Method of increasing the biogas yield of anaerobic fermentations and composition of short-chain branched monocarboxylic acids

Abstract

The present invention relates to a method of increasing the biogas yield of an anaerobic biomass fermentation, at least comprising the method steps of: a) providing an anaerobically active bacteria population suitable for generation of biogas from fermentable biomass and / or non-biogenic waste materials and b) once or more than once adding the fermentable biomass and / or non-biogenic waste materials to the bacteria population, wherein a mixture of at least three different branched C4-C5 monocarboxylic acids is added once or more than once to the bacteria population in method step a), in method step b) or in both method steps. The present invention further relates to a carboxylic acid composition at least comprising three different branched C4-C5 monocarboxylic acids.

Description

[0001] Methods for increasing the biomass yield of anaerobic fermentations and composition of short-chain, branched monocarboxylic acids

[0002] The present invention relates to a process for increasing the biogas yield of an anaerobic biomass fermentation, comprising at least the process steps: a) providing an anaerobically active bacterial population suitable for producing biogas from fermentable biomass and / or non-biogenic residues, and b) adding the fermentable biomass and / or the non-biogenic residues to the bacterial population once or several times, wherein in process step a), in process step b), or in both process steps, a mixture of at least three different branched C4-C5 monocarboxylic acids is added to the bacterial population once or several times. Furthermore, the present invention relates to a carboxylic acid composition comprising at least three different branched C4-C5 monocarboxylic acids.

[0003] The need for a rapid and comprehensive restructuring of current energy consumption habits is becoming increasingly clear. Aside from human-caused global climate change, the scarcity and finite nature of fossil-carbon-based energy sources means that alternative supply concepts must be made available for market readiness and implemented more quickly than previously thought. Technically mature solutions exist for substituting fossil fuels, and these already cover a significant portion of energy demand. Examples include wind energy and photovoltaics, which are capable of providing relatively large amounts of green electricity. Unfortunately, the locations for suitable electricity generation and subsequent consumption are far apart, meaning that the electricity must be transported over long distances.Decentralized power generation would be desirable, but raises unresolved questions regarding suitable site conditions and the temporary storage of excess energy. As an alternative to green power generation, direct substitution of fossil natural gas through the use of biogas in the form of methane is possible and known. As the product names suggest, this type of substitution has the advantage of providing the same chemical substance, but from renewable biogenic raw materials. Furthermore, methane captured from biogas can be used as a synthetic building block in the chemical industry for a variety of purposes. This so-called material utilization for the provision of sustainably produced chemical products such as artificial fertilizers or plastics is an essential component of the transformation of industry toward a more sustainable economy.

[0004] Through the availability of raw material sources at acceptable costs and the continued use of existing gas infrastructures, such as burners, storage facilities, and / or pipeline networks, biogas concepts can make an important contribution to the transformation of the existing energy and chemical industries. However, it would be desirable to reduce the cost of providing biogas by increasing production efficiency. A disadvantage of current biogas production processes is the incomplete conversion of fermentable carbon into carbon dioxide and methane ("biogas"). Processes for increasing biogas yield are therefore a highly sought-after technology for improving the supply of sustainably produced energy and materials.

[0005] The patent literature also contains a wide variety of approaches to increasing biogas production.

[0006] For example, EP1 828 065 B1 describes the use of a thermophilic, anaerobic, acetogenic, hydrogen-producing bacterium to increase methane production in a biogas-producing system, wherein biomass is fermented under anaerobic and thermophilic conditions by a microbial community comprising polymer-degrading microorganisms, acetogenic microorganisms and methanogenic microorganisms.

[0007] CN 1 167 792 C discloses a bioactive additive for biogas fermentation. The additive is characterized by providing 100 g of active additive per cubic meter of feed liquid, with the formula for the bioactive additive per 100 g of biogas fermentation being: saccharification enzyme 40-60 g, amylase 20-45 g, cellulase 5-15 g, and protease 3-10 g.

[0008] DE102008055490A1 further describes a process for producing biogas from biomass in a fermentation reactor, wherein a microorganism of the species Clostridium sartagoformum is added to the biomass.

[0009] Such state-of-the-art solutions may offer further potential for improvement, particularly with regard to simplicity, reproducibility and controllability of the increase in biogas production.

[0010] It is therefore the object of the present invention to at least partially overcome the disadvantages known from the prior art. In particular, the object of the present invention is to provide a process and a composition that are easy to use and lead to a significant increase in biogas production in anaerobic fermentations even in small quantities.

[0011] The object is achieved by the features of the respective independent claims, directed to the method according to the invention and the composition according to the invention. Preferred embodiments of the invention are specified in the subclaims, in the description, or in the figures. Further features described or shown in the subclaims, in the description, or in the figures may constitute a subject matter of the invention, individually or in any combination, unless the context clearly indicates otherwise.

[0012] According to the invention, a process for increasing the biogas yield of an anaerobic biomass fermentation is provided, wherein the process comprises at least the following process steps: a) providing an anaerobically active bacterial population suitable for producing biogas from fermentable biomass and / or non-biogenic residues; b) adding the fermentable biomass and / or the non-biogenic residues to the bacterial population once or several times; wherein in process step a), in process step b) or in both process steps, a mixture of at least three different branched C4-C5 monocarboxylic acids is added to the bacterial population once or several times.

[0013] Surprisingly, it was found that the addition of short-chain monocarboxylic acids in strong dilution to a biomass fermentation leads to a significant increase in overall biogas production and, in particular, in the methane yield. The differences in the biogas yield arise compared to standard biogas fermentations, which do not receive the inventive supplementation with short-chain monocarboxylic acids. The added amounts of short-chain carboxylic acids are so small that the increase in biogas and, in particular, methane production could be attributed to the metabolism of the carboxylic acids themselves. An increase in methane yield also occurs in cases where the anaerobically active bacteria responsible for converting the biomass are preconditioned using short-chain carboxylic acids without the addition of biomass.Without being bound by theory, it is assumed that the addition of the short-chain monocarboxylic acids has a direct influence on the physiology, synthesis performance, and composition ratio of the metabolizing bacterial population. It cannot be completely ruled out that selection and counter-selection processes known in microbiology play a role. Thus, the fermentation system is influenced from a biological and systemic perspective, but not from a chemical or chemical-catalytic perspective. Secondary effects, such as a pH adjustment of the fermentation environment or metabolic effects in the bacterial population, are very unlikely, since the short-chain monocarboxylic acids are only used in high dilutions.The effect is definitely evident both when fermentable biomass is added before the conversion and when fermentable biomass is added simultaneously to the anaerobically active bacterial population.

[0014] The process according to the invention is a process for increasing the biogas yield from anaerobic biomass fermentation. This increase in biogas yield can be combined with conventional biomass fermentation processes. Due to the effect of the carboxylic acid addition on the converting microorganisms themselves, the process is largely independent of the biomass used and the specific fermentation conditions. However, it is important that the fermentation conditions are anaerobic, i.e., that the fermentation takes place largely in the absence of air. Various gases can be produced as biogases during biomass fermentation. These include, for example, carbon dioxide, nitrogen, oxygen, hydrogen, hydrogen sulfide, and ammonia, with methane being the preferred biogas here.An increase in gas yield occurs in cases where an additional amount of gas is obtained through biological processes, whereby the additional gas contribution is higher than the contribution resulting from the theoretical metabolism of the added monocarboxylic acids. According to the invention, the carboxylic acids are not considered as a substrate for the conversion, but rather as a modulator of the conversion kinetics and efficiency of the bacterial population.

[0015] The process comprises process step a), in which an anaerobically active bacterial population is provided, whereby the bacterial population is suitable for producing biogas from fermentable biomass and / or non-biogenic residues. The basis of fermentation is the presence of an active bacterial culture or population capable of breaking down complex biomass of animal or plant origin into smaller chemical components. The anaerobically active bacteria can therefore provide all conversions of biomass as such. These conversions include hydrolytic properties in the first stage of degradation. This means that longer-chain basic substances can be broken down into shorter fragments, such as simple sugars, glycerol, fatty acids, and amino acids. As such, the population is also capable of carrying out the second phase of the conversion, acidification.The fragments formed in the first stage are converted into secondary products such as fatty acids, alcohols, hydrogen, or carbon dioxide. The bacterial population is also capable of acetogenesis of the converted basic substances. During this phase, the anaerobic bacteria primarily produce acetic acid, hydrogen, and CO2. Based on these conversion products, hydrogen and carbon dioxide, biogas, primarily in the form of methane, is ultimately produced by strictly anaerobic bacteria. In addition to the commonly known biomass substrates, other carbon sources, for example from an industrial environment, can of course also be used. This is possible in cases where the bacterial population is fundamentally suitable for decomposing these industrial waste or residues.Suitable non-biogenic residues include, for example, fermentable cellulosic waste from the paper industry, sewage sludge from industrial or municipal wastewater treatment plants, and fermentable waste streams from the chemical industry. In process step a), no biomass is or has yet been actively added to the bacterial culture. The anaerobic bacterial population can be present, for example, in the form of a culture as such or mixed or blended with other substances, for example, in the form of sludge. Other substances, besides the anaerobic bacteria, can be water, sand, or soil. The other additives can contribute to the conversion or be inert with regard to biogas synthesis.

[0016] The process comprises process step b), in which the fermentable biomass and / or the non-biogenic residues are added to the bacterial population once or several times. Plant, animal, or other fermented biomass is added to the bacterial population to achieve batch or continuous biogas production. Depending on the fermentation design, the entire biomass can be added once. However, it is also possible to add the biomass in divided portions to the bacterial population at different times. The addition times can depend, for example, on the current conversion and biogas production. Plant biomass is the biodegradable part of products, waste, and residues from agriculture or forestry and related industries.Animal biomass consists of or contains non-living components (biomass) of animal origin, such as dead or shed body parts, animal carcasses, and slaughterhouse waste. These include, for example, shed or torn hair, feathers, or scales. Also included are exuviae, pupal casings, cocoon remains, eggshells, egg membrane remains, and excrement. Animal biomass also includes, for example, excreta or fish residues from fishing, aquaculture, and insect farming waste. The biomass is added by incorporating, stirring, or generally blending the biomass and the bacterial population.

[0017] In process step a), in process step b), or in both process steps of the process according to the invention, a mixture of at least three different branched C4-C5 monocarboxylic acids is added to the bacterial population once or several times. The conditioning of the bacterial culture by adding monocarboxylic acids can therefore take place before the addition of biomass, during the addition of the biomass, or in both process steps. Small amounts of branched or straight-chain monocarboxylic acids are then actively added to the bacterial culture or indirectly by adding them to the biomass. The monocarboxylic acids can be added to the bacterial population by adding the monocarboxylic acids as such or, for example, in a form dissolved in water. Another way of adding the pure or water-soluble short-chain monocarboxylic acids is by prior application to solid, inert carrier substances, which can simplify handling.The monocarboxylic acids can be added to the bacterial population once or in several doses. Repeated additions can be made at regular or irregular intervals. Repeated additions can be interrupted for certain periods of time. The monocarboxylic acids have one carboxylic acid group and a total C number of 3 to 5. The addition of at least three different monocarboxylic acids leads to better results than the addition of just one monocarboxylic acid. In addition to the at least three monocarboxylic acids, other monocarboxylic acids or other chemical components can be added to the fermentation. If the monocarboxylic acids are added before the actual conversion of biomass to condition the bacterial population, the amount based on the dry matter mass of the activated sludge can be, for example, greater than or equal to 0.0001 wt.% and less than or equal to 1 wt.%, more preferably greater than or equal to 0.0002 wt.-% and less than or equal to 0.2 wt.%, and particularly preferably greater than or equal to 0.001 wt.% and less than or equal to 0.01 wt.%. These figures therefore refer to the weight of the pure dry matter of the activated sludge used.

[0018] The monocarboxylic acids are branched carboxylic acids. In particular, the addition of short-chain, branched monocarboxylic acids can lead to an improvement in biogas and, in particular, methane gas yield in biomass fermentation.

[0019] In a further preferred embodiment of the process, the monocarboxylic acids can be selected from the group consisting of 2-methylbutyric acid, 3-methylbutyric acid, and isobutyric acid. In particular, the addition of three different isomers of butyric acid monocarboxylic acids and valeric acids can lead to an improvement in biogas and, in particular, methane gas yield in biomass fermentation.

[0020] In a further preferred aspect of the process, the addition of the carboxylic acid mixture can occur in process step a). The conditioning of the anaerobic bacterial culture can preferably also occur before the start of the actual biogas production, i.e., before the addition of biomass. In this case, the mixture of monocarboxylic acids is added only before the addition of biomass. A highly controlled and manageable basic system is obtained, which retains the ability to produce large quantities of biogas in the form of methane even with a time lag between the addition of biomass.

[0021] According to a preferred characteristic of the process, the biomass fermentation can be a continuous biomass fermentation, with the carboxylic acid mixture being added, at least in part, together with the biomass in process step b). Continuous biomass fermentation occurs when biomass is added to an ongoing fermentation over a longer period of time, for example, several weeks or months. The carboxylic acid mixture can be added to the bacterial population simultaneously or with a time delay. However, it is also possible for the carboxylic acid mixture to be added to the fermentation mixed with the biomass. This addition can result in a long-term increase in biogas production.

[0022] According to a further preferred characteristic of the process, the biomass fermentation can be a continuous biomass fermentation and the addition of the monocarboxylic acid mixture together with the biomass can take place in a continuous biomass fermentation in process step b) and, for example, after several weeks or months, the addition of the carboxylic acid mixture can be interrupted or stopped.

[0023] In a preferred embodiment of the process, the addition of the monocarboxylic acid mixture can take place in process step b), wherein the addition of the monocarboxylic acid does not take place immediately after the addition of the biomass. Adding the monocarboxylic acids within a relatively short time interval after or before the addition of the biomass has proven to be particularly advantageous. This applies in particular in the context of continuous fermentation. In a further preferred embodiment of the process, the addition of the carboxylic acid mixture can take place at a time interval of greater than or equal to daily and less than or equal to weekly. Adding the monocarboxylic acids within a relatively short time interval has proven to be particularly advantageous. This applies in particular in the context of continuous fermentation.

[0024] Within a preferred aspect of the process, the weight ratio between the total carboxylic acid mixture added in process steps a) and / or b) and the dry matter biomass can be greater than or equal to 1:1,000,000 and less than or equal to 1:100 based on the weight of biomass used in process step b). The addition of these amounts of monocarboxylic acid to the fermentation has proven very effective in increasing the methane gas yield during fermentation. The amount of methane produced can be significantly increased by these amounts of monocarboxylic acid. The addition amounts are based on the weight of the biomass. The total weight added counts, excluding the water content. In the case of the addition of moist biomass, for example in the form of grass clippings, the addition amount is calculated based on the dry weight of the biomass excluding the water content.If dried biomass is added, only the weight of the added amount is taken into account. Inorganic components in the biomass are not taken into account. In the context of an ongoing, continuous fermentation, with a theoretically infinite amount of biomass added, the amount of biomass added is considered within a one-month addition interval and the amount of monocarboxylic acids added is calculated accordingly. The weight ratio between the total carboxylic acid mixture added in process steps a) and / or b) and the dry matter biomass can preferably be greater than or equal to 1:1,000,000 and less than or equal to 1:100, furthermore preferably greater than or equal to 1:500,000 and less than or equal to 1:5,000 and furthermore preferably greater than or equal to 1:100,000 and less than or equal to 1:1,000. The ratio is to be understood such that at the lower limit per 100.At least one part of monocarboxylic acids must be used per 1,000 parts by weight of dry biomass. At the upper limit, less than one part of monocarboxylic acids must be used per 100 parts by weight of dry biomass. The dry matter content of the biomass or other residues can be determined, for example, using DIN EN 15934:2012 - Method A.

[0025] In a further preferred embodiment, the weight ratio between the total carboxylic acid mixture added in process steps a) and / or b) and the dry matter biomass can be greater than or equal to 1:2,000 and less than or equal to 1:200, based on the weight of biomass used in process step b). Within these weight ratios, a particularly high increase in biogas and, in particular, methane yield results.

[0026] Within a preferred aspect of the process, the weight ratio between the total monocarboxylic acid mixture added in process steps a) and / or b) and the dry weight of the bacterial population, calculated based on the dry weight of bacterial population to the weight of monocarboxylic acids added, can be greater than or equal to 1:100 and less than or equal to 1:1,000,000 based on the dry weight of the bacterial population present in process step a). Within these monocarboxylic acid addition quantities, significant increases in biogas yield result at relatively low additional costs. Preferably, the ratio can be greater than or equal to 1:200 and less than or equal to 1:500,000, more preferably greater than or equal to 1:1,000 and less than or equal to 1:100,000. The dry weight of the bacteria can also be determined using DIN EN 15934:2012 - Method A, whereby the dry weight then also includes inorganic substances.

[0027] In a further preferred embodiment of the process, each of the three monocarboxylic acids in the mixture can have a weight fraction of greater than or equal to 20 wt.% and less than or equal to 70 wt.%, wherein the weight fractions add up to 100 wt.%. In particular, monocarboxylic acid mixtures with a significant quantitative proportion of different monocarboxylic acids can contribute to improving the methane yield of anaerobic fermentation. Preferably, each of the monocarboxylic acids in the mixture can have a weight fraction of greater than or equal to 25 wt.% and less than or equal to 60 wt.%, further preferably a weight fraction of greater than or equal to 30 wt.% and less than or equal to 50 wt.% The weight fractions relate to the total added amount of monocarboxylic acids according to the invention, wherein the amount of monocarboxylic acids then adds up to 100 wt.%.The mixture may also contain other substances, although these additional components do not contribute to the weight ratio of the monocarboxylic acids. In particular, the mixture may contain three different monocarboxylic acids.

[0028] Within the scope of a further preferred embodiment of the process, each of the monocarboxylic acids in the mixture can have a weight fraction of greater than or equal to 25 wt.% and less than or equal to 50 wt.%, wherein the weight fractions add up to 100 wt.%. In particular, monocarboxylic acid mixtures with a significant proportion of different monocarboxylic acids can contribute to improving the methane yield in anaerobic fermentations. Preferably, each of the monocarboxylic acids in the mixture can have a weight fraction of greater than or equal to 30 wt.% and less than or equal to 42 wt.%; furthermore, the weight fraction can be greater than or equal to 31 wt.% and less than or equal to 38 wt. The weight fractions relate to the total added amount of monocarboxylic acids of the corresponding size. In particular, three different monocarboxylic acids can be present in the mixture.

[0029] In a further embodiment of the process, the monocarboxylic acid mixture can comprise at least three different branched monocarboxylic acids selected from the group of C4-C5 monocarboxylic acids, wherein each of the three monocarboxylic acids in the mixture has a weight fraction of greater than or equal to 30 wt.% and less than or equal to 40 wt.%, wherein the weight fractions add up to 100 wt.%. The addition of at least three different monocarboxylic acids in approximately equal amounts and without large amounts of other monocarboxylic acid additives appears to be particularly suitable for increasing the methane gas yield in anaerobic fermentations. The methane yield is significantly increased, and the additional costs for adding the monocarboxylic acids are kept low due to the small amounts used. In this way, the economic efficiency of the overall process can be increased.

[0030] In a preferred embodiment of the process, the biomass can be green waste biomass. Especially when using biomass of plant origin, the fermentation efficiency of the bacterial population can be significantly increased by adding the monocarboxylic acid mixture. Significantly more methane is produced, which improves the economic efficiency of the overall process.

[0031] In a further preferred embodiment of the process, the green waste can be selected from the group consisting of bamboo, sugarcane, grass, clover, legumes, alfalfa, pasture grass, or mixtures thereof, whereby the green waste can be added to the fermentation as fresh produce, silage, or as a mixture of fresh produce and silage. The conversion of green waste from the above-mentioned group to biogas can be significantly improved by the addition of monocarboxylic acids. Significantly more methane is produced, which improves the economic efficiency of the overall process.

[0032] In a preferred embodiment, the biomass can comprise or consist of grain. The grain can be selected, for example, from the group consisting of corn, wheat, rye, rice, millet, barley, oats, triticale, and spelt, or mixtures thereof. The grain can be added to the fermentation as fresh grain, silage, or as a mixture of fresh grain and silage. The addition of the monocarboxylic acid mixture according to the invention can lead to particularly high increases in methane yield in the metabolism of this biomass.

[0033] In a preferred embodiment, the biomass can be selected from animal biomass. The animal biomass can, for example, consist of dead or shed body parts, animal carcasses and waste from slaughterhouses, lost or torn hair, feathers or scales, exuviae, pupal casings, cocoon remains, eggshells, egg membrane remains, excrement, excretions or remains of fish from fishing and aquaculture, and excretions and remains from insect breeding. The addition of the monocarboxylic acid mixture according to the invention can lead to particularly high increases in methane yield in the metabolism of this biomass.

[0034] In a further preferred aspect of the process, the biogas can be methane. By adding a mixture of different short-chain monocarboxylic acids, the synthesis performance and composition of the anaerobic bacterial population with respect to methane can be significantly improved.

[0035] Furthermore, according to the invention, a monocarboxylic acid composition comprises at least three different branched C4-C5 monocarboxylic acids, wherein the weight fraction of each individual one of these monocarboxylic acids in the mixture is greater than or equal to 27.5 wt.% and less than or equal to 37.5 wt.%. A monocarboxylic acid composition with the above-specified proportions of branched C4-C5 monocarboxylic acids can, as a supplement in anaerobic fermentations, contribute to a significant improvement in the synthesis performance based on the value product methane. The increase in synthesis performance results from a physiological effect of the mixture on the bacterial population and not from the metabolism of the monocarboxylic acids themselves. The composition can preferably have a weight fraction of each individual one of these monocarboxylic acids in the mixture of greater than or equal to 30.0 wt.% and less than or equal to 35.0 wt.%.The total weight proportions of the monocarboxylic acids according to the invention add up to 100 wt.%. However, the mixture may also contain additional components. These may be, for example, auxiliaries, solvents, or other components, the weight of which, however, is not used to calculate the weight ratios of the monocarboxylic acids usable according to the invention. The mixture can particularly preferably consist of the monocarboxylic acids according to the invention. In particular, three different monocarboxylic acids can be present in the mixture.

[0036] In a further preferred embodiment of the monocarboxylic acid composition, the carboxylic acid mixture can comprise 2-methylbutyric acid, 3-methylbutyric acid, and isobutyric acid. In particular, mixtures of the above-mentioned monocarboxylic acids can have a particularly positive effect on the methane yield in a biogas fermentation. In particular, methane production can be significantly increased. Preferably, the composition can consist of greater than or equal to 90 wt. % of these monocarboxylic acids. Preferably, the weight ratio of the three monocarboxylic acids in the mixture can be 1:1:1. Particularly preferably, the mixture can consist of these three monocarboxylic acids. In particular, three different monocarboxylic acids can be present in the mixture.

[0037] Further advantages and advantageous embodiments of the inventive objects are illustrated by the figures and explained in the following examples. It should be noted that the figures are for descriptive purposes only and are not intended to limit the invention in any way.

[0038] Examples

[0039] A) Static fermentation test with grass silage

[0040] The influence of a short-chain monocarboxylic acid mixture on the biogas synthesis performance of an anaerobic fermentation was investigated using a fermentation test. A 1:1:1 (by weight) mixture of the three monocarboxylic acids 2-methylbutyric acid, 3-methylbutyric acid, and isobutyric acid was used as the monocarboxylic acid mixture. Grass silage was used as the biomass. The grass silage had the following characteristics: dry matter content of 29.8% OS (according to DIN EN 15934:2012), a loss on ignition of 87.7% TS (according to DIN EN 15935:2021), and an organic dry matter content of 26.3%. The monocarboxylic acids were used to precondition the bacterial population. They were added in process step a), i.e., before the addition of biomass. The addition of the monocarboxylic acids was carried out in divided amounts by regular addition of the acid mixture over a period of 4 weeks at an incubation temperature of 40°C.In parallel, a bacterial population was run as a control under the same conditions but without the addition of the additive. 30g of grass silage was then mixed with 500g of the conditioned inoculation sludge and 500g of the control mixture, and this mixture was then made up to a total volume of 1000 ml with water. The inoculation sludge had a dry matter content of approximately 4% and a loss on ignition of approximately 71%. The mixtures were transferred to gas-tight reaction vessels with solenoid-controlled gas outlets. The mixtures were incubated in a water bath heated to 40°C (mesophilic). Gas production was recorded using a drum gas meter. The methane content in the biogas was determined using a methane IR sensor. Three independent batches were run per experiment. The control (inoculation sludge without further addition of monocarboxylic acids) was run in duplicate.

[0041] The additions of the monocarboxylic acid mixture according to the invention as stated above and water for the controls were as follows: The addition quantities are given in g and refer to 1 liter of inoculation sludge. The information in the header refers to the weight addition quantities of monocarboxylic acids relative to the volume of 1 liter of inoculation sludge.

[0042] The fermentation tests after adding the biomass were conducted at a temperature of 40°C. 500 g of inoculant sludge and 30 g of substrate were fermented. The following fermentation results were obtained: oTS = organic dry matter, NI = standard liter

[0043] In all batches, gas production began immediately after the start of the study. A pronounced lag phase without gas production was not observed. The batches with the conditioned bacterial populations exhibited a higher outgassing rate from the outset compared to the control batch. After 10 days of incubation, the batches with 1:2,500 and 1:10,000 were each approximately 19% higher than the control batch in terms of specific methane yield. The additional yield of the 1:50,000 batch, at around 15%, was slightly lower than the first two batches with higher addition rates of monocarboxylic acids. Although the additional yields of the batches with the conditioned inoculation sludge decreased over the course of the experiment, they remained significantly higher than those of the control batch until the end of the experiment.

[0044] At the end of the study after 30 days, the 1:2,500 approach showed a specific methane yield of 231.0 Nl / kg oTS, approximately 11% higher than the control approach (208.2 Nl / kg oTS). The 1:10,000 approach achieved 233.2 Nl / kg oTS, corresponding to an additional yield of approximately 12%. At 222.9 Nl / kg oTS and approximately 9.5% additional yield, the approach with an addition rate of 1:50,000 was still slightly below the approaches with additions of 1:2,500 and 1:10,000. However, the differences between the conditioned approaches, at < 3%, are within the experimental deviations and are not considered significant. The percentage yield increases relative to the total organic yield are slightly higher than the respective methane yield increases at 14.5% (1:2,500), 15.1% (1:10,000), and 11.7% (1:50,000). This is due to the higher methane content of the control approach.

[0045] Figure 1 shows the difference in methane production between the control and the experimental setup with a 1:10,000 addition rate. It is clearly visible that methane production is increased, particularly at the beginning of the conversion. This effect diminishes over time, but even after very long periods, preconditioning the bacterial population leads to an improved methane yield. Due to its magnitude, the improved methane yield cannot be attributed to the metabolism of the monocarboxylic acids. The improved yield must be due to physiological conditioning of the bacteria, with subsequent improved conversion of the biomass.

[0046] This conditioning effect can also be quantified. The increase in methane yield achieved by adding monocarboxylic acids can be quantified, for example, according to Buswell and Mueller. Assuming complete degradation of the monocarboxylic acids during fermentation, a theoretical maximum gas volume for this degradation results.

[0047] The stoichiometries of the individual amino acid transformations are as follows:

[0048] Isobutyric acid mole = C4H7O2 + 1.25 H2O = 2.375 CH4 + 1.625 CO2

[0049] 2-Methylbutyric acid Mol = C5H10O2 + 1.5 H2O = 3.25 CH4+ 1.75 CO2

[0050] 3-Methylbutyric acid Mol = C5H10O2 + 1 ,5 H2O = 3,25 CH4 + 1 ,75 CO2 The molar amounts result in the corresponding gram amounts

[0051] Isobutyric acid MW = 88.1 C4H7O2 + 1.25 x 18 H2O = 2.375 x 16 CH4 + 1.625 x 44 CO2

[0052] E 88.1g C4H7O2+ 22.5g H2O = 38g CH4+ 71.5g CO2

[0053] 2-Methylbutyric acid MW = 102, 1 C5H10O2 + 1.5 x18 H2O = 3.25 x 16 CH4+ 1.75 x 44 CO2

[0054] E 102.1g C5H10O2 + 27g H2O = 52g CH4+ 77g CO2

[0055] 3-Methylbutyric acid MW = 102.1 C5H10O2 + 1.5 x18 H2O = 3.25 x 16 CH4 + 1.75 x 44 CO2

[0056] E 102.1g C5H10O2 + 27g H2O = 52g CH4+ 77g CO2

[0057] This results in the following quantity relations:

[0058] 0.43 g of methane is formed per gram of isobutyric acid MW = 88.1.

[0059] 0.51 g of methane is formed per gram of 2-methylbutyric acid MW = 102.1.

[0060] 0.51 g of methane is formed per gram of 3-methylbutyric acid MW = 102.1.

[0061] For a 1:1:1 mixture, this results in 0.48g of methane per gram of mixture.

[0062] The experiments conducted demonstrate that a significant increase in methane yield is achievable even with a highly diluted additive. In this example, a specific methane yield increase of 18.8 NI / kg of dry biomass was achieved. This corresponds in kg: 18.8 NI methane = 0.84 mol = 0.01343 kg of additional methane yield per 1 kg of dry biomass (dry biomass). In this example, a total of 20 pg of additive was added at several intervals during conditioning to a dry biomass (dry biomass) total of 22.25 g. This results in a ratio of 1:1112.5 additive to dry biomass [g / g]. This example shows that with 1 kg of additive, 67.15 kg more methane is produced when using 1112.5 kg of biomass than in the control experiment without additive. The added additive itself produces 0.48 kg of methane per kg, which must be deducted from the previously mentioned amount. The net additional yield after adding 1 kg of additive is 66.67 kg of methane.The additional methane yield is therefore 138.9 times the theoretical amount of gas production attributable to the addition of the additive. The leverage of the addition thus scales with a quantitative factor of 138.9 (calculated in kg / kg of additive to methane). The estimable range of the leverage factor can be specified within a range of greater than or equal to 100 and less than or equal to 500.

[0063] B) Static fermentation test with dry chicken manure (HTK)

[0064] The influence of a short-chain monocarboxylic acid mixture on the biogas synthesis performance of an anaerobic fermentation was investigated using a fermentation test according to Example A. However, in this experiment, dried chicken manure (HTK) was used as the biomass instead of grass silage. Comparable results were obtained. By adding small amounts of a monocarboxylic acid mixture according to the invention, the biogas synthesis performance, and in particular the methane synthesis performance, can be significantly increased even when using HTK as the biomass.

[0065] C) Static fermentation test with maize silage

[0066] The influence of a short-chain monocarboxylic acid mixture on the biogas synthesis performance of an anaerobic fermentation was conducted using a fermentation test according to Example A). However, corn silage was used as the biomass instead of grass silage in this experiment. Comparable results were obtained. By adding small amounts of a monocarboxylic acid mixture according to the invention, the biogas synthesis performance, and in particular the methane synthesis performance, can be significantly increased even when corn silage is used as the biomass. Example D) Continuous fermentation test: grass silage

[0067] The influence of a short-chain monocarboxylic acid mixture according to the invention on the biogas synthesis performance of an anaerobic fermentation was investigated using a continuous fermentation test. A 1:1:1 (by weight) mixture of three monocarboxylic acids, 2-methylbutyric acid, 3-methylbutyric acid, and isobutyric acid, was used as the monocarboxylic acid mixture. Grass silage served as the biomass. The monocarboxylic acids were used to precondition the bacterial population. The addition took place in process step a) combined with process step b), i.e., before and during the addition of biomass. The addition of the monocarboxylic acids was carried out in divided portions, by daily addition of the acid mixture over a period of 21 days at an incubation temperature of 40°C in a mixed reactor with a working volume of 70 liters.In two parallel conditioned fermentation tests, 7 mL of the monocarboxylic acid mixture was added daily, and a bacterial population was run as a control under the same conditions but without the addition of the additive. The inoculating sludge had an organic dry matter content of approximately 8%. Subsequently, 250 g of dry matter mass of grass silage was added daily to the 70 liters of conditioned inoculating sludge. In one variant, 0.5 mL of monocarboxylic acid mixture was added to the conditioned fermentation tests at a ratio of 1:500 based on the added organic dry matter mass of grass silage, and in another variant, 0.25 mL of monocarboxylic acid mixture was added to the conditioned fermentation tests at a ratio of 1:1000 based on the added organic dry matter mass of grass silage. Gas production was recorded using a drum gas meter.A variant with daily addition of 0.5 mL of the monocarboxylic acid mixture showed a daily increase in biogas production of approximately 10% relative to the total amount of biogas in the control system, which did not add any monocarboxylic acid mixture, after 13 days of daily addition of 250 grams of dry matter mass of grass silage. This demonstrated that the synthesis performance of a continuous fermentation can also be significantly improved. It was also shown that the addition of the monocarboxylic acids can be carried out concurrently with the addition of biomass.

Claims

Patent claims 1. Method for increasing the biogas yield of an anaerobic Biomass fermentation, comprising at least the process steps: a) providing an anaerobically active bacterial population suitable for producing biogas from fermentable biomass and / or non-biogenic residues; b) adding the fermentable biomass and / or the non-biogenic residues to the bacterial population once or several times; characterized in that in process step a), in process step b) or in both process steps, a mixture of at least three different branched C4-C5 monocarboxylic acids is added to the bacterial population once or several times.

2. Process according to one of the preceding claims, wherein the monocarboxylic acids are selected from the group consisting of 2-methylbutyric acid, 3-methylbutyric acid and isobutyric acid.

3. Process according to one of the preceding claims, wherein the addition of the monocarboxylic acid mixture takes place in process step a).

4. Process according to one of claims 1 or 2, wherein the biomass fermentation is a continuous biomass fermentation and the addition of the monocarboxylic acid mixture, at least in part, takes place together with the biomass in process step b).

5. The method according to claim 4, wherein the addition of the monocarboxylic acid mixture takes place at a time interval of greater than or equal to daily and less than or equal to weekly.

6. Process according to one of the preceding claims, wherein the weight ratio between the total amount of the additive added in process steps a) and / or b) Carboxylic acid mixture and dry matter biomass is greater than or equal to 1:1,000,000 and less than or equal to 1:100 based on the biomass weight used in process step b).

7. Process according to one of claims 1 to 5, wherein the weight ratio between the total carboxylic acid mixture added in process steps a) and / or b) and the dry matter biomass is greater than or equal to 1:2,000 and less than or equal to 1:200 based on the weight of biomass used in process step b).

8. Process according to one of the preceding claims, wherein each of the monocarboxylic acids in the monocarboxylic acid mixture has a weight fraction of greater than or equal to 20 wt.% and less than or equal to 70 wt.%, wherein the weight fractions of the monocarboxylic acids in the monocarboxylic acid mixture add up to 100 wt.%.

9. Process according to one of the preceding claims, wherein each of the monocarboxylic acids in the monocarboxylic acid mixture has a weight fraction of greater than or equal to 25 wt.% and less than or equal to 50 wt.%, wherein the weight fractions of the monocarboxylic acids in the monocarboxylic acid mixture add up to 100 wt.%.

10. The process according to any one of the preceding claims, wherein the monocarboxylic acid mixture comprises at least three different branched monocarboxylic acids selected from the group of C4-C5 monocarboxylic acids, wherein each of the three monocarboxylic acids in the mixture has a weight fraction of greater than or equal to 30 wt.% and less than or equal to 40 wt.%, wherein the weight fractions of the monocarboxylic acids in the monocarboxylic acid mixture add up to 100 wt.%.

11. A method according to any one of the preceding claims, wherein the biomass is a green waste biomass.

12. The method according to claim 11, wherein the green material is selected from the group consisting of bamboo, sugar cane, grass, clover, legumes, alfalfa, pasture grass or mixtures thereof, wherein the green material can be added to the fermentation as fresh material, silage or as a mixture of fresh material and silage.

13. The process according to any one of the preceding claims, wherein the biogas is methane.

14. A monocarboxylic acid composition comprising at least three different branched C4-C5 monocarboxylic acids, wherein the weight fraction of each of these monocarboxylic acids in the mixture is greater than or equal to 27.5 wt.% and less than or equal to 37.5 wt.%.

15. A monocarboxylic acid composition according to claim 14, wherein the Monocarboxylic acid mixture consisting of greater than or equal to 90 wt.% of the monocarboxylic acids 2-methylbutyric acid, 3-methylbutyric acid and isobutyric acid.

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