EP4146781A1

EP4146781A1 - Carbon dioxide-neutral bio converter facilities for producing biogas using hydrogen and activated carbon compositions in the fermentation liquid of the bio converter

Info

Publication number: EP4146781A1
Application number: EP21732190.0A
Authority: EP
Inventors: Sven Nefigmann
Original assignee: Nefigmann GmbH
Current assignee: Nefigmann GmbH
Priority date: 2020-05-09
Filing date: 2021-05-05
Publication date: 2023-03-15
Also published as: DE102020002755B4; DE102020002755A1; US20230279321A1; WO2021228428A1; CA3185658A1

Abstract

The invention relates to a carbon dioxide-neutral bio converter facility (BKA) according to figure 1, comprising: - at least one bio converter (BK) for a single-stage or multistage production of biogas (BG) by fermenting biomass (BM) in a fermentation liquid (GF) which is moved using agitation means in the presence of elemental hydrogen, hydrogenotrophic and methanogenic archaea, and activated carbon compositions (K; KM), - an ammonia store (NH3) which, by means of an ammonia line (NH3L), is connected to - an ammonia cracker (AC) for producing hydrogen and nitrogen (H2/N2) by catalytically cracking ammonia, and - a line (LH2/N2) for introducing the generated hydrogen (H2) or the hydrogen-nitrogen mixture (H2/N2) into the at least one bio converter (BK), and/or - a device (VBK) for treating the activated carbon compositions (K; KM) with hydrogen (H2) at a high pressure, comprising a pressure line (25) and an injection lance (28) for injecting the hydrogen-containing carbon compositions (K; KM) into the fermentation liquid (GF), wherein the ammonia is produced using renewable energy, and the ammonia cracker (AC) is operated using the renewable energy. The invention also relates to a conversion method, to a method for injecting hydrogen-containing carbon compositions (H2K; H2KM), and to the use of the fermentation products (KBM).

Description

Carbon dioxide-neutral bio-converter systems for the production of biogas with hydrogen and activated carbon masses in the fermentation liquid of the bio-converter

Field of invention

The present invention relates to carbon dioxide-neutral bioconverter plants for the production of biogas with elemental hydrogen and activated carbon masses in the fermentation liquid of the bioconverter.

In addition, the present invention relates to carbon dioxide-neutral conversion processes for the production of biogas in bioconverters of bioconverter plants by fermenting biomass in a fermentation liquid moved with agitating agents in the presence of elemental hydrogen, hydrogenotrophic and methanogenic archaea and activated coal masses.

Last but not least, the present invention relates to the use of the converted biomass and fermentation products produced by the carbon dioxide-neutral conversion processes and / or the activated carbon masses used in the process as fertilizer or for the production of terra preta.

State of the art

In order to produce methane gas, biomass is fermented anaerobically in bioconverters. In the context of the present invention, the term “fermentation” or “fermentation” is understood to mean the conversion of biological, in particular organic materials with the aid of microorganisms (bacteria, fungi and / or other cell cultures). Fermentation can also take place through the addition of metabolically activated enzymes or other biologically activated molecules, such as nutrient substrates of the microorganisms. Fermentation can include both aerobic processes, e.g. acetic acid fermentation, and anaerobic processes, e.g. lactic acid fermentation.

In their article "Increasing the biogas yield by adding biochar" in Müll und Abfall, 2014, pages 476 to 480, Dipl. Wi.-Ing. Jan-Markus Rödger, M.Eng.- M.Sc. Waldemar Ganagin, Dipl. -Ing. agr. Andreas Krieg, B.SC. Christian Roth and Prof. Dring. Achim Loewen the increase in biogas yield by adding biochar.

1

CONFIRMATION COPY In this article it becomes clear that by adding large particles of coal to the post digester, the excess yield of methane gases increased by 24% within 91 days.

The German patent application DE 10 2014 111 287 A1 discloses a method for generating methane in bioconverters from biomass, in which hydrogen is fed to the bioconverters. The hydrogen is preferably obtained by electrolysis of water. The use of activated coal masses is not described.

The German patent application DE 10 2015 012 436 A1 discloses the use of carbon nanoparticles, coal microparticles and / or coal macroparticles to promote the growth of microorganisms and / or to increase metabolism and / or catabolism and / or anabolism and / or to increase the yield of various products and / or or to protect the concrete walls in converters.

The German patent DE 102016004026 B4 discloses the use of floating bodies with activated coal mass to increase the methane yield when converting the fermentation liquid.

The American patent application US 2012/0100590 A1 discloses a bioconverter for the production of methane with electrolysis cells for the electrolysis of water. The fermentation liquid contains hydrogenotrophic and methanogenic archaea. The use of activated coal mass in fermentation or conversion of the fermentation liquid is not described.

The American patent application 2012 / 0088266A1 describes a bioconverter for the production of hydrogen by a hydrogen-producing bacterial mixture in a fluidized bed. The fluidized bed contains activated carbon particles and particles of steel, gravel, glass and coal ash coated with them. The well-known bioconverter is not suitable for the production of methane.

In the German patent application dated September 22, 2019 with the file number 10 2019 006 623.5, which was not previously published, a bioconverter for the single-stage or multi-stage production of biogas through fermentation of biomass in a fermentation liquid moved with agitating agents in the presence of elementary hydrogen, hydrogenotrophic and methanogenic archaea is activated Coal masses described. The elemental hydrogen is in situ and / or outside the fermentation liquid by electrolysis of water generated in at least one internal and / or external electrolysis cell. The electrolysis cells are protected from direct contact with the activated carbon mass. The hydrogen can also be fed into the fermentation liquid from an external hydrogen supply. Examples of suitable external hydrogen supplies are pressurized gas cylinders and pressure vessels which are filled with metal hydrides such as aluminum hydride or lithium aluminum hydride, which release the elemental hydrogen again at higher temperatures. However, the hydrogen can also be fed into the fermentation liquid from a hydrogen-generating bioconverter together with carbon dioxide.

A method for cracking preheated ammonia at a temperature of 500 ° C. to 1100 ° C. is known from the American patent application US 2019/0084831 A1. Nickel oxides, iron oxides, manganese, platinum, palladium, lanthanum oxides, molybdenum and / or zirconium are used as cracking catalysts. A nickel catalyst supported on magnesium-aluminum spinel is particularly preferred. The resulting hydrogen-nitrogen mixture is cooled to 40 ° C to 300 ° C, freed from residual ammonia and used as fuel for turbines.

European patent EP 2 007 680 B1 discloses the use of zirconium oxide nitride catalysts for the decomposition of ammonia into hydrogen and nitrogen. The catalysts are said to be particularly suitable for fuel cells.

The Japanese patent application JP 2018021089 W discloses a cracking catalyst based on zeolite for ammonia in a fuel cell, which is not intended to aggregate. The actual catalysts are metal microparticles.

From the Japanese patent application JP 2009059933 A a cracking catalyst for ammonia is known which is composed of a support made of cerium oxide, aluminum oxide and zirconium oxide and contains at least one transition metal.

Furthermore, a method for cracking ammonia into a gas mixture of 75% hydrogen and 25% nitrogen is known from European patent 3,028,909 B1. The gas mixture is burned for heating purposes with air as an oxidizing agent or used as fuel in a heat engine. Before using it in a boiler or heat engine, additional ammonia can be added to increase the energy content. The use of hydrogen-nitrogen mixtures, which have been produced by the catalytic cracking or the splitting of ammonia, in bioconverters which contain activated coal masses is not described.

It would be desirable to use activated carbon masses, which contain absorbed or adsorbed hydrogen, as the process material. Unfortunately, the capacity of activated carbon for hydrogen at the process temperatures is very low.

Lately attempts have been made to achieve a fuel cell revolution with activated charcoal stores made from bamboo. With the activated carbon storage, 60 g of hydrogen can be stored in 20 g of bamboo activated carbon at 1 bar - but only at -196 ° C (INGENIEUR.de Technik - Karriere - News, 10/30/2018).

Binary tetrahydrofuran hydrogen chlathrate hydrates have long been investigated for their storage capacity for hydrogen. It is not known whether they can be used as process materials together with activated carbon in bioconverters.

Object of the invention

The present invention was based on the object of providing carbon dioxide-neutral bioconverter plants in which the methane yield is even higher than in the known bioconverter plants. In addition, the methane obtained should have a high degree of purity. The carbon dioxide-neutral conversion process in question should be able to be carried out easily and safely, and the activated carbon masses used should be able to be separated off in a simple manner. Last but not least, hydrogen sources should be provided for the carbon dioxide-neutral bioconverter plants, which no longer have the problems of storing hydrogen as a gas or as a metal hydride, but through which hydrogen can be safely produced as required.

Solution according to the invention

Accordingly, the carbon dioxide-neutral bioconverter plant for the single-stage or multi-stage carbon dioxide-neutral production of biogas by fermentation of biomass in a fermentation liquid agitated in the presence of elemental hydrogen and hydrogenotropic and methanogenic archaea and activated carbon mass was found. In the following, this carbon dioxide-neutral bioconverter plant is referred to as “bioconverter plant according to the invention”.

Advantageous embodiments emerge from the dependent claims 2 to 22.

In addition, the carbon dioxide-neutral, single-stage or multi-stage process for the production of biogas with the aid of the bioconverter system according to the invention was found in accordance with claim 23, which is referred to below as the “conversion process according to the invention”.

Advantageous embodiments emerge from the dependent claims 24 to 27.

Furthermore, the method for injecting hydrogen-containing, pulverulent, activated coal masses into the fermentation liquid of a bioconverter was found in accordance with patent claim 28, which is referred to below as the “injection method according to the invention”.

An advantageous embodiment of the injection method according to the invention emerges from the dependent patent claim 29.

Last but not least, the use of the converted biomasses or fermentation products produced by the conversion process according to the invention and the activated coal masses used in the conversion process according to the invention was found as fertilizer and for the production of terra preta according to claim 30, which is hereinafter referred to as "use according to the invention".

Advantages of the invention

In view of the prior art, it was surprising and not foreseeable for the person skilled in the art that the object on which the present invention was based could be achieved with the aid of the bioconverter system according to the invention, the conversion method according to the invention, the injection method according to the invention and the use according to the invention. Surprisingly, the bioconverter plant according to the invention and the conversion process according to the invention enabled a significant increase in the methane yield to be achieved.

The activated and / or passive abrasion and erosion and / or erosion could be suppressed by introducing the activated coal masses into the bioconverter systems according to the invention in suspended bodies, floating bodies, solid layers, immobile, fluid-permeable containers, fluidized bodies of a fluidized bed, magnetizable particles and / or a fixed bed will. This had the advantage that the activated coal mass decomposed more slowly than the biomass.

The activated coal masses were no longer recovered by participating in the material flow. This resulted in the activated carbon masses remaining longer in the conversion process according to the invention, as a result of which the microorganisms which had been introduced by inoculation also had a longer residence time.

Before and / or during the conversion process according to the invention, the activated carbon mass could be loaded with trace elements, micro-elements, ultra-trace elements, ultra-micro-elements, bulk elements, nutrients, essential nutrients, carbohydrates, fats, proteins, minerals and / or vitamins.

In particular, it was surprising that heavy metals could be bound by the activated coal masses, as a result of which the converted biomass or fermentation products had particularly low heavy metal values. As a result, they could be used excellently as fertilizer or for the production of terra preta.

Because the activated coal masses used in the conversion process according to the invention bound these heavy metals particularly tightly through adsorption and chemisorption and no longer released them to the environment, they could also be used excellently for the production of terra preta and as fertilizer.

Further valuable fertilizers and raw materials for terra preta could be obtained by combining the conversion products and the related activated coal masses. The main advantage, however, was that the hydrogen in the bioconverter systems according to the invention could be made available in catalytic ammonia crackers as required, so that not hydrogen but only ammonia had to be stored.

The further essential advantage was the particularly high yield of methane with a degree of purity> 90% by volume, preferably> 95% by volume. In addition, the almost complete or complete conversion of carbon dioxide into methane made it possible to dispense with a complex and expensive gas scrubber with NaOH.

The essential advantage of the bioconverter system BKA according to the invention was its carbon dioxide neutrality. It could also be designed to act as a carbon sink.

Detailed description of the invention

The bioconverter system according to the invention and its peripherals, which include a central electronic control unit or data processing system, electronic, mechanical, hydraulic control circuits, measuring devices, flow meters, gas meters, pressure gauges, pressure relief valves, throttle valves, pressure holding valves, flow valves, actuators, transport lines for liquids, gases, sludge and solids, Energy sources, power sources, pumps and viewing windows, are made of mechanically stable, acid and base stable, corrosion-resistant, temperature-stable, pressure-stable and dimensionally stable materials. Examples of suitable materials are steel, stainless steel, chrome steel, anodized aluminum, metal alloys, thermoplastic and thermosetting plastics, concrete, ceramics, glass ceramics and glasses.

For the bioconverter plant according to the invention and the preservation method according to the invention, all biomasses that are commonly used and contain carbon-carbon bonds can be considered.

Examples of suitable biomasses are manure, liquid manure, faeces, fermentation residues, dry ferments, sewage sludge, ferments, composts, biowaste, vegetable waste, leaves, lumber, mash, pomace, food industry waste, biotechnological waste, genetic engineering waste, animal waste, celluloses, hemicelluloses, lignin, Biomass and waste containing celluloses, hemicelluloses and / or liginocelluloses, high molecular weight proteins and structural proteins, concentrates of the biological purification stages from sewage treatment plants, chemical washers and filters, waste water, solid deposits from exhaust air treatment, food, feed, seaweed, aquatic plants, algae and organic compounds such as carboxylic acids and their esters produced by hydrolysis, acidogenesis and acetogenesis.

Further examples of suitable biomasses are in particular farm manure such as cattle manure, pig manure, cattle manure, poultry manure and horse manure without straw, renewable raw materials such as corn silage, whole-plant grain silage (GPS), green rye silage, cereal grains, grass silage, sugar beet, fodder beet, sugar beet, green rye, grass, and grass. Substrates from the processing industry such as spent grains, grain mash, potato mash, fruit mash, raw glycerine, rape press cake, potato pulp, Z-pressed pulp, molasses, apple pomace, vine pomace as well as green and grass clippings such as green waste.

In addition, the »List of" Biogenic Waste and Waste with Relevant Biogenic Components "in accordance with Section 3 (6) of the 2009 funding guidelines for domestic environmental funding, Kommunal Kredit Public Consulting, Version 08/2018, Kommunalkredit Public Consulting GmbH, Vienna," and »“ What has to be considered in the agricultural recycling of bio-waste? “, LfL, Bavarian State Research Center for Agriculture, 3rd edition, May 2013 (Internet only)«.

By using the biomasses listed above, secondary waste from agriculture in particular can be used for methane production and thus significantly reduced.

The biomasses are usually fed into the fermentation liquid in the bioconverter of the bioconverter plant according to the invention via at least one biomass inlet.

The fermentation liquid is moved with the help of at least one agitating agent. In general, the fermentation liquid should be moved at a speed at which the microorganisms are not damaged. Examples of suitable agitation means are stirrers, in particular blade stirrers and paddle stirrers, and at least one side circle or bypass, which drains or sucks the fermentation liquid near its surface from at least one, in particular one, outlet by means of at least one circulating pump and preferably as a return through at least one return line to at least one circular return manifold for injecting the return flow into the lower area of the fermentation liquid in the reactor volume. The fermentation or conversion of the biomass takes place in the presence of elemental hydrogen.

According to the invention, the hydrogen is generated in at least one ammonia cracker by the catalytic cleavage of ammonia. The catalytic cleavage of ammonia is preferably carried out at temperatures of 300 ° C. to 700 ° C., preferably 400 ° C. to 650 ° C. and in particular 500 ° C. to 600 ° C. and a pressure of 1.0 bar to 50 bar, preferably 1, 0 bar to 40 bar and in particular 1.0 bar to 30 bar carried out.

Examples of suitable cracking catalysts are copper nanoparticles doped with traces of ruthenium. If these are heated and at the same time irradiated with light, the energy barrier is lowered, whereby the ammonia can be split at lower temperatures than usual (see http://news.rice.edu/2018/10/04/light-makes-rice -u-catalyst- more-effective-2 /).

Further examples of suitable cracking catalysts are nickel, zirconium oxide nitride, iron oxide, manganese, platinum, palladium, lanthanum oxide, nickel-ruthenium alloys and iron oxide supported on aluminum oxide (cf. European patents EP 2 007 680 B1 and EP 3 028 990 B1 and American patent application US 2019/0084831 A1).

The at least one ammonium cracker is preferably designed as a double-tube reactor in which at least one heating source is arranged in the central tube. The at least one heating source is preferably at least one burner which is operated with preferably hot air as the oxidizing agent and with the biogas generated in the at least one bioconverter. In addition, the hydrogen-nitrogen gas mixture and / or the hydrogen generated in the at least one ammonium cracker can also be fed in. If necessary, natural gas can also be added.

Instead of at least one open flame, or in addition to this, resistance heating, induction heating and / or hot process gases and exhaust gases from chemical plants and power plants can be used.

For better heat transfer to the at least one catalyst in the cracking tube (outer tube) surrounding the central tube (heating tube), the at least one open The flame of the at least one burner in the heating chamber heats a metallic packing bed with high thermal conductivity. Packing beds made of copper are preferably used.

The cracking tube contains at least one of the cracking catalysts described above in the form of packed beds and / or in monolithic form, as is known, for example, from catalysts for cleaning engine exhaust gases. An example of such a monolithic shape is the monolithic system described in the translation DE 602 21 141 T2 of the European patent specification EP 1 444475 B1.

The at least one ammonium cracker can be arranged vertically or horizontally. When it is arranged vertically, its at least one heating chamber is located with the at least one burner at its lower end. The at least one ammonium cracker is preferably arranged horizontally.

The outside diameter of the cracking tube is preferably 5 cm to 50 cm, more preferably 6 cm to 40 cm and in particular 8 cm to 30 cm. The outer diameter of the central tube is preferably 3 to 40 cm, more preferably 3 cm to 30 cm and in particular 3 to 20 cm. The wall thickness of the tubes is preferably 1 mm to 5 mm, preferably 1.5 mm to 4 mm and in particular 2 mm to 3 mm.

The length of the double-tube ammonia cracker is preferably 50 cm to 10 m, more preferably 60 cm to 8 m and in particular 1 m to 7 m.

The double-tube ammonia cracker is preferably encased in a 10 cm to 40 cm thick insulation layer for thermal insulation. Examples of suitable materials for the construction of the insulation layer are mineral fibers selected from the group consisting of aluminum silicate wool, alkaline earth silicate wool, aluminum silicate zirconium wool,

High-temperature glass wool, polycrystalline aluminum oxide wool, aluminum oxide ceramic fibers, mullite ceramic fibers, yttrium oxide ceramic fibers, silicon carbide, silicon carbide nitride and silicon boride nitride carbide fibers, alkali-resistant glass fibers, quartz fibers, silica fibers, basalt fibers, boron crystal fibers, single crystal fibers Slag fibers and nanotube fibers and their mixtures.

The lines in which the heated ammonia and the heated air are routed are preferably also thermally insulated with insulating layers. The ammonia is taken from at least one pressure bottle in liquid and / or gaseous form, depending on the requirements of the at least one bioconverter of the bioconverter system according to the invention. The respective flow rate is set by an electronically monitored and regulated pressure reducer. The ammonia is then passed via at least one ammonia line to at least one first recuperator, in which it is heated by the hot exhaust gases discharged from the central pipe, preferably to 300 ° C. to 500 ° C., before it is introduced into the cracking pipe via at least one ammonia line.

The hot hydrogen-nitrogen gas mixture produced in the cracking tube contains hydrogen and nitrogen in a volume ratio of 3: 1. It can contain up to 5% by volume, preferably up to 4% by volume and in particular up to 2% by volume of unreacted ammonia. The hot gas mixture is fed through at least one hydrogen-nitrogen line to at least one second recuperator, in which the air fed to the burner is heated.

Preferably, after the at least one second recuperator, the gas mixture is cooled in a customary and known cooling device to preferably <70.degree. C., preferably <65.degree. C., particularly preferably <60.degree. C. and in particular to 50 to 60.degree.

To support the hydrogen production by the at least one ammonia cracker, electrolysis devices that are operated with renewable energies can also be used.

Before the gas mixture enters the hydrogen-nitrogen distributor in the at least one bioconverter, the ammonia is preferably bound by activated carbon which is impregnated with phosphoric acid. The resulting by-product activated carbon / ammonium phosphate is itself a product of value and can be used, for example, to produce terra preta.

In another embodiment, the cooled gas mixture is passed through sulfuric acid, in which the ammonia is bound as ammonium sulfate. The ammonium sulfate solution is also a valuable product and can be used, for example, as a liquid fertilizer. In yet another embodiment, the hydrogen is separated from the cooled, ammonia-containing or ammonia-free gas mixture using a module with hydrogen-selective membranes. Examples of suitable hydrogen-selective membranes are SEPURAN® Noble membranes from Evonik, which are described in the international patent application WO 2006/017022, page 18, line 9, to page 20, line 13, described in the article by Jinchang Zhu et al., Facile hydrogen / nitrogen Separation through graphene oxide membranes supported on YSZ ceramic hollow fibers, in Journal of Membrane Science, Volume 535, 2017, Pages 143 to 150, the membrane described in the German patent DE 10 2008 048 062 B3, page 8, paragraph [0054], the composite membrane described in the American patent application US 2009/0277331 A1 in Examples 1 to 6 or the in the German patent application DE 2307 853 described membrane.

The ammonia-free hydrogen-nitrogen gas mixture and / or the hydrogen is or are passed into the hydrogen distributor at a pressure of preferably 1.0 bar to 5 bar, preferably 1.0 bar to 4 bar and in particular 1.0 bar to 3 bar, from where the mixture and / or the hydrogen emerges or emerges from the hydrogen nozzles into the fermentation liquid GF. Some of the hydrogen can also be used as fuel for the ammonia cracker.

The feed lines for the liquid and / or gaseous ammonia, the ammonia heated in the first recuperator, the air, the air heated in the second recuperator and the biogas as well as the discharges of the hydrogen-nitrogen mixture produced are designed in a spiral shape around the thermal expansion and contraction to compensate for mechanical stresses generated.

The activated coal masses to be used according to the invention can be produced from mineral coal, partially pyrolysed coal, biochar, activated charcoal, animal charcoal, animal waste charcoal, bone charcoal, pyrogenic carbon of different degrees of pyrolysis and lignite. The coals can be functionalized, surface modified, pretreated, washed, soaked in, soaked in and dried, dried and moistened, soaked in and partially dried and / or extracted.

In addition, the coals can be used as nanoparticles such as carbon nanotubes, fullerenes, graphene and / or nanocons with an average particle size of 1 nm to <1 μm, as microparticles with an average particle size of 1 μm to <1 mm and as macroparticles mean particle size> 1 mm. The average particle sizes can be measured by the person skilled in the art using the customary and known methods which are adapted to the respective orders of magnitude.

In addition, the activated carbon mass can be in the form of magnetizable, activated carbon particles, as described, for example, in German patent DE 10 2014 100 850 B4, page 7, paragraph [0074] to page 8, paragraph [0084], and the German patent application DE 102014 100849 A1 is described.

Preference is given to using biochar, in particular animal charcoal, bone charcoal and / or plant charcoal. Biochar is preferred. The biochar particularly preferably has an inner surface according to BET of at least 300 m ² / g, particularly preferably of at least 500 m ² / g and in particular of at least 700 m ² / g, which favors the growth of bacteria. It has a high capillary density, which ensures particularly effective material flows and a substrate supply. Their pH value is particularly preferably 8 to 8.7, which is particularly advantageous for the growth of the archaea. The H / C ratio is preferably <0.7, preferably <0.6 and in particular <0.5 according to the guideline of the European Biochar Certificate. Optimized biochar is described in the company brochure of LUCRAT® GmbH, biochar optimized ,, Energy-Dezentral 2018 / Eurotier.

In the production of the activated carbon masses, the above-described carbons with trace elements, micro-elements, ultra-trace elements, ultra-micro-elements, bulk elements, nutrients, essential nutrients, carbohydrates, fats, proteins, minerals, vitamins, humic substances, 5- (hydroxymethyl) furfural, inorganic nitrates and / or adhesives are functionalized, surface modified, soaked and dried, dried and moistened and / or soaked and partially dried and / or loaded with hydrogenotrophic and / or methanogenic archaea.

The trace elements, ultra-trace elements, micro-elements and ultra-micro-elements from the group consisting of lithium, rubidium, cesium, strontium, barium, chromium, cobalt, iron, fluorine, bromine, iodine, copper, manganese, molybdenum, tungsten, mercury, selenium, Boron, aluminum, thallium, lead, silicon, zinc, arsenic, antimony, nickel, rubidium, tin and vanadium, and the bacteria selected from the group of archaea. The trace elements, micro-elements, ultra-trace elements and ultra-micro-elements are preferably selected from the group consisting of chromium, cobalt, iron, fluorine, iodine, copper, manganese, molybdenum, selenium, silicon, zinc, arsenic, nickel, rubidium, tin and vanadium.

The trace elements, micro-elements, ultra-trace elements, ultra-micro-elements and / or the bulk elements are preferably present in natural and / or synthetic minerals and / or ceramics and / or metals that are so poorly soluble that they contain the trace elements, micro-elements, ultra-trace elements, ultra-micro-elements and / or Only slowly release bulk elements to the fermentation liquid in the sense of slow release. An example of a natural mineral is asbolan containing cobalt or limestone doped with trace elements, micro-elements, ultra-trace elements and ultra-micro-elements.

In a particularly preferred embodiment, the trace elements, micro-elements, ultra-trace elements, ultra-micro-elements and / or bulk elements are in the form of their complexes.

The complexing agents are preferably selected from the group of bidentate, tridentate, tetradentate and pentadentate ligands and higher-dentate ligands such as crown ethers and nitrogen analogs. In particular, the complexing groups contain boron atoms, oxygen atoms, nitrogen atoms, phosphorus atoms, sulfur atoms and / or selenium atoms.

The complexing agents from the group consisting of lignin, starch, polysaccharides, amino acids, polyvinyl alcohols, polyglycols, polyethyleneimines, acetylacetone, ethylenediamine, diethylenetriamine, iminodiacetate, triethylenetetramine, triaminotriethylamine, NTA nitrilotriacetic acid, are very particularly preferred.

Bis (salicylidene) ethylenediamine, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate, oxalate, citrate, dimethylglyoxime, 8-hydroxyquinoline, 2,2'-bipyridine, 1,10-phenanthroline, dimercaptosuccinic acid , 1, 2-bis (diphenylphosphino) ethane, 2- (2-aminoethylamino) ethanol, ethylenediamine triacetate, EDTA ethylenediamine tetraacetate, EGTA (ethylene glycol bis (aminoethyl ether) -N, N, N ', N'-tetraacetic acid), DOTA (1 , 4,7,10-tetraazacyclododecane 1,4,7,10-tetraacetic acid), NTA (nitrilotriacetic acid), EDDS (ethylenediamine disuccinic acid), D-penicillamine, deferoxamine, citric acid, polycarboxylates, zeolites, phosphonates, triethanolamine, gluconates, alanine diacetic Sodium salt (ADA), methylglycinediacetic acid (MGDA), diethylenetriaminepentaacetic acid (DTPA), propylenediaminetetraacetic acid (PDTA), Isoascorbic acid (E315), sodium isoascorbate (E316), citric acid (E330), sodium citrate (E331), potassium citrate (E332), calcium nitrate (E333), tartaric acid (E334), sodium tartrate (E335), potassium tartrate (E337), (E337), sodium potassium tartrate Sodium phosphate (E339), potassium phosphate (E340), calcium phosphate (E341), calcium trateate (E354), triammonium citrate (E380), calcium EDTA (E385), polyoxyethylene sorbitan monolaurate (polysorbate 20) (E432), polyoxyethylene sorbitan monoleate (E432) (polysorbitan 332)

Polyoxyethylene sorbitan monopalmitate (polysorbate 40) (E434),

Polyoxyethylene Sorbitan Monostearate (Polysorbate 60) (E435), Polyoxyethylene Sorbitan Tristearate (Polysorbalt 65) (E436), Beta-Cyclodextrin (E459), Diphosphate (E450), Triphosphate (E451), Polyphosphate (E452), Sodium76), Gluconuconic Acid (E576), Glucatuconic Acid (E576) Potassium gluconate (E577), calcium gluconate (E578), iron II-gluconate (E579), phytate, bentonite, zeolites and montmorillonite.

The activated coal masses can be fixed

In one embodiment, the fixed, activated carbon masses can be present as at least one layer which is fixed with the aid of at least one adhesive. The at least one adhesive can form a separate layer or be present in a mixture with the fixed, activated carbon mass.

Suitable adhesives can be selected from the group consisting of biopolymers, polysaccharides, chemically curing adhesives, polymerization adhesives, cyanoacrylate adhesives (superglues), methyl methacrylic adhesives, anaerobically curing adhesives, unsaturated polyesters (UP resins), radiation curing adhesives, polycondensation adhesives , Silicone-silane crosslinked polymer adhesives, lignin adhesives, polyimide adhesives, polysulphide adhesives, polyaddition adhesives, epoxy resin adhesives, polyurethane adhesives, silicone-polyisocyanate adhesives, physically setting adhesives, solvent-based adhesives, cement-based adhesives, cement-based cement, dispersion-based adhesives, cement-based adhesives Adhesives, plastisols, adhesives without a solidification mechanism and slaked lime and adhesives based thereon.

The above adhesives can have partially open structures; they can be wrapped, partially wrapped, not wrapped and / or on one, held together by point connections Background glued and / or have a backbone. Hardeners and / or plasticizers can also be added to them.

The above adhesives for the carbon nanoparticles, coal microparticles and / or coal macroparticles, which are functionalized, surface-modified, soaked, soaked and dried, dried, dried and moistened, and soaked and partially dried, are only listed by way of example and not exhaustively. The list is therefore intended to clarify the variety of possibilities, and the person skilled in the art can easily specify further possibilities on the basis of his general specialist knowledge.

Biodegradable and / or organic adhesives are preferably used.

Activated carbon masses fixed in this way can be used, for example, to coat the walls of the bioconverter, as is described in German patent application DE 10 2015 012436 A1.

Furthermore, the fixed, activated carbon masses can be enclosed in immobile, fluid-permeable containers. Examples of suitable containers are bags, sacks, buckets, cans, boxes, envelopes and cardboard boxes made of paper, paper-like materials, textile, metal and / or any combination thereof. Freezer bags, ziplock bags, garbage bags, all-purpose bags, cloth bags, shopping nets, air-permeable bags for storing food and vacuum cleaner bags can also be considered. In addition, valve sacks, cross-bottom sacks, block-bottom sacks, pinch sacks, flat sacks, folded sacks and / or nets can be used. It is essential that these containers are permeable to the fermentation liquid, but do not release any electrically conductive particles into the reactor volume.

The containers can be introduced into the bioconverter according to the invention in different ways. They can be placed on the floor, on the side walls, in front of the side walls, in the middle of the bioconverter and / or on the stirrers and / or on and / or in systems such as carrier materials such as curtains, grids, wood and / or in any other body be introduced.

In a further embodiment, the bioconverter according to the invention contains at least one, preferably at least two, preferably at least three, particularly preferably at least four and in particular at least five floats that carry the activated and preferably fixed coal masses in the fermentation liquid.

The floating bodies can move freely in the fermentation liquid or are anchored on the surface of the reactor floor, the lid, the roof or the cover, preferably on the surface of the reactor floor, of the bioconverter.

The float to be used according to the invention comprises at least one float, at least one fixed, activated carbon mass and at least one weighting.

The at least one fixed, activated coal mass and the at least one weighting are balanced in such a way that the float keeps the float in the fermentation liquid in suspension, preferably vertically or essentially vertically.

In the context of the present invention, the term "in suspension" includes the case that the float of the floating body is partially or completely submerged in the fermentation liquid or floats on the surface of the fermentation liquid.

The size and weight of the float can vary very widely and can therefore be excellently adapted to the structural features of a given bioconverter according to the invention and the requirements of a given conversion method according to the invention.

The total length of the float, i.e. the distance from its weighting to the highest point of the float, is preferably 10 to 100 cm.

The weight of the float is preferably 10 to 1000 g.

The buoyancy bodies to be used according to the invention can have the most varied of shapes and sizes. It is essential that their buoyancy is sufficient to keep the float in suspension. The necessary buoyancy can be determined by calculation or with the help of a few simple experiments.

The buoyancy bodies can be hollow bodies, solid bodies or sponge-like bodies. It is essential that they do not decompose in the fermentation liquid. You can use any have three-dimensional shapes. Examples of suitable shapes are Platonic solids such as spheres, pyramids, cylinders, octahedra, dodecahedron or icosahedron. Hemispheres or rings are also possible. Their size depends on the weight of the fixed, activated coal masses that they are supposed to keep in suspension. Suitable materials for the floats are plastics, wood, light metals or glass. Plastics are preferably used for hollow bodies. Plastic or wood are preferably used for solid bodies.

Examples of suitable polymers that are stable to the fermentation liquid are polyolefins such as polyethylene, polypropylene, polybutadiene, polyisoprene and their copolymers, polyvinyl aromatics such as polystyrene, poly (alpha-methylstyrene) and their copolymers, poly (meth) acrylates, polyesters, polyethers, polyamides , Polyesterimides, polyketones, polyetherketones or polysulfones. The person skilled in the art can easily select further suitable polymers on the basis of his general specialist knowledge. It is also advantageous if the polymers are three-dimensionally crosslinked. Yet another advantage results when the polymers are biodegradable.

The hollow bodies can be filled with air, nitrogen or helium. Preferably air is used. But they can also be evacuated. The hollow bodies can also contain points in their walls that are dissolved by the fermentation liquid over time, so that they fill up gradually or rapidly with the fermentation liquid, as a result of which the floating bodies sink to the bottom of the reactor. This can also be done in a controlled manner by installing valves in the wall that can be opened by radio remote control. The floats that have sunk to the bottom of the reactor can then be disposed of in a simple manner.

The production of the buoyancy bodies can be carried out in the most varied of ways. For the production of massive buoyancy bodies, abrasive processes such as machining, cutting, grinding or milling come into consideration. For the production of hollow bodies, structural processes such as injection molding or 3-D printing can be considered.

The float to be used according to the invention comprises at least one fixed, activated carbon mass. For special applications, several, for example 2 to 30 fixed, activated carbon masses can also be used. The amount of the fixed, activated carbon mass is chosen so that it is kept in suspension together with the weighting or, if the float is anchored on the reactor floor, solely by the at least one float.

In one embodiment, the fixed, activated carbon mass can be present as at least one layer which is fixed with the aid of at least one adhesive. The at least one adhesive can form a separate layer or be present in a mixture with the fixed, activated carbon mass.

The above adhesives can have partially open structures, they can hold together by point connections, they can be encased, partially encased, not encased, glued to a background and / or have a backbone. Hardeners and / or plasticizers can also be added to them.

Biodegradable and / or organic adhesives are preferred. The activated carbon mass fixed with the aid of adhesives can, in one embodiment, be fixed on the surface of the buoyancy bodies and / or the weights.

The weights themselves are preferably solids, which have a higher density than the fermentation liquid. Examples of suitable weights are natural and synthetic minerals, synthetic and natural ceramics, glass and metals. They can have a wide variety of three-dimensional shapes and can therefore be perfectly adapted to the respective float. Examples of suitable three-dimensional shapes are given above for the floats.

In special cases, the dead weight of the fixed, activated coal mass can take over the function of loading.

The activated coal masses described above are also fixed by pouring them into containers that are held in suspension by the floats and the weights.

It is essential for the container that it is semipermeable so that the fermentation liquid can come into contact with the fixed, activated coal mass.

The materials for the containers must be mechanically stable and must not be attacked by the fermentation liquid. Examples of suitable materials are the polymers, metals or glass listed above. The shape of the containers depends primarily on the spatial requirements of the fermentation reactor and the requirements of the conversion process carried out with the aid of the fermentation reactor. For example, the containers can be in the form of stockings, sacks, tubes or boxes, which are optionally provided with through-holes. The containers themselves can in turn be divided into at least two compartments.

In the context of the present invention, “through bores” are understood to mean openings of any shape and size. So they can have a round, triangular, square, hexagonal, star-shaped and / or slot-shaped outline. The clear width can also vary widely and can therefore be perfectly adapted to the requirements of the individual case. The clear width can be in the order of magnitude of 1 nm to 5 mm. It is essential that the clear width is not so large that parts of the fixed, activated coal mass lose their hold on the total mass and get into the fermentation liquid. In a particularly advantageous embodiment, the containers have the shape of stockings made of a permeable woven or knitted fabric. Glass fabric stockings are very particularly preferred.

The containers can preferably be emptied and refilled with fresh, fixed, activated carbon mass. For this purpose, closable filling openings can be provided. The closure devices can be flanges and matching insertion channels, hose clamps, threads or closure caps.

In order to prevent the float from getting into the moving devices of the bioconverter and damaging the devices and the float, or from the float clogging the inlets and outlets of the bioconverter, it is advantageous if the float or floats are behind a protective grille or protective net is or are located. This protective grille still allows the hover discs to move freely within the fenced-in area, but it prevents the hover discs from reaching the critical areas of the bioconverter.

There is also the possibility that the floats are connected to one another to form associations, for example with threads, wires or chains.

The fixed, activated coal masses described above are described in detail in German patent specification 102016004026 B4, page 4, paragraph [0034], to page 7, paragraph [0080], page 9, paragraph [0087], to page 11, paragraph [0122] , in connection with Figures 1 to 11 described.

In a further advantageous embodiment, the activated coal masses are in the form of powders with an average particle size> 1 mm, pressed pellets, pressed rods or pressed rings in floating bodies that float on and / or on the surface of the fermentation liquid. These floating bodies are preferably produced from the polymers described above by injection molding. They preferably consist of a lid which is detachably connected to the can that receives the activated carbon masses. For example, the lid can be connected to the box by tongue and groove connections. The walls of the floating bodies have flow openings that allow the entry of hydrogen and / or a hydrogen-nitrogen mixture, the drainage of the fermentation liquid and the exit of biogas. The floats can have any shape, such as hollow cylinders that float vertically in the liquid, hollow cones that float with the tip down, or plate-shaped floats whose height is smaller than their horizontal diameter. The plate-shaped floating bodies can have any contours. So they can be triangular, square, pentagonal, hexagonal or octagonal. The ceiling, the side walls and / or the bottom of the floating body can be straight and flat or curved convex. The corners of the floats can also be rounded. It is advantageous if the floating bodies cannot collapse to form a closed parquet-like structure on the surface, but rather that there are openings between them that facilitate the exit of the biogas.

In a further advantageous embodiment, the activated plastic masses are encased in fluid-permeable spherical containers, preferably with a diameter of 0.5 cm to 5 cm. The fluid-permeable spherical containers are made up of at least one of the polymers described above, which contain ^{fillers with a density of> 1 g / cm 3.} These vertebral bodies can advantageously be whirled up in a fluidized bed in the fermentation liquid, which creates a particularly large contact surface. When the agitation means are switched off, the vortex bodies sink to the sieve trays of the fluidized bed reactors, after which they can be stirred up again.

In yet another preferred embodiment, the activated carbon masses are fixed on and / or in at least one, in particular one, fixed bed. Any materials can be used as a carrier for the fixed bed, as long as they are not attacked by the fermentation liquid. The fixed bed can, however, also be made up of pressed pellets, balls, rings and sticks made from the activated carbon masses. The at least one fixed bed is preferably located in at least one, in particular a fixed bed reactor, which is located in at least one, in particular one, upstream side circle of at least one two-stage converter. Here, the fermentation liquid from the at least one bioconverter of the first stage is sucked off at its bottom and passed as an overflow stream through the at least one fixed bed reactor and from its upper end fed back into the at least one bioconverter of the first stage from above.

In yet another preferred embodiment, pulverulent, activated coal mass, in particular activated carbon microparticles, which are suspended in the fermentation liquid, are used. In an alternative embodiment of the bioconverter system according to the invention, it comprises at least one device for treating activated coal masses, preferably pulverulent, activated carbon masses and in particular activated carbon microparticles, with hydrogen at higher pressure with at least one pressure line and at least one spray lance for injecting the hydrogen-containing, activated carbon masses as a spray cone in the fermentation liquid of the at least one bioconverter.

In yet another preferred embodiment of the bioconverter system according to the invention, the 1. Phase: hydrolysis, the 2nd phase: acidogenesis or acidification phase and the 3rd phase: acidogenesis or vinegar-forming phase carried out in at least one first bioconverter. The fermentation liquid in the reactor volume has a pH value <7.

The 4th phase: methanogenesis is carried out in at least one second bioconverter. The fermentation liquid in the reactor volume has a pH value> 7.

The bioconverter system according to the invention preferably also comprises at least one secondary fermenter to complete the methanogenesis. The converted fermentation liquids can be conveyed from floor space to floor space. The gas spaces of the at least two or at least three bioconverters listed above are connected to one another via gas lines.

In a preferred embodiment, the fermentation products are passed into a solid-liquid separator. The solid fermentation products are discharged via a solids discharge and fed to further use as fertilizer or for the production of terra preta. The liquid fermentation products can be used as liquid fertilizer or they can be returned to at least one bioconverter.

In yet another preferred embodiment, gaseous biomass can also be added to the fermentation liquid of the at least one bioconverter. Examples of suitable gaseous biomasses are landfill gases, sewage gases, digester gases and swamp gases.

In yet another preferred embodiment, the fermentation liquids, in particular in the 4th phase: methanogenesis, carbon dioxide from other carbon dioxide sources are fed. In addition to pressure cylinders, carbon dioxide-containing exhaust gases from incineration ovens, internal combustion engines, cement ovens and lime ovens come into consideration. Their thermal energy can be used to heat the fermentation liquid and the at least one ammonia cracker. This further preferred embodiment is outstandingly suitable for the sequestration of carbon dioxide, so that the bioconverter plant according to the invention in question is not only carbon dioxide-neutral, but also serves as a carbon dioxide sink.

For the bio-converter system according to the invention described above, it is essential that the ammonia is produced with the aid of renewable energies and the at least one ammonia cracker is operated with the aid of renewable energies.

Renewable energies can be solar energy, bioenergy from biomass in various forms, hydropower, wind energy and geothermal energy.

Solar energy with photovoltaics, solar thermal energy, solar chemistry and updraft power plants, bioenergy with biomass in various forms, with vegetable oil, wood, biodiesel, bioethanol, cellulosic ethanol, biogas, BtL (biomass-to-liquid) fuels and bio-hydrogen, are preferred Hydropower with dams and dam walls, run-of-river power stations, water mills, power buoys, wave energy of the sea, flow energy of the sea and sea heat and the wind energy generated by wind turbines, air wind power stations and windmills.

For the bioconverter plant according to the invention and the method according to the invention it is essential that the fermentation liquid and optionally the activated biochar mass contain hydrogenotrophic microorganisms and anaerobic microorganisms, in particular archaea.

Examples of suitable hydrogenotrophic archaea are Methanosaeta spp. and Metanosarcina spp. Further examples can be found in the international patent application WO 2011/003081, page 25, paragraph [0099]. Methanothermobacter Thermautotropicus lines and variants emerge from the European patent EP 2 661 511 B1.

Examples of suitable methanogenic archaea are Chlostridium spp., Selenomonas spp., Acetobacterium spp., Pelobacterium spp., Butyrobacterium spp., Eubacterium spp., Laczobacillus spp., Riminococus spp., Streptococcus spp. Propionibacterium spp., Butyrivibrio spp. and Acetivibrio spp .. Further examples are listed in Tables 2 and 3 of the international patent application WO 2011/003081.

The at least one bioconverter is used to carry out the conversion process or fermentation process according to the invention. With the aid of carbon in the form of the activated coal masses described above, this promotes the growth of useful microorganisms and / or the increase in metabolism and / or catabolism and / or anabolism and / or increases the yield of biogas with respect to the coal mass without loss or almost without loss . Through electrolysis and the use of hydrogenotrophic methanogenic microorganisms and archaea, the yield of biogas is increased beyond the previously known level.

The conversion process according to the invention is preferably carried out at temperatures of 45.degree. C. to 100.degree. C., more preferably 50.degree. C. to 80.degree. C. and in particular 50.degree. C. to 75.degree. The pressure in the bioconverter according to the invention is preferably> 1.0 bar, preferably> 2 bar and in particular> 3 bar. In general, for safety reasons, the pressure should not exceed 30.0 bar. The shifting process according to the invention is particularly preferably carried out at a pH of 5.5 to 8.5 and preferably 6 to 7.5.

It is particularly advantageous that the converted biomasses or fermentation products produced by the conversion process according to the invention and / or the activated coal masses used in the process can be used excellently as fertilizers and / or for the production of terra preta.

If the magnetizable, activated carbon particles described above are used, drained converted biomass with the magnetizable, activated carbon particles is passed through at least one outlet into at least one magnetic separator, preferably into at least one magnetic separator according to German patent application DE 10 2014 100 849 A1, in which the particles are retained . The converted biomass freed from the particles can be drained from the at least one magnetic separator via at least one outlet. If necessary, part of the converted biomass from which the particles have been removed can be pumped back into the at least one reactor volume via at least one return line with the aid of at least one feed pump. As soon as the at least one magnetic separator has reached its capacity limit, which is determined by magnetic measurements on the at least one outflow from the at least one Magnetic separator can be determined, the at least one drain from the at least one bioconverter is closed, and the particles can be removed from the magnetic separator with the help of suitable devices, if necessary reactivated, ie dried and with methanogenic and hydrogenotrophic archaea and with preferably up to 1.0 % By weight of inorganic nitrates, trace elements, ultra-trace elements, micro-elements, ultra-micro-elements and bulk elements as well as nutrients, essential nutrients, carbohydrates, fats, proteins, minerals and vitamins and fed back into the bioconverter BK.

The embodiment described below is only given by way of example and is not exhaustive. On the basis of his general specialist knowledge, the person skilled in the art can specify further possibilities without his own inventive step. It therefore goes without saying that the features mentioned above and explained in more detail below can be used not only in the specified combinations and configurations, but also in other combinations and configurations or on their own without departing from the scope of the present invention.

Brief description of the figures

The invention will now be explained in more detail on the basis of the exemplary embodiments, reference being made to the accompanying FIGS. 1 to 4. It shows in a simplified, not to scale representation:

FIG. 1 shows the plan view of the schematic representation of a bio-converter system BKA according to the invention with an ammonia cracker AC and a bio-converter BK;

FIG. 2 shows the plan view of the longitudinal section through a liquid-permeable floating body SCH in the fermentation liquid GF with pellets PK made from activated coal masses K;

FIG. 3 shows the top view of the schematic representation of a further embodiment of the bioconverter system BKA according to the invention with a bioconverter BK1 for hydrolysis, acidogenesis and acetogenesis, a bioconverter BK2 for methanogenesis and a bioconverter BK for post fermentation; and FIG. 4 shows the top view of the schematic representation of a device V BKA for treating activated coal masses (K; KM) with hydrogen (H2) at higher pressure and for injecting hydrogen-containing, activated coal masses (H2K; H2KM) into the fermentation liquid of bioconverters.

In Figures 1 to 4, the reference symbols have the following meaning:

AC ammonia crackers

AG exhaust gas from the heating pipe HR

AGL exhaust pipe

AKB1 process for magnetic, activated carbon particles KM containing, converted biomass and fermentation products BM

AKB2 Drainage for converted biomass and digestate KBM BG biogas methane freed from magnetic, activated coal particles KM

BG1 methane-carbon dioxide mixture

BGA biogas discharge

BGS biogas collecting line

BGZ biomass feed for gaseous biomass BMG

BK bioconverter

BK1 bioconverter for hydrolysis, acidogenesis and acetogenesis, pH value of the fermentation liquid GF <7

BK2 bioconverter for methanogenesis, pH value of the fermentation liquid GF> 7

BK3 post digester

BM biomass liquid-solid

BMG Biomass gaseous

BMGV distributor for the gaseous biomass BMG

BMZ biomass inflow

BR burner

CH4 methane

C02 carbon dioxide

C02V carbon dioxide distributor

CR crack tube

DE cover of the float SCH

DO can of the float SCH ES Electronic data processing system for the electronic control of the bioconverter system BKA

FA solids discharge for the solid fermentation products BM

FFS liquid-solid separator for fermentation products BM FL flame

FNV All-round tongue and groove connection G gas compartment

GF fermentation liquid

GFR1 Return for the liquid fermentation products BM from the liquid-solid separator FFS to BK3

GFR2 Return for the liquid fermentation products BM from the liquid-solid separator FFS to BK2 via GFR1

GFR3 return for the liquid fermentation products BM from the liquid-solid separator FFS to BK1 via GFR 1 and GFR 2 H2 hydrogen

H2K activated carbon mass containing hydrogen K

H2KM hydrogen-containing, activated, magnetic carbon mass KM

H2 / N2 hydrogen-nitrogen mixture

HD hydrogen nozzle, hydrogen-nitrogen nozzle

HK heating chamber

HL hot air duct

HR heating pipe

HS hydrogen sensor

HV hydrogen distributor, hydrogen-nitrogen distributor K activated carbon mass KAT cracking catalyst

KBM Converted biomass or digestate BM

KM Magnetizable carbon mass, magnetizable activated carbon mass, filter cake, magnetizable activated carbon particles L air

LAN2 nitrogen outlet line LC02 carbon dioxide line LGM gas mixture line,

LH2 line for hydrogen H2

LH2 / N2 line for hydrogen-nitrogen mixture H2 / N2

LK line for powdery, activated coal masses K LN2 nitrogen purge line

MFK Metallic packing, heat exchanger N2 nitrogen

NH3 ammonia

NH3L ammonia line

Ö opening

OF Surface of the moving fermentation liquid GF

PK pellets from activated coal mass K

RB reactor bottom

RL return line

RV reactor volume

RW reactor wall

SCH float

SLI input signal line from HS to ES

SLI1 input signal line from HS1 to ES

SLI2 input signal line from HS2 to ES

SLO output signal line

T Magnetic separator 9

V1 Electronically controlled pressure reducer and flow valve

V2 Electronically controlled flow valve for hydrogen H2 or for hydrogen-nitrogen mixtures H2 / N2

V3 Electronically controlled flow valve for biogas

V4 Electronically controlled flow valve for the supply of air L VBK Device for the treatment of activated coal masses K with hydrogen H2 at higher pressure

WT1 heat exchanger (recuperator) for heating ammonia NH3 and for cooling exhaust gas AG

WT2 heat exchanger (recuperator) for heating the air L and for cooling down hydrogen H2 or a hydrogen-nitrogen mixture H2 / N2 ZR central tube

- ► Direction of flow and / or direction of transport of liquid, solid and / or gaseous substances and mixtures of substances

1 thick matter pump for conveying the liquid fermentation products BM from BK1 to BK2

2 thick matter pump for conveying the liquid fermentation products BM from BK2 to BK3 3 thick matter pump for conveying the liquid fermentation products BM from BK3 to FFS

4 thick matter pump for returning the liquid fermentation products BM from FFS to BK3 and BK2

5 Thick matter pump for returning the liquid fermentation products BM from FFS to BK1 6 Injector for H2 / N2 or H2

7 Injector for BG1

7.1 Electronically controlled three-way cock

8 Injector for carbon dioxide

9; 10 Electronically controlled three-way cocks. 11 Electronically controlled flow valve. 12 Pressure vessel

12.1 Tubular upper area 12.2 Conical lower area 12.3 Removable, pressure- and vacuum-tight cover 13 Shut-off valve for vacuum and overpressure

14 Passage valve for hydrogen H2 or hydrogen / nitrogen mixture H2 / N2

15 Passage valve for activated carbon mass H2 / K containing hydrogen; H2 / KM

16 Passage valve for pulverulent, activated coal masses K; KM 17 Passage valve for nitrogen N2 18 Dosing device for powdery, activated coal masses K; KM rotary valve

19 pressure gauges

20 Safety valve, pressure holding valve 21 Strainer 22 Vacuum pump 23 Blind flange

24 three-way stopcock

25 Pressure line for hydrogen-containing, powdery, activated coal masses K

26 check valve; Throttle check valve 27 Sealed leadthrough of the pressure line 25 through the reactor wall RW 28 spray lance

29 spray cones made of hydrogen H2 and hydrogen-containing, powdery, activated carbon masses H2K; H2KM

30 Turbulence in the fermentation liquid GF of the bioconverter BK

31 Spray lance for hydrogen H2 or hydrogen-nitrogen mixture H2 / N2 32 Spray cone 33 Compressor; compressor 34 centrifugal separator; cyclone

35 solids discharge

Detailed description of the figures Production example 1

The production of activated coal mass K

The activated carbon masses K used in the following were produced from beech charcoal with an inner surface according to BET of 800 m ² / g, a high capillary density and a pH of 8 to 8.7. The beech charcoal was loaded with methanogenic and hydrogenotrophic archaea and with 1% by weight of inorganic nitrates, trace elements, ultra-trace elements, micro-elements, ultra-micro-elements and bulk elements as well as nutrients, essential nutrients, carbohydrates, fats, proteins, minerals and vitamins, so that the activated carbon mass K resulted.

The coal mass K was used with advantage as pellets PK in the floating bodies SCH according to FIG. 2 described below. Nutrients for the microorganisms could be added to the fermentation liquids GF described below via feed lines, which have not been shown for the sake of simplicity.

Production example 2

The production of magnetizable, activated carbon particles KM

The magnetizable, activated carbon particles KM were produced based on example 2 of German patent DE 10 2014 100 850 B4, page 8, paragraph [0082]. For this purpose, 55.5 kg of industrially produced microcrystalline cellulose were poured into a 1000 liter HTC reactor together with 600 l of deionized water. For the hydrothermal reaction with oxidic ferrites, 33.4 kg of manganese-zinc-ferrite powder with a particle size of 30 to 80 μm were added. The mixture was stirred slowly to prevent blockage of the stirrer. A temperature of 250 ° C. and a reaction time of 20 hours with a heating rate of 5 ° C./minute were selected as the reaction conditions. The reaction temperature was controlled with a PID temperature controller. The accuracy of the controller was set to ± 1.0 degrees Celsius. The pressure was on not controlled, but recorded during the reaction. The mixture was continuously stirred at 90 rpm throughout the hydrothermal treatment. After the completion of the reaction, the heating equipment was turned off and the reactor was allowed to cool. In general, it took 15 hours for the reactor to cool from 250 ° C to 25 ° C while the pressure fell from 45 bar to 5.0 bar. The gaseous by-product was discharged and the solid magnetizable coal mass KM was filtered off. The resulting filter cakes KM were crushed, dried and loaded with methanogenic and hydrogenotrophic archaea and with 1% by weight of inorganic nitrates, trace elements, ultra-trace elements, micro-elements, ultra-micro-elements and bulk elements as well as nutrients, essential nutrients, carbohydrates, fats, proteins, minerals and vitamins so that magnetizable, activated carbon particles KM resulted.

Production example 3

The hydrogen H2 used for the production of ammonia was produced by the electrolysis of water. The electricity required for this was supplied by appropriately sized photovoltaic systems. The Haber-Bosch process was used for the production of ammonia from nitrogen N2 and hydrogen H2, whereby the thermal and electrical energy required for the systems was supplied by solar power plants. Thus only renewable energies were used in the production of ammonia.

Figure 1

1. Carbon dioxide-neutral bio-converter system BKA for a single-stage

Conversion procedure

1.1 The bioconverter BK

The BK bioconverter was of the usual and well-known design and was designed for an output of 75 kW _ei and an annual yield of 643,000 kWh of electricity.

The fermentation liquid GF contained cattle manure and shredded maize silage as biomass BM, two types of methanogenic microorganisms (e.g. Methanosaeta spp. And Methanosarcina spp.) And two types of hydrogenotrophic microorganisms (e.g. Methanothermobacter thermautotropicus and Methanobacterium formicium). The BM biomass was fed into the BK bioconverter via the BMZ biomass feeder. The fermentation liquid GF was stirred with a paddle stirrer (not shown) driven by an explosion-proof electric motor in such a way that the fermentation was not disturbed.

The fermentation liquid GF also contained floating bodies SCH according to FIG. 2, which floated on the fermentation liquid GF, and dispersed, magnetizable, activated carbon particles KM according to production example 2. It filled the reactor volume RV to about 4/5. Above their surface was the gas space G, in which the biogas BG accumulated. In the gas space G there was also a hydrogen sensor HS for determining the hydrogen concentration in the gas phase. Its determined value of the hydrogen concentration served as a control variable for the productivity of the ammonia cracker AC. For this purpose, the measurement signal was sent via the input signal line SLI to an electronic data processing system for the electronic control ES, where it was processed. The data processing system then gave a control signal via the output line SLO to the electronically controlled actuator of the electronically controlled pressure reducer and flow valve V1 of the ammonia supply NH3, whereby the amount of ammonia that was directed to the ammonia cracker AC was regulated. A concentration of 2 to 3% by volume of hydrogen H2 in gas space G was considered to be advantageous because this increased the calorific value of the biogas BG.

The biogas BG produced by fermentation from methane and small amounts of hydrogen, which increased the calorific value, was discharged via the outlet pipe BGA. The content of hydrogen sulfide, carbon dioxide, carbon monoxide, ammonia and oxygen in the biogas BG was below the respective detection limits. The methane content> 90% by volume of the biogas therefore had the methane content required for feeding into the L-gas network according to DVGW G 262 (German Association for Gas and Water).

The hydrogen H2 was introduced into the fermentation liquid GF in the form of fine gas bubbles via an annular hydrogen distributor HV with hydrogen nozzles HD, which was arranged horizontally above the reactor bottom RB. In it, the hydrogen H2 was converted during fermentation and mainly converted the carbon dioxide formed into methane according to equation 1:

C0 ₂ + 8 H ₂ = CH ₄ + 2 H ₂ O (1). The converted biomass KBM was drained continuously or discontinuously together with magnetizable, activated carbon particles KM via the outlet AKB1. New biomass BM was fed in continuously or discontinuously via the biomass feed BMZ. In addition, any losses of magnetizable, activated carbon particles KM were compensated for by adding fresh KM particles to the fermentation liquid GF with a powder feeder (not shown).

The drained converted biomass KBM with the magnetizable, activated carbon particles KM was passed via the outlet AKB1 into a magnetic separator T according to German patent application DE 10 2014 100 849 A1, in which the particles KM were retained. The converted biomass KBM freed from the particles KM was drained from the magnetic separator via the outlet AKB2. If necessary, part of the converted biomass KBM freed from the particles KM was pumped back into the reactor volume RV via the return line RL with the aid of a feed pump (not shown). As soon as the magnetic separator T had reached its capacity limit, which could be determined by magnetic measurements on the process AKB2, the process AKB1 was closed and the particles KM were removed from the magnetic separator using suitable devices (not shown), if necessary reactivated, ie dried and loaded with methanogenic and hydrogenotrophic archaea and with 1% by weight of inorganic nitrates, trace elements, ultra-trace elements, micro-elements, ultra-micro-elements and bulk elements as well as nutrients, essential nutrients, carbohydrates, fats, proteins, minerals and vitamins, and returned to the bioconverter BK .

1.2 The hydrogen production

The production of the hydrogen H2 as a hydrogen-nitrogen mixture H2 / N2 was based on the method described in European patent EP 3 028 990 B1, page 8, FIG. 1, in conjunction with pages 4 and 5, paragraphs [0025] to [ 0029], described method.

The components of the ammonia cracker (AC) for the production of hydrogen H2 were made of corrosion-resistant, thermostable and pressure-resistant V4A steel, so that the ammonia cracker (AC) could be operated at temperatures of up to 700 ° C and pressures of up to 30 bar.

The ammonia was from the ammonia supply NH3 with a flow rate and a pressure that was controlled by the electronic data processing system ES Pressure reducers V1 were regulated as required, passed through the ammonia line NH3L into the recuperator WT1. The hydrogen H2 requirement of the bioconverter was determined by the hydrogen sensor HS; As soon as the hydrogen concentration in gas space G fell below the detection limit of the hydrogen sensor HS, the sensor HS gave a signal via the input signal line SLI to the data processing system ES, which in turn sent a control signal to open the actuator of the pressure reducer V1 via the output signal line SLI. If the concentration of the hydrogen H2 in the gas space G exceeded 4% by volume, the command to close the pressure reducer V1 was issued in the same way.

In the recuperator WT1, the ammonia was heated to 450 ° C. by the hot exhaust gas AG discharged from the heating pipe HR or the central pipe ZR of the horizontally arranged ammonia cracker AC via the exhaust pipes AGL. The HR heating pipe; ZR was arranged in the middle of the ammonia cracker AC and contained a metallic packing MFK made of copper, which was heated with the help of the flame FL of the burner BR and the thermal energy on the cracking catalyst KAT, which is located in the heating pipe ZR; HR located concentrically surrounding outer tube or CR crack tube, transmitted. Nickel supported on aluminum oxide was used as the cracking catalyst KAT. Its temperature was 600 ° C. The ammonia cracker AC was thermally insulated by a 30 cm thick layer (not shown) of high-temperature glass wool.

The hot ammonia flowed through the cracking catalyst KAT and was split into hydrogen H2 and nitrogen at 600 ° C. The resulting gas mixture H2 / N2 contained the hydrogen H2 and the nitrogen in a volume ratio of 3: 1. It still contained up to 5% by volume of ammonia.

The burner BR in the heating chamber HK was supplied with the biogas BG produced in the bioconverter BK, i.e. with renewable energy, the flow of which was regulated by the electronically controlled flow valve V3, air L as the oxidizing agent, the flow of which was regulated by the electronically controlled flow valve V4, and optionally fed by the gas mixture withdrawn from the line for the hydrogen-nitrogen mixture H2 / N2 LH2 / N2, the inflow of which was regulated by the electronically controlled flow valve V2. The flame was ignited piezoelectrically. The air L was passed through the recuperator WT2, where it was heated by the hot gas mixture H2 / N2. The temperature of the gas mixture H2 / N2 fell to 100 ° C. The ammonia-containing gas mixture H2 / N2 was cooled to 55 ° C. in a cooling device (not shown) after the recuperator WT2. Before the gas mixture H2 / N2 entered the hydrogen-nitrogen distributor HV in the bioconverter BK, the ammonia was bound by activated carbon which was impregnated with phosphoric acid. The resulting activated charcoal / ammonium phosphate by-product was itself a valuable product and could be used, for example, to produce terra preta.

In another embodiment, the cooled gas mixture H2 / N2 was passed through sulfuric acid, in which the ammonia was bound as ammonium sulfate. The ammonium sulfate solution was also a valuable product and could be used, for example, as a liquid fertilizer.

In yet another embodiment, the hydrogen H2 was separated from the cooled, ammonia-containing gas mixture H2 / N2 with the aid of a module (not shown) with hydrogen-selective SEPURAN® Noble membranes from Evonik and fed into the hydrogen distributor HV at a pressure of around 1.5 bar , from where it emerged from the hydrogen nozzles HD into the fermentation liquid GF. Part of the hydrogen H2 could also serve as fuel for the AC ammonia cracker.

The entire BKA bio-converter system was centrally controlled by the electronic data processing system. The control signals were determined by temperature and pressure measuring devices, gas flow meters, hydrogen sensors HS, ammonia sensors and biogas sensors. The control signals were sent to the actuators of the valves V1, V2, V3 and V4 via output lines (not shown for reasons of clarity).

The ammonia and the hydrogen H2 required for its production as well as the energy for the ammonia cracker AC were produced using renewable energies from solar energy, such as photovoltaics, solar thermal energy, solar chemistry and updraft power plants, bioenergy from biomass in various forms, such as vegetable oil, wood, biodiesel, bioethanol, Cellulosic ethanol, biogas, BtL (biomass-to-liquid) fuels, and bio-hydrogen, hydropower, such as dams and dam walls, run-of-river power plants, water mills, power buoys, wave energy from the sea, flow energy from the sea and heat from the sea, as well as wind energy, such as wind turbines, air wind power stations and windmills, provided.

1.3 Conclusion The BKA bioconverter system according to the invention had the essential advantage that hydrogen could be produced from ammonia as required, so that all problems of storing hydrogen were avoided from the outset, since the ammonia could be stored in large quantities without any problems at comparatively low pressure. With the hydrogen generated, carbon dioxide in particular could be converted into methane and water, resulting in a particularly high quality Biogas BG with a methane content of> 99% by volume measured using a methane sensor. Since the ammonia cracker AC could also be heated with the generated biogas BG and additionally with the hydrogen-nitrogen mixture H2 / N2 and / or hydrogen H2, the inventive bio-converter system BKA was particularly energy-efficient.

Figure 2

2. Float SCH with activated coal masses K

FIG. 2 shows the top view of the longitudinal section through a liquid-permeable floating body SCH with pellets PK made from activated carbon masses K. The floating bodies SCH could be used excellently in the bio-converter BK of the bio-converter system BKA according to the invention.

The float SCH had a 12-sided outline and was used with advantage in the bioreactor BK of FIG. It consisted of a slightly convex shaped lid DE and a slightly convex shaped can DO, both of which were held together by a circumferential tongue and groove connection FNV, and was filled with pellets PK made of activated carbon mass K. The beech charcoal described in the production example was used as the coal mass K. The float SCH had an outside diameter of 10 cm and an inside diameter of 9 cm. Its wall thickness was therefore 0.5 cm. The distance from the central platform of the lid DE to the side edges was 9 cm. The length of the side edges was each 8 cm. The corners and the edges were slightly rounded (not shown). The walls of the floating body SCH had openings Ö through which the hydrogen H2 or the hydrogen-nitrogen mixture H2 / N2 as well as the Fermentation liquid GF flowed in and came into contact with the pellets PK. The biogas BG formed was able to escape through the openings Ö in the cover DE into the gas space G of the reactor volume RV.

The floating bodies SCH were produced by injection molding from an impact-resistant acrylonitrile-butadiene-styrene copolymer. With this embodiment of the floating bodies SCH, on the one hand, a comparatively dense covering of the surface OF of the fermentation liquid GF was achieved. On the other hand, this occupancy was not so dense that the biogas BG was prevented from escaping.

Figure 3

3. Carbon dioxide-neutral bioconverter system BKA for a multi-stage

Conversion procedure

3.1 Preliminary remark

The carbon dioxide-neutral bio-converter system BKA according to the invention for the multi-stage conversion process comprised the bio-converter BK1; BK2 and BK3. These were of a customary and known type, as described for FIG. The carbon dioxide-neutral bioconverter system BKA was designed for an output of 75 kW _ei and an annual yield of 643,000 kWh of electricity.

For the 4th phase: methanogenesis or methane-forming phase, the microorganisms listed in FIG. 1 were used.

A mixture of the farm manure cattle manure, pig manure, cattle manure, poultry manure and horse manure without straw, corn silage, whole grain grain silage (GPS), green rye silage, grain grains, grass silage, sugar beet and fodder beet was used as biomass BMZ.

3.2 The bioconverter BK1

The BK1 bioconverter was designed for the 1st phase: hydrolysis, the 2nd phase: acidogenesis or acidification phase and the 3rd phase: acidogenesis or vinegar-forming phase. The fermentation liquid GF in the reactor volume RV had a pH of <7. The liquid-solid biomass BM was introduced into the fermentation liquid GF, which was stirred with a paddle stirrer, via the biomass feed line BMZ. In the lower area of the reactor volume RV, the gaseous biomass BMG, in the present embodiment landfill gas, was passed through the biomass inlet BGZ into the ring-shaped distributor BMGV for the landfill gases BMG, from which it emerged in the form of gas bubbles that dissolved in the fermentation liquid GF .

Hydrolysis was initially initiated by various types of exoenzymes secreted by microorganisms. The resulting low molecular weight oligo- and monosaccharides, amino acids, fatty acids and glycerine were converted in acidogenesis by acid-forming microorganisms into lower fatty acids, carboxylic acids, especially acetic acid, alcohols, hydrogen sulfide, ammonia, hydrogen and carbon dioxide. In acidogenesis, the lower fatty acids and carboxylic acids as well as the lower alcohols were converted to acetic acid by acetogenic microorganisms.

The resulting gaseous fermentation products (BG1), which mainly consisted of carbon dioxide and hydrogen, were pumped from the gas space (G) through the pipeline (LBG1) with the aid of the injector (7) through the three-way valve (7.1) into the bioconverter (BK2) and emerged from the ring-shaped carbon dioxide distributor (C02V) as gas bubbles (C02).

In a further procedure, carbon dioxide-containing exhaust gases (C02) from lime kilns were pumped through the pipeline (LC02) with the aid of the injector (8) to the electronically controlled three-way valve (7.1) and mixed there with the gaseous fermentation products (BG1) for carbon dioxide sequestration. The resulting gas mixture was also passed through the gas mixture line (LGM) to the carbon dioxide distributor (CO 2V). In yet another embodiment of the method, a gas mixer (not shown) was used instead of the three-way valve (7.1). The heat energy was extracted from the hot exhaust gases (C02) from the lime kilns by means of heat exchangers (not shown) and used to heat the fermentation liquids (GF).

The converted liquid-solid fermentation products (KBM) were pumped at the bottom of the reactor (RB) of the bioconverter (BK1) with the help of the thick matter pump (1) through a connecting pipe into the bottom space of the bioconverter (BK2). 3.3 The bioconverter (BK2)

The 4th phase, methanogenesis, took place in the bioconverter (BK2). The fermentation liquid (GF) contained activated carbon microparticles (K), which were loaded with hydrogenotrophic and methanogenic archaea. A hydrogen-nitrogen mixture (H2 / N2) cooled to 50 ° C., that ammonia crackers (AC) (see FIG. 1) had been produced and freed from ammonia, was fed through the hydrogen-nitrogen line (LH2 / N2) is pumped into the ring-shaped hydrogen-nitrogen distributor (HV) below the carbon dioxide distributor (C02V) at a pressure of 10 bar. There the gas mixture (H2 / N2 emerged as fine gas bubbles into the fermentation liquid, which were mixed with the carbon dioxide bubbles (C02) and the activated carbon microparticles (K). The rising gas bubbles dissolved in the fermentation liquid (GF), and that through the Methanogenesis resulting biogas (BG) accumulated in the gas space (G). With the hydrogen probe (HS1) located in the gas space (G), the hydrogen content of the biogas (BG) was measured. The measured values were sent to the central station via the input signal line (SLI1) electronic data processing system (ES), which regulated the inflow of the hydrogen-nitrogen gas mixture (LH2 / N2) by means of the control signals sent via the output signal line (SLO).

The biogas (BG) was fed from the bioconverter (BK2) into the biogas collecting line (BGS).

The resulting converted liquid-solid fermentation products (KBM) were conveyed together with part of the activated carbon microparticles (K) from the bottom space of (BK2) via a connecting pipe with the aid of the thick matter pump (2) into the bottom space of the secondary fermenter (BK3).

3.4 The post digester (BK3) and the solid-liquid separator (FFS)

The post digester (BK3) served to complete the methanogenesis and thus to increase the methane yield.

The hydrogen content of the biogas (BG) was measured with the hydrogen probe (HS2) located in the gas space (G) of (BK3). The measured values were sent to the central electronic data processing system (ES) via the input signal line (SLI2) which regulated the inflow of the hydrogen-nitrogen gas mixture (LH2 / N2) into the bioconverter (BK2) by the control signals sent via the output signal line (SLO).

The biogas (BG; CH4) that had accumulated in the gas space (G) was also fed into the biogas collecting line (BGS) and to the biogas discharge line (BGA), from where it was used for further use.

The post-fermented, converted liquid-solid fermentation products (KBM) were pumped together with part of the activated carbon microparticles (K) from the bottom space of (BK3) into the solid-liquid separator (FFS) using the thick matter pump (3). The liquid converted fermentation products (KBM) were separated from the solid converted fermentation products (KBM). The latter were discharged via a customary and well-known solids discharge (FA) for further use as fertilizer or for the production of terra preta.

The liquid converted fermentation products (KBM) could flow through the return (GFR1; GFR2; GFR) with the help of the thick matter pumps (4; 5) with the corresponding position of the three-way cocks (9; 10) and the passage valve (11) into the bottom spaces of the bioconverters (BK3 ; BK2; BK1) are funded.

3.5 Conclusion

The resulting biogas had a methane content of 99% by volume. The small proportions of hydrogen (H2) increased the calorific value. A major advantage of the carbon dioxide-neutral bio-converter system (BKA) was that it was also ideally suited for the sequestration of carbon dioxide (C02).

Figure 4

4. Device (VBK) for the treatment of activated carbon masses (K) with hydrogen (H2)

The device (VBK) for the treatment of activated carbon masses (K) with hydrogen (H2) was made of pressure-resistant stainless steel. For the treatment, a powder of carbon microparticles (K) activated with hydrogenotrophic and methanogenic archaea was first poured into the pressure vessel (12) using a rotary valve (18) through the pipe (LK) and the open valve (16). The passage valves (14; 15; 17) in the hydrogen or hydrogen-nitrogen line (LH2; LH2 / N2) in the pressure line (25) and in the nitrogen purge line (LN2) are closed. The pressure vessel (12) had a volume of 100 L and had a tubular upper area (12.1) and a conically tapering lower area (12.2). It was closed with a convex, removable, pressure- and vacuum-tight cover (12.3). The pipeline (LK) was passed through the cover (12.3). In addition, a pressure gauge (19) and a safety and pressure holding valve (20) were arranged on the cover (12.3).

After filling, the passage valve (16) was closed and the pressure vessel (12) was evacuated through the sieve (21) using the vacuum pump (22) after opening the shut-off valve (13) for vacuum and overpressure until a vacuum <1, 0 mbar was reached. The shut-off valve (13) was then closed and the hydrogen-nitrogen mixture (H2 / N2) was pumped under pressure with the compressor (33) through the open passage valve (14) to the spray lance (31) and from it as a spray cone (32) sprayed into the powdery bulk of the activated carbon microparticles (K). These were violently swirled around. After a pressure of 50 bar had been reached, the valve (14) was closed and the hydrogen-nitrogen mixture (H2 / N2) was allowed to act on the activated carbon microparticles (K) for 30 minutes. As a result, the pressure in the pressure vessel (12) fell by 5 bar. After the rest period, the passage valve (15) and the three-way cock (24) to the check valve (26) were opened, and the contents of the pressure vessel (12) were blown through the pressure line (25) to the spray lance (28) and used as a spray cone ( 29) from hydrogen-containing, powdery, activated carbon masses (H2K) and gas bubbles from the hydrogen-nitrogen mixture (H2 / N2) sprayed into the fermentation liquid (GF) of the bioconverter (BK). Numerous eddies formed in the fermentation liquid (GF), which promoted the mixing of the substances. The passage (27) of the pressure line (25) through the reactor wall (RW) was sealed fluid-tight with a flexible seal in order to cushion the pressure surges when blowing in. After the pressure equalization, the check valve (26) closed. The three-way valve (24) was now opened to the nitrogen purge line (LN2), which led to the cyclone (34), and closed in the direction of the check valve (26). The passage valve (17) was opened and nitrogen (N2) was supplied through the nitrogen purge line (LN2), the line (LK), the pressure vessel (12), the passage valve (15), the pressure line (25), the three-way valve (24 ) and blown through the nitrogen purge line (LN2) into the cyclone (34), in which residues of the hydrogen-containing, powdery, activated carbon masses (H2K) were separated from the gas phase and passed into a collecting container (not shown) via the solids discharge (35). The nitrogen was discharged through the nitrogen discharge line (LAN2). In the injection process according to the invention, despite the low affinity between hydrogen and activated carbon, significantly more hydrogen was absorbed by the pulverulent, activated carbon microparticles (K) than usual. In addition, the contact between hydrogen and the hydrogenotrophic and methanogenic archaea has been significantly improved, which significantly accelerates fermentation or fermentation.

Claims

1. Carbon dioxide-neutral bioconverter plant (BKA), at least comprising at least one bioconverter (BK) for the carbon dioxide-neutral, single-stage or multi-stage production of biogas (BG) by fermentation of biomass (BM; BGM) in a fermentation liquid (GF) moved with agitating agents in the presence of elemental hydrogen, hydrogenotrophic and methanogenic archaea and activated carbon masses (K; KM), at least one ammonia supply (NH3), with at least one ammonia line (NH3L) with

- at least one ammonia cracker (AC) is connected to the production of hydrogen and nitrogen (H2 / N2) through the catalytic splitting of ammonia with the help of renewable energies, and

- At least one line (LH2 / N2) for introducing the generated hydrogen (H2) or the hydrogen-nitrogen mixture (H2 / N2) directly into the at least one bioconverter (BK) and / or at least one device (VBK) for treating activated coal masses (K; KM) with hydrogen (H2) at higher pressure with at least one pressure line (25) and at least one spray lance (28) for injecting the hydrogen-containing, activated coal masses (H2K; H2KM) as a spray cone (29) into the fermentation liquid ( GF) of the at least one bioconverter (BK), wherein the ammonia is produced using renewable energies and the at least one ammonia cracker (AC) can be operated using renewable energies.

2. Carbon dioxide-neutral bioconverter system (BKA) according to claim 1, characterized in that the at least one ammonia supply (NH3) is at least one pressurized gas cylinder.

3. Carbon dioxide-neutral bioconverter system (BKA) according to claim 1 or 2, characterized in that the at least one ammonia cracker (AC) as Double tube reactor is designed, wherein in the central tube (HR; ZR) at least one heating source is arranged and in the cracking tube (CR) at least one cracking catalyst (KAT) is contained.

4. Bioconverter system (BKA) according to one of claims 1 to 3, characterized in that the at least one heating source has at least one heating room (HR) with at least one metallic packing bed (MFK) as a heat exchanger and at least one heating chamber (HK) with at least one burner ( BR) and at least one flame (FL).

5. Carbon dioxide-neutral bioconverter system (BKA) according to claim 4, characterized in that the burner (BK) with at least one fuel selected from the group consisting of biogas (BG), biogas (BG) natural gas mixtures, hot hydrogen (H2 ), hot hydrogen-nitrogen gas mixture (H2 / N2) and mixtures of at least two of the aforementioned fuels, and with hot air (L) as the oxidizing agent.

6. Carbon dioxide-neutral bio-converter system (BKA) according to one of claims 1 to 5, characterized in that the at least one ammonia cracker (AC) has at least one pressure reducer (V1) with an electronically controlled actuator, at least one ammonia line (NH3L) to at least one first recuperator ( WT1) for heating the ammonia (NH3) with the hot exhaust gas (AG) supplied via at least one exhaust gas line (AGL) from the central pipe (ZR), at least one ammonia line (NH3L) for the supply of the heated ammonia (NH3) from the at least a first recuperator (WT1) to the cracking tube (CR) with the at least one cracking catalyst (KAT), at least one line (LH2 / N2) for discharging the at least one hot hydrogen-nitrogen gas mixture (H2 / N2) from the cracking tube (CR ) to at least one second recuperator (WT2) to heat the to the at least one burner (BK) guided air (L) and for cooling the hydrogen-nitrogen gas mixture (H2 / N2), at least one cooling device for cooling the hydrogen-nitrogen gas mixture (H2 / N2) or the separated with the help of at least one hydrogen-selective membrane Hydrogen (H2) to <70 ° C and at least one device for separating the ammonia (NH3) from the hydrogen-nitrogen gas mixture (H2 / N2) before it is introduced into the at least one hydrogen-nitrogen distributor (HV) of the at least one Bioconverter (BK) and / or before its introduction into the at least one device (VBK) for the treatment of activated coal masses (K; KM) with hydrogen (H2) at higher pressure with at least one pressure line (25) and at least one spray lance (28) for spraying the hydrogen-containing, activated coal masses (H2K; H2KM) as a spray cone (29) into the fermentation liquid (GF) of the at least one bioconverter (BK),

7. Carbon dioxide-neutral bioconverter system according to one of claims 1 to 6, characterized in that the feed lines for the liquid and / or gaseous ammonia (LNH3), the ammonia (NH3) heated in at least one first recuperator (WT1), the air (L) , the air (L) heated in at least one second recuperator (WT2) and the biogas (BG) as well as the discharges (LH2 / N2) of the generated hydrogen-nitrogen mixture (H2 / N2) are designed in a spiral shape.

8. Carbon dioxide-neutral bioconverter system (BKA) according to one of claims 1 to 7, characterized in that it contains at least one device (VBK) for treating activated carbon masses (K; KM) with hydrogen (H2) at higher pressure, each of which contains at least one Pressure vessel (12) with a tubular upper area (12.1), a conically tapering lower area (12.2), a horizontal ceiling (12.3) and a passage valve (15) for hydrogen-containing, activated coal masses (H2K; H2KM), - a vacuum pump (22) with an upstream shut-off valve (13) for vacuum and overpressure and an upstream sieve (21) inside the pressure vessel (12),

- A manometer (19) and a safety valve or pressure holding valve (20), a nitrogen purging line (LN2) with a passage valve (17) for nitrogen (N2) to the pressure vessel (12), a metering device (18) for pulverulent, activated coal masses (K ; KM) with a line (LK) for the powdery, activated carbon masses (K; KM) to the pressure vessel (12), a spray lance (31) for hydrogen (H2) or a hydrogen-nitrogen mixture (H2 / N2) in the lower Area (12.2), a line for hydrogen (LH2) or a line (LH2 / N2) for a hydrogen-nitrogen mixture (H2 / N2), a compressor (33) and an upstream passage valve (14).

9. Carbon dioxide-neutral bioconverter plant (BKA) according to one of claims 1 to 10, characterized in that the activated carbon masses (K; KM) in the fermentation liquid (GF) of the at least one bioconverter (BK)

- in floats, each containing

- at least one float,

- at least one fixed, activated carbon mass and

- at least one weighting, freely movable or attached to the at least one reactor floor (RB)) by anchors, in floating bodies (SCH), fixed in at least one layer with the aid of at least one adhesive, in the fluidized bodies of a fluidized bed of a three-phase fluidized bed bioconverter (BK), enclosed in at least one immobile, fluid-permeable container, in at least one fixed bed in at least one fixed bed reactor which is located in at least one run-up side circle of a two-stage converter, and / or

- Present as magnetizable, activated carbon particles (KM).

10. Carbon dioxide-neutral bioconverter plant (BKA) according to one of claims 1 to 9, characterized in that the at least one bioconverter (BK) has at least one biomass inlet (BMZ) for liquid-solid biomass (BM) in the upper region of the at least one reactor volume (RV ) in the at least one gas phase (G) and / or in the at least one moving fermentation liquid (GF) and / or at least one biomass inlet (BGZ) for gaseous biomass (BMG) in the at least one moving fermentation liquid (GF) in the lower area of the at least has a reactor volume (RV) and at least one outlet each with a thick matter pump (1; 2; 3) for converted biomass or fermentation products (KBM) on the reactor base (RB).

11. Carbon dioxide-neutral bioconverter system (BKA) according to one of claims 1 to 10, characterized in that it has at least one bioconverter (BK1) with a fermentation liquid (GF) of a pH value <7 and a thick matter pump (1) for conveying the liquid firm Fermentation products (KBM) from at least one bio-converter (BK1) to at least one bio-converter (BK2),

- At least one bioconverter (BK2) with a hydrogen-containing fermentation liquid (GF) with a pH value> 7 and a thick matter pump (2) for conveying the liquid-solid fermentation products (KBM) from the at least one bioconverter (BK2) to at least one post-fermenter (BK3 ) and at least one secondary fermenter (BK3) with a thick matter pump (3) for conveying the liquid-solid fermentation products (KBM) from the at least one secondary fermenter (BK3) to at least one liquid-solid separator (FFS) with solids discharge (FA).

12. Carbon dioxide-neutral, single-stage or multi-stage conversion process for the production of biogas (BG) through fermentation of biomass (BM) in a fermentation liquid (GF) moved with agitation agents (AG) in the presence of elemental hydrogen, hydrogenotrophic and methanogenic archaea microorganisms and activated coal masses ( K; KM), characterized in that it is carried out in at least one carbon dioxide-neutral bioconverter system (BKA) according to one of claims 1 to 11.

13. Method for injecting hydrogen-containing, powdery activated coal masses (H2K; H2KM) into the fermentation liquid (GF) of at least one bioconverter (BK) under pressure, at least comprising the following process steps:

(A) Provision of at least one device (VBK) for the treatment of activated coal masses (K; KM) with hydrogen (H2) at higher pressure, each comprising at least one pressure vessel (12) each with a tubular upper region (12.1), a conical one tapering lower area (12.2), a horizontal ceiling (12.3), a valve (15) for hydrogen-containing, activated carbon masses (H2K; H2KM), a pressure gauge (19), a safety valve or pressure control valve (20), a nitrogen purge line (LN2) with a passage valve (17) for nitrogen (N2) to the pressure vessel (12), a metering device (18) for pulverulent, activated coal masses (K; KM) with a line (LK) for the pulverulent, activated coal masses (K; KM) to the pressure vessel (12),

(B) Filling in powdery, activated coal masses (K; KM) with the aid of a metering device (18) via a line (LK) into the at least one pressure vessel (12) with the passage valve (25) closed.

(C) Evacuation of the at least one filled pressure vessel (12) with the passage valve (25) closed with at least one vacuum pump (22) each with an upstream shut-off valve (13) for vacuum and overpressure and an upstream sieve (21) within the pressure vessel (12) until a vacuum of ^ 1.0 mbar is reached,

(D) Closing the shut-off valve (13) and injecting hydrogen (H2) or a hydrogen-nitrogen mixture (H2 / N2) under higher pressure into the lower area (12.2) with at least one spray lance (31) in the form of at least one spray cone (32) until a pressure> 10 bar is reached, with the gases flowing through at least one line (LH2) for the hydrogen (H2) or at least one line (LH2 / N2) for the hydrogen-nitrogen mixture (H2 / N2) at least one compressor (33) are passed and compressed there, after which the compressed gases are conveyed through at least one upstream passage valve (14) to the at least one spray lance (31),

(E) Closing the passage valve (14) and opening the passage valve (15) to the pressure line (25) with the check valve (26) and the sealed passage (27) for the pressure line (25) through the reactor wall (RW) and passing the hydrogen-containing , powdery, activated carbon mass (H2 / K; H2 / KM) to the spray lance (28) and injecting the hydrogen-containing, powdery activated carbon mass (H2K; H2KM) in the form of a spray cone (29) made of hydrogen (H2) and hydrogen-containing, powdery , activated carbon mass (H2 / K; H2 / KM).

14. Process for the injection of hydrogen-containing, powdery, activated carbon masses

(H2K; H2KM) in the fermentation liquid (GF) at least one bioconverter (BK) under

Printing according to claim 13, characterized by the following process steps: (F) Turn the three-way valve (24) in the pressure line (25) after pressure equalization, so that the part of the pressure line (25) is closed in the direction of the check valve (26) and opened in the direction of the nitrogen purge line (LN2) and the centrifugal separator (34) will, and

(G) Open the passage valve (17) for nitrogen (N2) in the nitrogen flush line (LN2) and flush the pressure vessel (12), the pressure line (25), the three-way valve (24) and the subsequent nitrogen flush line (LN2), separating any existing ones pulverulent coal masses (K; KM;

H2K; H2KM) in the centrifugal separator (34) and discharging from the solids discharge (35) and discharging the nitrogen (N2) through the nitrogen outlet line (LAN2) from the centrifugal separator (34).

15. Use of the biomass or fermentation products (KBM) converted in the carbon dioxide-neutral bioconverter plant (BKA) according to one of claims 1 to 10 and / or the activated carbon masses (K; KM) used in the carbon dioxide-neutral process according to claim 12 as fertilizers and for production from Terra preta.