EP2205709A1 - Procédé d'estérification à catalyse hétérogène d'acides gras - Google Patents

Procédé d'estérification à catalyse hétérogène d'acides gras

Info

Publication number
EP2205709A1
EP2205709A1 EP08845101A EP08845101A EP2205709A1 EP 2205709 A1 EP2205709 A1 EP 2205709A1 EP 08845101 A EP08845101 A EP 08845101A EP 08845101 A EP08845101 A EP 08845101A EP 2205709 A1 EP2205709 A1 EP 2205709A1
Authority
EP
European Patent Office
Prior art keywords
fatty acids
free fatty
conversion
catalyst
acidic
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Withdrawn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
EP08845101A
Other languages
German (de)
English (en)
Inventor
Wulf Dietrich
Dieter Heinz
Leslaw Mleczko
Shaibal Roy
Heinrich Morhenn
Robert Tyron Hanlon
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.)
Bayer Intellectual Property GmbH
Original Assignee
Bayer Technology Services GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE102007052064A external-priority patent/DE102007052064A1/de
Priority claimed from DE102008007431A external-priority patent/DE102008007431A1/de
Application filed by Bayer Technology Services GmbH filed Critical Bayer Technology Services GmbH
Publication of EP2205709A1 publication Critical patent/EP2205709A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the invention relates to a process for the esterification of free fatty acids in vegetable and animal fats with alcohols on heterogeneous acidic ion exchange resin catalysts at temperatures of 60 to 120 0 C.
  • Vegetable and animal fat and oils often contain significant amounts of free fatty acids.
  • the content of free fatty acids can be between 0 and 100%.
  • This proportion of free fatty acids can not be converted in the production process for biodiesel by transesterification of triglycerides with methanol to the corresponding fatty acid methyl esters and leads to yield losses or to the fact that raw materials with a high content of free fatty acids are not suitable for biodiesel production. Therefore, a pretreatment of the fats is necessary, in which the content of free fatty acids is reduced by conversion to fatty acid alkyl esters.
  • EP 0192035 (Example 1), an addition of 0.2 l of methanol per 1 l of oil with an acid number of 10 (corresponding to a content of free fatty acids of 5% by weight) is required.
  • an acid number of 10 corresponding to a content of free fatty acids of 5% by weight
  • a quantity of catalyst - - Of 7 liters per liter of oil per hour necessary, resulting in considerable reactor volumes and accordingly high investment costs.
  • a maximum acid number of 60 mgKOH / g may be present in the starting material (corresponds to a concentration of free fatty acids of about 30 wt .-%), among other things, results from the calculated , only very small space-time yield of 34 g of fatty acid methyl ester per liter of reactor volume and hour in the
  • catalysts show the phenomenon of so-called leaching known to the person skilled in the art, which comprises the discharge of catalyst material into the product. It is in this context advantageous if the catalyst consists of substances which are at least chemically similar to the starting materials, or products of the process within which it is used, thus contamination of the product by
  • Catalysts which include the ion exchange resins are advantageous.
  • the task is to develop a method that reduces the content of free fatty acids to the requirements of a downstream transesterification stage by the reaction achieved high conversion of the free fatty acids at elevated temperatures and the lowest possible alcohol excess, so that the process allows an improvement in the space-time yield and thus the required apparatus size compared to the method of the prior art.
  • starting materials for the process according to the invention are all fats and oils in
  • Non-exhaustive examples of natural fats and oils are coconut oil, palm oil,
  • synthetic fats and oils can also be used at least partial esterification of glycine with fatty acids
  • Preferred starting materials are vegetable fats, animal fats, vegetable oils and / or oil, in particular palm oil, palm oil fatty acid distillates (PFAD), jatrophaol, recycled fats from used edible oils and / or wastewater treatment and beef tallow and poultry fat
  • fatty acids include ahphatic carboxylic acids of the formula (I)
  • R ' stands for an aliphatic, linear or branched carbon radical having 6 to 22 carbon atoms and optionally one or more double bonds.
  • Non-conclusive examples of these are caproic acid, caprylic acid, 2-ethylhexanoic acid, capnic acid, lauric acid, isotendecanoic acid, mypalic acid, palmitic acid, Palmaric acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petrose acid,
  • Linoleic acid Linoleic acid, linolenic acid, Elaeostea ⁇ nsaure, Arachinsaure, Gadolemsaure, Behensaure and Erucasaure and their technical mixtures
  • the acid number of the starting material in the process according to the invention can be up to 200 mg KOH / g, preferably from 5 to 60 mg KOH / g and more preferably from 10 to 40 mg KOH / g
  • the acid number in this context indicates the mass of potassium hydroxide in mg, which is required to neutralize 1 g of the sample to be tested (DIN 53402, latest version DIN EN ISO 21 14)
  • the acidic, heterogeneous ion exchange resin catalysts according to the invention are preferably strongly acidic polymeric macroporous resins with free sulfonic acid groups
  • the ion exchange resin catalysts used preferably have an activity of at least 0.1 kg of free fatty acid per kg of catalyst. This activity is particularly advantageous, since this reliably enables the process according to the invention with the advantageous catalyst loadings according to step 1) and / or 3)
  • the acidic, heterogeneous ion exchange resin catalyst is in
  • Particles or particle debris wherein the particles more preferably between about 0.5 mm and 1 mm in diameter
  • particle debris are preferably used in the form of a fixed bed.
  • the particle bedding in the form of a fixed bed is carried out in such a way that the fixed bed uses the catalyst particles described above
  • Preferred lengths of such a fixed bed in the form of particle bedding are between 1 and 10 m
  • Non-conclusive examples include suitable compaction of the bedding, or use of baffles in the bedding
  • Preferred alcohols in the context of the process according to the invention are monohydric or polyhydric C r to C 5 -alcohols or mixtures thereof.
  • the valence of an alcohol in connection with the present invention describes the number of
  • Non-limiting examples of monohydric, preferred alcohols are butanol, isopropanol, propanol, ethanol and / or methanol.
  • water-soluble polyols such as ethylene glycol and / or glycerine can also be used.
  • Methanol is particularly preferred
  • the alcohol is used in step 1) of the inventive method preferably in a molar excess based on the free fatty acids of 5 to 40, In one particularly preferred embodiment, the alcohol is added to the starting material in a molar ratio of 5 to 20, most preferably from 10 to 20 added.
  • the conversion of the free fatty acids according to step 1) of the method according to the invention is preferably carried out at temperatures between 80 to 95 0 C.
  • the pressure of the process according to the invention after step 1) is selected such that it corresponds at least to the vapor pressure of the alcohol used under the otherwise given process conditions.
  • the vapor pressures of the alcohols according to the invention under various environmental conditions are known to the person skilled in the art, or in the VDI
  • the preferred pressures are advantageous because this prevents alcohol from escaping from the reaction mixture by evaporation during the reaction. Thus, he is available during the turnover in maximum amount, so that the desired space
  • Time yields can be achieved.
  • An increase over the amount of 5 bar is not advantageous only because it avoids the need to use special pressure vessels for carrying out the method according to the invention.
  • the special pressure vessels are more expensive due to their special design and therefore in terms of the economy of the process may be disadvantageous.
  • step 1) of the process according to the invention is carried out so that the reaction time of the free fatty acids with the alcohol does not exceed 30 minutes. This means that fluid elements remain on average only a time less than or equal to 30 minutes in the reaction zone according to step 1).
  • the reaction time can be set, e.g. by passing the free fatty acids and the alcohol over the acidic ion exchange resin catalyst at a certain rate.
  • reaction time is advantageous because it has been shown in the context of the method according to the invention that this time represents the limit within which already high conversions of the free fatty acids can be achieved, so that a further increase in the
  • step 1) of the method according to the invention the method is operated so that a specific catalyst loading of the acidic, heterogeneous ion exchange resin catalyst is set. This is preferably adjusted depending on the acid number of the starting material.
  • Catalyst loading in the context of the present invention describes the mass of free fatty acid per mass of acid heterogeneous ion exchange resin catalyst and time, expressed in kilograms kg-hr
  • the set catalyst loading may generally be from 0.1 to 10, preferably from kg - h kg kg 0.15 to 5, more preferably from 0.2 to 3. kg - h kg - h
  • a catalyst loading of 0.1 to 4 is preferred. kg - h kg
  • a catalyst loading of 0.3 to 10 is preferred.
  • Particularly kg - h kg is then preferred a catalyst load 0.4 to 5.
  • Very particular preference is kg - h kg then a catalyst loading of 0.5 to 3 kg - h
  • a lower catalyst load is in each case inefficient, since more free fatty acid could be implemented and thus would not meet the goal of a high space-time yield.
  • a higher catalyst load leads to inadequate conversions of the free fatty acids and thus also to lower space-time yields.
  • the adjustment of the catalyst loading can be done by adjusting the mass flow of the free fatty acids, or adjusting the amount of catalyst.
  • step 1) of the process the acidic, heterogeneous ion exchange resin catalyst is present in the reaction zone in a continuous alcoholic phase in which the free fatty acids are finely dispersed.
  • Possibilities of achieving finely divided dispersion of one phase in another include structural measures in and / or in front of the reaction zone, e.g. in the form of internals that favor special phase relationships (perforated plates, static mixers, nozzles, etc.), but also process measures, such as changes in the
  • reaction zone in which the conversion is carried out is vertically flowed through from top to bottom.
  • reaction mixture is the reaction mixture
  • Reaction zone a two-phase mixture of fatty acids and alcohol, wherein generally the density of the alcoholic phase is less than that of the fatty acid phase.
  • the alcoholic phase has a significantly better wettability of the catalyst used than the fatty acid phase, whereby by an operation in which the alcohol forms a continuous phase in which the fatty acid is finely dispersed, the physical properties of the two Phases are exploited in an optimal way. In this way, a particularly intensive contact of the reaction mixture with the catalyst surface can be achieved.
  • a finely divided dispersion referred to in the context of the present Invention the presence of drop sizes of the fatty acid phase in the alcohol phase of on average not more than 2 mm.
  • This finely divided dispersion leads to a more uniform loading of the catalyst in the reaction zone with the two phases, which in turn leads to increased conversions.
  • step 1) of the process it is possible to reduce the temperatures at which the conversion is carried out, " without a significant ' loss the ' This in turn requires reduced energy inputs into the process, which is economically advantageous.
  • step 1) is advantageous because the conversion based on the proportion of free fatty acids is greater than 98.0%, so that so that the solution of the problem to achieve an improvement in the space-time yield achieved becomes.
  • the process according to the invention and its preferred further development can be carried out with or without a separation of water according to step 2).
  • a separation of water, and optionally alcohol is at least partially carried out together with this.
  • step 2 Is a separation of water according to step 2) of the inventive method desirable so in this preferred process variant of the resulting stream either further processing by transesterification of the triglycerides according to a conventional, known in the art process or optionally a further conversion according to step 3) des fed to the inventive method.
  • Step 2) of the process according to the invention is preferably carried out in such a way that only water is separated, so that the optionally unreacted alcohol is still available for further processing by transesterification or further conversion according to step 3) of the process according to the invention and the process is thus in accordance with Solving the task leads to an increased space-time yield.
  • Possible methods for the separation of water, and optionally alcohol at least partially together with it include, as non-conclusive examples, distillation,
  • Rectification, evaporation or membrane processes which are known in their appropriate embodiments to those skilled in the art.
  • Particularly preferred is a selective separation of the water by means of a membrane.
  • Very particular preference is given to a selective separation by means of a hydrophobic membrane, such as, for example, commercially available microporous polypropylene membranes.
  • this preferred process variant can be used with or without further
  • Step 3) of the process according to the invention added again alcohol. It is particularly preferred in the in step 3) an amount of alcohol less than or equal to
  • step 3) Alcohol amount of those added in step 1). Most preferably, in step 3) an amount of alcohol is added which corresponds exactly to that in the preceding
  • Steps 1) and optionally step 2) has been implemented and / or separated.
  • step 3) of the process according to the invention under the correspondingly preferred conditions with regard to temperature and / or pressure and / or residence time and / or catalyst loading, as indicated in step 1) of the process according to the invention.
  • step 3) is carried out such that in the reaction zone in which the further conversion is carried out, the acidic, heterogeneous ion exchange resin catalyst is present in a continuous alcoholic phase in which the free fatty acids are finely dispersed.
  • step 3 Analogous to the preferred further development of step 1), as has already been described above, a better wetting of the catalyst can also be achieved here by such an operation of the process and thus an increased conversion can be achieved.
  • step 3) of the process this is of particular advantage, since wetting and uniform loading of the catalyst is particularly important in the case of a further conversion. This is due to the fact that the beginning of the
  • Reaction zone of step 3) the proportion of starting material in the stream is lower than in step 1) of the process.
  • the expected sales with otherwise the same operating conditions lower than before.
  • a maximum wetting must be achieved in order to achieve advantageous conversions in terms of the desired space-time yields. This is made possible by such operation as described above.
  • step 1) of the process process engineering measures are preferred in order to ensure a finely divided dispersion of the fatty acid phase in the alcoholic phase.
  • a particularly preferred measure is that the Christszörie that is running in "of the further Umsalz is flowed through vertically from top to bottom.
  • step 3) is carried out more than once.
  • the sequence of step 2) and step 3) of the method according to the invention is carried out more than once.
  • step 3 is advantageous because a conversion based on the free fatty acids in the starting material before the first esterification reaction of more than 99.7% is achieved, so that thus the solution of the problem an improvement of the space -Time yield is achieved.
  • a very particularly preferred variant of the process according to the invention comprises all steps 1) to 3), wherein in step 2) water, if appropriate together with alcohol, is separated off and / or separated in step 1) and / or step 2)
  • Alcohol is added again in the amount that the same molar ratio of alcohol based on the originally added to the process amount of fatty acid as in step 1) is restored.
  • All processes according to the invention, or their preferred embodiments or their preferred individual steps can be carried out continuously or batchwise.
  • at least step 1), preferably step 1) and step 3) of the process according to the invention, as well as any preferred variant thereof, are carried out continuously with a fixed bed reactor.
  • the fixed bed reactor particularly preferably contains a bed of catalyst particles, which is continuously flowed through by starting materials and alcohol (s).
  • the non-batchwise reaction and / or separation of the substances according to the inventive steps continuously describes in this connection.
  • the preferred reaction time for the residence time of the starting material and / or alcohols given for these steps is the same in this process step (eg in a fixed bed reactor) put.
  • Reaction temperature a significant acceleration of the reaction and thus a significant increase in the space-time yield by factors of about 5 to 20 over the prior art. In large-scale implementation, this corresponds to an approximately corresponding reduction of the required reactor volume and thus results in an economic advantage.
  • Another advantage of the method according to the invention results from the reduction of the required excess alcohol.
  • halving the amount of methanol required reduces the energy requirement for methanol separation by 3.28 MJ per kg of free fatty acid fed to esterification (in a typical technical plant with a capacity of 12.5 t / h of oil) an acid number of 25 corresponds to an energy saving of 0.9 MW).
  • Fig. 1 shows a sketch of a particularly preferred embodiment.
  • the starting material (1) is continuously fed with the alcohol (2) to the first reaction stage (10), according to step 1) of the process according to the invention.
  • the reaction stage consists of a flow tube reactor containing a fixed bed consisting of a bed of catalyst particles (particle diameter 0.5 to 1 mm) with a length of 1 to 10 m.
  • the diameter of the fixed catalyst bed results from the volume flow of the streams (1) and (2) such that the average residence time of these two streams in the catalyst bed is 5 to 30 minutes.
  • Flow rate of the liquid phase is 1 to 5 mm / s and the friction pressure loss in the particle bed is less than 0.5 bar / m.
  • the conversion of free fatty acids at the exit of the first reaction stage is e.g. about 95%.
  • the separation step may e.g. a falling film evaporator or a distillation column operated at atmospheric or reduced pressure.
  • the stream (5) is substantially anhydrous after the separation stage and is mixed with further alcohol (6) and fed to a further reaction stage (30). This reaction stage corresponds in its structure to the reaction stage (10).
  • the conversion of free fatty acids at the outlet of the second reaction stage corresponds to electricity
  • Fig. 2 shows a sketch of a particularly preferred embodiment.
  • the starting material (1) is continuously fed from below with the alcohol (2) of the first reaction stage (10), in accordance with step 1) of the process according to the invention.
  • the reaction stage consists of a flow tube reactor containing a fixed bed consisting of a bed of catalyst particles (particle diameter 0.5 to 1 mm) with a length of 1 to 10 m.
  • the diameter of the fixed catalyst bed results from the volume flow of the streams (1) and (2) such that the average residence time of these two streams in the catalyst bed is 5 to 30 minutes.
  • Flow rate of the liquid phase is 1 to 5 mm / s and the friction pressure loss in the particle bed is less than 0.5 bar / m.
  • the conversion of free fatty acids at the outlet of the first reaction stage is for example about 95%.
  • the separation stage may be, for example, a falling film evaporator or a distillation column operated at atmospheric or reduced pressure.
  • the stream (5) is largely anhydrous after the separation stage and is mixed with further alcohol (6) and fed to another reaction stage (30) from above, so that the reaction zone is vertically flowed through from top to bottom.
  • This reaction stage corresponds in its structure to the reaction stage (10). Sales to free Fatty acids at the outlet of the second reaction stage (corresponding to stream (7)) is for example about 90% based on the starting material (5) of the second reaction stage and, for example, about 99.7% based on the starting material (1) of the first reaction stage.
  • the reaction product was collected in a receiver and transferred to a rotary evaporator. With the help of the rotary evaporator, the unreacted methanol and water was separated by vacuum distillation. After vacuum distillation, a water content of 0.04% by weight was determined in the distillation residue.
  • Drops of the disperse phase can be identified. At a mean droplet diameter of about 2 mm, a sinking rate of about 28 mm / s was measured, the thus - 1 - was significantly greater than the average empty tube velocity of the reaction mixture, so that it was concluded that the drops are oil, which has a significantly higher density than methanol in the experimental conditions.
  • Example 4 Further conversion at lower temperatures - flow from above
  • Example 5 Sales and further sales of free fatty acids - flow from below
  • the reaction mixture was fed from below, so that the reaction zone vertically from The empty tube velocity of the reaction mixture in the reactor was 0.92 mm / s.
  • the reaction mixture was fed through a neck having a circular opening with a diameter of 0.5 mm in the narrowest cross section

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Fats And Perfumes (AREA)

Abstract

La présente invention concerne un procédé d'estérification d'acides gras libres dans des graisses végétales et animales, avec des alcools en présence de catalyseurs à résine échangeuse d'ions acides hétérogènes, à des températures de 60 à 120 °C.
EP08845101A 2007-10-30 2008-10-16 Procédé d'estérification à catalyse hétérogène d'acides gras Withdrawn EP2205709A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102007052064A DE102007052064A1 (de) 2007-10-30 2007-10-30 Verfahren zur heterogen katalysierten Veresterung von Fettsäuren
DE102008007431A DE102008007431A1 (de) 2008-02-01 2008-02-01 Verbessertes Verfahren zur heterogen katalysierten Veresterung von Fettsäuren
PCT/EP2008/008762 WO2009056230A1 (fr) 2007-10-30 2008-10-16 Procédé d'estérification à catalyse hétérogène d'acides gras

Publications (1)

Publication Number Publication Date
EP2205709A1 true EP2205709A1 (fr) 2010-07-14

Family

ID=40282276

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08845101A Withdrawn EP2205709A1 (fr) 2007-10-30 2008-10-16 Procédé d'estérification à catalyse hétérogène d'acides gras

Country Status (20)

Country Link
US (1) US8536357B2 (fr)
EP (1) EP2205709A1 (fr)
CN (1) CN101842472B (fr)
AR (1) AR070952A1 (fr)
AU (1) AU2008318000A1 (fr)
BR (1) BRPI0818795A8 (fr)
CA (1) CA2703811A1 (fr)
CL (1) CL2008003098A1 (fr)
CO (1) CO6270373A2 (fr)
CR (1) CR11401A (fr)
EA (1) EA201000583A1 (fr)
IL (1) IL204737A0 (fr)
MX (1) MX2010004637A (fr)
NI (1) NI201000074A (fr)
NZ (1) NZ584969A (fr)
SV (1) SV2010003552A (fr)
TW (1) TW200946673A (fr)
UY (1) UY31414A1 (fr)
WO (1) WO2009056230A1 (fr)
ZA (1) ZA201002940B (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011033346A1 (fr) * 2009-09-15 2011-03-24 Council Of Scientific & Industrial Research Procédé de conversion en biodiesel d'huiles peu coûteuses à teneur élevée en acides gras libres (agl)
EP2522712A1 (fr) 2011-05-13 2012-11-14 Cognis IP Management GmbH Procédé pour obtenir des esters d'alkyl d'acides gras inférieurs à partir de graisses et d'huiles
US8629291B1 (en) * 2012-11-27 2014-01-14 Menlo Energy Management, LLC Esterification of biodiesel feedstock with solid heterogeneous catalyst
US8580119B1 (en) 2012-11-27 2013-11-12 Menlo Energy Management, LLC Transesterification of biodiesel feedstock with solid heterogeneous catalyst
US8957242B2 (en) 2013-03-15 2015-02-17 Renewable Energy Group, Inc. Dual catalyst esterification
FR3015515B1 (fr) 2013-12-19 2016-02-05 IFP Energies Nouvelles Procede de pretraitement d'huiles vegetales par catalyse heterogene de l'esterification des acides gras
US10087397B2 (en) * 2014-10-03 2018-10-02 Flint Hills Resources, Lp System and methods for making bioproducts
ITUB20153130A1 (it) * 2015-08-14 2017-02-14 Pharmanutra S P A Acidi grassi cetilati, impianto per la loro preparazione e relativo uso
ES2660207B8 (es) * 2016-09-21 2019-01-10 Bio Oils Huelva S L Procedimiento de alta eficacia para la producción de alquil-ésteres de ácidos grasos mediante catálisis ácida y procedimiento de tratamiento
CN116478374A (zh) * 2023-03-15 2023-07-25 河北隆海生物能源股份有限公司 一种磺酸功能化多孔有机聚合材料及其制备方法与应用

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6042495A (ja) * 1983-08-17 1985-03-06 日清製油株式会社 油脂脱臭留出物のメチルエステル化法
DE3501761A1 (de) * 1985-01-21 1986-07-24 Henkel KGaA, 4000 Düsseldorf Verfahren zur vorveresterung freier fettsaeuren in rohfetten und/oder -oelen
DE19600025C2 (de) * 1996-01-03 1998-12-03 Henkel Kgaa Verfahren zur Herstellung von Fettstoffen
JP4156486B2 (ja) * 2003-10-14 2008-09-24 花王株式会社 脂肪酸エステルの製造法
US20060245949A1 (en) 2005-04-13 2006-11-02 Par Technologies, Llc Electromagnetically bonded pumps and pump subassemblies and methods of fabrication
AU2006254851A1 (en) * 2005-06-09 2006-12-14 Biosphere Environmental Energy Llc Systems and methods for esterification and transesterification of fats and oils
ITMI20060082A1 (it) * 2006-01-19 2007-07-20 Maurizio Germani Processo per la preparazione di biodiesel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009056230A1 *

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Publication number Publication date
NI201000074A (es) 2010-09-23
CN101842472B (zh) 2014-01-29
AU2008318000A1 (en) 2009-05-07
CO6270373A2 (es) 2011-04-20
CA2703811A1 (fr) 2009-05-07
US20090294358A1 (en) 2009-12-03
TW200946673A (en) 2009-11-16
BRPI0818795A8 (pt) 2016-04-26
CR11401A (es) 2010-11-02
MX2010004637A (es) 2010-05-14
WO2009056230A1 (fr) 2009-05-07
CL2008003098A1 (es) 2009-12-18
AR070952A1 (es) 2010-05-19
ZA201002940B (en) 2011-07-27
CN101842472A (zh) 2010-09-22
SV2010003552A (es) 2011-02-21
UY31414A1 (es) 2009-03-02
BRPI0818795A2 (pt) 2015-04-22
NZ584969A (en) 2012-05-25
EA201000583A1 (ru) 2010-10-29
US8536357B2 (en) 2013-09-17
IL204737A0 (en) 2010-11-30

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