DE202010017799U1 - Carbon-based storage material - Google Patents

Abstract

Particulate, water, nutrient and microorganism-absorbing, carbon-based storage material with an increased specific surface area, containing further organic and / or inorganic additives, characterized in that the inorganic carbon component is produced by thermal treatment of coal and / or of natural and / or artificially organic compounds was produced with the exclusion of oxygen at high temperatures, and that the storage material can reversibly absorb and release aqueous liquids and organic and / or inorganic substances dissolved therein.

Description

The invention describes a novel and useful carbon-based water and nutrient-storing material with increased specific surface area for optimizing soils and plant substrates, which may contain various organic and inorganic additives. The carbon-based storage material according to the invention differs significantly in its composition and its spectrum of action from conventional soil additives.

The nature and composition of the base material, which results from inorganic coking from industrial coking processes, promises due to its particular surface texture in combination with organic polymers such. As polyacrylates or cellulose derivatives and various inorganic minerals such as the rock flour accelerated improvement of barren soil structures, especially of nutrient-poor sandy soils in arid regions of the world by the special ability to bind large amounts of aqueous liquids, dissolved nutrients and microorganisms and needs the environment again To make available.

In the living soil, referred to below as the substrate, there are permanently extraordinarily complex life processes and interactions between the multifarious microorganism flora and the micro- and macro-soil fauna that are in exchange. The basis for healthy plant growth is therefore a plant substrate that not only provides all vital nutrients, minerals, trace elements and above all sufficient moisture at all times. The suitable habitat for a variety of non-pathogenic microorganisms should also provide a good plant substrate for sustainable plant growth.

The living plant, via its roots, is in continuous interaction with the area of life of the microorganisms that inhabit the substrate. The growth of this microorganism flora, especially in the immediate root area, the rhizosphere, is therefore of crucial importance for the control of plant growth. An improved, loosened soil structure allows optimal supply of soil and root with oxygen and promotes microbial activity.

The practice of excessive fertilization of soils using inorganic NPK fertilizers and organic manure, which has been standard practice for decades, has meanwhile led to largely over-fertilized, compacted and microorganism-poor soil substrates. The consequences are contaminated groundwater, eutrophicated surface waters, soil erosion phenomena due to lack of water storage capacity and nutrient-poor crops, especially those depleted of trace elements.

To improve soil structures, a variety of proposals have been published, especially in the field of soil additives and additives, which are intended to compensate for the many-sided problems. Examples of this can be found in the patents US 5,741,346 . US 6,254,654 and US 2006/0130397 ,

From South America, it is known that the native people of the Amazon, with the addition of burned and charred wood to the soils called "black soils", were able to achieve very good harvest results. Coal is a globally naturally occurring, carbon-rich, brown to black solid. Coal occurs in the form of stratified sediment deposits and is one of the most important fossil fuels. Coal is formed by heat and pressure over millions of years from dead plant remains.

Lignite is a brown to black colored combustible rock resulting from accumulations of plant materials and subsequent chemical and physical transformation processes that have taken place over very long periods of time. In humid surroundings, the peat bog, the dead plants were largely protected from the usually occurring rotting process due to the high groundwater level and the low-oxygen water. Peat, the sponge-like, water-saturated organic material of plant origin, is the source material for lignite. In the anhydrous state lignite contains up to 70% carbon.

Hard coal or anthracite is a deep black, sometimes shining shiny material, contains more bound carbon than any other form of coal and has the least amount of volatile compounds. These materials produce the highest temperatures and heat output in the combustion process.

Coal as a component of mixtures for use as a soil additive is already in the writings DE 197 13 879 A1 . DE 198 25 168 A1 . DE 10 2007 047 533 A1 . US 6,775,948 and US 4,541,857 mentioned. The use of raw lignite in combination with compost and, if necessary, an organic or inorganic fertilizer for fertilization purposes is also described therein. However, the plant availability of the nutrients from the raw lignite is limited. A special feature of the coal materials in terms of Water storage capacity and possible positive effects due to its surface structure is not described.

The better suitability of fly ash from coal and lignite combustion as soil adjuvants is described in the patents US 4,469,503 . US 4,985,060 . US 5,451,240 and US 6,287,358 , Fly ash is a component of residues from the coal combustion and is z. B. formed in chimneys of coal power plants. Another type results from the bottom ash of blast furnaces. Depending on the formation and the chemical composition of the coal which is burned, the composition of the fly ash varies considerably. However, all types contain significant amounts of silica and calcium oxide, which are the predominant constituents of the coal bearing rock strata. Traceous or even percentile toxic components may for example consist of elements or compounds of arsenic, beryllium, boron, cadmium, chromium VI, cobalt, lead, manganese, mercury, molybdenum, selenium, strontium, thallium and vanadium, associated with dioxins and polyaromatic hydrocarbons. Such combustion products, as well as fly ashes, are subject to regulations in most countries as waste products and may not be introduced into the soil for these purposes. The use of charcoal, activated carbon or oxidized lignite for soil improvement is mentioned in the writings US 2002/0174697 . US 5,127,187 and US 2004/0111968 ,

The best properties are thermal, oxygen-terminated, organic, carbon-rich materials from peat, lignite, wood, plant remains and shells. Through the pyrolytic process, the organic hydrocarbon components are converted into a highly porous, very surface-rich, inorganic carbon. Compounds of sulfur, carbon oxides and other volatile components are largely removed. Similarly suitable, porous, inorganic carbon products can also be prepared from artificially produced, saturated or in particular unsaturated organic polymers. Possible examples would be polymers of styrene, acrylic acid, butadiene, ethylene, propylene, vinyl acetate, etc., and mixtures or copolymers thereof.

• a) Holzkohle ist ein poröser schwarzer Feststoff, welcher aus einer amorphen Form des Kohlenstoffs besteht und als Rückstand durch Erhitzen von Holz unter Luftausschluss bei Temperaturen bis zu 350°C erhalten werden kann. Holzkohle enthält ca. 83% Kohlenstoff und wird als Filter- und Absorptionsmaterial verwendet.
• b) Kokskohle ist der Rückstand aus der trockenen Destillation von Stein- oder Braunkohle bei Temperaturen zwischen 500°C und 1480°C. Bei diesem pyrolytischen Prozess werden die flüchtigen Bestandteile abgetrennt und abhängig vom Rohstoff resultiert ein Produkt mit einem anorganischen Kohlenstoffanteil von 88–92%. Der Schwefelanteil ist gering, der von Calzium- und Magnesiumoxid relativ hoch. Die spezifische Oberfläche vergrößert sich bei diesem Vorgang auf 300–500 m²/g. Kokskohle ist ein industriell hergestelltes Produkt und wird als Brennstoff und in der Stahlherstellung verwendet. Kokskohle kann grundsätzlich auch aus Holzkohle und ähnlichen kohlenstoffhaltigen Rohstoffen hergestellt werden.
• c) Aktivkohle besteht aus hochporösem, teiloxidiertem und stark absorbierendem Kohlenstoff, welcher in einem aufwändigen und kostspieligen Verfahren u. a. durch Gasaktivierung mit Kohlendioxid/Luftgemischen bei 700–1000°C aus Holzkohle, Torf, Braunkohle oder auch Anthrazit erzeugt wird. Die aktive Oberfläche liegt bei 1000–2000 m²/g. Aktivkohle wird hauptsächlich zur Gasreinigung, Wiederaufbereitung von Lösungsmitteln oder auch als Gegenmittel für verschiedene Gifte in der Medizin eingesetzt.

Depending on the production method, different types of pyrolysis products, which are produced by heating organic materials, can be distinguished:

• a) Charcoal is a porous black solid which consists of an amorphous form of carbon and can be obtained as a residue by heating wood in the absence of air at temperatures up to 350 ° C. Charcoal contains about 83% carbon and is used as a filter and absorbent material.
• (b) coking coal is the residue resulting from the dry distillation of coal or lignite at temperatures between 500 ° C and 1480 ° C. In this pyrolytic process, the volatiles are separated and depending on the raw material results in a product with an inorganic carbon content of 88-92%. The sulfur content is low, that of calcium and magnesium oxide is relatively high. The specific surface increases in this process to 300-500 m ² / g. Coking coal is an industrially produced product and is used as a fuel and in steelmaking. Coking coal can in principle also be produced from charcoal and similar carbonaceous raw materials.
• c) activated carbon consists of hochporösem, partially oxidized and highly absorbent carbon, which is produced in a complex and costly process, inter alia, by gas activation with carbon dioxide / air mixtures at 700-1000 ° C from charcoal, peat, brown coal or anthracite. The active surface is 1000-2000 m ² / g. Activated carbon is mainly used for gas purification, solvent reprocessing or as an antidote for various poisons in medicine.

The pyrolysis products from the high temperature treatment above 500 ° C, z. Based on wood or lignite (coking carbon: active surface about 300-500 m ² / g) are due to their greatly increased surface area and the associated enormous absorption capacity for a long time in filtration technology (eg., For wastewater, drinking water , Bath water, gases). These inorganic, highly carbon-containing pyrolysis products are comparable in their properties with activated carbon (active surface about 1000-2000 m ² / g) and beyond even considerably cheaper to produce.

The problem to be solved is the need to find suitable raw materials for the production of soil additives, which in terms of effectiveness, price, availability and environmental compatibility can be a promising basis for broad, commercial applications in various fields of crop production. It was therefore natural to use highly porous, surface-rich inorganic carbon products from pyrolysis or high-temperature coking processes for the purpose of substrate improvement in plant cultivation. An important argument for the widespread use of such inorganic carbon products is also that the carbon contained remains permanently bound in the soil and thus no longer to an increase in the climate-damaging carbon dioxide in the atmosphere.

The most interesting product for use as soil additive is finely divided and cost-effective coking coal, which results from the industrial pyrolysis process as residue. The product is produced at temperatures above 500 ° C and, depending on the raw material used, the inorganic carbon content is 88-92%. Other residues contained therein do not cause any environmental problems. The opposite is the case. The elements calcium and magnesium are important trace elements for plant growth. These favorable properties are already mentioned in the patent DE 509 524 from 1930, with the addition of coke in suitable granulation to bring about a quality improvement in solidified clay, clay and loam soils. Mixtures or composites based on this raw material with modified and optimized properties with regard to a possible soil improvement, in particular by adding organic polymers and inorganic additives, are not mentioned.

In the evaluation of different test series, it has been shown that turf grass seedlings on mixtures of pure sand and a simple variant of the subject matter based on cocarbon material compared to a reference sample, which had only grass seed on pure sand as a plant substrate, significant differences in growth and Color. While there were hardly any differences at first when germinating the seeds, after a few weeks of the growth phase with repeated dry periods, the pure sand-containing reference sample produced exclusively bright and short stalks of grass. The sample containing the storage material according to the invention achieved a significantly larger biomass in connection with very strong, dark green blades of grass. After the respective dry periods when water was omitted, the grass of the sample mixed with the soil additive was also able to recover considerably faster than the grass of the reference sample.

Further experiments with a similar structure also showed that sand substrates containing the storage material of the invention in combination with small amounts of a conventional NPK fertilizer produced longer and greener blades of grass for several weeks compared to reference samples to which only NPK fertilizer was added. because measurable water-soluble NPK fertilizer components were rinsed out of the reference sample with each water addition. The grass of the reference sample gradually lost its color and plant growth decreased significantly. This negative effect could not be detected in the sample with the storage material according to the invention in this form.

The invention is therefore based on the object of providing a surface-rich, carbon-based storage material which has hitherto not been described in this composition, which improves any plant substrate in its properties in such a way that it indirectly initiates, excites and sustainably supports plant and microbial growth. Such storage materials for soil improvement based on carbon from the pyrolysis process in combination with organic polymers and inorganic additives, are not yet described.

The stated object is achieved according to the invention in materials of the generic type by the characterizing features of claim 1). Further advantageous embodiments of the material according to the invention are specified in the dependent claims. It seems to be important to use carbonaceous raw materials, which were pyrolyzed at temperatures above 300 ° C, preferably above 500 ° C. The carbon content of these products is high, averaging over 80%, along with a highly active specific surface area of over 300 m ² / g. This improves compared to conventional soil additives and the absorption capacity for water and nutrient salts.

In a modifiable form according to claim 2), the carbon-based storage material according to the invention holds and stores particularly large amounts of water and substances dissolved therein. Illustratively, some organic polymers that can support and even significantly improve the good storage properties of the carbon-based memory material of the present invention are shown. Preference is given to water-soluble or water-dispersible additives, in particular starch, wheat flour, cellulose, gelatin, alginates or organic polymers and / or copolymers from the group of polyamides, polyesters, polyurethanes, polyethylenes, polyesters, polyacrylic acids, polyacrylates, polyvinylpyridines, polypyrolines, polyvinylpyrolidones, polyvinyl alcohols , Polyalkylene glycols, polyvinyl ethers, polyvinylamines, polyvinylsulfonic acids, polystyrenesulfonic acids, proteins, caseins used. It should be noted that this list is not exhaustive and is exhaustive. If necessary, a reversible delivery of the stored liquids in the storage material according to the invention to the plant substrate takes place. This gives a permanent and continuous plant availability. Too high concentrations of dissolved nutrients lead to over-fertilization and toxic Effects that can negatively impact plant and microbial growth. Such problems are avoided by carefully matching the composition of the plant substrate to the growth conditions of the plants.

According to claim 3) is added to the addition of rock flour, which are added to the inventive carbon-based storage material, the desired humus formation. In addition, minerals and other, special inorganic materials and salts act as pH regulators and also as suppliers of important minerals and nutrients.

According to claim 4), a targeted substrate preparation can be carried out by means of the carbon-based storage material according to the invention. Depending on the nature of the substrate or needs of the plants often a small proportion of inorganic NPK fertilizer salts in the storage material is sufficient. To combat pathogenic microorganisms (germs, fungi, viruses, other plant pests), which may already have colonized an existing plant substrate, biocides such. As quaternary ammonium compounds, cationic surfactants or peroxides, which create a low-germ environment as possible, as additives for the storage material in question. The biocides must be biodegradable in the substrate, so that after the subsequent necessary, targeted addition of microorganisms, if necessary. By additional administration of peat, manure, animal manure, manure, sewage sludge, organic household waste, compost or mixtures thereof, rebuild the beneficial microbial flora can.

Accordingly, in the case of very nutrient-poor growth substrates, the use of modified storage materials according to the invention, which already contain plant-available organic carbon from the so-called C suppliers, may become necessary for the development of microorganisms. The problem is also solved according to claim 5) and 6).

According to claim 7), the carbon-based storage material according to the invention can be made available as a water-loaded product. This is of great interest if, in arid areas, rapid absorption or release of water appears necessary due to extremely fluctuating boundary conditions such as temperature and humidity. The water absorption in the absolutely dried, carbon-based storage material according to the invention takes place with a marked time delay.

The multilayered design possibilities of the carbon-based storage material according to the invention enable the production of many different products as additives for soils or plant substrates in order to solve the most diverse problems in the field of soil improvement, such as possible extended versions and applications of the storage material according to the invention, which in the claims 8) 12) are described.

• – ein besseres Pflanzenwachstum/höhere Ernteerträge/größere Biomassen
• – eine intensive Grünfärbung der Blätter von Grünpflanzen
• – eine höhere Widerstandsfähigkeit gegen wiederholte Austrocknung
• – eine höhere Widerstandsfähigkeit gegen Staunässe im Wurzelbereich
• – eine höhere Widerstandsfähigkeit gegen Pflanzenschädlinge
• – eine intensivere Aromaentwicklung bei vielen Pflanzen und Früchten
• – ein stärker ausgeprägter Geschmack bei vielen Nutzpflanzen
• – eine Erhöhung des Gehaltes an Spurenelementen in den Pflanzen
• – weniger Verschwendung von Wasser und anderer Ressourcen
• – Verringerung der Kohlendioxid-Emissionen durch dauerhafte Bindung von Kohlenstoff im Boden

The use of selected products from the range of the carbonaceous storage materials according to the invention as soil additives causes:

• - better plant growth / higher crop yields / larger biomass
• - an intense green color of the leaves of green plants
• - a higher resistance to repeated dehydration
• - a higher resistance to waterlogging in the root area
• - a higher resistance to plant pests
• - a more intense aroma development in many plants and fruits
• - a more pronounced taste in many crops
• - An increase in the content of trace elements in the plants
• - less waste of water and other resources
• - Reduction of carbon dioxide emissions through permanent carbon sequestration in the soil

EXAMPLE 1

100 g carbon (particle size <60 microns), prepared by thermal treatment of lignite at temperatures above 1000 ° C with exclusion of air, are in a beaker with 100 g of finely ground volcanic rock (particle size <100 microns) and 90 g of ground vermiculite (particle size <0 , 5 mm), 10 g of polyacrylic acid (carbomer 50,000). Subsequently, 80 ml of an aqueous solution of methylcellulose (3 wt.%) Are added with stirring. The mixture is dried at T> 80 ° C and, after cooling to room temperature, broken into smaller pieces (particle size <1 mm). The resulting product is a homogeneous, free-flowing black solid that can be used as a soil conditioner.

EXAMPLE 2

100 g of carbon (analogous to Example 1) are mixed with 60 g of finely ground diabase ( Particle size <100 microns) and 40 g of sodium polyacrylate (particle size <100 microns) mixed. Subsequently, 80 ml of an aqueous solution of methylcellulose (3 wt.%) Are added with stirring. The mixture is dried at T> 80 ° C and broken after cooling to room temperature by means of a ball mill into smaller pieces. The resulting product is a homogeneous, free-flowing black solid which can be used as a soil conditioner, especially for water storage.

EXAMPLE 3

100 g of carbon produced from the wood-based pyrolysis process are mixed with 50 g of finely ground diabase (particle size <100 μm), 30 g of ground vermiculite (particle size <0.5 mm), 10 g of polyacrylic acid (carbomer 50,000) and 10 g of a commercial, inorganic NPK fertilizer mixed. Subsequently, 80 ml of an aqueous solution of methylcellulose (3 wt.%) Are added with stirring. The mixture is dried at T> 80 ° C and broken after cooling to room temperature into smaller pieces. The resulting product is a homogeneous, free-flowing black solid which can be used as a soil conditioner additive, especially for nutritional purposes.

EXAMPLE 4

500 g of the product from Example 1) are mixed with 2 kg of peat (moisture content max 10% by weight). The resulting product is a homogeneous, blackened solid mixture which can be used as a soil additive.

EXAMPLE 5

500 g of the product from Example 1) (coarse grain size) are mixed with 1 kg finely shredded bark mulch and 1 kg peat. The resulting product is an inhomogeneous, blackened solid mixture that can be used as a bottom cover to minimize water loss due to evaporation.

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

• US 5741346 [0006]
• US 6254654 [0006]
• US 2006/0130397 [0006]
• DE 19713879 A1 [0010]
• DE 19825168 A1 [0010]
• DE 102007047533 A1 [0010]
• US 6775948 [0010]
• US 4541857 [0010]
• US 4469503 [0011]
• US 4985060 [0011]
• US 5451240 [0011]
• US 6287358 [0011]
• US 2002/0174697 [0011]
• US 5127187 [0011]
• US 2004/0111968 [0011]
• DE 509524 [0016]

Claims (12)

Particulate, water, nutrient and microorganism-absorbing, carbon-based storage material with increased specific surface area containing further organic and / or inorganic additives, characterized in that the inorganic carbon component by thermal treatment of coal and / or natural and / or artificially produced produced organic compounds under exclusion of oxygen at high temperatures, and that the storage material reversibly absorb and release aqueous liquids and organic and / or inorganic substances dissolved therein. Carbon-based storage material according to the preceding claim, characterized in that the organic additive is at least one as water-soluble or water-dispersible additive, in particular starch, wheat flour, cellulose, gelatin, alginate and / or one or more different organic polymers and / or copolymers from the Group of polyamides, polyesters, polyurethanes, polyethylenes, polyacrylic acids, polyacrylates, polyvinylpyridines, polypyrrolines, polyvinylpyrrolidones, polyvinyl alcohols, polyalkylene glycols, polyvinyl ethers, polyvinylamines, polyvinylsulfonic acids, polystyrenesulfonic acids, proteins, caseins represents. Carbon-based storage material according to one of the preceding claims, characterized in that the inorganic additive contained is a natural and / or artificially produced finely ground inorganic solid selected from the group of volcanic and lava rocks, basalts, tuffs, bentonites, clay minerals, feldspar, silicates, quartzes , Zeolites, carbonates, metal salts, metal oxides and / or mixtures thereof. Carbon-based storage material according to one of the preceding claims, characterized in that at least one further additive, in particular from the group of plants for growth-promoting and -regulierenden or regulating substances such as fertilizers, humic substances, growth hormones, pesticides, biocides, surfactants, microorganisms or mixtures from it, is included. Carbon-based storage material according to one of the preceding claims, characterized in that at least one organic nutrient supplier, in particular selected from the group of guano, peat, natural lignite, animal manure, animal manure, animal meal, blood meal, manure, sewage sludge, organic household waste, compost or mixtures thereof , is included. Carbon-based storage material according to one of the preceding claims, characterized in that at least one filler, in particular selected from the group of cellulose, textiles, straw, mineral fibers, wood chips, horn shavings, husks and shells of fruits or mixtures thereof, is included. Carbon-based storage material according to one of the preceding claims, characterized in that the water content to 0.1 to 80 wt.%, Preferably to 0.1 to 50 wt.%, Particularly preferably up to 40 wt.%, Based on the total mass of the wet Storage material is set. Carbon-based storage material according to one of the preceding claims, characterized in that the storage material is very finely divided, free-flowing, in particular flowable. Carbon-based storage material according to one of the preceding claims, characterized in that the storage material is processed into shaped bodies, in particular spheres, pellets or rods. Soil or plant substrate according to one of the preceding claims, characterized in that the carbon-based storage material is incorporated in the soil or in the substrate, in particular mixed therewith and that the carbon-based storage material in a proportion of 0.1 to 90 wt.%, In particular 0 , 1 to 50 wt.%, Preferably 0.1 to 20 wt.% Based on the plant substrate to be produced, is used. Soil or plant substrate according to one of the preceding claims, characterized in that the carbon-based storage material for the stabilization of slopes, green areas of dry and sandy areas, deserts, golf courses, lawns, roofs and for use in viticulture, in agriculture and forestry, in the flower and plant breeding as well as on riding places serves. Soil or plant substrate according to one of the preceding claims, characterized in that the carbon-based storage material in combination with seed and / or seedlings serves as a germination accelerator.