EP1888504A1

EP1888504A1 - Transesterification methods

Info

Publication number: EP1888504A1
Application number: EP06763136A
Authority: EP
Inventors: Jochen Ackermann; Alexander May; Udo Gropp; Hermann Siegert; Bernd Vogel; Sönke BRÖCKER
Original assignee: Evonik Roehm GmbH
Current assignee: Roehm GmbH Darmstadt
Priority date: 2005-05-20
Filing date: 2006-05-12
Publication date: 2008-02-20
Also published as: TW200712049A; MX2007014488A; RU2452725C2; TWI331141B; MY143355A; KR20140004264A; JP2008545636A; CA2608317A1; KR20080039835A; BRPI0610862A2; WO2006122912A1; DE102005023976A1; US8889899B2; CN101203480A; ZA200709985B; RU2007146752A; CA2608317C; AU2006249010A1; US20080194862A1; CN104276949A

Abstract

The invention relates to transesterification methods, comprising the steps of A) mixing an organic acid a) with an ester b) and B) transferring the alcohol group of the ester b) to the acid a) in order to obtain the ester of the acid a) and the acid of the ester b), whereby the step B) is carried out in a distilling apparatus.

Description

Process for transesterification

The present invention relates to processes for the transesterification of organic acids with organic esters. Esters are generally prepared by reacting acids with alcohols or esters with an alcohol different from the alcohol residue of the ester. However, in special cases, esters are also obtained by transferring an alcohol residue from an organic ester to the acid group of an organic acid. This reaction is described, for example, in "Organikum", Wiley-VCH, 21st edition on page 494.

This reaction is often advantageous if the immediate reaction of the acid with the alcohol is difficult. Furthermore, this type of preparation is preferred if the organic ester used as starting material is obtained inexpensively in large quantities or is obtained as a by-product.

However, the above reaction has certain disadvantages. These result in particular in that the transesterification set forth above generally represents an equilibrium reaction. Accordingly, in the isolation of the products initially carried a large amount of starting materials originally used.

Furthermore, the implementation described in the literature requires a relatively large amount of energy due to the problems outlined above.

For these reasons, such a reaction has not hitherto been carried out on a larger scale.

In view of the prior art set out above, it was therefore an object to provide a method for transesterification which can be carried out simply and inexpensively. Another object of the invention was to provide a method in which the products can be obtained very selectively.

Another object of the present invention is to provide a process for transesterification, which can be carried out in high yields and with low energy consumption.

Furthermore, the process of the present invention should be practicable on an industrial scale.

These and other non-explicitly stated objects, which, however, are readily derivable or deducible from the context discussed herein at the outset, are solved by methods having all the features of patent claim 1. Advantageous modifications of the inventive methods are protected in the claims based on claim 1 ,

By carrying out the transfer of the alcoholic residue in a still, it is possible, in a manner which can not easily be foreseen, to carry out a process comprising the steps

A) mixing an organic acid a) with an organic ester b) and

B) transferring the alcohol residue of the ester b) to the acid a), whereby the ester of the acid a) and the acid of the ester b) are obtained, which has a particularly low energy requirement.

Moreover, the following advantages are achieved by the method according to the invention. > The products are obtained selectively and in many cases without the formation of significant amounts of by-products.

> The process according to the invention gives the products in high yields.

The process according to the invention can be carried out inexpensively, the energy requirement being particularly low.

The process of the present invention can be carried out on an industrial scale.

According to the invention, an organic acid a) is mixed with an organic ester b). The term organic acid is well known in the art. Usually, these are understood to mean compounds having groups of the formula -COOH. The organic acids may comprise one, two, three, four or more groups of the formula -COOH. These include, in particular, compounds of the formula R (-COOH) _n , in which the radical R is a group having from 1 to 30 carbon, which comprises in particular 1-20, preferably 1-10, in particular 1-5 and particularly preferably 2-3 carbon atoms, and n represents an integer in the range of 1 to 10, preferably 1 to 4 and more preferably 1 or 2.

The term "1 to 30 carbon group" denotes residues of organic compounds having 1 to 30 carbon atoms. In addition to aromatic and heteroaromatic groups, it also includes aliphatic and heteroaliphatic groups, such as, for example, alkyl, cycloalkyl, alkoxy, cycloalkoxy, cycloalkylthio and alkenyl groups. The groups mentioned can be branched or unbranched. According to the invention, aromatic groups are radicals of mononuclear or polynuclear aromatic compounds having preferably 6 to 20, in particular 6 to 12, carbon atoms.

Heteroaromatic groups denote aryl radicals in which at least one CH group has been replaced by N and / or at least two adjacent CH groups have been replaced by S, NH or O.

Preferred aromatic or heteroaromatic groups according to the invention are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1,3,4-oxadiazole , 2,5-diphenyl-1, 3,4-oxadiazole, 1, 3,4-thiadiazole, 1, 3,4-triazole, 2,5-diphenyl-1, 3,4-triazole, 1, 2.5 -Triphenyl-1, 3,4-triazole, 1, 2,4-oxadiazole, 1, 2,4-thiadiazole, 1, 2,4-triazole, 1, 2,3-triazole, 1, 2,3,4 - tetrazole, benzo [b] thiophene, benzo [b] furan, indole, benzo [c] thiophene, benzo [c] furan, isoindole, benzoxazole, benzothiazole, benzimidazole, benzisoxazole, benzisothiazole, benzopyrazole, benzothiadiazole, benzotriazole, dibenzofuran, dibenzothiophene , Carbazole, pyridine, bipyridine, pyrazine, pyrazole, pyrimidine, pyridazine, 1, 3,5-triazine, 1, 2,4-triazine, 1, 2,4,5-triazine, tetrazine, quinoline, isoquinoline, quinoxaline, quinazoline , Cinnoline, 1,8-naphthyridine, 1,5-naphthyridine, 1,6-naphthyridine, 1,7-Nap hthyridine, phthalazine, pyridopyrimidine, purine, pteridine or quinolizine, 4H-quinolizine, diphenyl ether, anthracene, benzopyrrole, benzooxathiadiazole, benzooxadiazole, benzopyridine, benzopyrazine, benzopyrazidine, benzopyrimidine, benzotriazine, indolizine, pyridopyridine, imidazopyrimidine, pyrazinopyrimidine, carbazole, aciridine, phenazine, Benzoquinoline, phenoxazine, phenothiazine, acridizine, benzopteridine, phenanthroline and phenanthrene, which may optionally be substituted.

Preferred alkyl groups include methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl, tert-butyl, pentyl, 2-methyl Methylbutyl, 1, 1-dimethylpropyl, hexyl, heptyl, octyl, 1,1,3,3-tetramethylbutyl, nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyl and the eicosyl group.

The preferred cycloalkyl groups include the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups which are optionally substituted with branched or unbranched alkyl groups.

The preferred alkenyl groups include the vinyl, allyl, 2-methyl-2-propylene, 2-butenyl, 2-pentenyl, 2-decenyl and 2-eicosenyl groups.

Preferred heteroaliphatic groups include the aforementioned preferred alkyl and cycloalkyl groups in which at least one carbon moiety is replaced by O, S or a group NR ⁸ or NR ⁸ R ⁹ , and R ⁸ and R ^{9 are} independently one to six carbon atoms having alkyl, a 1 to 6 carbon atoms having alkoxy or an aryl group.

Very particular preference according to the invention to the acids and / or esters according to the invention is branched or unbranched alkyl or alkoxy groups having 1 to 20 carbon atoms, preferably 1 to 12, advantageously 1 to 6, in particular 1 to 4 carbon atoms and cycloalkyl or cycloalkyloxy groups with 3 to 20 carbon atoms, preferably 5 to 6 carbon atoms.

The radical R may have substituents. Among the preferred substituents are i.a. Halogens, in particular fluorine, chlorine, bromine, and alkoxy or hydroxy radicals.

The particularly preferred acids a) include, inter alia, (meth) acrylic acids. The term (meth) acrylic acids is known in the art, including In addition to acrylic acid and methacrylic acid and derivatives of these acids are to be understood. These derivatives include, inter alia, β-methylacrylic acid (butenoic acid), α, β-dimethylacrylic acid, β-ethylacrylic acid, and β, β-dimethylacrylic acid. Preference is given to acrylic acid (propenoic acid) and methacrylic acid (2-methylpropenoic acid).

The organic acids a) can be used individually or as a mixture of two, three or more different acids.

The organic ester b) used for transesterification is also known in the art. Such compounds generally include groups of the formula -COO-R ', wherein R' represents a 1 to 30 carbon group.

The organic esters may comprise one, two, three, four or more groups of the formula -COO-R '. These include, in particular, compounds of the formula R (-COO R ') _n , in which the radical R represents from 1 to 30 carbon-containing group which comprises in particular 1-20, preferably 1-10, in particular 1-5 and particularly preferably 2-3 carbon atoms and n represents an integer in the range of 1 to 10, preferably 1 to 4, and more preferably 1 or 2, and the group R 'represents a group of 1 to 30 carbon.

The term "1 to 30 carbon group" has previously been defined.

The acid radical of the ester b) differs from the organic acid a) in at least one feature. For example. For example, the acid radical of the ester b) may have more carbon atoms than the organic acid a). In addition, the ester b) may have a different substitution pattern than the acid a). For example, the acid residue of the ester b) others Substituents, for example, have a different number of hydroxyl groups than the acid a)

The boiling point of the organic ester b) is preferably smaller than the boiling point of the ester a) obtained from the acid a) by reaction. Preferably, the difference is the boiling point at least 5 ⁰ C, particularly preferably at least 1O ⁰ C, this difference to a pressure of 1 bar and the boiling point of the pure substances is related.

The alcohol residue of the organic ester b) is also known in the art. Preferably, the alcohol residue has 1-20 carbon atoms, more preferably 1-10, especially 1-5 and most preferably 1-3 carbon atoms. The alcohol residue can be derived from a saturated or unsaturated alcohol as well as from an aromatic alcohol, for example phenol. The saturated alcohols preferably used include, among others. Methanol, ethanol, propanol, butanol, in particular n-butanol and 2-methyl-1-propanol, pentanol, hexanol and 2-ethylhexanol.

Particular preference is given to using an α-hydroxycarboxylic acid alkyl ester as the organic ester b). These include, inter alia, α-hydroxypropionic acid methyl ester, α-hydroxypropionic acid ethyl ester, α-hydroxyisobutyrate and ethyl α-hydroxyisobutyrate.

The organic esters b) can be used individually or as a mixture of two, three or more different esters.

In step A), at least one organic acid a) is mixed with at least one organic ester b), it being possible to use any process known for this purpose. The preparation of this mixture can done in the still. Furthermore, a mixture can also be produced outside the distillery.

In step B) the alcohol residue of the organic ester b) is transferred to the organic acid a), the ester of the acid a) and the acid of the ester b) being obtained. The conditions of this reaction, also referred to as transesterification, are known per se.

The reaction is preferably carried out at temperatures in the range of 5O ⁰ C to 200 ⁰ C, particularly preferably 7O ⁰ C to 13O ⁰ C, more preferably 8O ⁰ C to 12O ⁰ C and most preferably 9O ⁰ C to 110 ° C.

The reaction can be carried out at reduced or elevated pressure, depending on the reaction temperature. This reaction is preferably carried out at the pressure range of 0.02-5 bar, in particular 0.2 to 3 bar and particularly preferably 0.3 to 0.5 bar.

The molar ratio of organic acid a) to organic ester b) is preferably in the range of 4: 1-1: 4, in particular 3: 1 to 1: 3 and particularly preferably in the range of 2: 1-1: 2.

The transesterification may be carried out batchwise or continuously, with continuous processes being preferred.

The reaction time of the transesterification depends on the molar masses used and the reaction temperature, which parameter can be within wide limits. The reaction time of the transesterification of at least one organic ester b) with at least one organic acid a) is preferably in the range of 30 seconds to 15 hours, more preferably 5 minutes to 5 hours and most preferably 15 minutes to 3 hours. In continuous processes, the residence time is preferably 30 seconds to 15 hours, more preferably 5 minutes to 5 hours, and most preferably 15 minutes to 3 hours.

In the preparation of methyl methacrylate from α-Hydroxyisobuttersäuremethylester the temperature is preferably 60 to 130 ⁰ C, more preferably 80 to 12O ⁰ C and most preferably 90 to 110 ⁰ C. The pressure is preferably in the range of 50 to 1000 mbar, especially preferably 300 to 800 mbar. The molar ratio of methacrylic acid to α-hydroxyisobutyric acid methyl ester is preferably in the range of 2: 1-1: 2, in particular 1, 5: 1-1: 1.5.

The selectivity is preferably at least 90%, particularly preferably 98%. The selectivity is defined as the ratio of the sum of amounts formed of organic esters a) and organic acids b), based on the sum of the converted amounts of organic esters b) and organic acids a).

The reaction mixture may include, in addition to the reactants, other ingredients such as solvents, catalysts, polymerization inhibitors, and water.

The reaction of the organic ester b) with at least one organic acid a) can be catalyzed by at least one acid or at least one base. In this case, both homogeneous and heterogeneous catalysts can be used. Particularly suitable acidic catalysts are, in particular, inorganic acids, for example sulfuric acid or hydrochloric acid, and organic acids, for example sulphonic acids, in particular p-toluenesulphonic acid, and acidic cation exchangers. Particularly suitable cation exchange resins include in particular sulfonic acid-containing styrene-divinylbenzene polymers. Particularly suitable cation exchange resins can be obtained commercially from Rohm & Haas under the trade name Amberlyst® and from Bayer under the trade name Lewatit®.

The concentration of catalyst is preferably in the range of 1 to 30 wt .-%, particularly preferably 5 to 15 wt .-%, based on the sum of the organic ester used b) and the organic acid a).

Among the preferred polymerization inhibitors include phenothiazine, Tertiärbutylcatechol, hydroquinone monomethyl ether, hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidinooxyl (TEMPOL) or mixtures thereof; wherein the effectiveness of these inhibitors can be partially improved by the use of oxygen. The polymerization inhibitors may be in a concentration in the range of 0.001 to 2.0 wt .-%, particularly preferably in the range of 0.01 to 0.2 wt .-%, based on the sum of the organic ester used b) and the organic Acid a) can be used.

According to a particular aspect of the present invention, the transesterification can be carried out in the presence of water. Preferably, the water content is in the range of 0.1-50 wt .-%, more preferably 0.5-20 wt .-%, and most preferably 1-10 wt .-%, based on the weight of the organic ester used b ).

By adding small amounts of water, surprisingly, the selectivity of the reaction can be increased. Despite the addition of water, the formation of methanol can be kept surprisingly low. At a water concentration of 10 to 15 wt .-%, based on the Weight of the organic ester used b), preferably form less than 5 wt .-% methanol at a reaction temperature of 12O ⁰ C and a reaction time or residence time of 5 to 180 min.

According to the invention, the transfer of the alcohol residue of the organic ester b) to the organic acid a), i. the transesterification, in a still. For this purpose suitable distillation plants are well known and are often used for separation.

At least one organic ester b), for example an α-hydroxycarboxylic acid alkyl ester, and at least one organic acid a), for example (meth) acrylic acid, can be introduced into the distillate individually or as a mixture. The distillation conditions are preferably selected so that exactly one product is removed by distillation from the still, leaving the second product in the sump and continuously removed therefrom. Preferably, the ester a) obtained by the reaction is removed by distillation while the obtained acid b) is discharged from the bottom.

The still can be made from any suitable material. These include u.a. Stainless steel and inert materials.

If a catalyst is used, it may be provided in each area of the still. For example, the catalyst can be provided in the region of the bottom or in the region of the column. In this case, however, the starting materials should be brought into contact with the catalyst.

Furthermore, catalyst can be provided in a separate region of the still, this region being connected to the further regions of the still, for example the bottom and / or the column. This separate arrangement of the catalyst region is preferred wherein the reactants can be passed cyclically through the catalyst region. This produces continuously the ester of organic acid a), for example alkyl (meth) acrylate, and the acid of the organic ester b), for example α-hydroxycarboxylic acid.

This preferred embodiment surprisingly succeeds in increasing the selectivity of the reaction. In this connection, it should be noted that the pressure of the reaction can be adjusted independently of the pressure within the distillation columns. As a result, the boiling temperature can be kept low without the reaction time or the residence time increases accordingly. In addition, the temperature of the reaction can be varied over a wide range. This can shorten the reaction time. In addition, the volume of catalyst can be chosen arbitrarily, without having to take into account the geometry of the column consideration. Furthermore, for example, another reactant can be added. All of these measures can contribute to increasing selectivity and productivity, with surprising synergy effects.

A preferred embodiment of a still is shown schematically in FIG. The educts can be introduced into the distillation column (3) via a common line (1) or separately via two lines (1) and (2). The addition of the educts preferably takes place via separate lines. The starting materials can be supplied at the same stage or in any position of the column.

The temperature of the reactants can be adjusted via a heat exchanger in the feed, the necessary aggregates are not shown in Figure 1. In a preferred variant, the reactants are metered separately into the column, wherein the metered addition of the lower-boiling component below the position for the Feeding the high-boiling compound takes place. Preferably, the lower-boiling component is added in vapor form in this case.

For the present invention, any multi-stage distillation column (3) having two or more separation stages can be used. The number of separation stages in the present invention refers to the number of plates in a tray column or the number of theoretical plates in the case of a packed column or a packed column.

Examples of a multistage distillation column with trays include those such as bubble-cap trays, sieve trays, tunnel trays, valve trays, slotted trays, sieve-slotted trays, sieve-bubble trays, nozzle trays, centrifugal trays, for a multistage distillation column with packing such as Rasch ig-rings, Lessing rings, Pall Rings, Berl saddles, Intalox saddles and for a multistage distillation column with packings such as Mellapak (Sulzer), Rombopak (Kühni), Montz-Pak (Montz) and catalyst bag packs, for example Kata-Pak.

A distillation column having combinations of regions of soils, regions of packing or regions of packing may also be used.

The column (3) can be equipped with internals. The column preferably has a condenser (12) for condensing the vapor and a sump evaporator (18).

The distillation apparatus preferably has at least one region, referred to below as the reactor, in which at least one catalyst is provided. This reactor may be within the distillation column. However, this reactor is preferably arranged outside the column (3) in a separate area, one of these preferred embodiments being explained in greater detail in FIG. In order to carry out the transesterification reaction in a separate reactor (8), a portion of the downwardly flowing liquid phase can be collected within the column via a collector and passed as a partial stream (4) from the column. The position of the collector is determined by the concentration profile in the column of the individual components. The concentration profile can be controlled via the temperature and / or the return. The collector is preferably positioned so that the stream led out of the column contains both reactants, particularly preferably the reactants in a sufficiently high concentration and very particularly preferably in the molar ratio of acid: ester = 1.5: 1 to 1: 1.5. Furthermore, a plurality of collectors may be provided at different locations of the distillation column, wherein the molar ratios can be adjusted by the amount of reactants withdrawn.

In addition, another reactant, for example water, can be added to the stream removed from the column in order to adjust the product ratio of acid / ester in the cross-transesterification reaction or to increase the selectivity. The water can be supplied via a line from the outside (not shown in Figure 1) or removed from a phase separator (13). The pressure of the water-enriched stream (5) can then be increased via a means for increasing the pressure (6), for example a pump.

By increasing the pressure, formation of vapor in the reactor, for example a fixed bed reactor, can be reduced or prevented. As a result, a uniform flow through the reactor and wetting of the catalyst particles can be achieved. The stream can be passed through a heat exchanger (7) and the reaction temperature can be adjusted. The current can be heated as needed or be cooled. In addition, the product ratio of ester to acid can be adjusted via the reaction temperature.

In the fixed bed reactor (8), the transesterification reaction takes place on the catalyst. The reactor can be flowed through downwards or upwards. The reactor effluent (9) containing, to a certain extent, the products and the unreacted starting materials, the proportion of the components in the reactor effluent depending on the residence time, the catalyst mass, the reaction temperature and the reactant ratio and the amount of water added, is first passed through a heat exchanger ( 10) and adjusted to a temperature which is advantageous when introduced into the distillation column. Preferably, the temperature is set which corresponds to the temperature in the distillation column at the point of introduction of the stream.

The position where the stream leaving the reactor is returned to the column may be above or below the position for the removal of the reactor feed, but is preferably above. Before returning to the column, the stream can be vented via a valve (11), wherein preferably the same pressure level is set as in the column. In this case, the distillation column preferably has a lower pressure. This embodiment has the advantage that the boiling points of the components to be separated are reduced, whereby the distillation at a lower temperature level, thereby energy-saving and thermally gentle can be performed.

In the distillation column (3) then takes place the separation of the product mixture. The low boiler, preferably the ester formed in the transesterification, is separated overhead. Preferably, the distillation column is driven so that the water added before the fixed bed reactor is also separated off as overhead product. The am Head withdrawn, vaporous stream is condensed in a condenser (12) and then separated in a decanter (13) in the aqueous and Produktesterhaltige phase. The aqueous phase can be discharged via the line (15) for workup or completely or partially recycled via line (17) back into the reaction. The stream from the ester-containing phase can be driven via line (14) partly as reflux (16) on the column or be partially discharged from the still. The high boiler, preferably the acid formed in the cross-esterification, is discharged as the bottom stream from the column (19).

Hereinafter, the present invention will be explained in more detail by way of examples.

example 1

In a Reaktivdestille set forth in Fig. 1 4619 g of α-hydroxyisobutyrate (HIBSM) and 3516 g of methacrylic acid (MAS) were supplied over a period of 48 hours. The reaction was carried out at a temperature of 12O ⁰ C and a pressure of 250 mbar. Resulting α-hydroxyisobutyric acid (HIBS) was removed from the sump. Methyl methacrylate (MMA) was distilled off. The reaction was carried out in the presence of 16% by weight of water, based on the weight of α-hydroxyisobutyric acid methyl ester. The reaction was carried out using an acidic catalyst (cation exchanger, Lewatit® type K2431 from Bayer).

This results in a selectivity of 99%, which is defined as the ratio of the sum of amounts of MMA and HIBS formed to the sum of the converted amounts of HIBSM and MAS. Examples 2 to 18

Example 1 was substantially repeated except that no water was added to the reaction mixture. The reaction took place under the conditions given in Table 1, in particular with regard to the temperature, residence time and molar ratio of the educts. The selectivity of the reactions defined as the ratio of amounts of MMA and HIBS formed to quantities of HIBSM and MAS converted is also shown in Table 1.

Table 1

Examples 19 to 38

Example 1 was essentially repeated, but the reaction was carried out under the conditions given in Table 2, in particular with regard to the temperature and residence time. The molar ratio of HIBSM / MAS was 1: 1. Furthermore, different proportions of water were added, these also being set forth in Table 2. The selectivity of the reactions as well as the molar ratio of HIBS to MMA defined as the ratio of amounts of MMA and HIBS formed to quantities of HIBSM and MAS converted are also shown in Table 2.

Table 2

The above examples show that esters of very high selectivity can be formed by the present invention, with the ratio of products such as (alkyl) methacrylate to α-hydroxycarboxylic acid being close to unity even at relatively high water concentrations.

Accordingly, relatively little methanol is formed. The molar ratio of the products can also be controlled via the temperature.

Claims

claims

A process for transesterification comprising the steps

A) mixing an organic acid a) with an ester b) and

B) transferring the alcohol residue of the ester b) to the acid a), the ester of the acid a) and the acid of the ester b) being obtained, characterized in that the transfer of the alcohol residue of the ester b) to the acid a) according to Step B) is carried out in a still.

2. The method according to claim 1, characterized in that the method is carried out continuously.

3. The method according to claim 1 or 2, characterized in that the reaction step B) is carried out under acid catalysis.

4. The method according to any one of the preceding claims, characterized in that the acid comprises a) 1 to 10 carbon atoms.

5. The method according to claim 4, characterized in that the acid is methacrylic acid and / or acrylic acid.

6. The method according to any one of the preceding claims, characterized in that the ester b) 1 to 10 carbon atoms.

7. The method according to claim 6, characterized in that the ester is a 2-hydroxypropanoic acid ester and / or a 2-Hydroxybutansäureester.

8. The method according to any one of the preceding claims, characterized in that the alcohol radical has 1 to 10 carbon atoms.

9. The method according to claim 8, characterized in that the alcohol residue is derived from methanol and / or ethanol.

10. The method according to any one of the preceding claims, characterized in that the transesterification is carried out at a temperature in the range of 5O ⁰ C to 200 ⁰ C.

11. The method according to any one of the preceding claims, characterized in that the transesterification is carried out in the presence of water.

12. The method according to claim 11, characterized in that the water concentration is 0.1 to 50 wt .-%, based on the weight of the organic ester used b).

13. An apparatus for carrying out a method according to any one of claims 1 to 12, comprising at least one distillation column (3) and at least one reactor (8).

14. The apparatus according to claim 13, characterized in that the head of the distillation column (3) is connected to a phase separator (13), wherein the phase separator (13) with the reactor (8) is in communication.

15. The apparatus according to claim 13 or 14, characterized in that at least one line between the reactor (8) and the distillation column (3) is equipped with a means for increasing the pressure (6).