U.S. patent application number 13/900658 was filed with the patent office on 2013-12-05 for optimized process for upgrading bio-oils of aromatic bases.
The applicant listed for this patent is IFP Energies nouvelles. Invention is credited to Hugues DULOT, Raphael HUYGHE, Alain QUIGNARD, Olivier THINON.
Application Number | 20130324775 13/900658 |
Document ID | / |
Family ID | 46634220 |
Filed Date | 2013-12-05 |
United States Patent
Application |
20130324775 |
Kind Code |
A1 |
QUIGNARD; Alain ; et
al. |
December 5, 2013 |
OPTIMIZED PROCESS FOR UPGRADING BIO-OILS OF AROMATIC BASES
Abstract
A process for preparing aromatic compounds from a liquid biofuel
feedstock by introducing the feedstock into a hydroreforming stage
in the presence of hydrogen and a hydroreforming catalyst that
contains a transition metal of a group 3 to 12 element and an
activated carbon, silicon carbide, silica, transition alumina,
alumina-silica, zirconium oxide, cerium oxide, titanium oxide, or
an aluminate of a transition metal substrate, to obtain a liquid
effluent that contains an aqueous phase and an organic phase, a
stage for hydrotreatment of the organic phase, a hydrocracking
stage, recycling a fraction that boils higher than 160.degree. C.
in said hydrocracking stage, a separation into a fraction
containing naphtha and a fraction that boils higher than
160.degree. C., a stage for catalytic reforming of the fraction
containing naphtha to obtain hydrogen and a reformate that contains
aromatic compounds and a stage for separation of the aromatic
compounds of the reformate.
Inventors: |
QUIGNARD; Alain;
(Roussillon, FR) ; THINON; Olivier; (Roanne,
FR) ; DULOT; Hugues; (Rueil-Malmaison, FR) ;
HUYGHE; Raphael; (Saint Andeol Le Chateau, FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
IFP Energies nouvelles |
Rueil-Malmaison Cedex |
|
FR |
|
|
Family ID: |
46634220 |
Appl. No.: |
13/900658 |
Filed: |
May 23, 2013 |
Current U.S.
Class: |
585/319 |
Current CPC
Class: |
C10G 2400/30 20130101;
C10G 69/10 20130101; C10G 3/50 20130101; C10G 3/42 20130101; C10G
2300/1011 20130101; Y02P 30/20 20151101 |
Class at
Publication: |
585/319 |
International
Class: |
C10G 3/00 20060101
C10G003/00 |
Foreign Application Data
Date |
Code |
Application Number |
May 30, 2012 |
FR |
1201544 |
Claims
1. Process for the production of aromatic compounds starting from a
liquid feedstock that comprises at least one bio-oil, said
feedstock being introduced into at least the following stages: A
first hydroreforming stage in the presence of hydrogen and a
hydroreforming catalyst that comprises at least one transition
metal that is selected from among the elements of groups 3 to 12 of
the periodic table and at least one substrate that is selected from
among activated carbons, silicon carbides, silicas, transition
aluminas, alumina-silicas, zirconium oxide, cerium oxide, titanium
oxide, and the aluminates of transition metals, taken by themselves
or in a mixture, for obtaining at least one liquid effluent that
comprises at least one aqueous phase and at least one organic
phase, A second stage for hydrotreatment of at least one portion of
the organic phase of the effluent that is obtained from the first
hydroreforming stage in the presence of hydrogen in at least one
reactor that contains a hydrotreatment catalyst, operating at a
temperature of between 250 and 400.degree. C., at a pressure of
between 2 MPa and 25 MPa, at an hourly volumetric flow rate of
between 0.1 h.sup.-1 and 20 h.sup.-1, and with a total amount of
hydrogen mixed with the feedstock such that the
hydrogen/hydrocarbon volumetric ratio is between 100 and 3,000
Nm.sup.3/m.sup.3, A third hydrocracking stage of at least one
portion of the effluent that is obtained from the second
hydrotreatment stage, in the presence of hydrogen, in at least one
reactor that contains a hydrocracking catalyst, operating at a
temperature of between 250 and 480.degree. C., under a pressure of
between 2 and 25 MPa, at a volumetric flow rate of between 0.1 and
20 h-1, and with an amount of hydrogen that is introduced such that
the hydrogen to hydrocarbon volumetric ratio is between 80 and
5,000 Nm.sup.3/m.sup.3, in which at least one portion of the
fraction that boils at a temperature that is higher than
160.degree. C. that is separated at the end of said third
hydrocracking stage is recycled in said third hydrocracking stage,
A separation of the effluent that is obtained at the end of the
third hydrocracking stage into at least one fraction that contains
naphtha and a fraction that boils at a temperature that is higher
than 160.degree. C., A fourth stage for catalytic reforming of the
fraction containing naphtha that is obtained from the separation
operating in the presence of a catalytic reforming catalyst, under
a pressure of between 0.1 and 4 MPa, at a temperature of between
400 and 700.degree. C., at a volumetric flow rate of between 0.1
and 10 h.sup.-1, and with a hydrogen/hydrocarbon ratio of 0.1 to
10, making it possible to obtain hydrogen and a reformate that
contains aromatic compounds, and a stage for separation of the
aromatic compounds of the reformate obtained at the end of the
catalytic reforming stage.
2. Process according to claim 1, in which said first hydroreforming
stage is carried out at a temperature of between 250 and
450.degree. C., and at an absolute pressure of between 3.4 and 27.6
MPa (500 and 4,000 psi), at a volumetric flow rate of between 0.5
h.sup.-1 and 5 h.sup.-1 relative to the bio-oil and with an amount
of hydrogen that is introduced such that the volumetric ratio of
hydrogen to hydrocarbons is between 50 and 2,000
Nm.sup.3/m.sup.3.
3. Process according to claim 1, in which said liquid feedstock
comprising at least one bio-oil also contains other liquid
feedstocks obtained from the biomass, with said liquid feedstocks
being selected from among vegetable oils, alga or algal oils, fish
oils, fats of vegetable or animal origin, and alcohols obtained
from the fermenting of sugars of the biomass, or mixtures of such
feedstocks, which may or may not be pretreated.
4. Process according to claim 1, in which said liquid feedstock
consists entirely of bio-oil.
5. Process according to claim 1, in which the hydroreforming
catalysts comprise Ni, Cu, NiCr, NiMo or NiMn on activated carbon
or on alumina or nickel aluminate.
6. Process according to claim 1, in which a stage for separation of
at least one organic phase, at least one aqueous phase, and at
least one gaseous phase can be carried out between said second
hydrotreatment stage and said third hydrocracking stage.
7. Process according to claim 6, in which said organic phase is
fractionated in a fractionation zone into at least one light
fraction that boils at a temperature of between 80 and 160.degree.
C. and into at least one heavy fraction that boils at a temperature
that is higher than 160.degree. C.
8. Process according to claim 7, in which said heavy fraction that
boils at a temperature that is higher than 160.degree. C. is sent
into said third hydrocracking stage and said light fraction is sent
directly into the fourth catalytic reforming stage, mixed with the
fraction that contains naphtha separated at the end of said third
hydrocracking stage.
9. Process according to claim 1, in which said hydrocracking
catalyst comprises metals of groups 8 to 10 that are selected from
among nickel and cobalt, combined with at least one metal of group
6, selected from among molybdenum and tungsten and a substrate that
is selected from among alumina, silica, silica-aluminas, zeolites,
magnesia, clays, and the mixtures of at least two of these
minerals.
10. Process according to claim 9, in which the substrate of said
hydrocracking catalyst comprises at least one FAU-structural-type Y
zeolite.
11. Process according to claim 1, in which the entire fraction that
boils at a temperature that is higher than 160.degree. C.,
separated at the end of the third hydrocracking stage, is recycled
in said third stage.
Description
FIELD OF THE INVENTION
[0001] This invention relates to a process for the production of
aromatic compounds starting from liquids obtained from biomass and
in particular starting from liquefied biomass obtained from the
pyrolysis of biomass, also called bio-oil. In a more specific
manner, the invention relates to a process for conversion of
bio-oil into BTX-type aromatic compounds comprising a
hydroreforming stage, followed by a hydrocracking stage in a fixed
bed of rigorous conditions suitable for maximizing the production
of light aromatic precursors and a catalytic reforming stage.
STATE OF THE ART
[0002] The aromatic compounds, in particular the C6-C8 aromatic
compounds, i.e., benzene, toluene and xylenes/ethylbenzene (BTX),
are major intermediate compounds in petrochemistry for the
synthesis of resins, plasticizers and polyester fibers.
[0003] The primary BTX production source is the catalytic reforming
(or aromatizing according to English terminology) that is used by
refiners for improving the octane number of the gasoline by
manufacturing aromatic compounds. Starting from naphtha, this
process produces a fraction that is rich in aromatic hydrocarbons,
called reformate, from which it is possible to extract, separate
and transform the aromatic compounds.
[0004] Today, the production of aromatic compounds is based
essentially on a petroleum origin. The current international
context is first marked by a desire to reduce dependency as regards
raw materials of fossil origin and then owing to the significance
of the problems linked to global warming and greenhouse gas
emissions. In this context, the search for new feedstocks obtained
from non-fossil sources constitutes stakes of growing importance.
Among these feedstocks, it is possible to cite, for example,
biomass.
[0005] Taking into account abundant and renewable biomass reserves,
an attractive alternative for the production of intermediate
products in petrochemistry is the use of liquids obtained from
biomass, in general also called bio-oil or else bio-crude.
[0006] The liquid products that are obtained by thermochemical
liquefaction of cellulosic biomass are called bio-oils. The process
for thermochemical liquefaction of biomass can be performed, for
example, with or without the presence of catalyst, in the presence
of a cover gas or a gas that contains hydrogen and water. The
thermochemical processes in general convert the biomass into
liquid, gaseous, and solid products. Among these processes, those
called rapid pyrolysis processes tend to maximize the liquid yield.
During rapid pyrolysis, the temperature of the biomass, optionally
divided, is quickly raised to values that are higher than
approximately 300.degree. C. and preferably between 450 and
600.degree. C. and in a preferred manner between 450 and
550.degree. C., and the liquid products are condensed in the form
of bio-oil. Ringer et al. (Large-Scale Pyrolysis Oil Production: A
Technology Assessment and Economic Analysis, M. Ringer, V. Putsche,
and J. Scahill, NREL Technical Report NREL/TP-510-37779, November
2006) studied the different technologies implemented for the rapid
pyrolysis of biomass on a large scale. They comprise boiling
fluidized beds, circulating fluidized beds, ablative pyrolysis
reactors, vacuum pyrolysis reactors, and rotating cone pyrolysis
reactors.
[0007] The bio-oils and in particular the bio-oils obtained from
the rapid pyrolysis of biomass are complex mixtures of greatly
oxygenated polar hydrocarbon-containing products obtained from the
breakage of biopolymers and having physical and chemical properties
limiting their direct use.
[0008] The bio-oils of pyrolysis have undesirable properties such
as: (1) The corrosiveness due to their high content of water and
organic acids; (2) A low specific calorific value because of the
high content of oxygen, typically on the order of 40% by weight;
(3) Chemical instability, in storage as well as under elevated heat
conditions, due to the abundance of reactive oxygenated functional
groups such as the carbonyl group, which can bring about
polymerization during storage and consequently a separation of
phases; (4) A viscosity and a tendency toward the separation of
relatively high phases under high shearing conditions, in an
injector, for example; (5) Solid coal particles obtained from
pyrolysis, which will always be present in non-filtered bio-oils in
small amounts such that the bio-oil/coal particles ratio is higher
than 10:1 and preferably higher than 50:1. However, said particles
can cause the clogging of stationary internal combustion engines or
can poison post-treatment catalysts.
[0009] All of these aspects are combined to make handling,
shipping, storage and use of the bio-oils difficult and costly,
thus making their integration into the systems and the current
technologies for production of heat and energy very
problematic.
[0010] During the last twenty years, the approach consisting in
carrying out direct hydrotreatment of bio-oil for the purpose of
converting it into hydrocarbons or stable oxygenated liquids has
been the object of intensive studies. Elliott published a detailed
study of these numerous historical developments, including the work
done with model compounds known for being present in the bio-oils
(Historical Developments in Hydroprocessing BioOils, D. C. Elliott,
Energy & Fuels 2007, 21, 1792-1815).
[0011] One of the major obstacles to the direct catalytic
hydrotreatment of bio-oils resides in their tendency to polymerize
when they are subjected to higher temperatures than approximately
100.degree. C., which gives rise to the formation of solids at
higher temperatures than approximately 140.degree. C., with
consequences such as the clogging of feedstock lines, furnaces and
reactors as well as the rapid deactivation of the catalyst, and
even the clogging of the inlet of the reactor.
[0012] Nevertheless, an effective hydrotreatment process remains to
be found. The difficulties encountered find their origin in the
rapid thermal polymerization of bio-oil, which leads to the
clogging of lines and reaction equipment as well as to rapid
deactivation of the catalyst. In other words, with temperatures
that are typically required for the hydrotreatment of bio-oils, the
polymerization reactions are essentially faster than the
hydrotreatment reactions, which ultimately bring about the
formation of solid in the equipment under reaction conditions.
Furthermore, the consumption of hydrogen of this type of
hydrotreatment remains very high: from 4 to 6% relative to the
initial dry biomass.
[0013] There is therefore a need for an improved process for
hydrotreatment of bio-oils that minimizes the formation of solids,
the deactivation of catalyst, and the consumption of hydrogen, and
that maximizes the yield of deoxygenated oil that is produced.
[0014] The purpose of this invention is to produce BTX-type
aromatic compounds from a liquid feedstock that comprises at least
one bio-oil by using a process that comprises a hydroreforming
stage, followed by a hydrocracking and catalytic reforming
stage.
SUMMARY OF THE INVENTION
[0015] This invention relates to a process for the production of
aromatic compounds, in particular of the BTX type, starting from a
liquid feedstock that comprises at least one bio-oil, whereby said
feedstock is introduced into at least the following stages: [0016]
A first hydroreforming stage in the presence of hydrogen and a
hydroreforming catalyst comprising at least one transition metal
that is selected from among the elements of groups 3 to 12 of the
periodic table and at least one substrate that is selected from
among the activated carbons, silicon carbides, silicas, transition
aluminas, alumina-silicas, zirconium oxide, cerium oxide, titanium
oxide and the transition metal aluminates, taken by themselves or
in a mixture, for obtaining at least one liquid effluent that
comprises at least one aqueous phase and at least one organic
phase, [0017] A second stage for hydrotreatment of at least one
portion of the organic phase of the effluent that is obtained from
the first hydroreforming stage in the presence of hydrogen in at
least one reactor that contains a hydrotreatment catalyst,
operating at a temperature of between 250 and 400.degree. C., at a
pressure of between 2 MPa and 25 MPa, at an hourly volumetric flow
rate of between 0.1 h.sup.-1 and 20 h.sup.-1, and with a total
amount of hydrogen mixed with the feedstock such that the
hydrogen/hydrocarbon volumetric ratio is between 100 and 3,000
Nm.sup.3/m.sup.3, [0018] A third stage for hydrocracking at least
one portion of the effluent that is obtained from the second
hydrotreatment stage, in the presence of hydrogen, in at least one
reactor that contains a hydrocracking catalyst, operating at a
temperature of between 250 and 480.degree. C., under a pressure of
between 2 and 25 MPa, at a volumetric flow rate of between 0.1 and
20 h-1, and with an amount of hydrogen that is introduced such that
the hydrogen to hydrocarbon volumetric ratio is between 80 and
5,000 Nm.sup.3/m.sup.3, in which at least one portion of the
fraction that boils at a temperature that is higher than
160.degree. C., separated at the end of said third hydrocracking
stage, is recycled in said third hydrocracking stage, [0019] A
separation of the effluent that is obtained at the end of the third
hydrocracking stage into at least one fraction that contains
naphtha and a fraction that boils at a temperature that is higher
than 160.degree. C., [0020] A fourth stage for catalytic reforming
of the naphtha-containing fraction that is obtained from the
separation operating in the presence of a catalytic reforming
catalyst, under a pressure of between 0.1 and 4 MPa at a
temperature of between 400 and 700.degree. C., at a volumetric flow
rate of between 0.1 and 10 h.sup.-1, and with a
hydrogen/hydrocarbon ratio of 0.1 to 10, making it possible to
obtain hydrogen and a reformate that contains aromatic compounds,
[0021] A stage for separating aromatic compounds from the reformate
that is obtained at the end of the catalytic reforming stage.
[0022] One advantage of this invention is to provide a process,
starting from a liquid feedstock that comprises at least one
bio-oil, comprising a hydroreforming stage followed by a
hydrotreatment stage and then a hydrocracking stage that made it
possible to obtain, after separation, a naphtha fraction that is
particularly well suited by its naphtheno-aromatic chemical nature
and by its very small amount of impurities for the production of
aromatic compounds by the catalytic reforming. Its unique structure
imparts to it excellent reactivity relative to aromatization
reactions.
[0023] In a first step, the hydroreforming stage makes it possible
to obtain a liquid effluent that comprises at least one aqueous
phase and at least one organic phase also containing large amounts
of impurities: heteroelements of sulfur, nitrogen and oxygen as
well as olefins and polyaromatic compounds. Before sending the
light fraction (naphtha) of said organic phase into the catalytic
reforming stage, it thus is necessary to carry out a hydrotreatment
stage that makes possible the elimination of nitrogen-containing,
oxygenated and sulfur-containing impurities, and then a stage of
rigorous hydrocracking with recycling of the distilling fraction
beyond 160.degree. C. to maximize said naphtha. This hydrocracking
stage thus makes it possible to obtain a significant naphtha
fraction by cracking.
[0024] Likewise, the rigorous conditions of the hydrocracking stage
make it possible to increase the naphtha fraction yield and
therefore ultimately to increase the yield of aromatic compounds
and hydrogen produced during the reforming.
DETAILED DESCRIPTION OF THE INVENTION
[0025] In accordance with the invention, the feedstock that
comprises at least one bio-oil that is treated in the process
according to the invention is a liquid feedstock. Throughout the
rest of the text, liquid feedstock is defined as a feedstock that
comprises less than 2% by weight, and preferably less than 1% by
weight, relative to the bio-oil, of solid particles dispersed in a
liquid. This corresponds to a bio-oil/solid particles ratio that is
greater than 50:1 and preferably greater than 100:1. Said feedstock
therefore is not a suspension.
[0026] A bio-oil is a complex mixture of oxygenated compounds,
obtained from the breakage of biopolymers that are present in the
original biomass. In the case of the lignocellulosic biomass, the
structures that are obtained from these three primary components,
cellulose, hemicellulose and lignin, are well represented by the
components of the bio-oil.
[0027] In particular, a bio-oil is a highly-oxygenated polar
hydrocarbon-containing product that in general comprises at least
10% by weight of oxygen, preferably 10 to 60% by weight of oxygen
relative to the total mass of said bio-oil. In general, the
oxygenated compounds are alcohols, aldehydes, esters, ethers,
organic acids and aromatic oxygenated compounds. In the case where
the bio-oil is obtained by rapid pyrolysis, a portion of the oxygen
is present in the form of free water representing at least 5% by
weight, preferably at least 10% by weight, and in a preferred
manner at least 20% by weight of bio-oil. These properties make the
bio-oil totally immiscible with the hydrocarbons, and even with the
aromatic hydrocarbons that generally contain very little or no
oxygen.
[0028] The bio-oils are advantageously obtained from the biomass
and are preferably selected from among plants, grasses, trees, wood
chips, seeds, fibers, seed husks, aquatic plants, hay, and other
sources of lignocellulosic materials, such as, for example, those
coming from municipal waste, food-processing waste, lumber scrap,
slaughterhouse waste, and agricultural and industrial waste (such
as, for example, sugar cane debris, waste obtained from the
cultivation of oil palm, sawdust or straw). The bio-oils can also
come from paper paste and by-products of paper that may or may not
be recycled, or by-products obtained from paper mills.
[0029] The bio-oils are advantageously obtained by thermochemical
liquefaction of the biomass, preferably by pyrolysis, and, in a
preferred manner, by rapid pyrolysis, or slow pyrolysis with or
without a catalyst (in the presence of catalyst, mention is then
made of catalytic pyrolysis). Pyrolysis is a thermal breakdown in
the absence of oxygen, with thermal cracking of gas, liquid and
solid feedstocks. A catalyst can advantageously be added for
reinforcing the conversion during the so-called catalytic
pyrolysis. The catalytic pyrolysis generally provides a bio-oil
that has an oxygen content that is lower than that of the bio-oil
obtained by thermal breakdown, but the bio-oil yield is generally
lower. The selectivity between the gas, the liquid and the solid is
in a ratio with the reaction temperature and the dwell time of the
vapor. The processes for pyrolysis of the biomass, in particular
rapid pyrolysis, are well described in the literature, such as, for
example, in A. V. Bridgewater, H. Hofbauer, and S. van Loo, Thermal
Biomass Conversion, CPL Press, 2009, 37-78.
[0030] Slow pyrolysis is advantageously carried out at a
temperature of between 350 and 450.degree. C. and preferably on the
order of 400.degree. C. and with a long dwell time of between
several minutes and several hours, which promotes the production of
a solid product that is also called a product of carbonization or
wood carbon. In particular, slow pyrolysis generally makes possible
the production of 35% by weight of gas, 30% by weight of liquid,
and 35% by weight of carbonization product. The gasification
processes operating at very high temperatures, preferably higher
than 800.degree. C., promote the production of gas, and in
particular more than 85% by weight of gas. The intermediate
pyrolysis is advantageously carried out at a temperature that is in
general between 450 and 550.degree. C. and with a short dwell time
of the vapor, preferably between 10 and 20 seconds, which promotes
the liquid yield. In particular, the intermediate pyrolysis in
general makes possible the production of 30% by weight of gas, 50%
by weight of liquid, and 20% by weight of carbonization
product.
[0031] Rapid pyrolysis is advantageously carried out at a
temperature of generally between 450 and 550.degree. C. and with a
very short dwell time of the vapor, preferably between 0.5 and 2
seconds, which maximizes the liquid yield: in particular, rapid
pyrolysis in general makes possible the production of 10-20% by
weight of gas, 60-75% by weight of liquid, and 10-20% by weight of
carbonization product. The highest liquid yields are therefore
obtained within the framework of the rapid pyrolysis processes of
wood, with a liquid yield that can reach up to 75% by weight. A
portion of the oxygen is present in the form of free water
representing at least 5% by weight, preferably at least 10% by
weight, and in a preferred manner at least 20% by weight of the
bio-oil.
[0032] Preferably, the bio-oils that are used in the process
according to this invention are obtained by rapid pyrolysis of the
biomass.
[0033] The bio-oils can also advantageously be obtained by
thermochemical liquefaction of the biomass such as, for example, by
hydropyrolysis of the biomass. The liquid feedstock that is treated
in the process according to the invention preferably comprises a
bio-oil content of between 10 and 100% by weight relative to the
total mass of said feedstock.
[0034] The liquid feedstock that comprises at least one bio-oil
that is used in the process according to the invention can also
advantageously contain other liquid feedstocks that are obtained
from the biomass, with said liquid feedstocks advantageously being
selected from among vegetable oils, alga or algal oils, fish oils,
fats of vegetable or animal origin, and alcohols obtained from the
fermenting of sugars of the biomass, or mixtures of such
feedstocks, which may or may not be pretreated. The vegetable oils
or the oils that are derived from animal fats essentially comprise
triglyceride-type chemical structures that one skilled in the art
also knows under the name fatty acid triesters as well as free
fatty acids, whose fat chains contain a carbon atom number of
between 9 and 25.
[0035] Said vegetable oils can advantageously be crude or refined,
totally or in part, and obtained from vegetables that are selected
from among canola, sunflower, soybean, palm, olive, coconut, copra,
castor oil, cotton, oils from peanuts, flax, and sea-cabbage, and
all of the oils that are obtained from, for example, sunflower or
canola by genetic modification or hybridization, with this list not
being limiting. Said animal fats are advantageously selected from
among the fats composed of residues from the food industry or
obtained from the catering industry. Cooking oils, various animal
oils such as fish oils, tallow and lard can also be used.
[0036] Said liquid feedstock comprising at least one bio-oil can
also advantageously be treated in a mixture with at least one
hydrocarbon-containing liquid feedstock that is derived from
petroleum and/or coal. The petroleum-derived liquid
hydrocarbon-containing feedstock can advantageously be selected
from among the direct distillation vacuum distillates, the vacuum
distillates originating from a conversion process, such as those
obtained from processes of coking, hydroconversion in a fixed bed
or hydrotreatment of heavy fractions in a boiling bed, the products
obtained from fluid catalytic cracking units, such as, for example,
the light diesel fuel of catalytic cracking (LCO) of different
origins, the heavy diesel fuel of catalytic cracking (HCO) of
different origins, and any fluid catalytic cracking distillate
fraction that in general has a distillation interval of
approximately 150.degree. C. to approximately 370.degree. C., the
aromatic extracts and the paraffins obtained during the preparation
of lubricating oils and oils that are deasphalted with solvent, by
themselves or in a mixture. The coal-derived liquid
hydrocarbon-containing feedstock can advantageously be selected
from among the products that are obtained from the liquefaction of
coal and the aromatic fractions originating from pyrolysis or
gasification of coal and shale oils or products derived from shale
oils, by themselves or in a mixture, pretreated or not.
[0037] To the extent that the hydrogen is produced on the inside
during the hydroreforming stage of the liquid feedstock comprising
at least one bio-oil, the consumption of hydrogen for the
co-treatment in a mixture with the petroleum- and/or coal-derived
hydrocarbon-containing feedstocks is reduced.
[0038] Preferably, said liquid feedstock comprising at least one
bio-oil can advantageously be a mixture of one of any of the
feedstocks cited above, with said feedstocks being able to be
pretreated or not.
[0039] In a preferred variant, said treated liquid feedstock in the
process according to the invention consists entirely of
bio-oil.
[0040] Hydroreforming
[0041] In accordance with the invention, said liquid feedstock
comprising at least one bio-oil, optionally at least one petroleum-
and/or coal-derived liquid hydrocarbon-containing feedstock,
optionally other liquid feedstocks obtained from biomass,
optionally mixed with at least one portion of the organic phase of
the effluent that is obtained from the hydroreforming stage that is
recycled, is introduced into said first hydroreforming stage.
[0042] The reaction is designated here under the term of
"hydroreforming" since it brings about a characteristic change in
the distribution of molecular weight of the feedstock comprising at
least one bio-oil. Preferably, the hydroreforming stage is a stage
of the hydrotreatment/hydroconversion type in which the liquid
feedstock comprises at least the bio-oil and preferably in which
the bio-oil is partially deoxygenated and partially hydroconverted.
Said hydroreforming stage is carried out with a partial production
of hydrogen that is internal to the reaction.
[0043] In a preferred manner, said hydroreforming stage is a
partial deoxygenation and partial hydroconversion stage. Partial
deoxygenation and partial hydroconversion is defined as a reaction
in which the oxygen content in the organic phase is reduced to a
content of between 5 and 25% by weight, making it possible to
obtain less than 20% by weight of a fraction boiling at a
temperature that is higher than 600.degree. C.
[0044] During said first hydroreforming stage, the bio-oil is
transformed for the purpose of stabilizing the product, making it
miscible with hydrocarbons, bringing about an easy water-phase
separation in bio-oil, lowering its viscosity, lowering its
corrosiveness, converting in particular the fractions of high
molecule weight into smaller molecules and lowering its oxygen
content.
[0045] The Product of the Hvdroreforming Stage
[0046] In accordance with the invention, said first hydroreforming
stage makes it possible to obtain at least one liquid effluent that
comprises at least one aqueous phase and at least one organic
phase.
[0047] A gaseous phase is also advantageously obtained, with said
gaseous phase containing for the most part CO.sub.2, CO, and C1-C4
light gases, such as, for example, methane. Said gaseous phase can
advantageously be separated from said aqueous and organic phases in
any separator that is known to one skilled in the art.
[0048] Said aqueous phase and said organic phase are advantageously
separated by decanting.
[0049] The analysis of the liquid effluent does not show any sign
of polymerization.
[0050] Said aqueous phase comprises water and can also comprise
organic materials, primarily acetic acid and methanol (case of
bio-oil of rapid pyrolysis), dissolved in said aqueous phase. The
aqueous phase essentially contains water formed by
hydrogenation-deoxygenation and water contained in the
non-pretreated bio-oil that has not been converted and in general
less than approximately 20% by weight of dissolved organic
materials. For the pyrolysis bio-oils, the aqueous phase that is
separated during the first reforming stage typically contains
approximately 10% by weight of acetic acid and a smaller proportion
of methanol. Preferably, the acetic acid and the methanol are
recovered in the aqueous phase because they consist of upgradable
by-products. Acetic acid can advantageously be recovered by
different known means such as distillation or evaporation,
crystallization in salt form, of an alkaline earth, for example, or
by extraction with solvent, by means of liquid ion exchangers, for
example. Because of its low boiling point and the absence of
formation of azeotropes with water, methanol is simply recovered by
distillation. Preferably, acetic acid and methanol taken together
comprise at least 80% by weight of organic components in the
aqueous phase.
[0051] The organic phase contains partially deoxygenated bio-oil
and hydrocarbons. Partially deoxygenated bio-oil is defined as a
bio-oil that contains less than 25% by weight of oxygen and
preferably less than 15% by weight of oxygen relative to the total
mass of said organic phase. The organic phase therefore comprises
less than 25% by weight of oxygen, preferably less than 15% by
weight of oxygen, and in a preferred manner less than 10% by weight
of oxygen relative to the total mass of said organic phase.
[0052] Thus, said organic phase is deoxygenated to a sufficient
degree to make it miscible with hydrocarbon-containing feedstocks
such as the ones used in a petroleum refinery at elevated
concentrations. In general, said organic phase can be mixed freely
with most of the hydrocarbon-containing products at concentrations
that can reach at least 30% by weight. Furthermore, to the extent
that the oxygen content is essentially reduced and the bio-oil is
already partially converted, the hydrogen requirements during
subsequent stages in the refinery are greatly minimized. In
addition, said organic phase is stabilized in such a way as to be
able to be treated subsequently in a refinery without running the
risk of solids forming by polymerization or polycondensation.
[0053] The organic phase preferably contains less than 25% by
weight of oxygen and preferably less than 15% by weight of oxygen
and less than 5% by weight of water, preferably less than 2% by
weight of water relative to the total mass of said organic phase.
The consumption of hydrogen during said first hydroreforming stage
is preferably less than approximately 2% by weight of bio-oil.
[0054] Preferably, the total acid number (TAN) is less than
approximately 100 KOH/g of oil. The total acid number is expressed
in terms of mg of KOH/g of oil. It is the amount of potassium
hydroxide in milligrams that is necessary for neutralizing the
acids in one gram of oil. There are standard methods for
determining the acid number, such as the ASTM D 974 and DIN 51558
methods (for mineral oils, biodiesels), or methods that are
specific to biodiesels using the European standards EN 14104 and
ASTM D664, widely used on the world scale.
[0055] The higher calorific value (PCS) exceeds approximately 35
MJ/kg in the organic phase that is obtained from said first
hydroreforming stage.
[0056] Typically, during the first hydroreforming stage, the
organic phase yields relative to the dry biomass, i.e., comprising
0% moisture, introduced into the pyrolysis stage, are between 15
and 45% by weight, and preferably between 15 and 40% by weight. The
aqueous phase yields relative to the dry biomass are between 10 and
50% by weight, and preferably between 10 and 40% by weight. The
gaseous phase yields relative to the dry biomass are between 5 and
30% by weight. The conversion of the organic fraction of bio-oil
into partially deoxygenated bio-oil represents at least 70% by
weight.
[0057] According to one variant, at least one portion of the
organic phase of the effluent that is obtained from the first
hydroreforming stage is recycled in said first hydroreforming
stage. Preferably, the recycling rate that is equal to the ratio of
the mass flow rate of said organic phase to the mass flow rate of
the non-pretreated bio-oil is between 0.05 and 10, in a preferred
manner between 0.05 and 5, and in a very preferred manner between
0.05 and 1.
[0058] The recycling rates that are used make it possible to have,
overall, a feedstock that is stable enough thermally to be able to
be introduced into the preheating furnace as well as into the
hydroreforming reactor without running the risk of clogging, to
facilitate the reactions of conversion and deoxygenation of the
bio-oil on the catalyst, to improve the dissolution of gaseous
hydrogen in the recycled organic phase that is obtained from the
first hydroreforming stage, and to better manage the exothermicity
generated by the reactions, while minimizing the recycling of all
or part of the organic phase obtained from hydroreforming so as to
minimize the investment costs as well as the operating costs.
[0059] The recycled organic phase in said first hydroreforming
stage, and obtained from this stage, is also used to lower the
volumetric mass of the partially deoxygenated bio-oil that is
produced during this first stage, which facilitates the release of
the partially deoxygenated bio-oil phase and the aqueous phase at
the hydroreforming outlet. This separation that is easily done
during the cooling of the reaction mixture is another advantage
that the presence of the recycled organic phase obtains in the
reaction mixture of the first hydroreforming stage.
[0060] Another advantage, the presence of the recycled organic
phase in the reaction mixture, tends to expel water from said
organic phase, the water content thus being as small as possible,
which is favorable to the use of said organic phase as an
industrial fuel or as a feedstock for subsequent treatment stages.
Thus, said phase, said organic phase, obtained from the first
hydroreforming stage contains less than 5% by weight of water,
preferably less than 2%.
[0061] In accordance with the invention, the catalyst that is used
in the first hydroreforming stage preferably comprises at least one
transition metal that is selected from among the elements of groups
3 to 12 of the periodic table and at least one substrate selected
from among the activated carbons, the silicon carbides, the
silicas, the transition aluminas, the alumina-silicas, zirconium
oxide, cerium oxide, titanium oxide, and the transition metal
aluminates, taken by themselves or in a mixture. Preferably, the
catalyst comprises a metal of group 10, by itself or in combination
with at least one metal of groups 3 to 12, and in a preferred
manner at least one metal of groups 5, 6, 8, 9, 10, and 11 of the
periodic table. In a preferred manner, the catalyst comprises Ni,
by itself or in combination with at least one metal that is
selected from among Cr, Mo, W, Fe, Co and Cu.
[0062] The metal content of group 10 and preferably nickel,
expressed in terms of percentage by weight of metal oxide of group
10, is advantageously between 1 and 20% by weight, preferably
between 5 and 15% by weight relative to the total mass of said
catalyst.
[0063] In the case where said metal of group 10 is used in
combination with at least one metal of groups 3 to 12, the metal
content of groups 3 to 12 is advantageously between 1 and 20% by
weight relative to the total mass of said catalyst.
[0064] Preferably, the substrate is selected from among activated
carbons, silicas, transition aluminas, silica-aluminas, and
transition metal aluminates. These substrates can be taken by
themselves or in a mixture.
[0065] Preferred catalysts are selected from among the catalysts
comprising Ni, Cu, NiCr, NiMo or NiMn on activated carbon or on
alumina or nickel aluminate.
[0066] Preferably, said catalyst is prepared according to the
conventional methods such as co-mixing or impregnation followed by
one or more heat treatments.
[0067] Said catalyst is advantageously used in the first
hydroreforming stage in a reduced or sulfurized form.
[0068] Operating Conditions
[0069] Preferably, said first hydroreforming stage is carried out
at a temperature of between 250 and 450.degree. C., preferably
between 250 and 400.degree. C., and in a preferred manner between
270 and 360.degree. C., and at an absolute pressure of between 3.4
and 27.6 MPa (500 and 4,000 psi), preferably between 3.4 and 20.7
MPa (500 and 3,000 psi), and in a preferred manner between 6.9 and
20.7 MPa (1,000 and 3,000 psi), and in a more preferred manner
between 15 and 20.7 MPa, at an elevated hourly volumetric flow rate
relative to bio-oil, preferably greater than 0.2 h.sup.-1, in a
preferred manner between 0.5 h.sup.-1 and 5 h.sup.1, and in a more
preferred manner between 1 h.sup.-1 and 5 h.sup.-1, and with an
amount of hydrogen that is introduced such that the volumetric
ratio of hydrogen to hydrocarbons is between 50 and 2,000
Nm.sup.3/m.sup.3 and preferably between 100 and 1,000
Nm.sup.3/m.sup.3.
[0070] Preferably, the liquid feedstock comprising at least bio-oil
is not preheated, or only preheated to a temperature that is less
than 80.degree. C. before being introduced into the first
hydroreforming stage. Actually, extended heating or storage at an
elevated temperature can cause deterioration.
[0071] There are no limitations relative to the equipment designed
to carry out the process. The latter can be conducted
intermittently or continuously. Nevertheless, for large-scale
industrial applications, it will be preferable to operate
continuously.
[0072] The hydroreforming reaction can be carried out in any
reactor that facilitates the effective dispersion of bio-oil in the
reaction mixture. A simple perfectly stirred continuous reactor
(CSTR) is suitable in intermittent mode. For continuous
applications, downward co-current packed-bed reactors, moving-bed
reactors, boiling-bed reactors or slurry reactors will be more
suitable. While keeping the catalyst in the reactor, the
technologies of moving-bed reactors and boiling-bed reactors offer
the advantage of making possible the easy replacement of the
catalyst during continuous operations, which imparts a greater
flexibility to the operation of the unit, increases the operational
factor and maintains activity based on near-constant time. These
technologies also accept feedstocks that contain a few solids or
that produce solids during reactions, which is not the case of the
technology of a fixed-bed reactor, except in using reactors of
switchable-guard reactors, for example. The technology of the
slurry reactor, according to English terminology, offers the same
advantages as the technologies of moving-bed reactors and
boiling-bed reactors and the additional advantage of operating with
a fresh catalyst, therefore with maximum activity, but the drawback
of greatly complicating the recovery of the catalyst that exits
from the reactor with the effluents. Other reactors that meet the
principles indicated here are within the grasp of one skilled in
the art who is versed in the technology of chemical reactors and
are found within the framework of this invention.
[0073] Hydrogen Consumption
[0074] During the first hydroreforming stage, internal reforming of
the bio-oil into carbon oxides and hydrogen oxides is done with a
relatively high yield of hydrocarbons and a relatively low
consumption of hydrogen. The hydrogen consumption is therefore
moderated during the first hydroreforming stage, and the internal
production of hydrogen by hydroreforming makes it possible to
perform the process with a very limited external consumption of
hydrogen.
[0075] A portion of the hydrogen that is necessary to the reaction
in the first hydroreforming stage is generated internally, a priori
from water that is present in the bio-oil, by hydroreforming a
portion of the bio-oil, in such a way that a significant portion of
oxygen is released in the form of carbon dioxide, and the net
hydrogen demand is to a large extent less than in the case of the
direct hydrogenation-deoxygenation process. The other portion of
hydrogen that is necessary to the reaction is of external origin.
Typically, the hydrogen consumption during the first hydroreforming
stage is less than approximately 2% by weight of the mass of
bio-oil introduced into the reactor, and the corresponding emission
of CO.sub.2 for producing it is much less than in the case of
hydrogenation-deoxygenation-type processes (HDO), with a
consumption of at least 4 or 5% by weight of external hydrogen
(according to the oxygen content of the feedstock).
[0076] The hydrogen of external origin can advantageously be
supplied starting from fossil resources, by partial
gasification/oxidation or by vapor reforming, by vapor-reforming of
the bio-oil itself (although this involves a loss of energy
efficiency of the carbon), by vapor reforming of the methane that
is produced and light gas fractions and/or fractions comprising
light oxygenated compounds that are obtained from the first
hydroreforming stage or the subsequent hydrotreatment/hydrocracking
stage. It is also possible to make the CO that is recovered react
with the water that is produced to obtain hydrogen by means of the
known reaction for conversion of the gas into water by "water gas
shift" according to English terminology (WGS). Thus, the overall
process, from the biomass to the final hydrocarbon-containing
product, could be self-sufficient in hydrogen.
[0077] During the first hydroreforming stage, a moderate amount of
gaseous hydrocarbon, essentially methane, is formed. This methane
fraction can advantageously be reformed by means of the so-called
steam methane reforming (SMR) for the purpose of producing
bio-hydrogen for stages of hydroreforming or hydrotreatment and/or
hydrocracking.
[0078] It is also possible to use bio-coal obtained from the
pyrolysis stage as a feedstock for the gasification reactor for the
purpose of producing synthetic gas (CO+H.sub.2). This synthetic gas
can also be used for producing bio-hydrogen for stages of
hydroreforming or hydrotreatment and/or hydrocracking.
[0079] Thus, by implementing the SMR process and/or gasification of
bio-coal, the process for converting and upgrading the bio-oil can
be self-sufficient in hydrogen, without requiring the supply of
hydrogen of fossil origin.
[0080] We have furthermore discovered that the partially
deoxygenated bio-oil and more particularly the organic phase
comprising at least said partially deoxygenated bio-oil that is
produced by hydroreforming can be converted into aromatic
compounds.
[0081] Hydrotreatment Stage
[0082] In accordance with the invention, at least one portion and
preferably all of the organic phase of the effluent that is
obtained from the first hydroreforming stage is sent into said
second hydrotreatment stage in the presence of hydrogen in at least
one reactor that contains a hydrotreatment catalyst, operating at a
temperature of between 250 and 400.degree. C., preferably between
320 and 380.degree. C., at a pressure of between 2 MPa and 25 MPa,
preferably between 5 MPa and 20 MPa, and at a hourly volumetric
flow rate of between 0.1 h.sup.-1 and 20 h.sup.-1 and preferably
between 0.5 h.sup.-1 and 5 h.sup.-1 and with a total amount of
hydrogen mixed with the feedstock (including the chemical
consumption and the recycled amount) such that the
hydrogen/hydrocarbon volumetric ratio is between 100 and 3,000
Nm.sup.3/m.sup.3 and preferably between 100 and 1,000
Nm.sup.3/m.sup.3.
[0083] Said hydrotreatment catalyst advantageously comprises an
active phase that comprises at least one metal of group 6 that is
selected from among molybdenum and tungsten by itself or in a
mixture, preferably combined with at least one metal of groups 8 to
10, preferably selected from among nickel and cobalt, by itself or
in a mixture, and a substrate that is selected from the group that
consists of alumina, silica, silica-alumina, magnesia, clays and
mixtures of at least two of these minerals. Said substrate can also
contain other compounds such as, for example, oxides that are
selected from the group that consists of boron oxide, zirconia,
titanium oxide, and phosphoric anhydride. In a preferred manner,
said substrate consists of alumina, and preferably also [eta-],
[theta-], [delta-] or [gamma-]alumina.
[0084] The total amount of metal oxides of group 6 and groups 8 to
10 in the hydrotreatment catalyst that is used is advantageously
between 5 and 40% by weight, preferably between 6 and 35% by weight
relative to the total catalyst mass. In the case where said
catalyst comprises nickel, the nickel oxide content is
advantageously between 0.5 and 12% by weight and preferably between
1 and 10% by weight relative to the total catalyst mass. In the
case where the catalyst comprises molybdenum, the molybdenum oxide
content is advantageously between 1 and 35% by weight of molybdenum
oxide (MoO.sub.3) and preferably between 5 and 30% by weight of
molybdenum oxide, with these percentages being expressed in terms
of % by weight relative to the total catalyst mass. A preferred
catalyst is advantageously selected from among the catalysts NiMo,
NiW or CoMo on an alumina substrate.
[0085] Said catalyst that is used in the second hydrotreatment
stage can also advantageously contain at least one doping element
that is selected from among phosphorus and boron. Said element can
advantageously be introduced into the matrix, or, preferably,
deposited on the substrate. It is also possible to deposit the
silicon on the substrate, by itself or with phosphorus and/or
boron. The oxide content in said element is advantageously less
than 20%, and preferably less than 10% relative to the total
catalyst mass.
[0086] The metals of the catalysts that are used in the second
hydrotreatment stage of the method according to the invention can
be metals or sulfur-containing metal phases. For maximum
efficiency, these metal-oxide-based catalysts are usually converted
at least partially into metal sulfides. The metal-oxide-based
catalysts can be sulfurized by means of any technique that is known
in the prior art, for example in the reactor (in-situ) or ex-situ,
by putting the catalyst into contact, at an elevated temperature,
with a hydrogen sulfide source, such as dimethyl disulfide
(DMDS).
[0087] To the extent that the biomass normally contains only a very
small amount of sulfur, the use of non-sulfur-containing catalysts
should make it possible to avoid any risk of sulfur contamination
in the fuels that are produced. Among the other metal-oxide-based
catalysts that are suitable for the hydrotreatment stage, it is
possible to cite the metal phases that are obtained by reduction
under hydrogen. The reduction is done in general at temperatures of
between approximately 150.degree. C. and approximately 650.degree.
C., under a hydrogen pressure of between approximately 0.1 and
approximately 25 MPa (14.5-3,625 psi).
[0088] Optional Separation
[0089] One stage for separation of at least one organic phase, at
least one aqueous phase, and at least one gaseous phase can
optionally be implemented between said second hydrotreatment stage
and said third hydrocracking stage.
[0090] Said separation stage can advantageously be carried out by
methods that are well known to one skilled in the art, such as the
flash, distillation, stripping, liquid/liquid extraction methods,
etc.
[0091] Nitrogen-containing, oxygenated and sulfur-containing
impurities are removed from the organic phase that is obtained from
the second hydrotreatment stage and optionally separated.
[0092] According to one variant of the invention, said organic
phase that is optionally separated can also be fractionated in a
fractionation zone into at least one light fraction that has an
initial boiling point that is higher than 70.degree. C. or higher
than 80.degree. C., and a final boiling point that is lower than
160.degree. C. or lower than 170.degree. C. or lower than
180.degree. C., and into at least one heavy fraction that boils at
a temperature that is higher than 160.degree. C. or higher than
170.degree. C. or higher than 180.degree. C.
[0093] In this variant, said heavy fraction that boils at a
temperature that is higher than 160.degree. C. or higher than
170.degree. C. or higher than 180.degree. C. is preferably sent
into said third hydrocracking stage of the process according to the
invention, and said light fraction is preferably sent directly into
the fourth stage of catalytic reforming, mixed with the fraction
that contains naphtha separated at the end of said third
hydrocracking stage.
[0094] The fractionation zone preferably comprises a fractionation
cross-section that integrates a high-pressure high-temperature
(HPHT) separator, and then atmospheric distillation.
[0095] Hydrocracking Stage
[0096] In accordance with the invention, at least one portion of
the effluent that is obtained from the second hydrotreatment stage,
and preferably at least one portion, in a preferred manner all of
the organic phase of the effluent that is obtained from said
optionally separated second hydrotreatment stage, mixed with a
recycling of at least one portion and preferably all of the boiling
fraction at a temperature that is higher than 160.degree. C.
separated at the end of a third hydrocracking stage, is sent into
said third hydrocracking stage in the presence of hydrogen in at
least one reactor that contains a hydrocracking catalyst, operating
at a temperature of between 250 and 480.degree. C., under a
pressure of between 2 and 25 MPa, at a volumetric flow rate of
between 0.1 and 20 h.sup.-1, and with an amount of hydrogen that is
introduced such that the hydrogen to hydrocarbon volumetric ratio
is between 80 and 5,000 Nm.sup.3/m.sup.3.
[0097] Preferably, the feedstock of said third hydrocracking stage
is the organic phase of the effluent that is obtained from the
second hydrotreatment stage, optionally separated and/or
fractionated.
[0098] The concatenation of said second hydrotreatment stage
followed by the third hydrocracking stage of the process according
to the invention of said third hydrocracking stage makes it
possible to carry out, on the one hand, a rigorous hydrocracking so
as to obtain a high fraction yield as well as a very deep
hydrotreatment that makes it possible to obtain a naphthenic
fraction that is pure enough in terms of impurities to not poison
the catalysts of catalytic reforming.
[0099] Hydrocracking is defined as hydrocracking reactions
accompanied by hydrotreatment reactions (hydrodenitration,
hydrodesulfurization), hydroiosmerization, hydrogenation of
aromatic compounds and opening of naphthene rings.
[0100] The hydrocracking stage according to the invention operates
in the presence of hydrogen and a catalyst at a temperature of
preferably between 320 and 450.degree. C., in a preferred manner
between 350 and 435.degree. C., under a pressure of between 3 and
20 MPa, at a volumetric flow rate of between 0.1 and 6 h.sup.-1, in
a preferred manner between 0.2 and 3 h.sup.-1, and with an amount
of hydrogen that is introduced such that the volumetric ratio of
hydrogen to hydrocarbons is between 100 and 3,000
Nm.sup.3/m.sup.3.
[0101] In accordance with the invention, at least one portion of
and preferably all of the fraction that boils at a temperature that
is higher than 160.degree. C., preferably higher than 170.degree.
C., and in a preferred manner higher than 180.degree. C., separated
at the end of the third hydrocracking stage, is recycled in said
third stage.
[0102] These operating conditions that are used in said third
hydrocracking stage make it possible to obtain a high yield of
naphtha fraction boiling at a temperature that is lower than
160.degree. C. Said operating conditions make it possible to attain
conversions per pass of the products having boiling points that are
higher than 160.degree. C., preferably higher than 170.degree. C.,
and in a preferred manner higher than 180.degree. C. into lighter
products, higher than 30% by weight, in a preferred manner between
50 and 100% by weight, and in a very preferred manner between 70
and 100% by weight. The conversion per pass of products having
boiling points that are higher than 160.degree. C. into lighter
products are defined as being: (mass of 160.degree. C.+in the
feedstock entering into said stage-mass of 160.degree. C.+in the
effluent existing from said stage)/(mass of 160.degree. C. in the
feedstock entering into said stage).
[0103] Said second hydrotreatment stage and said third
hydrocracking stage can advantageously be carried out in a
fixed-bed reactor or in a so-called entrained-bed: moving-bed
reactor, boiling-bed reactor or suspension reactor. It is possible
to use a single catalyst or several different catalysts,
simultaneously or successively, in the case of a fixed-bed reactor.
Said stages can be carried out industrially in one or more
reactors, with one or more catalytic beds. The reaction exothermy
during hydrotreatment is limited by any method that is known to one
skilled in the art: recycling of the liquid product, cooling by
recycled hydrogen, etc.
[0104] Said third hydrocracking stage according to the invention is
preferably carried out in a so-called two-stage diagram, for
maximizing the naphtha yield, optionally combined in an optional
manner with a conventional hydrotreatment catalyst located upstream
from the hydrocracking catalyst. The so-called two-stage
hydrocracking diagram is widely known in the prior art.
[0105] The hydrocracking catalysts that are used in the third
hydrocracking stage are all of the bifunctional type combining an
acid function with a hydrogenating function. The acid function is
provided by substrates whose surface areas in general vary from 150
to 800 m2/g and that have a surface acidity, such as halogenated
aluminas (chlorinated or fluorinated, in particular), the
combinations of boron and aluminum oxides, amorphous
silica-aluminas and zeolites. The hydrogenating function is
provided either by one or more metals of group 6 of the periodic
table, or by a combination of at least one metal of group 6 of the
periodic table and at least one metal of groups 8 to 10.
[0106] Said hydrocracking catalyst can advantageously comprise
metals of groups 8 to 10, preferably selected from among nickel and
cobalt, preferably combined with at least one metal of group 6,
selected from among molybdenum and tungsten and a substrate. The
element content of groups 8 to 10 is advantageously between 0.5 to
20% by weight of oxide, and the element content of group 6 is
advantageously between 1 to 40% by weight of oxide, preferably
between 5 to 30% by weight relative to the total mass of said
catalyst. The total content of metal oxides of groups 6 and 8 to 10
in the catalyst is generally between 5 and 40% by weight relative
to the total mass of said catalyst. In the case where the catalyst
comprises at least one metal of group 6 in combination with at
least one non-noble metal of groups 8 to 10, said catalyst is
preferably a sulfur-containing catalyst.
[0107] The hydrocracking catalyst can also contain a promoter
element that is selected from among phosphorus, silicon and boron.
This element may have been introduced into the matrix or preferably
have been deposited on the substrate. The concentration of said
element is usually less than 20% by weight (on the basis of oxide)
and most often less than 10% relative to the total mass of said
catalyst. When boron trioxide (B.sub.2O.sub.3) is present, its
concentration is less than 10% by weight.
[0108] In an advantageous manner, the hydrocracking catalyst is
selected from among the catalysts that comprise the following
combinations of metals: NiMo, CoMo, NiW, CoW, NiMoP, and preferably
NiMo, NiW, NiMoWP and NiMoP, and in an even preferred manner
NiMoP.
[0109] Said hydrocracking catalyst advantageously comprises a
substrate that is selected from the group that is formed by
alumina, silica, silica-aluminas, zeolites, magnesia, clays and the
mixtures of at least two of these minerals. This substrate can also
contain other compounds and, for example, oxides that are selected
from among boron oxide, zirconia, titanium oxide, and phosphoric
anhydride.
[0110] Preferably, the substrate of said catalyst comprises at
least one zeolite and in a preferred manner an FAU-structural-type
Y zeolite, so as to maximize the yield in hydrocracking naphtha and
then ultimately in aromatic compounds after catalytic reforming of
said naphtha.
[0111] Preferably, the hydrocracking catalyst comprises a Y zeolite
content of between 2 and 40% by weight and preferably between 10
and 35% by weight relative to the total mass of said catalyst.
[0112] Other preferred catalysts are so-called composite catalysts
and comprise at least one hydrogenating-dehydrogenating element
that is selected from the group that is formed by the elements of
group 6 and groups 8 to 10 and a substrate based on a
silica-aluminum matrix and based on at least one zeolite as
described in the application EP1711260.
[0113] Prior to the injection of the feedstock, the catalysts that
are used in the process according to this invention are preferably
subjected to a sulfurization treatment (in-situ or ex-situ).
[0114] Separation
[0115] In accordance with the invention, the effluent that is
obtained at the end of the third hydrocracking stage undergoes at
least one separation stage so as to recover at least one fraction
that contains naphtha and a fraction that boils at a temperature
that is higher than 160.degree. C., and preferably higher than
180.degree. C. The fraction that contains naphtha is defined as
being a fraction that boils at a temperature that is lower than
160.degree. C. and preferably lower than 180.degree. C.
[0116] In accordance with the invention, at least one portion of
the fraction that boils at a temperature that is higher than
160.degree. C., preferably higher than 170, and in a preferred
manner higher than 180.degree. C., is recycled in said third
hydrocracking stage. Preferably, the entirety of said fraction is
recycled in such a way as to maximize the naphtha fraction yield.
Said fraction is therefore recycled until used up in said third
hydrocracking stage. In the case where the entirety of said
fraction is recycled, a purging can advantageously be
implemented.
[0117] The separation stage can advantageously be carried out by
methods that are well known to one skilled in the art, such as the
flash, distillation, stripping, liquid/liquid extraction methods,
etc. It preferably comprises a fractionation cross-section that
integrates a high-pressure high-temperature (HPHT) separator and
then an atmospheric distillation.
[0118] A gaseous fraction can also advantageously be separated.
Said gaseous fraction can then be advantageously treated in a
hydrogen purification unit. The recovered hydrogen is
advantageously recycled in said second hydrocracking stage and/or
in said first hydroreforming stage. The gases containing
undesirable nitrogen-containing, sulfur-containing and oxygenated
compounds are evacuated.
[0119] The fraction that contains naphtha can optionally be
separated into a light naphtha fraction (C5-C6) having a boiling
point that is lower than 80.degree. C. and preferably lower than
70.degree. C. that is preferably at least in part subjected to an
isomerization process for producing isomerate (basis for highway
gasoline) and a heavy naphtha fraction that has an initial boiling
point that is higher than 70.degree. C. or 80.degree. C., and a
final boiling point that is lower than 160.degree. C., or
170.degree. C., or 180.degree. C. Said heavy naphtha fraction is at
least in part and preferably entirely subjected to the catalytic
reforming stage for producing a reformate that is rich in aromatic
compounds. The isomerization processes are widely known in the
prior art; the isomerization makes it possible to transform a
linear paraffin into isomerized paraffin for the purpose of
increasing its octane number.
[0120] In one variant, said fraction that contains naphtha is sent
in its entirety into the third catalytic reforming stage, without
preliminary separation.
[0121] The fraction that contains the naphtha that is obtained
after separation of the hydrocracking effluent has a strong
naphthene content and very few impurities owing to rigorous
hydrocracking. It is thus a particularly well suited feedstock for
catalytic reforming.
[0122] Catalytic Reforming
[0123] In accordance with the invention, the fraction that contains
naphtha that is obtained from the separation is sent into a fourth
catalytic reforming stage that makes it possible to obtain hydrogen
and a reformate that contains aromatic compounds.
[0124] The chemical reactions involved in the reforming stage are
numerous. They are well known; for reactions beneficial to the
formation of aromatic compounds, it is possible to cite: the
dehydrogenation of naphthenes, the isomerization of cyclopentane
rings, isomerization of paraffins, dehydrocyclization of paraffins,
and for negative reactions, hydrogenolysis and hydrocracking of
paraffins and naphthenes. Likewise, it is known that the catalysts
of catalytic reforming are particularly sensitive to poisoning that
can be caused by metal impurities, sulfur, nitrogen, water and
halides.
[0125] The catalytic reforming stage can be carried out, according
to the invention, according to any one of the known processes,
using any one of the known catalysts, and it is not limited to a
particular process or catalyst. Numerous patents deal with
processes for reforming or production of aromatic compounds with
continuous or sequential regeneration of the catalyst.
[0126] The process diagrams in general use at least two reactors,
in which a catalyst moving bed--through which a feedstock that
consists of hydrocarbons and hydrogen passes, a feedstock heated
between each reactor--circulates from top to bottom. Other process
diagrams use fixed-bed reactors.
[0127] The continuous process for catalytic reforming of
hydrocarbons is a process that is known to one skilled in the art;
it makes use of a reaction zone that comprises a series of 3 or 4
reactors in series, working in a moving bed, and has a zone for
regeneration of the catalyst that itself comprises a certain number
of stages, including a stage for combustion of coke deposited on
the catalyst in the reaction zone, an oxychlorination stage, and a
final stage for reduction of the catalyst with hydrogen. After the
regeneration zone, the catalyst is reintroduced at the top of the
first reactor of the reaction zone. This process is described in,
for example, the application FR2801604 or else FR2946660.
[0128] Said fourth stage of catalytic reforming advantageously
operates under a pressure of between 0.1 and 4 MPa and preferably
between 0.3 and 1.5 MPa, at a temperature of between 400 and
700.degree. C., and preferably between 430 and 550.degree. C., at a
volumetric flow rate of between 0.1 and 10 h.sup.-1 and preferably
between 1 and 4 h.sup.-1, and with a, preferably recycled,
hydrogen/hydrocarbon ratio (mol.) of 0.1 to 10 and preferably
between 1 to 5, and more particularly 2 to 4.
[0129] The catalyst that is used in said catalytic reforming stage
advantageously comprises a substrate that is selected from among
the refractory oxides and the zeolites and at least one noble metal
that is selected from among platinum and palladium, and preferably
at least one promoter metal that is selected from among tin and
rhenium, at least one halogen, and optionally one or more
additional elements that are selected from among alkalines,
alkaline-earths, lanthanides, silicon, elements of group IV B,
non-noble metals, and elements of group III A. These catalysts are
extensively described in the literature.
[0130] Said catalytic reforming stage makes it possible to obtain a
reformate that comprises at least 70% of aromatic compounds
comprising a number of carbon atoms of between 6 and 11 relative to
the total reformate mass. The conversion in general exceeds
80%.
[0131] The hydrogen that is produced in the catalytic reforming
stage is preferably recycled in the first hydroreforming stage
and/or in the second hydrotreatment stage and the third
hydrocracking stage.
[0132] Separation of Aromatic Compounds of the Reformate
[0133] In accordance with the invention, the aromatic compounds are
separated from the reformate that is obtained at the end of the
catalytic reforming stage.
[0134] Said stage for separation of the aromatic compounds
contained in the reformate can advantageously be used by any method
that is known to one skilled in the art. Preferably, it is carried
out by liquid-liquid extraction, extractive distillation,
adsorption and/or crystallization. These processes are known by one
skilled in the art.
[0135] The liquid-liquid extraction makes it possible to extract
the aromatic compounds in the solvent constituting the extract. The
paraffinic or naphthenic fractions are insoluble in solvent. In
general, solvents are used such as sulfolane,
N-methyl-2-pyrrolidone (NMP) or dimethyl sulfoxide (DMSO).
[0136] The primary extractive agents used in the extractive
distillation are N-methyl-2-pyrrolidone (NMP), n-formylmorpholine
(NFM), and dimethylformamide (DMF).
[0137] In said separation stage, transalkylation stages
advantageously can be used to maximize the BTX yield.
[0138] Thus, aromatic compounds, essentially of the BTX (benzene,
toluene, xylenes and ethyl benzene) type, are obtained.
[0139] A fraction that contains the aromatic compounds that are
heavier than the BTX, i.e., the C9+ aromatic compounds, can
advantageously be separated and recycled in the reforming
stage.
DESCRIPTION OF THE FIGURE
[0140] FIG. 1 illustrates a particular embodiment of the process
according to the invention.
[0141] The bio-oil obtained from the rapid pyrolysis of the biomass
is introduced via the pipe (1), mixed with hydrogen (3) and the
organic phase (8) that is obtained from the hydroreforming stage,
in the first hydroreforming zone (2). The liquid effluent that is
obtained from the hydroreforming zone via the pipe (4) is
introduced into a separator (5). A gaseous phase that for the most
part contains CO.sub.2, H.sub.2S and C1-C4 light gases, such as,
for example, methane, is separated via the pipe (7), and an aqueous
phase is also separated via the pipe (6). An organic phase that
contains partially deoxygenated bio-oil and hydrocarbons is drawn
off via the pipe (8), and a portion of said organic phase is
recycled in the hydroreforming zone. The non-recycled part of said
organic phase is then sent into a second hydrotreatment zone (9).
The effluent that is obtained from the second hydrotreatment stage
is introduced via the pipe (10) into a separator. A gaseous phase
(13), an aqueous phase (12), and an organic phase (14) are
separated, and nitrogen-containing, oxygenated and
sulfur-containing impurities are removed from the organic phase
that is sent into a third hydrocracking stage in a hydrocracking
zone (15), in the presence of hydrogen (3). The effluent that is
obtained from the second hydrocracking stage via the pipe (16) is
sent into a separator (17). A fraction that boils at a temperature
that is higher than 160.degree. C. is separated in the pipe (18)
and recycled in the third hydrocracking stage upstream from the
zone (15). A light naphtha fraction that boils at a temperature of
less than 80.degree. C. can also be separated in the pipe (20). A
heavy naphtha fraction that has an initial boiling point that is
higher than 70.degree. C. or 80.degree. C. and a final boiling
point that is lower than 160.degree. C. is separated in the pipe
(19) and sent into a fourth catalytic reforming stage in the zone
(23). The reformate that is obtained at the end of the catalytic
reforming stage in the pipe (24) is then separated in the one
separator (25). A fraction that contains the BTX aromatic compounds
is separated in the pipe (26) and a fraction that contains the
aromatic compounds that are heavier than the BTX, i.e., the C9+
aromatic compounds, is also separated in the pipe (27).
[0142] The examples below illustrate the invention without limiting
its scope.
EXAMPLES
[0143] Experiments have been conducted with a bio-oil obtained by
rapid pyrolysis of hardwood mixtures. The operating conditions of
rapid pyrolysis are a temperature of 500.degree. C. and a dwell
time of the vapors on the order of one second. Table 1 below
exhibits the data obtained following the analysis of this
bio-oil.
TABLE-US-00001 TABLE 1 Analysis of Bio-Oil Density at 20.degree.
C., g/cm.sup.3 1.21 Kinematic viscosity at 20.degree. C.,
mm.sup.2/s 182.6 pH 2.5 Higher calorific value, MJ/kg.sup.a 18.03
Lower calorific value, MJ/kg.sup.b 16.46 Water content, % by mass
20.7 Pyrolytic lignin, % by mass 19.0 Carbon, % by mass 43.9
Hydrogen, % by mass 7.39 Nitrogen, % by mass <0.05 Oxygen, % by
mass 47.3 Sulfur (ppm) 92 .sup.aThe higher calorific value is
measured with a calorimetric bomb. .sup.bThe lower calorific value
is calculated by means of the following equation: LHV (J/g) = HHV
(J/g) - 218.13 * H % (% by weight)
Example 1
Preparation of C1 Hydroreforming Catalysts
[0144] The C1 catalyst is a catalyst of formulation NiCr/C. The
precursors of nickel and chromium, in their nitrate form
(respectively Ni(NO.sub.3).sub.2 and Cr(NO.sub.3).sub.3), are
provided by Aldrich. The substrate is an activated carbon in the
form of cylindrical extrudate provided by the Norit Company (RX3
Extra). This C1 catalyst is obtained by dry impregnation with an
aqueous solution that contains the precursors of nickel and
chromium. The solution volume is equal to the volume of water
uptake of the substrate (i.e., the maximum water volume that can
penetrate into its porosity). The concentrations of nickel and
chromium precursors in solution are determined in such a way as to
obtain the target contents on the final catalyst: 10% by weight of
nickel and 5% by weight of chromium. After impregnation of this
aqueous solution, the catalyst is allowed to mature at ambient
temperature for 4 hours in a water-saturated chamber and then dried
in an oven at 70.degree. C. in air for 3 hours and finally
undergoes a heat treatment at 300.degree. C. for 3 hours under
nitrogen (at a flow rate of 1.5 L/h/g of catalyst).
TABLE-US-00002 TABLE 1 Formulation of the C1 Catalyst. Catalyst C1
Substrate Activated Carbon Ni (% by Weight) 10.2 Cr (% by Weight)
4.9 Mo (% by Weight) --
Example 2
Production of a Reformate that Contains More than 70% by Weight of
Aromatic Compounds from a Non-Pretreated Bio-Oil
[0145] This example illustrates the production of an oxygen-free
reformate that contains more than 70% by weight of BTX aromatic
compounds from the treatment of a non-pretreated bio-oil liquid
feedstock with the characteristics that are described in Table 1,
according to the process of the invention.
[0146] For the first hydroreforming stage, the non-pretreated
bio-oil is first introduced, mixed with an organic liquid phase
that is obtained from the hydroreforming stage, according to a 1:3
ratio (organic liquid phase:bio-oil) simulating a recycling rate of
0.33, in the autoclave reactor with a hydroreforming catalyst.
[0147] 15 g of C1 catalyst prepared according to Example 1 is
reduced in a reduction cell at 300.degree. C. for 3 hours in 30
NL/h of hydrogen and then introduced, in a glove bag under inert
atmosphere, into a basket that is placed in the autoclave reactor
with 75 g of bio-oil and 25 g of the organic liquid phase that is
obtained from the hydroreforming stage. The reactor is closed in an
airtight way and purged with nitrogen and then with hydrogen. The
reactor is then put under pressure at 4.83 MPa (700 psia) with
18.37 NL of H.sub.2, and then gradually heated while being stirred
at 330.degree. C. and kept at this temperature for 3 hours during
which the maximum pressure reached was 13.9 MPa (2,016 psia). The
equivalent volumetric flow rate, defined as the ratio of the
bio-oil volume introduced into the product of the catalyst volume
by the test duration, is equal to 0.7 h.sup.-1. The reactor is then
quickly cooled and brought to ambient temperature, which brings the
pressure to 1.17 MPa (170 psia). The reaction gas phase that is
produced, 4.9 NL in all, is sent into a collecting bottle and
analyzed. Analysis by gas phase chromatography indicates that it
contains 63.9% H.sub.2, 21.6% CO.sub.2, 10.6% CH.sub.4, and 3.0% CO
by volume.
[0148] The basket that contains the catalyst is recovered outside
of the liquid that is produced, which is separated into 50.33 g of
a higher homogeneous organic liquid oil phase with a density of 980
kg/m.sup.3 and 38.37 g of a lower aqueous phase. No deposit of tar
is observed in the reactor. The organic liquid phase contains
13.93% by weight of elementary oxygen and 4.68% by weight of water,
(2.36 g) of water, determined by elementary analysis and
Karl-Fischer metering.
[0149] The overall net consumption of hydrogen rises to 15.26 NL
(1.39 g), which corresponds to approximately 1.85% by weight
relative to the bio-oil mass that is introduced. Starting from data
above, the yields of organic liquid phase and aqueous phase are
determined at 38.5% and 29.4% by weight respectively, relative to
the bio-oil, or 27.8% and 21.2% by weight, respectively, on the
basis of the dry biomass containing 0% moisture.
[0150] The organic liquid phase that is obtained from the
hydroreforming stage is then sent into a flushed fixed-bed reactor
in the presence of a conventional hydrotreatment catalyst for a
hydrotreatment stage (HDT). The hydrotreatment catalyst that is
used comprises 4.3% by weight of NiO, 21% by weight of MoO.sub.3,
and 5% by weight of P.sub.2O.sub.5, supported on a gamma-alumina.
Prior to the test, this catalyst is sulfurized in-situ at a
temperature of 350.degree. C., using a feedstock that contains the
additive heptane of 2% by weight of dimethyl disulfide (DMDS).
[0151] 25 mL/h of the organic liquid phase obtained from the
hydroreforming stage is introduced into an isothermal reactor and
with a fixed bed that is charged with 25 ml of hydrotreatment
catalyst. The corresponding volumetric flow rate is equal to 1
h.sup.-1. 800 Nm.sup.3 of hydrogen/m.sup.3 of feedstock is
introduced into the reactor that is kept at a temperature of
320.degree. C. and at a pressure of 10 MPa (1,450 psia). So as to
keep the catalyst in the sulfur state, 50 ppm by weight of sulfur
in the form of DMDS is added to the feedstock. Under the reaction
conditions, the DMDS is totally broken down for forming methane and
H.sub.2S.
[0152] At the end of 1 hour of operation of the test, 19.63 g of a
hydrocarbon liquid phase with a density of 842 kg/m.sup.3,
containing 0.12% by weight of water, 0.2% by weight of elementary
oxygen (quantification limit of the analyst) and 99.7% by weight of
hydrocarbons, has been recovered. The net hydrogen consumption
corresponds to 2.2% by weight relative to the mass of organic
effluent that is sent to the hydrotreatment stage, which
corresponds to a net hydrogen consumption of 0.9% by weight
relative to the bio-oil. The overall yield of
hydrocarbon-containing liquid is equal to 29.7% by weight relative
to the bio-oil or 21.4% by weight on the basis of dry biomass.
[0153] The hydrocarbon-containing liquid that is obtained from the
hydrotreatment stage is then sent into a flushed fixed-bed reactor
in the presence of a hydrocracking catalyst that simulates the
conversion reactor for the hydrocracking stage. The hydrocracking
catalyst that is used comprises 3.3% by weight of NiO, 16% by
weight of MoO.sub.3, and 3.8% by weight of P.sub.2O.sub.5 supported
on a commercial Y zeolite of reference CBV 712 mixed with a
gamma-alumina in a mass ratio of 1:4 (zeolite mass:alumina mass).
Said catalyst is sulfurized.
[0154] 25 mL/h of hydrocarbon-containing liquid that is obtained
from the hydrotreatment stage is introduced into an isothermal
reactor and with a fixed bed charged with 25 mL of hydrocracking
catalyst. The corresponding volumetric flow rate is equal to 1
h.sup.-1. 1,000 Nm.sup.3 of hydrogen/m.sup.3 of feedstock is
introduced into the reactor that is kept at a temperature of
380.degree. C. and a pressure of 12 MPa (1,740 psia). The effluent
that is recovered at the outlet of the reactor is cooled, flashed,
and fractionated into three distillation fractions: PI-80.degree.
C., 80-180.degree. C. and 180.degree. C.+. The PI-80.degree. C. and
80-180.degree. C. fractions are recovered, and the 180.degree. C.+
fraction is recycled in a continuous way at the inlet of the
reactor. The conversion per pass of products having boiling points
of higher than 180.degree. C. of product having a boiling point of
less than 180.degree. C. is estimated at 50%. The overall yield of
the naphtha fraction having boiling points of between 80 and
180.degree. C. is equal to 22.5% by weight relative to the bio-oil
or 16.2% by weight on the basis of the dry biomass.
[0155] The 80-180.degree. C. naphtha fraction is then sent into a
flushed fixed-bed reactor in the presence of a reforming catalyst.
The reforming catalyst that is used comprises 0.3% by weight of
platinum, 0.3% by weight of tin, and 1.0% by weight of chlorine
supported on a gamma-alumina. The catalytic reforming stage was
carried out in continuous mode in a fixed-bed reactor with 2.5 g of
catalyst at 520.degree. C., a total pressure of 0.9 MPa, an
H.sub.2/HC ratio of 1.7, and a WHSV of 2 h.sup.-1. The catalyst is
first reduced in-situ at 500.degree. C. for 2 hours. The product at
the outlet of the reactor is cooled, recovered, and an aliquot is
analyzed by gas chromatography for determining the contents of
benzene, toluene and xylene aromatic compounds. 3.6% by weight of
hydrogen relative to the mass flow rate of the feedstock that is
introduced into the reforming reactor is generated. The overall
yield of reformate is equal to 91% by weight relative to the
feedstock that is introduced or 20.5% by weight relative to the
bio-oil or 14.7% by weight on the basis of the dry biomass. The
reformate contains 3.1% by weight of benzene, 13.0% by weight of
toluene, 23.2% by weight of xylene, 27.4% by weight of C9 aromatic
compounds, and 9.4% by weight of C10 aromatic compounds. The
overall yield of total aromatic compounds and BTX represents,
respectively, 15.6% by weight and 8.1% by weight relative to the
bio-oil or 11.2% by weight and 5.8% by weight relative to the dry
biomass.
[0156] These results show that a reformate that contains more than
70% by weight of aromatic compounds and approximately 40% by weight
of BTX (measured by gas phase chromatography) can be obtained from
the treatment of a non-pretreated bio-oil according to the
concatenation of the
hydroreforming/hydrotreatment/hydrocracking/catalytic reforming
stages. This example does not integrate the aromatic complex making
it possible to separate and to maximize the BTX yield.
[0157] The entire disclosures of all applications, patents and
publications, cited herein and of corresponding application Ser.
No. 12/01544 FR, filed May 30, 2012, are incorporated by reference
herein.
* * * * *