Cetane Improvement In Diesel
Hydrotreating
emand for higher performance
Greg Rosinski
Technical Services Engineer
D in diesel engines has resulted
in an increase in minimum
cetane numbers for diesel fuel. It is
Charles Olsen expected that the desire for higher
Worldwide Technical Services cetane will continue as indicated by
Manager the recommendations of the World
Wide Fuels Charter. Thus, it is impor-
tant for refiners to understand the
ADVANCED REFINING effects of both feedstock and pro-
TECHNOLOGIES cessing parameters on the cetane of
Chicago, IL USA diesel fuel to enable them to more
effectively manage their distillate
hydrotreating units to meet ever more
stringent fuels specifications.
While some diesel is produced in
hydrocrackers, the vast majority of
diesel is processed in diesel
hydrotreaters (DHT’s) which usually
co-process streams such as FCC
12 www.e-catalysts.com
LCO, LCGO, SR diesel, and
Kerosene. The units processing
significant amounts of cracked
stocks need special attention in
order to meet product cetane
requirements. To understand why
this is so it is necessary to know
what cetane is, and how the differ-
ent molecular species influence it.
The cetane number is a measure of
the ignition quality of diesel fuel and
is based upon the compound
cetane or hexadecane which is
assigned a cetane number of 100.
It is analogous to the octane num-
ber in gasoline. Gasoline octane
increases with olefin, aromatic, and
iso-paraffin contents, whereas
cetane number increases with
paraffin and naphthene contents.
 Table I
Cetane Number of Pure Compunds

Compound Formula Cetane

Number
n-Decane C10H22 76
n-Pentadecane C15H32 95
Paraffins

n-Eicosane C20H42 110

3-Ethyldecane C12H26 48
4,5-Diethyloctane C12H26 20
Heptamethylnonane C16H34 15
Isoparaffins
8-Propylpentadecane C18H38 48
7,8-Diethyltetradecane C18H38 67
9,10-Dimethyloctadecane C20H42 59
Decalin C10H18 48
3-Cyclohexylhexane C12H24 36
Naphthenes
2-Methyl-3-cyclohexylnonane C16H32 70
2-Cyclohexyltetradecane C20H40 57
1-Methylnaphthalene C11H10 0
n-Pentylbenzene C11H16 8
Biphenyl C12H10 21
Aromatics 1-Butylnaphthalene C14H16 6
n-Nonylbenzene C15H24 50
2-Octylnaphthalene C18H24 18
n-Tetradecylbenzene C20H34 72

Thus, a fuel with a high cetane value
has low octane and visa versa.
Table 1 lists some pure compounds
and their corresponding cetane
number. As can be seen, paraffins,
particularly normal paraffins, have
very high cetane numbers while
aromatics, especially naphthalene
type aromatics, have very low
cetane numbers. Certain distillate
range materials like FCC LCO are
high in naphthalenes which
explains the low cetane number of
LCO feedstocks.
The actual cetane number is rarely
analyzed in refineries since it
requires a specialized motor for its
determination. Most refiners’ use
cetane index, typically, ASTM D-976
and ASTM D-4737. D976 uses the
API gravity and the 50% distillation
point, whereas D4737 uses the
gravity with the 10%, 50% and 90%
distillation points. The two equa-
tions are shown below.
ASTM D-976
cetane index = -420.34+0.016*API 2
+0.192*API*log(T50)+65.01*log
(T50)–0.0001809 *T502
Where T50 is the D86 50% point in
degrees °F
ASTM D-4737
Cetane index= 45.2+0.0892*(T10-
215)+[0.131+0.901* B]*[T50-260]
+[0.0523–(0.420)*(B)*][T90-
310]+[0.00049]*[(T10-215)2
–(T90-310)2] + (107)*(B) + (60)*B2
Where: B = Exp[-3.5*(sp. gr. – 0.85)] –
1 and the D86 temperatures are in °C
Figure 1 compares the cetane index
(D976) for a number of different distil-
late feed sources. It is readily appar-
ent that FCC LCO’s have the lowest
cetane while straight run (SR) materi-
als have the highest cetane. Distillate
feeds derived from coking operations
tend to have a cetane similar to SR
material, while kerosene tends to have
somewhat lower cetane owing to the
lower boiling point. For the diesel
range materials, the feeds with
lower API gravity (LCO) have lower
cetane index demonstrating that
within a given boiling range the API
is a reasonable tool for estimating
the cetane index.
Figure 2 shows the cetane index as
a function of poly aromatics content
for a variety of distillate feeds. The
LCO’s clearly have the highest con-
centration of poly aromatics and
correspondingly lower cetane
index. The SR, LCGO and vacuum
bottom gas oil (VBGO) all have con-
siderably lower PNA content with
higher cetane index values com-
pared to the LCO’s. Kerosenes
have very low polynuclear aromatics
(PNA) content, but because of the
lower molecular weight (kerosene
generally has compounds contain-
ing less than 16 carbon atoms) the
cetane index is slightly lower than
for SR diesel material. The figures
make it clear that when it comes to
cetane, LCO is a problem due to the
high PNA content.

ART Catalagram® 106 Special Edition Fall 2009 13

Treating feedstocks that contain Figure 1
LCO will become more challenging Cetane Index of Various Distillate Feeds
as LCO yields increase and cetane 60
requirements become more strin- 55
gent. With this in mind, it is useful to
50
survey the level of performance cur-

Cetane Index (D976)

45
rently being achieved in commercial
diesel hydrotreating units today. 40

This will help to define what the rea- 35

sonable level of cetane uplift that 30
can be expected is, and if there is a
25
practical maximum uplift that can
be achieved via hydrotreating. It is 20

also useful to ascertain whether 15

current operations indicate if 10
cetane changes (decreases) during 5 10 15 20 25 30 35 40 45 50

the cycle. All of these are important Feed API

questions for refiners interested in LCO Straight Run Kerosene
LCGO/VBGO
increasing diesel yields from lower
quality feedstocks.
Figure 2
There are a number of parameters Cetane Index and Polynuclear Aromatics (PNA’s)
which influence cetane improve- 60

ment in the diesel hydrotreater. 55

Hydrogen partial pressure and 50
Feed Cetane Index (D976)

LHSV are key operating conditions

45
which effect the product cetane.
Catalyst selection also plays an 40

important role since at higher pres- 35

sures NiMo catalysts have a higher 30
PNA saturation activity compared to
25
CoMo catalysts.
20

Figures 3 shows the level of cetane 15

increase (measured by delta cetane 10
index) that has been achieved com- 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
mercially as a function of unit LHSV. Feed PNA’s, vol.%
Generally speaking, as LHSV LCO Straight Run Kerosene
LCGO/VBGO
decreases the potential cetane
improvement increases. At a LHSV
around 1 hr-1 or less, cetane index Figure 3
increases of 10 or more numbers Effect of LHSV on Cetane in a Variety of Commercial Units
are achievable (provided the H2
14.0
pressure is high enough), while at a 13.0
LHSV greater than about 1.7 hr-1 12.0
the cetane improvement is about 4 11.0
numbers or less.
Delta Cetane Index

10.0
9.0

Figure 4 summarizes the cetane 8.0

increase as a function of unit pres- 7.0

6.0
sure. Not surprisingly, higher pres-
5.0
sure units tend to achieve much
4.0
larger cetane increases. In these 3.0
examples, the cetane uplift is typi- 2.0
cally less than 6 numbers when the 1.0
unit pressure is less than 1000 Psig. 0.0
Cetane uplift increases to 8-10 num- 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0

bers as pressure increases beyond LHSV

1000 psig. The data in Figures 3 Refiner A Refiner B Refiner C Refiner D Refiner E Refiner F

14 www.e-catalysts.com
 Figure 4 and 4 also suggest there might be a
Effect of Unit Pressure on Product Cetane practical limit to cetane improve-
ment achieved from typical
14.0
13.0
hydrotreating. Comparing the
12.0
cetane uplift achieve by Refiners A
11.0 and C shows about 8-10 number
10.0 improvement for both units despite
Delta Cetane Index

9.0 the difference in operating pressure

8.0 at similar LHSV.
7.0
6.0 Figure 5 summarizes the commer-
5.0
cial data in another way. It shows
4.0
how the cetane increase correlates
3.0
with the API gravity of the feed. In
2.0
1.0
general, the cetane uplift increases
0.0 as the feed API decreases. Figure 6
400 600 800 1000 1200 1400 1600 1800 2000 2200 shows how the observed API
Reactor Inlet Pressure, Psig increase correlates with the cetane
Refiner A Refiner B Refiner C Refiner D Refiner E Refiner F index increase. This data shows
that the API uplift is a reasonable
predictor for the cetane increase.
Figure 5
Feed API Has a Significant Impact on Cetane Uplift The hydrogen consumption is
14 another important consideration
13 when discussing cetane improve-
12 ment. There is a general rule of
11 thumb that says the hydrogen con-
10 sumption is roughly equal to (100*
Delta Cetane Index

9 API Uplift) or (100* Cetane uplift).

8 Averaging the H2 consumption
7
required for the observed cetane
6
5
increase with the units discussed
4
here indicates that the H2 consump-
3 tion varies from about (80*Cetane
2 uplift) at low pressure (Refiner D) to
1 (150-175* Cetane uplift) for the high
0 pressure units (Refiners A & C). The
16 18 20 22 24 26 28 30 32 34 36 38 40 42 44
data suggests the rule of thumb is a
Feed, API
reasonable estimate for H2 con-
Refiner A Refiner B Refiner D Refiner E Refiner F
sumption for units operating below
Figure 6 about 1000 psig.
API Uplift and Cetane Increase
for Several Commercial Units These data demonstrate that as the
11 unit conditions (LHSV and pressure)
10 get more favorable for PNA satura-
9
tion, the cetane uplift increases.
However, is cetane uplift constant
8
during an entire cycle?
Delta Cetane Index

6 Figure 7 summarizes the observed

5 cetane from three ULSD units cur-
4 rently using SmART systems.
Refiner A is a high pressure unit with
3
a LHSV around 1. The feed to this
2
unit contains 40-50 vol.% LCO. This
1 unit has not experienced a signifi-
0 cant decline in cetane uplift during
0 1 2 3 4 5 6 7 8 9 10
the cycle. Refiner B is a higher
Delta, API
LHSV unit, with a lower pressure
Refiner A Refiner B Refiner D Refiner E Refiner F

ART Catalagram® 106 Special Edition Fall 2009 15

than Refiner A, but the feed is rela- Figure 7
tively light with about 35-40 vol.% Variation in Cetane Uplift During a Cycle
LCO and LCGO. Despite the lower
pressure and higher LHSV, this 14

refiner also did not see an apprecia- 13

12
ble decline in cetane uplift during
11
the cycle. Refiner C is a higher
10

Delta Cetane Index

pressure unit with a lower LHSV
9
compared to Refiner B. The feed is 8
high in sulfur with large (>80 vol.%) 7
amounts of cracked stock, espe- 6
cially LCO. This unit does show a 5
slow, steady decline in cetane uplift; 4
the cetane uplift is 2-3 numbers 3

lower after more than two years on 2

stream. This suggests that units 1

0
with difficult feeds containing high 0 100 200 300 400 500 600 700 800 900 1000 1100
fractions of LCO and other cracked Days on Stream
stocks, or units without sufficient
Refiner A Refiner B Refiner C
hydrogen, will experience decreas-
ing cetane uplift during the cycle.
Figure 8
As mentioned previously, the cata- The Catalyst System Has a Huge Impact on Cetane Uplift
lyst system will also have an impact 15
on the degree of cetane uplift 14
achieved in a hydrotreater. It is
13
common knowledge that NiMo cata-
Cetane Index Increase

12
lysts have a higher saturation activi-
ty than CoMo catalysts, and there- 11

fore a NiMo catalyst is expected to 10

deliver greater cetane uplift. Figure 9

8 summarizes pilot plant data which 8
demonstrates this. These data were 7
generated using a 50% LCO con-
6
taining feed, and shows that the
5
NiMo catalyst results in almost twice
4
the cetane uplift compared to the
620 625 630 635 640 645 650 655 660 665 670
CoMo catalyst. The SmART Catalyst
Temperature, ˚F
System, which utilizes both the
CoMo and NiMo catalyst, results in NiMo CoMo SmART

a cetane uplift which is nearly 2

numbers higher than the all CoMo
system with only a small increase in
hydrogen consumption. For H2 con-
strained refiners this is an ideal
solution for improving the product
cetane.

16 www.e-catalysts.com