WO2010146041A2 - Combustible renouvelable - Google Patents

Combustible renouvelable Download PDF

Info

Publication number
WO2010146041A2
WO2010146041A2 PCT/EP2010/058356 EP2010058356W WO2010146041A2 WO 2010146041 A2 WO2010146041 A2 WO 2010146041A2 EP 2010058356 W EP2010058356 W EP 2010058356W WO 2010146041 A2 WO2010146041 A2 WO 2010146041A2
Authority
WO
WIPO (PCT)
Prior art keywords
evaporator
acid
acid oil
fuel
oil
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2010/058356
Other languages
English (en)
Other versions
WO2010146041A3 (fr
Inventor
John Mcneil
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aquafuel Research Ltd
Original Assignee
Aquafuel Research Ltd
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
Application filed by Aquafuel Research Ltd filed Critical Aquafuel Research Ltd
Publication of WO2010146041A2 publication Critical patent/WO2010146041A2/fr
Publication of WO2010146041A3 publication Critical patent/WO2010146041A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/06—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a liquid
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • 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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/10—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for with the aid of centrifugal force
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/16—Refining fats or fatty oils by mechanical means
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/22—Fuels; Explosives
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/26—Oils; Viscous liquids; Paints; Inks
    • G01N33/28—Oils, i.e. hydrocarbon liquids
    • G01N33/2805—Oils, i.e. hydrocarbon liquids investigating the resistance to heat or oxidation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/26—Oils; Viscous liquids; Paints; Inks
    • G01N33/28—Oils, i.e. hydrocarbon liquids
    • G01N33/2835—Specific substances contained in the oils or fuels
    • G01N33/2876—Total acid number
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the present invention relates to a method of determining the suitability of an acid oil or fat for combustion in a compression ignition engine.
  • Other aspects provide a novel renewable fuel, and an apparatus and method for the preparation of such a fuel.
  • Naturally occurring renewable oils and fats are extracted from plants or rendered from animals in distinction from fossil fuels.
  • fatty acids that can combine with glycerine to form a variety of naturally occurring oils and fats, including oils and fats derived from seeds, such as rape, sunflower and ground nut, or fruit, such as palm or coconut, as well as oils and fats derived from fish or animals.
  • oils and fats are used for substances in a liquid state at ambient temperatures, whereas fats tend to be solid or semi-solid at room temperatures.
  • Acid oils Oils and fats that contain free fatty acids are commonly known as acid oils or fatty acid oils.
  • the term “acid oil” can refer to various oils and fats and for clarity includes crude oil derived from seeds, fruit, fish or animals. Such oil will normally contain significant amounts of free fatty acids as well as other contaminants.
  • the crude oil may be oil that has been simply pressed from seeds or fruit, or may be a blend of pressed oil and soil extracted oil.
  • Acid fat is acid oil that is in a solid or semi-solid state at normal ambient temperature and crude acid fat is also derived from seeds, fruit, fish or animals.
  • the term “acid oil” will be used herein to include acid fats unless the context otherwise dictates.
  • Acid oils and fats are characterised by different parameters related to the physical and chemical properties of the substance.
  • a number of parameters are used to define the suitability of the material to be used as the fuel in internal combustion engines.
  • these parameters are the acid number and the iodine number.
  • the acid number is used to quantify the amount of acid present in biodiesel, and in particular is a measure of the amount of carboxylic acid groups in a fatty acid.
  • the acid number is defined as the mass of potassium hydroxide (base) in milligrams needed to neutralise the acid groups in one gram of biodiesel.
  • Wartsila stipulates a maximum acid number of 5,0 mg KOH/g and a maximum iodine number of 120 for the renewable fuels for its diesel engines.
  • MAN Diesel stipulates a Total Acid Number (TAN) of less than 4 mg KOH/g and an iodine number less than 125 g/100g for its biof ⁇ el.
  • R1-R5 are different hydrocarbon substituents.
  • a disadvantage of this method is that it is limited to distillate fuels with relatively low acid number 2 or 3, albeit higher than those specified in the standards. For fuels with a very high acid number a large amount of the additive would be required, rendering the method impractical.
  • the invention provides stable combustion of acid oils without any detrimental corrosion of standard diesel engine fuel injection equipment or significant deposit formation on the injector nozzle tip.
  • renewable compression ignition engine fuel from acid oils and fats is of particular applicability for combined heat and power (CHP) plants.
  • CHP combined heat and power
  • Figure 1 shows acid and iodine numbers of conventional diesel fuels and acid oils suitable for use in an embodiment of the invention
  • Figure 2 shows the acceptable region of electrical conductivity values measured at 60 0 C and acid numbers for the renewable acid oils and fats in accordance with aspect of the invention
  • Figure 3 shows apparatus for the treatment of acid oils and fats according to a preferred embodiment of the invention
  • Figure 4 shows the nozzle deposits of a compression ignition engine fuel injector after 1.5 hours running on an acid oil prepared according to the present invention
  • Figure 5 shows the nozzle deposits of a compression ignition engine fuel injector pump after 1.5 hours running on simply cleaned acid oil
  • Figure 6 shows a compression ignition engine fuel pump after 1.5 hours running on an acid oil prepared according to the present invention
  • Figure 7 shows a compression ignition engine fuel pump after 1.5 hours running on simply cleaned acid oil
  • Figure 8 shows a fuel injection needle of a compression ignition engine after 1.5 hours running on an acid oil prepared according to the present invention.
  • Figure 9 shows a fuel injection needle of a compression ignition engine after 1.5 hours running on simply cleaned acid oil.
  • the shaded rectangular region of Figure 1 indicates the accepted range of acid numbers and iodine numbers of fuels that may be used in compression ignition engines. As can be seen, this region includes a number of fuel specifications currently in use in different countries, including those adopted by MAN and
  • Wartsila Those fuels lying in the shaded region but having acid numbers greater than 0.5 generally require some modifications to be made to the engine before they can be used. These modifications may include, for example, replacement seals and injection equipment materials.
  • Naturally-derived oils and fats typically have acid numbers between about 10 and 500, for example tallow, rapeseed oil distillate and palm fatty acid distillate (PFAD).
  • PFAD palm fatty acid distillate
  • these oils are unsuitable for use in standard engines, even with modifications, due to their high acidity. Therefore, currently these acid oils must be treated to reduce the level of fatty acids to an acceptable amount.
  • the apparatus and method of aspects of the present invention renders these acid oils and fats suitable for direct feeding to a compression ignition engine, without reducing their acid numbers.
  • decreasing the conductivity of crude acid oil drastically reduces its corrosive properties and the resultant acid oil can then be combusted in an engine with little or no modification. This could be achieved by removing highly-conducting impurities and impurities with a high dielectric constant, for example by centrifuging the acid oil and then (optionally) passing it through an evaporator.
  • Figure 2 shows this dependence. If values of EC (pS/m) of the acid oil measured at 60 0 C lie on the curve or fall below it (in the hatched region) then the acid oil could be used in the engine without any danger of inflicting corrosive damage onto the injection equipment or cylinders. Thus, the hatched area of Figure 2 defines the safe operating region.
  • the hatched area is defined by Equation 1 :
  • FIG. 3 shows a schematic of an embodiment of apparatus for the treatment of acid oils according to an embodiment of the present invention.
  • the acid oil to be treated is stored in a tank 1.
  • the acid oil then flows or is pumped into a centrifuge 2.
  • centhfugation process is primarily used to remove conductive impurities and impurities with high dielectric constant like glycerine ( ⁇ ⁇ 47) from the acid oil.
  • Glycerine is an undesirable component of fuel as it causes injector deposits and may adversely affect cold weather operation of compression ignition engines.
  • any free glycerine is quickly separated from the remaining acid oil.
  • the heavy glycerine residue can then be removed.
  • the centrifuge 2 is typically heated to a temperature between 35 and 100 0 C. This reduces the viscosity of the acid oil making the separation of the glycerine more efficient.
  • the raised temperature may also cause the loss of some water from the acid oil by evaporation.
  • the oil has to be passed through a centrifuge a number of times.
  • the acid oil passes once through the centrifuge 2 to remove the majority of the glycerine and the resultant acid oil supernatant is then (optionally) transferred into an evaporator 3.
  • the electrical conductivity of the resultant stream is measured using the conductivity meter 5 that could be an in-line device or any electrical conductivity meter suitable for measuring the conductivity of low- conductive fluids.
  • valve 6 is closed, valve 7 is opened and the acid oil is recirculated for the reprocessing.
  • the evaporator 3 is used to remove any remaining conductive impurities or impurities with the high dielectric constant (for example, water ( ⁇ ⁇ 80) and free glycerine), from the acid oil.
  • the high dielectric constant for example, water ( ⁇ ⁇ 80) and free glycerine
  • the evaporator 3 has a heat exchange surface held at an elevated temperature onto which the acid oil flows.
  • the heat exchange surface typically includes the hot walls of the evaporator.
  • the temperature of the evaporator 3 is typically in the range 45 to 200 0 C, and is more preferably between 70 and 130°C. These temperatures accelerate evaporation of water from the acid oil.
  • the evaporator 3 comprises a vacuum pump for generating reduced pressure in the evaporating chamber 3. This facilitates the removal of the higher boiling point glycerine without requiring higher temperatures.
  • the reduced pressure is generally in the range 0.5 to 250 millibar (50-2500 Pa). Preferably the reduced pressure is less than 5 millibar (500 Pa).
  • the evaporator 3 is a thin-film evaporator.
  • the evaporator 3 is a wiped-film evaporator in which the thin film of acid oil is created by wiper blades that move over the surface of the heated walls of the evaporator 3.
  • the wipers pump the liquid through the chamber of the evaporator 3 and are particularly advantageous when processing more viscous oils.
  • the contaminant vapours that are formed then pass to a condenser (not shown).
  • the vapours condense on the cold surfaces within the condenser and the resultant liquid is removed.
  • the condenser may be external to the evaporator 3 or more preferably the condenser is an internal condenser.
  • the evaporator 3 may be a short-path evaporator. This has the advantage that higher vacuums may be achieved in the evaporator 3, further lowering the boiling point of contaminants.
  • the oil may be passed through the evaporator 3 a number of times.
  • the acid oil is cycled through the evaporator 3 until no more distillate is collected.
  • the residence time of the acid oil in the evaporator 3 is very short, and may only be a few seconds, the additional time taken to make multiple passes does not add significantly to the overall time taken to dry the acid oil and remove conductive contaminants like glycerine or water.
  • the treated oil is deemed substantially free of conductive contaminants.
  • the acid oil leaves the evaporator 3 it is substantially free of both water and glycerine.
  • the removal of these substances significantly decreases the conductivity of the acid oil and in general the conductivity of the dried acid oil is less than half that of the crude oil.
  • the electrical conductivity of crude palm fatty acid oil distillate was measured to be 4700 pS/m at 60 0 C, and this dropped to 1560-1630 pS/m following the drying process.
  • the conductivity of crude tallow was measured to be 15400 pS/m at 60 0 C, while the conductivity of dried tallow was only 5800-6700 pS/m.
  • the treated fuel has a conductivity less than half the value for the crude acid oil, preferably less than 45%, notably less than 35%.
  • the apparatus described above provides a means for producing a renewable fuel from acid oils and fats previously deemed unsuitable for combustion in a compression ignition engine 4 due to their high acid and iodine numbers. This is achieved by a reduction in the electrical conductivity of the oil by the removal of unwanted water and glycerine, which would otherwise be detrimental to the operation of the engine 4.
  • the method described above therefore, does not decrease the acid number of the oil but only decreases its electrical conductivity by removing high-conductive contaminants and contaminants with the high dielectric constant. Further, the additional removal of glycerine not only prevents the build-up of deposits in the engine, but also further decreases the conductivity of the acid oil, as pure glycerine has a relatively high conductivity of between 4000 and 5000 ⁇ S/cm.
  • Palm fatty acid oil distillate (PFAD) with acid number 298 and iodine number 57 was centrifuged using an SA-1 Westfalia centrifuge to remove particulate debris and free glycerine. The supernatant oil was then passed several times through a rotary evaporator at 90 0 C and 2 millibar (200 Pa) residual pressure until no evolution of distillate was observed. The treated acid oil was then combusted in a Lister-Petter four cylinder direct injection compression ignition engine at constant power and speed (typical power generation conditions).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Pathology (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Biochemistry (AREA)
  • Food Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Microbiology (AREA)
  • Wood Science & Technology (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)

Abstract

L'invention porte sur un procédé pour déterminer l'aptitude d'une huile ou d'une graisse acide à être un combustible renouvelable pour la combustion dans un moteur à allumage par compression, le procédé comportant : (a) la mesure de la valeur de conductivité électrique (EC) à 60°C et de la valeur d'un indice d'acidité (AN) d'un échantillon de l'huile ou de la graisse acide ; (b) la détermination du fait que les valeurs se trouvent dans la région hachurée sur la figure 2, et (c) si les valeurs se trouvent dans la région hachurée, la détermination du fait que l'huile ou la graisse acide est appropriée pour la combustion dans un moteur à allumage par compression.
PCT/EP2010/058356 2009-06-16 2010-06-15 Combustible renouvelable Ceased WO2010146041A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0910293.0 2009-06-16
GB0910293A GB2472185B (en) 2009-06-16 2009-06-16 Renewable fuel

Publications (2)

Publication Number Publication Date
WO2010146041A2 true WO2010146041A2 (fr) 2010-12-23
WO2010146041A3 WO2010146041A3 (fr) 2011-03-03

Family

ID=40940844

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/058356 Ceased WO2010146041A2 (fr) 2009-06-16 2010-06-15 Combustible renouvelable

Country Status (2)

Country Link
GB (1) GB2472185B (fr)
WO (1) WO2010146041A2 (fr)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0502891B1 (pt) * 2005-07-06 2015-11-24 Fundação Regional Integrada processo de produção de biodiesel sem catalisador em meio contínuo
EP1956070A4 (fr) * 2005-11-30 2013-06-19 Nippon Oil Corp Composition de gasoil
US7635328B2 (en) * 2005-12-09 2009-12-22 Pacific Centrifuge, Llc Biofuel centrifuge
US20080040970A1 (en) * 2006-03-30 2008-02-21 Thomas Anthony Davanzo Systems for producing biodiesel and processes for using the same
JP2009007554A (ja) * 2007-05-29 2009-01-15 Goto Kunio バイオティーゼル燃料の製造装置およびその製造方法
US20090001997A1 (en) * 2007-06-29 2009-01-01 Yingjie Lin Systems and methods for determining a total acid number associated with biodiesel in a mixture of biodiesel and petrodiesel
FR2919303B1 (fr) * 2007-07-24 2012-11-30 Jean Pierre Esterez Procede de preparation d'esters d'acides gras a partir de flocon de graines oleagineuses.

Also Published As

Publication number Publication date
WO2010146041A3 (fr) 2011-03-03
GB2472185B (en) 2011-08-17
GB2472185A (en) 2011-02-02
GB0910293D0 (en) 2009-07-29

Similar Documents

Publication Publication Date Title
Sanford et al. Feedstock and biodiesel characteristics report
Dwivedi et al. Potential and limitation of straight vegetable oils as engine fuel–An Indian perspective
Fattah et al. Effect of antioxidants on oxidation stability of biodiesel derived from vegetable and animal based feedstocks
Engler et al. Effects of processing and chemical characteristics of plant oils on performance of an indirect-injection diesel engine
Hussan et al. Tailoring key fuel properties of diesel–biodiesel–ethanol blends for diesel engine
Soriano Jr et al. Evaluation of biodiesel derived from Camelina sativa oil
Thangarasu et al. Physicochemical fuel properties and tribological behavior of aegle marmelos correa biodiesel
Siva et al. Production of biodiesel by transesterification of algae oil with an assistance of nano-CaO catalyst derived from egg shell
Dwivedi et al. Investigation of cold flow properties of waste cooking biodiesel
BR112012029618A2 (pt) óleo com base em plantas extraído e queimado
Abubakar et al. Production of biodiesel from baobab seed oil
Firemichael et al. Production and characterization of biodiesel and glycerine pellet from macroalgae strain: Cladophora glomerata.
WO2010146041A2 (fr) Combustible renouvelable
CN101511975A (zh) 包含植物油的替代性有机燃料制剂
US20180187110A1 (en) Lubricity additive for fuel with a low sulphur content
CN102224222A (zh) 生物燃料组合物、其制备方法和燃料供给方法
Sarin et al. Bio‐diesel lubricity: correlation study with residual acidity
Raj et al. Standards for Biodiesel
Setyawardhani et al. Tertiary butylhydroquinone influence over oxidation stability of biodiesel from waste cooking oil
Dumitru Degumming Role of Sunflower Oil (Helianthus annuus) on Biodiesel Quality
Fuad et al. Production of Biodiesel Distillate with Low Monoglycerides for B40 Component by Using Distillation Technique with 1 and 30 Plates Column
CN109563424A (zh) 用于具有低硫含量的燃料的润滑性添加剂的制造方法
Islam et al. Exploring the Potential of Trigonella foenum-graecum Seed Oil as a Feedstock for Biodiesel: Production and Properties
Tsuchiya et al. Improved Jatropha oil separation by entrainer-aided supercritical CO2 extraction
Bello et al. Methanol and glyceride contents of Egunsi melon oil, its biodiesel and blends with diesel fuel

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10730399

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10730399

Country of ref document: EP

Kind code of ref document: A2