DE102011010329A1 - Composite material, useful e.g. as nitrogen-phosphorus-potassium fertilizer, comprises superabsorber polymer, (in)organic filler, soil additive, binding agent and solid and/or liquid fermentation residues fermented from biomass - Google Patents

Abstract

Composite material comprises (a) at least one natural and/or synthetic superabsorber polymer; (b) at least one organic and/or inorganic filler and/or soil additive preferably based on eruptive rock, organic and/or inorganic fertilizer preparation and/or organic, also present in fiber form, and/or inorganic aggregate, active ingredient and/or binding agent; and (c) solid and/or liquid fermentation residues fermented from biomass. Composite material comprises (a) at least one natural and/or synthetic superabsorber polymer; (b) at least one organic and/or inorganic filler and/or soil additive preferably based on eruptive rock, organic and/or inorganic fertilizer preparation and/or organic, also present in fiber form, and/or inorganic aggregate, active ingredient and/or binding agent; and (c) solid and/or liquid fermentation residues fermented from biomass, where (a) is from hydrogel composite, and the amount of (a) is >= 2 wt.% and at least the 5-times of its dead weight of (a) under time-dependant increase in the volume of waters and/or aqueous solutions is stored and again delivered. An independent claim is included for the preparation of the composite material comprising mixing and/or kneading the above components in an input or two-screw mixer and/or one or two-shaft plowshare mixer.

Description

Technical area

The invention encompasses water and / or aqueous solutions, including nutrient solutions, organically based composite materials which store and release the water and the aqueous solutions, comprising at least one natural and / or synthetic superabsorbent polymer (SAP) and / or at least one hydrogel composite with superabsorbent material. Properties, preferably for use, but not exclusively, as soil additives and / or fertilizers, in particular as combined nitrogen, phosphorus and potassium fertilizers (NPK fertilizer), water storage, water and nutrient supplier for growth, germination and the cultivation of plants, as Plant substrate or as a soil additive, also in admixture with soil and / or soil and / or plant substrates, to improve the soil climate and promote the formation of humus, as a carrier material for solid and liquid fertilizers, insecticides, pesticides, bactericides and fungicides and as a compost and additive for Improvement v on compost and for recultivation of semi and arid areas, dry and desert areas, also formed as compacted, compacted shaped bodies, such as pellets and / or granules and / or formed as mats with addition of organic fibers, these composite materials according to the invention produced under Use of and / or containing:
at least one hydrogel composite and fermentation residues from fermented biomass in the form of aqueous suspension (digestate slurry) and / or partially dewatered fermentation residue suspension and / or dried fermentation residue solids obtained therefrom (fermentation residues dry matter) and the biomass used for fermentation containing plant biomass and / or or manure and / or animal manure and / or kitchen and / or slaughterhouse waste and / or organic sewage sludge and the composite material according to the invention preferably fermentation residues from fermented renewable resources (NAWARO), which fall under the generic term of the so-called energy plants contains.

The inventive composite material may contain in preferred embodiments: wood ash and / or residues such as those in the thermal utilization (incineration) and / or pyrolysis of energy crops and / or ashes and / or residues such as these in the combustion / pyrolysis of early tertiary lignite (lignite ) accumulates.

In addition, structure-forming organic fillers and / or inorganic, mineral fillers and mineral active substances, preferably selected from the group of materials of quartz sands, clay, shale, sedimentary rocks, gneiss, trass, basalt, dolomite, magnesite, bentonite, natural and / or or synhthetic zeolite and / or fine, blown particles of igneous rocks, such as distended perlite and vermiculite particles.

The composite material according to the invention has, due to its composition and the formation mechanisms, harder superabsorbent properties and can also be classified as fertilizer hydrogel composite and / or compost hydrogel composite.

In addition, the invention encompasses various embodiments and compositions which make it possible to produce and apply the respectively suitable compositions of the composite material according to the invention for specific applications.

Furthermore, the invention relates to the processes for producing the composite materials according to the invention and their preferred fields of application.

Background information

The world's scarce resources of fossil fuels, such as oil, gas, coal and uranium, as well as the environmental demand and need to reduce global CO ₂ emissions for environmental and economic reasons, combined with the increasing demand for energy and basic raw materials for the synthesis of chemical Raw materials, has meant that the cultivation and utilization of biomass for direct thermal utilization as an energy carrier and the production of biogas, biofuels and synthetic raw materials in the future more and more importance. For example, the International Energy Agency (IEA) predicted a global increase in primary energy use of more than 50% between today and 2030 (INTERNATIONAL ENERGY AGENCY, PARIS 2006).

• – Die energetische Nutzung von Biomasse jeglicher Art, setzt nur soviel CO₂ frei wie bei beim Aufwuchs und/oder der Produktion gebunden wurde.
• – Nachwachsende Rohstoffe also so genannte Energiepflanzen können nachhaltig produziert werden, dies gilt auch für schnell wachsende Holzsorten.
• – Die Verwendung von nicht schnittfähigem und nicht verwertbarem

The energetic use of biomass as an energy source with preference for renewable raw materials (NAWARO) has considerable advantages:

• - The energetic use of biomass of any kind, releases only as much CO ₂ as was tied up in the growth and / or production.
• - Renewable resources, so-called energy crops can be sustainably produced, this also applies to fast-growing wood varieties.
• - The use of uncut and non-recyclable

Wood accumulation from sustainable forestry makes economic and ecological sense.

• – Energie- und Wärmegewinnung aus festen biogenen Brennstoffen vorzugsweise Holz.
• – Biogasproduktion mittels anaeroben Vergärung von beispielsweise Biomasse aus pflanzlicher Biomasse, Gülle, tierischem Kot, Küchen- und Schlachtabfällen, Abwasserschlamm usw.

The current energetic use of biomass includes:

• - Energy and heat recovery from solid biogenic fuels, preferably wood.
• - Biogas production by anaerobic digestion of, for example, biomass from vegetable biomass, manure, animal manure, kitchen and slaughterhouse waste, sewage sludge, etc.

In the future, the generation of energy through the utilization of biomass from renewable raw materials (NAWARO) and in particular the production of biogas by fermentation of plant-based biomass, which consists of so-called energy crops, such as corn, wheat, sugar beet and others, will be particularly important. a. m., also in combination with animal manure, etc., which are grown specifically for the production of biogas and are therefore in competition with the cultivation of plants for food production, since most sort-pure use of energy crops is required as biomass.

From an ecological point of view and also for reasons of economic efficiency, the expansion of the necessary acreage for the cultivation of energy crops to meet the increasing demand is very problematic and the fact that the problem of the sustainable utilization of accumulating residues, such as the fermentation residues in the production of Biogas and the comparable stillage from bioethanol production has not yet been solved, as well as the recovery of the ashes, which in the thermal utilization (combustion) of energy plants and wood in the form of or ash, fly ash, filter and Zyklonasche primarily as Oxides of calcium, magnesium, phosphorus and potassium are incurred.

At an average biogas plant with a capacity of 500 KW _(el) ³ digestate (Gärrestegülle) fall as a suspension and an aqueous solution having a solids content of about 5-8% wt .-% of a year approximately 10,000 m, depending on the composition of the Fermentation coming biomass and production technology and must be stored as so-called farm fertilizer and can be applied only conditionally.

This so-called fermentation residue contains, in addition to the plant residues, the following bioavailable, partially dissolved, plant nutrients, which are listed, for example, in the following table in comparison to unfermented cattle manure. Table 1 Comparative values of the ingredients of unfermented cow manure (Rohgüllle) to digestate based on various biomass mixtures. raw slurry digestate parameter Unit ref. Cattle manure (crude manure) Cattle manure + NAWARO Pig manure + NAWARO NAWARO 100% dry matter % of FM 9.1 7.3 5.6 7.0 acidity pH 7.3 8.3 8.3 8.3 Ratio carbon / nitrogen C / N: 10.8 6.8 5.1 6.4 Kg / t FM Kg / t FM Kg / t FM Kg / t FM nitrogen N-total 4.1 4.6 4.6 4.7 Ammonium N NH ₄ -N 1.8 2.6 3.1 2.7 phosphorus P ₂ O ₅ 1.9 2.5 3.5 1.8 potassium K ₂ O 4.1 5.3 4.2 5.0 Magenesium MgO 1.02 0.91 0.82 0.84 calcium CaO 2.3 2.2 1.6 2.1 sulfur S 0.41 0.35 0.29 0.33 Organic substance 74.3 53.3 41.4 51.0 FM = fresh mass; kg / t FM = content in kg in 1000 kg fresh mass;
NAWARO = vegetable based biomass.

The essential micronutrients such as Cu and Zn are not recorded.

Digested manure is, depending on the composition of the starting biomass and the solids content still very good pumpability but very viscous in the homogenized state and the solids in the suspension tend to float. In addition, there is an outgassing of ammonia, methane and hydrogen sulfide. However, it is lower than, for example, unfermented, unfermented bark or pig manure.

The term liquid fermentation residue liquid manure is not correct, since with it no clear demarcation is given to only partially fermented animal excrements thus excrement and urine based manure.

All fermentation residues based on biomass therefore contain considerable amounts of readily plant-available nitrogen, as well as phosphorus, potassium, sulfur and trace elements. The nutrient composition of the digestate may vary widely, depending on the substrates used. Since only small amounts of NH ₃ escape from the substrate, most of the nitrogen remains in the digestate and thus represents a high-quality organically-based fertilizer. Digestate residues are thus basically suitable as a substitute or supplement for fertilization with nitrogen-containing mineral fertilizer of the fertilizer type: NPK (nitrogen-phosphorus-potassium).

In the industrial combustion, thermal utilization of wood and energy crops falls on average, in the form of various ash fractions, a total ash amount of 0.5-0.8% wt .-% of. When burning forest wood in the form of wood chips with beef mixture average 0.8 to 1.4% and is very dependent on the combustion technology.

Resilient statistical surveys of the amount of suitable wood ash produced as fertilizer additive in Germany are currently not available but are estimated to be more than 800,000 tonnes per year, taking into account the industrial combustion of wood pellets.

The elemental content of wood ash (rust-combustion chamber fractions), averaged, statistical value from various types of useful and energy wood, is calculated in g / kg (rounded): phosphorus: 12; Potassium: 65; Calcium: 270; Magnesium: 25;

These elements are in oxide form or partially already carbonized. These wood ashes are hydrophilic and water is moistened in the pores physically on the one hand by capillary forces, but also chemically as water of hydration (hydration of oxides) stored. Scanning electron micrographs showed differently shaped inorganic particles with fine layers and porous crystalline structures.

The dry ash particles swell to rosette-like crystals by water, resulting in a volume increase of about 12%. The components of these particles were found in X-ray diffractograms as calcite, portlandite and calcium silicates. After drying, these structures are retained, resulting in a sustainable increase in water storage capacity.

The described Rostaschen are therefore due to the composition, regardless of all relevant legal requirements as Bodenhilfsstoffe and / or as a basic multi-mineral fertilizer with the type-determining mineral constituents CaO, K ₂ O, MgO and P ₂ O ₂ , wood ash can instead of dolomite used in fertilizer preparations or as dolomite substitute. Table 2 Nutrient contents and pH values of wood ash and dolomite (according to Zollner et al., 1997) in% by weight in dry matter: nutrient element wood ash dolomite calcium 15-46 30-45 Magenesium 1-2 8-22 potassium 3-4 0 phosphorus 1-2 0 PH value 10-13 8-9

From the aspect of sustainability, the reduction and improvement of CO ₂ pollution / balance and from general ecological aspects, in the future on the basis of digestate and wood ash, the agricultural areas should be returned to the agricultural areas in suitable form as effective soil improvers and / or fertilizers , Where the use in combination of digestate from biogas production is of particular importance.

On the basis of approx. 5,800 biogas plants operated in Germany at the end of 2010, with a total capacity of 2,400 MW _(el) , this results in a liquid fermentation residue accumulation of approx. 45,000,000 m ³ per year, calculated as dry matter (DM) with an average TM content of 5%, an amount of> 2,000,000 tonnes of digestate dry matter. This corresponds to an accumulation of available nitrogen for plants of> 220,000 tons per year. This could mainly replace the industrially produced nitrogen fertilizer, which is currently used in agriculture for the cultivation of energy crops for biogas production and ecologically in terms of sustainable organic agriculture is questionable.

In 2010, around 2,150,000 hectares were cultivated in the Federal Republic of Germany with renewable raw materials for energy recovery and biomass production. The average withdrawal of nutrients from the agricultural areas will be demonstrated using the example of silo and grain maize.

Over the next 5 years, an increase in acreage of up to 10% pa is expected. The return of the extracted nutrients in the soil is an indispensable requirement. Table 4 Average nutrient deprivation of silage and grain maize in kg / ha nutrient Silo maize (28% TM) 100 dt green mass Grain corn (86% TM) Grains 10 dt Straw (10 dt) Nitrogen N _-ges. 30-40 12-16 5-9 Phosphorus P ₂ O ₅ 15-25 6-11 5-7 Potassium K ₂ O 35-50 4-6 15-25 Magnesium MgO 7-13 2-3 2-4 Lime CaO 10-18 2-3 5-7 Sulfur S 3-5 - -

There are no reliable figures for the seizure from the pure combustion of untreated energy wood (fast-growing NAWARO wood species). The rough estimates currently lie for the territory of the Federal Republic of Germany at several thousand tons per year.

The future accumulation of residual fermentation residues and wood ash, which are naturally based fertilizers and therefore recyclables due to their composition and possible uses, is on the rise.

For the future expansion of the energetic use of biomass, it is necessary that the problem of processing and recycling of residual materials (secondary raw materials) such as fermentation residues and wood ashes in the material cycle ecologically sustainable and economically acceptable and thus also humus-forming substances are fed and by this recycling the arable soil the minerals and nitrogen extracted by the intensive cultivation of energy crops is available again.

Furthermore, it is necessary to find solutions and methods that will lead to a significant increase in agricultural or forest biomass production and not by genetically modified crops or by the extreme expansion of energy crops to produce biomass. An increase in yield in the education of Upper and Unteridischer biomass is objective.

Additional measures must be taken to prevent soil compaction as a result of intensification of agriculture, and the lack of harvest residues and the heavy exploitation of water and nutrients do not reduce the humus content in the soil. The degradation of humus causes considerable ecological problems. As u. a. decreasing soil fertility and erosion also due to the reduced water retention capacity of the arable soils due to the constantly deteriorating soil structure.

It will be necessary in the future to meet the increasing global demand. Biomass-based biomass-based soil improvers and fertilizers, which should also act as a long-term water storage facility, enable the cultivation of energy crops on karst and open land, in arid and semi-arid areas, and in hot climates in developing countries; so that there can be covered with renewable resources, the rising energy demand and in alternating crop rotation of energy crops and crops for the food supply on site.

The latest FNR study from 2010 on the subject of biogas and digestate ("Guideline Biogas - from extraction to use"). Published 2010. by the Fachagentur Nachwachsende Rohstoffe e. V. (FNR), OT Gülzow · Hofplatz 1 · 18276 Gülzow-Prüzen, within the framework of the project "Guidance on the production and use of biogas" produced with funding from the Federal Ministry of Food, Agriculture and Consumer Protection under the funding designation (FKZ): 22005108 summarizes the state The technology for the production of biogas based on biomass and the preparation and use of the resulting fermentation residues as fertilizers and soil improvement substrates informative together.

In that regard, in the following disclosures and references to the prior art, as far as it is not patent and intellectual property literature, reference is made to this study or reference is made.

The recovery of the so-called raft ash from the thermal utilization of wood and energy-using biomass from renewable raw materials is just beginning and has not yet reached the experimental stage beyond the experimental stage. This also applies mutatis mutandis to the unmixed pork as incurred in the combustion of early tertiary lignite, which has plant origin.

However, wood ash should be used in the future as a preferred secondary raw material and aggregate for the production of fertilizers. However, the infrastructure required for the recycling of wood ash has yet to be created by forestry and the processing industry. In addition, as with the use and use of digestate as fertilizer and / or fertilizer secondary raw materials, there are significant legal obstacles to national legislation and the fact that some of these valuable bio-based raw materials are classified as waste. Furthermore, there is a lack of feasible, inexpensive product and process technologies.

The use of wood ash as a mineral additive instead of lime, dolomite, phosphate in soil additives, contributes to the fact that the interference in the sensitive ecosystem by the intensive forestry does not lead to further brownfields.

State of the art

digestate

The prior art is supplementary and summarizing, with reference to the above (background information) and the cited study of the FNR "Guide Biogas - from extraction to use", to the part of the digestate and their recovery, processing and application:
Many proposals for the further processing and application of fermentation residues have been described in the specialist literature in recent years and are the subject of numerous patent applications and studies. In practice, however, more than 90% of the fermentation residues from biogas plants are applied unchanged to the arable land as so-called farm manure or disposed of as waste.

The return as so-called manure is, however, due to the transport and handling costs and the legal restrictions in most agricultural states on maximum quantities for the application per hectare and time limit for the application only for smaller plants up to max. 500 KW _el possible.

In addition, this requires the intermediate storage of significant amounts of liquid digestate in storage tanks with stirrers, which must be designed to ensure that no ammonia, methane or hydrogen sulfide escapes into the atmosphere.

However, this recovery and storage practice for digestate is not possible with the existing large-scale plants with some MW _el output, because for these plants, the raw materials (energy crops) come from supraregional cultivation and transport for cost and environmental reasons is not possible, as it is From an ecological point of view, it would make sense to return the nitrogen extracted from the soil and the mineral nutrients and the humus-forming components back to the agricultural areas, which were removed from them by the cultivation of energy crops. So far as the resulting digestate suspensions can not be applied unchanged as organic fertilizer, a solids separation by means of decanter, Siebschneckenpressen, Siebtrommelpressen and other mechanical processes in a liquid phase and a solid phase with a dry matter of about 20-35% wt .-% is made.

The solid phase of the fermentation residues can also be stored and applied as manure with the problem already outlined or, or as in the PCT / EP / 2006/009681 proposed to be processed in a complex process to fertilizer pellets. This requires an enormous amount of energy during the drying of the partially dewatered fermentation residues and during the subsequent pelleting and / or compaction. More than 60% of the nutrient-containing liquid fraction can not be incorporated into the pellets and must be laboriously cleaned and disposed of as waste water.

Fermentation residues from a dry matter content of about 30 wt .-% can be composted in a preferably thermophilic Nachrotte. The digestate but are u. a. usually only, due to their dense structure, for admixture with other compost varieties and there to improve the plant-available nutrient balance. The pore volume and water storage capacity of digestate compost is not very pronounced and, like peat products, it tends to become entangled with increased water supply.

It is u. a. proposed to dry the separated digestate solid and produce from it, for example in pellet form, substitute fuels. Irrespective of the fact that there is no market for such a product and the energy balance is not balanced, incineration leads to increased pollutant emissions, corrosive combustion and incineration as a disposal problem due to the massive accumulation of heavy metals like lead, cadmium.

90% or more of the total mass of the fermentation residues from the wet fermentation makes up the aqueous phase, which after the separation of the solids is partly used again as process water for the treatment of the biomass to be fermented or can serve to produce a nutrient concentrate. In addition, for the processing and / or utilization of the separated liquid digestate fraction according to the prior art, inter alia, proposed and partially already implemented: Table 3 Shows examples / processing techniques of the treatment of liquid fermentation residue fractions in keywords technology process objectives Description Notes Aerobic-thermophilic post-treatment Germ reduction; Stripping ammonia, reducing odor emissions; Pre-separation of solids, min. 3% dissolved organ. Dry matter required, Ammonia stripping air stripping (pH> 1 1 steam stripping (T = 100 ° C) Removing the nitrogen load; Production of liquid or solid nitrogen fertilizer; Pre-separation of solids, at least 3% dissolved organ. Dry substance, carried out with air or steam; phosphate precipitation Production of phosphate fertilizer Proven method Evaporation of water Extraction of nutrient concentrate; Generation of a clean condensate; Pre-separation of all solids required, vacuum evaporation allows high performance; Reverse osmosis membrane method Production of nutrient concentrate and pure permeate; Tight temperature window and only partially suitable for practical use; simultaneous precipitation Precipitation of N, P, K from the aqueous fraction Elaborate procedure

The overview acc. Table 3 is not exhaustive and is not a detailed description of the product and process.

In the not yet published PCT / DE / 2010/00840 It is proposed and claimed that a composite material preferably compost, obtained from digestate and / or manure, is added. The addition, however, refers exclusively to compost on the basis of digestate and manure so on digestate and manure, which were subjected to a secondary fermentation again.

In summary, however, it can be stated with respect to the known state of the art with regard to workup, application, products and process technologies that all product proposals and processes in the implementation are very complicated and have not prevailed and the digestates are still predominantly applied as manure or deposited as waste and the separated liquid fraction, as far as it is not also applied as manure, is disposed of to a large extent as waste water after appropriate pretreatment.

The justified ecological demand for a sustainability and a material cycle in the cultivation and the utilization of energy crops and biomass by the return of the valuable residues is not fulfilled so far. The problem of an agargerechten but also cost-effective processing / recycling of the residues has not been satisfactorily resolved. This also applies to the utilization of fermentation residues from the so-called dry fermentations, which ultimately also result in fermentation residues whose water content is still> 50% by weight. In that regard, the term dry fermentation process is misleading or incorrect.

Wood and vegetable ash

The problem and the state of the art in the recovery and processing of wood ash, which is given in the thermal utilization of wood and energy crops, is analogous. The largest part of the resulting wood ash is disposed of as waste in landfills and is no longer in the recycled ecological cycle. Valuable minerals are irretrievably withdrawn from arable land and forest areas and are no longer returned.

In addition to the very limited direct application, for example in the field of forestry, as part of the so-called forest fertilization or forest liming, wood ashes to improve the Mineral content of compost, added to this or mixed in fertilizer preparations and / or in mineral soil additives. Also as a mineral supplement to culture and planting soil substrates and compost wood ashes are used to a very limited extent.

The handling of the very fine and dusty ash fractions in the direct application as fertilizer or soil additive is problematic. In addition, the strong alkalinity of the wood ashes, which additionally greatly affects the handling of the given irritant and corrosive effects on the skin and in the eyes.

There are known products and processes that the wood ashes are converted into granules and / or pellets by the conventional and conventional methods with water and binder and compacted or roller compacted and then granulated. As an example reference is made to the DE 10 2006 019 939 B4 , It is proposed to use a combination of ashes of wood and bark as a soil conditioner and / or fertilizer. In the published patent application DE 10330713 A1 It is proposed that the minerals contained in the wood ash be extracted with water and made from fertilizers. The supply of available nitrogen for plants and other plant nutrients should be made by separate addition of these substances.

All these on wood ash and / or bark ash and vegetable ash based products but has in common that the manufacturing process are very complex and therefore expensive and soil additives and / or fertilizers, which consist mainly of wood ash, in the agriculture and forestry not universally as a soil additive and / or whole fertilizer can be used. In addition, the soil structure is not substantially improved by the sole incorporation of these wood ash products and the formation of humus is not promoted.

In the not yet published PCT / DE / 2010/00840 It is proposed and claimed that also wood-grate ash in particulate form similar in structure to finely-milled expanded perlite particles are added to a composite material.

Superabsorbents, polymeric hydrogel composites and hybrid materials

According to the prior art, it is known that superabsorbent polymers (SAP), preferably in the form of sodium polyacrylate and potassium polyacrylate, are capable of stably binding large quantities of human urine and / or blood and wound secretions to form hydrogels so that they may be used as stable gel mass can be disposed of. The use as a water-saving additive in the agricultural sector is also known and the subject of many publications and relevant industrial property rights and protective rights. The disadvantages of using these superabsorbent polymers (SAP) as soil additives are described in detail in the PCT / DE 2009000943 treated.

In the already cited PCT / DE 2009000943 the composition, structure and application of hydrogel composites are disclosed and the treatment of odorous liquids. However, the invention claimed implementation of fermentation residues from fermented biomass with hydrogel composites to a composite material with independent properties and applications, however, is not the subject of this invention. This also applies to the in the EP 1879932 B described superabsorbent, which are formed as polymeric hybrid materials and the claimed applications.

invention task

The invention task is, with reference to claim 1, and to the descriptive part of this claim and with reference to the subclaims 2 to 25, the task of finding methods and products that make it possible using fermented digestate, of various origin and composition, even with the addition of wood ash and other additives, to produce them by means of a simple mixing, kneading and Homnogenisierungstechnik, which are by their composition, properties and applications, overcome the disadvantages of the prior art and inexpensive to produce. In addition, reference is made to the statements in accordance with. The Background Information section in this description.

The products according to the invention, ie the composite materials, preferably in the form of fertilizer preparations, are, with explicit reference and inclusion in the applications according to claim 25, preferably the functions and properties of a water and nutrients storing and this again releasing soil optimizer (soil adjuvant) and a Complete fertilizer and / or Identify fertilizer preparations for universal use in the agricultural sector and are to return the soil, the organic and mineral nutrients extracted from intensive cultivation, back into plant-available form, in particular the nitrogen extracted from the soil.

The object of the invention explicitly includes the requirement that by the inventive composite and fertilizer preparation using digestate optionally with the addition of other organic and / or inorganic additives, preferably wood ashes of different compositions, in the presence of water in the total mass, tailor-made soil additives and / or Fertilizers can be built and these products are able to promote the above and below ground growth of a variety of plants and / or increase the formation of total biomass and / or to increase the yield of fruit crops.

In addition, the humus formation should be promoted and prevent nitrification and the leaching of nutrients in the soil and volatile nitrogen compounds in the composite material be bound and also these composite and fertilizer preparations should loosen up the soil structure and be attached to the earth crumbs.

The Kompositmaterilaien invention must ensure that contained in the digestate nutrients and minerals, particularly the nitrogen compounds are fixed so that they are available to the plants but there are no output losses at the expense of existing nitrogen loading by NH ₃ emissions, which at brin supply off of Digestate and manure with NH ₄ -N can be between 40-50% and of the total N between 25-30%.

The composite and fertilizer preparations are also intended to serve as a long-term water storage and nutrient storage, so save water and aqueous solutions and give it back and this effect should be achieved by the fact that the composite and fertilizer preparation containing hydrogels forming natural and / or synthetic superabsorbent polymers, as these known to the Increased training of above- and below-ground biomass positively influence. The effect of underground and aboveground biomass increase is thereby to be increased.

This effect has already been described in many studies and proven in field and greenhouse plantings and is the subject of the theory of the invention PCT / EP / 2009/061804 and PCT / EP / 2009/061909 , The exact mechanisms of action have not yet been completely clarified.

In addition, the preparation of the hydrogel is to be made by a simple and inexpensive technology, so that it is economically acceptable even for smaller, agriculturally operated biogas plants.

In the absence of a uniform nomenclature throughout the literature and for a better understanding and delimitation of the teaching of the invention to the prior art, the material designations and definitions: superabsorbent, SAP, hydrogel composite and polymeric hybrid material will be explained below.

According to the theory of the invention, superabsorbents, superabsorber polymers or, as is commonly used in the specialist literature, in short form SAP, all crosslinked and / or partially crosslinked natural and / or synthetic polymers which are capable of producing large amounts of water under time-dependent volume increase. or aqueous solutions, to receive a hydrogel and retain under pressure. The water storage capacity can be up to 1000 times the weight of the SAP.

Because of these characteristics, these SAPs are mainly used in sanitary articles such as baby diapers, incontinence products or sanitary napkins and in recent years as a long-term water storage in the agricultural sector and for the production of water-storing and releasing soil additives and soil optimizers in agriculture and forestry, horticulture etc.

Typical SAP (superabsorbent polymers) are, for example, the potassium and sodium salts of partially or neutralized and crosslinked polymers based on polyacrylic acid or the SAP based on acrylamide and acrylic acid as co- and / or graft polymers. The substance group of superabsorbents (SAP) are also so-called SAP hybrid materials in which organic and / or inorganic fillers were incorporated into the polymer matrix in the polymerization and bound therein, such as for example in the PCT / EP / 2006/009681 Although these are often referred to as pure hydrogel composite (HGK) for purposes of differentiation from pure SAP. According to the teaching of the invention, these hybrid polymeric materials can be assigned to the hydrogel composites due to comparable product composition.

A hydrogel composite (HGK) is therefore according to generally accepted technical understanding, a homogeneous preparation of at least one synthetic and / or natural SAP with inorganic and / or organic, preferably mineral fillers, carriers, and active substances incorporated in the polymer matrix are and / or in which the SAP particles are completely or partially enveloped by these or bound to them and the SAP is present at least partially in hydrogel form in the composite material. Typical designs, properties, production and application of special hydrogel composites (HGK) are, for example, in US Pat PCT / DE2009 / 000943 and PCT DE / 2010/000840 described.

MOF

The following describes the structure and properties of MOFs (Metal Organic Frameworks), which in a further development of the invention serve as additional water storage and storage medium for volatile gas constituents, such as ammonia , Methane and hydrogen sulfide in the material composites of the invention find use.

MOFs are extremely microporous crystalline materials composed of metal nodes, the so-called SBUs (Structural Building Units) and organic molecules (linkers), as connecting elements between the nodes. One-, two- and three-dimensional networks can be formed. Preferably, MOFs with three-dimensional networks are used because of their pore structure for the production of the material composites according to the invention. For possible applications as a storage medium, the large inner surface (up to more than 4500 m ² / g) is important. The pore size can be precisely determined by the size of the organic ligands, so that only molecules of a certain size fit into it.

In contrast to zeolites, ie inorganic crystals with pores of similar size, MOFs are less temperature resistant, however, the potential variety of tailored MOFs over the zeolites is of considerable advantage and also their lower mass density is of considerable advantage for the use according to the invention.

Presentation of the invention

It has now surprisingly, with reference to claim 1, found that by implementing preferably hydrous digestate with at least one hydrogel composite (HGK) by a simple mixing and kneading process, the object of the invention is fully and inexpensively solved.

The claims 2 to 21 disclose further advantageous and claimed embodiments of the invention.

This result was surprising, because it is known that the addition of pure superabsorbent polymers (SAP) leads to binding of the water content contained in the digestate by hydrogel formation but results in this implementation process a greasy, mud-like and very homogeneous mass, which is not for the Use as a soil additive and / or fertilizer with long-term water storage properties is suitable and leads in the claimed invention claimed applications to an undesirable or to a counterproductive soil compaction.

For the preparation of the composite materials according to the invention both liquid digestate suspensions with, for example, a solids content of 3 to 15 wt .-% and / or the separated aqueous, digestate fraction from which the undissolved solids were removed and this aqueous fraction in the form of a partially dewatered concentrate and / or partially dewatered and / or dried fermentation residues are used and / or appropriate blends.

The desired properties and nutrient composition of the material composites according to the invention can be determined by the selection of the fermentation residues based on their origin, nature and ingredients.

For example, it is possible to use the fermentation residues that result from the fermentation of biomass with the main constituent of corn to produce material composites with the specific nutrients that has ultimately removed this plant from the ground.

It was surprising and not to be expected that in the PCT / DE2009 / 000943 and PCT / DE / 2010/000840 described hydrogel Komoposite are basically suitable for the preparation of the composite materials according to the invention on the basis of digestate and / or composted digestate. This also applies to the superabsorbent which are formed as hybrid materials as in the EP 1879932 B disclosed.

Furthermore, it has been found that formation of the hydrogel composite (HGK) with the production technique according to the invention can be carried out in one work step and / or the material composite according to the invention is formed overall as a hydrogel composite.

It has also been shown that a subsequent anaerobic composting of digestate, which were previously implemented to a composite material according to the invention, leads to a significant improvement in the compost quality and abbreviates the decomposition process and it allows the water balance and the temperature control in the rump to positively influence. This is especially important in thermophilic composting and sanitization. The hydrogel composites contained act as a heat storage and not only as a water reservoir. With regard to the mechanism of action, reference is made to the teaching of PCT / EP / 72010/060 277 , which is also applicable to hydrogel composites.

The material composites of the invention advantageously permit a sustainable and cost-effective use of the digestate obtained in biogas plants and in other fermentation plants, as well as the use of the secondary raw material wood ash as a mineral nutrient supplement. The material composite prepared and put together according to the invention releases the nutrients contained after the application advantageously slower than corresponding unprocessed discharged fermentation residues, so that advantageously reduces the over-fertilization of fields and the entry of nutrients, in particular nitrides, nitrates and phosphates in the groundwater becomes. The integrated Langzeitwasserspeicher- and discharge capacity has a positive effect because it provides the plant roots sustainably with water and dissolved nutrients, even in periods of drought, but also prevents that with above-average water intake, or by continuous rain, the stored nutrients are washed out.

It was surprising that during the fertilization with the material composites according to the invention in a wide variety of crops in comparison to the use of pure digestate as farmyard fertilizer, significant yield increases were recorded and the formation of the underground and above-ground biomass was increased. This also compared to the yield increases that were achieved only by the application of SAP.

Subsequent examples of use and implementation can only begin to show the diverse compositions of the composite materials according to the invention and their application and possible uses as a fertilizer preparation and must inevitably be limited to a few examples because of the required traceability of the theory of the invention.

The properties and advantages of the embodiments of the composite materials according to the invention are correspondingly assigned and commented on.

It should be noted that the selected compositions of the composite materials according to the invention are not aligned according to the provisions of the fertilizer and waste legislation in Germany and the EU and also not plant physiological requirements, because it is apparent from the entire teaching of the invention that the modular system a corresponding Adaptation by selection and combination of all primary and secondary raw materials is possible.

• – es muß mindestens in der Gesamtmasse des Material-Komposits ein Anteil an SAP von > 2 Gew-% enthalten sein,
• – soweit Hybridmaterial als SAP bzw. Hydrogel-Komposit zum Einsatz kommt, muss der Anteil der einpolymerisierten Füllstoffe mindestes 10 Gew-% betragen und der Anteil der Polymermatrix in der Gesamtmasse des zugesezten Hybridmaterials bei mindestens 10 Gew-% liegen, so dass eine optimale Ausbildung des Kompositmaterials erfolgt,
• – die Partikelgröße von SAP der im Kompositmaterial und/oder in dem darin ausgebildeten und/oder enthaltenen Hydrogel-Komposit muss < 1000 my, vorzugsweise < 500 my und besonders bevorzugt < 200 my sein, dadurch wird das Wasserspeicher- und Abgabevermögen wesentlich erhöht und auch Feinstteilchen gebunden.
• – das zeitabhängige Wasseraufnahme- und Abgabevermögen des Kompositmaterials muss mindestens dem 5-Fachen des Eigengewichtes entprechen um die Pflanzenwurzel ausreichend mit Wasser und wasserlöslichen gespeicherten Nährstoffen versorgen zu können und ausreichend überschüssiges Wasser aufgrund starken Regenfällen und/oder Überwässerung schnell zu speichern und um dadurch auch den Einsatz in heißen Klimazonen und semi-ariden und ariden Gebieten zu ermöglichen.

It has been found in addition and must be explicitly stated and stated that the following must be ensured for optimum design of the material composites of the invention:

• It must contain at least in the total mass of the material composite a proportion of SAP of> 2% by weight,
• - As far as hybrid material is used as SAP or hydrogel composite, the proportion of polymerized fillers must be at least 10% by weight and the proportion of the polymer matrix in the total mass of the zugssezten hybrid material at least 10% by weight, so that an optimal training the composite material takes place,
• The particle size of SAP in the composite material and / or in the hydrogel composite formed and / or contained therein must be <1000 my, preferably <500 my and more preferably <200 my, as a result the water storage and release capacity is substantially increased and also Very fine particles bound.
• - The time-dependent water absorption and release capacity of the composite material must be at least 5 times its own weight to be able to provide the plant root sufficiently with water and water-soluble stored nutrients and quickly store enough excess water due to heavy rainfall and / or overhydration and thereby also the To enable use in hot climates and semi-arid and arid areas.

embodiments

Unless otherwise stated, the secondary raw materials digestate and wood ash are defined as follows and provided with a type designation which is correspondingly listed in the exemplary embodiments. Table 5 Garreste suspension from biogas plant - Type: GSA Biomass: Maize and Co. 10% admixture of cattle slurry Form: viscous aqueous suspension / solution as obtained from fermenter TM% of FM (suspension) pH N _ges Kg / t FM NH ₄ -N Kg / t FM P ₂ O ₅ Kg / t FM K ₂ O Kg / t FM MgO Kg / t FM CaO Kg / t FM S Kg / t FM 7.1 8.3 4.6 2.7 1.7 4.8 0.8 2.0 nb TM = dry matter; FM = fresh mass; t = 1000 kg Table 6 Digested liquid phase (filtrate) Type: GSAF recovered from Type: GSA Form: FM = aqueous solution / suspension with fine suspended solids TM% of FM (suspension) pH N _ges Kg / t FM NH ₄ -N Kg / t FM P ₂ O ₅ Kg / t FM K ₂ O Kg / t FM MgO Kg / t FM CaO Kg / t FM S Kg / t FM 4.61 8.2 4.00 2.48 1.29 4.32 0.59 1.58 nb TM = dry matter; FM = fresh mass; t = 1000 kg. Table 7 Digested solids phase Type: GSA35 recovered from Type: GSA Form: FM = at 35% by weight TM / solids from digestate Type: SLA TM% of FM (Suspen sion) pH N _ges Kg / t FM NH ₄ -N Kg / t FM P ₂ O ₅ Kg / t FM K ₂ O Kg / t FM MgO Kg / t FM CaO Kg / t FM S Kg / t FM 35 8.2 0.60 0.22 0.41 0.48 0.21 0.42 nb TM = dry matter; FM = fresh mass; t = 1000 kg

The contents and active substances declared in the fermentation residue fractions are subject to analytical parameters from individual determinations and fluctuations caused by the raw material, which inevitably result from the biological processes.

Compositions of SAP (superabsorbent polymer) and hydrogel composites

Super Absorbent Polymer (SAP) Type: 200

• Polymer agent for hydrogel composites
• Chemical Structure: Modified crosslinked copolymer acrylamide / acrylic acid, potassium salt;
• Grain size: <200 microns
• Potassium content: 5 calculated as K ₂ O wt .-% in
• Nitrogen content: 13 calculated as carbamide backbone
• Classification: SAP type 200 is classified as NK fertilizer (13 + 5) with long-term effect. (Supplier: E & W GreenLand International GmbH, 13599 Berlin)

Super Absorbent Polymer (SAP) Type: 1280

• Polymer agent for hydrogel composites
• Chemical Structure: Modified Crosslinked Acrylic Acid Polymer, Potassium Salt;
• Grain size: <850 microns
• Potassium content: 7.5 calculated as K ₂ O in% by weight
• Nitrogen content: not applicable
• (Supplier: E & W GreenLand International GmbH, 13599 Berlin)

Hydrogel composite (HGK) Geoplant type: 50/80 Shape: fine granules

Composition in% by weight:

• SAP Type 1280 (mod.): 50
• Lava stone flour: 20
• Perlite particles, puffed: 20
• Water: 10
• (Manufacturer: E & W GreenLand International GmbH, 13599 Berlin)

Hydrogel composite (HGK) Geoplant type: 50/50 Shape: fine granules

Composition in% by weight:

• SAP Type 200 (mod.): 50
• Lava stone flour: 20
• Perlite particles, puffed: 20
• Water: 10
• (Manufacturer: E & W GreenLand International GmbH, 13599 Berlin)

Wood ash type: MH1

• Shape: porous coarse ash / fine ash mixture with a bulk density of approx. 300 g / liter
• Typing: mixed firewood mix of mixed forest wood
• Standardized as: Basic compound fertilizer

Type-determining ingredients (minimum contents indicated as oxides): CaO 35% K ₂ O 6% MgO 3% P ₂ O ₅ 2%

The elements Ca, K, Mg present as a mixture of oxides and carbonates and P in oxidic, carbonate or silicate bond.

In the case of the following exemplary embodiments, only the value: N _ges (total nitrogen) was deliberately used in the nutrient calculation of the composite materials according to the invention, since the nitrogen content from the nitrogen enrichment in the composite materials by the SAP polymers (copolymers) based on acrylic acid / acrylamide did not occur until the time-dependent biodegradation of the polymers is available. Trace elements and mineral nutrients from the lava powder are not covered. Not even the content of silicates. Example 1 - Composite material composition in wt .-% and Kg - batch size 1000 kg No. Material / Raw Material Designations Type Proportion% by weight Share in kg Corr. Dry mass (TM) in kg 1 digestate GSA 70 700 50 (ger ^1. ) 2 Perlite particles, inflated <500 my 15 150 150 3 Hydrogel composite (HGK) SAP polymer content: 50% by weight 50/50 15 150 135 4 buzz 100 1000 335 (ger ^1. ) = rounded
Preparation: 2 and 3 were premixed in a two-shaft vacuum ploughshare mixer (with integrated rotary chopper knife) and then the homogenized (stirred) digestate suspension was added at a temperature of 20 ° C and mixed in and at a temperature of about 30 ° C. The material composite under vacuum and with running mixer withdrawn 330 kg of water.

Key figures finished product

• Dry matter (TM) in% by weight: 50 (ger.)
• Water content in weight%: 50 (ger.)
• Shape and consistency: free-flowing, earth-like structure
• Odor: earthy, moist - without smelly ammonia perception
• Color: brown
• Water storage capacity: 15 times its own weight under time-dependent volume increase.

Nutrient indicators kg in 1000 kg composite material - Example 1: N _tot P ₂ O ₅ K ₂ O MgO CaO 4.8 1.8 10.1 0.84 2.09

The determined nutrient key figures are for experimental purposes only reference values. The analytical methods must be partially revised and adapted.

The composite material can be stored and applied in this form as a soil additive and fertilizer without loss of nitrogen and is also ideal as an additive to compost and soil and Kukultursubstraten to improve their nutrient balance, Strukrur and the water storage capacity.

After further dehydration, brought to a water content between 10-15 wt .-%, by gently circulating air drying, the composite material can be converted with all conventional Kompaktierungsverfahren to pellets and / or granules. It was surprising that the composite material according to the invention can be dried very rapidly at about 35 ° C. to 50 ° C. even at low temperatures in the circulating air dryer.

Whereby it can not be entirely avoided that small amounts of ammonia escape, which must be extracted.

In an advantageous development of the invention, natural and / or synthetic zeolites are therefore added with reference to claim 3, so that the volatile components of ammonia are incorporated and fixed in the pores of the zeolites. It has proven to be particularly advantageous that mixtures of zeolites with different pore sizes are used, so that on the one hand the ammonia dissolved in water is stored and on the other hand also forming gaseous formative cleavages are bound. Depending on the addition amount is additionally achieved, especially when activated, which means anhydrous zeolites, are used, that in addition water is bound, so that can be completely or partially dispensed with a post-drying of the wet material composites of the invention. The zeolites can be introduced directly and / or as part of the added hydrogel composites.

For a further advantageous embodiment of the invention was found with reference to claim 9, that the addition of special MOFs (metal organic framworks) alone and / or in combination with zeolites, MOFs (metal organic framworks) brings improved results, since the extremely large Surface and pore capacity only very small aggregate quantities with very large storage capacity requires.

Particular preference is given, for example, to the use of MOFs for storing and fixing the nitrogen load in the production of inventive material composites in which, for example, the aqueous filtrates, sugates according to the digestate type GSAF are used. This applies in particular if they are concentrated in a preliminary stage by dehydration.

The nutrients stored in the MOFs are not washed out in the soil, but are available to the plants over a long period of time and serve as additional water storage. Example 2 - Composite material Composition in wt .-% and Kg - batch size 1000 kg No. Material / Raw Material Designations Type Share weight% Share in kg Corr. Dry matter (TM) in kg 1 digestate GSA 35 58 580 203 2 wood ash MH1 18 180 180 3 Hydrogel composite (HGK) SAP polymer content: 50% by weight 50/50 24 240 216 4 buzz 100 1000 600 (ger ^1. ) (ger ^1. ) = rounded
Preparation: 1, 2 and 3 were in a two-shaft vacuum plow Scharmischer (with integrated rotary chopper knife) 3 min. intimately mixed and then the crumbly Matrialkomposit, which was structured similar to compost, discharged.

Key figures finished product

• Dry matter (TM) in wt.%: 60
• Water content in wt.%: 40
• Shape and consistency: pourable, compost-like structure
• Odor: earthy, moist - without smelly ammonia perception
• Color: brown
• Water storage capacity: 18 times its own weight under time-dependent volume increase.

Nutrient indicators kg in 1000 kg composite material - Example 2: N _ges P ₂ O ₅ K ₂ O MgO CaO 6.6 3.8 9.0 5.52 63.2

The material composite is very homogeneous, capable of sprinkling and discharging with the usual agricultural equipment and machinery. It can be stored in this form in silos or bagged or processed as described in Example 1 on. But it is also ideal for further implementation by means of anaerobic Nachrotte for the production of quality compost.

A further advantageous embodiment of the Matrialkomposite invention is achieved daduch that at least 5 wt .-% of fermented residues, preferably from digestate-based compost is added.

The wood ash used in Example 2 can be in the composite material of the invention also completely and / or partially by plant ash and / or ash (combustion chamber ash) from the thermal utilization (incineration) of early tertiary lignite (lignite) obtained replaces.

A further improvement of the structural properties of the material composite according to the invention is achieved by adding lignite-xylitol fibers which serve to improve the soil structure in the long term. This is because these fibers rot only very slowly and also promote humus formation in the soil through their humic constituents. This effect can be significantly enhanced if finely ground lignite xylitol and / or early tartar brown coal (soft lignite) are incorporated into the composite material according to the invention. These additions also significantly improve the C / N ratio in the composite material.

To improve the structure, the composite materials CFP (Coir Fiber Pith) with a proportion of> 4 wt .-% is added in a further inventive design.

CFP is a renewable secondary raw material that accumulates millions of tonnes of waste per year in the production of coconut fibers and has a cork-like but open-cell, highly porous structure and a high water and discharge capacity. The lignin content in CFP can be up to 40% by weight and, since it is very difficult to degrade over a period of 4-5 years by the white and brown rot fungi, in particular by P.ostereatus, the long-term action as soil improver is ensured. The cellulose and hemicellulose fractions contained in CFP degrade faster and also improve the C / N ratio in the composite material according to the invention. Example 3 - Composite material composition in wt .-% and Kg - batch size 1000 kg No. Material / raw material designations Type Proportion% by weight Share in kg Corr. Dry mass (TM) in kg 1 digestate GSA 45 450 32 (ger ^1. ) 2 Nat. Zeolites, activated clinoptolite 5 50 50 3 Hydrogel composite (HGK) SAP polymer content: 50% by weight 50/50 50 500 450 4 buzz 100 1000 532 (ger ^1. ) = rounded
Production: 2 and 3 were in a two-shaft ploughshare mixer (with integrated rotary chopper knife) 2 min. intimately mixed and is about a liquid dosage with the mixer running within 2 min. added and then again 1 min. remixed. Thereafter, the formed as a flowable fine granules material composite discharged, stored in the silo and then filled into bags or other containers.

Key figures finished product

• Dry matter (TM) in wt.%: 53.2
• Water content in wt.%: 46.8
• Shape and consistency: free-flowing, not moist, fine-grained fine granules
• Odor: earthy, moist - without smelly ammonia perception
• Color: gray-brown
• Water storage capacity: 35 times its own weight under time-dependent volume increase.

Nutrient indices in kg per 1000 kg of composite material - Example 3: N _ges P ₂ O ₅ K ₂ O MgO CaO 14.45 0.8 11.25 0.36 0.9

This composite material (Example 3) is suitable as a soil additive and long-term water storage with fertilizing effect primarily for use in garden and Lanschaftsbau and for use in hobby gardeners. Of course, concentrated fermentation residue filtrate (Sugat) can also be used for this composition according to the invention of the material composite if the nutrient content is to be increased. The composite material has an earth-like structure and can therefore easily be homogeneously mixed under all plant soil, plant and culture substrates and immediately attaches to the earth crumbs and / or substrate particles.

It has been found that a further advantageous embodiment of the composite material according to the invention is achieved by adding thereto at least 2%, calculated as dry matter, of magnesium, and / or calcium lignosulfonate, which is then present as complex of the type "lignin-based alkali hydroxide" and completely and / or partially carbonated by the action of CO ₂ . The addition of lingosulfonate from sugar-containing and / or fully and / or partially desugared lingosulfonate waste liquor from the pulp industry acts as a binder in the material composite, in particular in the compositions which, after drying, are compacted to pellets and / or granules to a residual moisture content of <20% by weight / or be formed. Example 4 - Composite material composition in wt .-% and kg batch size 1000 kg No. Material / raw material designations Type Proportion% by weight Share in kg Corr. Dry mass (TM) in kg 1 digestate GSA 40 400 28.5 (ger ^1. ) 2 Perlite particles, inflated <150 my 5 50 50 3 SAP hybrid material ² SAP polymer fraction: about 23% by weight lava rock flour / silicates and others about 29% by weight water: 48% GH ³ 55 550 286 4 buzz 100 1000 361.5 (ger ^1. ) = rounded
SAP hybrid material ² control values from inception control declared by the manufacturer as partially neutralized polyacrylic acid, rock powder and water; GH ³ = SAP hybrid material of the brand GEOHUMUS accordingly EP 18799328
Note: The hybrid material GH ² has an open-pored, sponge-like structure and the particle size is 2-5 mm.
Manufacturer: Geohumus International GmbH, 60388 Frankfurt a. M.
Preparation: 2 and 3 were mixed in a single-shaft rotary compulsory mixer and then fed by volumetric metering a screw mixer and under pressure and kneading at a Temperature of about 25 ° C converted to the composite material. This composite material of rubber-like, plastic consistency was then discharged through a perforated disc with a rotating knife set in the form of extruded granules with a diameter of 3 mm and a length of about 4-5 mm.

Key figures finished product

• Dry matter (by weight) in% by weight: 36.1
• Water content in wt.%: 63.9
• Shape and consistency: elastic strand granules, slightly sticky
• Odor: earthy, moist - without smelly ammonia perception
• Color: gray-brown
• Water storage capacity: 25 times its own weight under time-dependent volume increase.

Nutrient indicators kg in 1000 kg composite material - Example 4: N _ges P ₂ O ₅ K ₂ O MgO CaO 1.8 0.7 3.55 0.32 0.80

The material composite according to this composition, as far as a direct discharge in the agricultural sector is to take place, must be dried to a residual moisture content of about 40% by weight. After this drying, the very porous Matrialkomposit can then be applied agrargerecht with all conventional mechanical Austragungsvorrichtungen for mineral fertilizers.

This embodiment of the material composite according to the invention is ideally suited for mixing and for use in combination with separated fermentation residues with a dry matter from 30% by weight, which is to be applied as a homogeneous, free-flowing mixture, such as farm fertilizer.

It has been shown that an immediately ausbringungsfähiges Matrialkomposit gem. Example 4 is possible if SAP hybrid materials with a water content <20 wt .-% are used.

It has been found in a development of the invention that, for example, the composite material gem. Embodiment 4 is suitable for the production of flat mats which can be produced for example by means of calenders. For solidification of the sheet-like structure, the material composite naturally based fibers, such as coconut fibers, xylilt fiber, cellulose fiber u. a. m., Are added.

A further advantageous development of the invention with regard to composition and production is achieved in that burnt lime (calcium oxide) and / or calcined dolomite (calcium-magnesium oxide) and / or dolomite half burned and / or in the preparation by means of a screw mixer, as described for example in Example 4 non-carbonated wood and / or plant ash is submitted, which then binds by the hydroxide formation with the aqueous constituents of the digestate water and this beyond the stoichiometric ratio by physical water binding in the total mass.

The alkaline earth hydroxides are then converted to the corresponding carbonates by the action of CO ₂ . The resulting water is stored or partially escapes.

The exothermic process according to the conversion equation using the example of CaO: CaO + H ₂ O = Ca (OH) ₂ + 15.2 Cal. Although it leads to an increase in temperature during the mixing process, which can drive out, inter alia, ammonia, unless it is largely bound by the inventive addition of MOFs and / or zeolites. As a result of the addition of the alkaline earth metal oxides according to the invention it is thus possible to produce largely surface-dry, earth-like, compact composite materials which can be used as water-storing, strongly basic mineral fertilizers.

By the addition of lignosulfonate compounds and their implementation gem. Claims 20 and 21, the dissolving power of the nutrients and minerals contained in the composite material according to the invention be influenced and also the water storage and discharge capacity. It is in this context on the DE Laid-Open 25 43 169 directed.

 Example 5 - Composite material

For the construction of an earth-moist fine granules, which is to be used as a basic soil conditioner for so-called forest fertilization with a good water storage and dispensing capacity, the composition is gem. Example 3 constructed as follows and acc. Example 3 prepared. Instead of the digestate type GSAF, an up-concentrated filtrate with a dry mass of, for example, 10% by weight and more can also be used.
Composition in wt .-% and Kg - batch size 1000 kg No. Material / raw material designations Type Proportion% by weight Share in kg Corr. Dry mass (TM) in kg 1 digestate GSAF 36 360 16.6 (ger ^1. ) 2 wood ash MH1 26 260 260 3 Hydrogel composite (HGK) SAP polymer content: 50% by weight 5080 38 380 342 4 buzz 100 1000 618.6 (ger ^1. ) = rounded

Key figures finished product

• Dry weight (DM) in weight%: 62 (ger.)
• Water content in wt .-%: 38 (ger.)
• Shape and consistency: earth-moist fine granules
• Odor: earthy, moist - without smelly ammonia perception
• Color: light gray - brownish
• Water storage capacity: 35 times its own weight under time-dependent volume increase.

Nutrient data kg in 1000 kg composite matrix - Example 5: N _ges P ₂ O ₅ K ₂ O MgO CaO 1.44 5.7 28.4 8.0 91.6

The product condition similar to the composite material acc. Embodiment 3 with reduced nitrogen content.

According to claim 5, the composite material can also be formed overall as a hydrogel composite, which is understood in the teaching of the invention that, for example, all dry ingredients with reference to claim 1 and the subsequent claims, including the SAP shares, for the composite material to be formed, if necessary Also, dried fermentation residues, without the addition of water and / or water-containing digestate, are intimately mixed and then the water-containing digestate and possibly additional process water is added to this mixture, so that there is an overall formation of the composite material as a stable homogeneous, uniformly structured Hydrogel composite comes.

The implementation of fermentation residues by adding already formed hydrogel-rich hydrogel composites to a uniform "total hydrogel composite" is fluid and there are some hybrids before. The mechanisms of action are not yet fully understood.

The inventively claimed formation of the composite material as NPK fertilizer, according to claim 19, is achieved in that as an effective SAP in HGK, inter alia, an SAP copolymer used which is typified by NK fertilizers and enriched by the nitrogen loads and mineral constituents contained in the fermentation residues, thus enabling the production of a wide variety of NPK fertilizers with long-term water storage properties. The possibly required additional mineral components can be introduced, for example, via wood and vegetable ashes.

The composite material can serve as an ideal carrier for solid and liquid fertilizers, insecticides, pesticides, bactericides and fungicides, etc., which are homogeneously incorporated and / or are.

The found manufacturing techniques allow a simple technical and cost-effective implementation of the invention with conventional and robust standard machines. The broad description of the invention, the selected embodiments and illustrations disclose, without being exhaustive of the embodiments and applications of the invention, the variety of possible compositions of the digestate composite materials, their use and manufacture.

A comprehensive utilization and application of digestate in the global agriculture in the form of the water-storing composite materials according to the invention contributes, by the return of mineral and organic nutrients in the field soil and the associated increase in biomass production and the resulting higher conversion of CO ₂ in the plants significantly contributes to a reduction in the negative CO ₂ balance. In addition, significant amounts of synthetic nitrogen fertilizer can be saved.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 2006/009681 [0044, 0071]
• DE 2010/00840 [0049, 0057]
• DE 102006019939 B4 [0055]
• DE 10330713 A1 [0055]
• DE 2009000943 [0058, 0059]
• EP 1879932 B [0059, 0082]
• EP 2009/061804 [0066]
• EP 2009/061909 [0066]
• DE 2009/000943 [0072, 0082]
• DE 2010/000840 [0072, 0082]
• EP 72010/060277 [0084]
• EP 18799328 [0114]
• DE 2543169 [0123]

Claims (25)

Water and / or aqueous solutions, including aqueous nutrient solutions, storing and the water and the aqueous solutions again releasing composite material, in particular as a shaped body preferably used, but not exclusively, as a soil additive and / or fertilizer, also as a mat with the addition of fibrous materials, a) at least one natural and / or synthetic superabsorbent polymer, b) at least one organic and / or inorganic, mineral filler and / or soil adjuvant, preferably based on igneous rock and / or organic and / or inorganic fertilizer preparation and / or organic, also present in fiber form, and / or inorganic additive and / or active ingredient and / or binder. characterized in that c) solid and / or liquid fermentation residues from fermented biomass is contained, d) that according to a) contained in the composite natural and / or synthetic superabsorbent polymer (SAP) is formed as a hydrogel composite (HGK), e ) the calculated proportion of pure superabsorbent polymer (SAP) in the total mass in the sum> 2 wt .-%, f) at least 5 times its own weight with time-dependent increase in volume of water and / or aqueous solutions stores and can deliver again , Composite material according to claim 1c), 1e) and 1f), characterized in that a) it contains at least one hybrid material with superabsorbent properties, b) the mass fraction of the fillers copolymerized into the polymer matrix of the hybrid material is at least 10% by weight, c) the polymer matrix is a natural and / or synthetic superabsorbent polymer (SAP), d) the polymer matrix constitutes at least 10% by weight of the total mass of the hybrid material. Composite material according to Claims 1 and 2, characterized in that natural and / or synthetic zeolite is contained in this and / or in the hydrogel composite added and / or formed in the preparation. Composite material according to claims 1 and 3, characterized in that in this and / or added in the preparation and / or formed hydrogel composite expanded, ground, porous rock particles, preferably based on igneous rock are included. Composite material according to claims 1 to 4, characterized in that this is formed overall as a hydrogel composite. Composite material according to claims 1 to 5, characterized in that in this and / or in the manufacture added and / or formed hydrogel composite at least 1% by weight of mineral wood-based ash and / or an inorganic, mineral residue, such as this in the thermal utilization (combustion) of energy crops and / or digestate and / or incurred in the thermal utilization of lignite and / or produced therefrom, a compacted molded body is included. Composite material according to claims 1 to 6, characterized in that this and / or added during preparation and / or formed hydrogel composite, Coir contains fiber Pith (CFP). Composite material according to claims 1 to 7, characterized in that the total content of Coir Fiber Pith (CFP) in the composite material is> 4% by weight. Composite material according to claims 1 to 8, characterized in that at least one crystalline compound belonging to the group of MOFs (Metal Organic Frameworks) is contained in this and / or in the hydrogel composite added and / or formed in the preparation. Composite material according to claims 1 to 9, characterized in that the original particle size in the added and / or contained in the preparation of the formed hydrogel composite SAP <1000 my preferably <500 my and more preferably <200 my. Composite material according to Claims 1 to 10, characterized in that the hydrogel composite added and / or formed in this and / or in the preparation contains at least 5% by weight of compost based on fermented residues. Composite material according to claims 1 to 11, characterized in that it is completely formed by anaerobic post-fermentation as compost. Composite material according to Claims 1 to 12, characterized in that the hydrogel composite contained therein and / or added and / or formed in the preparation comprises at least one SAP in the form of a potassium salt of a crosslinked and / or partially crosslinked polyacrylic acid-polyacrylamide copolymer and / or graft polymer contains. Composite material according to Claims 1 to 13, characterized in that the SAP contained therein and / or hydrogel composite added and / or formed in the preparation comprises at least one potassium salt of a crosslinked and / or partially crosslinked polyacrylic acid-polyacrylamide copolymer and / or graft polymer a nitrogen content (N)> 10% by weight, calculated as carbamide nitrogen, and the potassium content (K)> 3% by weight, calculated as potassium oxide (K ₂ O). Composite material according to claims 1 to 14, characterized in that this and / or added in the preparation and / or formed hydrogel composite contains at least 2 wt .-% mineral ash (wood ash) derived from the thermal utilization of wood and / or plants. Composite material according to Claims 1 to 15, characterized in that this and / or the hydrogel composite formed and / or added during production contains at least 2% by weight of mineral ash originating from the thermal utilization of early-tertiary lignite. Composite material according to Claims 1 to 16, characterized in that this and / or the hydrogel composite formed and / or added during production contains brown coal xylitol in the form of fibers and / or ground particles. Composite material according to claims 1 to 17, characterized in that this and / or the hydrogel composite formed and / or added in the preparation contains early tartar brown coal (lignite). Composite material according to claims 1 to 18, characterized in that it is designed as NPK fertilizer (nitrogen-phosphorus-potassium fertilizer). Composite material according to claims 1 to 19, characterized in that this and / or the hydrogel composite formed and / or added in the preparation contains unsweetened and / or partially sugared and / or sugar-containing calcium and / or magnesium and / or magnesium lignosulfonate complex on the basis of lignin liquor from pulp production. Composite material according to claims 1 to 20, characterized in that the lignosulfonate compound contained is wholly and / or partially converted by reaction with alkaline earth oxides as Ligninsulfonathydroxid complex which is partially and / or completely in carbonated form by the action of CO ₂ . Production of the composite material according to the invention according to claims 1 to 21 composed, characterized in that this is produced in a mixing and / or kneading process by means of a single or twin screw mixer and / or single or Zweiwellenpflugscharmischer. Production of the composite material according to the invention according to claims 1 to 21 composed and prepared according to claim 22, characterized in that for the production of fermentation residues with a water content> 75 wt .-% are used. Preparation of the composite material according to the invention according to claims 1 to 21 and made according to claim 22, characterized in that in the production of quicklime (calcium oxide) and / or calcined dolomite (calcium-magnesium oxide) and / or Dolomithalbbrannt and / or non-carbonated and / or only partially carbonated wood and / or plant ash added and / or presented and reacted with water-containing fermentation residues. Use of the composite material according to claims 1 to 24 composed and prepared as a soil additive, fertilizer, in particular as a combined nitrogen, phosphorus and potassium fertilizer (NPK fertilizer), water storage, water and nutrient supplier for growth, germination and the cultivation of Plants, as a plant substrate or as a soil additive, also in admixture with soil and / or earth substrates, to improve the soil climate and promote the formation of humus, as a carrier material for solid and liquid fertilizers, insecticides, pesticides, bactericides and fungicides and as a compost, additive for improvement of compost and for recultivation of semi-arid and arid areas, dry and desert areas and as storage for plant-available, even volatile nitrogen compounds. Increase in above-ground and underground biomass formation in plants of all kinds.