Note: Descriptions are shown in the official language in which they were submitted.
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PROCE S S FOR CONVERSION OF A CELLULOSIC MATERIAL
FIELD OF THE INVENTION
The invention relates to a process for conversion of
a cellulosic material and use of the products produced in
such a process.
BACKGROUND TO THE INVENTION
With the diminishing supply of crude mineral oil,
use of renewable energy sources is becoming increasingly
important for the production of liquid fuels. These fuels
from renewable energy sources are often referred to as
biofuels.
Biofuels derived from non-edible renewable energy
sources, such as cellulosic materials, are preferred as
these do not compete with food production. These biofuels
are also referred to as second generation, or advanced,
biofuels. Most of these non-edible cellulosic materials,
however, are solid materials that are cumbersome to
convert into biofuels.
W02010/135734 describes a method for co-processing a
biomass feedstock and a refinery feedstock in a refinery
unit comprising catalytically cracking the biomass
feedstock and the refinery feedstock in a refinery unit
comprising a fluidized reactor, wherein hydrogen is
transferred from the refinery feedstock to carbon and
oxygen of the biomass feedstock. In one of the
embodiments W02010/135734 the biomass feedstock comprises
a plurality of solid biomass particles having an average
size between 50 and 1000 microns. In passing, it is
further mentioned that solid biomass particles can be
pre-processed to increase brittleness, susceptibility to
catalytic conversion (e.g. by roasting, toasting, and/or
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torrefication) and/or susceptibility to mixing with a
petrochemical feedstock.
A disadvantage of the process as described in
W02010/135734, however, is that proper handling of the
biomass feedstock comprising the solid biomass particles
is critical to avoid instability of the feedstock,
clogging of feed lines to a fluidized catalytic cracking
unit and/or coking in a fluidized catalytic cracking
unit.
The article of F. de Miguel Mercader et al,
published in the Journal of Applied Catalysis B:
Environmental, 2010, volume 96, pages 57-66, describes a
process for catalytic cracking of an hydrodeoxygenated
pyrolysis oil, derived from forest residue, together with
long residue in a catalytic cracking reactor. Although
the described process gives good results it is indicated
that the hydrodeoxygenation reactions lead to a better
product (with respect to fluidized catalytic cracking
(FCC) co-processing) at the expense of hydrogen. In
addition, it is indicated that during hydrodeoxygenation,
reaction conditions are critical to obtain thermally
stable molecules suitable for further processing in a FCC
unit. Figure 9 of the article further illustrates the
competition between hydro(deoxy)genation and
(re)polymerization of the pyrolysis oil. As explained in
the article, fast polymerization reactions may cause
plugging of a reactor.
It would therefore be an advancement in the art to
provide a less critical process for conversion of a
cellulosic material.
SUMMARY OF THE INVENTION
Such an advancement has been achieved with the
process according to the invention. Accordingly the
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present invention provides a process for conversion of a
cellulosic material comprising
a) a liquefaction step, comprising
- contacting a cellulosic material with a liquid
solvent at a temperature of equal to or more than
200 C; or
- contacting a cellulosic material with a liquid
solvent at a temperature of equal to or more than
100 C in the presence of a catalyst,
to produce a final liquefied product;
b) a catalytic cracking step, comprising contacting at
least part of the final liquefied product with a
fluidized catalytic cracking catalyst at a temperature of
equal to or more than 400 C, to produce one or more
cracked products.
Without wishing to be bound by any kind of theory it
is believed that due to its composition, the final
liquefied product allows for a more stable feedstock to a
fluidized catalytic cracking process than any pyrolysis
oil and/or any solid biomass particles.
In addition it has been found that in the process
according to the invention coking may be minimized.
The process according to the invention therefore
provides a less critical process for conversion of a
cellulosic material.
The one or more cracked products may advantageously
be fractionated to produce one or more product fractions
and optionally hydrotreated to produce one or more
hydrotreated product fractions. These one or more product
fractions and/or one or more hydrotreated product
fractions and/or one or more products derived therefrom
can advantageously be used as a biofuel component. The
present invention therefore further provides a process
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for the production of a biofuel comprising blending such
biofuel components with one or more other components to
produce a biofuel. The produced biofuel may
advantageously be used in a transportation vehicle.
DETAILED DESCRIPTION OF THE INVENTION
In the liquefaction step a cellulosic material is
contacted with a liquid solvent to produce a final
liquefied product. This step may also be referred to
herein as a liquefaction or liquefying of the cellulosic
material. The liquefaction or liquefying may be carried
out by means of a liquefaction or liquefying reaction.
By liquefaction (also herein referred to as
liquefying) is herein understood the conversion of a
solid material, such as cellulosic material, into one or
more liquefied products.
By a liquefied product is herein understood a
product that is liquid at a temperature of 20 C and a
pressure of 1 bar absolute (0.1 MegaPascal) and/or a
product that can be converted into a liquid by melting
(for example by applying heat) or dissolving in a
solvent. Preferably the liquefied product is a liquefied
product that is liquid at a temperature of 80 C and a
pressure of 1 bar absolute (0.1 MegaPascal). The
liquefied product may vary widely in its viscosity and
may be more or less viscous.
Liquefaction of a cellulosic material can comprise
cleavage of covalent linkages in that cellulosic
material. For example liquefaction of lignocellulosic
material can comprise cleavage of covalent linkages in
cellulose, hemicellulose and/or lignin present and/or
cleavage of covalent linkages between lignin,
hemicelluloses and/or cellulose.
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As used herein, cellulosic material refers to
material containing cellulose. Preferably the cellulosic
material is a lignocellulosic material. A lignocellulosic
material comprises lignin, cellulose and optionally
hemicellulose.
Advantageously the liquefaction step makes it
possible to liquefy not only the cellulose but also the
lignin and hemicelluloses.
Any suitable cellulose-containing material may be
used as cellulosic material in the process according to
the present invention. The cellulosic material for use
according to the invention may be obtained from a variety
of plants and plant materials including agricultural
wastes, forestry wastes, sugar processing residues and/or
mixtures thereof. Examples of suitable cellulose-
containing materials include agricultural wastes such as
corn stover, soybean stover, corn cobs, rice straw, rice
hulls, oat hulls, corn fibre, cereal straws such as
wheat, barley, rye and oat straw; grasses; forestry
products such as wood and wood-related materials such as
sawdust; waste paper; sugar processing residues such as
bagasse and beet pulp; or mixtures thereof.
Step a) may further comprise drying, torrefaction,
steam explosion, particle size reduction, densification
and/or pelletization of the cellulosic material before
the cellulosic material is contacted with the liquid
solvent. Such drying, torrefaction, steam explosion,
particle size reduction, densification and/or
pelletization of the cellulosic material may
advantageously allow for improved process operability and
economics.
Before being used in the process of the invention,
the cellulosic material is preferably processed into
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small particles in order to facilitate liquefaction.
Preferably, the cellulosic material is processed into
particles having a particle size distribution with an
average particle size of equal to or more than 0.05
millimeter, more preferably equal to or more than 0.1
millimeter, most preferably equal to or more than 0.5
millimeter and preferably equal to or less than 20
centimeters, more preferably equal to or less than 10
centimeters and most preferably equal to or less than 3
centimeters. For practical purposes the particle size in
the centimeter and millimeter range can be determined by
sieving.
If the cellulosic material is a lignocellulosic
material it may also have been subjected to a pre-
treatment to remove and/or degrade lignin and/or
hemicelluloses. Examples of such pre-treatments include
fractionation, pulping and torrefaction processes.
By a liquid solvent is herein preferably understood
a solvent that is liquid at a pressure of 1 bar
atmosphere (0.1 MegaPascal) and a temperature of 80 C or
higher, more preferably 100 C or higher. Most preferably
a liquid solvent is herein understood to be a solvent
that is liquid at the temperature and pressure at which
the liquefaction step is carried out.
In one preferred embodiment the liquid solvent
comprises or is water.
In another preferred embodiment the liquid solvent
comprises or is an organic solvent. By an organic solvent
is herein understood a solvent comprising one or more
hydrocarbon compounds. By a hydrocarbon compound is
herein understood a compound that contains at least one
hydrogen atom and at least one carbon atom, more
preferably a hydrocarbon compound is herein understood to
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contain at least one hydrogen atom and at least one
carbon atom bonded to eachother via at least one covalent
bond.
In addition to hydrogen and carbon the hydrocarbon
compound may contain for example heteroatoms such as
sulphur, oxygen and/or nitrogen. Examples of hydrocarbon
compounds that may preferably be present in the organic
solvent include acetic acid, formic acid, levulinic acid
and gamma-valerolactone and/or mixtures thereof.
The organic solvent may comprise polar and/or non-
polar hydrocarbon compounds. In a preferred embodiment
the organic solvent comprises at least one or more polar
hydrocarbon compounds. Preferably the organic solvent
comprises more than one, more preferably more than two,
more preferably more than three different polar
hydrocarbon compounds. A measure of the polarity of a
polar hydrocarbon compound is its log P value, where P is
defined as the partition coefficient of a compound in a
two phase octanol-water system. The log P value can be
determined experimentally or calculated according to
standard procedures as discussed in Handbook of Chemistry
and Physics, 83rd Edition, pages 16-43 to 16-47, CRC
Press (2002).
In one embodiment the organic solvent may preferably
comprise one or more polar hydrocarbon compound(s), which
one or more polar hydrocarbon compound(s) preferably
is/are a hydrocarbon compound having a polarity of log P
less than +3, more preferably less than +1. In another
embodiment, the polar hydrocarbon compound is a
hydrocarbon compound having a polarity of log P less than
+0.5. In a further embodiment, the polar hydrocarbon
compound is a hydrocarbon compound having a polarity of
log P less than 0.
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In another embodiment the organic solvent may
preferably comprise one or more non-polar hydrocarbon
compounds(s), which one or more non-polar hydrocarbon
compound(s) preferably is/are a hydrocarbon compound
having a polarity of log P in the range from +5 to +10,
more preferably in the range from +7 to +8.
In a preferred embodiment the organic solvent
comprises one or more carboxylic acids. By a carboxylic
acid is herein understood a hydrocarbon compound
comprising at least one carboxyl (-CO-OH) group. Such
carboxylic acids can be polar hydrocarbon compounds as
herein described above. More preferably the organic
solvent comprises equal to or more than 5 wt% carboxylic
acids, more preferably equal to or more than 10 wt%
carboxylic acids, most preferably equal to or more than
20wt% of carboxylic acids, based on the total weight of
organic solvent. There is no upper limit for the
carboxylic acid concentration, but for practical purposes
the organic solvent may comprise equal to or less than
90wt%, more preferably equal to or less than 80wt% of
carboxylic acids, based on the total weight of organic
solvent. Preferably the organic solvent comprises at
least acetic acid, levulinic acid and/or pentanoic acid.
Especially acetic acid may be useful as it can be
simultaneous used as (part of) the organic solvent as
well as used as an acid catalyst.
In another embodiment the organic solvent comprises
paraffinic compounds, naphthenic compounds, olefinic
compounds and/or aromatic compounds. Such compounds may
be present in refinery streams such as gasoil, fuel oil
and/or residue oil. These refinery streams may therefore
also be suitable as organic solvent in the liquefaction
step. This is explained in more detail below.
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In another preferred embodiment the organic solvent
comprises at least a part of a liquefied product.
Preferably part of the liquefied product (for example
part of a final liquefied product and/or part of an
intermediate liquefied product as described herein below)
is therefore recycled to the liquefaction step to be used
as organic solvent. In a preferred embodiment equal to or
more than 10 wt%, more preferably equal to or more than
20 wt% of the organic solvent is obtained from an
intermediate and/or final liquefied product.
In a preferred embodiment any recycle of liquefied
product(s) comprises a weight amount of liquefied
product(s) of 2 to 100 times the weight of the cellulosic
material, more preferably of 5 to 20 times the weight of
the cellulosic material.
In a preferred embodiment at least part of the
organic solvent is derived from cellulosic, and
preferably lignocellulosic, material. For example in a
preferred embodiment at least part of the organic solvent
may be generated in-situ during liquefaction of the
cellulosic material. More preferably at least part of the
organic solvent is obtained by acid hydrolysis of
cellulosic, and preferably lignocellulosic, material.
Examples of possible hydrocarbon compounds in the organic
solvent that may be obtained by acid hydrolysis of
cellulosic, and preferably lignocellulosic, material
include acetic acid, formic acid and levulinic acid.
Hydrocarbon compounds which are obtainable from such acid
hydrolysis products by hydrogenation thereof may also
suitably be used. Examples of such hydrogenated
hydrocarbon compounds include gamma-valerolactone which
is obtainable from levulinic acid by hydrogenation,
tetrahydrofufuryl and tetrahydropyranyl components which
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are derived from furfural or hydroxymethylfurfural, mono-
and di- alcohols and ketones which are derived from
sugars, and guaiacol and syringol components which are
derived from lignin. Preferably the organic solvent may
comprise one, two or more of such hydrocarbon compounds.
Further, the above compounds may also become part of the
final liquefied product. Hence, in a preferred embodiment
the final liquefied product or part thereof may comprise
one, two or more of the above listed, optionally
hydrogenated, compounds such as gamma-valerolactone,
which can be obtained from levulinic acid by
hydrogenation; tetrahydrofufuryl and tetrahydropyranyl
components, which can be derived from furfural or
hydroxymethylfurfural; mono- and/or di- alcohols and/or
mono- and/or di-ketones, which can be derived from
sugars; and/or guaiacol and/or syringol components, which
can be derived from lignin.
One or more hydrocarbon compounds in the organic
solvent may advantageously be obtainable from the
cellulosic material liquefied in the liquefaction step.
The hydrocarbon compound(s) may for example be generated
in-situ and/or recycled and/or used as a make-up organic
solvent, affording significant economic and processing
advantages.
In one embodiment at least part of the organic
solvent in the liquefaction step is not generated in situ
by conversion of the cellulosic material. Such an ex-situ
provided organic solvent may co-exist with an in-situ
formed organic solvent. Such a solvent that is not
generated in-situ but is ex-situ provided may therefore
herein also be referred to as "co-solvent".
In a preferred embodiment the organic solvent
comprises at least one or more hydrocarbon compound(s)
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that are at least partly obtained and/or derived from a
source other than the cellulosic material used as a
feedstock in the liquefaction step, for example a
petroleum source (herein also referred to as fossil
source). These one or more hydrocarbon compounds (s) may
for example be mixed with the cellulosic material before
starting the liquefaction or may be added to the reaction
mixture during the liquefaction.
As explained in more detail herein below, in one
embodiment the organic solvent in the liquefaction step
comprises one or more hydrocarbon compounds that also may
be suitable to act as a fluid hydrocarbon co-feed in the
catalytic cracking step. In a further embodiment the
organic solvent used in the liquefaction step contains
one or more hydrocarbon compounds obtained from a
conventional crude oil (also sometimes referred to as a
petroleum oil or mineral oil); an unconventional crude
oil (that is, oil produced or extracted using techniques
other than the traditional oil well method); a renewable
source (such as for example a vegetable oil); or a Fisher
Tropsch oil and/or a mixture thereof. More preferably the
organic solvent used in the liquefaction step comprises
or consists of a fraction of a petroleum oil or renewable
oil. Preferably the organic solvent comprises or consists
of a straight run (atmospheric) gas oils, flashed
distillate, vacuum gas oils (VGO), light cycle oil, heavy
cycle oil, hydrowax, coker gas oils, diesel, gasoline,
kerosene, naphtha, liquefied petroleum gases, atmospheric
residue ("long residue") and vacuum residue ("short
residue") and/or mixtures thereof. Most preferably the
organic solvent comprises or consists of a long residue.
Hence, preferably the co-solvent as mentioned above,
is an organic solvent that comprises or consists of a
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petroleum oil or a fraction thereof. The advantage of
using a petroleum oil or a fraction thereof as an organic
solvent or organic co-solvent is that this organic
solvent or co-solvent may also be a suitable feed to the
catalytic cracking step. When the organic solvent or
organic co-solvent comprises or is a petroleum oil or a
fraction thereof, this may lead to a more efficient and
cheaper operation and hardware as no separation of such a
organic solvent or organic co-solvent may be needed.
In a preferred embodiment, the present invention
therefore also provides a process for conversion of a
cellulosic material comprising
a) a liquefaction step, comprising contacting a
cellulosic material with an organic solvent at a
temperature of equal to or more than 100 C in the
presence of a catalyst, wherein the organic solvent
comprises a fraction of a petroleum oil, to produce a
final liquefied product;
b) a catalytic cracking step, comprising contacting a
mixture of at least part of the final liquefied product
and the fraction of a petroleum oil with a fluidized
catalytic cracking catalyst in a fluidized catalytic
cracking reactor at a temperature of equal to or more
than 400 C, to produce one or more cracked products. One
skilled in the art will understand that the liquefied
product in step b) may suitably be the final liquefied
product or any part thereof.
The fraction of a petroleum oil is preferably chosen
from the group consisting of straight run (atmospheric)
gas oils, flashed distillate, vacuum gas oils (VGO),
light cycle oil, heavy cycle oil, hydrowax, coker gas
oils, diesel, gasoline, kerosene, naphtha, liquefied
petroleum gases, atmospheric residue ("long residue") and
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vacuum residue ("short residue") and/or mixtures thereof
as indicated above. At least part of this fraction of a
petroleum oil or the whole of this fraction of a
petroleum oil may be contacted with the fluidized
catalytic cracking catalyst in step b).
In a preferred embodiment the liquefaction step
comprises contacting the cellulosic material
simultaneously with the fraction of a petroleum oil, with
a source of hydrogen, with a hydrogenation catalyst, and
optionally with an acid catalyst, at a temperature of
equal to or more than 150 C to produce a final liquefied
product.
Other preferences are as described elsewhere herein.
In one embodiment, the organic solvent is partly
derived from cellulosic, preferably lignocellulosic,
material and partly derived from a petroleum source. In a
preferred embodiment the organic solvent comprises a
mixture of i) a fraction of a petroleum oil and ii) one
or more hydrocarbon compounds that may be obtained by
acid hydrolysis of cellulosic, preferably
lignocellulosic, material.
In a preferred embodiment the organic solvent
comprises at least one or more carboxylic acids, such as
for example acidic acid, levulinic acid and/or pentanoic
acid, which carboxylic acid(s) are preferably present
before beginning the liquefaction reaction, that is,
which carboxylic acid(s) are preferably not in-situ
obtained and/or derived from the cellulosic material
during the reaction.
Advantageously, the organic solvent may be water-
miscible at the reaction temperature of the liquefaction
step. In a preferred embodiment, the liquefaction step
comprises contacting the cellulosic material with a
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solvent mixture comprising the organic solvent and water.
Hence, in a preferred embodiment the liquid solvent may
comprise a solvent mixture containing water and an
organic solvent.
The water in the solvent mixture may for example be
generated in-situ during the liquefaction step. The
organic solvent is preferably present in an amount of
less than or equal to 95% by weight, more preferably less
than or equal to 90% by weight and most preferably less
than or equal to 80% by weight, based on the total weight
of water and organic solvent. Further the organic solvent
is preferably present in an amount of more than or equal
to 5% by weight, more preferably more than or equal to
10% by weight, and most preferably more than or equal to
20% by weight, based on the total weight of water and
organic solvent. The organic solvent is preferably
present in an amount of from 20% to 60% by weight, based
on the total weight of the water and organic solvent.
Preferably water is present in an amount of less
than or equal to 95% by weight, more preferably an amount
of less than or equal to 90% by weight, and most
preferably less than or equal to 80% by weight, based on
the total weight of water and organic solvent. Further
water is preferably present in an amount of more than or
equal to 5% by weight, more preferably in an amount of
more than or equal to 10% by weight, most preferably 20%
by weight, based on the total weight of water and organic
solvent. Preferably, water is present in an amount of
from 40% to 80% by weight based on the total weight of
the water and organic solvent. Preferably a solvent
mixture contains the organic solvent and water in a
weight ratio of organic solvent to water of less than or
equal to 9:1, more preferably less than or equal to 8:2.
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Further a solvent mixture preferably contains the organic
solvent and water in a weight ratio of organic solvent to
water of more than or equal to 1:9 more preferably more
than or equal to 2:8.
The cellulosic material and the organic solvent or -
if a solvent mixture containing water and organic solvent
is present - the solvent mixture are preferably mixed in
a solvent mixture or organic solvent-to-cellulosic
material ratio of 2:1 to 20:1 by weight, more preferably
in a solvent mixture or organic solvent-to-cellulosic
material ratio of 3:1 to 15:1 by weight and most
preferably in a solvent mixture or organic solvent-to-
cellulosic material ratio of 4:1 to 10:1 by weight.
The liquefaction step may be carried out in the
presence or absence of a catalyst. The use of a catalyst
advantageously allows one to lower the reaction
temperature.
Hence, in one embodiment the liquefaction step may
comprise contacting a cellulosic material with an organic
solvent, optionally in the essential absence of an
externally provided acid catalyst, at a temperature of
equal to or more than 200 C, more preferably equal to or
more than 250 C, still more preferably a temperature of
equal to or more than 300 C and preferably a temperature
equal to or less than 450 C.
In another embodiment the liquefaction step may
comprise contacting a cellulosic material with an organic
solvent in the presence of a, preferably acid, catalyst
at a temperature of equal to or more than 100 C, more
preferably a temperature of equal to or more than 150 C ,
still more preferably a temperature of equal to or more
than 200 C and preferably a temperature of equal to or
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less than 450 C, more preferably a temperature of equal
to or less than 350 C.
Preferably the catalyst is an acid catalyst. The
acid catalyst for use in liquefaction step to the
invention may be any acid catalyst known in the art to be
suitable for liquefying of cellulosic material. For
example, the acid catalyst may be a Bronsted acid or a
Lewis acid. Further the acid catalyst may be a
homogeneous catalyst or a heterogeneous catalyst.
Preferably the acid catalyst is a homogeneous or finely
dispersed heterogeneous catalyst, most preferably the
acid catalyst is a homogeneous catalyst. Preferably the
acid catalyst remains liquid and stable under the
liquefaction conditions and preferably it is sufficiently
strong to effect cleavage of the covalent linkages and
dehydration of the cellulosic material.
Preferably the acid catalyst is a Bronsted acid and
more preferably the acid catalyst is a mineral or organic
acid, preferably a mineral or organic acid having a pKa
value below 5.0, more preferably below 4.25, still more
preferably below 3.75, even more preferably below 3.0,
and most preferably below 2.5.
Examples of suitable mineral acids include sulphuric
acid, para toluene sulphonic acid, nitric acid,
hydrochloric acid and phosphoric acid, and mixtures
thereof. In a preferred embodiment, the acid catalyst
used in the liquefaction step is sulphuric acid or
phosphoric acid.
Examples of suitable organic acids which may be used
in the liquefaction step include levulinic acid, acetic
acid, oxalic acid, formic acid, lactic acid, citric acid,
trichloracetic acid and mixtures thereof. If the acid
catalyst is an organic acid, it may suitably be an
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organic acid that is generated in-situ or ex-situ (i.e.
provided externally). By an in-situ generated organic
acid is herein understood an organic catalyst that is
generated in-situ during liquefaction of the cellulosic
material. An example of such an in-situ generated organic
acid may be acetic acid or formic acid.
The acid catalyst is preferably present in an amount
of less than or equal to 35% by weight, more preferably
less than or equal to 20% by weight, even more preferably
less than or equal to 10% by weight and still more
preferably less than or equal to 5% by weight, and most
preferably less than or equal to 1% by weight, based on
the total weight of organic solvent or - if applicable -
solvent mixture and acid catalyst. Further the acid
catalyst is preferably present in an amount of more than
or equal to 0.01% by weight, more preferably more than or
equal to 0.1% by weight and most preferably more than or
equal to 0.2% by weight, based on the total weight of
organic solvent or - if applicable - solvent mixture and
acid catalyst. It will be appreciated that for any given
acid catalyst the amount of acid required will depend on
the strength of the acid. In one preferred embodiment,
the acid catalyst is present in an amount of from 1% to
10% by weight, preferably from 2% to 5% by weight, based
on the weight of organic solvent or - if applicable -
solvent mixture and acid catalyst.
In a preferred embodiment at least part of the
liquefied product obtained after liquefaction of the
cellulosic material is hydrogenated. Liquefaction and
hydrogenation may be carried out simultaneously or
hydrogenation may be carried out subsequent to the
liquefaction.
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In one embodiment the liquefaction step comprises
contacting the cellulosic material with the organic
solvent in the presence of an acid catalyst at a
temperature of equal to or more than 150 C to produce an
intermediate liquefied product; and subsequently
hydrotreating the intermediate liquefied product with a
source of hydrogen in the presence of a hydrotreatment
catalyst to produce a final liquefied product. Preferably
hydrotreating of the intermediate liquefied product
comprises hydrogenating of the intermediate liquefied
product and preferably the hydrotreatment catalyst is a
hydrogenation catalyst.
In another embodiment the liquefaction step
comprises contacting the cellulosic material
simultaneously with the organic solvent, a source of
hydrogen, the acid catalyst and a hydrogenation catalyst
at a temperature of equal to or more than 150 C to
produce a final liquefied product. In this case the
liquefaction step can advantageously comprise the
simultaneous hydrolysis and hydrogenation of the
cellulosic material, resulting in an improved degree of
liquefaction. By simultaneous contact is understood
contact of the cellulosic material with one of the
specified features in the presence of the remaining
features. In this way simultaneous hydrolysis and
hydrogenation of the cellulosic material can be effected
as any hydrolysis product can be in-situ hydrogenated.
The hydrogenation catalyst is preferably a
hydrogenation catalyst that is resistant to the
combination of the organic solvent (or if applicable the
solvent mixture) and, if present, the acid catalyst.
For example the hydrogenation catalyst can comprise
a heterogeneous and/or homogeneous catalyst. In a
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preferred embodiment the hydrogenation catalyst is a
homogeneous catalyst. In another preferred embodiment the
hydrogenation catalyst is a heterogeneous catalyst. The
hydrogenation catalyst preferably comprises a
hydrogenation metal known to be suitable for
hydrogenation reactions, such as for example iron,
molybdenum, cobalt, nickel, copper, ruthenium, rhodium,
palladium, iridium, platinum and gold, or mixtures
thereof. The hydrogenation catalyst comprising such a
hydrogenation metal may be sulfided.
In a further embodiment sulfided hydrogenation catalysts
may be used such as for example a catalyst based on
Molybdenum sulfide, potentionally including Cobalt and/or
Nickel as a promotor.
If the hydrogenation catalyst is a heterogeneous
catalyst, the catalyst preferably comprises a
hydrogenation metal supported on a carrier. Suitable
carriers include for example carbon, alumina, titanium
dioxide, zirconium dioxide, silicon dioxide and mixtures
thereof. Examples of preferred heterogeneous
hydrogenation catalysts include ruthenium, platinum or
palladium supported on a carbon carrier. Other preferred
examples of heterogeneous hydrogenation catalysts include
ruthenium supported on titanium dioxide (Ti02), platina
supported on titanium dioxide and ruthenium supported on
zirconium dioxide(Zr02). The heterogeneous catalyst
and/or carrier may have any suitable form including the
form of a mesoporous powder, granules or extrudates or a
megaporous structure such as a foam, honeycomb, mesh or
cloth. The heterogeneous catalyst may be present in a
liquefaction reactor comprised in a fixed bed or
ebullated slurry. Preferably the heterogeneous catalyst
is present in a liquefaction reactor as a fixed bed.
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If the hydrogenation catalyst is a homogeneous
hydrogenation catalyst, the catalyst preferably comprises
an organic or inorganic salt of the hydrogenation metal,
such as for example the acetate-, acetylacetonate-,
nitrate-, sulphate- or chloride- salt of ruthenium,
platinum or palladium. Preferably the homogeneous
catalyst is an organic or inorganic acid salt of the
hydrogenation metal, wherein the acid is an acid which is
already present in the process as acid catalyst or
product.
The source of hydrogen may be any source of hydrogen
known to be suitable for hydrogenation purposes. It may
for example include hydrogen gas, but also an hydrogen-
donor such as for example formic acid. Preferably the
source of hydrogen is a hydrogen gas. Such a hydrogen gas
can be applied in the process of the invention at a
partial hydrogen pressure that preferably lies in the
range from 2 to 200 bar absolute (0.1 to 20 MegaPascal),
more preferably in the range from 10 to 170 bar absolute
(1 to 17 MegaPascal), and most preferably in the range
from 30 to 150 bar absolute (3 to 15 MegaPascal). A
hydrogen gas can be supplied to a liquefaction reactor
co-currently, cross-currently or counter-currently to the
cellulosic material. Preferably a hydrogen gas is
supplied counter-currently to the cellulosic material.
The liquefaction step can be carried out at any
total pressure known to be suitable for liquefaction
processes. The process can be carried out under a total
pressure that preferably lies in the range from 2 to 200
bar absolute (0.1 to 20 MegaPascal), more preferably in
the range from 10 to 170 bar absolute (1 to 17
MegaPascal), and most preferably in the range from 30 to
150 bar absolute (3 to 15 MegaPascal).
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The liquefaction process according to the invention
can be carried out batch-wise, semi-batch wise and
continuously.
During the liquefaction step, the cellulosic
material is liquefied, i.e. the cellulosic material is
converted into one or more liquefied products, to produce
a final liquefied product.
By a final liquefied product is herein preferably
understood a liquefied product which is ready to be
forwarded to the catalytic cracking step. The final
liquefied product may have been hydrogenated (as
explained herein above) or not. Further the final
liquefied product may have been separated from the
reaction effluent or not. Preferably the final liquefied
product has been hydrogenated and/or is obtained after
one or more separations as described herein below.
The reaction effluent produced in the liquefaction
step may include so-called humins, the liquefied
product(s) and for example water, co-solvent, acid
catalyst, and/or hydrogenation catalyst and/or gaseous
products such as for example hydrogen. In a preferred
embodiment step a) may further comprise separating a
final liquefied product from a reaction effluent produced
in the liquefaction step.
By humins is understood the solid insoluble material
remaining after liquefaction. It is sometimes also
referred to as char.
The liquefied product(s) may comprise monomeric
and/or oligomeric compounds and optionally excess water
produced during the liquefaction process. From the
liquefied product a product containing monomeric and
oligomeric compounds may be separated. Also part of the
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liquefied product may be separated for recycling to the
liquefaction step as organic solvent.
The reaction effluent is preferably forwarded to a
separation section. In the separation section insoluble
humins, monomeric and/or oligomeric compounds and/or
water, co-solvent and/or acid catalyst can be separated
off from the reaction effluent.
In one embodiment the humins may be separated from
the reaction effluent in a manner known to be suitable
for this purpose. Preferably such humins are separated
off via filtration or settling. Any humins formed in the
liquefaction step can be converted to diesel, kerosene
and gasoline fraction in the catalytic cracking step of
the process according to the invention or in another
conventional refinery step.
In another embodiment the liquefied products and/or
any co-solvent are separated from the reaction effluent
in a manner known to be suitable for this purpose.
Preferably liquefied products and/or any co-solvent are
separated off by liquid/liquid separation techniques,
such as phase separation, (solvent) extraction and/or
membrane filtration or (vacuum) distillation.
If desired the monomeric products and oligomeric
products may be conveniently separated from eachother
using one or more membranes. For example, monomeric
compounds and/or optionally water can be separated from
any C9-C20 oligomeric compounds and C20+ oligomeric
compounds by a ceramic membrane(for example a TiO2
membrane) or a polymeric membrane(for example a Koch MPF
34 (flatsheet) or a Koch MPS-34 (spiral wound) membrane).
The C9-C20 oligomers and the C20+ oligomers can
conveniently be separated from eachother with for example
a polymer grafted Zr02 membrane. The use of membranes for
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these separations can advantageously improve the energy
efficiency of the process.
In another embodiment excess water produced during
the liquefaction step is removed by distillation,
pervaporation and/or reversed osmosis.
In a preferred embodiment, at least part of any
water, co-solvent, acid catalyst and/or hydrogenation
catalyst is advantageously recovered to be recycled for
re-use in the liquefaction step. In a further preferred
embodiment, this recycle stream also contains at least
part of any monomeric compounds and/or oligomeric
products. Any excess of water, co-solvent, acid catalyst
, hydrogenation catalysts and/or monomeric compounds is
preferably purged via a purge stream. In the liquefaction
step, preferably more than or equal to 50% by weight,
more preferably more than or equal to 60% by weight and
most preferably more than or equal to 70% by weight of
the cellulosic material may advantageously be liquefied
into liquefied product, preferably in less than 3 hours.
When the co-solvent is an organic co-solvent such as
a petroleum oil or a fraction of a petroleum oil, it may
be advantageous not to recycle the co-solvent but to co-
feed the co-solvent with the final liquefied product into
the catalytic cracking step. If the liquefaction step
comprises hydrogenating of the one or more liquefied
products, the petroleum oil or a fraction of the
petroleum oil may suitably also be hydrogenated. This may
be advantageous during the catalytic cracking step.
The catalytic cracking step comprises contacting at
least part of the final liquefied product with a
fluidized catalytic cracking catalyst at a temperature of
equal to or more than 400 C, to produce one or more
cracked products.
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In one embodiment the final liquefied product or
part thereof may comprises one, two or more compounds
chosen from the group consisting of gamma-valerolactone
and/or levulinic acid; tetrahydrofufuryl and/or
tetrahydropyranyl; furfural and/or hydroxymethylfurfural;
mono- and/or di- alcohols and/or mono- and/or di-ketones;
and/or guaiacol and/or syringol components.
In a further embodiment the final liquefied product
or part thereof is a fraction of the reaction effluent
obtained from the liquefaction step which comprises or
essentially consists of one or more, preferably
monomeric, compounds containing equal to or less than 9
carbon atoms, preferably equal to or less than 6 carbon
atoms and most preferably equal to or less than 5 carbon
atoms. More preferably the final liquefied product in
this embodiment comprises one or more compounds
containing equal to or less than 9 carbon atoms,
preferably equal to or less than 6 carbon atoms and most
preferably equal to or less than 5 carbon atoms and/or
having a molecular weight of equal to or less than 200
Dalton and/or having an atmospheric boiling point of
equal to or less than 200 C as determined at 0.1
MegaPascal.
Preferably such a final liquefied product includes
hydrocarbon compounds and/or oxygenates, such as for
example alcohols. For example such a final liquefied
product may comprise or may consist of mono- and/or di-
alcohols and/or mono-and/or di-ketones which are derived
from sugars. More preferably such final liquefied product
is a final liquefied product containing butanone, butanol
and/or furfural.
In another embodiment the final liquefied product or
part thereof is a fraction of the reaction effluent
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obtained from the liquefaction step which comprises or
essentially consists of one or more, preferably
monomeric, compounds containing equal to or more than 9
carbon atoms, preferably equal to or more than 10 carbon
atoms, and most preferably equal to or more than 11
carbon atoms. More preferably the final liquefied product
in this embodiment comprises one or more compounds
containing equal to or more than 9 carbon atoms,
preferably equal to or more than 10 carbon atoms and most
preferably equal to or more than 11 carbon atoms, and/or
having a molecular weight of equal to or more than 200
Dalton and/or an atmospheric boiling point of equal to or
more than 200 C as determined at 0.1 MegaPascal.
The final liquefied product or part thereof can be
produced as described above. The final liquefied product
or any part thereof to be contacted with the fluidized
catalytic cracking catalyst can optionally be obtained
after a separation step as described above. The final
liquefied product or any part thereof can be fed to a
fluidized catalytic cracking reactor in an essentially
liquid state, in an essentially gaseous state or in a
partially liquid-partially gaseous state. When entering
the fluidized catalytic cracking reactor in an
essentially or partially liquid state, the final
liquefied product or any part thereof preferably
vaporizes upon entry and preferably is contacted in the
gaseous state with the fluidized catalytic cracking
catalyst.
In a preferred embodiment the catalytic cracking
step comprises contacting at least part of the final
liquefied product and a fluid hydrocarbon co-feed with
the fluidized catalytic cracking catalyst, preferably in
a fluidized catalytic cracking reactor, at a temperature
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of equal to or more than 400 C, to produce the one or
more cracked products. That is, in a preferred embodiment
also a fluid hydrocarbon co-feed other than the at least
part of the final liquefied product may be added into a
fluidized catalytic cracking reactor.
By a hydrocarbon co-feed is herein understood a co-
feed that contains one or more hydrocarbon compounds. By
a fluid hydrocarbon co-feed is herein understood a
hydrocarbon feed that is not in a solid state. The fluid
hydrocarbon co-feed is preferably a liquid hydrocarbon
co-feed, a gaseous hydrocarbon co-feed, or a mixture
thereof. The fluid hydrocarbon co-feed can be fed to a
catalytic cracking reactor in an essentially liquid
state, in an essentially gaseous state or in a partially
liquid-partially gaseous state. When entering the
catalytic cracking reactor in an essentially or partially
liquid state, the fluid hydrocarbon co-feed preferably
vaporizes upon entry and preferably is contacted in the
gaseous state with the fluidized catalytic cracking
catalyst.
The fluid hydrocarbon co-feed can be any non-solid
hydrocarbon co-feed known to the skilled person to be
suitable as a co-feed for a catalytic cracking unit. The
fluid hydrocarbon co-feed can for example be obtained
from a conventional crude oil (also sometimes referred to
as a petroleum oil or mineral oil), an unconventional
crude oil (that is, oil produced or extracted using
techniques other than the traditional oil well method) or
a Fisher Tropsch oil and/or a mixture thereof.
The fluid hydrocarbon co-feed may even be a fluid
hydrocarbon co-feed from a renewable source, such as for
example a vegetable oil.
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In one embodiment the fluid hydrocarbon co-feed is
derived from a, preferably conventional, crude oil.
Examples of conventional crude oils include West Texas
Intermediate crude oil, Brent crude oil, Dubai-Oman crude
oil, Arabian Light crude oil, Midway Sunset crude oil or
Tapis crude oil.
More preferably the fluid hydrocarbon co-feed
comprises a fraction of a, preferably conventional, crude
oil or renewable oil. Preferred fluid hydrocarbon co-
feeds include straight run (atmospheric) gas oils,
flashed distillate, vacuum gas oils (VGO), light cycle
oil, heavy cycle oil, hydrowax, coker gas oils, diesel,
gasoline, kerosene, naphtha, liquefied petroleum gases,
atmospheric residue ("long residue") and vacuum residue
("short residue") and/or mixtures thereof. Most
preferably the fluid hydrocarbon co-feed comprises a long
residue.
The composition of the fluid hydrocarbon co-feed may
vary widely. The fluid hydrocarbon co-feed may for
example contain paraffins, olefins and aromatics.
Preferably the fluid hydrocarbon co-feed comprises
equal to or more than 1 wt% paraffins, more preferably
equal to or more than 5 wt% paraffins, and most
preferably equal to or more than 10 wt% paraffins, and
preferably equal to or less than 100 wt% paraffins, more
preferably equal to or less than 90 wt% paraffins, and
most preferably equal to or less than 30 wt% paraffins,
based on the total fluid hydrocarbon co-feed. By
paraffins both normal-, cyclo- and branched-paraffins are
understood.
In a preferred embodiment the fluid hydrocarbon co-
feed comprises or consists of a paraffinic fluid
hydrocarbon co-feed. By a paraffinic fluid hydrocarbon
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co-feed is herein understood a fluid hydrocarbon co-feed
comprising at least 50 wt% of paraffins, preferably at
least 70 wt% of paraffins, based on the total weight of
the fluid hydrocarbon co-feed. For practical purposes the
paraffin content of all fluid hydrocarbon co-feeds having
an initial boiling point of at least 260 C can be
measured by means of ASTM method D2007-03 titled
"Standard test method for characteristic groups in rubber
extender and processing oils and other petroleum-derived
oils by clay-gel absorption chromatographic method",
wherein the amount of saturates will be representative
for the paraffin content. For all other fluid hydrocarbon
co-feeds the paraffin content of the fluid hydrocarbon
co-feed can be measured by means of comprehensive multi-
dimensional gas chromatography (GCxGC), as described in
P.J. Schoenmakers, J.L.M.M. Oomen, J. Blomberg,
W. Genuit, G. van Velzen, J. Chromatogr. A, 892 (2000)
p. 29 and further.
Examples of paraffinic fluid hydrocarbon co-feeds
include so-called Fischer-Tropsch derived hydrocarbon
streams such as described in W02007/090884 and herein
incorporated by reference, or a hydrogen rich feed like
hydrotreater product or hydrowax. By Hydrowax is
understood the bottoms fraction of a hydrocracker.
Examples of hydrocracking processes which may yield a
bottoms fraction that can be used as fluid hydrocarbon
co-feed, are described in EP-A-699225, EP-A-649896, WO-A-
97/18278, EP-A-705321, EP-A-994173 and US-A-4851109 and
herein incorporated by reference.
In a preferred embodiment the fluid hydrocarbon co-
feed comprises equal to or more than 8 wt% elemental
hydrogen, more preferably more than 12 wt% elemental
hydrogen (i.e. hydrogen atoms), based on the total fluid
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hydrocarbon co-feed on a dry basis (i.e. water-free
basis). A high content of elemental hydrogen, such as a
content of equal to or more than 8 wt%, allows the
hydrocarbon feed to act as a cheap hydrogen donor in the
catalytic cracking process. A particularly preferred
fluid hydrocarbon co-feed having an elemental hydrogen
content of equal to or more than 8 wt% is Fischer-Tropsch
derived waxy raffinate. Such Fischer-Tropsch derived waxy
raffinate may for example comprise about 85 wt% of
elemental carbon and 15 wt% of elemental hydrogen.
When a fluid hydrocarbon co-feed is present, the
weight ratio of fluid hydrocarbon co-feed to liquefied
product(s) (or part thereof) is preferably equal to or
more than 50 to 50 (5:5), more preferably equal to or
more than 70 to 30 (7:3), still more preferably equal to
or more than 80 to 20 (8:2), even still more preferably
equal to or more than 90 to 10 (9:1). For practical
purposes the weight ratio of fluid hydrocarbon co-feed to
liquefied product(s) (or part thereof) is preferably
equal to or less than 99.9 to 0.1 (99.9:0.1), more
preferably equal to or less than 95 to 5 (95:5). The
fluid hydrocarbon co-feed and the final liquefied product
(or part thereof) are preferably being fed to a fluidized
catalytic cracking reactor in a weight ratio within the
above ranges.
The amount of liquefied product(s), based on the
total weight of liquefied product(s) and fluid
hydrocarbon co-feed supplied to a fluidized catalytic
cracking reactor, is preferably equal to or less than 50
wt%, more preferably equal to or less than 30 wt%, most
preferably equal to or less than 20 wt% and even more
preferably equal to or less than 10 wt%. For practical
purposes the amount of liquefied product(s) present,
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based on the total weight of liquefied product(s) and
fluid hydrocarbon co-feed supplied to a fluidized
catalytic cracking reactor, is preferably equal to or
more than 0.1 wt%, more preferably equal to or more than
1 wt%.
The catalytic cracking step is preferably carried
out in a fluidized catalytic cracking reactor. The
fluidized catalytic cracking reactor can be any fluidized
catalytic cracking reactor known in the art to be
suitable for the purpose, including for example a
fluidized dense bed reactor or a riser reactor. Most
preferably the catalytic cracking step is carried out in
a riser reactor. Preferably this fluidized catalytic
cracking reactor is part of a fluidized catalytic
cracking (FCC) unit.
In one embodiment, where the organic solvent in the
liquefaction step comprises one or more hydrocarbon
compounds that also may suitable act as a fluid
hydrocarbon co-feed, preferably a mixture of the
liquefied product(s) and any organic solvent may be
supplied to the fluidized catalytic cracking reactor. For
example when a petroleum oil or a fraction thereof is
used as a co-solvent in the liquefaction step, the fluid
hydrocarbon co-feed as described herein may comprise or
consist of such a co-solvent. In a further embodiment the
organic solvent used in the liquefaction step is chosen
from the fluid hydrocarbon co-feeds described above.
Preferences for the fluid hydrocarbon co-feed are as
described herein above.
In another preferred embodiment, the fluidized
catalytic cracking reactor is a riser reactor and the
fluid hydrocarbon co-feed is supplied to a riser reactor
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at a location downstream of the location where the
liquefied product(s) is/are supplied to a riser reactor.
In a still further embodiment, a mixture of the
liquefied product(s) and a first hydrocarbon co-feed
(which may for example be the organic solvent when the
organic solvent is chosen from the described fluid
hydrocarbon co-feeds) is supplied to a riser reactor at a
first location and a second fluid hydrocarbon co-feed is
supplied to the riser reactor at a second location
downstream of the first location. Preferences for the
first and second fluid hydrocarbon co-feed are as
described herein above.
By a riser reactor is herein understood an elongated
essentially tube-shaped reactor suitable for carrying out
catalytic cracking reactions. The elongated essentially
tube-shaped reactor is preferably oriented in an
essentially vertical manner.
Examples of suitable riser reactors are described in
the Handbook titled "Fluid Catalytic Cracking technology
and operations", by Joseph W. Wilson, published by
Pennell Publishing Company (1997), chapter 3, especially
pages 101 to 112, herein incorporated by reference.
The riser reactor may be a so-called internal riser
reactor or a so-called external riser reactor as
described therein.
Most preferably the internal riser reactor is an
essentially vertical essentially tube-shaped reactor,
that may have an essentially vertical upstream end
located outside a vessel and an essentially vertical
downstream end located inside the vessel. The vessel is
suitably a reaction vessel suitable for catalytic
cracking reactions and/or a vessel that comprises one or
more cyclone separators and/or swirl tubes. The internal
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riser reactor may be especially advantageous in the
catalytic cracking step as it may be less prone to
plugging, thereby increasing safety and hardware
integrity.
The length of the riser reactor may vary widely. For
practical purposes the riser reactor preferably has a
length in the range from equal to or more than 10 meters,
more preferably equal to or more than 15 meters and most
preferably equal to or more than 20 meters, to equal to
or less than 65 meters, more preferably equal to or less
than 55 meters and most preferably equal to or less than
45 meters.
In a preferred embodiment the liquefied product(s)
produced in the liquefaction step are supplied to a riser
reactor, at the bottom of this riser reactor. This may
advantageously result in in-situ water formation at the
bottom of the reactor. The in-situ water formation may
lower the hydrocarbon partial pressure and reduce second
order hydrogen transfer reactions, thereby resulting in
higher olefin yields. Preferably the hydrocarbon partial
pressure is lowered to a pressure in the range from 0.7 to
2.8 bar absolute (0.07 to 0.28 MegaPascal), more
preferably 1.2 to 2.8 bar absolute (0.12 to 0.28
MegaPascal).
It may be advantageous to also add a lift gas at the
bottom of the riser reactor. Examples of such a liftgas
include steam, vaporized oil and/or oil fractions, and
mixtures thereof. Steam is most preferred as a lift gas
from a practical perspective. However, the use of a
vaporized oil and/or oil fraction (preferably vaporized
liquefied petroleum gas, gasoline, diesel, kerosene or
naphtha) as a liftgas may have the advantage that the
liftgas can simultaneously act as a hydrogen donor and
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may prevent or reduce coke formation. Further if a fluid
hydrocarbon co-feed is used as an organic solvent in the
liquefaction step, also vaporized organic solvent may be
used as a liftgas.
The fluidized catalytic cracking catalyst can be any
catalyst known to the skilled person to be suitable for
use in a cracking process. Preferably, the fluidized
catalytic cracking catalyst comprises a zeolitic
component. In addition, the fluidized catalytic cracking
catalyst can contain an amorphous binder compound and/or
a filler. Examples of the amorphous binder component
include silica, alumina, titania, zirconia and magnesium
oxide, or combinations of two or more of them. Examples
of fillers include clays (such as kaolin).
The zeolite is preferably a large pore zeolite. The
large pore zeolite includes a zeolite comprising a
porous, crystalline aluminosilicate structure having a
porous internal cell structure on which the major axis of
the pores is in the range of 0.62 nanometer to
0.8 nanometer. The axes of zeolites are depicted in the
'Atlas of Zeolite Structure Types', of W.M. Meier,
D.H. Olson, and Ch. Baerlocher, Fourth Revised
Edition 1996, Elsevier, ISBN 0-444-10015-6. Examples of
such large pore zeolites include FAU or faujasite,
preferably synthetic faujasite, for example, zeolite Y or
X, ultra-stable zeolite Y (USY), Rare Earth zeolite Y
(= REY) and Rare Earth USY (REUSY). According to the
present invention USY is preferably used as the large
pore zeolite.
The fluidized catalytic cracking catalyst can also
comprise a medium pore zeolite. The medium pore zeolite
that can be used according to the present invention is a
zeolite comprising a porous, crystalline aluminosilicate
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structure having a porous internal cell structure on
which the major axis of the pores is in the range of 0.45
nanometer to 0.62 nanometer. Examples of such medium pore
zeolites are of the MFI structural type, for example,
ZSM-5; the MTW type, for example, ZSM-12; the TON
structural type, for example, theta one; and the FER
structural type, for example, ferrierite. According to
the present invention, ZSM-5 is preferably used as the
medium pore zeolite.
According to another embodiment, a blend of large
pore and medium pore zeolites may be used. The ratio of
the large pore zeolite to the medium pore size zeolite in
the cracking catalyst is preferably in the range of 99:1
to 70:30, more preferably in the range of 98:2 to 85:15.
The total amount of the large pore size zeolite
and/or medium pore zeolite that is present in the
cracking catalyst is preferably in the range of 5 wt% to
40 wt%, more preferably in the range of 10 wt% to 30 wt%,
and even more preferably in the range of 10 wt% to 25 wt%
relative to the total mass of the fluidized catalytic
cracking catalyst.
Preferably, the liquefied product(s) and any fluid
hydrocarbon feed flow co-currently in the same direction.
The fluidized catalytic cracking catalyst can be
contacted in a cocurrent-flow, countercurrent-flow or
cross-flow configuration with such a flow of the
liquefied product(s) and optionally the fluid hydrocarbon
feed. Preferably the catalytic cracking catalyst is
contacted in a cocurrent flow configuration with a
cocurrent flow of the liquefied product(s) and optionally
the fluid hydrocarbon feed.
In a preferred embodiment the catalytic cracking
step comprises:
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a fluidized catalytic cracking step comprising contacting
at least part of the final liquefied product with a
fluidized catalytic cracking catalyst at a temperature of
equal to or more than 400 C, to produce one or more
cracked products and a spent fluidized catalytic cracking
catalyst;
a separation step comprising separating the one or more
cracked products from the spent fluidized catalytic
cracking catalyst;
a regeneration step comprising regenerating spent
fluidized catalytic cracking catalyst to produce a
regenerated fluidized catalytic cracking catalyst, heat
and carbon dioxide; and
a recycle step comprising recycling the regenerated
fluidized catalytic cracking catalyst to the fluidized
catalytic cracking step.
The fluidized catalytic cracking step is preferably
carried out as described herein before.
The separation step is preferably carried out with
the help of one or more cyclone separators and/or one or
more swirl tubes. Suitable ways of carrying out the
separation step are for example described in the Handbook
titled "Fluid Catalytic Cracking; Design, Operation, and
Troubleshooting of FCC Facilities" by Reza Sadeghbeigi,
published by Gulf Publishing Company, Houston Texas
(1995), especially pages 219-223 and the Handbook "Fluid
Catalytic Cracking technology and operations", by Joseph
W. Wilson, published by Pennell Publishing Company
(1997), chapter 3, especially pages 104-120, and chapter
6, especially pages 186 to 194, herein incorporated by
reference.
In addition the separation step may further comprise
a stripping step. In such a stripping step the spent
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fluidized catalytic cracking catalyst may be stripped to
recover the products absorbed on the spent fluidized
catalytic cracking catalyst before the regeneration step.
These products may be recycled and added to a stream
comprising one or more cracked products obtained from the
catalytic cracking step.
The regeneration step preferably comprises
contacting the spent fluidized catalytic cracking
catalyst with an oxygen containing gas in a regenerator
at a temperature of equal to or more than 550 C to
produce a regenerated fluidized catalytic cracking
catalyst, heat and carbon dioxide. During the
regeneration coke, that can be deposited on the catalyst
as a result of the fluidized catalytic cracking reaction,
is burned off to restore the catalyst activity.
The oxygen containing gas may be any oxygen
containing gas known to the skilled person to be suitable
for use in a regenerator. For example the oxygen
containing gas may be air or oxygen-enriched air. By
oxygen enriched air is herein understood air comprising
more than 21 vol. % oxygen (02), more preferably air
comprising equal to or more than 22 vol. % oxygen, based
on the total volume of air.
The heat produced in the exothermic regeneration
step is preferably employed to provide energy for the
endothermic catalytic cracking step. In addition the heat
produced can be used to heat water and/or generate steam.
The steam may be used elsewhere in the refinery, for
example as a liftgas in a riser reactor.
Preferably the spent fluidized catalytic cracking
catalyst is regenerated at a temperature in the range
from equal to or more than 575 C, more preferably from
equal to or more than 600 C, to equal to or less than
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950 C, more preferably to equal to or less than 850 C.
Preferably the spent fluidized catalytic cracking
catalyst is regenerated at a pressure in the range from
equal to or more than 0.5 bar absolute to equal to or
less than 10 bar absolute (0.05 MegaPascal to
1 MegaPascal), more preferably from equal to or more than
1.0 bar absolute to equal to or less than 6 bar absolute
(0.1 MegaPascal to 0.6 MegaPascal).
The regenerated fluidized catalytic cracking
catalyst can be recycled to the fluidized catalytic
cracking step. In a preferred embodiment a side stream of
make-up fluidized catalytic cracking catalyst is added to
the recycle stream to make-up for loss of fluidized
catalytic cracking catalyst in the reaction zone and
regenerator.
In the process according to the invention one or
more cracked products are produced. In a preferred
embodiment this/these one or more cracked products is/are
subsequently fractionated to produce one or more product
fractions.
Fractionation may be carried out in any manner known
to the skilled person in the art to be suitable for
fractionation of products from a catalytic cracking unit.
For example the fractionation may be carried out as
described in the Handbook titled "Fluid Catalytic
Cracking technology and operations", by Joseph W. Wilson,
published by Pennell Publishing Company (1997), pages 14
to 18, and chapter 8, especially pages 223 to 235, herein
incorporated by reference.
In a further embodiment at least one of the one or more
product fractions obtained by fractionation are subsequently
hydrotreated with a source of hydrogen, preferably in the
presence of a hydrotreatment catalyst to produce a
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hydrotreated product fraction. The hydrotreatment step may
for example comprise hydrodeoxygenation,
hydrodenitrogenation and/or hydrodesulphurization.
The one or more product fractions and/or the one or
more hydrotreated product fractions and/or any fractions
derived therefrom can conveniently be used as a biofuel
component. Such a biofuel component may conveniently be
blended with one or more other components to produce a
biofuel. Examples of such one or more other components
include anti-oxidants, corrosion inhibitors, ashless
detergents, dehazers, dyes, lubricity improvers and/or
mineral fuel components, but also conventional petroleum
derived gasoline, diesel and/or kerosene fractions.
By a biofuel is herein understood a fuel that is at
least party derived from a renewable energy source. The
biofuel may advantageously be used in the engine of a
transportation vehicle.
Examples:
Example 1:
About 30 grams of birch wood and 1.70 grams of
palladium acetate (Pd(OAc)2) were loaded into a Premex
Batch autoclave of 300 ml equipped with electrical
heating, stirrer, injection system, manometer and
temperature recording.
Stirring was started (300 rpm) and the autoclave was
closed. Stirring speed was increased to 750 rpm and a
solution of water (84 g), acetic acid (36 g) and
sulphuric acid (0.86 g) was injected. The autoclave was
pressurised with hydrogen (H2) to 4 MegaPascal (40 bar)
and subsequently heated in 70 min to 200 C. Reactor
pressure was subsequently increased to 8 MegaPascal (80
bar) by adding H2. The reaction was continued for 60 min,
occasionally H2 was added to maintain the pressure at 8
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MegaPascal. The reaction was stopped by rapid cooling to
room temperature (20 C), subsequently H2 was vented and
143.2 g of a first total product (including liquid, tar,
insoluble humins and catalyst) was collected. In a duplo
experiment applying identical conditions a second total
product (143.7 g) was prepared.
The first and second total product were combined. To
the combined total products methyl-tetrahydrofuran (m-
THF, 400 grams) was added. The mixture of methyl-
tetrahydrofuran and total products was stirred for 10
minutes at room temperature (20 C) and subsequently
filtered over a P3 glass filter to produce a filtrate and
a filter cake.
The filtrate was stored overnight (about 12 hours)
to facilitate phase separation and produce a top organic
layer and a bottom aqueous layer. The top organic layer
was collected.
The filter cake on the P3 filter were washed with m-
THF (300 g) to produce a m-THF solution. The m-THF
solution was combined with the top organic layer. The m-
THF was removed from the combination of top organic layer
and m-THF solution by vacuum distillation at 80 C, 20
mbar (2 KiloPascal) to produce 25.1 grams of a liquefied
product. To this liquefied product again 200 g m-THF was
added and this solution was subsequently washed with 10
w% of NaHCO3 (25 g) and water (25 g). The m-THF was again
removed by vacuum distillation at 80 C, 20 mbar (2
KiloPascal) to produce 23.4 grams of a brownish black
coloured viscous liquefied product.
The brownish black coloured viscous liquefied
product was characterized by SEC (RI/UV) (size exclusion
chromatography with UV and refractive index detectors),
Gas Chromatography and 13C-Nuc1ear Magnetic Resonance
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(13C-NMR). Elemental analysis of carbon, hydrogen and
oxygen resultedin C: 63.5 w% ( 0.3), H: 7.89 w% ( 0.1),
0 (by calculating the balance): 27.3 w% ( 0.5). The
brownish black coloured viscous liquefied product had a
H/Ceff of 0.85. Total acid number (TAN) was determined to
be ( 5) mg KOH/g. The above brownish black coloured
viscous liquefied product was used as a final liquefied
product. A heavy feed mixture comprising long residue was
used as a fluid hydrocarbon co-feed. The final liquefied
product was blended with the fluid hydrocarbon co-feed to
prepare a feed mixture containing a weight percentage of
wt% of the final liquefied product based on the total
weight of final liquefied product and the fluid
hydrocarbon co-feed. The feed mixture was injected into
15 the fluidized catalyst bed of a MAT-5000 fluidized
catalytic cracking unit. The fluidized catalyst bed
contained 10 grams of FCC equilibrium catalyst containing
ultra stable zeolite Y. The fluidized catalyst bed was
kept at 520 C and about 1 bar absolute (about 0.1
20 MegaPascal). The run included 7 experiments with 7
catalyst to feed weight ratios, namely catalyst/feed
weight ratios of 3, 4, 5, 6, 6.5, 7 and 8.
When compared with a feed consisting of 100wt% fluid
hydrocarbon co-feed, the feed mixture of final liquefied
product and fluid hydrocarbon co-feed is more reactive.
The feed mixture of final liquefied product and fluid
hydrocarbon co-feed shows a similar yield of valuable
products (gasoline, light cycle oil and LPG) and a
similar coke yield when compared to the reference feed.
Detailed results are provided in Table 1.
The results in table 1 have been normalized and
where applicable are calculated on a dry basis , i.e.
without H20.
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For the conversion calculation in table 1, first a
corrected weight of the total feed was calculated by
subtracting the weight of one water molecule for each
oxygen atom that has not been converted into CO or CO2
from the feed. Conversion is subsequently defined as the
weight in grams of drygas + LPG + gasoline + coke divided
by the corrected weight in grams of the total feed.
Hence, conversion = [Weight drygas + LPG + gasoline +
coke ] / [weight of the total feed - (weight of oxygen in
feed - weight of oxygen in CO and CO2) *18/16]*100%.
For the product yield calculation in table 1, first a
corrected weight of the total feed is calculated by
subtracting the weight of one water molecule for each oxygen
atom that has not been converted into CO or CO2 from the feed.
Subsequently the product yield is defined as the weight in
grams of the specific product divided by the corrected weight
in grams of the total feed. In other words, the product yield
distribution is on hydrocarbon basis. Hence, product yield for
product X = [weight X]/[weight of the total feed - (weight of
oxygen in feed - weight of oxygen in CO and CO2)*18/16]*100%
As water could not be measured experimentally on the
small scale of this example, it is calculated in table 1 from
the measured oxygen content of the feed and correcting for the
measured amounts of CO and CO2 formed. Assuming that there are
no partially converted oxygenates in the product, this
"assumed water yield" then gives the oxygen balance. Hence,
water = [(weight of oxygen in the feed - weight of oxygen in
CO and COA *18/16 ] / [weight of the total feed] * 100%.
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Table 1: product after fluidized catalytic cracking (FCC)
of a 100 wt% fluid hydrocarbon co-feed reference feed and
product after FCC of a feed mixture consisting of 20wt%
final liquefied product and 80wt% fluid hydrocarbon co-
feed (at a constant cat/oil ratio of 3.0 and a
temperature of 520 C)
20wt %
100 wt%
liquefaction
FHCF -
product and 80
reference
wt% FHCF
Oxygen content in feed
6.5
mixture (wt%)
Water (wt%) 6.9
Conversion at Cat/Oil 3
61.5 62.1
ratio
Gasoline yield (wt%) 45.1 44.2
LCO yield (wt%) 25.0 24.4
HCO yield (wt%) 7.3 7.0
Slurry oil yield (wt%) 6.1 6.1
Coke yield (wt%) 5.8 6.0
LPG yield (wt%) 9.0 10.0
Drygas yield (wt%) 1.6 1.9
CO2 yield (on C basis) 0.1 0.3
CO yield (wt%) (on C
0.1 0.2
basis)
FHCF=Fluid Hydrocarbon Co-Feed; LCO=Light Cycle Oil;
HCO=heavy Cycle Oil, LPG=liguefied Petroleum Gas.
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Example 2:
Furfural respectively furfuryl alcohol was used as an
artificial representative of a final liquefied product.
In addition a heavy feed mixture having a composition as
illustrated in tables 2a and 2b was used as a fluid
hydrocarbon co-feed.
Table 2a: Boiling range distribution of the fluid
hydrocarbon feed as determined by gas chromatography
according to ASTM D2887-06a.
wt% C wt% C wt% C
IBP 240 34 410 68 476
2 281 36 414 70 481
4 306 38 417 72 486
6 321 40 421 74 492
8 333 42 425 76 498
10 342 44 428 78 504
12 351 46 432 80 511
14 358 48 435 82 519
16 365 50 438 84 527
18 371 52 442 86 548
377 54 445 88 563
22 382 56 449 90 585
24 387 58 453 92 n.d.
26 392 60 458 94 n.d.
28 397 62 462 96 n.d.
401 64 467 98 n.d.
32 405 66 471 FBP n.d.
n.d: not determined
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Table 2b: Element analyses of fluid hydrocarbon co-feed
Feed description. [C] [H] [0] [S] [N]
[wt%] [wt%1 [wt%1 [ppm] [PPm]
fluid hydrocarbon
86.65% 12.65% 0.00% 3360 2220
co-feed
The furfural respectively furfuryl alcohol was blended
with the fluid hydrocarbon co-feed to prepare a feed
mixture containing a weight percentage of 20 wt% of
furfural respectively furfuryl alcohol based on the total
weight of the feed mixture. The feed mixture was
injected into the fluidized catalyst bed of a MAT-5000
fluidized catalytic cracking unit. The fluidized catalyst
bed contained 10 grams of FCC equilibrium catalyst
containing ultra stable zeolite Y. The fluidized catalyst
bed was kept at 520 C and about 1 bar absolute (about
0.1 MegaPascal). The catalyst/feed weight ratio was 3.
The effective molar ratio of hydrogen to carbon (H/Ceff)
of furfural respectively furfuryl alcohol is 0.0
respectively 0.4. By the effective molar ratio of
hydrogen to carbon (H/Ceff) is understood the molar ratio
of hydrogen to carbon after the theoretical removal of
all moles of oxygen, present in the oil on a dry basis,
via water production with hydrogen originally present,
presuming no nitrogen or sulphur present (H/Ceff = (H-
2*0)/C).
The feed mixture comprising furfural respectively
furfuryl alcohol shows a slight decrease of valuable
products (gasoline, light cycle oil and LPG) and a slight
increase in coke yield when compared to the reference
feed. Detailed results are provided in table 2c.
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The below results in table 2c have been normalized and
calculated on a dry basis , i.e. without H20.
For the conversion calculation, first a corrected weight
of the total feed is calculated by subtracting the
weight of one water molecule for each oxygen atom that
has not been converted into CO or CO2 from the feed.
Conversion is subsequently defined as the weight in
grams of drygas + LPG + gasoline + coke divided by the
corrected weight in grams of the total feed. Hence,
conversion = [Weight drygas + LPG + gasoline + coke ] /
[weight of the total feed - (weight of oxygen in feed -
weight of oxygen in CO and CO2)*18/16]*100%
For the product yield calculation, first a corrected
weight of the total feed is calculated by subtracting
the weight of one water molecule for each oxygen atom
that has not been converted into CO or CO2 from the
feed. Subsequently the product yield is defined as the
weight in grams of the specific product divided by the
corrected weight in grams of the total feed. In other
words, the product yield distribution is on hydrocarbon
basis. Hence, product yield for product X = [weight
X]/[weight of the total feed - (weight of oxygen in feed
- weight of oxygen in CO and CO2)*18/16]*100%
As water could not be measured experimentally on
this small scale, it is calculated from the measured
oxygen content of the feed and correcting for the
measured amounts of CO and CO2 formed. Assuming that
there are no partially converted oxygenates in the
product, this "assumed water yield" then gives the
oxygen balance. Hence, water = [(weight of oxygen in the
feed - weight of oxygen in CO and CO2) *18/16 ] /
[weight of the total feed] * 100%.
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Table 2c: product after fluidized catalytic cracking
(FCC) of a 100 wt% fluid hydrocarbon co-feed reference
feed and product after FCC of a feed mixture consisting
of 20wt% furfural resp. furfuryl alcohol and 80wt% fluid
hydrocarbon co-feed (at a constant cat/oil ratio of 3.0
and a temperature of 520 C)
100 wt% 20 wt% 20 wt%
FHCF- Furfural + Furfuryl
reference 80wt% FHCF alcohol +
80 wt% FHCF
Oxygen content in 0.0 6.7 6.5
feed (wt%)
Conversion (%) 61.9 61.1 62.5
Gasoline yield 45.1 40.9 41.7
(wt%)
LCO yield 24.4 24.6 23.5
(wt%)
HCO yield 7.4 7.3 6.8
(wt%)
Slurry oil yield 6.2 6.2 6.0
(wt%)
Coke yield (wt%) 5.7 8.8 8.9
LPG yield (wt%) 9.5 9.5 10.0
Gasoline+LCO+LPG 79.1 75.0 75.2
yield (wt%)
Drygas yield (wt%) 1.7 1.8 1.9
CO2 yield (wt% on 0.0 0.1 0.1
C basis)
CO yield (wt% on C 0.0 0.3 0.3
basis)
FHCF=Fluid Hydrocarbon Co-Feed; LCO=Light Cycle Oil;
HCO=heavy Cycle Oil, LPG=liguefied Petroleum Gas.
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Example 2, further shows the advantage of co-feeding a
complete final liquefied product, which is a mixture of
several components, to the FCC unit, rather than a feed
containing only furfural or furfuryl alcohol.
Example 3 :
Respectively tetrahydrofuran (THF), butanone and 2-
butanol were used as an artificial representative of a
final liquefied product. In addition a vacuum gas oil
(VGO) was used as a fluid hydrocarbon co-feed.
The tetrahydrofuran (THF), butanone or 2-butanol
respectively was blended with the fluid hydrocarbon co-
feed to prepare a feed mixture containing a weight
percentage of 20 wt% of tetrahydrofuran (THF), butanone
or 2-butanol respectively, based on the total weight of
the feed mixture. The feed mixture was injected into the
fluidized catalyst bed of a MAT-5000 fluidized catalytic
cracking unit. The fluidized catalyst bed contained 10
grams of FCC equilibrium catalyst containing ultra stable
zeolite Y. The fluidized catalyst bed was kept at 550 C
and about 1 bar absolute (about 0.1 MegaPascal). The
catalyst/feed weight ratio was 3.
The effective molar ratios of hydrogen to carbon (H/Ceff)
of tetrahydrofuran (THF), butanone and 2-butanol
respectively are 1.5, 1.5 and 2.0 respectively.
The feed mixture comprising respectively tetrahydrofuran
(THF), butanone or 2-butanol shows a similar yield of
valuable products (gasoline, light cycle oil and LPG) and
for butanone and 2-butanol even a decrease in coke yield
compared to the reference feed. Detailed results are
provided in table 3.
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Table 3: product after fluidized catalytic cracking (FCC) of
a 100 wt% fluid hydrocarbon co-feed reference feed and
product after FCC of a feed mixture consisting of 20wt% THF,
butanone or 2-butanol respectively and 80wt% fluid
hydrocarbon co-feed (at a constant cat/oil ratio of 3.0 and a
temperature of 550 C)
100 wt% 20wt% 20wt% 20wt%
FHCF- THF + Butanone 2-Butanol
referen 80 wt% + 80wt% + 80wt%
ce* FHCF* FHCF* FHCF*
Oxygen content 0.0 4.3 4.4 4.4
in feed (wt%)
Conversion (%) 59.1 61.9 60.6 63.7
Gasoline yield 40.7
37.0 39.3 39.8
(wt%)
LCO yield (wt%) 28.7 25.9 27.4 25.4
HCO yield (wt%) 7.0 6.7 6.8 6.2
Slurry oil yield 5.2
5.4 5.1 4.7
(wt%)
Coke yield (wt%) 3.9 5.6 4.0 3.2
LPG yield (wt%) 11.8 15.7 14.5 18.2
Gasoline+LCO+LPG 81.2
78.6 81.2 83.4
yield (wt%)
Drygas yield 2.8
3.7 2.8 2.5
(wt%)
CO2 yield (wt% 0.00
0.01 0.01 0.00
on C basis)
CO yield (wt% on 0.00
0.03 0.00 0.00
C basis)
FHCF=Fluid Hydrocarbon Co-Feed; LCO=Light Cycle Oil;
HCO=heavy Cycle Oil, LPG=liguefied Petroleum Gas.
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The above results in table 3 have been normalized and
calculated on a dry basis , i.e. without H20.
For the conversion calculation, first a corrected weight
of the total feed is calculated by subtracting the
weight of one water molecule for each oxygen atom that
has not been converted into CO or CO2 from the feed.
Conversion is subsequently defined as the weight in
grams of drygas + LPG + gasoline + coke divided by the
corrected weight in grams of the total feed. Hence,
conversion = [Weight drygas + LPG + gasoline + coke ] /
[weight of the total feed - (weight of oxygen in feed -
weight of oxygen in CO and CO2)*18/16]*100%
For the product yield calculation, first a corrected
weight of the total feed is calculated by subtracting
the weight of one water molecule for each oxygen atom
that has not been converted into CO or CO2 from the
feed. Subsequently the product yield is defined as the
weight in grams of the specific product divided by the
corrected weight in grams of the total feed. In other
words, the product yield distribution is on hydrocarbon
basis. Hence, product yield for product X = [weight
X]/[weight of the total feed - (weight of oxygen in feed
- weight of oxygen in CO and CO2)*18/16]*100%
As water could not be measured experimentally on
this small scale, it is calculated from the measured
oxygen content of the feed and correcting for the
measured amounts of CO and CO2 formed. Assuming that
there are no partially converted oxygenates in the
product, this "assumed water yield" then gives the
oxygen balance. Hence, water = [(weight of oxygen in the
feed - weight of oxygen in CO and CO2) *18/16 ] /
[weight of the total feed] * 100%.
