DE10351274A1 - Metal compound of humic acids, their preparation, compositions containing them and use thereof - Google Patents

Abstract

Disclosed is a metal compound of humic acids of the general formula M-Hu, where M is the cation Fe (II) and / or Zn (II) and / or Cu (ii) and / or Mn (II) and Hu is a humic acid radical.

Description

The The present invention relates to a metal compound of humic acids, the Preparation, compositions containing them and use the same.

State of the art:

According to Römpp lexicon Natural substances, Georg Thieme Verlag 1997, p 297 f is understood by humic acids (Humic acids) a chocolate-brown, dust-like powder, which under high volume increase little soluble in water, but soluble in brownish color in alkaline aqueous Solution. The humic acids are strongly acidic (hydroxy and polyhydroxycarboxylic acids), are predominantly as salts. humic acids arise from dead plant material in the course of Humus Bldg. in soils chemical and biological reactions (humification). Your composition is inconsistent and dependent on the type of phenol and amino group-containing precursors. Humic acids come in humus-rich soils, in peat and lignite, but not in hard coal. You improve the physical soil structure. Low molecular weight humic acids dissolve in the surface water and cause its brown color (especially intense in marshes). The residence time of humic acids in Soil is time-limited as it is affected by microorganisms and action be decomposed from air-oxygen to carbon dioxide and water. Humic acid additives in animal feed can the intake of heavy metals such as cadmium and lead from food reduce, because the humic acid complexes undigested excreted. Humic acids are found as ingredients in Tort, peat garbage, mud baths and in the Kasseler Braun [a Natriumhum (in) at] practical application.

Hitherto, applications of iron (III) -humate as an iron source for the treatment of agricultural plants against chlorosis have been known. This iron (III) humate (iron humate product) is produced as a by-product in drinking water treatment ( US 5,302,180 . US 5,411,569 . US 5,446,179 ). The formation of iron (III) humates takes place by the addition of iron (III) sulfate to the natural humic-containing water. After US 5,354,350 (= WO 95/16648) citric acid-soluble iron (III) humate is used for the same purpose, which is water-insoluble.

From the EP 0 531 868 A1 Furthermore, the formation of humic acid-iron (II) -carboxymethyl-cellulose complex compounds is known, resulting from the addition of Fe (II) sulfate solution to the mixture of raw lignite extract and carboxymethyl cellulose. A water-soluble granules with 6% iron in EDDHA form is used for example under the name SEQUESTRENE ^® 138 FE of Synergenta as iron fertilizer and to remedy iron deficiency chlorosis. However, this preparation is harmful to health, irritating to the skin and can corrode metals. Hitherto commercially available iron humates in liquid form tend to flocculate.

The previously known iron (III) or iron (II) complex humates are insofar disadvantageous that they either not metabolized directly in plants can be since iron (III) humate is insoluble in water or in the case of iron (II) complex human compounds there is a risk of soil contamination through which synthetic chelating agents exist.

Description of the invention:

metal compounds

Of the Invention is initially the task is to provide special new metal compounds of humic acids.

These The object is solved by the features of claim 1. These Metal compounds have biologically advantageous properties for animal and plants.

The The invention therefore relates to a metal compound of humic acids of general formula M-Hu, where M is the cation Fe (II) and / or Zn (II), Cu (II) and / or Mn (II) and Hu is a humic acid residue is. These metal compounds can both as single metals of humic acids, as a mixture of metal compounds humic acid or as an in situ generated mixture of the humic acid metal compounds.

To the Example, the iron (II) -Humat invention has the advantage that the iron is already present in bioavailable form as iron (II) is. This facilitates its uptake in plants - without reduction precursor. The further advantage of the iron (II) -Humates invention, that you have the natural, humic substances occurring in lignite as the chelating agents used. this leads to to that the natural Humic substances released after iron absorption in the plants where there is no risk of soil contamination. The Iron (II) humate according to the invention is produced as a powder or granules, which is before use completely in aqueous solutions can dissolve and thus not the problem of flocculation when storing liquid iron humates having.

According to a preferred embodiment of the invention, the metal compound is an iron (II) compound of humic acid, a zinc compound of humic acid, a copper (II) compound of humic acid and / or a manganese (II) compound humic acid.

According to a preferred embodiment of the invention, the metal compound M-Hu has a solubility in distilled water at 20 ° C of more than 20 g / dm ³ , preferably more than 50 g / dm ³ , in particular more than 100 g / dm ³ .

To a further preferred embodiment of the invention the total content of the metals is more than 5% by weight to 15% by weight, preferably 5 to 10 wt .-%.

To a further preferred embodiment The present invention relates to the metal compound of the invention as powder or as granules and it contains no additional complexing substances.

To a further preferred embodiment is the metal compound of the invention in aqueous solutions stable in the pH range of 6 to 11.

To a further preferred embodiment the invention is the metal compound of the invention as a concentrated solution stable opposite Calcium ion exchange, especially in alkaline solutions.

manufacturing:

Of the Invention is further based on the object, a manufacturing method for the Metal compounds according to the invention of humic acids provide. This process comes without the use of ecological questionable chelating agent and is technically simple designed. This object is achieved by the features of the manufacturing claim solved.

The The invention thus further relates to a process for the preparation of Metal compounds of humic acids of the type described above by providing a water-containing solution an alkaline compound of humic acid, adding at least one water-soluble Metal salt M-X, where M is for the chemical elements Fe (II), Zn (II), Mn (II) and X is a salt a mineral acid is in a crowd at 5-15 Wt .-% of the metal compound to produce, contacting the alkali compound the humic acid with the metal salt M-X, control of the pH during the reaction, optionally work-up the metal compound of humic acid in a known manner.

To a preferred embodiment of Invention, the provision of the alkali salt of humic acid by Alkali extraction of coal, especially lignite, Leonardite, Compost, Tort, sea slime or other humus containing materials as alkaline crude extract or by dissolving the alkali compound of Humic acid.

To a preferred embodiment of The invention relates to the alkali metal compounds of humic acid to the Sodium, potassium or ammonium compound, preferably the potassium or the sodium compound.

To a preferred embodiment of Invention, the adjustment to the pH by means of a basic substance, an acid or by means of a buffer system.

To a preferred embodiment of Invention is the water-containing solution of water. Otherwise you can also other chemically inert solvents, such as alcohols having 1 to 6 carbon atoms to be present.

To a preferred embodiment of Invention, the addition of the metal salt M-X, in solid form, dissolved in water, preferably in dissolved Shape.

To a further preferred embodiment becomes the method according to the invention done in the way that contacting the alkali compound of humic acid with the metal salt M-X is carried out under inert gas. As an inert gas both Nitrogen as well as noble gases are used, whereby nitrogen is preferred.

To a preferred embodiment of Invention is the salt of the water-soluble metal salt M-X selected from Nitric or sulfur containing mineral acids, in particular from sulfur atoms containing mineral acids.

Under mineral acids For the purposes of the present invention is meant nitric acid, nitrous Acid, sulphurous acid, Sulfuric acid, being sulfuric acid is preferred.

To a preferred embodiment of Invention, the contacting takes place by mixing at temperatures between 10 ° C and the boiling point of the reaction mixture, preferably between 18 ° C and 90 ° C and contacting via a Period from 0.5 hours to 72 hours, preferably 1 hour to 6 hours.

To a preferred embodiment of Invention, the contacting takes place until the pH value has reached constant value.

According to a further preferred embodiment, the control of the pH is performed so that you by the pH statverfahren or pH-flowver drive takes place.

To a preferred embodiment of Invention, the workup of the metal compound of humic acid by Removal of the water by drying, preferably by contact or convection drying, in particular up to a residual moisture less than 20% by weight, more preferably less than 15% by weight.

compositions:

The The invention further relates to a composition, in particular biologically active composition containing at least one metal compound humic acid of the type described above and / or prepared according to the method described above.

cause is the composition of the invention either in the form of a veterinary or medicinal product for human or a nutritional supplement.

Here it is preferred that the composition is encapsulated or coated, which encapsulation or coating is enteric-coated, ie only degradable in the slightly acidic to alkaline medium. We refer to Schöffling, drug theory, Stuttgart, German Pharmacist Verlag, 3rd ed. 1998, pages 164-180, in particular p. 176-179. Examples include methacrylic acid (Eudragit ^®), Celluloseester as cellulose acetate phthalate or cellulose ethers such as ethyl cellulose.

For the application as animal feed additive is a quantity of 200-2,000 mg iron (II) humat (production of iron humate based on sodium humate) per kg of animal feed recommended. Drug can because of its solubility Here also the drinking water are added directly (3-10 mg / kg mast weight).

alternative can the composition of the invention also as a treatment for plant deficiency diseases or as a fertilizer be used. The HUMIRON invention is for both the direct Usable as well as as a mixture with soluble fertilizers like NPK, DAP or Urea and also with herbicides.

typically, in a foliar application 0.1-5 kg, preferably 0.25-2.5 kg, in particular 0.5-1 kg of the metal compound of the invention humic acid used with at least 200 L of water per hectare and possibly foliar fertilizers or pesticides added.

Foliar application:

Dissolve 3-5 g of the metal compound of humic acid in water and apply after planting or after the appearance of deficiency symptoms. Repeat after 2-3 weeks if necessary.
Pea fruit: 20-50 g / 10 L per tree
Citrus fruits: 10 g / 10 L per tree
Grapes: 10-20 g / 10 L per vine
Field crops and vegetables: 1.5 kg per hectare

at a soil application will be 0.25 to 10 kg, preferably 1-2 kg inventive metal compound humic acid with stirring dissolved to 500 L of water per hectare (Spray mixture or nutrient solution) and the solution applied before sowing or between rows of plants.

The same dosages also apply to the treatment of plant-deficiency diseases, such as. the chlorosis.

Soil application:

Apply 30-100 g / tree of the metal compound of humic acid in sandy soils and 100-300 g in heavy soils annually in spring, both before and during spring growth or when deficiency symptoms appear.
Pea fruit: 10 g / tree per 10 cm stem diameter.
Citrus fruits: 5-10 g / m ² (nurseries), 150-250 g in sandy soils and 250-500 g in heavy soils, 100-150 g / tree for annual maintenance programs.
Berries and grapes: 75-150 g per 10 m.
Vegetables, turf: 5 kg / ha / eg forage grasses, cotton, legumes, rice, cereals, onions, potatoes, tomatoes, cabbage).
Flax: 10 kg per hectare.
Cut flowers: 10-20 g / 100 L in summer, 5-10 g / 100 L in winter.
Ornamental plants: 25-50 g / m ³ (potted plants) 5-10 g / m ³ (bedding plants).
Ornamental woods: 60-70 g / tree (scattered) or per 10 L of water.
Roses: 10-15 g / m ³ (sprinkled) or 25-50 g on 10 L of water.

uses:

The The invention further relates to the use of the metal compound humic acid of the type described above and / or produced according to the above-described Procedure for the treatment of mineral deficiency diseases and as a component of fertilizers in plants, especially useful plants.

Among plants within the meaning of the present Invention is understood in particular shrubs, trees and flowers. Preference is given to the use in crops.

Under Crops within the meaning of the present invention are both understood Protein supplying plants like fat / oil supplying plants, fodder plants, grasses, vegetables, medicinal and aromatic plants, legumes, industrial crops, Carbohydrate producing plants, fruits, stimulants and sugar producing plants.

Examples of protein-producing plants are:
Arachis hypogaea, Bauhinia esulenta, Cajanus cajan, Canavalia ensiformis, Cicer arietinum, Glycine max, Lens culinaris, Macrotyloma geocarpum, Phaseolus lunatus, Phaseolus vulgaris, Pisum sativum, Psophocarpus tetragonolobus, Vicia faba ssp. faba, Vigna mungo, Vigna radiata, Vigna subterranea, Vigna umbellata, Vigna unguiculata (L.) Walp. ssp. unguiculata.

Examples of fat / oil producing plants are:
Arachis hypogaea, Brassica napus ssp. napus, Brassica rapa ssp. oleifera, Cannabis sativa, Carthamus tinctorius, Cocos nucifera, Cyperus esculentus, Elaeis guineensis, Glycine max, Helianthus annuus, Linum usitatissimum, Olea europaea, Orbignya speciosa, Papaver somniferum, Prunus dulcis, Ricinus communis, Sesamum indicum, Theobroma cacao, Vitellaria paradoxa. Glycine max, Arachis hypogaea

Examples of fodder plants and grasses are:
Agropyron cristatum, Agrostis alba, Agrostis gigantea, Alopecurus pratensis, Andropogon gayanus, Arrhenatherum elatius, Axonopus affinis, Brachiaria brizantha, Brachiaria purpurascens, Bromus anomalus, Bromus inermis, Cenchrus catharticus, Chinochloa polystachya, Chloris gayana, Cynodon actylon, Cynosurus cristatus, Dactylis glomerata , Digitaria decumbens, Elymus anadensis, Festuca elatior, Festuca ovina, Hyparrhenia aucta, Ischaemum angustifolium, Lolium perenne, Melinis minutiflora, Panicum coloratum, Panicum maximum, Paspalum dilatatum, Pennisetum purpureum, Phalaris arundinacea, Phalaris canariensis, Phleum pratense, Poa pratensis, Schizochyrim semiberbe, Setaria sphacelata, Themeda triandra.

Examples of vegetables are:
Allium cepa var. Cepa, Allium porrum L. var. Porrum, Apium graveolens var. Rapaceum, Asparagus officinalis, Bactris gasipaes, Beta vulgaris ssp. vulgaris var. cicla, Beta vulgaris ssp. vulgaris var. vugar, Brassica napus var. rapifera Metzg., Brassica oleracea ssp. oleracea, Brassica oleracea ssp. oleracea convar. botrytis, Brassica rapa ssp. pekinensis, Ceratonia siliqua, Cichorium endivia, Cichorium intybus, Cucumis sativus, Cucurbita pepo, Cyamopsis tetragonoloba, Cynara scolymus, Daucus carota ssp. sativus, Ipomoea aquatica, Lycopersicon esculentum, Scorzonera hispanica, Sechium edule, Solanum melongena, Spinacia oleracea.

Examples of medicinal and aromatic plants are:
Allium sativum L. var. Sativum, Capsicum annuum, Capsicum frutescens, Humulus lupulus, Melilotus officinalis, Piper nigrum, Vanilla planifolia.

Examples of legumes are:
Abelmoschus esculentus, Aechyomene americana, Alysicarpus rugosus, Bauhinia esculenta, Calopogonium mucunoides, Clitoria ternatea, Crotalaria ochroleuca, Desmodium tortuosum, Dioclea violacea, Galactia mollis, Indigofera oblongifolia, Lablab purpureus, Lathyrus sativus, Lespedeza striata, Leucaena leucocephala, Lotus corniculatus, Lupinus luteus , Macroptilium lathyroides, Medicago sativa, Melilotus alba, Mucuna deeringiana, Neonotonia wightii, Onobrychis viciifolia, Pisum sativum, Pueraria lobata, Stizolobium pruriens, Stylosanthes fruticosa, Tephrosia candida, Teramnus labialis, Trifolium alexandrinum, Trigonella caeruela, Zornia diphylla.

Examples of industrial plants are:
Agave sisalana, Antelaea azadirachta, Ceroxylon alpinum, Chrysanthemum cinerariifolium, Copernicia prunifera, Corchorus capsularis, Corchorus olitorius, Crotalaria juncea, Hibiscus cannabinus, Musa textilis, Ochroma pyramidale, Parthenium argentatum, Quercus suber, Revea brasiliensis, Simmondsia chinensis.

Examples of carbohydrate-producing plants are:
Amaranthus caudatus, Avena sativa, Chenopodium quinoa, Cichorium intybus, Colocasia esculenta, Digitaria exilis, Dioscorea alata, Dioscorea bulbifera, Dioscorea cayenensis, Dioscorea esculenta, Dioscorea opposita, Dioscorea rotundata, Echinochloa frumentacea, Eleusine coracan, Eragrostis tef, Fagopyrum esculentum, Helianthus tuberosus Hordeum vulgare, Inula, Ipomoea batatas, Manihot esculenta, Maranta arundinacea, Metroxylon sagu, Oryza sativa, Panicum miliaceum, Paspalum scrobiculatum, Pennisetum americanum, Secale cereale, Setaria italica, Solanum tuberosum, Sorghum bicolor, Triticum aestivum, Xanthosoma sagittifolium, Zea mays ,

Examples of fruits are:
Actinidia chinensis, Anacardium occidentale, Ananas comosus, Annona cherimola, Carica papaya, Carya illinoinensis, Citrullus lanatus ssp. Vulgaris var. vulgar, Citrus deliciosa, Citrus limon, Citrus maxima, Citrus medica, Citrus sinensis, Citrus x paradisi, Cucumis melo, Eriobotrya japonica, Fortunella margarita, Hippophae rhamnoides, Juglans regia, Litchi chinensis, Macadamia integrifolia, Malus domestica ssp. domestica, Mangifera indica, Mephelium lappaceum, Musa x acuminata, Passiflora edulis, Persea ameri cana, Phoenix dactylifera, Physalis peruviana, Pistacia vera, Prunus armeniaca, Prunus avium, Prunus cerasus, Prunus domestica, Prunus persica, Psidium guayava, Pyrus communis, Ribes nigrum, Ribes rubrum, Ribes uva-crispa, Rubus idaeus, Tamarindus indica, Vitis vinifera. Vitis amurensis, Rutaceae (botanical plant family), Rosaceae (botanical plant family)

Examples of stimulants are:
Camellia sinensis, Catha edulis, Coffea arabica, Cola acuminata.

Examples of sugar supplying plants are:
Arenga pinnata, Beta vulgaris L. ssp. vulgaris convar. vulgaris var. altissima Döll, Saccharum officinarum, Sorghum saccharatum.

The Invention finally relates the use of the metal compound of humic acid of the type described above and / or prepared according to the procedure described above for Prophylaxis and for the treatment of mineral deficiencies in vertebrates, preferably mammals and in humans.

Under the class of vertebrates fall in particular the class of amphibians, the class of reptiles, the class of birds and the class of mammals.

Especially The metal compounds of the invention are preferably the humic acids but used in farm animals and pets. Among livestock in the sense The present invention is understood to mean cattle, sheep, pigs, Poultry. Within the meaning of the present invention, domestic animals are understood Fish, dogs, cats, horses, birds.

The The invention finally relates to the use of the metal compound humic acid of the type described above and / or produced according to the above-described Procedure as a dietary supplement in vertebrates, preferably mammals, in particular Livestock.

The The present invention will now be described with reference to a figure.

It shows

FIG. the comparison of the chlorophyll content (chl a, Chl b, and the sum both values) in leaves of tomato plants (Lycopersicum esculentum Mill.) after addition various iron supplements.

In The figure shows that opposite the untreated tomato plants (control) through the use of iron compound of the invention humic acids (HUMIRON) opposite classic inorganic iron fertilizer (FeSO4) and the potassium compound of humic acids (Humin-P 775) as starting material for the inventive compound a synergistically multiple better yield of chlorophyll a (chl a) and chlorophyll b (chl b) is obtained. Also against ferrous EDTA will be several times higher Obtained chlorophyll yield. Compared to the synthetic Chelating agent EDDHA does not get a better chlorophyll content been, for is the product of the invention but ecologically harmless and produces no soil contamination by the synthetic Chelate.

In the course of the evaluation, 54 tomato plants were used in 5 l containers each with an aqueous hydroponic nutrient solution of the following mineral contents (in mmol / L): potassium dihydrogen phosphate: 1, potassium nitrate: 5, calcium nitrate tetrahydrate: 5, Magnesium sulfate heptahydrate: 2, manganese sulfate hydrate: 0.009, zinc sulfate heptahydrate: 0.0007, copper sulfate pentahydrate: 0.0003, ammonium molybdate tetrahydrate: 1.7 x 10 ^-5 , boric acid: 0.046. This nutrient solution served as a control. For comparison, an iron content of 0.015 mmol / l of iron was added in the form of the following fertilizers: 4.17 mg / L ferrous sulfate pentahydrate, or 7.16 mg / L humic-P (humic acid potassium compound), or 8 mg / L HUMIRON ( Iron (II) compound of humic acid), or added to 5.7 mg / L EDTA with iron content or 10.24 mg / L FE-EDDHA.

Of the Chlorophyll content was measured photometrically after acetone extraction the characteristic deep red fluorescence at 644 and 662 nm determined.

The The present invention will now be described by way of example in the form of preparation examples explained in more detail.

Preparation Example 1 (Iron (II) compound humic acid)

150-180 g of Potassium humate (Humin-P 775, manufacturer: Humintech GmbH, Dusseldorf) is dissolved in 1000 mL of water. the pH of the solution obtained embossed about 9.0.

To 1 L solution of potassium humate is added 1 L solution of 16-17 wt.% FeSO ₄ .7H ₂ O with stirring under the pH control, which is done by adding the concentrated KOH solution. The reaction mixture is stirred for a further 4-5 hours until pH values remain constant and it is dried by spray-drying. The yield is 300-350 g of product with the following analysis data: HS content - 50-55% Fe content - 7-10% H ₂ O content - 11% (calculated on dry matter, the difference to 100% results from the presence of potassium and sulfate.) The product obtained has a storage stability of at least 3 years.

Preparation Example 2 (zinc salt of humic acid)

Preparation Example 1 was repeated, but using 1% by weight of zinc (II) sulfate instead of the iron (II) sulfate heptahydrate. The resulting product has a water solubility of at least 20 g per dm ^{3 of} water.

Preparation Example 3 (Manganese (II) salt of humic acid)

Preparation Example 1 was repeated, but using 1% by weight of manganese (II) sulfate instead of the iron (II) sulfate heptahydrate. The product obtained has a water solubility of at least 20 g per dm ^{3 of} water.

Preparation Example 4 (copper (II) salt of humic acid)

Preparation Example 1 was repeated, but using 16-17% by weight of copper sulfate instead of the iron (II) sulfate heptahydrate. The product obtained has a water solubility of at least 20 g per dm ^{3 of} water.

Production Example 5 (Metal compound mixture of humic acid)

Preparation Example 1 was repeated, but using instead of the iron (II) sulfate heptahydrate 7% by weight of iron (II) sulfate, 1% by weight of manganese (II) sulfate, 1% by weight of zinc sulfate and 1% by weight of copper sulfate. The product obtained has a water solubility of at least 20 g per dm ^{3 of} water.

Claims (28)

Metal compound of humic acids of the general formula M-Hu, being M for the cation Fe (II) and / or Zn (II) and / or Cu (ii) and / or Mn (II) stands and Hu a humic acid residue is. Metal connection according to claim 1, characterized in that that it is an iron (II) compound of humic acid. Metal connection according to claim 1, characterized in that that it is a zinc compound of humic acid. Metal connection according to claim 1, characterized in that that it is a manganese (II) compound of humic acid. Metal connection according to claim 1, characterized in that that it is a copper (II) compound of humic acid A metal compound according to any one of claims 1 to 5, characterized in that it has a solubility in at least. Water at 20 ° C of more than 20 g / dm ³ , preferably 50 g / dm ³ , in particular more than 100 g / dm ³ has. A metal compound according to any one of claims 1 to 6, characterized in that the total content of the metals 5 wt .-% to 15% by weight, preferably 5% by weight to 10% by weight. A metal compound according to any one of claims 1 to 7, characterized in that they as powder or granules present and that they have no additional contains complexing substances. A metal compound according to any one of claims 1 to 8, characterized in that they are in aqueous solutions in the pH range of 6 until 11 is stable. A metal compound according to any one of claims 1 to 9, characterized in that it is stable as a concentrated solution across from Calcium ion exchange, especially in alkaline solutions, is. Process for the preparation of metal compounds of humic acids according to any of the claims 1 to 10 through - Provision a water-containing solution an alkaline compound of humic acid, - Add at least one water-soluble Metal compound M-X, where M is for the chemical elements Fe (II) and / or, Zn (II) and / or Cu (II), and / or Mn (II) and X is a salt of a mineral acid, in an amount of 5 to 15% by weight of the metal compound to produce - To contact the alkali compound of humic acid with the metal salt M-X, - Control the pH during the reaction - possibly. Working up of the metal compound of humic acid in a known manner. Method according to claim 11, characterized in that that the provision of the alkaline compound of humic acid by Alkali extraction from coal, lignite, leonardite, peat, compost, Sea slime or other humus-containing materials as alkaline Raw extract or by dissolving the alkaline compound of humic acid he follows. A method according to any one of the claims 11 or 12, characterized in that it is the alkali metal compounds of humic acid to the sodium, potassium or ammonium compound, preferably the potassium compound or sodium compound. A method according to any one of claims 11 to 13, characterized in that the adjustment to the pH by means of a basic substance, an acid or by means of a buffer system he follows. A method according to any one of claims 11 to 14, characterized in that the water-containing solution is water is. A method according to any one of claims 11 to 15, characterized in that the addition of the metal salt M-X, in solid form, dissolved in water, preferably in dissolved Form, takes place. A method according to any one of claims 11 to 16, characterized in that the salt of the water-soluble Metal salt M-X selected is from mineral acids containing nitrogen and / or sulfur atoms, in particular from sulfur atoms containing mineral acids. Method according to any one of claims 11 to 17, characterized in that the contacting by mixing at temperatures between 10 ° C and the boiling point of the reaction mixture, preferably between 18 ° C and 90 ° C takes place and that contacting over a period of 0.5 to 72 hours, preferably 1 to 6 hours he follows. A method according to any one of claims 11 to 18, characterized in that the contacting takes place as long as until the pH has reached a constant value. A method according to any one of claims 11 to 19, characterized in that the contacting of the alkali compound humic acid with the metal salt M-X under inert gas. A method according to any one of claims 11 to 20, characterized in that the workup of the metal compound humic acid by removing the water by drying, preferably by contact or convection drying takes place, in particular up to a residual moisture less than 20% by weight, more preferably less than 15% by weight. Composition, in particular biologically active Composition containing at least one metal compound of humic acid according to any of the claims 1 to 10 and / or produced according to any one of claims 11 to 21st A composition according to claim 22 as an agent for Treatment of plant-deficiency diseases or as a fertilizer. A composition according to claim 22 in the form of a veterinary or Medicinal product for human use or a dietary supplement. Composition according to Claim 24, characterized that she encapsulated or coated, this encapsulation / coating is preferably enteric-coated, so only in slightly acidic to alkaline solution is degradable. Use of the metal compound of humic acid after any of the claims 1 to 10 and / or produced according to any one of claims 11 to 21 for the treatment of mineral deficiencies and as an ingredient of fertilizers Plants, especially useful plants. Use of the metal compound of humic acid after any of the claims 1 to 10 and / or produced according to any one of claims 11 to 21 for the prophylaxis and treatment of mineral deficiencies in vertebrates, preferably mammals and in humans. Use of the metal compound of humic acid after any of the claims 1 to 10 and / or produced according to any one of claims 11 to 21 as a dietary supplement in vertebrates, preferably mammals and in humans.