Shell DeNOX System

Conference on NOx / NO2 control techniques

on

21 / 22 March 2001 , Paris

by

ADEME / INFOMILL

title :

A Catalytic System for NOx and Dioxins Removal,

applications, performance and costs

from : CRI - Environmental Catalyst and Systems

Paper from:

O.L.Maaskant
c/o CRI Catalyst Co. Ltd.,
Woking, UK

M.Miggelbrink
CRI Technology Services
The Hague , NL

Contact details:
Koninginnegracht 23
2501 AN The Hague ,NL
ph. +31-70-3111700
fax. +31-70-3111730
E-mail onno_maaskant@cricatalyst.com

Page -1-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

Content

1.0 Introduction
2.0 SCR- principle
3.0 Shell Denox System (SDS)
4.0 SDS on ethylene cracking furnaces
5.0 SDS on nitric acid plants
6.0 SDS on a waste incineration plant
7.0 Shell De-Dioxin System (SDDS) for Dioxin and Furan destruction
8.0 Cost of NOx and Dioxin removal
9.0 Summary
9.1 Reference list

1.0 Introduction.
CRI International, Inc. is a member of the Royal Dutch/Shell Group of companies. The prime
activities of CRI are research and development, manufacture and supply, servicing and
handling, regeneration and recycling of catalyst for refinery, chemical and environmental
processes.
During any combustion but also in many chemical processes, nitrogen oxides (NO, NO2 and
N2O) are formed. NO and NO2 when released into the atmosphere and combined with water
are the components responsible for the formation of acid rain. NO and NO2 together with
volatile organic compounds (VOCs) are responsible for the smog formation (ground level
ozone) which contributes to respiratory aliments. N2O contributes to the global warming and
depletion of the ozone layer. Industry therefore is faced with increasingly stricter emission
legislation with respect to emitting NOX and VOCs.
CRI has developed a low temperature approach for the removal of NOX from process gasses
and flue gas streams.
Since its introduction in Japan in the 1970s, Selective Catalytic Reduction (SCR) of NOX with
ammonia has widely gained acceptance as being the most effective and technologically
proven method for deep NOX removal. Although the Shell DeNOx System (SDS) operates on
the same principle as SCR, it is able to operate at lower temperatures and lower pressure
drop than conventional systems. In consequence, the DeNOx unit can be installed
immediately before the stack, thereby avoiding any negative effects on the other (upstream)
plant operations. To date this system has been successfully applied for the removal of NOX
from off gasses originating from nitric acid, caprolactam and catalyst manufacturing plants,
gas turbines, refinery furnaces and waste incinerators.

The Shell Denox System can also be designed for the simultaneous removal of NOx and
Dioxins , as well as for the dedicated removal of Dioxins alone.

Page -2-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

2.0 SCR-principle
Ammonia is injected before the catalyst layer at a temperature between 120C and approx.
450C. The NOX reacts with the ammonia to harmless products nitrogen and water.

Reactions from literature (a.o).

4NO + 4NH3 + O2 4N2 + 6H2O (main / fastest reaction)
6NO2 + 8NH3 7N2 + 12H2O
6NO + 4NH3 5N2 + 6H2O
NO + NO2 + 2NH3 2N2 + 3H2O

The Shell
Ammonia injection Denox System
nozzle
N2
NOX
H2 O
NH3
NOX
H2 O
NH3
N2
Flue gas NOX

3.0 Shell DeNOx System (SDS)

SDS differs from conventional SCR systems in two important aspects: the catalyst and the
modular reactor design. The catalyst consists of porous particles (extrudates) with a diameter
of 1,0 mm or 1,6 mm. Due to the high activity of the catalyst, high NOX removal efficiencies
combined with a low ammonia slip, can be obtained at relatively low temperatures (upwards
of 120C).
The reactor system is based on the so-called Lateral Flow Reactor (LFR). The LFR is a
packed bed-type reactor and offers the advantages of a low pressure drop, even at high
space velocities which results in a low power consumption or power loss in case of e.g. a gas
turbine. Furthermore, the LFR design makes possible the use of relatively small catalyst
pellets, beneficial for avoidance of diffusion limitation, and additionally facilitates fast loading
(and unloading) of the reactor.

Page -3-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

3.1 LFR Principle.

Flue gas

Catalyst
Particles

Permeable
wall

Development of the LFR has resulted in a modular construction system, thereby providing a
large degree of flexibility in the design of the DeNOx units for specific applications. As a
consequence of the high catalyst activity and the flexibility of the reactor design, the most
economical solution can be found for each application (with respect to NOX removal, NH3 slip,
temperature, pressure drop and available plot space).
Furthermore, the modular construction of the LFR offers considerable benefits with respect to
construction costs. Recent case studies made for actual applications of the Shell DeNOx
System give a cost range of $ 400/mt NOX removed for nitric acid plants to $ 1800/mt NOX
removed for gas turbines.

3.2. Applications.
The Shell DeNOX System already has proven his capabilities in:
refinery heaters and furnaces,
caprolactam plants,
gas turbines and engines,
catalyst plants,
cracking furnaces,
nitric acid plants,
waste incineration , municipal / industrial

See: reference list of SDS installations attached

A number of applications will be discussed into more detail below.

Page -4-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

4.0 SDS on ethylene cracking furnaces.

The demand for plastics such as polyethylene (PE) and polypropylene (PP) continuously
increases with the growth of the worlds population. The worlds capacity of hydrocarbon
cracking facilities also grows accordingly.
The cracking capacity worldwide is approx. 70.000.000 mt/y of which 20.000.000 mt/y is
located in Europe.
The flue gasses from these furnaces contain an average of 200 mg/Nm3 NOX. Cracking
furnaces worldwide produce some 28.000 tons per year. In Europe this is 8.000 ton NOX per
year. So far, only a few cracking furnaces are equipped with an SCR.

The Shell DeNOX System (SDS) is already successfully applied at three ethylene-cracking
furnaces in Germany and two furnaces in The Netherlands. Due to these five units the yearly
NOX emission in Europe will decrease with some 400 ton.

4.1 Possible locations for installing Shell DeNOx System.

The Shell DeNOX System for a cracking furnace can be installed at three different locations.
The first two locations are in the heat recovery section before and after the economizer and
down stream the furnace in the flue gas duct before the induced fan.

Every location has its own features and is more or less suitable for installing a DeNOX unit.

Arrangement Arrangement

2 3

Economizer

Superheater

Flue gas from

furnace

Location Approx. Advantages Disadvantages

Temperature
1 270 - 310 C Small catalyst quantity, Difficult and expensive for
No additional reactor required, existing furnaces (large

Page -5-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

Location Approx. Advantages Disadvantages

Temperature
turnaround),
Long, narrow duct results in
difficult ammonia distribution
2 150 - 210 C No additional reactor required, More catalyst required,
Difficult and expensive for
existing furnaces (large
turnaround),
Long, narrow duct results in
difficult ammonia distribution
3 150 - 210 C Easy, end of pipe solution for More catalyst required,
existing furnaces, Additional reactor required,
Possibility for prefab,
Minimum shut down period
because of easy tie-in,
Minimum effect on upstream
process,
No changes in standardized
layout and engineering of
cracker section,
Easy ammonia injection and
distribution in flue gas duct.

For existing cracking furnaces, because of the difficulty and high costs for breaking into the
existing heat recovery section the location end of pipe is the far most economical attractive
location. Even for new still to build cracking furnaces it even might be more economical to
install the DeNOX end of pipe. This option should at least be considered.

5.0 SDS on Nitric Acid plants

5.1 Introduction.
In todays competitive markets Nitric acid plant operators are faced with many challenges,
e.g. reducing costs and meeting more stringent emission levels. This paper examines ways
of meeting these emission requirements at minimal cost or in the case of SCR replacements
at a cost saving.

During the engineering phase of a SCR installation project, the yearly operation costs are
calculated. These costs include hardware depreciation, capital cost and catalyst depreciation.
Typically this is the phase when the specification of the SCR system is adjusted such that the
yearly operating costs are minimized. However, some costs are often forgotten or under-
estimated. Two of these costs are the additional high-pressure steam to the turbine required
to overcome the pressure drop due to the SCR system, and the potential decrease in
throughput. These are costs which can be minimized by using the low pressure drop Shell
DeNOx System.
Experience shows that operators frequently consider these last two costs to be negligible.
However, recent calculations show the yearly steam cost can easily be $100-300,000
(approx. $50-125,000 per 10 mbar pressure drop) depending on normal operation pressure
and plant size. The same figures can be calculated for throughput effects when the turbine,

Page -6-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

compressor/expander train is the capacity-determining factor (bottleneck). For example, for a

high-pressure (10 barg.) single pressure plant, every 10 mbar additional pressure drop can
cause a capacity decrease of 0,05%. This negative throughput effect can increase to 0,5%
for low or atmospheric pressure plants.

The information given in this paper may not be directly applicable to all plants, however, it
should motivate process engineers responsible for the day to day operation, to take a
different look at the economics of their plant.

It is our experience that when capital for investments is limited, cost and/or energy reducing
projects are of interest, especially when potential long term cost savings are available.

5.2 Selective Catalytic Reduction (SCR) Installation and Cost.

It is self-evident nowadays that environmental measurements or precautions have an
increasingly high priority with authorities. Even plants with new high pressure absorption
technology, emitting relatively low NOX concentrations are facing demands to reduce the
emitted NOX load.

New plants have high capacities to make them economically more attractive. However, these
plants with flue gas quantities in excess of 200,000 Nm3/hr with extended absorption systems
still emit a total NOX load of some 1,000 1,500 t/yr. This quantity is equivalent to a small
size plant e.g. 30,000 Nm3/hr with a NOX concentration of some 3,000 ppmv.
A further pressure on operators apart from the authorities is the local community. This results
from the visibility of the plume from Nitric acid plants, due to the high NO2 concentration in
the flue gas.

Companies considering installing an SCR are frequently concerned about the impact on the
overall plant performance. Generally SCR suppliers have limited knowledge of the plant
operation and consequently can give limited advice on optimal installation.

CRI as a supplier of SCR systems to the nitric acid industry, has taken note of and is
addressing these concerns. CRI together with an engineering consultant specialized in nitric
acid production has constructed a dynamic model which optimizes SCR installation taking

into account all the costs including those given below in 2.1. For each case the model is
adjusted to the plant specific configuration. Then together with the customer the various
effects are calculated. In this way the optimum location and design for the SCR can be
determined based on economics, technical feasibility and safe operation.

5.2.1 Typical costs for an SCR.

1. Gaseous ammonia ($100-$180/mt) required for NOX conversion.
2. Hardware depreciation; often it is possible to more rapidly depreciate investments
related to environmental emission control.
3. Capital cost; the internal cost of capital is usually 12-18%.
4. Catalyst depreciation. Catalyst is an operating cost and not a capital cost as the
catalyst lifetime is limited, hence it should be depreciated accordingly.
5. Additional steam cost. The increased pressure drop due to the SCR results in an
increased high-pressure steam consumption by the turbine. A limited amount of
energy is recovered from the exothermic reaction of NH3 and NOX.

Page -7-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

6. Decreased throughput. In case the turbine is operating at maximum capacity, then

additional pressure drop can reduce throughput. The throughput decrease (or
potential increase when retrofitting a low pressure drop system) can vary between
0.05% for high pressure plants and 0.5% for low or atmospheric pressure plants. On
a tonnage basis this appears to be a small impact, but on a yearly basis and
throughout the life of a plant the cost can become significant.

5.3 Minimizing operating costs.

5.3.1 For a new grass roots plant.

The flue gas originating from present generation nitric acid plants contains relatively low
concentrations of NOX. However, these plants often need an SCR to meet stringent future
standards, e.g. emission levels of 50 ppmv. To cope with upstream process fluctuations a
design value of below 40 ppmv is advisable. These emission levels can no longer be
achieved with absorption techniques, as extraordinary high investments in adsorption
columns would be necessary.
Among the many cost optimizations to be reviewed, three are considered below.

1. Ammonia cost. This cost is inherent to SCR technology, and is fixed by the NOx
reduction required. The cost is minimized by designing for a low ammonia
concentration at the reactor outlet, however, this is balanced by the extra catalyst
and/or mixing which may be required to achieve very high NH3 conversion. A further
consideration is that high ammonia slip at the reactor outlet could lead to NH4NO3
formation downstream of the expander where temperatures are low leading to unsafe
operation

2. Depreciation and capital cost of the installation. This cost is related to installation size,
which in turn is related to the NOX reduction requirement. The SCR size is indirectly
related to pressure drop. The lower the pressure drop, the larger the SCR reactor and
consequently, the higher the investment and capital cost. Whereas the operating cost
increases with decreasing SCR size, as at higher pressure drop, more high pressure
steam is required by the turbine. The total cost is the balance of the two; as the costs
vary differently with SCR size there is a minimum which represents the optimum
investment/capital cost and steam cost savings.

3. The trade-off between the absorption section size and SCR should be studied.
Present absorbers can be designed to emit low NOX concentrations, however,
removing the last NOX present in the gas stream requires excessive absorption
length. On the other hand, the difference in investment for an SCR decreasing NOX
from a concentration of e.g. 600 ppmv to 50 ppmv (NOX conversion 91,7%) is
relatively small compared to a NOX reduction from 300 ppmv to 50 ppmv (NOX
conversion 83.3%).

Although the above are only a few of the cost optimizations to be considered when finalizing
the equipment specification during the basic engineering, it shows that an evaluation of the
sensitivities can reduce the total investment considerably. Throughput limitations when
installing a SCR in a new plant should not be an issue.

Page -8-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

Evaluating the impact of installing an SCR is always advised, even when an SCR is not
immediately necessary as space can be reserved for later installation in the most optimal
location.

5.3.2 Retrofitting an SCR to an existing plant.

Both older generation plants with flue gas containing relatively high NOX concentrations and
newer generation plants face pressure to reduce NOX emissions. The specification of the
SCR should be evaluated thoroughly, as many of the previously mentioned aspects were
probably not taken into account in the original plant design. The optimal SCR specification is
also determined by available plot space, which is a constraint in the optimization process.

When an SCR is designed, an investigation of the possible pressure and temperature

windows leads to a number of possible installation locations. These are then evaluated to
determine the optimum location based on both economic and technical feasibility, and safe
operation e.g. NH4NO3 formation.

Simultaneously, the effect of the SCR pressure drop is evaluated, as particularly for existing
plants, the cost due to additional steam and throughput decrease, can readily exceed the
total SCR cost (hardware depreciation, capital, catalyst and ammonia costs).

5.3.3 For an existing plant with SCR.

Customers in this category have several reasons to study the performance and or economics
of the SCR.
Plant de-bottlenecking could lead to unacceptable increase in NOX outlet
concentrations and / or increase in NOx - load (tonnes/hr).
Increased NOX reduction requirements.
Security of catalyst supply.
Optimisation of the total plant economics as part of a cost reduction strategy.

These plants are particularly amenable to study through the medium of dynamic modeling.
Adjusting the existing SCR, either by changing the internals or even completely changing out
the existing system can led to significant savings. In one case the removal of an existing SCR
and replacement by a Shell DeNOx System has led to the customer saving between $500-
1,000,000 per year in operating costs.

Customers with existing NOX emission control units with high pressure drops such as CH4
combustors, or even SCRs with high pressure-drops, e.g. 75 to 100 mbar are advised to
reconsider their present systems as the economics of these plants can be improved
significantly.

5.4 Summary.
The above gives direction as to how emission control costs can be minimized for new and
existing plants without emission control equipment. Further it suggests how plants with
existing emission control units may be able to make significant cost savings through retrofit
with more suitable optimized technology.
CRI installs the Shell DeNOx System in a way that achieves optimal economics for the total
plant, whilst ensuring that the operation is technically uncomplicated and most importantly
safe.

Page -9-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

See: reference list for SDS on nitric acid plants attached

6.0 The Shell DeNOX System on a waste incineration plant

The Dutch environmental directive for Emission regulations for waste incineration plants
1993, defines the maximum NOX emission level to be 70 mg/Nm3 (@ 11% O2). Since then
various technologies have been applied to waste Incineration plants to reduce NOX to below
the maximum allowable level.
At the WATCO waste incineration plant, the Shell DeNOx system was chosen to remove
NOX. This system has been successfully used for NOX removal from flue-gases originating
from gas turbines, refinery furnaces, nitric acid and caprolactam plants containing between
50 and 15,000 ppm NOX (see attached reference list).
Given the operational experience gained at WATCO, it is now possible to demonstrate the
cost effectiveness of the Shell DeNOx System as applied to a waste incineration application.

In summary the Shell DeNOx System applied at the WATCO waste incineration plant fulfils
all requirements in a cost effective manner.

Shell DeNOx System process design at WATCO Roosendaal, The Netherlands

With respect to design conditions, the catalyst volume is primarily determined by the flue gas
volume, the desired NOX conversion and the ammonia slip. The pressure drop is determined
by the choice of module type. The design of the Shell DeNOx System is based on laboratory
testing, reference unit data and computer modeling. A summary of the process conditions
and design requirements is given in the table below.

Table 1. Process conditions and design requirements.

(concentrations corrected to a dry volume basis and normalized to 11% oxygen)
Process Conditions
Flue Gas volume < 66,000 Nm3/hr (wet)
Temp.(exit bag house) 120 C
Gas composition
Oxygen > 10 % vol
Water < 24 % vol
NOX < 600 mg/Nm3
SOX < 75 mg/Nm3
Dust < 10 mg/Nm3
Design requirements
NOX emission < 70 mg/Nm3
NOX removal > 88 %
NH3 slip <5 mg/Nm3
Operation Temperature < 245 C
Pressure drop < 10 mbar

A schematic of the flue gas cleaning system at the WATCO waste incineration plant, of which
the Shell DeNOx System is part, is shown, overleaf, in figure 2. This scheme shows that the
flue gas coming from the bag-house filter is heated by the exhaust gases with the help of a

Page -10-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

gas-gas heat-exchanger. Following the heat exchanger the optimal gas temperature is
reached with the help of an in-line burner. After the burner, evaporated ammonia is injected
into the flue gas. Special attention is paid to the ammonia distribution and mixing as this is of
great importance in achieving low NOX and ammonia emissions. Subsequently, the gases
pass thorough the reactor over the catalyst.

Table 2. Actual operating conditions.

(concentrations corrected to a dry volume basis and normalized to 11% Oxygen)
Actual
Flue gas volume 50 - 60,000 Nm3/hr (wet)
Operation temperature 200 - 245 C
NOX inlet 250 - 350 mg/Nm3
NOx outlet / NH3 slip
operator setting < 45 / < 1 mg/Nm3
test - run <2/<3 mg/Nm3
(see note below)
SOX 20 25 mg/Nm3
Pressure drop 27 mbar

Note: when operating with a slightly higher NH3 slip it is possible to increase NOx conversion
to even higher levels.

It is clear that at the normal operating temperature of 245C, the NOX (< 70 mg/Nm3) and
NH3 (< 5 mg/Nm3) emission requirements are readily achieved. During part of the test run
when the unit was hand-operated NOX emissions below 2 mg/Nm3 and ammonia emissions
below 1 mg/Nm3 (within the noise level of the analyser) were achieved, consistent with a
NOX conversion of around 99%.
The NOX emissions were likewise measured over a two day period at an operating
temperature of 200C. Similarly at this temperature and under typical operating conditions
(NOX and SOX inlet concentrations) the emissions were well below the legal requirements.
The pressure drop over the unit depends on the temperature and the flue gas throughput,
and lies between 2 and 7 mbar in agreement with CRIs calculated value.

b) Operating Experience
The Shell DeNOx system requires little attention from the operators. Except for the ammonia
injection pump, the unit has no moving parts which require regular maintenance.
The process control is, also, extremely simple. The temperature is automatically controlled by
the in-line burner and the NOX emission is automatically controlled by the ammonia injection
pump. Both control loops have performed according to expectation since the unit start-up.
The choice of settings (PID control points) for the automatic control of NOX requires some
care. An ammonia buffer is created by ammonia adsorption on the catalyst. This is positive in
that it damps out peaks in NOX concentration or flue gas volume, which do not need to be
directly controlled. However, it may slow the response to changes in the process conditions
(concentrations, flows, ammonia injection) if not well controlled. The control settings for the
feed-back control system must be chosen such that a gradual change towards the required
emission level is achieved in order not to cause the system to oscillate, as shown in figure 3.
With the settings used at WATCO the NOX emissions can be readily maintained below 70

Page -11-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

mg/Nm3 (@ 11 % O2). The start-up, shut-down and safety procedures have been completely
automated and function according to expectation.
The Shell DeNOx System can be rightly called an end-of-pipe technology. Because of the
high activity at low temperatures the unit can be installed as the final process step prior to the
stack without having any negative effect on the upstream units.
c) Reliability
As discussed earlier the Shell DeNOx System has little sensitive equipment and therefore
has a high degree of operational reliability.
Only one trip of the system has occurred since start-up, which was caused by a fall in the gas
pressure to the in-line burner. This trip was caused by external factors not under control of
the site.
After four months of operation there is no suggestion of a reduction in the catalyst activity or
of a build-up in the pressure drop over the system. On this basis a catalyst life span of many
years is expected.

Page -12-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

Figure 2. Schematic of the Flue gas cleaning system at WATCO.

Flue Gas
From Carbon
Incinerator Injection

Semi-Dry NH3
Scrubber Bag
Houses Injection
Shell
Denox
In-Line Reactor
Burner
Lime
Lime
Injection
ESP Slurry Heat
Mixer Exchanger
Lime
Lime Make-Up NH3
Bleed
Feed
Particle Removal HCl, SOx, Dioxin & Dust Removal NOx Removal

Page -13-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

7.0 The Shell De-Dioxin System (SDDS) for Dioxin and Furans
destruction.
The Shell Dioxin Destruction System is a proven low temperature technology for dioxin
emission reduction. Its cost effectiveness compared to other dioxin control technologies is
leading to its application throughout the world. Unlike technologies based on carbon
adsorption where the dioxins are only transferred to solid particles, which require further
processing, catalytic systems destroy the dioxin compounds in a single process step. The
Shell Dioxin Destruction System converts dioxins to a mixture of harmless gases. A typical
reaction is shown below.

C12HNCI8-NO2+(9+0.5n)O2 (n-4)H2O+12CO2+(8-n)HCI

(in paragraph 8.7. we will explain that combined NOx and dioxin removal will be possible
within the same SDS /SDDS technology concept).
The Process
The process does not require the addition of any reactant. Only oxygen is required for the
destruction.
The two main features of the Shell Dioxin Destruction System (SDDS) which enable the
dioxins to be reduced to extremely low levels at low flue gas temperatures are the catalyst
and the module which contains the catalyst. The catalyst, S-090, was developed in Shells
Amsterdam Research Laboratories. It is a high activity, high metals loaded catalyst with high
surface area and porosity. These features give the catalyst its low temperature activity. The
physical shape of the catalyst is typically a trilobe extrudate of from 1 to 4 mm diameter and
nominally 3 to 6 mm length. It is manufactured in CRIs ISO 9002 certified catalyst
manufacturing plant in Ghent, Belgium. Each batch of catalyst is carefully tested in CRIs
laboratories to insure that the physical properties and the activity meet CRIs rigorous
standards of excellence. The catalyst is contained in a stainless steel module called a Lateral
Flow Reactor.

The Lateral Flow Reactor technology , as described earlier in this paper is a way to expose
the greatest amount of catalyst surface to the flue gas at the lowest possible pressure drop.

Flue gas enters the Lateral Flow Reactor in numerous gas inlet channels, which are blocked
at the opposite end. The flue gasses then must travel laterally through catalyst layers to
reach the outlet channels. As the flue gas passes through these catalyst layers the dioxin
compounds are oxidized and destroyed by the active metals on the catalyst to form primarily
water and carbon dioxide.
The combination of the high activity catalyst with the LFR allows the Shell Dioxin Destruction
System to easily achieve high dioxin conversions. From inlet concentrations of up to 100ng
TEQ/Nm3, the Shell Dioxin Destruction System can achieve over 99.9% destruction of dioxins
and furans, down to the standard regulated emission limit of less than 0.1ng TEQ/Nm3. The
ability to engineer the depth of the catalyst layers within the Lateral Flow Reactor allows the
Shell Dioxin Destruction System to be designed for very low-pressure drop if required.

Page -14-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

For small gas volumes, a single catalyst reactor module can be utilized to meet dioxin
emission requirements. For larger flue gas flows, multiple modules are required. These
modules are arranged in a single layer in an engineered reactor house to insure complete
flue gas passage through the catalyst layers.

Conclusion
The Shell Dioxin Destruction System has been successfully applied to meet required dioxin
emission limits on both liquid waste incinerators, after the wet acid gas scrubber, and solid
waste incinerators, after acid gas and particulate removal systems.
The low operating temperature and the ability to design for low pressure drop allows the
Shell Dioxin Destruction System to be positioned at the tail end of most existing processes,
just prior to the stack. Since the system can be located downstream of the scrubber and
particulate removal systems, catalyst poisoning is minimized allowing long catalyst life. As the
last operation in the flue gas cleanup system, the Shell Dioxin Destruction System insures
that the required dioxin emission limits are met. The compact, lightweight nature of the unit
can allow ease of retrofit on existing facilities where space is limited. Installation at the end of
the process results in significant savings in installation and operating costs with minimal
downtime for installation.

8.0 Cost of NOX and Dioxin removal

8.1. Cost expressed as Euros per mt NOx removed

In this paragraph a number of examples will be presented on NOx removal costs. A way of
expressing these costs is US $, Guilders or Euros per ton NOx removed. This way it will be
possible to compare the costs of various NOx removal technologies. The most cost-effective
technology will result in the lowest cost when expressed in f.i. Euros per ton NOx removed.
This method of calculating becomes of particular interest with NOx emission trading
system (which is currently under study by the Dutch Government).
In order to remove maximum tons of NOx SCR is currently the only viable technology. The
Shell Denox System can be simply designed for NOx conversion levels of over 95% by a
small incremental quantity of catalyst resulting in a small extra catalyst cost (other costs
remain essentially the same). As however the quantity of NOx removed has substantially
increased , the net effect is that the cost of NOx removal decreases at lower NOx emission
levels. The above is presented in the following curve basis a gas turbine application.

Page -15-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

Shell DeNOX System Gas Turbine

3500

3000

2500 Total cost

Cost/ton NOX removed

2000 [nfl]

1500
Capital Charge
1000

500 Catalyst
Ammonia
Maintenance
0 Red. Power output

50 60 70 80 90 100

NOX removal [%]

Page -16-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

8.2. Cost expressed as Total Installed Cost (TIC)

Following curves demonstrate that TIC costs increase , as can be expected, with
increasing flue gas flow.
However when cost (as expressed in Euro per mt NOx removed) is set against flue
gas flow volume than the cost curve is leveling off beyond 100.000 Nm3/h.

Cost for NO X re m ova l (Dfl pe r M T NO X )

6000
Remov al c os t (Dlf /ton NO X remov ed)

5000

4000

3000

2000

1000

0
0 100 200 300 400 500

Flow rate [Nm3 /hr x 1000]

Cost for NO X re m ova l (P roje ct costs)

7
Projec t c os ts [Dlf x 10 6 ]

0
0 100 200 300 400 500
Flow rate [Nm3 /hr x 1000]

Furthermore it is shown that the above curves (all typically basis 95% NOx conversion) show
little differentiation for gas turbine (NOx inlet 100 ppmv), waste incineration (NOx inlet 300
ppmv) or furnace applications (NOx inlet 200 ppm).

Page -17-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

8.3. Waste incineration

On the basis of capital costs (including a capital charge) and operating costs
(maintenance, operators, ammonia, natural gas, etc.) i.e. the total installed cost, a
cost estimate can be made for NOX removal.
From the actual process conditions it can be calculated that on a yearly basis
approximately 130 MT of NOX is removed. When applying the usual factors for fixed
and operating costs , interest and depreciation then a cost is calculated of NGL 3850
per ton NOx removed ( reference article in LUCHT, number 4, December 1996).
Indeed given the relatively small scale of the WATCO installation, it is evident these
costs are relatively low.

8.4. Nitric acid

Furthermore, the modular construction of the LFR offers considerable benefits with
respect to construction costs. SCR is often referred to in the literature as being an
expensive method of reducing NOX emissions. While this assertion can be seen to
contain a modicum of truth when considering the high costs often associated with the
use of conventional honeycomb systems (which can be equivalent to sums in excess
of $ 10,000/ton NOX removed), Shell DeNOx technology should help to change this
picture. Recent case studies for actual applications made for the Shell DeNOx
System on the basis of total project costs (Capex, Opex) give a range of cost from
400 $/MT NOX removed for Nitric acid plants to 1,800 $/MT NOX removed for gas
turbines.

NOx removal cost, $/MT NOx

500

450

400

350

300
400 300 200 100 0
NOx content in outlet, ppmv

8.5 Gas turbines

Dutch case
For the required NOX-reduction (> 93%) 6 catalyst modules were needed.
With smart engineering of the layout of the reactor the retrofit costs were limited, so

Page -18-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

the total investment costs for the DeNOx system were much lower than originally
foreseen.

Cost / Performance data:

Investment costs Euro 1,400.000
Annual running costs Euro 150.000
Total annual costs Euro 345.000
Ton NOx removed per year 320
Cost per ton NOx removed Euro 1.100
NOx-in 270 mg/Nm3 (215 g/GJ)
NOx-out < 18 mg/Nm3 (15 g/GJ)
Performance > 93%

The system was installed within a normal shut down period i.e. within 10 days.

California GT case
In this case SDS is installed at 3 x 40 MW GT with a flue gas flow of 370,000 Nm3/h
each with temperature of 170oC.
Annualizing the engineering, procurement and construction capital cost, plus O&M
cost, over a 5-year life yields a cost effectiveness value of $ 2480 per ton of NOX
removed. This contrasts with refinery project cost effectiveness values of $ 4000 to
$ 8000 per ton NOX removed for ultra low NOX burners and $ 10.000 to
$ 12.000 per ton NOX removed for conventional SCRs installed on existing refinery
gas turbines / furnaces.

8.6 Cost of Dioxin removal

Biomass application in furniture industry

For a dedicated Dioxin removal project in W.Europe following data apply :
- flue gas flow 20,000 Nm3/h
- temperature 180 oC
- dioxin inlet 5 ng/Nm3 (TEQ)
- dioxin outlet < 0.05 ng/Nm3 (TEQ)

Cost for the Shell Dioxin Destruction System plus cost of integration into
existing installation (excl. analyser costs) estimated to be in Euros 100.000.

8.7. Cost of combined NOx and Dioxin removal

In the case of combined NOx and Dioxin removal the Shell System only need to be designed
for NOx removal (rather than for dioxin removal) as NOx is the more difficult component to
remove. Under these design and operating conditions the dioxins will then be removed
(simultaneously with the NOx) to very low values (< 0.05 ng/Nm3). This means that no extra
or additional catalyst volume will be required for additional dioxins removal.
There is no extra cost involved for dioxin removal.

Page -19-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

An example is the Watco waste incineration plant (see above) where simultaneously NOx is
removed (over 90%) as well as the dioxins (from 0.5 to below 0.001 ng/Nm3 TEQ).

9.0 Summary

The so-called Shell Denox System is a compact , cost-effective and highly efficient
technology to remove NOx from industrial flue gases. Particularly for low temperature (end-
of-pipe type) applications this technology is recommended. Also for applications with extreme
high NOx levels (over 3000 ppmv NOx) the System can meet extremely low NOx outlet and
NH3 slip levels. The System can be designed for very low pressure drop levels.
The Shell System can be used for dedicated NOx removal from various types of industrial off-
gases, as well for combined NOx and dioxin removal. In that case no additional catalyst
volume is required for the extra dioxin removal requirement.

9.1. Reference list

see attached

Page -20-

CRI Catalyst UK
ADEME conference March 2001 -rev.1
Shell DeNOX System

Application Location Design Conv. (%) Temp, (C) Flow, (Nm3/hr)

Refinery Heater Los Angeles 87 215 22,000

Sweden 90 177 100,000

Ethylene Cracker Germany 65 160 350,000

Germany 85 140 50,400

Electric Arc Furnace Australia 94 200 22,000

Gas Engine The Netherlands 85 120 2,000

Austria 85 260 3,000

Gas Turbine San Francisco 91 204 250,000

San Francisco 93 177 (3x) 370,000
Gulf Coast 90 175 48,000
San Francisco 93 185 (3x) 350,000
The Netherlands 89 170 (2x) 275,000
The Netherlands 92 185 150,000

Incineration The Netherlands 89 240 66,000

Italy 94 175 5,400
Germany 95 260 14,000
UK 88 200 7,000
Ireland 87 280 31,000
France 87,5 250 17,000

Nitric Acid Plant South Africa 88 205 70,000

Denmark 83 170 30,000
USA 96 250 27,000
Malaysia 90+ 485 36,000
USA 90+ 460 70,000
UK 90 380 144,000
UK 95 225 108,000
The Netherlands 85,5 258 275,000
Spain 95 220 50,000

Caprolactam The Netherlands 96 260 32,000

Korea 98 260 42,000
Korea 97 270 47,500
Taiwan 97 187 46,000
India 97 200 8,100

Chemical Process USA 99+ 200 30,000

Catalyst Plant Belgium 98 250 23,500

San Francisco 96 240 15,500
San Francisco 96 240 3,500
UK 93 270 13,000
Germany 98+ 200 14,000

Page -21-

CRI Catalyst UK
ADEME conference March 2001 -rev.1