Proc. Estonian Acad. Sci. Chem.

, 2003, 52, 3, 130–142

Advances in petrol additives research

Heino Rang* and Jüri Kann
Institute of Chemical Engineering, Tallinn Technical University, Akadeemia tee 15, 12618 Tallinn,
Estonia

Received 10 June 2003, in revised form 4 July 2003

Abstract. A review about the use of petrol additives and the latest results in respective research and
development is presented. Today it is not possible to guarantee the stable work of an engine and
cleaner air by reducing the concentration of toxic compounds in exhaust gases without petrol
additives. These additives control deposits, give an antiknock effect, enhance the combustion process,
stabilize petrol, prevent corrosion, etc. Today it is known that the most important additives are the
deposit control additives. Ethanol with a small amount of water and other additives enhance the
combustion process. The improved combustion decreases fuel consumption and reduces air pollution.

Key words: petrol blends, additives, detergents, combustion improvers, antiknock agents, ethanol,
water.

INTRODUCTION

In this paper a short review about the development of petrol additives research
and the latest results in this field are presented. The role of additives in petrol
blending is increasing. The number of respective publications, especially patents,
has grown as well. The latest patents are concentrated mostly upon the deposit
control or cleanliness additives, which are mainly detergents. Antiknock
additives are the second largest class of objects amongst the recent patents, but
the number of these patents has grown on the basis of metal (manganese, iron)
compounds, which cannot be regarded as modern additives. However, it can be
hoped that they have no future. Combustion catalysts and improvers have also an
important role to play. Typical fuel additives are oxidation inhibitors or
antoxidants, which are especially necessary for petrol containing cracking
blending components. These additives prevent oxidation, polymerization, and
polycondensation processes in petrol. They reduce gum formation and further

*
Corresponding author, heino.rang@chemnet.ee

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deposit formation. Beside inhibitors, antioxidants, and stabilizers this class of
additives includes inhibitors that prevent corrosion and rust formation and also
metal deactivators inhibiting gum formation catalysed by some metals. These
additives are mostly phenol or amine derivatives. Among the recent patents in
this field, there are not any new groups of chemical compounds.
In 2002, of the published patents and patent applications 57% described
deposit control additives, 26% antiknock agents, 5% combustion improvers, 5%
water stabilizers in petrol, 3% antioxidants, inhibitors, stabilizers, and others
(emission reducing additives, antiwear agents, de-emulsifiers, etc.). The modern
additives are complex mixtures containing many ingredients. The content of
hydrocarbons (mainly alkenes and aromatics) and also oxygenates (methyl tert-
butyl ether, ethanol, etc.) in petrol determines the type and amount of additives to
be used. Some of the additives have often many functions, for instance deposit
control and inhibition, deposit control and combustion improvement, deposit
control and antiwear function, etc.
In the petrol additives research some reviews have been published earlier
[1–10]. Taking into consideration the new trends and problems in this research
field a short review about deposit control additives, antiknock agents, combustion
improvers, and problems concerning the water content in petrol is presented here.

DEPOSIT CONTROL ADDITIVES

Deposit control additives are petrol soluble detergents, which must be

compatible with the lubricating oil. The detergents hinder the formation of
deposits. They also enter into the deposit particle to remove it from the inner
surface of the engine and disperse it into fuel. The effect is based on the decrease of
the surface tension. Three major areas of engine deposits are the fuel metering
system (carburettor and fuel injectors), the induction system (manifold, intake
ports, and intake valves), and the combustion chamber (piston top and cylinder
head area) [1]. In 1954 Chevron Co. was the first to introduce petrol detergents to
keep the carburettors or fuel injectors clean. These additives are usually low
molecular weight amines and amine carboxylates, which compete with deposit
precursors and also help to disperse deposits. High molecular weight polybutene
amines developed by Chevron Co. in 1970 control deposits on intake valves,
manifolds, and ports. In this field polybutene amines were joined with polyether
amines [2]. Combustion chamber deposits cause also the knock effect, decreasing
thus the octane value. Deposit control agents in the combustion chamber are
compounds with high temperature stability, mainly succinimide derivatives [3, 4].
A review about nitrogen compounds as intake valve and combustion chamber
deposits control additives was published by Sakulpaisith [5]. Polyether amines,
polyisobutylene amines, and polyisobutylene succinimides as fuel additives reduce
the intake valve deposit by 45–60% from the base fuel and lower somewhat the
combustion chamber deposit when compared to the base fuel. Combustion
chamber deposits cause an increase in the octane number requirement or an

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“octane appetite” or ORI (octane number increase) is greater. The combustion
chamber deposit control additives are also called anti-ORI additives. Deposits in
the combustion chamber increase the temperature therein. The higher temperature
causes a growing formation of nitrogen oxides from nitrogen and oxygen in the
emission. All types of engine deposits increase fuel consumption and exhaust
emissions (carbon monoxide, hydrocarbons, and nitrogen oxides). A clean engine
means cleaner air. Modern additives do not only hinder deposit formation but also
clean the engine up. Advances in engine and also fuel technology reduce the
possibilities of deposit formation, but do not stop their formation in the engine.
Some vehicles are very sensitive to deposits while others are not. The composition
of petrol hydrocarbons affects deposit formation.
Alkenes and especially alkadienes as well as compounds with heteroatom play
an important role in the forming of deposits. In modern petrol blending alkadienes
are eliminated. Alkenes from catalytic cracking streams form deposits in the
introduction system, especially in the intake ports and valves. The alkenes content
in European petrol is up to 18%, in the United States it is in the range 6.0–9.5%.
The alkenes content in modern petrol and engine oil are the main factors causing
the formation of engine deposits [6]. Aromatic hydrocarbons, especially the higher
boiling compounds (cumene, isobutyl benzene, etc.), are the major factor in base
fuel that affect combustion chamber deposits. These components are found in
reformats and also in cracking streams. Aromatic hydrocarbons content in
European petrol is up to 42% and in the United States 20–25%.
The best components in petrol blends are alkylates and isomerisates. The
production of alkylates forms in Europe approximately 5% and in the United States
approximately 12% of petrol blending components. The production of isomerisates
is approximately 5% of all petrol blending streams both in Europe and the USA.
Thermally stabile polyalkylene polyamines were synthesized at first from poly-
isobutene chloro derivatives and the corresponding amine. The residues from the
production of these products are dangerous for the environment. These additives
can also contain traces of chlorine compounds, which cause corrosion in the
engine. Chlorine free polyetheramines are of better value. They are synthesized
from alcohols by oxyalkylation. After that the hydroxyl group is cyanethylated and
finally the obtained nitrile is reduced to amine [11–13].
Lubrizol Corp. patented an effective aromatic amide as a fuel intake system
deposit control agent in 1994. These amides contain hydroxy, alkoxy, and other
polar groups [14].
A novel class of petrol detergents, polyether hydroxyethylaminoethyl
oxalamides, was patented by Texaco Inc. [15]. The additives that control the
combustion chamber deposits must be thermally stabile. Alkenylsuccinimides
obtained from succinic anhydride and amine, polyalkenylamine or its oxyalkyl
derivative are effective. Succinimides are also used as intake valve deposits
control additives [4, 16, 17]. The petrol detergency additives based on bisalkenyl-
succinic acid imides were patented, and it was shown that the efficiency of these
compounds increases with increasing nitrogen content in the molecule [18].

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 Texaco patented a novel class of asymmetric urea derivatives of either hydro-
carboxyloxypolyether amine alone, or a hydroxyloxypolyether amine and a
tertiary aminoalkyl primary amine [19]. The reaction products of 4-alkyl-2-
morpholinone with an alkylphenoxypolyoxyalkylene amine together with poly-
ethenepolyamine succinic acid anhydride derivatives and polyalkenes as fuel
detergent additives are also interesting [20].
A large number of deposit control additives are amines. Oligomeric alkene
monoamine for instance was prepared by epoxidizing an oligomeric alkene to form
an oligomeric alkene aldehyde and an oligomeric alkene monoamine, which is
obtained over oxime. This method gives a chlorine free product [21]. Hydrocarbyl-
substituted polyoxyalkene amines [22], polyether amines [23], esteramines [24],
and polyisobutene amines, hydrazines, and azides [25] are also patented. From
nitrogen compounds amides (for instance alkoxylated poly(oxyalkylene)triamides
[26], polyether alcohol monoamides [27], alkanolamides comprising an
alkoxylated urea, etc. [28]) also play a great role in deposit control. Guanidine,
urea, or thiourea substituted carboxylic acids or their salts as deposit control agents
also reduce wear [29].
In the large group of succinic acid derivatives an effective additive was lately
patented by Lubrizol Corp. [30]. It must be repeated that it is very essential to
synthesize the nitrogen containing additives without a step over halogen
containing compounds. An interesting way was presented by Kinder et al. [21].
Carbamine acid derivatives are also detergent additives for deposit control [31].
An interesting group of deposit control agents can be obtained by the Mannich
condensation; these are so-called Mannich compounds [32–39]. The aldehyde or
ketone compound in the Mannich reaction can derive from a polyalkene, especially
polyisobutene, also an amine compound [33]. High molecular weight Mannich
condensates prevent also the clogging of engine oil [32]. A wide set of nitrogen
compounds, Mannich amines, polyalkenyl succinimides, polyalkylene carbamates
are patented by Shell Oil Co. [35].
Other nitrogen compounds are patented as fuel additives as well, for instance,
polyalkylpyrrolidines and fuel soluble salts thereof having an average molecular
mass in the range of 500 to 5000 [40]. Methacrylate polymer containing primary
amino group reduces deposits [41].
Poly(oxyalkylene)pyridyl and piperidyl ethers [42] and pyridyl and piperidyl
esters of polyalkylphenoxyalkanols control deposits in engine [43].
The patenting of new ether compounds as deposit, especially intake valve
deposit, control additives continues [44, 45]. Ether derived from tetrahydro-
furanylmethanol or polytetrahydrofuran is also a petrol detergent additive [46, 47].
Carboxylic acid alkoxylates together with polybutene amines act in a similar
manner [48].
Potassium, sodium, calcium, and other metal salts of aminophenol carboxylic
acid derivatives prevent the formation of deposits. They also are catalysts of
petrol combustion [49].

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 It is interesting to note that elemental phosphorous or amine salt of a
phosphorous based acid in the mixture with ferrocene is patented as a valve seat
deposit control agent [50, 51]. On the other hand it is known that ferrocene can
cause deposits.
It was shown that some flakes of combustion chamber deposits are
hydrophilic and water is far more effective to take these away than petrol or other
organic solvents [10]. This indicates that a small water content in fuel reduces the
amount of deposits. Lubrizol Corp. patented a copolymer of alkenes and maleic
anhydride, which is effective in producing a stable and clear aqueous fuel
emulsion [52]. Ethanol in this case plays also a positive role [53]. It may be
possible to clean the engine and exhaust gases when seawater components are
added to petrol [54]. Corrosion problems, however, arise here.
The following is a list of the most essential patents and patent applications
about deposit control additives published in 2002: polyisobutenylphenols [55],
phenol alkylated by polyisobutene and after that propoxylated [56], alkoxylated
fatty amines [57], hydroalkyl- and aminoalkyl-terminated polyoxyalkenes [58],
poly(oxyalkene)amine and aromatic esters [59], polyoxyalkene aminoalcohol
[60], amidoamine-terminated polyoxyalkene [61], hydrocarbyl compounds [62],
and oleic alkanolamide and alkoxylated oleic acid [63]. Succinic derivatives,
which were synthesized unfortunately over halogen compounds, were also
patented [64]. Deposit control amine and other nitrogen compounds can also
have inhibiting and stabilizing properties.

ANTIKNOCK ADDITIVES

Tetraethyl lead has been added to petrol since the 1930s as an effective
antiknock and also antiwear additive. In 1996 it was totally banned in the USA
and replaced by methyl tert-butyl ether [65]. In Europe leaded petrol is not
absolutely forbidden although in the standards the maximum lead content
allowed in petrol is 0.005 g/L [66]. Lead is a hazardous neurotoxin. On the other
hand, the elimination of lead compounds from petrol would cause the wear of the
engine, especially of the exhaust valve seat, due to a lack of local lubrication.
This problem has been resolved by alkali metal based anti-valve seat recession
additive technology. Additive compounds containing alkali metals, especially
potassium, are used for instance in Austria already since 1990. Germany and also
Estonia were mentioned by Wilkes [67] as countries where unleaded petrol
containing alkali metal based anti-valve seat recession technology is partially
applied. In connection with the toxicity of tetraethyl lead new agents to reduce
the antiknock effect were patented already in the 1980s. It was shown that
molybdenum compounds are not only lubricating oils with antiwear additives,
but they also act as petrol antiknock agents [68]. Also tri-, tetra-, and pentaethyl
bismuth are patented as nontoxic antiknock additives [69]. Iron compounds, so-
called ferrocenes, are used as antiknock agents, but they form deposits in the
engine. Methylcyclopentadienyl manganese tricarbonyl (MMT) and other

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manganese compounds have been used to enhance the octane value of petrol, but
they are toxic [70]. In spite of their unsuitability as antiknock additives, iron
[71, 72] and manganese compounds [73, 74] are described for this purpose in
many patents. To call ferrocene and similar fuel additives as modern [75] in 1998
is slightly strange.
It is highly probable that the widely used effective antiknock additive methyl
tert-butyl ether (MTBE) will be replaced by ethanol [76]. There are also many
other suggestions to replace the toxic MTBE, for instance by dimer of isobutene
[77]. This case is doubtful because the octane number of isobutene dimer is
approximately the same as that of isooctane and it is not very stable. 1,3-Diamino-
propane enhances the ignition quality if 3.0–5.0% is added to petrol and it performs
better than MTBE [78]. However, this compound probably increases the nitrogen
oxides content in emissions. 2,3-Dimethyl-2-methoxybutane can replace
effectively MTBE. Its solubility in water and its toxicity are very low [79], but its
price is supposedly higher than that of MTBE. Dimethyl carbonate is patented as
an antiknock additive [80]. Oligomers of C2–C5 alkenes etherificated with
methanol or ethanol have low water solubility and they can replace MTBE [81]. A
paper about lithium organic compounds as antiknock additives was published by
Mavrin et al. [82]. It is interesting that high-molecular polyalkenes (e.g. poly-
isobutene, molecular mass 20 000–9 000 000) with detergents and other additives
are patented by BASF as octane number increasing agents [83]. It was shown by
Flynn et al. [84] that 1,3-dioxolane has the ability to be an effective oxygenate for
reformulated petrol and its blending costs are equivalent to those of ethanol.

COMBUSTION IMPROVERS

Combustion improvers include combustion catalysts and ignition promoters.

Alkali or alkali earth metal compounds in which, for instance, the anion is a
polymeric sulphonated phenol [85] are patented as deposit control agents. These
alkali metal compounds are undoubtedly also combustion improvers. Combustion
catalysts are commonly alkali or other metal salts and they are used in ppm
concentrations. A list of the essential patents of combustion catalysts will be
presented. Iron and cerium enolates in a concentration of 3–200 ppm are patented
as combustion improving additives [86]. Many metallic compounds that do not
dissolve in petrol and are in the form of dispersion have been patented: chromium-,
magnesium-, manganese-, and cobalt oxides [87]; tetravalent cerium oxide [88];
selected from IIA and IIB group metal oxides, hydroxides, and peroxides [89];
potassium molybdate [90]; noble metals and rhenium complexes [91]. Unsoluble
compounds can cause deposits in engine. It is better when the combustion catalyst
is soluble in petrol.
Aromatic sulphonates, phenates, and salicylates of magnesium, calcium, and
barium as combustion enhancers are described [92]. The most essential compounds
as fuel catalysts are alkali or alkali earth metal derivatives, especially potassium
salts of organic acids soluble in petrol. Of potassium or sodium compounds the

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former with a better solubility are more effective. The combustion end products of
these compounds are carbonates.
Next some alkali and alkali earth metal derivatives as petrol additives will be
described. Succinic acid derivatives were patented by Shell Oil Co. already in
1987 [93, 94]. It was shown that alkali metal salt of a partial ester of an alkyl
polyether alcohol is a spark aider and anti-valve stick agent in petrol composi-
tions [95]. By improving the combustion process, the accompanying deposit
formation can be diminished. The salts of sulphosuccinic acid esters are
enhancers of petrol combustion [96]. Dioctylsulphosuccinate potassium salt and
the detergent polybutene amine are patented as antiwear additives [97]. The
potassium salt is surely a combustion improver and polybutene amine acts as a
deposit control agent. Alkali naphthenates are also combustion enhancers in
petrol [98, 99]. Potassium salt of dodecyl naphthalene sulphonic acid as a petrol
additive reduces also wear in the engine [99]. Bratsky et al. [49] patented
potassium salts as detergents to reduce deposits, and these are also combustion
enhancers. Some petrol soluble potassium salts of organic acids or phenolates are
unstable in petrol ethanol blends. Therefore Orr [100] patented stable salts,
especially potassium phosphates, as combustion enhancers in petrol ethanol
blends. In our investigation it was also shown that salts stable in petrol ethanol
blends act as combustion catalysts [101]. A patent was lately published where it
was shown that hydroxylamine salts are combustion improvers [102]. Potassium
salts as petrol additives are not only combustion catalysts but also antiwear
agents. It was shown [67] that at potassium levels in the fuel above 5 ppm wt/wt,
valve seat recession is halted completely within 10 hours of treatment. The
“memory effect” (which exists when lead compounds are used) was also found to
be longer when a higher fuel potassium concentration was used.
Compounds that can be classified as combustion supporters but not as
catalysts, for instance nitroalkanes, have been patented [103, 104]. In these
patents it is noted that nitroalkanes as petrol additives reduce nitrogen oxides
emissions. Generally, reducing nitrogen oxides content in exhaust gases is
connected with reducing the combustion temperature in the combustion chamber.
It was not clear whether the nitroalkanes reduce the combustion temperature or
not. Usually nitrogen compounds in petrol increase the nitrogen oxides emission.
Ethylacetate as a petrol additive to improve combustion is patented as well [105].
Ethylacetate may be interpreted as an oxygenate. Oxygen in oxygenates supports
combustion. Alcohols and ethers and also aldehydes as oxygenates added to
petrol decrease the carbon monoxide and hydrocarbons content in emission and
improve combustion [106]. But the instability of aldehydes can be an obstruction
to their use as oxygenates.

WATER IN PETROL

Water is usually regarded as an unsuitable component in petrol. As hydro-

carbons are very hydrophobic compounds there are no problems with the water

136
content in the hydrocarbonic petrol at all. The hydrophilic oxygenate additives
such as ethanol in petrol blends can promote the increase of water content in
these mixtures. It was demonstrated that a low water content in petrol reduces the
concentration of toxic compounds (CO, NOx) in motor emissions. It is also
useful for powering spark ignition engines [107, 108]. Water in petrol decreases
the calorific value of the motor fuel but a low concentration of water improves
the combustion process in the engine. The problem is to stabilize the water and
petrol blends. There are many patents since 1971 concerning the stabilization of
water in petrol. Acetals and alcohols as fuel additives improve the octane number
value and also increase the water tolerance of petrol [109]. A small amount of
submicron structured water added to ethanol and blended then with petrol
enhances the combustion process [110]. The same effect is obtained also with
ordinary water. It was shown by Bertha [111] that C5–C10 and carboxylic amides
C5–C10 as additives stabilize the water content by 10–40% in hydrocarbon fuel. It
must be mentioned that the water content in fuel as high as 40% cannot influence
positively the combustion process. The same can be noted about the patent by
Wenzel [112] in which the water content in petrol was up to 36% and it was
stabilized by alcohols, ethoxylated alcohols, fatty acids, or ethanolamines. The
stabilizer concentration must be very high to inhibit the water separation from
petrol blends containing 36 or 40% of water.
The vapour pressure of petrol and alcohol blend can be reduced by adding a
surfactant compound comprising an alkanolamide, e.g. lauryl diethanolamide,
alcoxylated alcohol, and alkoxylated fatty acid [113]. These additives can also
stabilize water in petrol. Demirbas [114] found that C3–C5 alcohols are the most
effective blending agents in reducing phase separation in methanol or ethanol,
petrol, and water blends. In our investigation [101] it was shown that petrol and
ethanol blend with a low water content, hydrophilic potassium combustion
catalyst (0.1–200 ppm), and a detergent additive is a stable clear liquid, which
enables to decrease essentially the toxic components in emission and also
deposits in the engine. Fuel compositions comprising alcohol, petrol, and water
converting this hazy or potentially hazy blend into a clear and stable solution by
adding anionic surfactant of an aminated polyisopropoxylated, polyethoxylated
alkylphenol have been patented by Texaco Inc. [115]. Polyisobutenamines
known as deposit control additives are suitable emulsifiers for water and petrol
blends [54, 116]. A water and ethanol containing petrol blend that contains
furfuryl alcohol and ethene oxide is patented [117], but it must be mentioned that
these additives are relatively unstable. Many surfactants have been patented for
stabilizing alcohol, petrol, and water blends (for instance 118–120).

CONCLUSIONS

Additives play a key role in the modern petrol blends. Deposit control,
antiknock, antioxidant, combustion improver, and all additives in the class of
inhibitors are the most important agents to reduce the fuel consumption and

137
concentration of toxic compounds in engine exhaust gases. These additives
guarantee the stable work and prolong the age of the engine. It is very essential to
combine the combustion catalysts with deposit control additives. The modern
additives are combined from many agents and are multifunctional. Ethanol as an
octane number and combustion improver with a small amount of stabilized water
in the petrol blend enhances the combustion and reduces the toxic components
concentration in emissions.

ACKNOWLEDGEMENT

We would like to thank the Estonian Science Foundation for financial

assistance (grant No. 5018).

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Edusammud bensiini lisandite uurimisel

Heino Rang ja Jüri Kann

On esitatud ülevaade bensiini lisandite kasutamisest, uurimistöö arengust ja vii-

mase aja saavutustest. Käesoleval ajal pole võimalik tagada mootorite stabiilset
funktsioneerimist ja mootori heitgaasides mürgiste komponentide kontsentratsiooni
vähendamist, ilma et kasutataks bensiini lisandeid. Lisandeiks on vahendid, mis
vähendavad mootori saastumist, parandavad detonatsioonikindlust ja põlemisprot-
sessi, stabiliseerivad bensiini, vältimaks oksüdatsiooni, polümerisatsiooni ja polü-
kondensatsiooni ning ka mootori korrosiooni või mis muul moel aitavad säästa
mootorit. Olulisimaiks lisandeiks on kujunenud detergendid, mis vähendavad moo-
tori saastumist. Etanooli, vähese vee ja teiste lisanditega rikastatud bensiinisegu
parandab põlemisprotsessi mootoris, see tagab kütuse kulu vähenemise ja puhtama
õhu.

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