U.S. patent application number 14/277834 was filed with the patent office on 2014-11-20 for process for converting a solid biomass material.
This patent application is currently assigned to Shell Oil Company. The applicant listed for this patent is Shell Oil Company. Invention is credited to Josiane Marie-Rose GINESTRA, Johannes Pieter HAAN, Robert Wilfred Matthews WARDLE.
Application Number | 20140343333 14/277834 |
Document ID | / |
Family ID | 50884869 |
Filed Date | 2014-11-20 |
United States Patent
Application |
20140343333 |
Kind Code |
A1 |
GINESTRA; Josiane Marie-Rose ;
et al. |
November 20, 2014 |
PROCESS FOR CONVERTING A SOLID BIOMASS MATERIAL
Abstract
A process for converting a solid biomass material comprising: a)
providing a solid biomass material; b) contacting a feed comprising
the solid biomass material and a petroleum-derived hydrocarbon
composition, which petroleum derived hydrocarbon composition has a
C7-asphaltenes content of equal to or more than 1.0 wt %, based on
the total weight of the petroleum-derived hydrocarbon composition,
co-currently with a source of hydrogen in one or more ebullating
bed reactors comprising a catalyst at a temperature in the range
from 350.degree. C. to 500.degree. C. to produce a reaction
product.
Inventors: |
GINESTRA; Josiane Marie-Rose;
(Richmond, TX) ; HAAN; Johannes Pieter;
(Amsterdam, NL) ; WARDLE; Robert Wilfred Matthews;
(Ince, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Shell Oil Company |
Houston |
TX |
US |
|
|
Assignee: |
Shell Oil Company
Houston
TX
|
Family ID: |
50884869 |
Appl. No.: |
14/277834 |
Filed: |
May 15, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61824279 |
May 16, 2013 |
|
|
|
Current U.S.
Class: |
585/14 ;
585/242 |
Current CPC
Class: |
C10G 2300/1096 20130101;
C10G 2300/206 20130101; C10G 3/55 20130101; C10G 2400/06 20130101;
C10G 1/083 20130101; C10L 1/023 20130101; C10G 2300/1011 20130101;
C10G 65/12 20130101; C10G 2400/04 20130101; C10L 1/026 20130101;
C10G 3/50 20130101; C10G 1/002 20130101; C10G 2300/1014 20130101;
C10G 1/065 20130101; C10G 3/42 20130101; Y02P 30/20 20151101 |
Class at
Publication: |
585/14 ;
585/242 |
International
Class: |
C10G 1/00 20060101
C10G001/00 |
Claims
1. A process comprising: a) providing a solid biomass material; and
b) contacting a feed comprising the solid biomass material and a
petroleum-derived hydrocarbon composition, which petroleum derived
hydrocarbon composition has a C7-asphaltenes content of equal to or
more than 1.0 wt %, based on the total weight of the
petroleum-derived hydrocarbon composition, co-currently with a
source of hydrogen in one or more ebullating bed reactors
comprising a catalyst at a temperature in the range from
350.degree. C. to 500.degree. C. to produce a reaction product.
2. The method of claim 1 further comprising: c) fractionating the
reaction product obtained in step b) into two or more product
fractions and separating one or more product fraction(s) having a
final boiling point of equal to or less than 370.degree. C. at 0.1
MPa.
3. The method of claim 2 further comprising: d) upgrading the one
or more product fraction(s) having a final boiling point of equal
to or less than 370.degree. C. at 0.1 MPa in one or more
hydrocarbon conversion processes to produce one or more upgraded
product fraction(s) having a final boiling point of equal to or
less than 370.degree. C. at 0.1 MPa;
4. The method of claim 3 further comprising: e) blending the one or
more upgraded product fraction(s) having a final boiling point of
equal to or less than 370.degree. C. at 0.1 MPa with one or more
other components to prepare a liquid fuel composition.
5. The process of claim 2, wherein the liquid fuel composition is a
liquid fuel composition suitable for use in a spark-ignition engine
and/or a liquid fuel composition suitable for use in an
auto-ignition engine.
6. The process of claim 1, wherein the solid biomass material is a
torrefied solid biomass material.
7. The process of claim 1, wherein the solid biomass material is a
micronized solid biomass material.
8. The process of claim 1, wherein the petroleum-derived
hydrocarbon composition has an initial atmospheric boiling point of
equal to or more than 350.degree. C.
9. The process of claim 1, wherein the petroleum-derived
hydrocarbon composition comprises a Micro Carbon Residue in the
range from equal to or more than 10% wt to equal to or less than 30
wt %, based on the total weight of the petroleum-derived
hydrocarbon composition.
10. The process of claim 1, wherein the reaction product produced
in step b) comprises a higher amount of aromatic compounds having a
boiling point of equal to or more than 370.degree. C. as compared
to a reaction product that one would have obtained using a feed
consisting of the petroleum-derived hydrocarbon composition.
11. The process of claim 1, wherein step b) comprises: contacting
the feed comprising the solid biomass material and the
petroleum-derived hydrocarbon composition co-currently with a
source of hydrogen in a first ebullating bed reactor to produce a
first reaction product comprising one or more aromatic compounds
and one or more un-converted asphaltenes; and contacting the first
reaction product co-currently with a source of hydrogen in a second
ebullating bed reactor comprising a catalyst at a temperature in
the range from 350.degree. C. to 500.degree. C. to produce a second
reaction product.
12. The process of claim 1, wherein step b) comprises: mixing a
feed comprising the solid biomass material and a co-feed comprising
the petroleum-derived hydrocarbon composition to produce a mixture;
and contacting the mixture co-currently with a source of hydrogen
in one or more ebullating bed reactors comprising a catalyst at a
temperature in the range from 350.degree. C. to 500.degree. C. to
produce a reaction product.
13. The process of claim 6, wherein step b) comprises: mixing a
feed comprising the torrefied solid biomass material and a co-feed
comprising the petroleum-derived hydrocarbon composition to produce
a mixture; and contacting the mixture co-currently with a source of
hydrogen in one or more ebullating bed reactors comprising a
catalyst at a temperature in the range from 350.degree. C. to
500.degree. C. to produce a reaction product.
14. The process of claim 7, wherein step b) comprises: mixing a
feed comprising the micronized solid biomass material and a co-feed
comprising the petroleum-derived hydrocarbon composition to produce
a mixture; and contacting the mixture co-currently with a source of
hydrogen in one or more ebullating bed reactors comprising a
catalyst at a temperature in the range from 350.degree. C. to
500.degree. C. to produce a reaction product.
15. A composition comprising: a plurality of hydrocarbon compounds
having a boiling point of equal to or less than 370.degree. C., a
first fraction comprising equal to or more than 1 wt % to equal to
or less than 99 wt % of biomass-derived hydrocarbon compounds; and
a second fraction comprising equal to or more than 1 wt % to equal
to or less than 99 wt % of petroleum derived hydrocarbon compounds;
wherein the first fraction has a weight ratio W.sub.B of aromatics
to paraffins; wherein the second fraction has a weight ratio
W.sub.P of aromatics to paraffins; and wherein the weight ratio
W.sub.B is lower than the weight ratio W.sub.P.
16. A composition comprising: a plurality of hydrocarbon compounds,
which composition has a C7-asphaltenes content of equal to or more
than 0.1 wt %, based on the total weight of the composition and
which composition comprises in the range from equal to or more than
8.0 wt % to equal to or less than 30 wt % of one or more aromatic
compounds, which one or more aromatic compounds each comprise equal
to or more than 3 aromatic ring structures and have a boiling point
equal to or higher than 370.degree. C.
17. The composition of claim 16 wherein the composition comprises
in the range of equal to or more than 9.0 wt % to equal to or less
than 20 wt % of one or more aromatic compounds.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This non-provisional application claims the benefit of
61/824,279 filed May 16, 2013, the disclosures of which are
incorporated herein by reference.
TECHNICAL FIELD OF THE INVENTION
[0002] The present invention relates to a process for converting a
solid biomass material. More specifically the present invention
relates to a process for converting a solid biomass material in a
reaction product comprising one or more cracked products. In
addition the present invention relates to a process for the
preparation of biofuel and/or biochemical.
BACKGROUND TO THE INVENTION
[0003] With the diminishing supply of crude petroleum oil, use of
renewable energy sources is becoming increasingly important for the
production of liquid fuels and/or chemicals. The use of renewable
energy sources may also allow for a more sustainable production of
liquid fuels and/or chemicals and more sustainable CO.sub.2
emissions that may help meet global CO.sub.2 emissions standards
under the Kyoto protocol.
[0004] The fuels and/or chemicals from renewable energy sources are
often referred to as biofuels and/or biochemicals. Biofuels and/or
biochemicals derived from non-edible renewable energy sources, such
as cellulosic materials, are preferred as these do not compete with
food production. These biofuels and/or biochemicals are also
referred to as second generation, renewable or advanced, biofuels
and/or biochemicals. Most of these non-edible renewable energy
sources, however, are solid materials that are cumbersome to
convert into liquid fuels.
[0005] International patent application WO2013/064563 describes a
method comprising upgrading of a pyrolysis oil, which method
comprises evaporating water from a mixture comprising the pyrolysis
oil and a high boiling hydrocarbon (having an initial boiling point
of at least 130.degree. C. at a pressure of 100 kiloPascal).
[0006] The pyrolysis oil is suitably obtained or derived from
biomass comprising lignocellulosic material, such as for example
wood chips. The de-watered pyrolysis oil mixture may be used as a
feedstock for hydrocarbon conversion processes. As an example of
such a hydrocarbon conversion process, in passing, hydrocracking is
mentioned. As further explained in International patent application
WO2013/064563 in a preferred embodiment the high boiling
hydrocarbon or a mixture of high boiling hydrocarbons has an
asphaltenes content of equal to or more than 0.2 wt %, still more
preferably equal to or more than 2.0 wt %.
[0007] Although this process performs satisfactory, a further
improvement in quality of the product would be advantageous. It
would be an advancement in the art to provide a process that allows
one to convert a solid biomass material into a product having an
improved product quality.
SUMMARY OF THE INVENTION
[0008] It has now surprisingly been found that an improved product
quality can be obtained by co-currently contacting with hydrogen, a
mixture of a solid biomass material, preferably a torrefied solid
biomass material, and an asphaltene containing petroleum derived
hydrocarbon composition instead of a dewatered mixture of pyrolysis
oil and such petroleum derived hydrocarbon composition.
[0009] Accordingly in some embodiments, there is provided a process
for converting a solid biomass material comprising: a) providing a
solid biomass material; and b) contacting a feed comprising the
solid biomass material and a petroleum-derived hydrocarbon
composition, which petroleum derived hydrocarbon composition has a
C7-asphaltenes content of equal to or more than 1.0 wt %, based on
the total weight of the petroleum-derived hydrocarbon composition,
co-currently with a source of hydrogen in one or more ebullating
bed reactors comprising a catalyst at a temperature in the range
from 350.degree. C. to 500.degree. C. to produce a reaction
product.
[0010] In some embodiments, the process further comprises c)
fractionating the reaction product obtained in step b) into two or
more product fractions and separating one or more product
fraction(s) having a final boiling point of equal to or less than
370.degree. C. at 0.1 MPa. In some embodiments, the process further
comprises upgrading the one or more product fraction(s) having a
final boiling point of equal to or less than 370.degree. C. at 0.1
MPa in one or more hydrocarbon conversion processes to produce one
or more upgraded product fraction(s) having a final boiling point
of equal to or less than 370.degree. C. at 0.1 MPa. In some
embodiments, the process further comprises e) blending the one or
more product fraction(s) having a final boiling point of equal to
or less than 370.degree. C. at 0.1 MPa with one or more other
components to prepare a liquid fuel composition.
[0011] Preferably the liquid fuel composition is a liquid fuel
composition suitable for use in a spark-ignition engine and/or a
liquid fuel composition suitable for use in an auto-ignition
engine.
[0012] Embodiments provided may surprisingly result in a reaction
product, product fraction(s), fuel component(s) and/or liquid fuel
composition(s) containing 1-ring, 2-ring, 3-ring and/or 3+-ring
aromatics. Without wishing to be bound to any kind of theory it is
believed that such aromatics, which may be formed in-situ during
step b) are capable of solubilizing any of the
unconverted-C7-asphaltenes that may still be contained in the
reaction product obtained in step b). By "solubilizing" is herein
preferably understood the "keeping in solution." Further, the
aromatics that were present in the feed may be more preserved as
less of the aromatics present may be hydrogenated in the process of
the invention. In addition, it may be advantageous to add biomass
in step (b), resulting in an increase in aromatics in the heavy
fraction that allows one to have less fouling at the back-end of
the unit, as the heavy (>370.degree. C.) product is more
stable.
[0013] In particular, embodiments provided may surprisingly result
in a reaction product, product fraction(s), fuel component(s)
and/or liquid fuel composition(s) containing 1-ring, 2-ring, 3-ring
and/or 3+-ring aromatics, which 1-ring, 2-ring, 3-ring and/or
3+-ring aromatics, which aromatics are more heavy than those in the
reaction product, product fraction(s), fuel component(s) and/or
liquid fuel composition(s) obtained after converting only a
petroleum-derived hydrocarbon composition without the solid biomass
material. Suitably one or more product fraction(s), fuel
component(s) and/or liquid fuel composition(s) boiling below
370.degree. C. (as determined at 0.1 MPa) can be obtained, where
the content of 1-ring, 2-ring, 3-ring and/or 3+-ring aromatics has
been reduced, whilst further one or more product fraction(s), fuel
component(s) and/or liquid fuel composition(s) boiling above
370.degree. C. (as determined at 0.1 MPa) can be obtained, where
the content of 1-ring, 2-ring, 3-ring and/or 3+-ring aromatics has
been increased.
[0014] This shift from lighter to more heavy aromatics has at least
two advantages. Firstly the increased content of heavy aromatics
(i.e. aromatics boiling above 370.degree. C.) appears advantageous
in stabilizing un-converted asphaltenes in the reaction product.
Secondly the decreased content of light aromatics (i.e. aromatics
boiling below 370.degree. C.) advantageously allows for the
production of cleaner burning product fraction(s), fuel
component(s) and/or liquid fuel composition(s), that have a reduced
sooth exhaust when burned.
[0015] Further, embodiments provided may advantageously result in
an increase of paraffin make as compared to coverting of only a
petroleum-derived hydrocarbon composition without the solid biomass
material.
[0016] Hence, embodiments provided may surprisingly allow one to
prepare relatively clean biocarbon containing product fraction(s),
fuel component(s) and/or liquid fuel composition(s) that may have a
good energy content and/or may be used to reduce sooth exhaust
and/or to meet global CO.sub.2 emissions standards under the Kyoto
protocol.
[0017] Accordingly, there are also compositions obtainable or
obtained in any of the processes according to the invention. In
some embodiments, there is provided a composition comprising or
consisting of a plurality of hydrocarbon compounds, such
hydrocarbon compounds having a boiling point of equal to or less
than 370.degree. C., comprising in the range from equal to or more
than 0.1 wt % to equal to or less than 99.9 wt % of a fraction
consisting of biomass-derived hydrocarbon compounds; and in the
range from equal to or more than 0.1 wt % to equal to or less than
99.9 wt % of a fraction consisting of petroleum derived hydrocarbon
compounds; wherein the fraction consisting of biomass-derived
hydrocarbon compounds has a weight ratio W.sub.B of aromatics to
paraffins; wherein the fraction consisting of petroleum-derived
hydrocarbon compounds has a weight ratio W.sub.P of aromatics to
paraffins; and wherein the weight ratio W.sub.B is lower than the
weight ratio W.sub.P.
[0018] Other advantages and features of embodiments of the present
invention will become apparent from the following detailed
description. It should be understood, however, that the detailed
description and the specific examples, while indicating preferred
embodiments of the invention, are given by way of illustration
only, since various changes and modifications within the spirit and
scope of the invention will become apparent to those skilled in the
art from this detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Illustrative embodiments of the invention have been
illustrated by the following non-limiting figures:
[0020] FIG. 1 illustrates one embodiment according to some aspects
provided.
[0021] FIG. 2 illustrates the particle size distribution of the
milled torrefied wood used in the examples.
DETAILED DESCRIPTION
[0022] As mentioned, there is provided a process for converting a
solid biomass material comprising: a) providing a solid biomass
material; and b) contacting a feed comprising the solid biomass
material and a petroleum-derived hydrocarbon composition, which
petroleum derived hydrocarbon composition has a C7-asphaltenes
content of equal to or more than 1.0 wt %, based on the total
weight of the petroleum-derived hydrocarbon composition,
co-currently with a source of hydrogen in one or more ebullating
bed reactors comprising a catalyst at a temperature in the range
from 350.degree. C. to 500.degree. C. to produce a reaction
product.
[0023] In step a), a solid biomass material is provided. By a solid
biomass material is herein understood a solid material obtained or
derived from biomass. By biomass is herein understood a composition
of matter of biological origin as opposed to a composition of
matter obtained or derived from petroleum, natural gas or coal.
Without wishing to be bound by any kind of theory it is believed
that such material obtained from a renewable source may contain
carbon-14 isotope in an abundance of about 0.0000000001%, based on
total moles of carbon. Preferably the solid biomass material is a
material containing cellulose and/or lignocellulose. Such a
material containing "cellulose" respectively "lignocellulose" is
herein also referred to as a "cellulosic", respectively
"lignocellulosic" material. By a cellulosic material is herein
understood a material containing cellulose and optionally also
lignin and/or hemicellulose. By a lignocellulosic material is
herein understood a material containing cellulose and lignin and
optionally hemicellulose. Hence, suitably the solid biomass
material is a material that is not used for food production.
[0024] Examples of solid biomass materials include aquatic plants
and algae, agricultural waste and/or forestry waste and/or paper
waste and/or plant material obtained from domestic waste. Examples
of cellulosic or lignocellulosic materials include for example
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
and/or forestry residues such as wood and wood-related materials
such as sawdust and bark; waste paper; sugar processing residues
such as bagasse and beet pulp; or any combination thereof.
[0025] More preferably the solid biomass material comprises or
consists of a cellulosic or lignocellulosic material selected from
the group consisting of wood, sawdust, bark, straw, hay, grasses,
bagasse, corn stover and/or mixtures thereof. The wood may include
soft wood and/or hard wood.
[0026] The solid biomass material may have undergone drying,
torrefaction, steam explosion, demineralization, particle size
reduction, densification and/or pelletization and may hence be
provided in a torrefied, steam exploded, demineralized, densified
and/or pelletized form.
[0027] Preferably the solid biomass material in step a) is a
torrefied solid biomass material. One preferred embodiment
comprises a step of torrefying the solid biomass material at a
temperature of more than 200.degree. C. to obtain a torrefied solid
biomass material that can be contacted with the catalytic cracking
catalyst in step a). The words torrefying and torrefaction are used
interchangeable herein.
[0028] By torrefying or torrefaction is herein understood the
treatment of the solid biomass material at a temperature in the
range from equal to or more than 200.degree. C. to equal to or less
than 350.degree. C. in the essential absence of a catalyst and in
an oxygen-poor, preferably an oxygen-free, atmosphere. By an
oxygen-poor atmosphere is understood an atmosphere containing equal
to or less than 15 vol. % oxygen, preferably equal to or less than
10 vol % oxygen and more preferably equal to or less than 5 vol %
oxygen. By an oxygen-free atmosphere is understood that the
torrefaction is carried out in the essential absence of oxygen.
[0029] Torrefying of the solid biomass material is preferably
carried out at a temperature of more than 200.degree. C., more
preferably at a temperature equal to or more than 210.degree. C.,
still more preferably at a temperature equal to or more than
220.degree. C., yet more preferably at a temperature equal to or
more than 230.degree. C. In addition torrefying of the solid
biomass material is preferably carried out at a temperature less
than 350.degree. C., more preferably at a temperature equal to or
less than 330.degree. C., still more preferably at a temperature
equal to or less than 310.degree. C., yet more preferably at a
temperature equal to or less than 300.degree. C. Torrefaction of
the solid biomass material is preferably carried out in the
essential absence of oxygen. More preferably the torrefaction is
carried under an inert atmosphere, containing for example inert
gases such as nitrogen, carbon dioxide and/or steam.
[0030] The torrefying step may be carried out at a wide range of
pressures. Preferably, however, the torrefying step is carried out
at atmospheric pressure (about 0.1 MegaPascal (MPa)). The torrefied
solid biomass material has a higher energy density, a higher mass
density and greater flowability, making it easier to transport,
pelletize and/or store. Being more brittle, it can be easier
reduced into smaller particles. Preferably the torrefied solid
biomass material has an oxygen content in the range from equal to
or more than 10 wt %, more preferably equal to or more than 20 wt %
and most preferably equal to or more than 30 wt % oxygen, to equal
to or less than 60 wt %, more preferably equal to or less than 50
wt %, based on total weight of dry matter.
[0031] In a further preferred embodiment, any torrefying or
torrefaction step further comprises drying the solid biomass
material before such solid biomass material is torrefied. In such a
drying step, the solid biomass material is preferably dried until
the solid biomass material has a moisture content in the range of
equal to or more than 0.1 wt % to equal to or less than 25 wt %,
more preferably in the range of equal to or more than 5 wt % to
equal to or less than 20 wt %, and most preferably in the range of
equal to or more than 5 wt % to equal to or less than 15wt %. For
practical purposes moisture content can be determined via ASTM
E1756-01 Standard Test method for Determination of Total solids in
Biomass. In this method the loss of weight during drying is a
measure for the original moisture content.
[0032] Preferably, the solid biomass material in step a) is a
micronized solid biomass material. By a micronized solid biomass
material is herein understood a solid biomass material that has a
particle size distribution with a mean particle size in the range
from equal to or more than 5 micrometer to equal to or less than
5000 micrometer, as measured with a laser scattering particle size
distribution analyzer. One preferred embodiment comprises a step of
reducing the particle size of the solid biomass material,
optionally before or after such solid biomass material is
torrefied. Such a particle size reduction step may for example be
especially advantageous when the solid biomass material comprises
wood or torrefied wood. The particle size of the, optionally
torrefied, solid biomass material can be reduced in any manner
known to the skilled person to be suitable for this purpose.
Suitable methods for particle size reduction include crushing,
grinding and/or milling. The particle size reduction may for
example be achieved by means of a ball mill, hammer mill, (knife)
shredder, chipper, knife grid, or cutter.
[0033] Preferably the solid biomass material has a particle size
distribution where the mean particle size lies in the range from
equal to or more than 5 micrometer (micron), more preferably equal
to or more than 10 micrometer, even more preferably equal to or
more than 20 micrometer, and most preferably equal to or more than
30 micrometer to equal to or less than 5000 micrometer, more
preferably equal to or less than 1000 micrometer and most
preferably equal to or less than 500 micrometer. In one especially
preferred embodiment, the solid biomass material has a particle
size distribution where the mean particle size is equal to or more
than 100 micrometer to avoid blocking of pipelines and/or nozzles.
Most preferably the solid biomass material has a particle size
distribution where the mean particle size is equal to or less than
3000 micrometer to allow easy injection into a reactor. For
practical purposes the particle size distribution and mean particle
size of the solid biomass material can be determined with a Laser
Scattering Particle Size Distribution Analyzer, preferably a Horiba
LA950, according to the ISO 13320 method titled "Particle size
analysis--Laser diffraction methods".
[0034] Hence, a preferred embodiment comprises a step of reducing
the particle size of the solid biomass material, optionally before
and/or after torrefaction, to generate a particle size distribution
having a mean particle size in the range from equal to or more than
5, more preferably equal to or more than 10 micron, and most
preferably equal to or more than 20 micron, to equal to or less
than 2 cm, more preferably to equal to or less than 5000 micrometer
(micron), more preferably equal to or less than 1000 micrometer and
most preferably equal to or less than 500 micrometer to produce a
micronized, optionally torrefied, solid biomass material.
[0035] In an optional embodiment the particle size reduction of
the, optionally torrefied, solid biomass material is carried out
whilst having the solid biomass material suspended in a
petroleum-derived hydrocarbon composition as described in more
detail below, to improve processibility and/or avoid dusting.
[0036] In addition, step a) may comprise dimineralizing of the
solid biomass material. During such a demineralization amongst
others chloride may be removed.
[0037] The optionally torrefied and/or optionally micronized solid
biomass material provided in step a) or part thereof may be
forwarded directly or indirectly to step b). For example the solid
biomass material may first be stored for a period "t" before
forwarding. Such a period "t" may preferably lie in the range from
1 hour to 1 month.
[0038] In step b) the, optionally torrefied and/or optionally
micronized, solid biomass material and a petroleum-derived
hydrocarbon composition, which petroleum-derived hydrocarbon
composition has a C7-asphaltenes content of equal to or more than
1.0 wt %, based on the total weight of the petroleum-derived
hydrocarbon composition, are contacted co-currently with a source
of hydrogen in one or more ebullating bed reactors comprising a
catalyst at a temperature in the range from 350.degree. C. to
500.degree. C. to produce a reaction product.
[0039] The petroleum-derived hydrocarbon composition may comprise
one or more hydrocarbon compounds and preferably comprises two or
more hydrocarbon compounds. By a hydrocarbon compound is herein
understood a compound containing hydrogen and carbon. Such
hydrocarbon compound may further contain heteroatoms such as
oxygen, sulphur and/or nitrogen. The petroleum-derived hydrocarbon
composition may also comprise hydrocarbon compounds consisting of
only hydrogen and carbon.
[0040] In a preferred embodiment, the C7-asphaltenes content of the
petroleum-derived hydrocarbon composition may be equal to or more
than 2.0% wt (percent by weight), more preferably equal to or more
than 5.0% wt, still more preferably equal to or more than 7.0% wt,
and suitably even equal to or more than 10.0% wt, based on the
total weight of the petroleum-derived hydrocarbon composition. For
practical purposes the C7-asphaltenes content of the
petroleum-derived hydrocarbon composition may be equal to or less
than 30.0% wt, suitably equal to or less than 25.0% wt or even
equal to or less than 20.0% wt, based on the total weight of the
petroleum-derived hydrocarbon composition. Preferably the
C7-asphaltenes content of the petroleum-derived hydrocarbon
composition lies in the range of from 2.0% wt to 30.0% wt, most
preferably in the range of from 5.0% wt to 20.0% wt, based on the
total weight of the petroleum-derived hydrocarbon composition. As
used herein, asphaltenes content or C7-asphaltenes content is as
determined by IP143, using n-heptane as a solvent.
[0041] Preferably, the petroleum-derived hydrocarbon composition
comprises a Micro Carbon Residue (MCR) in the range from equal to
or more than 5% wt to equal to or less than 35 wt %, more
preferably in the range from equal to or more than 10% wt to equal
to or less than 30 wt %, and most preferably in the range from
equal to or more than 15wt % to equal to or less than 25wt %, based
on the total weight of the petroleum-derived hydrocarbon
composition.
[0042] Suitably, the petroleum-derived hydrocarbon composition has
an initial atmospheric boiling point of equal to or more than
250.degree. C. Preferably, the petroleum-derived hydrocarbon
composition has an initial atmospheric boiling point of equal to or
more than 300.degree. C., more preferably equal to or more than
350.degree. C. In specific preferred embodiments, the initial
atmospheric boiling point of the petroleum-derived hydrocarbon
composition may even be above 500.degree. C. No specific upper
limit exists, but for practical reasons the initial atmospheric
boiling point of the petroleum-derived hydrocarbon composition may
be equal to or lower than 1000.degree. C.
[0043] In preferred embodiments, the hydrogen to carbon weight
ratio (H/C ratio) of the petroleum-derived hydrocarbon composition
may preferably be in the range of from 0.10 to 0.14 w/w, even more
preferably in the range of from 0.11 to 0.13 w/w.
[0044] Preferably the H/C Atomic Ratio (suitably calculated as the
weight percentage of hydrogen divided by the weight percentage of
carbon, multiplied by 12) of the petroleum-derived hydrocarbon
composition may be in the range from equal to or more than 1.0 to
equal to or less than 2.0, preferably in the range from equal to or
more than 1.2 to equal to or less than 1.6.
[0045] As used herein, boiling point is the atmospheric boiling
point, unless indicated otherwise, with the atmospheric boiling
point being the boiling point as determined at a pressure of 100
kiloPascal (i.e. 0.1 MegaPascal). As used herein, initial boiling
point, final boiling point and boiling point range are as
determined by ASTM D2887. As used herein, pressure is absolute
pressure. As used herein, asphaltenes content or C7-asphaltenes
content is as determined by IP143, using n-heptane as a
solvent.
[0046] In a preferred embodiment the petroleum-derived hydrocarbon
composition comprises shale oil, oil derived from oil sands,
bitumen, a straight run (atmospheric) gas oil, a flashed
distillate, a vacuum gas oil (VGO), a coker (heavy) gas oil, an
atmospheric residue ("long residue"), a vacuum residue ("short
residue") and/or mixtures thereof. Most preferably the
petroleum-derived hydrocarbon composition comprises an atmospheric
residue, a vacuum residue or a mixture thereof. The
petroleum-derived hydrocarbon composition may suitably also be
derived from an unconventional oil resource such as oil shale or
oil sands. For example the petroleum-derived hydrocarbon
composition may comprise a pyrolysis oil derived from oil shale or
oil sands.
[0047] In step b) the feed comprising the solid biomass material
and a petroleum-derived hydrocarbon composition is contacted
co-currently with hydrogen in one or more ebullating bed reactors
comprising a catalyst. Preferably the one or more ebullating bed
reactors comprise 2 or 3 ebullating bed reactors. Preferably the
one or more ebullating bed reactors are lined up in sequence, where
conveniently the catalyst is forwarded through the ebullating bed
reactors in a direction counter current to the direction of the
feed.
[0048] Instead of or in addition to one or more ebullating bed
reactors also one or more moving bed reactors and/or one or more
slurry reactors, may be used. It is also possible to use a
combination of ebullating bed reactors, moving bed reactors and/or
slurry reactors. That is, step b) may be carried out in one or more
reactors where each reactor individually can be an ebullating bed
reactor, a moving bed reactor or a slurry reactor. For example the
one or more reactors may comprise or consist of one or more
ebullating bed reactors and/or one or more slurry reactors. Most
preferably the one or more reactors are one or more ebullating bed
reactors. Such one or more ebullated bed reactors may each
conveniently comprise a liquid phase comprising the dewatered
hydrocarbon-containing mixture; a solid phase comprising one or
more catalysts; and a gaseous phase comprising hydrogen gas.
[0049] In preferred embodiment the solid biomass material may be
supplied to the reactor with the help of a pneumatic transport,
with the help of a so-called screw-feeder; with the help of a
so-called hopper or any combination thereof. Such pneumatic
transport, screw-feeder or hopper can suitably be used to supply
the solid biomass material to the reactor as a mixture, slurry or
suspension in a solvent such as for example the petroleum-derived
hydrocarbon composition as described above, but can also be used to
supply the solid biomass material to the reactor as dry matter
(i.e. in the absence of a solvent).
[0050] The feed to the one or more reactor(s) may comprise or
consist of a feed of solid biomass material and a co-feed of
petroleum-derived hydrocarbon composition; or the feed to the one
or more reactor(s) may comprise or consist of a mixture of the
solid biomass material and the petroleum-derived hydrocarbon
composition.
[0051] In a preferred embodiment, step b) comprises mixing the,
optionally torrefied and/or optionally micronized, solid biomass
material and the petroleum-derived hydrocarbon composition to
produce a mixture and contacting this mixture co-currently with the
source of hydrogen.
[0052] The mixture of the solid biomass material and the
petroleum-derived hydrocarbon composition can be produced in any
manner known to the skilled person in the art. In a preferred
embodiment, however, such a mixture is already provided in step a)
during a particle size reduction step as indicated herein
above.
[0053] Preferably, the solid biomass material and the
petroleum-derived hydrocarbon composition may be mixed and/or
co-feeded into a reactor in a weight ratio of solid biomass
material to petroleum-derived hydrocarbon composition (grams solid
biomass material/grams petroleum-derived hydrocarbon composition)
of at least 0.5/99.5, more preferably at least 1/99, still more
preferably at least 2/98, and even still more preferably at least
5/95, respectively. Preferably, the solid biomass material and the
petroleum-derived hydrocarbon composition may be mixed and/or
co-feeded in a weight ratio of solid biomass material to
petroleum-derived hydrocarbon composition (grams solid biomass
material/grams petroleum-derived hydrocarbon composition) of at
most 75/25, more preferably at most 70/30, even more preferably at
most 60/40, and most preferably at most 50/50 respectively. In an
especially preferred embodiment the petroleum-derived hydrocarbon
composition and the solid biomass material may be mixed and/or
co-feeded in a weight ratio of solid biomass material to
petroleum-derived hydrocarbon composition (grams solid biomass
material/grams petroleum-derived hydrocarbon composition) in the
range from 1/99 to 30/70, more preferably in the range from 5/95 to
25/75, most preferably in the range from 10/90 to 20/80.
[0054] Step b) is preferably carried out at a temperature in the
range from equal to or more than 350.degree. C. to equal to or less
than 470.degree. C., more preferably in the range from equal to or
more than 380.degree. C. to equal to or less than 460.degree. C.,
most preferably in the range from equal to or more than 400.degree.
C. to equal to or less than 450.degree. C.; and at a total pressure
in the range from equal to or more than 1 MegaPascal (MPa) to equal
to or less than 40 MPa, more preferably in the range from equal to
or more than 5 MPa to equal to or less than 30 MPa, most preferably
in the range from equal to or more than 8 MPa to equal to or less
than 25 MPa.
[0055] The source of hydrogen in step b) is preferably a hydrogen
gas. The source of hydrogen, respectively such hydrogen gas, may
conveniently comprise in the range from 0.1 to 10.0 volume % of
hydrogensulfide (H.sub.2S). Preferably the hydrogen is provided at
a hydrogen partial pressure in the range from equal to or more than
1 MegaPascal (MPa) to equal to or less than 40 MPa, more preferably
in the range from equal to or more than 5 MPa to equal to or less
than 30 MPa, most preferably in the range from equal to or more
than 8 MPa to equal to or less than 25 MPa. Most preferably the
hydrogen is provided at a hydrogen partial pressure in the range
from equal to or more 15 MPa to equal to or less than 20 MPa.
[0056] Preferably the quantity of hydrogen contacted with the feed
(i.e. the feed comprising or consisting of solid biomass material
and petroleum-derived hydrocarbon composition) preferably lies in
the range from 0.1 to 2 normal cubic meters (Nm.sup.3) per kg of
feed. In a preferred embodiment the hydrogen gas is provided in a
partial pressure that is in the range from 50% to 99%, more
preferably in the range from 60% to 95%, still more preferably in
the range from 70% to 90%, most preferably in the range from 80% to
90% of the total pressure.
[0057] In one embodiment, the one or more one or more ebullating
bed reactors in step b) are so-called hydrocracking reactors. By a
hydrocracking reactor is herein understood a reactor that is
suitable for hydrocracking of a feed. In another embodiment the
catalyst in step b) is a so-called hydrocracking catalyst. By a
hydrocracking catalyst is herein understood a catalyst that is
suitable for hydrocracking of a feed.
[0058] In another embodiment the one or more one or more ebullating
bed reactors in step b) are so-called Resid Upgrading reactors. By
a Resid Upgrading reactor is herein understood a reactor that is
suitable for upgrading of a so-called residual feed, such as for
example a vacuum residue and/or a atmospheric residue. In another
embodiment the catalyst in step b) is a so-called Resid Upgrading
catalyst. By a Resid Upgrading catalyst is herein understood a
catalyst that is suitable for upgrading of a so-called residual
feed, such as for example a vacuum residue and/or a atmospheric
residue.
[0059] The catalyst is preferably a catalyst comprising one or more
metals of group VIII of the periodic table and/or one or more
metals metal of group VIB of the periodic table. For example the
catalyst may comprise a metal selected from the group comprising
nickel, palladium, molybdenum, tungsten, platinum, cobalt, rhenium
and/or ruthenium. More preferably the catalyst is a nickel/tungsten
comprising catalyst, a nickel/molybdenum comprising catalyst,
cobalt/tungsten comprising catalyst or cobalt/molybdenum comprising
catalyst. Most preferably the catalyst is a nickel/molybdenum
(Ni/Mo) catalyst. Suitably the above mentioned metals may be
present in an alloy or oxide form.
[0060] Preferably the catalyst further comprises a support, which
may be used to carry the metal or metals. Such a catalyst
comprising one or more metals on a support is herein also referred
to as heterogeneous catalyst. Examples of suitable supports include
alumina, silica, silica-alumina, zirconia, titania, and/or mixtures
thereof. In one embodiment the support may comprise a zeolite, but
preferably comprises amorphous alumina, silica or silica-alumina.
Instead or in addition of these, the support may comprise one or
more zeolites.
[0061] Most preferably the catalyst comprises one or more oxides of
molybdenum, cobalt, nickel and/or tungsten on a carrier comprising
one or more zeolites, amorphous alumina, silica, silica-alumina or
any combination thereof. The catalyst may be prepared in any manner
known to be suitable by the person skilled in the art. In a
preferred embodiment, the catalyst is a so-called extruded
catalyst, prepared by extrusion of its components.
[0062] In a preferred embodiment the catalyst is a sulfided
catalyst. The catalyst may be sulfided in-situ or ex-situ. In a
preferred embodiment the catalyst is sulfided in-situ or its
sulfidation is maintained in-situ by contacting it with a stream of
hydrogen that comprises hydrogensulfide, for example a stream of
hydrogen that contains in the range from 0.1 to 10 wt %
hydrogensulfide based on the total weight of the stream of
hydrogen.
[0063] In step b) preferably a reaction product is produced
comprising one or more cracked products. By a cracked product is
herein understood a product comprising one or more compounds
obtained by cracking of one or more larger compounds.
[0064] In a preferred embodiment the reaction product or part
thereof is subsequently fractionated to produce one or more product
fractions.
[0065] For example a product fraction boiling in the gasoline range
(for example from about 35.degree. C. to about 210.degree. C.); a
product fraction boiling in the diesel range (for example from
about 210.degree. C. to about 370.degree. C.); a product fraction
boiling in the vacuum gas oil range (for example from about
370.degree. C. to about 540.degree. C.); and a short residue
product fraction (for example boiling above 540.degree. C.).
[0066] Preferably some embodiments therefore comprise an additional
step c) comprising fractionating the reaction product obtained in
step b) into two or more product fractions and separating one or
more product fraction(s) having a final boiling point of equal to
or less than 370.degree. C. at 0.1 MPa.
[0067] Further some embodiments can optionally comprise an
additional step d) comprising optionally upgrading of one or more
product fraction(s) in one or more hydrocarbon conversion processes
to produce one or more upgraded product fraction(s). More
preferably, step d) would comprise optionally upgrading of one or
more product fraction(s) having a final boiling point of equal to
or less than 370.degree. C. at 0.1 MPa in one or more hydrocarbon
conversion processes to produce one or more upgraded product
fraction(s) having a final boiling point of equal to or less than
370.degree. C. at 0.1 MPa.
[0068] The one or more hydrocarbon conversion processes may for
example include a fluid catalytic cracking process, a thermal
cracking process, a hydrogenation process, a hydro-isomerization
process, a hydro-desulphurization process or any combination
thereof. For example the one or more product fractions obtained by
fractionation may or may not be further hydrotreated or
hydroisomerized to obtain a hydrotreated or hydroisomerized product
fraction. The, optionally hydrotreated or hydroisomerized, product
fraction(s) may be used as biofuel and/or biochemical
component(s).
[0069] In a preferred embodiment the, optionally hydrotreated or
hydroisomerized, one or more product fractions produced in the
fractionation can be blended as a biofuel component and/or a
biochemical component 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 or a chemical that is at
least party derived from a renewable energy source. For example, a
preferred embodiment can comprise a further step e) comprising
optionally blending the one or more, optionally upgraded, product
fraction(s) having a final boiling point of equal to or less than
370.degree. C. at 0.1 MPa with one or more other components to
prepare a liquid fuel composition. Preferably the liquid fuel
composition is a liquid fuel composition suitable for use in a
spark-ignition engine and/or a liquid fuel composition suitable for
use in an auto-ignition engine.
[0070] Examples of one or more other components with which the,
optionally hydrotreated or hydroisomerized, one or more product
fractions may be blended 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.
[0071] As indicated above, embodiments of the invention also
include compositions obtainable or obtained in any of the processes
according to the invention. Examples of such compositions include
reaction products, product fractions, fuel components and/or liquid
fuel compositions.
[0072] For example, there is provided a composition comprising or
consisting of a plurality of hydrocarbon compounds, such
hydrocarbon compounds having a boiling point of equal to or less
than 370.degree. C., comprising in the range from equal to or more
than 1 wt % to equal to or less than 99 wt % of a fraction
consisting of biomass-derived hydrocarbon compounds; and in the
range from equal to or more than 1 wt % to equal to or less than 99
wt % of a fraction consisting of petroleum derived hydrocarbon
compounds; wherein the fraction consisting of biomass-derived
hydrocarbon compounds has a weight ratio W.sub.B of aromatics to
paraffins; wherein the fraction consisting of petroleum-derived
hydrocarbon compounds has a weight ratio W.sub.P of aromatics to
paraffins; and wherein the weight ratio W.sub.B is lower than the
weight ratio W.sub.P.
[0073] There is also provided a composition comprising a plurality
of hydrocarbon compounds, such hydrocarbon compounds having a
boiling point of equal to or less than 370.degree. C., a first
fraction comprising equal to or more than 1 wt % to equal to or
less than 99 wt % of biomass-derived hydrocarbon compounds; and a
second fraction comprising equal to or more than 1 wt % to equal to
or less than 99 wt % of petroleum derived hydrocarbon compounds;
wherein the first fraction has a weight ratio W.sub.B of aromatics
to paraffins; wherein the second fraction has a weight ratio
W.sub.P of aromatics to paraffins; and wherein the weight ratio
W.sub.B is lower than the weight ratio W.sub.P.
[0074] By a biomass-derived hydrocarbon compound is herein
understood a compound comprising at least one biomass-based carbon
atom.
[0075] In view of its origin, the fraction consisting of
biomass-derived hydrocarbon compounds or the first fraction may
comprise in the range from equal to or more than 0.1 wt %, more
preferably equal to or more than 0.5 wt %, still more preferably
equal to or more than 1 wt %, even more preferably equal to or more
than 5 wt %, and most preferably equal to or more than 10 wt % to
equal to or less than 100 wt %, suitably equal to or less than 50
wt % or suitably equal to or less than 30 wt % of bio-carbon, based
on the total weight of carbon present in the composition. For the
purpose of this invention, unless explicitly indicated otherwise,
bio-carbon may be understood to mean biobased carbon as determined
according to ASTM test D6866-10 titled "Standard Test Methods for
Determining the Biobased Content of Solid, Liquid and Gaseous
samples using Radiocarbon Analysis", method B. Further carbon or
elemental carbon as mentioned herein refer to carbon-atoms.
Bio-carbon may herein also be abbreviated as Bio-C.
[0076] FIG. 1 illustrates an example of a process according to some
aspects provided herein. In FIG. 1 a feed of wood (102), such as
for example poplar wood is converted in a chopper (104) into wood
chips (106). The wood chips (106) are torrefied in a torrefaction
unit (108) to produce torrefied wood chips (110). The torrefied
wood chips (110) are milled in a mill (112) to produce micronized
torrefied wood particles (114) having a particle size distribution
with a mean particle size of about 34 micron. A feed of micronized
torrefied wood particles (114) is pumped via a solids pump (116)
into a screw blender (124), where it is blended with a co-feed of
short residue (120), which short residue (120) is pumped via pump
(122) into the screw blender (124). In the screw blender (124), a
mixture (126) comprising the micronized torrefied wood particles
and the short residue is produced. The mixture (126) is blended
with a stream of hydrogen gas (130) and forwarded, optionally via
one or more screw feeders, hoppers and/or pneumatic feeders (not
shown), into a first ebullated bed reactor (140) comprising an
ebullating bed with a catalyst (142). In the first ebullated bed
reactor (140) and the first ebullating bed with catalyst (142), the
mixture (126) and hydrogen gas (130) are at least partially
converted under conditions comprising a temperature of 425.degree.
C., a mixture feed rate of 70 gram per hour and a hydrogen flow
rate of 50 standard liters per hour, to produce an at least
partially converted reaction product (145). This at least partially
converted reaction product (145) is blended with a stream of
hydrogen gas (132) and forwarded to a second ebullated bed reactor
(144) comprising an ebullating bed with a catalyst (146) wherein a
second fully converted reaction product (147) is produced. The
reaction product (147) is forwarded to a fractionator (150), where
it may, for example, be fractionated into a product fraction (158)
boiling in the gasoline range (for example from about 35.degree. C.
to about 210.degree. C.); a product fraction (156) boiling in the
diesel range (for example from about 170.degree. C. to about
370.degree. C.); a product fraction boiling in the vacuum gas oil
range (154); and a short residue product fraction (152) (for
example boiling above 540.degree. C.). The product fraction boiling
in the vacuum gas oil range (154) and/or the short residue product
fraction (152) may advantageously be used as a feed in for example
a fluid catalytic cracking process.
[0077] Illustrative embodiments are further illustrated by the
following non-limiting examples.
EXAMPLES
Example 1
Feed Preparation for Comparative Example
[0078] Pyrolysis oil was produced by pyrolysis of forest residue at
a temperature of about 500.degree. C. in an inert atmosphere. The
pyrolysis oil had a water content of about 23.9 wt % as determined
by Karl Fisher titration according to ASTM6304, based on the total
weight of the sample. The elemental composition of the pyrolysis
oil is summarized in table 1 below.
TABLE-US-00001 TABLE 1 Composition of Pyrolysis Oil from Forest
Residue. C, H, N, S, O (**), % wt. % wt. % wt. % wt. % wt. Basis
40.1 7.6 0.1 <0.00 52.2 Wet basis* 60.5 7.4 0.1 <0.00 32.0
Dry basis (calc. from wet basis***) *C, H, N according to ASTM
D5291 and S according to ASTM D2622 (**) Oxygen content calculated
by difference, i.e. by subtracting carbon, hydrogen, nitrogen and
sulphur content from 100 wt %. ***Water content of about 23.9 wt %
as determined by Karl Fisher titration according to ASTM6304 was
subtracted from the total mass before calculation of the
percentages on a dry basis.
[0079] A 12 kilogram (kg) mixture was prepared by mixing the above
pyrolysis oil with a so-called Arabian Medium Vacuum Residue (a
petroleum-derived hydrocarbon composition) in a weight ratio of
pyrolysis oil to Arabian Medium Vacuum Residue of 5:95. Some
characteristics of the Arabian Medium Vacuum Residue are provided
in table 2.
[0080] The Arabian Medium Vacuum Residue was preheated to a
temperature of about 80.degree. C. and conveyed to a vessel,
whereafter a specific amount of pyrolysis oil was added such as to
allow a mixture to be formed containing 5 wt % (weight %) of
pyrolysis oil and 95 wt % of Arabian Medium Vacuum Residue.
[0081] Water was removed from the resulting mixture during about 2
hours by means of a rotating vacuum evaporator set at about
90.degree. C. at a pressure of about 25 mbar (2.5 KiloPascal (KPa))
to obtain a dewatered pyrolysis oil-containing mixture. The water
content of the dewatered pyrolysis oil-containing mixture was
analyzed by means of a Karl Fisher titration pursuant to ASTM D6304
to be about 0.13 wt %, based on the total weight of the mixture.
Based on a 60% yield during the water evaporating step, the
dewatered pyrolysis oil-containing mixture was estimated to contain
around 3% wt dewatered pyrolysis oil. Approximately 10 kg of this
dewatered pyrolysis oil-containing mixture was sampled for the
reaction below.
TABLE-US-00002 TABLE 2 Characteristics of Arabian Medium Vacuum
Residue Property Method Results Density @ 60.degree. F.
(15.6.degree. C.), kg/l ASTM D - 70 1.0238 Micro Carbon Residue, %
wt. ASTM D - 4530 22.74 Nickel, ppmw. ASTM D - 5863A 47 Vanadium,
ppmw. ASTM D - 5863A 124 Iron, ppmw. ASTM D - 5863A 29 Toluene
Insolubles, % wt. ASTM D - 473 0.03 Viscosity @ 100.degree. C., cSt
ASTM D - 445 2153 Viscosity @ 149.degree. C., cSt ASTM D - 445 229
Ash content, % wt. ASTM D - 482 0.05 Water content, by
distillation, % v/v. ASTM D - 95 0.05 Saturates, % wt. ASTM D -
4124 6.2 Naphthenic Aromatics, % wt. ASTM D - 4124 41.4 Polar
Aromatics, % wt. ASTM D - 4124 39.7 Heptane Insolubles, % wt. IP -
143 12.7 Total, % wt. Sum of saturates, 100 naphtenic aromatics,
polar aromatics and heptanes insolubles Pentane insolubles, % wt.
IP - 143M 18.9 Carbon content, % wt. ASTM D - 5291 83.54 Hydrogen
content, % wt. ASTM D - 5291 10.12 Nitrogen, % wt ASTM D - 5291
0.39 H/C Atomic Ratio (H % wt/C % wt)* 1.45 atomic weight carbon
(12) Sulphur content, % wt. ASTM D2622 5.81 (X-ray) Chloride
content, ppmw <10 TAN, mg KOH/g ASTM D - 664 0.25
Example 2
Feed Preparation for Example According to One Illustrative
Embodiment of the Invention
[0082] As solid biomass material a sample of torrefied Poplar wood
with a composition as listed in table 3 was ball milled and
subsequently sieved (milled torrefied wood (TW)). The sample had a
water content of 3.6% wt. The particle size distribution can be
seen from FIG. 2. The cumulative values for 10% and 90% are
respectively 6.6 and 82.6 micrometers (.mu.m), whilst the milled
torrefied wood had a particle size distribution with a mean
particle size of 32.4 .mu.m. A sample of approximately 10 kilogram
(kg) of a mixture of the milled torrefied wood and Arabian Medium
Vacuum Residue was prepared. The mixture contained milled torrefied
wood and Arabian Medium Vacuum Residue in a weight ratio of milled
torrefied wood to Arabian Medium Vacuum Residue of 5:95.
[0083] Arabian Medium Vacuum Residue with characteristics as
summarized in table 2 was heated to 80.degree. C. and in a
fume-cupboard under stirring the milled torrefied wood was blended
into the Arabian Medium Vacuum Residue.
TABLE-US-00003 TABLE 3 Composition of torrefied Poplar wood sample.
O (by C, H, N, S, difference), % wt. % wt. % wt. % wt. % wt. 52.6
6.0 <0.2 0.013 41.4 Wet basis 54.6 5.8 0.014 39.6 Dry basis
(calc. from wet basis)
Example 3
Conversion
[0084] The conversion was carried out in a simulated two-stage
ebullated bed unit that consisted of two continuous stirred tank
reactor (CSTR) units connected together in series. Each CSTR unit
consisted of a one liter autoclave equipped with a Robinson Mahoney
catalyst basket.
[0085] For the comparative example, a flow of hydrogen gas was
added to a feed of dewatered pyrolysis oil-containing mixture as
prepared in example 1 prior to entering the first CSTR.
[0086] For the example according to one illustrative embodiment of
the invention, a flow of hydrogen gas was added to a feed of the
mixture containing milled torrefied wood and Arabian Medium Vacuum
Residue as prepared in example 2 prior to entering the first CSTR.
The feed vessel and the transfer lines to the reactor were kept at
120.degree. C., as an optimum for limited sedimentation and
sufficiently low viscosity to pump the feed to the reactor.
[0087] Both liquid and gas flowed from the first CSTR unit to the
second CSTR unit, with no interstage addition or withdrawal. The
product was obtained from the second CSTR unit. The operating
conditions are summarized in table 4. The operating conditions were
the same for both CSTR units.
[0088] In each CSTR unit, the combined flow of hydrogen gas and
feed was contacted with a sulphided catalyst in the form of
cylindrical extrudates having a diameter of about 1 mm containing 6
wt % molybdenum and 2.4 wt % nickel on a alumina carrier (the
catalyst was commercially obtained from Criterion). The catalyst
was loaded into the CSTR units in its oxide form, whereafter
sulfidation of the catalyst was carried out in situ, with a heavy
feed containing about 6wt % sulfur at a flow rate of 58.2
grams/hour a pressure of 15.5 MegaPascal (MPa) with a temperature
ramp of 32.degree. C. per hour to 400.degree. C. followed by an
overnight soak at 400.degree. C.
TABLE-US-00004 TABLE 4 Operating Conditions Condition Value
Catalyst amount per reactor, (grams) 29.75 Liquid feed rate,
(gram/hour) 67 H2flow rate, (standard liters/hour)* 47.2 Total
pressure (MPa) 15.5 Liquid temperature, .degree. C. 424 Overall
catalyst based LHSV (hr.sup.-1) ** 0.55 *standard liters/hour are
determined at 20.degree. C. and 0.1 MPa. ** ml of feed/per hour/per
ml catalyst bed.
[0089] A run was carried out containing five working periods as
reflected in table 5. In the first working period (0 to 104 hours)
a feed consisting only of Arabian Medium Vacuum Residue was
contacted with the hydrogen and the catalyst; in the second working
period (104-188 hours) a feed comprising the mixture as prepared in
example 1 was contacted with the hydrogen and the catalyst; in the
third working period (188-256 hours) again a feed consisting only
of Arabian Medium Vacuum Residue was contacted with the hydrogen
and the catalyst; in the fourth working period (257-328 hours) a
feed consisting of the mixture of milled torrefied wood and Arabian
Medium Vacuum Residue was contacted with the hydrogen and the
catalyst; and in the fifth working period (328-424 hours) again a
feed consisting only of Arabian Medium Vacuum Residue was contacted
with the hydrogen and the catalyst. During the run, the catalyst
was not refreshed.
TABLE-US-00005 TABLE 5 Overview of work periods and used feedstock.
Period 1 Period 2 Period 3 Period 4 Period 5 0-104 104-188 188-256
257-328 328-424 hours hours hours hours hours AMVR* DWPO- AMVR*
AMVR and AMVR* only mixture** only milled torrefied only as
prepared wood mixture in example 1 as prepared in example 2 *AMVR =
Arabian Medium Vacuum Residue **DWPO-mixture = dewatered pyrolysis
oil-containing mixture
[0090] During each of the working periods samples of the total
liquid product (TLP) were collected. The total liquid product (TLP)
samples were collected on the last day before a feed switch took
place. This TLP was nitrogen stripped to remove any residual H2S.
The stripped TLP was subsequently analyzed for sulphur content,
micro carbon residue (MCR) content and boiling point distribution.
TLP yield on feed was about 90%.
[0091] The boiling fractions for the stripped TLP obtained with the
feed containing only Arabian Medium Vacuum Residue (comparative);
for the stripped TLP obtained for the feed containing the dewatered
pyrolysis oil-containing mixture as prepared in example 1
(comparative); and for the stripped TLP obtained for the feed
containing the mixture of milled torrefied wood and Arabian Medium
Vacuum Residue as prepared in example 2 (according to the
invention) are listed in table 6.
[0092] The components in the fraction boiling below 370.degree. C.
(i.e. the gasoline and diesel range fractions) were analyzed and
are summarized in table 7. The components in the fraction boiling
above 370.degree. C. (i.e. the vacuum gas oil and short residue
range fractions) were analyzed and are summarized in table 8
(components with boiling up to 470.degree. C. could be determined
only).
[0093] The elemental composition of the stripped TLP is summarized
in tables 9, 10 and 11, this includes the sulphur content.
[0094] Further the Bio-carbon content was determined ASTM D6866 for
the stripped TLP boiling fractions above and below 370.degree. C.
The results are summarized in table 12. The results in the below
tables show that the process according to the invention allows one
to advantageously convert a solid biomass material to produce a
Bio-carbon containing liquid composition that has an improved
product quality.
[0095] The Bio-Carbon content of the feeds and distilled fractions
are given in Table 12 are based on .sup.14C measurements by SUERC
Radiocarbon Dating Laboratory in Edinburgh, Scotland. SUERC reports
the .sup.14C data as weight percentage of total C. This value needs
to be multiplied by the C content of the fraction to get the
.sup.14C level based on the whole fraction. Subsequently this
number needs to be multiplied by its yield (on feed) and deviding
this number by the amount of Bio-C in the feed in order to obtain
the Bio-C yield on feed.
[0096] For example TW has a C content of 52.6% wt. (which is all
Bio-C). When blended at 5% wt. in the SR the Bio-C content of the
feed is: 0.05*52.6=2.63% wt. The .sup.14C content of
<370.degree. C. fraction was measured by SUERC as 2.1% wt. (mass
.sup.14C/mass total C). By multiplying this value with the total
carbon content (mass total C/mass total product) the Bio-C content
on total product is obtained: 2.1*86.7/100=1.82% wt.
[0097] The TLP yield on feed is 90% wt. and the yield of the
<370.degree. C. fraction on TLP is 38.6% wt. Hence the yield of
the <370.degree. C. fraction on feed is: 0.9*38.6=34.7% wt. Then
the Bio-C yield of this fraction on feed is: 34.7*1.82/2.63=24%
wt.
TABLE-US-00006 TABLE 6 Yield Pattern of the Boiling Ranges of the
Stripped TLP as Measured by SIMDIST (simulated distillation ASTM
D7169). DWPO-mixture** Mixture TLP Boiling AMVR* as prepared as
prepared fraction only in Example 1 in example 2*** Gasoline 7.5%
wt. 7.5% wt. 12.5% wt. range: <210.degree. C. Diesel range: 30%
wt. 30.5% wt. 28.0% wt. 210-370.degree. C. Vacuum Gas Oil 33% wt.
33.5% wt. 31.5% wt. range: 370- 540.degree. C. Short Residue 29.5%
wt. 28.5% wt. 28% wt. range: >540.degree. C. Total 100% wt. 100%
wt. 100% wt. *AMVR = Arabian Medium Vacuum Residue **DWPO-mixture =
dewatered pyrolysis oil-containing mixture ***Mixture of AMVR and
milled torrefied wood
TABLE-US-00007 TABLE 7 Component Distribution in the
<370.degree. C. Stripped TLP Boiling Fractions, as Determined by
2-Dimensional Gas Chromatography. DWPO-mixture** Mixture AMVR* as
prepared as prepared Components only in Example 1 in example 2***
Paraffins (% wt.) 31.93 31.34 34.82. Naphtenes (% wt.) 18.36 18.10
19.04 di-Naphtenes (% wt.) 3.97 4.16 4.05 mono-Aromatics 16.28
16.36 16.17 (% wt.) Naphtenes-mono- 13.40 13.99 12.19 Aromatics (%
wt.) di-Aromatics (% wt.) 7.23 7.32 6.41. Naphtenes-di- 5.84 5.95
4.92 Aromatics (% wt.) tri-Aromatics (% wt.) 2.33 2.08 1.89
>three Ring 0.66 0.69 0.51 Aromatics (% wt.) *AMVR = Arabian
Medium Vacuum Residue, based on a sample of stripped TLP obtained
in period 3 as illustrated in table 5 **DWPO-mixture = dewatered
pyrolysis oil-containing mixture ***Mixture of AMVR and milled
torrefied wood
TABLE-US-00008 TABLE 8 Component Distribution in the 370.degree.
C.-470.degree. C. Stripped TLP Boiling Fractions, as Determined by
2-Dimensional Gas Chromatography. DWPO-mixture** Mixture as AMVR*
as prepared prepared Component only in Example 1 in example 2***
Paraffins (% wt.) 7.08 7.16 7.37 Naphtenes (% wt.) 4.59 4.55 4.70
di-Naphtenes (% wt.) 0.08 0.06 0.08 mono-Aromatics 6.00 6.08 6.34
(% wt.) Naphtenes-mono- 1.71 1.90 1.79 Aromatics (% wt.)
di-Aromatics (% wt.) 1.75 1.87 2.08 Naphtenes-di- 1.08 1.41 1.32
Aromatics (% wt.) tri-Aromatics (% wt.) 2.44 2.64 3.04 >three
Ring 5.29 5.06 6.45 Aromatics (% wt.) *AMVR = Arabian Medium Vacuum
Residue, based on a sample of stripped TLP obtained in period 3 as
illustrated in table 5 **DWPO-mixture = dewatered pyrolysis
oil-containing mixture ***Mixture of AMVR and milled torrefied
wood
TABLE-US-00009 TABLE 9 TLP Elemental Composition and Density. O/C
H/C Molar Density C H N S O by dif. molar ratio times kg/m3 MCRT
Period % wt. % wt. % wt. % wt. % wt. ratio 100 at 15.degree. C. %
wt. * only 1 87.2 11.5 0.278 0.732 0.29 1.58 0.25 931.1 6.0 PO- 2
87 11.4 0.318 0.900 0.38 1.57 0.33 936.9 6.5 ** as ed in ple 1
*only 3 87 11.3 0.339 1.105 0.26 1.56 0.22 941 7.5 re as 4 85.9
11.4 0.336 1.089 1.27 1.59 1.11 908.3 85.9 ed in e 2*** * only 5
86.9 11.1 0.379 1.431 0.19 1.53 0.16 951.6 86.9 = Arabian Medium
Vacuum Residue -mixture = dewatered pyrolysis oil-containing
mixture re of AMVR and milled torrefied wood indicates data missing
or illegible when filed
TABLE-US-00010 TABLE 10 Elemental Composition and Density of
<370.degree. C. Fraction. Density C H N S O by dif. H/C ratio
O/C ratio kg/m3 Period % wt. % wt. % wt. % wt. % wt. molar molar *
100 at 15.degree. C. * 1 87 12.73 0.08 0.132 0.06 1.76 0.05 858.4 -
2 87 12.72 0.098 0.156 0.03 1.75 0.02 857.7 ** red le 1 nly 3 86.9
12.72 0.109 0.221 0.05 1.76 0.04 857.6 as 4 86.7 12.91 0.1 0.185
0.10 1.79 0.09 842.9 in le * 5 86.8 12.69 0.125 0.323 0.06 1.75
0.05 858.9 = Arabian Medium Vacuum Residue -mixture = dewatered
pyrolysis oil-containing mixture re of AMVR and milled torrefied
wood indicates data missing or illegible when filed
TABLE-US-00011 TABLE 11 Elemental Composition of >370.degree. C.
Fraction. C N O by dif. H/C ratio O/C ratio Period % wt. H % wt. %
wt. S % wt. % wt. molar molar * 100 * 1 87.3 10.8 0.393 1.015 0.49
1.48 0.42 - 2 87.0 10.6 0.444 1.200 0.71 1.47 0.61 ** red le 1 nly
3 87.1 10.5 0.463 1.604 0.34 1.45 0.30 as 4 85.4 10.5 0.484 1.578
2.09 1.47 1.84 in le * 5 87.0 10.3 0.514 1.283 0.99 1.42 0.86 =
Arabian Medium Vacuum Residue -mixture = dewatered pyrolysis
oil-containing mixture re of AMVR and milled torrefied wood
indicates data missing or illegible when filed
TABLE-US-00012 TABLE 12 Bio-Carbon content and yields
DWPO-mixture** as Mixture as prepared prepared in example 1 in
example 2*** <370.degree. C. >370.degree. C. <370.degree.
C. >370.degree. C. fraction fraction fraction fraction TLP, %
wt. 36.4 63.6 38.6 61.4 Feed, % wt. 32.8 57.2 34.7 55.3 ntent in
1.8 2.6 t. ntent in 2.0 0.35 1.82 0.60 % wt. ld, % wt. 36.4 11.1 24
12.6 -mixture = dewatered pyrolysis oil-containing mixture re of
AMVR and milled torrefied wood indicates data missing or illegible
when filed
[0098] Therefore, embodiments of the present invention are well
adapted to attain the ends and advantages mentioned as well as
those that are inherent therein. The particular embodiments
disclosed above are illustrative only, as the present invention may
be modified and practiced in different but equivalent manners
apparent to those skilled in the art having the benefit of the
teachings herein. Furthermore, no limitations are intended to the
details of construction or design herein shown, other than as
described in the claims below. It is therefore evident that the
particular illustrative embodiments disclosed above may be altered,
combined, substituted, or modified and all such variations are
considered within the scope and spirit of the present invention.
The invention illustratively disclosed herein suitably may be
practiced in the absence of any element that is not specifically
disclosed herein and/or any optional element disclosed herein.
While compositions and methods are described in terms of
"comprising," "containing," or "including" various components or
steps, the compositions and methods can also "consist essentially
of" or "consist of" the various components and steps. All numbers
and ranges disclosed above may vary by some amount whether
accompanied by the term "about" or not. In particular, the phrase
"from about a to about b" is equivalent to the phrase "from
approximately a to b," or a similar form thereof. Also, the terms
in the claims have their plain, ordinary meaning unless otherwise
explicitly and clearly defined by the patentee. Moreover, the
indefinite articles "a" or "an," as used in the claims, are defined
herein to mean one or more than one of the element that it
introduces.
* * * * *