Int. j. eng. sci., Vol(3), No (11), November, 2014. pp.

114-119

TI Journals

International Journal of Engineering Sciences

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ISSN:
2306-6474
Copyright 2014. All rights reserved for TI Journals.

An Investigation on the Effects of using Formaldehyde as an Additive

on the Performance of an HCCI Engine Fueled with Natural Gas
Khosrow Gholaminejad
Department of Engineering, Islamic Azad University, Sari, Iran.

Alireza Majidian *
Department of Engineering, Islamic Azad University, Sari, Iran.

Omid Jahanian
Department of Mechanical Engineering, Babol University of Technology, Babol, Iran.
*Corresponding author: A_majidian@yahoo.com

Keywords

Abstract

HCCI
Additive
Formaldehyde
Single Zone

Homogeneous charge compression ignition (HCCI) combustion is a spontaneous multi-site auto ignition of a lean
premixed fuelair mixture, which has high heat release rate, short combustion duration and no evidence of ame
propagation. In this paper, the effect of additives such as formaldehyde (CH2O) for the control of ignition in naturalgas HCCI engines have been investigated by adopting a single-zone model in Chemkin Pro software. The chemical
kinetic mechanism incorporated the GRI-3.0 mechanism that considers 53 species and 325 reactions. It was found that
an additive-free mixture did not ignite for the intake temperature of 315 K. A mixture containing a small quantity of
additives at the same temperature was ignited. The results demonstrate the role of formaldehyde on the start of
combustion, Indicated work, imep and emissions. Overall, the enhanced reactivity of CH4 in the presence of small
amounts of additives could be used in HCCI engines fueled with methane to alleviate the high intake temperature
requirements. Single zone kinetic modeling results show the trends consistent with the experimental results.

Introduction
Homogeneous charge compression ignition (HCCI) engines are being considered as a promising alternative to the existing spark ignition (SI)
and compression ignition (CI) engines. HCCI engines have the potential in reducing the emissions of nitrogen oxides (NOx) and particulate
matter (PM), while maintaining high thermal efficiency. The HCCI engine concept promises to combine the advantages of both CI and SI
engines, while minimizing their drawbacks. In an SI engine, the charge is well mixed and then introduced into the cylinder which minimizes
particulate emissions. In a diesel engine, it adopts compression ignition and has no throttling losses, which leads to high efficiency. However,
unlike either of these conventional engines, combustion occurs simultaneously throughout the cylinder volume rather than forming a flame front.
HCCI engines have the potential to be lower cost than diesel engines because they would likely use a lower-pressure fuel-injection system. The
homogeneous lean burn operation associated with HCCI engines will yield lower gas temperatures and hence NOx, as compared to both SI and
CI counterparts [1]. Furthermore, un throttled part load operation eliminates pumping losses leading to improved fuel economy over SI engines.
As the HCCI concept operates on the premise of auto ignition, this allows the use of elevated compression ratios (1925:1).
Conventional diesel fuel for HCCI could pose several problems arising from inherent physical and chemical characteristics. For example, in
order to achieve a homogeneous diesel/air mixture, early injection timings are required, because the vaporization of diesel fuel is poor. Early fuel
injection tends to splash the spray at the wall of the cylinder. This aggravates the formation of a homogeneous mixture, thus, emissions of THC,
CO, and PM will be increased and the engine thermal efficiency will be decreased [2].
A natural-gas fuel is an alternative for diesel fuel as it easily forms a uniform mixture. The application of natural- gas to an internal-combustion
engine should be by way of compression ignition if high thermal efficiency and low NOx emission are expected. However, the auto ignition of
natural-gas under diesel-like conditions requires temperatures as high as 12001250 K [3]. This high temperature requirement mandates that
either a high compression ratio or a high intake air temperature be used, both of which have negative effects on engine performance and
durability.
Although recent investigations on HCCI combustion appear promising, several problems can appear. The ignition timing is very difficult to
control and is considered as one of the barriers in realizing the engine. Therefore, controlling the ignition timing over a wide range of conditions
is challenging. Several methods have been proposed to control HCCI combustion: varying the amount of exhaust gas recirculation (EGR) so that
the auto ignition temperature of the fuel is reached during the compression stroke. This can be done by closing the exhaust valve early [412]
using variable valve timing to change the amount of hot exhaust gases retained in the cylinder. This technique is particularly attractive because
its time response could be made sufficiently fast to handle rapid transients. Although this technology has shown strong potential, performance is
not yet fully proven, and cost and reliability issues must be addressed. The control of ignition timing could be also achieved either by addition of
promoters [3, 13 15] (additives reducing ignition delay time) or blending low cetane number fuels (such as natural-gas and methanol) with high
cetane number fuels [2,5].
The aim of the present work is to investigate the effect of several potential additives on the ignition timing of a natural- gas HCCI engine. The
effect formaldehyde (CH2O) on the ignition timing is investigated by Chemkin Pro software.

Materials and methods

In the developed zero-dimensional model, the whole combustion chamber is considered as a control volume. Energy and mass conservation
equations should be solved simultaneously for this system. The energy conservation equation for this control volume can be described as,

Equation (1) can be rewritten for the mixture of several chemical species as,

(1)

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An Investigation on the Effects of using Formaldehyde as an Additive on the Performance of an HCCI Engine Fueled with Natural Gas
International Journal of Engineering Sciences Vol(3), No (11), November, 2014.

(2)

As Q is only due to heat transfer to cylinder wall and the mixture is a perfect gas,

(3)

By separating the temperature terms, the first differential equation of the model can be obtained,

(4)

This equation describes that the in-cylinder temperature variations, originate from two sources:
Energy transfer through control volume border
Variation in chemical composition of the sys-tem
The mass conservation in chemical reacting systems is defined as the conservation of chemical elements. The rate of mole fraction variation of
chemical species can be computed as,

(5)

Equation (5) should be written for every chemical component and this set of equations must be solved simultaneously with equation (4). A
detailed chemical kinetics mechanism is needed to determine the production/consumption rate of each chemical component ( ). Now, there is a
need for another differential equation to enclose the differential equations sys-tem. This equation defines the rate of variations in combustion
chamber [16] via a slider-crank formula,
=

1+

+1

(6)

The Mass Action rule [17] explains the reaction rate for each direction of an equilibrium reaction depends on reactants' concentration and their
stoichiometric coefficients. Therefore, the reaction rate is,
[ ] [ ]

[ ]

(7)

The rate constant k is determined by Arrhenius relation in equation (8).

(8)

Each chemical reaction mechanism consists some primary reactions which are either simple or with a third body. A simple primary reaction can
be assumed as,

= 1,2, ,

(9)

For each simple primary reaction, the reaction rate equation turns to,
=

[ ]

[ ]

(10)

Some primary reactions need a third body to be done. As the concentration of the third body affects the reaction rate, it differs from equation
(10) and should be written as,

(11)

The third body concentration includes the concentrations of all species due to their enhance factor. Therefore, the reaction rate for these types of
primary reactions is,
=

[ ]

[ ]

(12)

The coefficients can be obtained from different sources like NASA polynomials [18]. So the production/consumption rate of each chemical
component can be calculated as,
=

(13)

For defining , it is common to use Woschni heat transfer model for traditional inter-nal combustion engines, but due to the rapid combustion
period of HCCI engines, a modified relation [19] has been used in this paper. This modified model describes,

= (

(14)

where the convection heat transfer coefficient is,

= 129.8

( ) = 3.34 10

2.28
(

+ ( )

The engine specifications assumed in this research are shown in Table 1.

(15)

Khosrow Gholaminejad, Alireza Majidian *, Omid Jahanian

116

International Journal of Engineering Sciences Vol(3), No (11), November, 2014.

Table 1. Main characteristics of the Volvo TD100 1-cylinder [20]

Engine geometric properties
Displaced volume
1600 cm3
Bore
120.65 mm
Stroke
140 mm
Connecting rod length
260 MM
Engine speed
1000 rpm
Trapped compression ratio(at IVC)
19:1
Intake valve close
13 ABDC(at 1 mm lift)
Exhaust valve open
39 BBDC(at 1 mm lift)

Formaldehyde is the simplest aldehyde in organic compounds category with chemical formula CH2O. It is one of the intermediate species of
natural gas combustion mechanism. It can in-crease the combustion reaction rates when used as an additive.
Table 2 shows the physical properties of formaldehyde in comparison to major gases in natural gas composition. Formaldehyde is categorized as
a hazardous material and it should be used un-der tight legislations. According to EPA regulations [21], the allowed quantity of formaldehyde in
air is 16ppb.
The simulation is started at IVC where fresh charge at specified pressure, temperature and equivalence ratio is inducted into the cylinder and
stopped at the end of the expansion stroke. The cylinder wall, piston and head are all assumed to be at a uniform temperature of 422 K and the
equivalence ratio is 0.259 in all conditions.
Table2. Formaldehyde properties in comparison to major gases in natural gas composition [21]
Properties
Chemical Structure
Molar Weight (g/mole)
Auto ignition Tem. (K)
Explosive Limits (%)

Formaldehyde
CH2 O
30
430
7-73

Methane
CH4
16
595
5-15

Ethane
C2H6
30
515
3-12.5

Propane
C3H8
44
470
2-9.5

The present analysis considers a single-zone model that ignores spatial variations in the combustion chamber, treating heat loss as a distributed
heat transfer rate, proportional to the temperature difference between the average gas temperature and a time-averaged wall temperature. This is
a drastic simplification of the actual condition within a combustion chamber. In particular, the boundary layer, which contains significant amount
of mass, must be at a lower temperature than the bulk gas near TDC. Due to the assumed temperature uniformity, our estimates of burn duration
and the heat release processes will be shorter than in experiments. That is, the boundary layer and crevices will always react last and extend the
heat release rate compared to this simulation.
Peak cylinder pressure and rate of pressure rise thus can be over-predicted with the single-zone model, and the model cannot accurately predict
CO and hydrocarbon emissions, which primarily depend on crevices. However, predictions of start of combustion and NOx, which depend on the
peak temperature of the core gases inside the cylinder, have been shown to be determined with reasonable accuracy [5]. Since the aim of this
study is basically to investigate the effect of different formaldehyde on the ignition timing of a natural-gas HCCI engine, the single-zone model
can reasonably capture the relative effectiveness of various additives.

Results and discussion

First, the influence of inlet air/fuel temperature without adding additives has been studied.
Figures 1 and 2 show the pressure and temperature trends for five different temperatures at IVC.

345 K

360 K

375 K

350
300
Pressure(atm)

250
200
150
100
50
0

-30

-20

-10

0
CAD,ATDC

10

20

Fig. 1. In cylinder pressure variation for five different inlet temperatures at IVC

30

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An Investigation on the Effects of using Formaldehyde as an Additive on the Performance of an HCCI Engine Fueled with Natural Gas
International Journal of Engineering Sciences Vol(3), No (11), November, 2014.

345K

360K

375K

390K

405K

Temperature(K)

2000
1800
1600
1400
1200
1000
800
600
400
200
0
-30

-20

-10

10

20

30

CA,ATDC
Fig. 2. In cylinder temperature variation for five different inlet temperatures at IVC

As seen in the figures, there is no combustion in the case TIVC= 345K because the mixture pressure and temperature do not reach the auto
ignition limit. In such a case, it is usually noted that the engine is out of its operating range.
In case TIVC=375K, the combustion occurs slightly after TDC. By increasing the inlet temperature to TIVC=390K, the combustion occurs before
TDC and the maximum value of pressure and temperature rises. It can be seen that the combustion phenomena is highly concerned to initial
temperature and it can be used as a control parameter. Inlet air preheating and using hot EGR are some available ways to set the initial
temperature of the mixture. In other hands, it should be mentioned that increasing inlet mixture temperature would lead to lower engine
volumetric efficiency and amount of fuel interring the cylinder.
Formaldehyde has a lower auto ignition temperature in comparison to other natural gas components, therefore it is logical that using
formaldehyde as an additive would advance the HCCI combustion. Fig. 3 shows the effects of adding formaldehyde on the combustion case.

100%CH4
97%CH4,3%CH2O
350

99%CH4,1%CH2O
96%CH4,4%CH2O

98%CH4,2%CH2O
95%CH4,5%CH2O

300
Pressure(atm)

250
200
150
100
-5

-3

50
-1

1
CAD,ATDC

Fig. 3. The effects of using formaldehyde on pressure trend at TIVC=375K

Results show that even adding 1% formaldehyde to natural gas at will lead to combustion whereas the natural gas would not individually ignite
in this condition. With 1% additive, the combustion starts before TDC. Adding more formaldehyde would end in more advanced combustion.
For a detailed study on the effects of using formaldehyde as an additive on the performance of an HCCI engine, the engine major parameters
such as gross values of indicated work and power, mean effective pressure, and NO x emissions have been considered. (Fig. 4)
The amount of additive was held in 1-5% range according to previous experiments [10, 11].
Comparing engine power and output work in different cases shows that these parameters rise slowly by increasing additive amount up to a
maximum value then a reverse trend is observable. The maximum value obtained with 2% formaldehyde. Although specific fuel consumption
linearly increases by adding more formaldehyde but it should be mentioned that natural gas with no additive would not ignite at this condition
and adding formaldehyde causes the engine to work at higher temperature that extremely increases No x.

Khosrow Gholaminejad, Alireza Majidian *, Omid Jahanian

118

International Journal of Engineering Sciences Vol(3), No (11), November, 2014.

20.05

2.41

Power(KW)

Work(KJ)

20

2.4

19.95

2.39

19.9
0.01

0.02

0.03

0.04

0.05

0.01

CH2O Volume Fraction

1.5

NOX(PPM)

MEP(MPA)

1.504

1.496
1.492
0.01

0.02

0.03

0.04

CH2O Volume Fraction

0.02

0.03

0.04

0.05

CH20 Volume Fraction

0.05

7
6
5
4
3
2
1
0.01

0.03

CH20 Volume Fraction

0.05

Fig. 4. The effects of using formaldehyde on engine performance

It should be noted that almost the total amount of formaldehyde added to the fuel would burn during combustion stroke. In TIVC=375K with 5%
additive, the mass fraction of formaldehyde at EVO is in the order of 10-14 . The same results were previously presented in different studies [1214]. Indeed, there should be a special consideration about the technologies used for formaldehyde addition and control strategies to avoid
additive leakage.

Conclusion
The results of this study can be summarized as below:

The developed single zone zero dimensional model can predict SOC in HCCI engine with appropriate uncertainty and it is suitable for
comparative on studies.

The temperature of inlet mixture strongly affects the combustion of HCCI engine. Decreasing initial temperature would cause the
engine to go out of operating range and in-creasing initial temperature would result in more advanced combustion.

Lower auto ignition temperature of formaldehyde causes advance combustion in natural gas HCCI engine. Adding 5% formaldehyde
would lead to more than 10 CA advance in SOC.

It is possible to change HCCI operating range by adding formaldehyde. In the specified HCCI engine, the mixture would not ignite but
even adding 1% formaldehyde would result in mixture combustion.

There is an optimum value of additive for each operating condition, which results in higher engine power. This optimum value is 2%.

As the main source of NO x in HCCI engine is concerned to thermal NOx, adding formaldehyde to natural gas would increase engine
NO x emissions because the maximum cylinder temperature and high temperature duration would increase by adding formaldehyde.

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