Methods for disintegration / separation and breakdown of plant covering materials and constituents for the extraction and production of plant constituents and plant fiber products
Patent Information
- Application Number
- DE502018016326
- Authority / Receiving Office
- DE · DE
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2017-03-28
- Filing Date
- 2018-03-27
- Publication Date
- 2026-01-29
- Estimated Expiration
- 2038-03-27
AI Technical Summary
Existing methods fail to completely and gently separate plant hull materials from seeds, kernels, and grains at room temperature or reduced temperatures without initiating seedling maturation, altering constituents, or generating harmful compounds, and do not effectively separate germs or root-like structures while preserving the integrity of the seeds, grains, or kernels.
A method involving immersion in a solution containing cationic amino acids and/or peptides, which allows for the gentle disintegration and hydration of plant hull materials at elevated temperatures, enabling the spontaneous detachment of hull materials while maintaining the integrity of the remaining constituents, and facilitates the separation of seedlings or sprouts.
The method achieves complete and gentle separation of plant hull materials, prevents germination, and preserves the integrity of seeds, grains, or kernels, allowing for the easy recovery of valuable fractions such as soluble proteins and carbohydrates, and produces cellulose-based fibers suitable for human consumption.
Description
background
[0001] Nearly all plant products used for reproduction, such as seeds, kernels, or grains, as well as other plant products like fruits, are enclosed by at least one hull layer. This serves to prevent the activation or initiation of a growth process, to preserve and / or nourish them, and / or to enable structural development. This is achieved by these hull layers providing complete protection against physical or chemical alterations. During the developmental phase of plant products, these hull layers supply water and nutrients and are the site of formation for the constituents contained in seeds or grains, such as proteins, carbohydrates, and fats. Therefore, these hull layers contain a variety of enzymes and compounds responsible for the production of the constituents of the enclosed contents.Therefore, these outer layers also contain high concentrations of precursor and starting compounds of these constituents, such as carboxylic acids (e.g., ascorbic acid or cinnamic acid), enzymes, antioxidants, or pigments. Furthermore, the outer layers synthesize or store compounds intended to counteract decomposition or attack by micro- or macroorganisms. These include, for example, odorants, flavor compounds, and toxins. Once the ripening of the plant products is complete, the outer layers compact, and the nutrient supply ceases. The degree of compaction varies among different seeds and kernels. This process typically involves the cross-linking of lignin and / or cellulose to form a compact and continuous layer. This also seals the water-conducting capillaries within the layer.This provides the plant products with mechanical protection against disintegration, as well as protection against swelling of the enclosed constituents and against water loss. In the dried state, such coating layers are bonded to the enclosed mass without any gaps. Therefore, the coating layers of plant products intended for reproduction are very difficult or even impossible to separate from the enclosed constituents by physical means. This applies particularly to the coating layer that is directly adjacent to the enclosed constituents. Physical separation is especially impossible if the coating layer is very thin and has similar physical properties, such as elasticity or density, to the enclosed constituents. This is the case, for example, with...This applies to the hull of walnuts or soybeans, where purely mechanical selective removal of the hull after drying is not possible. Seeds, kernels, and grains of plants are important food components and are sometimes provided whole or whole, or ground and / or in fractions. For many seeds and grains, it is necessary to completely remove one or all of the hull layers, as their presence in the food leads to undesirable effects. These can include unpleasant sensory effects, such as a bitter taste or discoloration of the resulting product, as well as an unfavorable alteration of the mouthfeel due to the particle dimensions created during processing and the differing hardness of the hull material compared to the constituents of the plant products.Many such hull layers can swell upon absorption of water, forming a water-filled cavity between the hull layer and the enclosed mass of constituents. It is known that such swelling occurs very slowly, or not at all, in a water bath at room temperature, but can be significantly accelerated or initiated in hot water or a stream of steam. Heating also advantageously destroys and / or inactivates organic compounds with toxic and / or anti-nutritive properties, such as ureases or thrypsin inhibitors. Organic compounds that lead to undesirable sensory effects, such as a bitter taste or an astringent effect, cannot usually be eliminated by heating and remain in the hull-free seeds, grains, or kernels.A disadvantage of moist heating is that it leads to several undesirable effects. Firstly, proteins present in the treated plant seeds and grains are at least partially denatured, and beneficial organic compounds, such as vitamins, are inactivated. Secondly, the starch content swells more significantly. Furthermore, fatty acids can be chemically modified, leading, for example, to the formation of trans fats or epoxides, which have harmful health effects. Therefore, methods that allow the separation of hull materials at room temperature or with only slight heating are preferable to methods that involve heating the plant materials.
[0002] No methods are known in the prior art for the complete and simple separation of hull materials from plant seeds and kernels at room temperature or even reduced temperatures. In particular, there are no reports on how to prevent seedling maturation or sprouting when storing plant products intended for reproduction in an aqueous medium at room temperature or slightly elevated temperatures. Therefore, there is a need for methods that allow the complete and simple removal of hull material from plant coverings, shells, or glumes without initiating seed, grain, or kernel maturation, altering their constituents, or generating harmful / toxic compounds.Methods for breaking down plant materials into soluble components and insoluble fiber components are known from documents WO-02 / 067698A2, US-4919952A and WO-2006 / 111604A1.
[0003] Many seeds, kernels, and grains contain root-like structures, also known as germs or sprouts. Often, their presence in the product intended for human consumption is undesirable, and / or there is an interest in obtaining these germs or root-like structures as a separate valuable fraction, for example, for the production of germ oil. Therefore, the separation of germs and / or root-like structures is desirable in many areas. To achieve this, the outer layers must be removed, as the germs and root-like structures are structurally connected to the other components of the seeds or kernels and are located within the innermost outer layer. In state-of-the-art processes, germs are separated mechanically by impact.This inevitably leads to damage or spalling of the constituents of the seeds, grains, or kernels, as well as the inclusion or removal of fragments of the hull material. No prior art methods are known that allow the separation of these structures from one another under gentle conditions and while preserving the integrity of the separated seedlings / root-forming units and the other constituents of the seeds, grains, or kernels. In particular, no method exists that allows seedlings / root-forming units to be separated from the other constituents of seeds, kernels, and grains under gentle conditions, while simultaneously and gently separating the hull materials completely, such that the different fractions can be easily separated from one another and retained in their original form.Therefore, a process is desirable that can meet these conditions and obtain plant seeds and kernels in a disintegrated state, and in which the separated hull material is preserved in a condition suitable for further use.
[0004] Of economic interest, however, are also the husks, shells, or chaff removed from plant seeds and kernels that are unsuitable for human consumption. These are sometimes produced in large quantities, for example, during the processing of rice or sunflower seeds. This husk material generally has no nutritional value, as it consists primarily of cellulose and / or lignins in the form of high-molecular-weight compounds and therefore cannot be broken down by the human digestive system. Furthermore, as described previously, it often contains or is firmly attached to organic and / or inorganic compounds that cause an unpleasant taste, smell, or color, or are even toxic or antinutritional. On the other hand, it may contain or be attached to organic compounds that have health-promoting effects and whose presence in a foodstuff is desirable.Therefore, there is also interest in making husks, shells, or glumes accessible to human consumption in a suitable form. Plant husk materials, in the form obtainable according to the state of the art, are used as animal feed, soil fertilizer, or starting material for fermentation processes. Methods that make it possible to process husk material in such a way that it is suitable for use in human consumption without undesirable sensory or nutritional effects, and while preserving and retaining health-promoting compounds, are not known in the state of the art. Thus, there is a need to disintegrate or break down plant husk material in such a way that it can be freed from undesirable components / compounds and brought into a physical form suitable for human consumption.
[0005] Surprisingly, a method has been found that allows for both the gentle removal of hull materials from plant seeds and grains while preserving the integrity of the constituents, and the gentle separation of seedlings / root forms. Furthermore, the method can provide a disintegrated hull material separated from the other constituents of the starting material. Due to the manufacturing conditions, toxins, anti-nutritional compounds, and / or compounds causing undesirable sensory effects are inactivated, removed, and / or neutralized. Surprisingly, a method can also be provided for disintegrating and digesting the separated hull material, opening up new and advantageous applications for the separated and digested hull materials.
[0006] Cellulose-based fibers constitute the main component of the indigestible carbohydrates in plant materials used for consumption, essentially representing the total amount of dietary fiber. Indigestible means that these compounds cannot be broken down by enzymes in the human gastrointestinal tract, such as amylases, and thus cannot be cleaved into absorbable C-6 sugar compounds. Therefore, cellulose-based fibers remain largely unchanged in the intestinal contents and are thus components of stool. Their water-binding capacity makes them a crucial regulator of colonic consistency, which in turn influences the transit time of the resulting feces. The importance of a high-fiber diet in preventing intestinal diseases and bowel movement problems has been clearly demonstrated in numerous clinical studies.It has been shown that a high-fiber diet can reduce the rate of colorectal cancer. Furthermore, a reduction in elevated cholesterol levels and the associated risk of cardiovascular disease has been demonstrated. The stool-regulating function of high-fiber foods in cases of chronic constipation, which is particularly common in older adults, has also been documented. In addition, probiotic effects resulting from the partial breakdown of cellulose-based fibers by the microbiome of the human colon have been recorded. Such effects are thought to contribute to a lower incidence of cancers outside the colon, for example, through short-chain fatty acids or phytosterols that are produced or released from the microbial breakdown of cellulose-based fibers and can pass through the colon wall.World health organizations and the FDA strongly recommend a daily intake of 30 grams of dietary fiber (dry matter). This target is not met in the vast majority of diets practiced in industrialized nations as well as in emerging economies. There is an inverse correlation between dietary fiber consumption and the incidence and severity of obesity and diabetes mellitus, and consequently, mortality. However, despite all available information and education on the subject, the practical implementation of dietary fiber recommendations is difficult for various reasons, such as limited availability among working people or implied social behavior.There is therefore a great need to provide dietary fiber that can be added to or supplemented with food preparations and that meets the sensory and functional requirements of a food product, thereby increasing the mass fraction of dietary fiber in the food.
[0007] Surprisingly, it was found that the inventive methods for disintegrating plant husks and shells also lead to the breakdown of the remaining constituents of a plant starting material, in particular grains, kernels, and nuts, but also other plant products. Specifically, it was found that through the inventive disintegration of husks or shells, which results in the complete breakdown or separation of other constituents of the plant starting material from the husks or shells, the soluble constituents of the plant starting material are hydrated and can be very easily and completely dissolved in an aqueous distribution volume and separated from the husks and shells. Further positive properties were subsequently discovered regarding the recoverability of the dissolved soluble organic compounds.Thus, an aggregation process was found that makes it very easy to aggregate and condense the dissolved soluble organic compounds, especially proteins and carbohydrates, allowing them to be separated using known process techniques and obtained as pure fractions. Description
[0008] The invention relates to a method in which plant hull materials are disintegrated, thereby accelerating the softening of plant hull materials compared to prior art methods and under gentle conditions. Gentle in this context means that the separable hull material and the other constituents of the starting material, in particular kernels, grains, and nuts, retain their integrity; that is, they preferably remain physically intact, meaning, for example, that no fragmentation occurs. Product-friendly further means that mechanical alteration occurs to a significantly lesser extent than with prior art methods.Product-friendly also means that the temperature increase can be limited to preferably < 120 °C, more preferably < 100 °C, further preferably < 90 °C, further preferably < 75 °C, further preferably < 60 °C, further preferably < 50 °C, and even more preferably < 40 °C. Product-friendly also means that, in a pulping process using higher temperatures, organic compounds, especially cellulose-based fibers and lignin-rich shells, can be obtained without requiring mechanical comminution of the starting material. Thus, different product-friendly effects can be achieved in the various implementations of the process, which have a direct impact on the obtainable products and / or process economics.The method is particularly suitable for completely separating the coating materials from other constituents of a plant starting material without compromising the overall structural integrity of the plant product enclosed by the coating material or causing it to disintegrate. In a preferred embodiment, this is achieved by immersing the seeds, grains, or kernels, from which separation of the coating material is desired, in a solution containing soluble compounds for disintegration. In one embodiment, the compounds for disintegration are cationic amino acids and / or peptides.Surprisingly, it was found that this process leads to a rapid onset of hydration of plant hull materials even at room temperature or reduced temperatures, which proceeds significantly faster and more completely than with an aqueous solution containing compounds known in the art, such as NaOH. Furthermore, it was found that plant hulls disintegrated and hydrated using one of the methods according to the invention can be detached much more easily than by treatment with other aqueous solutions. Surprisingly, it was observed that during the disintegration and hydration of plant hulls according to the invention, depending on the plant species, the same location or...In the same region of the hull layer, thinning / dissolution occurs, leading to spontaneous or slight mechanical alteration of the hull material. From this point, slight mechanical shearing of the hull causes tearing to proceed, while maintaining the integrity of the remaining hull material. It has been found that, depending on the duration and concentration of the amino acids / peptides, complete perforation can occur spontaneously or be facilitated by a very small input of mechanical energy, e.g., in the form of shearing, thereby completely and in one piece detaching the hull material from the seeds, grains, or kernels. It has been demonstrated that reliable and complete removal of the hull material can be ensured by one of the embodiments of the inventive method.
[0009] A preferred method is one for the product-friendly disintegration / perforation or removal of the coating material of plant seeds, grains or kernels.
[0010] Surprisingly, a practically selective disintegration of the plant hull material, with largely complete preservation of the integrity of the remaining constituents of the seeds, grains, or kernels, can be achieved when these are immersed in a solution containing dissolved amino acids and / or peptides under elevated temperature conditions. This results in the spontaneous detachment of the hull material. As expected, the disintegration process of the hull material accelerates when heated to temperatures above 80° or 90°C. Surprisingly, however, the time required for this can be kept so short that no relevant swelling, disintegration, or damage occurs to the other constituents of the seeds, grains, or kernels enclosed by the hull material. Thus, selective disintegration of the plant hull material can advantageously be carried out under conditions that are gentle on the other constituents of the seeds, grains, or kernels.In one embodiment, a solution according to the invention containing fully immersed seeds, grains, or kernels is heated, preferably to temperatures above 70°C. Preferably, the seeds or kernels are stirred during the process. It has been shown that under these conditions, the coating materials detach completely. Here, too, the coating material retains its integrity except at the point of perforation. Surprisingly, it has been found that the seeds or kernels in the solutions containing dissolved amino acids and / or peptides did not swell more at elevated temperatures than they did in a cold aqueous solution.
[0011] A preferred method is one for the complete separation of hull material from plant seeds or kernels.
[0012] A preferred method is one for the disintegration and digestion of plant starting material in which process step b) is carried out together with thermal and / or mechanical disintegration or thermal and / or mechanical disintegration is carried out in a process step b1) following process step b).
[0013] Surprisingly, it was found that increasing concentrations of amino acids and / or peptides slowed or completely prevented germination / sprouting in seeds, grains, or kernels soaked in such solutions. For example, soybeans soaked for eight days in a solution containing lysine at a concentration of 0.4 molar showed a volume increase of 160% by volume and a significant detachment of the outer layers, but no sprouting occurred. In contrast, soybeans soaked in water for the same period produced sprouts 2 to 4 cm long. However, the outer layer was difficult to remove completely. Furthermore, these beans exhibited a volume increase of 280% by volume. This effect has also been documented in other seeds and grains, such as kidney beans.Furthermore, a highly advantageous effect was observed that can be used to utilize the seedlings / sprouts. It was found that after the detachment of the hull material, achieved by immersing the starting material in a digestion solution according to the invention, either spontaneously or through slight mechanical alteration of the hull, and provided the seed or grain had undergone slight swelling, a seedling / sprout that had already formed was present in a detached form and could be very easily separated from the seed or grain. This could be achieved simply by passing the pre-treated seed or grain through a tube or husk, whereby both the hull material and the seedling / sprout were separated from the seed or grain. Thus, the mechanical separation of seedlings or sprouts can be considerably simplified.Furthermore, seedlings or sprouts can be detached and separated from seeds or grains in a single operation, together with the disintegrated hull material.
[0014] A preferred method is one for the disintegration and breakdown of plant starting material, in which, in addition to disintegration and / or separation and / or dissolution of plant covering materials, a seedling / sprout is separated.
[0015] A method for facilitating the separation of seedlings / sprouts is preferred.
[0016] A preferred method is one for the disintegration and breakdown of plant starting material, which results in a slowing down / prevention of the ripening of plant seeds and / or grains.
[0017] Surprisingly, it was found that seeds and grains freed from their enclosing hull material using one of the methods according to the invention can be further processed in a particularly advantageous manner. This applies especially to further processing for the extraction of the individual constituents of the seeds and grains. It was demonstrated that when seeds and grains, from which the hull materials had been removed according to the invention and which had swelled to between 100 and 200 vol%, were ground to a fine-grained mass in a short time using a blade mill, this mass could then be completely separated into its constituents using an aqueous extraction process. A particularly advantageous aspect is that, compared to an untreated seed or grain, a significantly lower energy input is required and no dust is generated during grinding.Therefore, one of the methods according to the invention is also directed towards the disintegration and hydration of plant starting material, in which a disintegration / separation of shells and / or husks takes place.
[0018] A preferred method involves not only the disintegration / separation of the husks and / or shells of a plant starting material, but also the disintegration / hydration of the remaining constituents of the plant starting material. Seeds, grains, and kernels are preferred. Further investigations have shown that the individual constituents of seeds or grains pretreated in this way can be easily separated using an aqueous digestion process. In a preferred embodiment of the process, seeds or grains are completely freed from their husk materials using one of the methods according to the invention and are then, either directly or in the course of the process while still swollen, subjected to a grinding or comminution process, resulting in a fine-grained, non-dusty mass which is then mixed with a digestion solution.In one embodiment, the solids are preferably separated by filtration immediately following or after a digestion phase. This preferably yields complex or complexed carbohydrates in particle form, as well as cellulose-based fibers, with the filter residue. Preferably, these are completely or largely completely free of soluble constituents of the starting material, in particular proteins and soluble carbohydrates. Furthermore, the filtrate yields a largely or completely fiber-free aqueous solution containing dissolved soluble proteins and carbohydrates. Surprisingly, the dissolved soluble compounds can be aggregated and condensed very advantageously, allowing them to be easily separated from the aqueous dispersion phase.Preferably, the protein fraction is selectively removed by condensation / aggregation / complexation and / or a filtration or centrifugal separation technique and obtained as a pure product. Such selective condensation / aggregation / complexation of the dissolved proteins can be achieved, for example, by adding an organic acid, such as citric acid or acetic acid. Thus, one of the processes according to the invention can be used to both free plant seeds and kernels from their hull / shell material and to very easily separate the resulting plant seeds, kernels, and grains into their individual constituents. It has been shown that after swelling seeds, grains, or kernels with an aqueous solution containing none of the compounds according to the invention for disintegration or separation, the resulting plant seeds, kernels, and grains can be easily separated into their individual constituents.The initial method did not allow for the disintegration / digestion of the constituents of the seeds, grains, or kernels, followed by their distribution in an aqueous distribution volume. Surprisingly, separation of the constituents hydrated by the inventive method in an aqueous distribution volume was achievable when disintegrating compounds containing one of the solutions according to the invention were used. Preferred compounds for disintegration / digestion are amino acids and / or peptides.For a process in which the husk material is first disintegrated, combined with swelling of the seeds, grains, or kernels with the solutions according to the invention, followed by mechanical disintegration, it has been shown that, in contrast to processes in which the husks / shells were separated using a different method, further exposure to an aqueous solution according to the invention, containing disintegration compounds, is not required for complete breakdown of the plant material constituents. Thus, in one embodiment, the process enables both the disintegration, breakdown, and separation of plant husks and shells, as well as the subsequent disintegration / breakdown of the remaining constituents of the starting material, along with their separation and recovery.Surprisingly, an aqueous digestion solution according to the invention can be used to achieve both the disintegration of plant hull material and its separation from seeds, grains or kernels, as well as the subsequent digestion of the constituents of the seeds, grains or kernels by an aqueous digestion process.
[0019] A preferred method is one in which aqueous disruption and separation of the constituents of seeds, grains or kernels is enabled by disintegration and / or separation of the hull material and / or swelling of the seed(s), grain or kernel(s) by an aqueous solution containing dissolved amino acids and / or peptides.
[0020] A preferred method is one for separating plant hull material while maintaining the structural integrity of the separated hull materials and / or the constituents of the plant seed(s), grain(s) or kernel(s).
[0021] A preferred method is for producing plant sheath material preparations for use as a fiber preparation.
[0022] Preferred are plant-based coating material preparations obtainable by a process for disintegration and digestion of plant-based starting material.
[0023] The use of plant hull preparation for fiber production is preferred. A method for processing plant seeds, grains, or kernels is preferred.
[0024] Surprisingly, a disintegration of a plant starting material according to the invention also results in the recoverability of constituents contained therein. In a preferred embodiment, the disintegration is carried out to obtain soluble proteins and carbohydrates, as well as cellulose-based fibers and / or lignin-rich hulls. In particular, for a disintegration according to the invention with sulfites and urea, in addition to disintegration, a digestion of seeds, grains, and kernels could be achieved, which, using the methods disclosed herein, leads to a complete dissolution of proteins. These proteins are then present in a dissolved state and can be aggregated, condensed, separated, and recovered using the methods disclosed herein.For example, it was demonstrated for soy kernels that when they were fully immersed in an aqueous solution containing sodium sulfite and / or urea at a concentration of 1 wt% and the medium was heated to 125°C at an atmospheric pressure of 1.4 bar, the constituents could subsequently be completely dispersed in an aqueous distribution volume when the suspension was passed through a colloid mill with high shear. Filtration of the resulting aqueous distribution phase yielded a fraction of solids that was free of soluble residues upon microscopic analysis.On the other hand, the dissolved proteins present in the filtered process fluid could be aggregated / complexed with aggregation / complexation compounds, causing them to condense and sediment. After sedimentation, they could be separated from a free aqueous phase by filtration or centrifugal separation techniques, resulting in a pasty, creamy mass. Chemical analysis revealed a protein concentration of 75 wt%. Similar results were obtained for the disintegration of other plant-based starting materials, such as sunflower seeds, corn grits, or jatropha and rapeseed press cake. Protein isolates or concentrates were regularly available.
[0025] Thus, in a preferred embodiment of the process, disintegration is carried out with or without one of the exclusion methods according to the invention to obtain soluble constituents of the plant starting material. AtAccording to the inventive process, an aqueous disintegration solution comprising an aqueous solution with a pH in the range of 6.5 to 13 is used.
[0026] Therefore, a method for disintegration and disruption of plant starting material comprising the following process steps is preferred. a) Provision of a plant starting material, b) Treatment of the starting material with a disintegration solution and retention in the disintegration solution until disintegration is achieved, c) Distribution of the constituents of the disintegrated starting material in a distribution volume, d) Separation of solid constituents from dissolved constituents of the starting material, e) Recovery of valuable fractions of separated constituents by, e1) Fractionation of cellulose-based fibers from lignin-rich shells using an eddy current process and obtaining purified fractions of cellulose-based fibers and lignin-rich shells, e2) Aggregation / complexation of dissolved proteins by complexing agents and separation of the sedimented aggregated / complexed condensed proteins, obtaining an aggregated / complexed protein mass.
[0027] Optionally, process step b) can be carried out together with thermal and / or mechanical disintegration, or alternatively, thermal and / or mechanical disintegration can be carried out in optional process step b1) following process step b).
[0028] The solid constituents obtained by a disintegration process in which the amino acids and / or peptides according to the invention were not present in the disintegration solution exhibited a distinct, species-specific odor. Therefore, a process for the disintegration and digestion of plant starting material comprising the following process steps is preferred. a) Provision of a plant starting material, b) Treatment of the starting material with a disintegration solution containing amino acids and / or peptides and retention in the disintegration / digestion solution until disintegration is achieved, c) Distribution of the constituents of the disintegrated starting material in a distribution volume, d) Separation of solid constituents from dissolved constituents of the starting material, e) Recovery of valuable fractions of separated constituents by, e1) Fractionation of cellulose-based fibers from lignin-rich shells using an eddy current process and obtaining purified fractions of cellulose-based fibers and lignin-rich shells, e2) Aggregation / complexation of dissolved proteins by complexing agents and separation of the sedimented aggregated / complexed condensed proteins, obtaining an aggregated / complexed protein mass.
[0029] A preferred process implementation is characterized by the following process steps: Process for the disintegration and digestion of plant starting material with the process steps a) Provision of a plant starting material, b) Treatment of the starting material with a disintegration solution and retention in the disintegration solution until disintegration is achieved, c) Distribution of the constituents of the disintegrated starting material in a distribution volume, obtaining solid and dissolved constituents of the plant starting material, d) Separation of solid constituents from dissolved constituents of the plant starting material, e) Recovery of the separated constituents of the plant starting material as valuable material fractions by, e1) Fractionation of cellulose-based fibers from lignin-rich shells of the solid constituents of the plant starting material using an eddy current process and obtaining purified fractions of cellulose-based fibers and lignin-rich shells,e2) Aggregation / complexation of dissolved proteins of the dissolved constituents of the plant starting material by complexing agents and separation of the sedimented aggregated / complexed condensed proteins, yielding an aggregated / complexed protein mass.
[0030] Optionally, process step b) can be carried out together with thermal and / or mechanical disintegration, or alternatively, thermal and / or mechanical disintegration can be carried out in optional process step b1) following process step b).
[0031] Comparative studies have shown that, using the amino acids and / or peptides according to the invention, the obtainable cellulose-based fibers and / or lignin-rich shells were immediately free of odor and / or taste substances.
[0032] Furthermore, it is particularly advantageous that the disintegrated hull material can preferably be completely and in one piece separated from the plant seeds, grains, or kernels. In a preferred embodiment, the separation of the disintegrated hull material / shells is preferably carried out with a device that exerts a tangential shear force on one or more sides of the plant seeds and grains prepared according to the invention. The shear force can be applied as pressure on the outside of the plant seeds, grains, or kernels or as a shearing motion. Suitable devices known from the prior art include, for example, jaw presses.In a particularly preferred embodiment, the removal of a coating layer is achieved by first allocating the plant seeds, grains, or kernels into storage containers of defined diameter ranges using a size sorting device from the prior art. From these storage containers, individual seeds, grains, or kernels are introduced into a funnel or shaft by a further device, so that the seeds or kernels are arranged in a preferred longitudinal orientation. In a preferred embodiment, one or more seeds or kernels are pressed or forced through an elastic sleeve / tube or one or more perforated septa(s) by means of a ram or a compressed air device. Preferably, the coating material is completely removed in this process.Preferably, the plant seeds, grains, or kernels are driven / catapulted out of the stripping device by the acceleration they have experienced and collected in a further storage container. The ejected hull material is preferably separated by a different trajectory than that of the seeds, grains, or kernels freed from the hull material, for example, by gravity or wind separation, and conveyed into another container. In a further preferred embodiment, the hull material is separated by a device in which the plant seeds, grains, or kernels pretreated according to the invention are fed, either sorted by their diameter or unsorted, onto a system of at least two approximately or completely parallel tubes that rotate uniformly and / or non-uniformly and / or in opposite directions.The seeds, grains, or kernels are rotated and transported within the gap formed by the tubes. Preferably, at least one or more of the tubes rotate at different speeds. This creates a tangential shear force on the outer covering of the seeds, grains, or kernels, causing the covering to tear. During the rotational movement of the seeds, grains, or kernels within the rod, the torn covering is then carried away, for example, by acceleration and / or an airflow. This allows the seeds, grains, or kernels, freed from their coverings, and the covering material itself to be collected in separate containers.
[0033] A device for separating and removing disintegrated hull materials and shells of seeds, grains or kernels is preferred, by applying tangential shear forces to the disintegrated hull material / shells.
[0034] A device for perforating / separating / cutting off the hull material of plant seeds, grains or kernels is preferred.
[0035] Surprisingly, it was found that one of the methods according to the invention produced bonding layers between plant covering material. andThe layers present on, or formed from, seeds, grains, or kernels can be removed very easily and advantageously. For example, when separating skins from almonds and soybeans, it was found that when this was done with water or by one of the methods according to the invention and the swollen skin was mechanically removed, a soapy-viscous to mucilaginous layer remained on the seeds, grains, or kernels. This layer became sticky during drying and led to the exposed seeds, grains, or kernels adhering to it. It was found that the intermediate layer swollen by a digestion solution according to the invention, which is located on the surfaces of exposed plant seeds, grains, or kernels, but can also be present on the surfaces of the separated hull materials, can be removed very easily by a rinsing process with cold water.This was not possible with exposed intermediate layers not obtained using the methods according to the invention, or only possible through a rinsing process carried out with hot water. Rinsing of the intermediate layer can be carried out, for example, with water. Therefore, the disintegration / exclusion of intermediate layers / connective layers of the shells and husks of the plant starting material is preferably achieved by using one of the aqueous solutions according to the invention, containing compounds for disintegration. Dissolved amino acids and / or peptides are particularly preferred. However, aqueous or alcoholic solutions containing other compounds can also be used; the addition of ionic and / or nonionic surfactants is preferred.Preferably, the rinsing process is carried out using a prior art device for cleaning objects, such as a focused jet of water or steam, or by inducing a movement of the plant material to be cleaned, resulting in shear forces between the material being cleaned and / or a mechanical movement, as in a washing machine. Surprisingly, it was found that plant seeds or kernels treated in this way exhibited altered drying behavior. For example, kidney beans or pumpkin seeds dried more quickly when the interlayer was partially or completely removed using one of the methods according to the invention and then rinsed away. For instance, it was observed with dried pumpkin seeds that no skin formed during drying after the interlayer was removed according to the invention.Furthermore, the individualization was considerably easier than if a disintegration / separation of the intermediate layer had taken place.
[0036] A preferred method is one for disintegration / dissolution / detachment of an intermediate layer between plant covering material and plant seeds, grains and kernels.
[0037] A preferred method is one for the disintegration and disruption of plant starting material, in which a disintegration / dissolution / detachment of an intermediate layer between plant covering material and plant seeds, grains and kernels takes place.
[0038] Surprisingly, it was found that the methods according to the invention can also be used to disintegrate / detach and remove adhesions and connecting structures of plant seeds and kernels. For example, it was shown that the kernels of a pumpkin or melon could be removed very easily and without residue from the strand- or septum-like tissue structures that supply and mechanically stabilize them when the seeds or kernels, together with the adhering structures, were immersed in one of the solutions according to the invention and disintegrated. Such easy removal of adhering tissue structures could not be achieved by treatment with water or aqueous solutions containing, for example, surfactants, under otherwise comparable conditions.
[0039] Surprisingly, seeds, grains, or kernels produced using one of the methods according to the invention and immersed for a sufficiently long time in one of the liquids according to the invention, containing cationic amino acids and / or peptides, exhibit a significantly reduced or completely eliminated inherent taste. Further investigations have shown that the reduction or elimination of an unpleasant / astringent taste depends on the duration of exposure to the liquids according to the invention for disintegration, containing cationic amino acids or peptides, or on the duration of perforation of the outer layer(s) of the plant seeds, grains, or kernels. It has also been shown that the reduction or elimination of the unpleasant / astringent taste depends on the duration of exposure to the liquids according to the invention for disintegration, containing cationic amino acids or peptides, or on the duration of perforation of the outer layer(s) of the plant seeds, grains, or kernels.Elimination of a characteristic flavor that occurs in plant seeds or kernels treated with one of the methods according to the invention, following the removal of unpleasant / astringent sensory effects. This allows the methods according to the invention to eliminate / remove undesirable sensory effects and a characteristic flavor of the treated plant seeds, grains, or kernels separately or in combination with the coating material, in a highly advantageous manner. Thus, low-flavor or tasteless plant seeds, grains, or kernels that are intact and completely free of any coating layer can be produced under gentle product conditions.It has been demonstrated that this reduction of sensorially perceptible constituents of plant seeds, grains, or kernels, achieved through exposure to the disintegration liquids according to the invention, containing cationic amino acids or peptides, has a significant effect on the products obtainable from the treated plant seeds, grains, or kernels. For example, it has been shown that the constituents, which can be obtained in separate fractions in further digestion processes, are completely or practically free of odor and taste substances that trigger a species-typical, unpleasant, or astringent sensory effect. This is particularly advantageous for the starch and protein fractions obtainable in this way.
[0040] A preferred method is one for disintegration / separation of plant covering materials and for obtaining a separated covering material and / or plant product that is low in odor and / or taste or odorless and / or tasteless.
[0041] A preferred method is one for the disintegration and digestion of plant starting material, wherein the disintegration solution contains amino acids and / or peptides.
[0042] Further advantageous effects of the process arise with regard to the separated husk materials obtained. Surprisingly, it has been found that separated husk materials can be obtained that are practically or nearly free of any unpleasant taste or astringent sensory effects. Furthermore, the plant husk materials disintegrated by the process are maximally swollen and easily molded into any desired shape. For example, they can be formed and / or pressed into a sheet and can be cut without breaking. It has been shown that thin strips or other geometric shapes can be cut from husks obtained in this way, particularly since the husks can be deformed flat without breaking. This effect allows the obtainable and still swollen husks to be compressed together, forming, for example, sheets or films.A further advantage is that the separated husks obtained according to one of the disintegrative processes according to the invention are free or practically free of any unpleasant taste or release substances that trigger an astringent sensory perception. Therefore, the husks obtained can also be used in food preparation. In particular, fibers that can also be obtained from such husks are especially well suited for texturizing foods and food preparations. Furthermore, the obtainable disintegrated husk materials exhibit improved swelling properties compared to husk material obtained by other techniques. Thus, the processes according to the invention are particularly well suited for producing low-tasting or taste-neutral fibrous textures with good processability and good swelling capacity.The inventive process enables the production of coating material preparations that can be used in various applications, e.g., for texturing food. The term coating material preparation refers to a combination / composite / texture of disintegrated coating materials that have been made malleable through a disintegration process according to the invention.
[0043] A preferred method is for producing textures of plant-based wrapping material that is low in taste or tasteless and / or can be joined together to form planar and cuttable or trimmable sheets or films and / or is highly swellable.
[0044] A preferred method is one for the disintegration and digestion of plant-based starting material for the production of fiber products from plant husk materials.
[0045] A preferred method is one for disintegration and disruption of plant starting material for the production of a plant coating material preparation.
[0046] A preferred method is one for the disintegration and breakdown of plant starting material, in which product-friendly disintegration / perforation or detachment of the covering material of plant seeds, grains or kernels takes place.
[0047] Surprisingly, it has been shown that compacted plant husk material can also be broken down and its components recovered using one of the disintegration processes according to the invention. It was found that plant husks immersed in one of the aqueous solutions according to the invention for an extended period swelled, releasing cellulose-based fibers in layers. Furthermore, it was found that the plant husks dissolved rapidly and completely when treated in one of the solutions according to the invention in an autoclave under suitable temperature and pressure conditions. The resulting mass consisted predominantly of broken-down cellulose-based fibers, which could be easily purified of the proteins and soluble carbohydrates contained therein using filtration techniques.The cellulose-based fibers of the dissolved hull materials exhibited, in some cases, significantly different properties than the cellulose-based fibers of the grains or kernels that had previously enclosed them as hull material and been treated with the aqueous digestion method described above. For example, the cellulose-based fibers obtained from disintegration and digestion of the hull material differed in size and shape. The cellulose-based fibers obtained from digestion of the hull material had a higher aspect ratio of longitudinal to transverse dimensions than those obtained from disintegration and digestion of the other constituents of the seeds, grains, or kernels.It is assumed that these differences also account for the different sensory perceptions found for the cellulose-based fibers of seeds, grains, or kernels and for those of the corresponding decongested hull material. Furthermore, cellulose-based fibers obtained from hull materials exhibited different functional properties than those obtained from the disintegration / decomposition of plant seeds, grains, or kernels. For example, highly pigmented cellulose-based fibers were obtained from the decongested hull material of kidney beans. Additionally, the disintegrated and decongested shells of dried almonds and avocado pits, for instance, exhibited a particularly delicate melting sensation upon tasting.Furthermore, in the production of doughs and food preparations, it has been shown that such cellulose-based fibers have better emulsifying and stabilizing properties than cellulose fibers.
[0048] A preferred method is for obtaining cellulose-based fibers from the hull material of plant seeds, grains or kernels.
[0049] Furthermore, it was demonstrated that carbonates and sulfites are suitable for disintegrating cellulose-based fibers. When basic compounds were used for disintegration of plant starting materials containing not only cellulose-based fibers and / or lignin-rich husks but also proteins and soluble carbohydrates, the solutions and the digested plant material turned an intense brown color, which is undesirable. Surprisingly, it was found that if the starting material had already been digested, and in particular if dissolved or soluble proteins and carbohydrates had already been separated, discoloration leading to a reduction in the quality of cellulose-based fibers did not occur when carbonates or sulfites were present in the aqueous digestion medium.For example, in the disintegration of soybean meal with a 1 wt% urea solution containing arginine at a concentration of 0.05 molar, complete disintegration of the hull material was achieved after heating to 90°C for 60 minutes. This also resulted in a digestion that allowed for the almost complete separation of soluble proteins and carbohydrates, which were filtered off with the process fluid. The resulting optically clear fiber mass was tasteless and odorless and contained fibers that were 38 wt% (dry matter) smaller than 100 µm, 82 wt% (dry matter) smaller than 250 µm, and 18 wt% (dry matter) larger than 250 µm. The fiber mass was further disintegrated with a 0.5 wt% sodium carbonate solution at 80°C for 20 minutes, without any discoloration of the process fluid or the cellulose-based fibers.The resulting cellulose-based fibers were subsequently softer in texture than before further disintegration and had a particle size of < 100 µm at 65 wt% (dry matter) and < 250 µm at 98 wt% (dry matter). The fiber masses had an excellent mouthfeel upon tasting, described as creamy and smooth. Therefore, according to the invention, a two-stage disintegration / digestion process can also be carried out, in which first a disintegration / digestion of shell / husk material with separation of dissolved soluble constituents of the starting material takes place, followed by a disintegration of cellulose-based fibers and / or lignin-rich shells. Surprisingly, it was found that solutions containing sulfites are also suitable for effecting the disintegration of cellulose-based fibers.It was demonstrated that spent grain, which after fermentative digestion contained only small amounts of soluble proteins and carbohydrates and was disintegrated in a 1 wt% aqueous sodium sulfite solution at 85°C for 90 minutes, could be dispersed into a suspension of cellulose-based fibers using a colloid mill. The resulting cellulose-based fibers were sensorially very soft and had a particle size of < 100 µm at 78 wt% (dry matter) and < 250 µm at > 95 wt% (dry matter).
[0050] A preferred method is for obtaining cellulose-based fibers from the hull material of plant seeds, grains or kernels.
[0051] Furthermore, it was found that aroma- and / or dye-free cellulose-based fibers can also be produced using the disintegration / digestion compounds according to the invention. For example, sugar beet pulp, which had only a low residual content of soluble carbohydrates after molasses extraction, was disintegrated using a 1% sodium bisulfite solution or a 2% sodium bicarbonate solution at 90°C for 90 minutes. The disintegrated pulp mass was then treated with a shear mixer, yielding a suspension of cellulose-based fibers. However, the resulting fiber masses still had a strong earthy odor and taste and were therefore unsuitable for consumption.By further digestion with solutions of the amino acids and / or peptides according to the invention, into which the dehydrated fiber masses were immersed for 60 minutes at 50°C, the cellulose-based fibers were odorless and tasteless after dehydration and re-rinsing of the fiber masses and were rated as very soft and creamy in sensory testing. Furthermore, sieve analysis showed that the cellulose-based fibers were < 100 µm at 80% and 85% wt.% (DM) and < 250 µm at > 94% and 96% wt.% (DM).
[0052] Further investigations into the use of cellulose-based fibers have shown that very good sensory (e.g., creaminess) and functional qualities, such as swelling volume, are achieved particularly when disintegration and digestion of soluble constituents of the starting material have taken place, resulting in a low residual content of soluble carbohydrates and proteins, as well as other soluble organic compounds, in the resulting cellulose-based fibers. Therefore, a process for disintegration and digestion of plant material is preferred that ensures a residual content of readily water-soluble organic compounds in cellulose-based fibers of preferably < 5 wt%, more preferably < 2.5 wt%, and further preferably < 1.0 wt%.
[0053] A preferred method is one for the disintegration of cellulose-based fibers and the disruption and separation of soluble constituents contained therein.
[0054] A preferred method is for the disintegration of cellulose-based fibers and the digestion and separation of soluble constituents contained therein, yielding odorless and / or tasteless cellulose-based fibers with a residual content of < 5 wt% of readily water-soluble organic compounds.
[0055] A preferred method according to the invention is wherein the readily water-soluble organic compounds have a water solubility of >100 g / L at 20°C, preferably >140 g / L at 20°C, and the poorly water-soluble organic compounds have a water solubility of <100 g / L at 20°C, preferably <75 g / L at 20°C.
[0056] A preferred method is for the disintegration of cellulose-based fibers and the disruption and separation of soluble constituents contained therein, yielding odorless and / or tasteless cellulose-based fibers with a residual content of < 5 wt% of readily water-soluble organic compounds, wherein the aqueous disintegration solution(s) contains sulfites and / or carbonates.
[0057] It was further found that the sensory and functional properties of the cellulose-based fibers are present when decompacting has occurred through the disintegration / digestion process and when this decompacting is combined with the separation of soluble constituents that were complexed with the cellulose-based fibers. A corresponding decompacting was also found for the lignin-rich shells obtainable according to a process according to the invention.
[0058] A preferred method is one for the disintegration and digestion of plant starting material, in which decompacting of cellulose-based fibers and / or lignin-rich shells is produced.
[0059] Furthermore, it was surprisingly found that even compacted and lignin-containing husk material can be disintegrated and digested using one of the processes according to the invention, and that the extractable cellulose-based fibers can be recovered. It was found that the addition of additives is suitable for disintegrating and / or breaking down, or even completely dissolving, lignin-containing structures that hinder the digestion of cellulose-based fibers. The combination of the aqueous solutions according to the invention, containing dissolved amino acids and / or peptides, together with the digestion additives according to the invention, proved crucial for the recovery of cellulose-based fibers from lignin-containing plant husk materials and for the dissolution of lignin polymers under gentle product conditions.Disintegration of lignin polymer structures can be achieved with a moderate temperature increase to 60–80°C. It has been shown that using increased pressure at temperatures between 90 and 140°C significantly accelerates disintegration / disintegration, particularly with simultaneous pressurization, as is possible in an autoclave. The cellulose-based fibers retain their structural integrity and exhibit exceptionally low perceptible hardness. Furthermore, these fibers have been found to have a particularly low fiber-length density of < 50 mg / 100 m. These cellulose-based fibers also possess excellent sensory properties, such as a delicately melting mouthfeel. Surprisingly, cellulose-based fibers can also be obtained from coconut fibers and orange peels using this disintegrative process.Suitable additives for dissolving and / or dissolving lignin- or linin-containing polymer structures, which are suitable for use together or in sequential order with the aqueous solutions according to the invention and can be used individually or in combination with each other, are preferably sulfite compounds, such as sodium sulfite or sodium bisulfite, furthermore sulfate compounds, such as NaSO 4, furthermore urea and urea derivatives, such as thiourea, furthermore detergents, such as sodium lauryl sulfate or DDT, furthermore carbonates, such as sodium carbonate.
[0060] A preferred method is for the disintegration / dissolution of lignin-containing structures and the recovery of lignin-based shell components and cellulose-based fibers.
[0061] A preferred method is one for dissolving plant husk material.
[0062] The preferred option is lignin-containing coating material obtained after a process for disintegration and digestion of plant-based starting material.
[0063] Surprisingly, it was found that plant-based cellulose fibers can be extracted and purified from various plant products unsuitable for food preparation, as well as from plant waste, and obtained using the processes according to the invention. These fibers can then be provided as odorless and tasteless cellulose-based fibers that exhibit excellent functional properties for the production of food preparations and simultaneously have positive stool-regulating properties. Therefore, it is also an object of the invention to provide processes and methods for obtaining and providing functional or functionalizable cellulose-based fibers.
[0064] It was demonstrated that by using cellulose-based fibers in the production of flour- and / or starch-containing foods, the amount of flour or starch can be reduced by the same order of magnitude as the amount of cellulose-based fibers added, without compromising the quantitative or qualitative baking result. When cellulose-based fibers were coated on their inner surfaces with a leavening agent such as yeast or sodium bicarbonate, an increase in baking volume and a more uniform distribution of the air pockets formed were achieved compared to the original recipe. At the same time, the baked goods with cellulose-based fibers exhibited higher pressure stability and, compared to the reference recipe, offered a better mouthfeel and a more harmonious flavor.
[0065] Furthermore, it has been shown that cellulose-based fibers can be used as a fat substitute in food preparations. For example, by replacing 50% by weight of an oil or fat with the cellulose-based fibers produced according to the invention, a similar consistency / volume and equivalent or better sensory quality characteristics can be achieved than in preparations made with a conventional amount of fats or oils.
[0066] Furthermore, it was surprisingly found that biogenic abrasive and non-abrasive scouring and cleaning agents can be produced using one of the processes according to the invention. It was found that lignin-containing coating materials, and in particular lignin-based shells, were completely or partially dissolved by the process steps according to the invention. This resulted in the formation of particles ranging from very small to very small, whose surfaces became rougher with increasing duration and intensity of the aqueous disintegration / exclusion processes using solutions containing dissolved disintegration compounds. Simultaneously, the outer contours became rounded and eventually no longer sharp-edged. Particularly preferred disintegration compounds are amino acids and / or peptides.Through partial or complete dissolution of lignin-based shells, spatial structures are formed on the surface that exhibit excellent absorption properties for organic and inorganic particles and facilitate the solubility of surfactants. During the cleaning of vessels, it was observed that the lignin-based shell components obtained using one of the aqueous disintegration / digestion processes according to the invention, particularly in combination with a surfactant, enabled a significantly improved cleaning effect, especially with regard to encrusted organic or inorganic deposits. In contrast to prior art abrasives, however, no scratches occurred when a glossy lacquer surface was cleaned of incrustations using the lignin-based shell material disintegrated and digested according to the invention.Thus, the methods according to the invention are suitable for producing abrasive or non-abrasive biogenic scouring agents from lignin-based coating materials.
[0067] A preferred method is one for the production of abrasive and non-abrasive biogenic scouring agents.
[0068] The use of lignin-containing coating material as an abrasive and non-abrasive biogenic scouring agent is preferred.
[0069] Surprisingly, a simple aqueous process can be used to both disintegrate plant husk materials, ensuring subsequent, technically straightforward, and completely separate them. This process also enables the dissolution of the husk materials, allowing for the extraction and recovery of the solid constituents. Thus, previously difficult-to-obtain or unobtainable plant husk materials contaminated with other organic substances can be obtained in pure fractions. Furthermore, the disintegration / digestion process allows for the recovery of the basic components (constituents) of the extracted husk materials, which can be used as valuable resources. Therefore, the process can be used to produce fiber products from plant husk materials through disintegration / separation and dissolution.
[0070] A preferred method is for the production of fiber products obtainable by disintegration and / or separation and / or dissolution / digestion of plant sheath materials using aqueous solutions containing dissolved compounds for disintegration / digestion.
[0071] Thus, the object of the invention can be solved by a method for producing fiber products obtainable by disintegration and / or separation and / or dissolution of plant sheath materials using aqueous solutions. Detailed description
[0072] The outer layer of plant seeds or kernels undergoes structural and functional changes after the growth phase. This includes shrinkage and irreversible closure of the water-conducting capillary structures. Furthermore, cellulose-based fibers keratinize. As a result, plant seeds, grains, and kernels enclosed by such outer layers are either not swellable by water or only swellable after prolonged exposure. This process also creates a generally very robust layer that effectively protects the enclosed plant product from mechanical damage. Surprisingly, aqueous solutions of dissolved amino acids and peptides are capable of disintegrating these compacted and keratinized plant outer layers.What was also surprising was that the disintegration processes are also suitable for further breaking down / dissolving the disintegrated plant husk material into its individual components, yielding pure fractions of solids as well as dissolved soluble compounds present in aqueous solution.
[0073] This effect was particularly pronounced when using cationic amino acids. Therefore, amino acids possessing one or more cationic charge groups, or peptides containing amino acids possessing one or more cationic charge groups, are especially preferred. Preferred amino acids include arginine, lysine, histidine, and derivatives thereof.
[0074] The peptides that can be used according to the invention can be di-, tri-, and / or polypeptides. The peptides according to the invention have at least one functional group that binds or can bind a proton. The preferred molecular weight is below 500 kDa, more preferably below 250 kDa, further preferably below 100 kDa, and particularly preferably below 1,000 Da. The preferred functional groups are, in particular, a guanidine, amidine, amine, amide, ammonium, hydrazino, hydrazono, hydroxyimino, or nitro group. The amino acids can have a single functional group, several functional groups of the same class, or one or more functional groups of different classes. Preferably, the amino acids and peptides according to the invention have at least one positive charge group or an overall positive charge. Peptides with cationic functional groups are particularly preferred.Preferably, the pH of the solution of cationic amino acids or peptides is in the range of 7 to 14, more preferably between 8 and 13, and further preferably between 8.5 and 12.5. In one embodiment, the pH can be adjusted to any desired pH range between 6 and 14 by adding an acid or a base. Acids and bases known in the art, such as sodium hydroxide or hydrochloric acid (HCl), can be used.
[0075] Particularly preferred peptides contain at least one of the amino acids arginine, lysine, histidine, and glutamine in any number and sequential order. Amino acids and / or derivatives containing at least one guadinino and / or amidino group are therefore particularly preferred. The guanidino group is defined as the chemical residue H₂NC(NH)-NH₂ and its cyclic forms, and the amidino group as the chemical residue H₂NC(NH)₂ and its cyclic forms. Guanidino compounds that, in addition to the guanidino group, possess at least one carboxylate group (-COOH) are preferred. It is further preferred if the carboxylate group(s) is separated from the guanidino group in the molecule by at least one carbon atom. Amidino compounds that, in addition to the amidino group, possess at least one carboxylate group (-COOH) are also preferred.Furthermore, it is preferred if the carboxylate group(s) is separated from the amidino group in the molecule by at least one carbon atom.
[0076] Furthermore, di-, tri-, or oligopeptides, as well as polypeptides composed of one, two, or more amino acids, are suitable. Short-chain peptides, e.g., RDG, are preferred. Peptides consisting of amino acids with both hydrophobic and hydrophilic side chains are particularly preferred, such as (listed alphabetically by amino acid name) GLK, QHM, KSF, ACG, HML, SPR, EHP, or SFA. Peptides with both hydrophobic and cationic and / or anionic side chains, such as RDG, BCAA, NCR, HIS, SPR, EHP, or SFA, are also particularly preferred. Other examples with four amino acids are NCQA, SIHC, DCGA, TSVR, HIMS, or RNIF, and with five amino acids are HHGQC, STYHK, DCQHR, HHKSS, TSSHH, and NSRR. RDG, SKH, or RRC are particularly preferred.
[0077] The application is carried out in the form of aqueous disintegration solutions in which the amino acids and / or peptides according to the invention are completely dissolved. The concentration of the amino acids and / or peptides can, in principle, be freely chosen; concentrations of 10 µmol to 3 mol / l are preferred, more preferably between 1 mmol to 1 mol / l, and further preferably between 100 µmol to 0.5 mol / l. The amino acids or peptides according to the invention can be present individually or in any combination in the aqueous solutions. The volume ratio of the aqueous phase containing the dissolved amino acids or peptides to the plant products or coating materials to be treated can, in principle, be freely chosen; however, complete wetting of the coating materials to be disintegrated / detached or dissolved should be ensured.It is preferred to immerse the plant materials to be treated completely in one of the solutions according to the invention.
[0078] Furthermore, it has been found that the process of disintegration of plant sheaths and shells can be accelerated by disintegration additives dissolved in aqueous disintegration solutions. Such compounds include, but are not limited to, the following: urea, NH₃, triethylamine, diethylamine; ionic or non-ionic surfactants, such as SDS or DMSO; antioxidants or sulfates and sulfites, such as sodium sulfite or sodium bisulfite; and carbonates, such as sodium carbonate or sodium bicarbonate. Preferably, the compounds are dissolved in water at a concentration between 0.1 and 30 wt%, more preferably at a concentration between 0.5 and 15 wt%, and most preferably at a concentration between 1 and 5 wt%. The compounds can be used individually or in any combination.
[0079] The process of disintegrating plant hull material can be controlled via various parameter settings, depending on the desired effect. For example, in one implementation, the hull material is hydrated and disintegrated in the germination area, such as in soybeans. This is sufficient, for instance, to mechanically strip the entire hull using a crushing device. For this purpose, for example, immersing intact beans in a solution containing 0.3 molar arginine at 25°C for 6 hours is sufficient. This can be verified by ensuring the hull can be completely removed by squeezing it with the fingers. In another application, walnuts, already hulled, were immersed in a 0.2 molar lysine solution at 35°C for 3 hours.After draining the solution, complete removal of the kernel skin was possible using a water jet device, with the resulting skins remaining largely intact. The walnuts obtained were > 98% skinned. All shells / skins obtained from the disintegration processes were soft and flexible. In another embodiment, chopped almonds were immersed in a 100 mmol histidine solution for 20 minutes at 20°C. They were then separated from the solution, and the detached kernel skin components were separated in a hydrocyclone. A removal of > 95% of the kernel skins was achieved. In yet another embodiment, kidney beans were skinned. For this purpose, the beans were immersed in a polylysine and histidine solution in an autoclave and treated at a temperature of 120°C and a pressure of 1.2 bar for 3 minutes. The skins could then be easily and completely removed with two fingers.
[0080] In preferred embodiments of the process, the method for disintegrating plant sheath materials can be applied to hydrate a sheath / skin and / or separate the texture of sheaths and skins at preformed locations and / or dissolve intermediate layers of sheath materials and / or soften sheaths and skins. Depending on the various requirements and differences in the starting materials, the specific conditions in a process must first be determined. Generally, however, the following parameter settings are preferred: The duration of exposure of the plant material to the aqueous disintegration solutions according to the invention is, in principle, freely selectable. An exposure duration between 5 minutes and 48 hours is preferred, more preferably between 10 minutes and 24 hours, and further preferably between 15 minutes and 12 hours.Sufficient exposure time can be easily determined by checking whether the desired effect, such as the peelability of a skin or husk, has been achieved in the treated plant products. The temperature at which the plant material is exposed to the aqueous disintegration solutions containing dissolved amino acids and / or peptides and / or other dissolved compounds for disintegration can, in principle, be freely chosen. However, a temperature range between 5° and 145°C is preferred, more preferably between 10° and 140°C, and further preferably between 15° and 80°C. Exposure preferably takes place under normal pressure conditions.In a preferred embodiment, a reduced or increased pressure is applied to the reaction mixture, preferably a pressure between 0.1 bar and 10 bar, more preferably between 0.5 bar and 5 bar, and further preferably between 0.8 bar and 3 bar. A simultaneous increase in temperature and pressure during exposure of the plant material to be treated with the aqueous disintegration solutions according to the invention is preferred. The exposure of the plant material with the aqueous disintegration solutions according to the invention is preferably carried out in an autoclave. The preferred treatment time in an autoclave is between 30 seconds and 60 minutes, more preferably between 1 minute and 30 minutes, and further preferably between 2 minutes and 15 minutes.
[0081] In a preferred embodiment, the hydrated and partially or completely disintegrated hull materials are fed to a device that enables the removal of the hull material. Numerous such devices exist in the prior art. Product-friendly designs are preferred, as these allow the advantageous effects of the inventive product-friendly treatment to be realized for the separation of the plant hull material. For example, hydrodynamic processes are suitable, in which a water jet applies shear forces to the hull material, leading to its separation. However, mechanical processes can also be very advantageous. In a particularly preferred embodiment, the pretreated seeds, grains, or kernels are sorted by size and conveyed into a blowing device.During this process, upon entering a flexible or rigid tube / sleeve, or during transport within it, the disintegrated hull material tears and is translocated / separated from the seed, grain, or kernel. Upon exiting the tube / sleeve, which can occur under pressure, the seeds, grains, or kernels are spatially separated from the hull material by various applicable methods, such as utilizing gravity or by means of air classification. The suitability of a disintegrated plant material for carrying out the separation of the hull material can be determined, for example, by whether the disintegrated hull material can be easily stripped by light rubbing with the palms of the hands.
[0082] In a preferred embodiment, the inventive disintegration of plant hull materials takes place following a mechanical disintegration process. Particularly preferred are meal from which oil removal has occurred and / or the separation of other valuable material fractions, such as proteins and / or carbohydrates, is desired. It has been shown that even such coarse to fine-grained plant products can be purified of hull components using the inventive disintegration solutions. Eddy current or sieving processes can also be used for their separation.
[0083] In one embodiment, the hydratability and detachability of the plant husk material by aqueous disintegration solutions containing dissolved amino acids and / or peptides and / or other dissolved compounds for disintegration is increased by the addition of surfactants and / or digestion agents. In another embodiment, the aqueous solutions may contain disintegration aids or additives, such as alcohols or surfactants. Preferred alcohols are methanol and ethanol. Preferred surfactants are urea, thiourea, sodium lauryl sulfate, and DMSO. Preferred digestion agents are sodium bisulfite and sodium sulfite. The concentration required for each application must be determined individually.
[0084] Preferably, the coating material(s) is separated immediately after the plant products are exposed to one of the aqueous disintegration solutions according to the invention. However, separation can also be carried out at a later time. It has been shown that if the coating material has been disintegrated or partially dissolved using one of the methods according to the invention, even coating materials that have dried in the meantime can be easily separated by dissolving / swelling them in water. Therefore, the methods according to the invention can also be used to prepare plant products for easier separation of the coating material at a later time. It has been found that this alone renders the pretreated coating material partially or completely odorless and / or tasteless.In one embodiment, a method according to the invention is therefore also used for the taste neutralization / debittering of coating materials with or without simultaneous disintegration / detachment of the coating products. The duration of the exposure required for this, as well as the temperature and pressure conditions, must be determined individually.
[0085] In a further preferred embodiment of the process, the coating materials disintegrated and separated from plant starting materials and / or mechanically separated from the plant starting material are immersed in one or consecutively several disintegration solutions containing dissolved amino acids and / or peptides and / or other compounds for disintegration. Advantageously, this continues or initiates a disintegration process, whereby the coating material can be completely wetted. This allows, for example, the softening of previously brittle and easily breakable coating materials, resulting in these disintegrated coating materials exhibiting very high flexibility and preventing breakage. The preferred form of disintegration for this purpose is achieved by long-term immersion in one of the aqueous solutions according to the invention.A duration between 15 minutes and 30 days is preferred, more preferably between 60 minutes and 14 days, and further preferably between 10 hours and 7 days. The concentrations of the dissolved amino acids and / or peptides are to be adjusted accordingly; the values given above can be used as a guide. Disintegration is preferably carried out at room temperature. According to the invention, the pH is to be adjusted between 6.5 and 13, more preferably between 7 and 12, and further preferably between 8 and 12.5. In a further preferred embodiment, the conditioning / softening of plant husk material is carried out by a short-term treatment in an autoclave. It has been found that the softening of the separated husk material can also occur at elevated temperature and pressure with a short exposure time. A temperature range of 80 to 140°C is preferred, more preferably between 90 and 130°C, and further preferably between 100°C and 121°C.The preferred pressure is between 0.5 and 10 bar, more preferably between 0.8 and 5 bar, and further preferably between 1.0 and 2 bar. The exposure time is preferably between 20 seconds and 10 minutes, more preferably between 30 seconds and 8 minutes, and further preferably between 40 seconds and 3 minutes. It is preferred to subject the cladding materials, disintegrated and softened by the aforementioned process embodiments, to a thorough rinsing in water. Such disintegrated cladding materials do not dissolve further when left in neutral water. They can be stored in this water in an unchanged state for a long period exceeding 6 months. Alternatively, they can be dried and stored. It is preferred to produce a composite / texture from the individual cladding material components. This is advantageously achieved by pressing the cladding materials, e.g.,on a screen press, which can be used, for example, to produce shaped sheets. These compacts can then be dried, for example, in a drying cabinet. The resulting compressed cladding material composite sheets are characterized by their enormous swelling capacity when immersed in water, preferably > 200 wt%, more preferably > 300 wt%, and further preferably > 400 wt%. Preferably, during the processing to obtain disintegrated, moldable cladding materials, conditioning and / or functionalization of the disintegrated cladding material is also carried out in one or more additional or simultaneous processes using one of the processes described above or below. Advantageously, disintegrated softened / flexible plant-based cladding materials that are completely or almost completely odorless and / or tasteless have also been produced using this process."Approximately" means > 98%. In other words, a reduction of more than 98% of the previously present odor and / or taste compounds has occurred. Furthermore, disintegrated and softened coating materials release no or virtually no dyes into an aqueous medium. For example, in one application, it was demonstrated that the coating material of garlic could be formed into a tasteless, highly flexible sheet.
[0086] Furthermore, additives can be added to the aqueous disintegration solutions according to the invention, which contain dissolved amino acids and / or peptides, thereby achieving further particularly advantageous effects that, for example, condition and / or functionalize and / or enhance the disintegration of the plant husk material. In one embodiment, carboxylic acids are completely dissolved in the aqueous solutions containing cationic amino acids and / or peptides. This is particularly advantageous because the cationic compounds allow the carboxylic acids to be completely dissolved in an aqueous medium, forming nanoemulsions. This advantageously enables a reduction in the exposure time required to achieve the detachment of plant husk material in many applications.Furthermore, the coating materials can be advantageously loaded with dissolved carboxylic acids during the hydration process initiated by the aqueous solutions according to the invention, or incorporated and / or applied to the hydrogenated cellulose-based fibers. This allows, on the one hand, the production of coating materials with modified surface properties, such as hydrophobic properties or antimicrobial functionality. On the other hand, upon disintegration / dissolution of the coating materials, cellulose-based fibers loaded with carboxylic acids, such as omega-3 fatty acids, can be produced. Preferred carboxylic acids dissolved in the aqueous solutions according to the invention include fatty acids such as monounsaturated or polyunsaturated fatty acids like oleic acid or linolenic acid, and also organic acids such as acetic acid or ascorbic acid.The preferred concentration of the carboxylic acids can be between 1 µmol and 3 mol / l, more preferably between 1 mmol and 1 mol / l, and further preferably between 100 µmol and 0.5 mol / l. Preferably, the carboxylic acids are completely dissolved in the aqueous disintegration solutions according to the invention. The total amount of carboxylic acids is therefore limited by the number and concentration of the cationic compounds present in the solution mixture that enable the dissolution of the carboxylic acids.
[0087] Further compounds can also be added to the aqueous disintegration solutions. In a preferred embodiment, ionic or non-ionic surfactants are added as additives. This is particularly advantageous in the recovery of cellulose-based fibers from sheath materials that contain a significant proportion of fats or waxes. The use of urea or creatine as an additive is also preferred. In one embodiment, additives are used to achieve a better / more complete disintegration of the cellulose-based fibers from the organic matrix.
[0088] In another process iteration, in addition to disintegration, the components (constituents) of the plant covering material are also broken down and separated.
[0089] In a preferred embodiment of the process, lignin and / or lignin-containing polymer structures, as well as keratinized cellulose-based fibers, are disrupted / dissolved by a combination of disintegration compounds in the form of an aqueous solution or a sequential series of aqueous solutions with one or more disintegration additive(s). Sodium sulfite, sodium bisulfite, urea, thiourea, sodium lauryl sulfate, and DMSO, as well as carbonates such as sodium bicarbonate, are particularly preferred. The concentration of the disintegration additives in an aqueous solution, in which they are preferably present in dissolved form, is preferably between 50 µmol and 3 mol / l, more preferably between 1 mmol and 2 mol / l, and further preferably between 200 mmol and 1 mol / l. The compounds or aqueous solutions can be used together with the dissolved amino acids and / or peptides according to the invention or in a temporal sequence.A preferred digestion process involves using the dissolved amino acids and / or peptides together with the additives. The preferred temperature for digesting lignin and / or lignin-containing polymer structures is preferably between 40° and 140°C, more preferably between 60° and 130°C, and further preferably between 80° and 120°C. Simultaneous pressure application to the reaction mixture is preferred. An overpressure of 0.5 to 10 bar is preferred, more preferably between 0.8 and 8 bar, and more preferably between 1 and 6 bar. The exposure time of the starting material with the aqueous solutions must be determined individually, as the degree of cross-linking of the lignin polymers and the degree of keratinization of the cellulose-based fibers in the starting materials can vary considerably. Sufficient exposure time can be easily determined by taking a sample from the reaction vessel.Sufficient exposure time is present, in particular, when dark brown to black structures of the plant sheathing materials are absent or only present to a small extent, or have disintegrated into minute particles. Furthermore, the exposure time is sufficient if no coherent fiber structures are visible in a microscopic analysis.
[0090] It has been found that lignin-based hull material is disintegrated by applying the methods according to the invention and can be obtained in the form of, for example, an intact shell or shell fragments. Lignin-containing shell materials are found, for example, in the seeds or grains of jatropha, rapeseed, sunflowers, or in the kernels of apples and pears. The plant hull material can be in an intact state or in a partially or completely mechanically or thermally disintegrated state, such as after the extraction of an oil fraction or in the form of pomace after juicing. The methods according to the invention serve to recover valuable material fractions that can still be obtained.
[0091] In another embodiment of the process, the press residues of plant seeds, such as the press cake of rapeseed or jatropha, obtained, inter alia, from an aqueous pulping process, were treated with the solutions according to the invention by soaking them thoroughly. Soaking means completely moistened, but not wet. After 4 hours, the solid constituents in water were dispersed using a mixer. The solid components were separated by means of a filter and fed to a further process stage with the aqueous pulping mixtures. In one embodiment, for example, a solution containing 0.2 molar lysine and 10 wt% urea can be used for this purpose, in which the solid filter residue is soaked for 6 hours.The liquid phase is then removed using a chamber filter press, and the filter residue is dispersed in water. This residue is then separated into two solid fractions using a hydrocyclone: cellulose-based fibers and lignin-based shell components. It has been demonstrated that the constituents of the fiber components can be separated using methods for disintegration and detachment of lignin-based components, allowing for the singulation of the various fiber components. This process, in particular, enables the recovery of large quantities of lignin-based shell components as a separable, valuable material fraction.
[0092] Depending on the origin of the starting material and the chosen disintegration / digestion process, dehydration procedure, or exposure to a bleaching agent, the obtainable cellulose-based fibers exhibit varying degrees of keratinization. This results in crystalline areas that lead to a distinctly perceptible solid sensation in the mouth and a fine-grained chewing feel, which is undesirable. Surprisingly, it was found that in a disintegration / digestion process using the amino acids and / or peptides according to the invention, keratinization of cellulose-based fibers practically does not occur. Furthermore, it was found that if keratinization of the cellulose-based fibers does occur, it can be significantly reduced or completely reversed by disintegration with a solution containing the amino acids and / or peptides according to the invention.It was demonstrated that sugar beet pulp, after disintegration with a sodium sulfite solution at 130°C and a pressure of 1.2 bar for 10 minutes, yielded a mass of cellulose-based fibers that, after homogenization and removal of the free liquid, exhibited a high degree of keratinization and was therefore inedible. Immersion in a 0.3 molar arginine solution, combined with mixing, disrupted the keratinization, resulting in virtually no granularity after 3 hours.
[0093] A preferred method is one for the disintegration / dissolution of the keratinization of cellulose-based fibers.
[0094] In a preferred embodiment of the process, the lignin-based shells or fragments, already obtained from one of the processes described herein or from another process, are subjected to a disintegration process using one of the disintegration solutions. The preferred aim is to achieve a partial dissolution and / or complete dissolution of the lignin polymer structures. Naturally, the complexity of these structures varies in the different shell materials, so the precise reaction conditions must be individually adapted. It is preferred to disintegrate and dissolve the lignin-based shells or fragments in a solution of sodium sulfite, preferably together with dissolved amino acids and / or peptides and / or urea and / or carbonates, at elevated temperature and preferably under elevated pressure.Preferred concentrations of sodium sulfite or sodium bisulfite, but also of sodium carbonate or sodium bicarbonate, are 0.1 to 3 molar, more preferably 0.3 to 2 molar. Preferred concentrations of dissolved amino acids and / or peptides (individually or together) are 0.1 to 3 molar, or up to the solubility limit, more preferably 0.2 to 2 molar. A pH of the disintegration solution between 8 and 13 is preferred, more preferably between 8.5 and 13, and further preferably between 9 and 12.5. The preferred temperature is between 60 and 180 °C, more preferably between 70 and 160 °C, and further preferably between 80 and 140 °C. The preferred pressure increase is 0.1 to 20 bar, more preferably 0.2 to 10 bar. The duration of disintegration depends on the process parameters and the starting material.A disintegration period of between 10 minutes and 24 hours is preferred, more preferably between 15 minutes and 10 hours, and further preferably between 15 minutes and 6 hours. Preferably, the disintegrated and / or partially dissolved and / or dissolved shells or fragments are subjected to extensive rinsing with water or a suitable surfactant mixture. The rinsing process is complete when the rinsing solution remains clear. The resulting fraction of lignin-based shells is preferably subjected to a drying process. In a preferred embodiment, the removal of bound water is carried out using a sieve or a centrifugal process. Vibrating sieves and centrifuges are preferred. The lignin-based shell material, which is usually free-flowing by this point, can then be completely removed, e.g.,The product is dried in a belt drying device or vacuum drying oven to a residual moisture content of preferably < 20% by weight, more preferably < 15% by weight, and further preferably < 10% by weight. It is stored dry until use.
[0095] Since cellulose-based fibers are also released / dissolved during the disintegration process, a preferred process embodiment separates the cellulose-based fiber fraction before, during, or after further processing. This can preferably be achieved using known process techniques. Eddy current processes are preferred, in which a semi-selective discharge of particles of different densities and with different settling behavior occurs. The use of a hydrocyclone is preferred. The purity of the resulting fraction of lignin-based shell components can be determined, for example, by microscopic analysis. A purity of the obtainable fractions of > 90% is preferred, more preferably > 95%, and further preferably > 98.5%. On the other hand, the presence of cellulose-based fibers in the fraction of lignin-based shell components is generally not problematic.It has been shown that the presence of > 5% cellulose-based fibers in the fraction of lignin-based shell components reduces the scratchability of scratch-sensitive surfaces, which can be caused by high contact pressure from abrasives.
[0096] In a preferred embodiment, size selection and / or comminution of the lignin-based shell particles to a defined size is carried out at any point during the process. Preferably, this occurs towards the end of the processing. Size sorting is preferably performed by means of retention using sieve devices. This can be carried out for both dry and water-suspended lignin-based shell particles. Comminution can also be performed for dried or saturated lignin-based shell particles. Cutting or grinding mills are suitable, for example. The obtainable size distributions can be determined using commercially available analytical sieve devices.
[0097] Depending on the plant material used, the intensity of the disintegration process, and the fragmentation of the peel material, flat or particulate particles of lignin-based peel components are formed. Chemical analysis revealed a lignin content of > 40 wt%. Particulate particles with a lignin content of > 40 wt% are preferred, more preferably > 50 wt%, further preferably > 60 wt%, even more preferably > 75 wt%, and most preferably > 90 wt%. The composition can be determined by analytical methods.
[0098] A preferred method involves disintegrating a plant starting material to obtain particulate particles / shell components that have a lignin content of > 40 wt%.
[0099] It was found that these lignin-based shell components exhibit abrasive removal properties, or scouring properties, against organic or inorganic incrustations on various surfaces. Surprisingly, differential abrasive properties were found in the lignin-based shell components resulting from the processing methods. It was demonstrated that when mechanically crushed lignin-based shell material, obtained from one of the pulping processes for coating materials, was treated with a constant contact pressure to remove incrustations from scratch-sensitive surfaces such as glossy lacquer or high-gloss plastic surfaces, scratches and grooves formed during the removal of the adhesions.In contrast, no furrowing / scratching of the surfaces occurred when a disintegration process according to the invention was used to break down the plant husk material, under otherwise identical cleaning / removal conditions for firmly adhering contaminants and an identically selected contact pressure. Thus, the lignin-rich husks acquire a differential abrasive property through disintegration, which allows surface contaminants and, in particular, encrusted contaminants, for example, organic materials such as proteins, to be removed without causing discrete abrasion (furrows / scratches) of abrasion-sensitive (scratch-sensitive) surfaces, as is the case with high-gloss plastic surfaces or glossy lacquers.
[0100] Abrasive, in this context, refers to the removal of adhesions, deposits, or incrustations present on a material surface, such as metals, ceramics, glass, plastics, paints, or biological materials like leather. Abrasive, in this context, does not imply damage to the surface integrity of the abrasively treated materials. Microscopically, micro- and / or nanosurface irregularities were observed in lignin-based shells or fragments produced by one of the process steps; however, the outer contours were sharp-edged and / or pointed. These lignin-rich shell fragments exhibited excellent abrasive properties on incrustations in metals, glass, or ceramics, which could be removed significantly more easily compared to prior art abrasives.No scratch marks were visible here, which was the case when cleaning painted and plastic surfaces containing such lignin-rich shell particles. Surprisingly, it was found that further disintegration of the lignin-based shell particles according to the methods described herein yielded particles with rounded and flat-arched outer contours, yet they still exhibited abrasive effects on encrusted residues on surfaces. These rounded lignin-based shell particles did not scratch when suspended in a soap solution and moved across a high-gloss painted or plastic surface with a contact pressure of 0.2 N. Both forms of lignin-based shell particles share a high degree of lift-off / removal property on incrustations. Furthermore, both forms exhibit micro- and / or nano-surface roughness.The preferred lignin-based shell particles, which can be used for abrasive, scratch-free applications, have any desired spatial dimension. Preferably, they are disc-shaped particles. However, other spatial structures are also possible. In a preferred embodiment, the particles preferably have an average particle size between 100 µm and 3 mm, more preferably between 200 µm and 1 mm, and even more preferably between 300 µm and 800 µm. In one embodiment, the size sorting is carried out by a sieving device. Agitable sieves, such as vibrating sieves or air classifiers, are preferred.
[0101] Preferred is the production of abrasive particles from plant-based raw materials for the lifting / removal of surface incrustations.
[0102] Preferred is the production of abrasive particles from lignin-based shells for the lifting / removal of surface incrustations.
[0103] In one embodiment, the lignin-based shell components are therefore disintegrated to preferably 95 wt%, more preferably > 97 wt%, further preferably > 99 wt%, and even more preferably until all lignin-based shell components are in a completely rounded shape. With this quality feature, a non-scratch abrasive scouring agent is available, which can be used to abrasively clean easily scratched surfaces, e.g., those of paints and plastics. Preferably, the non-scratch abrasive scouring agent produced according to the invention is formulated by adding the lignin-based shell components produced according to the invention to a surfactant / soap solution and suspending them therein. The lignin-based shell components can be added to the surfactant / soap solution in a still-moist or dried form and preferably by means of a high-speed shear mixer.
[0104] For use as an abrasive, the lignin-based hull components can be used in wet, partially dried, or dried and powdered form. The hull components of Jatropha and rapeseed grains / seeds are particularly suitable for the production of abrasive scouring agents from lignin-based hull components.
[0105] In a preferred embodiment, the disintegration / dissolution of the plant hull material according to the invention is carried out together with, or in immediate succession to, the disintegration / dissolution of the plant seeds, kernels, or grains. This is particularly advantageous because it can be done with the same aqueous disintegration / dissolution solutions. For this purpose, it is generally necessary to select a longer exposure time and / or different process parameters than those used for the disintegration / detachment / dissolution of hull materials. In particular, an extension of the exposure time may be required; preferably, an exposure time between 10 minutes and 48 hours, more preferably between 30 minutes and 24 hours, and further preferably between 1 hour and 12 hours.Furthermore, it is preferred that the temperature of the reaction mixture be increased during exposure to the aqueous solutions according to the invention; temperatures between 20° and 140°C are preferred, more preferably between 30° and 120°C, and even more preferably between 40° and 80°C. In a particularly preferred embodiment, following the disintegration of the entire plant starting material, the constituents of the starting material are digested, whereby the soluble components, such as proteins and soluble carbohydrates, are completely dissolved in an aqueous distribution volume, and the solid constituents, such as cellulose-based fibers and lignin-rich husks, are suspended in the aqueous distribution phase. A volume of water is preferably selected that ensures easy separation of the solid constituents.A preferred water addition volume ratio to the process mixture resulting from the disintegration process is 2:1 to 200:1, more preferably 5:1 to 100:1, and further preferably 10:1 to 50:1. The temperature at which this process step can take place is arbitrary, but a temperature range between 5° and 95°C is preferred. The distribution volume is preferably added by means of intensive mixing, preferably using high-performance shear mixers / dispersers or homogenizers. The presence of a sufficient distribution volume, or of a distribution or disintegration of the constituents of the starting material, can be verified by taking a sample from the suspended mixture and filtering it. If, for example in a microscopic analysis, the filterable solid constituents show no adhesion of soluble constituents, the process is complete.Preferably, the suspended solids are subsequently separated, preferably by filtration or a centrifugal separation process. Preferably, dissolved constituents are separated in the aqueous distribution volume after the separation of the solid constituents, of which preferably < 5 wt%, more preferably < 2.5 wt%, and further preferably < 1 wt% are present in the separated aqueous distribution volume. Preferably, dissolved proteins are separated by adding dissolved compounds to the aqueous distribution volume containing dissolved proteins and optionally other soluble constituents of the starting material to initiate aggregation / complexation. These compounds are preferably one or more organic acids, preferably carboxylic acids such as citric acid, lactic acid, or ascorbic acid.However, other acids can also be used, such as HCl or phosphoric acid. Furthermore, combinations of different acids are possible. The pH of the aqueous solution containing dissolved compounds for aggregation / complexation, in which the condensation and / or aggregation and / or complexation of the dissolved proteins and / or other dissolved compounds according to the invention takes place, is preferably in a range between [value missing in original text]. 4,5and 13, more preferably between 6 and 12, and further preferably between 6.5 and 11. Furthermore, complexing agents, such as calcium and / or magnesium compounds, like calcium chloride or magnesium chloride, can be added before, during, and / or after the acid addition. The salinity of the aqueous distribution volume can also be modified. The amount added depends on the concentration of the dissolved and aggregable compounds and must therefore be determined in each case. It has been found that a sufficient amount is reached, for example, when clearly visible aggregates have formed, with the previously cloudy distribution phase simultaneously becoming clear. However, analytical methods can also be used: in the case of protein aggregation according to the invention, after their separation, preferably < 5 wt%, more preferably < 2.5 wt%, and further preferably < 1 wt% of dissolved proteins are present in the process liquid.
[0106] In a preferred embodiment of the process, the added aggregating / complexing agent(s) is / are mixed with a stirrer and gentle agitation of the process liquid. Thorough mixing is essential. The duration of the mixing is, in principle, freely selectable. In a preferred embodiment, mixing occurs only for the duration of the addition of one or more aggregating / condensing agents, or for a period between 10 seconds and 5 minutes, more preferably between 20 seconds and 2 minutes. In a particularly preferred embodiment, a settling period is observed following the addition of one or more aggregating / condensing agents, during which no or only minimal mixing of the mixture takes place.Similarly, the required condensation phase time can be determined, preferably between 5 minutes and 10 hours, more preferably between 10 minutes and 5 hours, and even more preferably between 15 minutes and 2 hours. If the stand time is to be minimized, the sufficiently short minimum stand time after addition of the complexing / aggregating agent can be determined using a centrifuged sample. The completeness of the condensation and / or aggregation and / or complexation achieved by the complexing / aggregating agent(s) is then checked by adding the same and / or a different solution containing an aggregating agent to the supernatant of the centrifuged sample. If no further aggregation occurs, the extraction process of dissolved proteins is complete.In a preferred embodiment of the process, after aggregation / complexation of the dissolved proteins, the aggregates / complexes sediment. Preferably, these aggregates / complexes subsequently condense, allowing them to be easily separated from the free aqueous phase of the process medium.
[0107] In a preferred embodiment of the process, the aggregated / complexed and condensed compounds / proteins are made recoverable in the form of a sediment. Preferably, the sediment phase is discharged via a bottom outlet and fed into a further process step. The condensation phase preferably takes place at ambient temperatures, ideally within a temperature range of 15 to 40°C. In further advantageous embodiments, this phase is carried out at a lower or higher temperature. A temperature range of 5° to 15°C on the one hand and 40° to 80°C on the other is preferred. Selecting a lower temperature can be advantageous, for example, in the recovery of thermolabile compounds. Selecting a high temperature, e.g., 60°C, can be chosen, for example, to kill microorganisms, e.g., by pasteurization, in the case of microbial contamination of the starting material.On the other hand, heating can also inactivate allergens, certain toxins, and antinutritional compounds.
[0108] A preferred method is for obtaining a protein-containing sediment consisting of aggregated / complexed and condensed proteins.
[0109] A preferred method is for obtaining and preserving proteins from plant starting materials, obtainable by disintegration / digestion with separation of dissolved proteins, followed by aggregation / complexation and condensation.
[0110] The recovered protein mass can be used immediately or subjected to further purification steps.
[0111] In investigations into the isolation of dissolved proteins from aqueous solutions containing other dissolved soluble constituents, obtained by separation in aqueous solutions containing dissolved disintegration / digestion compounds, it was found that the hydration of the proteins achievable with this method, by appropriately selecting the process parameters, allows for the obtaining of a very pure fraction. "Pure" here means that the protein fractions have a protein content of preferably > 60 wt%, more preferably > 70 wt%, further preferably > 80 wt%, and even more preferably > 85 wt%, and most preferably > 90 wt%.
[0112] It was found that such pure protein fractions can be produced in particular by using a large distribution volume after a digestion of the constituents according to the invention. Proteins dissolved in this way pass, for example, through a membrane filter with a pore permeability of at least 1 µm. This allows for size-selective separation of dissolved proteins. Furthermore, it was shown that, especially in this situation of optimal hydration of the dissolved proteins and the presence of a physiological pH range, a very rapid and pronounced interaction with the complexing / aggregating agents listed herein occurs, resulting in the aggregation of the hydrated proteins, displacing or excluding the process water.This can be recognized, for example, by the formation of three-dimensional structures visible to the naked eye, accompanied by partial or complete clarification of the process fluid, which then settle only very slowly. The process fluid is subsequently moderately to intensely colored and contains odor and taste compounds as well as soluble carbohydrates. Thus, the process of hydration and subsequent condensation of soluble proteins necessitates that the compounds previously detached from the proteins remain in a dissolved state in the process water phase and do not bind with or are carried away by the condensing proteins.
[0113] A preferred method is for the production of protein condensates and / or protein concentrates and / or protein isolates from organic starting material using aqueous solutions containing dissolved disintegration / digestion compounds.
[0114] In a further preferred embodiment, the disintegration / detachment / dissolution of the plant hull material and / or the other constituents of the starting material is carried out on seeds, grains, or kernels that have already been thermally and / or mechanically disintegrated / divided / comminuted. This reduces the required exposure time for the aqueous solutions according to the invention.
[0115] Mechanical methods that exert shear forces on the treated hull materials are preferred for the removal and separation of the disintegrated / parted / detached hull materials. In a preferred embodiment, the removal and separation are carried out by rollers on or between which the pretreated seeds / kernels are transported and simultaneously subjected to tangential shearing. The simultaneous provision of a rinsing device or a blower to separate the removed hull materials is particularly preferred.
[0116] In one embodiment, the disintegration / detachment or removal of an intermediate layer located on the plant seeds or kernels and / or on the separated hull material is achieved by a longer residence / exposure time in / with one of the aqueous liquids according to the invention than is required for the disintegration / detachment / separation of plant hull materials. An exposure time between 1 minute and 72 hours is preferred, more preferably between 10 minutes and 48 hours, and further preferably between 30 minutes and 24 hours. The temperature of the reaction mixture can be chosen arbitrarily; a temperature range between 5° and 120°C is preferred, more preferably between 10° and 100°C, and further preferably between 15° and 70°C. The application of physical shear forces to the material to be purified of an intermediate layer is preferred.These shear forces are preferably applied to the reaction mixture, for example, by rotating the container or an agitator. Preferably, shear forces can also be generated by a rinsing / spraying device. The sufficient exposure time and application of shear forces for rinsing off the intermediate layer can be easily verified by a person skilled in the art by examining the treated product for its physical surface properties, such as the presence of a coating or skin formation, during drying.
[0117] In one embodiment, the plant hull materials are disintegrated / partially dissolved or dissolved without being removed from the plant product. It has been shown that hull materials that have been at least partially dissolved or swollen by exposure to the aqueous solutions according to the invention no longer need to be removed, or only partially removed, from the plant seed or grain, since they no longer interfere with the further use of the seed or grain. In another embodiment, the separated plant hull materials are disintegrated / partially dissolved / dissolved by one of the methods according to the invention. This is particularly of interest if further valuable substances contained in the plant hull material are to be extracted and recovered, or if cellulose-based fibers can be produced and recovered.The concentrations of the cationic amino acids and / or peptides, as well as the exposure time and the temperature and pressure of / on the reaction mixture(s) must be determined depending on the application. Cellulose-based fibers and lignin-rich shell parts
[0118] The type and composition of bran materials naturally vary depending on the type of plant material. For flour production, the bran is usually separated before milling, as it is generally undesirable in the resulting products. This typically requires significant processing effort and results in the loss of grain / seed material due to mechanical breakdown. Fibers, which are present as structural components in seeds, kernels, and grains, as well as in other plant materials, cannot be completely separated or isolated using state-of-the-art methods, as they are fully bound and compacted with the constituents. In particular, mechanical separation of these fibers is not possible with current technology.It was therefore completely surprising that both the lignin-rich husk components and the cellulose-based fibers of the plant starting materials could be separated and decompacted and obtained in a directly pure form using the methods described herein. Following a disintegration / digestion process, after extensive removal of bound water from the solid components, no or virtually no proteins, soluble carbohydrates, odor or taste compounds, or other organic or inorganic detachable compounds were found. Microscopic examination revealed no adhering organic components.
[0119] The lignin-rich shell fragments have a lignin content of 30–95 wt%. They occur as submillimeter-sized platelets or in an amorphous form. After drying, they are free-flowing and pourable. They possess a considerable water retention capacity, which can exceed 40%. Microscopically, the cellulose-based fibers have a cotton-like, three-dimensional structure with mean diameters between 50 µm and 500 µm and an aspect ratio (length / diameter) of 1:1 to 1,000:1. These are isolated / discrete structures that are not interconnected and have a very low linear density of preferably < 70mg / 100m, more preferably < 50mg / 100m, more preferably < 30mg / 100m, more preferably < 20mg / 100m, more preferably < 15mg / 100m and most preferably < 10mg / 100m.It was found that such cellulose-based fibers differ considerably from cellulose fibers produced from, for example, stems or wood, in their chemical composition, secondary and tertiary structure, and physicochemical properties. Furthermore, it was found that both the recoverable cellulose-based fibers and the lignin-rich bran components exhibited a significant water-binding capacity exceeding 200 vol%. In addition, it was found that both the lignin-rich bran components and the cellulose-based fibers are free or virtually free of odors, flavors, or dyes soluble in aqueous media.Therefore, the lignin-rich shell components and cellulose-based fibers obtainable by the process are directly usable in the form as they can be obtained and produced by the processes according to the invention or after drying, which can be carried out using techniques from the prior art, or they can be subjected to further processing.
[0120] A preferred method is one in which pure lignin-based shell parts and / or cellulose-based fibers are obtained from a plant-based starting material, with a water binding capacity of > 200 vol%.
[0121] Surprisingly, dried lignin-based shell components exhibit not only a high water binding capacity and high water retention capacity, but also an extremely high binding capacity for oils and fats. In tests with various lignin-based shell components, this capacity ranged from 250 to 550 wt%. Remarkably, hydrophobic interactions between the surfaces resulted in very rapid transport of oils and fats along the outer surfaces of the granules. This allows oils and fats to be transported against a pressure gradient through poured lignin-based granules via capillary forces on the inner and outer surfaces. The delivery head in tests using riser pipes exceeded 5 cm. Furthermore, it was demonstrated that the dried and powdered cellulose-based fibers also exhibited a very high binding capacity for oils and fats, ranging from 220 to 360 wt%.
[0122] A preferred method is one in which pure lignin-based shell parts and / or cellulose-based fibers are obtained from a plant-based starting material, with an oil and / or fat binding capacity of > 200 wt%.
[0123] Lignin-rich shell fragments and / or cellulose-based fibers, with an oil and / or fat binding capacity of > 200 wt%, obtainable by a process of disintegration and digestion of plant starting material.
[0124] Surprisingly, it was found that the lignin-rich hull components and the cellulose-based fibers present in the filter residue of many of the investigated plant-based starting materials, such as rapeseed and jatropha press residues, can be easily separated from one another using state-of-the-art techniques. Eddy current processes, such as hydrocyclones, are preferred for this purpose, but filtration techniques can also be employed. It was demonstrated that this makes it possible to obtain pure fractions of cellulose-based fibers on the one hand and lignin-rich hull components on the other, in which no or virtually no proteins, soluble carbohydrates, odor or flavor compounds, or other organic or inorganic leachable compounds are present, or from which dyes leach in an aqueous medium.
[0125] The resulting shell or fiber fractions are preferably freed from any remaining bound water by a pressing process. Alternatively, centrifugal processes can be used. The dewatered shell or fiber fractions can be used in their obtained form or completely dried. Drying methods are known from the prior art. Warm air drying is preferred. Advantageously, the lignin-rich shell components obtained after drying are readily available in an easily separable and free-flowing form.
[0126] It was found that the produced cellulose-based fibers differ in their chemical composition compared to cellulose fibers and cellulose derivatives. While practically no elements other than C, H, and O could be identified in cellulose fibers and cellulose derivatives, numerous elements such as N, S, P, Fe, Cl, Na, Ca, K, Ni, Cl, Cu, and others were present in cellulose-based fibers. Based on the bonding properties observed in the cellulose-based fibers, it can be assumed that these elements belong, at least in part, to functional groups that are covalently linked, either directly or indirectly, to the polymeric backbone structures. A covalent indirect link can occur, for example, via a sugar residue or a peptide.However, it is also conceivable that non-covalently bonded compounds are connected to the polymer backbone via electrostatic interactions, which these functional groups or elements possess. The presence of functional groups on the surfaces of the cellulose-based fibers is responsible for many of the effects observed so far.
[0127] Like the cellulose-based fibers, the lignin-based husk components exhibit large internal surface areas, which account for their enormous water-binding capacity. This makes them particularly suitable for water retention and storage in arable soils. When dried, they are exceptionally easy to store and transport. They exhibit optimal miscibility with all soil types tested (e.g., clay, humus). The water absorption and water retention index of all soils tested was significantly increased by the addition of lignin-rich husk components.
[0128] The use of lignin-rich shell fragments to improve the water binding and retention capacity of cultivation soils is preferred.
[0129] Lignin-based shell particles exhibit excellent oil and grease absorption properties in their dried state, making them ideally suited for absorbing oils and greases, e.g., from surfaces or from air / gas mixtures containing oils and greases. The absorbed oils and greases do not spontaneously leach from the lignin-based shell particles, and the oil- or grease-saturated material does not "caking," thus maintaining excellent transportability. Furthermore, it has been demonstrated that the adsorbed oils and greases can be completely removed from the lignin-based shell particles using solvents, and that the particles retain their original reabsorption capacity for oils and greases. Lignin-based shell particles have a low bulk density and can be permeated by air or gas streams with minimal resistance. This has been shown to be useful for...Lignin-based shell components are ideally suited for removing oil and grease droplets from gas mixtures containing oil and fat vapors, such as the exhaust air from deep fryers. This makes them perfect for surface applications or for capturing oil from air / gas mixtures.
[0130] The use of lignin-based shell components for the absorption and binding of oils and fats from surfaces and from air / gas mixtures is preferred.
[0131] The use of lignin-rich shell parts and / or cellulose-based fibers, with an oil and / or fat binding capacity of > 200 wt%, for the absorption of fats and oils is preferred.
[0132] The cellulose-based fibers obtainable by the methods according to the invention surprisingly exhibited special properties that differ from those of cellulose fibers obtainable from wood pulping processes. For example, it was shown that both hydrophilic and hydrophobic compounds could be incorporated into the same cellulose-based fibers. Furthermore, it was found that after drying such loaded cellulose-based fibers, the release of the incorporated or encapsulated hydrophilic or hydrophobic compounds was significantly delayed. This was particularly the case when the fibers were applied layer by layer to a substrate or when the material was built up layer by layer.
[0133] Thus, a method can be provided for the very simple, effective, and reliable disintegration / dissolution, decompacting, and separation of plant hull materials from plant seeds and grains using aqueous disintegration solutions containing biologically harmless compounds that do not interfere with the resulting products or even enhance their material value. The quality of plant seeds, grains, and kernels can be significantly improved compared to the prior art through the gentle removal of the plant hull material according to the invention; in particular, the integrity of the treated plant seeds, grains, and kernels is preserved. Simultaneously, a sensory improvement of plant seeds, grains, and kernels can also be achieved, e.g., by debittering.Furthermore, the process can also be used for further processing of the treated plant materials. In addition, valuable substances such as vitamins or antioxidants can be extracted and recovered from the disintegrated / partially or dissolved plant hull materials. In particular, this yields decompacted cellulose-based fibers that exhibit special physical properties and are very well suited for food preparation due to their excellent sensory effects. Thus, a simple, cost-effective, and gentle process for the disintegration / processing of plant material can be provided, which is universally applicable and biologically safe. Definitions Plant-based raw materials
[0134] The term "starting materials," as used herein, encompasses all biogenic products that exhibit one or more tissue textures, either enclosing or delimiting, partially or completely enclosing or connecting, or forming a composite material structure. The term "plant sheathing material" specifically refers to all enclosing or delimiting, partially or completely enclosing, or connecting tissue structures that can be separated as a layer and are commonly referred to as skin, husk, covering, shell, septa, or chaff. This term is not limited to a specific material composition of the tissue texture of the plant sheathing material referred to herein. In principle, the starting materials can contain any proportion of different constituents as well as other components and compounds.Typical constituents include, in particular, biopolymers such as cellulose or lignin, which can exist in various compositions and different textural forms / composite structures. These composite structures preferably consist of a gap-free compaction of one or more of the constituents. Preferred starting materials are plant-based, such as seeds, grains, kernels, nuts, beans, beets, tubers, vegetables, fruits, or roots.
[0135] These can be in the form of unripe, ripe, mature, overripe, aged, or damaged raw materials. Contaminated or spoiled plant raw materials are also suitable. The plant raw material can be completely intact, damaged, crushed, peeled, pressed, ground, or otherwise disintegrated; this also includes grits or flours, such as those produced after mechanical oil extraction, known as press cakes. This also includes raw materials, and especially plant raw materials, that have previously undergone a thermal and / or liquid extraction process, e.g., with an alcohol or an organic solvent such as hexane. Furthermore, plant raw materials that have undergone thermal treatment are also included.This also includes plant products obtainable from a pulping and / or fermentation process, particularly residues such as brewery residues (e.g., in the form of spent grain or spent grain flour), pomace from must production, or olive pomace. Furthermore, cocoa bean residues are included.
[0136] Furthermore, residues from press residues, such as those obtained during the production of juices (e.g. apple, tomato or carrot juice) or pomace, e.g. of grapes or apples, or extracts such as those obtained during the production of jellies or liqueurs (e.g. blackberry jelly, cassis), are preferred.
[0137] Furthermore, peeling, revetting or coring products from plant-based raw materials can be used.
[0138] This definition includes, in particular, all plant-based products. seeds, such as flaxseed, poppy seeds, chia seeds, amaranth, chili peppers, tomatoes, anise, and field peas; Grains,e.g. rapeseed, camelina, oats, hemp, wheat, buckwheat, rye, barley, corn, sunflowers, green spelt, jatropha; kernels, e.g. apples, pears, grapes, oranges, cherries, plums, apricots, peaches, serviceberries, medlars, mirabelle plums, rowan berries, pumpkins, melons, avocados; Beans such as soybeans, broad beans, moth beans, mung beans or kidney beans, coffee beans, peas, lentils, such as duckweed, and also lupins or sesame; Vegetables, such as cauliflower, broccoli, kohlrabi, zucchini, peppers, artichokes or okra; Beet family plants, such as carrots or sugar beets; Fruit, such as apples, pears, quinces, bananas, breadfruit, mango, kiwi, passion fruit, melons, passion fruit, figs, pumpkin, pineapple, avocado, olives, mango, chayote, guava, papaya, tamarillo, marmay apple, grapefruit, oranges, lemons or grapes; Berries,such as rosehips, gooseberries, blueberries, blackberries, strawberries, elderberries, currants, cranberries, mulberries, chokeberries, raspberries, blackberries, sea buckthorn; furthermore Tuberous plants and roots, such as potatoes, beetroot, sweet potato, turmeric, cassava, horseradish, celery, radish, ginger, arakasha, taro, wasabi, yacon, black salsify, asparagus, parsnip, turnips, Jerusalem artichokes, cattails, swedes, Siberian angelica, yam, sunflower root, garlic, onions, devil's claw or ginkgo; likewise Cucumbers such as salad or gherkins, also eggplants or zucchini, also acorns; nuts, such as almonds, hazelnuts, peanuts, walnuts, cashew nuts, Brazil nuts, percan nuts, pistachios, chestnuts, marrons, dates, or coconuts. Also sugar cane.
[0139] Dried starting materials are preferred. Pre-crushing by a mechanical process is preferred. A GMO-free plant-based starting material for the production of GMO-free products is preferred.
[0140] The main constituents of plant seeds, grains, and kernels consist of proteins, carbohydrates, cellulose-based fibers, and lignin-rich hulls. They also contain, among other things, vitamins, phytosterols, minerals, antioxidants, flavorings, and colorings. Cellulose-based fibers
[0141] The term "cellulose-based fibers", as used herein, encompasses all corpuscular structures of plant starting materials consisting of a cellulose backbone, exhibiting at least 2 of the following characteristics: an origin from a plant-based starting material, an aspect ratio of a longitudinal and transverse diameter of 1:1 to 1,000:1, a water binding capacity of > 200 wt%, a proportion of chemical compounds and functional groups of > 2.5 wt% that do not correspond to the elements C, H or O.
[0142] The cellulose-based fibers can already be present in a loose composite with other compounds or components, such as in a matrix that has been broken apart by a pressing or impact process, as is the case with pressed oilseeds or ground grains, or they can be present in a stable composite structure that prevents the cellulose-based fibers from being released, as is the case, for example, with vegetables or fruits. In an unprocessed starting material, the cellulose-based fibers nevertheless exist in a gap-free composite with other constituents of the starting material. The compacted composite contains soluble proteins and carbohydrates. Such cellulose-based fibers are thus present in a compacted form. The cellulose-based fibers according to the invention exhibit three-dimensional spatial and surface structures in their decompacted form.They can then exist in a composite structure with other solids, such as lignin-rich shells, which can be broken down into spherical or particulate fragments by physical measures such as mechanical comminution and / or thermal treatment.
[0143] The cellulose-based fibers falling under the definition are characterized by structural features and physical properties that they share. In their decompacted form, they exhibit, in particular, spatial structures in the form of free fibers, networks, or spatial woven structures. The cellulose-based fibers according to the invention preferably have a planar and / or corpuscular geometry. In particular, they are characterized by a low linear density of < 20 mg / 100 m. They can encapsulate, surround, or incorporate pigments as structural components of the fibers according to the invention. Other organic or inorganic compounds can also be components of the cellulose-based fibers or be permanently bonded to them in an aqueous medium.
[0144] The cellulose-based fibers obtained in decompacted form using the methods according to the invention exhibit these properties, which can be verified using methods from the prior art. Lignin-rich shell components
[0145] The terms "lignin-rich hull components" or "lignin-based hulls," as used herein, encompass all cladding and supporting structures of the plant starting material that have a lignin content of > 30 wt%. Preferred lignin-rich hull components have a lignin content of > 40 wt%, more preferably > 50 wt%, further preferably > 60 wt%, even more preferably > 75 wt%, and most preferably > 90 wt%. They have no specific external shape, ranging from flat and polymorphic to corpuscular and round. Their dimensions depend on the manufacturing process and can range from a few micrometers to several millimeters. Lignin-rich hull components are present, for example, in the press residues of rapeseed or jatropha seeds at a weight fraction of 8 to 15 wt%. Disintegration / Disclosure
[0146] The term "disintegration" encompasses all processes that lead to the separation / dissolution of water-impermeable tissue structures or textures of the starting material, resulting in the creation of cracks, gaps, or fissures in the covering or shell materials of the plant starting material, up to and including the complete disruption of tissue textures with exposure of the enclosed surfaces of the seeds, grains, or kernels of the plant starting material. Crucially, disintegration leads to hydration of the covering material and / or the interface or space between the disintegrated covering material and the surface of the enclosed seed, grain, or kernel. This also includes partial or localized, or complete, dissolution of the plant covering material with the exposure / release of its individual components.The disintegration referred to here also applies to the plant material that is / was enclosed by sheaths and shells. This process likewise involves the separation / detachment of the constituents of the material, caused by their hydration. This disintegration results in the hydration of constituents that are bonded to each other by covalent or electrostatic forces, as is the case with gap-free composite structures or keratinized cellulose aggregates. This hydration releases the individual constituents, allowing them to spontaneously separate within an aqueous distribution volume or be detached from one another by gentle shearing.The "aqueous digestion" referred to herein, which is also simply called "digestion" for simplicity, occurs when the binding energy to other compounds / constituents is reduced by the hydration of individual compounds / constituents to such an extent that the hydrated compounds / constituents spontaneously disperse in an aqueous phase or can be separated from one another by a small amount of energy input. Therefore, the terms "disintegration" and "digestion," as used herein, can also be used synonymously. Aqueous disintegration / dissolution solution
[0147] The terms "aqueous disintegration solution" or "aqueous digestion solution" are used herein to refer to an aqueous solution of dissolved substances for disintegration and for the separation of constituents of the starting material. In a preferred embodiment of the process, the substances for disintegration or for the separation of constituents of the starting material are one or more amino acids and / or peptides present in water in a completely dissolved form. The water may be clarified, clarified and purified process water, deionized, partially deionized, well water, or municipal water. The preferred substances present in dissolved form for the separation of constituents of the starting material are naturally occurring amino acids and / or peptides consisting of or containing these amino acids.The aqueous solutions for digestion according to the invention are preferably solutions of one, two, or more amino acids and / or peptides, present in the individual and / or total concentration in a range of 10 µmol / l to 3 µmol / l, more preferably between 1 µmol / l and 1 µmol / l, and further preferably between 0.1 µmol / l and 0.5 µmol / l. These can be L- or D-forms or racemates of the compounds. The use of the L-form is preferred. Preferred amino acids include alanine, arginine, asparagine, aspartic acid, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, phenylalanine, proline, serine, treonine, tryptophan, tyrosine, and valine. The amino acids arginine, lysine, histidine, and glutamine are particularly preferred. Derivatives of the aforementioned amino acids are also preferred. The peptides that can be used according to the invention can be di-, tri- and / or polypeptides.The peptides according to the invention have at least one functional group that binds or can bind a proton. The preferred molecular weight is below 500 kDa, more preferably below 250 kDa, further preferably below 100 kDa, and particularly preferably below 1,000 Da. The preferred functional groups are, in particular, a gunanidine, amidine, amine, amide, hydrazino, hydrazono, hydroxyimino, or nitro group. The amino acids can have a single functional group, several of the same class of compounds, or one or more functional groups of different classes of compounds. Preferably, the amino acids and peptides according to the invention have at least one positive charge group or an overall positive charge. Therefore, cationic amino acids are particularly preferred. Particularly preferred peptides contain at least one of the amino acids arginine, lysine, histidine, and glutamine in any number and sequential order.Particularly preferred are amino acids and / or derivatives thereof containing at least one guanidino and / or amidino group. The guanidino group is defined as the chemical residue H₂NC(NH)-NH₂ and its cyclic forms, and the amidino group as the chemical residue H₂NC(NH)₂ and its cyclic forms. These guanidino and amidino compounds preferably have a partition coefficient KOW between n-octanol and water of less than 6.3 (KOW < 6.3). Arginine derivatives are particularly preferred. Arginine derivatives are defined as compounds comprising a guanidino group and a carboxylate group or an amidino group and a carboxylate group, wherein the guanidino group and carboxylate group or the amidino group and the carboxylate group are separated by at least one carbon atom.At least one of the following groups is located between the guanidino group or the amidino group and the carboxylate group: -CH₂-, -CHR-, -CRR'-, where R and R' independently represent any chemical residues. Of course, the distance between the guanidino group and the carboxylate group or the amidino group and the carboxylate group can also be more than one carbon atom, for example in the following groups -(CH₂)n-, -(CHR)n-, -(CRR')n-, with n = 2, 3, 4, 5, 6, 7, 8, or 9, as is the case, for example, in amidinopropionic acid, amidinobutyric acid, guanidinopropionic acid, or guanidinobutyric acid. Compounds with more than one guanidino group and more than one carboxylate group include, for example, oligoarginine and polyarginine. Other examples of compounds that fall under this definition are guanidinoacetic acid, creatine, and glycocyamine. Preferred compounds share the general formula (I) or (II) as a common feature. where R, R', R", R‴ and Rʺʺ independently of each other -H, -CH=CH 2 , -CH 2 -CH=CH 2 , -C(CH 3 )=CH 2 , -CH=CH-CH 3 , -C 2 H 4 -CH=CH 2 , -CH 3 , -C 2 H 5 , -C 3 H 7 , -CH(CH 3 ) 2 , -C 4 H 9 , -CH 2 -CH(CH 3 ) 2 , -CH(CH 3 )-C 2 H 5 , -C(CH 3 ) 3 , -C 5 H 11 , -CH(CH 3 )-C 3 H 7 , -CH 2 -CH(CH 3 )-C 2 H 5 , -CH(CH 3 )-CH(CH 3 ) 2 , -C(CH 3 ) 2 -C 2 H 5 , -CH 2 -C(CH 3 ) 3 , -CH(C 2 H 3 ) 2 , -C 2 H 4 -CH(CH 3 ) 2 , -C 6 H 13 , -C 7 H 15 , Cyclo-C 3 H 5 , cyclo-C 4 H 7 , cyclo-C 3 H 9 , Cyclo-C 6 H 11 ,-C≡CH, -C≡C-CH 3 , -CH 2 -C≡CH, -C 2 H 4 -C≡CH, -CH 2 -C≡C-CH 3 represent, or R' and R" together form the residue -CH 2 -CH 2 -, -CO-CH 2 -, -CH 2 -CO-, -CH=CH-, -CO-CH=CH-, -CH=CH-CO-, -CO-CH2-CH2-, -CH2-CH2-CO-, -CH2-CO-CH2- or -CH2-CH2-CH2-; X represents -NH-, -NRʺʺ-, or -CH2- or a substituted carbon atom;and L represents a C1 to C8 linear or branched and saturated or unsaturated carbon chain with at least one substituent selected from the group comprising or consisting of -NH2, -OH, -PO3H2, -PO3H-<, -PO32-<, -OPO3H2, -OPO3H-<, -OPO32-<, -COOH, -COO-<, -CO-NH2, -NH3+<, -NH-CO-NH2, -N(CH3)3+<, -N(C2H5)3+<, -N(C3H7)3+<, -NH(CH3)2+<, -NH(C2H5)2+<, -NH(C3H7)2+<, -NHCH3 , -NHC 2 H 3 , -NHC 3 H 7 , -NH 2 CH 3 +< , -NH 2 C 2 H 5 +< , -NH 2 C 3 H 7 +< , -SO 3 H, -SO 3 -< , -SO 2 NH 2 , -C(NH)-NH 2 , -NH-C(NH)-NH 2 , - -NH-COOH, or ;
[0148] It is preferred that the carbon chain L is in the range from C 1 to C 7, more preferably in the range from C 1 to C 6, further preferably in the range from C 1 to C 5, and most preferably in the range from C 1 to C 4.
[0149] Preferably L represents -CH(NH 2 )-COOH, -CH 2 -CH(NH 2 )-COOH, -CH 2 -CH 2 -CH(NH 2 )-COOH, -CH 2 -CH 2 -CH 2 -CH(NH 2 )-COOH, -CH 2 -CH 2 -CH 2 -CH 2 -CH(NH 2 )-COOH, or -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH(NH 2 )-COOH.
[0150] Compounds of general formula (III) as shown below are also preferred: where the remainders X and L have the meanings revealed herein.
[0151] Also suitable are di-, tri-, or oligopeptides, as well as polypeptides composed of one, two, or more amino acids. Short-chain peptides, e.g., RDG, are preferred. Particularly preferred are peptides consisting of amino acids possessing both hydrophobic and hydrophilic side chains, such as (listed alphabetically by amino acid) GLK, QHM, KSF, ACG, HML, SPR, EHP, or SFA. Peptides possessing both hydrophobic and cationic and / or anionic side chains, such as RDG, BCAA, NCR, HIS, SPR, EHP, or SFA, are also particularly preferred. Further examples with four amino acids are NCQA, SIHC, DCGA, TSVR, HIMS, or RNIF, and with five amino acids are HHGQC, STYHK, DCQHR, HHKSS, TSSHH, and NSRR. RDG, SKH, or RRC are particularly preferred.
[0152] The digestion / disintegration solutions according to the invention may contain or include further substances that are completely dissolved therein. Particularly preferred substances are: sulfites, such as sodium sulfite or sodium bisulfite, and / or urea, and / or carbonates, such as sodium carbonate or sodium bicarbonate. Furthermore, substances for adjusting the pH of the solution, in particular a base or acid, such as urea or NaOH, sodium carbonate, sodium bicarbonate, or triethylamine, or acetic acid or uric acid, or substances with surfactant properties, such as DMSO or SDS. Stabilizers, such as antioxidants or reducing agents, may also be included. Furthermore, preferred substances that enable the disintegration of constituents of the starting material are substances selected from the group of sulfites and sulfates. Sodium sulfite and sodium bisulfite are particularly preferred.Furthermore, cationic nitrogen compounds, such as diethylamine or triethylamine, are present. In the aqueous disintegration / digestion solutions, the listed substances can be present individually or in any combination with each other and / or with other substances in dissolved form. The preferred concentration at which a single substance is present in dissolved form is between 0.001 and 30 wt%, more preferably between 0.01 and 15 wt%, and further preferably between 0.1 and 10 wt%. The pH of the aqueous solutions is preferably in the range of 7 to 13, more preferably from 8 to 13, and further preferably from 8.5 to 12.5. Decompacting
[0153] The term "decompacting," as used herein, refers to the partial or complete separation of a gap-free composite of identical or different constituents, resulting in the separation of these constituents from one another and / or the formation of gaps containing a gas or liquid medium. In particular, the decompacting referred to here is the hydration of filamentous and / or tissue-like water-insoluble structures of cellulose-based fibers and lignin-rich shells, leading to separability. This hydration enables the spatial separation of the soluble constituents within an aqueous distribution volume, resulting in the formation of three-dimensional structures of decompacted water-insoluble cellulose-based fibers that are free or nearly free of water-soluble compounds. Distribution solution
[0154] The term "distribution solution," used synonymously herein with "distribution volume," refers to an aqueous phase added to a reaction mixture that enables the distribution and separation of soluble dissolved, soluble solid, and complex insoluble components of the starting material. In a distribution volume according to the invention, these components are present in a readily separable form. The presence of a sufficiently large distribution volume can be verified by taking a sample and determining the separability of the dissolved and suspended components using techniques and methods as described herein. Condensation / Aggregation / Complexation
[0155] The terms "condensation / aggregation / complexation" encompass all physical and / or chemical processes that lead to the combination of similar and / or dissimilar organic and / or inorganic compounds, resulting in condensates, aggregates, or complexes. These solids can be separated from the aqueous phase of an aqueous process mixture using suitable separation methods. The term "condensate" refers to a spatial approximation of macromolecular structures, which thereby form a measurable three-dimensional structure. The binding forces are electrostatic, resulting from hydrophobic or hydrophilic binding energies. In general, "aggregation" means the accumulation or gathering of atoms, molecules, and / or ions into a larger assembly, the aggregate.The accumulation or aggregation is caused by van der Waals forces, hydrogen bonds, and / or other types of chemical or physicochemical bonds. In this context, "complexes" are understood to be macroscopically visible formations that are linked together by condensates and / or aggregates to form a larger composite structure. Due to the low bond energies of the condensates / aggregates and complexes, the individual compounds can be easily extracted from the composite structures, for example, through a mixing process, and separated. In contrast, coagulates are three-dimensional structures of small to macromolecular compounds that are formed by a chemical reaction in which covalent bonds between the molecular structures are formed and / or broken. In a coagulate, the individual compounds cannot be separated or isolated from one another by a dissolution process in water, or only to a limited extent.The condensation / aggregation / complexation referred to herein differs from coagulation, which occurs particularly through a precipitation reaction with a (strong) acid, resulting in denaturation and the partial or complete loss of at least the original tertiary structure of the proteins. This is not the case with the aggregation / complexation or condensation according to the invention. Denaturation of compounds is recognizable, for example, by a lower water-binding capacity, which is considerably higher in the condensates / aggregates and complexes referred to herein. Complexing agent / aggregating agent
[0156] The terms "complexing agent" or "aggregating agent" are used here to refer to one or more organic and / or inorganic substances that initiate, maintain, and / or accelerate the condensation, aggregation, or complexation of water-soluble constituents / organic compounds in an aqueous process mixture. They may, among other things, have a catalytic, destabilizing, displacing, and / or releasing effect on the constituents to be condensed, aggregated, or complexed, leading to a clumping of the constituents / organic compounds. The substances may also cause this effect by altering the pH and / or salinity and / or may themselves participate in the clumping process.
[0157] The preferred aggregating agents include, in particular, organic acids, especially citric acid, ascorbic acid, lactic acid, adipic acid, and EDTA. Furthermore, inorganic acids, especially phosphoric acid, are preferred. Calcium, magnesium, and aluminum ions are also preferred, preferably provided in the form of a salt, e.g., calcium chloride or magnesium chloride. Carbonate anions are also preferred, preferably provided in the form of salts, e.g., sodium carbonate or sodium bicarbonate. Silicate anions are also preferred, preferably provided as a dissolved salt, e.g., sodium metasilicate.
[0158] The complexing agents can be applied in solid form, preferably as a fine powder, or in fully dissolved form in an aqueous medium. Aqueous solutions are preferred. The concentration is preferably in the range of 1 mmol to 5 mol / l, more preferably between 100 mmol and 3 mol / l, and further preferably between 200 mmol and 2 mol / l. Constituents of the starting material / Organic compounds
[0159] The terms "constituents of the starting material" and "organic compounds," used synonymously herein, encompass all organic compounds of biogenic origin that constitute or contain the starting materials referred to herein and that can be extracted from these biogenic starting materials by one of the processes described herein. These compounds can be individual substances, e.g., in the form of molecules, or complex compounds, e.g., in the form of polymers. Corresponding to the different possible origins, organic compounds from various substance groups are found, occurring individually, but mostly in different combinations and in varying proportions. Therefore, only the essential substance groups to which the organic compounds can be assigned are listed below, without being limited to them: proteins, including albumins, globulins, and oleosins.Furthermore, lipids such as mono-, di-, or triglycerides, waxes, wax acids, hydroxy and mycolic acids, fatty acids with cyclic hydrocarbon structures such as shikimic acid or 2-hydroxy-11-cyclohepttylundeic acid, mannosteryl erythritol lipid, pigments such as carotenes and carotenoids, chlorophylls, and their degradation products, as well as phenols, phytosterols, especially β-sitosterol and campesterol, and sigmasterol, sterols, sinapines, and squalene. Phytoestrogens such as isoflavones or lignans. Carbohydrates that exist in polymeric form and are water-insoluble, such as cellulose, or in complexed form, such as starch, or in water-soluble form, such as glucose or fructose. Furthermore, steroids and their derivatives, such as saponins, as well as glycolipids, glycoglycerolipids and glycerosphingolipids, as well as rhamnolipids, sophrolipids, trehalose lipids, and mannosterylerythritol lipids.Likewise, polysaccharides, including pectins such as rhamnogalacturonans and polygalacturonic acid esters, arabinans (homoglycans), galactans and arabinogalactans, as well as pectic acids and amidopectins. Also included are phospholipids, in particular phosphotidylinositol, phosphatides such as phosphoinositol, long-chain or cyclic carbon compounds, fatty alcohols, hydroxy and epoxy fatty acids. Likewise, glycosides, lipoproteins, phytate or phytic acid, and glucoinosilates. Furthermore, vitamins, such as retinol (vitamin A), and derivatives such as... B. Retinoic acid, riboflavin (vitamin B2), pantothenic acid (vitamin B5), biotin (vitamin B7), folic acid (vitamin B9), cobalamins (vitamin B12), calcitriol (vitamin D) and derivatives, tocopherols (vitamin E) and tocotrienols, phylloquinone (vitamin K) and menaquinone. Furthermore, tannins, terpenoids, curcuminoids, xanthones. But also flavorings, i.e., odor and taste substances, colorings, phospholipids and glycolipids, waxes or similar substances.Wax acids and fatty alcohols. Furthermore, water-insoluble biopolymers, such as lignins and cellulose, which are preferably present in the form of tissue-like composite structures. Proteins
[0160] The term "proteins," as used herein, refers to macromolecules composed of amino acids linked together by peptide bonds. The proteins referred to here contain more than 100 amino acids. They can exist in their primary, secondary, or tertiary structure, as well as in a functionally active form. The secondary structure can have a spatial geometry such as an α-helix, β-sheet, β-loop, or be randomly coiled. Also included are supramolecular compounds of proteins, such as collagen, keratin, enzymes, ion channels, membrane receptors, genes, antibodies, toxins, hormones, or coagulation factors.Due to their ubiquitous occurrence in all life forms and environments, the proteins referred to herein can be macromolecular compounds in one of the specified forms, whose physiological function was, for example, shaping, supporting, transporting, or defending, or serving for reproduction, energy production or metabolism, or promoting / transforming reactions. This includes, in particular, proteins according to the given definition that can be extracted from the starting materials described herein. Methods Method for providing plant-based starting material.
[0161] Depending on the different origins and methods of obtaining the starting materials usable according to the invention, these can be in different forms and states. For example, they can be whole / intact seeds, grains, kernels, nuts, vegetables, fruits, flowers, ovaries, or roots, and / or plant materials that are wholly or partially degraded, broken open, crushed, ground, smashed, or pressed, and / or plant materials in which a fermentative or disintegrative process, in particular through autolysis / microbial degradation / physical-chemical reaction, has partially or completely taken place, and / or they are residues from agricultural production / food manufacturing or processing.The broken, divided, crushed, pulverized, liquidated, or dissolved plant starting materials can be in the form of cohesive or fragmented pieces, aggregated (e.g., pellets or pressed mass), loosely bound (e.g., granules or bulk material), or in isolated forms (e.g., flour or powder), or as a suspension. The consistency, shape, and size of the plant starting materials are generally irrelevant; however, crushed plant starting materials that facilitate digestion are preferred. Preferably, the maximum diameter of the dispersible plant particles is between 100 µm and 100 cm, more preferably between 0.5 mm and 50 cm, further preferably between 1 mm and 20 cm, and even more preferably between 2 mm and 5 cm.The form of the suitable plant-based starting materials is arbitrary, as is their consistency, which can be hard or soft, or they can be in a liquefied form. The starting material can be at any temperature; a heated starting material, such as that obtained after pressing, is preferred. If the plant-based starting material does not meet the suitable properties / requirements for one of the processes according to the invention, these conditions can be achieved using methods available from the prior art. These include, in particular, methods that enable and / or facilitate the processing of the plant-based starting material according to the invention. These include, in particular, mechanical methods for comminuting the plant-based starting material.In particular, for process optimization, it may be necessary to first shred and dry plant material, or to dry it and then shred it. In one embodiment of the process, the shredded and then dried plant material is further reduced to a specific particle size before process step a), preferably between 10 µm and 2 cm, and more preferably between 30 µm and 5 mm. However, the invention also provides for shredding that takes place during or after the addition of a disintegration / digestion solution. In one embodiment of the process, lignin-containing components of the plant materials are first mechanically removed. These can be, for example, covering materials of the plant materials, such as skins, husks, or shells, like those of apple or grape seeds. Mechanical methods for this are known in the prior art.The starting materials are placed in a suitable container, which can preferably be filled from the top and has a closable outlet at the bottom. Methods for the preparation and use of aqueous solutions for disintegration and digestion of the starting material
[0162] The digestion solutions according to the invention are prepared using the digestion substances according to the invention, as defined herein. For this purpose, one or more of the substances are dissolved in water, which may be clarified process water, completely ion-free water, or well or municipal water. Dissolving the substances may require increasing the temperature and / or continuing the mixing process for up to two days. Preferably, the pH of the solution of cationic amino acids or peptides is in the range of 7 to 13, more preferably between 8 and 13, and further preferably between 8.5 and 12.5. In an embodiment not fully conforming to the invention, the pH can be adjusted to any desired pH range between 6 and 14 by adding an acid or a base. Acids and bases known in the art, such as sodium hydroxide or hydrochloric acid (HCl), can be used.
[0163] Methods for carrying out the procedural step b): Mixing the starting material with a disintegration solution and leaving it in the disintegration solution until disintegration is achieved.
[0164] In this process step, the wetting of the surfaces of the constituents within the plant starting material must be ensured. This can be achieved using prior art methods with intact or disintegrated plant starting materials. The digestion solutions can be prepared at any temperature and added to the starting material. Application can be in droplet form, e.g., as an aerosol, drop by drop or jet, continuously or discontinuously to, into, and / or onto the starting material. In a preferred embodiment, this is carried out under anaerobic and / or inert gas conditions. Preferably, the plant material to be digested is immersed in an aqueous digestion solution. Application is carried out by supplying a prepared digestion solution from a storage container to the starting material via a feed line in an adjustable quantity.
[0165] A disintegrated form of husks and shells exists when the husks or shells can be spontaneously detached / separated, wholly or partially, from the plant material, for example, in an aqueous distribution volume, by a water jet, or by slight mechanical force. Disintegration of constituents of the husk or shell material, or of the constituents of the plant material, occurs when the individual constituents of the plant material are dissolved or can be dissolved from a solid and water-insoluble compound or from a surrounding composite structure (e.g., shells). Dissolved in this context means that the individual compounds / constituents can be spontaneously separated in an aqueous distribution volume. Dissolvable here means that the disintegrated or dispersed constituents can be separated or dissolved.Compounds can be easily and completely separated in an aqueous distribution volume with a low energy input. Physical methods, such as heating or mechanical reduction, can also be used for this purpose.
[0166] In principle, thermal disintegration is advantageous when the plant-based starting material has a high water content, as is the case with fresh fruits and vegetables. Here, disintegration preferably occurs through the transfer of thermal energy by water or steam. Preferably, pressure is applied simultaneously.
[0167] Mechanical disintegration is particularly advantageous when the plant-based starting materials have a low water content and / or are enclosed in husks / shells that are impermeable to water. Furthermore, a mechanical process is preferable if another fraction of the plant-based starting material, such as oil, is to be removed first. In a preferred embodiment of the process, disintegration of plant materials is achieved by mechanically comminuted the raw material, either wholly or partially, placing it in a water bath, and heating it until the portion of the raw material containing essentially the recoverable constituents of the starting material becomes so soft that it disintegrates into a pulpy or liquid phase under slight pressure, e.g., by crushing it with the fingers.This is particularly advantageous when, due to the differing strengths of various structures, the different structures, such as the mesosperm and the peel, can be easily differentiated and mechanically separated as layers following one of the aforementioned disinteration processes. In a preferred embodiment, heating is carried out in conjunction with pressure increase in an autoclave. In a preferred embodiment, plant sheath materials are removed before and / or after disintegration of the plant starting material.
[0168] In a particularly preferred embodiment, the plant material is disintegrated by prior immersion in one of the aqueous solutions according to the invention, containing an aqueous disintegration / digestion solution according to the invention. In principle, the volume or weight ratio can be freely chosen; however, it is advantageous if the plant material is completely wetted by the digestion solution. A water volume ratio of the aqueous digestion solution to the mass of the plant material between 0.3 and 30 is preferred, more preferably between 0.5 and 20, further preferably between 0.7 and 10, and even more preferably between 0.8 and 5. In a variant of the process, the plant material is impregnated with one of the digestion solutions during the application of one of the disintegration processes or immediately thereafter.In one variant of the process, the impregnation takes place directly together with compounds that enable / accelerate the disintegration of the plant starting material. The duration of exposure to the digestion solution depends on the plant starting materials used. A duration between 1 minute and 48 hours is preferred, more preferably between 10 minutes and 14 hours, and even more preferably between 20 minutes and 6 hours. The temperature at which the plant starting material is exposed to the aqueous digestion solutions is, in principle, freely selectable. A temperature between 5° and 140°C is preferred, more preferably between 10° and 120°C, and even more preferably between 15° and 90°C.
[0169] Methods for carrying out the process step c) Distribution of the constituents of the disintegrated starting material in a distribution volume.
[0170] In a preferred embodiment, the shell / cover material and / or plant starting material, which was disintegrated in a previous process step, is dissolved in water to completely hydrate the separated constituents, thereby ensuring they are present in a singular form and without any connection or adhesion to other constituents. The distribution volume according to the invention is a volume of water that guarantees the singularity and separation of the shell / cover material and / or the constituents of the starting material.
[0171] When separating coating material, a very small volume of water may suffice, applied, for example, by a water jet. If disintegration and digestion are carried out, the required distribution volume must be large enough to allow complete hydration of the soluble or detachable constituents and to ensure the isolation of the dissolved and insoluble constituents of the starting material. If a digestion mixture is involved, the required distribution volume is preferably determined by preparing a dilution series with a sample from the previous process stage (e.g., 10 g of the separation / disintegration mixture). After a stirring phase of 3 minutes, the suspension is filtered (100 µm sieve size). The filter residue is analyzed (visually or microscopically) for deposits / adhesions of soluble and water-soluble compounds.A suitable solution of an aggregating agent is then added to the filtrate in increasing doses. A sufficiently large distribution volume is present when there are no deposits / adhesions to the solid constituents of the starting material that are present in the filter residue, and when complete condensation and / or aggregation and / or complexation of the dissolved soluble constituents present in the distribution mixture can occur.
[0172] A preferred ratio of water volume to dry mass of the starting product is 5:1 to 500:1, more preferably 10:1 to 150:1, and further preferably 15:1 to 50:1. Clarified process water from subsequent process steps, or deionized or untreated municipal or well water, can be used for this purpose. The method of introduction or contact between the separation / separation mixture and the aqueous phase of this process step is arbitrary. A preferred method is introduction using a high-performance shear mixer or another intensive mixer, together with the aqueous phase. This is particularly advantageous because it allows for immediate hydration and singulation. Stirring devices that create turbulent flow, such as propeller or jet mixers, are also preferred.The distribution process can be continuous or discontinuous and can be carried out at any temperature; preferably, the temperature range of the aqueous suspension is between 6° and 90°C, more preferably between 10° and 60°C, and more preferably between 18° and 40°C. The duration of the distribution process is arbitrary; preferably, it is from 1 minute to 24 hours, more preferably from 5 minutes to 5 hours, and more preferably from 10 minutes to 1 hour.
[0173] The partitioning process during the digestion of the constituents of a starting material is considered complete when a representative sample taken from the partitioning mixture is filtered through a coarse (1 mm mesh) and then a fine (100 µm) sieve, and no visible aggregates of different constituents of the plant starting materials are discernible in the filter residue, either microscopically or visually. Successful partitioning of the starting material's constituents can also be verified by placing a sample of the partitioning mixture into a graduated cylinder and observing the rapid separation of three phases, or, in the presence of lipids, four readily distinguishable phases. This separation should not take longer than four hours.
[0174] A further aspect of the invention is the control and optional adjustment of the pH of the distribution solution. This can be done with alkalis or acids from the prior art; preferred acids are hydrochloric acid or formic acid, and preferred bases are sodium hydroxide or urea. A pH of the distribution solution between [value missing] is preferred. 7 and 13, more preferably between 7 and 12.5 and further preferably between 7.5 and 11.
[0175] The volume of water required for carrying out the following process steps according to the invention is provided in a suitable container.
[0176] Methods for carrying out process step d): Separation of solid constituents from dissolved constituents of the starting material.
[0177] The solid constituents of the starting material referred to herein are organic compounds that cannot be further dissolved by any of the disintegration / digestion processes according to the invention and cannot be obtained as particulate structures by filtration, and which do not pass through a sieve with a particle size of 10 µm. Preferably, the solid constituents are obtained by means of filtration techniques from the prior art. However, techniques can also be used in which the solid solids are separated from the liquid mixture, for example by centrifugal acceleration, e.g., in a screen decanter or an eddy current process. Following process step d), the process liquid or the distribution mixture preferably contains < 5 wt%, more preferably < 2.5 wt%, and further preferably < 1 wt% of solid solids having a maximum particle size of > 10 µm.
[0178] Methods for carrying out process step e) recovery of the separated constituents of the plant starting material as valuable material fractions
[0179] In a preferred embodiment, the fractions separated from each other in process step d) are fed to separate treatment stages: e1) Fractionation of cellulose-based fibers from lignin-rich shells of the solid constituents of the plant starting material by means of an eddy current process and obtaining purified fractions of cellulose-based fibers and lignin-rich shells, e2) Aggregation / complexation of dissolved proteins of the dissolved constituents of the plant starting material by means of complexing agents and separation of the sedimented aggregated / complexed condensed proteins, obtaining an aggregated / complexed protein mass.
[0180] If only one material fraction is to be recovered, only one of the two process steps can be applied.
[0181] In process step e1), different or identical disintegrated solids are separated, preferably in the form of shell / cladding material or cellulose-based fibers and / or lignin-rich shells (or components). When separating different solids, this can be achieved using filtration techniques or eddy current processes. Filtration is preferably carried out by suspending the solid material in water and preferably passing it through a sieve and / or the suspension through sieve material with different mesh sizes while agitating the sieve. In eddy current processes, the fiber mass is also preferably suspended. The water phases exiting the upper and lower reaches of the separation device are filtered, and the sieve fractions are recovered.Preferably, a volume ratio of the process solution to the volume of the plant material from process stage b) is used between 0.1:1 and 10,000:1, more preferably between 0.5:1 and 1,000:1, further preferably between 1:1 and 500:1 and more preferably between 2:1 and 20:1.
[0182] The process step is completed when, in a macroscopic or microscopic analysis, a purity of the different solid fractions obtained is preferably > 95 wt%, more preferably > 97 wt% and further preferably > 99 wt%.
[0183] Process step e2) is feasible if soluble constituents have been removed from the starting material by a disintegration / digestion process and are present in the process liquid from the previous process step, which has been purified of solid particles. In a preferred embodiment, this process step involves condensation and / or aggregation and / or complexation of the dissolved proteins and / or other dissolved organic and / or inorganic compounds in the filtrate from the previous process step. The aim of this aggregation process is to achieve a fusion of dissolved or hydrated constituents, and in particular the proteins, forming a condensed phase / mass that can be separated using known separation techniques and obtained with as little water as possible. The addition of one or more suitable aggregating agents is preferred.Suitable aggregating agents include acids, preferably organic acids such as acetic acid, ascorbic acid, citric acid, lactic acid, and malic acid, but also inorganic acids such as HCl, sulfuric acid, or phosphoric acid; salts such as NaCl, KCl, MgCl₂, CaCl₂, NaSO₄, and AlCl₂; complexing agents such as EDTA; and adsorbents such as calcium oxide, magnesium oxide, kaolin, or other clay minerals. Soluble divalent cations, particularly aluminum, calcium, and magnesium salts, are also preferred. Combinations of the aggregating agents listed herein are advantageous, such as a combination of citric acid and aluminum chloride. Carbonates such as sodium carbonate, sodium bicarbonate, or calcium carbonate are also preferred. Silicate compounds, especially sodium metasilicate, sodium orthosilicate, and other soluble silicates, are also suitable.The pH of aqueous solutions containing dissolved aggregating agents can, in principle, be freely chosen and depends on the effectiveness of the aggregation achievable. If necessary, a buffer to adjust the pH of the aggregating agent solution can be added. Suitability can be easily determined by a person skilled in the art by adding and mixing various aggregating agents in increasing concentrations to samples of the fiber-free process solution from process step d), and then examining the completeness of aggregation / complexation of the dissolved constituents. For this purpose, one or more of the aggregating solutions / aggregating agents are added to the supernatant after centrifugal separation of the condensates and mixed.If, after a standing time of at least 10 minutes, no sediment forms upon renewed centrifugation and the aqueous phase is clear or almost clear, sufficient aggregation / condensation of the dissolved constituents has occurred. In a further embodiment, the aggregating agent(s) is applied as a solid, preferably in powdered form, which is added to the reaction mixture. Aggregation / complexation can be observed with the naked eye after a short residence time. The appropriate concentration can be selected by centrifuging a sample solution in which aggregation / complexation / condensation has occurred and treating the supernatant again with the same and / or different aggregating agent solutions.If no visible condensates / aggregates / complexes can be formed and / or separated as a result, the solution contains < 6 wt%, preferably < 4 wt% and most preferably < 2 wt% of dissolved proteins.
[0184] The aggregating agents are completely dissolved in water, which is preferably ion-free or deionized. The concentration of the aggregating agent(s) depends on the process conditions and must be determined individually. A concentration range of 1 mmol to 5 mol / l is generally preferred, more preferably between 100 mmol and 3 mol / l, and further preferably between 200 mmol and 2 mol / l. The volume of the solution containing one or more aggregating agents, or in the case where aggregating agents are provided with different aqueous solutions, is added continuously or discontinuously, dropwise or in a jet. Preferably, the reaction mixture is agitated, preferably under slightly turbulent or laminar flow conditions that prevent the disintegration of any forming condensates / aggregates / complexes. Preferably, the reaction mixture is thoroughly mixed.Preferably, process control is achieved by visual inspection of the condensation progress or by monitoring the turbidity of the developing clarified aqueous phase. The completeness of the condensation / aggregation / complexation of the dissolved compounds can be easily verified using the previously described method, and one or more aggregating agents can be added to the reaction solution if necessary. The duration of the mixing is, in principle, freely selectable. In a preferred embodiment, this occurs only for the duration of the addition of one or more aggregating agents or for a duration between 10 seconds and 5 minutes, more preferably between 20 seconds and 2 minutes.
[0185] The temperature at which condensation and / or aggregation and / or complexation occurs can, in principle, be freely chosen. A temperature between 6° and 90°C is preferred, more preferably between 10° and 60°C, and even more preferably between 18° and 40°C. Maintaining a specific pH range is preferred; the optimum pH is determined by the selection or combination with the aggregating agent. The optimal pH range can be determined using the method described above. The pH of the aqueous solution containing dissolved compounds, at which the condensation and / or aggregation and / or complexation of the dissolved proteins and / or other dissolved compounds according to the invention occurs, is preferably in a range between 5 and 13, more preferably between 6 and 12, and even more preferably between 6.5 and 11.In a particularly preferred embodiment, a settling period is observed following the addition of one or more aggregating agents, during which no or only minimal mixing of the mixture occurs. The required duration of the condensation phase can be determined analogously to the method described herein; preferably, this duration is between 5 minutes and 10 hours, more preferably between 10 minutes and 5 hours, and more preferably between 15 minutes and 2 hours. If the settling period is to be reduced to a minimum, the sufficiently minimum duration after the addition of the aggregating agent can be easily determined by centrifuging a sample and verifying, analogously to the method described above, the completeness of the condensation and / or aggregation and / or complexation achieved by the condensing agent(s).The condensation phase preferably takes place at ambient temperatures, ideally within a temperature range of 15° to 40°C. In further preferred embodiments, this phase occurs at temperatures between 5° and 15°C on the one hand, and between 40° and 90°C on the other. Selecting a lower temperature can be advantageous, for example, when obtaining thermolabile compounds. A higher temperature, e.g., 60°C, can be chosen, for example, to inactivate microbial contamination of the starting material, e.g., by pasteurization. Furthermore, heating can also inactivate allergens, certain toxins, and antinutritive compounds. In a preferred embodiment of the process, the condensed / aggregated / complexed proteins are obtained as a sediment. Sedimentation is complete when no further sedimentation occurs.Preferably, the sediment phase is discharged via a bottom outlet and fed to a further dehydration process or directly to a drying process, such as spray or milling spray drying or freeze-drying.
[0186] In a preferred embodiment of the process, the condensed / aggregated / complexed compounds of this process step are dehydrated to remove bound process water, purify, condition, and / or make them easily transportable or formulateable. The sediment obtained at the end of this process step is preferably in the form of a suspension up to a viscous, cream-like mass. Water removal is preferably carried out using filtration techniques. Application to a belt filter is preferred. The preferred filters have a mesh size of 50 to 500 µm, more preferably 80 to 350 µm, and further preferably 100 to 320 µm. Filter fabrics made of polypropylene or other hydrophobic polymer fibers are preferably used. Preferred devices are belt filters, chamber filters, filter presses and chamber filter presses, as well as vacuum belt filters.Centrifugal processes are preferred, with centrifuges or decanters being particularly suitable. The residual water content of the obtainable dehydrated condensate mass can be selected according to the specific process, so that, for example, a flowable, spreadable, or dimensionally stable protein mass is obtained. In principle, the aim is to achieve the most complete possible separation of the bound process water. When using a decanter, separation preferably occurs with > 2,000 g, more preferably with > 3,000 g, and further preferably with > 3,500 g. The residence time in a decanter is preferably > 10 seconds, more preferably > 20 seconds, and further preferably > 30 seconds. A pressing process for removing bound process water is also preferred. Preferably, process water is removed in a filter device with a water-permeable filter fabric / material.Preferably, the condensed or already dehydrated mass, for example in a filter chamber, is subjected to pressure, thereby reducing the residual moisture content to the desired level. It is preferred that the process be carried out at ambient temperatures in a range between 15° and 40°C. In further advantageous embodiments, temperatures in the range between 5° and 15°C or between 40° and 80°C can be selected. A dehydrated mass with a residual moisture content of < 90 wt% is preferred, more preferably < 80 wt%, further preferably < 70 wt%, and even more preferably < 60 wt%, and still more preferably < 40 wt%. Method for testing water retention capacity
[0187] The water retention capacity can be determined using state-of-the-art methods. In one such method, the water content of a 0.5 g sample is determined, and this sample is suspended in 50 ml of distilled water in a 100 ml Erlenmeyer flask. After agitation for 1 hour at 20 °C, the free aqueous phase is removed by feeding the sample onto a G3 glass frit. The sample material, along with the frit, is then centrifuged at 2000 g for 15 minutes. The volume of liquid removed by centrifugation and the sample weight are determined. The water retention value (WRR) is calculated using the following formula. WRR % = Proben − Feuchtmasse − Proben − Trockenmasse Proben − Trockenmasse × 100
[0188] The hydration volume can be determined by mixing the obtained decompacted cellulose-based fibers (e.g., 100 g with a water content of 100 wt%) in an aqueous phase with a neutral pH and a volume-to-solid-mass ratio of > 1,000:1 for 3 minutes using an intensive mixer. The unbound aqueous phase is then allowed to drain through a sieve with a mesh size of 50 µm. After 1 hour, the volume of the cellulose-based fiber mass is determined. Mechanical dewatering is then performed, followed by drying to a residual moisture content of < 10 wt%. The volume is then determined, and the volume ratio is calculated.
[0189] Oil retention capacity can be determined analogously using a liquid lipid phase, such as a paraffinic oil.
[0190] The water solubility (NSI) of proteins is determined according to the standard procedure AOCS 1990, (Daun and DeClercq, 1994) Applications
[0191] The process is applicable in principle to all plant products. It is used in particular for the breakdown, detachment / removal of plant husks, as well as their partial or complete dissolution or decomposition.
[0192] The process is also suitable for partially dissolving or partially dissolving separated plant hull material. Particularly preferred for this purpose are peels, e.g., from potatoes, apples, pumpkins, as well as husks or core material, e.g., from sunflowers or wheat seeds, or from apples or pears. A preferred method is also one in which plant hull materials, such as skins, peels, pods, or husks, have been separated using one of the processes according to the invention or using another method, and are further broken down using one of the processes according to the invention. The process is therefore particularly suitable for separating plant hulls from seeds and kernels, especially when these are present in a compacted form. The process is therefore particularly suitable for partially dissolving or partially dissolving peels, pods, or skins, e.g.,Dried nuts, such as walnuts or hazelnuts, almonds, beans, such as soybeans or kidney beans, kernels, such as apple, orange, or grape seeds, or even avocado or jatropha kernels, legumes, such as rice, corn, or peas and beans, and also dried seeds and kernels, such as those of rapeseed, sunflowers, wheat, rye, oats, lupins, and camelina. Various preferred products can be produced using the process embodiments according to the invention. For example, dehulled grains and kernels can be provided that have been produced under very gentle conditions. By foregoing a temperature increase for the dehulling process, grains and kernels with unchanged integrity of their constituents can be obtained. In particular, the formation of trans fatty acids or thermal reaction products does not occur.In one embodiment, grains and kernels, as well as other starting materials, are obtained that are enriched with amino acids and / or peptides. In another embodiment of the process, this or another functionalization increases the oxidative stability of the plant product.
[0193] In further advantageous embodiments, disintegrated coating materials can be obtained that can be produced in foodstuffs, e.g., as a separating layer or as a swelling agent in a tasteless form. Such highly malleable coating / fiber condensates, suitable for texturizing food, exhibit excellent swelling capacity and water-binding properties and thus also serve to keep food preparations fresh.
[0194] In further embodiments, pure fractions of the constituents are obtained from the cladding materials, which were previously unobtainable and exhibit outstanding properties that can be used in numerous areas of life.
[0195] Lignin-based hull components have demonstrated excellent water retention capacity. Therefore, a preferred application is their addition to soils to improve water retention, particularly in cultivated soils. This yields lignin-rich hull fractions that, due to their high water retention capacity, natural degradability, and biocompatibility, can be used to improve soil quality, especially in crop cultivation. Lignin-rich hull components can also be used for the adsorption and / or storage / transport of lipid phases. They can therefore also be used for oil absorption / separation. Furthermore, they can be used in the formulation of animal feed products. Of particular value are lignin-based hull components that, through a disintegrative process, acquire an abrasive cleaning effect and can thus be used to treat / clean scratch-sensitive surfaces.Therefore, a biogenic and biodegradable abrasive cleaning agent can also be provided.
[0196] The cellulose-based fibers produced according to the invention can, in principle, be used in all areas of life as well as in industrial processes and procedures. Cellulose-based fibers obtained and produced according to the inventive method are particularly suitable for applications in human nutrition. They are especially suitable as a dietary food additive for calorie-reduced food preparation. Furthermore, cellulose-based fibers are suitable for dietary weight reduction. They can also be used as a substitute for, or to reduce, soluble carbohydrates such as pectins or starches in food preparations. Additionally, they can be used as a substitute for, or to reduce, oils or fats in food preparations. Cellulose-based fibers are suitable for regulating intestinal activity and modifying / softening stool consistency.Furthermore, they can be used as a dietary anti-constipation aid. Cellulose-based fibers can also be used in animals to regulate stool consistency and for dietary weight reduction. Additionally, cellulose-based fibers are suitable for thickening and stabilizing liquid or flowable foods and food preparations. Cellulose-based fibers increase the water-binding and retention capacity of food preparations. This makes cellulose-based fibers suitable for maintaining the water content in foods or food preparations for longer, keeping them fresh, and reducing the risk of dehydration. Furthermore, cellulose-based fibers can be used to introduce and / or stabilize substances / compounds or microorganisms in foods or food preparations.This allows, for example, the stabilization and distribution of labile compounds, such as vitamins or antioxidants, in foods or food preparations. Furthermore, it allows the introduction of microorganisms with increased metabolic activity, such as yeasts or lactic acid bacteria, into foods. These properties of cellulose-based fibers can also be used to cultivate algae or other microorganisms and utilize them for the production of substances, compounds, or gases with increased efficiency. Cellulose-based fibers produced according to the invention are particularly suitable for the production of lotions, creams, ointments, or pastes for application to the skin or mucous membranes.In these cases, they enable improved water retention on the surface of skin and mucous membranes, as well as improved emulsification of hydrophilic and lipophilic compounds and the incorporation of compounds such as antioxidants or sunscreens, leading to improved smoothness of the skin and mucous membranes. Furthermore, cellulose-based fibers are very well suited as release agents for food products cooked at high temperatures with direct or indirect heat, such as roasted, baked, grilled, or fried foods. Thus, cellulose-based fibers can be used as a release agent or as a substitute for breading / breadcrumbs, for example, in preparations of meat or fish and meat or fish products, potato preparations, or dough preparations. Cellulose-based fibers are also suitable for formulating or preserving other nutrients or food components.This is particularly relevant in the production of protein products, such as protein concentrates or isolates. Preparations containing oils / fats and / or soluble or complexed carbohydrates, or odorants and flavorings, can also be produced, formulated, and / or stored using the cellulose-based fibers according to the invention. Furthermore, cellulose-based fibers are suitable for creating a long-lasting feeling of moisture on mucous membranes. Therefore, cellulose-based fibers are particularly suitable for treating dry oral mucosa. In addition, cellulose-based fibers are suitable for reducing odors; in particular, they can be used to reduce or prevent bad breath.
[0197] Furthermore, proteins can be provided in a highly pure form for human and animal nutrition. The resulting protein fractions are particularly suitable for formulating food preparations and for use, for example, in meat and sausage products, baking mixes, creams and beverages, or in infant formula or as tube feeding. The preservation and use of the protein fractions as a hypoallergenic concentrate or protein isolate is preferred. The production of GMO-free products, obtainable from plant-based, GMO-free starting material, is also preferred. Examples
[0198] The crude protein content of the samples was determined according to LMBG §3 5 L 03.00-27 via nitrogen determination using the Dumas method. A factor of 6.25 was used to convert the nitrogen content to the crude protein content of the samples. The nitrogen determination was performed using the Leco FP-528 system.
[0199] The water-binding capacity (WBC) of the solid fractions was determined at room temperature. 2 g of sample were weighed to the nearest 0.01 g into a centrifuge tube and mixed with 40 ml of demineralized water for one minute using a test tube shaker. After 5 minutes and again after 10 minutes, the mixture was vigorously mixed for 30 seconds using the same shaker. The mixture was then centrifuged at 1000 g and 20 °C for 15 minutes. The supernatant was decanted, and the centrifuge tube was weighed. The weight of the water-saturated sample was then determined.
[0200] The fat-binding capacity of the solid fractions was determined at room temperature. 3 g were dispersed in 20 ml of oil (commercial corn germ oil) in a 25 ml graduated centrifuge tube. Centrifugation was then performed for 15 min at 700 g. The volume of unbound oil was determined. The oil-binding capacity is expressed in ml of oil per g of sample.
[0201] To determine protein solubility at a defined pH, the C.V. Morr method was used. One gram of sample was weighed into a 100 mL beaker. While stirring, 40 mL of a 0.1 mol / L sodium chloride solution with antifoam was added. The pH was adjusted to the desired value with 0.1 mol / L hydrochloric acid or 0.1 mol / L sodium hydroxide solution. The mixture was transferred to a 50 mL volumetric flask and made up to the defined volume with 0.1 mol / L sodium chloride solution. 20 mL of the solution were pipetted into a centrifuge tube and centrifuged for 15 min at 20,000 g. The resulting supernatant was filtered through a Whatman No. 1 filter. The nitrogen content of the filtered supernatant was determined according to Dumas (Leco FP 521 system).
[0202] All tests were carried out under normal pressure conditions (101.3 Pa) and at room temperature (25 °C), unless otherwise stated. Example 1
[0203] Investigation into the disintegration of plant peels and coverings.
[0204] The following starting materials were used for the investigations: 1) soybeans, 2) kidney beans, 3) almonds, 4) walnuts. The materials were provided without their outer shells (3) and 4)) and in dried form. 200 g of each material were placed in a container containing an aqueous solution without (a) or with one of the following dissolved substances: b) 0.1 molar sodium hydroxide solution, c) 0.3 molar arginine, d) SDS 1 wt%, e) 300 mmol / l lysine, f) 300 mmol / l histidine and glycine, g) 0.3 molar RDG. Every 10 minutes, individual beans / nuts were removed from the solutions for analysis. The maximum exposure time was 4 hours. The beans and nuts removed from the solutions were immediately examined by reflected light microscopy for perforations / dissolution of the shell material.Furthermore, the detachability of the hull material was investigated by applying manual tangential pressure to the hull material and by using a centered water jet generated at a pressure of 3 bar. Another portion of the beans and nuts was placed in a water bath at 25°C. In each case, it was recorded whether and to what extent the hull material could be partially or completely detached, or detached spontaneously. The consistency of the detached hull material was also examined. Results:
[0205] The husks of the beans or nuts showed clearly visible swelling after only a few minutes of immersion in the aqueous solutions of test series c), e), f), and g), which continued to increase over time, whereas this swelling was only noticeable after 40 and 20 minutes, respectively, in pure water or in test series b) and d). The visible swelling was associated with the husk material becoming movable relative to the bean / nut surface.
[0206] Microscopic analysis of the husk material revealed that the presence of the starting materials in the aqueous solutions of test series c), e), f), and g) in the area of the seedling had caused a superficial decomposition of the husk material, exhibiting a suture-like circular (1) or longitudinal (2 + 3) orientation / pattern. This was not observed after exposure to the other solutions. Over time, perforation of the husk material in this area regularly occurred, exposing the bean / nut and resulting in the separation of identical geometries of the husk material. Exposure in test series b) led to a dark discoloration of the husk material and / or the exposed starting material.
[0207] Immersion in pure water did not result in any spontaneous detachment of the coating material from any of the materials during the test period. Only small fragments could be detached by applying a tangential force at the end of the test. In test series b) and d), spontaneous and partial detachment of the coating material was observed after 380 minutes and 400 minutes, respectively. Tangential force resulted in partial detachment of the coating material in 1) and 3) after 180 and 240 minutes, respectively, and in 2) and 4) after 280 and 360 minutes, respectively. Complete detachment was not possible. For the materials immersed in solutions c), e), f), and g), spontaneous separation of the coating material occurred after 30 to 100 minutes. For all preparations in series c), e), f) and g), complete spontaneous separation was achieved after 110 to 180 minutes.In these preparations, partial detachment by tangential pressure was first possible after 10 to 20 minutes, and complete detachment after 20 to 40 minutes. The coating material obtained in test series b) and d) was not very elastic, regardless of the exposure time. The detached coating material from test series c), e), f), and g) was soft and flexible after an exposure time of 20 to 40 minutes, and planar compression without tearing of the coating material was possible. Example 2 Investigations into the disintegration of coating material and separation of coatings and seedlings.
[0208] For the investigations, a) soybeans, b) kidney beans, and c) lentils were used, all in dried form. Aqueous solutions were used in the test series that contained either 1) no substances or 2) NaOH 0.5 wt%, 3) sodium carbonate 1 wt%, 4) arginine 0.3 molar, or 5) lysine-isoleucine + DMSO 0.3 molar. In test series A), 100 g of each starting material was completely immersed in the solutions, and the time of visible sprouting was determined by analyzing continuous video recording. The time until a sprout length of 5 mm was also recorded was also determined. The test duration was limited to 72 hours. In test series B), 500g of starting materials were soaked in water for a period of time that resulted in a germ growth of 5 mm, and then portions of 100g each were added to the aqueous test solutions 1) to 5).The samples were stored for the period that, according to the experimental procedure of Example 1, had resulted in spontaneous perforation of the coating material, allowing for easy and complete separation of the coating material. At this point, half of the sample material was removed and placed in a filling device that ensured compressed air passage through a silicone tube. The frequency of complete separation of the seedling and the coating material was investigated. Series C) of the experiment was conducted using the starting materials from Series B) that remained in the test solutions until a total immersion time of 48 hours was reached. During this period, video recordings were made to detect any further growth of the seedlings.At the end of the investigation, the husks and seedlings were separated using the same method as in investigation series B). The completeness of the separation of husk material and seedlings was examined, and the length of the seedlings was compared with that of investigation series B). Furthermore, the separated husk materials were homogenized in a water bath using a shear mixer (UltraThurrax, T18, 20.00 rpm, 30 s), and the resulting suspensions were then tasted. Results:
[0209] After immersion in water, sprouting occurred relatively simultaneously in the respective starting materials, with uniform growth of the sprouts. Immersion in solutions 2) and 3) resulted in a delay of 12 and 18 hours, respectively, compared to immersion in pure water, and by 30 hours in solution 5. In solution 4), no sprouting (b) and c)) or only very slight sprouting (< 5 mm) occurred in the starting materials within the specified time. In test series B), further sprouting occurred in the starting materials, which was significantly delayed or prevented when stored in solutions 4) and 5). Complete stripping of the outer layer and sprouts was achieved in 36% and 28% of the beans and lentils after immersion in solutions 2) and 3), respectively. This was possible in 92% and 90% of the preparations immersed in solutions 4) and 5), respectively.In the preparations of test series C), slight growth was observed when immersed in solutions 2) and 3), whereas this was not observed in preparations immersed in solutions 4) and 5). Tasting of the suspensions revealed an unpleasant and soapy taste when immersed in solutions 2) and 3), while the suspensions were practically tasteless after immersion of the starting materials in solutions 4) and 5). Example 3: Investigation into the disintegration of water-containing starting materials and the separability of constituents.
[0210] The following starting materials were used for the investigations: 1. Butternut squash, 2. Quince, and 3. Celery. The materials were thoroughly cleaned and divided into 4 or 8 parts and immersed in the following aqueous solutions: a) Lysine 0.1 molar + urea 1 wt%, b) Polyarginine 0.1 molar + SDS, c) Arginine 0.1 molar, d) Histidine-isoleucine 0.1 molar + sodium sulfite 1 wt%. Tests with pure water were conducted as a reference under otherwise identical conditions. The solutions were heated to 90°C for 1 hour, after which the immersed material pieces were removed and allowed to cool. The removability of the outer husk was then examined. The assessment focused on whether the husk material could be easily removed manually, with minimal mesosperm adhesion, and in large pieces. Furthermore, the divisibility of the skinned material was investigated by adding it to water in a container at a weight ratio of 1:10.The mixture was then distributed using a shear mixer (Silverson, L5M, UK; 35 mm / 8,000 rpm) for 30 seconds. The suspensions were then separated from the free water phase using a vacuum Büchner funnel. The pasty material was mixed with pure water at a volume ratio of 2:1, passed through a sieve with a mesh size of 0.8 mm, and again separated from the free water phase. Immediately afterward, a sensory evaluation was performed by four experts. The presence of odor and taste qualities, as well as the sensory properties in the mouth and during swallowing, were assessed. Results: In the reference tests, the outer coating layer could not be separated (preparation 3) and could only be separated in small pieces (especially preparation 2), with significant mesosperm adhesion remaining. In the preparations that had been disintegrated in solutions a) to d), the outer coating layers could be easily separated (b) and d)) to very easily (a) + c)).Correspondingly, medium-sized or large, cohesive pieces of the hull material were separated without mesosperm attachment. The skinned reference sample could not be completely pulverized, resulting in a large quantity of small, cohesive aggregates in the sieve residue. The preparations disintegrated with solutions a) to d) were in the form of a mucilaginous suspension that passed through the sieve practically without residue. Sensory evaluation revealed that the pastes obtained from the reference samples exhibited an intense, species-typical odor and taste. Furthermore, a dull (2.) to granular mouthfeel (especially in preparation 3) was perceptible. In the samples obtained by disintegration with solutions a) to d), no or practically no species-typical odor or taste was perceptible. In all cases, a pleasant mouthfeel, described as "soft" and "creamy," was noted.The particles were not perceptible. Example 4 Investigation into the disintegration and breakdown of plant covering and shell material.
[0211] The following starting materials were used: 1. Soybean meal after hexane extraction, 2. Corn meal, 3. Apple pomace, 4. Grape seed flour. 300 g each were placed in containers with a) pure water and the following aqueous solutions: b) histidine-valine-leucine 0.2 molar + sodium sulfite 1 wt%, c) arginine 0.1 molar, d) lysine 0.3 molar + sodium bisulfite 0.5 wt%, e) sodium sulfite 0.5 wt% + sodium carbonate 0.1 wt%, in a weight ratio (solid:aqueous phase) of 1:10. The containers were exposed to an autoclave at a temperature of 125°C and a pressure of 1.2 bar for 5, 15, and 30 minutes. After cooling, the entire suspension was homogenized for 90 seconds using a shear mixer (Silverson, L5M, UK; 35 mm / 8,000 rpm). This was followed by wet sieving using a vibrating sieve tower analyzer with sieve sizes of 500 µm, 250 µm, 100 µm, and 50 µm.The residual moisture content was determined from a sample of the sieve fractions, and the dry mass of each fraction was calculated from this. Samples were also taken for microscopic analysis. These samples were analyzed for the presence of recognizable shell structures and their relative proportion compared to other fiber structures. Furthermore, a chemical analysis was performed to determine the content of soluble carbohydrates and proteins. An aqueous solution containing 10 wt% citric acid and 10 wt% calcium chloride, in a volume ratio of 1 to 3 vol%, was added to the aqueous phases obtained after sieve separation to achieve a pH of the process fluid between 4.8 and 5.4. After a single mixing, a standing period of 2 hours was observed. Subsequently, any supernatant, which was clear or slightly cloudy, was poured off, and the sediment phase was directed onto a filter bed.After 10 hours, the dehydrated mass was removed from the filter and chemically analyzed for protein and carbohydrate content. These fractions were then tasted. Furthermore, a sensory evaluation of the fiber masses from each sieve tower fraction was performed according to Example 3 after rinsing and removal of the free water phase using a sieve press.
[0212] Results: After homogenization, predominantly large-caliber particles were obtained through thermal disintegration in a water bath, with only a minor influence of the duration of thermal exposure. In contrast, the particles obtained through disintegration in solutions b) to e) were considerably smaller even after a short heating time. Microscopic analysis of thermal disintegration (a)) alone revealed shell or hull fragments at all time points and in all sieve fractions. In contrast, with solutions b) to e) after a short exposure time, shell or hull fragments were only detectable to a small extent in the sieve fractions with a sieve size > 250 µm, and were no longer present after a longer exposure time.While the majority of the soluble carbohydrates and proteins present in the starting materials were still present in the particle masses after purely thermal disintegration, only small to minimal amounts of soluble compounds were detectable in the particle fractions after digestion with solutions b) to e). Accordingly, practically no proteins or carbohydrates could be recovered from the aqueous filtrate after purely thermal degradation by means of aggregation-initiated aggregation. In contrast, the theoretically calculated amounts of proteins, derived from the quantitative analysis of the starting material minus the amount of protein determined in the particles, could be recovered from the filtrate phases of the digestion solutions b) to e) using the aggregation and dehydration process.The protein / carbohydrate fractions obtained after digestion with solutions b) to e) were practically odorless and tasteless. While the fibers obtained by purely thermal digestion were still rated as predominantly hard and fibrous upon tasting, the fiber fractions obtained by disintegration with solutions b) to e) were classified as soft to very soft, delicate, and creamy. Microscopic analysis of the sieve residues after disintegration and digestion with solutions b) to e) revealed that the particles were large-volume fiber structures, which further analyses showed to be cellulose-based fibers. Example 5 Investigation into the breakdown and separability of lignin-rich shell components and cellulose-based fibers.
[0213] An aqueous digestion process was carried out on the press residues of jatropha kernels (JPK) and rapeseed (RPK). Proteins and carbohydrates were separated using an aqueous solution, and the solids were then freed from the water content using a chamber filter press. The residue had a residual moisture content of 40 wt% and an intense and unpleasant, plant-like odor (therefore, no tasting was performed). For the digestion of the filter residue, 100 g of the crumbly residue was used in each of the following experiments. This residue was added to the following solutions and stirred continuously for 4 hours: 1. Lysine 0.3 mol / l, 2. Polyarginine + Glutamine 0.2 mol / l, 3. Histidine + RDG 0.2 mol / l, 4. NaOH 0.5 N, 5. Water. Subsequently, the solids were separated using a filter and rinsed twice with water on the filter. The samples were then distributed in 2 liters of tap water (LW) using a water mixer for 60 seconds.After passing through a pre-screen with a 500 µm mesh size, the agitated suspension was pumped into a hydrocyclone (Akavortex, nuclear power plant, Germany) at a differential pressure of 1 bar. The underflow was collected, mixed with tap water at a ratio of 1:5, and returned to the hydrocyclone. The upperflow from both separation processes was cleaned of suspended solids by a vibrating screen with a 100 µm mesh size, yielding screen residue 1 (SR 1). The underflow was separated from the free water phase and microparticles by a 200 µm vibrating screen, yielding screen residue 2 (SR 2). The masses of lignin-rich shells (SR 2) and a sample of the cellulose-based fibers from (SR 1) were spread on a fine sieve and dried with warm air. The remaining mass of the cellulose-based fibers was stored under refrigeration after pressing out the bound water, in order to carry out further investigations.Samples were then taken for microscopic and chemical analysis. The dried SR2 was separated by rolling. Samples were taken for top-down microscopic analysis and chemical analysis of the particle composition. To test the water-binding capacity, 100 g each were placed in a narrow-bottomed beaker with a lateral outlet at the bottom. Water was added dropwise from the top onto the beaker material until water emerged from the outlet. The weight ratio between the amount of dry matter and the bound water was calculated. The same experiment was performed with lamp oil instead of water, and the oil-binding capacity was calculated. A sample of SR1 was suspended in deionized water at a volume ratio of 1:10 for 3 minutes by stirring, and the dimensions of the cellulose-based fibers contained therein were then determined using a FiberLab FS 300 (Valmet).The obtained fractions were examined using reflected light microscopy to detect adhesions of organic components (e.g. proteins), as well as the presence of agglomerates and clumping of the fiber components and other constituents of the plant starting material. Results:
[0214] The filter residue, containing the solids obtained after an aqueous digestion process, could be easily resuspended and hydrated in water after disintegration with digestion solutions 1) - 3). This was evident from the rapid, spontaneous separation of the lignin-rich shell fractions from the cellulose-based fibers, which sedimented rapidly, while the cellulose-based fibers exhibited only a low sedimentation rate. Such behavior was not observed in the dispersed fiber fraction treated with solutions 4) and 5). Using a hydrocyclone, the first separation of the samples treated with solutions 1) - 3) yielded an estimated separation efficiency of approximately 80% for the topstream fraction and approximately 70% for the bottomstream fraction. After the second separation, the lignin-rich shell fraction was significantly reduced.Separation of the individual solid phases yielded a separation result of > 95% for both fractions. For the samples treated with solutions 4) and 5), such separation was either not possible or incomplete (<60% purity). Microscopically, no deposits of organic components were visible on the resulting solid preparations in samples treated with digestion solutions 1) - 3), while the remaining samples showed significant deposits of organic materials, some of which were present in the form of large aggregates. For the preparations treated with digestion solutions 1) - 3), a water-binding capacity of between 250 and 300 wt% and an oil-binding capacity of between 280 and 320 wt% were determined for the dried lignin-rich shells. The corresponding water and oil binding capacities of fractions obtained with solutions 4) and 5) were < 150 wt% and < 120 wt%, respectively.For the dried cellulose-based fibers produced with the pulping solutions 1) - 3), the water binding capacity was 290 to 340 wt% and the oil binding capacity was 220 to 310 wt%. For the fractions obtained from a process with solutions 4) and 5), the corresponding values were < 100 wt% and < 80 wt%, respectively.
[0215] The chemical analysis of the shell fractions obtained with the digestion solutions 1) - 3) revealed a lignin content between 52 and 73 wt%.
[0216] The volume dimensions of cellulose-based fibers, which were resuspended after this disintegration process, showed significantly larger volumes (+158 to +340 vol%) for fibers treated with solutions 1) to 3) than for those treated with solutions 4) and 5). Chemical analysis revealed that the protein or soluble carbohydrate content in the cellulose-based fibers and lignin-rich shell components was <1 wt% after disintegration with solutions 1) to 3), while the other preparations showed a protein and soluble carbohydrate content >10 wt%. Sensory evaluation revealed that the fiber components treated with solutions 1) to 3) were free of odor and taste, while the other preparations had an unpleasant taste and odor. Example 6 Investigation into digestion conditions for plant-based starting materials.
[0217] The following press residues, in pellet form, and milled products, in flour form, with the specified content of their constituents, were analyzed: Soybean press cake (SPK): Protein 38% w / w, Carbohydrate 26% w / w, Fiber 21% w / w, Oil 11% w / w, Other 4% w / w; Rapeseed press cake (RPK): Protein 35% w / w, Carbohydrate 21% w / w, Fiber 30% w / w, Oil 9% w / w, Other 5% w / w; Jatropha press cake (JPK): Protein 32% w / w, Carbohydrate 22% w / w, Fiber 25% w / w, Oil 13% w / w, Other 8% w / w; Oat flour (HM): Protein 40% w / w, Carbohydrate 30% w / w, Fiber 18% w / w, Oil 8% w / w, Other 4% w / w; Lentil flour (LM): Protein 33% w / w, Carbohydrate 33% w / w, Fibre 25% w / w, Oil 6% w / w, other 3% w / w.The required digestion time was first determined by digesting 50 g of each of the starting products in 1000 ml vials containing aqueous solutions of: a) arginine 0.2 molar, b) histidine and lysine 0.1 molar each, c) polyarginine 0.1 molar and glutamic acid 0.1 molar, d) NH₄⁺ 0.2 molar, e) KOH 0.2 molar, f) urea 0.3 molar, g) sodium carbonate 0.5 wt%, h) sodium sulfite 0.2 wt%, at a mixing frequency of 50 / min. The digestion time was then observed to determine when no visible solid aggregates remained in the forming suspension. At this point, the respective suspension was passed through a vibrating sieve with a mesh size of 100 µm, and the filter residue was examined microscopically, as described in Example 5.A test was then conducted to determine the minimum volume required for complete penetration and digestion of the starting materials. This involved adding 50 ml of the digestion solution to every 100 g of the products, starting with a weight ratio of 1:1. The mixture was mixed slowly for the time determined in the preliminary investigation, which was necessary for complete digestion with each respective digestion solution. At the end of the minimum contact time, samples were taken and centrifuged at 3000 rpm for 3 minutes. A sufficient volume for complete swelling was defined as the mass ratio between the starting material and the digestion solution (Pref) at which only a minimal free liquid layer remained as supernatant after centrifugation of a sample.10g of each of the preparations, in which maximum swelling was achieved with the minimum required volume of the respective preparation, were added to 90ml of tap water, dispersed by shaking, and then passed through a vibrating sieve with a mesh size of 100µm. The eluate was passed through a 10µm fine sieve. The respective filter residue was suspended in water, and the particulate structures present were analyzed microscopically after identical filtration (procedure as in Example 1). In a repeat experiment, the sieve residue was dried, and the amount of substance retained particles was determined. In a further investigation, 100g of the mass of preparation P ref was mixed in 900ml of water using a laminar mixer for 5 minutes. The suspension was then passed through a vibrating sieve.The sieve residue was freed from bound water in a chamber filter press, and the residual moisture content was determined. The residue was then suspended in a 0.5 molar NaOH solution and mixed for one hour. The suspension was passed through the vibrating screen again, and the filter residue was dried using a chamber filter press. Results:
[0218] Despite a significantly larger swelling volume observed with solutions a) - c), g) and h) compared to solutions d) - f) (+160 to +260 wt% vs. +80 to +160 wt%), the time required to achieve this was significantly shorter (8 to 20 minutes vs. 40 to 300 minutes). Microscopic analysis of the sieve residue (100 µm sieve size) after distribution of the samples of the digestion mixtures at the time of maximum swelling in a distribution volume prepared with solutions a) - c), g) and h) revealed no aggregates of solids that were practically free of adhering organic residues. In contrast, the sieve residue of the digestion mixtures prepared with solutions d) - f) contained numerous aggregates / conglomerates of solids, some of which were completely encased in organic matter, at the time of maximum swelling Qmax.In contrast to the sieve residues of the samples obtained with solutions a) - c), g) and h), which contained decompacted, large-volume, and expanded cellulose-based fibers, such fibers were only sporadically and slightly expanded. On the fine filter (10 µm sieve size) of the eluate from the previous filtration, practically no particulate structures were visible after digestion with solutions a) to c), g) and h), whereas the eluates obtained from digestion with solutions d) to f) contained numerous solid particles, some of which clogged the filter surface; these particles were predominantly cellulose-based fibers heavily coated with organic compounds.The dry weight of the sieve residues after digestion and distribution of the soluble and dissolved constituents was significantly higher for samples obtained from digestion with solutions d-f) than for those obtained by digestion with solutions a-c), g), and h) (+130 to +350 wt%). Digestion of the sieve residue with an alkali resulted in virtually no further protein release from the material obtained after digestion with solutions a-c), g), and h), whereas between 8 and 22 wt% of proteins were leached from the sieve residue of the digestion mixture after preparation with solutions d-f). Example 7 Investigation into applications of lignin-based plant peels for oil binding
[0219] The lignin-rich shell fractions obtained from experiment 5 (Jatropha (JS), Rapeseed (RS)) by digestion methods 1) - 3), as well as lignin-rich shell fractions from Jatropha and Rapeseed digested with NaOH (NO), were air-dried and separated. The mean particle size distribution and bulk density were determined. The dried shell material was filled to a height of 20 cm into a 10 mm diameter glass tube with a conical tip at the bottom, sealed by an open-pore PP fabric. The weight of the filled shell mass was determined. For comparison, commercial oil adsorbents (ÖAM1: Clean Sorb, BTW, Germany; ÖAM2: PEA SORB, Zorbit, Germany) were filled into similar glass tubes in the same manner.The filled glass tubes were mounted vertically in a holder, with the tips immersed in a bath of sunflower oil in one experiment and oleic acid in another. The height of the oil rise, clearly identifiable by a change in color or reflection of the adsorbent, was recorded every 5 minutes. The experiments were stopped after 2 hours, and the oil rise height (O-StH 1) and the difference in volume between the oil bath and the initial volume (ads. Oil 1) were determined. The entire contents of the riser tubes were then carefully blown into a beaker and weighed. 100 ml of ethanol was then added to each tube. The suspensions were agitated for 30 minutes under anaerobic conditions and heated to 60°C using a magnetic stirrer. The liquid phase was then drained using a Büchner funnel, and the sieve residue of the tray or adsorbent masses was rinsed twice (with ethanol / H₂O). The residue was then dried at 60°C for 12 hours.The weight and consistency of the dried masses were then determined (weight difference). Subsequently, the experiment was repeated with the obtained dried mass fractions, and the oil rise height (oil rise height 2) and the volume of adsorbed oil (adsorbed oil 2) were determined again.
[0220] Results (numerical results in Table 1): In contrast to lignin-based peels purified with an alkaline solution, the lignin-based plant peels obtained and produced with the digestion solutions according to the invention exhibited a very rapid and high absorption capacity for oils, which was also superior to that of commercial oil adsorbers. This applied to both the absorption capacity against gravity and the total adsorbed volume. Removal of the adsorbed oils by a solvent was largely complete in the lignin-based plant peels obtained with the digestion solutions according to the invention, whereas in lignin-rich peels obtained without the invention, the adsorbed oil could only be incompletely removed. Extraction of the adsorbed oil was also incomplete in the commercial products.In a subsequent cycle using the previously purified adsorbents, the rate and amount of oil absorption of the lignin-rich shell components, which had been prepared with the digestion solutions according to the invention, were comparable to that of the previously conducted experiment, while the oil adsorption performance of the other purified preparations remained significantly below that of the first application cycle. Table 1 Ö-StH 1 (cm) ads. Oil 1 (ml) Weight difference (g) Ö-StH 2 (cm) ads. Oil 2 (ml) JS 6,4 3,1 3,1 6,4 3,1 RS 5,8 2,9 2,8 5,7 2,8 SS 5,2 2,8 2,7 5,2 2,7 AS 5 2,6 2,6 5,2 2,6 JS-NO 2,3 1,1 0,5 0,8 0,4 RS-NO 1,2 0,9 0,4 0,5 0,2 ÖAM1 3,2 1,9 1,1 2,2 0,8 ÖAM2 3,6 2,2 1,6 2,6 1,2 O-StH1 = Oil riser height, 1st cycle; ads. Oil1 = Amount of adsorbed oil, 1st cycle; Weight difference = Difference in weight of adsorbent before / after solvent extraction; O-StH2 = Oil riser height, 2nd cycle; ads. Oil2 = Amount of adsorbed oil, 2nd cycle; Example 8 Investigation into the use of lignin-rich plant peels for oil separation from oil-containing aerosols.
[0221] Lignin-rich plant peels from Jatropha (JKP) from Example 5, prepared with the exclusion solutions a) arginine 0.2 molar (JKPa) and d) NH₄ 0.2 molar (JKPd), were distributed between two 10 x 10 cm sieve plates with a fill height of 2 cm, and the sieves were secured in a frame. The sieve frame was inserted into an air duct with a tight seal on the sides. A compressed air source ensured a constant airflow (70°C) through the filter at a volume flow rate of 50 m³ / h. An ultrasonic nebulizer was placed in the airflow, vaporizing an oil-water emulsion at a constant rate. The pressure building up below the filter was monitored with a pressure sensor. Above the sieve, the air outlet passed through an oil mist separator (Contec), which ensured 99.5% oil retention from the air mixture.For comparison, conventional air filters (LF), steel mesh filters (SGF), activated carbon filters (AKF), and a membrane filter (MF) were installed in the air duct in further tests. The tests were terminated after 30 minutes, during which time a volume of 20 ml of oil was vaporized. The membrane filter was then removed, and the difference in weight compared to the initial value was determined. The lignin-rich shell particles were removed from the filter housing and suspended in acetone in a beaker, and the bound oil was extracted. The separated acetone phases were vaporized, and the residue was weighed. The oil separation rate was calculated from the weight difference between the oil adsorption fleece and the vaporized oil.
[0222] Results: When using a membrane filter and an activated carbon filter, a pressure increase occurred in the supply air duct (max. pressure difference 35 and 52 mbar, respectively) due to an increase in airflow resistance. When using JKPd), the initial pressure was higher than in tests with lignin-rich shell fragments obtained with the digestion solutions according to the invention (JKPa). With JKPd, no pressure increase occurred in the supply duct during the course of the test, whereas the pressure increased slightly with preparation JKPd. The oil separation rate for the conventional air filters was between 48 and 62 wt%. Lignin-rich shell fragments not produced according to the invention had an oil separation rate of 55 wt%, while the lignin-rich shell fragments produced with the digestion solutions according to the invention exhibited an oil separation rate of 98 wt%.From this fraction, 18.4 g of oil could be recovered by extraction, whereas from the preparation JKPd) only 5.2 g could be recovered. Example 9 Investigation into the abrasive cleaning behavior of lignin-based shells.
[0223] The shell fraction obtained in Example 5 from a rapeseed press cake digestion using digestion solutions 1) and 2) was treated in a further disintegration / digestion stage using the following methods: 1) Arginine 0.3 molar, 2) Arginine 0.3 molar + urea 10 wt%, 3) Arginine 0.1 molar + NaSO₃ 1 wt%, 4) NaOH 0.5 N, 5) Water. The compounds were completely dissolved in deionized water. 10 g of the shell fraction were suspended in 200 ml of each solution and stirred for 20 minutes. The suspensions were then treated in an autoclave at 120°C and 2 bar for 11 minutes. Afterward, they were thoroughly rinsed with water through a sieve. Following pressing, the particles were dried and separated. Samples were taken for analysis. Suspension of shell fractions in a non-ionic surfactant.Two milliliters of the surfactant solution containing the shells were applied to a high-gloss plastic surface encrusted with various materials such as egg whites, sauces, or pasta dough. A 500g wooden stamp was moved 30 times coaxially to the surface of the plastic film over the encrustations by an automated pusher device. The surfaces were then rinsed. After drying, the degree of residual soiling and the presence of scratches or grooves were assessed.
[0224] Results: Microscopic analysis revealed that the lignin-based shell fragments produced using methods 1 to 3 were completely isolated and had significantly smaller surface dimensions than those obtained using methods 4 and 5. The shell fragments produced using methods 1 to 3 were predominantly rounded and had smooth outer contours. The shell fragments obtained using methods 4 and 5, on the other hand, predominantly had acute-angled and jagged outer contours.
[0225] The surfaces treated with lignin-rich shell fractions produced by processes 1 to 3 showed complete removal of surface contaminants, whereas the shell fractions obtained by processes 4 and 5 still exhibited residual adhesion. The surfaces treated with the lignin-rich shells produced by processes 1 to 3 were free of scratches. Surfaces treated with shell fractions obtained by processes 4 and 5 showed moderate to pronounced scratches. Example 10 Investigations into digestion methods for obtaining cellulose-based fibers
[0226] The following experimental procedures were carried out on 1 kg each of A) rapeseed press cake, B) corn grits, C) whole soybeans, D) sugar beet pulp after extraction of the molasses: Aqueous digestion by placing materials A) and B) into a bath of digestion compounds at a temperature of a) 25°C and b) 60°C for 60 minutes each under continuous stirring, c) furthermore by means of thermal disintegration in an autoclave at 125°C of materials C) and D) placed in the digestion solutions for 15 minutes each. The following solutions were used for digestion: 1. Water, 2. 0.1 N sodium hydroxide solution, 3. 30% sulfuric acid solution, 4. Aqueous solution of arginine 0.3 molar, 5. Aqueous solution of lysine 0.3 molar and glutamine 0.2 molar, 6. 1.5 wt% solution of sodium bisulfite, 7. 0.5 wt% solution of sodium bicarbonate.The resulting mixtures were then freed from free liquid by centrifugation, resulting in solid masses. To separate dissolved components, the masses were dissolved in 10 liters of water each and finely dispersed with a stirrer for 10 minutes. The aqueous phase was then separated using a vibrating sieve with a mesh size of 200 µm. Samples were taken from the resulting fractions for analysis. The drip-free masses were weighed and then dried in a drying oven. The water-binding capacity was calculated from the weight difference between the wet and dried masses. The wet samples were microscopically analyzed for fiber structure and the degree of coating / clumping with other organic components. The resulting dry material was analyzed for its content of soluble carbohydrates and proteins.The number of fibers (pcs) per gram of wet mass, the maximum volume expansion, and the aspect ratio were analyzed using a fiber analyzer (FiberLab FS300, Valmet). Results:
[0227] Digestion of the starting materials with water could not be achieved. Partial digestion of starting materials A) and B) was possible with an alkali at room temperature, but not with digestion solution 3. Extensive digestion was achieved with digestion solution 2 at elevated temperature (A)b) and B)b)) as well as thermal disintegration (C) and D)). Digestion with a sulfuric acid solution was not possible under the experimental conditions. Complete digestion was achieved with digestion solutions 4–7 under all experimental conditions. Microscopic examination of the processes in which macroscopically complete digestion was not achieved revealed the presence of solid particles and / or fibers, some of which were partially encapsulated by other organic compounds or components, as well as the presence of aggregates with other fibers or organic compounds.In chemical analysis, soluble carbohydrates and proteins were detected in the sieve residue after macroscopically incomplete digestion. In the digestion experiments carried out with digestion solutions 4–7, macroscopically complete separation of components not corresponding to cellulose-based fibers was achieved in all trials (the filtrate solutions also passed through a 20 µm sieve without residue formation). The volume of the non-drip masses obtained after the digestion procedures with digestion solutions 4–7 was significantly larger than the volumes of the digestion masses after the digestion procedure with water or an alkaline solution. Accordingly, the water-binding capacity was considerably lower (80–190 wt%) with these procedures than with decompacted cellulose-based fibers obtained with digestion solutions 4–7 (680–850 wt%).Correspondingly, chemical analyses showed that the masses of cellulose-based fibers obtained after using digestion solutions 4-7 contained a residual content of soluble carbohydrates of < 1 wt% and of proteins of < 0.5 wt%. In the other digestion products, the contents of soluble carbohydrates and proteins ranged between 15 and 37 wt%. The dried aggregates of products with a residual content of > 1 wt% of soluble carbohydrates and proteins were very hard and could only be incompletely hydrated. In contrast, the aggregates obtained after drying from a digestion using digestion solutions 4-7 could be completely hydrated within 5 minutes. Powders could be obtained by milling, which swelled rapidly in water and yielded a soft fiber mass upon re-concentration.Analysis of the dimensions and number of cellulose-based fibers, obtained after a digestion process using digestion solutions 4-7, showed a broad and uniform distribution in a range between 20 µm and 600 µm, with a fiber count of 550 to 237 pcs / g and an aspect ratio of 2.5:1 to 22:1. The linear density ranged from 0.8 to 2.5 mg / 100 m. Example 11 Investigation into the production of cellulose-based fibers from mechanical pulping processes
[0228] For the experiments, 1 kg of each of the following starting materials was used: A) soybean meal, B) oat flakes, C) grape seed flour.
[0229] The following procedural steps were carried out: V1) Milling of the starting materials to an average particle size of 100 µm. This was followed by air classification using a fine classifier (Netsch CFS 5); V2) Milling of the starting materials to an average particle size of 100 µm. This was followed by the addition of an aqueous solution containing the following compounds in dissolved form: a) Arginine 0.2 molar, b) Histidine and Lysine 0.1 molar each, c) Polyarginine 0.1 molar and Glutamic Acid 0.1 molar, d) NH₄⁺ 0.2 molar, e) KOH 0.2 molar, f) Urea 0.3 molar, in a weight ratio of 1:1, ensuring that the starting material remained completely immersed in the aqueous solution for 4 hours. The entire reaction mixture was then rinsed with water in a volume ratio of 1:10 using a hand blender. The suspension was passed through a sieve with a mesh size of 200µm.The sieve residue was rinsed twice with the same volume of an aqueous phase and then rolled out onto a porous PP film in a layer thickness of 1 mm and dried. The dried mass was then milled. V3) The starting materials, in their unmilled form, were added to the following aqueous solutions: a) Arginine 0.3 molar, b) Polylysine 0.2 molar, c) Polyglutamate 0.2 molar and Histidine 0.4 molar, d) Triethylamine 0.2 molar, e) NaOH 0.2 molar, f) Sodium carbonate 0.3 wt%. The volume of aqueous solutions added was chosen to ensure complete saturation of the starting material. The mixtures were allowed to stand for 24 hours. They were then stirred into water in a volume ratio of 1:10 and mixed with a stick mixer. The suspension is then passed through a sieve with a mesh size of 200µm.The sieve residue was rinsed twice with the same volume of an aqueous phase and then rolled out onto a porous PP film in a layer thickness of 1 mm and dried. The dried masses were then milled. Chemical analyses for the content of soluble carbohydrates and proteins (according to Example 5) were performed on the resulting dry masses. 50 g of the resulting powdered fiber masses were dissolved in 500 ml of water at a temperature of 30°C with continuous stirring for 1 hour. 100 ml of this solution were placed in a narrow-bottomed graduated cylinder, and the sedimentation time was determined, the time it took for the visible fibers to settle below the 50 ml mark.
[0230] Samples were also taken for fiber dimension analysis (analysis according to Example 6). The remaining suspension was concentrated to achieve a residual moisture content of 40–50% by weight. The resulting paste-like masses were tasted by four expert testers. The following properties were assessed: inherent taste, granularity, mouthfeel, and swallowing sensation.
[0231] Results: The fiber fractions from digestion test V1 still contained larger amounts of soluble carbohydrates (24–36 wt%) and proteins (18–29 wt%). The fiber masses from digestions V2 and V3, prepared with digestion compounds a)–c), showed residual contents of soluble carbohydrates and proteins of < 0.5 wt%. After using the other compounds (d)–f)) for digestion, the fiber masses obtained contained soluble carbohydrate contents of 12–22 wt% and protein contents of 14–25 wt%. The fiber fraction obtained from digestion test V1 was compacted and could only be partially hydrated in water; it sedimented very rapidly after being placed in the graduated cylinder.The powdered fiber fractions produced from digestion experiments V2 using digestion compounds d)-f) were partially hydrated, while the powdered fibers from digestion experiment V3, also using digestion compounds d)-f), showed little hydration. The sedimentation time determined was 15-25 minutes for V2 and 4-10 minutes for V3 for digestion products obtained with these digestion compounds. In contrast, complete hydration was observed for the powdered material from digestion experiments V2 and V3 using digestion compounds a)-c). The dissolved cellulose-based fibers from these digestion fractions exhibited a very low sedimentation rate in a graduated cylinder, with the volume of dissolved cellulose-based fibers only settling below 50 ml after 12 to 27 hours.The average fiber lengths ranged from 150 to 300 µm, and the fiber width from 11 to 19 µm. The fiber length weight ranged from 1.2 to 5.1 mg / 100 m. Tasting of the wet fiber material from digestion test V1 revealed a significant presence of odor and taste compounds corresponding to those of the starting materials. The fiber fractions from digestion tests V2 and V3, prepared with digestion compounds d)-f), also exhibited odor and taste characteristics of the starting material, albeit at a lower intensity. However, they were unpalatable due to the intense odor or taste of the respective digestion compound. In contrast, the fiber fractions from digestion tests V2 and V3, obtained with digestion compounds a)-c), showed no odor or taste compounds, and thus the odor and taste were rated as neutral.Furthermore, cellulose-based fibers obtained in experiments V2 and V3 with the digestion solutions a) - c) showed no granularity, a more pleasant mouthfeel and a pleasant swallowability. Example 12 Investigation into the production of cellulose-based fibers from organic starting materials.
[0232] The manufacturability of cellulose-based fibers with a residual protein and / or carbohydrate content of < 1 wt% and which do not release any odors, flavors or dyes into an aqueous medium was investigated using various pretreated starting materials.
[0233] Test series I.An organic mass enriched with cellulose-based fibers, obtained through the extraction of soluble proteins from soy kernels and unhulled kidney beans, was used. For preparation, the kernels or unhulled beans were mechanically crushed and soaked for 4 or 8 hours in a solution of polyarginine and histidine, or lysine and polyglutamate, respectively. The organic mass, with a solids content of 40 wt% (dry matter), was suspended in water at a volume ratio of 1:10 or 1:5, followed by intensive mixing and filtration through a 100 µm sieve. The sieve residue consisted predominantly of cellulose-based fibers, but also contained significant amounts of shell material and complex organic solids (starch granules).The fiber masses were dissolved in water at a volume ratio of 1:10 and pumped through a hydrocyclone (Akavortex, nuclear power plant, Germany). The upper run was collected and filtered (50 µm screen) using a curved screen. The screen residue was analyzed.
[0234] Test series II.Thermally disintegrated plant material, in which cellulose-based fibers were still aggregated into large clumps, was used for the pulping process. The starting materials were quince, carrots, and celery, which underwent thermal treatment in a water bath at temperatures between 90° and 98°C for 1 to 3 hours and were then ground into a homogeneous mass using a stick blender. Analysis revealed aggregates larger than 2,000 µm comprising more than 15% by weight. Furthermore, a species-typical odor and taste were present. The masses were dewatered using a chamber filter press to a residual moisture content of 50–80% by weight. The masses obtained were suspended in a weight ratio of 1:5 in an aqueous solution containing a) Arginine 0.3 molar, b) Poly-Lysine, Urea 10%), c) Arginine 0.1 molar + NaSO 3 10% and the suspension was treated in an autoclave for 8 and 16 minutes at a temperature of 120°C.The digested material was filtered and rinsed twice exhaustively with water. Samples were taken from the final sieve residue for analysis.
[0235] Test series III.Mechanically disintegrated plant material with a high pigment content was digested. For this purpose, a purée of beetroot, the fiber fraction of a digestion of sunflower seed press cake with an arginine solution, and the fiber fraction of an aqueous digestion of corn grits were used. The starting materials were first dehydrated to a residual moisture content of 40 to 70%. Subsequently, the materials were suspended in aqueous solutions containing a) polyarginine, urea 5%; b) lysine 0.3 molar, SDS 2%, histidine 0.3 molar; c) arginine 0.1 molar, DMSO 2%, in a weight ratio of 1:5 to 1:10 using a hand blender. The suspensions were stirred for 24 hours at 60°C in one test series (T60) and treated in an autoclave for 8 minutes at 120°C in another test series (T120). The resulting suspensions were filtered and rinsed twice thoroughly with water. Samples were taken from the final sieve residue for analysis.
[0236] The analysis performed included the analysis of the size distribution of the cellulose-based fibers, the protein and soluble carbohydrate content (according to Example 7), investigations into the solubility of dyes (testing by immersion of the test fraction in water and aqueous surfactant solutions for 48 hours with subsequent filtration and spectroscopic analysis of the filtrate), and a sensory evaluation by 4 experts according to the criteria of Example 3. Results: Experimental Series I: The decompacted cellulose-based fibers, separable using a vortex flow technique, were practically free of visible or measurable residues of shell materials or aggregates of other components of the starting material, such as starch complexes. Furthermore, a selection of large-volume fibers was achieved, exhibiting a narrower diameter spectrum with a fiber length that was 98% < 1,000 µm and was smaller or narrower than that present in the starting material. Experimental Series II: Fiber analysis showed that the treatment resulted in the comminution and decompacting of cellulose-based fiber complexes, which exhibited a diameter spectrum significantly shifted to the left. Particles with a diameter > 2,000 µm were either absent or present in a proportion of <0.1%.Test series III: No dyes could be extracted from the masses of decompacted cellulose-based fibers obtained from either test series T60 or T120 using aqueous solutions.
[0237] The decompacted cellulose-based fibers obtained in test series I to III had a protein and / or soluble carbohydrate content of < 0.1 wt%.
[0238] All cellulose-based fiber masses obtained were found to be odorless and tasteless in sensory testing. Furthermore, all preparations were found to be very soft when chewed, to provide a pleasant mouthfeel, and to cause no unpleasant sensations when swallowed. Example 13 Study on the industrial production of baked goods from / with cellulose-based fibers.
[0239] The following products were manufactured on an industrial scale: A) chips, B) biscuits, and C) gingerbread. Production of the raw materials: A) 100 kg of decompacted cellulose-based fibers from soybean meal (produced according to Example 11 (with an arginine solution)) with a moisture content of 70% by weight are mixed with 3 kg of a seasoning mixture using an automatic kneading / stirring machine for 2 hours to form a homogeneous dough. The dough is pumped by a screw pump into a filling device, which dispenses a defined volume of the mixture into the molds of a device. After filling, the mold is sealed by a counterpart, allowing steam to pass through, so that the dough is formed into 3 mm thin discs (5 cm in diameter) within the completely enclosed mold. The entire mold plate is then heated to 140 °C for 5 minutes. The chips that fall out when the molds are opened are conveyed by a belt into an oven, where they are heated to 180 °C for 2 minutes.The cooled chips are then packaged airtight and vapor-tight in an anhydrous nitrogen atmosphere. 31 kg of chips are obtained. Visual, tactile, and sensory inspections are carried out after storage periods of 2, 6, and 12 months. The appearance remained unchanged, as did the breakability and surface texture. The consistency was rated as crisp at all times during tasting, and a pleasant mouthfeel was noted. No changes in taste characteristics occurred during storage. B) 50 kg of decompacted cellulose-based corn fibers (produced according to Example 11 V2 b)) with a residual moisture content of < 20% by weight are folded into a foam mixture consisting of 40 kg egg whites and 10 kg egg yolks, as well as 35 kg of icing sugar and flavorings that had been whipped together, along with 200 g of sodium bicarbonate.The pourable batter was poured into 30 cm diameter baking tins, 2 cm high, and baked at 180°C for 20 minutes. After cooling, the sponge cake bases were removed and packaged airtight and vapor-tight in a nitrogen atmosphere. Visual, tactile, and sensory evaluations were carried out after storage periods of 2, 6, and 12 months. The appearance remained unchanged, as did the indentation resistance and surface texture. At all time points, the consistency was described as slightly crisp, and the mouthfeel as soft and rounded. There was no change in the flavor characteristics during storage. C) 50 kg of decompacted cellulose-based kidney bean fibers (produced according to Example 12 V1) with a residual moisture content of < 25% by weight were mixed with 50 kg of ground almonds, 10 kg of chopped candied lemon and orange peel, 500 g of sodium bicarbonate, and a spice mix.The mixture was kneaded into 60 kg of a mixture made from eggs and powdered sugar. After a resting period of 2 hours, the dough was portioned and rolled out to a thickness of 1 cm on baking sheets and baked at 180°C for 20 minutes. After cooling, the baked goods were cut into pieces and packaged airtight and steam-tight. Visual, tactile, and sensory evaluations were carried out after storage periods of 2, 6, and 12 months. The appearance remained unchanged, as did the pressure resistance and surface texture. At all times, the consistency was described as tender and crisp, and a full mouthfeel was noted. No changes in appearance, pressure resistance, or flavor occurred during storage. Example 14
[0240] 50 kg of soybean meal were soaked in a mixer with 70 liters of a 0.1 molar arginine solution using a spray device and allowed to stand for 1 hour after thorough soaking. Subsequently, 70 liters of water were added, and the mixture was dewatered to a residual moisture content of 60% by weight using a filter press. The filter residue was suspended in 70 liters of a 0.5% by weight sodium sulfite solution, and the mixture was held in an autoclave at a temperature of 128°C and a pressure of 1.2 bar for 10 minutes. The mixture was then dewatered using a screen press. The screen residue was introduced into 200 liters of process water and dispersed for 10 minutes using a shear mixer (Silverson L5M-A with a fine dispersing tool / 10,000 rpm). The suspension was then centrifugally screen-filtered.The sieve residue is obtained as an odorless and tasteless creamy mass, functionalized with a nanoemulsion solution, and then dried to dryness on a belt dryer. The dried cellulose-based fibers, which were present as thin platelets, were completely hydrated in water within 3 minutes and had a soft, creamy texture. The filtrate phases combined from all steps were mixed with a 20 wt% citric acid solution, which was distributed with gentle agitation. After 6 hours, the sediment phase was drained via a bottom drain of the vessel and passed onto a belt filter with a mesh size of 80 µm. The aggregate mass was then dewatered under continuous belt feed. A creamy protein mass was obtained that was completely soluble in water, and the resulting solution passed completely through a 10 µm sieve without residue. The protein mass was odorless and tasteless.
Claims
1. Method for the disintegration and unlocking of plant starting material with the process steps a) providing a plant-based starting material, b) adding a disintegration solution comprising an aqueous solution with a pH in the range of 6.5 to 13 to the starting material and leaving it in the disintegration solution until disintegration, c) dispensing of the constituents of the disintegrated starting material in a dispensing volume to obtain solid constituents and dissolved constituents of the plant-based starting material, d) separation of solid constituents from dissolved constituents of the plant-based starting material, e) obtaining the separated constituents of the plant-based starting material as materials for further utilization by, e1) fractionating of cellulose-based fibers from lignin-rich shells of the solid constituents of the plant-based starting material by means of an cyclone separation technique to obtain purified fractions of cellulose-based fibers and lignin-rich shells, e2) aggregation / complexation of dissolved proteins of the dissolved constituents of the plant starting material by complexing agents and separation of the sedimented aggregated / complexed condensed proteins to obtain an aggregated / complexed protein mass.
2. The method according to claim 1, wherein the process step b) takes place together with a thermal and / or mechanical disintegration or a thermal and / or mechanical disintegration in a process step b1) takes place after the process step b).
3. The method according to claim 1 or 2, wherein the disintegration solution contains amino acids and / or peptides, sulfites, preferably sodium sulfite or sodium bisulfite, urea, and / or carbonates, preferably sodium carbonate or sodium hydrogen carbonate.
4. The method according to any one of claims 1 to 3, wherein a decompaction of cellulose-based fibers and / or lignin-rich shells is prepared.
5. The method according to any one of claims 1 to 4, in which the plant-based starting material is placed in a solution in which soluble compounds are present in a dissolved state for disintegration at a temperature of < 75°C, resulting in a gentle product-sparing disintegration / perforation or detachment of cladding material of plant seeds, grains or kernels, and / or for separating plant-based casing material while maintaining the structural integrity of the separated casing materials and / or the constituents of the seed(s), grains or kernels.
6. The method according to any one of claims 1 to 5 for producing of fiber products, from plant-based-cladding materials.
7. The method according to any one of claims 1 to 6, wherein in addition to a disintegration and / or separation and / or dissolution of plant cladding materials, a separation of a seedling / sprout takes place.
8. The method according to any one of claims 1 to 7, wherein it comes to slowing down / inhibiting of a ripening of plant-based seeds and / or grains.
9. The method according to any one of claims 1 to 8, wherein the plant-based starting material is cladding material of plant seeds, grains or kernels.
10. The method according to any one of claims 1 to 9, for the recovery of lignin-based cladding fractions and cellulose-based fibers and / or for obtaining a protein-containing sediment consisting of aggregated / complexed and condensed proteins.
11. Lignin-rich cladding fractions and / or cellulose-based fibers, having an oil- and / or fat-binding capacity of > 200% by weight, obtainable by a process according to any one of claims 1-10.