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    34/34 ABSTRACT A liquid fuel composition includes alcohols of four carbon atoms and additives,the liquid fuel composition being for ignition by compression. Variousexamples pertain to a liquid fuel composition With alcohols of four carbonatoms and additives, With ignition by compression to a diesel cycle fuel engineWhere the fuel can be able to be produced by means of biotechnology fromreneWable biologic source, including processes of fermentation of sugars ormaterials available on sugar and ethanol plants. As an example, a produced fuelcan be used conventionally as replacement of diesel in urban transportation vehicles or roads and can be an altemative to diesel fuel. The composition can be employed alone or mixed to fossil diesel oil (e. g., in the engine, etc.).
    公开号:SE1350297A1
    申请号:SE1350297
    申请日:2011-08-11
    公开日:2013-06-12
    发明作者:Jose Antonio Fabre
    申请人:Marco Antonio Falquete；
    IPC主号:
    专利说明:

    1/34 "LIQUID FUEL COMPOSITION WITHALCOHOLS OF FOUR CARBON ATOMS AND ADITIVES, WITHIGNITION BY COMPRESSION" This patent of invention is related to liquidenergy source ignited by compression aiming at providing a diesel cycle fuelthat can be produced from renewable biologic sources by means ofbiotechnology, including processes of fermentation of sugars or materialsavailable on sugar and ethanol plants. Thus, the produced fuel will be usedconventionally as replacement for diesel in urban transportation vehicles orroads and will be an altemative to diesel used on sugar and ethanol plants,which reduces the emission of fossil carbon in the sugar and alcohol production,with advantages of fossil sources replacement, reduction of emission of carboncompounds, proper consumption, compatible cost, life cycle maintenance ofsystem compounds, greater safety and reduced evaporation loss.
    Intemal combustion engines with compressionignition (diesel cycle engine) are known from the pioneering work of RudolphDiesel, which demonstrated the possibility and adequacy of thermal machinesin which the fuel ignition occurs by heating of air-fuel mixture, caused only bythe compression of the mixture in the combustion chamber, without the need ofusing a spark generated by an electric system, as in spark ignition engine (Ottocycle engine).
    Diesel cycle engines are in general 30% moreefficient at converting thermal energy to mechanical energy than Otto cycleengines with the same power. For this reason, trucks, buses, civil constructionmachines, agricultural machinery, power generators, irrigation motor pumps, vehicles etc. are powered by diesel engines. Modem diesel engines, used mainly 2/34 in cars, have low emission of harmful gases. When compared to Otto engines ofequivalent power, they have a reduced emission of carbon dioxide, just becauseof the greater efficiency of energy conversion. However, the great majority ofdiesel engines use diesel fuel (of fossil origin) that contributes to greenhouseeffect and have emission of harmful products and pollutants, mainly particulatematter, nitrogen oxides and sulfur derivatives.
    Nowadays there is a clear trend towards thedevelopment of fuels from biological sources (biofuels) that have a productioncycle in which at least half of carbon issued during the biofuel buming isrecovered by the biological growing process, in general by capturingatmospheric carbon in the photosynthesis process. Production cycles, however,add carbon in many steps of the biofuels manufacturing process, particularly bythe fueling of agricultural machines, trucks and irrigation motor pumps.Production cycle of ethanol from sugarcane, for instance, is one of mostefficient in capturing carbon, but uses diesel fuel intensively. One of theobjectives on this invention is to provide a fuel for diesel cycle that can beproduced by biotechnological methods, including processes of fermentation ofsugars or materials available in sugar and ethanol plants. Thus, the fuel can bean altemative to diesel fuel employed at sugar and ethanol plants, reducing thefossil carbon emission in the production cycle of sugar and alcohol.
    Among the biofuels, the most widely used isethanol, in spark ignition engines (Otto cycle), as a compound mixed togasoline, or rather as relatively pure fuel. Ethanol has a high octane rating, thatis, proper antiknock characteristic to spark ignition. Thus, it is possible toconfer proper octane rating to gasoline, replacing tetraethyl lead, a toxic compound. When used in mixture with gasoline, ethanol is anhydrous, once the 3/34 presence of water prevents a stable mixture with gasoline. When used withoutany other mixture in Otto cycle engines, ethanol is hydrated. Ethanol is used inmany countries mixed with gasoline, reaching in Europe and United States ratesup to 85% in Volume of ethanol in ethanol/gasoline blends (E85). In Brazil,pure hydrated alcohol is widely used.
    However, ethanol has some disadvantages.
    - Ethanol contains low calorific powercomparing to gasoline. On average, the energy content of hydrated ethanol isonly 70% of energetic content of gasoline with 22% ethanol (blend supplied toBrazilian market).
    - Hydrated Ethanol has a higher corrosion ratewhen compared to gasoline.
    Technologies allowing the use of ethanol oralcohol in compression ignition engines (diesel cycle) include blends andemulsions of ethanol and/or other alcohol in diesel fuel or oil fractions. Oftensuch mixtures or emulsions use butanol or isobutanol as a co-solvent, anauxiliary with a polar character interrnediate between ethanol and hydrocarbons,so as to increase the stability of mixture.
    Mixtures tested and taken to market presentstability problems, as ethanol and diesel are poorly miscible. Many of thempresented a phase separation some time after mixture, such separation beingaggravated by environmental conditions such as low temperatures, air humidityetc. Surfaces degradation problems such as cavitation and corrosion occur frequently, due to physical separation between the compounds caused by the friction efforts and dynamic pressure differences found in the pumping system 4/34 and fuel injection. Besides, these mixtures still do not represent a completelyrenewable fuel, because use fossil fuels in large proportion.
    Another current technology is the mixture tohydrous ethanol of additives capable of increasing the ethanol explosivity, inorder to allow its ignition by compression. 2-EHN and organic peroxides areconventionally used to increase diesel fuel explosivity, however they are notused as additive to ethanol, because its added content vs. increase in the cetanenumber curve tends to asymptote after 8% in volume of additive content, butdoes not reach the cetane number of 42 required for a proper ignition of dieselfuel or hydrated ethanol.
    All nitrates present stability problems (acidicor alkaline hydrolysis), especially in presence of water. Hydrated ethanol, byits water content, shows a tendency to hydrolyze, generating free acid whichincreases with storage period, leading to increased nozzles corrosion. Even innitrate-free media, durability is reduced by the presence of steam in the injectornozzle and exhaust valves. For this reason, the maintenance of systems forhydrated ethanol has a reduced time when compared to diesel systems. Themaintenance manual for Scania”s ethanol-fueled buses for BEST Projectindicates change of injector nozzle every 22,000 km, while the nozzle change indiesel systems occurs every l20,000 km.
    Besides the durability problems related tohydrated ethanol, due to great difference of calorific power of ethanol related todiesel, there is an increase in the consumption measured as L/h of ethanol/ L/h of diesel ratio between 1.5 and 2.0. This greater consumption, combined with 5/34 cost of additives, tends to make economically impracticable ethanol projects,which are very important from an environmental point of view.
    One other technology to ethanol employmenton vehicle engines and equipment conventionally operating in diesel cycleconsists on "ottolization", that is, transformation of engines originally workingin diesel cycle to run on the Otto cycle, by adaptation of a spark plug in acylinder head of diesel engine. Such conversion, besides result in cost and timeto be performed, being difficult to reverse, implies in consumption flowincreases L/h ethanol L/h diesel above 2.0 once Otto cycle has a energyconversion efficiency about 30% lower than the diesel cycle of equivalentpower.
    Researching on Brazilian and intemationalpatents bank, we found the following patents: Chinese patent with publication number CN1016029686 and CN10143487 5 discloses options of hydrocarbons with ethanol.
    Patent CN 101580743 discloses a diesel fuel orgasoline compound of fuel materials mixture, tar and solvents derivate fromindustrial or organic wastes, 10-50% of butanol, isopropanol, d-terc-butyl-p-cresol or their mixtures, 10-25 % diene-ring iron, or kerosene, solvent oil,mineral oil, lubricating oil, vegetable oil or mixtures thereof. This patent doesnot employ substantially butanol as main fuel.Patent CN 101402887 is a compoundsubstantially composed of ethanol (75 to 90%) to act as diesel at low temperatures, containing, among other compounds, 2 to 10% butanol or isobutanol. Basically, butanol acts as co-solvent for several compounds. 6/34 Patent CN 101376848 describes an ethanol-diesel mixture with proportion between 60-85% of diesel. Butanol is used inthe content between 0.5 and 1.5% as co-solvent to aid in the stability ofresulting emulsion.
    The American patent US 2009013591 show afuel mixture including 15-95% of gasoline or diesel, from 5 to 85% of alcohol,among them butanol, characterized by the ethers use of glycerol as additive.
    Chinese patent CN 101235325 reveals a diesel-methanol mixture, being diesel 23-50%, methanol 35-70% where two amongVarious other components are isobutanol 0-3% and butanol 0-3%.
    Chinese patent CN 101215483 presents adiesel-methanol mixture comprising between other compounds, 0.25 - 0.6% ofterc-butanol.
    Patent CN 1800313 reveals a gasolineemulsion with alcohols and dimethyl ether that may have 2-3% of 2-butanol.
    Patent CN 1730619 presents a fuel emulsionthat contains methanol, oil, diesel, terc-butanol, fatty acid ester of sorbicalcohol, polyoxyethylene and monomethyl polyethylene.
    Patent CN 1796513 describes an additive todiesel comprising ethanol, ketones, silicones, n-butanol and benzyl alcohols.
    Patent CN 1769398 presents a fuel with 65-80% methanol, which may contain, among others, 5-10% butanol.
    Patent CN 1590515 describes a fuel formed bythe diesel mixture, benzene, gasoline, butanol and ammonium salt of fatty acid.
    Patent EP 0403516 presents a polyalkyleneglycols additive to hydrated ethanol in the ration between 12-20%, however the 7/34 examples show proper results in polyalkylene glycols contents exceeding 17%for conventional engines with typical compression ratio of l8:l.
    Patent US 5628805 describes ethoxylatedpolyol to be added to hydrated ethanol in the ration between 5 and 10 % v/v.Currently, this technology is being used in Stockholm (Sweden), and it is beingtested in several cities of the World, applied in Scania engines, by means of theproject BEST (BioEthanol for Sustainable Transportation). But to be used in theration of 5%, it is required an engine specially projected for fuel, with acompression rate higher than that used in conventional diesel engines. While theconventional diesel engines compression rate is about 17:1, the Scania dieselengines compression rate dedicated to ethanol is about 24:l. This limits its useto dedicated engines, and prevents that the “flexfluel” technology is used, thatis, neither fuel thus formulated could be used in a large base of existingconventional engines, or ethanol-dedicated engines could be used with properdiesel to conventional compression rates (oil, biodiesel, vegetable oil etc.).
    Patent US 2378466 presents organic nitratesuse such as ethyl nitrate, ethylene glycol dinitrate (EGDN), triethylene glycoldinitrate (TEGDN), tetraethylene glycol dinitrate (TetraEGDN), as additivescapable of increasing the diesel ignition.of ethanol altematives Recently, options emerged from renewable sources. Among the options, 4-carbons alcohols,mainly n-butanol and isobutanol can be produced by renewable biotechnologyprocess, with advantages such as a slightly lower calorif1c value than gasoline,higher solubility in hydrocarbons, lower corrosiveness, higher boiling and flashpoints, which makes handling and storage of the fuel safer and reduce evaporation losses. The conventional process for butanol production by 8/34 microbiological fermentation is the process ABE (Acetone-Butanol-Ethanol),Which uses sugars fermentation by the bacterium Clostrídium acetobutylicum.Introduced in the early XX century by the industrial chemist, Zionist movementleader and first president of the State of Israel Chaim Weizmann, the processhas its focus on the acetone production being used in large scale to obtainmentof Cordite eXplosive (double based powder). Subsequently, the process Wassupplanted in terms of economic feasibility by the petrochemical process andfill into disuse.
    A development line currently employed is thegenetic modification of Clostridium genus that increases the ABE processproductivity and selectivity to expand the butanol production. Suchdevelopment line includes as n-butanol production processes, patents US5.753.474, US 2010143996, US 2010136641, CA 2699378,WO 2010024715,WO 2010024714, GB 2462642, WO 2010017230, US 2010036174, RU2375451, CN 101595218, WO 2009149270, KR 2010019127, US 2010086982,WO 2009142541, GB 2459756, CN 101423815, CN 101250496, and JP60172289.
    The Canadian patent CA 2548221 reveals anew bacterium, Clostrídium carboxidivorans, Which can synthesize biofuelsfrom CO, including ethanol and catalyze the acetate and butanol production. Italso can directly ferments lignocellulose to produce ethanol or other substances.
    Patents US 2009275787 and WO 2010031793use modified Clostridium bacteria to produce n-butanol from glycerin. Thisprocess is of particular interest, because great volume of glycerin are obtained in the fatty acids transesterification (biodiesel production), and there is not 9/34 demand to the planned Volume of glycerin that must enter in the Brazilianmarket due to increased biodiesel content on diesel.
    Patent US 2010093020 uses bacteriumEnterococcus genus genetically modified for optimized production of butanol.
    Patent WO 2009122192 uses in the butanolproduction, genetic bacteria modification of Bacillaceae family, preferablyGeobacíllus or Ureíbacillus.
    Patent WO 2009082690 uses genetic codemodification of many bacteria for butanol production.
    Patents US 2010143985, US 2010129885, US2010062505, WO 2009140159, WO 2009013159 present, for butanolproduction, a genetically modified yeast. The advantage of yeast is to use themnormally for ethanol production, making easier the process adjustment forexisting sugar and alcohol plants.
    Canadian Patent CA 2691998 employs thebacterium or yeast genetically modified for butanol production.Patent WO 2009105733 provides aphotosynthetic process using plants, algae and blue-green algae that mayproduce butanol directly from CO2 and Water. Thus, there is the direct carbonsequestration from atmosphere, With better energy use of the process, andcompetition reduction between the biofuels production process and foodproduction.
    Patent KR 20090025221 shows a process usingalgae to generate biomass, thus transforming it into alcohols or ketones, including butanol. 10/34 Patent WO 200900346 provides a processconverting C02 into gases, and which subsequently uses the fermentation ofsuch gases to obtain products, including butanol.
    Patents WO 2009103533, CA 2684860, WO2009086423, and WO 2010037111 provide modifications on yeasts forisobutanol production.
    Patent WO 2009149240 provides a productionprocess for isobutanol from the biomass fermentation by bacteria speciesEscherichia coli.
    The following patents provide non-specifiedmodified cells for butanol and ethanol production: WO 2009013160, US2009176288, WO 2009082148, WO 2008124523, WO 2009059254, and WO2008143704.
    Patent WO 2009078973 presents geneticmodifications on microorganisms for production of many value products, including butanol, from free fatty acids.
    Patent CN 101358187 foresees gammaradiation to modify cells or protoplasts to increase the butanol yield.Many processes apply conventional microorganisms of fermentation processes without genetic modification;however optimize the industrial process yield for obtaining butanol, or butanolfrom the fermentation broth, which increases yield, because the same lowbutanol contents make the fermentation media toxic for microorganismsproducing alcohol.
    Patents that disclose process changes: NL10355651, KR 100556322, WO 2010011769, CN 201367402, US 2008274524, 11/34 WO 2010000649, US 2010105115, WO 2009106835, WO 2009112335, WO2009100434, CN 101475932, US 2009162912, WO 2009087680, WO2009079362, CN 101418320, CN 101397236, CN 101429527, WO 2009062601 , US 2009017514, CN 101363031, WO 2009021503, CN101333545, WO 2009008616, WO 2008154301, CN 101302545, CN101250561, WO 2008124490, CN 101333545, CN101457238, DE 102006060610 and WO 2009079213.
    Patent CN 101165188 presents the butanolproduction from ground manioc or manioc starch.
    Patent US 2010087687 presents a process forVegetable biomass, animal or municipal Wastes exploitation, Which includesbutanol among the products.
    Patent MX 2009006782 presents a process toproduce biofuel, Which includes biobutanol from enzymes.
    Patent WO 2009128644 presents a metabolicnetwork model for metabolic characteristics analysis of microorganismsproducing butanol, and methods to select or change microorganisms to obtainhigh efficiency metabolic products.
    Patents US 2010058654, JP 2009220105, WO2009097312, KR 20090009330, JP 2008088140, and RU 2191769 presentcatalysts for processes that can convert ethanol produced from reneWablesources in butanol.
    Although it is desirable that the butanolbecome an economically feasible fuel produced from reneWable and biological sources (so called biobutanol), there are other patented solutions for 12/34 petrochemical processes to obtain butanol: patent US 2010048960 provides aprocess for producing butanol from butane.
    Patent US 2009239275 presents a process toproduces 2-butanol by petrochemical means.
    Patent WO 2005108593 provides an enzymaticcatalyst for production of 2-butanol from 2-butanone.
    Patent KR 20080106516 reveals a process forbutanol production from butene.
    Patent MX 2009008416 presents a productionprocess of many alcohols, including n-butanol and isobutanol.
    The following patents disclose fuels that usebutanol as part of its composition: Patent US 2010005709 shows an ethanolmixture, isopropanol and sec- or terc-butanol, no more than 3% methanol andno more than 15% C5 or larger. The obtainment process is a petrochemicalprocess Fischer-Tropsch type (obtaining alkanes from carbon monoxide andhydrogen), and the mixture is used as fuel to Otto cycle engines fuel (gasoline).
    Patent US 2009277079 shows a mixture to beused with isomers butanol gasoline with good cold ignition.
    Patent WO 2009120042 presents a process tochemically produce butyl butyrate from butyric acid and butanol fromfermentation. Ester can be used as biodiesel.
    Patent WO 2009114752 shows a process to usexenobiotic materials that are carbon sources, to produce biomass and/or biogas from microorganisms degrade carbon sources, and then using microorganisms to synthesize biofuels. One of biofuels cited is butanol. 13/34 Patent WO 2009106647 shows an engine withcompression ignition comprising two injection systems, where one systeminjects diesel or biodiesel, and the other injects a fuel more Volatile than diesel,such as hydrogen, LPG (Liquefied Petroleum Gas), natural gas, ethanol,propanol or butanol. Such biofuels hybrid system have been recently showed tothe market by many companies, always with a using ration between two fuelsnext to 50%/50% with some disadvantages: requirement of two fuel tanks,separated transportation / supply logistic for two fuels, from a injectionsophisticated control system Variable as required power load, and the purchaseby the user of injection system modification kit.
    Patent US 2009151232 discloses a dieselcomposition having between 9 and 20% of butanol, 0.4% to 4% of nitrate orbutyl nitrite, and the remaining base for light diesel, or uses a substantialamount (between 90.6 and 76%) of diesel derived from oil.
    Patent CN 101402888 offers an additivecompound and a diesel fuel of methanol containing, among other, 1 to 10% n-butanol. N-butanol acts as co-solvent, but the fuel is substantially composed ofmethanol, which has a low calorific power and is extremely toxic.
    Patent KR 20090003146 shows a mixture toreplace gasoline (Otto cycle engines), composed mainly of ethanol or methanol,containing among other, 5 to 8 % of butanol.
    Patent CN 101240199 shows a mixture ofalcohol-ether (65-70%), where the alcohol is a mixture of methanol, butanoland acetone, and ether is a mixture of any two ethers including dimethyl ether, isopropyl ether or methyl terc-butyl ether (MTBE). 14/34 Patent US 2010005709 shows a process toproduce alternative fuels, including obtaining Synthesis gas from renewablesources, convert this gas into olefins with chain substantially between C2 andC4, and hydrolyze these olefins. The resulting mixture of alcohols has butanol,and should be mixed into gasoline.
    Patent MX 2007010015 shows an alcoholsmixture from Cl to C5 or Cl to C8, with more ethanol than methanol, withoctane rating higher than ethanol, which could replace gasoline.
    Patent CN 101085938 reveals a syntheticbiological fuel with 10-50% of fuel derived from oil, such as naphtha, dimethylether and gasoline, 4.5-10% of one or more list that includes ether, acetone orbutanol.
    Patent CN 1884440 deals with the productionof fatty acid ester (biodiesel) terc-butyl using terc-butanol as thetransesterification reagent.
    Patent JP 2004285346 comprises an altemativefuel to gasoline, ethanol compound, and at least two compounds from the groupconsisting of diisopropyl ether, methyl terc-butyl ether, ethyl terc-butyl ether,dipropyl ether, tert-butanol, dibutyl ether and diethyl ether.
    Patent KR 20040044677 reveals an altemativefuel composed of 50-80% of mixed liquid extract of coal extracted frombituminous coal, 10-20% of ethanol or methanol from coal liquefaction, 5-15%of n-butanol extracted from coal liquefaction, and 5-10% and 5-10% tolueneextracted from the liquefaction of coal.
    Patent KR 20020009543 presents alcohol- based fuels to replace gasoline compound, among others, 5-15% butanol. 15/34 Patent KR 20030006529 comprises a fuel tointernal combustion engines, Otto cycle, compound, among others, 3-7 %butanol.
    Patent RU 2148075 presents based fuelcompositions, containing 0.0065-0-0.0075% of "oligoetilhidreto" siloxane and0.0025-0.0035% by Weight ofbutanol.
    Patent WO 9324593 discloses a diesel fuel,containing between 10 and 35% of ethanol in diesel mixture, also containingbutanol and alkyl peroxide.
    Patent KR 930011071 is an emulsion fuel of1000 parts of oil (gasoline ), 15-70 parts of siloxane or "oxosilano", 100-300parts of butanol, 3-7 parts of methanol, 10-20 parts of polyethylene glycol and1-3 parts of non-ionic surfactant.
    Patent JP 2022388 provides a fuel in alcoholemulsion form (methanol, ethanol, or butanol), benzene, toluene or xylene, andan aromatic rich fraction from the catalytic cracking fluid of oil refinery.
    European patent EP 0171440 shows a fuel forengine basically based in a hydrocarbons compound, Which additionallycontains alcohols and optionally ethers, ketones, aromatics, additives and leadcompounds that may contain 0-10% butanol.Patent CA 1221539 describes a stablecomposition of gasoline and ethanol, containing an additional alcohol, that maybe, among others, n-butanol and isobutanol.
    Patent US 4526586 comprises microemulsions from Vegetable oil, a Cl-C3 alcohol, Water and l-butanol as non-ionic surfactant. 16/34 Patent GB 2090612 shows a mixture for use ofdiesel comprising between 10 and 60% in gas oil, 10-60% of a Cl-CS alkylester, C12-22 fatty acid and 10-50% of a mixture which contains at least n-butanol and acetone.
    Patent US 4398920 deals with a fuel a mixturecontaining: (a) gasoline, gas oil, or fuel oil, (b) a mixture of butanol andacetone, optionally containing isopropanol and/or ethanol; and (c) methanol,where the mixture butanol/acetone (b) is prepared by proper organismsfermentation such as bacteria or fungi.
    Patent US 4368056 discloses a fuel formed bymixing butanol obtained from fermentation and glycerides obtained from afermentation process where the substrates are industrial wastes such as cheeseyeast, com cobs, wood chips etc.
    Paten US 4300912 describes a synthetic fuelconsisting of macromolecules of long chain formed by connection by methanoldistillation, butanol and kerosene oil with colloidal stabilizer.
    On all of these patents disclosing fuels whichemploy butanol as part of its composition, is revealed the use of isomericalcohols of butanol as fuel for Otto cycle engines, i.e., suitable for sparkignition, or mixtures motor fuel cycle diesel that will eventually have theirbutanol or alcohol isomers, but never with alcohols and butanol isomers as mainfuels.
    Butanol, isobutanol or other isomer alcohol of4 carbons by itself, do not have similar characteristic to diesel, that are required to work properly in diesel cycle engines, as showed below: 17/34 Butanol and its isomers have high octanerating, that is, resistance to detonation by compression, this feature is desirablein fuels for Otto cycle engines, however this is opposite to desirablecharacteristics of fuels for diesel engine cycle. In contrast, diesel fuels shouldhave a high cetane number, that is, greater explosiveness when initiated bycompression. Specifications of diesel used in Brazil require a number of cetanesequal or higher than 42, in accordance with standards ASTM D 613(measurement in single-cylinder engine CFR type) or ASTM D 6890(measurement of ignition delay in combustion chamber of constant volume IQTtype). Low cetanes number result in engine cold start difficulty, or even in thenon-ignition of fuel under compression, with total engine stop and accumulationof unbumed liquid fuel inside the engine cylinder.
    Butanol and isomers, despite of showingsimilar viscosity to diesel, do not have comparable lubricity to diesel, mainlythose types of diesel with high sulfur content. The low lubricity wear theinjection system, specially injection pumps rotors "common rail" type, wherepressures and friction efforts are very large, exhaust valves lock, causingpremature wear and rings fluttering, that is, a number of deleterious effects oncomponents of injection systems and on the engines. In accordance withBrazilian standards, diesel should present a maximum wear of 460 um in alubricity test FRR (High Frequency Reciprocating Rig), according to standardASTM D 6079.
    Alcohols, although butanol and isomers showsa less corrosive aggression compared to hydrated ethanol, presenting largermaterials corrosion when compared to diesel, generating wear problems to materials of injection system. 18/34 Butanol alcohols isomers undergo on oxidationby oxygen in the air during its storage, generating butryc acid, Which have anextremely unpleasant odor that can be solved by adding an antioxidant additive.
    "LIQUID FUEL COMPOSITION WITHALCOHOLS OF FOUR ATOMS OF CARBON AND ADITIVES WITHIGNITION BY COMPRESSION ", object of this patent, Was developed tosupply an alternative of energy supply to engines ignited by compression fromreneWable biological source With advantages of replacing fossil fuels, reductionin the emission of carbon compounds, proper consumption, compatible cost,maintaining the life cycle of system compounds, greater safety and reducedevaporation losses. The fuel of this patent may replace diesel, is based onsubstantial proportion of 4 carbons alcohol, such as n-butanol, isobutanol, sec-butanol and terc-butanol and is an altemative from reneWable sources, producedin sugar and alcohol plants, and may remove the fossil fuel using a greatamount in the production cycle of sugar and ethanol, in irrigation moto pumps,tractors, sugarcane transportation trucks, sugarcane harvesters and supporttrucks. Other interesting application Will be With urban buses fuel, because theenvironmental laws in many Brazilian states and municipalities includeambitious targets for reducing the use of fossil fuels.
    In the search of optimized formulation of fuelon this patent, Were conducted exhaustive searches and possible mixtures ofpractical tests carried out using the formulated fuels Which are presented intables I and II, With a description of the tests that prove the suitability of the fuel as described below: 19/34 Test I: Number of cetane number (DCN) inequipment IQT (Ignition Quality Tester) of AET (Advanced EngineTechnology), according to standard ASTM D6890; Test II: The cold start engine and pointadjustment: the test consisted on establishing if the engine starts after amaximum of 10 tums of crankshaft. If the start occurs, the result is noted"OK", otherwise is noted "does not occur".
    Test III: Diameter of wear scar in steel ball forevaluating lubricity in equipment HFRR (High Frequency Reciprocating Rig),according to standard ASTM D 6079; Text IV: Corrosion test of the injector nozzle:the injector nozzle is the item of greatest susceptibility to corrosion andpremature wear in injection systems of diesel engines. This test consists ofdipping an injector nozzle of multiple holes Bosch model DLLA 134 P 422,produced in steel DIN 18CrNi8, on the fuel under test, kept in over at 75°Cduring two weeks.
    Test V: The free acidity mixture after 2 weeksat 75 °C: the free acidity of fuel mixture was measured by the method ASTM D974 “Standard Test Method for Acid and Base Number by Color-IndicatorTitration”, immediately before and after the injector nozzle exposure to fuel for2 weeks at 75°C, as Test IV above.
    Test VI: electric 500CV, Test in and 8121, engine dynamometer Positron/Eatron, model maximum powermaximum rotation 5000 rpm: the test consisted on obtainment of power curve xrotation in Mercedes-Benz engine model OM 352A, turbocharged with turbine Lacombe to 5 points. 20/34 Test VII: Average consumption test: during thedynamometer test, the average consumption is measured to each rotation, onceadjusted the dynamometer curve to the fuel in test have the same power thandiesel in the same rotation. The consumption Was measured by the fuel massconsumed in a time period of 5 minutes, by the difference of fuel mass in aplastic drum on a scale.
    Test VIII: durability test of injector plasticdrum: the testes consisted on pumping the testing fuel by means of a rotatingVE type Bosch injector pump, model 0-460-424-369 in closed circuit, using thepump nominal flow, by a total of 1,000 h, at room temperature. After test ofl,000h, the pump is disassembled, its compound being assessed for Wear.
    Tests Were conducted compared to diesel, and the hydrated ethanol to select the content rates optimized in efficiency to tested additives.Table I: Results of ignition efficiency tests:Test Cold start test andComposition 5 v/v DCN, IQT _ _number po1nt adJustment_ _ Start OK, nominall Metropolitan d1esel 44 _ _po1nt of d1eselI gnition failure by2 n-butanol - the equipment.
    The start did notn-butanol 98 % 3 Triethylene GlycolDinitrate (TEGDN) 2 % happen easily,31.72 point With advancement of 2l/34 l2° related to diesel point. n-butanol 97.6 % Start Ok, point With advancement 4TEGDN 2,4 % 34.81 of l4° related todiesel point.Start Ok, point5 n-butanol 97 % With advancementTEGDN 3,0 % 36.4 of l4° related todiesel point.The start did notha en easil ,n-butanol 98 % pp ypoint With6 Tetraethylene Glycol32 advancement ofDinitrate (TetraEGDN) 2%l2° related todiesel point.Start Ok, point7 n-butanol 97.5 % 36 With advancementTetraEGDN 2.5 % of l4° related todiesel point.8 n-butanol 94 %isopropyl nitrate (IPN) 6 % l6 -n-butanol 95.1 %9 iso ro lnitrate IPN 4.9p Py ( ) 1 762 _%10 n-butanol 94.4 % 22/34 nitrate of 2-ethyl hexanol (2-EHN) 5.434 % 22 - lubricant Ultrazol 9525 0.135 % n-butanol 90.72 % 11 2-EHN 9.1495 % lubricant Ultrazol 9525 29.31 - 0.135 % n-butanol 88.85 % Start Ok, point 12 2-EHN 11.01 % With advancement lubricant Ultrazol 9525 34 of 16 ° related to0.13 % diesel point.n-butanol 94 % ethoxylated glycerin With Start Ok, pointan average of 10 ethylene13 With advancernentoxide units per unit35 of 16 ° related toglycerol (10 Glycereth EO)diesel point. 6% n-butanol 97 % nitrate of ethoxylated glycerin With an average of Start Ok, point 14 10 molar units of ethylene 34 With advancement oXide per glycerin molarunit (nitrate of glycereth 10EO ) 3%.
    DCN (IQT) cold start of 16° related to diesel point. 23/34 engine n-butanol 85 % 15 methyl ester of palm oil(palm methylic biodiesel, 21BMP) 15 %Start Ok, point16 n-butanol 75% 32 With advancementBMP 25% of 16 ° related todiesel point.Start Ok, point17 Isobutanol 97.6 % V/V 32 With advancementTEGDN 2.4 % V/V of 16 ° related todiesel point.97.393 % isobutanolStart Ok, point2.482 % TEGDN18 With advancernent0.125 % lubricant Ultrazol 32.61of 14° related to9525 A of Lubrizoldiesel point.Start Ok, point19 isobutanol 97.6 % V/V 35 With advancementTetraEGDN 2.4 % of l4° related todiesel point.Start Ok, pointisobutanol 89 % V/V With advancement20 35 2-EHN ll % of 14° related to diesel point. 24/34 Table II: Lubricity corrosion, dynamometric curve and durability tests results.
    Composition Diameter Injector Power Free Average Pump(V/V) nozzle CUTVC X t0tal Consump dllfablllt_ rotation acidity _ y 1,000hum corrosive t1onbeforeness and after L/ hexposureat 75°CmgKOH/gMetropolitan 400 No RPM RPM - non Weardiesel change CV L/h noticed1200 1000 -52 131500 1300 -95 171800 1500-132 19,52000 - 1800 -40 23Hydrated 844 Generali - 0.016 - -ethanol zed beforecorrosio0.156n, rustpresence fiftefin allnozzle. 25/34 n-butanol 822 Light 0.012 -corrosio beforen indicated 007afterby somerustpoints.2.505 % 644 Without - 0.013 -TEGDN, Cormsio before0.106 % :ignals 0.081lubricant but the afterUltrazol mixtufe9525A f Was° ShghflyLubrizol and yellowis97,389 % n- hbutanol2.502 % 473 No RPM 0.011 RPM non WearTEGDN, Corrosio CV before L/h noticed0.106 % n. 1200 0.06 1000_ s1gna1s,1ubr1cant Clear 50 after 15Kerokorr LA mixture 1 199C of 500 300BASF 0.102 96 19-4% 2111111- 1800 1500corrosive 134 23KeropurMFlex 3651 2000 - 1800 _of BASF, 36 26 97.29 % and 26/34 n-butanol 2.494 %TEGDN,0.094 %frictionmodiflerKerocorn3561 ofBASF, 0.041 % anticorrosiveKerokorr3232 ofBASF,97.371 % n-butanol 501 2.51 %TEGDN,0.102 %lubricantKerokorr LA99C ofBASF, 0.061 % anticorrosive Kerokorr 467 27/34 3232 of BASF 97.327 % isobu-tanol 2.506 % 398 No beforeTEGDN °°ff°Si° 0.0120.212 % :ignalsj afterlubricant Clear 0.010Kerokorr LA mixtufe 99C of BASF 0.1 121 % anti- corrosive Keropur MFlex 3651 of BASF and 97 . 1 699 % n-butanol Surprisingly, based butanol mixtures and isobutanol with derivate cetanenumber about 35, therefore below specification suitable for diesel oil of 42showed good cold start and good performance of the power curve x torque.Also surprisingly, additive contents were relatively low, allowing thealtematives to be economical. The average consumption, in general, in the range of 15% higher than the diesel consumption, which was also surprising, 28/34 once the ration between the lower calorific values of butanol and diesel is about 1.32 (38.6 MJ/L / 29.2 MJ/L). Lack of anti corrosive Water significant contents as well as metal surface of injector nozzle, can explain the low corrosion and great stability of the free acidity of mixture after periods of exposure to high temperature. Based on this researches and tests conducted there was an optimized formulation of this patent which consists of: -so to 99% of fuel formed by one more 4 carbons alcohol, such as n-butanol, isobutanol, sec-butanol and terc-butanol. - one or more additives capable of increasing the explosiveness of butanol, such as: 0.5 % to 5 % of Triethylene GlycolDinitrate (TEGDN) or 0.5 % to 5 % of Tetraethylene GlycolDinitrate (TetraEGDN) or 2 % to l5 % of nitrate of 2-ethyl hexanol(2-EHN) or 2 % to l5 % of tetrahydrofurfuryl nitrate(THFN); or 0.5 % to l5 % of polyethylene glycoldinitrate (PEGDN); or 2 % to l5 % of isoamyl nitrate (IAN), or2 % to l5 % of isopropyl nitrate (IPN), or2 % to 15 % of organic peroxides, or 2 % to 15 % of ethoxylated glycerin; or2% to 15% of ethoxylated glycerinnitrate; or 29/34 0 10 % to 60 % of esters of fatty acids. - 0.005% to 1.0% of one or morecommercially available additives to increase lubricity or friction modifiers, suchas carboxylic acids Kerokorr 99C and amine mixture and oleic acid Kerocom3561, both of BASF AG; mixture to ethoxylated amine Ultrazol 9525 A andmixture based on carboxylic acid ester Ultrazol 9555, both of LubrizolCorporation; mixtures based on carboxylic acid ester Tolad 9185 or Tolad9165; mixtures based on carboxylic acids Tolad 9101 or Tolad 9113 andmixtures based on amide Tolad 9137 or 9141R Tolad, all of Baker Hughes Inc.;polyethylene glycol; polypropylene glycol; or other compounds having thesame function commercially available. - 0.0005 to 1.0 % of a stabilizer additive(controller hydrolysis of nitrates) such as: ethanolamines, diphenylamine,diphenylureas (such as ethyl centralite), morpholine, or other compoundscharacter poorly alkaline. - 0.0005 to 1.0 % one or more anti-corrosiveadditives that act by forming film adsorbed on metal surfaces are commerciallyavailable, such as polyether-based mixture Keropur MFLEX 3651, mixturebased on acid amide KeroKorr carboxylic 3232, both of BASF AG; Tolad 3224or Tolad 3222, both of Baker Hughes; or other compounds commerciallyavailable.
    Other additives With known or allegedcharacteristics to modify the properties of butanol and its isomers alcohols asindicated in this patent may be used in the ranges indicated on it not limiting the inventive field of this patent. 30/34 It Will be readily recognized as an additionaladvantage, by a technician in the area of fuels, as fuel object of this patentpresents solubility in diesel fuel of conventional fossil fuels, fuel blends objectof this patent to diesel fuel can be made With effective results Without prejudice the current teachings of this patent.
    权利要求:
    Claims (7)
    [1] 1. "LIQUID FUEL COMPOSITION WITH ALCOHOLS OF FOUR CARBONATOMS AND ADITIVES, WITH IGNITION BY COMPRESSION ", Withoptimized formulation, characterized by, the following composition: - 50 to 99% of fuel formed by one or more 4carbons alcohol, such as n-butanol, isobutanol, sec-butanol and terc-butanol; - 0.5 % to 5 % of one or more additivescapable of increasing the explosiveness of butanol, composed by TriethyleneGlycol Dinitrate (TEGDN) or Tetraethylene Glycol Dinitrate (TetraEGDN) orthe mixture of both; - 0.005% to 1.0% of one or more additives toincrease lubricity or friction modif1ers, such as: carboxylic acids and aminemixture and oleic acid; mixture to ethoxylated amine and mixture based oncarboxylic acid ester; mixtures based on amide; polyethylene glycol,polypropylene glycol; - 0.0005 to 1.0 % of a stabilizer additive suchas: ethanolamines, diphenylamine, diphenylureas or morpholine; and - 0.0005 to 1.0 % one or more anti-corrosiveadditives such as: polyether-based mixture and mixture based on acid amide carboxylic. 32/34
    [2] 2. "LIQUID FUEL COMPOSITION WITHALCOHOLS OF FOUR CARBON ATOMS AND ADITIVES, WITHIGNITION BY COMPRESSION ", according to the claim 1, characterized by,alternatively additives capable of increasing the explosiveness of butanol arenitrate of 2-ethy1 hexanol (2-EHN) or tetrahydrofurfuryl nitrate (THFN) ofisoamyl nitrate (IAN) or isopropyl nitrate (IPN) or mixture of them and utilizedWith 2 % to 15 % in the formulation.
    [3] 3. "LIQUID FUEL COMPOSITION WITHALCOHOLS OF FOUR CARBON ATOMS AND ADITIVES, WITHIGNITION BY COMPRESSION ", according to the claim 1, characterized by,a1ternatiVe1y the organic nitrate be polyethylene g1yco1 dinitrate (PEGDN) With0.5 % to 15 % in the formulation.
    [4] 4. "LIQUID FUEL COMPOSITION WITHALCOHOLS OF FOUR CARBON ATOMS AND ADITIVES, WITHIGNITION BY COMPRESSION ", according to the claim 1, characterized by,alternatively the additives capable of increasing the explosiveness of butanol areorganic peroxides or ethoxylated g1ycerin or the mixture of both and utilizedWith 2 % to 15 % in the formulation.
    [5] 5. "LIQUID FUEL COMPOSITION WITHALCOHOLS OF FOUR CARBON ATOMS AND ADITIVES, WITHIGNITION BY COMPRESSION ", according to the claim 1, characterized by, 33/34 alternatively the additives capable of increasing the explosiveness of butanol areethoxylated glycerin nitrate and utilized With 2 % to 15 % in the formulation.
    [6] 6. "LIQUID FUEL COMPOSITION WITHALCOHOLS OF FOUR CARBON ATOMS AND ADITIVES, WITHIGNITION BY COMPRESSION ", according to the claim 1, characterized by, alternatively the additives capable of increasing the explosiveness of butanol areesters of fatty acids and utilized With 10 % to 60 % in the formulation.
    [7] 7. "LIQUID FUEL COMPOSITION WITHALCOHOLS OF FOUR CARBON ATOMS AND ADITIVES, WITHIGNITION BY COMPRESSION ", according to the claims 1 to 6,characterized by, the liquid combustible composition utilized pure or mixed With fossil diesel oil.
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    同族专利:
    公开号 | 公开日
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2016-06-14| NAV| Patent application has lapsed|
    优先权:
    申请号 | 申请日 | 专利标题
    BR1004630|2010-11-12|
    PCT/BR2011/000284|WO2012061909A1|2010-11-12|2011-08-11|A fuel composition based on four-carbon-atom alcohols and additives for diesel-cycle motors|
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