Predicting middle distillate properties
Development of on-stream correlation models to predict cloud point, flash point and
freezing point and increase production of on-spec jet fuel using a single analyser
MADI ASIRI
Saudi Aramco Total Refining and Petrochemical Company (SATORP)
W
e cannot opti-
mise what we
cannot measure
continuously and we cannot
increase refinery margin with-
out continuous process optimi-
sation. This study aims to find
a simple and cost-effective way,
with no capital investment, to
measure and predict contin-
uously the physical proper-
ties of middle distillate streams
without the need for additional
on-stream analysers. The first
part of the study focuses only
on hydrocracking middle distil-
late products (diesel and kero-
sene) while the second part will
deal with the other middle dis-
tillate streams (CDU, DCU, and
so on). The model developed
in this study can be integrated
with a DCS (or APC) system
to minimise product giveaway
and maximise the production
rate of middle distillate within
final specification limits.
Based on a deep understand-
ing of hydrocracking process
operation, catalyst function and
reaction chemistry, we started
our work with two differing
hydrocracking units: a two-
stage Isocracking unit (TSREC)
with a name plate capacity of
www.digitalrefining.com/article/1002285
59 000 b/d and 97% true net
conversion; and a single-stage
once-through Isocracking
unit (SSOT) with a name plate
capacity of 59 000 b/d and 50%
true net conversion (see Figure
1).
Cold flow properties, cloud
point and freezing point are
controlled by the reaction sec-
tion. In particular, the amount
of n-paraffins in the reactor
effluent, which has the big-
gest impact on middle distillate
cold flow properties, is con-
trolled by severity of operation
in the reaction section (WABT,
H2PP, LHSV and catalyst type).
However, in a hydrocracking
process unit, as part of the cat-
alyst selection and catalyst per-
formance guarantee, yields and
product quality must be guar-
anteed over the life cycle of the
selected catalyst.
In other words, the chemical
structure of the reactor effluent
(paraffins, iso-paraffins, naph-
thenes and aromatics) over the
cycle life of the catalyst must
show absolutely minor changes
to ensure product quality from
start of run conditions to end of
run conditions for the selected
catalyst.
Our first assumption is
that, since the internal chem-
ical structure of middle dis-
tillate shows minor structural
changes over the catalyst cycle
life, we can assume that both
cloud point and freezing point
are functions of the amount of
heavy hydrocarbons in the mid-
dle distillate; the heavy part of
the middle distillate will impact
both cloud point and freezing
point. However, since D86 data
can give us the required infor-
mation about the middle dis-
tillate streams, how heavy or
light they are and how tight
or wild is the middle distil-
late cut, there should be a rela-
tionship with the distillation
data (ASTM D86) and with
both cloud point and freez-
ing point in the hydrocracking
unit. Hence, both cloud point
and freezing point can be con-
trolled in day-to-day operations
by adjusting the fractionation
section’s operating conditions,
keeping in mind that opera-
tions in the reaction section
are almost steady and not fre-
quently changed. Usually, the
reaction section’s severity is set
to meet the nitrogen slip of the
pretreat reactor and the global
PTQ Q1 2019 1
 Make-up H2 10 hydrogen
Make-up
from offpilot compression section
5
0 H2S absorber /
VGO and Two-stage Isocracking Recycle gas compressor
HCGO feed
−5 reactor

CP, ºC
CLPS vapour
−10 HLPS/CLPS Unstabilised to offpilot PSA
−15 Lab Modelliquid naphtha
3wt% UCO bleed Sour LPG to
from MHC−20
unit Recycle gas Fractionation LPG treating unit
separation section section Naphtha
0 10 20 30 40 50 60 70 80
stabilisation 90 naphtha
Light
section
Time, days Heavy naphtha
Fractionation bottoms
Kerosene
product
Diesel
product
Unconverted oil
to offpilot FCC
Make-up H2 Make-up hydrogen
from offpilot compression section

H2S absorber /
VGO and Single-stage Recycle gas compressor
HCGO feed Isocracking reactor
CLPS vapour
HLPS/CLPS to offpilot PSA
liquid
Recycle gas Fractionation Sour offgas to offpilot
separation section section amine absorber
Unstabilised naphtha to
naphtha stabilisation section
Parameters TSREC SSOT in DHC unit
Operating capacity, BPSD 65 000 65 000 Kerosene
LHSV reactor no. (R1/R2/R3), 1/h 1.5/1.45/1.45 1.5/1.45/NA product
H2PP @ reactor inlet, Barg 155 155 Diesel
H2/oil ratio (1st stage/ 2nd stage), Nm3/Sm3 840/680 840/NA product
CATs (WABTs) reactor no. (R1/R2/R3), °C 370/385/350 365/380 Unconverted oil
Net conversion, % 95 55 to offpilot FCC
2nd stage PPC, % 50-55 NA 3 wt% bleed unconverted oil
2nd stage RCP, °C 375 NA to DHC unit
Hydrocrackers average operating conditions during model data collection

Figure 1 Block flow diagram of two hydrocrackers modelled for the study

conversion of the cracking reac-
tors during the catalyst life
cycle with normal acceptable
deactivation rate.
On the other hand, flash point
is a function of the amount of
light hydrocarbons (light ends)
in the middle distillate, which
can be controlled in the hydro-
cracking fractionation sec-
tion by adjusting the operating
conditions.
Based on all of the above
assumptions and information,
linear models were developed
to predict the physical proper-
ties of hydrocracking middle
distillate. The target properties
are cloud point, flash point and
freezing point. A total of eight
correlations were developed for
four product streams in two dif-
ferent hydrocrackers within the
refinery. These correlations are:
• Flash point and freezing point
for kerosene in both TSREC and
SSOT
• Flash point and cloud point
for diesel in both TSREC and
SSOT.
These models are tools to
allow for process optimisation
to maximise the middle distil-
late production rate and mini-
mise product giveaway within
product specifications by con-
tinuous measurement at the
operators’ panels. These cor-
relation models will add more
value to process optimisa-
tions and product quality con-
trol. Instead of waiting for lab
results once a day (or in some
cases twice weekly), the oper-
ations team will have continu-
ous data and information about
cloud point, flash point and
freezing point to enable them to
take immediate action and not
wait for the next day’s results
to see the impact of today’s
actions on product quality.
Cloud point is the lowest tem-
perature at which wax crys-
tals begin to form by gradual
cooling under standard condi-
tions. However, this parameter

2 PTQ Q1 2019 www.digitalrefining.com/article/1002285

 Standard error and model validation range

Models TSREC SSOT TSREC Kerosene SSOT Kerosene TSREC SSOT TSREC SSOT
Kerosene FP Kerosene FP Freezing point Freezing point Diesel FP Diesel FP Diesel CP Diesel CP
Standard error 0.82 1.21 1.21 1.7 1.7 1.4
Validate Range MAX T10%=203 T70%=234 T70%=230 T10%=294 T70%=351 T70%=346
T95%=270 T95%=252 T95%=373 T95%=375
Validate Range MIN T10%=167 T70%=197 T70%=192 T10%=248 T70%=303 T70%=316
T95%=215 T95%=212 T95%=332 T95%=342

Table 1

is an important property of the Objective • Maximise the middle distil-

fuel since the presence of solidi-
fied waxes can block filters and
negatively impact engine per-
formance. As the molecular
weight rises, the cloud point is
also incremented at low temper-
ature conditions. Furthermore,
cloud point is a measure of par-
affin content in wax form, which
is why no cloud point data are
reported for light cuts like naph-
tha or gasoline.
Freezing point is the temper-
ature at which a liquid changes
to a solid by cooling. Jet aircraft
are frequently exposed to low
operating temperatures and it is
essential that their fuels do not
freeze in these environments.
Plugging of filters and related
operational problems in the
fuel system are dependent on
freezing point; for this reason,
jet fuel specifications include
requirements for maximum
freezing point.
Flash point is the lowest tem-
perature at which vapours
above a volatile, combustible
substance ignite in air when
exposed to flame. The lower
the flash point, the easier it is
to ignite the vapour if an igni-
tion source is present. The
higher the flash point, the safer
the material is to handle. This
means that the temperature
limit to achieve safe storage
is below flash point. A higher
vapour pressure corresponds to
a lower flash point.
The aim of the study is to late production rate.
develop on-stream optimi-
sation tools (models) to ena- Data analysis and results
ble refiners to measure Building any model for mid-
physical properties in hydro- dle distillates to measure addi-
cracking units continuously, tional physical proprieties
and to have the opportunity demands a deep understanding
for continuous process opti- of process operations and what
misation by utilising a dis- impact dependent and inde-
tillation on-stream analyser pendent variables have on the
(ASTM-D86). Most refiners target properties. For instance,
depend on lab results to meas- in studying flash point the
ure these additional proper- most important variable is the
ties, a very slow process which amount of light hydrocarbons
reduces the opportunities for (light ends) in the product cut.
process optimisation, or they To study cloud point or freez-
need to have an individual ing point, the important var-
analyser for each property they iable is the amount of heavy
want to measure (see Table 2), hydrocarbons (heavy ends)
which involves a high capital in the product cut. However,
investment cost in addition to for every model certain stages
high operating costs. However, must be passed to be able to
it is not common to have so achieve a proper conclusion
many analysers installed in a and results:
single hydrocracking unit. The 1. Collecting lab historical data
optimisation models should 2. Finding the relationships of
aim to: dependent variables
• Continuously optimise mid- 3. Distillation (D86) analyser
dle distillate production calibration and validation
• Minimise middle distillate 4. Defining the on-stream mod-
product giveaway. el’s dependent variables
List of the tests according to the property for diesel and kerosene
Product stream Property Test Repeatability (r) Reproducibility (R) Notes
Diesel Flash point ASTM-D93 0.0.029×M 0.071×M M = mean
Cloud point ASTM-D5773 1.3°C 2.5°C result in (°C)
Kerosene Flash point IP-170 1.4°C 3.2°C
Freezing ASTM-D7153 0.6 °C 0.9°C
Table 2

www.digitalrefining.com/article/1002285 PTQ Q1 2019 3

 5. On-stream model validation.
10
5
On-stream distillation analys-
0 ers (OSA D86) are familiar and
−5 available in refineries to meas-
CP, ºC
−10 ure middle distillate distilla-
−15 Lab Model tion. The on-stream distillation
−20
0 10 20 30 40 50 60 70 80 90 analyser is the backbone of all
Time, days our models. However, we have
ensured that calibration of these
Figure 2a TSREC diesel cloud point (lab vs model) analysers has been done accord-
ing to ASTM-D3764. We have
developed the models as a func-
8 tion of the D86 analyser output
6
from the field and were able to
4
2 achieve excellent results. A sin-
0 gle distillation analyser can be
−2 used to give field data for two
−4 different streams (diesel and
−6
−8
kerosene) in any hydrocrack-
Lab CP

−10 ing operation which cycles in

−12 alternative mode between the
−14 two products, which is the case
−14 −12 −10 −8 −6 −4 −2 0 2 4 6 8
with the SSOT unit. A numerical
Model CP
method was used to predict all
of these properties as a function
Figure 2b TSREC diesel experimental (lab) CP vs model calculated cloud point of distillation (see Table 1).

Diesel cloud point

10
In general, as ambient temper-
5
ature decreases, the solubility
0
of n-paraffins also decreases in
−5
CP, ºC

the middle distillate fraction.

−10 Lab Model Precipitation occurs over a wide
−15
0 10 20 30 40 50 60 70 80 90 temperature range until solidi-
Time, days fication finally takes place. The
amount of n-paraffins in mid-
Figure 3a SSOT diesel cloud point (lab vs model) dle distillate has a direct effect
on the fraction’s cold proper-
10 ties (cloud point, pour point,
and cold filter plugging point).
The cold flow property (mainly
5
cloud point) is also important
from an economic point of view.
0
We have found that the diesel
cloud point correlates very well
−5 with the heavy end of the die-
Lab CP

sel distillation (T70% and T95%)

−10 in both hydrocracking units. For
−10 −8 −6 −4 −2 0 2 4 6 8 TSREC, a total of 25 days of sam-
Model CP ple results were used, and in
SSOT a total of 24 days of sam-
Figure 3b SSOT diesel experimental (lab) CP vs model calculated cloud point ple results were used to develop

4 PTQ Q1 2019 www.digitalrefining.com/article/1002285

the correlation model. Sample
collection was done carefully −50
Lab
and precisely to minimise sam- −55
Model
pling error. We were able to do −60
a smart process step change in −65

FzP, ºC
−70
the fractionation section to allow
−75
for variation in both distillation −80
and cloud point and to see the 0 10 20 30 40 50 60 70 80 90 100 110 120
response of the model during Time, days
the days of sample data collec-
tion and models validation. Figure 4a TSREC kero/jet freezing point (lab vs model)
The model’s results for die-
sel cloud point compared to the −50
lab results are shown in Figures
2 and 3 which show alignment −55
between the lab results and the −60
model outcome at any given
−65
time in two different hydroc-
Lab FZP, ºC

racking units. However, Figures −70

2b and 3b show the deviation
error between lab measured
cloud point (experimental) and
the model CP (calculated). The
models have an absolute stand-
ard deviation error (TSREC
cloud point, see Equation 1 =
1.7°C; SSOT cloud point, see
Equation 2 = 1.4°C). However,
as of today, there is no standard
API correlation to estimate the
cloud point from distillation:
TSREC Diesel cloud point (°C) = [(T70%)
× (0.16427)] + [(T95%) × (0.30471)] -
(165.33) (1)
SSOT Diesel cloud point (°C) = [(T70%)
× (0.29853)] + [(T95%) × (0.16907)] -
(160.42) (2)
Kerosene (jet) freezing point
We have found that jet freezing
point correlates very well with
the heavy end of the jet stream
(T70% and T95%) in both hydro-
cracking units, in exactly the
same way as the diesel cloud
−75
−80
−80 −75 −70 −65 −60 −55 −50
Model FZP, ºC
Figure 4b TSREC kerosene experimental (lab) freezing point vs model calculat-
ed freezing point
sel in order to save experimen- SSOT kero FzP (°C) = [(T70%) ×
tal time. A total of 38 sample (-0.02213)] + [(T95%) × (0.49808)] -
results were used to develop the (181.68) (4)
model in TSREC and a total of
25 sample results were used in Hydrocracker diesel and
SSOT. Figures 4a and 4b show kerosene (jet) flash point
the deviation error between lab Flash point is related to the vol-
measured freezing point (exper- atility of middle distillate and
imental) and the model freez- the presence of light and volatile
ing point (calculated) for TSREC. components. Equation 5 shows
Figures 5a and 5b show the the API standard method to esti-
equivalent data for SSOT. The mate the flash point of petro-
models show an absolute stand- leum fractions as a function of
ard deviation error of 1.21°C for ASTM D86 (T10%):
both unit models (TSREC freez-
ing point, see Equation 3; SSOT API Standard Method
freezing point, see Equation 4). 𝟏𝟏 𝟐𝟐. 𝟖𝟖𝟖𝟖𝟖𝟖𝟖𝟖𝟖𝟖
As of today, there is no standard !
𝑻𝑻𝒇𝒇𝒇𝒇
&=(
𝐓𝐓𝐓𝐓𝐓𝐓
1

point. We followed the same
steps for the jet freezing point
as we had done for the die-
sel cloud point. All of the step
changes were done at the same
time for both kerosene and die-
API correlation to estimate the
freezing point from distillation:
TSREC kero FzP (°C) = [(T70%) ×
(0.09898)] + [(T95%) × (0.32710)] -
(165.44) (3)
+ [(3.4254) × 10-3 ×
ln(T10) ] - (0.024209) (5)
where both flash point and T10
are in degrees Kelvin. Equation
5 predicts flash points with an

www.digitalrefining.com/article/1002285 PTQ Q1 2019 5

 to develop a correlation model
−60 to estimate the flash point for
−65 both diesel and kerosene. The
−70 flash point model has an abso-
lute standard deviation error of
FPZ, ºC

−75
Lab
−80 0.82°C for kerosene and 1.7°C
Model
−85 for diesel.
0 10 20 30 40 50 60 70 80 90 100 110 120 Figures 6a and 7a shows the
Time, days flash point model’s results and
Figures 6b and 7b show the lab
Figure 5a SSOT kero/jet freezing point (lab vs model) measured flash point (experi-
mental) and the model predicted
flash point (calculated):
−60

Diesel F.P. (°C) = [(T10%) × (0.5613)] -

−65
(58.868) (6)
−70
Kerosene F.P. (°C) = [(T10%) × (0.6239)]
- (58.448) (7)
Lab FzP, ºC

−75

−80 Kerosene flash point and

freezing point optimisation
−85
−85 −80 −75 −70 −65 −60 −55 A real example of the applica-
Model FzP, ºC tion of the developed model was
the ability to minimise jet prod-
Figure 5b SSOT kerosene experimental (lab) freezing point vs model calculated uct giveaway in hydrocracker
freezing point TSREC. Due to market demand,
jet has higher cracks than the
105 other hydrocracking unit prod-
Lab ucts, whole naphtha and diesel,
100 Model so the main objective is to max-
95 imise the jet production rate.
90 Because the model delivers the
ability to measure both flash
85
point and freezing point contin-
FP, ºC

80 uously, without the time delay

75
0 10 20 30 40 50 60 70 80 90 100
Time, days
Figure 6a Hydrocrackers TSREC AND SSOT diesel flash point
average absolute deviation of However, the estimated flash
6.8°C. However, there are some points were always higher than
relations in the open literature our data. So we have devel-
that correlate flash points to oped our own models to predict
either the initial boiling point or flash point as a function of T10%
the distillation temperature at to be in line with API selected
the 50% point (T50). variables.
We have applied the API A total of 30 days of results
standard method to both in each hydrocracking unit
streams, diesel and kerosene. (TSREC and SSOT) were used
required for lab results, we were
able to increase jet yield by 3%
(from 42-45%) which is equiv-
alent to 2000 b/d of extra pro-
duction. These tools allowed
operators to see the immedi-
ate impact on jet product qual-
ity with no more waiting until
the next day to see the results
of their actions. Now the opera-
tions team has the ability to see
full range distillation from the
on-stream distillation analyser,
including flash point and freez-
ing point, at the same time as
the results are calculated in DCS.

6 PTQ Q1 2019 www.digitalrefining.com/article/1002285

The front line operator can opti-
105
mise main unit fractionator
operation to increase the pro- 100
duction rate by dropping the
95
heavy end of whole naphtha
into jet (for lowest flash point) 90
and pulling the light end of die-

Lab FP, ºC
85
sel into jet (for highest freez-
ing point) without worrying 80
any more about getting off-spec
75
jet. Figure 8 shows the period 75 80 85 90 95 100 105
before and after utilisation of the Model FP, ºC
model. We can now see that we
are able to obtain more data per Figure 6b Hydrocrackers diesel experimental (lab) flash point vs model calcu-
day (four results per day) com- lated flash point
pared to the lab schedule which
was once daily. From day four,
105
the models were applied and Lab
installed in the DCS for a testing 100 Model
period. There was an increased 95
yield of approximately 3% by
90
the end of the testing period,
with the ability to operate close 85
to the highest freezing point
FP, ºC

80
of -47.5°C, compared to -53°C
75
before the model was applied, 0 10 20 30 40 50 60 70 80 90 100
and to be able to minimise the jet Time, days
freezing point giveaway.
Figure 7a Hydrocrackers (TSREC AND SSOT) kerosene flash point
Conclusion
To provide a larger number of
opportunities for optimising the 70
hydrocracking process, mod- 65
els were developed and applied
for the continuous monitoring 60
of physical properties including
55
flash point, freezing point and
cloud point of middle distillates.
Lab FP, ºC

The models employed available
on-stream distillation analysers
in the field to estimate proper-
ties in linear forms. The correla-
tion models are very simple and
give accurate results about mid-
dle distillate properties with an
absolute maximum standard
error of less than 2°C out. These
models were derived based on
distillation data alone, which can
be easily integrated in DCS with
the support of the on-stream
analyser in any hydrocracking
50
45
40
40 45 50 55 60 65 70
Model FP, ºC
Figure 7b Hydrocrackers kerosene experimental (lab) flash point vs model
calculated flash point
unit. The developed correlations will enable front line operators
will improve both diesel and to monitor target properties and
kerosene quality, minimise give- their impact on production rate
away of products, and increase continuously. There is no more
production rate. The models need to wait for lab results to see

www.digitalrefining.com/article/1002285 PTQ Q1 2019 7

 products and lubricants, 2nd ed (ASTM
−46 46 Manual Series: MNL44-2nd), 2007.
−47
45 8 Speight J G, Handbook of Petroleum
−48
Product Analysis, 2002.
−49 44
9 Treese S A, Pujado P R, Jones D S J,
−50 43 Handbook of Petroleum Processing, 2015.
−51
42 10 Hsu C S, Robinson P R, Springer
−52
Handbook of Petroleum Technology, 2017.

Yield, %
−53 FzP 41
11 Wauquier J-P, Petroleum Refining. Vol.
FzP, ºC

−54 FzP model

40 1 Crude Oil. Petroleum Products. Process
−55 Yield
Flowsheets, 1995.
−56 39
0 48 96 144 192 240 288 336 12 Scherzer J, Gruia A J, Hydrocracking
Time, hours Science and Technology, 1996.

Figure 8 TSREC jet data (freezing point vs yield)

Madi Asiri is an Operations

the immediate impact of process
changes on final product quality.
The kerosene production rate
increased by 2000 b/d in a single
unit. We believe the developed
models can be applied in any
hydrocracking unit and will give
excellent prediction of the tar-
get properties cloud point, flash
point and freezing point utilis-
ing a single on-stream analyser
for both diesel and kerosene.
Further reading
1 Zhu F (Xin X), Hoehn R, Thakkar V,
Yuh E, Hydroprocessing for Clean Energy:
Design, Operation, and Optimization,
2017.
2 Watkins B, Lansdown M, Understanding
Cloud Point and Hydrotreating
Relationships Revised, Chicago, IL, USA,
2012.
3 Refinery improves diesel cloud point
by switching to Topsoe’s catalysts, Haldor
Topsoe, cvr 41853816, CCM, 0063.2015/
Rev.0, 2015.
4 Hansen J A, Andersson A S, Optimising
middle distillate production in a
hydrocracker, 2017.
5 Dinkov R, Stratiev D, Penev D, Cholakov
G, Investigation On Diesel Cold Flow
Properties, Bulgaria, 2010.
6 Riazi M R, Characterization and
properties of petroleum fractions, 1st ed
(ASTM Manual Series: MNL50), 2005.
7 Kishore Nadkarni R A, Guide to ASTM
test methods for the analysis of petroleum
Superintendent with Saudi Aramco
Total Refining and Petrochemical
Company (SATORP), Saudi Arabia. He
graduated as a chemical engineer from
King Fahd University of Petroleum &
Minerals (KFUPM), Saudi Arabia, and
holds a graduate diploma in refining and
petrochemicals from IFP School, France.
Email: madi.asiri@satorp.com
LINKS
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