WO2009089590A1 - Additif pour combustible - Google Patents

Additif pour combustible Download PDF

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Publication number
WO2009089590A1
WO2009089590A1 PCT/AU2009/000050 AU2009000050W WO2009089590A1 WO 2009089590 A1 WO2009089590 A1 WO 2009089590A1 AU 2009000050 W AU2009000050 W AU 2009000050W WO 2009089590 A1 WO2009089590 A1 WO 2009089590A1
Authority
WO
WIPO (PCT)
Prior art keywords
fuel
fuel additive
complex
particles
approximately
Prior art date
Application number
PCT/AU2009/000050
Other languages
English (en)
Inventor
Jose Antonio Alarco
Peter Cade Talbot
Original Assignee
Very Small Particule Company Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from AU2008900211A external-priority patent/AU2008900211A0/en
Application filed by Very Small Particule Company Limited filed Critical Very Small Particule Company Limited
Priority to EP09702642A priority Critical patent/EP2247699A1/fr
Priority to AU2009204647A priority patent/AU2009204647A1/en
Priority to JP2010542479A priority patent/JP2011510122A/ja
Priority to US12/863,044 priority patent/US20110010986A1/en
Publication of WO2009089590A1 publication Critical patent/WO2009089590A1/fr

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/12Inorganic compounds
    • C10L1/1233Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof

Definitions

  • the present invention relates to a fuel additive.
  • the present invention relates to a fuel additive that is effective even with high sulphur content in the fuel.
  • Cerium oxide has been extensively used as a component in the catalyst of three-way converters for the elimination of toxic exhaust emissions in automobiles.
  • the cerium oxide contained within the catalyst can act as a chemically active component, working as an oxygen store by the release of oxygen in the presence of reductive gases, and removal of oxygen by interaction with oxidised species.
  • Cerium oxide may store and release oxygen by the following processes:
  • Cerium oxide has also been used as an additive to be added to fuels.
  • the cerium oxide provides a catalytic effect that has been found to reduce the emission of toxic exhaust gases.
  • Addition of cerium oxide has also been found to improve the combustion of the fuel as it passes through an internal combustion engine. Due to improved combustion, far less pollutants are formed.
  • cerium oxide is used as a fuel additive for diesel engines, an increase in efficiency of approx 10% has been achieved and a reduction in emissions of NOx gases of up to 65% has also been measured [ref Oxonica Website].
  • WO 03/040270 (the entire contents of which are herein incorporated by cross reference) describes a fuel additive which comprises a particle of cerium oxide which has been doped with a divalent or trivalent metal or metalloid which is a rare earth metal, a transition metal, including a noble metal, or a metal of groups HA, IHB, VB, or VIB of the periodic table, and a polar or non-polar organic solvent.
  • the doped cerium oxide particle described in this patent application may have the following formula:
  • M is the metal or metalloid as described above, particularly Rh, Cu, Ag, Au, Pd, Pt, Sb, Se, Fe, Ga, Mg, Mn, Cr, Be, B, Co, V and Ca as well as Pr, Sm, and Gd and x has a value of up to 0.3. Copper is particularly preferred.
  • the doped cerium oxide particle may have following formula:
  • M' is said metal or metalloid other than a rare earth
  • RE is a rare earth
  • y is one or 1.5 and each of n and k has a value up to 0.5, preferably up to 0.3.
  • Copper is the preferred metal or metalloid.
  • WO 2004/065529 (the entire contents of which are herein incorporated by cross reference) has a similar disclosure, but it relates to a method of improving the efficiency of a fuel for an internal combustion engine which comprises adding to the fuel prior to the introduction of the fuel to a vehicle or other apparatus comprising an internal combustion engine, cerium oxide and/or doped cerium oxide and, optionally, one or more fuel additives.
  • the doped cerium oxides that may be used in the invention described in this patent application will have the formula Cei -x M x ⁇ 2 , where M is the metal or metalloid as described above, particularly Rh, Cu, Ag, Au, Pd, Pt, Sb, Se, Fe, Ti, Ga, Mg, Mn, Cr, Be, B, Co, V and Ca as well as Pr, Sm, and Gd.
  • M is the metal or metalloid as described above, particularly Rh, Cu, Ag, Au, Pd, Pt, Sb, Se, Fe, Ti, Ga, Mg, Mn, Cr, Be, B, Co, V and Ca as well as Pr, Sm, and Gd.
  • the fuel additive may be provided in the form of a product to be mixed with the fuel at the point of dispensing the fuel (for example, at a service station).
  • the fuel additive may be poured directly into the fuel tank of a motor vehicle prior to or just after filling up the fuel tank of the motor vehicle.
  • the fuel additive may be mixed with the fuel in the fuel storage tanks at the service station.
  • the fuel additive mixed with the fuel at the point of production of the fuel, which is typically at an oil refinery.
  • PCT/ AU 2007/0004808 the entire contents of which are herein incorporated by cross reference, we describe a material that is useful as an exhaust emissions catalyst.
  • the present invention provides a fuel additive comprising one or more complex oxides having a nominal composition as set out in formula (1): A x B 1-y M y O n (1) wherein
  • A is selected from one or more group III elements including the lanthanide elements or one or more divalent or monovalent cations;
  • B is selected from one or more elements with atomic number 22 to 24, 40 to 42 and 72 to 75;
  • M is selected from one or more elements with atomic number 25 to 30; x is defined as a number where 0 ⁇ x ⁇ l ; y is defined as a number where 0 ⁇ y ⁇ 0.5.
  • the one or more complex oxides have a general composition as set out in formula (2):
  • B, M, P, x and y are as set out in formula (1).
  • A is selected from La, Ce, Sm and Nd
  • A' is selected from Sr, Ba, and Ca
  • B is selected from Ti, V, W and Mo
  • M is selected from Cu and Ni.
  • A is La and/or Ce
  • A' is Sr
  • B is Ti
  • M is Cu and/or Ni.
  • the complex oxide has the general formula as set out in formula (3):
  • At least one of the complex oxide phases is a perovskite with a general formula (4): A ⁇ A' w B 1.y M y O 3 ( 4 )
  • the perovskite component of the formula may suitably exhibit substantially homogenous and phase-pure composition.
  • the complex oxide material may have an initial surface area greater than approximately 15m 2 /g, preferably greater than approximately 20m 2 /g, more preferably greater than approximately 30m 2 /g, and a surface area after aging for 2 hours at
  • the complex oxide material may generally exhibit an average grain size of approximately 2 nm to approximately 150 run, preferably approximately 2 to 100 nm and has pores ranging in size from approximately 7 nm to approximately 250 nm, more preferably approximately lO nm to approximately 150 nm.
  • the average grain and pore size of the complex oxide materials may vary, depending on the specific complex oxide selected.
  • the complex oxide material may exhibit a substantially disperse pore size range.
  • the complex oxide material of the invention may be formed by mixing precursors of the elements described above in the general formula (1) followed by appropriate heat treatment to form the target phases.
  • the precursors may be of any suitable form such as salts, oxides or metals of the elements used.
  • the precursor mixture may be in the form of a mixture of solids, a solution or a combination of solids and solutions.
  • the solutions may be formed by dissolving salts in a solvent such as water, acid, alkali or alcohols.
  • the salts may be but are not limited to nitrates, carbonates, oxides, acetates, oxalates, and chlorides. Organometallic form of elements such as alkoxides may also be used.
  • Solid dispersions may also be used as suitable precursor materials.
  • Various methods of mixing precursors to produce the complex oxide may include but are not limited to techniques such as, mixing and grinding, co- precipitation, thermal evaporation and spray pyrolysis, polymer and surfactant complex mixing and sol gel. Where necessary, the final phase composition is achieved by thermal processing following mixing.
  • the heating step may be carried out using any suitable heating apparatus and may include but are not limited to, hot plates or other heated substrates such as used in spray pyrolysis, ovens stationary table furnaces, rotary furnaces, induction furnaces, fluid bed furnace, bath furnace, flash furnace, vacuum furnace, rotary dryers, spray dryers, spin-flash dryers.
  • a homogeneous complex oxide is formed by the method outlined in US Patent 6,752,679, "Production of Fine-Grained Particles", the entire contents of which are herein incorporated by cross reference.
  • a homogeneous complex oxide is formed, has nano-sized grains in the size range indicated and nano-scale pores in the size range indicated by using the method outlined in US Patent 6,752,679 and US Patent application 60/538867, the entire contents of which are herein incorporated by cross reference.
  • a homogeneous complex oxide is formed, has nano-sized grains in the size range indicated and nano-scale pores in the size range indicated and uses an aqueous colloidal dispersion of nano-scale particles as one of the precursor elements by using the method outlined in US Patent 6,752,679 and US Patent application 60/538867 and US patent application 60/582905, the entire contents of which are herein incorporated by cross reference.
  • the complex oxide is provided in the form of dispersed particles.
  • the dispersed particles may have a particle size of up to 300nm.
  • the dispersed particles may be formed by forming the complex oxide material in accordance with the methods as described in US Patent 6,752,679 or US Patent application 60/538867 or US patent application 60/582905 and subsequently grinding the complex oxide material to form dispersed particles. It has been surprisingly found that the agglomerated particles that are formed by the methods described in our US Patent 6,752,679 and US Patent application 60/538867 and US patent application 60/582905 are only loosely agglomerated and can be easily ground or milled to form dispersed particles.
  • A is Ce
  • B is Ti
  • y is zero
  • z is zero
  • n is 4. This results in a complex oxide having the formula CeTiO 4 .
  • the fuel additive in accordance with the present invention may further comprise one or more solvents.
  • the one or more solvents may comprise an organic solvent.
  • the one or more solvents may comprise a non-polar organic solvent or a polar organic solvent.
  • the person skilled in the art will readily understand that a number of solvents may be used in the fuel additive in accordance with the present invention.
  • the solvents are soluble in the fuel and act as a carrier or delivery agent for the particles of metal oxide.
  • a number of other components may also be added to the fuel additive. These other components may include:
  • the fuel additives of the present invention show enhanced resistance to deactivation or poisoning by sulphur.
  • the fuel additive in accordance with the present invention is particularly suitable for adding to fuels, such as diesel fuel, at the manufacturing facility of the fuels (which will typically be an oil refinery) or at bulk storage facilities for the fuel.
  • the present invention provides a method for making a fuel additive comprising the steps of forming a complex metal oxide of formula (1) as described above, the complex metal oxide being formed in the form of the agglomerated particles having nano sized grains, breaking the agglomerates of particles to form dispersed particles of complex metal oxide having a particle size of less than 300nm and adding said particles to a fuel.
  • the method may further comprise the step of mixing the particles with one or more solvents.
  • the solvent(s) are soluble in the fuel and act as a carrier or delivery agent for the particles of metal oxide.
  • Other additives, as described above, may also be added to the fuel additive.
  • the present invention provides a fuel additive comprising a solvent and one or more complex oxides having a nominal composition as set out in formula (1) above.
  • the solvent(s) are soluble in the fuel and act as a carrier or delivery agent for the particles of metal oxide.
  • the fuel additive may be in the form of a suspension or a dispersion of particles of the complex oxide in the solvent.
  • the present invention also provides a fuel comprising a hydrocarbon-based fuel and a fuel additive as described herein.
  • the hydrocarbon- based fuel may be diesel fuel.
  • n will be a value that essentially balances the oxygen with the metallic species in the formulae.
  • a complex metal oxide of the nominal formula La 0 gSr 0 2 T1O3 plus 10 w% CeO 2 was produced as follows.
  • a solution containing all the required elements except Ti was made by mixing 45mls of water, 1Og of nitric acid, 46.29g of lanthanum nitrate hexahydrate, 5.66g of strontium nitrate and 7.57g of cerium nitrate hexahydrate.
  • a complex metal oxide of nominal formula Lao.5Sro.25Tio.96Nio.O4On P ⁇ us ⁇ w% CeO 2 was produced using a similar method to Example 1. XRD analysis showed that the perovskite phase LaSr 0.5 Ti 2 O 6 and (Ce 5 La) 2 Ti 2 O 7 were the main types of phases present.
  • a complex metal oxide of nominal formula LaQ.8SrQ.2 ⁇ 0.96 ⁇ 0.04 ⁇ n P ⁇ us ⁇ w ⁇ ⁇ ) CeO 2 was produced using a similar method to Example 1. XRD analysis showed that the perovskite phase LaSr 0.5 Ti 2 O 6 and (Ce 5 La) 2 Ti 2 O 7 were the main types of phases present.
  • a complex metal oxide of nominal formula La 0 gSr 0 .2Tio . 93Nio.o 4 Cuo 03O 0 plus 10 w% CeO 2 was produced using a similar method to Example 1. XRD analysis showed that the perovskite phase LaSr 0 S Ti 2 O 6 and (Ce 5 La) 2 Ti 2 O 7 were the main types of phases present.
  • a complex metal oxide of nominal formula LaTi 0 95Ni 0 0 4 O n P ⁇ us 10 ⁇ 0 CeO 2 was produced using a similar method to Example 1. XRD analysis showed that the perovskite phase LaSr 0 5 Ti 2 O 6 and (Ce 5 La) 2 Ti 2 O 7 were the main types of phases present.
  • a complex metal oxide of nominal formula CeTi 0 96 Ni 0 04O 11 was produced using a similar method to Example 1. XRD analysis showed that the (Ce 5 La) 2 Ti 2 O 7 phase was the main type of phase present.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

L'invention porte sur un additif pour combustible comprenant un ou plusieurs oxydes complexes ayant une composition nominale telle qu'énoncée dans la formule (1) : AxB1-yMyOn; où A est choisi parmi un ou plusieurs éléments du groupe III comprenant les éléments des lanthanides ou un ou plusieurs cations divalents ou monovalents; B est choisi parmi un ou plusieurs éléments ayant un numéro atomique de 22 à 24, 40 à 42 et 72 à 75; M est choisi parmi un ou plusieurs éléments ayant un numéro atomique de 25 à 30; x est défini comme un nombre où 0 < x ≤ 1; y est défini comme un nombre où 0 ≤ y < 0,5.
PCT/AU2009/000050 2008-01-16 2009-01-16 Additif pour combustible WO2009089590A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP09702642A EP2247699A1 (fr) 2008-01-16 2009-01-16 Additif pour combustible
AU2009204647A AU2009204647A1 (en) 2008-01-16 2009-01-16 Fuel additive
JP2010542479A JP2011510122A (ja) 2008-01-16 2009-01-16 燃料添加剤
US12/863,044 US20110010986A1 (en) 2008-01-16 2009-01-16 Fuel additive

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2008900211A AU2008900211A0 (en) 2008-01-16 Fuel Additive
AU2008900211 2008-01-16

Publications (1)

Publication Number Publication Date
WO2009089590A1 true WO2009089590A1 (fr) 2009-07-23

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PCT/AU2009/000050 WO2009089590A1 (fr) 2008-01-16 2009-01-16 Additif pour combustible

Country Status (5)

Country Link
US (1) US20110010986A1 (fr)
EP (1) EP2247699A1 (fr)
JP (1) JP2011510122A (fr)
AU (1) AU2009204647A1 (fr)
WO (1) WO2009089590A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107573980A (zh) * 2017-09-11 2018-01-12 天津市职业大学 一种煤炭环保助燃剂及其制备方法
EP3553155A1 (fr) * 2018-03-12 2019-10-16 INDIAN OIL CORPORATION Ltd. Nanomatériaux à base de pérovskite comme agent d'amélioration de combustion de carburants liquides et gazeux

Families Citing this family (6)

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US8883706B2 (en) 2012-10-30 2014-11-11 The Clorox Company Anionic micelles with cationic polymeric counterions systems thereof
US8728454B1 (en) 2012-10-30 2014-05-20 The Clorox Company Cationic micelles with anionic polymeric counterions compositions thereof
US8728530B1 (en) 2012-10-30 2014-05-20 The Clorox Company Anionic micelles with cationic polymeric counterions compositions thereof
US8765114B2 (en) 2012-10-30 2014-07-01 The Clorox Company Anionic micelles with cationic polymeric counterions methods thereof
US8883705B2 (en) 2012-10-30 2014-11-11 The Clorox Company Cationic micelles with anionic polymeric counterions systems thereof
JP6892575B2 (ja) * 2016-03-01 2021-06-23 天馬微電子有限公司 液晶表示装置

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107573980A (zh) * 2017-09-11 2018-01-12 天津市职业大学 一种煤炭环保助燃剂及其制备方法
EP3553155A1 (fr) * 2018-03-12 2019-10-16 INDIAN OIL CORPORATION Ltd. Nanomatériaux à base de pérovskite comme agent d'amélioration de combustion de carburants liquides et gazeux

Also Published As

Publication number Publication date
JP2011510122A (ja) 2011-03-31
US20110010986A1 (en) 2011-01-20
EP2247699A1 (fr) 2010-11-10
AU2009204647A1 (en) 2009-07-23

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