Report on Harmful Chemicals in Gasoline Blending

In recent years an increased number of cases have been observed in which

chemical compounds are being blended into gasoline that could have a
detrimental effect on engine performance, human health and the environment.
The majority of those cases are related to gasoline blends being delivered to
Africa, Middle East and Asia, as Europe and the United States have regulations
in place that partially prohibit the use of these chemicals.

Considered to be a cheap source of octane, these chemicals could cause engine

problems, such as corrosion of engine parts, and could affect driving
performance. They are also harmful to human health and to the environment
in the long term when blended and burnt in transportation fuels.

Asian Clean Fuels Association (ACFA) has been recently alerted on this subject
by governments and the oil industry. Based on the information given to ACFA,
we have put together a summary on the non-traditional gasoline additives and
their potential effects when blended with gasoline. ACFA intends to further
investigate this matter, the results of which could be the subject of a future
article.

Introduction:

The non-traditional gasoline additives (NTGAs) are:

- Secondary-Butyl Acetate
- N-Methylaniline
- Acetone
- Methylal
- Methyl Acetate

These are organic compounds used as solvents in a wide range of industrial

applications. These solvents have recently been detected in gasoline blends
and are believed to be linked to several engine performance problems, such as
engine start-up and acceleration problems.

The use of the chemicals listed above in their targeted applications does not
provide any reason for health, safety and environmental concerns and is
regulated and monitored i.e. by REACH (Regulation, Evaluation, Authorisation
and Restriction of Chemicals), which is the European Union regulation
1907/2006/EC on chemicals, adopted to improve the protection of human
health and the environment from the risks that can be posed by chemicals.

1. Review of current policies on blending NTGAs in gasoline

We have reviewed current policies in a number of countries and regions,

namely Vietnam, China, the United States and Europe. We also cross-
referenced these findings against the World Wide Fuel Charter (WWFC), a
document released by engine and vehicle manufacturers from around the
world, including North America, Japan and Europe, which recommends diesel
and gasoline standards in order to harmonise worldwide fuel quality.

China

China has banned most chemical additives in the gasoline standard directive
GB17930-2013 dated Dec. 18 2013, which states that “Additives used in
gasoline for motor vehicles should not contain recognised harmful substances
and should be used by following up with the recommended safe dosage.
Chemicals, such as methylal, aniline-type compounds, halogens and those
containing phosphorus and silicon, etc. should not intentionally be added in
gasoline.”

China’s largest refiner, Sinopec Corp., has released additional test parameters
for gasoline purchased from third parties. NMA, total anilines, sec-methyl
acetate and methylal, etc. should not be detected or should remain below
detectable limits, using a middle infrared analyser.

United States

NTGAs were not found in the U.S. Environmental Protection Agency’s (EPA) List
of Registered Gasoline Additives.

Fuel additives in the United States are regulated under section 211 of the Clean
Air Act (as amended in January 1995). The EPA also regularly reviews the health
and net economic benefits of U.S. Clean Air Act policies.

Under section 211 of the U.S. Clean Air Act, all refiners and importers must
register their fuel additive products with the EPA before these products are
sold in the United States. All gasoline and diesel fuel additives produced and
commercially distributed for use in highway motor vehicles must be registered
with the EPA.

Europe

NTGAs are not in the list of recommended oxygenates in European Union (EU)
petrol standards.

Referring to EU EN 228:2012 and Directive 2009/30/EC, Automotive Fuels of

Unleaded Petrol—Requirements and Test Methods, none of the NTGAs were
found in the list of recommended oxygenates, and their use is restricted by the
European emission standards, Euro 5/6 standards (2209/2014): Regulation
715/2007.

Vietnam

It was reported that Vietnam had banned the use of SBA as an additive for
gasoline after finding high levels of the substance in cargoes imported from
Singapore. Its use as an octane booster had never been documented. The
impact of SBA, if used as a gasoline additive, on human health and motor
vehicles, is not known.

Vietnam has banned acetone as a gasoline additive due to “unknown” human

health effects and potential damage to vehicle engines.

WWFC

NTGAs are not in the list of recommended oxygenates under category 4 of the
WWFC, which refers to emission standards for unleaded gasoline for “markets
with advanced requirements for emission control.”

In the fifth edition of the WWFC, the oxygen limit was set at 2.7% by mass
percentage. It mentions in a footnote that “where oxygenates are used, ethers
are preferred.”

2. Hazard and Exposure Levels of NTGAs

The following table summarizes the hazards and exposure levels of the NTGAs
reviewed:

SBA NMA Acetone Methylal Methyl Acetate

CAS No. 105-46-4 100-61-8 67-64-4 109-87-5 79-20-9
UN Hazard class 3 – flammable liquids 6.1 – Poisonous 3 3 3
material
Physical danger: Mix Highly flammable Combustible with h.f. h.f h.f.
with air, explosive risk toxic fumes
Chemical danger: Reacts with strong Can produce toxic Generates fire and Explosion hazard, Fire, explosion risk
Reactive, fire hazard acids and oxidants fumes including NOx, explosion hazards in reacts violently with when decomposed,
risk reacts violently with contact with strong strong oxidants reacts violently with
strong acids and oxidants, harmful to strong oxidants,
oxidants plastics corrosive to metals,
harmful to plastics
Exposure route inhalation Inhalation Inhalation Inhalation Inhalation
Short-term exposure Mildly irritating, May cause Irritating to eyes and Irritating to eyes, skin Irritating to eyes and
risk harmful to central Methaemoglobin respiratory tract and respiratory tract respiratory tract,
nerve system harmful to central
nerve system
Long-term exposure Skin dryness and No data Skin dryness and Skin dryness and Skin dryness and
risk cracking cracking cracking cracking, harmful to
optic nerve
Inhalation risk Harmful by inhalation/ Harmful by inhalation/ Harmful by inhalation/ Harmful by inhalation/ Harmful by inhalation/
contaminated air contaminated air contaminated air contaminated air contaminated air
Occupational 200ppm (ACGIH) 0.05ppm (ACGIH) 500ppm (ACGIH) 1000ppm (ACGIH) 200ppm (ACGIH)
exposure Limit (TLV)
Toxicity to aquatic life No data Very toxic to aquatic No data
life
Data Sources: ICSC database, ACGIH, German Health Ministry, MSDSs

All types of NTGAs are categorized as flammable liquids under the United
Nations (UN) hazard classification system or, in the case of NMA, as a toxic
substance. Some research reports point out that NMA can cause damage to the
central nerve system and can also cause liver and kidney failure.

3. Effects of NTGAs on engine and fuel quality

The effects of each of these solvents when blended with gasoline on engine
performance and fuel quality are discussed below.

SBA

Sec-Butyl Acetate’s strong reaction with acids and oxidants and its strong
dissolving ability, which causes a swelling effect on any rubber-based engine
parts, may cause engine malfunction when it is used for a period of six hours or
more.

Because of its very low vapour pressure, SBA may cause the gasoline blend to
fall below the minimum requirement of 40 kPA (in countries that have a
minimum vapour pressure specification). Low Reid Vapour Pressure (RVP)
levels may lead to evaporation losses and a decrease in fuel efficiency.

NMA
A study conducted in China by Liu Jingdong in 2012 showed that adding aniline-
type additives can significantly improve the octane number of gasoline.
However, its use can at the same time result in gum formation, drastically
shorten the induction period, as well as sharply increase seal swell. High gum
levels cause higher carbon deposits in engine parts such as pistons. Shorter
induction times can cause gasoline stability to decline and antiknock. The
swelling of seal rings may cause oils to leak from engine pipes.

The table below highlights the effects of aniline blending on gasoline quality
and seal rings:

Gasoline Add 3% Aniline Add 5% Aniline

Research Octane 87 97 99
Number (RON)
Motor Octane 83 90 90.5
Number (MON)
Actual gum 1 3 3
(mg/100ml)
Induction period > 810 520 380
(min)
Seal ring swelling* 0.2 1.5 2.8
After 48 hours
Seal ring swelling* 0.3 3.1 4.2
After 96 hours
*(butadiene – acrylonitrile rubber)

The addition of NMA to gasoline could also cause heavier copper strip
corrosion, which can lead to engine corrosion. NMA also contains nitrogen.
When it reacts with oxygen, the result is nitrogen oxides (NoX), a harmful gas.
Gasoline blends with greater than 5% concentration of NMA can cause
sediments in the engine combustion chamber, which can cause failure in
octane-number reading by anti-knock sensors in the engine’s computer,
according to one study.

Acetone

Acetone is highly reactive to oxidants and has a negative impact on plastics.

When blended with gasoline, it can increase seal swell and dissolving risk,
potentially causing engine damage.

Methylal

This solvent has been mainly used as a cheap alternative to other gasoline
components, but with a density of 0.86g/m3 and an octane rating of 83-84
RON, it may not be efficient to use this as an octane enhancer. The negative
effect of methylal is that it also has swelling effects on plastics and thus could
cause damage to any auto parts made of plastic that it comes into contact with.

Methyl Acetate

Methyl Acetate is only sporadically considered for gasoline blending, especially

when its solvent value in other chemical applications falls below its blend value
in gasoline. Its octane contribution is offset by the product’s high density and
vapour pressure of 165 mm Hg at 20 °C.

Methyl acetate can react explosively in the presence of water and plastics,
making it highly unsuitable for gasoline blending, as there will be a certain
amount of water that ends up in gasoline due to condensation and there are a
lot more plastic parts in today’s automobile.

4. Conclusion

All these solvents show detrimental effects on engine parts which can
potentially cause engine damage or, at the least, oil system failure.

Due to their undetermined effects on human health and long-term effects on

air and water quality, these NTGAs are already prohibited, not recommended
or deselected in a few countries’ gasoline specifications.

Governments and policymakers need to look further into these concerns, and
the Clean Fuels industry needs to assist the auto manufacturing industry in its
efforts to regulate the use of chemicals that could be harmful to the engine, to
human health and the environment.