US20130014431A1 - Advanced, biomass-derived, low-sulfur bunker fuels - Google Patents

Advanced, biomass-derived, low-sulfur bunker fuels Download PDF

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US20130014431A1
US20130014431A1 US13/476,564 US201213476564A US2013014431A1 US 20130014431 A1 US20130014431 A1 US 20130014431A1 US 201213476564 A US201213476564 A US 201213476564A US 2013014431 A1 US2013014431 A1 US 2013014431A1
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fuel
oil
composition
bio
blended
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Abandoned
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US13/476,564
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English (en)
Inventor
Hong Jin
Cory B. Phillips
Daren E. DAUGAARD
Kristi A. Fjare
Robert A. Levine
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Phillips 66 Co
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Phillips 66 Co
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Priority to US13/476,564 priority Critical patent/US20130014431A1/en
Assigned to PHILLIPS 66 COMPANY reassignment PHILLIPS 66 COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DAUGAARD, DAREN E., JIN, HONG, LEVINE, ROBERT A., FJARE, KRISTI A., PHILLIPS, CORY B.
Priority to CA2841837A priority patent/CA2841837A1/fr
Priority to PCT/US2012/041874 priority patent/WO2013009419A1/fr
Publication of US20130014431A1 publication Critical patent/US20130014431A1/en
Abandoned legal-status Critical Current

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    • 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/302—Viscosity
    • 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

  • This present invention relates generally to a fuel composition. More specifically, the present invention relates to a novel biomass derived low sulfur bunker fuels composition and the method of making thereof.
  • Bunker fuel in general refers to class of marine transportation fuels. Traditionally, these fuels were highly viscous fluids primarily composed of heavy petroleum fractions designed to burn in large, low-speed diesel engines for large shipping vessels.
  • the bunker fuel was made up of heavy residual fuel oil (RFO) or “HFO”.
  • RFO heavy residual fuel oil
  • bunker fuel was sometimes referred to as “fuel oil No. 6”, “residual”, “boiler fuel” or “Bunker C” Bunker fuels were used for both steam (boiler) powered vessels and for diesel power vessels. Because of plant efficiency (40-45%) steam plants over time were replaced by more efficient diesel engines (50%).
  • Modern low-speed, direct drive, diesels are more efficient than medium speed engines, which require some sort of gear box or electric drive.
  • Modern medium speed diesels are capable of burning heavier, more viscous “bunker” fuels.
  • Bunker fuel is mainly used directly in compression ignition, as well as, boiler combustion applications for on-board power generation in the marine and shipping industry.
  • This traditionally heavy type of bunker fuel is used in 80% of the world's merchant fleet that utilize ocean routes. It is also used widely for stationary power and utility applications by developing nations.
  • bunker fuel was used for boiler combustion, which produced steam. This was used in turn in turbines to power the ships propeller and in generators to produce ship's electricity. The steam was also used to heat the ship's fuel.
  • a diesel powered ship steam either comes from waste heat boilers (economizers) that capture the residual heat left in diesel exhaust or from auxiliary boilers fired on heavy fuel or diesel.
  • Marine residual fuel is often referred to as intermediate fuel oil (IFO) which is generally a combination of heavy fuel oil (HFO) diluted with other lighter oil and/or distillate stocks to meet viscosity specifications.
  • IFO intermediate fuel oil
  • a classic Bunker fuel composition comprises intermediate fuel oil (IFO) mixtures that are rich in HFO (No. 6) and are balanced with combinations of atmospheric distillate fuel oils (No. 1, No. 2 heating oils and diesel fuel), vacuum gas oil (VGO) and FCC light-cycle oil (LCO).
  • the heavy fuel oil (HFO) used in Bunker fuel can also come from FCC slurry oil, heavy coker gas oil (HCGO), or other heavy petroleum fractions or intermediate refinery streams available in the event of temporary shutdowns of heavy oil processing units.
  • MDO marine diesel oils
  • MGO marine gas oils
  • ULSD diesel No. 2
  • LCO heating oil No. 2
  • LCGO hydrocracker diesel
  • Smaller watercraft such as ferries, fishing boats and some military ships use marine diesel only.
  • NRLM non-road, locomotive, marine
  • MDO does not require special heating. If some vessels operate in cold climates, special MDO fuels are blended for these extreme conditions. In the case of special equipment, such as Inert Gas Generators, MDO may be the fuel of choice, because it is more easily handled and burns cleaner with less effort. Finally, another application for MDO use is within ship incinerators.
  • bunker sulfur content must remain below 35,000 ppmw by Jan. 1, 2012 and below 5000 ppmw by 2020.
  • a commercial, market grade of low-sulfur bunker must contain less than 15,000 ppmw sulfur.
  • Greenhouse gas (GHG) restrictions will be much more difficult to administer and implement, however, this fact will not stop future legislation and rulings over the next few years in the U.S. and in Europe.
  • the IMO has developed a guideline for using a greenhouse gas emission index for ships.
  • residual based transportation fuel accounts for over 1% of the GHG emissions which were roughly 1,633 million metric ton for 2007.
  • Current reports have the global shipping industry responsible for 3-5% of the global GHG emissions and nearly 15-20% by 2050.
  • This present invention relates generally to a fuel composition and the process of making thereof. More specifically, the present invention relates to a novel biomass derived low sulfur bunker fuels composition and the method of making thereof.
  • Embodiment of the invention discloses a novel low sulfur bunker fuels composition derived from blending various biomass derived oils (or bio-oil)/by-products with other heavy residual fuel oils and distillates where final sulfur content is controlled by the ratio of bio-oil to other heavy residual fuel oils and distillates.
  • Embodiment of the invention also discloses a process of making a novel biomass derived low sulfur bunker fuels by blending various-biomass derived oils/by-products with other heavy residual fuel oils and distillates.
  • a blended fuel composition comprising a renewable based fuel and a petroleum based fuel.
  • the weight ratio of the renewable based fuel to the petroleum based fuel is from 1:20 to 20:1.
  • a method for preparing a blended fuel composition comprising blending a renewable based fuel with a petroleum based fuel in a ratio ranges from 1:20 to 20:1.
  • a blended fuel composition is provided from blending a renewable based fuel with a petroleum based fuel in a ratio ranges from 1:20 to 20:1.
  • the major advantage of this invention is to use a relatively inexpensive biomass to generate compounds that could be blended in current marine bunker fuels and contribute to the overall reduction of GHG emissions during ship transportation from a Life Cycle Assessment (LCA) view point. It is discovered in this invention that both the tax obligation and pollutant emissions can be reduced if the viscosity cutters and distillates are derived from a biomass source.
  • LCA Life Cycle Assessment
  • FIG. 1 is a diagrammatic illustration of a co-solvent-based process strategy for synthesizing cellulosic bunker fuel.
  • a renewable based fuel may comprise hydrocarbons that are derived from natural, replenishable feed stock which can be utilized as source of energy.
  • These renewable hydrocarbons are simple in structure and may contain molecular oxygen as represented in the general formula of C x H y O z where 1 ⁇ x ⁇ 20, 2 ⁇ Y ⁇ 44, and 1 ⁇ z ⁇ 3 including the following organic classes; alcohols, ketones, aldehydes and acids.
  • a renewable based fuel comprises a bio-oil component and a bio-co-solvent component.
  • Any oxygenated bio-oil feedstock may be used in the present invention.
  • the bio-oil component may include but is not limited to pyrolysis oil produced by a pyrolysis process.
  • Pyrolysis is the chemical decomposition of biomass by heating in the absence of oxygen.
  • U.S. Pat. No. 4,891,459 the contents of which are herein incorporated by reference in their entirety, describes one basic exemplary approach for the pyrolysis of biomass. Pyrolysis may be conducted at a variety of temperatures and pressures, with or without inert gases. Many different pyrolysis conditions are known in the art.
  • pyrolysis oils may be produced by pyrolysing a material of natural, replenishable origin selected from any type of biomass including agricultural residues, city waste, and aquatic biomass.
  • pyrolysis oils may be produced by pyrolysing plant fiber, lignins, wood, wood byproducts, miscanthus, switchgrass, hemp, corn, poplar, willow, sorghum, sugarcane, tree byproducts, leaves, eucalyptus, palm, pulping liquor, paper, plant byproducts, plant oils, plant solids, grasses, agricultural byproducts, yard-waste, garbage, municipal waste, agricultural waste, biologically derived manufacturing waste, animal byproducts, animal waste, bacterial solids, algal solids, and any combinations thereof.
  • bio-oil is dependent upon the biomass used for pyrolysis and conditions, but bio-oil will typically include derivatives of lignins, cellulose, hemi-cellulose, fiber, starches, sugars, proteins and other components not readily soluble during typical biomass processing, milling, pulping, gasification and the like.
  • Bio-oils produced from biomasses are a chemically complex mixture of compounds comprising generally a mixture of water, light volatiles, and non-volatiles.
  • bio-oil has a number of negative properties from a transportation fuel perspective such as thermal unstability, high acidity (corrosiveness), substantial water content (usually in the range of 15% to 30%), poor miscibility with hydrocarbon fuels, variable viscosity, low heating values (about half that of a typical diesel fuel), high oxygen content and low cetane number.
  • These negative properties are related to the oxygenated compounds contained in bio-oils that result in a 45 wt % oxygen content.
  • raw bio-oils may be pretreated before they are blended or used as a renewable fuel. Pretreatment may include filtration, neutralization and distillation prior to admixing with said petroleum based fuel to remove a stream comprising metals, water or sediment, and to neutralize any acidic components.
  • the pyrolysis bio-oil initially containing 30 wt % water was first partially dehydrated down to 6.4 wt % water on a rotary evaporator, then filtered overnight using Whatman #1 (11 micrometer pores) cellulosic filter paper. The filtrate was noticeably clearer afterwards.
  • This filtered bio-oil was mixed with cyclohexane in a 1:1 volume ratio and charged to a pot flask. This mixture underwent lab-scale, batch azeotropic, vacuum distillation until almost all of the cyclohexane and moisture were removed. The weight of dehydrated bio-oil was recorded. The final water content was roughly 0.14 wt %.
  • the pretreated bio-oil is blended with a polar, bio-derived co-solvent (bio-co-solvent) before sending to a heated storage tank.
  • a polar, bio-derived co-solvent bio-co-solvent
  • co-solvents to the final fuel blend is optional, and the type and concentration may be dependent on the blending methodology.
  • a bio-derived co-solvent may include common alcohol-based solvents such as, methanol, ethanol, propanol, butanol, pentanol, heptanol, octanol, nonanol, decanol, butanediol, propanediol, diethylene glycol, propylene glycol, furfuryl alcohol, glycerol, organic acids; formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, ketones; acetone, butanone, pentanone, ethyl isopropyl ketone, methyl isopropyl ketone, methyl isobutyl ketone
  • the pretreated bio-oil/bio-derived co-solvent mixture is blended with a petroleum based fuel.
  • the petroleum based fuel may comprise hydrocarbons derived from petroleum refining process. These heavy petroleum fractions may include; intermediate fuel oil (IFO) mixtures that are rich in heavy RFO (No. 6) and are balanced with combinations of atmospheric distillate fuel oils (No. 1, No. 2 heating oils and diesel fuel), light vacuum gas oil (VGO), FCC light-cycle oil (LCO), hydrocracked gas oil (HCGO), light coker gas oil (LCGO), deasphalted oil (bright stock) or visbreaker gas oil (VBGO).
  • the RFO part of IFO can be the bottoms of from the atmospheric distillation also referred to as “atmospheric reduced crude (ARC)” or the residue from vacuum distillation operations or vacuum reduced crude (VRC).
  • heavy RFO isn't used directly in the IFO blend, it many undergo visbreaking or deasphalting before being used where it becomes a tar or asphalt related by-product respectively.
  • These heavy petroleum fractions can also come from FCC slurry oil, heavy coker gas oil (HCGO) and comprise the intermediate fuel oil component disclosed in this embodiment.
  • a petroleum based fuel may include a full range of hydrocarbons derived from petroleum refining processes such as, light fuel oil, heavy residual fuel oil, atmospheric gas oil, vacuum gas oil, coker gas oils, light cycle oil, heavy cycle oil, slurry oil, hydrocracker gas oils, slop oils, unconverted gas oils, diesel fuel, heating oil, kerosene, jet fuel and various intermediate hydrocarbon streams of similar attributes
  • petroleum residual fuel oil may be obtained from refining and optionally hydroprocessing a crude petroleum source. It may be a single stream obtained from such a refinery process or a blend of several heavier petroleum fractions obtained by refinery processing via different processing routes.
  • the blended fuel composition to which the present invention is to use includes but is not limited to a marine low-speed diesel engine, for example a 380 cSt intermediate fuel oil (IFO) composition which is used in large cylinder bore (>500 mm) marine diesel engines manufactured by companies such as MAN, Wartsila and Rolls Royce. These engines are power plants capable of moving bulk carriers, large tankers and container vessels by delivering more than 50 kW. Therefore, the petroleum based component may be any known residual fuel oil (RFO), and it may itself comprise a mixture of various heavy petroleum components. It may also have a sulfur content of at least 3.5 wt %.
  • RFO residual fuel oil
  • the invention can be practiced at a high renewable based fuel concentration, wherein the renewable based component is up to 100% by weight of the finished fuel blend.
  • the renewable based component is typically up to about 15% by weight of the finished fuel blend, more typically up to about 25% by weight of the finished fuel blend, and alternatively up to about 50% by weight of the finished fuel blend.
  • the invention is also applicable at renewable based component concentrations as low as about 1, 5, and 10% by weight of the finished fuel blend, and even at very low renewable fuel concentrations as low as about 4, 3, 2, 1, and 0.5% by weight of the finished fuel blend.
  • a typical weight ratio of renewable fuel to bio-co-solvent is 2:1 and may be as high as 25:1.
  • compositions for both heavy fuel oil (HFO) and marine diesel oil (MDO) bunker fuel are given by blending various biomass derived oils/by-products with residual fuel oil and distillates.
  • the major advantage of this invention is to use a relatively inexpensive biomass to generate compounds that could be blended in current marine bunker fuels and contribute to the overall reduction of GHG emissions during ship transportation from a Life Cycle Assessment (LCA) view point.
  • LCA Life Cycle Assessment
  • Lifecycle GHG emissions of marine bunker fuels refer to emissions associated with the extraction and transport of crude oils, the production of bunker fuels at the refineries, the transport of bunkers fuels to the marine vessels, and the direct combustion of the bunker fuels to provide power on the marine vessels.
  • Current U.S. regulations do not account for GHG emissions associated with the manufacturing of the marine vessels or the engines that use bunker fuels as feeds, nor do they account for the GHG emissions associated with the building of infrastructure.
  • lifecycle GHG emissions for the biomass-derived fuels refer to emissions associated with the production, harvest, collection, storage, and transport of biomass to biorefineries, the conversion of biomass to a liquid transportation fuel at the biorefineries, the transport of the biomass-derived fuels to the blending terminals, the blending of the biomass-derived fuels and the marine bunker fuels into finished products, the delivery of the fuel products to the marine vessels, and the combustion of the fuels.
  • the biomass feedstocks may include, but are not limited to, agricultural residues, forest thinning materials, municipal solid waste (MSW), energy crops, aquatic species (such as algae), and commercially produced woody biomass (such as poplar wood).
  • MSW municipal solid waste
  • energy crops such as algae
  • commercially produced woody biomass such as poplar wood.
  • the resulting fuel products could achieve up to 80% GHG emission reduction relative to petroleum-based marine bunker fuels.
  • this novel fuel composition would lead to significant reduction of sulfur and/or PM (i.e., less than 1.5 wt % sulfur and 25% less ash content compared to current fuel specifications) in compliance with IMO regulation, providing a premium price advantage to the final fuel products.
  • Bio-oil generated from wood or other biomass sources such as, grain fibers or hulls is sent to a pre-treatment unit to remove any metals, water, and sediment and to neutralize any acidic components.
  • This pre-treated bio-oil is blended with a polar, bio-derived co-solvent and sent to a heated storage tank.
  • High-sulfur (>3 wt %) residual fuel oil (RFO) is sent from a near-by refinery into another heated storage vessel. The two oils are blended to produce a low-sulfur ( ⁇ 1.5 wt %) advanced cellulosic bunker fuel (LSFO)
  • Blend A As shown in Figure Table 1, high sulfur (1.85%), commercial RMG 380 bunker fuel is used to create Blend A.
  • the composition is a 3:1 ratio of RMG to treated bio-oil/co-solvent mixture. Neither the untreated bio-oil nor the bio-co-solvent contains sulfur.
  • Blend A qualifies as reduced carbon, low-sulfur ( ⁇ 1.5 wt %) blend with a minimum greenhouse gas (GHG) reduction of 6% as determined by life cycle assessment.
  • Blend A has a lower viscosity (148 cSt), higher flashpoint (78 C) and reduced ash content (330 ppm).
  • straight-run high-sulfur diesel from refinery, hydrotreated pyrolysis oil and/or stand-alone renewable diesel is blended directly to produce marine diesel oil (MDO) bunker-fuel.
  • MDO marine diesel oil

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  • Liquid Carbonaceous Fuels (AREA)
US13/476,564 2011-07-11 2012-05-21 Advanced, biomass-derived, low-sulfur bunker fuels Abandoned US20130014431A1 (en)

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US13/476,564 US20130014431A1 (en) 2011-07-11 2012-05-21 Advanced, biomass-derived, low-sulfur bunker fuels
CA2841837A CA2841837A1 (fr) 2011-07-11 2012-06-11 Fuels lourds elabores, derives de biomasse, a faible teneur en soufre
PCT/US2012/041874 WO2013009419A1 (fr) 2011-07-11 2012-06-11 Fuels lourds élaborés, dérivés de biomasse, à faible teneur en soufre

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