PROCESS FOR CONVERTING A SOLID BIOMASS MATERIAL

- Shell Oil Company

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° C. to 500° C. to produce a reaction product.

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Description
CROSS-REFERENCE TO RELATED APPLICATIONS

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

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

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 CO2 emissions that may help meet global CO2 emissions standards under the Kyoto protocol.

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.

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° C. at a pressure of 100 kiloPascal).

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 %.

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

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.

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° C. to 500° C. to produce a reaction product.

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° 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° 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° 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° 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.

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° C.) product is more stable.

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° 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° 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.

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° 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° 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.

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.

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 CO2 emissions standards under the Kyoto protocol.

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° 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 WB of aromatics to paraffins; wherein the fraction consisting of petroleum-derived hydrocarbon compounds has a weight ratio WP of aromatics to paraffins; and wherein the weight ratio WB is lower than the weight ratio WP.

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

Illustrative embodiments of the invention have been illustrated by the following non-limiting figures:

FIG. 1 illustrates one embodiment according to some aspects provided.

FIG. 2 illustrates the particle size distribution of the milled torrefied wood used in the examples.

DETAILED DESCRIPTION

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° C. to 500° C. to produce a reaction product.

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.

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.

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.

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.

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° 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.

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° C. to equal to or less than 350° 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.

Torrefying of the solid biomass material is preferably carried out at a temperature of more than 200° C., more preferably at a temperature equal to or more than 210° C., still more preferably at a temperature equal to or more than 220° C., yet more preferably at a temperature equal to or more than 230° C. In addition torrefying of the solid biomass material is preferably carried out at a temperature less than 350° C., more preferably at a temperature equal to or less than 330° C., still more preferably at a temperature equal to or less than 310° C., yet more preferably at a temperature equal to or less than 300° 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.

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.

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.

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.

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”.

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.

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.

In addition, step a) may comprise dimineralizing of the solid biomass material. During such a demineralization amongst others chloride may be removed.

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.

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° C. to 500° C. to produce a reaction product.

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.

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.

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.

Suitably, the petroleum-derived hydrocarbon composition has an initial atmospheric boiling point of equal to or more than 250° C. Preferably, the petroleum-derived hydrocarbon composition has an initial atmospheric boiling point of equal to or more than 300° C., more preferably equal to or more than 350° C. In specific preferred embodiments, the initial atmospheric boiling point of the petroleum-derived hydrocarbon composition may even be above 500° 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° C.

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.

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.

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.

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.

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.

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.

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).

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.

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.

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.

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.

Step b) is preferably carried out at a temperature in the range from equal to or more than 350° C. to equal to or less than 470° C., more preferably in the range from equal to or more than 380° C. to equal to or less than 460° C., most preferably in the range from equal to or more than 400° C. to equal to or less than 450° 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.

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 (H2S). 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.

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 (Nm3) 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.

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.

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.

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.

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.

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.

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.

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.

In a preferred embodiment the reaction product or part thereof is subsequently fractionated to produce one or more product fractions.

For example a product fraction boiling in the gasoline range (for example from about 35° C. to about 210° C.); a product fraction boiling in the diesel range (for example from about 210° C. to about 370° C.); a product fraction boiling in the vacuum gas oil range (for example from about 370° C. to about 540° C.); and a short residue product fraction (for example boiling above 540° C.).

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° C. at 0.1 MPa.

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° 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° C. at 0.1 MPa.

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).

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° 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.

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.

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.

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° 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 WB of aromatics to paraffins; wherein the fraction consisting of petroleum-derived hydrocarbon compounds has a weight ratio WP of aromatics to paraffins; and wherein the weight ratio WB is lower than the weight ratio WP.

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° 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 WB of aromatics to paraffins; wherein the second fraction has a weight ratio WP of aromatics to paraffins; and wherein the weight ratio WB is lower than the weight ratio WP.

By a biomass-derived hydrocarbon compound is herein understood a compound comprising at least one biomass-based carbon atom.

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.

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° 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° C. to about 210° C.); a product fraction (156) boiling in the diesel range (for example from about 170° C. to about 370° C.); a product fraction boiling in the vacuum gas oil range (154); and a short residue product fraction (152) (for example boiling above 540° 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.

Illustrative embodiments are further illustrated by the following non-limiting examples.

EXAMPLES Example 1 Feed Preparation for Comparative Example

Pyrolysis oil was produced by pyrolysis of forest residue at a temperature of about 500° 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 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.

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.

The Arabian Medium Vacuum Residue was preheated to a temperature of about 80° 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.

Water was removed from the resulting mixture during about 2 hours by means of a rotating vacuum evaporator set at about 90° 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 2 Characteristics of Arabian Medium Vacuum Residue Property Method Results Density @ 60° F. (15.6° 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° C., cSt ASTM D - 445 2153 Viscosity @ 149° 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

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 (μm), whilst the milled torrefied wood had a particle size distribution with a mean particle size of 32.4 μm. 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.

Arabian Medium Vacuum Residue with characteristics as summarized in table 2 was heated to 80° C. and in a fume-cupboard under stirring the milled torrefied wood was blended into the Arabian Medium Vacuum Residue.

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

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.

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.

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° C., as an optimum for limited sedimentation and sufficiently low viscosity to pump the feed to the reactor.

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.

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° C. per hour to 400° C. followed by an overnight soak at 400° C.

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, ° C. 424 Overall catalyst based LHSV (hr−1) ** 0.55 *standard liters/hour are determined at 20° C. and 0.1 MPa. ** ml of feed/per hour/per ml catalyst bed.

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 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

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%.

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.

The components in the fraction boiling below 370° 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° 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° C. could be determined only).

The elemental composition of the stripped TLP is summarized in tables 9, 10 and 11, this includes the sulphur content.

Further the Bio-carbon content was determined ASTM D6866 for the stripped TLP boiling fractions above and below 370° 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.

The Bio-Carbon content of the feeds and distilled fractions are given in Table 12 are based on 14C measurements by SUERC Radiocarbon Dating Laboratory in Edinburgh, Scotland. SUERC reports the 14C data as weight percentage of total C. This value needs to be multiplied by the C content of the fraction to get the 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.

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 14C content of <370° C. fraction was measured by SUERC as 2.1% wt. (mass 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.

The TLP yield on feed is 90% wt. and the yield of the <370° C. fraction on TLP is 38.6% wt. Hence the yield of the <370° 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 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° C. Diesel range: 30% wt. 30.5% wt. 28.0% wt. 210-370° C. Vacuum Gas Oil 33% wt. 33.5% wt. 31.5% wt. range: 370- 540° C. Short Residue 29.5% wt. 28.5% wt. 28% wt. range: >540° 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 7 Component Distribution in the <370° 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 8 Component Distribution in the 370° C.-470° 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 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° 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 10 Elemental Composition and Density of <370° 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° 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 11 Elemental Composition of >370° 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 12 Bio-Carbon content and yields DWPO-mixture** as Mixture as prepared prepared in example 1 in example 2*** <370° C. >370° C. <370° C. >370° 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

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.

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° C. to 500° 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° 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° 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° 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° 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° 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° 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° C. to 500° 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° C. to 500° 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° C. to 500° 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° C. to 500° 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° 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 WB of aromatics to paraffins;
wherein the second fraction has a weight ratio WP of aromatics to paraffins; and
wherein the weight ratio WB is lower than the weight ratio WP.

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° 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.

Patent History
Publication number: 20140343333
Type: Application
Filed: May 15, 2014
Publication Date: Nov 20, 2014
Applicant: Shell Oil Company (Houston, TX)
Inventors: Josiane Marie-Rose GINESTRA (Richmond, TX), Johannes Pieter HAAN (Amsterdam), Robert Wilfred Matthews WARDLE (Ince)
Application Number: 14/277,834
Classifications
Current U.S. Class: For Fuel Use Only (585/14); From Wood (585/242)
International Classification: C10G 1/00 (20060101);