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International Journal of Hydrogen Energy 29 (2004) 1527 1539

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Internal combustion engines fueled by natural gashydrogen mixtures

S. Orhan Akansua; , Zafer Dulgerb , Naz Kahramana , T. Nejat Veziro luc g
Faculty, Erciyes University, 38039 Kayseri, Turkey Faculty, Kocaeli University, 41100 Kocaeli, Turkey c College of Engineering, University of Miami, Coral Gables, FL 33124, USA
b Engineering a Engineering

Accepted 27 January 2004

Abstract In this study, a survey of research papers on utilization of natural gashydrogen mixtures in internal combustion engines is carried out. In general, HC, CO2 , and CO emissions decrease with increasing H2 , but NOx emissions generally increase. If a catalytic converter is used, NOx emission values can be decreased to extremely low levels. Consequently, equivalence zero emission vehicles (EZEV) standards may be reached. E ciency values vary with H2 amount, spark timing, compression ratio, equivalence ratio, etc. Under certain conditions, e ciency values can be increased. In terms of BSFC, emissions and BTE, a mixture of low hydrogen percentage is suitable for using. ? 2004 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
Keywords: CNG; Hydrogen; Mixtures; Engine

1. Introduction Most of the energy used in the world is supplied by fossil fuels. Burning of the fossil fuels generates waste materials, mainly emissions to the atmosphere in the form of combustion fuel gases and dust, as well as some ash and/or clinker. These waste materials have hazardous e ects on the environment, some of them locally, others with more widespread or even global impact [1]. Not only does the continued use of large amounts of fossil fuels pose a serious threat to the environment, but also the fuels themselves are nite in quantity. There are debates amongst experts about the extractable amount of fossil fuels. General opinion is that at the beginning of the 21st century almost half of the fossil fuels had already been consumed. The known worldwide reserves of petroleum are 1000 billion barrels and these petroleum reserves are predicted to be consumed in about 40 years [2]. Another problem with

Corresponding author. Tel.: +90-35-2437-4937/32129; fax: +90-35-2437-5784. E-mail address: akansu@erciyes.edu.tr (S.O. Akansu).

petroleum is the emission of pollutants, such as CO2 , NOx , CO and hydrocarbons (HC). Much greater amounts of coal are known to exist but conventional coal burning technology is much more polluting than for most other fuels, particularly in terms of the greenhouse gas emissions per unit of useful energy released. In order to decrease these pollutions, alternative fuels are being considered such as methane, hydrogen and mixtures of hydrogen and methane. Natural gas (NG) is a mixture of di erent gases. Concentration of these gases may di er from one source to another. One component of NG is methane, which is typically up to 99 percent of the total volume [3]. The composition of NG is never constant. Other constituents may include non-methane hydrocarbons such as ethane, propane and butane and in some cases, traces of higher hydrocarbons as well as inert gases like nitrogen, helium, carbon dioxide, hydrogen sulphide and sometimes water [3,4]. NG has excellent properties as a fuel. It is the cleanest of all fossil fuels and its reserves are 5288.5 trillion cubic feet, which is larger than crude oil [2]. It is easy to transport and store, available on demand, and cheaper than gasoline and diesel. It is cheap and available in great quantities in many parts of the world, has a high-octane value and therefore, suitable for engines of

0360-3199/$ 30.00 ? 2004 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2004.01.018

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Nomenclature BMEP BSCO BSCO2 BSFC BSHC BSNOx BTDC BTE ITE SI Equivalence ratio Break mean e ective pressure Break specic production of carbon monoxide, g=kW h Break specic production of carbon dioxide, g=kW h Break specic fuel consumption Break specic production of unburned hydrocarbons, g=kW h Break specic production of nitric oxides, g=kW h Before top dead center Break thermal e ciency Indicated thermal e ciency Spark ignition

as hydrocarbons, carbon monoxide, oxides of sulfur, organic acids or carbon dioxide, instead its main product is water. In todays world, where the e ects of global warming are a serious problem, the basic advantage of hydrogen combustion is that the greenhouse gas carbon dioxide (CO2 ) is not formed at all. The currently alternative fuels NG and hydrogen have been studied and according to literature, they prove to be safe, economic, scientic advantage and life cycle [813]. Adamson and Pearson compared hydrogen and methane according to safety, economics, e ciencies and emissions. They concluded that there are no overall clear benets in favor of either of the two fuels. The decision of which fuel becomes dominant may not be decided by any of these issues, but by which between the two rst develops the infrastructure, public image and availability. Whether this leads to another technological lock-in is still uncertain [9]. 2. Use of natural gashydrogen mixture in internal combustion engines CO2 , CO and total hydrocarbon (HC) emissions, which appear with combustion of NG, are reduced by the addition of hydrogen. In fact, with the hydrogen addition to natural gas, exhaust emissions contain very little amounts of HC, CO2 , CO and NOx . Hydrogen and natural gas combination is called as Hythane 1 . Natural gas and H2 engines have been studied with respect to di erent mixture percentages of natural gas (methane) and hydrogen. Many of these studies are discussed in the literature [1436]. Nagalingam et al. conducted experiments with an AVL engine, 523.001 type, speed 1200 rpm, fueled with 100/0, 80/20, 50/50, 0/100, CNG=H2 mixtures with single cylinder, four strokes, vertical, two intake valves, two exhaust valves, spark ignited engine, bore 125 mm, stoke 130 mm, and compression ratio 11.73 [14]. They found that loss of maximum engine output on hydrogen operation was about 23% and maximum percentage reduction in indicated thermal e ciency was about 12% at a speed of 1200 rpm. Increasing the size of the hydrogen engine for stationary applications could compensate power loss. Optimum spark timing decreased up to 20 BTDC for mixtures of pure hydrogen indicating increased ame speed. NOx emissions increased for pure hydrogen because of higher combustion temperature. Unburned hydrocarbons and carbon monoxide emissions decreased because of direct displacement of a carbon-based fuel with hydrogen. The performance of a hydrogen-supplemented natural gas engine was found to be in between natural gas and hydrogen engine performances for 0.80.9 equivalence ratios, depending on the amount of hydrogen supplementation. This experiment did not analyze engine speed or engine load.
1

high compression ratio with possible improvement of both engine power output and e ciency. Throughout history, there have been many studies regarding hydrogen as a fuel in internal combustion engines. First, Reverend Cecil in England planned to use hydrogen as fuel in 1820. Bursanti and Matteucci in Italy improved the hydrogen engine with a free piston in 1854. Rudolf Erren conducted studies with the hydrogen engine in Germany in 1920. Ricardo achieved high e ciency when working with hydrogen in an engine in 1924. Erren et al. stated the advantage of using hydrogen as a fuel regarding air pollution in 1930s [5]. Hydrogen has long been recognized as a fuel having some unique and highly desirable properties for application in engines. Today, hydrogen is being used in many applications. Adt and Swain tested e ciency and emission levels of a multicylinder automobile engine operating at part load on hydrogen and methanol [6]. They obtained that BTE of an engine fueled by hydrogen was higher than the methanol-fueled engine and NOx emissions of hydrogen-fueled engine were lower than the methanol-fueled engine. Tianshen et al. investigated supplying hydrogen together with methanol to SI engine as a combustion supporting fuel to improve its combustion characteristic [7]. They obtained that a small amount of hydrogen supplied to methanolair mixture would increase the ame propagation rate, shorten the ignition delay period, reduce the combustion time loss and improve the e ective thermal e ciency. In view of the versatility of internal combustion engines, hydrogen has been tried several times as an alternative fuel, though chie y intended to be used secondary to a shortage of fossil fuels. Hydrogen does not experience problems associated with liquid fuels, such as vapor lock, cold wall quenching, inadequate vaporization, poor mixing, and so forth. It has clean burning characteristics. When hydrogen is burned, hydrogen combustion does not produce toxic products such

Inc.

Hythane is a registered trademark of Hydrogen Consultants

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Yusuf in his M.Sc. thesis used 99% methane (CH4 ) and 80.08/19.92 CH4 =H2 mixture [15]. He used a Nissan 510 type, 1952 cc, maximum HP 92 and maximum speed 5200 rpm; bore 85:0 mm, stroke 86:0 mm, compression ratio 8.5:1 and four cylinder engine. He analyzed ame front growth rate (FFGR), and SI time for various equivalence ratios. Equivalence ratio of 0.535 was discarded because of lean limits of combustion of methane. Dulger investigated an 80% CNG and 20% H2 mixture burning SI engine numerically [16]. Swain et al. [17] and Yusuf [18] experimented the same mixture with a di erent engine. Yusuf used a Toyota 2TC type year 1976 1:6 l, 1588 cc, maximum HP 88 and maximum speed 6000 rpm, bore 85:0 mm, stroke 70 mm, compression ratio 9.0:1 and four cylinder engine. He modied the engine and decided to use only a single cylinder instead of four. He measured BSHC, BSCO, and BSNOx concentrations, spark advance, and calculated thermal e ciency varying equivalence ratio. The engine was tested at 1000 rpm, best e ciency spark advance and light loading condition. When methanehydrogen mixture is compared to pure methane operation with same equivalence ratios, methane and hydrogen mixture increased BTE and NOx , emissions while decreasing best e ciency spark advantage, unburned HCs and CO. Moreover, lean limit combustion of natural gas was reduced from 0.61 to 0.54. Lean limit of combustion was dened as operation with at least 38% of cycles not completing combustion. By hydrogen addition, equivalence ratios could be reduced about 15% without increasing combustion duration and ignition delay. Wallace and Cattelan experimentally studied natural gas and hydrogen mixtures in a combustion engine. Experiments were conducted studying emissions out of an engine fueled with a mixture of natural gas and approximately 15% hydrogen by volume [19]. Experiments were performed using a 3.1 Chevrolet Lumina, which has six cylinders, four stroke cycles, water cooled, 3:135 l, bore 89 mm, stroke 84 mm and compression ratio 8.8:1. In this study, BSFC of 85/15 CNG=H2 mixture is less than natural gas. BSFC values reduce for both natural gas and 85/15 CNG=H2 mixture while spark timing (BTDC) values increase. BSHC of CNG is higher than that of fuel mixture. But BSNOx emission values of 85/15 CNG=H2 mixture are higher than CNG. If a catalytic converter is used, BSNOx values are decreased drastically. Raman et al. reported that hydrogen is a useful additive for natural gas that enables leaner operation under part load conditions and improves BMEP at wide open throttle near the lean limit. Moreover, NOx values are reduced, if normal hydrocarbon emissions or fuel consumption observed with natural gas are not exceeded [20]. Hoekstra et al. experimented on 100/0, 89/11, 80/20, 72/28 and 64/36 CH4 =H2 percentage mixtures in a SI engine at 17 hp and 1700 rpm by changing equivalence ratios. They measured NOx and hydrocarbons. They found that NOx increases and HC decreases with increasing

equivalence ratios. They found extremely low NOx values at = 0:625 for 28 and 36 percent H2 blends [21,22]. Liu and Karim investigated knock characteristics in 100/0, 90/10, 70/30, 50/50, 30/70 and 0/100 CH4 =H2 proportions [23]. They simulated models and compared data of their ndings with previous work for knock characteristics. They stated that if hydrogen and methane have high intake temperature, knocking regions correspond to experimental values. However, hydrogen displays large deviations from experimental data at low intake temperatures, because of the high-energy release resulting from the rapid ame propagation during the combustion of hydrogen. Das surveyed utilization of hydrogen and natural gas mixtures in an internal combustion engine [24]. He claried that hydrogen blended with CNG enabled leaner operation under part load conditions and showed an improvement in BMEP. Also, hydrogen blended with CNG in small amounts resulted in environmental benet. Karim investigated knock limits associated with mixtures containing di erent percentages of H2 and CH4 , equivalence ratios and intake temperatures [25]. He stated that when hydrogen and methane was blended relatively in small amounts, excellent knock resistant qualities of methane are not undermined. Karim et al. studied experimentally with 100/0, 90/10, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70 and 20/80 CH4 =H2 proportions by varying equivalence ratios [26]. They investigated apparent ame initiation speed (m/s), average power output di erence, average indicated output e ciency, average ignition lag, average combustion duration ( CA), average maximum cylinder pressure, knocking regions in di erent %H2 and %CH4 percentage, di erent equivalence ratio and di erent BTDC (10 ; 20 ; 30 ). For 10 BTDC and 20 BTDC, with increasing concentration of hydrogen in the engine, power output increased, but for 30 BTDC, with the increasing concentration of hydrogen in the engine, power output decreased. The maximum power output was shown to be at 20 BTDC. If some amount of hydrogen was added to the methane as a fuel for the SI engine, performance characteristics of the engine increased drastically. Larsen and Wallace investigated emissions and e ciency of a turbocharged lean burn natural gas and hydrogen mixture fueled engine [27]. The emissions and e ciency of the 85/15 CNG=H2 mixture fuel by volume, were compared to the emissions and e ciency of pure natural gas using a turbocharged, six cylinders, four stoke, 3:1 l, SI engine. They tested at di erent speeds, di erent loads and di erent equivalence ratios for NOx , BSHC, CO=CO2 , exhaust temperatures and engine e ciencies. The results obtained with respect to the matrix and statistical testing clearly demonstrated the potential of methane and hydrogen mixture to reduce the exhaust concentrations of regulated pollutants and increase the e ciency of a SI engine. The emissions of primary concern in a lean-fueled engine were hydrocarbons and NOx . Consequently, the discovery that simultaneously lower levels of NOx and hydrocarbon emissions can

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be achieved with methane and hydrogen mixture fueling had important implications. Experiments were conducted to measure emissions of an engine fueled with a mixture of natural gas and approximately 15% hydrogen by volume. These were performed with 3.1 Chevrolet Lumina, which has six cylinders, four stroke cycles, was water cooled, 3:135 l, bore 89 mm, stroke 84 mm, and had a compression ratio of 8.8:1. Blarigan and Keller investigated the 100/0, 70/30 and 0/100 CH4 =H2 percentages [28]. They studied experimental and computational and used three-dimensional CFD code. NOx , thermal e ciency, BTDC and changed equivalence ratios were compared for various CH4 and H2 percentages. They reported that it is possible to build a high e ciency, equivalent zero emissions auxiliary power unit for hybrid vehicles fueled by hydrogen or 30% hydrogen/70% NG blends. Wong and Karim studied the kinetic e ects of the presence of some gaseous fuels and preignition reaction products with hydrogen in engines [29]. Shrestha and Karim investigated proportions of 100/0, 90/10, 80/20, 70/30, 20/80 and 10/90 CH4 =H2 percentages in di erent compression rates by varying equivalence ratios [30]. They stated that the addition of some hydrogen to methane in a S.I. engine enhanced the performance, particularly when operating on relatively low equivalence ratio mixtures. The optimum concentration of hydrogen in the fuel mixture for producing a power gain and avoiding knock appears to be about 2025% by volume over the range of conditions considered. Sierens and Rosseel investigated 100/0, 90/10 and 80/20 CNG=H2 percentages mixtures. They examined a V 8 Crusader T7400 spark engine at one particular speed (3800 rpm, compression ratio 8.5:1). They designed a fuel supply system and implemented a device that provides the engine with a hydrogen/natural gas mixture in variable proportions. The composition of this mixture can be set independently of engine operation. They stated that for methane and hydrogen mixture with low hydrogen content (up to 20 percent) a limited improvement in emissions could be obtained because of the con icting requirements for low hydrocarbons and low NOx . Extremely low emissions were not possible without exhaust after treatment. To reduce hydrocarbon emissions, must be less than 1.3 ( must be higher than 0.77), while for low NOx , must be at least 1.5 [31]. Das et al. investigated the thermal e ciency and BSFC of CNG and hydrogen as fuel in an internal combustion engine. They observed that the BSFC was reduced and the BTE improved with hydrogen operation compared to systems running on CNG. The BTE was as high as 31.19% for hydrogen operation compared to that of 27.59% for CNG [32]. Shudo et al. investigated combustion and emissions with regard to methane and hydrogen use. They performed the test with a four-stroke cycle single cylinder SI engine with a bore stroke of 85 88 mm and a compression ratio of 13. Thermal e ciency was increased and unburned hydrocar-

bon was decreased. NOx emissions tended to increase with hydrogen premixing, however the increase could be maintained at lower levels with retarded ignition timing without deteriorating thermal e ciency. They obtained great e ects of combustion promotion due to the hydrogen premixing, especially under lean conditions. The lean operation enables improvement of thermal e ciency and reduction of HC and NOx exhaust emission simultaneously [33]. Bauer and Forest studied the e ect of hydrogen addition to the performance of methane-fueled vehicles. They used a one-cylinder research engine at compression ratio 8.5:1. They analyzed brake power, ITE, spark degree (BTDC), BSFC, BSCO2 , BSCO, BSHC, BSNO in 100/0, 80/20, 60/40, 40/60 CH4 =H2 percentage by changing equivalence ratios, load and speed (700 and 900 rpm). They concluded that when compared to pure methane, hydrogen addition up to 60% volume was shown to lower the partial burn limit from an equivalence ratio of 0.580.34. There was a corresponding increase in brake power up to 8% (at = 1:0) and decrease in BSFC up to 14% (from = 0:58 to 1.0). For pollutant production, hydrogen addition up to 60% volume resulted in a decrease in BSCO2 up to 26% (from = 0:58 to 1.0), a decrease in BSCO up to 40% (for 0:95), a decrease in BSHC up to 60% (from = 0:58 to 1.0), and a increase in peak BSNO at = 0:83 of approximately 30% (for volumetric fraction =40%) [34]. Bauler and Forest presented the results using data of Ref. [34] for driving cycle simulations [35]. Karim investigated hydrogen as a SI engine fuel. He conducted that there were excellent prospects to achieve very satisfactory S.I. engine operation with hydrogen as the fuel and most of the subject whether hydrogen could be obtained abundantly and economically remained yet to be answered satisfactorily [36]. These results demonstrate that addition of hydrogen to methane reduces HC, CO and CO2 emissions while having a tendency to increase NOx emissions. However, since hydrogen enrichment enables operating with leaner mixtures, lean operation results in NOx reduction without sacrifying engine output and thermal e ciency. Moreover, due to high ame speeds of hydrogen, retarded ignition timing is also possible without lowering thermal e ciency and this reduces ame temperature and NOx levels consequently. Therefore, signicant reductions in NOx emissions are also obtained with hydrogen addition. Besides reducing Green House gases and atmospheric pollutants, hydrogen enrichment of natural gas also enhances combustion characteristics of the engine. Hydrogen addition reduces the equivalence ratio at lean limit of combustion of natural gas without increasing combustion duration, which results in higher thermal e ciencies and lower emission levels. Moreover, hydrogen addition shows some improvement in BMEP. The tests show that 2030% hydrogen enrichment of natural gas gives the most favorable engine operation. Higher hydrogen contents undermine the knock resistance

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characteristics of natural gas, lower power output of the engine and increase the fuel cost. Hydrogen content lower than 2030% does not make enough use of the performance enhancement potential of hydrogen. 3. Comparison of methanehydrogen mixtures While investigating the advantages and disadvantages of fuels such as methane, hydrogen and their mixtures, one has to consider the criteria such as emission, performance, e ciency and usability. Studies meant to conduct comparisons should have identical conditions. In comparisons, there are a lot of e ective parameters such as compression ratio, equivalence ratio, engine speed, engine volume, temperature, pressure, engine power, load and spark timing. Also, di erent measurement devices are used in each study. While comparisons are made, it is more suitable to compare on environmental and technical basis. 3.1. Environmental comparison This section can conveniently be divided in to three: (1) comparison in terms of NOx emissions, (2) comparison in terms of hydrocarbon emissions, (3) comparison in terms of CO and CO2 emissions.

3.1.1. Comparison in terms of NOx emissions Nitrogen oxides (NOx ) refer to a mixture of two compounds: Nitrogen monoxide (NO) and Nitrogen dioxide (NO2 ). Nitrogen monoxide is a colorless gas where nitrogen dioxide absorbs sunlight strongly at short wavelengths (appears blue and green). Fig. 1 illustrates BSNOx (g=kW h) values versus the equivalence ratios from di erent studies [17,20,22,27,31]. As seen in this gure, according to studies, with increasing H2 percentage, BSNOx values are increasing or decreasing. According to Refs. [17,27,31,21] and Bauer and Forest [34] (there is no data value in graphics), with increasing H2 percentage, BSNOx values are increasing. BSNOx values, which were obtained by Swain et al. Sierens and Rosseel, can be considered as high [17,31,34]. Bauer and Forest obtained about 21, 19, and 16 (g=kW h BSNOx ), 40% H2 + 60 CH4 , 20% H2 + 80% CH4 and 100% CH4 for equivalence ratio 0.8, respectively [34]. But, in the experiments performed by Raman et al. [20], with increasing H2 percentage, BSNOx values are decreasing. Moreover, if equivalence ratios are decreased, BSNOx values reach to a low value. It is interesting to note that Hoekstra et al. [22], as well as Larsen and Wallace [27] obtained extremely low NOx emission. Moreover, Blarigan and Keller tested and used three-dimensional CFD modeling [28]. They found a low value of emissions (EZEV limits).

13 12 11 10 9

[17] [20] [22] [27]

%C NG

100 % CH 4

[31]
G

H 4

BSNOx (g/kWh)

H 2+

8 7 6
%H 2

H 2 + 90 %

80

CN

10 0

CN H 2 + 70 % %

15

0%

1 00

CN

H 2 +8

4 3 2 1 0 0.5 0.6

100 2 00 % CN 0 rp G 10 0 m 65 %C 1 50 N .m 0 rp N G m 130 N .m 5% H 2 + 95 %

0%

CN

30

1 1%

10

15% H 2 + 85% CNG 2000 rpm 65 N.m 15% H 2 + 85% CNG 1500 rpm 130 N.m

2 0%

10

0%

CN

0.7

0.8

0.9

H + 2 89 %

H 2 +

85

28% H 2 + 72%CNG 20% H 2 + 80%CNG

C NG

10 %

20

CN

36% H 2 + 64%CNG

1.1

Equivalence Ratio
Fig. 1. BSNOx (g=kW h) values of di erent studies versus the equivalence ratios.

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Engine-Out BSNOx (g/kW-hr)

Post-Cat BSNOx (g/kW-hr)

3.5 3.0 2.5 2.0 1.5 1.0 20 22 24 26 Spark Timing (BTDC) 28 Natural Gas 85/15 CNG/H2

0.030 0.025 0.020 0.015 0.010 0.005 0.000 20 22 24 26 Spark Timing (BTDC) 28 Natural Gas 85/15 CNG/H2

(a)

(b)

Fig. 2. BSNOx (g=kW h) values versus the spark timing ( BTDC), (a) engine out, (b) after the catalytic converter.

14
CN G 1 100 %

13 12 11 10 9 BSHC (g/Kwh) 8 7 6 5 4 3 2 1

[23] [22] [27] [27]

100 %

5 0 0 rp N.m m 13 0
15

[32] [31] [36] [34]

CN G 2 .m m 65 N 0 0 0 rp

100 % CH4

20% H 2 + 80 % CH4 40% H 2 + 60 % CH4 60% H 2 + 40% CH 4 36% H 2 + 72 % CNG

15 %H 2 +8 5% CN

%H 2 +8 5% CN G2

20

G1

00

50 0r

00 rp m

H 2+

pm 13

65

10

0N

N .m

80

.m

H 2+ CN

90 G

100 % CNG
% CN G

11% H 2 +89 % CNG 20% H 2 +80 % CNG

0 0.5

0.55

0.6

0.65

0.7 0.75 0.8 Equivalence Ratio

0.85

0.9

0.95

1.05

Fig. 3. Brake specic hydrocarbons (BSHC g=kw h) values in di erent studies.

There are many studies on reduction of NOx by using hydrogen in an internal combustion engine. The most known methods of reductions of NOx are generally exhaust gas recirculation (EGR) system and excess air ratios (lean hydrogenair mixtures). Jorach et al. performed experiments on 6 0:5 for truck engine fueled by hydrogen and they discovered that exhaust NOx emissions were only about 10% of limits in Europe [37]. Allenby et al. carried out experiments on hydrogen rich EGR system fueled with NG engines [38]. Hydrogen concentrations were altered in the EGR system as 0, 10, 11, 16, 16.5 and 22. While EGR percentages were increased, the amount of H2 increased. They accom-

plished reduced NOx emissions while increasing EGR percentage, but HC emissions were measured high with increasing EGR percentage. Namely, as temperature was lowered, they discovered lower oxidation rate and a higher level of engine-out hydrocarbons. Das experimented on = 0:31.3 in a CFR engine fueled by hydrogen in di erent compression ratios [39]. NOx values reached maximum values at about = 0:951.05 ratios. In case of lean hydrogenair mixtures, NOx values were obtained at fairly low levels. He el investigated NOx emission and performance data for a hydrogen fueled internal combustion engine at 1500 and 3000 rpm using exhaust gas recirculation (EGR) [40,41]. He found

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6.5 Engine-out BSHC (g/kWh) 6.0 5.5 5.0 4.5 4.0 3.5 3.0 20.0 22.0 24.0 26.0 28.0 85/15 CNG/H2 Post-Cat BSHC (g/kWh) Natural Gas 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 20.0 22.0 24.0 26.0 28.0 85/15 CNG/H2 Natural Gas

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(a)

Spark Timing ( BTDC)

(b)

Spark Timing (BTDC)

Fig. 4. BSHC (g=kW h) values versus the spark timing ( BTDC), (a) engine out, (b) after the catalytic converter.

that using EGR was an e ective means to lower NOx emissions to less than 1 ppm while also increasing engine output torque. Moreover, the use of a catalytic converter lowered NOx to very low levels. Fig. 2 shows BSNOx (g=kW h) values versus spark timing ( BTDC); measurements were obtained after (a) engine out, (b) post of catalytic converter [19]. In Fig. 2a with 20 BTDC spark time, BSNOx value is lowest for 85/15 CNG=H2 mixture and Natural Gas. BSNOx values in Fig. 2b are very low. While BSNOx values of natural gas are higher than the 85/15 CNG=H2 mixture values in Fig. 2a, BSNOx values of 85/15 CNG=H2 percentage between 20 and 25 BTDC in Fig. 2b are lower than CNG; these values are very low. So, it is possible to obtain very low NOx values by adjusting spark advance to optimum and using post catalytic converter. 3.1.2. Comparison in terms of hydrocarbons Fig. 3 shows BSHC (g=kW h) values in di erent studies [22,27,31,34]. As seen in this gure, with increasing H2 percentage and equivalence ratio, BSHC values decrease. If fuel is to be 100% H2 fuel, the BSHC value will be zero. We can say that BSHC values decrease as the amount of H2 increases. With increasing equivalence ratios Swain et al. obtained the highest BSHC values in these studies. The maximum value is about 64 g=kW h, for a 20% H2 and 80% CH4 mixture with = 0:60. However, hydrocarbon emissions of 20% H2 and 80% CH4 mixture are less than pure methane [17]. In this gure, BSHC values of Ref. [27] are at its highest value. BSHC values increase with the increasing engine load. Fig. 4 depicts BSHC (g=kW h) values versus the spark timing ( BTDC). Measurements were obtained after (a) engine out, (b) post of catalytic converter [19]. In Fig. 4a, the most suitable spark time is 20 BTDC. After catalytic converter, BSHC values decrease about 15% and 25% for natural gas and 85/15 CNG=H2 mixture, respectively. With the use of a catalytic converter, the decrease in hydrocarbons with 85/15 CNG=H2 mixture is higher than natural gas.

9 8 7 BSCO (g/kWh) 6 5 4 3 2 1
10 20 0 % 00 C rp NG m 65 85 N 200 % C .m 0 r NG pm + 65 15% N.m H 2 100 20 % 00 C rpm NG 85 % 1500 CNG + 1 65 rpm 1 5% H N. 30 N m .m 2

0 0.6 0.65

0.7 0.75 0.8 0.85 0.9 Equivalence Ratio

80 % C H + 20 4 %H 2

10
100 % CH4

[17] [27]

0.95

1.05

Fig. 5. BSCO (g=kw h) values versus equivalence ratio in di erent studies.

3.1.3. Comparison in terms of CO and CO2 emissions Larsen and Wallace obtained 1.65 and 2:41 g=kW h CO values at 1500 rpm, = 0:65 equivalence ratio, using an 85/15 CNG=H2 and 100% CNG, respectively [27]. Yusuf measured all engine/fuel congurations performed similarly over normal operating ranges. An important variation took place with rich mixtures. In addition, 80/20 CH4 =H2 mixture showed a small but signicant reduction in BSCO output [17,18]. Bauer and Forests experiments demonstrated that production of CO was highly dependent on combustion stoichiometry and less so on engine. They obtained general reduction in BSCO with the addition of hydrogen because of the reduction of carbon in the fuel. They added up 60% hydrogen by volume and found that BSCO decreased up to 20 g=kW h (60/40 CH4 =H2 ) at = 1:0. In ultra lean region ( 0:4), an increase in BSCO was noted, due to incomplete combustion combined with sharply dropping power [34]. Fig. 5 shows BSCO emission values of some studies. As seen in this gure, a value between 0.65 and 0.8 placed BSCO values at a dramatically low level.

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800 750 BSCO2 (g/kWh) 700 700 rpm 650 600 550
= 0.90 = 0.80 = 0.75 = 0.70

800 750 BSCO2 (g/kWh) 700 900 rpm 650 600 550 0 0.2 0.4 H2/(CH4 + H2) 0.6 0 0.2 0.4 H2/(CH4 + H2) 0.6
= 0.90 = 0.80 = 0.75 = 0.70

Fig. 6. Brake specic carbon dioxide values (BSCO2 g=kw h) versus equivalence ratio for 700 and 900 rpm.

BrakeThermal Efficiency %

Fig. 6 illustrates BSCO2 values versus % addition of hydrogen for 700 and 900 rpm engine speeds [34]. As seen in this gure, with increasing H2 percentage, BSCO2 emission values decrease. They found that BSCO2 increased at lean equivalence ratios, as the power reduction was proportionally greater than the reduction in CO2 concentration in exhaust. Hydrogen addition up to 60% decreased BSCO2 by approximately 250 g=kW h (26%) at identical equivalence ratios. The increase in speed to 900 rpm increased BSCO2 by approximately 25 g=kW h (3%) [34]. BSCO2 values at 700 rpm were lower than at 900 rpm. 3.2. Technical comparison This section can conveniently be divided into four, viz., (1) Comparison in terms of BTE, (2) Comparison in terms of ITE, (3) Comparison in terms of knock characteristics, (4) Comparison in terms of BSFC. 3.2.1. Comparison in terms of BTE Fig. 7 depicts BTE versus equivalence ratio [17,31,34]. As seen in this gure, BTE of a 20% H2 + 80% CH4 mixture is higher than that of 100% CH4 [17]. Since only one cylinder was used in the experiment it is expected that e ciency be lower compared to an experiment using a four cylinder engine. According to experiments in Ref. [34], BTE values are decreasing, while increasing H2 percentage. The highest e ciency values are between 0.7 and 0.9 equivalence ratios. According to the study by Ref. [34], the maximum e ciency is at about = 0:750.8. Also, e ective e ciency had about = 0:750.8 equivalence ratio [17,31,34]. 3.2.2. Comparison in terms of ITE In the study by Karim et al. average indicated output e ciency (average ITE) versus equivalence ratio versus hydrogen percentage is converted to average ITE versus hydrogen percentage versus equivalence ratio. Fig. 8 shows indicated thermal e ciency versus H2 and CH4 mixtures. Fig. 8a shows average ITE at BTDC 10 . The maximum

32 30 28 26 24 22 20 18
* * *

20% H 2 + 80% CNG

* * * * * * * * * * * * * * *

10%

H2 +

NG * 0% C

100% CNG

100% CH 4
CH 4 20%H 2 + 80% 40% H 2 + 60% CH 4 60% H 2 + 40% CH 4

[17] [31] [34]

20% H 2 + 80% CH 4

16 14 12 10 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95 Equivalence Ratio 1 1.05
100% CH 4

Fig. 7. Brake thermal e ciency versus equivalence ratio.

average indicated output e ciency was demonstrated as 40% in 30% H2 + 70% CH4 mixture. According to these gures (a, b, c), maximum average ITE about is 50% in Fig. 9c. While BTDC is increasing, average ITE is increasing. The best spark timing 30 BTDC, the best equivalence ratio = 0:70.8 and the maximum e ciency values are observed at 20 H2 percent [25,26]. 3.2.3. Comparison in terms of knock characteristics Knock characteristics of natural gas and hydrogen mixtures were investigated [23,25,26,36]. Knock resistance characteristics of natural gas are excellent. If concentration of hydrogen is increased signicantly, knock is encountered earlier and involves a wider knocking region despite the widening of the operational limits of engine [25,26]. As a result, in relatively small hydrogen percentages, the knock resistance characteristics of methane are not undermined.

S.O. Akansu et al. / International Journal of Hydrogen Energy 29 (2004) 1527 1539
50 Indicated Thermal Efficiency % 48 46 44 42 40 38 36 34 32 30 0 0.2 0.4 H2/(CH4 + H2) 50 Indicated Thermal Efficiency % 48 46 44 42 40 38 36 34 32 30 0 0.2 = 0.70 = 0.75 = 0.80 = 0.90 0.4 H2/(CH4 + H2) 0.6 0.8 BTDC 30 0.6 0.8 = 0.70 = 0.75 = 0.80 = 0.90 BTDC 10 Indicated Thermal Efficiency % 50 48 46 44 42 40 38 36 34 32 30 0 0.2 0.4 H2/(CH4 + H2) 0.6 0.8 = 0.70 = 0.75 = 0.80 = 0.90 BTDC 20

1535

(a)

(b)

(c)

Fig. 8. Indicated thermal e ciency versus H2 and CH4 mixtures (a, b, c) for BTDC 10 , 20 and 30 , respectively.
900 + = 1.00
= 0.90 = 0.80 = 0.75 = 0.70

300 290 BSFC (g/kWh) 280 + 270 260 250 240 230 0 0.2 900 rpm +

800 700 BSFC (g/kWh) 600 500 400 300 200

2000 rpm 2200 rpm 2400 rpm 2600 rpm CNG Hydrogen

0.4

0.6

100

H2/(CH4 + H2)

2 3 4 BMEP (MPa)

Fig. 9. Brake specic fuel consumption values (BSFC g=kw h) versus equivalence ratio for 900 rpm and versus the BMEP (MPa).

3.2.4. Comparison in terms of BSFC Fig. 9 shows BSFC (g=kW h) values versus equivalence ratio for 900 rpm [34] (a) and versus the BMEP (MPa) [32] (b). According to Ref. [34], the di erence in BSFC (g=kW h) values was almost equal at 900 and 700 rpm. As hydrogen percentage in the mixture increased, BSFC

decreased. At the same time, BSFC values reached minimum when equivalence ratio was about 0.9. In Fig. 9b BSFC values are much greater for natural gas compared to hydrogen. When hydrogen fuel was used at 2200 rpm, BSFC was at a minimum value, but when natural gas was used as fuel, BSFC was minimum at 2600 rpm. Table 1 shows the

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S.O. Akansu et al. / International Journal of Hydrogen Energy 29 (2004) 1527 1539

Table 1 Comparison of some production hydrogen and natural gas prices [9,4259] Production process Cost $/GJ Hydrogen Steam methane reforming (SMR) natural gas Bailey [42] quoted in Adamson and Pearson [9] Ogden et al. [43] quoted in Adamson and Pearson [9] Various authors quoted in Basye and Swaminathan [44] quoted in Adamson and Pearson [9] Basye and Swaminathan [44] quoted in Adamson and Pearson [9] POX oil Steinberg and Cheng [45] Moore and Raman [46], IKARUS Report [47] quoted in Adamson and Pearson [9] Gasication of coal Bailey [42] quoted in Adamson Pearson [9] Bailey [42] quoted in Adamson Pearson [9] ChemEng News [48] and Liepa Borhan [49] quoted in Adamson Pearson [9] Natural gas Notes

4.30 Large scale SMR NG/ hydrogen Large scale SMR NG/ hydrogen 59 4.147.03

1.89

Natural gas cost $1.89 per GJ, 1980 gures No additional information provided on conditions Plant size 1.4 and 6.67 million N m/day, natural gas cost $2.15 and $1.9 per GJ, includes by product steam credits, 1994 and 1997 gures Plant size 0.028 and 0.0028 N m=day, 1997 gure Plant sizes are 36,200, 34,757 and 187=10 GJ/day assuming 24-h day, gures from 1995, 1989 and 1996, respectively First generation KoppersTotzek process, 1980 gures Second generation Koppers Totzek process, 1980 gures Both KoppersTotzek process, cost of coal feedstock $1.91 and $2.27 GJ, respectively, 1979 and 1986 costs, respectively No additional information provided on conditions Plant size 907 and 27 tonnes/day, respectively, gures from 1995 Hydropower feedstock, projected costs from EQHHPP Grid electricity feedstock, 1990 costs PV feedstock, 1990 costs PV feedstock, 1990 costs 0:08 MW capacity, electricity cost 2 cents=kW h, 1978 technology and costs 3:5 MW capacity, electricity cost 2 cents=kW h, 1978 technology and costs

1.92.15

Small scale SMR NG/ hydrogen POX heavy oil/ hydrogen

1027

7.7, 9.13 and 28

and and and and

Coal/hydrogen Coal/hydrogen Coal gasication/ hydrogen

8.50 6.90 4.219.95

Gasication of biomass Ogden et al. [43] quoted in Adamson and Pearson [9] Mann [50] quoted in Adamson and Pearson [9] Electrolysis Sprecht et al. [51] quoted in Adamson and Pearson [9] Dutta [52] quoted in Adamson and Pearson [9] Dutta [52] quoted in Adamson and Pearson [9] Dutta [52] quoted in Adamson and Pearson [9] Hammerli [53] quoted in Adamson and Pearson [9] Hammerli [53] quoted in Adamson and Pearson [9]

Biomass or coal/ hydrogen Biomass gasication/ hydrogen Electrolysis/LH2 Electrolyser/LH2 Electrolyser/LH2 Electrolyser/LH2 Bipolar Electrolyze/ pressurized hydrogen Bipolar Electrolyze/ pressurized hydrogen

810 1323

17.33 26.1 98.8 30.5 20.39 10.15

S.O. Akansu et al. / International Journal of Hydrogen Energy 29 (2004) 1527 1539 Table 1 Continued Production process Cost $/GJ Hydrogen Hammerli [53] quoted in Adamson and Pearson [9] DeLuchi [54] quoted in Adamson and Pearson [9] Basye and Swaminathan [44] quoted in Adamson and Pearson [9] Basye and Swaminathan [44] quoted in Adamson and Pearson [9] Lipman et al. [55] Shoji and Jones [56] Stamber [57] quoted in Rodriges et al. [58] Energy. gov [59] Bipolar Electrolyze/ pressurized hydrogen Electrolyser/LH2 Small scale electrolyze/hydrogen Alkaline water electrolyze/hydrogen 9.61 28.375.6 49.1 2030 6 0.52 12 2.510.9 Natural gas Notes

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3:5 MW capacity, electricity cost 2 cents=kW h, 1978 technology and costs Feedstock solar power, middle-term projected low and cost estimates Plant size 3 kg=day, 1996 gures, 65% e ciency

comparison of some production hydrogen and natural gas prices [9,4259]. According to Fig. 9a, in 80/20 CH4 =H2 mixture BSFC values are about 5% lower than 100% CH4 [34]. According to Fig. 9b, in 100% H2 mixture BSFC values are about 3.5 times lower than in 100% CH4 [42] because of hydrogens light weight than methane. According to Table 1, if we consider costs of these gases, natural gas is cheaper about 2.2 times than hydrogen (considering cheapest cost). The cheapest hydrogen production method is steam reforming and the most expensive one is electrolysis. A mixture of CNG and hydrogen with a low hydrogen percentage has a very reasonable cost. Moreover, in 80/20 CNG=H2 mixture, e ciency is higher about 10% than 100% CNG depending on and spark timing. If we consider e ciency and cheapest hydrogen production, costs of 80/20 and 90/10 CNG=H2 mixtures are 15% and 8% higher than natural gas for = 0:8, respectively.

Natural gas has almost perfect knock resistance characteristics and these characteristics do not signicantly vary with the small addition of hydrogen. BSFC values decrease with increasing hydrogen. Costs of 80/20 and 90/10 CNG=H2 mixtures are 15% and 8% higher than natural gas, respectively. Consequently, from the environmental, economics and technical perspectives, blending natural gas with relatively small amounts of hydrogen can signicantly improve the emission characteristics of internal combustion engines. However, widespread utilization of hydrogen fuel technology also o ers challenges related to production, transport, storage and cost. Currently, hydrogen is more expensive than fossil based fuels. The utilization of hydrogen as a vehicle fuel will be determined by economics. Competitive fuel and operational costs will be required for broad market penetration of hydrogen. But, hydrogens unchallenged potential to reduce greenhouse gases and atmospheric pollutants and opportunity to obtain a fuel produced from a variety of renewable sources will always make hydrogen a major candidate to fulll the world energy demand. Acknowledgements Dr. S.O. Akansu is supported by a TUBITAK, NATO-B2 Scholarship awarded by the Technical Research Council of Turkey. References
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4. Conclusion Results in this study can be summarized as follows: NOx emission values generally increase with increasing hydrogen content. However, if a catalytic converter, an EGR system or lean burn technique are used, NOx emission values can be decreased to extremely low levels. HC, CO2 and CO emissions values decrease with increasing hydrogen percentage. Under certain conditions (30 BTDC and 20% H2 percentage), e ciency value can be increased.

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