Facing New NOx Reduction Challenges in

Energy from Waste Systems

Oliver Gohlke, MARTIN GmbH für Umwelt- und Energietechnik

CONTACT
Dr. Oliver Gohlke
MARTIN GmbH für Umwelt- und Energietechnik
Leopoldstrasse 245
80807 München
Tel.: +49 89 35617 247
gohlke@martingmbh.de

INTRODUCTION
Sustainable urban development needs a reliable supply of heat and power as well as
efficient treatment of Municipal Solid Waste (MSW). New technologies for generating
Energy from Waste (EfW) will be of central importance in providing solutions in order to
meet these needs. In Europe, the more progressive cities use EfW as source of energy
and district heating. The emissions from EfW plants are strictly limited by the EU
Incineration Directive, which sets the limit on NOx emissions, for example, to 200 mg/m3s.
Moreover the need for further improvement is reflected by new German legislation
effective as of 27 January 2009, requiring 100 mg/ m3s (Umweltministerium, 2009), which
at an O2 of 7,5 % is equivalent to a NOx of 74 mg/ m3s (referred to 11 % O2). In the
Netherlands, there has long been a limit of 80 mg/ m3s. In France, a TGAP tax reduction
has been granted since 2009 provided that NOx values of less than 80 mg/ m3s are
reached in combination with high energy efficiency. Other countries are expected to follow
due to the national emission ceilings stipulated in the Gothenburg protocol and the
resultant EU directive 2001/81/EC.
NOx emissions from WTE in Germany
in mg/Nm3 (referred to 11 % O2)

New limit value of 17. BImSchV in Germany (2009)

SCR Technology SNCR Technology

Figure 1: German EfW plants sorted by DeNOx technology and yearly average emission (Lahl, 2007)
As shown in Figure 1, Selective Catalytic Reduction (SCR) technologies were used in
most cases to achieve the above-mentioned reduced NOx limits. However, there are
drawbacks to SCR systems such as high investment costs and the energy consumption
necessitated by the reheating of flue gas as well as the increased pressure loss.

Consequently, SCR falls short of the efforts to increase energy efficiency encouraged by
the EU Waste Framework Directive and its R1 requirement of 0,65 for new plants. New
technologies are therefore required to make it possible to reconcile both requirements:
reduced emissions and increased energy efficiency

This presentation will describe and assess three promising EfW technologies that comply
with these requirements:
- SNCR technology
(SNCR = Selective Non Catalytic NOx Reduction)
- SNCR with boiler integrated slip catalyst
(reduced pressure loss and no pre-heating necessary)
- VLN system (Very Low NOx combustion system: "VLN gas" is drawn off at the rear
end of the grate and is reintroduced into the upper furnace just below the SNCR
injection positions)

FORMATION OF NOX IN EfW PLANTS

NOx is the generic term for nitrogen oxides. The oxides emitted during the combustion of
waste are nitric oxide (NO), nitrogen dioxide (NO2) and nitrous oxide N2O.
The NOx limit value is given as a converted NO2 value, even though more than 95 % of
nitrogen oxides are emitted in the form of NO. NO is formed mainly in the furnace, while
NO2 is formed mainly after emission into the atmosphere by the oxidation of NO with the
air oxygen or ozone (O3). The latter process occurs slowly and plays a minor role in the
hot flue gas.

In principle, the current standard of knowledge differentiates between three mechanisms

for the formation of NO depending on the nitrogen source and the reaction medium:

- "Thermal NO" is produced by oxidation of atmospheric molecular nitrogen and notably

occurs at very high temperatures above 1500 °C (Wei chert, 2000; Zeldovich, 1946).
Due to the relatively low flue gas temperature levels usually present in EfW, the
formation of thermal NO can be regarded as negligible.
- "Prompt NO" appears in the area of the flame front (reaction zone) under fuel-rich
conditions at lower temperatures. However, it is generally accepted that prompt NO
represents an insignificant part in the overall NO formation, especially for the
combustion of solid fuels such as coal or waste.
- "Fuel NO" is by far the most predominant mechanism in the case of EfW. Municipal
waste contains chemically-bound nitrogen in the form of organic (e.g. amine, amide,
nitrile) or inorganic nitrogen compounds NH3 and HCN. Depending on the combustion
conditions, either N2 or NO is formed with NHi as an intermediate product.

Based on the predominant fuel NOx mechanism, the N content in the waste as well as
combustion conditions such as temperature, air distribution and residence time will be
crucial for predicting the NOx levels in the flue gas. According to Seifert (2003), the NOx
content of MSW is around 1 %. The origin of the Nitrogen in the waste is further detailed in
Table 1.
Table 1: Contributions to total Nitrogen content in MSW (Seifert, 2003)

% of N in carrier
Carrier of N (referred to total N in Origin
waste)
Food waste, garden waste,
Proteins >30
leather, fine fraction, paper

Polyamides 20 Textiles, plastics

Plastics, hard and soft
Polyurethanes <10
foams (e.g. in shoes)

The key to drawing conclusions from the NOx mechanism is to understand that under
oxidizing conditions, the NHi components released from the fuel react with molecular
oxygen and oxygen containing radicals O and OH to nitric oxide NO:

NHi + O2 ↔ NO + HiO Equation 1

NHi + OH ↔ NO + Hi+1 Equation 2
NHi + O ↔ NO + Hi Equation 3

Under oxygen-poor conditions, NO formation is inhibited because of the low concentration

of oxidizing radicals and the NHi radicals are converted preferentially with a nitrogenous
component to molecular nitrogen N2 (Fenimore, 1976):

NHi + NO ↔ N2 + HiO Equation 4

Figure 2Fehler! Verweisquelle konnte nicht gefunden werden. shows a summary of the
most important reaction steps in the fuel NO formation process.

NH3 +O H , N2
H +NO
Fuel
+O
N NHi H,O
,O
,O,O 2
+OH
2

HCN NO
, CH 2
+CH
NO recycle
Figure 2: Overview of the most important steps of fuel NO formation (NO recycle only relevant in
fuel-rich conditions; simplified reaction from HCN to NHi: HCN + OH
NH2 +CO)

SELECTIVE NON CATALYTIC NOX REDUCTION (SNCR)

SNCR systems are based on the selective reaction of ammonia [NH3] or urea [CO(NH2)2]
at temperatures of 850 to 1100°C. At the right temp erature, these reactants reduce the NO
to N2 in a sufficiently reactive way without being oxidized by the excess oxygen of the
combustion gases (Lyon 1987). Today’s research focuses on the development of
simplified reaction mechanisms to be implemented in Computational Fluid Dynamics
(CFD) codes. With these tools it will be possible to describe the interaction between
turbulent mixing, radiation and chemical reaction rates.
 NH2
N2 + H2O N2 + NH3

NO N2 - path
OH + NNH N2 + HNO
NO
M
N2 + H

OH H, OH
NH3 NH2 NH
O

O2
NH2

,O
NO + NH3

H
O
M
HNO NO + H NO - path

OH
NO + H2O

Figure 3: Reaction paths of NH3 and NO (Baumbach, 1990)

From the mechanism in Figure 3 it can be concluded that efficient SNCR is based on the
combination of different factors:

- sufficient stoechiometry of injected reactants

- efficient mixing of reactants with flue gases
- sufficient retention time (at temperature level)
- optimal excess oxygen content

The stoechiometry is defined by

n& NH3
β= ( n& NO being the difference of NO before and after the SNCR reaction)
n& NO

In an ideal case of mixing and reactivity, the best results could be attained with a β =1. In
practice only 50 - 60 % of NOx reduction is reached with the addition of ammonia or other
reductants at a stoechiometry of 2 (Dittrich, 2002).

Laboratory experiments show that retention times of 50 ms are sufficient for the SNCR
reaction. In practice it is necessary to obtain retention times at suitable temperatures of up
to 1 s in order to reach reasonable reduction rates. This is mainly due to the fact that the
mixing and turbulence is insufficient in incineration furnaces.
Figure 4: NOx conversion with SNCR depending on temperature and stoechiometry

An example of a typical EfW plant with emission value limits according to the European
Waste Incineration Directive (WID) is shown in Figure 5 (Spliethoff 2009). The WID
requires a NOx value of 200 mg/Nm3 (EU commission, 2000). These systems also reach
ammonia slip values of below 10 mg/m3s as often required in permits according to the
BREF (EU commission, 2006; if not mentioned otherwise: all emission values are meant to
be daily average values referred to 11% O2).

Figure 5: Typical European EfW plant with SNCR (longitudinal section of Zella-Mehlis plant)
SNCR WITH SLIP CATALYST
In many cases SNCR technologies are limited by the ammonia slip which increases in
case of severe NOx requirements. According to the BREF, a limit of 10 mg/Nm3 is
generally required at stack (EU commission, 2006). In order to achieve reduced NOx
values of 70 to 100 mg/Nm3, it is necessary to implement measures to reduce ammonia
slip, as indicated in Figure 7, by means of either a wet scrubber (shifting the ammonia
problem to the waste water) or a slip catalyst.

As shown in Figure 6, the operation point of the SNCR is preferably shifted to lower
temperatures in SNCR systems with slip catalyst. This results in a reduced stoechiometry
with a higher NH3 slip.

100 100

90 90
N O re d u c tio n b y S N C R [% ]

NO reduction rate

A m m o n ia s lip [m g /N m 3 ]
80 80

70
P re fe rre d o p e ra tio n

70
w ith s lip c a ta ly s t

60 60

50 50

40 40

30 NH3 slip
30

20 20

10 10

0 0
650 700 750 800 850 900 950 1000 1050 1100 1150 1200 1250
Temperature [°C]
Figure 6: SNCR operation with slip catalyst. Injection position preferably shifted to lower
temperatures
EfW plants in Mainz (Germany) and Brescia (Italy) are examples of operational plants
which use SNCR with a slip catalyst.
Table 1: Performance of SNCR with slip catalyst at the Brescia plant (Rossignoli, 2010)

Slip catalyst
Parameter Unit
Without With
NOx 80 - 90 60 - 70 mg/Nm3
NH3 slip 10-30 2-6 mg/Nm3
m3/h (25%
NH3 consumption 0,22 0,18
concentrated)
Figure 7: EfW plant with SNCR and ammonia slip catalyst (longitudinal section of Mainz plant)

VERY-LOW NOX PROCESS

Another option for achieving NOx values below 100 mg/m3s without the necessity of
additional scrubbers or catalytic converters for removing excess ammonia is the Very-Low
NOx process (VLN), which has recently been developed by MARTIN GmbH with its
cooperation partners CNIM, COVANTA and Mitsubishi Heavy Industries (MHI).

The VLN process is based on a classical grate-based combustion system for municipal
waste, where the so-called "VLN gas" is drawn off at the rear end of the grate and is
reintroduced into the upper furnace just below the ammonia injection positions (White et al.,
2009). The positive effect of this patented process is twofold: On the one hand, drawing off
the VLN gas leads to combustion conditions which promote the inherent NOx reduction
processes such that fuel NOx is to a large extent reduced to nitrogen. On the other hand,
the reinjection of the VLN gas cools the flue gases down and enforces their mixing with
injected ammonia or urea. This leads to improved efficiency of the SNCR system (Gohlke,
2010; see also Figure 9).

The VLN gas has a temperature of below 300 °C. It i s re-injected at a position where the
furnace temperature is around 1000 °C. This typical ly corresponds to a level of 8 to 12 m
above the grate, depending on the capacity of the unit and the type of waste. The overfire
air pressures are reduced to around 10 mbar and are thus considerably less than in
conventional EfW plant design. Nevertheless, superstoichiometric conditions are reached
at the overfire air level, which is an advantage compared to air-staged or fuel-staged
combustion systems. The residence time from the last combustion air injection at the
overfire air level to the 850 °C level in the furna ce is significantly increased. A further
advantage of the VLN system is the reduced flue gas velocity in the lower furnace due to
internal recirculation via the VLN duct. This leads to a reduction in the fly ash carried over
to the boiler.
 850 °C at > 2 s
NH3 or NOx< 80 mg/m3s
urea for NH3< 10 mg/m3s
DeNOx

VLN gas
as mixing agent
T < 300 °C
Last air
injection

Figure 8: VLN process description (NOx values referred to 11 % O2)

The VLN gas is re-injected into the front and rear side of the upper furnace, where the
space between front and rear wall is narrowed. This leads to an intensive barrier of
turbulence, which reduces the flue gas temperature and blocks the passage of flames or
unreacted material. Given test plant results, corrosion is expected to be significantly
reduced in the furnace above the VLN level as well as in the superheaters. However,
temperatures between the overfire air and the VLN level are higher than in conventional
combustion and higher grades of furnace protection material should be used there.
Another advantage of the VLN system is the reduced excess air rate, which allows cost
reduction in the boiler and flue gas cleaning and improves boiler efficiency.

The influence exerted on the SNCR efficiency by the temperature and excess oxygen
content is illustrated in the diagram of Figure 9.
 O2%
Reduction of NO[%]

Superstoichio- Understoichiometric
metric con- conditions
ditions

Temperature [°C]
Figure 9: NOx conversion with SNCR depending on temperature and excess oxygen content in the
flue gas (Spliethoff 1999)

NOx values of 80 mg/m3s with an NH3 slip of less than 10 mg/m3s have been reached in
the test plant in Bristol/USA. Further test plants in Thiverval/France and Oita/Japan have
confirmed these results. At the Thiverval plant, which has a municipal solid waste
throughput of 12 t/h, NOx was reduced from 190 mg/Nm3 to 80 mg/Nm3 during test
operation with the VLN components in 2008 (see Figure 10). Dry urea is used as the
SNCR reagent in Thiverval.
NOx in mg/m s (@ 11 % O2)

450
Normal operation
400
VLN
350
300
250
3

200
150
100
50
0
Without SNCR With SNCR
(35 kg/h dry urea)

Figure 10: NOx reduction with the VLN process at the Thiverval EfW plant
(results from 2008 testing)
CONCLUSIONS
Energy from waste systems have attained a high technological standard. In the EU,
emissions from EfW plants are largely reduced by applying the Waste Incineration
Directive (EU Commission, 2001) with its limit values for dioxins (PCDD/F), dust, NOx and
many other pollutants. The new German legislation laid down in the 17. BImSchV requiring
100 mg/m3s for future EfW plants indicates that further improvements are needed. The
problem is that although more stringent emission value may become compulsory, an
increase in energy efficiency will be encouraged by the Waste Framework Directive (EU
Commission, 2008). Consequently, new technologies enabling the achievement of both
requirements (reduced emissions and increased energy efficiency) are needed. Both
SNCR with slip catalyst and the VLN technology described in this paper offer promising
solutions to achieve these goals.

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