WO2018157183A1

WO2018157183A1 - Method for producing a fatty acid alkyl ester

Info

Publication number: WO2018157183A1
Application number: PCT/AT2018/060019
Authority: WO
Inventors: Matthias Binder; Josef Dörfler
Original assignee: Matthias Binder
Priority date: 2017-03-03
Filing date: 2018-01-23
Publication date: 2018-09-07
Also published as: AT519685A1; AT519685B1

Abstract

The invention relates to a method for producing a fatty acid alkyl ester, in particular a fatty acid methyl ester. According to said method a substance is produced using fat and/or oil, and said fat and/or oil is subjected to transesterification to produce the fatty acid alkyl ester, a nonpolar solvent being added to the substance prior to esterification and/or transesterification.

Description

Process for the preparation of a fatty acid alkyl ester

The invention relates to a process for preparing a fatty acid alkyl ester, in particular a fatty acid methyl ester, wherein a mass is provided with a fat and / or an oil, after which the fat and / or oil is subjected to transesterification to form the fatty acid alkyl ester.

Fatty acid alkyl esters, in particular fatty acid methyl esters, have lately acquired great importance as a fuel, so-called biodiesel, either as a pure fuel or in the form of an admixture with fossil diesel fuel.

There are a large number of variants based on alkali-catalyzed processes, such. WO 2002/038529 A1, WO 2004/029016 A1, WO 2000/075098 A1, WO 2002/02881 A1 and WO 2008/034485 A1. Among others, acid catalysts for the conversion of free fatty acids into fatty acid alkyl esters are used in these processes.

Also known are acid-catalyzed esterification and transesterification processes

Use of sulfonic acids.

In addition, various methods describe a transesterification and / or

Transesterification under pressure with different types of catalysts. Also, a heterogeneous catalysis, such. B. according to WO 2006/006033 A1 or WO 2007/012097 A1, is possible.

Enzymatic transesterification with lipases described, for. As in WO 2012/098114 A1, are known and described in detail as well as enzymatically catalyzed esterifications such. In WO 2008/125574 A1. Direct processing of extracted fats and oils

Oil extraction process according to the prior art and from a very complex organic matrix such as oil-containing distillation vats from the production of bioalcohol (eg., Bioethanol from oil / fatty raw materials without previous oil separation) in the form of thin still or thickened thin still, oil-containing Biomass concentrates with or without mechanical cell disruption are not yet known.

Oil separation processes based on a very complex organic matrix such as oil-containing distillation vats from the production of bioalcohol (eg bioethanol from oil / fat-containing raw materials without previous oil separation) in the form of thin still or thickened thin still, oil-containing biomass concentrates with or without mechanical cell disruption, work according to the state The technology largely with centrifuges and / or separators and / or static settlers to separate the mostly aqueous matrix of the oil-containing phase.

In the process of the prior art for the production of fats and oils from distillation vats, the fat and / or oil are entrained through all the stages of the evaporation and the quality of the fat and / or oil obtained is impaired by hydrolytic decomposition. Here are glycerides by the high

Temperatures, water vapor and by acid-catalyzing, short-chain carboxylic acids in fatty acids and glycerol cleaved.

In most cases, fats and oils with fatty acid contents of 10% or more are obtained, and the advantage of the mass ratios changed by the constriction is thereby unfavorably compensated.

The actual separation of the resulting fats and oils after concentration according to the prior art is usually carried out by centrifuges / separators. In addition to up to 1% of water or more partially hydrophilic components or impurities, such as Phosphoriipide, go into the oil phase and remain after the costly drying in the resulting oil. The percentages here and in the following, unless stated otherwise, relate to percent by weight (% by weight). In prior art extraction processes, the solvent used is always completely evaporated off to obtain a solvent-free grease and / or oil. This means a higher energy consumption and the necessary installation of additional equipment such as distillation columns, vacuum systems and capacitors. In addition, for an effective and clean separation of the hydrophobic and hydrophilic phase generally dynamic separation apparatus (separators, centrifuges) must be used, which on the one hand mean high investment, but in addition still high maintenance, maintenance and energy costs during operation.

In the case of degumming according to the prior art, accordingly, likewise

solvent-free grease and / or oil used after extraction or pressing.

There are a variety of procedures in this regard. Here on the one hand, the acid-catalyzed degradation of mucilage such as Phosphoriipide important so that the subsequent processing to

Fatty acid alkyl esters without problems such as emulsion formation and

Separation problems can be carried out and thus considerable

Process problems and production losses can be prevented.

On the other hand, efficient separation of all the hydrophilic products produced by the degradation is very important, not in the following

Fatty acid alkyl ester production to be problematic. In addition, most degumming processes are state of the art

Technique with aqueous, acidic degumming chemicals such as dilute phosphoric acid, which must then be separated by centrifuges and the resulting hydrophobic oil / fat phase must be dried by distillation to reduce the water content to harmless for further processing to fatty acid alkyl esters shares.

In all methods of transesterification according to the prior art, the separation of the resulting glycerol or the glycerol phase and in homogeneous catalysis, the separation of the catalyst from the fatty acid alkyl phase is very important, as well as the most complete removal of resulting alkali soaps.

Alkali soaps are formed in the reaction of fatty acids with the alkaline catalyst or in the use of hydroxides (eg potassium / sodium hydroxide) by the resulting reaction water (formation of the corresponding potassium or sodium). Methoxides) which cleaves fatty acid glycerides with the KOH in alkali soaps and glycerol - as desired in the production of soaps, but which are excreted as interfering by-products in the case of fatty acid alkyl ester production. Reaction water is also formed in the esterification of fatty acids. With the exception of glycerolysis (esterification with glycerol under vacuum and elevated temperature), this water remains at least partially in the reaction mixture and is not completely separated off with a phase separation, which causes an entry of interfering water into the following transesterification reaction. An efficient

However, separation of the resulting water of reaction is very important and necessary for connected transesterification.

Water in the transesterification causes in all processes that are alkaline

Catalysts work, soaps and thus significant losses or major challenges in the process.

In addition, water is a common companion of triglyceride starting materials; Especially in the case of used edible oils, Abscheiderfetten, animal fats and other problematic triglyceride starting materials, the water content can be up to about 2%, in certain cases, for example, high levels of free fatty acids and over 3%, with emulsion also over 8% water are possible. A corresponding drainage is therefore absolutely necessary.

The soaps are usually excreted in the various processes via the glycerol phase or washed out with water in multi-stage and complex process steps.

Purification of the fatty acid alkyl ester phase with ion exchangers is also possible. However, one must also keep the soap content as low as possible and also the content of free glycerin. This has a direct influence on the capacity of the ion exchanger and thus on the quality of the process.

In case of poor separation of soaps and / or glycerol from the

Fettsäurealkylesterphase arise considerable difficulties in the subsequent water washing, especially when using sodium-based catalysts (Na-methylate or NaOH) due to the fact that the resulting sodium soaps are a solid and are almost not separable. High levels of soap and glycerine also cause a high risk of

Emulsion formation in the transesterification or in the subsequent washing steps, which can lead to downtime of production plants.

The soap concentration is also dependent on the incoming content of free fatty acids in the triglyceride, which may be 1% for fresh oils and up to 5% and more for used edible oils.

The method according to WO 2000/075098 A1 describes the use of the polar glycerol phase with the alkaline catalyst as neutralization reagent, which neutralizes the fatty acids as soaps and removes them from the incoming triglyceride before the actual transesterification reaction.

This is a viable option, however, associated with significant losses since the

Fatty acids are lost as soaps and a significant part of the soaps remains dissolved in the triglyceride phase and hinders the separation of the polar glycerol phase of the fatty acid alkyl phase after the actual transesterification or cause significant problems in the subsequent washing / cleaning (emulsions, etc.) and stoppages of production facilities. In all processes, the completeness of the reaction is crucial. The currently applicable standards for z. For example, fatty acid methyl esters used as biodiesel prescribe low levels of glyceride. So max. 0.70% monoglyceride, max. 0.20%

Diglycerides and max. 0.20% triglycerides may be included in the biodiesel. When used in the admixture of biofuel in the fossil diesel a fatty acid methyl ester, especially the monoglyceride content is very crucial.

At higher levels of saturated fatty acid alkyl esters, especially in the

Admixture of fatty acid methyl esters in the fossil diesel, is by refineries However, a much lower monoglyceride content prescribed, for example, 0.50% or up to 0.20% when a palm oil-based fatty acid methyl ester is used. Low monoglyceride levels require a higher stoichiometric excess of methanol and higher levels of catalyst to push the reaction equilibrium to the side of the desired product. This in turn causes an increased residual solubility of glycerol and soaps or catalyst in the fatty acid alkyl ester phase and thus the above-mentioned difficulties.

One possibility for reducing the alkali content or the soap content in the fatty acid alkyl ester phase is the use of heterogeneous catalysts or the use of enzymatic catalysts. No soaps are released. However, in the reaction of glyceride in fatty acid alkyl esters with heterogeneous catalysts, these processes require very high temperatures, high pressures and excesses of alcohols, which have a negative effect on the processing costs and also reduce product quality due to the high temperatures.

In the case of enzymatic catalysts, a reaction at relatively low temperatures is possible, but also requires a high excess of alcohol and a reaction time of several hours.

Furthermore, one relies on the manufacturer of the corresponding lipase in the use of enzymes, so the catalyst is correspondingly expensive.

In both cases (heterogeneous and enzymatic catalysis) the conversion is not 100% and you miss most of the prescribed quality in the standards - in the case of fatty acid methyl esters the ester content. It is therefore necessary to introduce a further reaction step which compensates, if not increases, the economic advantages over homogeneous catalysts.

In addition, it is known that especially the monoglyceride content is a major problem. In some processes, the second reaction step after the heterogeneous or enzymatic catalysis is a homogeneous, and thus alkali-catalyzed, Reaction step performed, which compensates the previously mentioned benefits (soap, glycerin) again.

Compliance with the ester content or the "total glycerol content" is ensured in heterogeneous catalysis (process according to WO 2012/122197 A1), for example by distillation of the resulting fatty acid alkyl ester, as well as in the process

WO 2004/083350 A1, in addition to the increased sulfur content at the same time

Glyceride content almost to zero. The process according to WO 2007/012097 A1 provides for the distillation of the entire reaction mixture, ie the fatty acid alkyl ester with the by-product glycerol and the alkaline catalyst in the form of alkali and alkaline earth metal soaps

Bottom product, to be subsequently used again as a catalyst in the simultaneous esterification and transesterification.

Although the distillation of the entire mixture is advantageous due to the quality of the resulting fatty acid alkyl ester and glycerol, but the method is the same as the method according to WO 2012/122197 A1 not on the thermal stress and the expected decomposition products such. As acrolein and fat polymers or on the higher processing costs, which are caused by the high excess of alcohol and thermal energy.

Another possibility is offered by catalyst-free, supercritical processes in which a high pressure and temperature transesterification or simultaneous supply and

Transesterification is carried out.

The mostly one-step process also require very high excesses of alcohol and bring about the same problems as the previously described methods with fixed-bed catalysts such. B. residual solubilities of glycerol in the

Fatty acid alkyl ester phase, high energy input and incompleteness of the reaction in terms of compliance with the standard parameters. This can be counteracted with the addition of classic transesterification catalysts, but the initial advantage of the catalyst-free

Counteract the process. In general, not a single process provides a reasonable and economically viable overall solution to minimize residual solubility of glycerol in the fatty acid alkyl ester in either catalystless / heterogeneous or enzymatic processes and / or to reduce the resulting soaps to uncritical concentration or residual solubility of the catalyst in the fatty acid alkyl ester phase when using alkali catalysts Reduce quantities.

Further, all of the processes, particularly the use of used edible oils, precipitating fats, animal fats or other problematic triglyceride starting materials, reduce the solubility of polar impurities which subsequently remain in the alkyl ester and reduce quality, with the exception of costly and yield-reducing fatty acid alkyl ester distillation processes ,

Likewise, in most prior art processes, the amounts and contents of effluent from fatty acid alkyl ester purification are an additional problem.

Due to the catalyst residues, glycerol, salts and other components of the

Fatty acid alkylester laundry, especially in the production of biodiesel, which may also contain soaps, municipal wastewater treatment plants are often overwhelmed.

The object of the invention is to provide a method of the type mentioned, with which a phase separation is accelerated and the residual solubility of glycerol, soaps and residual catalyst in the fatty acid alkyl ester phase and generally the

Solubility of impurities in the glyceride phase or fatty acid alkyl ester phase is reduced, including the presence of water. This object is achieved when a non-polar solvent is added in a method of the type mentioned above the mass before esterification and / or transesterification. Advantageous variants of a method according to the invention are the subject of the dependent claims.

A method of producing fatty acid alkyl esters according to the present invention can be particularly applied by using vegetable oils, waste cooking oils, animal fats and oils, separating fats and, in general, fats and oils having predetermined levels of free fatty acids in the provided mass. The method is applicable both in the esterification of free fatty acids and in transesterification reactions.

The process is also advantageous in the extraction of oils and fats from a very complex organic matrix such as oil-containing distillation vats in the production of bioalcohol (eg bioethanol from oil / fatty raw materials without

preceding oil separation) in the form of thin still or thickened

Thin sludge, oil-containing biomass concentrates with or without mechanical

Cell disruption (eg Yarrowia lipolytica and oil-containing algal biomass), whereby the fatty acid alkyl ester production can be continued immediately without or with only partial previous separation of the organic solvent used.

Here, the process according to the invention in the extraction stage and the direct further processing of the extracted fat / oil with the process according to the invention offers a considerable advantage over the processes according to the prior art.

The method according to the invention can also be applied to the degumming of fats and oils. This results in a variety of improvements and benefits in process management, quality and cost-effectiveness.

The inventive use of non-polar solvents is carried out with simple mixing of the solvent. The solvent is preferably selected so that it is completely miscible with the fat and / or the oil and the hydrophobic fatty acid alkyl ester phase formed during the transesterification. Therefor the solvent may comprise at least one compound selected from the group consisting of n-, iso- or cycloalkane having 3 to preferably 30 carbon atoms, optionally substituted by halogens, and their ketone, ether and furan derivatives and / or aromatic compounds having 3 to preferably 30 carbon atoms, optionally substituted with nitrogen, oxygen and / or sulfur. Mixtures of such solvents can be used.

In particular, in the context of the invention, an n-alkane having 3 to 10 carbon atoms is added as the solvent.

Alkanes such as n-, iso-, cyclo-alkanes or aromatic compounds (including their halogenated forms and their ketone, ether and furan derivatives) with a

Minimum carbon content of 3 or mixtures thereof may be before one

Extraction step or before and / or after a reaction or purification step are introduced into the reaction mixture.

The solvent is preferably completely miscible with the fat / oil in the extraction step as well as in the hydrophobic fatty acid alkyl phase, but in the polar

hydrophilic phase is not or only minimally, whereby the nonpolar properties of the fat / oil or fatty acid alkyl ester phase increase dramatically. The polarity difference and the density difference are also increased.

According to the invention, the addition of solvents accelerates in addition to

Polarity difference, the settling or separation rate by the reduced viscosity and increases the quality of the separation of the polar phase of the hydrophobic fatty acid / fatty acid or fatty acid alkyl ester phase substantially.

In addition, in the present invention, the non-polar properties of the solvent push all polar and thus undesirable ingredients from the fatty / oil or fatty acid alkyl ester phase at least predominantly in the polar phase and thereby provide much higher process efficiency, reduction of back reactions in transesterification reactions and eliminate major problems For example, at

Use of too high stoichiometric amounts of alcohols in the transesterification incurred. With much more than stoichiometric addition of alcohols in transesterification reactions using alkaline catalysts, the completeness of the reaction is higher and the glyceride content is lower, but also the solubility of catalyst and free glycerol in the alkyl fatty acid phase is higher. This causes in the distillation of the excess alcohol back reactions of fatty acid alkyl esters in glycerides, which are catalyzed by the increased content of glycerol by the remaining catalyst. By using an additional solvent, the solubility of the free glycerol, of the catalyst and also of the excess alcohol is forced into the hydrophilic phase and, in the case of high excesses of alcohols, a phase separation is made possible in the first place.

Furthermore, when using the process according to the invention for alkali-catalyzed transesterification processes, both the resulting soaps and the catalyst used are almost completely forced into the polar phase, which leads to considerable advantages in connected purification steps.

In the esterification process according to the invention solvent is used to also increase the polarity and density difference and thus to force a better and cleaner separation of alkyl esters and the water of reaction containing hydrophilic phase or to allow the corresponding phase separation in the first place.

When carrying out aqueous purification steps, in the case of use according to the invention by the solvent, all the polar fractions are also almost completely forced into the aqueous phase, the remaining hydrophilic fraction in the aqueous phase

Alkyl fatty acid ester phase is very low.

The extraction of fats and oils from classic oilseeds such as rapeseed and

Soybeans in the prior art usually with n-hexane as extractant and is completely distilled off after completion of extraction from the oil and extraction meal. With the method according to the invention, the extraction is carried out with any suitable solvent and with the difference that the solvent is not distilled off from the oil / fat or not completely distilled off, but rather to a

According to the invention proportion remains in the extraction oil or fat and with in the

subsequent fatty acid alkyl ester production goes. This is particularly interesting for integrated manufacturing process systems, in which the processing from the oilseed to the finished fatty acid alkyl ester ranges. In this case, the method according to the invention offers considerable advantages over prior art methods.

The same inventive principle is used in the extraction / extraction of fats and oils from a very complex organic matrix such as oil-containing distillation vat from the production of bioalcohol (eg Distillers Com Oil from Bioalkoholherstellung without previous oil separation) in the form of Dünnschlempe or thickened

Dünnschlempe, oil-containing biomass concentrates such. B. oily algae biomass with or without mechanical Zellaufschluß applied.

An oil / fat extraction according to the invention with solvents simplifies the entire recovery process and the oil / fat can then be introduced directly into the process according to the invention for the preparation of fatty acid alkyl esters.

The extraction with the solvent according to the invention can be carried out before the separation of the solids ("wet cake") from the distillation still ("whole stills"). This reduces the losses of oil via the discharge of solids.

In comparison with prior art processes, in the case of extraction prior to separation of the solids, up to 90% of the contained oil, for example Distiller Com Oil, can be recovered. This is significantly more than on average 35% to 40% in prior art methods.

If the extraction after the solids separation before the constriction of

Completed distillation bottoms from the production of bio-alcohol, it prevents significant loss of quality and can use the inventive solvent in the subsequent process without separation.

The invention is also applicable after narrowing. The advantage here is as well as in an extraction before concentration at a much higher yield, easier handling, lower equipment complexity and drastically reduced water content of the extracted fat / oil. In both cases, both in the classical extraction in the course of oil mill processes as well as in the workup of distillation vats, by the drastically increased hydrophobic properties of the fat / oil phase by the extraction according to the invention hydrophobic impurities and only slightly hydrophobic impurities, which in the following Fatty acid alkyl ester production would cause significant problems, pushed by a large change in the distribution coefficient in the hydrophilic phase. Such impurities are, for example, phospholipids or proteins. According to the invention remains after the extraction, the total amount or parts of the inventive solvent in the fat / oil phase. If fat / oil is used for the fatty acid alkyl ester preparation according to the invention which does not yet contain a solvent according to the invention, it is added in the fatty acid alkyl production. The proportion of solvent can basically be selected within wide ranges. It is expedient if, based on the mass provided, 3% to 20%, preferably 5% to 15%, of solvent are added.

If a transesterification is carried out in several steps, the solvent is added in at least one step before the transesterification.

If the inventively obtained fats and oils or fats and oils from other sources require degumming ("degumming"), so this can also be done using the method according to the invention and the inventive

Solvent remain in the fat / oil phase or the fats and oils from other sources, the solvent of the invention are admixed.

The advantage of the method according to the invention is in turn also that hydrophilic components are removed from the hydrophobic and lipophilic phase and thus a significantly better degumming can be achieved. According to the invention, the degumming can be combined with the esterification of free fatty acids, since very low amounts of water in the fat / oil phase are due to the extraction according to the invention. Thus, the esterification reaction can be highly efficient and at the same time the degumming be carried out. This results in further advantages in the method according to the invention compared to the methods according to the prior art. On the one hand, a large part of the hydrophilic portions is forced into the so-called heavy phase due to the incoming phase separation by the additional increase in density and polarity differences, on the other hand is done by the density reduction and viscosity reduction much faster and cleaner separation than without inventive use of

Solvents.

Thus, in the esterification of fatty acids water of reaction, regardless of which catalyst is used. This water should be advantageously separated before the actual transesterification reaction of the glycerides in fatty acid alkyl esters. As a result of the embodiment of the method according to the invention, the majority of the water formed is forced into the hydrophilic, heavy phase and, as in the degumming according to the invention, is around or below 0.25% in the lipophilic, light phase. This effect is further enhanced when using acids as

Esterification catalysts, which are also almost completely forced into the hydrophilic phase.

The mixing behavior of the system fat / oil-alcohol solvent has proven particularly advantageous. Surprisingly, it was found that

For example, when using n-alkanes as a solvent in addition to the property of enhancing the hydrophobic properties, improving the separation behavior, etc. in addition significant amounts of alcohol in the hydrophobic phase of the esterification or combined degumming and esterification is solved, but only very little water, often less than 0.25%.

If glycerol is also added from the glycerol phase or from the glycerol phase preparation during degumming or combined degumming and esterification or transesterification before the phase separation, the water content in the lipophilic phase can be reduced to below 2,000 ppm (<0.2%). ), in particular below 1,000 ppm (<0, 1%) can be reduced.

The inventively increased solubility of alcohols in the lipophilic phase at the same time extremely low water content is a significant advantage in the subsequent transesterification of the glycerides, since a considerable amount of alcohol is already contained in the reaction mixture and no longer needs to be added.

In the esterification according to the invention, if no simultaneous or separate

Degumming is carried out, the reaction takes place continuously or batchwise, one or more stages, at room temperature to the boiling point of the alcohol and under pressure or without pressure, with the addition of alcohol and acid catalyst, which may also be a heterogeneous catalyst. The phase separation is carried out continuously or batchwise with static settling tanks or dynamic separators such as separators and centrifuges, wherein in the method according to the invention, the phase separation is so fast and complete that usually a static settling can be sufficient. In the method according to the invention, an extraction with glycerol phase can take place, which was obtained from the subsequent transesterification. This can be carried out at room temperature to the boiling point of the alcohol continuously or batchwise, under pressure or without pressure before the actual transesterification. The glycerol phase, which contains more than 90% of the alkaline transesterification catalyst due to the process of the invention, neutralizes unreacted free fatty acids and entrained acidic esterification catalyst and separates after completion of reaction again in a light, lipophilic and heavy, hydrophilic phase.

At the same time, the mixture of fat / oil, alcohol and solvent extracts all partial glycerides from the glycerol phase obtained from the transesterification and thus increases the yield of the process according to the invention. It can be stated that all unwanted constituents, such as alkali soaps from the neutralization of fatty acids, salts of the acidic esterification catalysts and residual water can be separated down to traces over the heavy phase and a fat / oil can be obtained which has no measurable acid number the water content is below 100 ppm. With a method according to the invention is therefore the water content is reduced to less than 500 ppm, in particular less than 300 ppm, and more preferably less than 100 ppm.

Surprisingly, the phase separation is fast and complete even if significant amounts of water and / or fatty acids in the fat / oil phase are, for example, the direct use of UCO and oil without upstream purification, esterification, drying or a combination thereof. Likewise, no increased alkaline soap content or water content in the extracted fat / oil phase is detectable.

The subsequent transesterification is carried out in one or more stages, at room temperature to the boiling point of the alcohol and under pressure or without pressure, with the addition of alcohol and alkaline catalyst, which may also be a heterogeneous catalyst. The phase separation is carried out continuously or batchwise with static settling tanks or dynamic separators such as centrifuges and / or separators, wherein in the method according to the invention, the phase separation is so fast and complete that usually a static settling is sufficient. If the transesterification is carried out in several stages, the glycerol phase obtained according to the invention can be introduced into the preceding transesterification stage, since the alkaline catalyst contained can once again have a catalyzing effect and the

Catalyst use can significantly reduce. The stoichiometric excess of alcohols in the transesterification reaction can be very high, since, in contrast to the processes of the prior art, the majority of the alkaline catalyst or any alkali soaps formed is forced into the heavy glycerol phase by the solvent used according to the invention and the subsequent phase separation is simple and done quickly.

Even with a moderate excess of alcohols, the content of alkali soaps can be more than 100%, especially when using alkali metal hydroxides as catalysts

2,500 ppm, with fatty acid contents of more than 1% in the starting glyceride also over

5,000 ppm and above. When using the method according to the invention, the content of alkali metal soaps in the fatty acid alkyl ester phase is also reduced at stoichiometric excesses of 200% to 300% alcohol and 1, 5% by weight alkali hydroxide to less than 250 ppm Alkaliseife.

A transesterification is preferably conducted on a basic basis with an alkali metal hydroxide and an alcohol (eg NaOH and methanol) or an alkali metal methoxide and an alcohol (eg.

Sodium methylate and methanol). The process of the invention is further characterized by a low level of free glycerol in the fatty acid alkyl ester phase, which, in contrast to the prior art processes, would cause considerable problems in the subsequent purification. The high excess of alcohols and higher additions or concentrations of alkaline catalyst lead to an almost complete reaction with very low residual amounts of glycerides. Especially with monoglycerides, the content is usually below 0.25 wt .-%, sometimes less than 0.20 wt .-%. The process is preferably carried out such that a glycerol content in the fatty acid alkyl ester is less than 0.5% by weight, preferably less than 0.35% by weight. As stated above, it is also possible to provide a composition which contains fatty acids. The fatty acids are also reacted, which increases the yield.

The content of monoglycerides in the obtained fatty acid alkyl ester phase is

crucial for the quality of the fatty acid alkyl ester, especially in the case of

Fatty acid methyl esters, which are used as biodiesel. Here, especially at high levels of saturated fatty acid methyl esters monoglyceride levels of below

0.50 wt .-%, in palm oil and animal fat methyl esters to below 0.25 wt .-% required, which can otherwise be achieved only with an expensive and complex distillation of the fatty acid methyl ester in a high vacuum. However, corresponding specifications are achieved with a method according to the invention.

In addition to the monoglycerides, the proportions of diglycerides and triglycerides in the application of the method according to the invention are very low and are at According to the invention execution under 0, 10 wt .-%, in many cases less than 0.05 wt .-%. In optimal conditions, these proportions are so low that they are no longer detectable. In addition, the use of the solvent leaves only traces of

Fatty acid alkyl ester in the glycerol phase, the effect of "entrainment" of

Fatty acid alkyl esters, but also glycerides in the glycerol phase is characterized by the

Use of solvents almost completely prevented. If the transesterification according to the invention is carried out with an alkaline catalyst such as an alkali metal hydroxide or an alkali metal alkoxide, the lower one allows

Residual solubility of catalyst and free glycerol in the process according to the invention distilling off the excess alcohol and the solvent, without thereby causing a back reaction of fatty acid alkyl ester in glycerides or to a

Emulsion formation comes. On the other hand, this is the case in many prior art methods.

In order to avoid this back reaction and emulsion formation, in the prior art prior to alcohol removal or drying of the fatty acid alkyl phase, a one-stage or multistage aqueous wash or a wash with strongly diluted acid or a combination thereof is carried out. The aqueous phase is subsequently separated from the fatty acid alkyl phase. This is done either by continuous or batch static settling or by centrifuges. For aqueous washes, in some prior art processes, 10% water or more, and when using sodium hydroxide as the transesterification catalyst, up to 40% water is also used because of the necessary multi-stage aqueous washes. This leads to an additional cleaning of the resulting aqueous phase, which consists of alcohol, water and / or dilute acid, glycerol, soaps and optionally of transesterification catalyst. In particular, the workup of the water / AI kohol- mixture means a greatly increased energy use and the need for Alkoholrektifikation to use the alcohol again in the transesterification can. This increases the processing and investment costs. When using alkali metal hydroxides as a catalyst, this effect is even higher. In practice, 0.15% to 0.50% soaps may be produced in the reaction mixture, which must subsequently be washed out or The soaps form only when the water is introduced into the crude fatty acid alkyl ester phase by the reaction of the hydroxide with water and the fatty acid alkyl ester, thus increasing the losses. This is problematic in that good mixing of water and crude fatty acid alkyl esters is important for efficient laundry. Too turbulent mixing, however, results in a strong emulsion formation, which can lead to the stoppage of the manufacturing process. in the

The process according to the invention can, unlike the processes of the prior art, be recycled without further work-up because of the absence of reverse reaction and the slight contamination with free glycerol, soaps and alkali catalyst, the recovered mixture of alcohol and solvent, but without triggering a reverse reaction. This is particularly important for the alcohol of crucial importance, since the complete cleaning and in the case of moisture in the alcohol, for example, by subsequent aqueous washing, the rectification of the alcohol can be omitted.

Firstly, the reverse reaction is prevented by the inventive method, secondly, significant amounts of energy saved by the reusable alcohol and third, a significantly cleaner fatty acid alkyl esters are obtained, the final cleaning is many times easier and cheaper.

When the process according to the invention is combined with an aqueous wash, it has surprisingly been found that almost the entire amount of the alcohol dissolved in the solvent fatty acid alkyl ester-alcohol phase changes into the aqueous phase. This significantly increases the cleaning effect and enhances the hydrophilic

Properties of the aqueous phase and increases the hydrophobic properties of the fatty acid alkyl ester phase. In the case of production of fatty acid methyl ester, a water content in the fatty acid alkyl ester phase could be determined after 1% water washing and static phase separation of less than 1,000 ppm, besides the small amount of alkali soaps of less than 20 ppm, sometimes less than 10 ppm. If more water remains in the fatty acid alkyl ester phase, removal of the water is much easier due to the solvent remaining, since the azeotrope is usually formed with the non-polar solvent. In addition, the condensate of nonpolar solvent and water usually separates into two phases and the solvent can usually be used again without further treatment. This can be particularly accurate inventive implementation after removing the solvent and the residual moisture of the fatty acid alkyl esters are used without further purification or refining. Also known is the cleaning with magnesium silicate powder ("dry wash" according to WO 2005/037969 A1), which adsorb free glycerol, soaps, alkali catalyst and other impurities through a large surface and structure and the raw

Clean fatty acid alkyl esters with it. This cleaning can be done before or after the separation of the excess alcohol, according to the manufacturer, about 1% adsorbent (mostly magnesium silicates) must be used per 1,000 ppm alkali soaps.

This cleaning method is very effective, but has the high cost of this

Absorbens and losses of fatty acid alkyl esters in the filter cake result and finally the landfill as waste as a further disadvantage. When cleaning with magnesium silicate powder ("dry wash") is combined with the process according to the invention, the lower concentration of free glycerol, soaps,

Alkali catalyst and other impurities the amount of adsorbent used drastically and thus also the mentioned disadvantages of magnesium silicate use. Also in this procedure, the separated alcohol or the alcohol solvent mixture can be used without further purification steps again in the production of fatty acid alkyl esters.

When using ion exchange resins for the fatty acid alkyl ester cleaning without prior alcohol separation, there is no risk of emulsification, but due to the high load of free glycerol, soaps, alkali catalyst and other impurities, the ion exchange capacity is quickly exhausted and it must be regenerated very often. This causes either short cycle times and thus frequent interruptions or high investment costs, if by high

Lonenaustauschermengen the cycle times are to be extended. When using alkali catalysts is usually preceded by an aqueous wash followed by drying to reduce the proportion of free glycerol, soaps and alkali catalyst and thus to extend the cycle times, but with all the disadvantages of the necessary treatment of the aqueous, alcohol-containing phase, which are processed got to. Furthermore, the fatty acid alkyl ester must be distilled absolutely dry, otherwise most of the ion exchange resins are deactivated. Will the cleaning of the combined with fatty acid alkyl ester with ion exchange resins with the inventive method, this has a decisive advantage over the methods of the prior art. Due to the small amounts of free glycerol, soaps, alkali catalyst and other impurities, even if alkali metal hydroxides are used as catalysts, the solvent and the alcohol can be advantageously reused without treatment or purification and the cycle times of the ion exchange resin increase drastically. Likewise, the decrease

Investment costs and by the reduced regeneration costs the running costs, as long as it is not a disposable resin. In addition, the drying of the fatty acid alkyl ester phase due to the unnecessary aqueous washing is eliminated.

A method according to the invention is particularly suitable for or for the production of biodiesel. In the following, the invention will be further discussed by way of examples. Example 1 - Transesterification of rapeseed oil

Rapeseed oil containing 0.25% free fatty acids and 2,000 ppm water was transesterified into biodiesel using a two step process using sodium methylate (30% solution) and methanol in a temperature range of 50 ° C to 60 ° C.

In a first transesterification step, 10% of methanol and 1.5% of sodium methylate, based in each case on rapeseed oil, were used for the transesterification and reacted for 30 minutes with constant stirring and then allowed to settle statically for 30 minutes. The obtained fatty acid methyl ester phase had a sodium content of 42 ppm.

In the second transesterification step, a 7.5% excess of methanol, based on the stoichiometric required amount, adjusted and a 1, 5% amount of sodium methylate used. According to the invention, different amounts of n-heptane were added in parallel batches (10%, 5% and 0%) 1 minute before completion of the second transesterification step and then allowed to settle statically for 30 minutes. In the batch without n-Heptanzugabe after weaning part of the

Excess methanol evaporated until the methanol content was 1, 5%.

The mixture was then allowed to settle again for 30 minutes and the resulting glycerol phase was removed. The obtained fatty acid methyl ester phases had a sodium content of only 26 ppm using 1.5% sodium methylate and the high excess of methanol when using 10% n-heptane, the batch with 5% a sodium content of 64 ppm and the batch without n Heptanzugabe after distilling off and settling a sodium content of 284 ppm.

Subsequently, a 1% water wash at about 50 ° C of each

Experimental approaches to which different amounts of n-heptane (10%, 5% and 0%) were added made. Table 1 below shows analytical results for the respective batches.

Table 1: In-process control in the biodiesel fraction after water washing

After the separation by distillation of n-heptane and methanol or in the batch without n-heptane after drying, quality-relevant parameters were determined in the finished biodiesel (see Table 2). Table 2: Selected analysis parameters in the produced biodiesel according to the production method according to the invention in comparison to the European standard DIN EN 14214: 10-04

By virtue of the n-heptane addition according to the invention, water-soluble constituents, such as catalyst residues and glycerol, were forced into the glycerol phase in an enhanced and enhanced manner from the biodiesel phase.

The risk of quality-reducing back reactions, such as the formation of monoglycerides in the batch without n-heptane addition, could be significantly reduced and the resulting fatty acid methyl esters showed a very low glyceride content.

Using palm oil, similar results could be obtained. Example 2 - Old cooking oil as starting material for biodiesel

As a starting product for the process test, a typical mixture obtained from the acid pre-esterification of waste cooking oil with sulfuric acid was used and had the following composition (in% m / m):

75.00% fatty acid triglycerides (= used cooking oil)

10.60% FAME (= fatty acid methyl ester resulting from the acid esterification of the free fatty acids) 0.75% FFA (= residual content of free fatty acids in the reaction product)

1, 51% water (= water in the reaction mixture including water of reaction as a result of

esterification)

1.13% sulfuric acid (= acidic esterification catalyst in the reaction mixture) 10.51% methanol (= remaining excess in the reaction mixture)

According to the invention 10% of n-heptane was added to the mixture at a temperature of about 55 ° C and stirred for 5 minutes. After switching off the stirring and static settling almost complete phase separation was present after 8 minutes and completed after 15 minutes. It was possible to separate 8.60% heavy phase.

The determination of the essential parameters in the light phase showed an acid number of 2.68 mg KOH / g (about 1.34% FFA) and a water content of 3.095 ppm.

This was followed by an extraction according to the invention with m / m 10% glycerol phase, which was obtained from a previous transesterification with potassium hydroxide. The

Glycerol phase contained about 8% water and about 5% soaps due to the use of KOH.

The extraction was carried out with stirring for 5 minutes at 50 ° C, then was allowed to settle static, with immediately after switching off the stirrer

Phase separation began and was complete after 10 minutes. Determination of the essential parameters in the light phase showed an acid value of 0.0 mg KOH / g, a water content of 840 ppm and a potassium content of only 9 ppm, which corresponded to a soap concentration of 72 ppm. By the high

Water content in the glycerol phase, the hydrophilic methanol was almost completely dissolved in the glycerol phase, the evaporable portion was 10.7% in the oil phase and therefore consisted largely of methanol.

In parallel, a portion of the batch was allowed to settle out of the esterification without addition of n-heptane. There was no phase separation; the mixture was cloudy under an emulsion-like consistency. One determined an expected high Water content of 14,000 ppm water according to Karl Fischer in the solution; even after glycerol phase addition, this value did not fall below 5,600 ppm. In addition, there was a significant effect of the temperature on the separation behavior in the absence of n-Heptanzugabe.

The oil phase obtained from the extraction with glycerol phase with n-heptane was then subjected to a two-stage transesterification with potassium hydroxide as a catalyst. The first transesterification was carried out with constant stirring using 1% KOH and 10% methanol at 55 ° C for 30 minutes, the second transesterification with 0.5% KOH and 9% methanol at the same temperature and reaction time. The phase separation started in the first and second transesterification immediately after switching off the stirrer and was complete after 20 minutes.

After completing the second transesterification step, a sample was taken from the fatty acid phase and analyzed. The values obtained could be determined with 0.28% monoglycerides, di- and triglycerides could not be determined because the values were below the limit of determination.

The evaporation rate in the fatty acid methyl ester phase after the first transesterification was 15.8%, the potassium content 12.7 ppm and after the second transesterification 14.7% evaporation rate and 52 ppm potassium. To determine the robustness of the method, after determination of the

Parameter in the fatty acid methyl ester phase, the separate phases mixed again and added without further addition of methanol or KOH again additional 10% rapeseed oil and the reaction at 58 ° C for 30 minutes with constant stirring

continued. As in the previous transesterification stages, an immediately beginning phase separation, which was complete after 20 minutes, appeared. The evaporation rate in the fatty acid methyl ester phase after the phase separation was 13%, the potassium content in the fatty acid methyl ester phase after 20 minutes settling time 20 ppm, when using a centrifuge as comparison 11 ppm potassium. Again, the glyceride levels were determined. The values could be determined with 0.35% monoglycerides and 0, 16% diglycerides become. Triglycerides could not be determined because the values are below the

Limit of determination.

Finally, a wash of the obtained fatty acid methyl ester phase was carried out with 1% water at 50 ° C. The stirring time at a slow stirring speed was only a few minutes.

The fatty acid methyl ester phase containing the added n-heptane and methanol, separated immediately after stopping the agitator of the aqueous phase, the static phase separation was completed after only 5 minutes.

The analysis of the obtained fatty acid methyl ester after water washing revealed a potassium value of 3 ppm potassium and a volatile content of 10.7%, consisting mainly of n-heptane and traces of methanol and a water value of 970 ppm. After the separation by distillation of n-heptane, methanol and traces of water, quality-relevant parameters were determined in the finished biodiesel. The corresponding values are shown in Table 3.

Table 3: Selected analysis parameters in the produced biodiesel according to the production method according to the invention in comparison to the European and American biodiesel standard

The distillatively separated azeotropic mixture of n-heptane and methanol requires no further purification and separation. Whose use was in the esterification tested several times and can be considered equivalent and its effect as the use of pure heptane.

Example 3 - Workup of a stillage

An oil and fat-containing sludge from the production of maize based on bioethanol was mixed with the solvent n-heptane at 50 ° C in order to efficiently separate and extract the oil fraction. The phase separation was carried out with a static settler. The separated oil / solvent mixture was then concentrated by partial distillative removal of the solvent n-heptane to a volume fraction in the range of 8% to 12% in order to obtain comparable values as in Examples 1 and 2. The resulting extracted Distillers Com Oil (DCO, corn oil derived from the vinasse) had properties as shown in Table 4.

Table 4: Thin / thick vats used and extracted Distillers Com Oil

Parameter Dünnschlempe "Thin Dickschlempe" Syrup "stilläge"

Dry matter (% m / m) 6.0 30.0

Oil content (% m / m) in the 1, 2% 7.3%

mash

Oil content (% m / m) in the TS 20.0% 24.3%

calc.

Extraction (1-stage) with n- 5% 10%

Heptanzugabe (% m / m) at

55 ° C

Yield of Com Oil 85% 90%

DCO-01 DCO-2

FFA content of 5.4% 14.3%

extracting oil

Water content after 142 ppm 320 ppm

Concentration to 8-10% n-heptane content The recovered corn oil DCO-1 and DCO-2 were subjected to acid esterification under conditions shown in Table 5 below.

Table 5: Formulation and reaction condition for the acid esterification of DCO

The phase separation started immediately after switching off the stirring element and was completed after 15 minutes.

The values obtained for free fatty acids and water in the light phase were 0.86% and 2.288 ppm water, respectively, for DCO-1 for FFA and for water, for DCO-2 for FFA 1.36% and 2.980 ppm.

The subsequent extraction with a glycerol phase based on potassium methylate (equivalently obtained amount of glycerol phase with a total of 1, 5% potassium methylate calculated on the amount of oil) resulted in both cases an FFA-free oil phase with an acid number of 0.0 mg KOH / g and a water content of 320 ppm for DCO-1 and 465 ppm for DCO-2, respectively.

The neutral distiller corn oil thus obtained was subjected to a two-stage transesterification in accordance with the invention, the glycerol phase obtained from the transesterification stage 2 containing the potassium methoxide contained as catalyst and methanol as

Transesterification alcohol in the transesterification stage 1 were used. Table 6: Recipe and reaction condition in the transesterification stage 1

The resulting fatty acid methyl ester phases were further processed without further analysis as shown in Table 7 in the transesterification stage 2.

Table 7: Recipe and reaction condition in transesterification stage 2

The resulting fatty acid phases had a very low potassium content of 52 ppm for DCO-1 and 42 ppm for DCO-2, respectively.

The fatty acid methyl esters of DCO-1 and DCO-2 contained in the transesterifications were subjected to distillation under reduced pressure and the methanol and the

Solvent completely evaporated. Subsequently, both were now solvent and methanol-free fatty acid alkyl esters to freeze the waxes and other sparingly soluble components cooled to 0 ° C and the precipitated waxes or other ingredients together with the rest Glycerol centrifuged by means of a centrifuge. As a result, the proportion of potassium further decreased because the soaps or catalyst were separated through the heavy phase together with the glycerin and the waxes. The Distillers Com Oil based and extracted according to the invention with solvent and solvent-derived fatty acid methyl esters were with an ion exchange resin from Lanxess with the type designation GF 202

finally cleaned. The fatty acid methyl esters obtained were in all parameters of EN 14214 and further characterized by a low glyceride content. Table 8 shows selected analysis results.

Table 8: Selected analysis results of the biodiesel produced from DCO compared to the standard requirement DIN EN 14214: 10-04

As the above examples demonstrate, the application of the invention is very flexible and per se allows application in combination with any known prior art method. In addition, the possibility exists with the

Processes according to the invention older production plants, according to the state of

Produce technology to convert to the inventive method. The invention is also applicable to extraction processes when the extractant

(Solvent) remains in the oil / fat phase, which in the subsequent

Fatty acid alkyl ester production without separation are used according to the invention can. At the same time, it is possible to use solvents which are substantially non-toxic, do not take part in the reaction and, after carrying out the process according to the invention, are easily, simply and inexpensively removable and reusable, in order to further increase economic efficiency.

Claims

claims

1. A process for the preparation of a fatty acid alkyl ester, in particular one

Fatty acid methyl ester, wherein a mass is provided with a fat and / or an oil, after which the fat and / or the oil is transesterified to form the fatty acid alkyl ester, characterized in that the mass before esterification and / or transesterification non-polar solvent is added.

2. The method according to claim 1, characterized in that the solvent with the fat and / or the oil and formed during the transesterification hydrophobic

Fatty acid alkyl ester phase is completely miscible.

3. The method according to claim 1 or 2, characterized in that the

Solvent at least one compound selected from the group consisting of n-, iso- or cycloalkane having 3 to preferably 30 carbon atoms, optionally substituted by halogens, and their ketone, ether and furan derivatives and / or aromatic

Compounds having 3 to preferably 30 carbon atoms, optionally substituted with nitrogen, oxygen and / or sulfur.

4. The method according to any one of claims 1 to 3, characterized in that an n-alkane having 3 to 10 carbon atoms is added as a solvent.

5. The method according to any one of claims 1 to 4, characterized in that a mass is provided with a proportion of fatty acids.

6. The method according to any one of claims 1 to 5, characterized in that based on the provided mass 3% to 20%, preferably 5% to 15%, solvents are added.

7. The method according to any one of claims 1 to 6, characterized in that the transesterification is carried out in several steps, wherein in at least one step before the transesterification, the solvent is added.

8. The method according to any one of claims 1 to 7, characterized in that a glycerol content in the fatty acid alkyl ester less than 0.5 wt .-%, preferably less than 0.35 wt .-%, is.

9. The method according to any one of claims 1 to 8, characterized in that a mass is provided which contains fatty acids.

10. The method according to any one of claims 1 to 9, characterized in that before the transesterification from the mass with the solvent, the fat and / or the oil is extracted, after which optionally a portion of the solvent is withdrawn.