Catalyst 1 – an organometallic
catalyst comprising iron in an organic matrix that aids in improving combustion
efficiency, comprising Ferrocene, C5H5FeC5H5.
Catalyst 2 - a partial oxidation
catalyst comprising vanadium (V) and phosphorus (P) oxides that aids in
emission reduction, comprising vanadium phosphate hydrate (VOPO4·nH2O), where n is 0.5, 1, or 2.
Catalyst 3 – an ammoxidation
catalyst comprising vanadium and antimony oxides that aids in emission
reduction, comprising a vanadium/antimony/tin oxide mixture (V4Sb6O8).
Carrier – a solvent,
2-Butoxyethanol (C6H14O2) that is miscible in
petroleum distillates, residual fuels, biofuels, and biofuel/petroleum fuel blends.
Once Ultimum5 is blended into liquid fuels at the manufacturer
specified rate, the total amount of elemental Fe, V, Sb, and P comprising the
catalysts blended into finished fuel is less than 0.560 mg/L
(parts-per-million, or ppm) when fuel is dosed according to manufacturer
specifications. In no case do any of the
metals or P added by treating fuel with Ultimum5 exceed known specific
tolerance limits for individual metallic elements. Currently, there are no known US, EU, or other
specific tolerance limits for V, P, Fe, or Sb in on-road type fuels – diesel or
petrol, with the exception of P for biodiesel (see below), where biodiesel
would be part of a biodiesel/petrodiesel blend.
Biodiesel has total aggregate limits for Group I1 and Group
II2 metals, but no GroupI or GroupII metals are contained in Ultimum5.
With regard to
specific tolerance limits, the lowest tolerance level for V and P in Marine
Fuel Oil (MFO) in either residual or distillate types, is 50 mg/Kg and 15 mg/Kg
respectively, where bulk density of those fuels is approximately 1 Kg/L3.
Total V content added by treatment with Ultimum5 is 0.050 mg/L.
Total P content added by treatment with Ultimum5 is 0.023 mg/L. Total levels of V and P added by treatment
with Ultimum5 are orders of
magnitude lower than their respective tolerance limits for MFO, whether
residual or distillate.
Biodiesel created
according to EN14214 and ASTM D6751 standards has phosphorus tolerance limits
of 4 mg/Kg and 10 mg/Kg respectively. The
bulk density of biodiesel conforming to the EN14214 standard is 0.86-0.90
Kg/L. Total P content added by treatment
with Ultimum5 is 0.023 mg/L. Total levels of P added by treatment with Ultimum5 are orders of
magnitude lower than either specified tolerance limit for biodiesel.
With respect to ash
content in MFO (residual or distillate), diesel conforming to EN590, SANS 342,
ASTM D975, and IS 1460 standards, the tolerance level is 0.010%, which equates
to 100 mg/Kg. In the case of biodiesel
conforming to the EN 14214 or ASTM D6751 standards, the sulfated ash tolerance
limit is 200 mg/Kg. In terms of total
added ash content, the amount of non-combustible solids added by Ultimum5 to a liter of any of
these fuels is a maximum of 0.658 mg when dosed at manufacturer-specified rates.
No ash or metals
tolerance limits were noted for gasoline standards in the EU or US.
The following provides
information on how the suite of catalysts in Ultimum5 works in relation to
combustion and emissions reduction.
During combustion,
Ferrocene is oxidized, thus creating CO2, H2O, and Fe2O3
(Hematite).
Fe2O3
is known as an oxidation catalyst, and has been commonly used as such in the
production of sulfuric acid (H2SO4) from SO2 4.
Fe2O3
facilitates the combustion reaction once combustion is initiated in the engine
cylinder in two related ways. The first
action of hematite is dissociating O2 into Oxygen free radicals 5. The second is reducing Activation Energy 6 with regard to oxidation reactions.
Activation energy is
the amount of energy required to initiate a chemical reaction, which, in the
case of petroleum fuels, is the reaction between oxygen free radicals and
hydrocarbons.
In a closed system
such as an engine's cylinder, these paired effects during fuel combustion
translate to more system energy available to do work per unit of fuel
consumed. This is commonly seen as an improvement in engine torque, as
shown below in a comparative engine output trial between untreated and treated
diesel.
The red line is with Ultimum5 and the grey line is normal untreated fuel.
Even with the catalytic effect of Ultimum5 on combustion efficiency and
engine output, fuel does not burn completely.
Nitrogen is present in the atmosphere entering the engine, and diesel
typically includes very low levels of Sulphur.
The resulting emissions typically comprise various atmospheric gases,
plus the results of oxidation reactions between oxygen and C, H, N, and S,
those being CO/CO2 NOX, and SOX, as well as residual
short chain hydrocarbons and particulates (soot).
Ultimum5 also contains catalysts that work post-combustion to
reduce emissions. The catalytic process by which Ultimum5 reduces NOX and SOX
is similar to Selective Catalytic Reduction (SCR) units, but there are
significant differences with the Ultimum5 emission reduction process.
By way of illustrating the difference between the SCR
process and how Ultimum5 acts, consider the SCR process. A solution containing ammonia (NH3)
or urea (NH2CONH2) is injected via an add-on mechanical
unit into the exhaust stream post-combustion.
Where urea is injected, thermal breakdown of urea in the exhaust gas
stream forms two compounds isocyanic acid (HNCO) and ammonia. Ammonia works as a free radical in concert
with the redox properties of the SCR catalytic converter unit to reduce NOX
(a combination of NO and NO2) to N2 and H2O. The simple form of the reaction is as
follows:
SCR Catalyst + NO + NO2 + NH3
→ N2 + H2O + SCR Catalyst7
The SCR chemical reaction set depends on NO/NO2
in the presence of reactive sites on the catalyst and NH3 acting as
a free radical first causing NO2 to further oxidize and react with
NH3, forming NH4NO3, which is then reduced by
NO to NH4NO2, which then decomposes to N2 and
H2O 8.
The catalysts in Ultimum5 are different than those typically used in SCR.
The Ultimum5 catalysts that affect emissions are used commercially
in redox reactions and are not specific only to Ultimum5.
Ultimum5 catalysts do not rely on ammonia or urea
injected into the exhaust stream post-combustion to act as a free radical to
reduce NOx to N2 and H2O. Instead, there is a two-step process, making
use of a highly selective partial oxidation catalyst and an ammoxidation
catalyst.
The reaction mechanism for V/P oxide catalysts in
terms of selective partial oxidation (as opposed to more complete oxidation
with other catalysts such as platinum-based ones) is not well documented.
However, it is known to exist, and for that reason, V/P oxide catalysts are
used extensively in the production of maleic anhydride from n-butane and
1-butene9. In terms of its
utility in Ultimum5, the partial oxidation catalyst selected for use (VOPO4·nH2O)
could create hydrocarbon free radicals (CH, CH2) from unburned
short-chain hydrocarbons that are in the exhaust stream, making use of its
partial oxidation properties by the following proposed reaction pathways:
VOPO4·nH2O + 4O + C3H8 à 2CH2 + CO2 +2H20
+ VOPO4·nH2O
VOPO4·nH2O + 2O + C2H6 à 2CH + 2H2O + VOPO4·nH2O
That said, Ultimum5 does not have the same shortcomings that SCR does,
where SCR only becomes effective once the system reaches a sufficient
temperature for catalysis to occur, which is typically between about 250°C and
430°C.
Ultimum5 also is not subject to catalyst “poisoning” (a
reduction in catalytic effectiveness due to reaction with emitted exhaust gases
that, over time, act to impede the catalytic effect). This is because active catalysts are being
continually supplied in the fuel. This
also obviates concern about thermal cycling breaking down the physical
structure of their catalytic converter over time.
The reason VOPO4·nH2O was selected for use in Ultimum5 was due to its effectiveness
for the purpose. The purpose was not to
completely oxidize unburned hydrocarbons, as might happen with platinum-based
or cerium-based catalysts. It was only to partially oxidize them, leaving
hydrocarbon free radicals to act in concert with the Ammoxidation catalyst to
reduce unwanted emissions in the exhaust stream.
Ammoxidation catalysts have been found to
be useful in reduction of NOX in exhaust emissions 9. Hydrocarbon free radicals act in a manner
similar to ammonia in SCR processes in the presence of the ammoxidation
catalyst. CO2, NOX
and SOX. In the presence of Ultimum5 ammoxidation catalyst (V4Sb6O8), are reduced to N2, molecular
S, molecular C, and H2O by the following reaction pathways:
V4Sb6O8
+ NOX + CH2 → N2 + CO2 + H2O
+ O2 + V4Sb6O8
V4Sb6O8
+ O2 + SOX + CH2 → S + CO2 + H2O
+ V4Sb6O8
V4Sb6O8
+ CO + CO2 + CH → C + O2 + H2O + V4Sb6O8
The reason V4Sb6O8
was selected for use in Ultimum5 was that its effectiveness as an ammoxidation catalyst, and therefore, its
ability to reduce NOx, SOx, CO, and CO2 in the presence of
hydrocarbon free radicals was sufficient for the purpose, but the catalyst was
not so effective as to impede the effectiveness of the hematite catalyst
generated during combustion of Ferrocene with regard to oxidation reactions.
As regards the
exhaust, it’s widely known that various metals are emitted in the exhaust
during diesel engine use, as part of particulate emissions 10, 11, 12, 13. Metallic emissions in diesel exhaust comes
from two sources: the fuel itself, or from metallic additives in engine oil and
wear metals deposited in engine oil 14.
With regard to the
total amount of metals plus P emitted as a result of Ultimum5 usage, consider the following; a vehicle with a fuel use rate of 30 miles per
gallon (3.785 liters/gallon) traveling at 60 miles per hour using fuel dosed
with Ultimum5 will emit less
than 0.0706 mg/minute of combined V, Sb, Fe, and P. The total amount of Fe, V, and Sb alone
emitted from a typical 6-cylinder diesel engine in exhaust is approximately 4.481
mg/minute14. Comparing the
two values, the total amount of metals and P emitted as a result of Ultimum5 usage under those
circumstances increases the total metal concentration of diesel exhaust by less
than 1.5%.
Typical additives used
for detergent purposes, sequestering water, improving cetane/octane levels,
etc., can only return engine efficiency and emissions to levels approaching
that of a clean, new engine. Because of
the unique catalytic formulation of Ultimum5 and how it affects both the combustion process and exhaust gas makeup, fuel
economy and emissions can be improved over and above levels observed in clean,
new engines. No other fuel additive can
successfully make that claim.