WO2004028675A1

WO2004028675A1 - Mixing device and covering device, use thereof and method for modifying and derivatising carbohydrates

Info

Publication number: WO2004028675A1
Application number: PCT/AT2003/000261
Authority: WO
Inventors: Dietmar Grüll; Ondrej Mikla; Marnik Wastyn
Original assignee: Südzucker Aktiengesellschaft Mannheim/Ochsenfurt
Priority date: 2002-09-27
Filing date: 2003-09-08
Publication date: 2004-04-08
Also published as: EP1542791A1; AT413698B; AU2003260156A1; ATA14612002A

Abstract

The invention relates to the use of a mixing device comprising a mixing chamber (2) which is provided with a displaceable mixer (4) and a sealingly guided press plate (3) for physical modification and/or chemical derivatisation of high-molecular and/or low molecular carbohydrates, proteins and/or mixtures thereof. The invention also relates to a mixing device for the physical modification and chemical derivatisation of high molecular and/or low molecular carbohydrates, proteins and/or mixtures thereof comprising at least one mixer and at least one sealingly guided press plate (3) in a mixing chamber (2) which can be closed by means of a lid (6) and a discharge device (5) comprising a feed part (5') and a discharge part (7). The invention further relates to the use of a mixing device for the physical modification and/or chemical derivatisation of high molecular and/or low molecular carbohydrates, proteins and/or mixtures thereof. The invention further relates to a method for physical modification and/or chemical derivatisation of high molecular and/or low molecular carbohydrates, proteins and/or mixtures thereof.

Description

Mixing device and covering device, use thereof and methods for modifying and derivatizing carbohydrates

The invention relates to the use of a mixing device for the physical modification and / or chemical derivatization of carbohydrates, proteins and mixtures thereof.

Furthermore, the invention relates to a mixing device for the physical modification and / or chemical derivatization of carbohydrates, proteins and mixtures thereof with a discharge device.

The invention further relates to the use of the mixing device with the discharge device for the physical modification and / or chemical derivatization of carbohydrates, proteins and mixtures thereof.

The invention further relates to a method for the physical modification and / or chemical derivatization of carbohydrates, proteins and mixtures thereof.

In the treatment of carbohydrates, proteins and mixtures thereof, such as those carried out in the food industry, paper industry or in other technical branches of industry, it is known to improve the physical and chemical properties, such as viscosity. This is generally e.g. in the case of polysaccharides, in particular starch, achieved through physical modification and / or chemical derivatization of the raw material, typical amounts of water, plasticizer and other agents being added. The treatment or implementation of the carbohydrates is based on the continuous homogenization of the components under special pressure conditions and the addition of energy or temperature. After completion of the mechanical and thermal treatment, the modified and possibly plasticized products can be expanded by changing the pressure, the volume increasing many times over in order to obtain a finished product that is ready for use or suitable for further processing.

So far, the autoclave has been used in this area, in which carbohydrates are treated in a discontinuous process, especially for the production of cold water borrowed starch derivatives. An aqueous starch suspension is chemically reacted with the addition of chemical reagents and constant stirring. Thermal energy is usually supplied via the housing wall by means of double jacket heating or else steam injectors. The reaction product is then subjected to a drying process - often using a drum dryer - in order to obtain a product that can be stored and transported. This process is investment-intensive, time-consuming and energy-intensive and, above all, low-viscosity properties of the starch can only be brought about by additional chemical interventions or extended thermal treatment.

A discontinuous process is known from US Pat. No. 3,527,606, in which starch in particle form is suspended in a thickener with a stirring agent for mechanical treatment of the material to be modified by means of centrifugal force. The starch particles are flung against the wall of the thickening cooker in order to achieve heat transfer between the particles and the wall for modification.

Another device that is also used and common in many other fields of application is the extruder, in which the material to be treated is subjected to a continuously working process. The extruder housing can be equipped with a cooling or heating jacket, as a result of which a constant process temperature is maintained. The retention times of the material to be treated in the extruder housing depend on the length of the extruder screw, but this often turns out to be disadvantageous because the retention times are limited thereby. Negative results are also due to the permanent forced movement of the material and the operating conditions in the extruder housing, which can only be changed slightly. When using this process for the production of plasticized starch, the production of highly viscous products is not guaranteed, since the starch molecules in the extruder are exposed to excessive thermal and mechanical stress and are degraded in the process.

A similar continuous starch modification method is described in EP 710 670 B1, the starch to be modified being in a continuous powder stream via an inlet opening into a closed cylindrical one Turboreactor housing is introduced with a cooling or heating jacket. A paddle wheel, the blades of which are arranged helically on the shaft, is used for centrifuging and the simultaneous advancement of the reaction material in the direction of an outlet opening. Any drying can be achieved by means of a turbo dryer, which is arranged at the outlet opening of the turbo-reactor and has a similar structure to the turbo-reactor. The end product produced by this process consists of a dry product, in particular a dry powder.

An attempt to solve the problem of discontinuous and continuous processes in terms of construction was made in US Pat. No. 5,455,342. This describes an apparatus and a method for modifying starch or other polymers. A mixing tank and a compression camera connected to it are used to pretreat and apply pressure to the starch to be modified. The pressure in the compression chamber is applied by a piston. A connecting line provided with a valve leads from the pressure chamber to a so-called "baffle chamber" - a tube with a plurality of baffles or rings arranged along the inside. The starch is pressed through the tube, the baffles generating turbulence in the material. The modified starch is discharged through an outlet line, after which the starch is stored or optionally dried.

The object of the present invention is now to improve and simplify the treatment of carbohydrates, proteins and / or mixtures thereof, so that on the one hand a wide range of starting materials can be used and on the other hand diverse. e.g. viscous properties of the end product are obtained, the above-mentioned problems being avoided.

This object is achieved according to the present invention in that a mixing device comprising a mixing chamber with a movable mixer and a sealingly guided press plate, as described in AT 382 090 B, for the physical modification and / or chemical derivatization of high molecular weight and / or low molecular weight carbohydrates, proteins and / or mixtures thereof is used. The use of this device known per se - below also referred to as a press mixer or press mixer - for physical modification and / or chemical derivatization corresponds to a combination of the continuous and discontinuous (in batches) operations described above. The use of this concept on the one hand enables the use of a broad spectrum of raw materials for dispersion and plasticization and on the other hand enables the end product to be given a wide range of properties, such as low or medium or high viscosity, depending on the specific starting product and the applied process conditions. For this purpose, low and high molecular weight carbohydrates, proteins and / or mixtures thereof are used according to the invention. Mixtures are also understood to mean mixtures with flours, since flours of vegetable origin contain protein. The mixing device used according to the invention is particularly well suited for this purpose, since it is very flexible in its mode of operation and, as a result, a large number of differently designed end products can be produced simply and efficiently. The modified carbohydrates, proteins and / or mixtures thereof or end products produced in this way are advantageous as functional raw materials and / or additives in areas of application which range from the food, cosmetics and pharmaceuticals industry, dishwashing detergents industry to the textile industry and paper industry to the construction and plastics industries. Furthermore, the products provided according to the present invention can be used for the production of insulating, insulating and building materials, such as composite materials, ceramic products, chipboard, plasterboard, packaging materials. Such a wide range of applications for such products is based on the fact that the mixing system used according to the invention makes it easy to individually control and control the operating conditions within the mixing device. These relate, for example, to the controllable movement of the material by means of the mixer (described in more detail below), which ensures homogenization that can be greatly influenced. Furthermore, these relate to the decoupled or, if desired, simultaneous application of pressure by the separately controllable press plate, which can be variably adjusted to the specific characteristics of the material to be converted. The mixing device u used according to the invention includes a sealable seal Mixing chamber or a reactor vessel with a mixing tool and a sealingly guided axially movable base plate, which functions as a press plate. The required reaction conditions of the material to be converted can be set individually using the rotatable and, independently of this, oscillatable mixer. The applied mechanical energy of the mixing tool heats, for example, powdery starch to such an extent that it converts to a plasticized mass with a natural water content. An additional admixture of solvent, such as when using conventional devices, is therefore no longer necessary, and a subsequent drying process, as with the autoclave process, is unnecessary. The individual adaptation of the operating conditions of the mixing device used according to the invention also includes working under vacuum, as a result of which treatment of inulin, for example, delivers particularly good results. The reactions can also be influenced using the press plate for applying pressure. For example, hydrophobizing substances have a lubricating effect during their treatment and the use of conventional devices, in particular the extruder, all too often leads to considerable problems of consistency in the product to be treated. The specific process conditions in the extruder cannot be regulated due to the inherent screw length, which results in an undesirable inhomogeneous nature of the material. In addition, in many cases hydrophobization is not possible at all, for example due to the consistency of the material to be processed in the extruder. If such hydrophobic substances are subjected to defined conditions of the continuous press mixture according to the invention, their residence times can primarily be increased or influenced in a controlled manner, as a result of which a higher degree of substitution can be achieved and the treated material has no lubricating effect during its implementation on. Accordingly, greater reaction yields of the starting products to be treated can also be achieved. Hydrophobization under which, according to the invention, etherification reactions with epoxyalkanes with chain lengths from C ₃ to C ₂₄ , esterification reactions with fatty acids, fatty acid chlorides, fatty acid anhydrides (homogeneous or mixed), alkyl succinic acids, alkyl succinic acid anhydrides three with chain lengths from C ₃ to C _24, for example, are easily accessible. Not only the consistency corresponds to an important requirement, but also material properties, such as viscosity, play an important role in the production of modified or plasticized carbohydrates. The process conditions are therefore also of importance in the case of carboxymethylation or cationization, with the mixing device used according to the invention being able to obtain end products which are satisfactory and meet the requirements extremely easily and efficiently.

With regard to the raw materials, there is a wide range of, among other things, high-molecular carbohydrates. Viscous properties can be achieved by means of the mixing device used according to the invention if native starch and / or degraded and / or already physically and / or chemically modified derivatives thereof are used. In addition to unchanged, high-molecular carbohydrates, carbohydrates that have already been treated can also be used as the starting material, as a result of which the properties of these materials can be further improved or changed with the aid of the above-mentioned mixing device, and therefore a wide range of uses of such treated products is also created.

The use of native starch as a starting product is particularly favorable when the native starch is made from starch from corn, waxy maize, amylomais, potatoes, amylose-free potatoes, sweet potatoes, wheat, wax wheat, roe, barley, oats, aranthanth, tapioca, cassava, rice, Wax rice, peas and millet is selected. These easily available substances are not only inexpensive, but also have extremely good properties with regard to their treatment or further processing and their industrial applicability.

Other cheap raw materials from the group of high-molecular carbohydrates, which can also be modified to satisfactory end products with the aid of the aforementioned mixing device, include, in addition to the above-mentioned substances, inulin, oligo-fructose, galactomannans such as guar, locust bean gum, cassia, tare gum and other hydrocolloids, as described for example in Ullmann's Encyclopedia of Industrial Chemistry, RL Whistler, JN BeMiller: Industrial Gums, Polysaccharides and Their Derivatives, Third Edition, Academic Press, London, 1993 be especially pectin.

With regard to the low molecular weight carbohydrates, it is advantageous if the starting materials include sugars and sugar alcohols. When using the aforementioned mixing device, such materials can be optimally processed into viscous end products. In modified form, they are also a good starting material in the chemical industry, in particular in the food and pharmaceutical industries, but also as a starting product for polymers, raw materials for washing, plasticizers, emulsifiers and the like.

In this context, it is advantageous if sugar, selected from sucrose, maltose, fructose, as well as glucose and palatinose®, is used.

Furthermore, it is advantageous if hydrogenated derivatives, such as e.g. Palatinit®, sorbitol, mannitol, xylitol, maltitol, lactitol and other sugars and sugar alcohols listed in Ulimann's Encyclopedia of Industrial Chemistry, 4th edition, volume 24, pages 749-793 can be used.

In particular, vegetable proteins can be mentioned as proteins, such as naturally occur together with the abovementioned starting products, but also animal protein, such as casein.

The use of the mixing plant used gives particularly good results if it is used for the production of carbohydrates, starting from mono- and / or disaccharides and / or their sugar alcohols. More precisely, the production of carbohydrates is the re-synthesis of carbohydrates, and the polycondensation which is generally used to build up new carbohydrates is very efficient with the aid of the device according to the invention. It is clear that monomers or mixtures of the individual monomers (mono-, disaccharides and their sugar alcohols) are used, which are press-mixed in the mixing plant. In this way, for example, sugar substitutes, which are used for the production of low-calorie foods, such as Polydextrose®, can be produced quickly and without great effort. Furthermore, the new synthesis of such carbohydrates using such a mixing device not only ensures an improved texture of the treated product, but also benefits the taste impression. Another object of the invention is to provide an improved mixing device for the physical modification and / or chemical derivatization of high molecular and / or low molecular weight carbohydrates, proteins and / or mixtures thereof. Specifically, this is a modified mixing device, which has been described in part above, whereby this concept for the treatment of the starting materials mentioned is to be optimized. The mixing device in question has at least one mixer and at least one sealing plate which is guided in a sealing manner in a mixing chamber which can be sealed by means of a cover. Furthermore, a discharge device with a feed part and with a discharge part is provided.

In the case of the above press mixing device according to AT 382 090 B, a discharge device is provided, but is not further specified. It is known that a moderate and gentle process is required for the discharge of modified or plasticized carbohydrates, so that the end product to be obtained can be removed from the mixing plant with satisfactory consistency and viscous properties. Especially during the discharge process, there is often the problem of insufficient, reduced expansion or inflation of the plasticized end products, since the treated material is discharged or squeezed out of the conversion device too quickly and / or inconsistently, so that the gelatinized material is inhomogeneous, i.e. only on its surface, expanding. Such a misconduct of implementation and discharge can even lead to the expanded discharge product developing a hardness comparable to that of glass and thus being a completely unusable product.

The high-pressure-resistant sealing device described in EP 916 877 A2 for the homogenization or dispersion of sensitive liquid phases or solids has a high-pressure-resistant mixing container with an axially displaceably mounted rotor as a mixing tool and a plate-shaped element or pressure plate mounted above it. The circumference of the pressure plate is equipped with a plurality of sealing elements. The mix to be treated is when the rotor and the plate-shaped element received and sheared in a gap between the rotor and the plate-shaped element. Using this device, on the one hand, it is possible to reduce the treatment times of the substances to be mixed, in addition to the rotation and pressing pressure, the shear also acts on the material and, on the other hand, the sealing elements ensure that the mixing container is securely sealed against atmospheric influences, but it does not offer a solution Disadvantages mentioned above during the discharge process of the treated material. A discharge device is not specified here either.

An earlier development of the sealing device just mentioned for homogenizing and dispersing liquid phases is known from EP 832 682 A1. In this mixing device, too, no discharge device is disclosed; the treated material is only removed by pushing up the plate-shaped element located on the top of the rotor, the material being removed as a whole, which again runs the risk that problems already mentioned occur easily during the discharge process.

It is an object of the present invention to provide a mixing device with an optimized discharge device, with which, on the one hand, an expansion of modified end products, in particular plasticized polysaccharides or starch, can be brought about slowly or controllably, depending on the material used, and without major additional expenditure, so that entire material can be easily and easily discharged as a foam-like inflated mass or removed from the mixing device.

This object is achieved in that the discharge device of a mixing device comprises forced conveying, such as a screw conveyor, preferably a single-screw extruder, and is preferably arranged on the cover of the mixing chamber, other arrangements, horizontally or vertically along the reaction container, are also conceivable , Cell wheel locks, spindle pumps such as Mohno pumps, gear pumps or the like can also be used as forced conveyors. Forced conveyance as a discharge device creates an extended combination of the continuous and discontinuous treatment concept of Starting products for the preservation of broadband viscous properties, since the pressure conditions applied to the positively conveyed material can be controlled. The unlimited control of the retention time and the application of pressure, which is possible in such a discharge device, allows the discharge product to be fully expanded in order to achieve optimal, high-quality and, above all, homogeneous material properties. In addition, the continuous movement of the discharge material creates a removal in defined, determinable batches, so that the discharge product can be removed from the mixing device as a sales manufacturer, but also as an easily processable strand. It is also conceivable for the discharge device to be heatable or coolable, so that an additional temperature effect or temperature maintenance on the positively conveyed material is possible. In addition, it is conceivable that a vacuum connection is provided in the area of the forced conveyance of the discharge device, so that negative pressure conditions within the discharge device and in the reaction container are permitted. This is advantageous in the treatment of, for example, polysaccharides or the production of highly esterified products, since water of reaction which has a disruptive effect on the conduct of the reaction or on the reaction yields can be removed in the press mixer during the reaction. The arrangement of the discharge device is disadvantageously designed such that it, preferably the extruder, is guided across the cover. Such a design of the cover, which corresponds to the lid of the mixing container, provides simple, direct access to the discharge device from the mixing chamber and thus at the same time a discharge or squeezing out of the material from the mixing chamber, which is forced but very controlled. takes place.

In order to provide access from the mixing chamber to the discharge device, it is expedient that such a connection is realized through at least one opening in the cover of the mixing chamber. More than one connection can also be provided, as a result of which the material to be mixed from the mixing chamber is taken up unhindered by the discharge device via the feed section of the forced conveying means, in particular of the extruder. With this opening, it is advantageous if it has a slit-like, has an elongated shape, but circular, rectangular, elliptical or similarly shaped openings can also be provided.

According to a further feature of the invention, the connection opening of the discharge device is arranged off-center in the cover. Such an eccentric arrangement ensures that the material to be discharged reaches the feed section of the extruder optimally.

In this context, it is expedient if the mixer of the mixing device and the sealing plate of the mixing chamber which is guided in a sealing manner can be displaced in the direction of the cover. The converted material is thereby moved in the direction of the cover or cover by the oscillating and rotatable mixing tool and is forced into the connection opening, which is connected to the discharge device, by the press plate, which is also sealingly guided in the direction of the cover. The mixer strips the material at the opening edges of the connection or its border, so that all of the material is removed from the mixing chamber. Of course, the arrangement of this connection opening can also be formed in the center or in the edge area, although complete emptying of the mixing chamber must be ensured, so that no remaining, unused mix remains in the mixing chamber. This inventive feature of the preferred axial displaceability of the mixer and the plate also serves not only for the maximum but metered discharge of the material to be mixed from the mixing chamber, but also for a thorough emptying thereof. For a particularly precise guidance of the mixed material into the discharge device, it is advantageous if the mixer and the sealing plate of the mixing chamber, which is guided in a sealing manner, can be moved close to the connection opening of the discharge device.

In addition, it is advantageous if the cover of the mixing chamber is provided with valves. Thus, not only working under different pressure conditions, such as vacuum, is fundamentally created, but also loading, ventilation, gassing or evacuation (for example in the form of a safety valve) is permitted. This also includes the possibility of metering in gaseous or liquid components or reagents or else removing undesirable, in particular volatile, by-products from the reaction of the treated starting products arise. Equipping the cover with valves has the particular advantage that continuous working conditions can be achieved; ie the valves are used for loading the chamber with fresh raw material and / or additional other components, in order to be removed immediately after sufficient, controlled conversion of the mixed material by means of the discharge device, with a refill with fresh raw material being able to take place via the valves at the same time without to stop operating the system. As an alternative to the continuous application of the work steps, it is also conceivable to operate discontinuous, semi-continuous or "batchwise" conditions. For this purpose, after the components to be treated have been introduced, the valves are kept closed until the activated discharge process of the mixture is completed via the discharge device, so that the mixing chamber and the discharge extruder are completely emptied. The system can then be subjected to cleaning by introducing cleaning agent (or water) into the mixing chamber, for example via valves or closable through openings, and keeping the system in operation until the interior of the system has been completely emptied.

It is expedient if pressure or temperature sensors for checking the mixing chamber are arranged on the underside of the cover facing the mixing chamber. The number as well as the arrangement and position can be configured as required. These sensors serve as control means; Accordingly, the type and type of the sensors should be selected in such a way that they enable accurate observation and possible correction of the reaction conditions of the mixing components in the mixing chamber. For example, if the energy required for the materials to be treated is inadequate, it can be detected by means of the temperature sensors and quickly compensated for by switching on heat. In this context, it is conceivable that such controls or regulations can be taken over by a connected computer or can also be carried out manually.

In order to achieve a uniform and uniform expansion of the mass, it is according to another inventive feature provided that a discharge valve is provided on the discharge part of the discharge device or the extruder. Here the type or type of valve is to be selected as a function of the material properties, the discharge part being removable or interchangeable with other different discharge parts. It is also conceivable that the discharge zone with the controllable passage opening can be adapted to any shape (depending on the subsequent use or further processing) of the discharged substance. Correspondingly, it is possible to discharge the converted end products in the form of a strand or other shape, for example already cut. For this purpose, a cutting device with a rotating knife blade can be attached to the end of the discharge device.

According to the invention, it is extremely expedient if the sealing plate guided in the mixing chamber is provided with mechanical seals, which are preferably made of hardened metal. This ensures that a wide range of material combinations can be subjected to treatment in the mixing chamber with discharge device without running the risk of causing wear, such as signs of corrosion, abrasion or other wear and tear. Conventional O-rings made of rubber material, Teflon-coated rubber, seals made of Viton or comparable materials can also be used, whereby it must be ensured that, depending on the material or mixture used, no harmful effects on the resilience or durability of these seals are brought about.

With regard to a physical modification and / or chemical derivatization of high molecular and / or low molecular weight carbohydrates, proteins and / or mixtures thereof, it is particularly advantageous if the mixing device with discharge device just described is used. This particular feature of the present invention, which is characterized by the use of the discharge device, consists in the realization of the optimized combination of the continuous with the discontinuous concept for the production of plasticized low, medium and highly viscous end products of high quality. For example, an immediately usable and high-quality composite material is rial can be produced in the simplest way using the device according to the invention. This is done simply by introducing carbohydrates, in particular starch or modified starch, together with plastics, such as polyethylene, polypropylene and other polyolefins, polystyrene, polyester, polyvinyl chloride and the like, into the mixing device in which the introduced material is plasticized and via the discharge device is immediately removed as a processable composite material. The directly connected continuous discharge has the particular advantage that the use of plasticizers, which are otherwise required in conventional devices such as the extruder, in order to produce a high-quality composite material, is considerably reduced or can even be saved entirely.

A mixing device with a discharge device is particularly advantageous if it is used for the production of carbohydrates or new synthesis, starting from mono- and / or disaccharides and / or their sugar alcohols. In this context, it is expedient if the above-mentioned mixing device is used together with the above-mentioned discharge device.

Another object of the present invention is to provide a method for the physical modification and / or chemical derivatization of high molecular and / or low molecular weight carbohydrates, proteins and / or mixtures thereof. Usual methods, such as the continuous and discontinuous processes explained at the beginning, are on the one hand. tels extruder and on the other hand by autoclave. It is also known that these two application methods can be connected in series and / or in parallel in order to take advantage of each individual method. However, even in such an arrangement, these techniques cannot overcome all of the disadvantages, as is the case, for example, with the reaction times of the conventional methods, which, inter alia, have already been discussed at the beginning. In this context, there are limited and / or incorrect feasibility for large requirements with regard to various types of high-quality viscosity properties of the end product. This includes the requirements for process-specific additives and / or reagents to arrive at a either high or low viscosity end product. For example, plasticizers are required as an additive in the plasticization of starch in order to obtain a product with demanding viscosity properties. Another example is that when carbohydrates are modified, an aqueous system must be present so that the substances can be modified and / or derivatized, especially in the case of starch as the starting product. Connected to this is the process-specific requirement for drying, which is usually realized in a batch process by means of a drum dryer. Further disadvantages lie in the relatively high capital investments, with additional large energy expenditures with relatively low efficiency of the chemical reactions in the systems. The inevitable result of this is that the techniques mentioned are cost-intensive and, due to the limited use of raw materials, also uneconomical.

In summary, the object of the present method is that the advantages of both continuous and discontinuous treatment methods mentioned above can be carried out in one process step. It is among other things also the aim of optimally modifying the starting products to be implemented, even with very little to no water content, the plasticized end product easily and, above all, it can be regulated, the necessary reagents added as desired and volatile by-products withdrawn at any time.

According to the present invention, the above objects are achieved in that the starting products are press-mixed by means of a press plate and a mixer, the guidance of the press plate and the mixer taking place decoupled from one another. The press plate, which can preferably be guided axially, exposes the material to feed on the one hand and to compressive stress on the other. The effect of the mixer on the starting products to be modified is the homogenization, i.e. the mixing, and additional thermomechanical treatment by applying pressure and temperature to the starting products to be modified. The decoupled guidance of the two construction parts enables the mix to be handled independently of one another. Depending on the requirements, which depend on the one hand on the type of raw material used and on the other hand on the desired objective of the nature of the end product (viscosity, millability, etc.), the starting products are extremely flexible and therefore easier to implement. This consists primarily in the controllable and individually adjustable residence times, which means that the reactions can run better and above all completely. In this context, it is also advantageous if the pressure and temperature conditions can be regulated within the mixing device used for this purpose. The result of this is that the chemical consumption required for the modification is better matched to the mixture to be treated, which also reduces it considerably, which is advantageous from an economic point of view.

With regard to the optimization of the process, it is advantageous if the starting products are press-mixed completely or almost solvent-free. The almost solvent-free treatment consists in an extremely small addition of, preferably water, to e.g. Bring carbohydrates into a hydrated state. According to the method according to the invention, this can also be done without the addition of water, since the natural water content of the starting products can be used for hydration due to the mode of action of the press plate or through the application of a defined pressure. For example, this is particularly advantageous when processing inulin, since the production of highly esterified products produces typical amounts of water which would have to be removed for the reaction to proceed favorably. According to the invention, this is no longer necessary, since it is also possible to work under negative pressure conditions. This not only creates economic savings in terms of water consumption, but also reduces the consumption of other chemical additional reagents, which are known to be required for incorporating the starting products into aqueous systems.

In this context, it is particularly expedient if the end products, after their physical modification and / or their chemical derivatization, are continuously discharged using a discharge device according to the present invention, which has already been set out above and is further explained below with reference to the accompanying drawing. The mode of operation of this type of discharge using the inventive method Discharge device consists in the conditions by which the substances are continuously, but according to the invention, forcedly conveyed in a controlled form. If the starting products for their modification are press-mixed with a small amount of solvent or water added according to the invention, the expansion of the material, which is important for starch production, can be completely or homogeneously achieved and, above all, a more favorable quality of the plasticized starch. This can be achieved by means of the slow, permanent forced movement by means of the discharge device according to the invention, in which sufficient pressure relief, which is necessary above all for expansion, can take place. If desired, it is also possible to discharge the modified end products under protective gas conditions. By means of the present invention, the end product, also modified according to the present invention, can be removed constantly and completely from the mixing system in a completely or - if necessary - almost ready-to-sell, preferably strand-like, condition. The finished end product is easy to handle, in particular can be further comminuted and / or better ground, which is important, for example, in the production of starch.

In the production or new synthesis of carbohydrates, starting from mono- and / or disaccharides and / or their sugar alcohols, it is advantageous if the required starting products, which also include monomers and their mixtures, are used independently of one another by means of a press plate and a mixer be press mixed. Furthermore, it is advantageous if the products treated in this way are then continuously discharged by means of a discharge device described above.

To clarify the present invention, a few examples are given below which show in Example 1 the preparation of carboxymethylinulin, Example 2 the breakdown of guar gum and Example 3 the hydrophobization of potato starch.

example 1

Manufacture of carboxymethylinulin

The mixing chamber of the press mixing plant is heated to 60 ° C riert. 2000 g of Inulin ST (from Orafti, BE) are filled into the mixing chamber. 719 g of sodium monochloroacetate are added, the mixing chamber is closed and the press plate is put into operation at the medium level. The contents of the mixing chamber are 5 min. At 150 rpm and an oscillation frequency of 10 strokes / min. homogenized with the mixer. After 5 minutes, the press mixer is switched off, the lid is opened and 50 g of sodium hydroxide microbeads are added. At approx. 30 rpm and frequency 10, nitrogen is blown in through a valve for 60 seconds and vented through another valve. After purging with nitrogen, the valves are closed. The speed of the stirrer is set to 250 rpm and the frequency to 15 strokes / min. raised and the press plate moved to a higher level. Under these conditions, the contents of the mixing chamber are treated mechanothermally. During this treatment, the temperature in the container rose from 55 ° C to 85 ° C. After 10 minutes the mixer speed is reduced to 50 rpm and the oscillation is switched off. The contents of the mixing chamber are continuously discharged in the form of a strand by the discharge device. The product strand is shredded, ground and analyzed. The content of glycolic acid and sodium monochloroacetate is determined by means of HPLC and the reaction efficiency is calculated.

With a theoretical degree of substitution of 0.5, a reaction efficiency of 78% was achieved.

Example 2

Degradation of guar gum

The mixing chamber of the press mixer is heated to 100 ° C. 2000 g of conventional guar gum is poured into the mixing chamber and enough ml of deionized water is added that the dry matter of the mass is 55%. The mixing chamber is closed and the press plate is set to a high operating level. The contents of the mixing chamber are vented through the valve. The content of the mixing chamber is at 15 strokes / min. homogenized with the mixer. The speed of the mixer is kept so that a constant temperature is maintained in the mixing chamber. Under these conditions, the contents of the mixing chamber are treated mechanothermally. This increases during this treatment Temperature in the chamber and is kept constant at the desired level. Under these conditions, the contents of the mixing chamber are treated mechanothermally for different lengths of time. At the end of the mechanothermal treatment, the press plate is moved down and the mixer speed is set to approx. 50 rpm. The contents of the mixing chamber are continuously discharged through the discharge device under extrusion conditions in the form of a strand. The product strand is shredded, ground and analyzed. The viscosity of a 10% solution is measured using a Brookfield RVT viscometer with a suitable spindle at 20 ° C and 50 rpm.

Examples 1 2 3 4

Temperature 140 ° C 140 ° C 145 ° C 155 ° C

Dwell time 70 min 210 min 70 min 150 min

Viscosity 3220 mPas 120 mPas 1458 mPas 166 mPas

Example 3

Hydrophobization of potato starch

The mixing chamber of the press mixer is heated to 100 ° C. 2000 g of native potato starch (Starchina 20,000 from Agrana Zucker and Starch AG, AT) and 50 g of sodium hydroxide microbeads are filled into the mixing chamber. 247 g of lauric acid are added, the mixing device is closed and the press plate is started. The content of the mixing device is 5 minutes at 150 rpm and oscillation frequency of 10 strokes / min. homogenized with the mixer. After 5 minutes, nitrogen is blown in through a valve at about 30 rpm and frequency 10 for 60 seconds and vented through the further valve. After purging with nitrogen, the valves are closed. The speed of the mixer is set to 250 rpm and the frequency to 15 strokes / min. raised and the press plate is also driven at high speed. Under these conditions, the contents of the mixing chamber are treated mechanothermally. During this treatment, the temperature in the container rises to 140 ° C. After 10 minutes, the speed of the mixer is reduced to 50 rpm and the oscillation is switched off. The contents of the container are continuously discharged in the form of a strand via the discharge device. The expanded product line is shredded, ground and analyzed. The content of bound lauric acid is determined and the reaction efficiency is calculated.

With a theoretical degree of substitution of 0.1, a reaction efficiency of 58% was achieved.

Furthermore, a preferred embodiment with regard to the use of a mixing device with a discharge device according to the present invention is illustrated with reference to the accompanying drawings.

In it show:

Figure 1 is a sketched overall view of the invention with mixing device and discharge device.

FIG. 2 is a top view of the discharge device according to FIG. 1 seen from the mixing chamber;

FIG. 3 shows a variant of the discharge device from FIG. 2;

4 shows a top view of the discharge device of an embodiment of the invention;

5 shows a sectional view of the arrangement according to FIG. 3 in the discharge plane;

6 is a detailed view V of FIG. 5th

In Fig. 1, the mixing device 1 with discharge device 5 is shown sketched, the mixing chamber 2 with sealingly guided press plate 3 and mixer 4 can be seen in the illustrated body 1 'of the device 1. The mixing chamber 2 or the reaction container essentially consists of a pressure-resistant cylinder (usually up to 30 bar) with, for example, 10 1 capacity and allows external temperature control, for example in the form of a double-wall heater (not shown). The mixer 4 is axially displaceable and is positioned at the position shown near the cover 6 of the mixing chamber 2, the mixer shaft 4 'being guided through the plate 3, while the press plate 3 is shown on the bottom of the mixing chamber; ie: is in the starting position or rest position. Furthermore, the press plate 3 can have a simple mechanical seal 3 ', for example made of hardened metal. A mixer, for example, is used as a mixer 4, which can rotate and / or oscillate at a selectable speed, torque and oscillation frequency. For example, there are (maximum) speed ranges up to 350 rpm, torque ranges up to 1500 Nm and Oscillation frequencies up to 30 strokes / min. reachable. The axially movable, sealingly guided reactor base or the pressure plate 3 can change the reaction volume in the mixing chamber 2 during the treatment of the material to be mixed and can also apply a corresponding pressure, while the mixer 4 brings about an optimal homogenization. The discharge device 5 in the form of an extruder is integrated in the cover 6 or connected to it (only shown in a hint). The feed section 5 'of the extruder is arranged in the extension of the mixer shaft 4'. The extruder screw (not shown) runs transversely to the mixer shaft 4 'in the cover 6 of the mixing chamber 2. The discharge part 7 of the discharge device 5 is arranged parallel to the feed part 5' of the extruder. 1 further shows the motor 12, which can be a conventional electric motor for driving the extruder screw 10 of the extruder and, for example, produces an output of approximately 5 kW.

FIG. 2 shows a view of the discharge device 5 according to FIG. 1, the cover 6 being visible from the mixing chamber 2. The cover 6 has an opening 8, which in the example shown is designed in an oval shape and is arranged off-center. The opening 8 represents the connection of the mixing chamber 2 with the discharge device 5. Through the opening 8, an extruder screw 10 is visible, which can correspond to that of a conventional single-screw extruder. For an effective pressing-out process when mixing plasticized starch, the screw flight 10 '- indicated by dashed lines according to FIG. 2 - preferably has a diameter of approximately 30 mm. Furthermore, three valves 9, 9 ', 9''are shown in FIG. 2, valves with a 0.5 inch diameter being used here, for example. For continuous operation of the system, in particular, it is necessary that the valves 9 allow the mixing chamber 2 to be charged with liquid, solid or gaseous substances under constant pressure. 2, a safety valve 9 'is also provided, which can be activated for ventilation of the system. The third valve 9 ″ is used to discharge volatile by-products that arise from the reaction of the polysaccharides to be treated, such as aggressive gases, for example chlorides or gaseous hydrochloric acid. Furthermore, pressure and / or temperature sensors 11 are shown, with which the reaction conditions inside the Mixing chamber 2 can be detected. The discharge zone 7 of the extruder with extrusion nozzle 7 'is positioned in the extension of the extruder screw 10. In the left part of FIG. 2, the motor 12 is arranged in the axial direction of the extruder screw 10.

FIG. 3 shows a variant of the discharge device 5, as in FIG. 2, the motor 12 of the extruder 5 being arranged perpendicular to the axis of the extruder screw 10. The pressure and / or temperature sensors 11 are positioned differently from those in FIG. 2.

Fig. 4 shows an embodiment of the invention, wherein the cover 6 is shown in a view from the mixing chamber 2. An embodiment is shown here which differs from that according to FIGS. 2 and 3. The equipment elements of the discharge device 5, in particular the cover 6, show different arrangements and larger dimensions. In detail, the opening 8 is arranged centered. Two pressure or temperature sensors 11 and two valves 9, 9 'are provided, valves with a diameter of 1 inch being used here, for example.

FIG. 5 shows a sectional view of the arrangement according to FIG. 3, the view showing a section along the longitudinal axis of the extruder screw 10, which is guided transversely through the cover 6. The material to be mixed from the mixing chamber 2 is taken in via the intake part 5 '(not shown) through the connection opening 8 (indicated by dashed lines) and conveyed in the direction of the discharge part 7 by the thread of the extruder screw 10 along the screw flight 10' in order to pass via a discharge channel 7 '' to be pressed out with the discharge valve 14 '' open. In this way, after the mechanical and hydrothermal treatment in the press mixing device at the end of the discharge extrusion, the modified material is naturally expanded or inflated and discharged in the form of a strand via the discharge channel 7 ″ and can be subjected to further utilization. FIG. 5 also shows valves 9 and pressure or temperature sensors 11, which are arranged similarly to FIGS. 2 and 3.

6 shows the detailed view V of the discharge zone 7 according to FIG. 5. Specifically, the discharge valve 14 ″, which is connected to the extruder screw 10 or the extruder shaft 13 (indicated by broken lines) via the screw element or the screw screw 15 is shown. In this exemplary embodiment, the modified material is discharged or squeezed out via the discharge channel 14 'in such a way that the closable discharge channel 14' is opened by loosening a locking means 16, preferably a locking screw, on the top of the discharge valve 14 ''. Loosening the locking means 16 causes an axially arranged slide 17 to move accordingly, whereby the discharge channel 14 '- here in the lower part of the discharge valve 14''- can be exposed. The material is transported with the help of the extruder screw 10 into the discharge zone 7 and over the discharge channel 14 'in order to be removed there in a metered manner. The modified material can thus be subjected to a further treatment, such as grinding or cutting, more easily. The discharge part 7 typically has a diameter of 2 to 10 mm and withstands a pressure of approximately 30 bar.

Regarding the specified technical data of the embodiments, it should be noted that they relate to laboratory conditions; accordingly, these are to be proportionally adapted for large-scale use of the device according to the invention.

Claims

claims:

1. Use of a mixing device comprising a mixing chamber with a movable mixer and a sealingly guided press plate for the physical modification and / or chemical derivatization of high molecular and / or low molecular weight carbohydrates, proteins and / or mixtures thereof.

2. Use of a mixing device according to claim 1, characterized in that the high molecular weight carbohydrates comprise native starch and / or degraded and / or chemically and / or physically modified derivatives thereof.

3. Use of a mixing device according to claim 2, characterized in that native starch is selected from corn, potatoes, cereals, rice, amaranth and cassava.

4. Use of a mixing device according to claim 1 or 2, characterized in that the high molecular carbohydrates include inulin, oligofructose, galactomannans such as guar, locust bean gum, cassia, tare gum and other hydrocolloids.

5. Use of a mixing device according to claim 1 or 2 for breaking down high molecular weight carbohydrates, such as galactomannans, in particular guar.

6. Use of a mixing device according to claim 1, characterized in that low molecular weight carbohydrates such as sugar and sugar alcohols are used.

7. Use of a mixing device according to claim 6, characterized in that sugars selected from sucrose, maltose, fructose, and glucose and Palatinose® are used.

Use of a mixing device according to claim 6, characterized in that hydrogenated derivatives, such as e.g. Palatinit®, sorbitol, mannitol, xylitol, maltitol, lactitol or the like can be used.

9. Use of a mixing device comprising a movable Mixer and a sealingly guided press plate for the production of carbohydrates, starting from mono- and / or disaccharides and / or their sugar alcohols.

10. Mixing device for the physical modification and / or chemical derivatization of high molecular and / or low molecular weight carbohydrates, proteins and / or mixtures thereof with at least one mixer (4) and at least one sealing plate (3) in a sealed manner by means of a cover (6) closable mixing chamber (2) and a discharge device (5) with a feed part (5 ') and with a discharge part (7), characterized in that the discharge device (5) comprises forced conveyance, such as a screw conveyor, preferably a single-screw extruder, and is arranged on the cover (6) of the mixing chamber (2).

11. Mixing device according to claim 10, characterized in that the cover (6) has at least one, preferably slot-like, elongated opening (8).

12. Mixing device according to claim 11, characterized in that the opening (8) in the cover (6) is arranged off-center.

13. Mixing device according to one of claims 10 to 12, characterized in that the mixer (4) and the sealingly guided press plate (3) in the direction of the cover (6) is displaceable.

14. Mixing device according to one of claims 10 to 13, characterized in that the cover (6) of the mixing chamber (2) is provided with valves (9, 9 ", 9 '').

15. Mixing device according to one of claims 10 to 14, characterized in that pressure or temperature sensors (11) are provided for checking the mixing chamber (2), preferably on the underside of the cover (6) facing the mixing chamber (2).

16. Mixing device according to one of claims 10 to 15, characterized in that at least one discharge valve (14 '') on Discharge part (7) of the discharge device (5) is provided.

17. Mixing device according to one of claims 10 to 16, characterized in that the press plate (3) mechanical seals (3 '), preferably made of hardened metal.

18. Use of a mixing device for the physical modification and / or chemical derivatization of high molecular and / or low molecular weight carbohydrates, proteins and / or mixtures thereof according to one of the preceding claims 1 to 8, characterized in that a mixing device (1) with discharge device (5) according to one of claims 10 to 17 is used.

19. Use of a mixing device for the production of carbohydrates starting from mono- and / or disaccharides and / or their sugar alcohols, characterized in that a mixing device (1) with discharge device (5) according to one of claims 10 to 17 is used.

20. Process for the physical modification and / or chemical derivatization of high molecular and / or low molecular weight carbohydrates, proteins and / or mixtures thereof, characterized in that the starting product is press-mixed by means of a press plate and a mixer, the guidance of the press plate and the mixer from one another decoupled.

21. The method according to claim 20, characterized in that the starting product is press mixed completely or almost solvent-free.

22. The method according to claim 20 or 21, characterized in that the starting product is continuously discharged after its physical modification and / or chemical derivatization with a discharge device according to one of claims 10 to 17.

23. Process for the production of carbohydrates starting from mono- and / or disaccharides and / or their sugar alcohols there- characterized in that the carbohydrates are produced according to process steps according to one of claims 20 to 22.

24. The method according to any one of claims 20 to 22 for the production of composite materials or composite materials.

25. The method according to any one of claims 20 to 22 for the production of cosmetic, food, paper, pharmaceutical products or the like.