Professional Documents
Culture Documents
Axens
patrick.sarrazin@axens.net
stephane.wambergue@axens.net
jerome.bonnardot@axens.net
frederic.morel@axens.net
IFP Solaize
christophe.gueret@ifp.fr
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.
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.
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.
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
6.0
5.1
56.7
59.2
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
compressors, one air cooler and gives flexibility for better heat integration compared to two
separated units.
VGO
Polishing
section
H2
Low S
VGO
Diesel from
Fractionation
to Stripping
0.6 1.5
1 600 2 200
0.30 0.50
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.
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
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
Coker etc
to Stripping
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.
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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