydrogen available in the two offgas streams was significant - approximately
45% of the total hydrogen demand for the new facilities. Based on this, the following
possible configurations were evaluated for integration of the ROG purification with
the SMR:

• Case A – ROG tail gas to fuel (the base case)

• Case B – ROG tail gas to SMR feed
• Case C – ROG directly to SMR feed

Case A – ROG Tail Gas to Fuel

In this case the offgas from the CCR and MHC / DHT units is purified in a dedicated
ROG PSA unit, and the tail gas is compressed to the refinery fuel gas header
pressure of 6 bar-g. Part of this tail gas is used as supplemental fuel in the SMR,
with the remainder exported to the refinery.

Natural gas from battery limits is compressed and used as feed in the SMR. A
separate PSA unit is used to purify the SMR gas, and tail gas from the SMR PSA at
0.3 bar-g is used directly as fuel for the reformer, supplemented by tail gas from the
ROG PSA unit.

In each case a small amount of hydrogen is recycled from the PSA outlet to the
SMR feed purification section for the hydrogenation and removal of organic sulfur.
The flows shown here neglect this recycle.

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 CCR MHC / DHT
22,493 4650
16

22,800 15
ROG 64,166

Nm3/h of 100 % H2
PSA
0.3
Pressure, barg

6 41,366
4,343

17 35 45,963
NATURAL
SMR SMR
GAS
PSA
4,597

FUEL
FG to
Header
2,271 2,072

Figure I - CASE A - ROG Tail Gas to Fuel

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Case B – ROG Tail Gas to SMR Feed
As in the first case, the refinery offgas is purified in a dedicated PSA unit. However
in this case the tail gas is compressed and sent to the SMR to be used as feed.
Since hydrogen in the tail gas is recovered as SMR feed instead of being burned as
fuel, it is not as critical to maximize the hydrogen recovery in the ROG PSA unit. A
higher tail gas pressure can then be used to reduce the requirement for tail gas
compression: 1.0 bar-g vs. the 0.3 bar-g used in Case A. This increased pressure is
particularly valuable in this case, since the tail gas must be compressed to the
natural gas pressure of 17 bar-g. Since the PSA unit performance is tied inversely
to the tail gas pressure, the increased pressure reduces the hydrogen recovery in
the PSA unit from 84 to 81.5%. Natural gas from battery limits is then mixed with the
tail gas from the offgas PSA, compressed, and sent to the SMR as feedstock. As in
Case A, the SMR product is then purified in a dedicated PSA, with the tail gas used
as SMR fuel. In this case the supplemental fuel for the SMR is natural gas.

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 CCR MHC / DHT
22,493 4,650
16
64,166
22,122 15
ROG
Nm3/h of 100 % H2
PSA
1.0
Pressure, barg

42,044
5,021

17 35 46,716
NATURAL SMR
GAS SMR
PSA
0.3 4,672
FUEL
NATURAL
GAS

Figure 2 - CASE B - ROG Tail Gas to SMR Feed

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Case C – ROG Directly to SMR Feed

In this case, the ROG PSA unit is eliminated and offgas from the CCR and
MHC/DHT unit is sent directly to the SMR feed compressor together with the
natural gas. The tail gas from the SMR PSA at 0.3 bar-g is used directly as fuel for
the reformer, with natural gas as the supplemental fuel.

CCR MHC / DHT

22,493 4,650

Nm3/h of 100 % H2

Pressure, barg 15
64,166

16

17 35 71,295
NATURAL SMR
GAS SMR PSA
7,129

FUEL
NATURAL
GAS

Figure 3 - CASE C - ROG Directly to SMR Feed

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Evaluation of the Different Cases

The assessment of the three cases, A, B and C, took into account expected
availability as well as capital and operating costs.

The direct utilization of the ROG as SMR feedstock in Case C eliminates one set of
compressors and a PSA unit. This provides lower complexity and fewer processing
steps, resulting in improved operability. Complexity of the other two cases is similar.

From an availability viewpoint, Cases A and B are preferable since high purity
hydrogen can be generated when either the ROG PSA or the SMR system are
unavailable.

The non-availability of ROG has approximately the same impact in all three cases,
particularly since adequate margin was built in to the design of the SMR to partially
compensate for the loss of ROG.

A loss of the ROG PSA tail gas compressor impacts only Cases A and B.

The various operational aspects are summarized in Table 2.

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 TABLE 2
Operating Issues

Issue A B C
Complexity More More Less
H2 Availability High High Normal
No availability of ROG 34% loss of H2 35% loss of H2 38% loss of H2
Loss of ROG PSA tail
Loss of fuel 10% loss of of H2 No impact
gas compressor
Loss of feed gas
66% loss of H2 65% loss of of H2 Total loss of H2
compressor or SMR

Table 3 shows the differences in the capital cost of the three cases using Case A as
the base case. The costs are referred to the first quarter 2005, Western European
basis.

Table 3
Capital Cost Differences

$MM

Case A B C
Feed Compressors --- +0.1 +0.1
Steam Reformer --- --- +8
SMR PSA --- --- +1
ROG --- -0.6 -2
Tail Gas Compressors --- +0.2 -1
Total Cost Difference --- -0.3 +6

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Operating Costs

In order to provide a consistent basis, the following operating parameters were

retained for each case:
• Steam to carbon ratio (3.0)
• Reformer inlet / outlet temperature (650/880°C)

The main process parameters - the resulting feed and fuel consumption, export
steam flows and related operating costs - are reported in the following tables.

TABLE 4
MAIN PROCESS PARAMETERS

A B C
H2 Recovered from ROG Nm3/hr 22,800 22,122 -
H2 Produced from SMR Nm3/hr 41,366 42,044 64,166
Total Hydrogen Production Nm3/hr 64,166 64,166 64,166

Reformer Absorbed Duty Gcal/hr 33.91 32.23 40.99

SMR PSA Efficiency % 90 90 90
ROG PSA Efficiency % 84 81.5 -

TABLE 5
FEEDSTOCK AND UTILITY CONSUMPTION

A B C
Natural Gas Feed Gcal/hr 131.2 69.0 90.8
Natural Gas Fuel Gcal/hr - 27.3 13.4
ROG Feed, Gcal/Hr Gcal/hr 115.6 115.6 115.6
ROG Tail Gas Export Gcal/hr 27.9 - -
HP Steam Export MT/hr 34.7 34.6 40.0

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 TABLE 6
FEEDSTOCK AND UTILITY COSTS - $MM/YR

A B C
Total Feed Plus Fuel
(Natural Gas plus ROG, 28.58 24.90 26.33
less ROG Tail Gas Export)
HP Steam Export (6.24) (6.23) (7.20)
Other
(Electricity, Demin water, 3.32 3.51 3.88
cooling water, LP steam)

Total 25.66 22.18 23.01

In Summary
• Case A and B show lower investment cost
• Case B and C show lower operating cost
• Case B shows the lowest combination of investment and operating cost

Case B was therefore selected.

Hydrogen Plant Design

In addition to developing the system configuration, the project also included design
of the hydrogen plant to meet the objectives of NIS Pancevo, including:
• Flexibility to use natural gas or LPG feedstock
• Efficient and reliable hydrogen supply
• Variable cost as low as possible without incurring excessively high
capital expenditure
• Ability to produce export steam cost effectively

NIS Pancevo’s main objectives were met by the installation of a Foster Wheeler
Terrace Wall® Steam Reformer with microalloy catalyst tubes and state-of-the-art
catalyst.

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 Because of the requirement for feedstock flexibility, a pre-reformer was integrated
with the Foster Wheeler Terrace Wall® primary reformer. This allowed extended
operation on heavier feedstocks, as well as improved energy efficiency. Since
heavier hydrocarbons are not present in the effluent from the pre-reformer, this
stream can be preheated to a higher temperature before it enters the reformer
radiant section. This reduces the load on the reformer radiant section and reduces
fuel requirements.

The other main features of the Terrace Wall ® furnace which insured that NIS-
Pancevo’s targets would be met are as follows:

1. The Terrace Wall ® design uses a single row of catalyst tubes located inside each
radiant cell. Specially selected burners are arranged in terraces at two levels along
a firing wall to create a nearly uniform heat flux to the double-fired tubes. Slightly
sloping walls assist in providing uniform heat distribution since they slope towards
the tubes as the gas cools. Since the burners are at two levels, flux adjustments can
be made along the tube length as the catalyst ages.

2. The entire Terrace Wall reformer, including radiant and convection sections, can be
brought to the site in modules. This reduces field labor as well as construction cost
and duration. These modules can be shipped over the road to virtually any location.

3. Since the selected reformer at Pancevo used natural draft, no fans were required
and reliability was improved. The Terrace Wall furnace also allows the ability to
install combustion air preheat, and switch to natural draft operation in case of fan
failure.

4. Burners are arranged in two firing levels, which allow optimization of the heater
efficiency and the hydrogen production in accordance with the type of feed, catalyst

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 life and unit load. There is virtually no limitation in turndown and the steam reformer
can maintain a high efficiency at reduced load.

5. The isolation and replacement of radiant tubes are simplified, since the inlet pigtails
are fully accessible while the outlet pigtails are easily accessible through removable
panels on the outlet manifold box. Each single tube can be removed from the top
without any additional work except the removal of the roof rain cover. In case of
tube failure the tube can be crimped and isolated with the heater in operation.

6. Loading or unloading of the catalyst requires only the removal of the top flange.
Loading of a complete charge of catalyst can be completed in two to three days.

In order to supply the maximum amount of steam to the refinery, combustion air preheat
was not selected and heat recovery was by maximizing steam generation. The Terrace
Wall® design, with the convection section placed on the top of the radiant section,
allowed natural draft operation. This eliminated the induced and forced draft fans,
which further improved the expected availability and reduced operating costs.

Foster Wheeler’s combination of hydrogen management and process expertise,

coupled with the expertise of Foster Wheeler Fired Heater Division, provided NIS
Pancevo with a cost-effective and highly reliable solution for meeting the hydrogen
demands associated with upgrading the refinery to a state-of-the-art facility.

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This paper has been reproduced for the author or authors as a courtesy by the National
Petrochemical & Refiners Association. Publication of this paper does not signify that the
contents necessarily reflect the opinions of the NPRA, its officers, directors, members, or staff.
Requests for authorization to quote or use the contents should be addressed directly to the
author(s)