The use of lubricity additives... D.

Claydon

David Claydon

ISSN 0350-350X
GOMABN 53, 4, 342-353
Stručni rad / Professional paper

THE USE OF LUBRICITY ADDITIVES

TO MAINTAIN FUEL QUALITY IN LOW SULPHUR
DIESEL FUEL
Abstract
The introduction of lubricity protection as part of the EN 590 diesel specification in
Europe has led to the wide-spread use of lubricity additives as a cost effective
means to achieve the required level of performance. At the moment there are a
number of different lubricity additive chemistries available to refiners and some
discussion as to the merits of the different products. During the initial introduction of
lubricity additives for low sulphur diesel fuel certain chemistries were found to have
negative interactions that led to field issues. These products were mainly acid based
and found to interact with basic components present both in the fuel and in the
lubricant. These issues led to a move to neutral lubricity additives being favoured in
preference to products based on acidic chemistry. However, even some of the
neutral chemistries were found to have negative harm effects.
In this paper we will discuss how the development of no harm testing of refinery
additives has led to the safe use of both neutral and acidic lubricity additives. The
well-established DGMK test protocol allows refiners to select the most cost effective
lubricity additive based upon extensive no harm testing in preference to selection
being based upon generic chemistry.
Key words: lubricity, additives, chemistry, testing
Sažetak
Uvođenje mazivosti kao zaštitne značajke u specifikaciju za dizelska goriva EN 590
u Europi je dovelo do rasprostranjenog korištenja aditiva za mazivost, kao jeftinog
načina za postizanje potrebne razine učinka. U ovom trenutku rafinerijama je
dostupan veći broj različitih kemijskih rješenja za te aditive, uz rasprave o boljim
svojstvima različitih proizvoda. Na početku uvođenja aditiva za mazivost u nisko-
sumporno dizelsko gorivo za određene je kemijske spojeve utvrđeno da imaju
negativne interakcije što je dovelo do problema u uporabi. Ti su proizvodi uglavnom
bili kisele osnove pa je utvrđeno da reagiraju s baznim (lužnatim) komponentama
prisutnim i u gorivu i u mazivu.

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D. Claydon The use of lubricity additives...

Ovi problemi su ukazali da aditivi neutralnih svojstava imaju prednosti nad onima
kisele osnove. Međutim, čak i neki od takvih aditiva imaju negativne učinke.
U radu će se raspravljati o razvoju neštetnog testiranja rafinerijskih aditiva koje je
dovelo do sigurnog korištenja i neutralnih i kiselih aditiva za mazivost. Uhodani
postupak DGMK testiranja omogućuje rafinerijama odabir najučinkovitijeg aditiva za
mazivost temeljem opsežnog neštetnog testiranja kojem daje prednost u odnosu na
odabir temeljen na generičkoj kemiji.
Ključne riječi: mazivost, aditivi, kemija, ispitivanje

Background
During the last few decades we have seen tremendous advances in the design of
diesel engine technology as vehicle manufacturers strive to meet the more
demanding government vehicle emissions regulations. This has also required oil
companies to make available fuels which will allow new vehicle hardware to
continue operating to the latest design specifications. The biggest impact of these
changes relates to the sulphur content of the fuels and this is captured schematically
in the Fig. 1.

Figure 1: Vehicle emissions regulations development during last two decades

The refinery processes required to produce these low sulphur diesel fuels results in
a fuel having a viscosity lower than conventional fuels and with a lower level of polar
and polycyclic aromatic compounds. This results in low sulphur diesel fuel having
poorer natural lubricity characteristics with the potential to cause vehicle mechanical
problems. The introduction of environmentally friendly city diesel in Sweden in 1991
led to an outbreak of vehicle field problems. Upon investigation it was found that the
removal of sulphur, aromatics and other polar compounds had resulted in fuels
having poor inherent lubricity characteristics.

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The use of lubricity additives... D. Claydon

Failures are manifested as pump mechanical issues which brought many vehicles to
a standstill. These failures were associated with passenger cars operating with
Bosch rotary pumps after only 3000 to 10000 km. At the same time complaints were
also seen in California where low sulphur and low aromatic fuels had been
introduced. The industry recognised that there was likely to be an additive solution to
this problem due to the fact that lubricity additives had been used to improve lubricity
and give pump protection in jet fuel for a number of decades. Tests were conducted
with an approved jet fuel lubricity additive using diesel fuel and the BOCLE lubricity
test. Extensive performance and no harm testing were conducted and the additive
was approved by the Swedish EPA for use as a diesel fuel lubricity additive. Before
the additive solution could be implemented it had been necessary to develop a
reliable test that could recreate the diesel pump failures as seen in the field and to
use this test to evaluate the additive solution. Bosch developed a pump test that
could be used to evaluate the propensity of a fuel to create wear in a diesel rotary
distribution pump. Many of the field problems were seen in the Bosch VP44 pump
used in the Opel Vectra and in direct injection engines. The pump test involved
evaluating a fuel under controlled conditions for a period of either 500 or 1000 hours.
Critical parts of the pump were weighed and visually rated prior to testing and then
re-checked after completion of the test. The visual rating involved comparing specific
pump parts with a set of parts from new, used and worn pumps. The pump was then
rated for wear using a scale from 0 to 10 where 0 represented a new pump condition
and 10 heavily worn. Acceptable performance was agreed to be at a level greater
than 3.5 with a repeatability of 0.5 [1]. The industry recognised that the pump test
was a useful tool for evaluating the lubricity characteristics of a diesel fuel but could
not be used as a quality control test.

Figure 2: Standard test for diesel fuel lubricity - High Frequency Reciprocating Rig
(HFRR) (Source: PCS instruments)

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D. Claydon The use of lubricity additives...

Consequently a working group was established with the objective of developing a

convenient and reproducible test that could measure the lubricity characteristics of a
fuel. This test is based upon a rig test in which the only lubrication between two
metal surfaces is the fuel. The diameter of the wear scar is assessed at the end of
the test. This test is controlled as CEC-F-06-A-96 and is known as the High
Frequency Reciprocating Rig (HFRR) test (Fig. 2).
Potential additive solutions
Now that a reliable wear test had been established and accepted by the industry it
was possible to evaluate a number of known chemistry as a potential solution to
poor wear from low sulphur diesel fuel. A number of lubricity additives were already
known to the industry due to the application in jet fuel and in low sulphur diesel fuel
that had been marketed in Scandinavia since 1991 in 50 ppm (class 2) and 10 ppm
(class 1) sulphur diesel fuel.
Most commercial lubricity additives were produced from long chain carboxylic acids.
If the acidic head group is left and not further reacted the product is classed as
acidic. When the carboxylic acid contains two head groups and two tails they are
classed as dimer acids or one head group and one tail they are mono-acidic
products. If the head group is reacted with an alkanol amine then the chemistry
would be an amide and alternatively reaction with polyhydric alcohols, amongst
others, would produce an ester. Both Esters and amides are classed as neutral
lubricity additives. An example of lubricity additive chemistry is shown in Fig. 3.

Oleic acid Glycerol mono-oleate

Figure 3: Examples of long chain carboxylic acid and their ester used
as commercial lubricity additives
(Source: Chemical Register)

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The use of lubricity additives... D. Claydon

Lubricity additives used in jet fuel were mostly based upon dimer acids whilst the
lubricity additives used in low sulphur diesel fuel at that time were mostly ester type
chemistry.
A number of oil companies decided to use the jet fuel dimer acids for the low sulphur
diesel fuels being marketed in Scandinavia due to the attractive treat-costs. A
number of vehicle trials were conducted and the dimer acids were seen to give
satisfactory protection against pump wear. ‘’No harm’’ fleet tests were conducted
and dimer acids were found to be fit for purpose. One major global oil company
decided to use the dimer acids for lubricity protection in Scandinavia and went to full
commercial use. However, after a short period of time a number of field problems
were reported when fuels were treated with dimer acid. Investigations were
conducted by the industry in order to understand the cause of the field problems. In
the meantime dimer acids were removed from the low sulphur diesel fuel application
pending the results of the investigation.

Amide

Acid Ester

Figure 4: Difference between acidic and neutral lubricity additives (ester and amide)
based on long chain carboxylic acid

The investigation started with analysis of blocked filters and pumps which had
stopped operating due to deposits on the cam plates and shafts that led to pump
failure. The analysis of pumps and filters clearly showed the formation of insoluble
carboxylate salts coming from acid-base reactions. Further studies showed that the
dimer acids, under certain conditions, were coming in contact with over based
calcium sulphonates used in crankcase lubricants.

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The mechanism of this interaction is shown below:

Figure 5: Origins of the filter blockage and pumps stopping

The investigation concluded that fuel additives can interact with lubricants in some
injection pumps and injectors in tight orifices and annular spaces. It was also found
that some truckers bleed or dispose of used engine oil by tipping into vehicle fuel
tanks, believing that this will reduce fuel consumption and maintenance costs and is
also a convenient way to dispose of used oil.
Since dimer acids were implicated with field issues the conclusions of the investi-
gation led to the withdrawal of dimer acids as lubricity additives in low sulphur diesel
fuels and more focus on neutral chemistries.

The question of Neutral or Acidic lubricity additives

The investigation led to the conclusion that the use of dimer acids in low sulphur fuel
had the potential for acid-base reactions which could have an impact on vehicle
operation mostly in the form of filter blockage and consequent fuel starvation. In
order to safeguard against a reoccurrence of this issue a number of laboratories and
rig tests were developed to evaluate existing and new lubricity additive chemistries.
Some of these tests are discussed in an SAE papers written by Neste oil [2].

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The use of lubricity additives... D. Claydon

These tests were, by definition, severe in order to reproduce the issues in a timely
manner. It was also convenient to use a dimer acid lubricity additive as a benchmark
in order to validate the no harm test. Most of the tests focused on acid-base
reactions and the impact on filters.
At the same time there was recognition that all acidic lubricity additives were not the
same in terms of acid-base reactions and mono-acidic lubricity additives were found
to be as cost effective as dimer acids without the same potential for field problems.
Mono-acidic additives were compared to the bad reference (dimer acids) in these
tests and gave very similar performance to neutral chemistries.
A number of the key tests are discussed below.
Aral engine oil compatibility test:
This is a severe test in which 10 g of neat lubricity additive is mixed with 10 grams of
a high TBN lubricant. This mixture is stored for 3 days at 90 °C and then visually
inspected for any signs of reaction and precipitate formation. The mixture is then
blended into 500 ml of diesel fuel and filtered through a 0.8 millipore cellulose filter. A
pass is classed as being able to filter the 500 ml in less than 180 seconds.
Typical performance for different chemistries is shown in Fig. 6.

Figure 6: Interaction between additive and lubricant by Millipore test

The dimer acid fails very quickly due to an acid-base reaction leading to insoluble
precipitates that block the Millipore filter. The mono-acidic lubricity additive easily
passed since 500 ml of treated fuel was filtered in 63 seconds, the same as the
amide and lubricant alone. This particular ester product also fails this test but this is
partly due to borderline solubility in this fuel due to the high treat-rates (20000 ppm)
used in this test.

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Shell / ESSO / Infineum lubricant interaction test

This test has been designed to evaluate the lubricity additives at more realistic treat-
rates (double recommended). The additive is mixed with the lubricant oil in a bottle
and 2000 ml of fuel is added and the mixture is shaken for 2 minutes to mix. This
mixture is then stored for 48 hours at 70 °C, allowed to cool to room temperature.
The mixture is filtered through a 3 micron filter at a rate of 20 ml/min. The pressure
drop across the filter is measured every 100 ml filtered.

Figure 7: Interaction between additive and lubricant by Shell/ESSO/Infineum test

These tests gave a clear indication that monoacid lubricity additives do not react
with the basic products found in high TBN lubricants. However, the next step was to
move from laboratory tests, which simulate real world conditions, to actual vehicle
tests. Afton Chemical developed a vehicle test based upon a heavy duty Caterpillar
truck which was known to be prone to filter blockage. This test was run for 5000
miles on the road and the vacuum across the filter was continuously monitored. The
evaluation of a dimer acid showed filter blockage after only 500 miles but the mono-
acid lubricity additive gave no vacuum increase after 5000 miles of operation as
shown in Fig. 8. The filters were examined after the test and there was clear
evidence of deposit build up on the filter operated with the dimer acid, the filter from
the mono acidic test was perfectly clean as seen in Fig. 9. Analysis of the deposits
on the failing filter showed clear evidence of carboxylate salts resulting from dimer
acid-base reactions.

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The use of lubricity additives... D. Claydon

Figure 8: Evaluation of lubricity additive by a heavy duti Caterpillar truck test

(Source: Afton Chemical Ltd)

Figure 9: Deposit of lubricity additive on the filters after a heavy duti Caterpillar
truck test (Source: Afton Chemical Ltd)

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The testing conducted at that time together with a better understanding of the
mechanism of failure, see Fig. 11 led to a wide acceptance of mono-acidic lubricity
additives. The mono-acid lubricity additives were not only seen to be more cost
effective than neutral chemistries, but also were proven to not cause field problems.
The micelles formed by the dimer acids are oligomeric / polymeric in nature in
contrast to the micelles formed by the monoacidic lubricity additives.

Figure 10: Appearance of deposit and plugged filter (Source: Afton Chemical Ltd)

Figure 11: Difference in micelles formation inclination in dimer acid, neutral and
mono-acidic lubricity additives (Source: Afton Chemical Ltd)
Since the beginning of the new millennium the use on mono-acidic lubricity additives
is well established globally and this is partly due to the rigorous approval test
procedures that have been established by the DGMK organisation in Germany. This
organisation is responsible for approving all additives to be used in German
refineries and this protocol has been adopted by many oil and additive companies
worldwide.

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At the present moment lubricity additives for diesel fuel produced in Germany has to
meet the requirements of DGMK research report 531-1 [3]. Once approved,
additives are listed on the DGMK approval list. Mono-acidic lubricity additives have
been evaluated against the existing test regime specified by the report 531-1 and a
summary of the tests and the results is shown in Table 1.
Table 1: Test protocols and results for mono-acidic lubricity additives
Test protocol Description of test Pass criteria Monoacid
evaluation
1A Engine oil The reference engine oil is heated to 40 °C and Mixture should be Clear & bright
compatibility then mixed with an equal amount of the additive to clear with no Filtration time of
be tested. When at room temperature the diesel indication of base fuel 55 s
fuel is mixed with additive/oil mixture and stored at chemical reaction Filtration time with
90 °C for 3 days. The fuel is assessed visually and and no significant additive 66 s
the filtered according to the SEDAB test. increase in filtration
time
1-B Emulsion Modified ASTM D1094 test with repeated fuel water No worse than No worse than
behaviour contact. Additive tested at 3 times recommended base fuel base fuel at
treat-rate 450 ppm
1-C Storage The neat additive is stored for 28 days at different No phase No phase
stability temperatures separation or gel separation
by visual inspection
1-D Compatibility 15 g of WASA and 10 g of the additive are mixed in Should not impact No impact on
with WASA and a glass vessel. The mixtures and the individual HFRR performance HFRR
MDFI components (MDFI, WASA and the lubricity
additive) are then stored under exclusion of light for Should not
14 days at 20 ± 2 °C. This is then examined increase filtration Base = 63 s
visually over time to check for separation time + additive = 57 s
After fourteen days storage the mixtures are
dissolved at a dosing rate of 250 mg/kg Should not No impact on cold
(corresponding to 150 mg/kg WASA and 100 mg/kg adversely impact flow properties
lubricity additive) with an additional 300 mg/kg cold flow properties
MDFI in diesel fuel containing no additive. of the treated fuel
Checks are then made to ensure no negative No negative
impact on cold flow properties and lubricity interaction with
performance. Filterability is also checked by WASA and MDFI
SEDAB
1-E Compatibility Two fuels are tested one treated with performance The combination of No negative
with performance additive and no lubricity and the same fuel treated additives should impact
additives with both. The two fuels are then tested for lubricity not negative impact
performance and filtration using SEDAB procedure. performance
1-F Influence on 500 ml of diesel fuel, containing 5 % RME, is filled The difference in Difference of
oxidative stability into two sealable glass vessels. One sample results of the two 0.34 hours which
remains untreated whilst the other sample is treated fuels should be is less than
with the lubricity additive. Both samples are left less than the repeatability of
standing for two weeks at room temperature and repeatability of the Rancimat test
then evaluated for oxidative stability by using the test method
Rancimat test.

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D. Claydon The use of lubricity additives...

These test results mean that mono-acidic lubricity chemistry is capable of meeting
the stringent requirements of the DGMK organisation as specified as part of DGMK
project 531. There are a number of commercial mono-acidic lubricity additives on
the DGMK approved list for use in German refineries.

The storage and handling of lubricity additives

Another important consideration not necessarily addressed by the DGMK test
protocol is the handling conditions of the different lubricity additive chemistries.
When using a lubricity additive it is important to ensure that the additive remains
homogeneous during storage and injection. Some mono-acidic additives have a
relatively high cloud point, meaning that precipitation can happen at normal winter
ambient temperatures. In this case dilution or heated storage may be required.
Another important consideration is the solubility of the lubricity additive in diesel fuel
when exposed to low temperatures. Some lubricity additives are known to have only
limited solubility in fuel after prolonged storage at low ambient temperatures.

Conclusion
It is a recognised fact that low sulphur diesel fuel has poor natural lubricity
characteristics which can be addressed by the use of lubricity additives. The
incorporation of an HFRR requirement in the European EN590 specification means
that lubricity additives are regularly used by refineries throughout the European
region and in countries exporting to Europe. Initial lubricity additive use in the early
90’s led to a number of field problems related to negative interactions between dimer
acid lubricity additives and crankcase lubricants but following a thorough investi-
gation the root cause of this issue has been well understood and is exclusively an
issue associated with dimer acids.
A number of relevant no harm tests were developed that have led to clear evidence
that field issues, when using low sulphur diesel treated with dimer acids, do not
occur through the use of mono-acidic lubricity chemistry. The introduction of the
DGMK project 531 and the use of proven no harm tests together with extensive
refinery use of mono-acidic lubricity additives has led to mono-acid chemistries
being accepted as a cost effective and safe option to neutral lubricity additives.
Literature
1. Mitchell K., Continued evaluation of diesel fuel lubricity by pump rig tests,
SAE 981363, 1998.
2. Baker J. et al., Int. J. Fuels Lubr. 6(3):2013, doi:104271/2013-01-2687.
3. DGMK-Information 04/08 Projects DGMK-Committee Fuels 2002-2008 p. 4 of 20.
Author
David Claydon, Afton Chemical, UK; E-mail: [email protected]

Received: 22.9.2014.
Accepted: 21.11.2014.

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