Rigorous hydrotreater simulation

An integrated approach to dealing with the complexities of producing

ultra-low-sulphur diesel, involving analytical support and process research
Michael C Hu KBC Advanced Technologies
Zbigniew Ring, Jenny Briker and Mure Te National Centre for Upgrading Technology

he need to be able to assess the process

alternatives for future production of low
and ultra-low sulphur diesel (ULSD) has
resulted in the development of a rigorous hydrotreater simulator, capable of predicting feedstock
and process condition effects on sulphur removal
below 10ppmw. How low the sulphur level will
eventually go throughout the world is still a
subject of debate, but the trend points to a near
zero sulphur requirement.
Although the technologies required to produce
low and ultra-low sulphur gasoline and diesel
are somewhat different, a significant increase in
overall refinery hydrotreating capacity or, more
specifically, the degree of hydrodesulphurisation
is inevitable. The additional sulphur reduction
will have to be achieved either by feed hydrotreatment for catalytic cracking conversion units
or hydrofinishing of final fuel products. This
article is concerned with the subject of ULSD.
There is no common strategy for refiners to
plan their future capital investment. They must
select the most economical process option and
plan their investment strategy based on available
technical know-how, refinery complexity and
local market economics. Usually, refineries will
work closely with process licensors and catalyst
vendors to accomplish this task. Nevertheless, it
is extremely useful to have a process simulator
capable of predicting hydrotreater performance
under ultra-low sulphur mode of operation for
various feedstocks and process conditions.
The development of this simulator requires a
good understanding of diesel feed and product
characterisation, comprehensive and realistic
process data, and rigorous kinetics modelling.
Recently, Canadas National Centre for
Upgrading Technology (NCUT) and KBC

ww.digitalrefining.com/article/1000221

Advanced Technologies, based in California, have

been cooperating in analytical research, pilot
plant testing, and process modelling to provide
an integrated tool for assessing alternative process options for future low and ULSD production.
After a brief literature review, the analytical
and hydroprocessing pilot plant facility at NCUT
is presented here, along with selected results of
pilot plant testing in terms of sulphur type analysis. The technical basis of KBC Profimatics
hydrotreater model, HTR-SIM is described in
detail.

Technical issues
To meet the current 500ppmw diesel sulphur
specification,
refineries
have
successfully
increased their hydro- desulphurisation (HDS)
capacity by either installing more active HDS
catalysts, raising reactor temperature (at a cost
of shorter catalyst cycle life), lowering reactor
space velocity (eg, dense bed loading, lower
throughput, or adding a new reactor), or improving reactor internals for good catalyst utilisation.
Adjustments in other process variables, such as
increased hydrogen partial pressure and reduced
hydrogen sulphide concentration, in the treat gas
recycle loop have also become more important.
To reduce diesel sulphur content from 500ppmw
to 15ppmw or less, substantial further increases
in operating severity and reactor volume will be
unavoidable. For example, Lamourelle and coworkers [Lamourelle, McKnight and Nelson; Clean
fuels: route to low-sulphur low aromatic diesel; NPRA
annual meeting, 2001] reported a required 200 per

cent increase in catalyst volume to switch from

500ppmw to 10ppmw S.
Selection of the right type of HDS catalyst,
cobalt/molybdenum (Co/Mo) versus nickel/

PTQ Q2 2002 1

aromatic rings in the dibenzothiophene structure prior to the removal

of sulphur by hydrogenolysis. This
K1
route is much slower than the direct
R
hydrogenolysis route. It is strongly
K2 R
S
influenced by hydrogen partial presK4
R
R K
3
sure and subjected to thermodynamic
DBT
S
equilibrium limitation.
R
R
R
R
The sulphur wall effect is believed
THDBT
CHB
to be the result of the equilibrium
limitation at high reactor temperaFigure 1 HDS mechanism
ture. Due to steric hindrance, some of
molybdenum (Ni/Mo), and the catalyst from the substituted dibenzothiophenes, particularly
within these two groups that is most suitable for those with alkyl-substituents at the 4 and 6 posithe feedstock at hand, also become much more tions, must be desulphurised through the
important for ultra-low sulphur production. hydrogenation route. One of the most unreacSome authors have reported the so-called tive sulphur compounds in the diesel range is
sulphur wall effect [Mayo et al; Elegant solutions the 4,6-dimethyl-dibenzothiophene. When the
for ultra-low sulphur diesel; NPRA annual meeting, diesel sulphur level is lowered to below
2001. Nash; Meeting the challenge of low aromatics 100ppmw, almost all of the remaining sulphur
belongs to the dibenzothiophene class.
diesel; NPRA annual meeting, 1989].
The removal of remaining sulphur to the 10 to
This effect limits the lowest sulphur level in
the diesel stream that is achievable by raising 15ppmw level is almost entirely carried out via
hydrotreater reactor temperature. The lowest the hydrogenation route. Therefore, Ni/Mo cataachievable sulphur level depends on the catalyst lysts with better hydrogenation activity are
type and hydrogen partial pressure. Under real- preferred for ULSD production. In order to accuistic hydrotreater conditions, it could be as high rately model the ultra-low sulphur HDS process,
as 20ppmw. The wall effect can be explained by the kinetics of hydrogenation and hydrogenolysis
of sulphur must be formulated in the
the hydrodesulphurisation mechanism.
It is well known that there are two distinct programme.
routes for sulphur removal by hydrotreating
(Figure 1). The first is direct hydrogenolysis. Analytical methodology
Almost all the sulphur present in the forms of For several years, NCUT has been involved in
mercaptans,
sulphides,
disulphides
and the development of analytical methods to charthiophenes, as well as a majority of benzothi- acterise distillates in terms of their hydrocarbon
ophenes and unsubstituted dibenzothiophenes, type and elemental composition. A new methodology has been developed that determines
is removed by this route.
The relative reactivity of the various sulphur detailed hydrocarbon type and elemental compocompounds differs significantly and within each sition of individual fractions of a total liquid
compound group. It has also been reported that product (TLP) without distillation, by providing
the reactivity of sulphur compounds also these compositions as by boiling-point
decreases monotonically with true boiling point distributions.
The sample is analysed in a few steps. The first
[Sau, Narasimhan and Verma; Studies in surface
step is conventional PIONA. A 0.1L injection
science and catalysis, 1997].
The Co/Mo HDS catalysts are most effective in results in the distribution by carbon number
removing sulphur via this route, even under (and hence boiling point), boiling point of parafmodest pressures. There is a small, positive fins, iso-paraffins, olefins, naphthenes, and
effect for higher hydrogen partial pressure and a aromatics found in the portion of the TLP that
negative effect of hydrogen sulphide in the recy- boils up to 200C. The heavier material is separated by the PIONA pre-fractionator and
cle gas.
The second route, particularly effective with Ni/ discarded.
The second step involves solid phase extraction
Mo catalysts, requires partial hydrogenation of
BHP

2 PTQ Q2 2002

w ww.digitalrefining.com/article/1000221

(SPE) analysis of another 20mg sample of TLP.

This method is based on the original SPE method
for class-type separation and was modified at
NCUT to facilitate olefins separation. Four
known-volume fractions, namely saturates,
aromatics, olefins and polars, are generated. The
SPE fractions are further analysed by gas chromatograph with a flame ionisation detector
(GC-FID) and gas chromatograph with a mass
selective detector (GC-MS). The GC-FID analysis
handles simultaneously two tasks.
First, the quantification of each SPE fraction
using external calibration, and second, determination of the simulated distillation (SimDis)
curve for each of the SPE fractions. SimDis is
required for calculation of by-boiling-point
hydrocarbon-type distribution of the GC-MS
results. The GC-MS- and GC-FID-related calculations are performed between 200C and final
boiling-point (FBP) of the sample.
Quantitation of the olefin and polar SPE fractions require only a single GC-FID run each. The
results of the individual steps are fed to software
developed at NCUT that reconciles and summarises final results in the form of a characterisation
table [Briker et al; Distribution of aromatics, HC
ratio and olefins in cracked liquid products from
MAT new approach for analyzing small size
samples; 40th International Petroleum Conference,
Bratislava, 17-19 Sept, 2001].

This table contains mass fractions of individual

hydrocarbon types in user-selected boiling-point
fractions of the TLP. The method may significantly reduce the total time required to complete
analysis, but its main advantage is that it
requires a very small sample. It is particularly
useful to look at product quality of individual
fractions of TLP when samples are inherently
available in very small quantities (eg, FCC-MAT
microactivity test or micro-hydroprocessing
reactor).
Following the treatment detailed in the previous paragraphs, the TLP sample is subjected to
elemental analysis using GC-AED that provides
sulphur, carbon, and hydrogen distributions by
boiling-point. The sulphur emission at 181nm is
used to collect the sulphur signal. At the same
time, the carbon signal is collected at 179nm,
which allows distribution by boiling-point of the
sulphur-to-carbon ratio. The carbon and hydrogen emissions of 496nm and 486nm respectively
are used to collect the signals for carbon and

ww.digitalrefining.com/article/1000221

hydrogen and calculate the hydrogen-to-carbon

ratio distributed by boiling-point.
The nitrogen content and distribution by boiling-point is determined by using a nitrogen
specific detector (NCD). For all the elements, the
distribution by boiling-point is calculated by
using the calibration parameters obtained from
analysing the mixture of paraffin standards (C5
to C44) at the same conditions as for the analysed
sample.
In the next step, sulphur compounds found in
the sample are identified by retention-time
matching, using the NCUT database. For highsulphur feedstocks, another SPE method has
been developed to separate saturate and aromatic
sulphur species using silver nitrate impregnated
silica gel. This method, together with 60m-long
chromatographic columns used in the GC-AED
and GC-MS instruments, facilitates good peak
separation and identification. The experimental
results used in this article are limited to this
method.

Pilot plant
Some pilot plant units used by NCUT to conduct
contract hydrotreating and hydrocracking pilot
plant testing programmes consist of two reactors
with an integrated fractionator and recycling of
unconverted products. These units have consistently generated precise data on catalyst stability,
yield distribution, gas make, and hydrogen
consumption under commercially realistic
conditions.
The pilot plant facility has been extensively
used in catalyst evaluation programmes for
commercial hydrotreating and hydrocracking
reactors, for process optimisation, and to support
process model development. The ULSD study
partially presented here was carried out using
NCUTs PP-1 unit. Table 1 summarises PP-1
capabilities and Figure 2 provides a schematic
diagram of this unit. The feedstock used in this

PP/1 capabilities at a glance

Maximum temperature
450C
Maximum pressure
180bar
Feed rate
20-400g/h
Maximum gas rate
300NL/h
Recycle rate
5-200gh/h

842F
2610psi
0.04-0.88lb/h
11.2scf/h
0.01-0.44lb/hr

Table 1

PTQ Q2 2002 3

Distillation
column

Compressor

Reactor 1

Stabiliser
column

Gas product to meter and analyser

H2 (H2S, NH3)

Reactor 2

Feed
pump

Interstage
sampler

High
pressure
phase
separator

N2

Liquid
product
receiver

Recycle
pump

Figure 2 PP-1 in series flow hydrocracker configuration

Feed analysis and pilot plant

test conditions
Feed stream
Density, g/ml
Carbon, wt%
Hydrogen, wt%
Total S, wt%

Total N, wt%
Distillation, D86, C
IBP

30 vol%

50 vol%

70 vol%

FBP

FCC LCO
0.9590
88.44
9.78
1.488
0.063
193
277
284
304
377

Test Conditions
Pressure, bar
70
WABT, C

320395
Space velocity, L/L/hr 1.5
vol% H2S in make-up H2 03

Table 2

10,000
HTRSIM
Pilot plant data

Results

Total S, ppmv

1,000

100

10

0
320

340

360

380

400

WABT, C

Figure 3 Total sulphur vs WABT

test was a commercially sampled FCC light cycle

oil (LCO). The LCO has been considered as the
most refractory feed component in a commercial
distillate hydrotreater and practically always
requires hydrotreating before being used as a
diesel-blending component.
The pilot plant
reactor was packed with 150ml of a highly active
commercial Ni/Mo hydrotreating catalyst. Table
2 summarises the feed analysis and pilot plant
test conditions.

4 PTQ Q2 2002

The total product sulphur content

was plotted against reactor temperature in Figure 3. Each of the data
points representing the experimental data is, in fact, two overlapping
squares since two mass balance runs
were conducted at each temperature. This illustrates the high quality
of the data generated in this study.
The difficulty of producing 10ppmw
sulphur product can be clearly seen
from the plot.
To better understand the kinetics
420
of sulphur removal, the sulphur
analytical procedure outlined earlier
was used to identify and quantify
each individual sulphur component
in both the feed and products. In
Figures 4, 5 and 6, only the sulphur chromatograms for feed and products from experiments
at 375C and 385C, respectively, are presented.
At about 375C, the thiophene and benzothiophene spices have been removed completely.
Consequently, the parts of the product chromatograms could be removed up to retention time
of 90 minutes. Above 385C reactor temperatures, the only remaining compounds were
4,6-dimethyl-dibenothiophene
and
related

w ww.digitalrefining.com/article/1000221

Kinetics modelling

C3DBTs
C3naphthothiophenes
Other C2DBTs
C2naphthothiophenes

4,6DMDBT

5
AED signal columns

Knudsen and Cooper; Ultra low sulfur

diesel: catalyst and process options;
NPRA annual meeting, 1999]

C4DBTs & C4NTHs

C3DBTs & C3NTHs

EDBT, 46 DMDBT
C2DBTs & C2NTHs

AED signal counts

DBT

compounds with more and longer

side chains.
The unsubstituted
LCO feed chromatogram (GCAED)
dibenzothiophenes and substituted
DBT=dibenzothiophene, NTH=naphthothiophene
dibenzothiophenes at positions other
4MDBT
than
4
and
6
disappeared
170
C1DBTs & C1NTHs
completely.
140
Close inspection of the amount of
Thiophenes and
conversion for each individual peak
110
benzothiophens
revealed that we could group the
80
sulphur compounds into three types:
the easy, difficult and very diffi50
cult groups. The easy sulphur group
20
included sulphides, mercaptans,
thiophenes and benzothiophenes.
10
The difficult sulphur included diben40
50
60
70
80
90
100
110
Retention time, min
zothiophenes with no substituents at
the 4 and 6 positions. The dibenzothiophene isomers substituted at the Figure 4 LCO feed sulphur chromatogram
4 and 6 positions were classified as
the very difficult sulphur. Similar
classification was also proposed by
375C Effluent
Tippett and co-workers [Tippett,

120

C4DBTs
C4naphthothiophenes

AED signal columns

There are two extreme approaches in

1
modelling
the
HDS
reaction.
4MDBT
Traditionally, a simple n-th order
kinetics (1.5 to 2) was applied to
1
model the removal of total sulphur.
90
92
94
96
98 100 102 104 106 108 110
This simple approach was successRetention time, min
fully used in reactor sizing for down
to the 500ppmw sulphur level. For Figure 5 Product sulphur chromatogram (WABT = 375C)
sulphur levels less than that, the nth order kinetics model becomes too
optimistic and is inadequate.
385C Effluent
2.0
The other extreme is based on a
MDBTs
4, 6 DMDBTs C3DBTs
C4DBTs
structural approach where HDS
C3naphtho- C4naphthoreactions are modelled based on
thiophenes
thiophenes
1.5
Other C2DBTs
each individual molecule type. This
C2naphthoarticle
takes
an
intermediate
thiophenes
1
approach and models HDS based on
three types of sulphur as classified
above. Sugimoto and co-workers
1.0
proposed a kinetics model based on
four types of sulphur [Sugimoto,
Tsuchiya and Sagara; Deep hydrodesulferization of light gas oil; NPRA
annual meeting, 1992]. However, as

0.0

90

95

100
Retention time, min

105

110

shown below, the three types of Figure 6 Product sulphur chromatogram (WABT = 385C)

ww.digitalrefining.com/article/1000221

PTQ Q2 2002 5

sulphur used in our work can simulate the kinetics of total sulphur removal to ultra-low levels
with sufficient accuracy.
For easy and difficult sulphur, the removal is
mainly realised via the direct hydrogenolysis
route, which can be described by the following
formula:
rS = k0 x eE/RT x [S] x [H2 P.P.]n

(1)

where,
rS =
rate of conversion for easy or difficult
sulphur
k0 = pre-exponential factor
E = activation energy
[S] = concentration of easy or difficult sulphur
n = n-th order H2 partial pressure effect
The k0 is hindered by the presence of H2S. The
pressure effect is usually minor for this route. A
typical n value of 0.5 to 0.6 is applied for
commercial HDS unit.
The modelling of the removal of the very difficult sulphur is more complex since there are two
parallel routes (direct and hydrogenation) to be
considered. Moreover, the hydrogenation route
is a reversible reaction. Based on the reaction
network given in Figure 1 and using 4,6-DMDBT
as an example, the HDS kinetics for the very
difficult sulphur can be described as follows.
Direct route

The kinetics expression is identical to Equation

1.
rS1 = k1 x [4,6-DMDBT] x [H2P.P.]n1

(2)

where,
rS1 = rate of conversion of the very difficult
sulphur via direct route
k1 = k0,1 x eE1/RT
[4,6-DMDBT]
=
concentration of
4,6- dimethyldibenzothiophene
n1
= n-th order H2 partial pressure effect for
direct route
Hydrogenation route

x [4,6-DMDBT] x [H2 P.P.]n2 k3 x [4,6-DMTHDBT]

(3)
r3 = k2 x [4,6-DMDBT] x [H2 P.P.]n2 k3 x [4,6-DMTHDBT]
k4 x [4,6-DMTHDBT] x [H2 P.P.]n3

(4)
rS2 = k2

where,
rS2 = rate of conversion of the very difficult
sulphur via hydrogenation route

6 PTQ Q2 2002

r3 = rate of formation of the partially saturated

4,6-DMDBT
n2
= n-th order H2 partial pressure effect for
hydrogenation
n1
= n-th order H2 partial pressure effect for
sulphur extraction
Vanrysselberghe and Froment reported that
the amount of partially saturated 4,6-DMDBT
was negligible. Therefore, we assumed the net
rate of formation of the partially saturated 4,6DMDBT, r3 is approximately zero. We also
assumed that n3 is much smaller than n2 and can
be ignored. By substituting [4,6-DMTHDBT]
into equation 3 and rearranging the formula, the
final rate equation derived for the hydrogenation
route is:
k2
rS2 =
x [4,6-DMDBT] x [H2 P.P.]n2
(k3/k4 +1)

(5)

where k2, k3 and k4 have their specific activation

energies E2, E3 and E4, respectively. The total
rate of removal of the very difficult sulphur is the
sum of the rates detailed in Equations 2 and 5.
The pilot plant data for the removal of the very
difficult sulphur were used to test this kinetic
model. Equation 5 fits the data quite well.
To fit the sulphur data at the ppmw range, a
value of 60kcal/mole was required for E2-E3.
The relatively high activation energy for dehydrogenation reaction promotes the reverse
reaction at high temperature and prevents
further reduction in the sulphur content. This
thermodynamic limitation has long been known
for hydrodenitrification reactions, but it became
a limiting factor for sulphur removal only
recently as a result of ULSD specifications.
As discussed in the previous section, the lowest
achievable sulphur level depends on feed quality,
catalyst type, and process conditions, particularly
hydrogen partial pressure.
Moreover, in a
commercial hydrotreater, when the catalyst is
approaching the end of run weighted average
bed temperature (WABT), the bottom portion of
the reactor could have already been in the equilibrium controlled temperature range. Therefore,
it is critical to consider this factor when sizing
the distillate hydrotreater and estimating reactor
cycle life.

Steady state simulator

In order to accurately evaluate alternative proc-

w ww.digitalrefining.com/article/1000221

ess options for ULSD production or optimise an

existing unit, many other distillate product qualities (eg, aromatic content, cetane number) and
process parameters (yields, hydrogen consumption) must be considered in the study. Moreover,
when catalyst deactivates, all those variables shift
along with higher reactor WABT. Therefore, the
reaction kinetics other than hydrodesulfurization
and catalyst deactivation must be considered
simultaneously.
These reaction kinetics include cracking, hydrodenitrification, aromatic saturation, naphthenic
ring opening, etc. A good feed property characterisation procedure is also required to account
for feedstock effects on various types of reactions. The need for this additional detail leads to
the conclusion that a comprehensive kineticsbased process model is needed to perform proper
ULSD evaluation.
KBC Profimatics has developed and commercialised
a
rigorous
and
kinetics-based
hydrotreater simulator, HTR-SIM, for commercial unit monitoring, process optimisation, and
LP studies. The technical basis of this model has
been described in detail elsewhere. The HTRSIM model rigorously simulates the reactor
section of a commercial hydrotreater including
the catalyst beds, high pressure separator,
makeup gas system, recycle/quench gas system,
and vent gas (purge) system.
Fresh feedstocks are broken down into carbon
number pseudo-components. Each carbon
number pseudo-component is assigned different
types of carbon in terms of aromatic, naphthenic
and paraffinic carbon fractions, as well as
sulphur, nitrogen and olefins, using bulk feed
properties and given distribution rules.
In the reaction section of the model, each
pseudo-component is included in a set of reaction
kinetics formulas for cracking, hydrodesulfurization, hydrodenitrification, aromatic saturation,
naphthene ring opening, and olefins saturation.
Then, numerical integration is carried along the
catalyst beds. Finally, the liquid product stream is
split into desirable product fractions for final
product quality determination.
The model is also designed to simulate catalyst
deactivation phenomena. For example, it will
track changes in the intrinsic reaction rate
constants based on coke deactivation rate and
catalyst age. Effects of changing operating conditions and feed properties on coke deactivation

ww.digitalrefining.com/article/1000221

rate are also included in the simulation. Finally,

the HTR-SIM hydrotreater model is embedded
in a Microsoft Excel-based interface for easy data
entry and results presentation.
Once calibrated with commercial test run data
or unit design data, the HTR-SIM model can be
used to study feed effect and process condition
effects (eg, WABT, reactor throughput, catalyst
volume, pressure effect, make up H2 purity).
Moreover, the kinetic rate constants can be easily
adjusted to reflect different type of catalysts (Co/
Mo versus Ni/Mo).
In terms of HDS, a Co/Mo catalyst will be
more effective in the direct route than a Ni/Mo
catalyst. On the other hand, a Ni/Mo catalyst
will be much more active in the hydrogenation
route. Some catalyst vendors have proposed a
concept of stacked-bed catalyst configuration for
ULSD application. This configuration could be
easily simulated by the HTR-SIM model, since
the model provides the user with the option of
up to three different catalysts in series.
Based on the work performed by NCUT, KBC
was able to enhance the capability of the HTRSIM simulator for ULSD study. The three types
of sulphur and the parallel direct and hydrogenation HDS routes have been implemented in the
simulator. To demonstrate the predictability of
HTR-SIM, the model was first tuned against the
pilot plant data at the lowest WABT (320C) and
then it was used to predict sulphur content
(extrapolate) at higher temperatures (model
predict mode).
A good match is evident in Figure 3, where the
model-predicted product sulphur content was
compared with pilot plant data as a function of
WABT. The model generates additional useful
process information for example, chemical
hydrogen consumption as a function of WABT.
Initially, hydrogen consumption increases with
WABT. However, after reaching the sulphur level
of about 10 to 15ppmw, the hydrogen consumption starts levelling off and goes through a
maximum. This coincides with the aromatic
content in the product as a function of
temperature.
The thermodynamic equilibrium limitation for
aromatic saturation has been attributed to the
deterioration of distillate product quality (eg,
diesel cetane number, smoke point and Saybolt
colour) associated with the high WABT operation, particularly at EOR.

PTQ Q2 2002 7

Of course, one of the very important applications for a hydrotreater simulator is to evaluate
various refinery feed streams for potential
processing in a diesel hydrotreater. In principle,
a refinery could analyse the feed sample for
sulphur types, quantify the refractory sulphurcontaining feed components, and determine how
difficult it would be to remove total sulphur from
that feed. However, work is going on to develop
a sulphur-type correlation based on bulk feed
properties such as type of feed, density, and boiling-point distribution.
A preliminary correlation has already been
built into the model, and KBC will continue

8 PTQ Q2 2002

working with NCUT to further refine this correlation. Particularly, it would be beneficial to
expand this correlation to heavier feed streams,
such as VGO cuts, for VGO hydrotreater application.

Links
More articles from: KBC Advanced Technologies
More articles from the following category:
Process Modelling & Simulation

w ww.digitalrefining.com/article/1000221