WO2010057660A1 - Adsorbants renfermant de l'oxyde d'aluminium pour la purification de biodiesel - Google Patents

Adsorbants renfermant de l'oxyde d'aluminium pour la purification de biodiesel Download PDF

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Publication number
WO2010057660A1
WO2010057660A1 PCT/EP2009/008292 EP2009008292W WO2010057660A1 WO 2010057660 A1 WO2010057660 A1 WO 2010057660A1 EP 2009008292 W EP2009008292 W EP 2009008292W WO 2010057660 A1 WO2010057660 A1 WO 2010057660A1
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biodiesel
adsorbent
alumina
containing component
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PCT/EP2009/008292
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German (de)
English (en)
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Ulrich Sohling
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Süd-Chemie AG
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Priority to EP09760491A priority Critical patent/EP2361150A1/fr
Publication of WO2010057660A1 publication Critical patent/WO2010057660A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28052—Several layers of identical or different sorbents stacked in a housing, e.g. in a column
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/58—Use in a single column
    • 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
    • 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

  • the invention relates to a process for the purification of biodiesel, biodiesel precursors, vegetable or animal fats and mixtures thereof.
  • Biodiesel because of its origin from renewable raw materials, has a neutral combustion
  • Biodiesel is produced by alcoholysis of triglycerides, one mole of triglyceride reacting with three moles of alcohol to one mole of glycerol and three moles of the corresponding fatty acid ester.
  • the reaction involves three reversible reactions whereby the triglyceride is gradually transformed into a diglyceride, a monoglyceride and finally into glycerol.
  • one mole of alcohol is consumed and one mole of a fatty acid ester is released.
  • Alcoholysis can be carried out under both acidic and basic catalysis.
  • the alcoholysis is usually carried out under alkaline catalysis, since the reaction proceeds under mild conditions at a high conversion rate and therefore relatively fast.
  • the alkaline catalysts used usually have a less corrosive effect on the synthesis reactors, so that, for example, a relatively inexpensive carbon-containing steel can be used for plant construction.
  • the alcoholysis of the triglycerides is carried out under homogeneous alkaline catalysis.
  • the alkoxide ion acting as a catalyst is produced by, for example, dissolving an alkali metal alcoholate in alcohol or reacting the pure alkali metal with the alcohol.
  • Methanolysis can also be a corresponding alkali metal hydroxide dissolved in methanol. Since in the alcoholysis of triglycerides phase separation by the resulting glycerol occurs relatively quickly, the major part of the alkaline catalyst is relatively quickly from the
  • the catalyst is usually used in an amount of 0.5 to 1 wt .-%.
  • the triglycerides used as starting materials can be obtained, for example, from vegetable or animal fat.
  • vegetable raw materials palm oil and soybean oil are mainly used in the worldwide production of biodiesel used. Rape oil and sunflower oil are of local importance.
  • Other starting materials of commercial importance are animal fats, such as beef tallow, as well as used frying fats. For the future, oils from the jatropha nut as well as from algae are discussed as raw materials.
  • biodiesel In order to ensure a uniform combustion of the biodiesel, the content of mono-, di- and triglycerides, as well as of soaps and glycerol, must be reduced as much as possible.
  • biodiesel may contain up to 0.2% by weight of monoglycerides, up to 0.8% by weight of diglycerides and up to 0.02% by weight of triglycerides.
  • the resulting in the production of biodiesel soaps must also be removed from the biodiesel, otherwise ash can form during combustion, which can be deposited and lead to damage to the diesel engine.
  • biodiesel is produced by alcoholysis of the triglycerides with methanol. Since the proton of the hydroxy group of the methanol is relatively acidic, methanol can be relatively easily converted by reaction with NaOH in the corresponding methanolate, which then causes the transesterification of the glyceride.
  • a disadvantage of this process is the high toxicity of the methanol.
  • methanol is produced petrochemically, so that only part of the biodiesel is based on renewable raw materials.
  • methanolysis methods are developed in which the triglycerides are cleaved using ethanol. This process has the advantage that both the fatty acid component and the ethanol can be obtained from renewable raw materials. Biodiesel based on fatty acid ethyl esters is therefore of particular interest for those countries in which large quantities of bioethanol are produced, for example Brazil or the USA.
  • Ethanol has lower acidity compared to methanol.
  • the pKa of ethanol is 15.9 while methanol has a pKa of 15.5.
  • Water has a pKa of 15.7.
  • the saponification of glycerides by water is the preferred reaction.
  • the reaction does not proceed completely, so that in the reaction mixture after the ethanolysis in addition to the fatty acid soaps even larger amounts of mono-, di- and triglycerides are present.
  • the release of glycerol often results in the formation of a very stable microemulsion. This considerably impedes the separation of the glycerol.
  • the glycerin can be separated by centrifugation or the emulsion can be broken by washing the mixture with a strong acid so that the soaps are converted to the corresponding fatty acids.
  • biodiesel Even after such a purification, the biodiesel still contains relatively high levels of mono-, di- and triglycerides. In many cases, the biodiesel produced in this way is still contaminated with up to 2 wt .-% monoglycerides. It does not therefore meet the specification for use as diesel fuel.
  • Biodiesel is made from natural resources. After alcoholysis, biodiesel therefore contains, in addition to soaps, mono-, di- and triglycerides, further impurities which vary in their proportions as well as in their composition within wide limits. These contaminants can also lead to difficulties in the production or use of biodiesel. If biodiesel is cooled down to room temperature after production or even when stored for a prolonged period of time, for example, small amounts of a fine, slightly soluble substance often fall
  • the fine precipitate can then cause, for example, the clogging of filters.
  • the fine precipitate consists of glycosides.
  • biodiesel which is made from vegetable material
  • the precipitate often consists of steryl glycosides.
  • Sterols are cholesterol-derived glycosides that only have a hydroxy group at C 3 , but no other functional groups. Most of them have a double bond in 5/6 position, more rarely in 7/8 or 8/9 position. They are formally alcohols and are therefore often referred to as sterols.
  • Naturally occurring steryl glycosides often include, in addition to the glycosidically linked steryl radical, a fatty acid with which the primary hydroxyl group of the sugar is acylated.
  • Non-acylated steryl glycosides can already be found in very low levels Concentrations cause the precipitation of solid aggregates of biodiesel. Even concentrations in the double-digit ppm range can lead to the formation of turbidity in biodiesel at room temperature. Non-acylated steryl glycosides have a very high melting point of about 24O 0 C. Turbidity or precipitation caused by non-acylated steryl glycosides can therefore not be resolved by heating the biodiesel to a higher temperature. If there are already deposits on a filter, this clogs in the presence of non-acylated
  • the biodiesel is subjected to a final inspection. If it is found that the test for blocking filters is not passed because the finished biodiesel still contains very small amounts of non-acylated steryl glycosides, this biodiesel can not be released.
  • WO 2007/076163 A describes a process for the treatment of biodiesel with adsorbents and the like for the removal of steryl glycosides.
  • Various adsorbents are described, with glucose, diatomaceous earth, clays and in particular magnesium silicate being used as the adsorbent in the examples.
  • WO 2008/055676 A describes a process for purifying a crude biodiesel, wherein the adsorbent used is a clay material having a specific surface area of more than 120 m 2 / g, a cumulative pore volume of 0.35 ml / g and a SiO 2 Content of more than 60 wt .-% is used.
  • the plant for the production of biodiesel comprises a first section in which a crude biodiesel is prepared by reacting the oil used as starting material with methanol in the presence of a catalyst. In a second section, excess methanol is recovered from the crude biodiesel. For this purpose, a portion of the methanol is first distilled off from the crude biodiesel. For shares still present in the biodiesel
  • the pre-purified biodiesel is then mixed with an adsorbent, such as magnesium silicate.
  • an adsorbent such as magnesium silicate.
  • the adsorbent is left in the biodiesel for about 10 to 15 minutes and then the purified biodiesel is separated from the adsorbent by filtration.
  • WO 2007/143803 A1 describes a process for the transesterification of vegetable or animal fats under base catalysis.
  • the catalysts used are strong bases which contain no metal ions. As a result, no soaps are to be formed in the transesterification, whereby the formation of emulsions can be avoided when washing the crude biodiesel with water.
  • Guanidinhydroxyde are used, which have a pK a in the range of 13.6 to 13.9, and quaternary ammonium hydroxides or alkoxides of guanidine.
  • Catalyst can be used both in homogeneous phase and in heterogeneous phase can be used.
  • the catalysts are useful for the alcoholysis of triglycerides using both methanol and ethanol.
  • the use of ethanol in the alcoholysis of triglycerides offers the possibility of producing a biodiesel whose starting materials can be obtained from renewable raw materials.
  • a disadvantage of the process is that the resulting biodiesel still contains relatively large amounts of impurities, in particular mono-, di- and triglycerides, soaps and glycosides, so that such ethylbiodiesel often does not yet meet the specifications, for example, for use in internal combustion engines are predetermined.
  • the invention therefore an object of the invention to provide a method for the purification of biodiesel, which allows efficient removal of impurities from crude biodiesel and which is particularly suitable for the purification of crude Ethylbiodiesel.
  • the method can be used for Use purification of crude biodiesel, as it is obtained immediately after the alcoholysis, in particular after separation of the glycerol phase.
  • the method can also be used for the post-purification of biodiesel, which still contains small amounts of impurities and, for example, does not meet a specific specification.
  • the process according to the invention can also be used routinely as a final purification stage for the further refinement of an already prepurified biodiesel.
  • a raw biodiesel is provided; the crude biodiesel is reacted with an adsorbent which contains at least one alumina-containing component which has an aluminum content, calculated as Al 2 O 3 , of more than 40% by weight; and a purified biodiesel is separated from the adsorbent.
  • a raw biodiesel is first provided.
  • biodiesel is meant a mixture of fatty acid alkyl esters commonly obtained in the alcoholysis of natural fats and oils. Alcoholysis may have been carried out under both acidic and alkaline catalysis. As alcohols can be used for the
  • Fats and oils are generally understood to mean triglycerides of long-chain fatty acids.
  • the fatty acids preferably comprise more than 10 carbon atoms and preferably comprise 15 to 40 carbon atoms.
  • the alkyl chain of the fatty acids is preferably straight-chain. It may be fully hydrogenated or may comprise one or more double bonds.
  • Suitable starting materials are vegetable fats, such as rapeseed oil, sunflower oil, soybean oil or palm oil. However, other vegetable fats can be used, such as jatropha oil or oils derived from algae. These oils are not suitable for human consumption.
  • agricultural land not suitable for the production of food can be used for the production of these crops.
  • the jatropha nut can also be cultivated on very barren soils that are not suitable for grain production.
  • animal fats can be used, such as beef tallow. It is also possible to use used fats, such as frying fats. It can be used both oils and fats, which go back to only one source. But it is also possible to use mixtures of fats or oils.
  • the fats or oils are preferably purified prior to alcoholysis in a known manner and, for example, degummed and / or deodorized. According to a preferred embodiment, fats or oils having a lecithin content of less than 10% by weight, in particular less than 5% by weight, more preferably less than 10 ppm, in particular less than 5 ppm, are used for the alcoholysis.
  • These fats and oils are usually cleaved by alcoholysis into glycerol and fatty acid esters.
  • the alcoholysis is preferably carried out under alkaline catalysis.
  • Alcohols which can be used in the production of biodiesel are customary alcohols, such as methanol, ethanol or propanol. The use of other alcohols is also possible.
  • biodiesel may in particular also refer to any mixture of fatty acid alkyl esters.
  • fatty acid alkyl ester may be straight-chain or branched and may comprise 1 to 28 carbon atoms.
  • the fatty acid alkyl ester may be, for example, a methyl, ethyl, propyl, butyl, pentyl or hexyl ester of a fatty acid.
  • the mixture of fatty acid alkyl esters comprises a content of at least 70 wt .-%, preferably of at least 85 wt .-%, preferably of at least 95 wt .-%, particularly preferably of at least 98 wt .-% of fatty acid alkyl esters, each based on the Total weight of the organic components of the mixture.
  • Biodiesel mixtures may contain any amount of mono-, di- and / or triglycerides.
  • the biodiesel has a low content of mono-, di- and / or triglycerides.
  • the biodiesel may have a maximum content of 2% by weight, preferably of at most 0.8% by weight for monoglycerides, a maximum content of 2% by weight, preferably at most 0.2% by weight, of diglycerides, and / or a maximum content of 2% by weight, preferably of not more than 0.2% by weight, of triglycerides, determined in accordance with the standard DIN EN 14214.
  • the mixture obtained in the alcoholysis of fats and oils is worked up in a conventional manner.
  • the glycerol phase can be separated from the crude biodiesel or the crude biodiesel can also be washed once or several times with water. But it is also possible that at the
  • Alcoholysis obtained crude biodiesel first to clean with the help of an adsorbent.
  • a crude biodiesel is understood as meaning any biodiesel which has a higher content of impurities than a biodiesel which has been purified by the process according to the invention. Accordingly, a "purified biodiesel” is understood to mean a biodiesel that has a lower impurity content than crude biodiesel.
  • Exemplary impurities that may be present in a crude biodiesel are mono-, di- or triglycerides, soaps or even glycosides, such as steryl glycosides.
  • a crude biodiesel can therefore be a biodiesel, as it is obtained immediately after the alcoholysis of the fats and / or oils, for example immediately after separation of the glycerol phase.
  • a raw biodiesel can also be a biodiesel which has already undergone purification stages after alcoholysis but, for example, still has too high a glycoside content, in particular too high a content of steryl glycosides, mono-, di- or
  • Triglycerides or soaps so it does not meet a specific specification and must be cleaned.
  • the crude biodiesel is added according to the invention with a special adsorbent.
  • the adsorbent can be incorporated in any desired form into the raw biodiesel to be purified. For example, it is possible to stir the adsorbent in ground form into the biodiesel.
  • the crude biodiesel is preferably moved during the purification, for example with the aid of a stirrer, so that the adsorbent intimately with the biodiesel is mixed and does not settle.
  • the amount of adsorbent added to the biodiesel depends on the amount of impurities contained in the crude biodiesel. If a raw biodiesel is used, as it is immediately after alcoholysis
  • Triglycerides is obtained, it makes sense to use larger amounts of the adsorbent. If, on the other hand, the process according to the invention is used for the post-purification of an already prepurified crude biodiesel which only contains small amounts of impurities, the amount of adsorbent added can correspondingly be kept low.
  • the treatment time during which the crude biodiesel is contacted with the adsorbent is intrinsically dependent on the relative amounts of crude biodiesel and adsorbent, as well as the amount of impurities contained in the crude biodiesel.
  • the adsorbent used in the process according to the invention has a relatively fast kinetics.
  • the contact time between raw biodiesel and adsorbent is longer than 5 minutes, preferably longer than 10 and according to a selected further embodiment longer than 15 minutes.
  • the treatment time is shorter than 120 minutes, according to another embodiment, shorter than 60 minutes and, according to another embodiment, shorter than 30 minutes.
  • the process according to the invention is preferably carried out at room temperature or, more preferably, at temperatures above room temperature.
  • the crude biodiesel therefore preferably has a temperature in the range of more than 15 ° C. during the treatment with the adsorbent, more than 30 ° C. in accordance with a further embodiment and more than 40 ° C. according to a further embodiment. In most cases, it is not necessary to heat the biodiesel to a high temperature.
  • the temperature is less than 100 0 C, according to another embodiment, less than 90 0 C and, according to one embodiment, less than 80 0 C.
  • the cleaning in particular a fine cleaning of the biodiesel, is preferably carried out at a temperature above room temperature.
  • a fine cleaning is understood to be a post-purification of an already prepurified biodiesel, the crude biodiesel containing only small amounts of impurities.
  • Such a fine cleaning can be carried out, for example, if the crude biodiesel is already less than 2.0% by weight, preferably less than 1.0% by weight, monoglycerides or less than 2% by weight, preferably less than 1% by weight.
  • the purified biodiesel then meets the specification, ie it contains less than 0.2 wt .-% monoglycerides, less than 0.8 wt .-% diglycerides and less than 0.02 wt .-% triglycerides ,
  • the solubility of impurities, which are present in solid form in the biodiesel is known to be better.
  • impurities present in solid form which have precipitated, for example, after cooling of the biodiesel, can be brought back into solution.
  • Working at elevated temperature also ensures that these solid impurities are depleted after adsorption on the adsorbent after re-dissolution and not just a filtration. This is of particular importance when the adsorbent is provided in the form of a column packing for the purification of the biodiesel. The formation of precipitates would clog the column and make it difficult to regenerate a column.
  • the biodiesel is separated again from the adsorbent.
  • usual methods can be used.
  • the adsorbent can be sedimented and the supernatant purified biodiesel decanted off. But it is also possible to separate the adsorbent, for example by filtration from the purified biodiesel.
  • the aluminum oxide-containing component used as adsorbent in the process according to the invention preferably has a very high specific surface area of more than 100 mVg.
  • the alumina-containing component has a specific surface area in the range of 100 to 750 m 2 / g, more preferably 120 to 700 m 2 / g, particularly preferably 140 to 650 m 2 / g.
  • the specific surface area is determined by the BET method.
  • the aluminum oxide-containing component of the adsorbent used in the process according to the invention preferably has a high pore volume.
  • the alumina-containing component preferably has a pore volume of more than 0.3 ml / g, more preferably a pore volume of more than 0.45 ml / g, particularly preferably more than 0.50 ml / g.
  • the pore volume is determined to be cumulative pore volume according to BJH (I.P. Barret, L.J. Joiner, P.P. Haienda, J. Am. Chem. Soc., 73, 1991, 373) for pores having a diameter of 1.7 to 300 nm.
  • BJH I.P. Barret, L.J. Joiner, P.P. Haienda, J. Am. Chem. Soc., 73, 1991, 373
  • Component has a pore volume of less than 1.4 ml / g.
  • the pore volume of the alumina-containing component is less than 1.3 ml / g and in another embodiment less than 1.2 ml / g.
  • the high specific surface area and the high pore volume enable a high adsorption capacity for the impurities contained in the crude biodiesel and a rapid kinetics of the adsorption, so that the process is particularly suitable for industrial use.
  • an adsorbent which contains an aluminum oxide-containing component which has an aluminum content, calculated as Al 2 O 3 , of more than 40% by weight, it being particularly preferred that the aluminum content (calculated as Al 2 O 3 ) at more than 45% by weight, more preferably more than 50% by weight, more preferably more than 60% by weight, more preferably more than 70% by weight and most preferably more than 75% by weight.
  • the alumina-containing component contains the aluminum in the form of, for example, a mixed oxide.
  • at least one further metal may be present in the alumina-containing component, such as silicon, titanium, magnesium, calcium and / or zirconium.
  • an adsorbent according to the invention which has a high proportion of aluminum oxide, it is also possible to remove impurities from crude biodiesel efficiently even when using small amounts of the adsorbent.
  • the use of the adsorbent with a high alumina content allows the removal of mono-, di- and triglycerides from crude biodiesel and with appropriate reaction, it is possible, for example, after the alcoholysis of the triglycerides and the separation of the glycerol phase to dispense with a step in the the raw biodiesel is washed with water.
  • the crude biodiesel can be reacted directly with the adsorbent, removing impurities of the biodiesel from the adsorbent from the crude biodiesel. This is particularly advantageous when the crude biodiesel comprises a high proportion of fatty acid soaps, which can lead to the formation of a stable emulsion in a water wash.
  • alumina-containing component aluminum oxides, aluminum hydroxides, boehmite or aluminosilicates are preferably used. These compounds may be mentioned in pure form or else in the form of mixtures of the abovementioned
  • connections are used.
  • aluminum oxide can both ⁇ -, ⁇ ⁇ and S-Al 2 O 3 are used.
  • aluminum oxides are used, with more preference being given to y-Al 2 O 3 .
  • the aluminas can be used in pure form or as a mixture of two or three of said phases. It is possible to use aluminum hydroxides of different composition, which may also have a different degree of dehydration or polymerization. Boehmite is AlOOH.
  • the alumina-containing component can be degraded from a natural source, so be a natural mineral. Preferably, however, synthetic compounds are used. These can be produced under controlled conditions and therefore lead to reproducible properties and results in the process according to the invention.
  • the adsorbent is preferably predominantly of the alumina-containing component. It is possible that the adsorbent in addition to the alumina-containing component, for example, contains a binder, wherein the binder is preferably selected from the group consisting of at least one clay mineral, at least one water glass and at least one organic polymer and mixtures thereof.
  • the proportion of the binder on the adsorbent is preferably in a range of 0.01 to 10 wt%, more preferably 0.05 to 5 wt%, and most preferably 0.1 to 1 wt%.
  • the proportion of the alumina-containing component in the adsorbent is more than 60 wt .-%, preferably more than 80 wt .-%, more preferably more than 90 wt .-%.
  • the difference to 100% could for example be formed in each case by a proportion of a binder, with which the alumina-containing component is bound to an adsorbent particle.
  • the adsorbent consists only of the alumina-containing component.
  • aluminas and their hydrates can be prepared by neutralizing basic aluminate solutions by the addition of acid. The precipitation of
  • Aluminum hydroxides or their hydrates can be assisted by the addition of crystallization nuclei. It is also possible to precipitate hydrated aluminum hydroxides from acidic solutions of aluminum salts by adding bases or by combining basic solutions of aluminates with acidic solutions of aluminum salts. The hydrated aluminas separated from the aqueous phase can then be converted to aluminas by annealing.
  • a suitable process for producing hydrated aluminas is described, for example, in WO 01/02297.
  • the aluminas and their hydrates can also be prepared via a sol-gel process.
  • aluminum alkoxides can be hydrolyzed for this purpose.
  • the hydrolysis can generally be carried out in a temperature range from 30 to 150 ° C.
  • the solid alumina hydrate is separated from the aqueous alcohol phase.
  • the obtained crystals may be aged under hydrothermal conditions.
  • the alumina-containing component is a synthetic aluminosilicate.
  • the aluminosilicates preferably have a silicon content, calculated as SiO 2 , of less than 60% by weight, preferably less than 55% by weight, more preferably less than 50% by weight.
  • the silicon content of the aluminosilicate, calculated as SiO 2 is more than 0.5% by weight, according to a further embodiment more than 0.75% by weight.
  • Aluminosilicates can be prepared, for example, by hydrolyzing organic aluminum compounds under acidic conditions and then aged together with silicic acid or silicic acid compounds under hydrothermal conditions.
  • Suitable organic aluminum compounds are, for example, aluminum alcoholates,
  • aluminosilicates which contain only SiO 2 and Al 2 O 3 as constituents.
  • Proportion of further metals calculated as the most stable oxide, is preferably chosen to be less than 1% by weight.
  • the adsorbent may be provided, for example, in the form of a powder.
  • An adsorbent in the form of a powder is suitable, for example, when the adsorbent is stirred into the crude biodiesel, that is in the form of a suspension.
  • the particle size of the powder is generally adjusted so that the adsorbent can be readily separated from the purified biodiesel within a suitable period of time by a suitable method, such as filtration.
  • a suitable method such as filtration.
  • the dry sieving residue of the adsorbent on a sieve having a mesh of 63 ⁇ m is preferably more than 25% by weight and is preferably in a range of 30 to 50% by weight.
  • the dry sieve residue on a sieve with a mesh size of 25 ⁇ m is preferably more than 80% by weight and is preferably in a range of 85 to 88% by weight.
  • the dry sieve residue on a sieve with a mesh size of 45 ⁇ m is preferably more than 35% by weight, particularly preferably more than 45% by weight.
  • the adsorbent in the form of a column packing but also larger particle sizes are suitable.
  • the adsorbent is preferably used in the form of granules.
  • a granulate is preferably used which has a particle size of more than 0.1 mm.
  • the granules have a particle size in the range of 0.2 to 5 mm, particularly preferably 0.3 to 2 mm.
  • the grain size can be adjusted, for example, by sieving.
  • the granules can be prepared by conventional methods, for example, by applying a finely ground adsorbent with a granulating agent, for example water, and then granulated in a conventional granulating in a mechanically generated fluidized bed.
  • a granulating agent for example water
  • other methods can be used to prepare the granules.
  • the powdered adsorbent can be formed for example by compaction to a granulate.
  • the adsorbent may also be provided as shaped articles, which may be obtained, for example, by extrusion of a plastic mass.
  • shaped articles which may be obtained, for example, by extrusion of a plastic mass.
  • Components such as a binder, prepared by adding a liquid, preferably water, a paste. This paste is then extruded and the extrudate comminuted, for example by cutting the extruded strand into short cylindrical pieces, and then drying the resulting shaped articles.
  • a liquid preferably water
  • a paste is then extruded and the extrudate comminuted, for example by cutting the extruded strand into short cylindrical pieces, and then drying the resulting shaped articles.
  • massive cylinders in this way e.g. also hollow cylinder can be produced.
  • the granules or the shaped bodies can still be heat-treated and sintered, for example, by heating. As a result, the stability of the granules or the shaped bodies can be increased.
  • the shaped body or the granules are preferably at a temperature of more than 300 0 C, according to another embodiment, to a temperature of more than 400 0 C, and heated according to yet another embodiment to a temperature of more than 500 0 C. According to one embodiment, the temperature is less than 1200 0 C, chosen according to another temperature lower than 1000 0 C.
  • the heat treatment is preferably selected for a duration of at least 30 minutes, according to a further embodiment for a duration of at least 60 minutes. According to one embodiment, the duration of treatment is chosen to be less than 5 hours.
  • the adsorbent can be added directly to the crude biodiesel, wherein the biodiesel is preferably stirred.
  • the amount of the adsorbent is preferably selected in a range of 0.05 to 5 wt .-%, particularly preferably 0.1 to 2 wt .-%. The percentages of the adsorbent are based on the weight of the crude biodiesel.
  • the adsorbent is provided in the form of a column packing.
  • the raw biodiesel can then be passed through the column packing.
  • the column packing may be provided, for example, in the form of a cartridge.
  • the crude biodiesel can then be passed through the cartridge until the adsorption capacity of the adsorbent contained in the cartridge is exhausted.
  • the cartridge can then be easily replaced with a new cartridge.
  • the cartridge may then be discarded or, as far as the separated contaminants are to be reused or the cartridge reused, the compounds bound on the adsorbent may also be eluted with a suitable eluent.
  • the adsorbent is provided in the form of a column packing, the adsorbent is provided in the form of larger granules to prevent excessive pressure drop across the column packing.
  • the adsorbent is preferably used in the form of a granule having a particle diameter of more than 0.1 mm, particularly preferably a particle diameter in the range of 0.2 to 5 mm.
  • the crude biodiesel is preferably heated to a temperature above room temperature before being added to the column.
  • regenerants are, for example, alcohols, mixtures of alcohols and alkanes or chlorinated hydrocarbons or aqueous surfactant-containing solutions.
  • the regeneration may also be carried out in a gradient wherein the biodiesel is first washed with a relatively nonpolar solvent from the column and then transferred to a more polar solvent, for example an alcohol such as methanol or ethanol, around the impurities bound to the adsorbent , in particular sterylglycosides, to elute from the column.
  • the adsorbents used in the process according to the invention preferably react neutral to slightly alkaline.
  • a suspension of 10 wt .-% of the adsorbent in water has preferably has a pH in the range from 5 to 9, more preferably 6 to 8.5, and most preferably in the range of 6.5 to 8.
  • the pH is determined by means of a pH electrode according to DIN ISO 7879.
  • a further increase in the activity of the adsorbent can be achieved according to one embodiment when the adsorbent is pre-dried.
  • the adsorbent has a water content of less than 5 wt .-%, according to another embodiment has a water content of less than 3 wt .-% and according to another embodiment has a water content of less than 2 wt .-%.
  • the adsorbent may also be advantageous to heat the adsorbent to a higher temperature to remove physically bound water.
  • the adsorbent may also be advantageous to heat the adsorbent to a higher temperature to remove physically bound water.
  • Adsorbent be heated to a temperature of more than 600 0 C. According to one embodiment, the temperature is chosen lower than 1000 0 C.
  • boehmite can first be used to remove the superficially bound water and to convert the hydrate into an oxide phase.
  • the inventive method is also particularly suitable for the removal of glycosides from biodiesel.
  • the method is suitable in particular for the post-purification of already prepurified biodiesel.
  • glycosides can be removed from the biodiesel if they are present in the biodiesel in only very small amounts.
  • a biodiesel that is already very pure is subjected to a post-purification.
  • the crude biodiesel has a glycoside content of less than 5,000 ppmw, more preferably less than 2,000 ppmw, most preferably less than 500 ppmw.
  • the inventive method is particularly suitable for the removal of very small amounts of glycosides, especially Sterylglykosiden.
  • the crude biodiesel has a glycoside content of less than 100 ppmw, more preferably less than 80 ppmw, most preferably less than 50 ppmw. According to one embodiment, the crude biodiesel has a glycoside content of more than 10 ppmw, according to another embodiment more than 20 ppmw.
  • Glycosides are generally understood to mean compounds of carbohydrates and aglycones.
  • carbohydrates both mono- and oligosaccharides in the
  • glycosides As aglycones, all compounds which can react with the carbohydrate to form a glycosidic bond can in themselves act.
  • the aglycone can be bound both ⁇ - and ⁇ -glycosidic.
  • As carbohydrates both aldoses and ketoses may be included, which may be present both as 5- and as 6-rings, ie as furanosides or pyranosides.
  • the process according to the invention is suitable for the separation of steryl glycosides from crude biodiesel.
  • Steryl glycosides are glycosides which include sterols as aglycone.
  • Sterols are nitrogen-free, polycyclic, hydroaromatic compounds, in particular derivatives of guanan or of perhydro-1H-cyclopenta- [ ⁇ ] -phenanthrene.
  • Examples of sterol glycosides are stiosteryl, stigmasterol or campesterol- ⁇ -glycoside.
  • the steryl glycosides are preferably in the form of a glycoside.
  • glycosides in particular steryl glycosides
  • the method according to the invention is particularly suitable for the purification of biodiesel, which still has low levels of contamination by glycosides, in particular steryl glycosides. These are present as a very fine precipitate.
  • the crude biodiesel therefore comprises the at least one glycoside, in particular sterol glycoside, in the form of a finely divided precipitate, the mean particle size of the precipitate (D50) being less than 200 ⁇ m, preferably less than 100 ⁇ m, according to one embodiment.
  • the particle size of the precipitate is in the range of 10 to 100 microns, more preferably in the range of 10 to 20 microns.
  • the average particle size is determined at room temperature (20 ° C.), for example by laser diffraction.
  • glycoside in particular Sterylglykosid, precipitates in the form of crystal agglomerates, wherein the agglomerates at
  • amorphous structure of gelly loosely interconnected crystallites usually do not consist of pure glycoside, in particular steryl glycoside, but also contain fatty acid esters which are adsorbed on the precipitate.
  • the adsorbents according to the invention are also suitable for the administration of glycosides of animal origin which are still present in the biodiesel. Impurities due to glycosides of animal origin are found in biodiesel when animal fats are used as raw material. These animal fats contain cholesterylglycerides, which can lead to biodiesel problems similar to those described for the sterylglycosides of plant origin.
  • the adsorbent used in the process according to the invention has a high adsorption capacity, in particular for mono-, di- and triglycerides, as well as fatty acid soaps and glycosides. If the process is used for a post-purification of a biodiesel containing only small amounts of impurities, it is sufficient if only a small amount of the adsorbent is added to the crude biodiesel.
  • the adsorbent can be easily separated after treatment, for example by filtration, again from the purified biodiesel. In one embodiment, the adsorbent is added in a proportion of less than 5% by weight, based on the crude biodiesel.
  • the adsorbent is added in an amount of less than 3 wt .-%, according to another embodiment in a proportion of less than 2 wt .-%.
  • the adsorbent is added to the crude biodiesel in a proportion of more than 0.2 wt .-%, according to another embodiment in a proportion of more than 0.5 wt .-%.
  • the crude biodiesel still contains relatively large amounts of impurities after the alcoholysis when the transesterification is carried out using ethanol. Because of the high binding capacity of the inventive Method used adsorbent, this is therefore particularly suitable for a biodiesel, which is composed essentially of fatty acid ethyl esters.
  • Fig. 1 a graphic representation of the monoglyceride content of a biodiesel which has been purified with various adsorbents;
  • Fig. 2 a graphic representation of the monoglyceride content of a biodiesel which has been purified with various pre-dried adsorbents.
  • the physical properties of the adsorbent were determined by the following methods:
  • the surface area and the pore volume were determined with a fully automatic nitrogen porosimeter from Micromeritics type ASAP 2010.
  • the sample is cooled in a high vacuum to the temperature of liquid nitrogen. Subsequently, it becomes continuous
  • Nitrogen dosed into the sample chambers By detecting the adsorbed amount of gas as a function of pressure, an adsorption isotherm is determined at a constant temperature. In a pressure equalization, the analysis gas is gradually removed and a desorption isotherm is recorded. To determine the specific surface area and the porosity according to the BET theory, the data are evaluated in accordance with DIN 66131.
  • the pore volume is further determined from the measurement data using the BJH method (I.P. Barret, L.G.Joiner, P.P. Haienda, J.Am.Chem.Soc.73, 1991, 373). This procedure also takes into account effects of capillary condensation. Pore volumes of certain volume size ranges are determined by summing up incremental pore volumes obtained from the evaluation of the BJH adsorption isotherm. The total pore volume by BJH method refers to pores with a diameter of 1.7 to 300 nm.
  • the water content of the products at 105 0 C is determined using the method DIN / ISO-787/2.
  • the strainer is connected to a vacuum cleaner which, through a suction slot rotating under the bottom of the sieve, passes through the sieve all the parts which are finer than the sieve sucks.
  • the strainer is covered with a plastic lid and the vacuum cleaner is switched on. After 5 minutes, the vacuum cleaner is switched off and the amount of remaining on the screen coarser fractions determined by differential weighing.
  • a graduated cylinder cut off at the 1000 ml mark is weighed. Then, the sample to be examined is filled by means of a Pulvertrichters so in a train in the measuring cylinder that above the conclusion of the
  • Measuring cylinder forms a Schüttkegel.
  • the pour cone is removed by means of a ruler, which is led over the opening of the measuring cylinder, and the filled measuring cylinder is weighed again. The difference corresponds to the bulk density.
  • IP 387/97 Filter Blocking Tendency a defined The amount of raw biodiesel to be analyzed is filtered through a 1.6 ⁇ m glass fiber filter. For a complete test, about 300 mL biodiesel is needed.
  • the filter was then first extracted with 4 mL of hexane and then the steryl glycosides washed with 1 mL of pyridine from the filter.
  • To the sample are added 100 ⁇ L of MSTFA (N-methyl-N- (trimethylsilyl) trifluoroacetamide) as the silylation reagent and 50 ⁇ L of tricaprine (71.3 mg of tricaprin per 10 mL of pyridine).
  • MSTFA N-methyl-N- (trimethylsilyl) trifluoroacetamide
  • tricaprine 71.3 mg of tricaprin per 10 mL of pyridine.
  • the mixture was allowed to stand for 20 min at 60 0 C and then added 7 mL of hexane.
  • the mixture is filtered through a 0.45 ⁇ m syringe filter. For the measurements, 1 ⁇ L each of the solution was injected into the GC / MS system.
  • the quantification of sterylglucosides was carried out by comparison with a calibration curve.
  • a stock solution of a pure Sterylglucosidmischung was prepared in pyridine, the concentration was set in the range of about 50 mg / 10 mL.
  • concentration was set in the range of about 50 mg / 10 mL.
  • volumes of the stock solution were measured and mixed with 100 ⁇ L MSTFA and 50 ⁇ L tricaprin solution. The mixture was allowed to stand for 20 minutes at 60 0 C and filtered after addition of 8 mL of hexane through a 0.45 micron syringe filter.
  • 1 ⁇ L each of the solution was injected into the GC / MS system. From the intensities of the MS signals, a calibration curve was created as a function of the injected sample quantity.
  • the amount of sterylglucosides contained in the samples was determined by comparing the intensity of the MS signals with the calibration curve.
  • aluminosilicates were used for the purification of crude biodiesel. These are under the names Siral ® 5, Siral ® 30, Siral ® 40 available. Furthermore, a boehmite was tested, which is sold under the name Pural ® SCC 150. As a further adsorbent aluminas were used, which are offered under the name Puralox ® . These adsorbents were manufactured by Sasol Germany GmbH,
  • Adsorbent 1 Siral 5 ®
  • Adsorbent 2 Siral ® 30
  • Adsorbent 3 Siral ® 40
  • Adsorbent 4 Puralox® ® KR-160
  • Adsorbent 5 Pural ® SCC 150
  • Adsorbent 6 Puralox ® SCCa-150/230
  • Table 1 Physical properties of the adsorbents (according to kauran reference) compared to a calcium bentonite
  • biodiesel (methyl ester) made from soybean oil was used.
  • the crude biodiesel had a non-acylated steryl glycoside content of 49 ppm.
  • the sterol glycoside content could be lowered below the detection limit.
  • the method according to the invention shows the same performance as the magnesium silicate used already in the art as an adsorbent (Magnesol ®).
  • the calcium bentonite used as a comparison shows only a low performance.
  • Adsorbent 0, 5 wt% 0.2 wt% 0.04 wt%
  • an ethylbiodiesel obtained from soybean oil was used, which had a monoglyceride content of 1.92% by weight, determined in accordance with DIN EN 14105. This was treated because of the high monoglyceride content with 7 wt .-% adsorbent.
  • the cleaning was carried out using magnesium silicate (Magnesol ®) and calcium bentonite.
  • Table 3 Content of monoglycerides in ethylbiodiesel samples after treatment with 7% by weight of adsorbent
  • Example 2 was repeated, but the adsorbents were previously dried for 45 minutes at 55 0 C in a drying oven. The water content after drying was less than 2% by weight for all adsorbents. Subsequently, the ethyl biodiesel sample with the dried adsorbents in the treated as described above. The content of monoglycerides determined in the filtrate is summarized in Table 4 and shown graphically in FIG.
  • Table 4 Content of monoglycerides in ethylbiodiesel after treatment with 7% by weight pre-dried adsorbent
  • the SiO 2 - containing aluminas from Siraltyp show the highest efficiency thereby. If the bound amount of monoglyceride is converted into a binding capacity, the result is 16.7% by weight of monoglyceride for adsorbent 3.
  • the adsorbents can thus be used very well for removing monoglycerides from biodiesel.

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Abstract

L'invention concerne un procédé de purification de biodiesel, caractérisé - en ce qu'un biodiesel brut est mis à disposition; le biodiesel brut est mis à réagir avec un adsorbant comprenant au moins un composant renfermant de l'oxyde d'aluminium qui présente une fraction en aluminium, calculée sous forme de Al2O3, supérieure à 40 % en poids; et en ce qu'un biodiesel purifié est séparé de l'adsorbant.
PCT/EP2009/008292 2008-11-21 2009-11-20 Adsorbants renfermant de l'oxyde d'aluminium pour la purification de biodiesel WO2010057660A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9528059B2 (en) 2011-06-21 2016-12-27 W. R. Grace & Co.-Conn. Catalytic purification of fatty acid alkyl esters used in fuels

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI1005000A2 (pt) * 2010-11-26 2013-03-26 Mineracao Curimbaba Ltda processo para obtenÇço de biodiesel a partir de àleos e/ou gorduras vegetais e/ou gorduras animais, virgens ou usados e biodiesel assim obtido

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005037969A2 (fr) * 2003-10-09 2005-04-28 The Dallas Group Of America, Inc. Purification de biodiesel a l'aide de matieres adsorbantes
WO2008055676A1 (fr) * 2006-11-07 2008-05-15 Süd-Chemie AG Procédé de purification de biocombustible
WO2009080287A2 (fr) * 2007-12-21 2009-07-02 Grace Gmbh & Co. Kg Traitement de biocombustibles

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19641142A1 (de) 1996-10-05 1998-04-16 Rewe Dea Ag Fu Verfahren zur Herstellung von dispergierbaren Alumosilikaten
DE19641141A1 (de) 1996-10-05 1998-04-16 Rwe Dea Ag Verfahren zur Herstellung von dispergierbaren Alumosilikaten
US5972057A (en) * 1997-11-11 1999-10-26 Lonford Development Limited Method and apparatus for producing diesel fuel oil from waste edible oil
DE19836821A1 (de) 1998-08-14 2000-02-24 Rwe Dea Ag Böhmitische Tonerden und aus diesen erhältliche phasenreine, hochtemperaturstabile und hochporöse Aluminiumoxide
DE19923558A1 (de) * 1999-05-21 2000-11-23 K D Pharma Bexbach Gmbh Verfahren zur Herstellung von geruchs- und geschmacksfreien ungesättigten Fettsäuren aus Naturölen und deren Verwendung
DE19930924A1 (de) 1999-07-06 2001-01-18 Rwe Dea Ag Verfahren zur Herstellung von Tonerdehydraten durch Fällung von Aluminiumsalzen in Gegenwart von Kristallisationskeimen
US20050188607A1 (en) 2004-01-31 2005-09-01 Lastella Joseph P. System for removal of methanol from crude biodiesel fuel
DE102005031945A1 (de) * 2005-07-08 2007-01-11 Construction Research & Technology Gmbh Verwendung von entfärbtem Biodiesel als Weichmacher
US20070151146A1 (en) 2005-12-29 2007-07-05 Inmok Lee Processes of Producing Biodiesel and Biodiesel Produced Therefrom
BRPI0603857A (pt) 2006-06-14 2008-01-29 Unicamp processo para transesterificação de óleos vegetais e gorduras animais, catalisado por base forte modificada para produção de ésteres alquìlicos
MX2009008612A (es) * 2007-02-13 2009-11-10 Mcneff Res Consultants Inc Dispositivos y metodos para la remocion selectiva de contaminantes de una composicion.
US20080318763A1 (en) * 2007-06-22 2008-12-25 Greg Anderson System for production and purification of biofuel

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005037969A2 (fr) * 2003-10-09 2005-04-28 The Dallas Group Of America, Inc. Purification de biodiesel a l'aide de matieres adsorbantes
WO2008055676A1 (fr) * 2006-11-07 2008-05-15 Süd-Chemie AG Procédé de purification de biocombustible
WO2009080287A2 (fr) * 2007-12-21 2009-07-02 Grace Gmbh & Co. Kg Traitement de biocombustibles

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9528059B2 (en) 2011-06-21 2016-12-27 W. R. Grace & Co.-Conn. Catalytic purification of fatty acid alkyl esters used in fuels

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