Professional Documents
Culture Documents
Oils
Carsten Heine, OELCHECK GmbH Jo Ameye, Fluitec International
Tags: oil analysis, oil oxidation, motor oils, oil changes, Case Studies
The use of biogas engines and their maintenance has become a hot topic over the last few
years. Biogas is a renewable fuel, so it qualifies for renewable energy subsidies in some
parts of the world. Biogas typically refers to a gas produced by the biological breakdown of
organic matter in the absence of oxygen. It is this type of gas that can be used as biofuel.
One type of biogas is produced by anaerobic digestion or fermentation of biodegradable
materials such as biomass, manure, sewage, municipal waste, green waste and energy
crops. Via this formation, biogas is produced that consists primarily of methane and carbon
dioxide. Another possible source of biogas is wood gas, which is created by gasification of
wood or other biomass. This type of biogas is comprised primarily of nitrogen, hydrogen and
carbon monoxide with trace amounts of methane.
As a renewable energy source, biogas can be utilized for electricity production on sewage
works in a combined heat and power (CHP) gas engine. If compressed, it can replace
compressed natural gas for use in vehicles, where it can fuel an internal combustion engine.
The methane, hydrogen and carbon monoxide gases can be combusted or oxidized with
oxygen. Air contains 21 percent oxygen. This energy release allows biogas to be utilized as
a fuel. Biogas can be used as a low-cost fuel in any country for any heating purpose, such
as cooking. It can also be employed in modern waste-management facilities where it can be
used to run any type of heat engine and generate either mechanical or electrical power.
Landfill gas typically has methane concentrations around 50 percent. Based on advanced
waste-treatment technologies, biogas can be produced with 55 to 75 percent methane. The
chemical composition of biogas varies depending upon the origin of the anaerobic digestion
process.
Methane within biogas can be concentrated via a biogas upgrader to the same standards as
fossil natural gas, becoming bio-methane. Carbon dioxide, water, hydrogen sulfide and
particulates (such as siloxanes) must be removed if present. These siloxanes are formed
from the anaerobic decomposition of materials commonly found in soaps and detergents.
During combustion of biogas-containing siloxanes, silicon is released and can combine with
free oxygen or various other elements in the combustion gas. Deposits are formed
containing mostly silica or silicates as well as calcium, sulfur, zinc and phosphorus. These
white mineral deposits accumulate to a surface thickness of several millimeters and must be
removed by chemical or mechanical means.
In comparison to natural gas engines, the operating conditions of biogas engines are
different because of higher combustion temperatures, 24/7 operation to avoid methane
release and contamination from carbon dioxide, water, hydrogen sulfide (acidic) and
particulates (siloxanes).
In general, gas engines are used to power cogeneration electrical power plants and are
preferred over diesel engines because of their lower exhaust emissions and lower fuel cost.
Formulation Changes for Gas Engine Oils
Gas engine oils used in biogas or natural gas engines have special formulations that differ
from diesel and gasoline engine oil formulations. This is because natural gas engines have:
A clean burning process with no soot contamination. Therefore, the oils require less
detergency/dispersancy (lower ash levels).
A gaseous fuel source with no risk of fuel dilution. The prevention of a viscosity
increase in the oil is more critical.
A hotter burning process, which is typically from 165 to 235 degrees C. Thus,
oxidation/nitration is of greater concern. (The heat may be caused by hot spots
within the oil’s circulation located near the piston rings and the combustion
chambers.)
For gas engines, the goal is to obtain a lubricant with higher thermal and oxidative stability
or to create a lubricant with a minimal oxidative degradation. Standard results for lubricants
with poor oxidation protection/control are:
These operating problems can be prevented by the combination of a good quality base oil
with a supplemental antioxidant package. A typical gas engine oil formulation may contain
multiple antioxidant additives to help protect the base stock from excessive heat or catalytic
degradation.
Antioxidants added alone or in synergistic combinations extend the operating life of the oil
by improving its oxidation stability. During their use in lubrication systems, oxidation
inhibitors will deplete to a certain critical level, at which point the fluid will start to
degrade/polymerize at an accelerated rate. When this happens, important changes in the
physical properties of the base stock occur. The oil or lubricant is no longer able to protect
the equipment, and its useful life is over.
There is a growing interest in methods predicting an oil change by measuring antioxidant
concentration during the lubricant’s lifetime. Monitoring the onset and the propagation of
oxidation will lower operating costs and allow users to detect abnormally oxidized and
degraded lubricants.
The basic mechanism of oxidative degradation and the role that different antioxidants play
begin with the formation of reactive compounds, better known as free radicals, hydro
peroxides and peroxides. These reactive compounds propagate into oxygenated
hydrocarbons, such as alcohol, acids and sludge. The antioxidants act in two ways: by
removing radicals (primary antioxidancy) or by decomposing hydro peroxides to form non-
reactive products, which do not participate in further oxidation of the lubricant. Currently, the
most commonly used primary antioxidants are the phenolic, phenates, salicylates and
amine types; the secondary antioxidants are usually sulfur or metal-containing additives.
Once the antioxidant additives are depleted, the base oil is more vulnerable to oxidation.
This may explain why the oil’s viscosity tends to increase as more operating hours
accumulate on the gas engine.
Figure 1 shows a RULER voltammogram for different gas engine oil formulations. As you
can see, the selection of different types of antioxidants is applied for the gas engine oil
formulations, where the following types of antioxidants are used: Zincdithiophosphates
(ZnDTP), aromatic amines, phenates, phenols and salicylates.
Figure 1. Multi RULER graphs representing different gas engine oil formulations.
Relationship between Antioxidants and Viscosity
Actual oil analysis specifications by acid number and base number in combination with
elemental analysis and contamination are no longer sufficient to define the correct oil
change intervals or detect changing operating conditions. One of the innovative oil analysis
techniques applied and selected for these oil diagnostic programs is individual antioxidant
monitoring by linear sweep voltammetric techniques (RULER technology).
By monitoring individual antioxidants, in comparison to acid number, operators will be able
to establish an accurate condition of the oil as part of the oil’s lifecycle evaluation.
Figure 2. Correlation between phenolic depletion (FTIR) and viscosity increase.
Antioxidant #1 and #2 depleted down to a value below 20 percent of the fresh oil
value.
The acid number showed the highest number with the lowest remaining antioxidant
concentrations.
AN and BN did not cross but were very close to each other at the end.
A viscosity increase was found. The viscosity at 100 degrees C was very close to 18
mm²/s, which is the limit for several engine manufacturers.
Figure 6. Correlation between antioxidants, AN, BN and viscosity for Jenbacher biogas
engines.
The degradation of the two antioxidants was not equal. The main antioxidant in this
formulation (antioxidant #2) showed a value of about 50 percent remaining
antioxidant level, while antioxidant #1 had only a value of about 20 percent
remaining antioxidant level.
Viscosity at 100 degrees C showed a slight increase.
AN and BN did not cross each other.
The i-pH-value sank under the limit (4.00) of biogas engines.
Figure 8. Correlation between antioxidants, i-pH value and viscosity for Jenbacher natural
gas engines.
The degradation of the two antioxidants was not equal. The main antioxidant in this
formulation (antioxidant #2) showed a value of about 40 percent remaining
antioxidant level, while antioxidant #1 had a value of about 55 percent remaining
antioxidant level.
Antioxidant #3 had a value of about 15 percent remaining antioxidant level.
Viscosity at 100 degrees C showed a slight increase.
AN and BN did not cross each other.
The i-pH value was below the limit of 4 for a longer period of time. This correlated to
the phenolic antioxidant, which was below 25 percent, since the time the i-pH value
crossed the line of 4.
Figure 10. Correlation between antioxidants, i-pH value and viscosity for Waukesha natural
gas engines.
Figure 13. FTIR spectra of one modern gas engine oil.
Figure 14. Detail of the phenolic inhibitor during 750 hours in use.
Although it is possible to observe the phenolic antioxidant in the FTIR spectra, only one
antioxidant can be monitored well. Therefore, another possibility was sought to check the
oxidation of the used oil in the engine.
An ASTM method for the determination of oxidation (ASTM D 7214-06), which includes a
special chapter for ester-containing fluids, may be a good alternative to DIN 51453. At the
moment, many gas engine oils are being compared using this ASTM method with the
corresponding results of viscosity increase, DIN oxidation, AN, BN and phenolic antioxidant.
It is recommended to replace the DIN oxidation method for used gas engine oils with a
more comprehensive method for the detection of the real oxidation of modern oil
formulations.
In conclusion, it was determined that antioxidant analysis can be useful both for small and
large oil reservoirs, as well as peak/base-load operations. The importance of individual
antioxidants in combination with other critical parameters may provide a better
understanding of the processes occurring during the oil’s lifetime. In addition, oil analysis
can be achieved as part of an improvement of oil lifecycle estimation as well as equipment
reliability and availability. However, for the monitoring of oxidation, especially for smaller
gas engines, it is useful to seek a better method than the traditional DIN oxidation method.