Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
  • C10L2200/0461—Fractions defined by their origin
  • C10L2200/0469—Renewables or materials of biological origin
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
  • C10L2200/0461—Fractions defined by their origin
  • C10L2200/0469—Renewables or materials of biological origin
  • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
  • C10L2290/02—Combustion or pyrolysis
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
  • C10L2290/24—Mixing, stirring of fuel components
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

• Embodiments of the present invention relate generally to more stable and valuable bio-oils made from biomasses, more specifically it relates to bio-oils that are useful as heating oil. Particularly, various embodiments of the present invention provide for a bio- oil useful as heating oil without the need to hydrotreat the bio-oil or use a similar deoxygenating process. Various embodiments also relate to renewable heating oils containing such bio-oil and an oxygenated acyclic component.
• renewable energy sources have become increasingly important.
• the development of renewable fuel sources provides a means for reducing the dependence on fossil fuels. Accordingly, many different areas of renewable fuel research are currently being explored and developed.
• biomass With its low cost and wide availability, biomass has increasingly been emphasized as an ideal feedstock in renewable fuel research. Consequently, many different conversion processes have been developed that use biomass as a feedstock to produce useful biofuels and/or specialty chemicals.
• Existing biomass conversion processes include, for example, combustion, gasification, slow pyrolysis, fast pyrolysis, liquefaction, and enzymatic conversion.
• One of the useful products that may be derived from the aforementioned biomass conversion processes is a liquid product commonly referred to as "bio-oil.” Bio-oil may be processed into transportation fuels, hydrocarbon chemicals, and/or specialty chemicals.
• the non-equilibrium liquids (pyrolysis oil or bio-oil) produced by fast pyrolysis are suitable as a fuel for clean, controlled combustion in boilers and for use in diesel and stationary turbines.
• bio-oil liquids offer some distinctive advantages for heating and power production over biomass gasification products and direct combustion of the biomass.
• Bio-oil from pyrolysis processes is the least cost liquid bio-fuel for stationary use and its net C0 2 -balance is better than that of other bio-fuels.
• bio-oil that could be used as a heating oil, alone or in combination with an oxygenated acyclic component, wherein such bio-oil, or heating oil containing such bio-oil and oxygenated acyclic component, had improved stability, less corrosiveness and higher heating value than prior art bio-oils without having to undergo hydrotreating or other deoxygenating processes.
• a renewable heating fuel oil composition derived from the thermochemical conversion of a cellulosic biomass wherein the renewable heating fuel oil composition comprises hydrocarbons consisting of (a) an oxygenated component present in an amount such that the renewable heating fuel oil composition has an oxygen content of less than about 30 weight percent, and (b) a non-oxygenated component having an aromatic content greater than about 40 weight percent.
• a renewable heating fuel oil composition derived from a cellulosic biomass wherein the renewable heating fuel oil composition is produced by a process comprising: (a) converting at least a portion of the cellulosic biomass material in an oxygen-poor environment in the presence of a catalyst material at a temperature in the range of from about 200 °C to about 1000 °C to produce a reaction product stream containing the renewable heating fuel oil composition; and (b) separating the renewable heating fuel oil composition from the reaction product stream such that the heating oil composition has a heating value of at least about 10,000 btu/lb without an oxygen-removing hydrotreatment step, and wherein the renewable heating fuel oil composition comprises mainly hydrocarbons and the hydrocarbons consist of (i) an oxygenated component present in an amount such that the renewable heating fuel oil composition has an oxygen content of less than about 30 weight percent, and (ii) a non- oxygenated component having an aromatic content greater than about 40 weight percent.
• a renewable fuel oil composition comprising: a) a first component comprising a bio-oil derived from the thermochemical conversion of biomass, wherein the bio-oil comprises: i) an oxygenated component having an oxygen content of at least about 5 wt%, and ii) a non-oxygenated component having an aromatic content of at least about 25 wt%; b) a second component comprising an oxygenated acyclic component comprising open chain molecules having 12 or more carbon atoms per molecule; and wherein the renewable fuel oil composition has a heating value of at least about 14,000 Btu/lb.
• FIG. 1 is a schematic diagram of a biomass conversion system according to one embodiment of the present invention.
• FIG. 2 is graph illustrating the stability of bio-oil samples over time.
• FIG. 3 is a graph illustrating data on the stability of pyrolysis oil at 90° C taken from Table 2 of Czernik, S.; Johnson, D. K. and Black, S. Stability of wood fast pyrolysis oil. Biomass and Bioenergy 1994. 7 (1-6), 187-192. DETAILED DESCRIPTION
• Fig. 1 illustrates a biomass conversion system suitable for use in producing bio-oil for use as a renewable heating oil, either alone or in combination with an oxygenated acyclic component, in accordance with the invention.
• the embodiments are intended to describe aspects of the invention in sufficient detail to enable those skilled in the art to practice the invention. Other embodiments can be utilized and changes can be made without departing from the scope of the present invention. The following detailed description is, therefore, not to be taken in a limiting sense.
• the scope of the present invention is defined only by the appended claims, along with the full scope of equivalents to which such claims are entitled.
• Pyrolysis refers to non-catalytic pyrolysis processes.
• Fast pyrolysis processes are pyrolysis processes for converting all or part of the biomass to bio- oil by heating the biomass in an oxygen-poor or oxygen-free atmosphere.
• the biomass is heated to pyrolysis temperature for a short time compared with conventional pyrolysis process, i.e. less than 10 seconds.
• Pyrolysis temperatures can be in the range of from about 200 °C to about 1000 °C.
• the biomass will be heated in a reactor using an inert heat carrier, such as sand.
• oxygen-poor refers to an atmosphere containing less oxygen than ambient air.
• the amount of oxygen should be such as to avoid combustion of the biomass material, or vaporized and gaseous products emanating from the biomass material, at the pyrolysis temperature.
• the atmosphere is essentially oxygen-free, that is, contains less than about 1 weight percent oxygen.
• Biomass catalytic cracking refers to a catalytic pyrolysis, wherein a catalyst is used to help facilitate cracking of the biomass components and derived compounds under fast pyrolysis type conditions. Accordingly, in a BCC process a dual role of the catalyst as heat carrier and catalyst itself is used in the reactor to facilitate the conversion of the biomass to bio-oil.
• the catalyst can be pre-mixed with the biomass before introduction into the reactor or be introduced into the reactor separately.
• the present invention is directed to bio-oil compositions having chemical and physical properties that are particularly suited for use as a heating oil or heating fuel in furnaces, boilers or stoves.
• the invention aims to define a renewable heating fuel oil composition with increased stability, lower corrosiveness, and increased heating value as compared with pyrolysis oil.
• the bio-oil of the current invention is useful as a renewable heating fuel oil composition, or a component of a renewable heating fuel oil composition, characterized by having a heating value greater than about 10,000 btu/lb.
• the heating value will be above about 11 ,000 btu/lb and, generally, from about 1 1 ,000 btu to about 18,000 btu/lb or about 14,000 btu/lb to about 18,000 btu/lb.
• the bio-oil, useful as a component of the renewable heating fuel oil composition of the current invention is characterized by being comprised of (i) an oxygenated component present in an amount such that the renewable heating fuel oil composition has an oxygen content of less than about 30 weight percent, and (ii) a non-oxygenated component having an aromatic content of at least about 25 weight percent.
• the oxygenated component is present in the bio-oil in an amount such that the renewable heating fuel oil composition has an oxygen content from about 5 weight percent to about 30 weight percent, more preferably, from about 12 weight percent to about 20 weight percent, and even more preferably from about 7 weight percent to about 18 weight percent.
• the aromatic content of the non-oxygenated component of the bio-oil will be at least about 40 weight percent, or from about 30 weight percent to about 70 weight percent, or from about 40 weight percent to about 60 weight percent.
• the oxygen content for the renewable heating fuel oil composition indicated here in is on a dry basis; that is without including the oxygen content of any water present in the renewable heating fuel oil composition.
• the present invention can result in much more stable renewable heating fuel oil compositions than the prior art.
• the renewable heating fuel oil composition of the present invention will have a stability parameter less than 15 centipoise per hour (cp/h), or no greater than 10 cp/h, or no greater than 5 cp/h, or no greater than 1 cp/h, or no greater than 0.5 cp/h.
• the stability parameter characterizes the stability of a renewable heating fuel oil over time.
• low stability bio-oil has a stability parameter greater than 75 cp/h
• intermediate-stability bio-oil has a stability parameter in the range of 30 to 75 cp/h
• high-stability bio-oil has a stability parameter of less than 30 cp/h.
• bio-oil with a stability parameter of less than 1 cp/h can be classified as ultra-stable bio-oii so that high- stability bio-oil is that with a stability parameter below 30 cp/h but at least 1 cp/h.
• FIG. 1 it depicts a biomass conversion system 10 that is suitable for producing the bio-oil which is useful as a renewable heating fuel oil composition, alone or in combination with an oxygenated acyclic component, in accordance with an embodiment of the current invention. It should be understood that the biomass conversion system shown in FIG. 1 is just one example of a system within which the present invention can be embodied.
• Embodiments of the present invention may find application in a wide variety of other systems where it is desirable to efficiently and effectively convert a biomass into a bio-oil useful as a renewable heating fuel oil composition, alone or in combination with an oxygenated acyclic component.
• the exemplary biomass conversion system illustrated in FIG. 1 will now be described in detail.
• the biomass conversion system 10 of FIG. 1 includes a biomass source 12 for supplying a biomass feedstock to be converted to bio-oil.
• the biomass source 12 can be, for example, a hopper, storage bin, railcar, over-the-road trailer, or any other device that may hold or store biomass.
• the biomass supplied by the biomass source 12 can be in the form of solid particles.
• the biomass particles can be fibrous biomass materials comprising a cellulose-containing material (cellulosic material). Examples of suitable cellulose-containing materials include algae, paper waste, and/or cotton linters.
• the biomass particles can comprise a lignocellulosic material.
• Suitable lignocellulosic materials include forestry waste such as wood chips, saw dust, pulping waste, and tree branches; agricultural waste such as corn stover, wheat straw, and bagasse; and/or energy crops such as eucalyptus, switch grass, and coppice.
• the solid biomass particles from the biomass source 12 can be supplied to a biomass feed system 14.
• the biomass feed system 14 can be any system capable of feeding solid particulate biomass to a biomass conversion reactor 16. While in the biomass feed system 14, the biomass material may undergo a number of pretreatments to facilitate the subsequent conversion reactions. Such pretreatments may include drying, roasting, torrefaction, demineralization, steam explosion, mechanical agitation, and/or any combination thereof.
• the catalyst may be introduced directly into the biomass conversion reactor 16.
• the catalyst may be fresh and/or regenerated catalyst.
• the catalyst can, for example, comprise a solid acid, such as a zeolite. Examples of suitable zeolites include ZSM-5, Mordenite, Beta, Ferrierite, and zeolite-Y. Additionally, the catalyst may comprise a super acid. Examples of suitable super acids include sulfonated, phosphated, or fluorinated forms of zirconia, titania, alumina, silica-alumina, and/or clays.
• the catalyst may comprise a solid base.
• suitable solid bases include metal oxides, metal hydroxides, and/or metal carbonates.
• the oxides, hydroxides, and carbonates of alkali metals, alkaline earth metals, transition metals, and/or rare earth metals are suitable.
• Other suitable solid bases are layered double hydroxides, mixed metal oxides, hydrotalcite, clays, and/or combinations thereof.
• the catalyst can also comprise an alumina, such as alpha-alumina.
• solid biomass materials generally contain minerals. It is recognized that some of these minerals, such as potassium carbonate, can have catalytic activity in the conversion of the biomass material. Even though these minerals are typically present during the chemical conversion taking place in the biomass conversion reactor 16, they are not considered catalysts.
• the biomass feed system 14 introduces the biomass feedstock into a biomass conversion reactor 16.
• biomass is subjected to a thermochemical conversion reaction that produces bio-oil.
• the reactor 16 can be any system or device capable of thermochemically converting biomass to bio-oil.
• the biomass conversion reactor 16 can be, for example, a fluidized bed reactor, a cyclone reactor, an ablative reactor, or a riser reactor.
• the biomass conversion reactor 16 can be a riser reactor and the conversion reaction can be catalytic enhanced fast pyrolysis or biomass catalytic cracking (BCC).
• BCC catalytic enhanced fast pyrolysis or biomass catalytic cracking
• the BCC conversion should occur in an oxygen-poor or, preferably, oxygen-free atmosphere.
• BCC is carried out in the presence of an inert gas, such as nitrogen, carbon dioxide, and/or steam.
• the BCC conversion can be carried out in the presence of a reducing gas, such as hydrogen, carbon monoxide, noncondensable gases recycled from the biomass conversion process, and/or any combination thereof.
• the BCC conversion process is characterized by short residence times and rapid heating of the biomass feedstock.
• the residence times of the conversion can be, for example, less than 10 seconds, less than 5 seconds, or less than 2 seconds.
• the BCC conversion may occur at temperatures between 200 and 1 ,000°C, between 250 and 800°C, or between 300 and 600°C.
• the catalyst is used as a heat carrier material and introduced into reactor 16 via line 26 at sufficient temperature to insure that the reaction mixture reaches a temperature between 200 and 1 ,000°C, between 250 and 800°C, or between 300 and 600°C.
• rapid heating of the solid biomass material can generally be accomplished by providing the solid biomass material in the form of particles having a low mean particle diameter.
• the mean particle diameter of the biomass is less than about 2000 pm, and more preferably less than about 1000 ⁇ .
• the pretreatment of the biomass material can help achieve the desired particle size.
• the conversion effluent 18 exiting the biomass conversion reactor 16 generally comprises gas, vapors, and solids.
• the vapors produced during the conversion reaction may interchangeably be referred to as "bio- oil,” which is the common name for the vapors when condensed into their liquid state.
• the solids in the conversion effluent 18 generally comprise particles of char, ash, and/or spent catalyst.
• the bio-oil (contained in effluent 18) exiting the biomass conversion reactor 16 will be characterized by being comprised of mainly hydrocarbons and the hydrocarbons consist of (i) an oxygenated component present in an amount such that the renewable heating fuel oil composition has an oxygen content of about 30 weight percent or less, and (ii) a non-oxygenated component having an aromatic content of at least about 25 weight percent.
• the oxygenated component is present in an amount such that the renewable heating fuel oil composition has an oxygen content (dry basis) of from about 5 weight percent to about 30 weight percent or, from about 12 weight percent to about 20 weight percent, or from about 7 to about 18 weight percent.
• the aromatic content of the non-oxygenated component will be at least about 40 weight percent, or from about 30 weight percent to about 70 weight percent, or from about 40 weight percent to about 60 weight percent. It is a distinct advantage of the current invention that the bio-oil does not need to be treated with an oxygen removing process, such as hydrotreatment, to achieve the above composition.
• an oxygen removing process such as hydrotreatment
• the conversion effluent 18 from the biomass conversion reactor 16 can be introduced into a solids separator 20.
• the solids separator 20 can be any conventional device capable of separating solids from gas and vapors such as, for example, a cyclone separator or a gas filter.
• the solids separator 20 removes a substantial portion of the solids (e.g., spent catalysts, char, and/or heat carrier solids) from the conversion effluent 18.
• the solid particles 22 recovered in the solids separator 20 can be introduced into a regenerator 24 for regeneration, typically by combustion. After regeneration, at least a portion of the hot regenerated solids can be introduced directly into the biomass conversion reactor 16 via line 26. Alternatively or additionally, the hot regenerated solids can be directed via line 28 to the biomass feed system 14 for combination with the biomass feedstock prior to introduction into the biomass conversion reactor 16.
• the substantially solids-free fluid stream 30 exiting the solids separator 20 can then be introduced into a fluids separator 32.
• a fluids separator 32 it is preferred and an advantage of the current invention that the bio-oil 30 entering the fluids separator 32 has not previously been subjected to a deoxygenation process such as, for example, hydrotreating.
• non-condensable gas is separated from the bio-oil.
• the fluids separator 32 can be any system capable of separating the bio-oil contained in stream 30 from the non-condensable gas.
• Suitable systems to be used as the fluids separator 32 include, for example, systems for affecting separation by fractional distillation, heated distillation, extraction, membrane separation, partial condensation, and/or non-heated distillation. As shown in FIG. 1 , non-condensable gases 40 removed from the fluids separator 32 may be, optionally, recycled via lines 40 and 42 to the biomass conversion reactor 16 for use as a lift gas.
• the resulting bio-oil 38 useful as a renewable heating fuel oil composition, alone or in combination with an oxygenated acyclic component is characterized by a heating value of at least about 10,000 btu/lb, or at least about 1 1 ,000 btu/lb, or from about 1 1 ,000 to about 18,000 btu/lb, or from about 14,000 to about 18,000 btu/lb without further treatment to remove oxygen, such as in an oxygen-removing hydrotreatment process.
• Such bio-oil can have an oxygen content that is less than about 20, 15, 12, 10, or 8 percent by weight of the bio-oil.
• the oxygen content can also be greater than about 5, 8, or 10 percent by weight of the bio-oil.
• the renewable heating fuel oil composition comprises:
• a second component comprising an oxygenated acyclic component comprising open chain molecules having 12 or more carbon atoms per molecule
• renewable heating fuel oil composition has a heating value of at least about 14,000, or at least about 15,000, or at least about 16,000 Btu/lb.
• the bio-oil described above comprises: i) an oxygenated component having an oxygen content of at least about 5 wt%, or from about 10 to about 30 wt%, or from about 12 to about 20 wt%, and ii) a non- oxygenated component having an aromatic content of at least about 25 wt%, or at least about 40 wt%, or from about 30 to about 70 wt%, or from about 40 to about 60 wt%.
• the oxygen content of the renewable heating fuel oil composition comprising the first and second components is from about 5 to about 30 wt%, or from about 12 to about 20 wt%, or from about 7 to about 18 wt%.
• the oxygenated component is present in the bio-oil in the range of from about 10 to about 90 wt%, or from about 20 to about 80 wt%.
• the non-oxygenated component is present in the bio-oil in the range of from about 15 to about 70 wt%, or from about 20 to about 60 wt%.
• the non-oxygenated aromatic content of the renewable heating fuel oil composition is from about 3 to about 60 wt%, or from about 25 to about 60 wt%.
• the first component is present in the renewable heating fuel oil composition in the range of from about 50 to about 99 wt%, or from about 60 to about 95 wt%; and the second component is present in the renewable heating fuel oil composition in the range of from about 0.5 to about 50, or from about 1 to about 50 wt%, or from about 2 to about 45 wt%, or from about 5 to about 40 wt%.
• the bio-oil is present in the renewable heating fuel oil composition in the range of from about 60 to about 95 wt%, or from about 70 to about 90 wt%; and the oxygenated acyclic component is present in the renewable heating fuel oil composition in the range of from about 5 to about 40 wt%, or from about 10 to about 30 wt%.
• the second component is selected from the group consisting of: a fatty acid methyl ester (FAME), biodiesel, biomass-derived diesel, an at least partially upgraded bio-oil or fraction thereof derived from the at least partial deoxygenation of a portion of the bio-oil, and combinations thereof.
• FAME fatty acid methyl ester
• the at least partially upgraded bio-oil or fraction thereof comprises less than about 20, or less than about 15, or less than about 10, or less than about 8, or less than about 6, or less than about 4 wt% oxygen, and can be prepared in accordance with the methods disclosed in co-pending U.S. Application No. 13/964,873, filed August 12, 2013, which has been incorporated by reference in its entirety herein.
• the second component has a heating value of at least about 14,000, or at least about 16000 Btu/lb.
• the open chain molecules having 12 or more carbon atoms per molecule are present in the second component in an amount of from about 70 to about 99 wt%, or from about 80 to about 99, or from about 85 to about 99.
• the open chain molecules having 12 or more carbon atoms per molecule are present in the renewable heating fuel oil composition in an amount of from about 3 to about 50 wt%, or from about 7 to about 40 wt%, or from about 8 to about 35 wt%.
• the renewable heating fuel oil composition is used as a fuel for a furnace, boiler, combustor, thermal oxidizer, turbine, or stove.
• the thermochemical conversion of the biomass to produce the bio-oil does not include an oxygen-removing hydrotreatment step.
• the renewable heating fuel oil composition has a stability parameter no greater than about 15, or no greater than about 10, or no greater than about 5, or no greater than about 1 , or no greater than about 0.5 cp/h.
• the bio-oil is produced by a process comprising: a) converting at least a portion of the biomass in an oxygen-poor environment in the presence of a catalyst material at a temperature in the range of from about 200 ° C to about 1000 " C to produce a reaction product stream containing the bio-oil; and b) separating the bio-oil from the reaction product stream; wherein steps a) and b) do not include an oxygen-removing hydrotreatment step.
• Sample A was produced by biomass catalytic cracking using a clay-type catalyst in a riser reactor operated at a reactor outlet temperature of about 550 °C.
• Samples B and C were produced by biomass catalytic cracking using a zeolite-type catalyst in a riser reactor operated at a reactor outlet temperature of about 600 °C.
• the oxygen content and heating value of the bio-oil were determined by ASTM D5291 and ASTM D240 test methods, respectively. The results are shown in Table 1.
• the heating value of typical pyrolysis bio-oils does not exceed 10,000 btu/lb as can be seen from a) Mahinpey, N.; Murugan, P.; Mani, T. and Raina, R. Analysis of bio-oil, biogas, and biochar from pressurized pyrolysis of wheat straw using a tubular reactor. Energy & Fuels 2009. 23 (5), 2736-2742; and b) Czernik, S. and Bridgwater, A. V. Overview of applications of biomass fast pyrolysis oil. Energy and Fuels 2004. 18 (2), 590-598.
• the accelerated thermal stability test used for the inventive bio-oil samples in these examples comprised heating the samples to 90° C and holding the samples at that temperature for 48 hours. Test amounts were taken from the samples at 0, 8, 24 and 48 hours and viscosity measurements were taken with the test amount temperature being at 40° C. Viscosity was measured using a modified version of ASTM D2983 using a higher temperature than standard due to the high viscosity of bio-oil at low temperature. Viscosity was measured at 40° C using a Brookfield viscometer. As indicated above, the increase in viscosity under these conditions correlates with room temperature storage such that 24 hours of testing time at 90° C is equal to the change in a year at near room temperature storage.
• bio-oil samples representative of the present invention, were produced from the conversion of yellow pine particles by biomass catalytic cracking using a zeolite- type catalyst in a riser reactor operated at a reactor outlet temperature of about 500 to 600 °C.
• the results of the stability test are illustrated in Fig. 2.
• typical pyrolysis oils submitted to this accelerated thermal stability test have all shown a nearly 100% increase in viscosity after eight hours (see Fig 3, which is a graphical representation of viscosity data for stored pyrolysis oil at 90 °C taken from Table 2 of Czernik et al.)
• bio-oil samples produced from southern yellow pine by biomass catalytic cracking using a zeolite-type catalyst in a riser reactor operated at a reactor outlet temperature of about 500 to 650 °C.
• the three bio-oil samples were subjected to the accelerated thermal stability test in order to establish the effect of increased stability in the heat value of bio-oils.
• ultra-stable bio-oils bio-oils with a stability parameter of less than 1 cp/h
• all exhibited low oxygen content and heating values greater than 10,000 btu/lb. Accordingly, the ultra-stable bio-oils all had superior heating value.
• a corrosion test was performed according to general test procedures ASTM G31 on stainless steel, at two different temperatures for the liquid and vapor phases of heating bio-oil samples produced from southern yellow pine by biomass catalytic cracking using a zeolite-type catalyst in a riser reactor operated at a reactor outlet temperature of about 500 to 650 °C.
• the samples contained 10 and 17 % wt. oxygen, produced as in Example 1. No corrosion was detectible.
• a low oxygen bio-oil (BO-16) was produced from the conversion of southern yellow pine wood particles by pyrolysis in the presence of a catalyst in a riser reactor operated at a reactor outlet temperature of about 650 °C.
• the resulting bio-oil had an oxygen content of 16.64 weight percent.
• the composition (in wt%) of the bio-oil is shown below in Table 3.
• bio-oil BO-16 Three separate portions of the bio-oil BO-16 were combined with FAME forming a BF5 blend containing 5 wt% FAME, a BF10 blend containing 10 wt% FAME, and a BF15 blend containing 15 wt% FAME.
• the thermal stabilities of the bio-oil, BF5, BF10, and BF15 were assessed based on changes in viscosity using the accelerated thermal stability test.
• the accelerated thermal stability test used for the bio-oil, BF5, BF10, and BF15 samples in this example comprised heating the samples to 90° C and holding the samples at that temperature for up to 48 hours. Viscosity was measured at 40° C using a Brookfield viscometer.
• BO-16 and BO-21 are bio-oil samples with 16wt% and 21wt% O-content, respectively. Separate portions of each bio-oil were combined with FAME forming blends containing different proportions of each of these components.
• Light scattering was used to assess the phase segregation stability of these blends using a Turbiscan MA2000 instrument.
• Turbiscan is an instrument for measuring light scattering in fluids. This system couples light scattering with a scan of the sample length to give a picture of its homogeneity or changes in homogeneity. The overlay of several scans over time enables stability analysis of the sample from 20 to 50 times faster than visual detection. The detected stability during a 16h scanning experiment is a measure of the fouling propensity of the blend. Table 5. Turbiscan assessed stability
• the term "and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself, or any combination of two or more of the listed items can be employed.
• the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination; B and C in combination; or A, B, and C in combination.
• the terms “comprising,” “comprises,” and “comprise” are open- ended transition terms used to transition from a subject recited before the term to one or more elements recited after the term, where the element or elements listed after the transition term are not necessarily the only elements that make up of the subject.

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• Organic Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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• 2015
  • 2015-01-13 EP EP15735268.3A patent/EP3094710A4/de not_active Withdrawn
  • 2015-01-13 CA CA2936685A patent/CA2936685A1/en not_active Abandoned
  • 2015-01-13 WO PCT/US2015/011160 patent/WO2015106251A1/en active Application Filing

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