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Reducing FCC unit NOx emissions

Mechanisms of FCC unit NOx formation and logical steps to minimise these
emissions are discussed. Performance examples using additives are provided

Charles Radcliffe Intercat (Johnson Matthey)

N
Ox emissions are becoming a worldwide ual pollutant depend on its potential to acidify,
issue. Reductions in NOx emissions from and the individual properties of the ecosystems
FCC units have been a requirement at and materials. The deposition of acidifying
many US refineries as a part of the negotiations substances still often exceeds the critical loads of
between the US Environmental Protection ecosystems across Europe. (Critical load is the
Agency (EPA) and the operators for consent ability of ecosystems to bear an environmental
decree settlements. A consent decree is effec- load ie, acidifying depositions without
tively a negotiated voluntary agreement by the significant damage.) Efforts to reduce the effects
refiner to reduce emissions levels. Many US of acidification are therefore focused on reducing
regional pollution-control authorities have also the emissions of acidifying substances.
now started to impose significantly lower NOx NOx and SO2 can also have direct and indirect
emissions limits for FCC units. impacts on human health, and can transform
European refiners are also now facing increas- into small-diameter particulate matter (see EN07
ingly stringent controls, as laid down under Energy-related particulate matter emissions
several EU-wide emissions limits and targets for published by the European Environment
the reduction of SO2 and NOx. They include the Agency), which, when inhaled, can cause respira-
National Emissions Ceiling Directive (NECD; tory problems. NOx is also a tropospheric ozone
2001/81/EC) and the United Nations Economic precursor that reacts in the atmosphere in the
Commission for Europe Convention on Long- presence of sunlight to form ozone, which, in
Range Trans-boundary Air Pollution Gothenburg high concentrations, can lead to significant
Protocol (UNECE 1999). These have culminated health impacts and damage to crops and other
in the European Commis-sions Clean Air For vegetation. Furthermore, an excessive input of
Europe programme (CAFE). This thematic strat- nutrients from atmospheric deposition leads to
egy on air quality was released in September eutrophication.
2005. The National Emissions Ceiling Directive
Reductions in NOx emissions from refineries includes emissions-reduction targets that are
are also becoming an issue of major public slightly stricter than the targets set in the
concern in other countries as air pollution levels Gothenburg Protocol, and requires the introduc-
in expanding major cities increase. tion of national emissions ceilings for emissions
The environmental issues underlying the of SO2, NOx and NH3 in each Member State, as
European legislation relate to acidification.1 well as setting interim environmental objectives
Acidification is caused by emissions of sulphur for reducing the exposure of ecosystems and
dioxide, nitrogen dioxide and ammonia into the human populations to damaging levels of
atmosphere, and their subsequent chemical reac- acid pollutants.
tions and deposition onto ecosystems and In terms of the energy sector, which includes
man-made structures. Deposition of acidifying refining, the most relevant NEC Directive targets
substances causes damage to ecosystems, and for the EU-25 as a whole are:
corrosion damage to buildings and materials. SO2: emissions reduction of 74% by 2010 from
The adverse effects associated with each individ- 1990 levels

www.digitalrefining.com/article/1000303 Catalysis 2008 1


States to establish programmes for reduc-
Full burn regenerator Flue gas line ing total emissions. Emissions limits for all
N2 in air plants were revised in 2007 under the
IPPC Directive. Adding to the pressure on
industry is the fact that the US refining
(Nitrogen sources) N + ? O2 NO Flue gas
industry has already gone down this route,
driven heavily by the Consent Decree
NH2/HCN CO settlements with the EPA.

Refinery NOx emissions reduction


Feed nitrogen NO + CO N + CO2 A significant portion of refinery NOx
Partial burn Co boiler Flue gas line normally originates from furnaces. For this
regenerator reason, low-NOx burners are usually
required in furnaces to meet BAT require-
Figure 1 Published routes to NOx formation in FCC regenerators ments. In addition, FCC NOx emissions
reductions are likely to be required to meet
NOx: emissions reduction of 53% by 2010 from BAT. Reducing FCC NOx emissions can actually
1990 levels. lead to cost reductions through reduced promoter
Other key policies that have contributed to the usage. This could also lead to further savings by
reduction of acidifying emissions across Europe providing increased furnace fuel flexibility within
include the Integrated Pollution Prevention and a bubble constraint. However, it should be noted
Control (IPPC) Directive (96/61/EC). This came that for partial-burn FCCs, the vast majority of
into force in 1999 with the aim of preventing or the NOx is produced in the CO boiler. These
minimising the pollution of water, air and soil by emissions cannot currently be controlled using
industrial effluent and other waste from indus- catalyst additives and so the issues addressed in
trial installations. It defines the basic obligations this discussion are not relevant to these units.
for operating licences or permits, and introduces
targets or benchmarks for energy efficiency. It FCC NOx formation chemistry
will also require the application of Best Available The published and generally accepted routes to
Techniques (BAT) in new installations from now NOx formation are illustrated in Figure 1.
on (and for existing plants over ten years, The UOP view on factors impacting NOx
according to national legislation). formation, as stated at the NPRA 2006 FCC
The Large Combustion Plant Directive conference, is summarised in Table 1.2
(2001/80/EC) is important in reducing emis- The complexity of the interaction between
sions of SO2, NOx and dust from combustion these many factors is a major issue, which makes
plants with a thermal capacity of greater than 50 multiple-unit NOx comparisons very difficult.
MW. The directive sets emissions limits for the Figures 2a and b are used to illustrate feed
licensing of new plants and requires Member effects, but it is debatable how much of this
effect is related to feed nitrogen, given the many
other operational changes and feedstock effects
UOPs view of important factors in NOx formation that result from switching between these types of
feed.
Feedstock effects Operation effects Contaminant metals such as vanadium, iron
Nitrogen speciation Regenerator temperature and nickel are known to lead to increased NOx
Con-carbon Excess oxygen emissions in most FCC units. Indeed, platinum
PONA Regenerator pressure
introduced in the form of CO promoters has a
Distillation NOx additives
Basic nitrogen CO promoter strong effect on NOx emissions, as Figures 2a
Total nitrogen Residence time and b demonstrate.
Residue content Regenerator design This CO promoter effect is perhaps to be
Slurry recycle Catalyst properties
expected from a catalyst that is used commer-
Feed preheat
cially for nitrogen oxidation in other processes.
Table 1 However, the complexity of the various metals

2 Catalysis 2008 www.digitalrefining.com/article/1000303


effects is illustrated by antimony.
Figure 3 shows antimony injection 800

causing a spike in NOx emissions. 3

Since antimony is known to poison


Pt-based promoters, this effect is
counter-intuitive.
Intercat (Johnson Matthey) does 600
not believe that the reaction
mechanisms shown in Figure 1
explain adequately the results that
are being seen commercially. This

Flue gas NOx, ppm


VGO + resid feed
is because in most studies of
400
commercial units there is no
measurable CO effect, feed nitro-
gen is not a significant driver of
NOx, and there is a strong depend-
ence of NOx on excess oxygen and
parameters related to oxygen 200
availability and distribution.
The central role of oxygen in the VGO feed

reactions of the regenerator is


illustrated in Figure 4. This shows
how the various oxidation reac- 0
tions compete for the available 0.0 0.5 1.0 1.5 2.0
Excess oxygen, mol%
oxygen. Increasing the usage of
oxygen in one series of reactions
can lead to a reduction in the Figure 2a Feed effect on NOx
availability of oxygen for a
competing set of reactions. For
example, taking O2 to move SO2 to
SO3 (as happens when using a SOx Example of response at constant excess O2
additive) can reduce NOx emis- 160

sions in some units.


The effect of excess oxygen on
NOx formation for four different 140

FCC units clearly showed evidence


of a strong dependence of flue gas
120
NOx levels on excess oxygen. There
Flue gas NOx, ppm

was a large degree of variability in


the data, implying that other vari- 100
ables are also important. Some of
the variables involved on a fifth
unit were determined by multivar- 80

iable regression analysis, which


Increasing CO promoter
was used to develop a model to
60
predict FCC NOx emissions. A
tight match between the measured
and model-predicted NOx for this 40
fifth unit showed that the regres- 0.3 0.5 0.7 0.9
E-cat platinum, ppmw
sion was an excellent match to the
unit data.
Table 2 shows the importance of Figure 2b CO promoter effect on NOx emissions

www.digitalrefining.com/article/1000303 Catalysis 2008 3


each of the independent varia-
Flue gas and ESP stack NOx bles relative to feed basic
350
Resid contamination of nitrogen. Feed basic nitrogen
300 FCC feed and some use ESP stack NOx
of pt promoter Regen flue gas NOx
was the least important varia-
250
Transition to FCC outage with CO
ble, while the highlighted
non-pt promoter
200 boiler in service variables are either directly or
NOx, ppm

150 indirectly related to oxygen


Antimony trial
100 availability and its distribution
50
in the regenerator, and are up
0 SNCR start-up
to 25 times more important.
28 Jun 03 14 Jan 04 1 Aug 04 17 Feb 05 5 Sep 05 24 Mar 06 10 Oct 06 The variations seen between
Date
different regenerators are
perhaps not surprising given
Figure 3 Effect of antimony on NOx that most were designed with
the objective of simply remov-
ing the carbon from the catalyst, and it is only in
the last few years that reactions other than the
# oxidation of carbon have become important.
# /n#/ What is emerging as a key factor in these other
# /n#/ reactions is the local availability of oxygen. In a
#/ /n#/
bubbling-bed regenerator, vertical mixing is
extremely good, but lateral mixing is poor.
Therefore, if the distribution of either the air or
spent catalyst is uneven, there will be regions
3 #/ . across the section of the regenerator where there
3 /n3/ (#. /n./ is an excess of oxygen, and other regions where
3 /n3/ .( /n#/ there is no excess oxygen at all. It is in the
3/ /n#/ . /n./
. /n./
former areas where the bulk of the NOx is
./ /n./ formed, while in the latter CO can be produced.
An example of this effect is shown in Table 3,
which shows the results of testing the flue gas
composition at three different points around the
Figure 4 The central role of oxygen circumference of one operating FCC regenerator
in the US.
Some process licensors have been aware of this
Relative importance of independent variables effect for many years, and have focused their
efforts on achieving better distribution by
Independent variable Relative effect Direction moving to fast, fluidised beds to improve lateral
Vol% excess O2 24.8 Positive mixing. The resulting improvements are illus-
Undisclosed variable 22.0 Positive trated in Figure 5.3 It is important to keep these
Regen dilute temperature 15.6 Negative
hardware design factors in mind when consider-
Regen dense temperature 10.8 Positive
Regen air rate 9.4 Positive ing revamps, as there have been several examples
Vol% CO2 7.2 Positive of dramatic changes in NOx emissions (both
Preheat 5.3 Negative increases and decreases) following regenerator
Expander inlet temperature 4.3 Negative
design changes.
Regen pressure 3.2 Negative
Feed rate 2.6 Negative The redistribution of oxygen is also believed to
O2 enrichment 2.5 Positive be one of the factors affecting how Nox-reduction
Vol% CO 2.1 Negative additives work. These additives include metals,
Feed basic nitrogen 1.0 Negative
which can exist in several different oxidation
Relative importance = model coefficient x data range states. These metals can absorb oxygen by chang-
ing to higher oxidation states in areas where
Table 2 there is a lot of excess oxygen, and then release

4 Catalysis 2008 www.digitalrefining.com/article/1000303


it in oxygen-deficient areas by reverting
to a lower oxidation state. This move- Example of regenerator flue gas distribution
ment of oxygen results in a more even
distribution of oxygen around the regen- O2, vol% CO2, vol% CO, ppm SO2, ppm NOx, ppm
Position 1 0.1 16.6 >10 000 482 7
erator, thereby helping to reduce NOx Position 2 1.4 15.6 4276 127 51
formation. Position 3 5.1 12.6 23 4 86

Steps to reduce FCC NOx formation Table 3


When a refiner is faced with the need to
reduce FCC NOx emissions and is unable to analysis are often surprising. It is worth noting
make hardware changes, there are a series of that the effect of some variables may be more
simple steps that can be followed. These have prominent in the short-term data and less prom-
been demonstrated commercially in a number of inent in the long-term data (or vice versa). This
units and have led to signifi-
cant cost reductions in many
200
of these cases.
Combuster-style
Bubbling bed regenerators
Step 1: determine unit operating 160

variable effects on NOx


Flue gas NOx, ppm

The first step in approaching 120


any Nox-reduction problem
should be to thoroughly under- 80
stand the existing regenerator
operation. The previously 40
noted Table 2 illustrates the
usefulness of regression analy-
0
sis for determining the effect 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
of major FCC operating varia- Excess oxygen, mol%
bles on regenerator NOx
emissions. Intercat (Johnson Figure 5 Effect of regenerator design on NOx emissions
Matthey) recommends this
analysis should be carried out
on several time scales to 75
ensure all operating variable
effects are fully understood. It
70
is recommended that the
following data sets be
regressed separately, and the 65
results of these separate
NOx, ppm

regressions compared with one


60
another:
Approximately one days
worth of one-minute data 55
Approximately one months
worth of hourly data
50
Approximately six months
Before COP shot
worth of daily data. With shot of COP
This set of regression analy- 45
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
ses should clearly show which O2, %
operating variables are having
the largest effect on NOx emis-
sions. The results of this Figure 6 Response of NOx emissions to Pt promoter shots

www.digitalrefining.com/article/1000303 Catalysis 2008 5


num promoter, the platinum
level on catalyst in most cases is
350 14.0
set high enough to ensure there
Stack SO2, ppm Stack O2, mol%
300 Stack NOx, ppm Stack CO, ppm 12.0 is minimal afterburn 99% of the
time. The problem with this is
COPNP
250 10.0 that afterburn is not always
NOx, CO, SO2, ppm

present. In most units, in the


200 8.0 absence of promoter, the amount

O2, mol%
of afterburn varies with time,
150 6.0
Pt with only occasional excursions
promoter
100
to high levels. This means that
4.0
when platinum is pre-blended in,
50 2.0 most of the time there is much
more platinum in the inventory
0 0.0 than is required to control after-
0.0 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Days
burning. In these units, this
excess platinum is usually a
major contributor to NOx
Figure 7 Other stack emissions are unaffected formation.
The next step to minimising
NOx emissions should therefore
NOx reduction with intercat additive be to stop pre-blending CO
1% additive present promoter and start adding this
180
same material separately. This
160
will allow the amount of CO
140 promoter used to be controlled
120 on-site.
No additive
NOx, ppm

100
Step 3: Establish a minimum level of
80
platinum promoter additions
60 Figure 6 shows how shot-dosed
40 promoter causes only small,
With additive
20 short-term spikes in NOx emis-
0
sions. The next step is therefore
0.0 0.5 1.0 1.5 2.0 2.5 to adopt a strategy of dosing
O2, %
promoter only when required to
suppress spikes in afterburn. This
Figure 8 Commercial trial of NOxGetter-B can be done manually or by using
an additive loader. A small addi-
is normal, and Intercat (Johnson Matthey)s tive loader can be connected to the DCS and
experience is that the short-term data effects are configured to automatically add just enough
usually the most meaningful. promoter to maintain a safe level of afterburn.
Once this information has been compiled, it This will safely minimise the quantity of Pt
should be possible to assess which operating promoter used and provide accurate records of
variables can be adjusted to minimise NOx emis- promoter additions. The reduced promoter usage
sions without significantly impacting the FCC resulting from this step can save money for the
operation. refiner, while at the same time minimising NOx
emissions.
Step 2: removal of any pre-blended platinum promoter Having minimised the usage of platinum
The previously shown Figure 2b (CO promoter promoter, the level of NOx reduction being
effect on NOx) shows the impact of platinum achieved can then be assessed. The decision can
promoter. When refiners use pre-blended plati- then be made as to whether further reductions

6 Catalysis 2008 www.digitalrefining.com/article/1000303


in NOx are required. If so, it will be
necessary to proceed to Step 4.
$ETERMINEWHATOPERATING /PERATETOMINIMISE./X
3TARTHERE VARIABLESAFFECT./XINYOUR WITHIN
UNITDATAWITH)NTERCATSHELP UNITOPERATINGCONSTRAINTS
Step 4: replace platinum promoter with a
non-platinum promoter such as COP-NP
It is possible to significantly reduce
./X
NOx emissions by substituting the -OVETOFULLBURNOR .O
&ULL
BURN
.O EMISSIONS 9ES
HARDWARECHANGES UNDERTARGET
platinum in the combustion REGEN

promoter with another material, 9ES


which is still active for CO oxida-
tion, but less selective for NOx
5SING
formation. This can dramatically PREPROMOTED
9ES 2EMOVEPROMOTER 2EMOVEPROMOTER
ANDADDSEPARATELY ANDADDSEPARATELY
lower NOx levels, while still main- CATALYST

taining good control of afterburn. ./X


.O
Intercat (Johnson Matthey)s COP- EMISSIONS
UNDERTARGET
9ES

NP contains such a combination of


metals specifically tailored to .O 5SING .O
PTPROMOTER
perform this function, and Figures
7 and 8 illustrate how this promoter
./X
allowed a refinery to meet their 5SENON PTPROMOTER
EMISSIONS 9ES
UNDERTARGET
NOx emissions and afterburn objec-
tives, while not impacting other
.O
emissions.
It is worth noting here that many
4RIAL./X 'ETTER!
refiners have chosen to keep a few
drums of platinum-based promoter
on hand during this stage of the ./X
EMISSIONS 9ES
trial to provide reassurance that UNDERTARGET
short-term afterburn excursions
can be handled. Although this was .O
4RIAL./X 'ETTER"
a prudent move with first-genera-
tion non-platinum promoters, it
should be made clear that this has .O
./X
EMISSIONS
)MPROVECATALYSTAIR
not proved necessary with DISTRIBUTION UNDERTARGET

COP-NP.
9ES

Step 5: trial a Nox-reduction additive


./ X
If NOx emissions are still not at or .O EMISSIONS 9ES
3UCCESS
9ES
UNDERTARGET
below the required level, the final
step in this process should be to try
using a Nox-reduction additive. If a
significant level of NOx reduction is Figure 9 Flow chart for NOx minimisation
being achieved by a non-platinum
CO promoter, the level of NOx reduction that respond well to these additives. However, it only
may be achieved with a separate NOx additive requires a short eight-day trial to establish which
could be limited. However, Nox-reduction addi- technology will work and which is best suited to
tives do offer a very cost-effective means of each unit. These two additives use very different
reducing NOx emissions in many units. technologies and either may work in any given
The effectiveness of Intercat (Johnson FCC unit.
Matthey)s two Nox-reduction additives Dosage levels for both additives are low.
(NOxGetter-A and NOxGetter-B) vary from unit NOxGetter-A is normally used at between 15% of
to unit, and it should be noted that not all units inventory. NOxGetter-B requires a very much

www.digitalrefining.com/article/1000303 Catalysis 2008 7


lower dosage level for maximum effectiveness, COP-NP, NOxGetter-A and NOxGetter-B (NOXGETTER-A and
normally less than 1%, or even just slightly higher NOXGETTER-B) are marks of Intercat (Johnson Matthey).
than CO-promoter levels in some units. These
catalytic NOx additives have significantly reduced
References
NOx emissions in many full-burn regenerators.
1 Wiesenthal T, EN06 Energy-related emissions of acidifying
If after carrying out all of the previous steps
substances, European Environment Agency leaflet, 26 June
NOx emissions are still above target, it will prob- 2006.
ably be necessary to look at hardware solutions 2 Lacijan L, UOP LLC, CAT-06-203 FCC regenerator design
to improve the spent catalyst and air distribution considerations, NPRA Cat Cracker Conference, 12 August 2006.
within the regenerator. This process to minimise 3 Anderson S, A combined technology testing for FCC NOx
NOx emissions can be summarised as a flow reduction, CAT-06-207, NPRA Cat Cracker Conference, 12 August
chart, as shown in Figure 9. 2006.

Conclusion
European refiners are being forced to reduce Charles Radcliffe is a senior technical service engineer for Intercat
(Johnson Matthey) in Europe. Email: cradcliffe@intercatinc.com
their FCC NOx emissions to comply with regula-
tions stemming from the EU target of a reduction
of 53% by 2010 from 1990 levels. There are a
number of effective tools available to operators Links
of FCC units to reduce their NOx emissions and
at the same time reduce their costs. Using the More articles from: Johnson Matthey Catalysts
step-by-step approach described in this article, a
refiner can identify the minimum emissions More articles from the following category:
Catalysts & Additives Emissions Control
achievable without hardware modifications in
Fluid Catalytic Cracking
the space of less than three months.

8 Catalysis 2008 www.digitalrefining.com/article/1000303