DE102006000870B3 - Preparation of saponified oleoresin containing carotinoid, comprises mixing solid form of unsaponified oleoresin containing carotinoid with small-size and/or powdery alkali metal hydroxide and saponifying the obtained mixture - Google Patents

Abstract

Preparation of saponified oleoresin containing carotinoid, comprises mixing solid form of unsaponified oleoresin containing carotinoid with small-size and/or powdery alkali metal hydroxide and saponifying the obtained mixture. Independent claims are included for: (1) saponified oleoresin containing carotinoid, obtained from the above process; and (2) feed containing saponified oleoresin containing carotinoid.

Description

The The invention relates to a method for producing saponified, carotenoid-containing oleoresin and saponified, carotenoid-containing Oleoresin.

On the world market are the so-called carotenoid-containing oleoresins (Extracts of marigold blossoms, paprika etc.) a "commodity", ie standardized Commodity. The subsequent treatment of these oleoresins takes place usually with the aim to gain high-purity carotenoids. in this connection the carotenoids are subjected to saponification.

Of the reason for saponification of oleoresins lies in chemical modification, in which the carotenoids in the plants are usually stored become. The plants synthesize e.g. the xanthophyll lutein together with two fatty acid residues to a luteindipalmitate or the like. required but is the pure, unesterified carotenoid. This is especially true for the Use in the animal feed sector. As a feed additive carotenoids (in particular xanthophylls) in particular for the pigmentation of egg yolk and the skin of poultry used. poultry can digest digestive carotenoids badly.

The saponification may be involved in a subsequent process of concentration to pure lutein or generally to pure xanthophylls. For example, in the US Pat. No. 6,262,284 described a simultaneous extraction, saponification and concentration. Characteristic of almost all methods of saponification is the use of aqueous KOH or NaOH or other alkali metal hydroxides. Basically, the saponification takes place via an alkaline ester hydrolysis.

For the feed sector There is an application that only saponifies the oleoresins to that saponified oleoresin subsequently in a solid formulation bring. The classical saponification process stands out the use of potassium hydroxide (about 15%), water (about 20%), oleoresin (about 50%), sometimes propanediol (about 20%) and / or ethanol. The Saponification temperatures are usually 65 to 90 ° C at a Time of about 6 hours. The reaction usually takes place in a kettle with a slow-moving anchor agitator instead. The slow-turning agitators are used because the Oleoresin has the property with increasing Degree of saponification more and more viscous become.

The conventional Process has the disadvantage that massive Solvent, Water and other additives are used to make the product to keep still flowable with increasing degree of saponification. These additives can not at all or only with considerable effort from the product be taken out. This requires additional equipment or has the Loss of additives result.

Therefore it falls Choice usually as possible cheap solvents. Due to the high temperatures and long reaction times is the Promoted oxidation of sensitive carotenoids. This leads to degradation reactions such as. radical chain reactions in the product.

From that The object of the invention is to provide a gentle, easy to handle and economical Process for preparing saponified, carotenoid-containing oleoresin improved quality to disposal to deliver.

The The object is achieved by a method having the features of the claim 1 solved. Advantageous embodiments of the method are specified in the subclaims.

at the method according to the invention for preparing saponified, carotenoid-containing oleoresin unsaponified, carotenoid-containing oleoresin in solid state located, small piece and / or powdered Alkali metal hydroxide mixed intensively and in this case the oleoresin saponified.

The inventive method is based on an intensive mixing of the two educts unsaponified, carotenoid-containing oleoresin and small-sized and / or powdered alkali metal hydroxide. The large, reactive surfaces of the alkali metal hydroxide are covered or wetted by the oleoresin. In combination with very high shear forces this leads to an immediate hydrolysis of the oleoresin. The comminution of the alkali metal hydroxide can go as far as colloidal milling. hereby arise very large, reactive and oleoresin covered or wettable surfaces, which promote the immediate hydrolysis of the oleoresin with the solid alkali metal hydroxide in particular. As a result, the temperature rise of the reaction mixture is reduced and achieved a gentle saponification. Due to the lower saponification temperatures, which may range in particular from about 40 to 60 ° C, there is little or no degradation of lutein. Basically, no further additives are required to make the reaction mixture flowable. As a result, the saponification process is cheaper. The saponification times are very short and the process is easily scalable. A system for carrying out the method can be built very compact and with a small footprint.

The carotenoid-containing oleoresin may be added to the process in solid and / or liquid Condition are supplied. The use of carotenoid-containing oleoresin in the solid state simplified the procedure. For liquefaction the oleoresin is melted to the melting temperature, the at about 53 ° C can lie. As a result, the wetting of the alkali metal hydroxide be promoted with oleoresin and thus the saponification reaction.

It is possible, the procedure kleinstückiges and / or powdery To supply alkali metal hydroxide. According to one Embodiment of the method is alkali metal hydroxide to kleinstückigem and / or powdery Crushed alkali metal hydroxide and this with the non-soap, carotenoid-containing oleoresin mixed. In this embodiment the process is comminuted or only partially comminuted Supplied alkali metal hydroxide and will this in a for the saponification suitable or this promotional way comminuted. The crushing is e.g. a breakage of alkali metal hydroxide in little pieces and / or grinding alkali metal hydroxide into a powder.

The Comminution of the alkali metal hydroxide is e.g. before the mix and reaction with the non-soaped, carotenoid-containing oleoresin carried out. According to one Embodiment of the method is the comminution of the alkali metal hydroxide simultaneously or temporally overlapping with the mixture and reaction of the alkali metal hydroxide with the unsaponified carotenoid-containing oleoresin. This can a particularly efficient comminution of the alkali metal hydroxide as well as intensive mixing and reaction of the educts can be achieved. Furthermore, can through the merging of the process steps the throughput increases, the Reaction times are reduced and the expenditure on equipment is reduced become.

The Procedure is basically with all Alkali metal hydroxides feasible, optionally also with combinations of different alkali metal hydroxides. According to one Embodiment is the alkali metal hydroxide KOH (potassium hydroxide) or NaOH (sodium hydroxide). These alkali metal hydroxides are good or inexpensive available.

For one intensive contact of the oleoresin with the small piece and / or powdery Alkali metal hydroxide is beneficial if air pockets be avoided in the mixture. For this is / will be in accordance with a Design the oleoresin and / or the alkali metal hydroxide in Degassing or mixing and / or reacting degassed.

The Process is carried out, for example, discontinuously. For this will be e.g. the educts in at least one discontinuous stirring and / or Grinder mixed and / or crushed and / or reacted. Possibly The alkali metal hydroxide is previously by means of a separate crushing device crushed and / or ground. For high production performance the method is according to a Implementation carried out as a continuous process in which the starting materials continuously supplied and the product is withdrawn continuously.

According to one Design, in particular for the continuous implementation of the Appropriate method, the reactants are fed to an extruder and mixed and implemented in this.

According to one Embodiment, the alkali metal hydroxide before entering the Extruder and / or comminuted in the extruder. A crushing in front Entry into the extruder is by means of at least one additional Crushing device (e.g., crusher or mill) feasible. Due to the high shear forces in the extruder can additionally or instead of crushing the alkali metal hydroxide in the extruder become.

According to one In another embodiment, the extruder is a twin-screw extruder. In the twin-screw extruder is controlled by a controlled reflux of the extrusion given a controlled mixing.

The Invention relates to embodiments in which the educts in the extruder screw in the same Fed to axial position become. According to one The educts become the screw flight of the extruder supplied in different axial positions. This makes it possible to separately compress, degas, and even out at least one reactant to crush and another educt in the thus prepared Feed in educt.

According to one In another embodiment, the educts before entering the extruder premixed and fed into the extruder at the same axial position.

According to one In another embodiment, the starting materials are premixed and degassed and then fed to the extruder.

According to one other continuous design of the process, not requires an extruder, the starting materials are in an inline Kolloidmahlvorrichtung crushed and premixed and in a downstream continuous Mixer thoroughly mixed and implemented. An in-line colloid milling apparatus comprises an in a funnel-arranged, conical grinding tool. Between the wide opening of the funnel and the big one Diameter of the grinding tool is a wide feed gap available. Between the small diameter of the grinding tool and the small opening of the Trichters is formed a narrow Austragsspalt. The grinding tool is rotated by a drive motor. It may be on the perimeter a helical Have profiling. When driving the grinding tool is the Ground material comminuted and conveyed from the feed gap to the discharge gap.

Of the continuous mixer is e.g. a stirrer with a suitable Agitator. According to one embodiment the continuous mixer is a static mixer. The static Mixer is a pipe with fixed internals. The fixtures cause a mixing of a flowing medium. When mixing In the static mixer, the reaction of the starting materials takes place at the same time.

According to one Embodiment is the reaction of the oleoresin with the alkali metal hydroxide temperature-controlled. For example, the temperature is controlled by cooling so that adverse Degradation reactions suppressed become.

According to one Another embodiment, the reaction at a temperature between 20 ° C and 100 ° C performed. Preferably is the maximum temperature is 65 ° C. For temperature control is e.g. the extruder and / or the in-line colloid milling device and / or the continuous mixer is cooled.

According to one further embodiment, the unwanted oxidation of the carotenoids counteracts, are fed to the reaction mixture antioxidants. According to one In another embodiment, the antioxidants include BHT and / or BHA and / or ethoxiquin and / or vitamin C and / or chemical modifications of vitamin C and / or tocopherols.

Basically the mixture of solid and / or liquid oleoresin and solid Alkali metal hydroxide sufficient flowability for a discontinuous or continuous processing. According to one embodiment the reaction mixture in addition a flow aid added. According to one embodiment is the flow aid Propanediol. For support the fluidity Considerably smaller amounts of flow aids are required as with conventional Saponification must be added to additives to the fluidity to obtain the reaction mixture.

Further The invention relates to saponified, carotenoid-containing oleoresin, prepared according to the method described above.

The Oleoresin has according to one Design a water content of 0 to 5 wt .-%. The water content is thus well below the water content of oleoresin, the at conventional Saponification process results.

According to one contains further embodiment the oleoresin does not decompose carotenoids or only a small one Proportion of decomposed carotenoids at the detection limit. Due to the Gentle treatment by the method according to the invention are the carotenoids if necessary decomposed to a very small extent.

Finally, refers the invention relates to a feed comprising a saponified, carotenoid-containing oleoresin of the above type.

following the invention will be explained in more detail by means of embodiments which are illustrated by the accompanying drawings. In the drawings demonstrate:

1 Apparatus for producing saponified, carotenoid-containing oleoresin with an extruder and comminution of the alkali metal hydroxide in the extruder in a longitudinal section;

2 Apparatus for preparing saponified, carotenoid-containing oleoresin with an extruder and a mill for comminuting the alkali metal hydroxide in a longitudinal section;

3 Apparatus for producing saponified, carotenoid-containing oleoresin with an in-line colloid mill and a static mixer in a longitudinal section.

The following preliminary investigations were carried out on a laboratory scale:
The materials used were unsaponified oleoresin containing 121 g / kg of total xanthophylls. In addition, KOH cookies and - in a part of the experiments - 1,2-propanediol and water.

Of devices and machines, a mortar, a mixer of the type Ultra Turrax were used (with a rated speed of 18000 min ^-1), and a heating plate beakers (with a capacity of 500 ml).

In a try V1 became KOH cookies in the mortar crushed.

The Oleoresin was melted in the beaker on the hot plate (Melting temperature about 53 ° C).

The Pre-shredded KOH was added to the molten oleoresin and the product mixed with the Ultra Turrax until the material not stir anymore left. The mixing time was about 2 to 3 minutes.

In an experiment V2 was proceeded as in V1, but the KOH was not pre-shredded, but was directly tried, the cookies with to crush the Ultra Turrax.

In a trial V3 was also proceeded as in V1, but with the stirring time was increased by addition of 1,2-propanediol.

in the Experiment V4 was as in experiment V1 proceeded, but the KOH dissolved in water and then mixed with the molten oleoresin.

• *GX = Gesamtxantophylle = Wertstoff

The test results are summarized in the table below.

• * GX = total xanthophyll = valuable substance

Based the measurement results for trial V4 can be seen that a water-containing mixture almost no saponification effect (degree of saponification: 4.88%) brings.

If however, the KOH in the unresolved Condition, finely divided with the oleoresin comes into contact, provides within the shortest possible time Time a very high degree of saponification. This is in the trials V1 and V2 the case (degree of saponification: 51.4% and 25.7%, respectively). The limits These conversions are in the mixing tool, because this sucks above a certain viscosity the oleoresin no longer and a further mixing is with high intensity not possible anymore.

attempt V3 proves that by the addition of propanediol as a flow aid, the mixture as long as low viscosity could be held that one practically complete Saponification took place (degree of saponification: 97.8%).

through an extruder can much higher shear be achieved than in an Ultra Turrax. Therefore, the Using an extruder a virtually complete saponification, even without Use of a flow aid.

According to 1 includes an extruder 1 in a housing 2 at least one cylinder 3 or snail, in which at least one snail 4 is arranged. The snail 4 is by means of a drive motor 5 drivable. The extruder 1 is for example a twin-screw or twin-screw extruder or a ring extruder.

In the area of an inlet 6 is the cylinder 3 with the small diameter of a funnel-shaped template and feeder 7 connected. The original and feed 7 is open at the big diameter. In the original and feeder 7 is a stirrer 8th arranged.

In the area of the inlet 6 has the snail 4 a gradually decreasing slope. Adjacent to the inlet 6 indicates the cylinder 3 a degassing area 9 on with at least one degassing duct 10 for air.

Adjacent to it is the cylinder 3 an infeed area 11 for solids with at least one inlet channel 12 for alkali metal hydroxide. This is followed by another degassing area 13 with at least one further degassing channel 14 for air.

This is followed by a meal area 15 in which the alkali metal hydroxide is finely ground. From the inlet 6 to the grinding area 15 decreases the pitch of the screw and its outer diameter. In the milling area 15 is reached the minimum slope and the maximum outside diameter. There, the extruder or the screw can have a special milling insert. In the Mahlreich 15 has the case 2 a cooling chamber 16 with a cooling water inlet 17 and a cooling water outlet 18 ,

Adjacent to it points the extruder 1 a reaction area 19 on, in which the snail 4 the same pitch and the same outside diameter as in the grinding area 15 having. Also the reaction area 19 is from a cooling chamber 20 surrounded, which enters another cooling water 21 and another cooling water outlet 22 having.

The reaction part 19 opens into an outlet channel 23 , The cross section of the outlet channel 23 falls below that of the cylinder 3 , The outlet channel 23 is designed for example as a nozzle head.

The extruder 1 becomes unsaponified, carotenoid-containing oleoresin via the template and delivery 7 fed. There the oleoresin becomes by means of a stirrer 8th evenly mixed and enters the inlet 6 to get off the snail 4 to the outlet channel 23 to be promoted. In the inlet 6 the educt is gradually compressed and from the snail 4 to the degassing area 9 transported. There, extruded air and other gases pass through the degassing duct 10 out.

In the feed area 11 Alkaline hydroxide is in particulate form through the inlet channel 12 metered.

In the following further degassing 13 is the mixture of oleoresin and alkali metal hydroxide from the screw 4 compressed, with air and other gases through the further degassing 14 escape.

In the milling area 15 The alkali metal hydroxide is finely ground and mixed intensively with the oleoresin. This takes place under constant cooling. The compaction, degassing and grinding operations in the areas 13 and 15 are already accompanied by an implementation of the educts with each other. In the reaction area 19 Finally, the essential part of the implementation takes place. The reaction is also cooled. Finally, saponified oleoresin from the outlet channel 23 squeezed out.

The extruder 1' from 2 is different from the extruder 1 from 1 in that the alkali metal hydroxide is first of all fed to a mill (eg roller mill, roller mill, agitator mill (eg agitator ball mill, gap agitator mill), in-line homogenizer (rotor-stator systems) - eg Silverson) 24 supplied becomes. The ground alkali metal hydroxide leaves the mill 24 through the entrance channel 12 in the feed area 11 , There and in the subsequent degassing 13 and amplified in the subsequent reaction area 19 the saponification reaction takes place. The saponified, carotenoid-containing product leaves the extruder 1' through the outlet channel 23 , The extruder 1' has no additional grinding area 15 and therefore can be slightly shorter than the extruder according to 1 be executed.

The device of 3 has a continuous kneader 25 with a kneading tool 26 on, the input side with a funnel-shaped template and feeder 27 connected, which is a stirrer 28 having.

On the output side is the kneader 25 with a pump 29 connected. The pump 29 is eg an eccentric screw pump, cellular wheel pump, gear pump. This is followed by a degassing area 30 on, with at least one degassing 21 connected is.

On the degassing channel 31 follows an in-line colloid mill 32 , The in-line colloid mill is eg a tooth colloid mill or a corundum disc mill. It is the output side with a reaction area in the form of a static mixer 33 connected.

Bulk alkali metal hydroxide and unsaponified carotenoid-containing oleoresin are added to the receiver and feed 27 fed. In it they are premixed.

Thereafter, the mixture enters the kneader 25 , From there it will be by means of the pump 29 withdrawn and in a degassing 30 compressed. There, the squeezed gas leaves the mass through the degassing 31 ,

The compressed mixture enters the in-line colloid mill 32 in which the alkali metal hydroxide is finely ground. Thereafter, the reaction mixture enters the static mixer 33 in which the saponification of carotenoids takes place. The saponified carotenoid-containing product leaves the device through an exit channel 34 ,

Claims (25)

Process for the preparation of saponified, carotenoid-containing Oleoresin in which unsaponified carotenoid-containing oleoresin with in the solid state, small-sized and / or pulverulent alkali metal hydroxide intensively mixed and thereby the oleoresin is saponified. The method of claim 1, wherein the carotenoid-containing Oleoresin in solid and / or liquid Condition supplied becomes. The method of claim 1 or 2, wherein the alkali metal hydroxide crushed and with the non-soaped, carotenoid-containing oleoresin is mixed. Method according to one of claims 1 to 3, wherein the comminution the alkali metal hydroxide simultaneously or temporally overlapping with the mixture and reaction of the alkali metal hydroxide with the unsaponified, carotenoid-containing oleoresin is performed. A process according to any one of claims 1 to 4, wherein the alkali metal hydroxide KOH and / or NaOH is. Method according to one of claims 1 to 5, wherein the oleoresin and / or the alkali metal hydroxide during comminution and / or mixing and / or reacting is / are degassed. Method according to one of claims 1 to 6, which is continuous Process is performed in which the reactants are fed continuously and the product continuously is deducted. Method according to one of claims 1 to 7, wherein the educts fed to an extruder and mixed and implemented in this. A method according to claim 8, wherein the alkali metal hydroxide crushed before entering the extruder and / or in the extruder. The method of claim 9, wherein the extruder is a twin-screw extruder. Method according to one of claims 8 to 10, wherein the educts be premixed before entering the extruder. Process according to Claim 11, in which the educts are premixed and degassed and fed to the extruder. Method according to one of claims 8 to 12, wherein the educts the screw flight of the extruder in different axial positions supplied become. Method according to one of claims 1 to 7, wherein the educts Crushed and premixed in an inline Koloidmahlvorrichtung and intense in a downstream continuous mixer mixed and implemented. The method of claim 14, wherein the continuous Mixer is a static mixer. Method according to one of claims 1 to 15, wherein the reaction the oleoresin is temperature-controlled with the alkali metal hydroxide. The method of claim 16, wherein the reaction at a temperature between 20 ° C and 100 ° C is performed. The method of claim 17, wherein the reaction at a maximum temperature of 65 ° C. A process according to any one of claims 1 to 18, wherein the reaction mixture Supplied antioxidants become. The method of claim 19, wherein the antioxidants BHT and / or BHA and / or ethoxiquin and / or vitamin C and / or chemical modifications of vitamin C and / or tocopherols include. A process according to any one of claims 1 to 20, wherein the reaction mixture a flow aid is added. Saponified, carotenoid-containing oleoresin prepared according to the method of any one of claims 1 to 21. Oleoresin according to claim 22, having a water content from 0 to 5 weight percent. Oleoresin according to claim 22 or 23, containing none or only a small proportion of decomposed carotenoids at the detection limit. Animal feed containing a saponified, carotenoid-containing Oleoresin according to one of the claims 22 to 24.