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Paper presented at the 9th Annual ERTC

Wednesday, 17 November 2004


Hilton Hotel, Prague

Direct production of Euro-IV diesel at 10 ppm sulfur


via HyC-10TM process

Patrick Sarrazin1, Jrme Bonnardot1, Stphane Wambergue1,


Frdric Morel1 & Christophe Guret2

Axens

89, bd Franklin Roosevelt - BP 50802


92508 Rueil-Malmaison Cedex France
Phone: +33 1 47 14 21 00

patrick.sarrazin@axens.net

stephane.wambergue@axens.net

jerome.bonnardot@axens.net

frederic.morel@axens.net

IFP Solaize
christophe.gueret@ifp.fr

9th ERTC meeting, Prague, 2004

Introduction
The future of the European refining is clearly linked to the possibility to adapt the refineries
schemes towards new market structure. Over the past two decades, the major challenge has
come from clean fuels production. The pressure on gasoline and diesel specifications has
pushed up both refiners and technology suppliers to innovate for reaching these new targets.
This challenge is not definitively overcome as shown by table 1, which presents the time
schedule for next stages of fuels specifications. In addition, the tax incentives policy driven by
some European countries such as Germany and U.K. speed up the process of modernization
of the European refining tool in such a way that, by 2005, most of the western Europe refiners
will be able to produce 10 wt ppm sulfur gasoline.
Sulfur, wt ppm
Gasoline
Diesel

EU 2000
150
350

EU 2005

10

102

50; 10
50; 10

EU 2009

2005 introduction of 10 ppm sulfur fuel available. 2Review clause: By end 2005, the European Commission

comprehensive review of non-sulfur parameters and alternative fuels and see if new specifications are necessary.
the outcome of the various commitments with the auto-manufacturers to reduce fuel consumption and CO2
emissions of new passenger cars, the effect of metallic additives on new pollution abatement technologies, and
the final date of on-road and non-road diesel 10 wt ppm introduction.

The diesel fuel is not staying back as the sulfur reduction is by far one of the most impressive
moves of this industry over the past 30 years, in a context of a tremendous increase of diesel
car sales in Europe. From now, the refining community will also have to take into account,
not only the products quality but also more and more the main fuels market evolution. At
mid-term, the context for European refining is a steady demand for low sulfur gasoline mainly
sustained by US imports, a continuous increase of ultra low sulfur diesel demand and a
reduction of the fuel oil demand. Together with a background of high oil prices observed over
the last couple of years, conversion is becoming a key word.

What is the strategy for Europe refining?


Even if the US demand for low sulfur gasoline may be decreasing at long term, it is still
strong for at least the turn of this decade. In fact, a move of the US market towards expansion
9th ERTC meeting, Prague, 2004

of clean diesel fuel is not likely to appear before 2010. This can be favored by pressure on
fuel consumption reduction and CO2 management. Therefore, for a standard European
refinery, which is generally equipped with an FCC unit, it is difficult to imagine a decrease in
gasoline production from that plant which is a major contributor to the gasoline pool.
However, as stated above the growing diesel market appeals for vacuum gas oil (VGO)
conversion, the attractiveness of which being enhanced by the present oil price. With such
constraints, the first step to conversion is mild hydrocracking (MHC). From the products slate
point of view, MHC allows to increase diesel production by hydroconversion of VGO, while
the hydrotreating reactions improve greatly the quality of residual VGO which becomes a
better feed to the FCC leading to higher gasoline yields, higher octane retention and low
sulfur products. At the end, MHC looks to be a perfect tool to increase diesel production
while maintaining or even increasing the FCC gasoline production.

Mild hydrocracking? yes, at which level of conversion?


Obviously, the answer to this question is specific for each refinery but from the above
discussion on clean motor fuel markets evolution, it is most likely that a sufficient throughput
has to be maintained towards FCC units. Therefore, the low-medium conversion range is
generally preferred (20 to 40 %). Unfortunately, up to a recent past, the objective of lowmedium conversion range associated with high diesel quality led to a kind of technical issue
as the smooth operating conditions applied at MHC section impact badly the diesel quality.
For a steady conversion, level during the cycle the diesel sulfur content increases up to
hundred ppm sulfur as the HDS activity drops. Moreover, the aromatic content of this cut is
found high and consequently the cetane index is poor [1].
Conversely, it is known that 10 wt ppm sulfur diesel through hydrocracking technology is
achieved under medium to high pressure (> 120 bar) at relatively high level of conversion (>
50 %) [2]. At the mean time that a low sulfur diesel is obtained the residual VGO becomes
short in quantity but eventually excessively hydrogenated to be routed to FCC unit. Under the
operating conditions necessary for high conversion, the whole feedstock is deeply
hydrogenated. Furthermore, the selectivity of hydrogen addition towards aromatics
components of the feed leads to a better saturation of the residue compare to the diesel cut
(see table 2). Apart if there is a need for high VGO conversion, this approach appears nonoptimized due to higher global hydrogen consumption.

9th ERTC meeting, Prague, 2004

To overcome potential over quality of the residue to FCC, Axens has licensed over the past 35
years mild hydrocracking units designed at low to medium operating pressure range (50 to
120 bars) targeting a customized FCC feed quality to limit both capital and operating costs.
The level of conversion thereby achieved ranges from 20 to 40 %. Under such conditions, the
diesel cut obtained cannot reach easily 10 wt ppm sulfur. Moreover, for an operation at
constant production of hydrotreated VGO to FCC unit the sulfur content of the diesel is
increasing from Start-of-run to End-of-run conditions. Hence, we have worked up on a route
to disconnect the diesel cut quality from the conversion level. This has led to the development
of a new process.

HyC-10TM process: the integrated route to 10 wt ppm diesel


To face the necessary improvement of the diesel cut coming from the low pressure mild
hydrocracking one could have think to send it to an external diesel hydrotreater. Assuming
that the hydraulic capacity exists, it is not straightforward. In fact, the diesel obtained through
low pressure mild hydrocracking, even with its low sulfur concentration is very refractory to
further hydrotreating as shown in table 3. The results has been obtained by comparison of the
HDS rate for a straight run diesel partially hydrotreated to get initial sulfur concentration
close to the one of a diesel coming from MHC conversion. We can notice that the
hydrotreated straight run diesel and the converted diesel from MHC presents a near equal total
sulfur level and distribution of refractory sulfur compounds as well as an equivalent
distillation. Under equivalent operating conditions, it appears that the HDS performance
achieved drops from 99.55 % down to 88.19 % with the straight run diesel and the converted
diesel respectively. This important difference in reactivity can be explained by:

The impact of higher organic nitrogen concentration,

The impact of higher aromatics content,

As it is well known that organic nitrogen and aromatics have an inhibitor effect on the deep
HDS reaction by competitive adsorption on active sites needed for the so-called
hydrogenation pathway [3].
Taking into account the specificity of this converted cut to be treated a solution has been
developed with IFP and patented. This has been done around the core of MHC unit leading to
a fully integrated scheme.
The figure 1 described the concept of HyC-10TM process, which delivers the right operating
conditions at the right location of the plant to optimize operating costs and save capital
9th ERTC meeting, Prague, 2004

expenditure. The VGO feed goes to a reaction section after mixing with the recycle gas and is
heated up before reactor. The resulting effluents are stripped and separated in a distillation
section. The hydrotreated VGO is sent to FCC unit or to storage while the diesel cut is sent to
a polishing reactor operated in a once-through mode, covered with the whole hydrogen makeup gas needed for both reaction sections.
Straight Run Diesel

Converted Diesel

already hydrotreated

from MHC

0.8373

0.8867

Sulfur, wt %

265

340

DBT, % of total sulfur

6.0

5.1

4-DBT, % of total sulfur

56.7

59.2

4,6-DBT, % of total sulfur

37.4

35.7

Nitrogen, wt ppm

14

254

Aromatics, wt %

25

56

5%

217

182

50 %

315

318

95 %

402

382

Operating Conditions

Base

Base

1.2

30

99.55

88.19

Feedstock
Specific gravity

ASTM D-2887, C

Product
Sulfur, wt ppm
HDS, %

Table 3: HDS Reactivity comparison between pre-treated Straight Run diesel & Converted
diesel from MHC.
In term of operating conditions, this scheme provides the highest hydrogen partial pressure in
the polishing reactor where it is needed to perform high hydrorefining on the converted diesel,
which is refractory to hydrodesulfuration and hydrogenation. Moreover, this approach
guarantees a diesel product quality steady for the whole cycle whatever the operation
variation of the MHC section. By disconnecting the diesel quality from the operation of the
MHC section it is then possible to improve other specifications than sulfur content such as
density or polyaromatics content. From the process point of view, this scheme saves two

9th ERTC meeting, Prague, 2004

compressors, one air cooler and gives flexibility for better heat integration compared to two
separated units.

VGO

Polishing
section

H2

Low S
VGO

10 ppm Sulfur Diesel

Diesel from
Fractionation

to Stripping

Figure 1: HyC-10TM simplified process scheme.


Based on the above scheme the table 4 presents order of magnitude economics of process
economics.
H2 consumption, wt %
ISBL, /bbl
Catalysts + utilities, /bbl

0.6 1.5
1 600 2 200
0.30 0.50

Table 4: Process economics

Commercial results
The first plant using this scheme has started up on June 2004 at Repsol YPF Puertollano
Refinery (Spain). The case objectives suit very well with the characteristics of the process, as
a conversion of around 35 % is required together with the production of 10 wt ppm sulfur
diesel cut.

9th ERTC meeting, Prague, 2004

The performances obtained are shown in table 5. Starting from a mixture of straight run VGO
and heavy coker gasoil (indicated by the high nitrogen content), the plant delivers 33.6 vol. %
of diesel at less than 4 wt ppm sulfur. This characteristics show that this cut is an excellent
blend component for the constitution of a Euro-IV commercial diesel in mixture with
additional desulfurized straight run cuts. As seen in table 5, the quality of the 65.8 vol. % of
the residue is excellent for further processing into FCC unit with an hydrogen content of 13
wt %.

Feedstock
Capacity, BPSD

37,000

Specific gravity

0.9253

Sulfur, wt %

2.11

Nitrogen, wt ppm

1 523

ASTM D-1160, C
10 %

337

50 %

439

90 %

520

Yields, vol. %
Naphtha

3.0

Diesel

33.6

Residue

65.8

Conversion, wt %

35

Products Quality

Diesel

Specific gravity

0.868

Sulfur, wt ppm

3.8

Cetane Index

47.7

ASTM D-86 95 %, C

359
Residue

Specific gravity

0.909

Sulfur, wt ppm

< 100

Nitrogen, wt ppm

< 100

H2 content, wt %

13.0

Table 5: Performances of the first HyC-10TM commercial plant at Puertollano refinery.

9th ERTC meeting, Prague, 2004

Future developments
The concept of the integrated scheme has been extended taking into account that the polishing
reactor implemented in the MHC unit can be designed to hydrotreat additional diesel cuts
from the refinery in mixture with the conversion diesel (see figure 2).

VGO
H2

Polishing
section

Diesel from

Low S
VGO

CDU, FCC, VB,

10 ppm Sulfur Diesel

Coker etc

to Stripping

Figure 2: HyC-10+ process concept.


This configuration can be used in order to allow a refinery to get rid of diesel cuts from other
plants such as heavy straight run diesel, light cycle oil, visbreaker gasoil, coker gasoil etc.,
which are not easy to treat in view of obtaining bases for the Euro-IV diesel specifications.
A new plant of this type has been awarded to us by Motor Oil Hellas at its Corynth refinery
and is presently under construction for a start-up scheduled in 2005.
During the studies of Corynth refinery modernization in view of clean fuels production, it has
appeared a need for VGO conversion to increase diesel production while increasing FCC
gasoline yield and quality. The FCC unit being equipped down stream with a first generation
Prime G unit, it has been found attractive to combine with HyC-10+ process to reach 15 wt
ppm sulfur FCC gasoline with co-production of ultra low sulfur diesel. The study also
revealed that the existing HDS unit would not be able to cope with 10 wt ppm sulfur target
with the heaviest diesel cuts. Moreover, there was clear incentive to improve overall diesel
pool density. The decision has been made to send the light straight run diesel cuts to the

9th ERTC meeting, Prague, 2004

existing HDS in order to limit the modification to a light revamping. The remaining diesel
cuts like heavy straight run diesel and light cycle oil have been incorporated in the basis of
design of polishing section of the new HyC-10+ unit to be co-processed with the diesel
coming from conversion in the MHC section.
The table 6 presents some elements of the basis for this plant. It can be seen that due to
operating conditions optimization it is then possible to use the polishing section to improve
more the diesel produced such as density (here required at 0.845) and polyaromatics content
(targeted at 5 % max.).
SR Diesel + Light
VGO to MHC

Cycle Oil
to polishing

Feedstock
Capacity, BPSD

37,000

22,000

Specific gravity

0.932

0.873

Sulfur, wt %

2.67

1.85

Nitrogen, wt ppm

1 392

523

D-1160

D-86

10 %

363

210

50 %

447

322

90 %

548

358

Conversion, wt %

32.5

ASTM, C

Products Quality

Diesel

Specific gravity

0.845

Sulfur, wt ppm

8 max.

Cetane Index

47 min.

Polyaromatics, wt %

5 max.
Residue

Specific gravity

0.897

Sulfur, wt ppm

< 600

Nitrogen, wt ppm

< 500

H2 content, wt %

13.2

Table 6: Basis of the first HyC-10+ plant under construction at Corynth refinery.

9th ERTC meeting, Prague, 2004

Conclusion
In a context of steady gasoline demand and diesel demand growth, the question of VGO
conversion is key. For the European refining this question must find an answer in the frame of
high quality products so-called ULSG and ULSD. In the case of mild hydroconversion of
VGO a specific process has been developed and demonstrates commercially since June 2004
the direct production of 10 wt ppm sulfur diesel.
The principle of HyC-10TM process, which disconnects the diesel quality from the MHC
operation, allows maintaining these performances throughout the entire cycle length. In
addition, the polishing section can be designed in order to co-process other difficult
feedstocks present in the refinery to reach not only sulfur but other properties like density and
polyaromatics. Such a scheme already has a commercial reference presently under
construction. This version called HyC-10+ process is a real opportunity to strongly improved
the refinery gasoline/diesel balance as well as the overall fuel pool qualities.

Acknowledgements
The authors express their gratitude to Repsol YPF and Motor Oil Hellas for having made this
publication possible.

References
1: P. Marion & C. Guret, 10th Refinery Technology Meet on Refining Operations in India
& Future Challenges, xxxx
2: M. F. Gonzalo, I. G. Balseyro, J. Bonnardot, F. Morel & P. Sarrazin, 8th ERTC, London, 2003
3: D. Due, D. Adamski & JC. Plumail, 6th ERTC, Madrid, 2001

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