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Section IV - Paper 42 - PD 9



i .Yamamoto - K. Kaneko - K. Kuwae - K. Hiratsuka *

Abstract. Synthesis gas can be produced by partial oxi- Résumé. On peut produire du gaz de synthèse par la
dation of natural gas with oxygen using the cylinder of an combustion partielle de gaz naturel avec l’oxygène, dans
internal combustion engine as a reactor. les cylindres d’un moteur à combustion interne comme
Aiming to develop and commercialize this procedure, réacteur.
authors have constructed an eight-cylinder, four stroke, Pour développer cette méthode en vue de l’application
spark ignition engine of 42 litres total stroke volume, and industrielle les auteurs ont construit un moteur à huit
conducted a number of tests including an endurance test cylindres et à quatre temps avec une cylindrée de 42 litres,
of 1000 hours continuous operation. à l’aide duquel ils ont effectué une série d’essais parmi
The measured values for the composition of the produced lesquels une épreuve d’endurance de 1000 heures de
gas and the power output of the test engine coincided marche continue.
with the theoretical values. From natural gas, the test La composition du gaz produit et le rendement du moteur
engine could produce hydrogen-carbon monoxide mixture sont en concordance avec le calcul théorique. En réglant
equivalent to 78 % and mechanical energy corresponding l’opération en vue d’obtenir le maximum de rendement en
to 7.5% of the calorific value, under the conditions of gaz de synthèse, on a récuperé 78% de la valeur calori-
maximum synthesis gas yield. fique du gaz naturel sous forme de valeur calorifique du
The engine withstood an endurance test of 1000 hours mélange hydrogène-monoxyde de carbone produit par le
continuous operation and no troubles were noticed moteur, et 7,5 % sous forme d’énergie mécanique.
during the test. Le moteur s’est très bien comporté à l’épreuve de 1000
The above results clearly prove that the production of heures de marche continue.
synthesis gas by an engine is commercially practicable. Les résultats prouvent.que le moteur à combustion interne
peut être utilisé pour la production industrielle de gaz de

Introduction ducted development work using a single cylinder

large-sized engine of 16.2 litres total stroke volume,
but detailed information was not reported.
In the past, the idea to produce synthesis gas by As t o the theoretical approach, Yamazaki3*4 calcul-
partial oxidation of natural gas with oxygen in the ated the values of the temperature and the pressure
cylinder of an internal combustion engine, and sim- in the combustion chamber, the gas composition
ultaneously to obtain energy, has been considered produced and the power output. The computed re-
already. Recently, this idea arouses interest again. sults’coincided with the experimental data obtained
In the first experiment of this kind, Eastman’ from the test conducted by Yamazaki and his co-
produced hydrogen-carbon monoxide mixture in 1947 worker using a C.F.R. engine.
using a C.F.R. engine. Following this, Szeszich2 con- This work confirmed the possibility to produce
synthesis gas in an engine with considerable effi-
* Authors’ Biographies vide last page ciency.

The aim of our work is to obtain detailed inform-
ation in order to commercialize the process and to
verify the safety and the reliability of the multi-
cylinder semi-commercial engine constructed to c.
conduct research for the above purpose. Y

Thermodynamics of the Methane-Oxygen Cycle

The reaction producing hydrogen and carbon mon- m
oxide by incomplete oxidation of methane with oxy-
gen is described by the equation: -

CH4 4-l / z 0 2 = CO -b 2Hz 4-8,260 Kcal/mol . . . . . . . (1)

However, the reaction (1) cannot be realized in
the cylinder of an engine because of shortage of ..
oxygen. The actual reaction is: -
ae o9 1.0
CHq -!- nO2 = aH2 f ß C 0 f y C 0 z f 6Hz0 f ~ 0 f2qCH4

. . . . . . . (2) MIXING RATIO &/CH4

Here, the ratio of oxygen to methane (n) is > O S . Figure 1
As a first step, a theoretical calculation was made RELATIONS BETWEEN O X Y G E N - M E T H A N R A T I O A N D
of the cycle of an internal-combustion engine run ( I N T A K E TEMPERATURE = 25 o C )
by incomplete combustion of an oxygen-methane
mixture. The composition of the burnt gas in the
cylinder was calculated assuming that the gas is in
equilibrium, and that no hydrocarbons except me-
thane are present.
An internal energy-entropy diagram was designed
and used for determining the temperatures and the Yrn
power output of the engine graphically. Some ty- w
pical results are shown in Fig. 1 and Fig. 2. a
Fig. 1 illustrates the values of the temperature in v)
the cylinder after the explosion and the expansion w
stroke. a
Fig. 2 shows the mechanical energy produced from
1 m3 methane, and the mean effective pressure
when the intake pressure is 1 kg/cm2 absolute.
For an engine with the compression ratio of 1:7 run
with a stoichiometrical mixture of hydrocarbon-air
for complete combustion at an intake pressure of
1 kg/cm2, the gas temperatures after the explosion
and the expansion stroke are 2910'K and 1950'K I I
0.7 O8 0.9 I.o
respectively and the mean effective pressure is
11.6 kg/cm25. MIXING RATIO 102 /CH4 1
In an engine run with an oxygen-methane mixture
Figure 2
- ratio of oxygen to methane 0.88 - the tempera- THEORETICAL P O W E R A N D M E A N EFFECTIVE
ture of the burnt gas is almost the same as with the PRESSURE A T S U C T I O N PRESSURE 1.0 kglcm2

430 IV142
hydrocarbon-air mixture while the mean effective volumes of hydrogen and carbon monoxide derived
pressure becomes twice as large as in the latter from a unit volume of methane are increased by
case. lowering the ratio of oxygen to methane. Maximum
By selecting an appropriate ratio of oxygen to yield was obtained at 02/CH4 = 0.80 in the experi-
methane, it is possible to reduce the temperature ment.
and the pressure within the combustion chamber to The reason why this experimental value differs
the level of those of an ordinary type gas engine. from the calculated value was that a certain amount
The performance of the engine which produces of methane remained in the experiment.
synthesis gas is characterized by the thermal effi- The most economical operating conditions in the
ciency of reformation and the thermal efficiency of ordinary partial oxidation process are such that max-
the combustion engine. imum yield of synthesis gas is obtained with min-
Fig. 3 illustrates the relation between the ratio of imum oxygen requirement. In the engine process an
increase of the ratio of oxygen to methane will
cause an increase of the power output. The propor-
tion of utility gas (hydrogen and carbon monoxide)
in the dry product gas is almost unaffected by the
mixing ratio. According to Szeszich'j, the power out-
put of the engine operated at Oz/CH4 = 0.72, satis-
fies 30 to 50 O/o of the power required for ammonia or
methanol synthesis. So, it is necessary to keep the
z ratio of oxygen to methane low.
z The ratio of oxygen to methane remarkably af-
II. fects the performance of the engine. If the ratio
is below 0.75, misfiring occurs due to spark plug
fouling, and if the ratio is higher than 0.95, knock-
J ing or pre-ignition occurs. In both cases, it is im-

i I
possible to run the engine. Therefore, the proper
range for the ratio of oxygen to methane is from
0.75 to 0.95.
soi lo
O1 aa as 1.0 It is necessary to supply natural gas and oxygen
separately through different intake manifolds in or-
der to prevent explosion of the supplied gas in the
Figure 3 suction pipe. However, the adoption of this con-
RELATIONS BETWEEN M I X I N G R A T I O , struction may cause unequal distribution of natural
A N D T H E R M A L EFFICIENCIES gas and oxygen to the cylinders, which limits the
(COMP. R A T I O 7 : 1 I N T A K E TEMP. = 258/o)
practicable range of the mixing ratios.
Considering the above points, 0.82 ratio of oxy-
oxygen to methane and the efficiencies, the com- gen to methane was selected as the standard oper-
pression ratio being 1:7, and the intake temperature ating condition for the test engine. Using mixed gas
being 25' C. of this ratio, the power output of a unit volume of
The maximum synthesis gas yield was found at oxygen-methane mixture is 1.8 times as large as
a ratio of oxygen to methane of approx. 0.75. that of a stoichiometrical hydrocarbon-air mixture.
It was decided to reduce the intake pressure to
0.35 kg/cm2 absolute, to obtain a brake mean effec-
Design and Operation of the Test tive pressure of 5.0 kg/cm2, a normal value for inter-
nal combustion engines. 500 r.p.m. were diosen as
Before the test engine was constructed, a number rotating speed, considering that a low piston speed
of experiments were conducted in a C.F.R. engine would improve the durability of the engine, and
in order to obtain operational data. The most im- reduce the percentage for unburnt methane and
portant factor is the ratio of oxygen to methane. The oxygen in the produced gas. As a test engine, a

IVf42 431
diesel engine with eight cylinders, 175 mm bore, and It was estimated that the engine would take in
220 mm stroke, modified into a four stroke spark- 125 m3 natural gas and 100 m3 oxygen per hour,
ignition engine, compression ratio 1:7, was used. and put out 285 ms hydrogen-carbon monoxide mix-
The test engine has two intake manifolds for na- ture per hour, along with 115 PS - under standard
turel gas and oxygen, respectively. The suction operating conditions. The maximum capacity of the
valves were designed to avoid mixing of the two test engine is 250 PS at 650 r.p.m., and the max-
gases till they were introduced into the cylinders. imum speed is 750 r.p.m.
Special valves were fixed to each suction port, to The design of the test apparatus is illustrated in
adjust the gas flow and distribute it equally to each Fig. 4. Both natural gas and oxygen are compressed
cylinder. to 1.3 kglcm2 absolute and - controlled by auto-


Figure 4

matic flow regulators - drawn into the cylinders partially overcome by adjusting the control valves
through individual manifolds. of the gas flow to the cylinders and by this means
To avoid the danger of flash ba& at the start, minimizing the difference of exhaust temperatures.
the engine is started with a mixture of natural gas However, the distribution is influenced by the run-
and air as in an ordinary gas engine. The air is ning conditions, mainly by the engine speed, and
replaced then by oxygen. it was impossible to make it perfectly equal.
Therefore, the suction system was improved, and
The produced gas flows into a cooling tower, an almost satisfactory result was obtained. Engine
where it is washed and cooled, and then exhausted operation became possible within the range from
through a chimney into the air. The power is ab- 0.75 to 0.95, ratio oxygen to methane, the contents
sorbed by a hydro-dynamometer. of methane and carbon in the produced gas were
The feed gas distribution is an important problem reduced, and flash back ceased to occur at any engine
for multicylinder engines. Due to unequal distribu- speed.
tion, misfire occurred in some cylinders while high The test engine could be operated with natural
exhaust temperatures were recorded in the other gas-air mixture and it produced up to 150 PS with-
cylinders due to knocking etc. and in some extreme out any difficulty. Table 1. shows typical results
cases flash back took place. These difficulties were of operation with natural gas-air mixture.

432 IV142
Typical operational data of the test
engine in the case of complete combustion


Engine Speed (r.p.m.). ............. .. 390 500 +& I

on oso WS ono
Flow Rate of Air (Nm3/h) .......... .. 280 272
Flow Rate of Natural Gas (Nm3/h) .. . . 32,6 28,2
Relative Fuel-Air Ratio ........... . . 0,94 1,05
Brake Power (PS) ................. . . 99 80
Thermal Efficiency (yo)............ . . 27,5 24,6
Exhaust Temperature (" C) ......... .. 533 568

Test Results

The semi-commercial type test engine was oper-

ated with natural gas (containing 94.8'10 methane,
2.3 O / o of carbon dioxide, 2.7 OJO of nitrogen, 0.2 O10 of
oxygen) and oxygen (containing 97,2 of oxygen
and 2.8'10 of nitrogen).
Samples of the produced gas were collected by
the sample collector attached to the exhaust port
behind each exhaust valve, or by the sample
collector fixed to the outlet of the exhaust manifold.
The collected gas was analyzed b y gas chromato-
graphy. Figure 5
Since it proved difficult to measure the quantity RELATIONSHIP BETWEEN G A S COMPOSITION A N D
O X Y G E N I M E T H A N E R A T I O S U C T I O N PRESSURE 0.3 k g l
of steam contained in the produced gas, it was com- cm2 A B S . DOTTED LINES S H O W T H E C A L C U L A T E D
puted by carbon and hydrogen balance, and the oxy- PRODUCT G A S C O M P O S I T I O N S
gen balance was used as a check.
The carbon in the produced gas was collected by
impinger, and weighed after drying as a solid piece. ponding to the ratio oxygenlmethane from 0.78 to
The carbon deposits in dry gas were 0.90. These temperatures were lower than the ex-
haust gas temperatures of ordinary type gas engines.
0.2g/m3at Oe/CH4 = 0.90 and 0.5 g/m3at OnICH4 = 0.80. Fig.6 illustrates the power output of the test en-
gine. Theoretically, the power output from 1 m3 of
Fig. 5 illustrates the relationship between gas methane varies within the range from 1,4 PS to 1,8
composition and the ratio oxygenlmethane. Dotted PS, if the ratio oxygenlmethane varies from 0.75 to
lines indicate the computed values. 0.90. Actual measurements, however, were in the
Test results are in good agreement with theoTet- range of 0.95 to 1.2 PS, the reason being that a
ical values - apart from the fact that considerable certain portion of the power is absorbed by mech-
quantities of unburnt methane and oxygen were anical friction. The measured outputs agree with the
found which were, however, considered negligible theoretical values, if it is assumed that the indicated
in the calculation. mean effective pressure is 95'10 of the theoretical
No influence of the rotating speed and the intake value and that the friction mean effective pressure
pressure on the gas composition could be observed. is 2.0 kg/cm2.
The temperatures of the exhaust gas were meas- Fig.6 shows that 70°/o of the theoretical power,
ured by thermocouples inserted into the exhaust or 7.s0/o of combustion heat of methane are avail-
ports; they varied from 400' C to 55OoC, corres- able as brake pressure under standard operating

IV142 433
conditions, provided that the brake mean effective
pressure is 5.0 kg/cm2.
Fig. 7 illustrates the measured thermal efficiency
of reforming at an intake pressure of 0.3 kg/cm2
absolute. The figure shows that the efficiency is in
the range from ?O to ?8O/o.

Endurance Test

Since the engine used in this synthesis gas process

has to withstand long continuous operation, a higher
durability than in the case of ordinary type engines
must be guaranteed. At the same time, the quantity
and the composition of the produced gas and the
power output are required to be constant. The
operation of the engine must be smooth and trouble
such as carbon accumulation, explosion in the suc-
tion port or crankcase should be avoided.
To obtain information regarding these problems,
a 1000 hours endurance test was carried out. The
operating conditions for this test were: oxygen-me-
Figure 6 thane ratio, 0.82; intake pressure 0.30 kg/cm2, and
RELATIONS BETWEEN P O W E R OUTPUT, SUCTION the engine speed 650 r.p.m. The engine produced
PRESSURE A N D O X Y G E N - M E T H A N E R A T I O 340 m3/h synthesis gas and 125 PS under these
(ENGINE SPEED: 500 r.p.m., IGNITION TIME: loo B.T.D.C.) conditions.
The temperature and the composition of the pro-
duced gas, engine speed, power output, flow rates of
reactants etc., were measured every three hours.
During the experiment only the flow rates of natural
gas and oxygen were controlled and the above
values were unchanged throughout the test, which
was successfully carried through without any trouble
or damage. After the test, the engine was dismantled
and a close inspection was made.
The carbon accumulation in the cylinder or piston
was similar to that of an ordinary diesel engine.
Wear of cylinder liner and piston was normal.
O The suction or exhaust valves were not over-
heated. The ignition system worked accurately
throughout the whole of the test.
The spark plugs had been considered as one of
the weakest parts of the engine, but no traces of
overheating or fouling were found on the sixteen
O .75 aeo 0.85 0.90 plugs, inserted in eight cylinders.
The above test confirmed that the spark plugs
can stand the working conditions, if they are re-
Figure 7 placed at every periodical examination.
MEASURED T H E R M A L EFFICIENCY OF REFORMING; No accumulation of carbon was found at the ex-
SUCTION PRESS. = 0.3 k g / c m 2 A B S . haust manifold or in the exhaust pipe. Contamination

434 IV142
and consumption of lubricating oil proved to be nor-
mal. TABLE 3
All these results confirmed that the engine can The costs of raw materials and utilities
stand continuous operation with natural gas-oxygen +
for the production of lo00 Nm3 CO H, (Dollars)
Engine Partial Steam
Process Oxidation Reforming
Economical Considerations
Natural Gas (0,8e/Nm3) 3,38 3,16 2,04
To examine the economical aspects of synthesis Catalyzer (250e/kg) . . . . . . ... 0,28
gas production by gas engine, the authors estimated
the consumptions of raw material, energy and wa- Utilities
ter and compared this process with other synthesis Fuel (0,8e/Nm3) ......... ... 1,68
Power (0,8e/kWh) .... - 0,63 0,84 0,18
gas production processes. As typical synthesis gas Steam (9,O!z/t) ........ - 0,21 - 0,47 -0,88
production processes, steam reforming and partial Boiler Water (i,&+). . 0,OO 0,Ol 0,02
oxidation were selected for comparison?, 8. Cooling Water (0,8e/t) 0,06 0,oo OJO
Total ................. 2,60 3,54 3,42

The product gas compositions and the material and utility Synthesis gas is an important base material for
consumptions for the production of 1000 Nm3 CO H, + the production of a number of important chemicals,
Engine Partial Steam
and its composition can be modified according to
Process Oxidation Reforming the use. In this comparison, only the production
cost of the crude gas is considered, irrespective of
Product Gas Composition the quantity and the properties of impurities.
H, (vol yo)........... 60,9 75,6 In Table 2, the consumption of raw materials, chem-
CO ................. 34,5 20,5 icals and utilities are shown along with the by-pro-
CO, ................. 23 394 ducts from 1000 m3C0 +
H2 production, Table 3
CH,. ................ 0,4 03 shows the cost of raw materials and utilities to pro-
o, .................. ... ... +
N, .................. 1,4 ... duce 1000m’CO H2.
H,/CO .............. 1,76 3,69 The engine method is the cheapest among the
CO H,/CH,. ....... 2,52 3,92 three, mainly due to the recovery of electrical
Materials energy.
Natural Gas (Nm3) ... 424 396 255
Catalyzer (kg). . . . . . . . . . . ... 0,11
Fuel (Nm3) . . . . . . . . . . . . . ... 195
Power (KWh) . . . . . . . . . . . 140 30 To develop a synthesis gas production process
Steam (kg) . . . . . . . . . . . . . 145 230 using a gas engine, a semi-commercial type, multi-
Boiler Water (t) ...... 0,25 0,52 0,98 cylinder spark-ignition engine was constructed and
Cooling Water (t)..... 8,O 0,3 13,O
a number of tests, including a 1000 hours endurance
By-products test, were carried out.
Power (KWh) ........ 105 ... ...
The following results were obtained:
Steam (kg) .......... 240 660 1210
1. The test engine can be operated within the range
Notice : of 0.75 to 0.95 ratio oxygen-methane without any
a) Natural gas contains 100% methane.
b) Engine process and partial oxidation process are combined
with an oxygen plant, which produces 95% pure oxygen. 2. Hydrogen and carbon monoxide are produced with
C) Engine is operated by gas mixture of O,/CH, = 0,80. 78O/o thermal efficiency, and 0.75 K W h of power
*) Total output is 305 KWh. 200 KWh is used to produce are recovered from 1 m3 methane, at maximum
synthesis gas yield.

IV142 435
Hiratsuka, Kosai / Japan / Mechanical Engineer / Department of
3.The temperature and pressure in the cylinders Mechanical Eng., Tokyo University / Group Head of 2nd Sect., Research
can be reduced to those of an ordinary engine b y Department, Kasado Works, Hitachi, Ltd.
arranging appropriate operating conditions.
4.The engine withstood 1000 hours continuous oper- This paper was presented on June 25, 1963, by
ation without any trouble. At constant flow rates K. HIRATSUKA.
of natural gas and oxygen, the quantity and com-
position of product gas and the power output were Discussion
kept unchanged.
From the above it is concluded that synthesis L. W. TER HAAR (Bataafse Internationale Petro-
gas production by gas engines is one of the most leum Mij., The Hague, Netherlands). I understand
economical processes being sufficiently reliable from the description of the engine process that gas
for industrial practice. is delivered at about atmospheric pressure. I take it
that the comparison given in table 2 is based on sudi
a low operating pressure and therefore would point
References out that the conclusion, that utility-wise the engine
method would be the cheapest, i s only valid for sub-
1. Eastman, B., Barber, E., and Reynolds, B.; Improvement of stantially atmospheric delivery pressures.
process and apparatus for the manufacture of Synthesis With the utility consumption shown for the partial
gas. U S . Pat. 722, 742 (1947). oxidation route gas delivery at about 30 kg/cm2 is
2. Szeszich, L.; Herstellung von Synthesegas im Otto-Motor attainable. For a fair comparison with the engine
bei gleichzeitiger Arbeitsgewinnung. Chemie-Ing.-Techn. process the latter should be charged with an addi-
28 Nr. 31 190 (1956). tional power consumption of about 225 KWh per
3. Yamazaki, K., and Mitsui, H.; Reforming of natural gas 1000Nm3 for compression of product gas to 30 kg/cmz,
by an engine. J. Industrial Chemistry (Japan) 62 No. 11, when the gas is to be used for synthesis at high
1681 (Nov. 1959).
pressures. This would increase the total materials
4. Yamazaki, K., and Mitsui, H.; Reforming of methane (na- plus utility cost for the engine process to 3,95$/
tural gas) by an engine, (Continued) J. Industrial Che-
1000 Nm3 for a gas delivery pressure of 30 kg/cm2,
mistry (Japan) 63 No. 8, 1361 (Aug. 1960).
which figure compares unfavourably with those of
5. Tanaka, K., and Awano, S.; Calculation of the gasoline-
the conventional routes.
cycle using the entropy-diagram of burnt gas. J. Soc.
In view of the above I should like to know whether
Mech. Engr. (Japan) 39 No. 230315 (June 1936).
the engine process could be carried out at much
6. Szeszich, L.; Die Anwendung der Gasmaschine in Syn-
thesebetrieben zu gleichzeitiger Erzeugung von Syn-
higher pressures than mentioned in the paper.
thesegas und Kraft durch partielle Verbrennung von Secondly, I should appreciate to learn what type
Methan mit Sauerstoff. 5th World Power Conference. of applications for the engine process the authors
84 E/9. (1956). have in mind.
7. James, G.R.; Which process best for producing hydrogen. K. HIRATSUKA replies. The cost estimation is
Chem. Engr. 63No. 25, 161. (Dec. 12, 1960). very complicated and is affected by many factors.
8. Singer Jr., S. C.,and Ter Hanr, L. W.; Reducing gas by For simplicity, we made the comparison of produc-
partial oxidation of hydrocarbons, C. E. P. 53, No. 7, 68 tion cost based on atmospheric operating pressure.
(July 1961). I admit that when it is based on a n operating pres-
sure of 30 kg/cm2, the additional power to compress
Authors' Biographies
synthesis gas up to 30 kg/cm2 is needed.
Yamamoto, Tamechika / Japan / Gas Chemist / Doctor of Engin., But the increase of utility cost at high operating
Hiroshima University I Director of Research Laboratory, Japan Gas-
pressure is common to ail processes. As to the partial
Chemical Co. Incorporation.
Kaneko, Kyozo / Japan / Gas Chemist / Department of Applied Chem.,
oxidation process, for example, a n additional power
Yamagata University / Chief of 3rd Sect. Research Laboratory, Japan consumption of about 90 KWh is necessary to com-
Gas-Chemical Co. 1ncorporat:on. press methane and oxygen from atmospheric pres-
Kuwae, Kazuo / Japan I Mechanical Engineer I Doctor of Engin., Kyoto
University / Assistant Manager of Rolling Stock Department, Kasado
sure to reacting pressure (which is neglected in
Works, Hitachi, Ltd. Table 2).

436 IV/42
Therefore, if an operating pressure of 30 kg/cm2 is As to the first question, I think that a gas engine
considered, additional power consumptions are 170 can be operated at increased delivery pressure of
K W h for the engine process and 90 KWh for the par- 2-3 kg/cm2 abs. But power recovery is reduced by
tial oxidation process; then the total materials plus increasing delivery pressure, so it is no use operating
utility costs become: at high pressure.
3.96 $/lo00 Nms for the engine process and And to the second, the engine process could be
4.26 $/i000 Nm3 for the partial oxidation process. applied to all the fields where hydrogen or synthesis
So, also when operation at high delivery pressure gas is wanted, especially in cases where the cost of
is considered, I think, the conclusion that the engine power is high and the cost of natural gas is low, and
process is favourable, need not be changed. a gas delivery of 1,000-10,000 Nm3/h is needed.


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