Note: Descriptions are shown in the official language in which they were submitted.
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PROCESS FOR THE PREPARATION OF A BIOFUEL AND/OR
BIOCHEMICAL
TECHNICAL FIELD OF THE INVENTION
The present invention relates to process for the preparation
of a biofuel and/or biochemical. In addition the present
invention provides processes to produce one or more cracked
products from a pyrolysis oil.
BACKGROUND OF THE INVENTION
With the diminishing supply of crude mineral oil, use of
renewable energy sources is becoming increasingly important
for the production of fuels and chemicals. These fuels and
chemicals from renewable energy sources are often referred to
as biofuels, respectively biochemicals. One of the advantages
of using renewable energy sources is that the CO2 balance is
more favourable as compared with a conventional feedstock of
a mineral source.
Biofuels and/or biochemicals derived from non-edible
renewable energy sources, such as lignocellulosic material,
are preferred as these do not compete with food production.
These biofuels and/or biochemicals are also referred to as
second generation biofuels and/or biochemicals.
Lignocellulosic material, such as wood, can be pyrolyized to
obtain a pyrolysis oil. It is currently believed, however,
that such pyrolysis oil cannot be converted in a simple,
direct or economically interesting manner, into biofuels
and/or biochemicals.
Ardiyanti et al. in their article titled "Process-product
studies on pyrolysis oil upgrading by hydrotreatment with
Ru/C catalysts", first presented at the AICHE 2009 spring
meeting in April 2009, mentioned that pyrolysis oil is not
suitable for the purpose of co-feeding into existing
refineries, either in hydrotreating or FCC units, because the
oil is not miscible with hydrocarbon feedstocks and shows a
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high tendency for coking, leading to blockage of feeding
lines and reactors. As an alternative a mild hydrotreating
process is suggested. The article describes a two step
hydrotreatment of a pyrolysis oil, obtained by fast pyrolysis
of forest residue. In the product two phases were formed,
viz, a black oil floating on top of a clear water layer. The
oxygen content of the oil was reduced by hydrodeoxygenation
to respectively 12.3 wt% and 11.5wt%. In the conclusion and
outlook, it is mentioned that FCC experiments with low-
residual product as co-feed are in progress to verify whether
the product is indeed suitable as a feedstock for refinery
units.
M.C. Samolada et al, in their article titled "Production of a
bio-gasoline by upgrading biomass flash pyrolysis liquids via
hydrogen processing and catalytic cracking", first published
in Fuel, vol. 77, no 14, pages 1667-1675, 1998, describe that
results of fluid catalytic cracking (FCC) of biomass flash
pyrolysis liquids are not encouraging due to high coking (8-
25wt%) and the low quality of the fuels obtained (about 20
wt% phenolics). They further noted that efforts towards
blending biomass flash pyrolysis liquids with petroleum
feedstocks prior to catalytic cracking were unsuccessful,
because of their minor miscibility with hydrocarbons. In the
article therefore a two-step process is proposed, including
thermal hydrotreatment and subsequent catalytic cracking of
biomass flash pyrolysis liquids. Thermal hydrotreatment is
said to serve as the stabilization step for the biomass
derived feedstock to FCC.
F. de Miguel Mercader et al, in their article titled
"Production of advanced biofuels: Co-processing of upgraded
pyrolysis oil in standard refinery units", Journal of Applied
Catalysis B: Environmental, volume 96, 2010, pages 57-66,
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describe that the direct co-processing of pyrolysis oil
itself in standard refinery units is problematic.
A. Oasmaa et al, in their article titled "Fast pyrolysis of
Forestry Residue 1. Effect of extractives on phase separation
of pyrolysis liquids", first published in Energy & Fuels,
volume 17, number 1, 2003, pages 1-12, describes that a two-
phase product is obtained by fast pyrolysis processes of
forestry residues. It is stated that the top phase differs
from the bottom phase, containing significant amount of
hydrocarbon-soluble extractives and low amount of water-
soluble polar compounds. Further the article indicates that
the top phase has a significantly higher heating value than
the bottom phase.
It would be an advancement in the art if a pyrolysis oil,
which essentially has not been pretreated or upgraded by
hydrotreatment or hydrodeoxygenation, could be used for the
production of biofuels and/or biochemicals.
It would also be an advancement in the art if a process could
be provided that allows direct processing of a pyrolysis oil,
which essentially has not been pretreated or upgraded by
hydrotreatment or hydrodeoxygenation, in an FCC unit.
SUMMARY OF THE INVENTION
Surprisingly such a process has now been found.
Accordingly the present invention provides a process for
the preparation of a biofuel and/or biochemical from a
pyrolysis oil, which pyrolysis oil essentially has not
been pretreated or upgraded by hydrotreatment and/or
hydrodeoxygenation, comprising the steps of
i) contacting the pyrolysis oil with a catalytic cracking
catalyst at a temperature of equal to or more than 400 C
in the presence of a hydrocarbon co-feed to produce one or
more cracked products;
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ii) fractionating one or more of the cracked products to
produce one or more product fractions;
iii) using one or more of the product fractions to produce
a biofuel and/or biochemical.
Step i) can be carried out in various manners and
accordingly the current invention also provides several
processes for producing the one or more cracked products.
In a first embodiment the present invention provides a
process to produce one or more cracked products comprising
the steps of
la) providing a pyrolysis oil, which pyrolysis oil
essentially has not been pretreated or upgraded by
hydrotreatment and/or hydrodeoxygenation, or a part
thereof containing in the range from equal to or more than
0 wt% to equal to or less than 25 wt% n-hexane
extractives;
lb) contacting the pyrolysis oil or the part thereof with
a catalytic cracking catalyst at a temperature of more
than 400 C in the presence of a hydrocarbon co-feed to
produce one or more cracked products.
In a second embodiment the present invention provides a
process to produce one or more cracked products comprising
the steps of
2a) providing a bottom phase of a pyrolysis oil, which
pyrolysis oil essentially has not been pretreated or
upgraded by hydrotreatment and/or hydrodeoxygenation, or a
part thereof;
2b) contacting the bottom phase of the pyrolysis oil or
the part thereof with a catalytic cracking catalyst at a
temperature of equal to or more than 400 C in the presence
of a hydrocarbon co-feed to produce one or more cracked
products.
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In a third embodiment the present invention provides a
process to produce one or more cracked products comprising
the steps of
3a) providing a pyrolysis oil, which pyrolysis oil
essentially has not been pretreated or upgraded by
hydrotreatment and/or hydrodeoxygenation, or a part
thereof;
3b) contacting the pyrolysis oil or the part thereof with
a catalytic cracking catalyst at a temperature of equal to
or more than 400 C in the presence of a hydrocarbon co-
feed to produce one or more cracked products; wherein the
combination of the pyrolysis oil or part thereof and the
hydrocarbon co-feed has an overall molar ratio of hydrogen
to carbon (H/C) of equal to or more than 1 to 1 (1/1).
The processes of the invention advantageously allow for
direct processing of pyrolysis oil, which essentially has
not been pretreated or upgraded by hydrotreatment and/or
hydrodeoxygenation, in a catalytic cracking unit, such as
for example an FCC unit. The process of the invention
advantageously allows the pyrolysis oil to be processed in
a catalytic cracking unit without the necessity of such a
hydrotreatment and/or hydrodeoxygenation to substantially
lower the oxygen content.
Surprisingly it has been found that in the processes
according to the invention the pyrolysis oil is sufficiently
miscible with a hydrocarbon co-feed such that co-processing
has been shown to be feasible.
In addition the hydrocarbon co-feed can advantageously
provide the hydrogen necessary to convert the oxygen in the
pyrolysis oil into water.
Further it has surprisingly been found that catalytic
cracking of a pyrolysis oil in the presence of a hydrocarbon
co-feed as explained below leads to a synergistic effect,
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where the coke make during the catalytic cracking step is
less than what would be expected on the basis of the sum of
the coke make for each feed when catalytically cracked
separately.
The process is further advantageous in that going from the
pyrolysis oil feed to the catalytic cracking products an
extensive reduction in Total Acid Number (TAN) is
obtained.
As no upgrading via any hydrotreatment is needed a more
simple and more economic process is obtained than the
processes of the prior art. Hence, the processes according to
the invention advantageously allow a simple, direct and
economically interesting route towards the conversion of
pyrolysis oil into biofuels and/or biochemicals.
DETAILED DESCRIPTION OF THE INVENTION
In step i) a pyrolysis oil is contacted with a catalytic
cracking catalyst at a temperature of equal to or more
than 400 C in the presence of a hydrocarbon co-feed to
produce one or more cracked products.
By a pyrolysis oil is herein understood an oil obtained by
pyrolysis. By such pyrolysis oil is preferably further
understood an oil obtained by pyrolysis that has essentially
not been pretreated or upgraded by hydrotreatment and/or
hydrodeoxygenation. An hydrotreatment and/or
hydrodeoxygenation to substantially reduce the oxygen content
of the pyrolysis oil can advantageously be avoided in the
processes according to the invention.
By a pyrolysis oil is further understood a "whole" pyrolysis
oil or a part thereof. As illustrated below, in certain
embodiments it is preferred to use specific parts of a
pyrolysis oil.
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Preferably the pyrolysis oil is derived from a renewable
energy source, that is, preferably the pyrolysis oil is
obtained by pyrolysis of a renewable energy source.
Any renewable energy source known to the skilled person to be
suitable for providing pyrolysis oil may be used. Preferably
the renewable energy source comprises a cellulosic material,
more preferably a lignocellulosic material. Hence, preferably
the pyrolysis oil is a pyrolysis oil derived from a
cellulosic material, more preferably a lignocellulosic
material.
Any suitable cellulose-containing material may be used as
renewable energy source in the pyrolysis. The cellulosic
material 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. In a more
preferred embodiment the pyrolysis oil is obtained by
pyrolysis of wood and/or a wood-related material, such as
forestry residue, wood chips and/or saw dust. In another
preferred embodiment, the wood and/or wood-related material
contains bark and/or needles. Most preferably the pyrolysis
oil is obtained by pyrolysis of wood and/or a wood-related
material containing pine wood or forestry residue.
By pyrolysis is herein understood the thermal decomposition
of a, preferably renewable, energy source at a pyrolysis
temperature of equal to or more than 350 C. The concentration
of oxygen is preferably less than the concentration required
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for complete combustion. More preferably the pyrolysis is
carried out in the essential absence of non-in-situ-generated
oxygen. A limited amount of oxygen may be generated in-situ
during the pyrolysis process. Preferably pyrolysis is carried
out in an atmosphere containing equal to or less than 5 vol.%
oxygen, more preferably equal to or less than 1 vol.% oxygen
and most preferably equal to or less than 0.1 vol.% oxygen.
In a most preferred embodiment pyrolysis is carried out in
the essential absence of oxygen.
The pyrolysis temperature is preferably equal to or more than
350 C, more preferably equal to or more than 400 C and most
preferably equal to or more than 450 C. The pyrolysis
temperature is further preferably equal to or less 800 C,
more preferably equal to or less than 700 C and most
preferably equal to or less than 650 C.
The pyrolysis pressure may vary widely. For practical
purposes a pressure in the range from 0.1 to 5 bar (0.01 to
0.5 MegaPascal), more preferably in the range from 1 to 2 bar
(0.1 to 0.2 MegaPascal) is preferred. Most preferred is an
atmospheric pressure (about 1 bar or 0.1 MegaPascal).
In a preferred embodiment the pyrolysis oil is provided by
so-called fast or flash pyrolysis of the renewable energy
source. Such fast or flash pyrolysis preferably comprises
rapidly heating the renewable energy source for a very short
time and then rapidly reducing the temperature of the primary
products before chemical equilibrium can occur.
In a preferred embodiment the pyrolysis oil is provided by
pyrolysis of the renewable energy source comprising the steps
of
- heating the renewable energy source in the essential
absence of oxygen to a temperature equal to or more than
350 C, preferably equal to or more than 400 C, and preferably
equal to or less than 800 C within 3 seconds, preferably
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within 2 seconds, more preferably within 1 second and most
preferably within 0.5 seconds;
- maintaining the renewable energy source at a temperature
equal to or more than 350 C, preferably equal to or more than
400 C, and preferably equal to or less than 800 C for between
0.03 and 2.0 seconds, preferably between 0.03 and 0.60
seconds, to produce one or more pyrolysis products;
- cooling the pyrolysis products to below 350 C within 1
second, and preferably within 0.5 seconds;
- obtaining the pyrolysis oil from the pyrolysis products.
Examples of suitable fast or flash pyrolysis processes to
provide the pyrolysis oil are described in A. Oasmaa et al,
"Fast pyrolysis of Forestry Residue 1. Effect of extractives
on phase separation of pyrolysis liquids", Energy & Fuels,
volume 17, number 1, 2003, pages 1-12; and A. Oasmaa et al,
Fast pyrolysis bio-oils from wood and agricultural residues,
Energy & Fuels, 2010, vol. 24, pages 1380-1388; US4876108;
US5961786; and US5395455, which are herein incorporated by
reference.
After pyrolysis of the renewable energy source, pyrolysis
products are obtained that may contain gas, solids (char),
one or more oily phase(s), and optionally an aqueous phase.
The oily phase(s) will hereafter be referred to as pyrolysis
oil. The pyrolysis oil can be separated from the pyrolysis
products by any method known by the skilled person to be
suitable for that purpose. This includes conventional methods
such as filtration, centrifugation, cyclone separation,
extraction, membrane separation and/or phase separation.
The pyrolysis oil may include for example carbohydrates,
olefins, paraffins, oxygenates (such as aldehydes and/or
carboxylic acids) and/or optionally some residual water.
Preferably, the pyrolysis oil comprises carbon in an amount
equal to or more than 25 wt%, more preferably equal to or
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more than 35wt%, and preferably equal to or less than 70 wt%,
more preferably equal to or less than 60 wt% (on a dry
basis).
The pyrolysis oil further preferably comprises hydrogen in an
amount equal to or more than 1 wt%, more preferably equal to
or more than 5wt%, and preferably equal to or less than 15
wt%, more preferably equal to or less than 10 wt% (on a dry
basis).
The pyrolysis oil further preferably comprises oxygen in an
amount equal to or more than 25 wt%, more preferably equal to
or more than 35wt%, and preferably equal to or less than 70
wt%, more preferably equal to or less than 60 wt%. Such
oxygen content is preferably defined on a dry basis. By a dry
basis is understood excluding water.
The pyrolysis oil may also contain nitrogen and/or sulphur.
If nitrogen is present, the pyrolysis oil preferably
comprises nitrogen in an amount equal to or more than 0.001
wt%, more preferably equal to or more than 0.1 wt%, and
preferably equal to or less than 1.5 wt%, more preferably
equal to or less than 0.5 wt% (on a dry basis).
If sulphur is present, the pyrolysis oil preferably comprises
sulphur in an amount equal to or more than 0.001 wt%, more
preferably equal to or more than 0.01 wt%, and preferably
equal to or less than 1 wt%, more preferably equal to or less
than 0.1 wt% (on a dry basis).
If present, the pyrolysis oil preferably comprises water in
an amount equal to or more than 0.1 wt%, more preferably
equal to or more than lwt%, still more preferably equal to or
more than 5 wt%, and preferably equal to or less than 55 wt%,
more preferably equal to or less than 45 wt%, and still more
preferably equal to or less than 35 wt%, still more
preferably equal to or less than 30 wt%, most preferably
equal to or less than 25 wt%.
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Preferably, the pyrolysis oil of the present invention
comprises aldehydes in an amount equal to or more than 5 wt%,
more preferably equal to or more than lOwt%, and preferably
equal to or less than 30 wt%, more preferably equal to or
less than 20 wt%.
Preferably, the pyrolysis oil comprises carboxylic acids in
an amount equal to or more than 5 wt%, more preferably equal
to or more than lOwt%, and preferably equal to or less than
25 wt%, more preferably equal to or less than 15 wt%.
Preferably, the pyrolysis oil comprises carbohydrates in an
amount equal to or more than 1 wt%, more preferably equal to
or more than 5wt%, and preferably equal to or less than 20
wt%, more preferably equal to or less than 10 wt%.
Preferably, the pyrolysis oil comprises phenols in an amount
equal to or more than 0.1 wt%, more preferably equal to or
more than 2wt%, and preferably equal to or less than 10 wt%,
more preferably equal to or less than 5 wt%.
Preferably, the pyrolysis oil comprises furfurals in an
amount equal to or more than 0.1 wt%, more preferably equal
to or more than lwt%, and preferably equal to or less than 10
wt%, more preferably equal to or less than 4 wt%.
By a hydrocarbon co-feed is herein understood a co-feed
that contains one or more hydrocarbon compounds (i.e.
compounds that contain both hydrogen and carbon). The
hydrocarbon co-feed is preferably a liquid hydrocarbon co-
feed. By a liquid hydrocarbon co-feed is understood a
hydrocarbon co-feed which is fed to a catalytic cracking
unit essentially in the liquid phase.
The hydrocarbon co-feed can be any hydrocarbon feed known
to the skilled person to be suitable as a feed for an
catalytic cracking unit. The hydrocarbon co-feed can for
example be obtained from a conventional crude oil (also
sometimes referred to as a petroleum oil or mineral oil),
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an unconventional crude oil (that is oil produced or
extracted using techniques other than the traditional oil
well method) or a renewable oil (that is oil derived from
a renewable source).
Preferably the hydrocarbon co-feed is derived from a,
preferably conventional, crude oil.
In one embodiment the 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, Midway
Sunset crude oil or Tapis crude oil.
More preferably the hydrocarbon co-feed comprises a
fraction of a, preferably conventional, crude oil or
renewable oil. Examples of fractions of a crude oil that
can be used as a hydrocarbon co-feed include straight run
(atmospheric) gas oils, flashed distillate, vacuum gas
oils (VGO), coker gas oils, atmospheric residue ("long
residue") and vacuum residue ("short residue") and/or
mixtures thereof. In one preferred embodiment the
hydrocarbon co-feed comprises comprises a long residue
and/or a vacuum gas oil.
In one embodiment the hydrocarbon co-feed has an Initial
Boiling Point (IBP) as measured by means distillation
based on ASTM D2887-06a at a pressure of 1 bar absolute
(0.1 MegaPascal) of equal to or more than 100 C,
preferably equal to or more than 150 C. An example of such
a hydrocarbon co-feed is vacuum gas oil.
In a second embodiment the hydrocarbon co-feed has an
Initial Boiling Point (IBP) as measured by means of
distillation based on ASTM D2887-06a at a pressure of 1
bar absolute (0.1 MegaPascal) equal to or more than 220 C,
more preferably equal to or more than 240 C. An example of
such a hydrocarbon co-feed is long residue.
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In a further preferred embodiment equal to or more than 70
wt%, preferably equal to or more than 80 wt%, more
preferably equal to or more than 90 wt% and still more
preferably equal to or more than 95 wt% of the hydrocarbon
co-feed boils in the range from equal to or more than
150 C to equal to or less than 600 C, as measured by means
of a simulated distillation by gas chromatography based on
ASTM D2887-06a.
The composition of the hydrocarbon co-feed may vary
widely. The hydrocarbon co-feed may for example contain
paraffins, olefins and aromatics.
In a preferred embodiment the hydrocarbon co-feed comprises
equal to or more than 8 wt% elemental hydrogen, more
preferably more than 12 wt% elemental hydrogen. A high
content of elemental hydrogen, such as a content of equal to
or more than 8 wt%, allows the hydrocarbon co-feed to act as
a cheap hydrogen donor in the catalytic cracking process.
Without wishing to be bound by any kind of theory it is
further believed that a higher weight ratio of hydrocarbon
co-feed to pyrolysis will enable more upgrading of the
pyrolysis oil by hydrogen transfer reactions.
In another embodiment at least part of the hydrocarbon co-
feed comprises a paraffinic hydrocarbon co-feed. Examples
of such paraffinic 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. The Fischer-Tropsch hydrocarbon stream may
optionally have been obtained by hydroisomerisation of
hydrocarbons directly obtained in a Fischer-Tropsch
hydrocarbon synthesis reaction.
The hydrocarbon co-feed according to the invention
preferably comprises equal to or more than 1 wt%
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paraffins, more preferably equal to or more than 2 wt%
paraffins, and most preferably equal to or more than 5 wt%
paraffins, and preferably equal to or less than 99 wt%
paraffins, more preferably equal to or less than 50 wt%
paraffins, and most preferably equal to or less than 20
wt% paraffins, wherein by paraffins both normal-, cyclo-
and branched-paraffins are understood.
In an especially preferred embodiment the hydrocarbon co-
feed contains:
1) a fraction of a crude oil, such as for example
(atmospheric) gas oils, flashed distillate, vacuum gas
oils (VGO), coker gas oils, atmospheric residue ("long
residue") and vacuum residue ("short residue"); in
combination with
2) a Fischer-Tropsch derived hydrocarbon stream and/or a
hydrotreater product.
In an especially preferred process the total feed
comprises
- from equal to or more than 0 wt% to equal to or less
than 99 wt%, preferably from equal to or more than 0 wt%
to equal to or less than 20 wt% of a Fischer-Tropsch
derived hydrocarbon stream and/or a hydrotreater product;
- from equal to or more than 0 wt% to equal to or less
than 99 wt%, preferably from equal to or more than 0 wt%
to equal to or less than 79 wt% of a fraction of a crude
oil, such as for example (atmospheric) gas oils, flashed
distillate, vacuum gas oils (VGO), coker gas oils,
atmospheric residue ("long residue") and vacuum residue
("short residue")
- from equal to or more than 1 wt% to equal to or less
than 35 wt%, preferably from equal to or more than 1 wt%
to equal to or less than 20 wt% of a pyrolysis oil or a
part thereof as described herein.
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The weight ratio of the pyrolysis oil to hydrocarbon co-
feed may vary widely. For ease of co-processing the
hydrocarbon co-feed and the pyrolysis oil are preferably
being fed to a catalytic cracking unit in a weight ratio
of hydrocarbon co-feed to pyrolysis oil of 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 hydrocarbon co-feed to pyrolysis oil is
preferably equal to or less than 99.9 to 0.1 (99.9:0.1).
Hence, the amount of pyrolysis oil present, based on the
total weight of pyrolysis oil and hydrocarbon co-feed, is
preferably equal to or less than 30 wt%, more preferably
equal to or less than 20 wt%, most preferably equal to or
less than 10 wt% and even more preferably equal to or less
than 5 wt%. For practical purposes amount of pyrolysis oil
present, based on the total weight of pyrolysis oil and
hydrocarbon co-feed, is preferably equal to or more than
0.1 wt%.
Preferably step i) is carried out in a catalytic cracking
unit, more preferably in a fluidized catalytic cracking
(FCC) unit.
The hydrocarbon co-feed and the pyrolysis oil can be mixed
prior to entry into a catalytic cracking unit or they can
be added separately, at the same location or different
locations to the catalytic cracking unit.
In one embodiment the hydrocarbon co-feed and the
pyrolysis oil are not mixed together prior to entry into a
catalytic cracking unit. In this embodiment the
hydrocarbon co-feed and the pyrolysis oil may be fed
simultaneously (that is at one location) to the catalytic
cracking unit, and mixed upon entry of the catalytic
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cracking unit; or, alternatively, the hydrocarbon co-feed
and the pyrolysis oil may be added separately (at
different locations) to the catalytic cracking unit.
Catalytic cracking units can have multiple feed inlet
nozzles. The pyrolysis oil and the hydrocarbon co-feed can
therefore be processed in the catalytic cracking unit even
if both components are not miscible by feeding each
component through a separate feed inlet nozzle.
It was, however, advantageously found that the pyrolysis
oil can be mixed with a, preferably liquid, hydrocarbon
co-feed. When mixing the pyrolysis oil with the,
preferably liquid, hydrocarbon co-feed, the pyrolysis oil
preferably comprises less than 25wt% n-hexane extractives;
comprises a bottom phase of a pyrolysis oil; and/or is a
pyrolysis oil which when combined with a, preferably
liquid, hydrocarbon co-feed provides a combination that
has a molar ratio of hydrogen to carbon of at least 1 to
1. In another preferred embodiment therefore the
hydrocarbon co-feed and the pyrolysis oil are mixed
together prior to entry into a catalytic cracking unit to
provide a feed mixture comprising the hydrocarbon co-feed
and the pyrolysis oil. In this embodiment the hydrocarbon
co-feed and the pyrolysis oil are preferably mixed at a
temperature in the range between equal to or more than
10 C, more preferably equal to or more than 20 C, still
more preferably equal to or more than 30 C and most
preferably preferably equal to or more than 40 C, and
equal to or less than 80 C, more preferably equal to or
less than 70 C and most preferably equal to or less than
60 C. When the feed mixture contains VG0 as a hydrocarbon
co-feed, a slightly lower temperature of equal to or more
than 10 C may be preferred, whereas when the feed mixture
contains Long Residue a slightly higher temperature of
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equal to or more than 30 may be preferred. Most
preferably, when the feed mixture contains VG0 as a
hydrocarbon co-feed, a temperature in the range from 10 C
to 25 C is preferred, whereas when the feed mixture
contains Long Residue a temperature in the range from 30 C
to 50 C is preferred.
The hydrocarbon co-feed and the pyrolysis oil may be mixed
in any manner known to be skilled person to be suitable
for such purpose. Preferably the hydrocarbon co-feed and
the pyrolysis oil are mixed by means of static mixing,
shaking and/or stirring.
The feed mixture may optionally be held in a stirred or
non-stirred feed vessel before being forwarded to a
catalytic cracking unit. It is one of the advantages of
the process according to the present invention that also a
non-stirred feed vessel may be used, thereby obtaining a
more simple operation process and/or saving upon
construction, energy and/or maintenance costs. In addition
experiments indicate that use of a non-stirred feed vessel
may surprisingly increase yields and reduce coking.
Preferably the feed mixture is held in such a stirred or
non-stirred feed vessel at a temperature in the range
between equal to or more than 10 C, more preferably equal
to or more than 20 C, still more preferably equal to or
more than 30 C and most preferably preferably equal to or
more than 40 C, and equal to or less than 80 C, more
preferably equal to or less than 70 C and most preferably
equal to or less than 60 C.
When the feed mixture contains VG0 as a hydrocarbon co-
feed, a slightly lower temperature of equal to or more
than 10 C may be preferred, whereas when the feed mixture
contains Long Residue a slightly higher temperature of
equal to or more than 30 may be preferred. Most
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preferably, when the feed mixture contains VG0 as a
hydrocarbon co-feed, a temperature in the range from 10 C
to 25 C is preferred, whereas when the feed mixture
contains Long Residue a temperature in the range from 30 C
to 50 C is preferred.
Preferably the feed mixture is injected into the catalytic
cracking unit, optionally after being held in a stirred or
non-stirred feed vessel, at a temperature in the range
between equal to or more than 10 C, more preferably equal
to or more than 20 C, still more preferably equal to or
more than 30 C and most preferably preferably equal to or
more than 40 C, and equal to or less than 80 C, more
preferably equal to or less than 70 C and most preferably
equal to or less than 60 C. When the feed mixture contains
VG0 as a hydrocarbon co-feed, a slightly lower temperature
of equal to or more than 10 C may be preferred, whereas
when the feed mixture contains Long Residue a slightly
higher temperature of equal to or more than 30 may be
preferred. Most preferably, when the feed mixture contains
VG0 as a hydrocarbon co-feed, a temperature in the range
from 10 C to 25 C is preferred, whereas when the feed
mixture contains Long Residue a temperature in the range
from 30 C to 50 C is preferred.
Subsequently the feed mixture may be contacted with the
catalytic cracking catalyst in a catalytic cracking unit.
The catalytic cracking catalyst can be any catalyst known
to the skilled person to be suitable for use in a cracking
process. Preferably, the catalytic cracking catalyst
comprises a zeolitic component. In addition, the 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
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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 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 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.
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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 catalytic cracking catalyst.
The pyrolysis oil is preferably contacted with the
catalytic cracking catalyst in the presence of the
hydrocarbon co-feed in a reaction zone, which reaction
zone is preferably an elongated tube-like reactor,
preferably oriented in an essentially vertical manner. The
pyrolysis oil, the hydrocarbon co-feed and the cracking
catalyst may each independently flow in an upward
direction or downward direction.
Preferably, however, the pyrolysis oil and the hydrocarbon
co-feed flow co-currently in the same direction. The
catalytic cracking catalyst can be contacted in a
cocurrent-flow countercurrent-flow or cross-flow
configuration with such a flow of the pyrolysis oil and
the hydrocarbon co-feed. Preferably the catalytic cracking
catalyst is contacted in a cocurrent flow configuration
with a cocurrent flow of the pyrolysis oil and the liquid
hydrocarbon cofeed.
In a preferred embodiment step i) comprises:
- a catalytic cracking step wherein the pyrolysis oil and
the hydrocarbon co-feed are cracked in a reaction zone in
the presence of the catalytic cracking catalyst to produce
one or more cracked products and a spent catalytic
cracking catalyst;
- a regeneration step, wherein spent catalytic cracking
catalyst is regenerated to produce a regenerated catalytic
cracking catalyst; and
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- a recycle step, wherein the regenerated catalytic
cracking catalyst is recycled to the catalytic cracking
step.
The temperature in the catalytic cracking step preferably
ranges from equal to or more than 450 C to equal to or
less than 650 C, more preferably from equal to or more
than 480 C to equal to or less than 600 C, and most
preferably from equal to or more than 480 C to equal to
or less than 560 C.
The pressure in the catalytic cracking step preferably
ranges from equal to or more than 0.5 bar to equal to or
less than 10 bar (0.05 MPa-1 MPa), more preferably from
equal to or more than 1.0 bar to equal to or less than 6
bar (0.15 MPa to 0.6 MPa).
The residence time of the catalytic cracking catalyst in
the reaction zone, where the catalytic cracking takes
place, preferably ranges from equal to or more than 0.1
seconds to equal to or less than 15 seconds, more
preferably from equal to or more than 0.5 seconds to equal
to or less than 10 seconds.
Preferably, the mass ratio of the catalytic cracking
catalyst to the total feed of pyrolysis oil and
hydrocarbon co-feed ranges from equal to or more than 3 to
equal to or less than 20. Preferably, the mass ratio of
the catalytic cracking catalyst to the total feed of
pyrolysis oil and hydrocarbon co-feed is at least 3.5. The
use of a higher catalyst to feed mass ratio results in an
increase in conversion.
In a preferred embodiment, the catalytic cracking step
further comprises a stripping step. The spent catalyst may
be stripped to recover the products absorbed on the spent
catalyst before the regeneration step. These products may
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be recycled and added to the product stream obtained from
the catalytic cracking step.
The regeneration step preferably comprises burning off of
coke, deposited on the catalyst as a result of the
catalytic cracking reaction, to restore the catalyst
activity by combusting the cracking catalyst in the
presence of an oxygen-containing gas in a regenerator. The
heat generated in the exothermic regeneration step is
preferably employed to provide energy for the endothermic
catalytic cracking step. The process according to the
invention advantageously allows for a sufficient amount of
coke deposited on the catalytic cracking catalyst such
that the exothermic regeneration step can be carried out
without supplying additional heat.
The regeneration temperature preferably ranges from equal
to or more than 575 C to equal to or less than 900 C,
more preferably from equal to or more than 600 C to equal
to or less than 850 C. The pressure in the regenerator
preferably ranges from equal to or more than 0.5 bar to
equal to or less than 10 bar (0.05 MPa to 1 MPa), more
preferably from equal to or more than 1.0 bar to equal to
or less than 6 bar (0.1 MPa to 0.6 MPa).
The regenerated catalytic cracking catalyst can be
recycled to the catalytic cracking step. In a preferred
embodiment a side stream of make-up catalyst is added to
such a recycle stream of regenerated catalytic cracking
catalyst to make-up for loss of catalyst in the reaction
zone and regenerator.
As indicated above, step i) can be carried out in various
manners.
In a first embodiment the part of or whole pyrolysis oil
in step i) comprises a pyrolysis oil or a part thereof
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containing equal to or less than 25 wt% n-hexane
extractives.
In a first embodiment step i) therefore comprises a
process to produce one or more cracked products comprising
the steps of
la) providing a pyrolysis oil or a part thereof containing
in the range from equal to or more than 0 wt% to equal to
or less than 25 wt% n-hexane extractives;
lb) contacting the pyrolysis oil or the part thereof with
a catalytic cracking catalyst at a temperature of more
than 400 C in the presence of a hydrocarbon co-feed to
produce one or more cracked products.
By n-hexane extractives are herein understood compounds
extractable from the pyrolysis oil into n-hexane (normal-
hexane) at a temperature of about 20 C and a pressure of
about 1 bar absolute (0.1 MegaPascal). n-Hexane
extractives can be determined according to Oasmaa et al,
in their article titled "Fast Pyrolysis of Forestry
Residue. 1. Effect of Extractives on Phase Separation of
Pyrolysis Liquids, volume 17, number 1, January /February
2003, page 5 and page 11 as herein incorporated by
reference.
Examples of such n-hexane extractives include rubbers,
tannins, flavonoids, lignin monomers (such as guaiacol and
catechol derivatives), lignin dimers (stilbenes), resin,
waxes, sterols, vitamins and fungi.
Preferably the pyrolysis oil or a part thereof contains in
the range from equal to or more than 0 wt% to equal to or
less than 25 wt% n-hexane extractives, more preferably in
the range from equal to or more than 0 wt% to equal to or
less than 20 wt% n-hexane extractives, still more
preferably in the range from equal to or more than 0 wt%
to equal to or less than 15 wtt n-hexane extractives,
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still more preferably in the range from equal to or more
than 0 wt% to equal to or less than 10 wt% n-hexane
extractives, even still more preferably in the range from
equal to or more than 0 wt% to equal to or less than 6 wt%
n-hexane extractives, and most preferably in the range
from equal to or more than 0 wt% to equal to or less than
3 wt% n-hexane extractives. For practical purposes a lower
limit of equal to or more than 0.01 ppm by weight may be
considered more preferably in the above ranges, and a
lower limit of equal to or more than 0.1 ppm by weight may
be considered most preferably in the above ranges.
In another, especially preferred embodiment the pyrolysis
oil or part thereof contains essentially no n-hexane
extractives.
The pyrolysis oil or part thereof, containing equal to or
less than 25 wt% n-hexane extractives, can be obtained in
any manner known by the skilled person to be suitable for
this purpose.
In one embodiment the pyrolysis oil or part thereof,
containing equal to or less than 25 wt% n-hexane
extractives, may be obtained by solvent extraction of the
n-hexane extractives from a pyrolysis oil or part thereof,
containing more than 25 wt% n-hexane extractives. Solvents
suitable in such solvent extraction include n-hexane but
also other hexanes, heptanes, pentanes, octanes, nonanes
or decanes. In addition, the use of solvents such as
acetone and or dichloromethane may be helpful.
In another embodiment the pyrolysis oil or part thereof
may be phase separated as described in more detail below,
to produce a bottom phase pyrolysis oil containing in the
range from equal to or more than 0 wt% to equal to or less
than 25 wt% n-hexane extractives, preferably in the range
from equal to or more than 0 wt% to equal to or less than
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20 wt% n-hexane extractives, more preferably in the range
from equal to or more than 0 wt% to equal to or less than
15 wt% n-hexane extractives, still more preferably in the
range from equal to or more than 0 wt% to equal to or less
than 10 wt% n-hexane extractives and most preferably in
the range from equal to or more than 0 wt% to equal to or
less than 6 wt% n-hexane extractives; and a top phase
pyrolysis oil preferably containing more than 25 wt% n-
hexane extractives, more preferably containing more than
30 wt% n-hexane extractives more preferably containing
more than 35 wt% n-hexane extractives and most preferably
containing more than 40 wt% n-hexane extractives, and
preferably containing equal to or less than 100 wt% n-
hexane extractives.
An example of how the pyrolysis oil or part thereof,
containing equal to or less than 25 wt% n-hexane
extractive can be obtained is provided by A. Oasmaa et al,
in their article titled "Fast pyrolysis of Forestry
Residue 1. Effect of extractives on phase separation of
pyrolysis liquids", first published in Energy & Fuels, an
American Chemical Society journal, volume 17, number 1
January-February 2003, pages 1-12.
In a second embodiment the part of or whole pyrolysis oil
in step i) comprises only a bottom phase pyrolysis oil or
a part thereof.
In a second embodiment step i) therefore comprises a
process to produce one or more cracked products comprising
the steps of
2a) providing a bottom phase of a pyrolysis oil or a part
thereof;
2b) contacting the bottom phase of the pyrolysis oil or
the part thereof with a catalytic cracking catalyst at a
temperature of equal to or more than 400 C in the presence
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of a hydrocarbon co-feed to produce one or more cracked
products.
In step 2a) a bottom phase of a pyrolysis oil is provided.
By the bottom phase of a pyrolysis oil is understood the
lowest of the phases that can be obtained when phase
separating a pyrolysis oil. Such phase separation may take
place because of significant polarity, solubility and
density differences of extractives and the highly
hydrophilic pyrolysis liquid compounds. The bottom phase
of a pyrolysis oil is sometimes also referred to as bottom
phase pyrolysis oil. The bottom phase pyrolysis oil can be
obtained from a pyrolysis oil that is suitable for phase
separation into at least a top phase and a bottom phase.
By a pyrolysis oil that is suitable for phase separation into
at least a top phase and a bottom phase is also understood a
pyrolysis oil that can be separated into at least a top phase
and a bottom phase with the help of a separation agent.
Preferably, however, the pyrolysis oil is a pyrolysis oil
that can be separated into at least a top phase and a bottom
phase without requiring the pyrolysis oil to be contacted
with a separation agent.
Preferably the pyrolysis oil is phase separated into at
least a top phase and a bottom phase to produce a top
phase pyrolysis oil and a bottom phase pyrolysis oil.
Hence, in a preferred embodiment the invention provides a
process to produce one or more cracked products comprising
the steps of
a) providing a pyrolysis oil or part thereof, which
pyrolysis oil or part thereof has essentially not been
pretreated or upgraded by hydrotreatment and/or
hydrodeoxygenation;
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b) phase separating the pyrolysis oil or part thereof into
at least a top phase and a bottom phase to produce a top
phase pyrolysis oil and a bottom phase pyrolysis oil;
c) contacting the bottom phase pyrolysis oil or part
thereof with a catalytic cracking catalyst at a
temperature of equal to or more than 400 C in the presence
of a hydrocarbon co-feed to produce one or more cracked
products.
Such a process to produce one or more cracked products can
subsequently conveniently be used as step i) in the above
described process for the preparation of a biofuel and/or
a biochemical from a pyrolysis oil. As indicated above, in
one embodiment the phase separation can be brought about
by contacting the pyrolysis oil with a separation agent.
By a separation agent is understood a compound that
assists in the separation of the pyrolysis oil into one or
more phases. In a preferred embodiment such separation
agent is an alcohol. Examples of alcohols that can be used
as a separation agent include ethanol and isopropanol. An
example of how isopropanol can be used as a separation
agent is provided by Oasmaa et al in their article titled
"Fast Pyrolysis of Forestry Residue and Pine. 4.
Improvement of the Product Quality by Solvent Addition",
Energy and Fuels 2004, volume 18, pages 1578 to 1583. If
an alcohol is used as a separation agent, such an alcohol
is preferably present in an amount of equal to or more
than 0.25 wt%, more preferably equal to or more than 0.5
wt%, still more preferably equal to or more than 1 wt% and
most preferably equal to or more than 2 wt%, based on the
total combination of alcohol and pyrolysis oil; and
preferably in an amount of equal to or less than 10 wt%,
more preferably equal to or less than 7 wt% and most
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preferably equal to or less than 5 wt%, based on the total
combination of alcohol and pyrolysis oil.
In another embodiment the phase separation can be brought
about by lowering the temperature (cooling) of the
pyrolysis oil after production. If phase separation is
brought about by cooling, the pyrolysis oil is preferably
cooled to a temperature equal to or above 15 C, more
preferably equal to or above 25 C and preferably equal to
or below 50 C, more preferably equal to or below 45 C. An
example of how cooling can be used to separate phases is
provided by Oasmaa et al in their article titled " Fast
Pyrolysis of Forestry Residue. 1. Effect of Extractives on
Phase Separation of Pyrolysis Liquids", Energy and Fuels
2003, volume 17, pages 1 to 12.
The bottom phase pyrolysis oil can subsequently be
separated from the top phase of the pyrolysis by any
method known to the skilled in the art to be suitable for
this purpose. Examples of phase separation methods include
settling, decantation, centrifugation, cyclone separation,
extraction and membrane techniques.
In the processes according to the invention the bottom
phase pyrolysis oil, which is being contacted with the
catalytic cracking catalyst at a temperature of equal to
or more than 400 C in the presence of a hydrocarbon co-
feed to produce one or more cracked products, may be
contaminated with minor amounts of other phases than the
bottom phase pyrolysis oil. These minor amounts of the
other phases may for example be dispersed or dissolved in
the bottom phase pyrolysis oil. Preferably the total
amount of pyrolysis oil, which is being contacted with the
catalytic cracking catalyst in the process of the
invention, consists for equal to or more than 90 wt%, more
preferably for equal to or more than 95 wt%, even more
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preferably equal to or more than 99 wt%, still more
preferably equal to or more than 99.9 wt% and most
preferably equal to or more than 99.99 wt% of bottom phase
pyrolysis oil, based on the total weight of pyrolysis oil
being contacted with the catalytic cracking catalyst.
Preferably the amount of any other phase pyrolysis oils
(i.e. not being bottom phase pyrolysis oil, also referred
to as non-bottom phase pyrolysis oils) is equal to or less
than 10 wt%, more preferably equal to or less than 5 wt%,
even more preferably equal to or less than 1 wt%, still
more preferably equal to or less than 0.1 wt% and most
preferably equal to or less than 0.01 wt%, based on the
total weight of pyrolysis oil being contacted with the
catalytic cracking catalyst. Most preferably any pyrolysis
oil being contacted with the catalytic cracking catalyst
in the process of the invention consists essentially only
of bottom phase pyrolysis oil. That is, most preferably
the catalytic cracking is carried out in the essential
absence of any non-bottom phase pyrolysis oil.
An example of a non-bottom phase pyrolysis oil is the top
phase pyrolysis oil.
In a preferred embodiment the bottom phase pyrolysis oil
contains in the range from equal to or more than 0 wt% to
equal to or less than 25 wt% n-hexane extractives, more
preferably in the range from equal to or more than 0 wt%
to equal to or less than 20 wt% n-hexane extractives,
still more preferably in the range from equal to or more
than 0 wt% to equal to or less than 15 wt% n-hexane
extractives, still more preferably in the range from equal
to or more than 0 wt% to equal to or less than 10 wt% n-
hexane extractives, even still more preferably in the
range from equal to or more than 0 wt% to equal to or less
than 6 wt% n-hexane extractives, and most preferably in
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the range from equal to or more than 0 wt% to equal to or
less than 3 wt% n-hexane extractives.
Further the bottom phase pyrolysis oil may contain water
(preferably in the range from 20-35 wt%), carboxylic acids
(preferably in the range from 5-15 wt%), alcohols
(preferably in the range from 0-5 wt%), carbohydrates
(preferably in the range from (25-40 wt%), and/or lignin
compounds (preferably in the range from 5-30wt%).
In a third embodiment the part of or whole pyrolysis oil
in step i) is a pyrolysis oil or part thereof which when
combined with a, preferably liquid, hydrocarbon co-feed
provides a combination that has a molar ratio of hydrogen
to carbon of at least 1 to 1. In a third embodiment step
i) therefore comprises a process to produce one or more
cracked products comprising the steps of
3a) providing a pyrolysis oil or a part thereof;
3b) contacting the pyrolysis oil or the part thereof with
a catalytic cracking catalyst at a temperature of equal to
or more than 400 C in the presence of a hydrocarbon co-
feed to produce one or more cracked products; wherein the
combination of the pyrolysis oil or part thereof and the
hydrocarbon co-feed has an overall molar ratio of hydrogen
to carbon (H/C) of equal to or more than 1 to 1 (1/1).
The combination of the pyrolysis oil or part thereof and
the, preferably liquid, hydrocarbon co-feed preferably has
an overall molar ratio of hydrogen to carbon (H/C) of
equal to or more than 1.1 to 1 (1.1/1), more preferably of
equal to or more than 1.2 to 1 (1.2/1), most preferably of
equal to or more than 1.3 to 1 (1.3/1).
In a preferred embodiment an effective molair ratio of
hydrogen to carbon (H/Ceff) is used. By the effective
molair ratio of hydrogen to carbon (H/Ceff) is understood
the molair ratio of hydrogen to carbon after the
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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).
Preferably the combination of the pyrolysis oil or part
thereof and the, preferably liquid, hydrocarbon co-feed
has an overall effective molair ratio of hydrogen to
carbon (H/Ceff) of equal to or more than 1 to 1, more
preferably of equal to or more than 1.1 to 1 (1.1/1), even
more preferably of equal to or more than 1.2 to 1 (1.2/1),
most preferably of equal to or more than 1.3 to 1 (1.3/1).
In one embodiment the desired molar ratio of hydrogen to
carbon (H/C) or desired effective molar ratio of hydrogen
to carbon (H/Ceff) can be obtained by using a specific
hydrocarbon co-feed. Examples of suitable hydrocarbon co-
feeds are listed above. A most preferred hydrocarbon co-
feed in this respect is a Long Residue.
In another embodiment the desired molar ratio of hydrogen
to carbon (H/C) or desired effective molar ratio of
hydrogen to carbon (H/Ceff) can be obtained by using a
specific weight ratio of the pyrolysis oil to the
hydrocarbon co-feed. Examples of suitable weight ratios
of the pyrolysis oil to the hydrocarbon co-feed are listed
above. Most preferred weight ratios of the hydrocarbon co-
feed to the pyrolysis oil in this respect lie in the range
from 7:3 to 9:1.
In step i) of the process according to the invention one
or more cracked products are produced. These one or more
cracked products can be further processed in any manner
known to the skilled person to be suitable for further
processing these products. Such further processing may for
example include fractionating and/or hydrotreating (such
as for example hydrodesulphurization, hydrode-
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nitrogenation, hydrodeoxygenation and/or
hydroisomerization) the one or more cracked products.
Preferably, the one or more cracked products are
fractionated into one or more product fractions. Examples
of such product fractions include drygas (including carbon
monoxide, carbon dioxide, methane, ethane, ethene,
hydrogen sulfide and hydrogen), LPG (including propane and
butanes with small amounts of propene and butenes),),
gasoline (boiling in the range from C5 to 221 C), light
cycle oils (LCO; boiling in the range from 221 C to
370 C), heavy cycle oil (HCO; boiling in the range from
370 C to 425 C) and/or slurry oil (boiling above 425 C)
In a preferred embodiment the one or more cracked products
contain in the range from equal to or more than 20 wt% to
equal to or less than 90 wt% of gasoline and LCO, more
preferably in the range from equal to or more than 30 wt%
to equal to or less than 80 wt% of gasoline and LCO.
In a preferred embodiment the product fractions, obtained
after fractionating the one or more cracked products, can
be used to produce a biofuel and/or a biochemical. For
example one or more product fractions can be blended with
one or more other components to produce a biofuel and/or a
biochemical.
By a biofuel respectively a biochemical is herein
understood a fuel respectively a chemical that is at least
partly derived from a renewable energy source.
Examples of one or more other components with which the
one or more product fractions may be blended include anti-
oxidants, corrosion inhibitors, ashless detergents,
dehazers, dyes, lubricity improvers and/or mineral fuel
components.
The present invention further comprises combinations of
the embodiments described in the description above.
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The invention is illustrated by the following non-limiting
examples.
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Example 1: Mixing bottom phase pyrolysis oil derived from
forest residue and a hydrocarbon feed.
A pyrolysis oil derived from forest residue was obtained from
VII. Pyrolysis of the forest residue was carried out using a
20kg/h capacity process development unit (PDU) as described
by Oasmaa et al in their article "Fast pyrolysis of Forestry
Residue.l. Effect of Extractives on Phase Separation of
Pyrolysis liquids" in Energy & Fuels 2003, 17, pages 1 - 12.
A bottom phase pyrolysis oil and a top phase pyrolysis oil
were obtained as described in this article.
Subsequently mixtures were prepared of:
= 20 wt% top phase pyrolysis oil from forest residue with
80 wt% vacuum gas oil (VGO).
= 20 wt% bottom phase pyrolysis oil from forest residue
with 80 wt% Heavy feed mixture.
In order to determine miscibility the following visual test
was carried out. Each mixture was heated in a glass bottle to
approximately 65 C and shaken intensively. Hereafter the
glass bottle was allowed to stand for 30 minutes at 65 C.
Subsequently the glass bottle was turned upside down to see
if there were two separate layers of liquid visible. When
allowing the glass bottle to stand for 30 minutes at 65 C
and then turning it upside down, a dark brown sticky material
on the bottom of the glass bottle indicates non-miscibility
of the pyrolysis oil fraction.
Details on the composition of the top phase pyrolysis oil,
the bottom phase pyrolysis oil, VG0 and Heavy feed mixture
can be found in table 1.
Further details on the composition of the VG0 and the Heavy
feed mixture are provided in tables 2 and 3 respectively.
Table 4 shows the visual test results of the miscibility of
20% top phase pyrolysis oil from forest residue with VG0 and
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of 20% bottom phase pyrolysis oil from forest residue with
Heavy feed mixture.
- 36 -
Table 1. Feed compositions (a = on a wet basis, b = calculated on a dry basis)
0
Feed properties MCR* C H 0 N S
Water H/C ratio H/Ceff w
o
,..,
w
(wt%) (wt%) (wt%) (wt%) ** (ppm
(1313m content (mol/mol) (mol/mol) 'a
c.,
w
vD
wt) wt)
(wt %) w
.6.
Heavy feed mixture 2.0 86.65 12.8 0 2220
3360 0 1.77 1.77
Vacuum gasoil 0.2 85.4 12.8 0 n.d.
n.d. 0 1.80 1.80
Bottom phase of 19.1 40.5 7.76 51.7 2420 168
24.5 n.d. n.d.
forestry residue
n
pyrolysis oil'
0
I.)
CO
H
Bottom phase of n.d. 53.6 6.7 39.6 n.d.
n.d. n.d. 1.49 0.94 m
w
in
w
forestry residue
I.)
0
H
pyrolysis oilb
w
1
0
a,
Top phase of 19.6 n.d. n.d. n.d. n.d.
n.d. n.d. n.d. n.d. 1
I.)
m
forestry residue
pyrolysis oil'
* Micro Carbon Residue
** Oxygen content calculated by difference, i.e. by subtracting carbon content
and hydrogen Iv
n
,-i
content from 100 wt%.
m
Iv
w
n.d. = not determined.
o
,..,
,..,
'a
c.,
vD
vD
m
v,
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Table 2: Composition of the VG0
Hydrogen, %wt 12.25
Carbon, %wt 85.64
Nitrogen, %wt 0.08
Sulphur, %wt 1.77
Basic Nitrogen, 237
ppmw
Nickel, ppmw 0.1
Vanadium, ppmw 0.4
Iron, ppmw 0.3
Sodium, ppmw 0.2
Bromine Number, 6.1
gram Br/100gram
Micro-Carbon 0.2
Residue, %wt
Non-vaporizable 0.37
Coke, %wt
Mono Aromatics, 5.72
%wt
Di Aromatics, %wt 3.35
Tri Aromatics, %wt 3.41
Tetra+ Aromatics, 2.8
%wt
Total Aromatics, 15.27
%wt
Density @ 60F, 0.8961
g/cc
API Gravity (60F) 25.8
Molecular Weight, 309
g/g-mole
Kinematic 13.69
Viscosity @ 100F,
cst
Kinematic 2.91
Viscosity @ 210F,
cst
Pitch (1000F+), 2.5
%wt
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Table 3: Composition of the heavy feed mixture
Micro-Carbon Residue, 2.0
%wt *
Density D70/4 0.8720
Mol. weight 385
Melting point 35-40 C
Aromatics via UV-analyses SMS-2783 (wt %):
MONO aromatics 4.27
DI aromatics 3.23
TRI aromatics 3.61
TETRA aromatics 1.69
TETRA+ aromatics 3.35
PENTA+ aromatics 1.66
HEXA+ aromatics 0.92
HEPTA+ aromatics 0.63
PYREN aromatics 0.00
Total aromatics 14.46
Table 4. Visual observation of the miscibility of the bottom
phase and the top phase of the pyrolysis oil in VG0 and Heavy
feed mixture.
VG0 Heavy feed mixture
Top phase of the
Poor Moderate
pyrolysis oil
Bottom phase
Poor Moderate
pyrolysis oil
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Example 2: Catalytic cracking of a mixture of top phase
pyrolysis oil from forest residue with VG0 in a non-stirred
feed vessel.
The mixture of 20 wt% top phase pyrolysis oil from forest
residue with 80 wt% vacuum gas oil (VGO) as prepared under
example 1 was transferred as a feed mixture to the feed
vessel of a MAT-5000 fluidized catalytic cracking unit. The
feed vessel was kept at 60 C during transfer. The feed
vessel was not stirred. A first test run was started
immediately after transfer of the feed mixture into the feed
vessel.
The first test run included the 7 experiments with 7 catalyst
to oil ratios, namely catalyst/oil ratios of 3, 4, 5, 6,
6.5, 7 and 8.
Each experiment was conducted as follows:
10 g of FCC equilibrium catalyst containing ultra stable
zeolite Y, was constantly fluidized with nitrogen. A precise
and known amount of feed was injected, and subsequently
flushed through a tube with nitrogen to the fluidized
catalyst bed during runtime of 1 minute. The fluidized
catalyst bed was kept at 500 C. The liquid FCC products were
collected in glass receivers at minus 18-19 C.
Subsequently the FCC catalyst was stripped with nitrogen
during 11 minutes. The gas produced during such stripping was
weighted and analyzed online with a gas chromatograph (GC).
Hereafter the FCC catalyst was regenerated in-situ at 650 C
for 40 minutes in the presence of air. During such
regeneration the coke was converted to 002, which was
quantified by on-line infrared measurement. After
regeneration the reactor was cooled to the cracking
temperature and a new injection was started. One cycle
including all catalyst to oil ratios took approximately 16
hours.
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The results of example 2 are reflected in below table 5.
Table 5. Cracked products obtained by catalytic cracking of
20 wt % top phase of pyrolysis oil from forest residue with
80 wt % VG0 at 500 C
Yields at 100 % 20% top phase 20% top phase Average of
60% VG0 pyrolysis oil pyrolysis oil 1st and
conversion + 80 wt% VG0 + 80 wt% VG0 2nd run*
1st run* 2nd run*
Drygas ** 1.4 2.4 2.4 2.4
LPG 9.6 9.7 14.3 12.0
Gasoline 45.3 35.3 43.4 39.3
Light Cycle 32.2 23.1 25.4 24.2
Oil (LCO)
Heavy Cycle 5.0 3.8 3.8 3.8
Oil (HCO)
Slurry oil 2.7 2.4 2.1 2.2
(SO)
Coke 3.7 19.1 8.4 13.8
CO 0.0 2.5 0.1 1.3
CO2 0.0 1.8 0.1 0.9
* The above results have been normalized and calculated on a
dry basis , i.e. without 11.1 wt% H20
As illustrated in table 5, the LPG, gasoline and coke make in
the 1st and 2nd run show substantial differences. The poor
reproducibility for the 1st and 2nd test run in example 2
indicates a poor miscibility of the top phase pyrolysis oil
and the VG0. The process in example 5 may therefore be less
robust when upscaling to a commercial scale.
As further illustrated in table 5, a substantial amount of
gasoline is prepared, allowing this gasoline to be used for
the production of a biofuel.
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Example 3: Catalytic cracking of a mixture of bottom phase
pyrolysis oil from forest residue with Heavy feed mixture in
a non-stirred feed vessel.
The mixture of 20 wt% bottom phase pyrolysis oil from forest
residue with 80 wt% Heavy feed mixture as prepared under
example 1 was transferred as a feed mixture to the feed
vessel of a MAT-5000 fluidized catalytic cracking unit. A
process identical to that described for example 2 was carried
out except that for example 3 the fluidized catalyst bed
during catalytic cracking was kept at 520 C instead of 500
C.
The results of example 3 are reflected in below table 6.
Table 6. Cracked products obtained by catalytic cracking of
of a mixture of 20 wt% bottom phase pyrolysis oil from forest
residue and 80wt% Heavy feed mixture .
Heavy feed Heavy feed Heavy feed
Average of
mixture mixture + mixture +
Yields at 2
(wt%) 20% bottom 20% bottom
60% consecutiv
phase (1st phase (2nd
conversion e runs
run) run)
(wt %)
(wt) (wt)
Water 0 10.9 10.9 10.9
Cat/Oil
2.9 4.2 3.9 4.1
ratio
Drygas 1.5 2.5 2.1 2.3
LPG 8.4 12.7 13.1 12.9
Gasoline 43.4 42.9 44.7 43.8
Light
Cycle Oil 25.1 21.2 21.5 21.4
(LCO)
Heavy
Cycle Oil 8.0 5.4 5.6 5.5
(HCO)
Slurry oil
6.9 4.8 4.9 4.8
(SO)
Coke 6.6 9.1 7.7 8.4
CO 0 0.8 0.2 0.5
CO2 0 0.5 0.2 0.3
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The good reproducibility for the 1st and 2nd test run in
example 3 indicates a good miscibility of the bottom phase
pyrolysis oil and the Heavy feed mixture. The process in
example 5 therefore is sufficiently robust to allow upscaling
to a commercial scale. In addition, coke yield is
considerably lower than the coke yield obtained in example 2
with the top phase of pyrolysis oil and using VG0 as a co-
feed.
Further, Elemental analysis of the Total Liquid Products
shows a large reduction in the amount of remaining oxygen,
as illustrated in table 7. Without wishing to be bound to any
kind of theory, it is therefore believed that direct co-
processing of the bottom phase of pyrolysis oil and a heavy
feed mixture in an FCC unit, in line with the process
according to the invention, also leads to a large reduction
in the Total Acid Number. Hence the process according to the
invention may also advantageously enable further downstream
processing of the catalytically cracked pyrolysis oil in a
refinery.
Table 7: Elemental analysis of Total liquid Products in
example 3(at Cat/Oil = 3)
C H 0 H/C
(wt %) (wt %) (wt %) (Mol/Mol)
1st run 87.1 11.28 1.6 1.55
2nd run 87.9 11.72 0.4 1.60
As further illustrated in table 6, a substantial amount of
gasoline is prepared, allowing this gasoline to be used for
the production of a biofuel.
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Example 4: Mixing bottom phase pyrolysis oil derived from
pine and a liquid hydrocarbon feed.
A pyrolysis oil derived from pine was obtained from VII.
Pyrolysis of the pine was carried out as described by Oasmaa
et al in their article "Fast pyrolysis of Forestry Residue.l.
Effect of Extractives on Phase Separation of Pyrolysis
liquids" in Energy & Fuels 2003, 17, pages 1 - 12. A top
phase pyrolysis oil from pine and a bottom phase pyrolysis
oil from pine were obtained as described in that same
article. Subsequently a mixture was prepared of:
= 20 wt% bottom phase pyrolysis oil from pine with 80 wt%
Heavy feed mixture.
Details on the composition of the bottom phase pyrolysis oil
from pine and Heavy feed mixture can be found in table 8.
- 44 -
Table 8. Feed compositions (a = on a wet basis, b = calculated on a dry basis)
0
Feed properties MCRT* C H 0 N S
Water H/C ratio H/Ceff w
o
,..,
w
(wt%) (wt%) (wt%) (wt%) ** (ppm
(1313m content (mol/mol) (mol/mol 'a
c.,
w
vD
wt) wt)
(wt %) ) w
.6.
Heavy feed mixture 2.07 86.65 12.8 0 2220
3360 0 1.77 1.77
Bottom phase of 21.8 39.8 7.8 52.4 496 42
23.9 n.d. n.d.
pine'
Bottom phase of n.d. 52.3 6.8 40.2 n.d.
n.d. n.d. 1.55 0.98 n
pineb
0
I.)
CO
H
* Micro Carbon Residue Test
m
w
in
w
** Oxygen content calculated by difference, i.e. by subtracting carbon content
and hydrogen I.)
0
H
content from 100 wt%.
w
1
0
a,
n.d. = not determined.
1
I.)
m
Iv
n
,-i
m
,-;
w
=
'a
c.,
m
u,
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Example 5: Catalytic cracking of a mixture of bottom phase
pyrolysis oil derived from pine and Heavy feed mixture in a
non-stirred and in a stirred feed vessel.
A process identical to that described for example 3 was
carried out except that for example 5 the mixture as prepared
in example 4 was used; the feed vessel was kept at 50 C; and
the process was carried out in a stirred and in a non-stirred
feed vessel. The feed vessel was stirred by an overhead
stirrer with 4 blades immersed in the feed vessel. The
results are summarized in table 9.
As can be seen in table 9 both in a non-stirred feed vessel
as well as in a stirred feed vessel consistent and
reproducible results can be obtained during the complete time
of one run cycle (about 16 hours). This illustrates that the
process according to the invention advantageously allows for
the process to be carried out without stirring the feed
vessel. As a result the process is more easily scaled up.
Table 9. Cracked products obtained by catalytic cracking of
a mixture of 80wt% Long Residue with 20wt% bottom phase oil
from pine (PBPO) at 520 C
With 20 With 20 With 20 With 20
Yields
Heavy feed wt% PBPO wt% PBPO wt% PBPO wt% PBPO
at 60%
mixture with with without without
convers
only stirring stirring stirring stirring
ion
st rd st n
2d
1 run 3 run 1 run
run
Water 0.0% 10.4 10.5 10.6 11.0
Cat/oil
2.8 4.4 4.5 4.5 4.4
ratio
Drygas 1.5 2.9 2.7 2.6 2.4
LPG 8.7 12.6 12.8 12.9 13.2
Gasolin
45.3 43.1 43.3 43.8 45.3
e
LCO 25.1 21.3 21.4 21.2 21.3
HCO 8.0 5.3 5.4 5.4 5.5
Slurry
6.9 4.6 4.9 4.7 4.7
oil
Coke 4.5 8.4 8.3 7.8 6.4
CO 0.1 1.0 0.9 0.9 0.6
CO2 0.0 0.8 0.8 0.8 0.5
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As further illustrated in table 9, a substantial amount of
gasoline is prepared, allowing this gasoline to be used for
the production of a biofuel.
Example 6 Catalytic cracking of a mixture of bottom phase
pyrolysis oil and Heavy feed mixture on a pilot scale.
Two experiments were performed using:
1) a feed containing 100 wt% conventional crude oil fraction;
and
2) a feed consisting of a blend of 9.5 wt% bottom phase
pyrolysis oil, 1 wt% surfactant and 89.5 wt% of a
conventional crude oil fraction.
The above feed, respectively the above blend, was heated to
82 C and transferred as a feed mixture to the feed vessel of
a pilot-scale fluidized catalytic cracking unit. The pilot-
scale fluidized catalytic cracking unit consisted of six
sections including a feed supply system, a catalyst loading
and transfer system, a riser reactor, a stripper, a product
separation and collecting system, and a regenerator. The
riser reactor was an adiabatic riser having an inner diameter
of 11 mm and a length of about 3.2 m. The riser reactor
outlet was in fluid communication with the stripper that was
operated at the same temperature as the riser reactor outlet
flow and in a manner so as to provide essentially 100 percent
stripping efficiency. The regenerator was a multi-stage
continuous regenerator used for regenerating the spent
catalyst. The spent catalyst was fed to the regenerator at a
controlled rate and the regenerated catalyst was collected in
a vessel. The catalytic cracking catalyst cntained ultra
stable zeolite Y.
Material balances were obtained during each of the
experimental runs at 30-minute intervals. Composite gas
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samples were analyzed by use of an on-line gas chromatograph
and the liquid product samples were collected and analyzed
overnight. The coke yield was measured by measuring the
catalyst flow and by measuring the delta coke on the catalyst
as determined by measuring the coke on the spent and
regenerated catalyst samples taken for each run when the unit
was operating at steady state.
Properties of the feed are provided in below table 10. The
results are summarized in table 11.
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Table 10: Feed properties
conventional
Bottom phase
Feed Description crude oil
Pyrolysis Oil
fraction
Hydrogen, %wt 7.8 11.9
Carbon, %wt 39.8 87.5
Oxygen, %wt 55.3 0.12
Nitrogen, ppmw 496 296
Sulfur, ppmw 42 166
Basic Nitrogen, ppmw 395 926
Nickel, ppmw < 0.2 < 0.3
Vanadium, ppmw < 0.2 < 0.3
Iron, ppmw 2 < 0.2
Sodium, ppmw 3.2 <0.2
Mono-Aromatics, %wt 4 7.8
Di-Aromatics, %wt 0.9 3.0
Tri-Aromatics, %wt 1 2.5
Tetra+ Aromatics, %wt 2.8 3.1
Total Aromatics, %wt 8.7 16.4
Micro-Carbon Residue' 21.8 <0.1
%wt
Molecular Weight,
323 364
g/g-mole
Kinematic Viscosity @ Unable to
7.1
100 C, cst determine
Bromine Number,
14.7 7
gBr/100g
Pitch (538 C+), %wt Unable to 2
determine
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Table 11: Cracked products obtained by catalytic cracking of
a conventional crude oil fraction with bottom phase oil and a
surfactant at 528 C
Yields at constant Blend 100wt % conventional
conversion crude oil fraction
Reactor Temp., C 528 528
Gas Residence time, sec 2.3 2.4
C/O Ratio 18.6 10.2
Conversion, %wt 70.5 70.4
C5-450F Naphtha, %wt 48.2 50.5
YIELDS, %wt
C2 & Lighter 1.8 2.7
C5-232 C Naphtha, %wt 48.2 50.5
LPG, %wt. 18.0 17.2
232-343 C, LCO 21.1 18.0
343-399 C, HCO 4.7 5.9
399 C+, CLO 3.6 5.7
Coke 4.6 2.6
Comparative example 7
An experiment was carried out as described above for
example 6, except that the feed contained 100 wt% bottom
phase pyrolysis oil. The experiment failed as the feed
line to the riser and the feed nozzle suffered rapid
plugging due to coke formation within 10 minutes from
starting of the feed pump.
