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What Refiners Need to Know About Diesel Cetane

By Process Pro Eric
Sep 07, 2015

Good tips on what you should know for Diesel Cetane.

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Refinery 101 18
Let’s face it… while maximizing diesel production trumps gasoline production these
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days, not many refinery operators, engineers, nor managers really understand diesel
Unit Operations 9
specs that well. The most commonly misunderstood spec is diesel cetane.
Product Value Upgrading 7
Cetane Number (CN) is a measure of a fuel’s ignition delay in an engine. A higher Market Analysis 27
cetane number indicates shorter ignition delay. Since diesel engines act somewhat
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oppose to gasoline engines, shorter ignition delay (i.e. higher cetane number) fuels
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provide better performance. This is why many refiners refer to cetane as the opposite
of octane. U.S. cetane number spec is set at 40, while fuels in EU and elsewhere can Safety & Environment 17
have cetane number specs of 51 or higher. Reliability and Maintenance 12

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Refiners who rely on cetane correlations can use the calculated Cetane Index (CI) to More Events
estimate cetane number. In the U.S. there are two ASTM test method correlations,
D976 and D4737, both of which rely on ASTM D86 distillation and density.

D976 is an older correlation that relies on two-variables – API and T50

D4737 is an updated correlation that uses four variables - API, T10, T50, and
T90

While D976 (two-variable) is often used as a surrogate test method for setting aromatic
specs in diesel fuel, it is often not used as a preferred means of calculating Cetane
Index these days. This is because a larger offset generally exists between the
measured Cetane Number (CN) and the calculated Cetane Index (CI) when using
ASTM D976.

D976 worked fairly well when the correlation was first developed and most diesel
formulations consisted primarily of straight run diesel components. As oil refining
technology advanced, diesel fuels had a higher composition of cracked and aromatic
stocks from Cokers and FCCs. Furthermore, in today’s environment where synthetic
and oil sand crudes distort “straight run” diesel qualities, more robust correlations
became necessary to better predict cetane.

For those engineers interested to know the equations behind the two-variable and four-
variable correlations, the formulas below show the calculation of CI by D976 and
D4737. While neither are exactly straight-forward, you can see that the four variable
equation has a higher complexity.
Since many refineries do not have cetane engines, most engineers do not appreciate
the offset between D976 & D4737 with the measured cetane number. The data below
shows various diesel streams and compares estimated cetane index with measured
cetane
number. In this first data set we
compare calculated cetane index
using both the 2-variable and 4-
 variable equations to the measured
cetane.

While this is a straight run kero

stream, the D4737 (4-variable)
correlation actually has a lower offset
as compared to D976. This kero
stream has a 550 deg F 90% and a 37
API.

In the next data set we have D4737

and D976 on a straight run diesel
stream compared to the measured
cetane number.

For this stream the D976 (2-variable)

correlation is a better predictor of
cetane number as compared to the
D4737. This straight run stream has a
90% distillation of 660 deg F and 31
API. As you can see, The 2-variable equation does a fairly decent job of cetane
prediction for traditional diesel properties.

In this last data set, the two cetane

correlations are compared to the
cetane number for a FCC LCO
stream.

Both correlations match rather poorly,

and interestingly enough there’s a
lower offset between the 2-variable
equation and the CN.
 The LCO stream has a distillation of
700 deg F 90% and API of 9…yes 9.

Although D4737 better predicts CI for diesels containing cracked stocks, the very low
API of this LCO breaks the correlation for an individual stream assessment.

To summarize the information above, each refiner should rigorously check the bias
between measured cetane number and calculated cetane index on an occasional
basis. Depending on the quality of your diesel stream, D976 and D4737 cetane index
correlations will provide vaying levels of accuracy.

A savvy process engineer should also be mindful of refinery configuration changes. It

can pay-out big bucks to scrutinize diesel giveaway when unit shutdowns occur. When
FCC units go offline and LCO production declines, one should re-assess the cetane
balance and not blindly use the ASTM CI correlations to predict cetane.

As one last tip to note, many refineries use cetane improver to increase the cetane
number of finished diesel fuel. While additives can truly improve Cetane Number (CN),
they do not affect Cetane Index (CI). Depending on whether your efinery is cetane
number or cetane index limited, improver may or may not make a difference. Also be
mindful that cetane improver has a response curve decline. Beyond an optimal dosage
rate, you receive limited benefit for incremental additive usage.

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Process Pro Eric : Note that I have updated the equation above to include
the missing parenthesis in the D4737 equation. Thanks for pointing out the
error.
Nov 18, 2013

Lionel : D4737 still does not work Please check the formula before
publishing it.
Nov 27, 2014

Process Pro Eric : Lionel, If you wish to send me your spreadsheet I will
confirm if you have the calculation copied correctly. You can send the file to
support@refinerlink.com.
Dec 01, 2014

Janis : If I know cetane index is over 40, is there a correlation or calculation

for aromatic percentage - for Title V air permit when we get diesel deliveries I
have to document both and suppliers only show cetane index.
Aug 05, 2015

Process Pro Eric : Janis, unfortunately i'm not aware of any correlation
between CI and Aromatics. I know of other refiners in your situation and they
run lab analysis to confirm the aromatics content.
Aug 09, 2015

Tony Evans : I used to run Cetane Engines for Chevron back in the day,
(ASTM D613), together with RON, & MON engines, still involved now with
Inspectorate in the UK. A lot of refiners do not have the expertise on hand for
D613, and have now plumped for the IQT testing apparatus
http://www.biofueltesting.com/product.asp?ID=3455 As a process engineer, I
had to optimize diesel production in a short diesel world, and to do this used
every componant available, to meet the CI spec, and using iso octyl nitrite to
get to CN spec. I have some blend optimisation programs available if anyone
needs
Sep 08, 2015

Tony Evans : Janis, the ignition quality of a diesel fuel is boosted by paraffin
content, and reduced by aromatic content. So, to optimize diesel blends in a
full conversion refinery, need to introduce LCGO to diesel blend pool. This
component reduces cetane, and to overcome the neg effects to cetane when
using highly aromatic LCGO, companies will use a cetane improver additive.
Sep 08, 2015

Marc Valleur : This is a very good illustration of the caution required when
using regressions. They are only valid in a specific operating window and any
extrapolation must be avoided. It was interesting to use Diesel Cetane Index
as an example because I feel that blending middle distillates has become
more complex than blending gasoline: a) A Euro V Diesel quality certificate
has typically 22 quality determinations b) An optimal blend recipe for diesel
can be 4 - 6 components out of a dozen in refineries with very complex
process scheme c) FAME of various grades used to produce Bio Diesel is
bringing new chemical species, impacting cold properties. In comparison,
adding ethanol to gasoline is easy. d) Typically more than a dozen of
additives, tracers, dyes, etc are used to produce the final commercial product,
much more than gasoline e) There are many grades of middle distillates,
including specialty products, such as arctic diesel In consideration of the
above, the operating window for diesel is very large which is difficult to
accomodate with a set of regression coefficients. My belief is that more
elaborate methods can fight complexity and I am convinced that we need to
track chemical species in order to have robust predictions of quality
determinations. Much progress has been made over the last 20 years using
lab and on-line spectrometers (NIR, MIR, Raman) for that purpose.
Sep 20, 2015

Antony Evans : Aside from the obvious implications to cold properties,

FAME as a blend component to Diesel, can also affect the Cetane,
filterability,and oxidation stability of the finished blend.
Sep 22, 2015

Marc Valleur : It is true that FAME improves many Diesel quality specs and
degrades cold flow proerties and oxydation stability. It also impacts density
and viscosity. Many of these commercial specs are controled using additives
such as cetane boster or lubricity improver. We need a good representation of
the non linear response to injection rates under various blend compositons.
This is an area where we still need progress to achieve operational
excellence, for instance performing in-line quality certification.
Sep 22, 2015

S Bose : Am going thru' the article for the first time. A question that comes -
tat the three illustrative graphs used in the text, what is the parameter plotted
on x-axis? Shall much appreciate a quick answer.
Apr 15, 2016
 Process Pro Eric : S Bose - there is no meaningful parameter plotted on the
x-axis (i.e. it is only time). The graphs are meant to illustrate the variation
between the calculated cetane index for the two equations compared to the
cetane number derived by engine.
Apr 16, 2016

Facundo : Hi! For D4737 method, the B parameter formula should be B =

exp(-3.5*DN) - 1
Sep 18, 2017

Tommy A : Hey guys, can you send me calculatation sheets as discussed

above that you don’t mind sending me? Tommy.arencibia@camincargo.com
Thanks guys.
Nov 17, 2017

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