DE102015209819B4 - New process for the preparation of novel epoxidized synthetic building blocks based on vegetable oils - Google Patents

Abstract

Process for the epoxidation of unsaturated compounds, the process comprising the following steps:
a) providing at least one unsaturated compound, at least one oxygen donor, at least one oxygen acceptor and at least one enzyme having perhydrolase activity,
b) reacting the at least one oxygen acceptor provided in step a) with the at least one oxygen donor provided in step a) in the presence of the at least one enzyme provided in step a) with perhydrolase activity in an inhomogeneously mixed, organic or oily phase and an aqueous phase containing reaction mixture to provide at least one peracid,
c) reacting the at least one peracid produced in step b) with the at least one unsaturated compound provided in step a), so that at least one epoxidized compound is obtained, and
d) obtaining the at least one epoxidized compound.

Description

The present invention relates to a process for the epoxidation of unsaturated compounds.

Vegetable oils and fats are very important for the chemical industry as renewable raw materials. The world production of the nine main vegetable oils in 2010/2011 amounted to 148 million tons. Epoxidized vegetable oils, in particular epoxidized triacylglycerides (ETAG), are valuable precursor compounds in oil chemistry and can be used as polymer building blocks for biopolymers, in particular biodureases.

Other uses of epoxidized fatty mixtures could be PVC plasticizers and stabilizers.

In contrast to conventional plastics, biopolymers are obtained from renewable raw material sources. In particular, their monomers can be synthesized by a biotechnological route.

The majority of industrially produced ETAGs are produced via the so-called Prileschajew epoxidation reaction. In this reaction, a peracid is used for oxygen transfer to the double bonds in an unsaturated fatty acid chain. The peracid is usually formed from hydrogen peroxide and acetic acid or formic acid under harsh reaction conditions and the use of a strong mineral acid or an ion exchange resin as a catalyst. In the presence of the strong acid in the reaction mixture and by the reaction temperature, unwanted side reactions, for example the formation of diols, hydroxy esters, estolides and other dimers, through the opening of the epoxide group, also referred to as oxirane.

This chemical epoxidation process can in principle be done in two different ways. The first reaction pathway comprises the ex situ formation of a peracid within a separated reactor, followed by a reaction of the peracid with the unsaturated compound to be epoxidized in another reactor. However, this reaction path is difficult to handle because of the safety precautions to be taken for storage of the produced explosive and highly corrosive peracid. The second reaction pathway is characterized by the in situ formation of the peracid. In this case, the reaction takes place under strongly acidic reaction conditions and a simultaneous epoxidation in the same reactor. This method prevents the dangerous storage and handling of ex situ formed peracids. However, after the complete reaction, high salt neutralization is required as a waste stream. In addition, the highly acidic and corrosive reaction conditions can lead to unwanted side reactions and corrosion in the system.

• DE 195 42 933 A1 offenbart die Epoxidierung von ungesättigten, natürlichen Lipiden und die weitere Umsetzung zu Glycidestern.
• DE 10 2009 018 634 A1 offenbart die Verwendung von epoxidierten Pflanzenölen, beispielsweise epoxidierten Leinsamen- oder Drachenkopfölen, zur Herstellung von Polyether-basierten Überzugsmaterialien.
• US 6,734,315 B1 offenbart eine Dünnfilm-Epoxidierung von ungesättigten Ölen oder Alkylfettsäureestern in einem kontinuierlichen Prozess. Bei diesem Verfahren werden verschiedene Hydroperoxide, beispielsweise Wasserstoffperoxid, tert-Butylhydroperoxid, Cumylhydroperoxid sowie Molybdate und Voctoate enthaltende Katalysatoren eingesetzt.
• In EP 0 100 119 A1 werden olefinische Komponenten, wie Ethylen, Propylen, 2-Buten und 1-Octen, unter Verwendung von wässrigem Wasserstoffperoxid als Oxidationsmittel in Gegenwart von Titan-haltigen, künstlichen Zeolithen und Lösungsmitteln epoxidiert. Dieser Prozess ist jedoch nachteilig, da die Epoxid-Ausbeute durch die anschließende säurekatalysierte Weiterreaktion der Epoxide mit Wasser oder dem Lösungsmittel verringert wird.
• US 5,675,026 offenbart eine Kombination von Zeolithen, welche sowohl Titan-Katalysatoren als auch neutrale oder säurereaktive Salze enthalten.
• WO 2012/098295 A1 offenbart die Verwendung von Peroxomonosulfat unter pHgeregelten Bedingungen, um epoxidierte pflanzliche Öle, vorzugsweise aus Rapsöl, herzustellen.
• US 2010/0197820 A1 offenbart die Epoxidierung von Sojaöl zusammen mit Stearinsäure in Toluol unter Verwendung einer Lipase.
• WO 2010/098651 A1 offenbart ein Verfahren zur Epoxidierung von pflanzlichen Ölen, insbesondere von Palm- oder Palmkernölen, durch chemo-enzymatische Umsetzung unter Verwendung einer Lipase als Biokatalysator. Diese Öle sind dadurch charakterisiert, dass sie einen relativ geringen Anteil an ungesättigten Fettsäuren, beispielsweise einen Anteil von 55% in Palmöl und von nur 20% in Palmkernöl, enthalten.
• WO 2010/015715 A2 offenbart, dass immobilisierte Lipasen aus Candida antarctica und Candida parapsilosis dazu verwendet werden können, Oxirangruppen in verschiedenen Pflanzenölen zu erzeugen.

Various methods for the epoxidation of vegetable oils have already been described in the prior art:

• DE 195 42 933 A1 discloses epoxidation of unsaturated, natural lipids and further conversion to glycidic esters.
• DE 10 2009 018 634 A1 discloses the use of epoxidized vegetable oils, for example, epoxidized linseed or dragonhead oils, to produce polyether-based coating materials.
• US 6,734,315 B1 discloses a thin film epoxidation of unsaturated oils or alkyl fatty acid esters in a continuous process. In this process, various hydroperoxides, for example hydrogen peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide and molybdate and Voctoate containing catalysts are used.
• In EP 0 100 119 A1 For example, olefinic components such as ethylene, propylene, 2-butene, and 1-octene are epoxidized using aqueous hydrogen peroxide as the oxidant in the presence of titanium-containing, artificial zeolites and solvents. However, this process is disadvantageous because the epoxide yield is reduced by the subsequent acid-catalyzed further reaction of the epoxides with water or the solvent.
• US 5,675,026 discloses a combination of zeolites containing both titanium catalysts and neutral or acid-reactive salts.
• WO 2012/098295 A1 discloses the use of peroxomonosulfate under pH controlled conditions to produce epoxidized vegetable oils, preferably rapeseed oil.
• US 2010/0197820 A1 discloses the epoxidation of soybean oil along with stearic acid in toluene using a lipase.
• WO 2010/098651 A1 discloses a process for the epoxidation of vegetable oils, in particular palm or palm kernel oils, by chemo-enzymatic reaction using a lipase as biocatalyst. These oils are characterized by containing a relatively low level of unsaturated fatty acids, for example, 55% in palm oil and only 20% in palm kernel oil.
• WO 2010/015715 A2 discloses that immobilized lipases from Candida antarctica and Candida parapsilosis can be used to produce oxirane groups in various vegetable oils.

Hilker et al. ("Chemo-enzymatic epoxidation of unsaturated plant oils", Chemical Engineering Science 2001, 56th Ed., No. 2, pp. 427-432) discloses a process for the chemo-enzymatic epoxidation of unsaturated vegetable oils wherein in a multiphase process the fatty acid is reacted with hydrogen peroxide in the presence of lipase to form a peracid and then the unsaturated compound is epoxidized and obtained with the peracid.

Several known from the prior art methods have the disadvantage that they can not be used on an industrial scale due to the existing security risks. There is therefore a need for a method that overcomes these security risks.

It is therefore an object of the present invention, in particular to overcome the aforementioned disadvantages, and in particular to provide a method in which unsaturated compounds can be epoxidized under mild and safety-harmless reaction compounds. In particular, methods should be provided which are suitable for large-scale application.

The technical problem underlying the invention is solved by the technical teaching of the independent claims.

1. a) Bereitstellen mindestens einer ungesättigten Verbindung, mindestens eines Sauerstoff-Donors, mindestens eines Sauerstoff-Akzeptors und mindestens eines Enzyms mit Perhydrolase-Aktivität,
2. b) Umsetzen des mindestens einen in Schritt a) bereitgestellten Sauerstoff-Akzeptors mit dem mindestens einen in Schritt a) bereitgestellten Sauerstoff-Donor in Anwesenheit des mindestens einen in Schritt a) bereitgestellten Enzyms mit Perhydrolase-Aktivität in einem inhomogen durchmischten, eine organische oder Ölphase und eine wäßrige Phase aufweisenden Reaktionsgemisch, sodass mindestens eine Persäure erhalten wird,
3. c) Umsetzen der mindestens einen in Schritt b) hergestellten Persäure mit der mindestens einen in Schritt a) bereitgestellten, ungesättigten Verbindung, sodass mindestens eine epoxidierte Verbindung erhalten wird und
4. d) Erhalten der mindestens einen epoxidierten Verbindung.

In particular, the present technical problem is solved by a process for the epoxidation of unsaturated compounds, the process comprising the following steps:

1. a) providing at least one unsaturated compound, at least one oxygen donor, at least one oxygen acceptor and at least one enzyme having perhydrolase activity,
2. b) reacting the at least one oxygen acceptor provided in step a) with the at least one oxygen donor provided in step a) in the presence of the at least one enzyme provided in step a) with perhydrolase activity in an inhomogeneously mixed, organic or oily phase and an aqueous phase containing reaction mixture to provide at least one peracid,
3. c) reacting the at least one peracid produced in step b) with the at least one unsaturated compound provided in step a), so that at least one epoxidized compound is obtained, and
4. d) obtaining the at least one epoxidized compound.

The term "enzyme with perhydrolase activity" is understood to mean that a peracid can be formed by the corresponding enzyme from a carboxylic acid or a carboxylic acid derivative, preferably a carboxylic acid ester, and an oxygen donor, preferably hydrogen peroxide, preferably in situ. The corresponding enzyme is thus capable of producing a peracid from carboxylic acids or carboxylic acid derivatives in the presence of an oxygen donor, in particular hydrogen peroxide H ₂ O ₂ , preferably present in aqueous solution or bound to urea.

The term "peracid" in the context of the present invention means a peroxy acid. Accordingly, the peracid as a functional group has a CO ₃ H group.

The term "lipase" is understood to mean an enzyme which is primarily suitable for hydrolyzing esters, in particular oil-soluble or water-soluble esters. The lipases of the invention also have the ability to form a peracid from a carboxylic acid or a carboxylic acid derivative, especially a carboxylic acid ester. A corresponding perhydrolase activity is not present in any lipase known in particular from the prior art.

The term "unsaturated compound" is understood according to the invention to mean a compound having at least one double bond which can be converted to an epoxide by means of an enzyme having perhydrolase activity, an oxygen donor and an oxygen acceptor.

The term "oxygen donor" is understood as meaning a compound which, under the reaction conditions preferably present according to the invention or according to the invention, can be transferred to an oxygen acceptor in the presence of an enzyme having perhydrolase activity. The oxygen donor preferably has a peroxide group, i. an O-OH group, on.

In the context of the present invention, the term "oxygen acceptor" is understood as meaning a compound which is capable of absorbing an oxygen of the oxygen donor in the presence of an enzyme having perhydrolase activity under the reaction conditions preferably present according to the invention or according to the invention. The oxygen acceptor preferably has a CO ₂ R group, where R is a hydrogen atom or a substituted or unsubstituted alkyl radical, preferably having 1 to 24 C atoms.

The "iodine number" in the context of the present invention is an index for the characterization of an unsaturated compound, preferably of fats and oils. It is a measure of the content of double bonds in the unsaturated compound, preferably a fat or an oil, preferably in an epoxidized oil. The iodine value is the amount of iodine that can be formally added to 100 g of the unsaturated compound, preferably fat or oil.

The term "max (OO) in%" is understood to mean the maximum epoxy oxygen content achievable in the respective oil. The epoxy oxygen content thus describes the mass fraction of the oxygen bound in epoxide groups based on the product mass. The maximum OO content can be calculated, for example, from the iodine value of the oil.

The term "inhomogeneous mixing" means that during the reaction in step b) and / or c) the aqueous phase which is immiscible or only in very small amounts with the organic or oily phase is only partially dispersed or emulsified in the organic or oily phase , The aqueous phase and the organic or oil phase can preferably form a phase boundary in the non-partially mixed state, ie in the idle state. Preferably, the reaction mixture according to steps b) and / or c) at least three different sections, wherein the first section predominantly, preferably to 90 wt .-% or more, preferably to 95 wt .-% or more, preferably 99 wt % or more, the aqueous phase, the second portion predominantly, preferably to 90 wt .-% or more, preferably to 95 wt .-% or more, preferably to 99 wt .-% or more, the organic or oil phase and the third section comprises a mixture of organic or oily phase and aqueous phase, wherein in the third section the organic or oily phase is preferably emulsified or dispersed in the aqueous phase or the aqueous phase is preferably emulsified or dispersed in the organic or oily phase. Particularly preferably, in the third section, the aqueous phase is emulsified or dispersed in the organic or oily phase. The first, aqueous portion preferably has little or no organic or oil phase, preferably in droplet form. The second section preferably has little or no aqueous phase. Preferably, the third section is between the first and second sections. Preferably, the emulsified or dispersed droplets of the organic or oily phase or the aqueous phase of the third section have a size distribution, wherein at least 50%, preferably at least 90% of all emulsified droplets have a particle size of greater than 10 μm, preferably greater than 20 μm and / / or at least 50%, preferably at least 90% of all droplets have a diameter of less than 1 mm, preferably less than 500 μm. The mass of the organic or oily phase in the third section is preferably greater by a factor of at least 10, preferably at least 100, than in the first aqueous phase. The proportion of the third portion (based on the total volume of the reaction mixture and a temperature of 20 ° C.) is preferably at least 10% by volume, preferably at least 20% by volume, preferably at least 30% by volume, and / or preferably not more than 90% by volume, preferably not more than 70% by volume, preferably not more than 50% by volume, preferably not more than 40% by volume. The term "inhomogeneous mixing" is preferably understood to mean that the organic or oily phase is not uniformly distributed in the reaction mixture, ie it is not uniformly emulsified or dispersed. Preferably, the concentration of the organic or oil phase in the aqueous phase is not the same everywhere. The presence of the three different sections, namely the first, second and third sections, can preferably be recognized by a different optical density. The transitions between the different sections are fluid.

The inhomogeneous mixing preferably also occurs in a fixed bed reactor, preferably in a fluidized bed reactor. Preferably, the aqueous phase and the organic or oil phase in the fixed bed, preferably in the fluidized bed, inhomogeneously distributed. The aqueous phase is preferably not homogeneously dispersed in the organic or oil phase.

Preferably, in addition to the organic or oil phase and the aqueous phase, the enzyme, preferably the immobilized enzyme, is inhomogeneously distributed in the reaction mixture. Preferably, the concentration of the enzyme, preferably of the immobilized enzyme, is inhomogeneous in the reaction mixture.

Due to the inhomogeneous distribution, it has surprisingly been found that a virtually constant conversion rate and / or yield-in comparison to a homogeneous mixing of the reaction mixture-is achieved. The inhomogeneous mixing also increases the cycle stability, including the recycling rate, of the enzyme used, in particular immobilized, whereby an increased number of reactions of the at least one unsaturated compound can be carried out with one and the same enzyme. This leads to significantly reduced costs with a virtually constant conversion rate and / or yield.

A "fragment of a protein" is understood to mean a subregion of a protein, this subregion still representing an enzyme with perhydrolase activity. In a preferred embodiment, the fragment has at least 100, preferably at least 150, preferably at least 200, preferably at least 250, preferably at least 300 amino acids. The homology of the fragment according to the invention over its entire length to the amino acid sequence encoding an enzyme having perhydrolase activity is at least 80%, preferably at least 85%, preferably at least 90%, particularly preferably at least 95%, preferably at least 96%, preferably at least 97%, preferably at least 98%, more preferably at least 99%.

In this case, the term "reaction mixture" is understood as meaning the mixture of all components present in step b) and / or c) in a reactor which are used in the process according to the invention or according to the invention for the epoxidation of the at least one unsaturated compound. Preferably, the reaction mixture at the beginning of step b) therefore comprises the at least one oxygen donor, the at least one oxygen acceptor, the at least one enzyme with perhydrolase activity, water and optionally at least one organic solvent, preferably consisting thereof. Preferably, the reaction mixture at the beginning of step c), the at least one unsaturated compound, the at least one peracid, and optionally water and / or at least one organic solvent, it preferably consists thereof. If the peracid is prepared in situ, the reaction mixture at the beginning of steps b) and c) preferably has the at least one unsaturated compound, the at least one oxygen donor, the at least one oxygen acceptor, the at least one enzyme with perhydrolase activity, Water and optionally at least one organic solvent, preferably consisting thereof. For the purposes of the present invention, "homology", also referred to as sequence homology, with respect to an amino acid sequence is understood as meaning variations in individual amino acids in the sequence which do not impair the function of the polypeptide change. Homology determination is performed by sequence comparisons with alignments using computer programs and special algorithms such as BLAST. The methods of an "alignment" are known to the person skilled in the art and are carried out using computer programs and special algorithms, for example BLAST. According to the invention, the alignment is preferably performed by the BLAST algorithm with the BLOSUM62 matrix.

The proteins with perhydrolase activity are preferably wild-type proteins or recombinantly produced proteins, preferably mutant perhydrolases.

The recombinant production is carried out by a known in the prior art method for culturing prokaryotic and eukaryotic host cells in a culture medium and under cultivation conditions that lead to the expression of the present proteins. Also known to those skilled in numerous methods for the isolation of correspondingly expressed proteins from a cell and / or from the culture medium.

An advantage of the present invention is that even non-edible oils with a high proportion of double bonds and / or a very long chain length, which are preferably obtained from industrial waste streams, can be epoxidized. The "non-edible oils" are characterized in particular by the fact that they have a high proportion of impurities not suitable for consumption. In particular, these non-edible oils have a proportion of not suitable for consumption impurities of at least 0.1 wt .-%, preferably at least 1 wt .-%, preferably at least 5 wt .-% (based on the total dry weight of the non-edible oil). Preferably, these oils have no food grade. Preferably, these oils have an erucic acid content of at least 0.1 wt .-%, preferably at least 1 wt .-%, preferably at least 5 wt .-%, (based on the total dry weight of the non-edible oil).

Advantageously, the present process makes it possible to provide, on an industrial scale, a very efficient and highly pure epoxidation of a wide variety of starting materials having at least one unsaturated compound.

According to the invention, by means of an enzyme having perhydrolase activity, which is preferably immobilized on a solid support, the oxygen acceptor, preferably a carboxylic acid, is oxidized by means of the oxygen donor. The enzyme converts the oxygen acceptor into a peracid. In a subsequently or simultaneously carried out further process step, at least one unsaturated compound is introduced into the reaction mixture in step b) and oxygen from the peracid spontaneously, that is, autocatalytically transferred to a double bond of the unsaturated compound, so that an epoxide is obtained. The epoxide thus prepared can then be recovered from the reaction mixture in a conventional manner, in particular isolated.

In a preferred embodiment, the reaction according to steps b) and c) takes place in a single reactor. According to this preferred embodiment, the peracid is formed in situ and immediately thereafter the epoxidation of the at least one unsaturated compound takes place.

In a preferred embodiment, the reaction according to step c) also takes place in an inhomogeneously mixed, an organic or oil phase and an aqueous phase having reaction mixture.

In step a), exactly one oxygen donor is preferably provided. In step a), preferably at least two different oxygen donors are provided.

In step a), exactly one oxygen acceptor is preferably provided. In step a), preferably at least two different oxygen acceptors are provided.

In step a), it is preferred to provide precisely one enzyme with perhydrolase activity, preferably a lipase with perhydrolase activity. In step a), preferably at least two different enzymes with perhydrolase activity, preferably two different lipases with perhydrolase activity, are provided.

In a preferred embodiment, in step a) as the at least one unsaturated compound an epoxidation mixture is used which has at least one unsaturated compound. Preferably, the Epoxidiergemisch is an oil. In step a), preference is given to using at least one alkene and / or at least one unsaturated fatty acid, preferably in free form. The oil preferably contains the unsaturated compounds, namely the unsaturated fatty acids, in the form of a triacylglyceride.

In step a), the unsaturated compounds in bound form, i. in the form of an ester, preferably in the form of a triacylglyceride. These unsaturated compounds present in bound form are preferably first hydrolyzed and / or transesterified before they are reacted in step c) with the peracid prepared in step b).

The product of the transesterification is methyl, ethyl, propyl or fatty acid esters with at least one, preferably one or more long-chain linear or branched monohydric or polyhydric alcohols or mixtures thereof.

In a preferred embodiment, the reaction according to step b) takes place in a first reactor and the reaction according to step c) takes place in a second reactor. According to this preferred embodiment, the formation of the peracid takes place ex situ. The peracid thus formed is added to the second reactor in this preferred embodiment, so that there presented at least one unsaturated compound according to step c) can be reacted with the peracid.

In a preferred embodiment, the reaction according to step b) and the reaction according to step c) take place in one and the same reactor. According to this preferred embodiment, the formation of the peracid takes place in situ. Accordingly, the peracid formed in situ is reacted with the at least one unsaturated compound in the same reactor.

Preferably, the reaction according to step c) takes place in a reactor having a capacity of at least 50 liters, preferably at least 100 liters, preferably at least 200 liters, preferably at least 300 liters, preferably at least 400 liters, preferably at least 500 liters, preferably at least 1,000 liters , preferably at least 2,000 liters, preferably at least 3,000 liters, preferably at least 4,000 liters, preferably at least 5,000 liters, preferably at least 20,000 liters.

Preferably, in step c) at least 1 kilo, preferably at least 5 kilo, preferably at least 10 kilo, preferably at least 50 kilo, preferably at least 100 kilo, preferably at least 200 kilo, preferably at least 300 kilo, preferably at least 400 kilo, preferably at least 500 kilos, preferably at least 1000 kilos, preferably at least 2,000 kilos, preferably at least 3,000 kilos, preferably at least 4,000 kilos, preferably at least 5,000 kilos, preferably at least 20,000 kilos, of at least one unsaturated compound.

The reaction medium present in step c) preferably has a volume, preferably at a temperature of 25 ° C., of at least 50 liters, preferably at least 100 liters, preferably at least 200 liters, preferably at least 300 liters, preferably at least 400 liters, preferably at least 500 liters , preferably at least 1,000 liters, preferably at least 2,000 liters, preferably at least 3,000 liters, preferably at least 4,000 liters, preferably at least 5,000 liters, preferably at least 20,000 liters, on.

The oxygen acceptor provided in step b) for the preparation of the peracid is preferably in an amount of at least 1 mol%, preferably at least 2 mol%, preferably at least 5 mol%, preferably at least 8 mol%, preferably at least 10 mol -%, preferably at most 20 mol%, preferably at most 15 mol%, preferably at most 10 mol%, preferably at most 8 mol%, preferably at most 5 mol%, preferably 1 to 10 mol%, preferably 2 to 8 Mol%, preferably 4 to 6 mol% (based on the present in the at least one unsaturated compound double bonds) added in step b).

Alternatively or additionally, the oxygen donor provided in step b) for the preparation of the peracid, preferably the aqueous or urea-bound hydrogen peroxide, is preferably added in molar excess (based on the double bonds present in the at least one unsaturated compound) in step b). The molar excess is preferably a 1.1-fold excess, preferably at least 1.2 times, preferably at least 1.5 times, preferably at most 1.2 times, preferably at most 1.8 times, molar Excess (based on the double bonds present in the at least one unsaturated compound).

In a preferred embodiment, a method is provided, wherein the at least one unsaturated compound is a non-edible vegetable oil, a food oil, at least one unsaturated free fatty acid, at least one unsaturated fatty acid ester, wherein preferably at least one, preferably exactly one fatty acid with a linear or branched mono- or polyhydric alcohol is esterified, at least one unsaturated dicarboxylic acid, at least one alkene, or mixtures thereof.

Preferably, the at least one unsaturated compound is one or more oils obtained as a waste stream in food or biodiesel production.

In a preferred embodiment, a method is provided wherein the at least one fatty acid is selected from the group consisting of myristoleic, palmitoleic, petroselic, oleic, gadolinic, erucic, linoleic, linolenic and ricinoleic acids or mixtures thereof.

Preferably, the at least one alkene is 9-octadecene.

Preferably, a method is provided wherein the unsaturated dicarboxylic acid is a 1,18-octadecenedioic acid.

Preferably, a method is provided wherein the vegetable oil is selected from the group consisting of scorpionfish, elderflower seed, mustard, junk, erucarab, black cumin, tall and rice oils, or mixtures thereof.

The at least one unsaturated compound is preferably oleic acid, linoleic acid, linolenic acid, gadoleic acid, erucic acid or a mixture thereof.

The at least one unsaturated compound is preferably an epoxidation mixture containing at least one unsaturated compound, also denominatable as a mixture to be epoxidized.

The epoxidation mixture preferably contains at least one polyunsaturated fatty acid.

The term "polyunsaturated fatty acid" is understood in the context of the present invention to mean a fatty acid which contains at least three double bonds, preferably at least four double bonds, preferably at least five double bonds, preferably at least six double bonds.

The Epoxidiergemisch preferably contains at least 12 wt .-% (based on the total dry weight of Epoxidiergemisches) at least one polyunsaturated fatty acid. The polyunsaturated fatty acid is preferably linolenic acid.

The Epoxidiergemisch preferably contains at least 35 wt .-%, preferably at least 50 wt .-%, preferably at least 60 wt .-% of at least one polyunsaturated fatty acid (based on the total dry weight of Epoxidiergemisches).

The Epoxidiergemisch preferably has a molar double bond content of at least 5, preferably at least 6, preferably at least 6.5, based on the molar amount of Epoxidiergemisches).

The epoxide mixture preferably has an iodine number of at least 50, preferably at least 170, preferably at least 190, preferably at least 200. The epoxidation mixture preferably has an iodine number of not more than 400, preferably of not more than 300, preferably of not more than 250.

The epoxidation mixture preferably has fatty acids having a carbon chain of 16 to 22 carbon atoms. The proportion of fatty acids having a carbon chain with 16 to 22 carbon atoms is at least 50% by weight, preferably at least 80% by weight, preferably at least 90% by weight, preferably at least 95% by weight, preferably 99% by weight (based on the total weight of the Epoxidiergemisches).

The epoxidation mixture preferably contains oleic acid, linoleic acid and linolenic acid. The epoxidation mixture preferably contains oleic acid, linoleic acid, linolenic acid, gadoleic acid and erucic acid. The epoxidation mixture contains alternatively or additionally as polyunsaturated fatty acid eicosapentaenoic acid (EPA) and / or docosahexaenoic acid (DHA).

The epoxidation mixture preferably contains the unsaturated fatty acids as free fatty acids and / or as fatty acid esters, preferably as fatty acid glycerides.

The epoxidation mixture is preferably selected from the group of oils according to Table 1 and any mixtures thereof.

Preferably, a method is provided, wherein the food oil is selected from the group consisting of sunflower, rapeseed, soybean, Färberdistel-, castor, olive, walnut, sesame, corn, grape seed, linseed and pumpkin seed oil or mixtures thereof.

Preferably, a method is provided, wherein the oxygen donor is selected from tert-butyl hydroperoxide, cumyl hydroperoxide, hydrogen peroxide and mixtures thereof. Preferably, the oxygen donor is an aqueous hydrogen peroxide solution or a hydrogen peroxide bound to urea. Preferably, the oxygen donor is a hydrogen peroxide bound to urea. Particularly preferred is an aqueous hydrogen peroxide.

Preferably, a method is provided, wherein the enzyme is used in solid form, for example immobilized, or in dissolved form.

In a preferred embodiment of the present invention, a process is provided, wherein the at least one oxygen donor, preferably the hydrogen peroxide, once at the beginning of process step b), or batchwise or continuously during process step b), preferably batchwise or continuously during process step b ) is supplied. By this procedure, the cycle stability of the at least one enzyme used can be additionally increased. The at least one enzyme thereby comes into contact with smaller amounts of hydrogen peroxide and its inactivation becomes thus reduced. In particular, by the batchwise or continuous addition of a possible inactivation of the at least one enzyme is reduced and thus increases the cycle stability of the at least one enzyme.

Preferably, a method is provided, wherein the enzyme with perhydrolase activity is an immobilized enzyme, preferably an immobilized lipase. Preferably, the enzyme, preferably the lipase having perhydrolase activity on an acrylic resin, preferably adsorbed on an oxirane-functionalized co-polymer of methacrylate, for example Immobead 150 or Sepabead EC-EP.

Preferably, a method is provided, wherein the enzyme having perhydrolase activity is a lipase from Candida and / or Rhizomucor.

Preferably, the lipase is an enzyme extract from at least one Pseudozyma strain, wherein the enzyme extract has perhydrolase activity.

In a preferred embodiment, the enzyme with perhydrolase activity is a hydrolase, preferably an esterase, lipase or perhydrolase, particularly preferably a lipase, wherein the lipase is preferably selected from a lipase from Candida, Rhizomucor, Thermomyces, Rhizopus, Burkholderia, Pseudozyma and Pseudomonas. Particularly preferred is a method is provided, wherein the enzyme with perhydrolase activity is a lipase from Candida or Rhizomucor.

Preferably, an enzyme with perhydrolase activity is provided, comprising a homologous amino acid sequence to a lipase selected from Candida, Rhizomucor, Burkholderia, Pseudozyma and Pseudomonas, in a preferred embodiment over its entire length a homology of at least 80%, preferably at least 85%, preferably at least 90%, preferably at least 95%, preferably at least 96%, preferably at least 97%, preferably at least 98%, particularly preferably at least 99% to the amino acid sequence shows.

A fragment of an enzyme having perhydrolase activity or a fragment of an enzyme having a homologous amino acid sequence to a perhydrolase may preferably be a fragment which is at least 100 Amino acids, preferably at least 150 , preferably at least 200 , preferably at least 250 , preferably at least 300 Includes amino acids. Preference is given to naturally occurring wild-type enzymes with perhydrolase activity or recombinantly produced enzymes. In a preferred embodiment, the enzyme can be present in free form, bound, immobilized, as a fragment of an enzyme, in a cell or as a cell extract.

Preferably, a method is provided, wherein the oxygen acceptor is selected from the group consisting of at least one free fatty acid, at least one fatty acid ester, ethyl acetate, dimethyl carbonate and mixtures thereof.

Preferably, the at least one oxygen acceptor is materially different from the at least one unsaturated compound. Alternatively preferably, the at least one unsaturated compound can also be used as oxygen acceptor.

Preferably, the present inventive method consists of the steps a) to d). Preferably, step d) comprises recovering, preferably isolating, the at least one epoxidized compound from the reaction mixture, preferably it consists thereof.

Ethyl acetate and / or dimethyl carbonate are particularly preferably used as oxygen acceptors. These can be advantageously relatively easily separated from the reaction mixture, in particular by distillation. Thus, a very pure epoxidized compound, in particular an epoxidized alkene, is preferably obtained.

Preferably, the oxygen acceptor is selected from the group consisting of at least one saturated free fatty acid, at least one saturated fatty acid ester, ethyl acetate, dimethyl carbonate and mixtures thereof. Preferably, the oxygen acceptor is selected from the group consisting of ethyl acetate, dimethyl carbonate and mixtures thereof.

Preferably, a method is provided, wherein the method is carried out in a stirred reactor or in a fluidized bed reactor. The process is preferably carried out in a fluidized-bed reactor.

Preferably, a method is provided, wherein the method is carried out in a combination of fixed bed reactor, preferably fluidized bed reactor, and a bubble column reactor.

In a preferred embodiment, the at least one enzyme is introduced into a fixed bed reactor, preferably in a fluidized bed reactor. The organic or oil phase containing at least one unsaturated compound and at least one oxygen acceptor, preferably via a dispersion unit, in the form of droplets, also referred to as bubbles, in an aqueous containing at least one oxygen donor, preferably hydrogen peroxide, and present in a bubble column reactor Phase registered so that the droplets of the organic or oil phase can ascend in the aqueous phase. Subsequently, due to their lower density, these droplets rise in the aqueous phase containing the at least one oxygen donor, preferably the hydrogen peroxide, thereby taking up the at least one oxygen donor, preferably the hydrogen peroxide, preferably saturated with it. The at least one oxygen donor, preferably the hydrogen peroxide, having, preferably saturated, organic or oil phase collects on the surface of the aqueous phase and is characterized by a fixed bed reactor having the at least one enzyme, preferably a fluidized bed reactor comprising the at least one enzyme, led, whereby the at least one unsaturated compound is converted to the epoxide. This specific procedure avoids prolonged contact of the at least one enzyme with high concentrations of hydrogen peroxide, thereby allowing prolonged enzyme use.

Preferably, a method is provided, wherein the reaction mixture additionally a linear or branched monohydric or polyhydric alcohol is added. In this particular embodiment, the enzyme catalyzes both the formation of the peracid and the esterification of an epoxy fatty acid present in the reaction mixture, or transesterification of an epoxy fatty acid ester present in the reaction mixture with the linear or branched monohydric or polyhydric alcohol added to a corresponding epoxy fatty acid ester.

Preferably, a method is provided, wherein the reactions in step b) and c) in a solvent, preferably in a non-polar or in a polar solvent or in a non-polar and a polar solvent, preferably in an ionic solvent, take place. In a particularly preferred embodiment, at least one organic solvent, preferably a nonpolar organic solvent, is added. The solvent is not involved in the reactions according to step b) and step c). It is preferably used to reduce the viscosity of the at least one unsaturated compound used, preferably of the Epoxidiergemisches used. In addition, it leads to improved homogenization of the different phases present in this process, which leads to an improvement in the reaction rate.

The non-polar solvent is preferably toluene, hexane, xylene, heptane, ethyl acetate, dimethyl carbonate or a mixture thereof. Toluene, hexane or a mixture thereof are preferably used as non-polar solvents. The compounds ethyl acetate and dimethyl carbonate act both as oxygen acceptors and as non-polar solvents. The polar solvent is preferably an alcohol or an alcohol mixture.

The reaction in step b) and / or step c) preferably takes place in the absence of a nonpolar solvent. Thus, the reaction according to step b) and / or c) is free of a nonpolar solvent.

In a particularly preferred embodiment, the oxygen donor is dissolved in water as a solvent, that is, in aqueous solution. In particular, the oxygen donor is an aqueous hydrogen peroxide solution. Preferably, in step b) the oxygen donor, preferably the hydrogen peroxide, is in the form of a 10 to 50% by weight, preferably 20 to 40% by weight, Solution, preferably aqueous solution, added.

Preferably, the reaction mixture is stirred continuously in step c), preferably with a stirring speed of 1 to 1000, preferably 50 to 1000, preferably 300 to 1000 revolutions per minute, depending on the reactor dimension.

The inhomogeneous mixing is preferred by a specific power input of less than 0.35 kW / m ³ , preferably less than 0.30 kW / m ³ , preferably less than 0.25 kW / m ³ , preferably less than 0, 20 kW / m ³ , preferably less than 0.15 kW / m ³ , preferably less than 0.10 kW / m ³ , preferably less than 0.05 kW / m ³ achieved. Preference is given in step b) and / or c) a specific power input of less than 0.35 kW / m ³ , preferably less than 0.30 kW / m ³ , preferably less than 0.25 kW / m ³ , preferably less than 0.20 kW / m ³ , preferably less than 0.15 kW / m ³ , preferably less than 0.10 kW / m ³ , preferably less than 0.05 kW / m ³ , preferably by means of a stirring unit, introduced into the reaction medium ,

The reaction in step b) preferably takes place at a temperature of at least 0 ° C., preferably 25 ° C., and at a maximum at a temperature of 80 ° C., preferably at most 50 ° C., preferably in a range from 25 to 50 ° C., preferably in a range of 30 to 40 ° C, instead.

Preferably, the reaction in step c) takes place at a temperature of at least 0 ° C., preferably 25 ° C., and at a maximum at a temperature of 80 ° C., preferably at most 50 ° C., preferably in a range from 25 to 50 ° C. ,

The removal of the enzyme, preferably immobilized enzyme, preferably takes place after step c). Alternatively or additionally, the washing of the at least one epoxidized compound, preferably the organic phase containing the non-polar solvent and the at least one epoxidized compound, preferably with deionized water and optionally with an alkaline sodium carbonate solution, preferably takes place after step c). The washing is preferably for the removal of free fatty acids from the reaction mixture.

In a preferred embodiment, a fixed bed reactor is used to epoxidize unsaturated compounds. Preferably, the fixed bed reactor is a fluidized bed reactor. As a fixed bed, preferably fluidized bed, an immobilized enzyme with perhydrolase activity is used. In this preferred process, the organic phase comprising the at least one unsaturated compound, the at least one oxygen acceptor, and optionally the at least one nonpolar solvent, and the, preferably aqueous, oxygen donor phase, preferably the hydrogen peroxide phase, are incorporated in the Fixed bed reactor, preferably in the fluidized bed reactor, introduced, preferably by means of pumps. Preferably, the organic phase and the, preferably aqueous, oxygen donor phase prior to addition to the fixed bed, preferably on the fluidized bed, mixed. Preferred are two or more fixed bed reactors, preferably fluidized bed reactors, in series, i. seen in the flow direction one behind the other, arranged. In this specific embodiment of the present invention, the oxygen donor, preferably the hydrogen peroxide, may be added in portions, preferably variably.

The stirred reactor and the fixed bed reactor, preferably the fluidized bed reactor, preferably have baffles. The stirred reactor preferably has baffles.

The stirred reactor preferably has a stirring unit. The stirring unit is preferably a disk stirrer or an impeller stirrer. Preferably, the impeller is in two stages.

The stirred reactor preferably has no baffles. The stirred reactor is preferably strombrecher-free. The stirred reactor preferably has baffles.

The term "stream breaker", also referred to as baffle, components of a reactor are understood to prevent the entire reaction medium due to its inertia by the action of the stirring unit evenly, i. without mixing, is moved. Preferably, the baffles or baffles are attached to the reactor wall or at the bottom. Baffles or baffles are preferably cylindrical baffles, paddle baffles, C-burrers or Δ-baffles. C-stream breakers have a C-shaped profile, with the concave side of the "C" is flown. The Δ-burr preferably has a profile of an isosceles triangle.

The reaction mixture obtained in step c) is preferably the product of the process according to the invention or of the process preferred according to the invention. The reaction mixture obtained according to step c) is used in an alternative, preferred embodiment exactly once or several times as starting material in the inventive or inventively preferred process for the epoxidation of unsaturated compounds are used so that the mixture obtained in step c), preferably additionally purified and / or washed, is reacted once or several times as a mixture comprising at least one unsaturated compound in step c).

There is also disclosed an epoxidized compound or a mixture of epoxidized compounds prepared by a method of the invention or preferred according to the invention.

The epoxidized compound or mixture of epoxidized compounds is preferably at least one epoxidized fatty acid, preferably at least one epoxidized fatty acid ester, epoxidized scorpionfish, epoxidized elderflower seed, epoxidized mustard, epoxidized crumb, epoxidized erucarose, epoxidized black cumin, epoxidized tallies. , epoxidized rice, epoxidized sunflower, epoxidized rapeseed, epoxidized soybean, epoxidized safflower, epoxidized castor, epoxidized olive, epoxidized walnut, epoxidized sesame, epoxidized corn germ, epoxidized grape seed, epoxidized linseed, epoxidized Pumpkin seed oil, epoxyoctadecane-1,18-diacid or any mixture thereof.

The product produced by the method according to the invention or preferred according to the invention has an epoxide oxygen content of at least 4 , preferably at least 8.5, preferably at least 10 , preferably at least 11 on. The epoxy oxygen content is preferably at a maximum in the product produced by the process preferred according to the invention or according to the invention 15 , preferably maximum 12 ,

The preferred embodiments of the present invention will become apparent from the dependent claims.

The present invention will be explained in more detail with reference to the following figures and the examples.

• 1A und 1B eine schematische Vorrichtung zur absatzweisen Epoxidierung, auch als portionsweise Epoxidierung bezeichnet, von mindestens einer ungesättigten Verbindung,
• 2 eine schematische Vorrichtung zur kontinuierlichen Epoxidierung von mindestens einer ungesättigten Verbindung in einem Wirbelschichtreaktor,
• 3 den Verlauf des Epoxidsauerstoffgehaltes (OO) in Prozent % über die Zeit t in Stunden h in einem 1 L Reaktor bei verschiedenen Drehzahlen und
• 4 den Verlauf des Epoxidsauerstoffgehaltes (OO) in Prozent % über die Zeit t in Stunden h in einem Reaktor 1 L und 10 L Reaktor bei verschiedenen Drehzahlen.

Show

• 1A and 1B a schematic apparatus for batch epoxidation, also referred to as portionwise epoxidation, of at least one unsaturated compound,
• 2 a schematic apparatus for the continuous epoxidation of at least one unsaturated compound in a fluidized bed reactor,
• 3 the course of the epoxide oxygen content (OO) in percent% over the time t in hours h in a 1 L reactor at different speeds and
• 4 the course of the epoxide oxygen content (OO) in percent% over the time t in hours h in a reactor 1 L and 10 L reactor at different speeds.

1A and 1B show a schematic device 10 and 15 for carrying out the method according to the invention or preferred according to the invention. In this case, the device has a reaction reactor 1 in which a stirring unit 2 is arranged. The stirring unit 2 ensures the mixing of the added components and thus to improve the epoxidation of at least one unsaturated compound. Furthermore, the device has four feed tanks 3 . 4 . 5 and 6 on, over lines 103 . 104 . 105 . 106 with the reaction reactor 1 are connected. In the supply containers 3 . 4 . 5 . 6 independently of one another, the individual components, namely the at least one unsaturated compound, the at least one oxygen donor, the at least one oxygen acceptor and the at least one solvent, can be introduced and the reaction reactor 1 by means of pumps 7 . 8th . 9 . 11 dosed and preferably added in portions or kontinulierlich. The reaction mixture obtained by the addition of the individual components can, preferably delayed in time for the addition of the components, from the reaction reactor 1 through a withdrawal unit 12 be removed, the reaction reactor 1 directly with the extraction unit 12 over the line 112 connected to each other. Furthermore, the reaction reactor 1 a supply line 122 via which an enzyme, preferably immobilized, can be added. Downstream to the extraction unit 12 is in the device 10 a filtration device 13 arranged with the removal unit 12 over a line 14 is directly connected. The filtration device 13 has two outlets, with an outlet with a return line 20 directly with the reaction reactor 1 connected via the filtered, immobilized enzyme, preferably lipase with perhydrolase activity back into the reaction reactor 1 can be returned. The further outlet of the filtration device 13 is immediately with a decanter 21 over a line 22 connected. In the decanter 21 separates the lighter, organic phase from the heavier, aqueous phase. The heavier, aqueous phase is above the discharge 23 from the decanter 21 executed. The lighter organic phase containing the at least one epoxidized compound is passed through an outlet via the conduit 24 in a mixer-settler contacting device 25 brought in. About the supply line 26 may be water or a solution of sodium carbonate in the addition tank 27 can be stored, be added. The mixer-settler contactor 25 has two outlets, with one outlet 28 for removing the water phase enriched with hydrogen peroxide and the at least one free fatty acid and the other outlet 29 the organic phase containing the at least one epoxidized compound via a conduit 29 in a distiller 30 transferred. In the distiller 30 the solvent is removed by distillation and via an outlet by means of the line 31 in a heat exchanger 32 transferred where the solvent cooled and then via a return line 33 by means of a pump 34 in the reaction reactor 1 is returned. The distiller 30 has also via a further outlet, by means of which the at least one epoxidized compound via a line 35 can be discharged.

2 shows a schematic representation of a device 40 , which is suitable for epoxidizing at least one unsaturated compound.

The device 40 has three fixed bed reactors 41 . 51 . 61 each with a supply line 42 . 52 . 62 on, taking the leads 42 . 52 . 62 - Seen in the process direction - each a mixing valve 43 . 53 . 63 is upstream. The mixing valves 43 . 53 . 63 each have two inlets and one outlet, the outlets of the mixing valves 43 . 53 . 63 each with the supply lines 42 . 52 respectively 62 are connected. The mixing valves 43 . 53 . 63 are with the one inlet over the supply lines 44 . 54 . 64 directly with an outlet of an addition tank 71 in which the oxygen donor can be stored, connected. For the metered and portionwise addition of the oxygen donor is in each case a metering device 45 . 55 . 65 , preferably a pump, on the respective supply line 44 . 54 . 64 arranged and designed so that the addition of the oxygen donor are metered and controlled. With the other inlet are the mixing valves 53 . 63 each with a line 56 . 66 directly each with the fixed bed reactor 61 . 71 connected. The other inlet of the mixing valve 43 is via a supply line 46 directly with a mixing device 49 connected. Into the mixing device 49 can over the supply lines 81 . 82 . 83 from storage containers 84 . 85 . 86 in each case the components used for the epoxidation of the at least one unsaturated compound, namely the at least one unsaturated compound, the at least one oxygen acceptor and the at least one solvent, dosed, and preferably in portions, are added. The dosage and portioning of the compounds is carried out by metering devices 87 . 88 . 89 that way on the supply lines 81 . 82 . 83 are arranged and designed so that the at least one unsaturated compound which doses at least one oxygen acceptor and the at least one solvent, and preferably in portions, can be added. Also, by the metering devices 87 . 88 . 89 the desired proportions of the various components in the mixing device 49 be set. The third fixed bed reactor seen in the process direction 61 also has an outlet, and is with a decanter 72 over a line 73 directly connected. The decanter 72 has a discharge line 74 for discharging the aqueous phase containing the oxygen donor, preferably hydrogen peroxide, on. Also, the decanter points 72 an outlet, which by means of a conduit 75 with a mixer-settler contacting device 76 is directly connected. The administration 75 is also over a line 77 with an adding device 78 via which an aqueous sodium carbonate solution (preferably 5 wt .-%) can be added. The mixer-settler contactor 76 has two outlets, with one outlet 79 for discharging the aqueous phase enriched with the oxygen donor and the free fatty acid, and an outlet, which by means of a conduit 90 with a distiller 91 is directly connected. The distiller 91 has two outlets, with one outlet 92 to remove the at least one epoxidized compound. The further outlet of the distillation device 91 is by means of a line 93 directly with a heat exchanger 94 connected. The heat exchanger has an outlet, whereby by means of the line 95 and the pump provided for metering 96 the condensed, at least one solvent present in the mixing device 49 can be returned. The supply lines 83 and 95 unite to a common leadership 97 which are in the mixing device 49 empties.

3 shows the course of the epoxy oxygen content (OO) of the product produced in percent% over time t in hours h in a 1 L reactor with disk stirrer and baffles at speeds of 350 rpm (curve with circles), 600 rpm (curve with triangles), 1000 rpm (curve with diamonds) and 1400 rpm (curve with squares). At a speed of 600 rpm, 1000 rpm and 1400 rpm, homogeneous mixing and, at 350 rpm, inhomogeneous mixing of the aqueous and organic phases is present. Out 3 can be seen that in an inhomogeneous mixing an approximately equal or same conversion rate and an approximately identical or the same epoxy oxygen content is obtained in the epoxidized product thus produced in comparison to products produced by homogeneous mixing of the aqueous and organic phase. 3 shows in particular the influence of different speeds on the conversion rate in a 1L reactor with disk stirrer and baffle breaker.

4 shows the course of the epoxy oxygen content (OO) of the product produced in percent% over time t in hours h (a) in a 1 L reactor with disk stirrer and baffles at a speed of 1000 rpm (curve with squares), (b) in one 10 L reactor with disk stirrer and baffles at a speed of 630 rpm (curve with diamonds) and (c) in a 10 L reactor with a two-stage impeller stirrer without beater at a speed of 450 rpm (curve with triangles). In (a) and (b) there is a homogeneous mixing and in (c) an inhomogeneous mixing. Out 4 It can be seen that in the case of inhomogeneous mixing of the aqueous and organic phases, an approximately identical or identical conversion rate and an approximately identical or identical epoxy oxygen content are obtained in the epoxidized product thus produced in comparison with products produced by homogeneous mixing of the aqueous and organic phases. 4 In particular, Figure 11 shows scale-up from 11 to 101 for a disk stirrer and baffles reactor. The speed in the 101-scale is calculated so that a constant, volume-specific power input takes place. Additionally shows 4 an alternative set-up with two-stage impeller without baffle, in which there is an inhomogeneous mixing in the form of larger drops. Table 1 source Percentage fatty acid content in individual oils M (oil) in gmor ¹ n (C = C) in moles per mole of oil max (OO) in% iodine Value C16: 0 C18: 0 C18: 1 C18: 2 C18: 3 C20: 1 C22: 1 C18: 1 OH And. Scorpionfish (g) 7 3 11 13 62 2 2 868.5 7.02 11,45 200.0 Dragon's Head (ng) 8th 3 11 13 62 1 2 868.0 6.99 11.41 197.0 Elderberry (g) 7 3 11 41 37 1 872.3 6.38 10.47 179.0 Elderberry (ng) 8th 3 11 40 37 1 873.5 6.32 10.38 174.0 Mustard (g) 3 2 23 9 9 10 37 7 960.9 3.79 5.94 102.0 Mustard (ng) 3 2 24 10 10 11 34 6 956.8 3.92 6.16 101.0 Erucarapsöl 15 13 9 5 58 0 985.4 4.21 6.4 108.4 Black Seed Oil 13 3 21 59 4 874.5 4.41 7.5 128.0 castor oil 3 4 4 5 1 1 67 15 779.0 2.18 4.3 70.9 Krambeöl 2 1 17 8th 5 3 55 9 991.6 3.53 5.39 88.0 linseed oil 6 5 19 17 53 0 873.9 6.60 10.79 187.0 rice oil 21 3 41 33 1 1 868.6 3.42 5.93 102.0 olive oil 12 5 75 6 1 1 875.7 2.79 4.84 80.0 walnut oil 7 3 16 61 12 1 875.2 5.39 8.97 152.0 Pumpkin seed oil 13 6 23 57 1 872.5 4.29 7.30 124.0 Safflower oil 5 3 76 13 3 883.1 3.27 5.59 91.0 sesame oil 10 5 39 44 2 876.3 4.04 6.87 117.0 corn oil 12 3 36 49 0 872.8 4.16 7.1 120.9 Grapeseed oil 9 5 22 64 0 875.0 4.68 7.9 135.7 rapeseed oil 5 2 62 20 8th 1 2 882.6 4.04 6.82 114.0 Sunflower oil 6 4 28 61 1 878.7 4.70 7.88 137.0 soybean oil 12 4 22 55 6 1 872.2 4.36 7.41 125.3 Legend: C16: 0 palmitic acid, C18: 0 stearic acid, C18: 1 oleic acid, C18: 2 linoleic acid, C18: 3 linolenic acid, C20: 1 gadoleic acid, C22: 1 erucic acid; g = cleaned, ng = not cleaned, And. = other components in%

Examples

1. Experiments on chemo-enzymatic epoxidation took place in a 1 L glass reactor with an internal diameter of 100 mm. The stirrer used was a 6-blade disc stirrer with a diameter of 38 mm, the reaction temperature of 30 ° C. was determined by means of the heating system thermostat D8 set. The power input at different stirrer speeds ( 350 . 600 . 1000 . 1400 rpm) was carried out via the agitator RZR 2102 the company Heidolph. As a stream breaker four flat plates were used with a flow face width of 0.1 × the reactor internal diameter, which were attached with a distance to the reactor wall of 0.02 × the reactor internal diameter.

The reaction mixture had dragonhead oil, which was mixed with 5 mol .-% of oleic acid based on the proportion of double bonds. The amount of solvent used of 60% by weight of toluene relates in percent to the total mass of the organic phase.

Per mole of C = C double bond 7.5 g of Novozym®435 were used. 2 moles of H ₂ O _{2 were} used per mole of C =C double bond. From this molar ratio results in the implementation of dragon's head oil and 60 wt.% Toluene, a characteristic disperse phase fraction of 0.343.

2. The reaction in the 10 L scale was carried out while maintaining the ratios of the reactants. In the experiment, the scalability of the approach was demonstrated in the 1L scale at 1000 rpm on the basis of a constant volume-related power input at 630 rpm. Another experiment without a baffler with a 2-stage impeller stirring system at 450 rpm shows the general feasibility of chemo-enzymatic epoxidation in an inhomogeneously mixed reaction mixture. The inhomogeneous mixing was, for example, visually recognizable by a difference in color in comparison to a homogeneous mixing and by a significantly accelerated settling of the aqueous phase after completion of the power input.

Claims (14)

Process for the epoxidation of unsaturated compounds, the process comprising the following steps: a) providing at least one unsaturated compound, at least one oxygen donor, at least one oxygen acceptor and at least one enzyme having perhydrolase activity, b) reacting the at least one oxygen acceptor provided in step a) with the at least one oxygen donor provided in step a) in the presence of the at least one enzyme provided in step a) with perhydrolase activity in an inhomogeneously mixed, an organic or oil phase and an aqueous phase containing reaction mixture to provide at least one peracid, c) reacting the at least one peracid produced in step b) with the at least one unsaturated compound provided in step a), so that at least one epoxidized compound is obtained, and d) obtaining the at least one epoxidized compound. Method according to Claim 1 wherein the at least one unsaturated compound is a non-edible vegetable oil, a food oil, at least one unsaturated dicarboxylic acid, at least one unsaturated fatty acid, at least one unsaturated fatty acid ester, at least one alkene or mixtures thereof. Method according to Claim 2 wherein the at least one fatty acid is selected from the group consisting of myristoleic, palmitoleic, petroselic, oleic, gadolein, eruca-, linoleic, linolenic and ricinoleic acid or mixtures thereof. Method according to Claim 2 wherein the non-edible vegetable oil is selected from the group consisting of scorpionfish, elderflower seed, mustard, junk, erucarose, black cumin, tall and rice oils, or mixtures thereof. Method according to Claim 2 wherein the food oil is selected from the group consisting of sunflower, rapeseed, soybean, safflower, castor, walnut, sesame, corn germ, grape seed, linseed, pumpkin seed and olive oil or mixtures thereof. Method according to Claim 2 wherein the dicarboxylic acid is a 1,18-octadecenedioic acid. Method according to one of the preceding claims, wherein the at least one oxygen donor is hydrogen peroxide, preferably an aqueous hydrogen peroxide solution or urea-bound hydrogen peroxide. Method according to one of the preceding claims, wherein the at least one oxygen donor is supplied once at the beginning of the process step b), batchwise or continuously during the process step b). A method according to any preceding claim, wherein the enzyme having perhydrolase activity is an immobilized enzyme. Method according to one of the preceding claims, wherein the enzyme with perhydrolase activity is a lipase from Candida and / or Rhizomucor. The method of any one of the preceding claims, wherein the oxygen acceptor is selected from the group consisting of at least one free fatty acid, at least one fatty acid ester, ethyl acetate, dimethyl carbonate, and mixtures thereof. Method according to one of the preceding claims, wherein the reaction mixture additionally a linear or branched monohydric or polyhydric alcohol is added. Method according to one of the preceding claims, wherein the method is carried out in a stirred reactor, in a fluidized bed reactor, in a fixed bed reactor or in a combination of fixed bed reactor and bubble column reactor. Method according to one of the preceding claims, wherein the reaction in step c) takes place in a non-polar solvent.

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