EP1838822A2 - Compositions pouvant etre utilisees comme biocarburant - Google Patents

Compositions pouvant etre utilisees comme biocarburant

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Publication number
EP1838822A2
EP1838822A2 EP06700480A EP06700480A EP1838822A2 EP 1838822 A2 EP1838822 A2 EP 1838822A2 EP 06700480 A EP06700480 A EP 06700480A EP 06700480 A EP06700480 A EP 06700480A EP 1838822 A2 EP1838822 A2 EP 1838822A2
Authority
EP
European Patent Office
Prior art keywords
oil
composition
weight
alcoholysis
carbon atoms
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.)
Withdrawn
Application number
EP06700480A
Other languages
German (de)
English (en)
Inventor
Ulrich SCHÖRKEN
Carolin Meyer
Matthias Hof
Nigel Cooban
Diana Stuhlmann
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.)
Cognis IP Management GmbH
Original Assignee
Cognis IP Management GmbH
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Filing date
Publication date
Application filed by Cognis IP Management GmbH filed Critical Cognis IP Management GmbH
Publication of EP1838822A2 publication Critical patent/EP1838822A2/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/62—Carboxylic acid esters
    • 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
    • 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
    • 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/1817—Compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/6445—Glycerides
    • C12P7/6458—Glycerides by transesterification, e.g. interesterification, ester interchange, alcoholysis or acidolysis
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/649—Biodiesel, i.e. fatty acid alkyl esters
    • 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
    • C10G2300/1003—Waste materials
    • 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
    • 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1826—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms poly-hydroxy
    • 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • 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
    • 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

  • compositions usable as biofuel are Compositions usable as biofuel
  • the invention is in the field of glycerides. It relates to compositions containing fatty acid esters and partial glycerides and their preparation, for example by enzymatic catalysis and their use as biofuel.
  • hydrocarbon-based fuels eg gas oils, fuel oils, gasoline, diesel, kerosene, etc.
  • additives for corrosion protection and lubricity and flow improvers or compounds are known, which improve the emission levels of gases such as CO, CO 2 or NO x .
  • bio-fuel is defined in Article 2.2 as follows: bio-ethanol, rapeseed oil methyl ester (RSME), biogas, biomethanol, biodimethyl ether, biohydrogen, synthetic biofuels and pure vegetable oils.
  • RSME rapeseed oil methyl ester
  • rapeseed oil methyl ester (RSME) is used as biodiesel. It is already possible that engines with pure biofuel are operated according to the EU directive. However, the addition of up to 2% RSME to normal diesel is likely to be required to comply with the EU directive.
  • This RSME consists in the conversion of the natural triglyceride into a methyl ester or ethyl ester.
  • the byproduct of this preparation route is crude glycerin.
  • biodiesel as rapeseed methyl ester arise 100 kg of free glycerol.
  • free glycerol With the increasing amount of biodiesel, the availability of glycerol increases. Since glycerine has a limited market size, which is already covered by previous productions, a disposal problem arises. This circumstance may limit the usual production route for biodiesel, as glycerol can no longer be counted as additional income, which will make this route economically unattractive.
  • the manufacturing process should be as environmentally friendly and economical as possible.
  • hydrolases especially lipases (EC 3.1.1.3) are already used in industrial processes for lipid cleavage or transesterification.
  • lipases EC 3.1.1.3
  • the classical chemical method of monoglyceride production proceeds via a base-catalyzed glycerolysis of triglycerides, typically giving a yield of 40-60% monoglyceride relative to the total glycerides. Further enrichment up to> 90% monoglyceride content takes place via physical separation methods such as molecular distillation or crystallization.
  • WO9013656 and WO9004033 describe the preparation of monoglycerides via enzymatic alcoholysis with various alcohols and a little water in the batch. Lipases are used in powder form or immobilized. In the examples, lipases become about 20 % By weight based on the triglyceride used and the alcohol component in 20-fold excess.
  • WO9116441, WO9116442 and US5116745 describe processes in which, in the presence of a solvent, an alcohol and an aqueous buffer, mixed regioselective alcoholysis and hydrolysis to 1,2-diglycerides and 2-monoglycerides is carried out using lipases.
  • EP407959 describes a process for the preparation of monoesters by a thermostable immobilized lipase in the presence of secondary or tertiary alcohols as solubilizers.
  • WO0206505 (Nippon Suisan Kaisha Ltd) describes regioselective lipase-immobilized alcoholysis with high alcohol excess and high enzyme use concentration, followed by reesterification of the monoglyceride.
  • JP03108489 and JP03187385 (Meito Sangyo Co. Ltd.) describe the regioselective hydrolysis of triglycerides with alkaline lipase with the addition of alkaline salts. It is a lipase that is active only under alkaline conditions.
  • JP03103499 (Meito Sangyo Co. Ltd.) describes the regioselective alcoholysis of PUFA triglycerides with isobutanol in the presence of an alkaline lipase.
  • the object of the present invention has consisted firstly of providing biofuel which complies with the guidelines of the European Parliament and in which the glycerol is present as a derivative and thus as little free glycerol as a by-product is formed in the production process.
  • the manufacturing process should be as environmentally friendly and economical as possible.
  • this resulted in finding a cost-effective enzymatic or chemical variant in order to increase the yield of monoglycerides and diglycerides from polyol esters, for example triglycerides.
  • the content of enzyme in enzymatic alcoholysis should be kept as low as possible. Description of the invention
  • the invention relates to a composition
  • a composition comprising alkyl esters having an alkyl radical containing 1 to 8 carbon atoms and partial glycerides, which has a glycerol content of free glycerol of not more than 2 wt .-% based on the total amount of the composition.
  • compositions which contain the stated components in the mixture and contain at most 2% by weight of free glycerol achieve the object of the invention in an outstanding manner.
  • a maximum glycerol content of not more than 1.3% by weight and more preferably of not more than 1.0% by weight is preferred, the evaluation being carried out using area percent in the GC analysis and the values for glycerol having to be calibrated on account of the strong absorption ,
  • the composition contains as alkyl esters methyl and / or ethyl esters.
  • the composition has a partial glyceride content of at least 10% by weight, and / or a triglyceride content of not more than 5% by weight and / or an acid number of not more than 5 based on the total amount of the composition. Preference is given to a monoglyceride content of at least 25% by weight.
  • the composition contains methyl and / or ethyl esters, monoglycerides and diglyceride in proportions of:
  • Methyl and / or ethyl esters 30-70% by weight, preferably 55-60% by weight
  • compositions in which the alkyl esters, and partial glycerides fatty acid esters of saturated or unsaturated, linear or branched fatty acids having an alkyl group having 8 to 22 carbon atoms are particularly preferred.
  • fatty acid esters which can be obtained from vegetable oils such as, for example, linoleate, oleate, palmitate, stearate and / or perlaronate.
  • vegetable oils such as, for example, linoleate, oleate, palmitate, stearate and / or perlaronate.
  • unsatisfied representatives are laurolein, myristolein, palmitoleic, petroseladin, oil, elaidin, ricinole, linoleic, linolaidin, linolenic gadolein, arachidone and erucic acid esters.
  • Mixtures of the methyl esters and / or ethyl esters of these acids are also suitable.
  • Preferred oils for obtaining the fatty acid esters are sunflower oil, rapeseed oil, thistle oil, soybean oil, linseed oil, peanut oil, tallow, olive oil, castor oil, palm oil, palm oil fractions such as palm olein or palm stearin, yatropha oil, coconut oil or palm kernel oil.
  • Peanut oil contains on average (based on fatty acid) 54% by weight of oleic acid, 24% by weight of linoleic acid, 1% by weight of linolenic acid, 1% by weight of arachidic acid, 10% by weight of palmitic acid and 4% by weight of stearic acid.
  • the melting point is 2 to 3 ° C.
  • Linseed oil typically contains 5% by weight of palmitic, 4% by weight of stearic, 22% by weight of oil, 17% by weight of linoleic acid and 52% by weight of linolenic acid.
  • the iodine number is in the range of 155 to 205, the saponification number is 188 to 196 and the melting point is about - 20 ° C.
  • Palm oil contains predominantly oleic acid. Palm oil contains as fatty acid components about 2 wt .-% myristic, 42 wt .-% palmitane, 5 wt .-% stearic, 41 wt .-% oil, 10 wt .-% linoleic acid.
  • Rapeseed oil typically contains about 48% by weight of erucic acid, 15% by weight of oleic acid, 14% by weight of linoleic acid, 8% by weight of linolenic acid, 5% by weight of icosenoic acid, 3% by weight of palmitic acid, 2% by weight of fatty acid components % Hexadecenoic acid and 1% by weight docosadienoic acid. Rapeseed oil from new breeding is enriched in terms of unsaturated components.
  • Typical fatty acid moieties here are erucic acid 0.5% by weight, oleic acid 63% by weight, linoleic acid 20% by weight, linolenic acid 9% by weight, icosenoic acid 1% by weight, palmitic acid 4% by weight, Hexadecenoic acid 2% by weight and docosadienoic 1% by weight.
  • Castor oil consists of 80 to 85 wt .-% of the glyceride of ricinoleic acid, besides about 7 wt .-% glycerides of the oil, to 3 wt .-% glycerides of linoleic and about 2 wt .-% of the glycerides containing palmitic and stearic acid.
  • Soybean oil contains 55 to 65 wt .-% of total fatty acids polyunsaturated acids, especially linoleic and linolenic acid.
  • sunflower oil whose typical fatty acid spectrum, based on total fatty acid looks like this: about 1 wt .-% myristic, 3 to 10 wt .-% palmitic, 14 to 65 wt .-% of oil and 20 bis 75% by weight of linoleic acid.
  • the fatty acid composition in the mixture results from the particular native fatty acid composition of the vegetable oil used and the particular quality of the raw material from which the methyl and / or ethyl esters and the monoglycerides are prepared.
  • Another object of the invention is a process for the production of biofuel in which triglycerides are enzymatically reacted in the presence of alcohols having a number of carbon atoms of 1 to 8 carbon atoms with an esterase which is activated by the addition of alkaline salts.
  • a triglyceride is cleaved in the presence of an alcohol into a 2-monoglyceride and two fatty acid esters.
  • more than 90% of the glycerin remains chemically bound in the product, and the low levels of glycerol released remain in the product in a single-phase solution.
  • this process does not produce any glycerol as a by-product, and accordingly the amount of raw material oil required can be significantly reduced.
  • the composition according to the invention can be prepared in an outstanding manner.
  • the reaction can be carried out very inexpensively by the use of small amounts of esterase, preferably lipase.
  • the reaction is carried out directly with the enzyme concentrate with the addition of an alkaline inorganic salt, which causes a strong activation of the enzyme. As a result, good conversion is achieved with low enzyme dosage even without stabilization of the enzyme by immobilization. An addition of solvents is not necessary.
  • the alcoholysis is carried out at temperatures of 10 ° to 40 ° C, preferably at 10 ° to 30 ° C and to maintain optimum regioselectivity and activity particularly preferably at a temperature of 15 ° to 25 ° C.
  • the reaction is carried out at a water content of 0.1-10% by weight, preferably 0.1-5% by weight and more preferably 0.1-2% by weight, based on the amount of triglyceride, the Water content of the liquid enzyme preparation is included.
  • the reaction also works with higher water contents, but then the content of free fatty acid formed is increased. High levels of free fatty acid are not desirable because they can be corrosive effect on engine parts in the form of use biodiesel at high temperatures.
  • the reaction time is preferably 12-48 h, depending on the enzyme concentration used.
  • all reactants are mixed and the reaction started by addition of the enzyme preparation.
  • the addition of the alcohol component having 1 to 8 carbon atoms, preferably methanol and / or ethanol, preferably ethanol, is carried out either completely at the beginning or metered over the reaction period.
  • the amount of alcohol used is variable, minimum 2 moles of alcohol to 1 mole of oil, maximum 50% by weight of alcohol and 50% by weight of oil in the batch.
  • the esterase can be deactivated by the heat and then the precipitated esterase optionally filtered off, wherein in addition to the precipitated esterase, the removal of additives or formulation constituents of the enzyme preparation used can be achieved.
  • the following optional steps can be connected to the inventive method.
  • a use concentration of 0.05-2% of the commercially available liquid preparation is used in relation to the amount of triglyceride used.
  • These commercially available enzyme liquid preparations have an average enzyme activity of 100,000 U / ml.
  • One enzyme unit U is defined as the amount of enzyme which converts one micromole of substrate per minute.
  • alkaline inorganic salts selected from the group which is formed for activating the esterase of hydroxides, carbonates and phosphates of sodium, potassium, calcium, magnesium and ammonium, pre-dissolved in water.
  • the amount of alkaline inorganic salts for activating the esterases according to the invention is between 0.00001 and 1 wt .-%, preferably between 0.0001 and 0.2 wt .-% based on the amount of triglyceride.
  • the amount of basic additive used depends on the amount of enzyme liquid preparation used which is buffered and on the strength of the base.
  • the strongest activation of Thermomyces lanugenosus lipase was achieved when added to the commercially available enzyme liquid preparation salts such as: trisodium phosphate, sodium carbonate, sodium hydroxide or ammonium hydroxide in amounts of 0.0001 - 0.2 wt .-% (based on the triglyceride content) were.
  • a faster monoglyceride synthesis rate was achieved than with Thermomyces lipase adsorbed on polypropylene.
  • the activation of the lipase is so strong that it can not be explained by the pH shift in the reaction medium alone.
  • Thermomyces lanugenosus lipase is used immobilized under the same conditions, no similar strong salt-activated activation can be seen.
  • This strong activation is very surprising since it is generally accepted that high activity can be achieved in the low-water medium only with lipases which are bound to a carrier. Due to this strong activation complex immobilization processes can be dispensed with and it leads to a simple plant concept.
  • a measurement of the pH of the reacted product mixture also shows that the pH is in the neutral to weakly acidic, which makes enzyme activation alone via pH shift unlikely.
  • Another object of the invention is a process for the preparation of monoglycerides, in which triglycerides are enzymatically reacted in the presence of alcohols having a number of carbon atoms of 1 to 8 carbon atoms with an esterase which immobilized and / or chemically modified is used.
  • the composition according to the invention can also be prepared in an outstanding manner with this enzymatic process.
  • the glycerin also remains chemically bound to over 90% in the product and the low levels of glycerol released remain dissolved in the product in a single phase.
  • this method does not produce any glycerine as a by-product and, accordingly, the amount of required raw material oil can be reduced decrease significantly.
  • the reaction can be carried out very cost-effectively by the repeated use of the immobilized and / or chemically modified esterase, preferably lipase. An addition of solvents is not necessary.
  • the alcoholysis is carried out at temperatures of from 10 ° to 60 ° C, preferably at 10 ° to 4O 0 C and to maintain optimal regioselectivity and activity particularly preferably at a temperature of 15 ° to 30 ° C.
  • the reaction is carried out at a water content of 0-10% by weight, preferably 0-5% by weight and more preferably 0-2% by weight, based on the amount of triglyceride.
  • the reaction works well at higher water contents, but then the content of formed free fatty acid is increased. High levels of free fatty acid are not desirable because they can be corrosive effect on engine parts in the form of use biodiesel at high temperatures.
  • the reaction time is preferably 1-48 h depending on the enzyme concentration used.
  • all reactants are mixed and the reaction started by addition of the enzyme preparation.
  • the addition of the alcohol component is carried out either completely at the beginning or dosed over the reaction period.
  • the amount of alcohol used is variable, minimum 2 moles of alcohol to 1 mole of oil, maximum 50% by weight of alcohol and 50% by weight of oil in the batch.
  • the esterase can be filtered off.
  • the following optional steps can be connected to the method according to the invention. > Adding water-absorbing agents during the enzymatic reaction to
  • carrier materials are suitable, which are suitable for the binding of enzymes.
  • plastics mineral carriers or resins which bind the esterases via hydrophobic interactions, e.g. Amberlite 16 (Rohm & Haas), Celite or Accurel MP 1000 (Membrana).
  • ion exchangers which bind the esterases via ionic and in some cases also hydrophobic interactions, such as, for example, Dowex Marathon WBA (Dow Chemicals) or Duolite A 568 (Rohm & Haas).
  • carriers capable of binding esterases via chemically reactive groups e.g. Eupergite (Degussa).
  • esterases are suitable for the adaptation of the esterases to the reaction system.
  • hydrophobic modifications such as, for example, coating with surfactants or chemical modification with fatty aldehydes can be used.
  • stabilization of the esterases via cross-linking for example by glutaraldehyde, DMA or EDC.
  • esterases Another suitable combination of chemical modification and immobilization is the adaptation of the esterases to the reaction system.
  • either the esterases can first be immobilized and then modified carrier-bound or already chemically modified esterases are immobilized.
  • the esterases to be used in the enzymatic methods of the invention are preferably those derived from an organism selected from the group consisting of Thermomyces lanugenosus, Candida antarctica A, Candida antarctica B, Rhizomucor miehei, Candida cylindracea, Rhizopus javanicus, Pancreatic pancreas, Aspergillus niger, Candida rugosa, Mucor javanicus, Pseudomonas fluorescens, Rhizopus oryzae, Pseudomonas sp., Chromobacterium viscosum, Fusarium oxysporum and Penicilium camenberti.
  • esterases from Thermomyces lanugenosus with the synonym: Humicola lanuginosa.
  • Esterases are enzymes that catalyze the formation and hydrolysis of esters; as hydrolases, they split their respective substrates by incorporating the elements of the water.
  • the esterases include, for example, the lipolytic lipases which are preferred esterases according to the invention.
  • Particularly preferred for the process according to the invention is the use of 1,3-regiospecific lipases, which are characterized in that they preferentially split off the fatty acids at the 1- and 3-position of triglycerides.
  • any 1,3-regioselective lipase or esterase can be used in free or immobilized form for the process according to the invention.
  • the lipase of Thermomyces lanugenosus manufactured by manufactureurer Novozymes, name Lipozyme TL 100 1 or Lipolase 100 EX
  • Another object of the invention is a process for the preparation of monoglycerides in which triglycerides are chemically reacted in the presence of alcohols having a number of carbon atoms of 1 to 8 carbon atoms.
  • the alcohols are used in a molar concentration lower than the molar concentration of glyceride-bound fatty acid.
  • the composition according to the invention can be produced by this process. With this method, at least a large part of the glycerol contained in the triglyceride remains in bound form in the product, so that less glycerol is formed than in the classical production of biodiesel.
  • alkaline catalysts are used in "a low-pressure transesterification or come strongly acidic catalysts in a low-pressure transesterification is used. Also part of the method are Hochdrucku- mesterungen in the presence of a chemical catalyst.
  • the salts of alcohols having a number of carbon atoms of 1 to 8 carbon atoms are preferably used with monovalent cations, particularly preferably the sodium and potassium salts of methanol and ethanol.
  • carbonates and oxides such as sodium carbonate or calcium oxide are preferably used.
  • the catalysts are used in a concentration of 0.01% by weight to 5% by weight, preferably in a concentration of 0.1% by weight to 1% by weight.
  • the alkaline catalysts can be prepared in situ from anhydrous NaOH or KOH and the corresponding alcohol.
  • the transesterification is carried out at a temperature of 40-120 ° C at a pressure of at most 2 bar.
  • the reaction is preferably carried out at a pressure of not more than 1, 2 bar.
  • the catalyst is neutralized by adding acid such as citric acid, phosphoric acid, hydrochloric acid or sulfuric acid and separated by separation.
  • the reaction time is preferably 0.1 to 10 hours, depending on the catalyst concentration used and the reaction temperature.
  • Preferred catalysts for the acidic low-pressure transesterification in homogeneous catalysis are mineral acids, in particular sulfuric acid, or aliphatic and aromatic sulfates. used.
  • the catalysts are used in a concentration of 0.01% by weight - 5% by weight.
  • the transesterification is carried out at a temperature of 40 - 160 ° C at a pressure of 5 bar maximum.
  • the catalyst is neutralized by the addition of an alkali such as, for example, aqueous NaOH or KOH and separated by separation.
  • the reaction time is preferably 0.5 to 25 hours, depending on the catalyst concentration used and the reaction temperature.
  • catalysts for the high-pressure transesterification metal salts or metal soaps are used, preferably salts or soaps of zinc such as zinc acetate or zinc stearate in a concentration of 0.01% by weight to 1% by weight.
  • the transesterification is carried out at a temperature of 120 - 250 0 C at a pressure of a maximum of 20 - 200 bar.
  • the catalyst is separated by filtration.
  • the reaction time is preferably 0.1-5 h, depending on the catalyst concentration used and the reaction temperature.
  • the chemical partial transesterification can be carried out in the process according to the invention as a batch reaction or as a continuous reaction.
  • the alcohol component can either be passed in gaseous countercurrent to the oil or, alternatively, in single phase with the oil under high pressure or low temperature conditions in cocurrent.
  • all reactants are mixed and the reaction started by adding the catalyst.
  • the addition of the alcohol component preferably methanol and / or ethanol, ethanol preferred, takes place either completely at the beginning or dosed over the reaction period.
  • the amount of alcohol used is variable, minimum 10 mol% alcohol, maximum 30 mol% alcohol based on the amount of oil used in the batch.
  • the catalyst can be filtered off or neutralized and washed out after the reaction. The following optional steps can be connected to the method according to the invention.
  • alcohol and / or water is partially or completely removed. Preference is given here to the distillative separation. In the distillation it is also possible to separate off any free glycerol still present which is produced in small amounts as a by-product.
  • Acid-containing fats and oils can be used without problems in the described acid-catalyzed low-pressure process and in the chemically catalyzed high-pressure process.
  • triglycerides of fats and oils are preferably used which have a high content of monounsaturated and / or polyunsaturated fatty acids and are selected from the group formed by sunflower oil, rapeseed oil, disperse oil, soybean oil, linseed oil, peanut oil , Tallow, olive oil, castor oil, palm oil, yatropha oil, coconut oil, palm kernel oil and waste oils such as used deep-frying fat.
  • the fats and oils can be employed in refined quality or in crude quality in the process according to the invention. Acidic fats and oils are easy to use in the described process.
  • alcohols as alcohol components having a number of carbon atoms of 1-8 C atoms. These may have linear or branched carbon chains and preferably represent primary or secondary alcohols and are preferably selected from the group which is formed from methanol, ethanol, 1-propanol, isopropanol; 1-butanol, sec. Butanol, ter. Butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-ethylhexanol.
  • methanol, ethanol or 1-propanol are used. Particularly preferred are methanol and ethanol or mixtures thereof, and particularly preferred is ethanol.
  • the ethanol used is preferably obtainable from biological sources, for example from the fermentation of carbohydrates.
  • the content of alcohol is preferably 10 to 50 wt .-% or 10 to 30 mol% in the chemical method based on the triglyceride, preferably 15 to 40 wt% or, 15 to 25 mol% used in the chemical process.
  • the monoglyceride content depends on the amount of alcohol used.
  • Another object of the invention is a composition obtainable by the inventive method.
  • the composition thus obtained mainly consisting of alcohol, alkyl ester, monoglyceride and diglyceride can be mixed directly to diesel fuel. Due to the e-emulsifying character of the monoglycerides formed, possibly formed fatty acids, free glycerol and small amounts of water in the product are dissolved in a single phase. Traces of water are better bound and no longer disturb the combustion process.
  • the educated Monoglycerides increase the lubricating properties.
  • the components in the composition according to the invention can, in their mixture, cause residual glycerine to be better burned in the combustion process.
  • alcohol can be completely or partially removed from the composition prepared according to the invention, for example by distillation, before admixing it with the diesel.
  • a fuel composition containing 90 to 99.5 wt% gas oil and 0.5 to 10 wt .-%, preferably 2 to 6 wt .-% of a composition according to the invention or a composition according to the invention Method can be produced.
  • gas oil is understood to mean all possible fractions of crude oil in the additive and non-additized state.
  • gas oil is preferably understood as meaning diesel.
  • Additives contained in said gas oil in an additive state and which may be included in addition to the compositions of the invention are additives selected from the group consisting of conductivity improvers, cetane improvers, CFPP / CP improvers, defoamers, lubricity improvers, corrosion inhibitors and dehazers.
  • Diesel fuels are obtained from gas oil by cracking or from tars recovered from the carbonization of lignite or coal. Diesel fuels are flame retardant mixtures of liquid hydrocarbons which are used as fuels for constant pressure or burner engines (diesel engines) and consist predominantly of paraffins with admixtures of olefins, naphthenes and aromatic hydrocarbons. Their composition is inconsistent and depends especially on the manufacturing method. Typical products have a density between 0.83 and 0.88 g / cm3, a boiling point between 170 and 360 ° C and flash points between 70 and 100 0 C.
  • Another object of the invention is the use of the inventive composition comprising alkyl esters having an alkyl radical containing 1 to 8 carbon atoms, and partial glycerides having a glycerol content of free glycerol of not more than 2 wt .-% based on the total amount of the composition or the preferred embodiment of this composition or compositions obtainable by the processes according to the invention as biofuel.
  • a biofuel has been provided in which only small amounts of free glycerol are present as a by-product.
  • an enzymatic conversion of pure vegetable oil and bioalcohol produces a mixture of alkyl ester and partial glycerides, which can be used as biofuel or as additive according to European Directive 2003/30 / EC.
  • a biofuel is produced and made available, which includes the benefits of raw materials from renewable sources.
  • Advantage of the bio-fuel according to the invention is in addition to the production by-products also the introduction of additional oxygen in the combustion path, which reduces exhaust gases.
  • the additional lubricating action of the partial glycerides leads to the need for the use of lubricity improvers is unnecessary.
  • the first production process saves energy because it proceeds purely enzymatically and without much purification of the final product.
  • a further object of the invention is the use of the inventive composition containing alkyl esters having an alkyl radical containing 1 to 8 carbon atoms, and partial glycerides and in particular methyl and / or ethyl esters, monoglycerides and methanol and / or ethanol which has a glycerol content of at most 2% by weight based on the total amount of the composition or the preferred embodiments of this composition or compositions obtainable by the processes according to the invention as an additive in fuel compositions and preferably in amounts of from 0.5 to 10% by weight, in particular from 1 to 5% by weight.
  • Particularly preferred is the use of the composition of the invention as an additive for improving the lubricity of fuel compositions.
  • glyceride mixtures with a high content of monoglyceride show good lubricating properties. It has thus been possible to show that the monoglycerides prepared by the process according to the invention can also be used as fuel additives in diesel fuel and show good lubricating properties.
  • the enzymatic process according to the invention makes it possible to use the regiospecific fatty acid composition of the naturally occurring oils.
  • the monoglyceride fraction mainly contains the fatty acid composition found in the 2-position of the oils.
  • the higher unsaturated fatty acids are preferentially bound in the 2-position. This allows e.g. starting from sunflower or thistle oil monoglycerides with a high content of linoleic acid. These monoglycerides have a lowered solidification point, which is particularly important for the use of monoglycerides as a diesel additive. Based on palm oil, e.g. to obtain a monoglyceride with a high content of oleic acid.
  • fuel compositions are understood as all energy-supplying operating materials whose free combustion energy is converted into mechanical work. These include all types of liquid at room temperature and normal pressure motor and aviation fuels.
  • Motor fuels eg for car or truck engines, usually contain hydrocarbons, for example gasoline or higher-boiling petroleum fractions.
  • the fuel compositions according to the invention are preferably diesel oil.
  • the immobilizates of mixtures 1 - 3 and 15 + 16 were purchased directly from the manufacturer in immobilized form.
  • the immobilizates of batches 4 to 8 were prepared by adsorption on acurel MP1000 (Membrana).
  • 1 Accurel MP 1000 was incubated for 1 h in 10 ml of ethanol. After decanting the ethanol, 10 g of water and 0.5 g each of the lipase preparation were added. The mixture was incubated overnight at room temperature. Subsequently, the immobilizate was separated by filtration and dried for 24 h on paper sheets at room temperature.
  • a weak activity is detected with Novozym 388, which is independent of the addition of basic salt.
  • the mixtures were stirred overnight at 8 ° C, then the enzyme immobilizate was filtered off.
  • the Irnmobilisat was dried overnight between paper towels at room temperature.
  • the immobilizate was weighed out and an immobilizate quantity corresponding to 0.2 g lipolase liquid preparation was used for the alcoholysis.
  • Immobilization of Lipolase on Accurel MP 1000 (Membrana) Alternatively: The immobilization was carried out as described above. After filtration of the immobilizate, 5 ml of a 200 mM Na 3 PO 4 solution were added. The complete mixture was dried at room temperature under vacuum. The aim of this additional step, it was "make mobilisat. The immobilized was weighed and a Immobilisatmenge" an already alkaline import 0.2 g Lipolase liquid preparation corresponds, used for the alcoholysis.
  • the content of glycerides and esters was analyzed by gas chromatography. The evaluation was carried out over area percent, with the excess free alcohols were not included. Samples were taken at the times indicated in the table.
  • the content of glycerides was analyzed by gas chromatography. The evaluation was carried out over area percent. The glycerol content was also analyzed by gas chromatography and is reported in uncalibrated area percent. According to mass balance, the absolute glycerol content is lower, but here the comparison of the relative values is decisive.
  • GC samples were taken for glycerol determination after 16 h and for glyceride determination after 40 h of reaction time. Acid numbers were determined after 16 h.
  • reaction rate was reduced with an increase in the alcohol content.
  • the reaction rate could be improved so that good monoglyceride formation is achieved even with a high molar excess of ethanol (batch 6).
  • Reaction temperature is in the range of 20 - 25 0 C.
  • the total mixture before washing with water still about 12 wt .-% free ethanol.
  • the content of free glycerol in the washed finished product is less than 0.05 wt .-%.
  • the product had a glycerin content after calibration of 1.1% by weight.
  • Example 12 Storage stability of the reaction products of Example 11
  • Example 11 The resulting products of Example 11 were stored at room temperature and in daylight in clear glass bottles for 55 days. Comparative GC studies were performed.
  • Example 13 Glycerol removal from the reaction products of Example 11
  • Example 10 Two samples of biofuel from an enzymatic production were tested as an additive to normal petrol station diesel. To this end, the product of Example 10 was used, which was used without glycerol removal (designation USC-CM-8327-131DS) and after glycerol removal via washing with water (designation USC-CM-8327-131).
  • the mixtures were each 2.5; 3 and 5 wt .-% tested in the gas station diesel for their behavior in the cold. For this purpose, the CFPP values of the samples were determined.
  • Batch 1 50 g of Accurel MP 1000 are incubated for 1 h with 500 g of ethanol. After separating off the ethanol, 500 g of water and 50 g of lipolase are added and the mixture is stirred for 24 h. After separation of the water, the immobilizate is dried. The immobilizate is placed in a 3 liter reactor and 1.6 kg of sunflower oil and 0.4 kg Ethanol and 8 g of water was added. The reaction mixture is incubated for 24 h at room temperature with stirring. After the end of the reaction, the immobilizate is filtered off and the excess water / ethanol mixture is withdrawn from the reactor. The sample is mixed with 16 g of tonsil and 2 g of water and incubated for 30 min at 80 ° C.
  • the ethyl ester / partial glyceride mixture is then subjected to short path distillation. At 175 ° C and a vacuum of 0.3 mbar, the ethyl esters are separated by distillation. The bottom product was used for the lubrication tests.
  • Lubricating properties were measured by HFFR (High Frequency Reciprocating Rig Test) according to CEC Method F-06-T-94.
  • HFFR High Frequency Reciprocating Rig Test
  • Various diesel fuels and monoglyceride mixtures based on sunflower oil and rapeseed oil from Example 15 were used as shown in the table below.
  • a total of 1600 kg of refined rapeseed oil, 640 kg of ethanol, 600 ml of 1 M NaOH, 7 l of water and 250,000 U lipase (esterase from Thermomyces, unit information according to manufacturer) are added to a 4000 l reactor, based on 1 kg rapeseed oil.
  • the mixture is stirred for 40 h, then the mixture is heated with stirring to 80 ° C and stirred for 2 h at 80 ° C, the container remains closed, so that no ethanol can escape. Then it will open Cooled to 50 ° C and filtered through a drum filter with 10 kg Celatom FW 14.
  • the product is bottled and stored at room temperature.
  • a total of 1600 kg of refined rapeseed oil, 640 kg of ethanol, 600 ml of 1 M NaOH, 7 l of water and 250,000 U lipase (esterase from Thermomyces, unit information according to manufacturer) are added to a 4000 l reactor, based on 1 kg rapeseed oil.
  • the mixture is stirred for 40 h, then the mixture is heated with stirring to 120 0 C.
  • Vacuum is placed on the reactor and the ethanol - water mixture is withdrawn from the reactor. The vacuum is slowly lowered until no more ethanol escapes from the batch. It is then cooled to 50 ° C and filtered through a drum filter with 10 kg Celatom FW 14.
  • the product is bottled and stored at room temperature.
  • Example 19 Analysis of the experimental products from Examples 17 and 18
  • the test products are a mixture consisting mainly of ethyl esters and monoglycerides based on the fatty acid composition of rapeseed oil. In lower proportions diglycerides are included, secondary components are fatty acids and triglycerides. The non-distilled approach contains additional ethanol and low water content. The test products are of good color, which corresponds to that of the oils used. The contents of organic and inorganic substances are low. Based on the glycerol analysis, it can be seen that the glycerol of the triglyceride is almost completely bound in the form of the partial glycerides and less than 5% of the glycerol is in free form.
  • Example 17 and Example 18 were stored for 3 months at room temperature in sealed drums.
  • the products are sufficiently stable in storage for use as a diesel additive or as a fuel additive for diesel.
  • the HFFR values of different blends of diesel with FAME were determined in comparison with a 3% blend of the inventive composition from Example 18 and thus the lubricity was investigated.
  • the test is described in ISO 12156. In the test, a metal pin is run over a metal plate and determines the size of the scar. As a result, the better the lubricity, the smaller the scar.
  • the composition according to the invention admixed with the diesel to give a 3% blend contained the following weight percent distribution:
  • Example 22 Suitability of the Composition According to the Invention from Example 18 as an Additive to Fuels According to EU Directive
  • Carbon Residue Micro (on 10% dist res): This test is used to determine the carbon residue in the diesel. For this purpose, a sample is evaporated in a stream of nitrogen and the residue weighed. "Micro" stands for the method. For materials where a residue of less than 0.1% is expected, a 10% distillation residue is prepared in advance and then measured.
  • FBP Final Boiling Point. The percentage refers to the proportion of vaporized diesel at the respective temperatures.

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Abstract

Composition qui contient un ester d'alkyle avec un radical alkyle contenant 1 à 8 atomes de carbone et des glycérides partiels et qui présente une teneur en glycérine libre de 2% en poids au maximum par rapport à la quantité totale de la composition. La présente invention concerne également un premier procédé de production de la composition selon la présente invention selon lequel des triglycérides sont mis en réaction enzymatique avec une estérase en présence d'alcools ayant de 1 à 8 atomes de carbone, ladite estérase étant activée par l'ajout de sels alcalins. Dans un autre procédé, les estérases sont immobilisées et / ou chimiquement modifiées. En outre, un procédé selon lequel la composition selon la présente invention est produite par transestérification partielle chimique est également décrit. La présente invention concerne enfin une composition pouvant être obtenue selon un procédé susmentionné ainsi que l'utilisation des compositions selon la présente invention en tant que biodiesel ou additif dans des compositions de carburant.
EP06700480A 2005-01-19 2006-01-10 Compositions pouvant etre utilisees comme biocarburant Withdrawn EP1838822A2 (fr)

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CA2595007A1 (fr) 2006-07-27
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BRPI0606422A2 (pt) 2009-06-30
CN101479372A (zh) 2009-07-08
US7799544B2 (en) 2010-09-21
JP2008527154A (ja) 2008-07-24
DE102005002700A1 (de) 2006-07-27
JP5094413B2 (ja) 2012-12-12
WO2006077023A3 (fr) 2008-02-28
WO2006077023A2 (fr) 2006-07-27

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