Title of Invention

"A PROCESS FOR THE PURIFICATION"

Abstract A process for the purification, down to less than 10 ppm of sulfur, of a sulfur-comprising, nitrogen-comprising and/or aromatic hydrocarbon feedstock, comprising a first stage of hydro-treating the hydrocarbon feedstock in the presence of a catalyst, after sulfurization of this catalyst, and a second stage of oxidizing desulfurization of the hydrotreated feedstock, wherein the catalyst is a modified hydrotreating catalyst comprising a support formed of refractory oxides, at least one metal from Group VIII and at least one metal from Group VI, both in the oxidized form, characterized in that it comprises at least one sulfone compound and/or sulfoxide compound derived from at least one benzothiophene compound.
Full Text The present invention relates to a process for the purification.
The present invention relates to a hydrotreating catalyst, to its method of preparation and to the use of this catalyst in a process for the purification of hydrocarbons, in particular those resulting from petroleum fractions with a boiling point preferably of between 4 0 and 5 60°C.
Currently, the demand for desulfurized, denitrogenated and dearomatized hydrocarbon compounds is increasing and numerous studies are being carried out for the purpose of developing catalysts which are increasingly effective with regard to the purification of hydrocarbons. However, these novel catalysts, which are targeted at obtaining sulfur contents of less than 10 ppm, are much more expensive and are accessible only from a limited number of producers. In addition, from their first regeneration, these catalysts exhibit a much lower activity than their initial activity in the fresh state under the same operating conditions. Only an additional specific rejuvenation treatment sometimes makes it possible to recover this initial activity, making it possible to achieve sulfur contents of less than 10 ppm.
Numerous "conventional" catalysts, based on supports formed of refractive oxides and comprising oxidized Co/Mo or Ni/Mo metal pairs, are still widely used today in ref ine'riess, in the fresh or regenerated state, either in hydrotreating or in hydrocracking. If it proves to be impossible to significantly increase their activity in desulfurization and/or denitrogenation treatments, these catalysts will eventually have to be recovered, stored or destroyed when the specifications with regard to the contents of sulfur in fuels become so restrictive that it will no longer be possible to

use them. In addition, there is a risk that this
storage or this removal of the solids will be subject
to environmental and safety restrictions and will then
generate significant additional costs for refiners.
The Applicant Company has thus envisaged rendering
"conventional" catalysts based on refractive oxides and
on metals from Groups VI and VIII more effective by
modifying them by novel means in order to confer
theiron desulfurization and denitrogenation activities
at least equivalent to those of the best catalysts on
the market and in particular greater than those of
these regenerated catalysts.
All hydrotreating or hydrocracking catalysts are
necessarily sulfurized before being used. This
sulfurization can be carried out either in situ, in the
hydrotreating reactor, or ex situ, using hydrogen
sulfide, mercaptans, sulfides, polysulfides and/or
native sulfur, these compounds being introduced alone,
as a mixture with a solvent or at the same time as the
feedstock. Some of these catalysts are modified before
sulfurization, this modification consisting in treating
these catalysts with chelating or sulfurizing
compounds. It is thus known to modify these catalysts
using acids of thioglycolic type or else thioalcohols,
thioacetone compounds and thiodiazoles or thiocyanates,
such as provided in particular by Sumitomo patents
(EP 289 211, EP 300 629, EP 338 788, EP 357 295,
EP 456 592, EP 478 365 and EP 506 206). Other catalysts
have been modified by treatment using alcohol-acid
organic compounds (EP 482 817) , optionally etherified
mono-, di- or polyalcohols (EP 601 722, US 3 954 673,
US 4 012 340 and WO 01/76741) or compounds of the
following types: urea, polyamines, EDTA, hydrazine and
other nitrogenous compounds (EP 181. 035, EP 335 754,
EP 1 043 069, WO 01/76741, US 3 954 673 and
US 4 012 340).
Patent EP 628 347 from Eurecat provides, in order to
modify and sulfurize catalysts based on refractory
oxides and on metals from Groups VI and VIII, for the
presulfurization of these conventional catalysts with a
mixture comprising a first sulfur compound with a
decomposition point TI of less than 220°C and a second
sulfur compound with a decomposition point T2 of
greater than 220°C. The first sulfur compound includes
a C-S or S-S structure and the second sulfur compound
includes at least one S=0 structure and is chosen from
compounds of sulfone or sulfoxide type, for example
alkyl, aryl, alkylaryl or arylalkyl sulfones.
All these modifications are targeted at improving the
effectiveness of these catalysts in hydrotreating, more
particularly in desulfurization, but require the use of
chemicals not always under the control of the refining
industry. In addition, these modifications do not
always make it possible to achieve the sulfur contents
required by the specifications expected in Europe by
2005 in 'middle distillates resulting from direct
distillation or refined fractions used as components of
diesel fuels.
In some countries, such as Sweden, the United States,
in particular in California, and others, the total
sulfur content of gas oils is already limited to 0.005%
by weight and this limitation may eventually become
general in the countries of the OECD. For Europe, this
objective of 0.005% by weight of total sulfur should be
achieved in 2005 but a content of 0.001% by 2010 is
already being raised.
US 3 945 914 A discloses a process for the
desulfurization of hydrocarbons by oxidation, in a
first stage, of at least a portion of the sulfurcomprising
hydrocarbons in the presence of oxidizing
compounds (peracids, hydroperoxides and peroxides) and
then conversion, in a second stage, of the oxidized
sulfur-comprising hydrocarbons to metal sulfides, after
bringing these compounds into contact with a metal at a
temperature of greater than 260°C.
The essential metal is molybdenum in the dissolved form
or the form supported on a refractive oxide of the
alumina type, optionally in combination with another
metal.
In this two-stage process, the sulfones and sulfoxides
of the benzothiophene derivatives, including the
sulfones and sulfoxides of the other sulfur-comprising
compounds predominant in the hydrocarbons, cannot be
absorbed by a solid catalyst as, at these temperatures,
they react with the metal to form metal sulfides, this
reaction promoting the desulfurization of the
hydrocarbons. In addition, according to this patent,
the support is not critical as it is not involved in
the sulfurization reaction of the metal (column 4,
lines 25 to 29) and the catalyst does not have to be
sulfurized.
The Applicant Company has designed a novel type of
hydrotreating catalyst based on refractive oxides and
on metals from Groups VI and VIII which makes it
possible to achieve a preset sulfur content with an
increase in reaction temperature of at least 5 to 25°C
with respect to an unmodified conventional catalyst,
all other operating conditions for the process,
pressure, amount of hydrogen and hourly space velocity
(HSV), being identical. Such an increase with regard to
the reaction, temperature makes it possible to envisage
the achievement of sulfur contents far below 50 ppm and
even below 10 ppm by varying these same operating
conditions.
A first subject matter of the present invention is thus
a hydrotreating catalyst comprising a support formed of
refractory oxides, at least one metal from Group VIII
and at least one metal from Group VI, both in the
oxidized form, characterized in that it comprises at
least one sulfone compound and/or sulfoxide compound
derived from at least one benzothiophene compound.
In the continuation of the present description, the
term "metal catalyst" will be used to refer to any
catalyst comprising a support formed of refractory
oxides and at least one metal from each of Groups VI
and VIII i"h the oxidized form.
The term "hydrotreating" is understood to mean any
process involving hydrogen for the purpose of reducing
the sulfur contents of the hydrocarbons treated,
whatever the refined fraction from which they
originate; processes comprising a hydrotreating
(desulfurization, denitrogenation and dearomatization)
or a hydrocracking are to be understood in particular.
The compound characteristic of the catalyst in
.accordance with the invention is chosen from sulfones
and sulfoxides of benzothiophenes, of dibenzothiophenes
and more generally of polyarylthiophenes, which may or
may not be substituted by alkyl or allyl hydrocarbon
chains optionally comprising aliphatic and/or aromatic
rings, and it can be used alone or as a mixture.
Preferably, this compound is a commercial sulfone
and/or sulfoxide compound or a product resulting from
the oxidation of the benzothiophene compounds present
in the hydrocarbon fractions obtained by refining crude
oils.
In a preferred embodiment of the invention, at least
one of the sulfone and/or sulfoxide compounds results
from the oxidation of a desulfurized or nondesulfurized
hydrocarbon -fr'action by an oxidizing compound chosen
from organic' and inorganic peroxides and hydroperoxides
i
and organic or inorganic peracids, optionally in the
presence of a catalyst. Hydrogen peroxide and tertbutyl
hydroperoxide are among the preferred oxidizing
agents.
Thus," the hydrotreating catalyst according to the
invention, while exhibiting characteristics of activity
and of selectivity comparable with, indeed even better
than, those of the commercially available catalysts,
can advantageously be prepared in a refinery and can
then be immediately used in this same refinery. In
addition, It exhibits the advantage of being able to be
prepared from regenerated catalysts already available
on site and which are much cheaper than the most
effective hydrotreating catalysts on the market as
regards hydrotreating.
In order to be effective in hydrotreating, the catalyst
will comprise at least 0.01% by weight of at least one
sulfone and/or sulfoxide compound and preferably from
0.01% to 10% by weight.
Another subject:matter of the invention is the process
for the preparation of the hydrotreating catalyst. It
necessarily comprises a stage of formation and/or of
deposition of sulfone and/or sulfoxide compounds at the
surface of a metal catalyst. The deposition of these
compounds can be carried out by impregnation, grafting
or formation at the surface of the catalyst.
More particularly, the process consists in introducing,
into a reactor comprising the metal catalyst, an
organic fluid- comprising at least one benzothiophene
compound and- an oxidizing compound from the group
consisting of organic or inorganic peroxides and
hydropero^ides 'and organic or inorganic peracids,
starting from ambient temperature and at atmospheric
pressure, -'and in then recovering the catalyst
supporting- the sulfoxide and/or sulfone compounds which
are formed'.
The organic fluid used is chosen from paraffin,
aromatic and naphthenic hydrocarbons and the solvents
for benzothiophene compounds, such as benzene, toluene
and/or xylene, and hydrocarbon fractions resulting from
the refining of crude oils. In a preferred form, the
organic fluid is a hydrocarbon fraction with minimum
and maximum boiling points varying from 40 to 560°C.
In its preferred embodiment, the process for the
preparation of the hydrotreating catalyst according to
the invention' consists in carrying out an oxidizing
desulfurization, in the presence of the metal catalyst,
of a hydrocarbon fraction with minimum and maximum
boiling points varying from 40 to 560°C. Preferably,
this metal catalyst comprises a support made of silica
and/or of alumina and a combination of metals from
Groups VI and VIII, in the oxidized form, chosen from
the group consisting of nickel/molybdenum,
cobalt/molybdenum, nickel/tungsten, nickel/cobalt/-
molybdenum and hickel/tungsten/molybdenum combinations.
This metal catalyst can be a freshly prepared or
commercial catalyst and it will be used fresh or after
regeneration, that is to say essentially after
combustion of the coke deposited on this catalyst
during a hydrotreating operation, in the context of the
present invention.
This preparation process according to the invention can
be carried out either ex situ, before charging to the
hydrotreating reactor, or in situ, in the reactor which
will be used subsequently as hydrotreating reactor.
Of course,- it will not be departing from the scope of
the invention: if this preparation process were applied
to any other catalytic support for the purpose of
increasing its activity in hydrotreating.
A third subject matter of the invention is the use of
this catalyst in a process for the hydrotreating of
hydrocarbons, after sulfurization in situ or ex situ of
this catalyst using at least one sulfur compound chosen
from hydrogen sulfide, mercaptans, sulfides and/or
polysi^lfides and other sulfurizing compounds, this
compound being introduced in the gaseous form, in the
liquid form, after dilution of the solid or the liquid
in a solvent, or directly in the liquid form,
optionally even as additive of the feedstock to be
hydrotreated. This sulfurization can also be carried
out solely by the feedstock to be hydrotreated.
A fourth subject matter of the invention is a process
for the purification, down to less than 10 ppm of
sulfur, of a sulfur-comprising, nitrogen-comprising
and/or aromatic hydrocarbon feedstock, this process
comprising a first stage of hydrotreating the
distillate in the presence of the modified metal
catalyst of the invention, after sulfurization of the
latter, and a second stage of oxidizing desulfurization
of the hydrotreated feedstock.
In a preferred form of this purification process, the
oxidizing desulfurization of the hydrotreated feedstock
is carried out in the presence of a metal catalyst and
of an oxidizing agent chosen from organic or inorganic
peroxides and hydroperoxides and organic or inorganic
peracids. Preferably, the oxidizing agent is hydrogen
peroxide or tert-butyl hydroperoxide. The metal
catalyst will -advantageously comprise a support made of
silica and/or of alumina and a combination of metals
from Groups VI and VIII, in the oxidized form, which
combination is chosen from the group consisting of
nickel/molybdenum, cobalt/molybdenum, nickel/tungsten,
nickel/cobalt/molybdenum and nickel/tungsten/molybdenum
combinations;-'
In a favored embodiment of the invention, in particular
when the hydrotreating and oxidizing desulfurization
operations are carried out in the same refinery, the
spent metal catalyst, but modified according to the
invention,c obtained at the end of the oxidizing
desulfurization cycle is used as hydrotreating catalyst
after sulfurization ex situ or in situ in the
hydrotreating reactor. The end of the oxidizing
desulfurization cycle can advantageously correspond to
the moment when the total sulfur content of the
effluent again rises above 10 ppm.
Taking the above into consideration, the process
according to the invention can be carried out in the
same reactor or in at least two separate reactors, for
example arranged in series.
In the configuration using two separate reactors, the
latter can operate alternately in hydrotreating and in
oxidizing desulfurization, each reactor carrying out a
different treatment during the same purification cycle.
The advantage of this embodiment is that only the
catalyst used in hydrotreating has to be discharged and
regenerated before being reused in oxidizing
desulfurization. Furthermore, the catalyst resulting
from the oxidizing desulfurization exhibits a much
higher activity than if it had been used directly in
hydrotreating.
Another configuration provides for one of the two
reactors to always operate in hydrotreating and for the
other reactor to always operate in oxidizing
desulfurization; the catalyst at the end of the
oxidizing desulfurization cycle is then discharged,
then • recharged to the hydrotreating reactor and,
finally, sulfurized according to conventional methods.
Furthermore, a conventional unmodified hydrotreating
metal catalyst is charged to the oxidizing
desulfurization reactor. As in the preceding
configuration, the hydrotreating catalyst still has to
be regenerated.
The purification process is particularly suitable for a
hydrocarbon feedstock with minimum and maximum boiling
points ranging from 40 to 560°C, it being possible for
this feedstock to originate in particular from an
atmospheric distillation, a vacuum distillation, an FCC
catalytic cracking, a hydrocracking, a coking or a
visbreaking.
The examples which follow are targeted at illustrating
the invention but have no limiting nature.
EXAMPLE I
In the present example, a description is given of the
preparation of five sulfurized catalysts which will be
used subsequently in desulfurization, denitrogenation
and dearomatization. All these catalysts are prepared
from a commercial catalyst A, composed of a combination
comprising 3% of cobalt and comprising 10% of
molybdenum on an alumina support, available
commercially and commonly used by refiners in their
hydrodesulfurization units.
The modification and/or sulfurization treatments
applied to this catalyst are summarized in table I
below.
(Table Removed)
* TBHP = 5M solution of tert-butyl hydroperoxide in
decane.
* dBTS = 5% dibenzothiophene sulfone in ethanol.
* DMDS = dimethyl disulfide.
* GOi : gas oil comprising 1% of sulfur.
* GO2 : gas oil comprising 50 ppm of sulfur.
The ex situ modification using gas oil comprising TBHP
is carried out as follows.
38 g of the TBHP solution are added to 600 g of direct
distillation gas oil (GOi) comprising 1% by weight of
sulfur (approximately 700 ml) placed in a roundbottomed
flask. 100 g of catalyst A are then added to
this mixture. The combined mixture is stirred at a
moderate rate at 70°C for 3 hours. The modified
catalyst is subsequently recovered by filtration, then
washed three times with 200 ml of toluene at ambient
temperature and, finally, washed with 3 times 200 ml of
pentane at ambient temperature. The catalyst thus
recovered is dried under air at 80°C for 3 hours in a
ventilated oven.
The in situ modification consists in introducing 100 ml
of catalyst A into the reactor of a pilot unit of
Catatest type. A gas oil (GOi or G02) , to which the TBHP
solution has been added, is passed over this catalyst
at an hourly space velocity (HSV) of 1 h"1 at
atmospheric pressure at a temperature of 70°C. After
7 hours (GOi) or 70 hours (G02) , the injection of
additivated gas oil is halted. A slight nitrogen stream
is passed in the downward flow mode for the purpose of
removing the excess gas oil present in the reactor.
The ex situ modification using dibenzothiophene sulfone
(dBTS) is identical to the modification using gas oil
and TBHP, apart from the fact that the gas oil/TBHP
mixture is replaced by the commercial sulfone in
solution in ethanol.
Catalysts B and C were obtained by wetting catalyst A
with direct distillation gas oil alone comprising 1% by
weight of sulfur, the operation being carried out as
described above for the ex situ and in situ
modifications. They constitute catalysts for
comparisons with the other four catalysts, D, E, F and
G, in accordance with the invention.
The catalysts were all sulfurized with a gas oil to
which 2% by weight of DMDS had been added, according to
the procedure recommended by the manufacturer of
catalyst A.
EXAMPLE II
The present example is intended to show that the
catalysts of the invention have a much higher activity
in hydrodesulfurization and denitrogenation than that
obtained with the unmodified commercial catalyst A.
Catalysts A, B, C, D, E, F and G of example 1 are
subjected, in a tubular reactor of a pilot
hydrotreating unit operating in downward flow, to a
first stage of stabilization by hydrotreating a direct
distillation gas oil. Subsequently, a hydrocarbon
feedstock comprising 75% by volume of direct
distillation gas oil and 25% by volume of a 220-350°C
hydrocarbon fraction resulting from catalytic cracking,
usually referred to as LCO (Light Cycle Oil), is
hydrotreated. The characteristics of the mixture are
given in table II below.
(Table Removed)
The operating conditions are given in table III below.
(Table Removed)
In order to compare the activities in desulfurization
and in denitrogenation, the reaction temperature is
adjusted so as to achieve either 98% desulfurization or
50% denitrogenation of the hydrotreated feedstock. The
lower this temperature for a given catalyst with
respect to the corresponding temperature for the
reference catalyst A, the more active this catalyst is
in desulfurization or in denitrogenation.
For the reference catalyst A, the temperatures
referenced THos and THDN respectively for the hydrodesulfurization
and the denitrogenation correspond to
the temperatures required to achieve 98%
desulfurization and 50% denitrogenation.
The results of the tests are given in table IV below.
(Table Removed)
Catalysts D, E, F and G (in accordance with the
invention) exhibit an activity in HDS and HDN which is
much higher than that of the reference catalyst A,
whereas catalysts B and C exhibit an activity
equivalent- to that of catalyst A.
EXAMPLE III
The activities of a fresh modified hydrotreating
catalyst according to the invention and of this same
catalyst, regenerated after a hydrotreating cycle and
then modified according to the invention, are compared
in the present example.
After a first hydrotreating cycle, the catalyst G of
example II is regenerated by combustion of the coke
under an oxidizing atmosphere at 450°C for at. least
5 hours. The regenerated catalyst is modified as
described in example II for catalyst G, and a catalyst
G' is obtained and is subsequently sulfurized as
described in example II. A new hydrotreating cycle
identical to the cycle applied to catalyst G is then
carried out.
The hydrotreating temperatures required for G and G'
are compared with respect to the reference catalyst A
in table V.
(Table Removed)
It is found, from this table, that, after regeneration
and modification again according to the invention, the
regenerated commercial catalyst regains virtually the
same performance as that of the fresh modified
catalyst.

We Claim:
1. A process for the purification, down to less than 10 ppm of sulfur, of a sulfur-comprising, nitrogen-comprising and/or aromatic hydrocarbon feedstock, characterized in that it comprises a first stage of hydro-treating the hydrocarbon feedstock in the presence of a catalyst, after sulfurization of this catalyst, and a second stage of oxidizing desulfurization of the hydrotreated feedstock, wherein the catalyst is a modified hydrotreating catalyst comprising a support formed of refractory oxides, at least one metal from Group VIII and at least one metal from Group VI, both in the oxidized form, wherein it comprises at least one sulfone compound and/or sulfoxide compound derived from at least one benzothiophene compound.
2. The process as claimed in claim 1, wherein said compound is chosen from sulfones and sulfoxides of benzothiophenes, of dibenzothiophenes and more generally of polyarylthiophenes, which may or may not be substituted by alkyl or allyl hydrocarbon chains optionally comprising aliphatic and/or aromatic rings, this compound being used alone or as a mixture with other compounds of the same group.
3. The process as claimed in either of claims 1 and 2, wherein said compound is a commercial sulfone and/or sulfoxide compound or a sulfone and/or sulfoxide compound originating from the oxidation of the benzothiophene compounds present in the hydrocarbon fractions obtained by refining crude oils.
4. The process as claimed in one of claims 1 to 3, wherein at least one of the sulfone and/or sulfoxide compounds results from the oxidation of a desulfurized or nondesulfurized hydrocarbon fraction by an oxidizing compound chosen from organic and inorganic peroxides and of the kind such as herein described and hydroperoxides and organic or inorganic peracids of the kind such as herein described, optionally in the presence of a metal catalyst.

5. The process as claimed in one of claims 1 to 4, wherein it comprises at least 0.01% by weight of at least one sulfone and/or sulfoxide compound.
6. The process as claimed in claim 1, wherein the oxidizing desulfurization is carried out in the presence of a metal catalyst based on refractory oxides supporting at least one metal from each of Groups VI and VIII and of an oxidizing agent chosen from organic or inorganic peroxides and hydroperoxides and organic or inorganic peracids, hydrogen peroxide and tertbutyl hydroperoxide being preferred.
7. The process as claimed in claim 1, wherein the modified metal catalyst obtained at the end of the oxidizing desulfurization cycle is used as hydrotreating catalyst, after ex situ sulfurization or in situ sulfurization in the hydrotreating reactor.
8. The process as claimed in one of claims 1, 6 and 7, wherein it is carried out in the same reactor or in at least two separate reactors.
9. The process as claimed in claim 8, wherein the two separate reactors operate alternately in hydrotreating and in oxidizing desulfurization, each carrying out a different treatment.
10. The process as claimed in claim 8, wherein one of the reactors always operates in hydrotreating and the other reactor always operates in oxidizing desulfurization.
11. The process as claimed in one of claims 1 and 6 to 10, wherein the hydrocarbon feedstock is a hydrocarbon feedstock with minimum and maximum boiling points of between 40 and 560°C.

Documents:

3003-DELNP-2005-Abstract-(03-03-2009).pdf

3003-delnp-2005-abstract.pdf

3003-DELNP-2005-Claims-(03-03-2009).pdf

3003-DELNP-2005-Claims-(24-06-2009).pdf

3003-DELNP-2005-Claims-(25-06-2009).pdf

3003-delnp-2005-claims.pdf

3003-DELNP-2005-Correspondence-Others-(03-03-2009).pdf

3003-DELNP-2005-Correspondence-Others-(24-06-2009).pdf

3003-DELNP-2005-Correspondence-Others-(25-06-2009).pdf

3003-DELNP-2005-Correspondence-Others-(31-03-2010).pdf

3003-delnp-2005-correspondence-others.pdf

3003-DELNP-2005-Description (Complete)-(03-03-2009).pdf

3003-delnp-2005-description (complete).pdf

3003-DELNP-2005-Form-1-(03-03-2009).pdf

3003-delnp-2005-form-1.pdf

3003-delnp-2005-form-18.pdf

3003-DELNP-2005-Form-2-(03-03-2009).pdf

3003-delnp-2005-form-2.pdf

3003-DELNP-2005-Form-3-(03-03-2009).pdf

3003-delnp-2005-form-3.pdf

3003-DELNP-2005-Form-5-(03-03-2009).pdf

3003-delnp-2005-form-5.pdf

3003-DELNP-2005-GPA-(24-06-2009).pdf

3003-DELNP-2005-GPA-(31-03-2010).pdf

3003-delnp-2005-gpa.pdf

3003-delnp-2005-pct-210.pdf

3003-DELNP-2005-Petition-137-(03-03-2009).pdf


Patent Number 235192
Indian Patent Application Number 3003/DELNP/2005
PG Journal Number 31/2009
Publication Date 31-Jul-2009
Grant Date 26-Jun-2009
Date of Filing 05-Jul-2005
Name of Patentee TOTALFINAELF FRANCE
Applicant Address TOUR TOTAL, 24, COURS MICHELET, 92800 PUTEAUX, FRANCE.
Inventors:
# Inventor's Name Inventor's Address
1 THIERRY CHOLEY RUE DU COQ 146, B-1180 BRUXELLES, BELGIUM.
2 JEAN-PIERRE DATH RUE D'ATH 53, B-7970 BELOEIL HAINAUT, BELGIUM.
PCT International Classification Number C10G 45/08
PCT International Application Number PCT/FR2004/000071
PCT International Filing date 2004-01-15
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 03/00439 2003-01-16 France