A blendable biofuel oil and method of manufacture thereof

Abstract

This invention generally relates to a biofuel oil and a method for the manufacture of a biofuel oil by pyrolysis of lignocellulosic biomass and catalytic upgrading. The invention also generally relates to blended fuel oils and a method for the manufacture of blended fuel oils, which comply with marine fuel oil standards, by combination of the biofuel oils of the present invention and at least one heavy fuel oil.

Description

A BLENDABLE BIOFUEL OIL AND METHOD OF MANUFACTURE THEREOFField of the invention

[0001] This invention generally relates to a biofuel oil and a method for the manufacture of a biofuel oil by pyrolysis of lignocellulosic biomass and catalytic upgrading. The invention also generally relates to blended fuel oils and a method for the manufacture of blended fuel oils, which comply with marine fuel oil standards, by combination of the biofuel oils of the present invention and at least one heavy fuel oil.Background to the invention

[0002] Marine shipping is a major driver of international trade and contributes to about 80% of all goods transported globally. Shipping consumes over 280 million tonnes of fossil fuel per annum and contributes 2-3% of global CO2 emissions. The scale of the shipping industry means it is not viable to promptly replace all existing ships or their propulsion systems, technology and fuel systems to be compatible with a completely new fuel source. For a period of at least 30 years or so, a substantial part of the shipping fleet will continue to use the current technology. Therefore, there is a need to develop fuels compatible with existing engine technology but with a greater renewable carbon content than current marine fuels. Biodiesel derived from plant and animal-based oils and fats is a partial solution but is in short supply, and may be produced in competition with food production as well as face competing demand from other transport and industrial sectors.

[0003] There is an ongoing need for a source of biofuel oil that is suitable for the marine sector with supply chains that can supply in volume.

[0004] Pyrolysis oils can be made from lignocellulosic materials using catalytic fast pyrolysis. Pyrolysis oils made from wood, grasses and forestry and agriculture residues, can meet many of the scale, supply chain and renewable requirements. However, pyrolysis oils are generally not seen as suitable for use as transportation fuel due to instability, high oxygen content, high water content, high acidity and corrosiveness and relatively low energy densities.

[0005] It is an object of the invention to provide a biofuel oil compatible with residual fuel oils and / or heavy fuel oils, and / or a blended marine or industrial fuel comprised of a biofuel oiland a residual fuel oil and / or heavy fuel oil with inherent stabilising properties, and / or at least to provide the public with a useful choice.

[0006] In this specification where reference has been made to patent specifications, other external documents, or other sources of information, this is generally for the purpose of providing a context for discussing the features of the invention. Unless specifically stated otherwise, reference to such external documents is not to be construed as an admission that such documents, or such sources of information, in any jurisdiction, are prior art, or form part of the common general knowledge in the art.Summary of the invention

[0007] In a first aspect, the invention provides a biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol comprising a benzene ring substituted with a hydroxyl group and a C2-C3 alkyl or C2-C3 alkenyl group at a position para to the hydroxyl group.

[0008] In some embodiments, the biofuel oil has a Higher Heating Value (HHV) greater than about 29 MJ / kg.

[0009] In another aspect, the invention provides a biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol comprising a benzene ring substituted with a hydroxyl group and a C2-C3 alkyl or C2-C3 alkenyl group at a position para to the hydroxyl group, wherein the biofuel oil has a Higher Heating Value (HHV) greater than about 29 MJ / kg.

[0010] In some embodiments, the biofuel oil has an acid number of less than about 15 mg KOH / g of biofuel oil.

[0011] In some embodiments, the benzene ring is optionally substituted with one or two additional groups selected from the group consisting of hydroxyl, methyl, and methoxy groups at any available position of the benzene ring.

[0012] In some embodiments, the one or more monomeric substituted phenol is a monomeric substituted monohydroxy benzene, a monomeric substituted cresole, a monomeric substituted guaiacol, a monomeric substituted catechol or a monomeric substituted syringol; wherein the monomeric substituted monohydroxy benzene, monomeric substituted cresole,monomeric substituted guaiacol, monomeric substituted catechol and monomeric substituted syringol is substituted with a C2-C3 alkyl or C2-C3 alkenyl group at a position para to the or a phenolic hydroxyl group of the monohydroxy benzene, cresole, guiacol, catechol, or syringol.

[0013] In some embodiments, the one or more monomeric substituted phenol is a compound of the formula (1):(Dwherein: R1is C2-C3 alkyl or C2-C3 alkenyl; and R2and R3are each independently selected from the group consisting of H, OH, Me, and OMe.

[0014] In some embodiments, the compound of formula (1) is a compound of the formula (2):(2).

[0015] In some embodiments, R2is independently selected from the group consisting of H, OH, Me, and OMe and R3is independently H; or R2and R3are each OMe.

[0016] In some embodiments, the one or more monomeric substituted phenol is selected from the group consisting of: cis-isoeugenol, trans-isoeugenol, eugenol, 4-ethylguaiacol, 4-ethylcatechol, 4-ethylsyringol, 4-ethyl-2-methylphenol, 4-ethylphenol, 4-a llylphenol, 4-allyl-2-methylphenol, 4-propylphenol, 2-methyl-4-propylphenol, 4-vinylguaicol and 4-propylguaiacol

[0017] In some embodiments, the one or more monomeric substituted phenol is selected from the group consisting of: cis-isoeugenol, trans-isoeugenol, 4-ethylguaiacol, 4-ethylcatechol, 4-ethylphenol, 4-propylphenol, and 4-propylguaiacol.

[0018] In some embodiments, the one or more monomeric substituted phenol has a molecular weight of less than about 200 g / mol.

[0019] In some embodiments, the biofuel oil comprises at least about 4 or 5% by weight of the one or more monomeric substituted phenol.

[0020] In some embodiments, the biofuel oil comprises at least about 6, 7, 8 or 9% by weight of the one or more monomeric substituted phenol.

[0021] In some embodiments, the biofuel oil comprises one or more degradation products selected from the group consisting of hydroxybenzene, toluene, and polyaromatics.

[0022] In some embodiments, the one or more degradation products are selected from the group consisting of hydroxybenzene, toluene, naphthalene, methylnaphthalene, and retene.

[0023] In some embodiments, the biofuel oil comprises the one or more monomeric substituted phenol and the one or more degradation products in a weight ratio of greater than about 3:1.

[0024] In some embodiments, the biofuel oil comprises the one or more monomeric substituted phenol and the one or more degradation products in a weight ratio of greater than about 4:1, about 5:1 or about 6:1.

[0025] In some embodiments, the biofuel oil has an oxygen content of less than about 35, about 30 or about 25% by weight.

[0026] In another aspect, the invention provides a biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol comprising a benzene ring substituted with a hydroxyl group and a C2-C3 alkyl or C2-C3 alkenyl group at a position para to the hydroxyl group, wherein the biofuel oil has an oxygen content of less than about 35, about 30 or about 25% by weight.

[0027] In some embodiments, the biofuel oil has a water content of less than about 15% by weight.

[0028] In another aspect, the invention provides a biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol comprising a benzene ring substituted with a hydroxyl group and a C2-C3 alkyl or C2-C3 alkenyl group at a position para to the hydroxyl group, wherein the biofuel oil has a water content of less than about 15% by weight.

[0029] In some embodiments, the biofuel comprises less than about 0.45, about 0.3, about 0.2 about 0.1% by weight levoglucosan.

[0030] In some embodiments, the biofuel has no levoglucosan detectable by GC-MS.

[0031] In another aspect, the invention provides a biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol comprising a benzene ring substituted with a hydroxyl group and a C2-C3 alkyl or C2-C3 alkenyl group at a position para to the hydroxyl group, wherein the biofuel comprises less than about 0.45, about 0.3, about 0.2 about 0.1% by weight levoglucosan or the biofuel has no levoglucosan detectable by GC-MS.

[0032] In another aspect, the invention provides a biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol comprising a benzene ring substituted with a hydroxyl group and a C2-C3 alkyl or C2-C3 alkenyl group at a position para to the hydroxyl group, wherein the biofuel oil: a. has a Higher Heating Value (HHV) greater than about 29 MJ / kg; b. has an oxygen content of less than about 35, about 30 or about 25% by weight; c. has a water content of less than about 15% by weight; and / or d. comprises less than about 0.45, about 0.3, about 0.2 about 0.1% by weight levoglucosan.

[0033] In a second aspect, the invention provides a biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol and one or more degradation products,wherein the one or more monomeric substituted phenol is selected from the group consisting of: cis-isoeugenol, trans-isoeugenol, eugenol, 4-ethylguaiacol, 4-ethylcatechol, 4-ethylsyringol, 4-ethyl-2-methylphenol, 4-ethylphenol, 4-a I ly I phenol, 4-allyl-2-methylphenol, 4-propylphenol, 2-methyl-4-propylphenol, 4-vinylguaicol and 4-propylguaiacol,wherein the one or more degradation products are selected from the group consisting of hydroxybenzene, toluene, naphthalene, methylnaphthalene, and retene, andwherein the one or more monomeric substituted phenol and one or more degradation products are in a weight ratio of greater than about 3:1, about 4:1, about 5:1 or about 6:1.

[0034] In some embodiments, the biofuel oil has a Higher Heating Value (HHV) greater than about 29 MJ / kg.

[0035] In another aspect, the invention provides a biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol and one or more degradation products,wherein the one or more monomeric substituted phenol is selected from the group consisting of: cis-isoeugenol, trans-isoeugenol, eugenol, 4-ethylguaiacol, 4-ethylcatechol, 4-ethylsyringol, 4-ethyl-2-methylphenol, 4-ethylphenol, 4-a I ly I phenol, 4-allyl-2-methylphenol, 4-propylphenol, 2-methyl-4-propylphenol, 4-vinylguaicol and 4-propylguaiacol,wherein the one or more degradation products are selected from the group consisting of hydroxybenzene, toluene, naphthalene, methylnaphthalene, and retene, andwherein the one or more monomeric substituted phenol and one or more degradation products are in a weight ratio of greater than about 3:1, about 4:1, about 5:1 or about 6:1, wherein the biofuel oil has a Higher Heating Value (HHV) greater than about 29 MJ / kg.

[0036] In some embodiments, the biofuel oil has an oxygen content of less than about 35, about 30 or about 25% by weight.

[0037] In another aspect, the invention provides a biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol and one or more degradation products,wherein the one or more monomeric substituted phenol is selected from the group consisting of: cis-isoeugenol, trans-isoeugenol, eugenol, 4-ethylguaiacol, 4-ethylcatechol, 4-ethylsyringol, 4-ethyl-2-methylphenol, 4-ethylphenol, 4-a I ly I phenol, 4-allyl-2-methylphenol, 4-propylphenol, 2-methyl-4-propylphenol, 4-vinylguaicol and 4-propylguaiacol,wherein the one or more degradation products are selected from the group consisting of hydroxybenzene, toluene, naphthalene, methylnaphthalene, and retene, andwherein the one or more monomeric substituted phenol and one or more degradation products are in a weight ratio of greater than about 3:1, about 4:1, about 5:1 or about 6:1, wherein the biofuel oil has an oxygen content of less than about 35, about 30 or about 25% by weight.

[0038] In some embodiments, the biofuel oil has a water content of less than about 15% by weight.

[0039] In another aspect, the invention provides a biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol and one or more degradation products,wherein the one or more monomeric substituted phenol is selected from the group consisting of: cis-isoeugenol, trans-isoeugenol, eugenol, 4-ethylguaiacol, 4-ethylcatechol, 4-ethylsyringol, 4-ethyl-2-methylphenol, 4-ethylphenol, 4-a I ly I phenol, 4-allyl-2-methylphenol, 4-propylphenol, 2-methyl-4-propylphenol, 4-vinylguaicol and 4-propylguaiacol,wherein the one or more degradation products are selected from the group consisting of hydroxybenzene, toluene, naphthalene, methylnaphthalene, and retene, andwherein the one or more monomeric substituted phenol and one or more degradation products are in a weight ratio of greater than about 3:1, about 4:1, about 5:1 or about 6:1, wherein the biofuel oil has a water content of less than about 15% by weight.

[0040] In some embodiments, the biofuel comprises less than about 0.45, about 0.3, about 0.2 about 0.1% by weight levoglucosan.

[0041] In some embodiments, the biofuel has no levoglucosan detectable by GC-MS.

[0042] In another aspect, the invention provides a biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol and one or more degradation products,wherein the one or more monomeric substituted phenol is selected from the group consisting of: cis-isoeugenol, trans-isoeugenol, eugenol, 4-ethylguaiacol, 4-ethylcatechol, 4-ethylsyringol, 4-ethyl-2-methylphenol, 4-ethylphenol, 4-a I ly I phenol, 4-allyl-2-methylphenol, 4-propylphenol, 2-methyl-4-propylphenol, 4-vinylguaicol and 4-propylguaiacol,wherein the one or more degradation products are selected from the group consisting of hydroxybenzene, toluene, naphthalene, methylnaphthalene, and retene, andwherein the one or more monomeric substituted phenol and one or more degradation products are in a weight ratio of greater than about 3:1, about 4:1, about 5:1 or about 6:1, wherein the biofuel comprises less than about 0.45, about 0.3, about 0.2 about 0.1% by weight levoglucosan or the biofuel has no levoglucosan detectable by GC-MS.

[0043] In another aspect, the invention provides a biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol and one or more degradation products,wherein the one or more monomeric substituted phenol is selected from the group consisting of: cis-isoeugenol, trans-isoeugenol, eugenol, 4-ethylguaiacol, 4-ethylcatechol, 4-ethylsyringol, 4-ethyl-2-methylphenol, 4-ethylphenol, 4-a I ly I phenol, 4-allyl-2-methylphenol, 4-propylphenol, 2-methyl-4-propylphenol, 4-vinylguaicol and 4-propylguaiacol,wherein the one or more degradation products are selected from the group consisting of hydroxybenzene, toluene, naphthalene, methylnaphthalene, and retene, andwherein the one or more monomeric substituted phenol and one or more degradation products are in a weight ratio of greater than about 3:1, about 4:1, about 5:1 or about 6:1, wherein the biofuel oil: a. has a Higher Heating Value (HHV) greater than about 29 MJ / kg; b. has an oxygen content of less than about 35, about 30 or about 25% by weight; c. has a water content of less than about 15% by weight; and / or d. comprises less than about 0.45, about 0.3, about 0.2 about 0.1% by weight levoglucosan.

[0044] In a third aspect, the invention provides a method for manufacturing a biofuel oil, the method comprising:a. pyrolysing a lignocellulosic biomass to produce a pyrolysis vapour;b. subjecting the pyrolysis vapour to the action of a catalyst composition under catalytic conditions to produce an upgraded vapour;c. condensing the upgraded vapour to produce a biphasic biofuel oil comprising an organic phase and an aqueous phase; andd. removing the aqueous phase from the organic phase to provide the biofuel oil;wherein the catalyst composition and catalytic conditions are selected to provide:• a biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol comprising a benzene ring substituted with a hydroxyl group and a C2-C3 alkyl or C2-C3 alkenyl group at a position para to the hydroxyl group

[0045] In some embodiments, the method further comprises subjecting the biofuel oil to caustic washing, aqueous washing or both caustic washing and aqueous washing.

[0046] In some embodiments, the method further comprises subjecting the biofuel oil to an additional water removal step.

[0047] In some embodiments, the water removal step comprises reducing the water content of the biofuel oil to less than about 5% by weight.

[0048] In some embodiments, the water removal step comprises evaporation and / or distillation.

[0049] In some embodiments, the lignocellulosic biomass is derived from a wood, softwood, or coniferous wood biomass.

[0050] In some embodiments, removing the aqueous phase from the organic phase comprises a mechanical separation.

[0051] In some embodiments, the mechanical separation is centrifugation.

[0052] In some embodiments, the aqueous phase comprises one or more carboxylic acids having a molecular weight of 300 g / mol or less.

[0053] In some embodiments, the catalyst composition comprises a catalyst with a porosity of from about 0 to about 120 m2 / g.

[0054] In some embodiments, the catalyst composition comprises an alkaline earth metal oxide catalyst or an alkaline earth metal carbonate catalyst.

[0055] In some embodiments, the catalyst composition comprises a calcium carbonate catalyst.

[0056] In some embodiments, the calcium carbonate catalyst is a calcite catalyst.

[0057] In some embodiments, the catalyst composition comprises a binder, preferably the binder comprises bentonite and / or kaolin.

[0058] In some embodiments, the catalytic conditions comprise a temperature of at least about 350 °C, preferably wherein the catalytic conditions comprise a temperature of from about 350 to 480 °C, more preferably herein the catalytic conditions comprise a temperature of from about 410 to 430 °C.

[0059] In some embodiments, the method comprises pyrolysing the lignocellulosic biomass at a temperature of at least about 350 °C.

[0060] In a fourth aspect, the invention provides a biofuel obtainable by the method of the third aspect.

[0061] In a fifth aspect, the invention provides a biofuel oil obtained by the method of third aspect.

[0062] In a sixth aspect, the invention provides a method for manufacturing a blended fuel oil, the method comprising blending a biofuel oil of any one of the first or second or fourth or fifth aspects with one or more heavy fuel oils.

[0063] In a seventh aspect, the invention provides a blended fuel oil comprising:a. the biofuel oil of any one of the first or second or fourth or fifth aspects, andb. one or more heavy fuel oils.

[0064] In some embodiments, the blended fuel oil comprises a biofuel oil of any one of the first or second or fourth or fifth aspects in an amount of at least about 10%, 15%, or 20% by volume of the blended fuel oil.

[0065] In some embodiments, the blended fuel oil has a total sediment potential (TSP) of less than about 0.1% by mass.

[0066] In some embodiments, the one or more heavy fuel oils comprises a residual fuel oil.

[0067] In broad terms, the present invention generally relates to a simple and cost-effective process for the production and modification of lignocellulosic pyrolysis oils that produces in abio-oil with a composition that is compatible and stable when blended with a residual fuel oil or heavy fuel oil while also being produced at good yields with energy density greater than nonupgraded pyrolysis oils. For example, the process may comprise:(1) pyrolising a lignocellulosic biomass to produce a stream of pyrolysis vapour(2) subjecting the vapour ex situ in a catalytic reactor to catalytic upgrading with a low-porosity, alkaline earth metal oxide or carbonate catalyst to produce an upgraded vapour or oil;(3) condensing the upgraded vapour or oil to a liquid bio-oil composed of an organic phase and an aqueous phase;(4) subjecting the liquid bio-oil to aqueous washing.

[0068] In another aspect, the present invention relates to a process comprising:(1) pyrolising a lignocellulosic biomass to produce a stream of pyrolysis vapour(2) subjecting the vapour ex situ in a catalytic reactor to catalytic upgrading with a low-porosity, alkaline earth metal oxide or carbonate catalyst to produce an upgraded vapour or oil;(3) condensing the upgraded vapour or oil to a liquid bio-oil composed of an organic phase and an aqueous phase;(4) separating the organic phase of the liquid bio-oil from the aqueous phase;(5) subjecting the organic phase of the liquid bio-oil to aqueous washing.

[0069] In another aspect, the present invention relates to a process comprising:(1) pyrolising the lignocellulosic biomass to produce a stream of pyrolysis vapour(2) subjecting the vapour ex situ in a catalytic reactor to catalytic upgrading with a low-porosity, alkaline earth metal oxide or carbonate catalyst to produce an upgraded vapour or oil;(3) condensing the upgraded vapour or oil to a liquid bio-oil composed of an organic phase and an aqueous phase;(4) subjecting the liquid bio-oil to aqueous washing; and(5) blending the washed bio-oil with a residual fuel oil or heavy fuel oil.

[0070] In another aspect, the present invention relates to a process comprising:(1) pyrolising the lignocellulosic biomass to produce a stream of pyrolysis vapour(2) subjecting the vapour ex situ in a catalytic reactor to catalytic upgrading with a low-porosity, alkaline earth metal oxide or carbonate catalyst to produce an upgraded vapour or oil;(3) condensing the upgraded vapour or oil to a liquid bio-oil composed of an organic phase and an aqueous phase;(4) separating the organic phase from the aqueous phase;(5) subjecting the organic phase of the bio-oil to aqueous washing; and(6) blending the washed organic phase of the bio-oil with a residual fuel oil or heavy fuel oil.

[0071] In another aspect, the present invention relates to a process comprising:(1) pyrolising the lignocellulosic biomass to produce a stream of pyrolysis vapour(2) subjecting the vapour ex situ in a catalytic reactor to catalytic upgrading with a calcium carbonate or calcite catalyst to produce an upgraded vapour or oil composed of an organic phase and an aqueous phase;(3) condensing the upgraded vapour or oil to a liquid bio-oil.

[0072] In one embodiment the lignocellulosic biomass is one or more of wood, wood residues, grasses and agricultural residues.

[0073] In one embodiment the lignocellulosic biomass is one or more of wood or wood residues.

[0074] In one embodiment the lignocellulosic biomass is wood in a particulate form.

[0075] In one embodiment the lignocellulosic biomass is a softwood or softwood residue.

[0076] In one embodiment the lignocellulosic biomass is wood from a Pinus species.

[0077] In one embodiment the lignocellulosic biomass is wood from Pinus Radiata.

[0078] In one embodiment the pyrolysis of the lignocellulosic biomass is fast pyrolysis and produces pyrolysis vapour.

[0079] In one embodiment the pyrolysis of the lignocellulosic biomass is fast pyrolysis conducted at a temperature between 400 and 600°C.

[0080] In one embodiment the pyrolysis of the lignocellulosic biomass is fast pyrolysis conducted at a temperature between 400 and 550°C.

[0081] In one embodiment the pyrolysis of the lignocellulosic biomass is fast pyrolysis conducted at a temperature between 450 and 550°C.

[0082] In one embodiment the pyrolysis vapour is catalytically upgraded in a catalytic reactor ex-situ of the pyrolysis reactor.

[0083] In one embodiment the pyrolysis vapour is catalytically upgraded in a catalytic reactor ex-situ of the pyrolysis reactor by a catalyst comprising one or more alkaline earth metal oxides or carbonates.

[0084] In one embodiment the pyrolysis vapour is catalytically upgraded in a catalytic reactor ex-situ of the pyrolysis reactor by a catalyst comprising one or more alkaline earth metal oxides or carbonates at a temperature between 300 and 600°C.

[0085] In one embodiment the pyrolysis vapour is catalytically upgraded in a catalytic reactor ex-situ of the pyrolysis reactor by a catalyst comprising one or more alkaline earth metal oxides or carbonates at a temperature between 350 and 550°C.

[0086] In one embodiment the pyrolysis vapour is catalytically upgraded in a catalytic reactor ex situ of the pyrolysis reactor by a catalyst comprising one or more alkaline earth metal oxides or carbonates at a temperature between 350 and 500°C.

[0087] In one embodiment the pyrolysis vapour is catalytically upgraded in a catalytic reactor ex situ of the pyrolysis reactor by a catalyst comprising one or more alkaline earth metal oxides or carbonates at a temperature between 400 and 540°C.

[0088] In one embodiment the pyrolysis vapour is catalytically upgraded in a catalytic reactor ex situ of the pyrolysis reactor by a catalyst comprising one or more alkaline earth metal oxides or carbonates at a temperature between 400 and 450°C.

[0089] In one embodiment the pyrolysis vapour is catalytically upgraded in a catalytic reactor ex situ of the pyrolysis reactor by a catalyst comprising one or more oxides of calcium.

[0090] In one embodiment the pyrolysis vapour is catalytically upgraded in a catalytic reactor ex situ of the pyrolysis reactor by a catalyst comprising one or more alkaline earth metal carbonates.

[0091] In one embodiment the pyrolysis vapour is catalytically upgraded in a catalytic reactor ex situ of the pyrolysis reactor by a catalyst comprising calcium carbonate.

[0092] In one embodiment the pyrolysis vapour is catalytically upgraded in a catalytic reactor ex situ of the pyrolysis reactor by a catalyst comprising calcite.

[0093] In one embodiment the pyrolysis vapour is catalytically upgraded in a catalytic reactor ex situ of the pyrolysis reactor by a catalyst comprising calcite derived from mussel shells or paper waste sludge.

[0094] In one embodiment the pyrolysis vapour is catalytically upgraded in a catalytic reactor ex situ of the pyrolysis reactor by a catalyst comprising calcite derived from mussel shells.

[0095] In one embodiment the catalyst has a porosity of between 0 and 80m2 / g, 0 and 50m2 / g or 0 and 30m2 / g.

[0096] In one embodiment the catalyst has a micro-porosity of less than 1 xl 0“2m2 / g, or less than 9x10’3m2 / g, or less than 8x10’3m2 / g, less than 7 x10-3m2 / g or less than 6 x 10’3m2 / g.

[0097] In one embodiment the catalyst is in pelletised form with a binder.

[0098] In one embodiment the catalyst is in pelletised form with a bentonite or kaolin binder.

[0099] In one embodiment the kaolin binder comprises between 20 and 30% by weight of the pelletised form of the catalyst.

[0100] In one embodiment the bentonite binder comprises between 0.01 and 20%, 5 and 15%, 8 and 12% by weight of the pelletised form of the catalyst.

[0101] In one embodiment the upgraded pyrolysis vapour is condensed to a liquid bio-oil and subjected to an aqueous wash.

[0102] In one embodiment the upgraded pyrolysis vapour is condensed to a liquid bio-oil comprised of an organic phase and an aqueous phase.

[0103] In one embodiment some or all of the aqueous phase of the liquid bio-oil is separated off and the organic phase of the liquid bio-oil is subject to an aqueous wash.

[0104] In one embodiment the aqueous wash consists of adding between 0.5 and 10 parts water by weight to 1 parts bio-oil, stirring, rested so oil and aqueous phases separate and removing the aqueous phase.

[0105] In one embodiment the aqueous wash consists of adding between 1 and 5 parts water by weight to 1 parts bio-oil, stirring, rested so oil and aqueous phases separate and removing the aqueous phase.

[0106] In one embodiment the aqueous wash consists of adding between 3.5 and 4.5 parts water by weight to 1 parts pyrolysis oil, stirring, rested so oil and aqueous phases separate and removing the aqueous phase.

[0107] In one embodiment the aqueous wash is conducted at 35°C.

[0108] In one embodiment the aqueous wash is conducted at ambient temperature.

[0109] In one embodiment the liquid pyrolysis oil is subjected to a water removal step prior to the aqueous wash.

[0110] In one embodiment the process for production of a blended fuel comprising a residual fuel oil on the one part and an upgraded pyrolysis oil on the other part comprises mixing the upgraded pyrolysis oil and the residual fuel oil in a ratio of that results in a blended fuel oil consisting of 5 to 40%, 10 to 30%, 12 to 20%, 12 to 18%, 14 to 16% pyrolysis oil by weight.

[0111] Any of the following embodiments, alone or in any combination of two or more, may apply to any one or more of the aspects herein.

[0112] It is intended that reference to a range of numbers disclosed herein (for example, 1 to 10) also incorporates reference to all rational numbers within that range (for example, 1, 1.1, 2, 3, 3.9, 4, 5, 6, 6.5, 7, 8, 9 and 10) and also any range of rational numbers within that range (for example, 2 to 8, 1.5 to 5.5 and 3.1 to 4.7) and, therefore, all sub-ranges of all ranges expressly disclosed herein are hereby expressly disclosed. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner.

[0113] This invention may also be said broadly to consist in the parts, elements and features referred to or indicated in the specification of the application, individually or collectively, and any or all combinations of any two or more said parts, elements or features, and where specific integers are mentioned herein which have known equivalents in the art to which this invention relates, such known equivalents are deemed to be incorporated herein as if individually set forth.

[0114] Although the present invention is broadly as defined above, those persons skilled in the art will appreciate that the invention is not limited thereto and that the invention also includes embodiments of which the following description gives examples.

[0115] In the description in this specification reference may be made to subject matter which is not within the scope of the claims of the current application. That subject matter should be readily identifiable by a person skilled in the art and may assist in putting into practice the invention as defined in the claims of this application.Brief description of the drawings

[0116] The invention will now be described by way of example only and with reference to the drawings in which:

[0117] Figure 1 shows the sedimentation rates as TSP (%) vs oxygen content (wt%) of blended fuels comprising a residual fuel oil and: (i) a non-catalysed lignocellulosic biofuel oil (Non-cat ORG, crosses), (ii) two zeolite catalysed lignocellulosic biofuel oils made using a processes comprising zeolite upgrading at 420 and 477 °C, respectively (Z 420, hollow triangles, and Z 477, black triangles), or (iii) two calcite catalysed lignocellulosic biofuel oils made using a processes comprising calcite upgrading between 390-460 and at 540 °C, respectively (Ca 390-460, hollow squares, and Ca 540, black squares), wherein the biofuel oil component is 10% by volume of the blended fuel oil as described in Example 1.

[0118] Figure 2 shows the sedimentation rates as TSP (%) vs oxygen content of blended fuels comprising a residual fuel oil and: (i) a biofuel oil made using a processes comprising calcite upgrading at 420 °C with a caustic wash (hollow circles), (ii) a biofuel oil made using a processes comprising calcite upgrading between 420 to 450 °C without a caustic wash (hollow squares), (iii) a biofuel oil made using a processes comprising calcite upgrading at 475 °C or more (black squares), (iv) a biofuel oil made using a processes comprising zeolite upgrading at 420 °C (hollow triangles), or (v) a biofuel oil made using a processes comprising zeolite upgrading at 480 °C, wherein the biofuel oil component 20% by volume of the blended fuel oil. (black triangles) as described in Example 2.

[0119] Figure 3 shows a schematic diagram of a catalytic fast pyrolysis apparatus implementing ex situ catalysis of pyrolysis vapours as described herein.Detailed description of the invention

[0120] The present invention is directed to a biofuel oil capable of being blended with heavy fuel oils or residual fuel oils to produce a marine or industrial fuel with renewable carbon content. The present invention is further directed to the resulting blended fuel, and to processes for making the biofuel oil and the blended fuel.

[0121] The biofuel oil of the present invention has a composition that balances a number of properties and characteristics, to be a suitable blendable fuel component, including energycontent, water content and acid number. The biofuel oil is characterised by the presence, in particular quantum, of certain molecules - monomeric substituted phenols as defined herein -that provide the biofuel oil with inherent dispersant properties and, in a blended fuel, stability against sedimentation.

[0122] The method of manufacture of the biofuel oils of the present invention involves upgrading and deoxygenating a pyrolysis oil vapour to increase the energy content and lower the acidity, while at the same time, generating and avoiding breaking down the compounds that provide the dispersant effect. Using this process provides a biofuel oil while avoiding complex and expensive multi-stage refining and multiple catalyst-based processing.

[0123] The process may further comprise blending the biofuel oil with a heavy fuel oil or residual fuel oil it a suitable ratio to produce a blended fuel oil. Alternatively, a method for manufacturing such a blended fuel oil may be carried out independently of the method for manufacturing the biofuel oil.

[0124] The present inventor in pursuance of production of a bio-based pyrolysis oil that is compatible for blending with residual fuel oils to produce a marine or industrial fuel with renewable carbon content and that requires the production of a bio-oil with a composition and properties that balance a range of different variables have developed a simple and cost-effective process for producing such a pyrolysis oil. Accordingly, the present invention relates to such a process for producing such a pyrolysis oil. It further relates to a process for the production of a blended fuel oil.

[0125] The inventor has determined that there is a composition for pyrolysis oils between highly upgraded pyrolysis oils and non-upgraded pyrolysis oils that significantly reduces sedimentation upon blending while also having acceptable energy density and have developed a simple process to reach this composition, avoiding complex and expensive multi-stage refining and multiple catalyst-based processing.

[0126] Testing was conducted to compare the compatibility of blended fuel oils comprising a pyrolysis oil and a residual fuel oil using three different pyrolysis oils - (i) a non-catalysed, nondeoxygenated pyrolysis oil; (ii) a zeolite catalysed pyrolysis oil; and (iii) a calcite catalysed pyrolysis oil produced in accordance with the present invention. The respective pyrolysis oils were blended with residual fuel oil. The residual fuel oil was a commercial low sulphur marinefuel oil originally produced in Singapore and sourced from Tank 402 at the Port of Tauranga with the resulting blended fuel comprising 10% pyrolysis oil by volume. As can be seen from Figure 1, the calcite catalysed oil's oxygen content was approximately midway between the noncatalysed pyrolysis oil and the zeolite catalysed pyrolysis oil but had significantly lower sedimentation levels when measured in accordance with industry standards including several data points that met the industry standard Total Solids Precipitated (TSP) requirements. The fact that the sedimentation was lower than samples with both higher and lower oxygen content indicates that other elements of pyrolysis oil other than just oxygen content play a significant role in causing or avoiding precipitation.

[0127] It is understood to some degree that precipitation upon blending occurs as a result of either asphaltenes from the residual fuel oil falling out of solution upon blending and aggregation into solids or sludge. A further mechanism behind precipitation is potential polymerisation of reactive species originating from the pyrolysis oil. There are theories that the right balance of polar molecules in the blend assists in inhibiting asphaltene aggregation and that avoiding high temperature conditions, and the balance and type of reactive species generated by the different processes for producing pyrolysis oils, has an influence on polymerisation. Choice of feedstock may also be significant in influencing the composition of the pyrolysis oil.Definitions

[0128] Unless otherwise stated, the singular forms "a", "an" and "the" include the plural reference.

[0129] The term "about" as used herein generally refers to a range of numerical values (e.g. ± 5 to 10% of the recited value) that those skilled in the art would consider equivalent to the recited value. Ranges can be expressed herein as from "about" one particular value, and / or to "about" another particular value. When such a range is expressed, the range is inclusive of the recited values.

[0130] The term "and / or" as used herein means "and" or "or", or both.

[0131] The term "(s)" following a noun as used herein means the plural and / or singular form of that noun.

[0132] The term "comprising" as used in this specification and claims means "consisting at least in part of". When interpreting statements in this specification and claims which include the term "comprising", other features besides the features prefaced by this term in each statement can also be present. Related terms such as "comprise" and "comprised" are to be interpreted in similar manner.

[0133] The compounds described herein may exist as conformational or geometric isomers, including cis, trans, syn, anti, entgegen (E), and zusammen (Z) isomers. All such isomers and any mixtures thereof are within the scope of the invention.

[0134] Also within the scope of the invention are any tautomeric isomers or mixtures thereof of the compounds described. As would be appreciated by those skilled in the art, a wide variety of functional groups and other structures may exhibit tautomerism. Examples include, but are not limited to, keto / enol, imine / enamine, and thioketone / enethiol tautomerism.

[0135] The general chemical terms used herein have their usual meanings.

[0136] The term "alkyl" as used herein refers to a straight-chain or branched saturated acyclic hydrocarbon group. In some embodiments, alkyl groups have from 1 to 3, from 2 to 3, or 2 or 3 carbon atoms. Such groups may be referred to herein as C1-3 alkyl, C2-3 alkyl, or C2 alkyl or C3 alkyl groups. Examples of alkyl groups include but are not limited to methyl (Me), ethyl (Et), n-propyl, isopropyl and the like.

[0137] The term "alkynyl" as used herein refers to a straight-chain or branched unsaturated acyclic hydrocarbon group having one or more carbon-carbon double bonds. In some embodiments, alkyl groups have from 2 to 3, or 2 or 3 carbon atoms. Such groups may be referred to herein as C2-3 alkynyl, or C2 alkynyl or C3 alkynyl groups. Example alkenyl groups include, but are not limited to, ethenyl, n-propenyl, isopropenyl and the like.

[0138] The term "polyaromatic" as used herein refers to any member of a class of organic compounds that is composed of multiple fused aromatic rings, for example naphthalene, methylnaphthalene, and retene. Polyaromatics are also known as polycyclic aromatic hydrocarbons.

[0139] As used herein, the term "substituted" is intended to mean that one or more hydrogen atoms in the group indicated is replaced with one or more independently selectedsuitable substituents, provided that the normal valency of each atom to which the substituent(s) are attached is not exceeded, and that the substitution results in a stable compound. The term "stable" as used herein, unless indicated otherwise, refers to compounds which possess stability sufficient to allow manufacture and which maintain their integrity for a period of time sufficient to be useful for the purposes described herein.

[0140] As used herein, the term "monomeric", with reference to a monomeric substituted phenol compound, means that the compound comprises only a single unit of the identified chemical moiety. For example, "a monomeric substituted catechol" consists of a single molecular unit of a substituted catechol compound.

[0141] The term "biofuel oil" as used herein, unless the context indicates otherwise, refers to a catalytically upgraded pyrolysis oil that is derived from biomass feedstock. The biofuel oil of the present invention may be suitable for use as a fuel (for example as a marine fuel) or suitable for use as a component of a blended fuel oil. The terms "biofuel oil", "bio-oil" "pyrolysis oil" and "catalytically upgraded pyrolysis oil" are used interchangeably herein, unless the context indicates otherwise.

[0142] The term "pyrolysis" as used herein, unless the context indicates otherwise, refers to a process involving the thermal decomposition of a biomass feedstock in the absence of oxygen or in an oxygen-deficient environment (i.e. less than 0.3 equivalence ratio).

[0143] The term "equivalence ratio", as used herein, unless the context indicates otherwise, refers to measure of the air-to-fuel mixture in combustion, defined as the actual air-to-fuel ratio divided by the stoichiometric ratio for complete combustion.

[0144] The term "catalytic upgrading" as used herein, unless the context indicates otherwise, refers to a process involving subjecting a pyrolysis vapour produced from a biomass feedstock by pyrolysis to the action of a catalyst to produce a catalytically upgraded pyrolysis vapour via a complex chemical reaction network including, but not limited to, hydrogenation, hydrodeoxygenation, cracking, hydrocracking, decarboxylation, polymerization, and decarbonylation. Catalytic upgrading can be carried out within the same reactor that that the pyrolysis is carried out in (referred to herein as in situ catalytic upgrading) or in a separate reactor from the pyrolysis reactor (referred to herein as ex situ catalytic upgrading). The terms" Ex situ catalytic upgrading" and "catalytically upgraded in a catalytic reactor ex situ" are used interchangeably herein.

[0145] The term "aqueous washing" and similar terms such as "aqueous wash" or "water wash" as used herein, unless the context indicates otherwise, refers to a process of washing the biofuel oil with an aqueous composition, including mixing the biofuel oil and the aqueous composition, and then separating the oil phase from the aqueous phase. The aqueous composition can be, for example, water. Aqueous washing may be carried out, for example, by adding two parts water to one part oil by weight, stirring or otherwise mixing the resultant mixture, for example for 1 hour at ambient temperature, and then separating the oil phase from the aqueous phase, such as by centrifuging (for example, at 3000 rpm for 5 minutes) and then removing the aqueous phase. A person skilled in the art would appreciate that aqueous washing can be conducted in a range of different ways, depending for example on the scale of the process. If the aqueous washing is the final aqueous wash the biofuel oil is subjected to, then the aqueous washing may be followed by a distillation and / or evaporation procedure or other suitable procedure to reduce the final water content of the oil.

[0146] The term "caustic washing" and similar terms such as "caustic wash" as used herein, unless the context indicates otherwise, refers to a process of adding to the biofuel oil a caustic or alkaline compound, such as KOH or NaOH, in a molar excess (for example, a 1.1, 1.2, 1.3, 1.4, or 1.5 molar excess) of an amount equivalent to the acid number of the biofuel oil, usually with water, followed by mixing, and then separating the organic phase. Caustic washing may be followed by aqueous washing to remove, for example, residual sodium or potassium, and the aqueous washing may be followed by a water reduction step.

[0147] The term "acid number", as used herein, means the carboxylic acid number (CAN) as measured in accordance with the method developed and described in Wu, L; Hu, X.; Mourant, D.; Wang, Y.; Kelly, C.; Garcia-Perez, M.; He, M.; Li, C-Z. Quantification of strong and weak acidities in biofuel oil via non-aqueous potentiometric titration. Fuel, 2014, 115, 652-657;http: / / doi.org / 10.1016 / j.fuel.2013.07.092) or the acid number as determined in accordance with ASTM D664. The acid number or CAN is determined in mg KOH / g of biofuel oil.

[0148] A caustic wash may be carried out, for example, by mixing the biofuel oil with a solution of water of approximately double the weight of the oil containing NaOH in a molaramount approximately 10% greater than the acid number, mixing the mixture is mixed, for example by stirring for 1 hour at ambient temperature, isolating the organic phase, for example after centrifugation (for example at 3000 rpm for 5 min), and then removing the aqueous phase / wash water. Such a caustic wash can be followed by a an aqueous wash (or water wash) as described herein, to remove the majority of the remaining sodium and at least some residual low molecular weight carboxylic acids.

[0149] The term "low molecular weight carboxylic acid" and similar terms such as "low molecular weight carboxylic acids" as used in herein, unless the context indicates otherwise, refers to carboxylic acids having a molecular weight of 300 g / mol or less. Typically, low molecular weight carboxylic acids have five or fewer total carbon atoms.

[0150] The terms " Higher Heating Value" and " HHV" as used herein with reference to a biofuel oil, unless the context indicates otherwise, refer to the heat of combustion of the biofuel oil as measured in MJ / kg in accordance with ASTM D240 Standard Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by Bomb Calorimeter.

[0151] The terms "total sediment potential" and " TSP", as used herein with reference to a fuel, such as a heavy fuel oils, blends of heavy fuel oils and blends of heavy fuel oils and biofuel oils of the present invention, unless the context indicates otherwise, refers to the total sediment potential of the fuel as a %, as measured in accordance with ISO 8217. Fuels are required to have a TSP of less than 0.1% by mass to comply with industry standard ISO 8217.

[0152] The terms "total sediment existent" and " TSE", as used herein with reference to a fuel, such as a biofuel oil or blended fuel of the present invention, unless the context indicates otherwise, refers to the total sediment existent of the fuel, which is a measurement of amount of sludge that is likely to be separated by a marine on-board centrifuge. TSE is a sediment test covered within and thus may be measured in accordance with ISO 8217 and 10907-1. Usually, the TSE is measured by heating a sample to 100 °C and passing the sample through filter paper, the amount of dry sludge retained on the filter paper correlates with the amount of sludge that is likely to be separated by a marine on-board centrifuge. When testing biofuel oils in particular, the filter paper retains also retains a quantum of polar molecules from the biofuel oils. Washing the filter with acetone prior to weighing the filter provides a TSE with improved accuracy.Monomeric substituted phenol compounds

[0153] The biofuel oils of the present invention comprise one or more monomeric substituted phenol compounds (monomeric substituted phenols).

[0154] The term "monomeric substituted phenol" as used herein, unless the context indicates otherwise, refers to a monomeric phenol compound comprising a benzene ring substituted with a hydroxyl group and a C2-C3 alkyl or C2-C3 alkenyl group at a position para to the hydroxyl group.

[0155] The one or more monomeric substituted phenol compounds are derived from lignocellulosic material, meaning they are derived from lignin, monolignols, terpenes, tannins and polysaccharides present in the lignocellulosic feedstock that is pyrolysed in the manufacture of the biofuel oils.

[0156] The inventor has surprisingly found that these monomeric substituted phenols may have dispersant or stabilising effect when the biofuel oils are blended with a heavy fuel oil, resulting in industrially acceptable levels of sedimentation of the resulting blended fuel oils, especially at high ratios of biofuel oil to heavy fuel oil, for example 10% by volume biofuel oil or above.

[0157] In various embodiments, the invention provides a biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol comprising a benzene ring substituted with a hydroxyl group and a C2-C3 alkyl or C2-C3 alkenyl group at a position para to the hydroxyl group. In various embodiments, the biofuel oil comprises at least about 3%, about 4%, about 5%, about 6%, about 7%, about 8% or about 9% by weight of one or more monomeric substituted phenol comprising a benzene ring substituted with a hydroxyl group and a C2-C3 alkyl or C2-C3 alkenyl group at a position para to the hydroxyl group. In various embodiments, the biofuel oil comprises from about 3 to about 9% by weight of one or more monomeric substituted phenol comprising a benzene ring substituted with a hydroxyl group and a C2-C3 alkyl or C2-C3 alkenyl group at a position para to the hydroxyl group. The weight percentages of the one or more monomeric substituted phenol are as measured by gas chromatography-mass spectrometry (GC-MS).

[0158] In various embodiments, the benzene ring is optionally substituted with one or two additional groups selected from the group consisting of hydroxyl, methyl, and methoxy groups at any available position of the benzene ring. In various embodiments, the benzene ring isoptiona lly substituted with one or two additional groups selected from the group consisting of hydroxyl, methyl, and methoxy groups at any available position ortho to the hydroxyl group.

[0159] In various embodiments, the one or more monomeric substituted phenol is a monomeric substituted monohydroxy benzene (i.e. a benzene substituted with a hydroxyl group and the C2-C3 alkyl or C2-C3 alkenyl group at a position para to the hydroxyl group, but not substituted at any other position of the benzene ring), a monomeric substituted cresole, a monomeric substituted guaiacol, a monomeric substituted catechol or a monomeric substituted syringol; wherein the monomeric substituted monohydroxy benzene, monomeric substituted cresole, monomeric substituted guaiacol, monomeric substituted catechol and monomeric substituted syringol is substituted with a C2-C3 alkyl or C2-C3 alkenyl group at a position para to the or a phenolic hydroxyl group of the monohydroxy benzene, cresole, guiacol, catechol, or syringol.

[0160] In various embodiments, the C2-C3 alkyl or C2-C3 alkenyl substituent can be selected from one or more of the group consisting of: ethyl, vinyl, propyl, prop-1 -enyl and prop-2-enyl.

[0161] In various embodiments, the one or more monomeric substituted phenol can be selected from one or more of the group consisting of: cis-isoeugenol, trans-isoeugenol, eugenol, 4-ethylguaiacol, 4-ethylcatechol, 4-ethylsyringol, 4-ethyl-2-methylphenol, 4-ethylphenol, 4-a llylphenol, 4-allyl-2-methylphenol, 4-propylphenol, 2-methyl-4-propylphenol, 4-vinylguaicol and 4-propylguaiacol. In various embodiments, the one or more monomeric substituted phenol can be selected from one or more of the group consisting of: cis-isoeugenol, trans-isoeugenol, 4-ethylguaiacol, 4-ethylcatechol, 4-ethylphenol, 4-propylphenol, and 4-propylguaiacol.

[0162] Other biofuel oil components, such as cresols and methylcatechol, are likely to be present in in fuel oils made by pyrolysis, often in significant volumes, and these components may have a minor dispersant effect. Non-upgraded pyrolysis oils and catalytically upgraded pyrolysis oils are diverse and very complex mixtures and as a consequence, thorough measurement and identification of chemical species and their yields can be impractical.

[0163] In various embodiments, the one or more monomeric substituted phenol can be a compound of the formula (1):OH(Dwherein: R1can be C2-C3 alkyl or C2-C3 alkenyl; and R2and R3can each be independently selected from the group consisting of H, OH, Me, and OMe.

[0164] In various embodiments, the compound of formula (1) can be a compound of the formula (2):OHR1(2).

[0165] In various embodiments, R2can be independently selected from the group consisting of H, OH, Me, and OMe and R3can be independently H; or R2and R3can each be OMe.

[0166] In various embodiments, the one or more monomeric substituted phenol has a molecular weight of about 200 g / mol or less.Degradation products

[0167] The biofuel oils of the present invention may further comprise one or more degradation products.

[0168] The term "degradation product" as used herein, unless the context indicates otherwise, refers to a compound selected from the group consisting of hydroxybenzene, toluene, and polyaromatics.

[0169] The degradation products are chemical compounds formed from the lignocellulosic feedstock used (for example from cellulose or other components of the lignocellulosic feedstock) during the pyrolysis and / or catalytic upgrading process used to produce a biofuel oil.

[0170] High levels of degradation products are indicative of a biofuel oil that has been processed in a manner where the dominant chemical pathways in the pyrolysis and catalytic upgrading process favours the yield of degradation products over the yield of monomeric substituted phenols from the feedstock, and are therefore indicative of reduced relative yields of monomeric substituted phenols. However, degradation products are not necessarily disadvantageous in a biofuel oil - they may be high in energy content. The ratio of monomeric substituted phenols to degradation products can be a useful measure of the suitability of a biofuel oil for producing a blended fuel stable to sedimentation comprising the biofuel oil and a heavy fuel oil.

[0171] In various embodiments, degradation products can comprise one or more degradation products selected from the group consisting of hydroxybenzene, toluene, naphthalene, methylnaphthalene, and retene.Method of manufacturing an upgraded biofuel oil

[0172] The present invention, in one aspect, is focused on a simple and low-cost process for producing upgraded biofuel oils favourable for blending with residual fuel oils resulting in sedimentation that falls within fuel standards and without giving an excessively corrosive blended fuel.

[0173] The biofuel oil can be produced via use of a mild, low cost, low porosity catalyst (for example, an alkaline earth metal oxide catalyst or an alkaline earth metal carbonate catalyst, for example, a catalyst comprised of calcite) that homogenously deoxygenates organic molecules and helps convert lignin oligomers to monomeric substituted phenols, but does not result in excessive or preferential cracking of the alkyl and alkenyl substituents from monomeric substituted phenols.

[0174] The preferred feedstocks for the biofuel oils are lignocellulosic biomasses. Without wishing to be bound by theory, it is believed the dispersant functionality inherent in the biofuel oil is provided by monomeric substituted phenols generated and preserved - when process andcatalyst parameters are appropriate - from lignin, and in some cases to a minor degree, from other constituents such as terpenes and polysaccharides in the lignocellulosic biomasses.

[0175] Wood, particularly softwood, are preferred feedstocks, but other lignocellulosic feedstocks having sufficient lignin and other constituents content to provide a sufficient quantity and quality of monomeric substituted phenols in the biofuel oils of the present invention may be used.

[0176] Without wishing to be bound by theory, it is believed that the use of ex-situ catalytic upgrading provides the advantage that both the pyrolysis and the catalytic upgrading can be optimised for generation and preservation of monomeric substituted phenols, and the catalytic upgrading can be performed at a lower temperature than pyrolysis which also favours preservation of monomeric substituted phenols. When wanting to produce a blendable biofuel oil, this flexibility when combined with a low porosity catalyst provides greater ability to select reaction conditions that result in an upgraded biofuel oil with a composition that has inherent dispersant properties and is suitable for blending with a residual fuel oil.

[0177] In various embodiments, the method for manufacturing a biofuel oil can comprise:a. pyrolysing a lignocellulosic biomass to produce a pyrolysis vapour;b. subjecting the pyrolysis vapour to the action of a catalyst composition and catalytic conditions to produce an upgraded vapour;c. condensing the upgraded vapour to produce a biphasic biofuel oil comprising an organic phase and an aqueous phase; andd. removing the aqueous phase from the organic phase to provide the biofuel oil;e. optionally subjecting the biofuel oil to caustic washing;f. optionally subjecting the biofuel oil to aqueous washing; andg. optionally subjecting the biofuel oil to an additional water removal stepwherein the catalyst composition and catalytic conditions are selected to provide:a biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol comprising a benzene ring substituted with a hydroxyl group and a C2-C3 alkyl or C2-C3 alkenyl group at a position para to the hydroxyl group.

[0178] In various embodiments, the catalyst composition and catalytic conditions are selected to provide: a biofuel oil comprising at least about 4, 5, 6, 7, 8 or 9% by weight of one or more monomeric substituted phenol comprising a benzene ring substituted with a hydroxyl group and a C2-C3 alkyl or C2-C3 alkenyl group at a position para to the hydroxyl group. In various embodiments, the catalyst composition and catalytic conditions are selected to provide: a biofuel oil comprising at least from about 3 to about 9% by weight of one or more monomeric substituted phenol comprising a benzene ring substituted with a hydroxyl group and a C2-C3 alkyl or C2-C3 alkenyl group at a position para to the hydroxyl group.

[0179] As well as producing a biofuel oil with an inherent dispersant effect when blended with heavy fuel oils, the process also reduces the acidity of the biofuel oil which not only makes it less corrosive but also removes a driver of polymerisation of aromatics that may also contribute to sedimentation or flocculation.

[0180] The biphasic biofuel oil will separate into a heavier organic phase and a lighter aqueous phase. In some embodiments, the organic phase is darker in colour than the aqueous phase. The aqueous phase will typically have a high-water content but also include lower molecular weight polar organic molecules such as low molecular weight carboxylic acids.Applying a mechanical separation technique such as centrifugation can improve separation of the organic and aqueous phases and enable enhanced separation of the phases and removal of the aqueous phase.

[0181] Caustic washes and aqueous washes (water washes) can decrease the water concentration in the biofuel oil to about 5% by weight.

[0182] In various embodiments, the aqueous wash consists of adding about 0.5 to about 10 parts water by weight to about 1 parts biofuel oil, then mixing, then allowing the oil and aqueous phases to separate, and then removing the aqueous phase. In various embodiments, the aqueous wash consists of adding about 1 to about 5 parts water by weight to about 1 parts biofuel oil, then stirring, then resting so that the oil and aqueous phases separate and then removing the aqueous phase. In various embodiments, the aqueous wash consists of addingabout 3.5 to about 4.5 parts water by weight to about 1 parts biofuel oil, then stirring, then resting so that the oil and aqueous phases separate and then removing the aqueous phase.

[0183] In various embodiments, the aqueous wash is conducted at about 10 to about 40 °C. In various embodiments, the aqueous wash is conducted at about 35 °C. In various embodiments, the aqueous wash is conducted at about ambient temperature.

[0184] Distillation can be used to decrease the water concentration in the biofuel oil to less than about 2% by weight. In some embodiments, the distillation is carried out at a temperature of 55 °C and pressure (vacuum) of 25 mbar, for example using a rotary evaporator.

[0185] In various embodiments, the additional water removal step comprises reducing the water content of the biofuel oil to below about 5% by weight. In various embodiments, the water removal step comprises reducing the water content of the biofuel oil to below about 4%, about 3%, about 2%, about 1% or about 0% by weight. In various embodiments, the water removal step comprises reducing the water content of the biofuel oil to from about 0 to about 5%, about 0 to about 4%, about 0 to about 3%, about 0 to about 2%, about 0 to about 1%, about 1 to about 5%, about 1 to about 4%, about 1 to about 3%, about 1 to about 2%, about 2 to about 5%, about 2 to about 4%, about 2 to about 3%, about 3 to about 5%, about 3 to about 4% or about 4 to about 5% by weight.

[0186] In various embodiments, the water removal step comprises evaporation and / or distillation. The evaporation and / or distillation may be carried out using any suitable apparatus, for example a thin film evaporator or a rotary evaporator.

[0187] In various embodiments, the catalytic upgrading conditions are selected to favour the generation and / or preservation of monomeric substituted phenols.

[0188] Such selecting includes the range of conditions and catalyst choice that results in monomeric substituted phenols being generated or preserved through the catalytic upgrading process and that they or their precursors are not excessively cracked to form toluene and phenol (hydroxybenzene) or converted into polyaromatics, such as naphthalene. Catalytic upgrading of biofuel oils is typically carried out to produce an oil with the highest possible HHV and the lowest possible oxygen content and therefore, catalysts with large numbers of dynamic activesites are preferred for traditional catalytic upgrading. This usually requires synthetic or transition metal catalysts and high upgrading temperatures.

[0189] The inventor has surprisingly found a catalytic system favourable for producing biofuel oils suitable for use as a component in a blended fuel oil is a mild severity process, i.e. conditions suited to only deoxygenate the oil to have the HHV reach acceptable levels, while not so much to excessively cleave the C2-3 alkyl or C2-3 alkenyl groups from the para position of the monomeric substituted phenols. This is contrary to the common expectation that highly deoxygenated biofuel oils should produce more homogenous fuels when blended with fossil fuels. The discovery that the monomeric substituted phenols described herein, when available in sufficient yields in the biofuel oil, can provide a significant and inherent dispersant effect was surprising. The method for producing these yields of monomeric substituted phenols means a biofuel oil can be produced which cannot be produced by a high severity process but has better blending performance than a high severity processed, highly deoxygenated biofuel oil.

[0190] Combinations of conditions and catalysts that are suitable for producing sufficient yields of monomeric substituted phenols can be determined experimentally by conducting pyrolysis and catalytic upgrading and washing and the composition of the resulting biofuel oil being analysed, by methods such as GC / MS, and confirmed with blending and sedimentation tests, such as TSP and TSE.

[0191] There are several catalyst composition and conditions variables that can be changed to produce an upgraded vapour including, but not limited to: catalyst choice, catalyst binders (if any), catalyst form and porosity, catalyst loading and temperature.

[0192] Generally, but dependent on the choice of catalyst, lower temperatures are preferrable and catalysts with milder active sites and low specificity appear to be favoured.

[0193] Without wishing to be bound by theory, it is believed that that lower temperatures may have the consequence of slightly reduced deoxygenation, slower reaction speeds and lower throughputs, which are beneficial for producing a biofuel oil of the present invention.

[0194] Volatile residence time in the reactor is another variable that can be influenced by catalyst form and porosity and gas flow rates.

[0195] In various embodiments, the method comprises subjecting the pyrolysis vapour to the action of a catalyst composition at a temperature of at least about 350 °C or more. In various embodiments, the method comprises subjecting the pyrolysis vapour to the action of a catalyst composition at a temperature of from about 350 to about 500 °C, about 350 to about 450 °C, about 350 to about 430 °C, about 350 to about 400 °C, about 400 to about 500 °C, about 400 to about 450 °C, about 400 to about 430 °C, about 430 to about 500 °C, about 430 to about 450 °C, or about 450 to about 500 °C. In various embodiments, the method comprises subjecting the pyrolysis vapour to the action of a catalyst composition at a temperature of at least about 420 °C. In various embodiments, the method comprises subjecting the pyrolysis vapour to the action of a catalyst composition at a temperature of about 420 °C.

[0196] In various embodiments, the method comprises pyrolysing a lignocellulosic biomass at a temperature of at least about 350 °C or more. In various embodiments, the method comprises pyrolysing a lignocellulosic biomass at a temperature of from about 350 to about 600 °C, about 350 to about 550 °C, about 350 to about 500 °C, about 350 to about 450 °C, about 350 to about 430 °C, about 350 to about 400 °C, about 400 to about 600 °C, about 400 to about 550 °C, about 400 to about 500 °C, about 400 to about 450 °C, about 400 to about 430 °C, about 430 to about 600 °C, about 430 to about 550 °C, about 430 to about 500 °C, about 430 to about 450 °C, about 450 to about 600 °C, about 450 to about 550 °C, about 450 to about 500 °C, about 500 to about 600 °C, about 500 to about 550 °C or about 550 to about 600 °C. In various embodiments, the method comprises pyrolysing a lignocellulosic biomass at a temperature of at least about 450 °C. In various embodiments, the method comprises pyrolysing a lignocellulosic biomass at a temperature of about 500 °C.

[0197] Without wishing to be bound by theory, it is believed that the use of low porosity catalysts at about 420°C may reduce the upgrading rate per unit of catalyst compared to something like a zeolite catalyst at about 530°C. However, if low porosity catalysts such as alkaline earth metal oxides or carbonates are used, their low cost and high availability means higher loadings of catalyst can be used, and their low propensity to deactivate can result in good throughputs and reduced down-time, such that the process is industrially viable.

[0198] Without wishing to be bound by theory, it is believed that the use of low porosity catalysts at 420°C may also result in the biofuel oil, immediately after catalytic upgrading, having a higher acid number due to the presence of more uncracked, less deoxygenated carboxylicacids. However, in embodiments where this occurs, a simple washing system that lowers acid number, corrosiveness and water content may be used.

[0199] In various embodiments, removing the aqueous phase from the organic phase comprises a mechanical separation, preferably centrifugation. In various embodiments, removing the aqueous phase from the organic phase comprises at least about 5 minutes of centrifugation at about 3000 rpm. In various embodiments, removing the aqueous phase from the organic phase comprises about 5 minutes of centrifugation at about 3000 rpm and a further about 5 minutes of centrifugation at about 3000 rpm.

[0200] In various embodiments, the catalyst composition comprises an alkaline earth metal oxide or carbonate catalyst. In various embodiments, the catalyst composition comprises an alkaline earth metal oxide or carbonate catalyst at a temperature of at least about 350 °C. In various embodiments, the catalyst composition comprises an alkaline earth metal oxide or carbonate catalyst at a temperature of from about 350 to about 500 °C, about 350 to about 480 °C, about 350 to about 450 °C, about 350 to about 430 °C, about 350 to about 400 °C, about 400 to about 500 °C, about 400 to about 480 °C, about 400 to about 450 °C, about 400 to about 430 °C, about 430 to about 500 °C, about 430 to about 480 °C, about 430 to about 450 °C, about 450 to about 500 °C, about 450 to about 480 °C or about 480 to about 500 °C. In a preferred embodiment, the catalyst composition comprises an alkaline earth metal oxide or carbonate catalyst at a temperature of from about 370 to about 4500 °C.

[0201] The inventor has surprisingly found the combination of low temperature and a non-porous, lower reactivity catalyst, such as calcium carbonate or calcite, to be beneficial for producing the biofuel oils of the present invention. The slower throughput when compared to a more aggressive and more specific catalyst such as synthetic zeolites at higher temperatures, can be offset by the use of a larger volume of catalyst especially when using a cheap catalyst. Low porosity catalysts tend to experience lower deactivation, lower re-generation costs and improve yields of the biofuel oil so the lower throughput per unit of catalyst can be offset by use of more catalyst and the maintenance requirements.

[0202] Without wishing to be bound by theory, it is believed that catalyst porosity and pore size may be a relevant factor to producing suitable yields of monomeric substituted phenols. Some catalysts are more likely to extensively crack substituents from lignin-derived compounds,such as the monomeric substituted phenol compounds present in the biofuel oils of the present invention. Non-porous catalysts and catalysts with large pore sizes may be less specific in their activity and thus be able to generate more monomeric substituted phenols from lignin and lignin derivatives while at the same time being less specific to smaller molecules and thus reducing cracking of the existing monomeric substituted phenols. The calcite (calcium carbonate) catalyst is preferably low in porosity and low in micropores. It also has a lower chemical reactivity than precious metal catalysts, zeolites and most metal oxides including calcium oxide. Low porosity reduces surface area and therefore requires higher catalyst loadings but also results in reduced catalyst de-activation and less specificity towards de-oxygenating only low molecular weight compounds and reduced cracking of desirable compounds.

[0203] This compares to the use of zeolites such as H-ZSM-5 which the present inventor's studies show only result in low levels of de-oxygenation of compounds with molecular weights of about 300g / mol or more.

[0204] Catalytic upgrading of pyrolysis oils using zeolites such as H-ZSM-5 at the high temperatures necessary to optimise deoxygenation results in very low levels of monomeric substituted phenol dispersant species in the upgraded oil, favouring the cracking of the compounds less than 200 g / mol that can access the pores in the catalyst.

[0205] In some embodiments, deoxygenation catalytic upgrading is carried out using synthetic zeolite catalysts. In some of such embodiments, the zeolite catalyst is used under moderate conditions. Figure 2 shows results using a zeolite catalyst at moderate conditions where some data points meet targeted TSP numbers. Compared to biofuel oils made using a calcite catalyst, the biofuel oils made using a zeolite catalyst (i) have lowered biofuel oil yields (at the same oxygen content), (ii) have monomeric substituted phenols peaking at not much over 3%, and (iii) tend to be less stable and non-homogeneous with highly upgraded light compounds and poorly upgraded heavy compounds due to zeolite substrate specificities. In some embodiments, rapid catalyst deactivation is also observed during the process using a zeolite catalyst.

[0206] Porosity can be defined using BET (Brunauer-Emmett-Teller) surface areas. For example, the porosity of H-ZSM-5 zeolite is 224 m2 / g and of calcite mussel shell pellets is 24 m2 / g.

[0207] There are different types of porous catalyst:a. microporous catalysts (wherein the pores have a diameter of less than about 2 nm), which have high surface areas for chemical functions but can limit transport;b. mesoporous catalysts (which have pores have a diameter of between about 2 to about 50 nm), which result in improved transport of larger molecules;c. macroporous catalysts (wherein the pores have a diameter of greater than about 50 nm), which further enhance mass transfer.

[0208] The inventor has found that in certain embodiments it is beneficial to use a catalyst that upgrades without discriminating between different sizes of substrate. Accordingly, in some embodiments, highly active microporous catalysts may not be preferred. In some embodiments, a very low porosity catalyst may be preferred, so the reaction occurs on the surface of the catalyst (also can help avoid coking or deactivation of the catalyst), or a mesoporous or microporous catalyst may be preferred, such that larger substrate compounds can enter.

[0209] The approximate micro-porosities of H-ZSM-5 zeolite is 9.451 x 10-2 m2 / g and of calcite mussel shell pellets is 5.902 x 10-3 m2 / g.

[0210] In a preferred embodiment, the catalyst composition comprises a catalyst with a porosity of from about 0 to about 120m2 / g, about 0 to about 80m2 / g, about 0 to about 50m2 / g, about 0 to about 30m2 / g, about 1 to about 120m2 / g, about 1 to about 80m2 / g, about 1 to about 50m2 / g, about 1 to about 30m2 / g, about 5 to about 120m2 / g, about 5 to about 80m2 / g, about 5 to about 50m2 / g, about 5 to about 30m2 / g, about 10 to about 120m2 / g, about 10 to about 80m2 / g, about 10 to about 50m2 / g or about 10 to about 30m2 / g.

[0211] Most monomeric substituted phenols, and their precursors are generated in the pyrolysis stage of the process from the lignin in the lignocellulosic feedstock and possibly in lesser volumes from other constituents in the feedstock. Data from comparative testing between catalytically upgraded biofuel oils and non-upgraded pyrolysis oils indicate that the yields of monomeric substituted phenols can increase or be concentrated in the catalytic upgrading stage with a suitable choice of catalyst and conditions. Thus, to generate a biofuel oil with inherent dispersant qualities, one of the goals of the catalytic upgrading is to deoxygenate thebiofuel oil without overly degrading these species and preferably also concentrating or generating more of these monomeric substituted phenols in the catalytic upgrading process.

[0212] In various embodiments, the catalyst composition comprises a binder. In a preferred embodiment, the binder comprises bentonite and / or kaolin.

[0213] The inventor has found that treating the crude biofuel oil to reduce the concentration of aldehyde compounds, the carboxylic acid content and the water content provides benefits to the final biofuel oil. This has a simultaneous fourfold beneficial effect:a. an increase in energy density;b. a reduction in acid number / corrosivity;c. a reduction in acid-driven polymerisation of unsaturated species in the biofuel oil or blended fuel oil;d. a slight concentrating effect of dispersing species in the blended fuel oils.

[0214] Without wishing to be bound by theory, it is believed that the reduction in acid-driven polymerisation of unsaturated species in the biofuel oil likely plays a role in further reducing sedimentation in both the biofuel oil and the blended fuel oils.

[0215] Without wishing to be bound by theory, it is believed that the concentrating effect of monomeric substituted phenol dispersing species in the blended fuel oils likely contributes to the reduction of sedimentation in both the biofuel oil and the blended fuel oils.

[0216] In various embodiments, the aqueous phase can comprise one or more low molecular weight carboxylic acids.

[0217] In various embodiments, the method for manufacturing a biofuel oil comprises:a. pyrolysing a lignocellulosic biomass to produce a pyrolysis vapour;b. subjecting the pyrolysis vapour to ex situ catalytic upgrading to produce an upgraded vapour, wherein the catalytic upgrading is performed in a catalytic reactor, the catalytic reactor comprising an alkaline earth metal oxide or carbonate catalyst;c. condensing the upgraded vapour to produce a liquid biofuel oil comprising an organic phase and an aqueous phase;d. removing the aqueous phase from the organic phase of the biofuel oil; ande. optionally subjecting the biofuel oil to caustic washing.

[0218] Use of ex-situ catalytic upgrading provides the advantage that both the pyrolysis and the catalytic upgrading can be optimised (i.e. catalytic upgrading can be performed at a lower temperature than pyrolysis). In an application where the goal is to produce a blendable bio-oil component, this flexibility, when combined with a low porosity catalyst provides greater ability to tune the resulting upgraded bio-oil to a composition that is suitable for blending with a residual fuel oil.

[0219] The extended period between the catalyst requiring regeneration and the low cost of the catalyst itself means that higher catalyst loading does not make the process uneconomic.

[0220] The process retains the advantages of using conventional pyrolysis apparatus, having a simple, single stage catalysis using an abundant and low-cost catalyst that is slow to deactivate, and yet still results in a pyrolysis oil that results in low sedimentation upon blending. Additional advantages include:(i) a significantly higher yield of pyrolysis oil when compared to zeolite;(ii) a de-oxygenation mechanism that de-oxygenates both low and high molecular weight compounds in the pyrolysis vapours unlike zeolite catalysts that tend to be specific to lower molecular weight compounds;(iii) a very simple aqueous washing step before blending;(iv) an energy density that is sufficiently high to be blended with residual fuel oil of 30% by weight or more; and(v) meets industry standards for sedimentation with at least some residual fuel oils.

[0221] Production of the pyrolysis oil can be followed by a simple aqueous wash before blending with a residual fuel oil. The water wash results in a slight reduction of water content inthe pyrolysis oil but also washes out some of the low molecular weight carboxylic acids in the pyrolysis oil reducing the Carbon Acid Number (CAN) of the resulting fuel as well as some low molecular compounds with carbonyl groups reducing the likelihood of sedimentation from polymerisation products.

[0222] Aqueous washing is selective towards the smallest carboxylic acids: formic >acetic> propanoic > butyric - the smaller compounds tend to be more polar so more easily removed by water. Larger molecules are less likely to be removed. In some embodiments, the recovered oil fraction is about 70-90% of original oil.

[0223] In some embodiments, even though the aqueous washing theoretically removes small polar species in the form of low molecular weight carboxylic acids and aldehydes this does not seem to have a negative effect on the inhibition of asphaltene aggregation upon blending, and apparently has a positive effect on reducing bio-oil polymerisation.

[0224] Aqueous washing can be as simple as mixing with an appropriate ratio of water (4:1 water to pyrolysis oil is around optimal in some embodiments), stirring is applied for about 1 hour at ambient temperature. The mix is then rested until phase separation occurs. Separating the phase by centrifugation may in some cases accelerate the phase separation but is not always necessary.

[0225] Ex-situ catalysis of pyrolysis vapours is most conveniently done using the catalyst in pellet form. When the catalyst is calcite derived from mussel shells or paper waste the catalyst pellets can be prepared by a first calcination step to burn of organic material followed by reducing the calcium carbonate feedstock to a powder then binding it into a pellet with a binder such as kaolin or bentonite. A bentonite binder enables the pellets to contain only about 10% binder by weight. A kaolin binder generally requires closer to 25% by weight binder content. A plasticiser such as carboxymethylcellulose aids in pelletising but is mostly burnt off when the pellets are calcined at approximately 550°C although depending on the quality of the feedstock, calcination may not be required when an inorganic binder is used. Some bentonites have a small iron content and kaolin has aluminium oxide content and so the binder may contribute some catalytic effect although measured results indicate this is minor.

[0226] The biofuel oil can potentially be made via a number of variations to the process and via the manipulation of a number of variables in the pyrolysis and upgrading process. In someembodiments, the preferred process includes ex situ catalytic upgrading of a fast pyrolysis oil utilising a moderately reactive, low porosity catalyst preferably followed by a soda wash and optionally a water wash of the biofuel oil.

[0227] A preferred method of manufacture of the biofuel oil includes the use of a low-porosity calcite or calcium carbonate catalyst in pellet form with a bentonite binder used in large volumes at a relatively low upgrading temperature around 420°C. This arrangement results in significant yields of monomeric substituted phenols and lowered yields of degradation products and testing in blends with residual fuel oils shows sedimentation levels well below industry standards.Catalytic reactor

[0228] A typical arrangement for conducting fast pyrolysis of a lignocellulosic biomass followed by ex situ catalytic upgrading of the pyrolysis oil is shown in Figure 3. The reference numbers referred to below correspond to those shown in Figure 3.

[0229] Comminuted lignocellulosic biomass is provided, and optionally pre-heated, in biomass hopper (1) and sand is provided by sand hopper (2). The biomass and sand are transported via conveyor system (3) to a temperature controlled pyrolysis reactor (4) which in Figure 3 is a fluidised bed reactor wherein the biomass is pyrolyzed under nitrogen and at an elevated temperature, usually between about 350 and about 600°C, and preferably about 500°C.

[0230] Char generated by the pyrolysis process is separated and sent to a char collector vessel (12).

[0231] The pyrolysis vapours are transferred to a gas cleaning system (5) and a catalyst vessel (6) where the pyrolysis oil is deoxygenated and upgraded in the presence of a catalyst at temperatures usually about 350 to about 490°C, and in a preferred form of the present invention about 420°C.

[0232] The pyrolysis vapour is then passed through an electrostatic precipitator (13) and an intensive cooler (7) where, with the aid of cooling jackets (8), the oil is condensed to liquid form and collected in an upgraded pyrolysis oil collector vessel (11).

[0233] Accompanying system components usually include a nitrogen source, filters (9), gas meters (10) and the like.Properties of biofuel oils

[0234] The biofuel oils have an improved energy potential, low acidity and low water content. Without wishing to be bound by theory, the low acidity may also have a beneficial effect on sedimentation via a reduction in acid driven polymerisation of aromatic groups.

[0235] In various embodiments, the biofuel oil can have a higher heating value (HHV) greater than about 29 MJ / kg. In various embodiments, the biofuel oil can have a higher heating value (HHV) greater than about 30, about 31, about 32, about 33, about 34, about 35, about 36, about 37, about 38, about 39 or about 40 MJ / kg. In various embodiments, the biofuel oil can have a higher heating value (HHV) of about 29 to about 40 MJ / kg.

[0236] In various embodiments, the biofuel oil can have an acid number of less than about 15 mg KOH / g of biofuel oil. In various embodiments, the biofuel oil can have an acid number of less than about 14, about 13, about 12, about 11, about 10, about 9, about 8, about 7, about 6, about 5, about 4 or about 3 mg KOH / g of biofuel oil. In various embodiments, the biofuel oil can have an acid number of from about 3 to about 15 mg KOH / g of biofuel oil, about 5 to about 15 mg KOH / g of biofuel oil, about 7 to about 15 mg KOH / g of biofuel oil, about 9 to about 15 mg KOH / g of biofuel oil or about 10 to about 15 mg KOH / g of biofuel oil.

[0237] In various embodiments, the biofuel oil comprises one or more degradation products as defined herein and wherein the biofuel oil comprises the one or more monomeric substituted phenols and the one or degradation products in a weight ratio of greater than about 3:1. In various embodiments, the biofuel oil comprises one or more pyrolysis degradation products and wherein the biofuel oil comprises the one or more monomeric substituted phenols and the one or degradation products in a weight ratio of greater than about 4:1, about 5:1 or about 6:1.

[0238] In various embodiments, the biofuel oil can be derived from a lignocellulosic biomass. In a preferred embodiment, the biofuel oil can be derived from wood, for example, wood residues, softwood, grasses, agricultural residues or coniferous wood biomass. In various embodiments, the wood is in particulate form. In various embodiments, the wood can be derived from a Pinus species. In various embodiments, the wood can be derived from Pinus radiata.

[0239] The preferred feedstocks for the upgraded pyrolysis oil are lignocellulosic biomass. The dispersant functionality inherent in the biofuel oil is provided by alkylphenols and similarmolecules generated and preserved, when process and catalyst parameters are appropriate, from lignin, and in some cases to a minor degree, from terpenes, polysaccharides and other components in the feedstock.

[0240] Wood and particularly softwood are ideal feedstocks but other lignocellulosic feedstocks have sufficient lignin and terpene content to provide a sufficient quantity and quality of monomeric substituted phenols provided the catalytic upgrading is tuned well enough to generate their formation and subsequently avoid cracking of the alkyl or alkenyl groups, and similar groups, from these molecules.Heavy fuel oils

[0241] Heavy fuel oils, as used herein, means a fuel oil of predominantly fossil fuel source. The term heavy fuel oils will be appreciated by a person skilled in the art to include oils left over from the refining process where most of the volatile and valuable chemicals are removed. Heavy fuel oils tend to be highly viscous mixtures of high weight molecular compounds.

[0242] In various embodiments, heavy fuel oils comprise one or more of the group comprising of: heavy fuel oil, residual fuel oil, low sulphur fuel oil, high sulphur fuel oil, boiler oil, bunker fuel and marine fuel oil.

[0243] For the purposes of this specification the term heavy fuel oil is intended to include derivatives of residual fuel oil, modified fuel oils, heavy fuel oils, high and low sulphur heavy fuel oils, very low sulphur fuel oil (VLSFO), bunker oil and similar compositions used as marine fuels and industrial fuels.

[0244] Residual fuel oil is a heavy, low-grade fuel oil produced from the residue left over after a crude oil refinery has processed more valuable products like gasoline and diesel.Method of manufacturing a blended fuel oil

[0245] In various embodiments, a method for manufacturing a blended fuel oil can comprise blending a biofuel oil of the present invention with one or more heavy fuel oils.

[0246] In various embodiments, a method for manufacturing a blended fuel oil can comprise:a. pyrolysing a lignocellulosic biomass to produce a pyrolysis vapour;b. subjecting the pyrolysis vapour to the action of a catalyst composition to produce an upgraded vapour;c. condensing the upgraded vapour to produce a biphasic / crude biofuel oil comprising an organic phase and an aqueous phase; andd. removing the aqueous phase from the organic phase to provide the biofuel oil;e. optionally subjecting the biofuel oil to caustic washing;f. optionally subjecting the biofuel oil to aqueous washing;g. optionally subjecting the biofuel oil to an additional water removal step;wherein the catalyst composition and catalytic conditions are selected to provide:a biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol comprising a benzene ring substituted with a hydroxyl group and a C2-C3alkyl or C2-C3alkenyl group at a position para to the hydroxyl group; andh. blending the biofuel oil with one or more heavy fuel oils.

[0247] In various embodiments, the blended fuel oil can comprise at least about 10% by volume biofuel oil. In various embodiments, the blended fuel oil can comprise at least about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29%, about 30%, about 31% about 32%, about 33%, about 34% or about 35% by volume biofuel oil. In various embodiments, the blended fuel oil can comprise about 10 to about 35%, about 10 to about 30%, about 10 to about 25%, about 10 to about 20%, about 10 to about 15%, about 12 to about 35%, about 12 to about 30%, about 12 to about 25%, about 12 to about 20%, about 12 to about 15%, about 15 to about 35%, about 15 to about 30%, about 15 to about 25%, about 15 to about 20%, about 18 to about 35%, about 18 to about 30%, about 18 to about 25%, about 18 to about 20%, about 20 to about 35%, about 20 to about 30%, about 20 to about 25%, about 25 to about 35%, about 20 to about 30% or about 30 to about 35% by volume biofuel oil.Properties of blended fuel oils

[0248] The biofuel oils of the present invention, and the process for making them, enables biofuel oils with inherent stabilising properties to be produced, and blended fuel oils that meet industry standards to be delivered.

[0249] In various embodiments, a blended fuel oil can comprise the biofuel oil of the present invention and a heavy fuel oil.

[0250] In various embodiments, the blended fuel oil comprises at least about 10%, about about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29%, about 30%, about 31% about 32%, about 33%, about 34% or about 35% by volume of the biofuel oil or fuel oil component of the present invention. In various embodiments, the blended fuel oil comprises about 10 to about 90% by volume of the biofuel oil or fuel oil component of the present invention. In various embodiments, the bended fuel oil comprises about 10 to about 80%, about 10 to about 70%, about 10 to about 60%, about 10 to about 50%, about 10 to about 40%, about 10 to about 30%, about 10 to about 25%, about 15 to about 90%, about 15 to about 80%, about 15 to about 70%, about 15 to about 60%, about 15 to about 50%, about 15 to about 40%, about 15 to about 30%, about 15 to about 25%, about 18 to about 90%, about 18 to about 80%, about 18 to about 70%, about 18 to about 60%, about 18 to about 50%, about 18 to about 40%, about 18 to about 30% or about 18 to about 25% by volume of the biofuel oil or fuel oil component of the present invention.

[0251] Upon blending the biofuel oil with a least one heavy fuel oil or residual fuel oil, particularly when the blend comprises around 20% or more of the biofuel oil, the blended oils comfortably meet testing requirements such as total sediment existent (TSE) and total sediment potential (TSP).

[0252] In various embodiments, the blended fuel oil can have a (TSP) of less than about 0.1%, about 0.05%, about 0.01% or less than 0.005% by mass.

[0253] In various embodiments, the blended fuel oil comprises one or more heavy fuel oil selected from: heavy fuel oil, residual fuel oil, low sulphur fuel oil, very low sulphur fuel oil, high sulphur fuel oil, boiler oil, bunker fuel and marine fuel oil. In a preferred embodiment, the one or more heavy fuel oil comprises a residual fuel oil.

[0254] When the concentration of monomeric substituted phenols in the biofuel oil is less than 3% by weight, blending said biofuel oil with a heavy fuel oil results in a blended fuel with unacceptable sedimentation properties. Increasing the concentration of monomeric substituted phenols in the biofuel oil, for example from 1% to 2% by weight, resulting in increased sedimentation in the resulting blended fuel oil. However, the inventor has surprisingly found that when the biofuel oil comprises 3% or more monomeric substituted phenols there can be less sedimentation in the resulting blended fuel oils and the amount of sedimentation can be within acceptable industry standards.

[0255] In various embodiments, the blended fuel oils comprise about 20% by volume or more of the biofuel oil, wherein the biofuel oil comprises about 3% or more of one or more monomeric substituted phenol comprising a benzene ring substituted with a hydroxyl group and a C2-C3alkyl or C2-C3alkenyl group at a position para to the hydroxyl group. In such some embodiments, the inventor has surprisingly found that blended biofuel oils show further reduction of sedimentation (as represented by a smaller TSP measurement value) when the biofuel oil comprises of about 4% or more monomeric substituted phenols. In such some embodiments, the inventor has surprisingly found that blended biofuel oils may have TSP measurements approaching zero when the biofuel oil comprises of about 5, 6, 7, or 8% or more monomeric substituted phenols.

[0256] The inventor has surprisingly found, in various embodiments, blended fuel oils with biofuel oil concentration of from about 15% to about 20% by volume, or more than 20% by volume, seem to perform very well as fuel oils. In such some embodiments, for example when the residual fuel oils or heavy fuel oils contain dispersant additives, when the concentration of biofuel oil in the blended fuel oils is less than 15% by volume, the resulting blended fuel oils may not perform as comparatively well as fuel oils.

[0257] Without wishing to be bound by theory, it is believed that the monomeric substituted phenols, that are inherent to the biofuel oil of the present invention, may interact or displace heavy fuel oil additives and their interactions with asphaltenes in the heavy fuel oil.

[0258] In various embodiments, blended fuel oils with 10% by volume or more, or 15% by volume or more biofuel oil produces a stable blended fuel oil. It will be appreciated by a personskilled in the art that blended fuel oils with biofuel oil concentrations of less than 10% by volume might result in a blended fuel oil that is comparatively less stable.

[0259] Use of the biofuel oil in blended fuel oils may have the added benefit of avoiding the use dispersant additives and the costs associated with their addition.

[0260] The following non-limiting examples are provided to illustrate the present invention and in no way limit the scope thereof.Examples

[0261] The process as described in the examples and embodiments are for the purposes of demonstration and other arrangements may be possible. The processes described may be operated in continuous, semi-continuous or batch processes and at different scales.Example 1

[0262] Testing was conducted to compare the stability to sedimentation as TSP (%) and oxygen content (wt%) of blended fuel oils comprising biofuel oils produced from lignocellulosic material under different conditions and a residual fuel oil. Five different biofuel oils were used: (i) a non-catalysed, non-deoxygenated biofuel oil (Non-cat ORG); (ii) two zeolite catalysed biofuel oils (Z 420 and Z 477); and (iii) two calcite catalysed biofuel oils of the present invention (Ca 390-460 and Ca 540) wherein the calcite catalyst was produced from mussel shells.

[0263] The respective biofuel oils were blended with residual fuel oil. The residual fuel oil was a commercial low sulphur marine fuel oil originally produced in Singapore and sourced from Tank 402 at the Port of Tauranga. The resulting blended fuel comprised 10% biofuel oil by volume.

[0264] The oxygen content and the TSP of the 5 blends were measured. The results are shown in Figure 1.

[0265] Figure 1 shows that the calcite catalysed biofuel oil's oxygen content was approximately midway between the non-catalysed pyrolysis oil and the zeolite catalysed biofuel oil but had significantly lower sedimentation levels when measured in accordance with industry standards including several data points that met the industry standard Total Solids Precipitated (TSP) requirements.Example 2

[0266] Further testing of biofuel oils was conducted, after identifying that monomeric substituted phenols were present in the biofuel oils. Doping of the biofuel oils by adding more of certain monomeric substituted phenols and in other instances testing biofuel oils with low levels of certain monomeric substituted phenols indicated a material effect of some monomeric substituted phenols on sedimentation when the doped pyrolysis oils were blended with residual fuel oils and sedimentation levels tested.

[0267] Catalysts were selected and produced, reaction conditions were adjusted and process steps adjusted to improve the production, preservation and concentration of monomeric substituted phenols.

[0268] Biofuel oil blends were produced, first by generating pyrolysis vapour via pyrolysis at 500 °C and then using: (i) a non-catalysed, non-deoxygenated pyrolysis oil; (ii) a biofuel oil made using a processes comprising calcite upgrading at 420 °C with a caustic wash, (iii) a biofuel oil made using a processes comprising calcite upgrading between 420 to 450 °C without a caustic wash, (iv) a biofuel oil made using a processes comprising calcite upgrading at 475 °C or more, (v) a biofuel oil made using a processes comprising zeolite upgrading at 420 °C, and (vi) a biofuel oil made using a processes comprising zeolite upgrading at 480 °C.

[0269] Samples of the biofuel oil made using a processes comprising calcite upgrading at 420 °C with a caustic wash were treated by centrifugation, followed by removal of the aqueous phase and then subjected to caustic washing and a further aqueous wash.

[0270] The oils were blended with residual fuel oil at a ratio of 20% biofuel oil to 80% residual fuel oil by volume and TSP (%) and oxygen content (wt%) testing conducted. The results are shown in Figure 2. The non-catalysed biofuel oils (data not shown) and zeolite catalysed biofuel oils failed TSP testing standards (more than 0.1% m / m (mass per mole) by some distance with results similar to the results for the 10% blend, as shown in Figure 1.

[0271] The TSP testing results for the calcite catalysed pyrolysis oils were better than the TSP results for zeolite catalysed pyrolysis oil upgraded under similar temperatures.

[0272] The test results for blends including catalytically upgraded bio-oil using calcite catalyst at 420 °C were better than those using the same calcite catalyst at 475 or 530 °C.

[0273] The fuel blends comprising the bio-oil that was upgraded using calcite at 420 °C and subjected to caustic washing, produced the best TSP test results consistently well below the 0.1% m / m maximum industry standard.

[0274] The best performing blends and their biofuel oil components can be co-related to the biofuel oils with greater than 3% monomeric substituted phenol.

[0275] The trends indicate that 20% blends perform better than 15% blends which in turn perform better than 10% blends. Blends below 10% very rarely meet the industry standard.

[0276] The TSP of the blended fuel oils incorporating the 420 °C calcite catalysed pyrolysis oil oils are shown in Figure 2 with 20% blended zeolite catalysed upgraded biofuel oil as comparators.Example 3

[0277] This Example describes a method for manufacturing a biofuel oil of the present invention. The method may be carried out on a laboratory scale.

[0278] In this Example, wood from Pinus Radiata was used as a feedstock.

[0279] Catalytic upgrading of pyrolysis volatiles was undertaken in an ex-situ reactor at temperatures between 340 °C and 500 °C resulting in a liquid product composed of an organic and an aqueous phase, the organic phase was separated. The resulting modified biofuel is usable as a fuel component in a blended marine (or industrial) fuel oil when blended with a residual fuel oil, heavy fuel oil, Low or High Sulphur Fuel Oil.

[0280] An exemplary catalytic pyrolysis apparatus for carrying out the method is shown in Figure 3. As described herein, the apparatus is a self-contained assembly consisting of a biomass and sand hopper, feeding screws, a reactor with overflow and knockout drums to remove entrained sand / char from the exhaust stream, a catalytic reactor and a condensation system. Spray condensers maybe available, but in certain embodiments the preferred condensation method for catalytic tests consists in an electro-static precipitator (ESP) followed by an intensive cooler.

[0281] Biomass was pyrolysed through the fluidised bed reactor using sand to promote fast heating and under nitrogen gas to avoid combustion at 450-550 °C. Volatiles were transferredto and upgraded in the catalytic reactor before going to the condensation system, where most of condensable volatiles were collected. Non-condensable gas passes through a filter to an external exhaust.Procedure

[0282] Silica sand (J61W, Industrial Sands Ltd) was sieved to be between 220 and 300 pm using mesh sieves.

[0283] Lignocellulosic biomass in the form of Pinus Radiata wood powder was sieved to between 0.5-2 mm.

[0284] Feeding screw frequencies were recalibrated as necessary to provide the desired sand and biomass flows.

[0285] If needed, catalyst pellets comprising 80% by weight powdered mussel shell, 10% bentonite binder were calcined or re-calcined in a muffle furnace.

[0286] The biomass feeder was filled with excess wood powder to at least half volume of the hopper to keep a constant feed rate. The sand hopper was filled with a weighted amount of sand and then fed into the pyrolysis reactor. The pyrolysis reactor screw was turned on and nitrogen gas was injected into the pyrolysis reactor. Heaters were turned on and the temperature of the reactor was brought to above 540°C with a target temperature of 500°C once the wood powder was added to the reactor.

[0287] The catalytic reactor was filled with 500 g of catalyst pellets and heated to 450°C.

[0288] The stirrer in the biomass hopper was started, and biomass was fed from the biomass hopper to the reactor screw.

[0289] Pyrolysis vapours were transferred to the catalytic reactor and were subsequently condensed.

[0290] The condensed liquid oil separates into an aqueous phase and an organic phase. The phases were separated, and the aqueous phase discarded.

[0291] The organic fraction of the condensed pyrolysis oil was subjected to an aqueous wash by adding 4 parts of water to 1 part of pyrolysis oil followed by stirring for 1 hour at ambienttemperature. The oil-water mixture was centrifuged twice for 5 minutes at 3000 rpm, before the aqueous phase was siphoned off.

[0292] The resulting pyrolysis oil may be blended with residual fuel oil in proportions that result in the resulting blended fuel oil being comprised of between 10 and 30% pyrolysis oil by volume.

[0293] TSE and TSP sedimentation measures were made. In at least one example an acetone wash step was implemented in addition to the prescribed standard methodology for TSE and TSP measurement.Example 4

[0294] This Example describes a further method for manufacturing a biofuel oil of the present invention.

[0295] Experiments were conducted using a semi-continuous set-up equipped with a bubbling fluidised bed reactor (height: 420 mm, internal diameter 100 mm) and a catalytic reactor (height: 330 mm, internal diameter: 73 mm) for ex situ upgrading of the pyrolysis volatiles.

[0296] Fluidisation of the bed was ensured by feeding pre-heated nitrogen at 14 litres per minute via the bottom of the reactor. Controlled amounts of wood powder and sand were mixed and fed into the pyrolysis reactor at a steady rate by way of calibrated auger screws with the resulting reactor temperature being 500 °C.

[0297] The released volatiles were carried to the gas cleaning system (comprised of a knockout vessel and two cyclones in series) located at the top of the pyrolysis reactor before going through a bed of calcined catalyst pellets in the catalytic reactor at 450 °C.

[0298] Treated volatiles leaving the catalytic reactor were carried to the condensation system which was composed of an electrostatic precipitator (ESP, 16-18 kV) and an intensive cooling column both jacketed with a coolant at -10 and -15 °C respectively.

[0299] Over a period of 90 minutes 810 g of biomass was used.

[0300] A char product was collected from overflow vessels, cyclones and the reactor and made up about 14.5% on a dry weight basis of the feedstock wood powder.

[0301] The condensed, catalysed pyrolysis oil was centrifuged twice for 5 minutes at 3000 rpm. before the aqueous phase was siphoned off and the resulting oil phase blended in different ratios with a residual fuel oil and the resulting blended oil subjected to standard sedimentation tests, TSE and TSP.Example 5

[0302] Tables 1 to 4 show a partial composition by GC / MS and properties analysis of biofuel oils of the present invention with other biofuel oils including a non-upgraded oil, pyrolysis oils catalytically upgraded at high temperatures and zeolite upgraded pyrolysis oils upgraded at a range of temperatures. The numbers in the table for each chemical represent concentration in the biofuel oil by wt% (weight%).

[0303] The data in the tables is partial and includes monomeric substituted phenols that are common in biofuel oils of the present invention when softwood is used as the feedstock. Other monomeric substituted phenols are present in the biofuel oil in small quantities but not recorded here. Biofuel oils of the present invention made from different lignocellulosic feedstocks may have different chemical composition. For instance, biofuel oil made from hardwoods will usually include 4-ethyl-syringol in significant quantities due to the different composition of hardwood lignin.Table 1 - Non-upgraded pyrolysis oil partial compositionPyrolysis oil Run 1 Run 2Catalyst none nonewash step water waterAcid number mg KOH / g 35 40HHV MJ / kg, dry ~ 28 ~ 28H2O wt% - 11.7Acetic Acid 1.00 1.09Levoglucosan 0.487 0.542Monomeric substitutedphenols4-ethylphenol 0.06 0.08propylguaiacol 0.11 0.144-Ethylcatechol 0.41 0.62cis-lsoeugenol 0.31 0.35trans-lsoeugenol 0.85 1.00propylphenol 107 0.04 0.06ethylguaiacol 137 0.24 0.26Lignocellulosic-deriveddegradation productsnaphthalene 128 0.01 0.01Methylnaphthalene 142 0.01 0.01Toluene 0.02 0.02Retene 0.01 0.02Hydroxybenzene 0.31 0.36Total Monomeric substituted 2.02 2.51phenolsTotal Lignocellulosic-derived 0.37 0.42degradation productsMonomeric substituted 5.46 5.98phenols to Lignocellulosic- derived degradationproducts ratioTable 2a – Pyrolysis oil catalytically upgraded using low porosity calcite catalyst at 420 °C (Runs 1-5)Pyrolysis Oil Run 1 Run 2 Run 3 Run 4 Run 5Catalyst calcite calcite calcite calcite calciteTemperature (°C) 420 420 420 420 420 wash step caustic caustic caustic caustic none Oxygen wt%, dry 14.78 16.53 16.53 15.67 19.06 Acid number mg <10 <10 <10 <10 41.5 KOH / gHHV MJ / kg, dry 33.9 33 33 33.5 31.7 H2O wt% 1.83 1.66 1.66 1.82 8.08 Acetic Acid 0.00 0.00 0.00 0.00 2.34 Levoglucosan 0.00 0.00 0.00 0.00 0.107 Monomericsubstituted phenols4-ethylphenol 0.36 0.40 0.40 0.42 0.35 propylguaiacol 0.95 0.78 0.86 0.90 0.55 4-Ethylcatechol 1.39 1.63 1.71 1.57 1.47 cis-lsoeugenol 0.60 0.75 0.61 0.58 0.48 trans-lsoeugenol 1.68 1.55 1.55 1.49 1.23 propylphenol 107 0.32 0.35 0.35 0.36 0.25 ethylguaiacol 137 1.24 1.45 1.19 1.20 1.17 Lignocellulosic-derived degradationproductsnaphthalene 128 0.02 0.02 0.02 0.02 0.01 Methylnaphthalene 0.02 0.03 0.03 0.03 0.02 142Toluene 0.00 0.00 0.00 0.00 0.05 Retene 0.27 0.23 0.25 0.25 0.20 Hydroxybenzene 0.80 0.87 0.89 0.91 0.85 Total Monomeric 6.53 6.91 6.67 6.53 5.51 substituted phenolsTotal Lignocellulosic- 1.11 1.14 1.18 1.20 1.14derived degradationproductsMonomeric 5.88 6.06 5.65 5.44 4.83substituted phenols toLignocellulosic- derived degradationproducts ratioTable 2b – Pyrolysis oil catalytically upgraded using low porosity calcite catalyst at 420 °C (Runs 6-9)Pyrolysis Oil Run 6 Run 7 Run 8 Run 9Catalyst calcite calcite calcite calciteTemperature (°C) 420 420 420 420wash step none none caustic causticOxygen wt%, dry 17.98 20.04 <10 <10Acid number mg - - - - KOH / gHHV MJ / kg, dry 31.3 31.5 33.6 33H2O wt% 7.14 6.72 - - Acetic Acid 1.83 1.97 0.137 0Levoglucosan 0.97 0.00 0.00 0.00Monomericsubstitutedphenols4-ethylphenol 0.29 0.34 - - propylguaiacol 0.55 0.47 - - 4-Ethylcatechol 1.35 1.26 2.645 2.654cis-lsoeugenol 0.52 0.44 0.65 0.798trans-lsoeugenol 1.35 1.09 2.261 2.636propylphenol 107 0.24 0.24 - - ethylguaiacol 137 1.17 1.10 1.9 2.145Lignocellulosic- deriveddegradationproductsNaphthalene 128 0.01 0.01 0.011 0.013 Methylnaphthalene 0.02 0.02 0.014 0.015142Toluene 0.04 0.03 0.049 0.02Retene 0.20 0.19 0.685 0.738Hydroxybenzene 0.82 0.84 1.768 1.664Total Monomeric 5.46 4.94 7.456 8.233substituted phenolsTotal 1.09 1.09 2.527 2.45Lignocellulosic- derived degradationproductsMonomeric 5.01 4.53 2.95 3.36substituted phenolsto Lignocellulosic- derived degradationproducts ratioTable 3a - Pyrolysis oil catalytically upgraded with calcite catalyst at high temperatures (Runs 1-4)Pyrolysis Oil Run 1 Run 2 Run 3 Run 4Catalyst calcite calcite calcite calcite Temperature °C 475 530 530 540wash step - - - - Oxygen wt%, dry 13.43 12.47 12.95 15.14Acid number mg 13.6 1.4 2.7 11.8 KOH / gHHV MJ / kg, dry 34.1 35.1 34.7 34.2 H2O wt% 5.1 4.01 4.3 5.54 Acetic Acid 0.23 0.06 0.03 0.19 Monomericsubstituted phenols4-ethylphenol 0.80 1.23 1.48 0.99 propylguaiacol 0.09 0.00 0.00 0.00 4-Ethylcatechol 0.38 0.00 0.36 0.84 cis-lsoeugenol 0.04 0.00 0.00 0.00 trans-lsoeugenol 0.41 0.00 0.00 0.00 propylphenol 107 0.68 0.96 0.97 0.68 ethylguaiacol 137 0.17 0.00 0.00 0.02 Lignocellulosic-derived degradationproductsnaphthalene 128 0.03 0.08 0.08 0.07 Methylnaphthalene 0.04 0.08 0.08 0.07 142Toluene 0.06 0.09 0.11 0.09 Retene 0.49 0.84 0.73 0.45 Hydroxybenzene 2.06 3.96 4.36 3.12 Total Monomeric 2.58 2.19 2.82 2.52 substituted phenolsTotal Lignocellulosic- 2.67 5.06 5.35 3.81 derived degradationproductsMonomeric substituted 0.97 0.43 0.53 0.66 phenols toLignocellulosic-deriveddegradation productsratioTable 3b - Pyrolysis oil catalytically upgraded with calcite catalyst at high temperatures (Runs 5-6)Pyrolysis Oil Run 5 Run 6Catalyst 3D printed 3D printedcalcite calciteTemperature °C 470 470wash step caustic causticOxygen wt%, dry 19.54 14.76Acid number mg KOH / g 37.7 17.8HHV MJ / kg, dry 30.8 33.9H2O wt% 9.46 2.02Acetic Acid 1.66 0.00Monomeric substitutedphenols4-ethylphenol 0.30 0.39propylguaiacol 0.13 0.314-Ethylcatechol 1.80 2.15cis-lsoeugenol 0.24 0.48trans-lsoeugenol 0.94 1.34propylphenol 107 0.20 0.29ethylguaiacol 137 0.51 0.69Lignocellulosic-deriveddegradation productsnaphthalene 128 0.02 0.03Methylnaphthalene 142 0.03 0.04Toluene 0.07 0.01Retene 0.17 0.23Hydroxybenzene 0.93 0.91Total Monomeric substituted 4.13 5.66phenolsTotal Lignocellulosic-derived 1.22 1.22degradation productsMonomeric substituted 3.39 4.64phenols to Lignocellulosic- derived degradationproducts ratioTable 4 - Pyrolysis oil catalytically upgraded using a zeolite catalyst and a range of reduced temperatures (< 550 °QPyrolysis oil Run 1 Run 2 Run 3 Run 4 Run 5Catalyst zeolite zeolite zeolite zeolite zeolite Temperature °C 363 420 420 477 477wash step - - Oxygen wt%, dry 20.5 21.5 17.5 13.3 13.3Acid number mg 40.2 19.7KOH / gHHV MJ / kg, dry 32.5 31.1 33.8 34.8 34.8H2O wt% 6.5 6.5 6.1 7.2 7.2Acetic Acid 0.95 0.86 0.43 0.33 0.25Monomericsubstitutedphenols4-ethylphenol 0.08 0.05 0.06 0.07 0.06 propylguaiacol 0.21 0.23 0.19 0.15 0.114-Ethylcatechol 0.61 0.63 0.53 0.57 0.53cis-lsoeugenol 0.37 0.41 0.37 0.28 0.26trans-lsoeugenol 1.28 1.43 1.29 1.00 0.94propylphenol 107 0.07 0.04 0.05 0.05 0.05ethylguaiacol 137 0.45 0.39 0.40 0.30 0.27Lignocellulosic- deriveddegradationproductsnaphthalene 128 0.97 1.27 1.86 2.13 2.09Methylnaphthalene 1.22 1.34 1.92 2.08 1.91142Toluene 0.63 0.48 0.94 1.10 1.09Retene 0.14 0.11 0.17 0.18 0.20Hydroxybenzene 1.45 1.05 1.60 1.77 1.49Total Monomeric 3.08 3.17 2.89 2.41 2.21substituted phenolsTotal 4.41 4.25 6.49 7.26 6.77Lignocellulosic- derived degradationproductsMonomeric 0.70 0.75 0.45 0.33 0.33substituted phenolsto Lignocellulosic- derived degradationproducts ratio

[0304] For Table 1, experiments were conducted using a semi-continuous set-up equipped with a bubbling fluidised bed reactor (height: 420mm, internal diameter 100mm). Fluidisation of the bed was ensured by feeding pre-heated nitrogen at 14 litres per minute via the bottom of the reactor. Controlled amounts of wood powder and sand were mixed and fed into the pyrolysis reactor at a steady rate by way of calibrated auger screws with the resulting reactor temperature being 500 °C.

[0305] Table 1, regarding the non-upgraded pyrolysis oil, shows the presence of isoeugenol and 4-ethylcatechol but low energy content and high acidity, both of which are generally undesirable. Without wishing to be bound by theory, it is believed that some of the lignin from the feedstock remains in oligomeric form.

[0306] Table 2 shows a partial compositional analysis of pyrolysis oils catalytically upgraded using a low porosity calcite catalyst under mild conditions, in this case about 420 °C. These results show consistent yields of monomeric substituted phenols over 5% by weight, and low yields of lignocellulosic-derived degradation products. Low sedimentation results in tests correlate strongly with the higher yields of monomeric substituted phenols and with the ratios of monomeric substituted phenols to lignocellulosic-derived degradation products.

[0307] Table 3 shows composition of pyrolysis oils upgraded using a calcite catalyst at a range of temperatures. The results show that even with a suitable catalyst the yields of monomeric substituted phenols decrease under conditions with runs over 500 °C giving lower yields of monomeric substituted phenols and higher yields of Lignocellulosic-derived degradation products.

[0308] Significantly, Table 4 shows that the high-temperature zeolite catalysed upgraded oils had lower yields of alkylphenols and alkenyl phenols and similar molecules and the higher yields of hydroxybenzene, toluene and polyaromatics such as naphthalene but that the amount of monomeric substituted phenols and the ratio of monomeric substituted phenols to degradation products can be improved using lower temperature conditions. The yields of monomeric substituted phenols approach zero at temperatures over 500 °C (data not shown), the normal conditions for catalytically upgrading pyrolysis oils for the purpose of optimising deoxygenation and HHV.

[0309] The composition of the biofuel oil upgraded with zeolite at lower temperatures i.e. below about 400 °C, shows the amount of monomeric substituted phenols exceeds about 3% by weight.

[0310] The data indicates that alkylphenols, alkenyl phenols and other monomeric substituted phenols are generated in the pyrolysis stage of the process mostly from lignin in the feedstock. Data from comparative testing between the upgraded biofuel oils of the present invention and non-upgraded pyrolysis oil indicate the yields of monomeric substituted phenolscan be maintained and increased in the catalytic upgrading stage depending on the catalyst and conditions used and that these compounds may be concentrated to a small degree via the washing steps.Industrial application

[0311] The process of the invention generally relates to a biofuel oil and the manufacture of a biofuel oil by pyrolysis of lignocellulosic biomass and catalytic upgrading. The invention also generally relates to the manufacture of blended fuel oils, which comply with marine fuel oil standards, by combination of the biofuel oils of the present invention and at least one heavy fuel oil. Therefore, the invention has applications in the production or blended marine and industrial fuels with a renewable component.

[0312] Those persons skilled in the art will understand that the above description is provided by way of illustration only, that changes, omissions and additions may be made without departing form the spirit and scope of the invention and that the invention is not limited to the specific or preferred embodiments described herein.

Claims

WE CLAIM:

1. A biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol comprising a benzene ring substituted with a hydroxyl group and a C2- C3 alkyl or C2-C3 alkenyl group at a position para to the hydroxyl group.

2. The biofuel oil of claim 1, wherein the biofuel oil has a Higher Heating Value (HHV) greater than about 29 MJ / kg.

3. The biofuel oil of claim 1 or 2, wherein the biofuel oil has an acid number of less than about 15 mg KOH / g of biofuel oil.

4. The biofuel oil of any one of claims 1 to 3, wherein the benzene ring is optionally substituted with one or two additional groups selected from the group consisting of hydroxyl, methyl, and methoxy groups at any available position of the benzene ring.

5. The biofuel oil any one of claims 1 to 4, wherein the one or more monomeric substituted phenol is a monomeric substituted monohydroxy benzene, a monomeric substituted cresole, a monomeric substituted guaiacol, a monomeric substituted catechol or a monomeric substituted syringol; wherein the monomeric substituted monohydroxy benzene, monomeric substituted cresole, monomeric substituted guaiacol, monomeric substituted catechol and monomeric substituted syringol is substituted with a C2-C3 alkyl or C2-C3 alkenyl group at a position para to the or a phenolic hydroxyl group of the monohydroxy benzene, cresole, guiacol, catechol, or syringol.

6. The biofuel oil any one of claims 1 to 4, wherein the one or more monomeric substituted phenol is a compound of the formula (1):(Dwherein:R1is C2-C3 alkyl or C2-C3 alkenyl; andR2and R3are each independently selected from the group consisting of H, OH, Me, and OMe.

7. The biofuel oil of claim 6, wherein the compound of formula (1) is a compound of the formula (2):OHR1(2).

8. The biofuel oil of claim 6 or 7, wherein: R2is independently selected from the group consisting of H, OH, Me, and OMe and R3is independently H; or R2and R3are each OMe.

9. The biofuel oil any one of claims 1 to 8, wherein the one or more monomeric substituted phenol is selected from the group consisting of: cis-isoeugenol, trans-isoeugenol, eugenol, 4-ethylguaiacol, 4-ethylcatechol, 4-ethylsyringol, 4-ethyl-2-methylphenol, 4-ethylphenol, 4-allylphenol, 4-allyl-2-methylphenol, 4-propylphenol, 2-methyl-4-propylphenol, 4-vinylguaicol and 4-propylguaiacol.

10. The biofuel oil any one of claims 9, wherein the one or more monomeric substituted phenol is selected from the group consisting of: cis-isoeugenol, trans-isoeugenol, 4- ethylguaiacol, 4-ethylcatechol, 4-ethylphenol, 4-propylphenol, and 4-propylguaiacol.

11. The biofuel oil of any one of claims 1 to 10, wherein the one or more monomeric substituted phenol has a molecular weight of about 200 g / mol or less.

12. The biofuel oil of any one of claims 1 to 11, wherein the biofuel oil comprises at least about 4 or 5% by weight of the one or more monomeric substituted phenol.

13. The biofuel oil of any one of claims 1 to 12, wherein the biofuel oil comprises at least about 6, 7, 8 or 9% by weight of the one or more monomeric substituted phenol.

14. The biofuel oil of any one of claims 1 to 13, wherein the biofuel oil comprises one or more degradation products selected from the group consisting of hydroxybenzene, toluene, and polyaromatics.

15. The biofuel oil of any one of claims 1 to 14, wherein the one or more degradation products are selected from the group consisting of hydroxybenzene, toluene, naphthalene, methylnaphthalene, and retene.

16. The biofuel oil of claim 14 or 15, wherein the biofuel oil comprises the one or more monomeric substituted phenol and the one or more degradation products in a weight ratio of greater than 3:1.

17. The biofuel oil of any one of claims 14 to 16, wherein the biofuel oil comprises the one or more monomeric substituted phenol and the one or more degradation products in a weight ratio of greater than about 4:1, about 5:1 or about 6:1.

18. A biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol and one or more degradation products,wherein the one or more monomeric substituted phenol is selected from the group consisting of: cis-isoeugenol, trans-isoeugenol, eugenol, 4-ethylguaiacol, 4-ethylcatechol, 4-ethylsyringol, 4-ethyl-2-methylphenol, 4-ethylphenol, 4-allylphenol, 4-allyl-2-methylphenol, 4-propylphenol, 2-methyl-4-propylphenol, 4-vinylguaicol and 4-propylguaiacol,wherein the one or more degradation products are selected from the group consisting of hydroxybenzene, toluene, naphthalene, methylnaphthalene, and retene, andwherein the one or more monomeric substituted phenol and one or more degradation products are in a weight ratio of greater than 3:1, about 4:1, about 5:1 or about 6:1.

19. A method for manufacturing a biofuel oil, the method comprising:a. pyrolysing a lignocellulosic biomass to produce a pyrolysis vapour;b. subjecting the pyrolysis vapour to the action of a catalyst composition under catalytic conditions to produce an upgraded vapour;c. condensing the upgraded vapour to produce a biphasic biofuel oil comprising an organic phase and an aqueous phase; andd. removing the aqueous phase from the organic phase to provide the biofuel oil;wherein the catalyst composition and catalytic conditions are selected to provide:• a biofuel oil comprising at least about 3% by weight of one or more monomeric substituted phenol comprising a benzene ring substituted with a hydroxyl group and a C2-C3 alkyl or C2-C3 alkenyl group at a position para to the hydroxyl group.

20. The method of claim 19, wherein the method further comprises subjecting the biofuel oil to caustic washing, aqueous washing or both caustic washing and aqueous washing.

21. The method claims 19 or 20, wherein the method further comprises subjecting the biofuel oil to an additional water removal step.

22. The method of claim 21, wherein the water removal step comprises reducing the water content of the biofuel oil to less than about 5% by weight.

23. The method of claim 21 or 22, wherein the water removal step comprises evaporation and / or distillation.

24. The method of any one of claims 19 to 23, wherein the lignocellulosic biomass is derived from a wood, softwood, or coniferous wood biomass.

25. The method of any one of claims 19 to 24, wherein removing the aqueous phase from the organic phase comprises a mechanical separation.

26. The method of claim 25, wherein the mechanical separation is centrifugation.

27. The method of any one of claims 19 to 26, wherein the aqueous phase comprises one or more carboxylic acids having a molecular weight of 300 g / mol or less.

28. The method of any one of claims 19 to 27, wherein the catalyst composition comprises a catalyst with a porosity of from about 0 to about 120 m2 / g.

29. The method of any one of claims 19 to 28, wherein the catalyst composition comprises an alkaline earth metal oxide catalyst or an alkaline earth metal carbonate catalyst.

30. The method of any one of claims 19 to 29, wherein the catalyst composition comprises a calcium carbonate catalyst.

31. The method of claim 30, wherein the calcium carbonate catalyst is a calcite catalyst.

32. The method of any one of claims 19 to 31, wherein the catalyst composition comprises a binder, preferably the binder comprises bentonite and / or kaolin.

33. The method of any one of claims 19 to 32, wherein the catalytic conditions comprise a temperature of at least about 350 °C, preferably wherein the catalytic conditions comprise a temperature of from about 350 to 480 °C.

34. The method of any one of claims 19 to 33, wherein the method comprises pyrolysing the lignocellulosic biomass at a temperature of at least about 350 °C.

35. A biofuel oil obtainable by the method of any one of claims 19 to 34.

36. A biofuel oil obtained by the method of any one of claims 19 to 34.

37. A method for manufacturing a blended fuel oil, the method comprising blending a biofuel oil of any one of claims 1 to 18 or claims 35 or 36 with one or more heavy fuel oils.

38. A blended fuel oil comprising:a. the biofuel oil of any one of claims 1 to 18, or claims 35 or 36, andb. one or more heavy fuel oils.

39. The blended fuel oil of claim 38, wherein the blended fuel oil comprises a biofuel oil of any one of claims 1 to 18 or claims 35 or 36 in an amount of at least about 10%, 15%, or 20% by volume of the blended fuel oil.

40. The blended fuel oil of claim 38 or 39, wherein the blended fuel oil has a total sediment potential (TSP) of less than about 0.1% by mass.

41. The blended fuel oil of any one of claims 38 to 40, wherein the one or more heavy fuel oils comprises a residual fuel oil.

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