WO2019052738A1 - Verfahren zur produktion von huminstoffen aus biomasse wie holz, rinde, getreidestroh, blättern, krautigen pflanzen sowie baumpilzen, klärschlamm und anderen organischen abfällen - Google Patents
Verfahren zur produktion von huminstoffen aus biomasse wie holz, rinde, getreidestroh, blättern, krautigen pflanzen sowie baumpilzen, klärschlamm und anderen organischen abfällen Download PDFInfo
- Publication number
- WO2019052738A1 WO2019052738A1 PCT/EP2018/070786 EP2018070786W WO2019052738A1 WO 2019052738 A1 WO2019052738 A1 WO 2019052738A1 EP 2018070786 W EP2018070786 W EP 2018070786W WO 2019052738 A1 WO2019052738 A1 WO 2019052738A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- biomass
- acid
- humic
- water
- hours
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic fertilisers
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic fertilisers
- C05F11/02—Other organic fertilisers from peat, brown coal, and similar vegetable deposits
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F7/00—Fertilisers from waste water, sewage sludge, sea slime, ooze or similar masses
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
Definitions
- the invention relates to a method for the chemical synthesis of humic substances from biomass according to the preamble of independent claim 1.
- the invention further relates to an alternative method for the chemical synthesis of humic substances from biomass according to the preamble of independent claim 13.
- the invention further relates to a method for chemical Synthesis of chitosan from biomass according to the generic term of
- Humic substances are natural, biogenic, heterogeneous, high molecular weight organic substances with a yellow to black color, the
- humic substances Conversion or degradation rate in the ecosystem is relatively low. Due to these recalcitrant properties, humic substances have a high residence or environmental life. Humic substances are polyfunctional and ubiquitously distributed in soils, sediments and waters and make up the major part of the total organic reservoir of these compartments.
- Humic substances are an important reservoir of organic carbon in aquatic and terrestrial environmental compartments; In surface waters about 50% of the dissolved organic carbon (DOC) is attributed to humic substances and, despite their polydisperse character, has typical physical and chemical properties which they identify as a group of substances. However, they do not fall into any discrete class of connections like Proteins, polysaccharides or polynucleotides, but are operationally defined and named after the term humus.
- the depot function which is essential for life, leads to a fundamental interest in the structure and functionality of this substance class as well as in its importance for ecosystems.
- Humic substances therefore play in
- Metal ions in the dissolved phase and the colloidal phase of the humic substances are complex because they are steady state equilibria.
- humic substances in terms of their composition and structure is difficult because it is a polydisperse class of substances and since conformations and complexing properties depend on parameters such as pH, Eh and ionic strength.
- Humic substances are produced via the path of decomposition of dead organisms and a subsequent humification process. In doing so, HSs become different via different chemical and biochemical pathways formed natural conditions, which is why no binding gene pathways and reaction mechanisms can be stated.
- Soils are the primary source of education and activity for humic substances.
- humic substances have already been detected in leaves and parts of plants without soil contact which are in the process of aging (senescence).
- Partial microbial decomposition of dead plant parts and animal remains and excrements of terrestrial and ground animals, under the influence of enzymes from high-polymer compounds, produces aliphatic and aromatic individual building blocks which are the starting materials for humic substances.
- the conversion of the organic substance into humic substances is called humification. From the
- HsV humic acid precursors
- Each particle can react with each other, which is why, as a result of random events, neither a linear course of reaction nor a defined chemical constitution of the end products can be expected.
- compositions, structures and properties of humic substances vary widely due to the variety of pathways and are dependent upon the conditions of the environment in which they are formed. Table 1 describes typical properties.
- Humic substances consist of different building blocks, especially lignin,
- Humic substances are typical despite their polydisperse character chemical and physical properties that they use as a group of substances
- humic substances are closely related to the type and amount of functional groups contained. Some functional groups are with their main origin and effect on the properties of
- humic substances Due to their heterogeneous composition, humic substances can not be subdivided according to structural aspects. Instead, the substance class is based on an alkaline extraction into the fractions
- Fulvic acid, humic acid and humins are classified.
- the humic substance fractions and their operational definitions are listed in Table 3.
- Fulvic acid, humic acid and humins are detectable after extraction from fossil parent substances such as Leonhardite or brown coal and can also be characterized with standards. In soil, some research groups believe that these substances are part of a soil continuum model (SCM) and not as such in a defined form. However, since the present invention produces humic acid and fulvic acid, and since these can be uniquely characterized with standards, these terms are used below.
- the fulvic acids differ from the humic acids of a sample essentially by their lower molecular weight, by the higher average oxygen, lower carbon and nitrogen content and by the usually higher content of functional groups. The proportion of polysaccharide building blocks can be up to 30% for fulvic acids, aromatic
- Fulvic acids as well as their salts, the fulvates, water-soluble and fortuitous metal ionic compounds, with metals which may have multiple oxidation states, are particularly preferably transition metals with several oxidation states such as iron (Fe (II) / Fe (III)), manganese (Mn (II) / Mn (IV), cobalt (Co (II) / Co (III)), chromium
- the humic acids have a higher molecular weight, contain more aromatic moieties and methylene groups, but fewer polysaccharide fragments than the fulvic acids. Humic acids are sparingly soluble in water and also form with polyvalent cations (calcium, magnesium, iron and
- humic substances do not have a uniform structural formula. It is believed that at least for high molecular weight humic substances in a sample, there are no two identical molecules. Even if it were possible to elucidate the structure of a humic substance particle, the result would not be of much use, since the other molecules present in a sample have different structures.
- the properties of humic substances observed from the outside are thus to be understood as the sum of many different individual properties; This is also evident in the characterization of humic substances. With different methods, wide mixed signals are obtained.
- humic substances By fractionation of humic substances can generally the degree of Polydispersity can be reduced.
- the fact that humic substances consist of a complex and heterogeneous mixture of compounds is shown by the failed attempts to separate these materials into fractions of discrete compounds. With the most diverse separation methods, only fractionations could be achieved which were able to determine and reduce the degree of heterogeneity of the samples, but none could even approximately isolate a material that was pure humic matter ('pure' in the classical sense as 'pure chemical' or 'pure group of chemicals'). In this regard, humic substances represent a unique category of natural products, which is characterized by their heterogeneity.
- manure e.g. Stable manure
- Farmyard manure acts to improve the soil and nutrients to the soil. It has been shown that stable manure has a positive influence on the water retention capacity of light sandy soils and the soil air balance. However, the duration of action of manure is relatively low. Humic acids are only present in cow dung up to 10%. Similarly, residues from the digestion of manure, green waste or organic waste can be used for soil improvement.
- Compost has a high air capacity. Its water retention capacity is low. Biodegradation by soil-borne bacteria takes place within a few weeks. Based on the starting material, only 3 to 10% of the incorporated carbon is recovered as humic substances in the end product, the majority of the carbon is released into the air via CO 2 formation or is removed during composting by leaching into the sewage treatment plant.
- Bark mulch is raw, unfermented (not composted) bark.
- Bark humus is composted bark.
- Bark humus has both soil-improving and fertilizing effects.
- Bark substrates are processed clay, peat or other aggregates prepared finished culture substrates or potting soil with 30% to 60% share of
- Bark humus From FR-PS 2 123 042, FR-PS 2 224 421, DE-PS 2 651 171 and DE 3 040 040 methods for composting and humification of shredded bark have become known, which will additionally add inorganic nutrients or peat composting process to to improve the product properties. However, all these products have a lower one
- wood waste substrates are also used. These specially treated wood waste products, like bark humus, have a low water retention capacity. Wood fibers that are not fertilized, in addition to bark humus additionally lower
- Untreated wood waste such as sawdust or wood chippings, will trap nitrogen in the soil, i. when applying such substances, sufficient nitrogen must be added in addition.
- sawdust it must be mixed very intensively with the soil, as sawdust nests prevent the penetration of water into the soil.
- wood products for soil improvement is thus rather disadvantageous. Therefore, wood pulp is often fertilized or as culture substrates in addition
- peat Plant growth are available. Also known is the sole use of peat products, which are characterized by its good water holding ability at the same time high air content. As a result, peat is considered
- Raw material for the production of humic acid soil improvers used in large quantities. Since it contains hardly any nutrients and has a low pH, targeted fertilization and limescale is necessary for different plant species. While the peat supply is associated with the destruction of valuable wetlands for rare animals and plants, lignite is cheap and in large quantities without appreciable additional environmental impact than
- Humic acid source available available.
- the humic acid selection from this and their use as soil improvers instead of peat can help to ensure that the habitats of the marshes are not irretrievably lost.
- DE 101 20 433 a process for the production of Dauerhumusstoffen from soft lignite is described. Thereafter, soft lignite should be mixed with clays or clays and subjected to wet pulping or other intimate mixing. This substance is to be introduced into soils. Since the product produced does not contain any short- and medium-term available humus constituents despite the high cost, the resulting products are not very suitable to contribute to soil improvement.
- humic acids Another source of humic acids are coconut-processing materials, in particular the short and dusty wastes of fiber processing otherwise difficult to use.
- the classical method for the extraction of humic acids is the extraction of peat or lignite with dilute aqueous sodium or potassium hydroxide solution. The humates dissolve in the extraction solution and are filtered off,
- Laid-open publication DE 19859068 A1 describes that lignite is suspended in an aqueous-ammoniacal medium having a pH of greater than 9 and in the process is partially dissolved and oxidized in the aqueous-ammoniacal medium.
- the organic fertilizer is recovered after thickening or drying as a dispersion.
- Starting brown coal can be added to this process with additions of lignin or cellulosic products from industry and forestry. An addition of macro and micronutrients is possible.
- Humic acids In order to increase the soluble amount of humic acid available to the plants, an additional oxidation step is instead incorporated, which means an increased technical complexity and only slightly increases the amount of available humic acids.
- the resulting / produced low molecular weight compounds are used only for pharmaceutical purposes such as the disinfection of Oral mucosa and decomposition of biofilms in the oral cavity.
- the complex sugars of hemicellulose, cellulose, lignin and chitin can also be oxidized by blowing in atmospheric oxygen or pure oxygen in a pressurized vessel with pressure increase and temperature increase after biomass firing, but then the oxidation is slower but more controlled expires.
- Humic substances are used entirely as fulvic acid or humic acid, and therefore this process is much more efficient than W02007125492A2.
- the rate of reaction of the subsequent oxidation is slowed down so much that a run-away of the oxidation reaction is prevented, which can easily be the case when using pure, refined sugars.
- Humic acids are described, for the production of which an aqueous solution of humates is added successively with sodium bicarbonate to lower the pH, a protein source such as animal meal or blood, citric acid, yucca extract, lime and Tang. This suspension is then fermented for 10 days. The solution obtained after separation of insoluble components is used as a soil conditioner.
- Mixture of protein materials and humates can be used as a plant growth stimulator.
- DE 101 23 283 describes a process by which fine-grained lignites are digested in alkaline solution and, after addition of inorganic supplementation and / or neutralization substances without further treatment steps, a stable humate-humic acid-continuous humus nutrient suspension is produced.
- This product has been proven in practice, but the effect is limited in extremely nutrient-poor soils.
- the published patent application DE 43 25 692 A 1 describes the structure of a hydrophobic layer in the soil to contain the evaporation, ie the evaporation of water from the soil.
- the approach used in the present patent is to curb transpiration, that is, consumption over the plant itself.
- inorganic and organic substances are used.
- the use of artificial inorganic and organic soil improvers in the form of polymers and hydrogels capable of reversibly storing water is also increasing. In most cases, these substances are only partially usable for use in desert soils, as these substances are not heat tolerant, only limited UV resistance and are no longer functional at high salt levels in the soil.
- artificial soil conditioners still have a number of unanswered questions regarding the metabolites that may be produced by natural degradation or chemical conversion in the soil.
- rock flours and clay minerals is intensified, but their effect is limited; In some cases, they still have antagonistic effects in the soil with regard to the availability of potassium and magnesium
- Humic acid may have a cation exchange capacity of between 200 to 700 meq / 100 grams depending on the distribution of the various components, while fulvic acids may reach between 500 to 1400 meq / 100 grams. Humic substances are also very interesting due to their
- the object of the invention is therefore to produce humic substances in closed processes from biomass and agricultural and wood-based waste, while avoiding waste with (almost) 100 percent
- Biomass humic substances having the features of independent claim 1 by an alternative method for the chemical synthesis of humic substances from biomass having the features of independent claim 13 and by a method for the chemical synthesis of chitosan from biomass having the features of independent claim 16.
- biomass in particular as the first biomass applies in the following
- a solution of KOH and / or NaOH in water in particular a 0.1 to 2.0 molar solution of KOH and / or NaOH in water, in particular a 1.0 molar solution of KOH and / or NaOH in water, will generally be considered as alkaline earth hydroxide solution .
- a solution of strong inorganic acids the following generally applies a solution of sulfuric acid and / or
- Phosphoric acid and / or nitric acid in particular a 0 to 40% solution of sulfuric acid and / or phosphoric acid and / or nitric acid,
- Phosphoric acid and / or nitric acid more preferably a 15 to 25% solution of sulfuric acid and / or phosphoric acid and / or nitric acid.
- a mother liquor is generally the liquid extract which is obtained after filtration and / or washing of a reaction mixture and / or solid.
- heating generally refers to heating and holding at a certain temperature range.
- titration may also be heating.
- a pressure vessel in the following, generally in a container which is suitable for carrying out a reaction under pressure and / or for carrying out a reaction under pressure. Under pressure, this means a pressure greater than that
- Oxygen in the following is generally pure oxygen or a gas mixture with oxygen. According to the invention, a process for the chemical synthesis of
- Humic substances from biomass in particular from a first biomass proposed, wherein the method comprises the following method steps. It is carried out with the first biomass of a Maillard reaction by heating the first biomass, in particular for 1 to 30 minutes, in particular for 10 to 15 minutes and in particular to 150-250 ° C, in particular to 160-220 ° C. , more preferably 170-190 ° C, is heated.
- a Maillard reaction is a non-enzymatic browning reaction, which can also be observed, for example, when frying and frying foods.
- amine compounds such as amino acids, peptides and proteins
- a Maillard reaction according to the invention is preferably carried out in a temperature range between 160 and 200 degrees Celsius, and the residence time in this temperature range is generally between 0 and 60 minutes, and preferably between 15 and 30 minutes.
- the Maillard reaction take place.
- the generated Maillard reaction of the first biomass is thus between sugars, starches and amino acids, peptides, proteins under heating.
- the first biomass may in particular be finely ground in order to favor the Maillard reaction by increasing the surface area.
- the water-soluble reaction products can also be extracted with hot water after the Maillard reaction from the resulting second biomass and then thickened.
- the remaining from the extraction of the second biomass first solid is torr under a protective gas atmosphere at 180-300 ° C, especially at 190-250 ° C, especially for 0.2 to 4 hours, torr especially for 1.5 to 2.5 hours.
- the first solid should therefore last several hours until
- Torrification is the thermal treatment of biomass without access of air, which can lead to pyrolytic decomposition and / or drying.
- aromatic structures are produced in the biomass by the torrification, which later react further in the oxidation step.
- the resulting torrified second solid is heated with a solution of a strong inorganic acid in excess, preferably heated to 120-180 ° C, in particular 110-170 ° C, in particular 130-165 ° C, in particular for 0.5 to 3 hours, specially heated for 1.5 to 2.5 hours
- Solid is oxidized with another oxidizing agent, such as by the torr e second solid is suspended with water and oxidized with the supply of oxygen, in particular in a pressure vessel, as described in more detail in the alternative method of the invention.
- Oxidizing agents such as hydrogen peroxide, in particular hydrogen peroxide in a low concentration, are also suitable for the oxidation of the biomass.
- the resulting wood acetic acid fractions can be condensed separately during the first solidification of the first solid.
- the first reaction mixture obtained after boiling the torrified second solid with a solution of a strong inorganic acid is filtered and washed with water.
- the fulvic acid formed by oxidation can therefore be dissolved by washing the remaining solid until the wash water is pH-neutral.
- the oxidation step converts the aromatic structures generated during the titration into aliphatic compounds,
- the third solid obtained from the first reaction mixture can be boiled at 120 to 160 ° C, especially at 130-150 ° C with alkaline earth hydroxide solution and dissolved. In this case, for example, refluxing with 1 molar KOH.
- the obtained after boiling the third solid with alkaline earth metal hydroxide solution second reaction mixture can be neutralized by means of sulfuric acid and / or nitric acid and precipitating solids can be separated.
- humic acid can be precipitated from the first mother liquor obtained after neutralization of the second reaction mixture. From a obtained after precipitation of the first mother liquor second
- Mother liquor can be precipitated and / or separated at pH 0 to pH 1, in particular at pH 0, calcium sulfate and / or magnesium sulfate and / or potassium sulfate, and / or the resulting second mother liquor can be concentrated and neutralized.
- the ratio of sugars to amino acids in the first biomass should be between 1: 1 to 1: 3, and preferably 1: 2.
- the Maillard reaction can not be complete.
- the level of sugar or amino acids can be increased. The proportion of the missing substance is therefore increased in the raw material.
- Carotenoids present in the raw material (in the first biomass) are formed during the process according to the invention as a further reaction product Strigolactone and Hydrolactone, in particular high levels of Strigolactonen and Hydrolactonen formed.
- the first solidification may be carried out in a temperature range of 180 to 300 degrees Celsius, preferably 190 to 250 degrees Celsius, more preferably 235 to 250 degrees Celsius.
- the first solid can also be pyrolyzed.
- the temperature of the titration may be maintained at a constant temperature for between 1 and 4 hours, preferably for 2 to 3 hours.
- the titration can be carried out under an inert protective gas such as carbon dioxide, argon, nitrogen or other known protective gases or under vacuum.
- the respective proportions of humic or fulvic acids in the end product can be controlled via the process temperature. At higher pyrolysis / titration temperatures, higher levels of fulvic acids are present as the formation of fulvic acids increases
- Humic acid is favored at lower temperatures.
- the obtained torrified second solid may be cooled under inert gas and / or refluxed with acid, the
- Acid boiling temperature between 1 10 to 180 degrees Celsius, preferably below 130 to 165 degrees Celsius.
- the acids used in acid cooking may be one or more acids, preferably one of the acids or a mixture of one or more of the acids sulfuric acid, nitric acid, phosphoric acid or concentrated acetic acid or citric acid.
- the acid concentrations in the acid cooking can be from 1% by mass to 40% by mass, preferably 15% by mass to 35% by mass, and more preferably 25% by mass
- Mass percent to 30 percent by mass of the solid used The material obtained from the acidification (first reaction mixture) can be filtered first and then the filter cake obtained can be washed with distilled water to pH neutral, the wash water is added to the filtrate of the first reaction mixture and then the filtrate plus wash water is concentrated.
- Fertilizer fraction can be removed from the process, this can predominantly Nitrates, phosphates, acetates, citrates and sulfates, depending on the type of acids used. Of course, these mineral salts can continue to precipitate in later steps of the concentration and then filtered off.
- the remaining after filtering the first reaction mixture third solid can be added to the cooking with alkaline earth metal hydroxide solution with 0.1 normal to 2 normal KOH, preferably with 0.5 normal to 1 normal KOH and under reflux at a temperature range of 130 to 160 degrees Celsius over 1 to Be cooked for 3 hours.
- the humic acid of the second reaction mixture can be neutralized by adjusting it to a pH of 8 to 9, preferably a pH of 8.5, and after concentration, the resulting salts (e.g., potassium salts) can be separated by filtration.
- potassium salts are to be understood inter alia salts of potassium and other alkali metals as well as sodium and lithium.
- the obtained humic acid can be successively oxidized to fulvic acid by adjusting a pH of about 14. This step can be carried out in particular after the neutralization of the second reaction mixture.
- the humic acid and fulvic acid can be enriched after neutralization with mineral ions or concentrated, and then further processed with a spray dryer in a powdered concentrate.
- Another alternative process according to the invention for the chemical synthesis of humic substances from biomass, in particular from a first biomass, comprises the following process steps
- a Maillard reaction is carried out by heating the first biomass, in particular for 1 to 30 minutes, in particular for 10 to 15 minutes and in particular at 150-250 ° C, in particular at 160-220 ° C, particularly preferably 170-190 ° C, heated.
- Soluble impurities are extracted by means of water from a second biomass obtained from the Maillard reaction.
- the first solid obtained after the extraction of the second biomass is torr under a protective gas atmosphere at 180-300 ° C, especially at 190-250 ° C, especially for 0.2 to 4 hours, torr especially for 1.5 to 2.5 hours.
- the torrified second solid is oxidized with an oxidizing agent, in particular suspended with water and oxidized with the introduction of oxygen. This step can be carried out in particular in a pressure vessel.
- the third reaction mixture obtained after the oxidation is filtered and washed with water.
- Potential oxidizing agents include oxygen, ozone,
- Peroxides such as hydrogen peroxide, hypochlorites, perchlorates, percarbonates and iodine are used
- the oxidation step may be performed by blowing air or oxygen into the 150 to 170 degree hot water-titrated material mixture using a stirred pressure vessel.
- the oxidation step may be performed by blowing air or oxygen into the 150 to 170 degree hot water-titrated material mixture using a stirred pressure vessel.
- calcium sulfate and / or magnesium sulfate and / or potassium sulfate can be precipitated and / or separated at pH 0 to pH 1, in particular at pH 0, and / or the resulting fourth mother liquor can be concentrated and neutralized.
- a process for the chemical synthesis of chitosan from biomass, in particular from a third biomass is furthermore disclosed
- a Maillard reaction is carried out by adding the third biomass for 1 to 30 minutes; in particular for 10 to 15 minutes and at 150-200 ° C, in particular at 160-180 ° C, is heated. Soluble impurities are extracted by means of water from a fourth biomass obtained by the Maillard reaction of the third biomass. A obtained after the extraction of the fourth biomass fifth solid is cooked at 140 to 180 ° C, especially at 150-170 ° C with alkaline earth hydroxide solution.
- a solid obtained after boiling the fifth solid with alkaline earth metal hydroxide solution can be further processed as a second solid whose processing has already been described in the above-described inventive method for the chemical synthesis of humic acid from biomass and the additional additional process steps, which are also described above.
- the following steps can be carried out, which can be carried out successively.
- further intermediate steps can be carried out, or, depending on the type of biomass, the chronology of the steps can be adapted.
- the following explanations are a very precise description of a possible procedure, which has already been described more broadly, with further optional and variable ones
- Step 1 Since many of the biomass types mentioned at the beginning have high sugars and protein contents, the sugar or starch present in the case of woody or straw-like biomass with appreciable contents of hemicellulose with the addition of amino acids is first of all given a humin-like substance group via a Maillard reaction. namely produced butenolides or Karrikine by heating to 160 to 220 degrees Celsius, preferably 170 to 190 degrees Celsius. After several minutes, between 0 to 30 minutes
- the Maillard reaction is completed so far that the resulting products can be separated via hot water extract from the remaining solid.
- the products of the Maillard reaction are preferably 10 to 15 minutes.
- the titration takes place under protective gas (CO 2, argon, nitrogen, etc.), with nitrogen being the preferred protective gas.
- protective gas CO 2, argon, nitrogen, etc.
- Wood acetic acid fraction is condensed out via a condenser and fed into fertilizer or pesticide production.
- Temperature and residence time control the compositional ratio of fulvic and humic acids in the final product. At low temperature and shorter residence time, a higher proportion of humic acids, and higher
- the residence time is also used to control the ratio of the carboxyl-carbonyl hydroxyl groups (step 3).
- the torrified solid is then mixed with a mixture of several acids, preferably sulfuric acid, phosphoric acid and nitric acid, at a concentration of 0 to 40%, preferably 15 to 35 %, more preferably 25-30%, boiled under reflux and oxidized.
- Cooking times at temperatures of between 1 10 to 170 degrees Celsius, preferably 130 to 150 degrees Celsius are between 0.5 to 3 hours, preferably 1.5 to 2.5 hours.
- the acid addition is about 20% more than that
- Fulvic acid can be attached as a mineral fulvate. This allows tailor-made fulvic acid partitions to be precisely defined
- a mixture of water and torrified material can also be oxidized in a pressure vessel with the injection of air or pure oxygen, wherein there is no as much pH drop as when using acids for oxidation.
- the resulting fulvic acid is in high depending on the concentration at pH 0
- fulvic acid amounts to between 1 and 15%, preferably less than 10%.
- Step 4 The solid remaining after the oxidation and separation of the fulvic acid is washed with distilled water until the water is pH neutral. Subsequently, this washing water fraction, which is still a relatively high
- the remaining solid consists of pure humic acid with adhering minerals from the acid treatment such as phosphorus, sulfur and
- potassium sulfate or potassium nitrate may be crystallized out, separated by filtration, and
- crystallized material of the separate fertilizer fraction are added in the appropriate mixing ratio or find use as a sole agent.
- the liquid humic acid precipitates when lowering the pH to pH 2 in its entirety as a crystalline humate.
- the liquid humic acid but only with the addition of acids, preferably one of the major acids sulfuric acid, phosphoric acid or nitric acid, more preferably sulfuric acid, with the formation of crystallizing potassium sulfate to the desired pH range of 8 to 9, preferably 8.5 lowered.
- the resulting potassium sulfate or potassium nitrate or potassium phosphate is removed by filtration or centrifugation and fed to the fertilizer production.
- the C02 also produced by the formation of carbonate is formed by carbonate formation as calcium carbonate, potassium carbonate or
- the raw material used or the carbon fraction are converted to 70% to 100% in humic substances and fertilizer.
- a tailor-made composition of humic substances and fertilizers is possible in every variation.
- CAC Cation exchange capacities
- the process control and the chemicals allow a reduction in costs compared to humic substances from peat, Leonhardite, lignite or Synthes by an order of magnitude. Most used biomasses generate additionally a contribution to expenses in the form of disposal fees and thereby additionally reduce the overall process costs.
- Figure 1 shows an exemplary FTIR analysis using a sigma humic acid standard 53680-10g lot no. NrBCBN171 1V; CAS NR1415-93-6 in comparison with a FTIR analysis of the product of a
- Humic acid samples yield almost congruent transmission curves in almost all wavelengths. Consequently, from a process according to the invention, valuable humic acid combinations which largely match the humic acid combinations from the soil result.
- Table 4 Summary of the general properties of the humic substance fractions in the form of general tendencies -32-
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Sustainable Development (AREA)
- Environmental & Geological Engineering (AREA)
- Fertilizers (AREA)
- Compounds Of Unknown Constitution (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Processing Of Solid Wastes (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112020002020-6A BR112020002020A2 (pt) | 2017-09-13 | 2018-07-31 | processo para a produção de substâncias húmicas a partir de biomassa tal como madeira, casca, palha de cereal, folhas, plantas herbáceas assim como fungos de árvores, lama de esgoto e outros despejos orgânicos |
AU2018331216A AU2018331216A1 (en) | 2017-09-13 | 2018-07-31 | Process for the production of humic substances from biomass such as wood, bark, cereal straw, leaves, herbaceous plants and also tree fungi, sewage sludge and other organic wastes |
JP2020513307A JP2020537623A (ja) | 2017-09-13 | 2018-07-31 | 木材、樹皮、穀物わら、葉、草本植物、木菌、下水汚泥およびその他の有機廃棄物などのバイオマスからの腐植物質の生産プロセス |
CA3072258A CA3072258A1 (en) | 2017-09-13 | 2018-07-31 | A process for the production of humic substances from biomass such as wood, bark, cereal straw, leaves, herbaceous plants as well as tree fungi, sewage sludge and other organic wastes |
US16/638,636 US20210130503A1 (en) | 2017-09-13 | 2018-07-31 | Process for the production of humic substances from biomass |
EP18749775.5A EP3681851A1 (de) | 2017-09-13 | 2018-07-31 | Verfahren zur produktion von huminstoffen aus biomasse wie holz, rinde, getreidestroh, blättern, krautigen pflanzen sowie baumpilzen, klärschlamm und anderen organischen abfällen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201762558051P | 2017-09-13 | 2017-09-13 | |
US62/558,051 | 2017-09-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2019052738A1 true WO2019052738A1 (de) | 2019-03-21 |
Family
ID=63103939
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2018/070786 WO2019052738A1 (de) | 2017-09-13 | 2018-07-31 | Verfahren zur produktion von huminstoffen aus biomasse wie holz, rinde, getreidestroh, blättern, krautigen pflanzen sowie baumpilzen, klärschlamm und anderen organischen abfällen |
Country Status (7)
Country | Link |
---|---|
US (1) | US20210130503A1 (de) |
EP (1) | EP3681851A1 (de) |
JP (1) | JP2020537623A (de) |
AU (1) | AU2018331216A1 (de) |
BR (1) | BR112020002020A2 (de) |
CA (1) | CA3072258A1 (de) |
WO (1) | WO2019052738A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE202021001026U1 (de) | 2021-04-27 | 2021-05-28 | IAB-Institut für Angewandte Bauforschung Weimar gemeinnützige GmbH | Phosphathaltiges Düngemittel bestehend aus erhitztem Klärschlamm und zusätzlichen Alkali- und/oder Erdalkalien aus Reststoffen der Kaligewinnung |
CN113399417A (zh) * | 2021-05-26 | 2021-09-17 | 华南理工大学 | 一种利用污泥制备腐植酸钠的方法与应用 |
US11124461B2 (en) | 2019-07-04 | 2021-09-21 | Incitec Pivot Limited | Fertilizer |
CN114452820A (zh) * | 2021-12-23 | 2022-05-10 | 南京师范大学 | 一种分离并测定腐殖酸含碳官能团的装置及其使用方法与应用 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113736098A (zh) * | 2021-08-04 | 2021-12-03 | 上海臻衍生物科技有限公司 | 医药黄腐酸标准品制造及其细胞实验的应用 |
CN113801340B (zh) * | 2021-09-26 | 2022-07-01 | 常州大学 | 一种煤与生物质共硝化提高原料中黄腐酸/腐植酸含量的方法 |
JP2023057596A (ja) * | 2021-10-12 | 2023-04-24 | G-8 International Trading 株式会社 | 有用物質の製造方法および製造装置 |
CN114137182A (zh) * | 2021-11-09 | 2022-03-04 | 孙晓彤 | 一种土壤中腐殖酸提取检测仪 |
CN116178748A (zh) * | 2023-01-17 | 2023-05-30 | 广西壮族自治区中国科学院广西植物研究所 | 低温热解-氧化法制生物质腐殖酸盐的制备方法及应用 |
CN116675873A (zh) * | 2023-05-24 | 2023-09-01 | 云南云天化股份有限公司 | 一种从褐煤中高效提取腐殖酸的方法 |
CN116444816B (zh) * | 2023-06-19 | 2023-08-22 | 中国农业科学院农业环境与可持续发展研究所 | 一种多级压力调节生物质水热转化腐植酸的方法 |
Citations (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2317991A (en) | 1940-03-18 | 1943-05-04 | Dow Chemical Co | Promoter, method, and product |
US3076291A (en) | 1963-02-05 | Seed germination promoter and method | ||
US3111404A (en) | 1961-11-06 | 1963-11-19 | Concho Petroleum Company | Method of forming a granular ammonium humate fertilizer |
US3264084A (en) | 1964-02-05 | 1966-08-02 | Concho Petroleum Company | Production of a soil nutrient in a minimal liquid environment |
US3544295A (en) | 1967-12-11 | 1970-12-01 | Nitto Chemical Industry Co Ltd | Process for inhibiting nitrification of ammonia nitrogen in soils and soil-treating materials therefor |
FR2123042A1 (en) | 1970-06-15 | 1972-09-08 | Rhone Progil | Vegetable compost - from tree-bark with added nitrogen cpds in aerated fermenters |
US3770411A (en) | 1971-07-29 | 1973-11-06 | Organic Labor Inc | Plant stimulant |
FR2224421A1 (en) | 1973-04-03 | 1974-10-31 | Europeen Cellulose | Horticultural compost material prodn. - from wood bark and waste wood with nitrogenous minerals and trace elements |
DE2265298A1 (de) | 1971-12-01 | 1977-06-02 | Hans Gilgen | Wasserspeichernder bodenschichtaufbau fuer vegetationsflaechen |
DE2651171B1 (de) | 1976-11-10 | 1977-12-29 | Walter Prof Dr Tepe | Verfahren zum kompostieren von rinde |
US4319041A (en) | 1980-09-18 | 1982-03-09 | Goff David W | Method of producing humic acid |
DE3040040A1 (de) | 1980-10-23 | 1982-06-03 | Huminal Vertriebsgesellschaft mbH, 6000 Frankfurt | Verfahren zur herstellung von bodenverbesserungsmitteln durch kompostieren von nadelholzrinde |
DE3318171A1 (de) | 1983-05-19 | 1984-11-29 | Karl 6902 Sandhausen Serwane | Verfahren und vorrichtung zur schaffung einer vegetationsschicht |
DE4325692A1 (de) | 1992-07-31 | 1994-02-03 | Shinetsu Chemical Co | Künstliche Bodenstruktur und Verfahren zur Verhinderung der Landverwüstung unter Anwendung derselben |
US5876479A (en) | 1997-07-15 | 1999-03-02 | Hedgpeth, Iv; Joel | Composition and method of manufacturing a liquid humic acid based soil enhancer |
DE19859068A1 (de) | 1998-12-22 | 2000-07-06 | Univ Dresden Tech | Organisches Düngemittel sowie Verfahren zu seiner Herstellung und Verwendung |
DE10123283A1 (de) | 2001-05-12 | 2002-11-14 | Ebauchesfabrik Eta Ag | Verfahren zur Herstellung organischer Bodenverbesserungsmittel |
DE10120433C1 (de) | 2001-04-26 | 2002-11-21 | Lausitzer Braunkohle Ag | Verfahren zur Herstellung von Dauerhumusstoffen |
DE10123903A1 (de) | 2001-05-17 | 2002-11-28 | Lausitzer Braunkohle Ag | Verfahren zur Herstellung eines Bodenverbesserungsstoffes |
WO2007125492A2 (en) | 2006-05-02 | 2007-11-08 | Pfeinsmith S.A. (Pty) Ltd | Acidic composition |
WO2008081407A2 (de) * | 2006-12-28 | 2008-07-10 | Schweiger, Martin | Aus biomasse hergestellter werk- und/oder brennstoff |
DE202009007252U1 (de) | 2008-06-06 | 2009-09-03 | Terratextura Baustoff- Und Vegetations-Technologie Gmbh | Huminkomplexe zur Wurzelstimulation von Pflanzen |
EP1358299B1 (de) | 2001-02-09 | 2014-04-02 | Guido Bossard | Verfahren zur herstellung von böden oder trennschichten |
-
2018
- 2018-07-31 CA CA3072258A patent/CA3072258A1/en not_active Abandoned
- 2018-07-31 WO PCT/EP2018/070786 patent/WO2019052738A1/de unknown
- 2018-07-31 AU AU2018331216A patent/AU2018331216A1/en not_active Abandoned
- 2018-07-31 EP EP18749775.5A patent/EP3681851A1/de not_active Withdrawn
- 2018-07-31 JP JP2020513307A patent/JP2020537623A/ja active Pending
- 2018-07-31 US US16/638,636 patent/US20210130503A1/en not_active Abandoned
- 2018-07-31 BR BR112020002020-6A patent/BR112020002020A2/pt not_active Application Discontinuation
Patent Citations (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3076291A (en) | 1963-02-05 | Seed germination promoter and method | ||
US2317991A (en) | 1940-03-18 | 1943-05-04 | Dow Chemical Co | Promoter, method, and product |
US3111404A (en) | 1961-11-06 | 1963-11-19 | Concho Petroleum Company | Method of forming a granular ammonium humate fertilizer |
US3264084A (en) | 1964-02-05 | 1966-08-02 | Concho Petroleum Company | Production of a soil nutrient in a minimal liquid environment |
US3544295A (en) | 1967-12-11 | 1970-12-01 | Nitto Chemical Industry Co Ltd | Process for inhibiting nitrification of ammonia nitrogen in soils and soil-treating materials therefor |
FR2123042A1 (en) | 1970-06-15 | 1972-09-08 | Rhone Progil | Vegetable compost - from tree-bark with added nitrogen cpds in aerated fermenters |
US3770411A (en) | 1971-07-29 | 1973-11-06 | Organic Labor Inc | Plant stimulant |
DE2265298A1 (de) | 1971-12-01 | 1977-06-02 | Hans Gilgen | Wasserspeichernder bodenschichtaufbau fuer vegetationsflaechen |
FR2224421A1 (en) | 1973-04-03 | 1974-10-31 | Europeen Cellulose | Horticultural compost material prodn. - from wood bark and waste wood with nitrogenous minerals and trace elements |
DE2651171B1 (de) | 1976-11-10 | 1977-12-29 | Walter Prof Dr Tepe | Verfahren zum kompostieren von rinde |
US4319041A (en) | 1980-09-18 | 1982-03-09 | Goff David W | Method of producing humic acid |
DE3040040A1 (de) | 1980-10-23 | 1982-06-03 | Huminal Vertriebsgesellschaft mbH, 6000 Frankfurt | Verfahren zur herstellung von bodenverbesserungsmitteln durch kompostieren von nadelholzrinde |
DE3318171A1 (de) | 1983-05-19 | 1984-11-29 | Karl 6902 Sandhausen Serwane | Verfahren und vorrichtung zur schaffung einer vegetationsschicht |
DE4325692A1 (de) | 1992-07-31 | 1994-02-03 | Shinetsu Chemical Co | Künstliche Bodenstruktur und Verfahren zur Verhinderung der Landverwüstung unter Anwendung derselben |
US5876479A (en) | 1997-07-15 | 1999-03-02 | Hedgpeth, Iv; Joel | Composition and method of manufacturing a liquid humic acid based soil enhancer |
DE19859068A1 (de) | 1998-12-22 | 2000-07-06 | Univ Dresden Tech | Organisches Düngemittel sowie Verfahren zu seiner Herstellung und Verwendung |
EP1358299B1 (de) | 2001-02-09 | 2014-04-02 | Guido Bossard | Verfahren zur herstellung von böden oder trennschichten |
DE10120433C1 (de) | 2001-04-26 | 2002-11-21 | Lausitzer Braunkohle Ag | Verfahren zur Herstellung von Dauerhumusstoffen |
DE10123283A1 (de) | 2001-05-12 | 2002-11-14 | Ebauchesfabrik Eta Ag | Verfahren zur Herstellung organischer Bodenverbesserungsmittel |
DE10123903A1 (de) | 2001-05-17 | 2002-11-28 | Lausitzer Braunkohle Ag | Verfahren zur Herstellung eines Bodenverbesserungsstoffes |
WO2007125492A2 (en) | 2006-05-02 | 2007-11-08 | Pfeinsmith S.A. (Pty) Ltd | Acidic composition |
WO2008081407A2 (de) * | 2006-12-28 | 2008-07-10 | Schweiger, Martin | Aus biomasse hergestellter werk- und/oder brennstoff |
DE202009007252U1 (de) | 2008-06-06 | 2009-09-03 | Terratextura Baustoff- Und Vegetations-Technologie Gmbh | Huminkomplexe zur Wurzelstimulation von Pflanzen |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11124461B2 (en) | 2019-07-04 | 2021-09-21 | Incitec Pivot Limited | Fertilizer |
US11691929B2 (en) | 2019-07-04 | 2023-07-04 | Incitec Fertilizers Pty Limited | Fertiliser |
DE202021001026U1 (de) | 2021-04-27 | 2021-05-28 | IAB-Institut für Angewandte Bauforschung Weimar gemeinnützige GmbH | Phosphathaltiges Düngemittel bestehend aus erhitztem Klärschlamm und zusätzlichen Alkali- und/oder Erdalkalien aus Reststoffen der Kaligewinnung |
CN113399417A (zh) * | 2021-05-26 | 2021-09-17 | 华南理工大学 | 一种利用污泥制备腐植酸钠的方法与应用 |
CN114452820A (zh) * | 2021-12-23 | 2022-05-10 | 南京师范大学 | 一种分离并测定腐殖酸含碳官能团的装置及其使用方法与应用 |
CN114452820B (zh) * | 2021-12-23 | 2023-08-15 | 南京师范大学 | 一种分离并测定腐殖酸含碳官能团的装置及其使用方法与应用 |
Also Published As
Publication number | Publication date |
---|---|
CA3072258A1 (en) | 2019-03-21 |
AU2018331216A1 (en) | 2020-03-19 |
US20210130503A1 (en) | 2021-05-06 |
EP3681851A1 (de) | 2020-07-22 |
BR112020002020A2 (pt) | 2020-08-11 |
JP2020537623A (ja) | 2020-12-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3681851A1 (de) | Verfahren zur produktion von huminstoffen aus biomasse wie holz, rinde, getreidestroh, blättern, krautigen pflanzen sowie baumpilzen, klärschlamm und anderen organischen abfällen | |
DE4133984A1 (de) | Verfahren zum biologischen aufschluss von mineralien | |
Bhosale et al. | Studies on physico-chemical characteristics of waxed and dewaxed pressmud and its effect on water holding capacity of soil | |
EP3247690A2 (de) | Bodenhilfsstoffe sowie verfahren zu deren herstellung sowie deren verwendung | |
DE102011010329A1 (de) | Wasser speicherndes und abgebendes organisch basiertes Kompositmaterial sowie dessen Herstellung und Anwendung | |
DE102011087635A1 (de) | Verfahren zur Herstellung bodenverbessernder Substrate sowie bodenverbessernde Substrate | |
DE102015100644A1 (de) | Herstellung eines flüssigen Bodenhilfsstoffes auf der Basis von Humin- und Fulvosäuren für den Einsatz als Boden- und Wasserhilfsstoff zur positiven Beeinflussung des Boden-Wasser-Pflanzen-Nährstoff-Haushaltes | |
EP0104355B1 (de) | Verfahren zur Herstellung eines vollwertigen Humusträgers und Düngers auf Rindenbasis | |
EP3630706B1 (de) | Dauerhumus-wasserspeicherhybrid | |
DE4009886C2 (de) | Verfahren zum Behandeln von Gülle | |
DE3040040A1 (de) | Verfahren zur herstellung von bodenverbesserungsmitteln durch kompostieren von nadelholzrinde | |
DE102009027007A1 (de) | Verfahren zur Herstellung von mineralischem Biodünger | |
EP2657212B1 (de) | Verfahren zur aufbereitung von organischen abfallstoffen und komposten, insbesondere von gärresten aus biogasanlagen | |
DE60009563T2 (de) | Mischung zur beschleunigung der kompostierung | |
DE102009051885A1 (de) | Organo-mineralisches Düngemittel und Verfahren zu dessen Herstellung | |
DE4240807C1 (de) | Organisch-mineralisches Düngemittel | |
Placek et al. | Methods for calculating carbon sequestration in degraded soil of zinc smelter and post-mining areas | |
WO1998048933A1 (de) | Biosorbentien für metallionen und verfahren zu ihrer herstellung | |
DE102013010007B4 (de) | Verfahren zur Auftrennung einer Suspension, danach hergestellte Produkte sowie die Verwendung derselben | |
EP3162784B1 (de) | Verfahren zur herstellung von biomassedünger aus in der gülle enthaltenen ionenlösungen | |
DE102015100645A1 (de) | Herstellung eines rieselfähigen Bodenhilfsstoffes auf der Basis von flüssiger Humin- und Fulvosäuren, sowie fester anorganischer und organischer Substanz für den Einsatz als Boden- und Wasserhilfsstoff zur positiven Beeinflussung des Boden-Wasser-Pflanzen-Nährstoff-Haushaltes | |
DE4040772C1 (de) | ||
DE19880157B4 (de) | Verfahren zur Vorbereitung einer Mikroorganismenmischung zur Bindung von atmosphärischem Stickstoff, zur Erhöhung der Löslichkeit von Phosphorverbindungen und zur Zersetzung von Lebensmittelölsediment und die genannte Mischung | |
DE2758010A1 (de) | Vollduengemittel zur dauernden biologischen bodenverbesserung und ertragssteigerung sowie verfahren zu deren herstellung | |
EP0399990A2 (de) | Bodenverbesserungsmittel |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 18749775 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 3072258 Country of ref document: CA |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112020002020 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 2020513307 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2018331216 Country of ref document: AU Date of ref document: 20180731 Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2018749775 Country of ref document: EP Effective date: 20200414 |
|
ENP | Entry into the national phase |
Ref document number: 112020002020 Country of ref document: BR Kind code of ref document: A2 Effective date: 20200130 |