DEVELOPMENT OF A CONVERTER FOR THE DETERMINATION OF AMMONIA IN EXHAUST GASES BY CHEMOLUMINESCENCE DVELOPPEMENT DUN CONVERTISSEUR POUR LA DTERMINATION PAR

CHIMILUMINESCENCE DE LAMMONIAC DANS LES GAZ DCHAPPEMENT

H. Top and A. Kiel N.V. Nederlandse Gasunie, Gasunie Research The Netherlands ABSTRACT In order to prevent sampling problems during the determination of NH3 in exhaust gases, an ammonia converter was integrated inside an electrically heated sample probe using a catalyst. Three different catalysts were tested for the conversion of NH3 into NOx. The best results were obtained from a commercially available, platinum based, oxidation catalyst. When this oxidation catalyst is set to a temperature of 600 oC, the oxidation catalyst almost completely oxidizes NH3 into NOx with a typical yield of approximately 98 %. The increase of NOx, due to the conversion of NH3 is analyzed on-line with a chemoluminescent NOx analyzer and is proportional to the original NH3 concentration in the sample. The ammonia converter shows no interference with other components inside the sample when set to temperatures above 450 oC. Below this temperature the oxidation catalyst acts like a SCR catalyst and reduces the NOx content in the sample by forming N2O. RSUM Afin dviter des problmes dchantillonnage dus la dtermination du NH3 dans les gaz dchappement, un convertisseur dammoniac faisant usage dun catalyseur a t intgr lintrieur dune sonde dchantillonnage chauffe lectriquement. Trois diffrents catalyseurs ont t tudis pour la conversion du NH3 en NOx. Les meilleurs rsultats ont t obtenus avec un catalyseur doxydation, base de platine, disponible dans le commerce. Lorsque ce catalyseur doxydation est port une temprature de 600 C, il oxyde presque compltement le NH3 en NOx, avec un rendement typique de 98 %. Laugmentation de NOx due la conversion du NH3 est analyse en ligne au moyen dun analyseur de NOx par chimiluminescence et est proportionnelle la concentration initiale de NH3 dans lchantillon. Lorsquil est port une temprature suprieure 450 C, le convertisseur dammoniac ne prsente aucune interfrence avec dautres composants prsents dans lchantillon. Au-dessous de cette temprature, le catalyseur doxydation agit comme un catalyseur SCR et rduit le taux de NOx de lchantillon par formation de N2O.

1.

INTRODUCTION

Due to its efficiency and selectivity, the Selective Catalytic Reduction (SCR) process is a widely spread technology for the control of nitrogen oxides (NOx) emissions from stationary sources. The NOx reduction process is based on the reaction between NOx and ammonia (NH3), or in some cases urea ((NH2)2CO), to produce nitrogen and water 1 according to the following equations: 4 NO + 4 NH3 + O2 2 NO2 + 4 NH3 + O2 4 N2 + 6 H2O 3 N2 + 6 H2O (1) (2)

Urea is usually applied in the form of a 40 w/w % solution in water in the urea-SCR-process. When such a solution is heated up to the exhaust gas temperature, the solvent evaporates and urea thermally decomposes (pyrolyzes) into ammonia and carbondioxide 2 according to the following equation: (NH2)2CO + H2O 2 NH3 + CO2 (3)

A disadvantage of the SCR-process is slip of un-reacted or excessive NH3 into the atmosphere together with the treated exhaust gases. Both NOx and NH3 are regulated (criteria) pollutants. This means that the NH3 slip of the SCR-process has to be minimized. It is very difficult to determine the concentration of NH3 in exhaust gases. This is caused by the high solubility of NH3 in water and the adsorption on the inner walls of sampling lines. Adsorption losses in the sample lines occur rapidly and measurement response times become unacceptably high. To prevent condensation of water vapor inside the measurement equipment, it is necessary to remove the water vapor from the sample. Cooling the sample far below its dew point usually does the removal of water vapor. Since also a large fraction of NH3 dissolves in the condensed water, only a small fraction of the initial NH3 concentration is detected by the analyzer. Cooling the sample gas can also lead to the formation of ammonium salts which can precipitate inside the sampling system and the analyzers. To avoid these sampling problems, Gasunie Research has found a new method for the determination of NH3 in exhaust gases by developing a special sample probe. This determination is based on the catalytic conversion of NH3 into NOx 3,4 and measuring the increase of NOx in relation to the initial NOx concentration. In cooperation with Environmental Products Manufacturing B.V. (EPM, the Netherlands) a prototype of a sample probe has been developed with an integrated, electrically heated catalyst. NH3 is oxidized with oxygen on the catalyst surface into nitric oxide (NO) and water according to the equation: 4 NH3 + 5 O2 4 NO + 6 H2O (4)

Simultaneously (unwanted) nitrogen dioxide (NO2), nitrous oxide (N2O) and nitrogen may be formed as well, in accordance with the following equations: 2 NO + O2 4 NH3 + 3 O2 4 NH3 + 4 O2 2 NO2 2 N2 + 6 H2O 2 N2O + 6 H2O (5) (6) (7)

Reaction (4) is applied industrially in the nitric acid (HNO3) synthesis process 5 using platinum gauzes as the catalysts, and is also known as the Ostwald process. The typical yield of NO in the synthesis process at atmospheric pressure and temperatures of 810 to 850 oC is approximately 97 %.

Oxides of nitrogen, at low concentrations (ppm v/v), are poorly soluble in water, hardly adsorb to the inner walls of sample lines and do not lead to the formation of salts. In this way NH3, converted into NOx, can be detected on-line with a suitable NOx measuring technique, like chemoluminescence. NH3 in the sample that passes through the integrated catalyst of the sample probe is oxidized and an amount of NOx proportional to the amount of NH3 is produced. The oxidized sample and the unchanged sample, passing through a separate sample probe, pass through individual sample lines to separate sample conditioning systems and are then introduced alternately into the same chemoluminescence NOx analyzer for the determination of the NOx concentration. The NH3 content of the sample passing through the catalyst has been oxidized into NOx while the sample in the other sample probe represents the original NOx content of the exhaust gases, so the difference can be calculated as the NH3 content: [NH3] = [N-total] [NOx] Where [NH3] [N-total] [NOx] : : : NH3 concentration NOx concentration of the sample measured with an ammonia converter (sum of [NH3], [NO] and [NO2] ) NOx concentration of the unchanged sample (sum of [NO] and [NO2] ) (8)

This paper describes the development of the ammonia converter and the performance characteristic of three different catalysts that were tested for the use as an ammonia converter. 2. 2.1. DETERMINATION OF NH3 IN EXHAUST GASES Sampling system

Exhaust gases contain a significant amount of water vapor (5 20 vol.%, depending on air to fuel ratio). Most of this water is chemically formed by the combustion of the fuel and the rest comes with the combustion air. To prevent condensation of water vapor inside the measurement equipment it is necessary to remove the water from the sample. Cooling the sample gas far below its dew point usually does the removal of water vapor. Wet and hot undiluted sample gas from the sample point enters a water cooled sample probe, which decreases the sample gas temperature to approximately 100 oC. Hereby, the temperature of the sample gas is low enough to transport it through a short Teflon sampling line (unheated) to a sample gas cooler. Inside the sample gas cooler the sample gas is cooled down to a temperature of 0 5 oC. This is done with two glassware coolers with a reservoir placed in series, mounted inside an isolated box containing water and melting ice. The condensed water from the sample gas retains in the reservoir. Afterwards, the conditioned sample gas contains approximately 0,6 0,9 vol.% water. The condensation step of the sample gas system is primarily meant for the separation of water vapor from the sample gas, without affecting the composition of the original sample gas. However, some (trace) components, like ammonia, will dissolve or react in the condensed water. Therefore it is not possible to measure these components on-line in exhaust gases with our sampling system.

2.2.

Ammonium Determination in Condensate

Until now, our currently used determination of NH3 was based on the ammonium (NH4+) concentration in the collected condensate of the sample gas cooler. Approximately 53 moles of NH3 dissolves in one dm3 water at a temperature of 0 oC. However, a chemical reaction also occurs when NH3 dissolves in water. In aqueous solution, NH3 acts as a base, acquiring hydrogen ions from water to yield ammonium and hydroxide ions according to the following equation: NH3 + H2O NH4+ + OH(9)

An equilibrium is established between dissolved NH3 and NH4+. Not all of the dissolved NH3 reacts with water to form ammonium ions. A substantial fraction remains in the molecular form in the solution. This is effected by pH, with higher pHs (> 7) forcing more NH4+ into the molecular form. The typical pH of exhaust gas condensate is about 3, so most dissolved NH3 will exist as NH4+. During a measurement (sampling time 20 to 30 minutes) the condensate of the sample gas cooler is collected in a reservoir. After finishing the measurement the collected condensate is stored in a vial and the cooler and reservoir are rinsed with demineralized water. Afterwards, at the laboratory, the ammonium concentration of the vials is analyzed with an UV-VIS spectral photometer (Cadas 50 S, DR Lange) at a wavelength of 694 nm. The principal is based on a color reaction of the ammonium ions. Ammonium ions react at pH 12,8 with hypo chlorite ions and salicylate ions in the presence of sodium nitroprusside as a catalyst to form indophenol blue. The mean value of the NH3 concentration is calculated, based on the measured ammonium concentration and the water content of the exhaust gases. 3. 3.1. EXPERIMENTS Prototype Ammonia Converter

Figure 1 shows the structure of the ammonia converter. The ammonia converter consists of an external heated converter tube that is placed inside a converter housing. The stainless steel converter tube has a length of 100 mm and an internal diameter of 20 mm. The catalyst is placed inside the converter tube and is accessible at the inlet of the converter tube. The external heater is made of an electric heating coil (400 W) which surrounds the full length of the converter tube to maintain a constant temperature of the catalyst. A separate temperature controller housing, controls the temperature of the heating coil within a range of approximately 100 oC to 900 oC. Hot, undiluted sample gas from the sample point enters the catalyst directly through a stainless steel tube of 4 mm inner diameter. Figure 1. Structure of the ammonia converter.

converter housing

sample inlet

oxidation catalyst

sample outlet

converter tube

heating coil

3.2.

Catalysts

Three different catalysts were tested for the conversion of NH3 into NOx: 1. HUG Engineering oxidation catalyst 2. Kemira Metalkat oxidation catalyst 3. Stainless steel 316 (self-made) The commercially available oxidation catalyst (diameter 20 mm and length 70 mm) from HUG Engineering (Switzerland) consists of a cordierite monolith with a platinum washcoat. This catalyst has a maximum allowable temperature of approximately 600 oC. The commercially available oxidation catalyst (diameter 20 mm and length 75 mm) from Kemira Metalkat o.y. (Finland) consist of a metal layer (50 m) with a platinum washcoat. The stainless steel catalyst is made of several stainless steal tubes (3 x 1 mm) with a length of 75 mm. 3.3. Test Facility

All laboratory experiments were performed on a 30 kW test facility of Gasunie Research, see figure 2. This facility produces exhaust gases with two natural gas fired burners. The gas flow rates (natural gas, primary and secondary combustion air) to the burners were controlled by mass flow controllers (Bronkhorst Hi-Tec). The temperature of the exhaust gases is controlled by an air cooled heat exchanger and set to a temperature of 360 oC. Ammonia (99,5 % purity), stored in a 50 liter cylinder, is injected downstream the heat exchanger and mixed with the exhaust gases. The ammonia flow rate (0 5 dm3(n)/h) is controlled by a mass flow controller (Bronkhorst HiTec). Sample gas from the facility was either pulled through a stainless steel, water-cooled sample probe or a heated sample probe with the integrated ammonia converter, by a membrane pump. The sample flow rate was set to a flow of 100 dm3(n)/h. Water vapor was removed from the sample with a sample gas cooler and the sample was filtered before entering the analyzers. The NO, NO2, NOx and N2O concentrations of the sample were analyzed using an Eco Physics CLD 700 chemoluminescent NOx analyzer and a Maihak Unor 610 NDIR N2O analyzer. Figure 2. Principle of the NH3 measurement downstream the test facility.
ammonia injection mfc

combustion chamber heat exchanger

mixer

mfc

secondary combustion air primary combustion air natural gas

sample probe with NH3 converter

sample probe of original sample

mfc

mfc

N2O analyzer Maihak UNOR

NOx analyzer Tecan CLD 700

temperature controller

sample gas cooler

drain

filter

valve

sample pump

4. 4.1.

RESULTS Conversion of Ammonia in a NH3/Air mixture

The relationship between the conversion of NH3 in air and converter temperature of both oxidation catalysts (HUG and Kemira) has been measured. Therefore, a flow of 25 m3(n)/h air was mixed with a flow of 2,0 dm3(n)/h ammonia. The calculated NH3 concentration of the mixture is 80 ppm v/v. The temperature of the mixture was approximately 20 oC. The converter temperature was varied between approximately 150 and 510 oC. The initial concentrations of the sample gas and the NO, NO2, NOx and N2O concentration at different converter temperatures are shown in figures 3 and 4 of respectively the HUG and Kemira oxidation catalyst. The conversion of NH3 has a large dependency on converter temperature. At low temperatures both catalysts form a significant amount of N2O. N2O formation of the HUG catalyst has an optimum at a temperature of approximately 200 oC, where 55 % NH3 is converted into N2O. The Kemira catalyst has an optimum at a temperature of approximately 275 oC, where 34 % NH3 is converted into N2O. When converter temperature increases, N2O formation decreases and NOx formation increases. At maximum converter temperature setting (510 oC), the HUG catalyst converts 83 % of the initial NH3 concentration into NOx and 7 % into N2O. The Kemira catalyst converts 59 % NH3 into NOx and 5 % into N2O. Figure 3. HUG oxidation catalyst: dependency of NH3 conversion in a NH3/air mixture on converter temperature.
80 NO NOx 60 NO2 N 2O 70

[N O], [N O 2 ], [N O x ] and [N 2 O] (ppm v/v)

50

40

S ample gas: AIR N H 3 80 ppm

30

20

10

0 100 150 200 250 300 350 400 450

o

500

550

600

650

700

CON VER TER TEM PER ATUR E ( C)

Figure 4. Kemira oxidation catalyst: dependency of NH3 conversion in a NH3/air mixture on converter temperature.
80 NO NOx NO2 N 2O 70

[N O], [N O 2 ], [N O x ] and [N 2 O] (ppm v/v)

60

50

40

30

Sample gas : AIR N H 3 80 ppm

20

10

0 100 150 200 250 300 350 400 450

o

500

550

600

650

700

CON VER TER TEM PER ATUR E ( C)

4.2.

Conversion of Ammonia in a NH3/Exhaust gas mixture

The relationship between the conversion of NH3 in exhaust gases and converter temperature of the three catalysts has been measured. Therefore, a flow of 1,5 m3(n)/h natural gas, 7 m3(n)/h primary combustion air and 13 m3(n)/h secondary combustion air were used to create a constant source of exhaust gases including oxides of nitrogen. The exhaust gases were mixed with a flow of 2,0 dm3(n)/h ammonia. The calculated NH3 concentration of the mixture is 106 ppm v/v. The temperature of the mixture was approximately 360 oC. The converter temperature of the three catalysts was varied between approximately 170 and 680 oC. The initial concentrations of the sample gas and the NO, NO2, NOx and N2O concentration at different converter temperatures are shown in figures 5, 6 and 7 of respectively the HUG, Kemira and stainless steel catalyst. The conversion of NH3, of both oxidation catalysts has a large dependency on converter temperature. At temperatures below approximately 330 - 430 oC, the oxidation catalysts act like a SCR catalyst (reactions 1 and 2). The original NOx concentration of the sample decreases and a reduction of almost 50 - 60 % is achieved at a temperature of 220 - 260 oC. Opposite to the NOx reduction a large amount of N2O is being formed. When converter temperature increases, both NOx reduction and N2O formation decreases. Above temperatures of approximately 330 430 o C the oxidation catalysts start to form NOx. The conversion of NH3 with the stainless steel catalyst is slightly dependent on converter temperature. At temperatures below approximately 400 oC the stainless steel 316 catalyst shows no conversion of NH3. Above this temperature, the catalyst starts forming NOx and no N2O is being formed. Figure 5. HUG oxidation catalyst: NH3 conversion in a NH3/exhaust gas mixture in relation to converter temperature.
300 NO 250 NO2 N 2O

[N O], [N O 2 ], [N O x ] and [N 2 O] (ppm v/v)

NOx

200

Sample gas : O2 NO N O2 8,5 vol.% 148 ppm 19 ppm 1 ppm

150

N O x 167 ppm 100 N2O N H 3 106 ppm 50

0 100 150 200 250 300 350 400 450

o

500

550

600

650

700

CON VER TER TEM PER ATUR E ( C)

Figure 6. Kemira oxidation catalyst: NH3 conversion in a NH3/exhaust gas mixture in relation to converter temperature.
300 250 NO NOx 200 Sample gas : 150 O2 8,5 vol.% NO2 N 2O

[N O], [N O 2 ], [N O x ] and [N 2 O] (ppm v/v)

N O 152 ppm N O 2 19 ppm 100 N O x 171 ppm N 2O 50 1 ppm N H 3 106 ppm

0 100 150 200 250 300 350 400 450

o

500

550

600

650

700

CON VER TER TEM PER ATUR E ( C)

Figure 7. Stainless Steel 316 catalyst: NH3 conversion in a NH3/exhaust gas mixture in relation to converter temperature.
300 250 NO NOx 200 NO2 N 2O

[N O], [N O2 ], [N O x ] and [N 2 O] (ppm v/v)

150

S ample gas: O2 8,5 vol.%

100

N O 148 ppm N O 2 16 ppm N O x 165 ppm N 2O 1 ppm

50

N H 3 106 ppm

0 100 200 300 400

o

500

600

700

CON VER TER TEM PER ATUR E ( C)

4.3.

Linearity of the Ammonia Conversion

The relationship between the conversion of NH3 and the concentration of NH3 in exhaust gases of the three catalysts has been measured. Therefore, a flow of 1,5 m3(n)/h natural gas, 7 m3(n)/h primary combustion air and 13 m3(n)/h secondary combustion air were used to create a constant source of exhaust gases including oxides of nitrogen. The NH3 concentration in the sample gas was varied by increasing the set point of the ammonia injection downstream the heat exchanger of the test facility. The temperature of the NH3/exhaust gas mixture was approximately 360 oC. The mean composition of the exhaust gas was approximately 8,5 vol.% O2, 151 ppm NO, 18 ppm NO2, 169 ppm NOx and 1 ppm N2O. The relative NOx formation (= conversion efficiency) and N2O formation of the catalysts are defined as follows: NOx formation = N2O formation= ([NOx]out [NOx]in) / [NH3]in 100 % 2 ([N2O]out [N2O]in) / [NH3]in 100 % (10) (11)

Figure 8 shows the linear relationship between ammonia conversion into NOx and the NH3 concentration in the sample gas of the three catalysts, and table 1 shows the relative NOx and N2O formation of different NH3 concentrations in exhaust gas.

Figure 8. Linearity of NH3 conversion into NOx.

300 R = 0.997 250 H UG Engineering K emira M etalkat
2

[N -totaal] - [N Ox ] (ppm v/v)

200

S tainless steel R = 0.998

2

150

100 R = 0.995
2

50

0 0 50 100 150 [N H 3 ] (ppm v/v) 200 250 300

Table 1. Relative NOx and N2O formation of different NH3 concentrations in exhaust gas.
NH3 injection in exhaust gases setpoint [NH3] dry basis dm3(n)/h 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0 ppm v/v 53 80 106 133 159 186 212 239 265 HUG Engineering catalyst 600 oC NOx N2O formation formation % 102 99 96 97 97 96 101 97 % 3 4 4 4 4 4 4 4 Kemira Metalkat catalyst 600 oC NOx N2O formation formation % 91 83 81 82 81 81 84 81 81 % 9 7 8 8 9 8 9 8 9 Stainless steel catalyst 680 oC NOx N2O formation formation % 40 45 50 50 49 48 50 49 48 % 0 0 0 0 0 0 1 1 1

4.4.

Additional tests

Because the oxidation catalyst of HUG Engineering showed the best results for the conversion of NH3 into NOx, some additional tests were carried out with this catalyst, involving the short-term stability and the response to sudden input variations of the NH3 concentration. The short-term stability of the conversion of a 80 ppm v/v NH3/air mixture was measured continuously during a period of 16 hours, with a converter temperature set to approximately 510 o C. NH3 conversion slightly decreased from 82 to 79 %. After recalibrating the measurement equipment at the end of the test period the same conversion was obtained as at the start of the test period. The decrease of the NH3 conversion was likely caused by the drift of the chemoluminescence NOx analyzer. Figure 9 shows the response of the ammonia converter to sudden changes of the NH3 concentration in the sample (respectively 80, 40, 20 and 10 ppm NH3). No memory effects were detected and a change in the NH3 concentration in the sample is rapidly detected by the chemoluminescence NOx analyzer. The response time (0 90 %) to a sudden change in the NH3 concentration is approximately 30 seconds.

Figure 9. Response test HUG oxidation catalyst.

80 70

60

[N Ox] (ppm v/v)

50

40

30

20

10

0 12:43 13:12 13:40 14:09 14:38 TIM E (hh:mm) 15:07 15:36 16:04 16:33

5.

DISCUSSION

Table 2 summarizes the performance characteristics of the three tested catalyst for the conversion of NH3 into NOx. The oxidation catalyst of HUG Engineering gives the best results for both air and exhaust gas mixtures with NH3. The stainless steel catalyst is a poor NH3 converter. Table 2. Performance characteristics.
Catalyst Sample gas Temperature conversion
o

NOx formation % 83 98 59 83 48

N2O formation % 7 4 5 8 0

HUG Engineering Kemira Metalkat Stainless steel 316

NH3/Air NH3/Exhaust gas NH3/Air NH3/Exhaust gas NH3/Air NH3/Exhaust gas

510 600 510 600 680

The two oxidation catalyst (HUG and Kemira) convert NH3 into N2O and the stainless steel catalyst doesnt convert NH3 into N2O. Based upon the initial NH3 and NOx concentration of the sample, N2O is formed by a combination of two different side reactions. The first reaction is the oxidation of NH3 into N2O (reaction 7) and the second reaction 1 is the reduction of NO with NH3 into N2O, according to the following equation: 4 NH3 + 4 NO + O2 4 N2O + 6 H2O (12)

The oxidation catalysts also catalyze the reaction rate of the chemical equilibrium between NO and NO2 (reaction 5). The ratio between NO and NO2 strongly depends on the O2 concentration and catalyst temperature. Figure 10 shows the theoretically ratio between NO and NO2 (when equilibrium is fully reached) at three different O2 concentrations (atmospheric pressure) as a function of temperature. At low temperature the equilibrium favors to form NO2. At a temperature of approximately 150 oC the equilibrium starts to form some NO and increases when temperature increases. At temperatures above 1000 oC only NO is formed.

At low converter temperatures of the oxidation catalysts, NO2 is nearly fully reduced by NH3 (reaction 2). On one hand, when converter temperature increases, the activity of the oxidation catalysts to oxidize NO into NO2 increases. On the other hand the NO2 concentration decreases with an increase in temperature due to the equilibrium. Figure 10. NO and NO2 equilibrium.
100 90 80 70 [O 2] = 1.0 vol.% [O 2] = 10.0 vol.% [O 2] = 20.94 vol.%

[N O 2 ] / [N O x ] x 100%

60 50 40 30 20 10 0 100 200 300 400 500 600

o

700

800

900

1000

TEM PERATURE ( C )

6.

CONCLUSIONS

In order to prevent sampling problems during the determination of NH3 in exhaust gases, an ammonia converter was integrated inside an electrically heated sample probe using a catalyst. The development of this special sample probe makes costly sampling techniques unnecessarily because NH3 is directly (hot and undiluted) converted into NOx. NOx doesnt adsorb to inner walls of sampling lines, hardly dissolves in water and doesnt lead to the formation of salts. Three different catalysts were tested for the conversion of NH3 into NOx. Two of the three catalysts are commercially available, platinum based, oxidation catalysts (HUG Engineering and Kemira Metalkat) and the third self-made catalyst is made of stainless steel 316 tubing. The best results were obtained from the two platinum based oxidation catalysts, the stainless steel 316 catalyst showed the lowest conversion of NH3 into NOx . However, this catalyst has the advantage that it doesnt convert NH3 into N2O. When the HUG Engineering oxidation catalyst is set to a temperature of 600 oC, the oxidation catalyst almost completely oxidizes NH3 into NOx with a typical yield of approximately 98%. Furthermore, the formed NOx consist mainly of NO, which can be transported without any significant loss through unheated sample lines. The increase of NOx is analyzed on-line with a chemoluminescence NOx analyzer and is proportional to the original NH3 concentration in the sample. The ammonia converter shows no interference with other components inside the sample when set to temperatures above 450 oC. Below this temperature the oxidation catalyst acts like a SCR catalyst and reduces the NOx content in the sample by forming N2O. With this technique we have significantly improved our current NH3 measuring technique, based on the trapping of NH3 into the condensate of a sample gas cooler and the determination of the ammonium content in the collected condensate by UV-VIS.

ACKNOWLEDGEMENTS The authors like to express their thanks to Kemira Metalkat, Hanwel and HUG Engineering for supplying the oxidation catalysts and valuable technical support. The authors also acknowledge the valuable contributions of Ben Wolkotte (Gasunie Research), Hans J. Brouwers, Geert Jan Deemter and Jan H.A. Rake (EPM) to this research and in the preparation of this paper. REFERENCES 1. Busca, G.; Lietti, L.; Ramis, G.; Berti, F. Applied Catalysis B: Environmental 18. 1998; pp 1-36 2. Koebel, M.; Elsener, M.; Marti, T. Combust. Sci. And Tech. Vol. 121. 1996; pp 85-102 3. Takahashi, S.; Yamashita, I.. JSME International Journal. Series II, Vol. 32, No. 3, 1989; pp 449-454 4. Megade zur, D.; Energietechniek 4 jaargang 71. 1993; pp 280-282 (in German). 5. European Fertilizer Manufacturers Association Home Page. http://www.efma.org (accessed December 1999). 6. Hoving, K.; Bekker, M.; Klimstra, J.; Top, H. CO2-Fertilisation via Exhaust Gas Treatment of Reciprocating Gas Engines: Developments and Experiences. International Gas Union, Nice, France, June 6-9, 2000.