hr. J. Hydrogen Energy, Vol. 23,No. 10,pp.

971-975,1998
F) 1998InternationalAssociationfor HydrogenEnergy
Pergamon ElsevierScienceLtd
All rightsreserved.Printedin GreatBritain
PII: so360-3199(97)00141-9 0X%3199,/98 $19.00+0.00

FORMATION AND RESTRAINT OF TOXIC EMISSIONS IN

HYDROGEN-GASOLINE MIXTURE FUELED ENGINES

LI JINGDING,* GUO LINSONGT and DU TIANSHEN*

* Department of Energy Engineering, Zhejiang University, Hangzhou, 310027,P.R. China. 7 Department of Manufacturing
Engineering, City University of Hong Kong, Kowloon, Hong Kong

Abstract-A little amount of hydrogen supplemented to the gasoline-air mixture can extend the flammability of the
mixture, increase the rate of flame propagation, accelerate the burning velocity of the lean mixture, thus improving
the economy and emissions of engines, and enhancing thermal efficiency.
In this paper, the mechanism of forming toxic emissions in spark ignition engines is expounded on basis of the
theory of chemical dynamics of combustion. And the mechanism of which toxic emissionsare restrained in the course
of the combustion of hydrogen-gasoline mixture is discussed. And last, the experimental investigation results of
restraining toxic emissions are introduced. 0 1998International Association for Hydrogen Energy

INTRODUCTION In this paper, the mechanism of forming toxic emis-

Toxic emissions from automobiles have become the
main factors which deteriorate the earth’s environment,
thus more strict emission regulation is mandated in many
areas of the world, especially in some large cities which
possess a great number of automobiles. At present, a
solar car, a battery car and a hydrogen-powered car are
regarded as the most promising substitutes for a pet-
roleum car in order that oil shortages and environmental
pollution can be overcome. But output power of a solar
car is too small for practical use, overweight of a battery
car restricts its application, storage and carriage of hydro-
gen for a vehicle are also difficult items. Therefore, a
“hybrid” car will be a new tendency of developing cars
in future. This kind of car has two fuel systems.When a
car is driven in urban districts, its “non-pollutants” fuel
system will be working. But while it is traveling a long
distance in rural districts, its petroleum fuel systemwill be
working. A car with a hydrogen-gasoline mixture fueled
engines can be considered as an embryonic form of the
“hybrid” car.
Toxic emissions in spark ignition engines can be
restrained by means of accelerating the burning velocity
of the lean mixture. This sort of combustion processcan
be obtained by adding hydrogen to gasoline-air mixture.
This is because hydrogen possessessuch characteristics
as wide flammable range, large diffuse coefficient, quick
burning velocity and low ignition energy.
sions in spark ignition engines is expounded on basis of
the theory of chemical dynamics of combustion. And the
mechanism of which toxic emissions are restrained in the
course of the combustion of hydrogen-gasoline mixture
is discussed. And last, the experimental investigation
results of restraining toxic emissions are introduced.
FORMATION MECHANISM OF TOXIC
EMISSIONS IN SPARK 1GNITlON ENGINES
NO,
NO, includes NO and NO,, but mostly NO, NO2 only
occupies under 10% of NO,. They originate from the
oxidization of N2 in the air under high temperature. For-
mation of NO submits to the extended Zeldovich Prin-
ciple. The reactions are as follows:
02eo-t0 (1)
O+N ,zNO+N (2)
k;
N+02gNO+0
ii (3)
Where reaction rate constants are:

971
912 LI JINGDING et al.

k: = 7.6 x lOI exp (-3800/T) gap effect, incomplete combustion and unburned HC
(Temperature range: 200&5000 K) oxided.
The flame sharp cool includes single surface sharp cool
k; = 1.6x IO” and double surface sharp cool. The former means that
(Temperature range: 300-5000 K) the flame goes out and the burning charge in bounding
k: =6.4x 109T*exp(-3150/T) layer in front of the flame is charged into unburned HC
(Temperature range: 300-3000 K) because heat energy of scattering through the cylinder
wall is more than that of the exoergic flame when the
k; = 1.5x 109T*exp(-19500/T) flame is near to the surface of cylinder. The latter means
(Temperature range: 100&3000 K) that the burning charge in circle gap between the top of
piston and the cylinder wall escapesburning of the first
kf is much larger than k2+,this indicates that activation time flame propagation.
energy of reaction (2) is much higher than that of reaction The gap effect means that the burning charge in circle
(3). Because N which reaction (3) needs is supplied by volume between the piston or piston rings and the cyl-
reaction (2), reaction (2) plays a leading role in forming inder wall and in other gaps goes out becausethe flame
NO. They are usually the main measuresof restraining is sharp cooled in compression stroke, and in expansion
NO declining combustion temperature, controlling 0, stroke, most of gasin the gap volume flows back cylinder,
concentration and shortening reaction period because 50% of it is unburned HC.
reaction (2) requires very high temperature up to 2000- The incomplete combustion occurs under operating
5000 K. conditions of low load and slow speed. Because of the
slow burning velocity, the flame has not spread to round
CO the whole chamber even in exhaust stroke. So a great
In the premixed hydrogen-air flame, CO formation deal of burning charge is cooled sharp and HC is largely
can be described as follows: increased.
Mechanism of HC oxidation is very complex, its reac-
RH-+R-+RO,-+RCHO+RCO-+CO (4) tion rate is approximately as follows:
where R is a hydrocarbon radical.
After having been formed in the combustion process, -WC1 = -6.7 x lO”exp(- 18735/T)X,cXoz@/RT)
dt
CO is slowly oxided into CO*, the reaction is:
(10)
CO+OH$COz+H (5)
where [ ] is concentration (mol/cm3); t is time (s); X,c
where reaction rate constant is: Xo, are respectively molar numbers of HC and 0,; T is
absolute temperature (K); p/RT is item of density
k& = 6.76x 10’0exp(-1102/T) (mol/cm3).
The characteristic reaction time of complete com-
Reaction rate of (5) is mainly affected by the con- bustion is:
centration of OH and H. If gasoline-air mixture is fueled 1 1 d[HC]
in spark ignition engines, formation of OH depends on -=-- (11)
the reactions: HC [HC] dt

co+o,eco+o (6) The higher temperature, the faster oxidation reaction

of HC. Actually, Oxidation of HC still continues in
O+H,O+20H k+ = 8.3 x 10i3exp(- 181OO/RT) exhaust system, which requires a rich 0, environment,
above 600 temperature and excess50 ms stay time.
(7)
CO+OH+C02+H (8) EXPERIMENT
H+O ,+OH+O k+ = 1.8x lO”exp(-8900/RT) An experimental apparatus
(9) The test engine is 165F model gasoline engine made in
It can be found that the rate at which CO is oxided China, whose stroke volume is 0.1261and effective power
into CO, is mainly affected by the concentration of 0,. is 4 PS at 3000 rpm. The test apparatus is shown in Fig.
CO will increase sharp while lacking in O2 (air-excess 1. In order to change components of hydrogen-gasoline
factor GI> 1) mixture within a wide range, two parallel fuel systems
(gasoline-air with a carburetor and hydrogen-air with a
HC
mixed device fuel system)are equipped. When the thi-ottle
valve of the mixed device is closed, the performance of
In gasoline engines, unburned HC is formed because the original engine can be tested, When hydrogen in a
of the flame sharp cool on the surface of cylinders, the high pressure gas cylinder flows into the mixed device
 FORMATION AND RESTRAINT OF TOXIC EMISSIONS 973

Electric
dynamometer
Exhaustgascooler
Waterseparator I I

Air

-P-
war’ Flow meters
analyzers
Fig. 1. Schematicdiagramof experimentalapparatus.

through a pressurereduction valve and a regulating valve,

various hydrogen-gasoline mixture components under
different vacuity of air inlet pipe can be obtained by
means of regulating the throttle valve of the carburetor
and the mixed device.
Fuel mixture consists of hydrogen, gasoline and air,
the component part of gasoline in the mixed device can NO
be indicated by air-excessfactor c(~: wm
as = ‘$,/(G, * -L-o) (12)
4000
where G, is the consumption of air (kg/h); G, is the 3000
consumption of gasoline (kg/h); L,, is theoretical air
quantity of completely burning 1 kg gasoline, 14.9. znffo
The component part of hydrogen can be indicated by
air-excessfactor an:
c[H = G/(G,*Gd (13)
0.6 0.? I.0 I. I ax
where GH is the consumption of hydrogen; LHOis theor- Fig. 2. Emissioncharacteristicswith gasolinefuel.
etical air quantity of completely burning 1 kg hydrogen,
34.42.
The total air-excess factor c+ is:
of regulating supplied gasoline quantity, and hydrogen
~1:= GAG, *L,, + G * -b,,) (14) flow is kept stable. Relative quantity of hydrogen in mix-
ture is increased and the flammable range of mixture is
or widened with decline of load. Emission characteristics on
ax = (@,* EH)/@,+ a”) (15) load at 3000 rpm, hydrogen Row 70 g/h is shown in Fig.
3. Figure 4 shows that emission concentration varies with
Toxic exhaust emissions are measured by means of an load while the engine is respectively fueled by gasoline-
exhaust gas analyzer made in China. Fig. 1 also shows air and hydrogen-gasoline mixture at hydrogen flow 70
an exhaust gas sampling and measuring device. g/h.
Experimental results ANALYSIS OF RESULTS
At first, the original gasoline engine is tested so as to Restraint of NO
obtain comparable data, and its emission characteristics In chain reactions of H oxidation, there is a reaction:
on load at 3000 rpm are shown in Fig. 2.
When testing a hydrogen-gasoline mixture fueled H,+O=H+OH (16)
engine, change of output power is controlled by means where reaction rate constant is:
974 LI JINGDING ef al.

co. NO k+ = 1.0x 10’4

mm wm
- 3000 k- = 2.0 x 10” exp (-23650/T)

Becausehydrogen supplementation makes N product

Fig. 3. Emission characteristics with hydrogen-gasoline mixture
(GH = 70 g/h).
of reaction (2) largely reduced, it is difficult that reaction
(17) moves towards right.
The experimental results show that, in the spark ’
ignition engine fueled by gasoline, maximum NO concen-
tration occurs near air-excess factor CI= 1, amounts to
4080 ppm (seeFig. 4). But in the engine fueled by hydro-
gen-gasoline mixture, NO concentration is about 1 time
lower than the former under all load conditions because
the engine operates in the lean mixture, a, = 1.07-1.72
(see Fig. 3), the burning is accelerated, but combustion
temperature does not go up highly. It can be deemed
that the rate of producing NO is mainly affected by 0
concentration after hydrogen supplemented. NO con-
centration gradually nears that of the engine fueled by
gasoline with increasing load and decreasing quantity of
hydrogen supplementation.

Restraint of CO
Chain reactions of H oxidation are as follows:

H1+M*$2H+M (18)
1 1 1 -\I 1 1 II HC
. bpm t H+O,$OH+O (19)

O+H,+ OHfH k+ = 3.3 x 10’2exp(-8000/RT)

(20)

OH+H,e H20+H k+ = 6.2x 10’3exp(-6000/RT)

t (21)
30 40 37 60 70 80 90 100 ‘.
where M* is an activation radical, M is a radical.
----- gasoline After hydrogen supplementation, chain reactions of
-hydrogen-gasoline mixtun@~=70g/h) CO oxidation are as follows:
Fig. 4. Comparison of emission characteristics with gasoline and
hydrogen-gasoline mixture. CO+OH$C02+H
H+O 2eOH+O
O+H,+OH+H
k+ = 1.8 x 10” i”*exp(-8900/RT)

CO is quickly oxided because OH concentration is

The activation energy of reaction (16) is much lower
than that of reaction (2), thus after hydrogen
supplemented, 0 mainly participates H2 oxidation reac-
tion (16) so that concentration of NO produced in N,
oxidation reaction (2) is erectly reduced. At the same
time, hydrogen supplementation also restrains reaction
of N oxided by OH becauseof the following reaction:
N+OHgNO+H
k-
where reaction rate constants are:
greatly increased after hydrogen supplementation.
On the other hand, the engine fueled by hydrogen-
gasoline mixture can operate in the lean mixture under
all load conditions so that CO concentration goeslargely
down. The experimental results show that, under 30%
rated power, the mixture is very lean, a, = 1.72,CX~
= 2.6,
aH = 5, CO concentration is only 950 ppm, which is 20
times lower than that of the engine fueled by gasoline at
(17) the same load condition. Therefore, it has very notable
effect on restraining CO emission adding hydrogen to
gasoline-air mixture.
 FORMATION AND RESTRAINT
HC emission
Figure 4 shows that whether or not hydrogen is sup-
plemented does not affect the rule of HC concentration
change. HC concentration is minimum under near 70%
rated power. If load is smaller or larger than 70% rated
power, the mixture will become thinner or thicker, and
decline of burning temperature or occurrence of incom-
plete combustion will lead HC increased. After hydrogen
is added, HC concentration somewhat comes down
(about l/5-1/3) under all load conditions because the
engine operatesin the lean mixture, the burning is acceler-
ated and high 0, concentration promotes complete
combustion and HC oxidation.
CONCLUSIONS
(1) Becauseof the characteristics of hydrogen, the lean
mixture can rapidly burn in hydrogen-gasoline mix-
ture fueled engines, thus toxic emissions are
restrained.
(2) When hydrogen is added to gasoline-air mixture,
0 mainly participates H, oxidation reaction so that
concentration of NO produced by N, oxidation reac-
OF TOXIC EMISSIONS 915
tion is about one time lower than when no hydrogen
is supplemented.
(3) Hydrogen-supplemented leads OH concentration lar-
gely increased so that CO oxidation reaction is accel-
erated, and the engine can operate in the lean mixture,
thus CO concentration is about twenty times lower
at the highest point than when no hydrogen is sup-
plemented.
(4) After hydrogen supplementation, the combustion of
the lean mixture speedsup so that HC concentration
goes down l/5-1/3.
Acknolvlr~~menfs-This research was supported by National
Natural Science Foundation of China. Sincere appreciation is
expressed to NSFC.
REFERENCES
1. Jingding, Li, et al., An Experimental .StucJvof Combustion of
Hydrogen/Gasoline Mixtures, SAE-China, 1984, No. 2, l-9.
2. Newell, H. K., Kinetics of engine-gnerated nitrogen oxides
and carbon monoxide. Proceedings of 12th International S.vm-
posium on Combustion, 1968, 603613.
3. Zaw Hein. Kyaw, et a/., Application of the HAJI jet system
for near nitrogen oxide (NO,) elimination in the SI engine,
IMechE Semin., 1993, 5. Worldwide engine emission stan-
dards and how to meet them, 49-55 (Eng.).