HYDROGEN GENERATION FOR MODERN REFINERIES

Luigi Bressan, Guido Collodi, Fabio Ruggeri

Foster Wheeler Italiana SpA
Via Caboto, 1 20094 Corsico – Milan - Italy

Abstract

With increasing demand for diesel, more stringent product specifications for cleaner
fuels, reduced fuel oil demand and the economic advantages in processing heavier sourer
crudes, the demand for hydrogen in refineries continues to grow.

As a result, a modern 10 mmtpa refinery will often require 150,000 Nm3/hr or more of
hydrogen.

This demand can be met by applying a systematic, cost-effective approach to hydrogen

management, including the optimisation and revamp of existing hydrogen generation
facilities.

The paper will focus on the design of a modern hydrogen production unit based on steam
reforming of hydrocarbons using a Foster Wheeler Terrace-WallTM furnace.

The paper will look at some of the key features of this design that deliver benefits in
operation and maintenance, and the high availability that is essential in hydrogen
production.

Introduction – Steam Reforming Principles

Hydrogen is increasingly being considered as a utility gas within the refining and
petrochemical industry. From an end user’s perspective, investment in hydrogen plant
capacity is often evaluated using the lifecycle cost of hydrogen, expressed for example as
Euros per Nm3. This is because the plant with the lowest capital cost may not always
produce the cheapest hydrogen, given the feedstock and utility costs commonly
experienced today.

For many years, steam methane reforming (SMR) plants have continued to be the
leading technology for generation of hydrogen in refining and petrochemical complexes.
These plants consist of four basic sections:

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• The first is feedstock treatment where sulphur and other contaminants are removed.
• The second is the steam methane reformer, which converts feedstock and steam to
syngas at high temperature and moderate pressure.
• The third section is the syngas heat recovery and incorporates CO shift reactor/s to
increase the hydrogen yield.
• The final section is raw hydrogen purification, in which modern plants employ a
pressure swing adsorption (PSA) unit to achieve the final product purity.
• In addition to the core process sections, compression is often needed to raise the
feedstock and product hydrogen pressures. `
SMR is a mature technology and is now less likely to yield any large step-changes in
economic benefit from technological developments. Incremental economic improvements
by means of a continuous improvement programme are the order of the day.

The Chemistry
The reforming reaction between steam and hydrocarbons is highly endothermic and is
carried out using specially formulated nickel catalyst contained in vertical tubes situated
in the radiant furnace of the reformer. The simplified chemical reactions are:

For saturated hydrocarbons

CnH2n+2 + nH2O = nCO + (2n+1)H2

for methane
CH4 + H2O = CO + 3H2 delta H = + 206 kJ/mol

In the adiabatic CO shift reactor vessel, the moderately exothermic water gas shift
reaction converts carbon monoxide and steam to carbon dioxide and hydrogen:

CO + H2O = CO2 + H2 delta H = - 41 kJ/mol

The PSA purification unit removes by adsorption from the hydrogen, the resulting CO,
CO2 and CH4 gases. The four process sections can also be seen in the following picture
nb.1 of a typical SMR hydrogen plant, in which the reformer stands at the centre and the
PSA is on the right.

The Hydrogen Plant in a Refinery

Refineries can use different feedstocks to produce hydrogen, such as natural gas,
refinery gas, LPG, light naphtha, heavy naphtha and even straight run naphtha,
depending on their internal value and availability, to assure the availability of the most
economical feedstock to the hydrogen plant.

The characteristics of the feedstock will define the processing capability of the plant.
However the correct selection of the hydrogen plant design and operating parameters
depends on the economic values attributed to the feedstock, the fuel and the steam
produced, these being the key process streams influencing the economics of the plant.

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Today, in most of cases, feedstock and fuel and steam have the same value on a calorific
basis and, as consequence, the optimum is achieved with the minimization of the
following mathematical formula:

( Feedstock(Gcal/h) + Fuel(Gcal/h) – Steam(Gcal/h) ) / H2 flowrate

(Net Thermal Efficiency)

where steam is the net export flow rate of steam from the plant.

Key process elements

Hydrodesulphurisation section
The feedstock is firstly hydrotreated and the resulting H2S is captured in a zinc oxide bed.
There are different desulphurisation schemes available, but the most commonly used is
the lead–lag arrangement eventually followed by a deep desulphurisation polishing bed.
The reaction temperatures are obtained by thermal exchange.

Pre-reforming section
The pre-reforming section is generally installed to eliminate long-chain hydrocarbons in
heavier feedstocks before entering the reforming section; this allows the use of reduced
steam-to-carbon ratios.

When natural gas is used as feedstock, the use of a re-reforming section lowers the
reforming duty thus reducing the cost of the steam reformer, which is the most
expensive part of the plant; for this reason, it is recommended that large size plants
should have a pre-reforming section.

Reforming section
The reforming section is the key section of the plant; Foster Wheeler uses its proprietary
Terrace WallTM technology. Steam reformer outlet temperatures up to 920°C can be used
with heat fluxes above 100,000 Kcal/(h*sqm).

The process effluent from radiant cell is sent to the process gas boiler, through the outlet
manifold, outlet cone and transition piece.

The hot gases leaving the radiant section are cooled down in the convection section
located on the radiant top, preheating the process stream, the pre-reformer feed stream,
if any, the feed gas to desulphurisation unit and producing superheated steam.

The required heat is supplied with ultra-low-NOX burners (forced- or natural-draft type).
Burners are placed at two different levels in the combustion chamber and they are
equipped with a double set of firing tips, one for refinery fuel gas and one for vent gas
from PSA unit.

The steam produced in the convection section and in the process gas boiler is separated
from water in the steam drum, placed above the convection section.

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The process gas boiler is natural-circulation-type and it is placed at grade level in the
middle of the radiant cell. Such an arrangement allows a transfer line to be avoided.

Syngas cooling and shift reaction section

The syngas cooling section is normally optimised using pinch technology aimed at finding
the optimum cooling scheme. For the shift reaction section there are four options
available:
1. High temperature shift
2. High temperature shift followed by a low temperature shift
3. Medium temperature shift
4. Isothermal shift

The adoption of the second option as an alternative to the first option is a matter of
economics; both alternatives need a steam-to-carbon ratio above 2.7 and this may
influence the economics when export steam has a high economic value.

The process steam consumption can be reduced when both the medium temperature and
the isothermal shift are adopted (unless steam is needed in the pre reforming section).
The medium temperature shift may generate excessive amounts of methanol in the
syngas stream with possible contamination problems unless design precautions are
taken.

When natural gas only is considered as feedstock it is possible to adopt steam to carbon
ratios below 2.0.

Pressure Swing Absorption (PSA) section

Hydrogen purification is obtained using the well-known PSA technology. The process
parameters need to be carefully defined in order to optimize capital cost. An
unnecessarily stringent specification in the hydrogen purity may cause undesired and
unnecessary capital cost; an example is the residual concentration of nitrogen that
should not be less than 100 ppm.

The proposed scheme is outlined in Figure 1.

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 Fig. 1 - Hydrogen production plant process flow scheme Steam

Hydrogen
Steam drum

Deaerator

PSA

Hydrogenator Steam Reformer CW

Desulphurizer Terrace WallTM
Pre-Reforming

Shift Reactor

Comb. Air

Air preheating Waste Heat Boiler

Make up water
Natural Gas

With the indicated scheme a Net Thermal Efficiency of less than 3.0 Gcal/Nm3 of
produced hydrogen can be easily achieved.

The Foster Wheeler Terrace-WallTM Steam Reformer

The patented Terrace-WallTM steam reformer heater is a side-fired heater with burners
located along lateral walls with flames vertically arranged. The catalyst tube section is
composed of a single row of vertical tubes, heated from both sides and aligned inside the
radiant cell. The catalyst tubes are flanged at the top in order to allow the loading and
unloading of the catalyst.

The reformer heater features a radiant section consisting of a firebox containing a single
row of catalyst tubes with two terraces on both sides of the tubes on which the burners
are installed.

Key Advantages
The following are the main advantages of the Terrace-WallTM design:

• A single train unit can produce up to about 200,000 Nm3/h of hydrogen

• Modular radiant section capability reducing site construction time and cost
• Can operate in natural draft mode
• Steam reformer outlet temperatures up to 920°C can be used with heat fluxes
above 100,000 Kcal/(h*sqm).
• Very compact design reducing the plot area requirement
• Minimum number of low NOx burners
• Operating cost saving (reduced number of rotating machines)
• Maintenance cost saving (very simple design)
• investment cost saving

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Foster Wheeler Terrace-WallTM reformers have been in operation for many years with a
very wide range of feedstocks and have been used for hydrogen, methanol and ammonia
production.

This technology offers several advantages over competing technologies, namely:

• High flexibility to handle a full range of feedstock from natural gas to heavy naphtha
• Uniform heat flux distribution giving long reformer tube life
• Sloped walls with two firing levels enabling control of flux density along the catalyst
tube
• High reliability
• Positive reformer furnace firing control
• Low maintenance requirement

The specific advantages of sloping walls include avoiding tube hot spots and prolonging
tube life:
• The inclined Terrace-Walls™ are uniformly heated vertically by the rising flow of hot
gases, with each terrace capable of being independently heated to provide the
particular heat flux desired in its zone. The operator can match the vertical heat flux
to the process heat demand within the catalyst tube. Controlled delivery of heat to
the reformer catalyst tubes helps control hotspots which can reduce the design life of
the tubes.
• The incline of the wall also localises the effectiveness of the terrace to that portion of
the heat-absorbing surface directly opposed to it. Actual experience has shown that
the Terrace-WallTM design accomplishes this to a far great extent than any flat wall
construction, and is distinctly better than in down-fired designs.
• Flame impingement on catalyst tubes is practically impossible in the Terrace-WallTM
design.

Continuous improvement and development

Recent developments to further enhance the design and performance of the Terrace-
WallTM reformer include:

1. Modified geometry of the radiant section to tailor flux profile and improve thermal
efficiency without increasing catalyst tube temperature.
2. Outlet pigtails arranged vertically providing better access for an easer welding and
nipping, which dispenses with the need for a cold bottom flange for catalyst
removal. Vacuum type catalyst removal systems allow removal of catalyst via the
tube inlet flange.
3. Reduced number of burners by about 30% due to increased capacity with the new
burners using staged fuel and staged air combustion techniques for lower NOx
emissions.

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Conclusions

Today’s refineries face the tremendous challenge of meeting an increasing demand for
cleaner transportation fuels, as specifications continue to tighten around the world, and
markets decline for high-sulphur fuel oil.

Innovative ideas and solutions to reduce refinery costs must always be considered,
including
• Identification and optimisation of the hydrogen distribution network
• Use of hydrogen recovery technologies to maximise availability and minimise capital
investment
• Multiple feedstock, utility and steam options
• Economic evaluation of solutions
• Optimization of new plant capacity

Significant experience and expertise in optimising and revamping existing hydrogen

systems can help our customers in finding the lowest-cost route to meeting their
hydrogen needs. If a new hydrogen plant is required, it is important that it is right-sized
in line with the client’s business objectives and with current, and potentially future needs.

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