The Institute of Energy's Second International Conference on COMBUSTION & EMISSIONS CONTROL: Proceedings of The Institute of Energy Conference Held in London, UK, on 4-5 December 1995

Chapter 1

Emissions Control

Outline

Chapter 1: COAL SELECTION FOR NOx REDUCTION IN PULVERISED FUEL COMBUSTION

Chapter 2: COMPARATIVE PERFORMANCE OF DIFFERENT COALS AND NATURAL GAS FOR THE REDUCTION OF NO BY REBURNING

Chapter 3: EMISSIONS CONTROL AND ITS IMPLICATIONS ON THE DOMESTIC GAS BURNER MANUFACTURER

Chapter 4: EXPERIMENTAL FLUID DYNAMIC CHARACTERIZATION OF A PREMIXED NATURAL GAS BURNER FOR DOMESTIC AND SEMI-INDUSTRIAL APPLICATIONS

Chapter 5: FLUE GAS DESULPHURISATION AT LONGANNET POWER STATION, SCOTLAND; A REGULATORS VIEW OF THE BPEO ASSESSMENT

Chapter 6: LOW-NOx COMBUSTION FOR PULVERIZED COAL-A COMPARISON OF AIR STAGING AND REBURNING

Chapter 7: PREDICTION OF THE PHASES PRESENT IN FLY ASH, THEIR COMPOSITION AND THE INFLUENCE OF THESE FACTORS ON ITS UTILITY AND DISPOSAL.

Chapter 8: REDUCTION OF N2O EMISSIONS FROM FLUIDISED BED COMBUSTION BY REVERSED AIR STAGING

Chapter 9: THE CONTROL OF THE EMISSIONS OF N2O AND NO DURING COMBUSTION OF COALS IN FLUIDISED BED SYSTEMS

Chapter 10: THE FORMATION OF AMMONIA IN IGCC GASIFIERS AND ITS CONTROL

COAL SELECTION FOR NOx REDUCTION IN PULVERISED FUEL COMBUSTION

J.R. Gibbins, F.C. Lockwood, C.K. Man and J. Williamson,     Imperial College, London

G.J. Hesselmann,     Babcock Energy Ltd, Renfrew

B.M. Downer and N.M. Skorupska,     National Power PLC, Swindon

A major factor affecting a coal’s performance in air-staged low-NOx burners is the amount of nitrogen remaining in the char after devolatilisation. Current standard proximate devolatilisation tests do not apply realistic heating conditions for PF combustion, but a recently-developed high-temperature wire-mesh reactor now allows relatively simple captive-sample measurements at heating rates of 10⁴ K/s. Char nitrogen data is reported for devolatilisation temperatures from 400°C to 1800°C, including values for a range of UK and world-traded coals for which NOx measurements from three full-scale low-NOx utility plants and/or a pilot combustor are available. The most general correlation between char nitrogen and combustion NOx is observed for a peak preparation temperature of 1800°C with 0.15 s (or 2 s) hold time or 1600°C with 2 s hold, conditions which give the maximum release of nitrogen from the char.

Keywords

coal

combustion

NOx

devolatilisation

char

test

INTRODUCTION

Pulverised coal combustion in large utility boilers can result in the production of significant amounts of oxides of nitrogen (NOx - principally NO in this type of plant). Although some of this NOx is formed from nitrogen in the combustion air, the principal source of NOx is generally the nitrogen contained in the coal itself since the latter is available in more reactive form. NOx is not the only possible end product for coal nitrogen, however, which can also form molecular nitrogen, N2. In this respect nitrogen differs from most other pollutant sources in coals (e.g. sulphur, chlorine, heavy metals) in having the potential to yield a totally non-polluting and readily-disposable residue. A simplified scheme for the formation of NOx and N2 from coal nitrogen during combustion is shown in Figure 1 (based on Pohl and Sarofim(1)).

Figure 1 Simplified scheme for coal N to NOx conversion.

Because of the relatively low capital and operating costs involved, combustion modifications to maximise N2 formation and minimise NOx formation are attractive, either on their own or in conjunction with further NOx reduction techniques applied after the main fuel combustion has taken place (e.g. reburn, SNCR, SCR). The main principal in minimising NOx formation during combustion is to minimise the oxygen supply to the burning coal for as long as possible. In practice this means reducing oxygen availability during coal devolatilisation and the accompanying homogeneous combustion of the volatiles. Although this may result in slightly longer reaction times these near-burner processes are intrinsically fast enough (order 0.1 s) to permit some increase within current plant geometries (i.e. with acceptable flame lengths). In contrast heterogeneous combustion of the residual char is a relatively slow process (order 1 s) which requires the presence of excess oxygen to achieve acceptable rates and final burnout. As a result, NOx formation from the char N is unlikely to be reduced significantly with air-staged low-NOx combustion systems.

The intrinsic nature of the coal is the main factor affecting nitrogen distribution between volatiles and char during devolatilisation. As natural materials coals exhibit widely different combustion behaviour due principally to:

(a) origin - coals were formed from a wide variety of plant materials over a range of geological periods, and

(b) rank –* the extent of geological maturation the coal has undergone which will vary principally with age, depth of burial and the temperatures which the coal has experienced.

Origin was not a consideration when industrial activities relied primarily on indigenous coals from a limited geographic area and usually a single period of origin (e.g. Carboniferous in UK and Eastern US). For coals of similar origins a wide range of properties of industrial interest correlate with rank, as illustrated by the well-known Seyler chart for UK coals. Because of this broad cross-correlation of properties many characterisation tests (e.g. carbon content, vitrinite reflectance) can be used to indicate rank and hence, by analogy with the known performance of other coals of similar rank from the same origin, the combustion behaviour.

Although most rank-indicating tests are clearly not directly related to combustion processes, the proximate volatile matter content (or the fuel ratio Johnson(2), the proximate fixed carbon divided by the volatile matter) might be considered to represent a more direct measure of a coal’s devolatilisation behaviour during combustion. This probably is the case for slow combustion of lump coal on a grate, but it is well-known that volatile yields under the rapid heating conditions applied in PF combustion are significantly higher than proximate yields. A previous wire-mesh study Gibbins et al(3) has confirmed that this is due to a combination of the absence of retrograde char-forming reactions within the bed of coal in a proximate analysis crucible when dispersed samples of finely ground coal are heated, and a greater release of volatiles from the particles themselves at higher heating rates. The enhancement is not constant, however, nor does it appear to vary in a consistent manner with rank. It therefore appears that, in as far as proximate volatile matter or fuel ratio does give some indication of PF combustion behaviour, this is also primarily due to the proximate VM being another reasonable indicator of rank within a series of coals from a similar origin.

With an increase in the use of world-traded coals and international participation in power station construction and operation projects, the commercial demand for information on the combustion behaviour of a wide range of overseas coals has increased. In this case correlations based on the results of empirical ‘ranking’ tests on indigenous coals have been found to be inadequate, particularly when comparing Northern Hemisphere coals with Southern Hemisphere (Gondwanaland) coals Carpenter and Skorupska(4). In principle new sets of rank-based correlations could be derived for each geological ‘family’ of coals. In practice this approach is difficult to implement because of the number of different correlations that would have to be derived. Even then the origin of a coal may not be easy to determine and blends of coals from significantly different sources can be encountered. A more satisfactory approach is the development of new tests which subject coal particles to conditions comparable to those that will be encountered during PF combustion, In this case the results can be used to indicate performance directly.

‘Drop tube’ entrained flow reactors are probably the most widely-used small-scale test facilities for the devolatilisation behaviour of coals under PF combustion conditions (4). A small flow of powdered coal is injected into a stream of (usually pre-heated) inert or weakly oxidising gas and passed down an externally-heated tube. Typically peak temperatures are limited to 1450°C (if relatively low cost silicon carbide heating elements are to be used) and particle residence times to 500 ms (to keep the tube length around 2m) although more realistic conditions are possible (e.g. up to 1700°C with 3 s residence time in a recent design Hutchings and Williamson(5)). The char sample is typically collected in a water-cooled probe at the bottom of the reactor tube. Volatile yields can be deduced either from the difference between the weights of coal fed and char collected or from the relative ash (or specific elemental Fletcher(6)) contents of the coal and the char, assuming the ash behaves as an inert tracer. In both cases, tars condensing with the sample may cause difficulties and a small amount of oxygen can be added to the inert sweep gas (usually nitrogen or argon) to promote tar breakdown Thompson and Stainsby(7). The char/volatile nitrogen partition can be determined from the total weight loss and the measured nitrogen content of the residual char. NOx formation in air-staged combustion of coal blends has been observed to correlate with char nitrogen yields from drop tube measurements, with an apparent conversion of about 30% of the char N to NOx Nakamura et al(8).

While drop tube reactors have yielded many insights into coal combustion behaviour, and arguably provide the most realistic conditions for small-scale experiments, they have some limitations to their use as a routine test. In the simpler designs, temperatures and residence times are near the lower margin of what might be considered appropriate for PF combustion. Total volatile yields (and hence char/volatile N partition) can also be difficult to determine accurately for coals with a low ash content or volatile ash constituents, while total char collection is always difficult to guarantee. To overcome some of these limitations, a captive sample test has been developed based on the high-temperature version of the wire-mesh reactor. This paper describes the apparatus, examines the nature of volatile and nitrogen release from coals devolatilised at elevated temperatures and shows the correlation between wire-mesh measurements and NOx formation in full size utility plant and test combustors.

APPARATUS AND TEST METHODS

The key characteristic of the wire-mesh apparatus is the use of a captive sample of coal held between two layers of mesh which also act as an electrical resistance heater. The coal sample can then be weighed before and after heating to establish the weight loss directly. Historically, peak temperatures achievable using WM apparatus have been limited to around 1100°C by the stainless steel mesh used, and heating rates to less than 10,000 K/s because of power supply and control limitations (4). As a result of a four-year development programme at Imperial College, peak temperatures have been extended to 2000°C using molybdenum mesh. A battery-powered DC power supply and a feedback control system based on a 486 PC allow heating rates up to 50,000 K/s. Temperatures are measured using a two-colour infra-red pyrometer calibrated against W3 thermocouples. A flow of helium across the wire-mesh sample holder prevents volatiles redepositing; the apparatus is limited to operation under non-oxidising conditions by the properties of the mesh material. The new apparatus is shown in Figure 2; additional technical details will be published elsewhere Pendlebury et al(9).

Figure 2 Wire-mesh test apparatus

After grinding and sieving to 125–150 μm for compatibility with the molybdenum mesh (63 μm wires x 106 μm aperture), coal samples are dried overnight in a nitrogen-purged oven at 105°C and then stored under nitrogen until required. Typically 5–10 mg of the sample coal are used for each devolatilisation test. Duplicate determinations are generally undertaken to establish reproducibility; yields are usually repeatable to within 2% of the original sample mass. The residual char from the WM runs can be almost entirely recovered from the mesh. Sufficient char (typically 2–7 mg) is available for duplicate CHN measurements using a Carlo Erba 1106 microelemental analyser. The use of reference chars as internal standard materials was found necessary to achieve reproducible char N measurements.

RESULTS AND DISCUSSION

The effect of temperature on volatile yields and volatile nitrogen yields from a UK bituminous coal is shown in Figure 3. With zero hold time at peak temperature, total volatile and nitrogen yields are roughly proportional for temperatures up to 1400°C. With extended hold times at 1000°C little further nitrogen release takes place, but at 1400° C a significant amount of additional volatile nitrogen is evolved Gibbins et al(10). The latter phenomenon is illustrated in more detail in Figure 4, showing nitrogen release from Daw Mill coal as a function of isothermal hold time at 1450°C. Nitrogen evolution is accompanied by a reduction in char hydrogen content, and ceases when the hydrogen content falls to negligible levels.

Figure 3 Effect of peak temperature on volatile and nitrogen yields from Kellingley coal

Figure 4 Effect of hold time at 1450°C on total volatiles, volatile nitrogen and char H content for Daw

The nature of nitrogen release can probably be interpreted as a two-stage process. Part of the nitrogen is evolved rapidly with the tars and other primary volatile products, but with little or no selectivity as the concentration of nitrogen in the volatiles remains roughly constant. This behaviour is consistent with the coal nitrogen being carried out of the coal within relatively large coal component fragments ‘broken away’ as volatile products (although subsequent secondary cracking reactions of these fragments is also a likely possibility). A second phase of nitrogen evolution then occurs when the temperature is sufficiently high for the condensed aromatic structures in the residual char to be disrupted. By definition (since they have already survived primary devolatilisation) these must be quite thermally stable, hence the elevated temperatures required. Large aromatic molecules are unlikely to be released from the char, and both experimental evidence Freihaut and Seery(11) and a simple consideration of the possible volatile products strongly suggest that the bulk of this nitrogen from secondary devolatilisation is evolved as HCN. This is also consistent with the inter-relationship between nitrogen and hydrogen release from the char.

Given the sensitivity of the char/volatiles nitrogen split to devolatilisation conditions, some difficulty exists in selecting the most appropriate test conditions to use for predicting char nitrogen contents under low-NOx combustion conditions. Residence times will clearly be short (order 100’s of ms), but particle temperatures will vary depending on particle size, trajectory etc. Particles will also attain very high temperatures (order 2000°C) as they ignite at the start of heterogeneous combustion, making the upper temperature limit for devolatilisation, as opposed to heterogeneous char combustion, difficult to define. Because of the problems of making an a priori prediction for the most appropriate conditions, a range of devolatilisation conditions have been used to test coals for which NOx emission levels from either full-size utility plants and/or a 45 MW single burner rig were available, Lam et al(12), King(13). In all cases, measured NOx emissions for 3% O2 in the flue gases are plotted against calculated Vernon(14) combustor exit NOx emissions for zero conversion of volatile nitrogen and 100% conversion of char nitrogen to NOx.

The test conditions initially selected, somewhat arbitrarily, as a compromise between what could conveniently be achieved with an earlier prototype version of the wire-mesh apparatus and estimates of actual conditions, were heating at 1000 K/s to 1450°C with 150 ms hold at peak temperature Man et al(15). As Figure 5 shows, a reasonable correlation is achieved with published NOx data for a number of coals (12) (corrected to 3% flue gas O2 where necessary (14)), but several discrepancies are also observed Man et al(16). One of these is for the S. African coal (SAF) burnt in the utility boiler, but this coal produced much less NOx in the single burner trials and, from observations made at the time, it appears likely that fouling in the furnace chamber leading to enhanced thermal NOx was at least partly responsible for the higher plant NOx levels. Although plant thermal NOx levels will obviously vary somewhat between coals and exact values are not known, differences in thermal NOx do not appear able to explain the case of the Colombian coal (COL), which gave a lower plant NOx value than predicted from the nitrogen content of chars prepared under these conditions.

Figure 5 Combustion NOx emissions vs. char N content for 1000 K/s heating to 1450°C with 0.15 s hold

Since it was considered that the devolatilisation conditions used might be unrealistic, principally because of too low a temperature and heating rate, the coals were re-tested at a heating rate of 10,000 K/s to 1600°C, again with 150 ms hold. It was thought that the Colombian coal might need these more severe conditions to approach an asymptotic nitrogen yield, while the other coals might have already achieved near-ultimate yields and would thus undergo relatively little further nitrogen loss. In fact all of the coals tested exhibited some additional nitrogen release, resulting in little improvement in the correlation for the Colombian coal (16).

To examine the correlation for conditions under which maximum rapid-heating N yields from the char were almost certain to be achieved, all coals were then additionally tested at 10,000 K/s to 1800°C and with 2 s hold at peak temperature, although it was recognised that these conditions would be more severe, particularly with regard to heating time, than would be encountered in actual plant. In this case, as shown in Figure 6 (16), results for all coals now appear to follow a consistent trend. Overall char nitrogen contents are, however, much reduced and either higher conversion rates of char nitrogen to NOx or a higher volatile/thermal NOx contribution would have to be invoked to interpret the observed trends.

Figure 6 Combustion NOx emissions vs. char N content for 10⁴ K/s heating to 1800°C with 0.15 s hold

To investigate the apparently anomalous results for the Colombian coal, a more detailed study of the effect of peak temperature and hold time was undertaken for it and the US coal, which gave similar NOx emissions in the same utility plant. The results are shown in Figure 7 (16), with total volatile yield, volatile nitrogen yield and char hydrogen content plotted as a function of temperature for both 150 ms and 2 s hold times. In this case 10,000 K/s heating was also used for the 1450°C values – results were very close to the 1000 K/s measurements and consistent with the lower heating rate giving a slightly increased time at temperature. Comparison between the Colombian and US coals confirms that significant differences in nitrogen release patterns exist. In particular, much less nitrogen (and hydrogen) is released during primary devolatilisation of the former (i.e. at 1450°C with 0.15 s hold). Therefore although the extended hold time at 1450°C gives a similar increase in volatile nitrogen yields from both coals, this still leaves the Colombian coal at a much lower total volatile nitrogen release.

Figure 7 Effect of temperature and hold time on volatile, nitrogen and hydrogen evolution during devolatilisation of USA and Colombian coal samples.

That the values for 1600°C with 0.15 s hold are similar to those for 1450°C with 0.15 s hold is perhaps not surprising, given that only an extra 15 ms of heating time between 1450°C and 1600°C (plus a slightly longer period during cooling) are available to add to the effect of the higher temperature. Again differences in the nitrogen distribution from primary devolatilisation predominate. Secondary devolatilisation of both chars can eventually run to completion at 1600°C, however, as evidenced by the very low char hydrogen contents after 2 s hold. This results in the combined primary and secondary devolatilisation nitrogen yields from the two coals now being comparable.

At 1800°C, the rates of the secondary devolatilisation processes are so high in both coals that they are completed by 150 ms, with essentially no further reaction taking place over the next 1.85 s. This confirms that similar char nitrogen contents can be obtained for these coals, to match the similar plant NOx emissions, without requiring unrealistically long heating times. More intense heating conditions are required than 150 ms at 1600°C, but either heating time and/or temperature could be increased to achieve parity. Based on the present data the hold time will fall rapidly from 2 s with increasing temperature. Given that the hydrogen content is already close to zero after 150 ms at 1800°C, and that negligible differences are observed between 1600°C and 1800°C with 2 s hold, it can also probably be concluded that no continuing increase in yields can be expected for temperatures beyond 1800°C.

On the basis of the results above, 10⁴ K/s heating to 1600°C with 2 s hold has been selected as suitable conditions for a routine wire mesh test for estimating the NOx formation potential of a coal. While perhaps not as close to actual boiler conditions as a shorter holding time at 1800°C, this operating mode still achieves the maximum feasible nitrogen release and applies less thermal stress to the apparatus. Figure 8 shows the previous utility plant and 45 MW single burner NOx measurements (plus three additional data points for another utility plant) plotted against NOx values for complete conversion of the char N obtained with these heating conditions. As expected, a reasonable correlation is obtained.

Figure 8 Measured NOx levels for utility plant. 45 MW single burner and 160 kw test rig with aerodynamically air-staged low-NOx burner and furnace air staging.

Also shown in Figure 8 are data points for an additional range of UK coals and a single Polish coal (POL) with combustion NOx measurements obtained in a 160 kW test combustor located at Babcock Energy Ltd’s Technology Centre at Renfrew operated with a model conventional aerodynamically air-staged low-NOx’ burner, and, for a sub-set of the coals, with additional furnace air staging Hesselmann and Marshall(17), Hesselmann(18). This facility consists of a 5 m long 0.5 m diameter refractory lined furnace arranged vertically with the burner firing downwards. Overfire air and gas/solid sampling ports are located along the furnace length allowing the full range of combustion conditions pertinent to large utility combustors to be investigated fully. Combustion NOx values with the low-NOx burner follow a similar trend to plant and larger-scale single burner data for the UK coals. Somewhat elevated NOx levels are measured for the Polish coal with the low-NOx burner. These are attributed to the much slower volatile release rate observed for this sample in the early stages of combustion, with the effects possibly amplified by the relatively small scale and/or the absence of adjacent burners. Under furnace air staging conditions, with significantly more time available for devolatilisation, the Polish coal exhibits similar behaviour to the UK coals. NOx measurements for the UK coal A are for a reduced thermal load (100 kW) in both combustion modes. The value shown for combustion in the low-NOx burner has been corrected to full load (160 kW), with an estimated uncertainty of +/− 50 ppm from the value shown. In the absence of sufficient load effect data no correction has been applied to the combustion NOx measurements for coal A in furnace air staging mode, although some increase from the plotted value can probably be expected.

With furnace air staging (0.9 primary zone stoichiometry) exit NOx levels are significantly reduced, but the slope of the correlation line (i.e. the char N to NOx conversion ratio) remains approximately unchanged at about 25%. The reduction is then apparently due almost entirely to a drop in the intercept of the correlation line, corresponding to the combined volatile and thermal NOx contribution. Although more data points are obviously required before firm conclusions can be drawn, if true this trend has several interesting implications. With respect to aerodynamic air-staged low-NOx burners it implies that some volatile and thermal NOx is being formed in the flame envelope that inevitably exists between the inner reducing zone(s), corresponding to the fuel and primary air flow, and the secondary/tertiary air flows, That the level of this NOx formation is not related to coal properties, together with previous results showing an increasing sensitivity to excess air levels for burner designs with less effective internal air staging (13), suggests that burner aerodynamics is the main determining factor. It also appears that in ‘second generation’ internally air-staged low NOx burners, char nitrogen contents are already close to the minimum that can be achieved. Hence, when furnace air staging is used to apply more severe (i.e. longer) heating during the reducing stage, char nitrogen contents cannot be reduced significantly. Performance improvements can still be derived, however, from the more complete conversion of potential volatile NOx precursors to N2 that can be achieved before the addition of the secondary air, and possibly also from reductions in peak flame temperatures leading to less thermal NOx.

CONCLUSIONS

A captive sample wire-mesh test has been developed which can apply coal devolatilisation conditions comparable to those likely to be encountered in PF combustion. Comparison with results from full size utility boilers has shown that both the bench-scale high temperature wire-mesh apparatus and the 160 kW test facility can give a good indication of large scale combustion performance.

The nitrogen content of wire-mesh chars from a range of world-traded and UK coals correlates with measured NOx emissions from three different full-size boiler plants fitted with low-NOx burners, a 45 MW single burner rig and the 160 kW combustor, provided that sufficiently severe heating conditions are employed for secondary devolatilisation of the char to proceed nearly to completion.

The wire-mesh apparatus test conditions (and by implication plant conditions) required for agreement imply peak particle temperatures in the region of 1600–1800°C for feasible residence times. Results also suggest that present ‘second generation’ internally air-staged low-NOx burners may already be achieving close to the maximum possible release of nitrogen from the char under reducing conditions. Convenient test conditions to give complete secondary devolatilisation and hence maximise rapid-heating nitrogen release appear to be 10,000 K/s heating to 1600°C with 2 s hold. These conditions achieve similar yields to 0.15 and 2 s hold at 1800°C.

A combination of measured wire-mesh char N contents and 160 kW combustor data suggest that reductions in thermal/volatile NOx formation may be more significant than reductions in char N content or char N to NOx conversion in contributing to the overall improvements in exit NOx levels that can be achieved with furnace air staging.

ACKNOWLEDGEMENTS

The development of the wire-mesh apparatus was supported by the UK Science and Engineering Research Council under Grants GR/89817 and GR/J14127. Its application for industrial test purposes is currently being investigated with funding from the UK Department of Trade and Industry under ETSU Contract C/00/00078, Babcock Energy Ltd and National Power PLC. The authors are grateful to National Power PLC and Babcock Energy Ltd for permission to incorporate plant and test rig combustion data in this paper but emphasise that this does not necessarily imply an endorsement by these organisations of the coal testing techniques described, nor the conclusions drawn.

REFERENCES

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2. Johnson, W.R., 1844, Senate Document 386. 28th Congress, (referred to in Chemistry of Coal Utilization Vol 1 (ed. H.H. Lowry), Wiley, NY, 1945).

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4. Carpenter, A. M., Skorupska, N. M.Coal combustion - analysis and testing IEACR/64. London: IE A, 1993.

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7. Thompson, A.W. and Stainsby, R.E, 1993., Nitrogen release and devolatilisation from power station coals by drop tube furnace Coal Research Forum Conf. on NOx, Imperial College, London.

8. Nakamura, T., Smart, J.P., van de Kamp, W.L. and Morgan, M.E., 1991, Effect of coal blends end qualities on the performance of a swirl stabilized internally air-staged p.f. burner Proc. Int. Conf. on Coal Sci. Newcastle: 331–335.

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12. Lam K.B., Wilkinson, P.J. and King, J.L, 1992., Application of low NOx axial swirl burners to Castle Peak B station 9th Conf. of the Electric Power Supply Industry (CEPSI), Hong Kong.

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18. Hesselmann, G.J., 1994, Air staging and rebuming DTI Contractors Conf. Nottingham.

COMPARATIVE PERFORMANCE OF DIFFERENT COALS AND NATURAL GAS FOR THE REDUCTION OF NO BY REBURNING

H. Liu, E. Hampartsoumian and B.M. Gibbs,     Department of Fuel and Energy, The University of Leeds, Leeds LS2 9JT, United Kingdom

The reburning performances of thirteen world coals of different rank and natural gas were investigated in an isothermal drop-tube reactor. The NO reduction by coal reburning was strongly related to the burnout of the reburning fuel. It was possible to reduce NO even in lean burned gases. Decreasing the primary flame NO concentration for coal reburning resulted in a significant deterioration of system performance in comparison to natural gas reburning, where the NO reduction efficiency was almost unaffected. The optimum reburn zone stoichiometry and peak NO reduction efficiency of natural gas reburning was found to depend on the method of varying the primary combustion zone equvalence ratio.

INTRODUCTION

Reburning or fuel staging is an in-furnace NOx control strategy that removes NOx from the combustion products after it is formed. Previous studies have shown that gaseous hydrocarbon fuels are effective reburning fuels for the reduction of NOx [1, 2, 3]. More recently, it has been demonstrated that coals can reduce NOx by reburning [4]. However, there are some uncertainties concerned with coal reburning, namely the effect of rank, particle size, fuel-N content, geographical origin and morphology of the coal.

Reburning is based on the expectation that NOx can be destroyed by reaction with hydrocarbon radicals and depends on the introduction of reburn fuels into the reaction zone to provide these hydrocarbon radicals [5]. A fraction of the primary fuel or an alternative fuel is introduced into the post flame (reburning) zone and usually some additional burnout air is also added to complete the combustion of fuels. The primary combustion zone can be operated with conventional or low-NOx burners, the latter providing an additional method for the reduction of NOx. For reburning, compared with air staging, it is not necessary that the primary zone is operated fuel rich, thus avoiding operational problems such as corrosion. The efficiency of the reburning process depends on several factors including the primary NOx level, reburn zone temperature, primary and reburn zone stoichiometry, residence time and reburn fuel type. The main conclusions drawn from bench and pilot-scale research studies [6–10] using gas and oil as the reburn fuels indicate that (i) lower levels of primary NOx tend to reduce the reburning efficiency, especially when the reburn fuel contains fuel-N (ii) higher reburn zone temperatures enhance the reduction of NOx when the reburn zone is operated under fuel-rich conditions so as to limit the formation of thermal- NOx, (iii) the optimum reburn zone stoichiometry is about 0.9 (iv) reburn zone residence time should be as long as possible to achieve high NOx reduction, and (v) methane is more effective as a reburn fuel than other hydrocarbon gaseous fuels, hydrogen and carbon monoxide.

The mechanism of coal reburning is more complex due to the heterogeneous nature of this fuel and the effects of rank, composition and fuel-bound nitrogen type. High volatile coals are expected to be the more efficient reburn fuels [11], although the selection of reburn coals based on the proximate and ultimate analyses alone may be too simplistic due to differences in pyrolysis behaviour (depending on temperature and heating rate) between coal types of similar volatile matter content. Smart and Morgan [12] have shown that fuel-N content has little effect on the reduction of NOx since the removal of primary NOx by reaction with volatile nitrogen intermediates, generated from the reburn fuel, is offset by the oxidation of fuel-N. The net effect of fuel-N on the exit NOx emission will depend on the primary NOx level. If the primary NOx level is already very low, the reburn fuel-N will have an adverse effect on NOx reduction. If the primary NOx level is high, the reburn fuel-bound nitrogen may have only a marginal effect.

Coal reburning efficiency is affected by the physical and chemical properties of the reburn coals, most of which are coupled and cannot be easily separated. The aim of the present study is to investigate the influence of the reburning coal rank on the reduction of NO and to compare coal reburning results with those of natural gas reburning. The well-defined and easily-controlled thermal environments within the experimental drop-tube reactor make it possible to compare NO reductions achieved by different reburning fuels under similar operating