Treatment methods for reducing gas emissions from farm waste for fertilizer

Abstract

The present invention relates to the use of methods and compositions for reducing the emission of environmentally harmful greenhouse gases methane and / or carbon dioxide from farm waste for fertilizer use during its storage.

Description

[Technical Field]

[0001] explanation The present invention relates to a treatment method for reducing the emission of the environmentally harmful greenhouse gases methane and carbon dioxide from stored farm waste for fertilizer (or farm manure). Furthermore, the present invention relates to the use of a composition to inhibit or reduce the emission of the environmentally harmful greenhouse gases methane and carbon dioxide from stored farm waste for fertilizer.

[0002] In the Federal Republic of Germany, farm waste for fertiliser is considered a fertiliser which must meet statutory requirements and standards. Its use and application as well as its sale must in particular comply with the current provisions of the Fertiliser Act, the Fertiliser Regulation and the Fertiliser Regulation as well as the EU guidelines.

[0003] For example, current fertilization regulations regulate the application rate and application period of farm manure for fertilizer. Therefore, farm manure for fertilizer may be subject to a restricted period during several months of the year, depending on the soil and crop type, during which it may not be applied to agricultural fields. As a result, livestock farms must provide sufficient storage space for liquid manure, manure water, slurry, solid manure, etc. According to current regulations, it is absolutely necessary to store farm manure for fertilizer for at least 150 days. [Background technology]

[0004] US Publication Nos. US 2002 / 0121117 A1 and US 2014 / 0311200 A1 describe the use of calcium cyanamide compositions to reduce unpleasant odors emanating from liquid waste, such as those caused by sulfur-containing compounds or ammonia.

[0005] Liquid wastes, manure, slurry, stable waste, etc. have always been very important in agriculture as fertilizer wastes. However, because livestock farms are concentrated in a limited space, especially in livestock sheds, these fertilizer wastes accumulate in an increased and concentrated form.

[0006] The storage of these farm wastes for fertilizer is also associated with various unresolved issues, for example, during the storage of farm wastes for fertilizer, the processes of aerobic and anaerobic fermentation and microbial decomposition of organic matter in the farm wastes for fertilizer produce greenhouse gases such as methane (CH4) and carbon dioxide (CO2), which are harmful to the environment.

[0007] For example, in 2016, around 59% of total methane emissions in Germany came from agriculture. This year, the management of farm waste for fertilizer (storage and application of liquid and solid waste) accounted for 19.2% of total methane emissions from agriculture in Germany. The most methane from farm waste for fertilizer comes from cow manure and, to a lesser extent, pig manure. In contrast, other animal groups (e.g., poultry, donkeys, horses) accounted for very small amounts (https: / / www.umweltbundesamt.de / daten / land-forstwirtschaft / beitrag-der-landwirtschaft-zu-den-treibhausgas#textpart-1).

[0008] A similar effect with regard to the emission of environmentally damaging gases can be observed in the storage of fermentation residues obtained from biogas-producing plants. These fermentation residues are also used as farm fertilizers, but also emit environmentally damaging gases during open storage.

[0009] In the past, there has been no shortage of experiments dealing with these problems. Many solutions have already been found that allow, for example, to reduce the emissions of environmentally damaging gases from farm waste for fertilizer. The possibilities for reducing emissions are varied and effective in different areas of agricultural production. Without claiming completeness, the following measures can be mentioned in this document: Measures in animal shelters, e.g., air purification, low-emission open shelters, improved hygiene. Cover liquid waste in the tank with straw chips, granules or a floating film. · Use of low-emission technologies in the application of farm waste for fertilizers, such as the direct incorporation of farm waste for fertilizers into soil. - Improved transportability of farm waste for fertilizer by separating it into solid and liquid phases. Modern and improved feeding methods with low protein multi-phase feeding.

[0010] During the storage of farm waste for fertilizer, the emission of harmful gases into the environment can be successfully achieved by closed storage vessels, collection of the gases produced and their further treatment or disposal, although the equipment required for this entails considerable costs. Summary of the Invention [Problem to be solved by the invention]

[0011] The present invention is therefore based on the problem of providing a treatment method for reducing methane and / or carbon dioxide gas emissions from farm waste for fertilizers during storage, which treatment method can be used economically and, moreover, does not impair the planned use of farm waste for fertilizers as agricultural fertilizers. [Means for solving the problem]

[0012] This problem is solved by the process according to claim 1 and the uses according to claims 9 and 10. Preferred embodiments of the invention are set out in the dependent claims.

[0013] Thus, according to a first embodiment, a method for reducing the emissions of methane (CH4) and / or carbon dioxide (CO2) from farm waste for fertilizer during storage is the subject of the present invention, said method comprising the following process steps: a) providing a storage tank for farm waste for fertiliser having a volume X; b) filling the storage tank with farm waste for fertilizer in an amount of at least 5% by volume of the volume X of the storage tank; c) adding a composition comprising calcium cyanamide (CaNCN) to the holding tank and contacting the composition with the fertilizer farm waste.

[0014] It is essential that calcium cyanamide, not cyanamide, be used here. Calcium cyanamide (CaNCN, CAS [156-62-7]) is the calcium salt of cyanamide (CH2N2, CAS [420-04-2]) and has long been known as a component and active ingredient in fertilizers. For example, industrially produced calcium cyanamide (also known as lime nitrogen) and calcium cyanamide-containing nitrate fertilizers, both approved as fertilizers in Europe, contain calcium cyanamide as an essential primary component. These fertilizers are used as soil fertilizers for a wide range of crops, including corn, potatoes, and rice.

[0015] According to the invention, farm waste for fertilizer means fertilizer as defined in the Fertilization Act (Section 2, paragraphs (1), (2), (3), (4) and (5) of the Fertilization Act of January 9, 2009 (BGBl. I, p. 54, 136), last amended by Article 1 of the Act of May 5, 2017 (BGBl. I, p. 1068)). Thus, farm waste for fertilizer according to the invention is fertilizer, which fertilizer is a) As animal feces aa) in the raising of animals for the production of food, or bb) In other cases of keeping animals in agriculture: b) as plant material in the process of plant production or in agriculture; Also in mixtures with each other or after aerobic or anaerobic treatment, Accumulated or generated.

[0016] The term "farm waste for fertilizer" therefore also includes, in particular: - Solid waste: farm waste for fertilizer purposes derived from animal faeces, including also stable bedding, in particular straw, sawdust, peat or other plant materials added in the course of animal rearing, or mixed with feed residues, the dry matter content of which exceeds 15%. - Liquid waste: Farm waste for fertilizer purposes derived from any animal faeces, including small amounts of stable litter or feed residues, or to which water has been added, the dry matter content of which does not exceed 15%. - Manure water or slurry: Fertilizer farm waste derived from animal feces, consisting of leached particles of urine and feces or stable litter mixed with water. Manure water or slurry may also contain small amounts of feed residues, wash water and rainwater. - Biogas fermentation residues: farm waste for fertilizer derived from residues resulting from the fermentation of organic matter, both plant and animal origin, from biogas plants.

[0017] The treatment method according to the invention is particularly suitable for reducing methane and / or carbon dioxide emissions from farm waste for liquid fertilizer, in particular from liquid waste, manure water and / or biogas fermentation residues.

[0018] Surprisingly, it has been found that a composition comprising calcium cyanamide is able to reduce the emissions of environmentally damaging methane (CH4) and carbon dioxide (CO2) from stored farm waste for fertilizer in a very effective and very efficient manner. It has been shown that an amount of 1.38 kg of a composition comprising calcium cyanamide per cubic meter of farm waste for fertilizer can significantly reduce methane and carbon dioxide emissions already 24 hours after addition of the composition (see Examples).

[0019] Therefore, the use of a composition comprising calcium cyanamide for reducing methane and / or carbon dioxide emissions from farm waste for fertilizer storage in a storage tank is also a subject of the present invention.

[0020] Methane and carbon dioxide are odorless gases. For environmental reasons, it is desirable to reduce or completely avoid the emission of these gases.

[0021] Calcium cyanamide-containing compositions have been used as fertilizers for a long time. However, the use of these fertilizers has been separated from the use of farm waste as fertilizer because the application of farm waste as fertilizer is bound by legal periods and these periods are different from the recommended application periods of calcium cyanamide-containing compositions. Therefore, to date, no reduction in emissions of environmentally damaging gases has been observed.

[0022] The research that forms the basis of the present invention also showed that during storage of farm waste for fertilizer treatment with a composition containing calcium cyanamide, no residues are produced that could be assessed as a drawback for use as a fertilizer, so that farm waste for fertilizer treatment according to the present invention can also be easily used as a fertilizer.

[0023] What is particularly important is that the nitrogen content of farm waste for fertilizers treated in this way also remains unchanged. This fact becomes particularly clear when comparing the amounts used in this application. For example, calcium cyanamide fertilizers approved in Europe, i.e., calcium cyanamide with nitrate, are usually applied at a rate of 400 kg per hectare (ha). In this application, a total nitrogen amount of 79.2 kg per hectare is applied to green or arable soils.

[0024] 30 m per hectare of green space or arable soil for farm waste used as fertilizer 3 Application rates up to 30 m per hectare are considered standard applications. The average amount of total nitrogen in liquid cow manure is about 0.40% (see also Example 1), which is 3 This application rate results in 120 kg of total nitrogen per hectare. When a composition containing 2.93 kg of calcium cyanamide per cubic meter of fertilizer manure is added to the fertilizer manure according to the present invention (see Example 1), the amount of total nitrogen in the treated fertilizer manure increases to only 0.46%. This means that the total amount of nitrogen added in the above application of fertilizer manure is only 18 kg more per hectare of green or arable soil.

[0025] In this way, the total amount of farm waste per hectare for fertilizer remains essentially unchanged. This means that nitrogen fertilizers conventionally used with farm waste for fertilizer, which have a different efficacy profile from that of the farm waste for fertilizer, can be used in consistent amounts throughout the year without concern for over-fertilization. Thus, the application of calcium cyanamide-containing compositions incorporated into farm waste for fertilizer according to the present invention is also clearly distinguishable from conventional fertilization using calcium cyanamide-containing fertilizers in terms of total nitrogen applied.

[0026] The treatment method according to the present invention is characterized by the fact that gas emissions from farm waste for fertilizer use are reduced solely by adding a composition comprising calcium cyanamide to the storage tank and contacting said composition with the farm waste for fertilizer use. It is therefore envisaged that treatment steps b) and c) may be carried out independently of any order according to the present invention. Thus, the addition of the composition according to treatment step c) can be carried out before, during or after the first charge of farm waste for fertilizer use into the storage tank. If carried out prior to the first charge, the addition should be carried out within a reasonable time before contacting the farm waste for fertilizer use. A period of less than one day will be understood to be reasonable.

[0027] The addition of the composition according to treatment step c) can be carried out in a completely empty storage tank or in a storage tank that is not completely empty, i.e., filled with residual contents. It is essential that the storage tank is or will be filled with farm waste for fertilizer to at least 5% by volume of its volume. In this way, the composition can be thoroughly mixed with the farm waste for fertilizer to ensure the effectiveness of the composition.

[0028] It is considered advantageous if, during or after the addition of the calcium cyanamide-containing composition to the fertilizer-grade farm waste in the storage tank, the calcium cyanamide-containing composition and the fertilizer-grade farm waste are mixed, particularly by circulating the contents of the storage tank with a propeller mixer or agitator pump. The calcium cyanamide-containing composition is then added to a storage tank containing at least 5% by volume of the fertilizer-grade farm waste and agitated. Further fertilizer-grade farm waste may then be added. After this addition is complete, the fertilizer-grade farm waste is recirculated within the storage tank. The storage tank may be partially or completely filled.

[0029] Tractor- or electric-motor-driven propeller mixers are suitable for circulating the fertilizer farm waste in the storage tank. Propeller agitators or integral mixers with submersible motors permanently mounted on the storage tank wall have proven particularly suitable, as have coupled tower-type propeller mixers submerged in the fertilizer farm waste in the storage tank and swung around in the tank by an attached tractor. Furthermore, agitator nozzles attached to feed pumps are suitable for circulating the fertilizer farm waste in the storage tank, particularly agitator nozzles with breakers or long-shaft agitator pumps with rotary pumps driven by electric motors or tractors.

[0030] According to a preferred embodiment of the present processing method, the addition of the composition according to processing step c) can be carried out all at once or in portions. Particularly preferably, the addition of the composition is i) once after or during the first addition of the first portion of farm waste to the storage tank for fertilizer; or ii) In multiple instalments, after each partial fill of the storage tank; or iii) It may be carried out once after or during the complete filling of the storage tank of farm waste for fertiliser.

[0031] It is thus possible to carry out the addition of the calcium cyanamide-containing composition during or after the partial or complete filling of the storage tank. Here too, it has proven advantageous if the contents of the storage tank are circulated during and after the addition of the calcium cyanamide-containing composition, in particular by means of a propeller mixer or agitator pump.

[0032] In most cases, farm waste for fertilizer is continuously produced by livestock breeding and collected in a storage tank, which is filled to at least 5% by volume. Here too, it is possible to add a composition containing calcium cyanamide before, during or after the continuous filling with farm waste for fertilizer. Here too, it proves advantageous if the farm waste for fertilizer in the storage tank is circulated during and after the addition of the composition containing calcium cyanamide.

[0033] It is also considered advantageous if the addition of the composition comprising calcium cyanamide takes place before, during and after the continuous or portion-wise filling of the farm waste for fertilizer into the storage tank. Here again, it has been found to be advantageous if the farm waste for fertilizer in the storage tank is circulated during and after the addition of the composition comprising calcium cyanamide.

[0034] The calcium cyanamide-containing composition is added to open and closed storage tanks containing farm waste for fertilizer. Closed storage tanks are, for example, tanks or vessels with tent roofs or concrete ceilings. Open storage tanks or vessels have no structural covering.

[0035] It should be emphasized here that the process according to the present invention can be carried out in a variety of storage tanks, without limitation. The size of the storage tank is not a determining factor. Therefore, the volume X can be any reasonable size. In particular, X is defined as a volume in cubic meters (m 3 ), especially the volume measured in 0.001 m 3 ≦X≦20,000m 3 The range is preferably 0.1 m 3≦X≦10,000m 3 and more preferably in the range of 1 m 3 ≦X≦10,000m 3 range, particularly preferably 10 m 3 ≦X≦10,000m 3 The range is.

[0036] The method is further characterized in that the addition of the composition comprising calcium cyanamide is carried out in a storage tank containing the fertilizer farm manure, where the temperature of the fertilizer farm manure ranges from 0° C. to 60° C. The treatment is applicable under winter and midsummer conditions, and is applicable to fertilizer farm manure directly derived from a fermentation process or in a secondary fermentation vessel or tank after biogas treatment.

[0037] According to the present invention, a composition comprising calcium cyanamide is used in a treatment method for reducing methane and / or carbon dioxide emissions from stored farm waste for fertilizer.

[0038] According to the present invention, the treatment time of farm waste for fertilizer with a composition comprising calcium cyanamide to reduce methane and / or carbon dioxide emissions is preferably at least 24 hours, more preferably more than 30 days, even more preferably more than 40 days, and especially more than 50 days, although storage times may also be much longer, for example up to or even exceeding 150 days if desired.

[0039] In accordance with the present invention, the addition of a composition comprising calcium cyanamide may in particular reduce methane and / or carbon dioxide emissions from farm waste for fertilizer use by at least 30% (compared to untreated farm waste for fertilizer use), more preferably by at least 40%, more preferably by at least 50%, more preferably by at least 60%, even more preferably by at least 70%, and particularly preferably by at least 80%.

[0040] Therefore, the use of a composition comprising calcium cyanamide for reducing methane and / or carbon dioxide emissions from farm waste for fertilizer storage in a storage tank is also a subject of the present invention.

[0041] Furthermore, tests have shown that the addition of calcium cyanamide-containing compositions can be carried out at any time during storage (see Examples). This indicates that addition after several weeks of storage of farm manure for fertilizer purposes is still possible, resulting in a reduction in methane and carbon dioxide emissions. Thus, the use of calcium cyanamide-containing compositions as fermentation stoppers or inhibitors of anaerobic fermentation of farm manure for fertilizer purposes and / or as inhibitors of microbial degradation of organic substrates in farm manure for fertilizer purposes during storage in storage tanks is also the subject of the present invention.

[0042] Preferably, compositions comprising 10 to 100% by weight of calcium cyanamide (% by weight based on the composition) may be applied in the uses or treatment methods according to the invention. Particularly preferred in this regard are compositions comprising at least 20% by weight, more preferably at least 25% by weight, more preferably at least 30% by weight, more preferably at least 35% by weight, more preferably at least 40% by weight, more preferably at least 45% by weight, more preferably at least 50% by weight, more preferably at least 60% by weight, and up to 100% by weight, in particular up to 95% by weight, in particular up to 80% by weight, in particular up to 55% by weight of calcium cyanamide (based on the composition).

[0043] In the context of the present invention, a designation in weight percent is to be understood as indicating the weight of a component or group of components based on the composition of the components of the composition totaling 100% by weight.

[0044] According to a further embodiment of the present invention, calcium cyanamide may be applied to a substrate. This substrate may be an agriculturally inert substance, an adjuvant approved for agricultural purposes, or a fertilizer. According to the present invention, calcium carbonate and / or related substances or inorganic fertilizers are particularly preferred as substrates. These substrates may be obtained from commercial processes and may contain a certain amount of free carbon, charcoal, or graphite. Simultaneously or separately, calcium cyanamide may be used in a mixture with additional components.

[0045] Therefore, compositions that can be particularly preferably applied in the use or treatment method according to the present invention are: a) calcium cyanamide; b) at least one compound from the group of carbonates, oxides and hydroxides, in particular from the group of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide, or a mixture thereof, c) More preferably, optionally free carbon, charcoal or graphite A composition comprising:

[0046] The proportion of other ingredients or substrates may vary. Preferably, the composition may comprise at least one compound from the group of carbonates, oxides or hydroxides, in particular from the group of magnesium carbonate, magnesium bicarbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium bicarbonate, calcium oxide and calcium hydroxide, or a mixture thereof, wherein the amount of at least one compound from the group of carbonates, oxides and hydroxides, or a mixture thereof, is at least 5% by weight, preferably at least 10% by weight, more preferably at least 15% by weight, more preferably at least 20% by weight, and at the same time not more than 50% by weight, in particular not more than 40% by weight, in particular not more than 35% by weight, in particular not more than 25% by weight (% by weight based on the composition).

[0047] The amount of free carbon, charcoal or graphite in the composition may be up to 15% by weight (based on the composition).

[0048] Furthermore, the composition may contain, on a production basis, up to 10% by weight of water (based on the composition).

[0049] Compositions which are particularly preferred and which may therefore be used in the use or treatment method according to the invention are: a) 25 to 95% by weight of calcium cyanamide; b) 5 to 40% by weight of at least one compound from the group of carbonates, oxides or hydroxides, in particular from the group of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide, or mixtures thereof (Based on the composition)

[0050] Therefore, in the use or treatment method according to the invention, more preferably the composition comprises: a) 25 to 95% by weight of calcium cyanamide; b) 5 to 40% by weight of at least one compound from the group of carbonates, oxides and hydroxides, in particular from the group of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide, or a mixture thereof, c) up to 15% by weight of free carbon, charcoal or graphite; d) up to 10% by weight of water may be used (based on the composition).

[0051] According to a more preferred embodiment of the use or treatment method according to the invention, the composition comprises: a) 60 to 95% by weight of calcium cyanamide; b) 5 to 25% by weight of at least one compound from the group of carbonates, oxides or hydroxides, in particular from the group of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide, or a mixture thereof, c) up to 15% by weight of free carbon, charcoal or graphite; d) up to 10% by weight of water may be used (based on the composition).

[0052] In the tests that form the basis of the present invention, compositions comprising, in particular, calcium cyanamide and at least one compound from the group of carbonates, oxides or hydroxides, in particular from the group of magnesium carbonate, magnesium bicarbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium bicarbonate, calcium oxide and calcium hydroxide, or mixtures thereof, have shown considerable success in reducing methane and carbon dioxide emissions from farm waste for fertilizers, a fact that is quite surprising, since, for example, calcium carbonate alone has no effect on this effect, and calcium hydroxide alone has an additional effect on the emissions of these gases (see Example 5).

[0053] Therefore, it is particularly preferred and therefore particularly preferred for use, a) calcium cyanamide; b) at least one compound from the group of carbonates, oxides or hydroxides, in particular from the group of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide, or a mixture thereof The subject of the present invention is a composition for reducing methane and / or carbon dioxide emissions from farm waste for fertilizer storage in a storage tank, comprising:

[0054] Particularly preferred is the use of a composition having the potential to reduce methane and / or carbon dioxide emissions from farm manure for fertilizer of at least 4.0 liters (l) of methane and / or carbon dioxide per kilogram of farm manure for fertilizer over a storage period of at least 150 days.

[0055] Furthermore, these tests have shown that a minimum amount of at least one compound from the group of carbonates, oxides, or hydroxides, particularly magnesium carbonate, magnesium bicarbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium bicarbonate, calcium oxide, and calcium hydroxide, or a mixture thereof, should be present in order to provide a long-lasting reduction in methane emissions. Therefore, it has been shown that a minimum amount of at least 5% by weight of a compound from the group of carbonates, oxides, or hydroxides, particularly magnesium carbonate, magnesium bicarbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium bicarbonate, calcium oxide, and calcium hydroxide, or a mixture thereof, should be present in the composition in order to provide a long-lasting reduction in methane emissions. If this minimum amount is not maintained, an increase in methane emissions may be observed after about 100 days (see Example 5).

[0056] Therefore, according to a further preferred embodiment of the use or treatment method according to the invention, the composition comprises: a) 60 to 95% by weight of calcium cyanamide; b) 5 to 25% by weight of at least one compound from the group of carbonates, oxides or hydroxides, in particular from the group of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide, or a mixture thereof, c) up to 15% by weight of free carbon, charcoal or graphite; d) up to 10% by weight of water may be used (based on the composition).

[0057] Using such a composition, methane and / or carbon dioxide emissions can be very effectively reduced or substantially suppressed. Therefore, according to a further preferred embodiment of the use or treatment method according to the invention, the composition comprises: a) 60 to 95% by weight of calcium cyanamide; b) 10 to 25% by weight of at least one compound from the group of carbonates, oxides or hydroxides, in particular from the group of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide, or a mixture thereof, c) up to 15% by weight of free carbon, charcoal or graphite; d) up to 10% by weight of water may be used (based on the composition).

[0058] More preferably, the composition may be provided without other compounds, particularly those not approved as fertilizers. Even more particularly preferably, the composition does not contain or contain urea. Urea has a nitrogen content of 46.6% by weight and therefore can lead to a significant increase in the nitrogen content in farm waste for fertilizer, which is the opposite of the problem addressed by the present invention.

[0059] According to a further preferred embodiment, the composition may be provided further comprising at least one salt from the group of the nitrates, in particular from the group of sodium nitrate, potassium nitrate, magnesium nitrate and calcium nitrate, or a mixture thereof.

[0060] Thus, in the use or treatment method according to the invention, the composition comprises: a) calcium cyanamide; b) at least one compound from the group of carbonates, oxides and hydroxides, in particular from the group of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide, or a mixture thereof, c) at least one salt from the group of nitrates, in particular from the group of sodium nitrate, potassium nitrate, magnesium nitrate and calcium nitrate, or a mixture thereof, d) More preferably, free carbon, charcoal or graphite may be used (based on the composition).

[0061] The amount of nitrate may vary, and the composition may contain up to 20% by weight of nitrate. Preferably, the composition may contain at least one salt selected from the group consisting of nitrate, in particular the group consisting of sodium nitrate, potassium nitrate, magnesium nitrate and calcium nitrate, or a mixture thereof, and the amount of nitrate is 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, more preferably 5% by weight or less, and more preferably at least 1% by weight (based on the composition).

[0062] Therefore, in the use or treatment method according to the invention, the composition is particularly preferably a) 25 to 95% by weight of calcium cyanamide; b) 5 to 40% by weight of at least one compound from the group of carbonates, oxides or hydroxides, in particular from the group of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide, or a mixture thereof, c) up to 20% by weight of at least one salt from the group of nitrates, in particular from the group of sodium nitrate, potassium nitrate, magnesium nitrate and calcium nitrate, or mixtures thereof, d) up to 15% by weight of free carbon, charcoal or graphite; e) up to 10% by weight of water may be used (based on the composition).

[0063] According to a particularly preferred embodiment of the use or treatment method according to the invention, the composition comprises: a) 50 to 80% by weight of calcium cyanamide; b) 5 to 25% by weight of at least one compound from the group of carbonates, oxides or hydroxides, in particular from the group of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide, or a mixture thereof, c) 1 to 15% by weight of free carbon, charcoal or graphite; d) up to 10% by weight of water may be used (based on the composition).

[0064] According to an alternatively preferred embodiment of the use or treatment method according to the present invention, the composition comprises: a) 35 to 55% by weight of calcium cyanamide; b) 15 to 35% by weight of at least one compound from the group of carbonates, oxides or hydroxides, in particular from the group of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide, or a mixture thereof, c) 1 to 20% by weight of at least one nitrate selected from the group consisting of sodium nitrate, potassium nitrate, magnesium nitrate and calcium nitrate, or a mixture thereof; d) 1 to 15% by weight of free carbon, charcoal or graphite; e) up to 10% by weight of water may be used (based on the composition).

[0065] More particularly preferably, calcium cyanamide, and even more preferably calcium cyanamide or nitrate-containing calcium cyanamide in accordance with Regulation (EC) No. 2003 / 2003 of the European Parliament and of the Council of 13 October 2003 on fertilizers, may be used as the calcium cyanamide-containing composition in the treatment methods and uses according to the present invention.

[0066] The compositions according to the invention, in the uses according to the invention and in the treatment methods according to the invention, can be used in different application forms and can be adapted to the needs of the user. Thus, the compositions described herein can be used in solid form, in particular in the form of powders or granules, or in the form of suspensions, in particular in the form of suspensions of these solids.

[0067] The total amount of calcium cyanamide-containing composition applied can also vary within relatively wide limits, both in the use according to the present invention and in the treatment method according to the present invention. It is therefore indicated that the composition can be used in an amount of 0.5 to 10 kg per cubic meter of farm waste for fertilizer use, particularly 1.0 to 10 kg per cubic meter of farm waste for fertilizer use, in particular 1.0 to 8 kg per cubic meter of farm waste for fertilizer use, particularly preferably 1.0 to 6 kg per cubic meter of farm waste for fertilizer use, and most preferably 1.0 to 5 kg per cubic meter of farm waste for fertilizer use. It is essential that the composition contains calcium cyanamide, particularly in the amounts described herein. Therefore, the composition may further preferably contain any of the above-mentioned compositions. Independently, the composition may therefore also contain other ingredients. [Brief explanation of the drawings]

[0068] [Figure 1] FIG. 1 is a chart of methane and CO2 emissions from Example 1. [Figure 2] FIG. 2 is a chart of methane and CO2 emissions from Example 2. [Figure 3] FIG. 3 is a chart of methane and CO2 emissions from Comparative Example 3. [Figure 4] FIG. 4 is a chart of methane and CO2 emissions from Example 4. [Figure 5] FIG. 5 is a chart of methane and CO2 emissions from Example 5. [Figure 6] FIG. 6 is a chart of methane and CO2 emissions from Example 5. [Figure 7]FIG. 7 is a chart of methane and CO2 emissions from Example 5. [Figure 8] FIG. 8 is a chart of methane and CO2 emissions from Example 5. [Figure 9] FIG. 9 is a chart of methane and CO2 emissions from Example 5. DETAILED DESCRIPTION OF THE INVENTION

[0069] Example Example 1 Reducing methane and CO2 emissions from liquid cow waste 1.1 component: Fresh liquid cow waste (= farm waste for fertilizer): - From a dairy barn (Obing region, Bavaria) - No dilution with rinse water, wash water or similar water - No stable rugs - taken from the preliminary chamber of the discharge channel in the direction of the slurry pit - Analysis: Total nitrogen: 0.40% by weight Ammonium (NH4): 0.13% by weight (equivalent to 0.10% NH4 nitrogen). Nitrate nitrogen: < 20mg / kg Dry matter: 11.93% by weight pH value: 7.4(13°C) Conductivity: 19.5mS / cm(13°C)

[0070] Composition containing calcium cyanamide (Composition 1): - Calcium cyanamide: 44.0% by weight - Calcium nitrate: 11.1% by weight - Calcium hydroxide: 13.4% by weight - Calcium carbonate: 10.0% by weight - Free carbon: 10.0% by weight - Magnesium carbonate: 2.3% by weight - Water: 9.2% by weight

[0071] Fertilizer "Calcium cyanamide containing nitrates" as listed in Article 3(b) of A.1. Nitrogen fertilizers of Regulation (EC) No. 2003 / 2003 of the European Parliament and of the Council of 13 October 2003 on fertilizers.

[0072] 1.2 Testing Procedure: A 6-liter polyethylene (PE) wide-neck container with a tight-fitting lid was provided with 3024 mL (corresponding to 2953 g) of liquid cow waste of the composition described above (see 1.1). 8.86 g of Composition 1 (corresponding to a composition containing 2.93 kg of calcium cyanamide or 16.1 mol of calcium cyanamide per cubic meter of liquid cow waste) was then added and stirred. After stirring, the pH and conductivity of the mixture were measured, and the wide-neck container was immediately sealed. A hole was drilled in the lid of the wide-neck container, into which a sealed gas storage bag (nominal volume 5.6 liters) was connected to collect the released gas. This structure prevented atmospheric oxygen from entering the wide-neck container, thereby preventing atmospheric CO2 from distorting the measurement results. The mixture was stored for exactly 156 days without stirring or agitation at a temperature of 23±1°C, a pressure of 960-980 hPa, and an altitude of 493 m above sea level (NHN). At regular intervals, the full storage bag was replaced, the volume of the stored gas was determined volumetrically, and the gas composition was analyzed by gas chromatography.

[0073] Measurements after stirring: pH value: 7.5 (22°C) Conductivity: 19.8 mS / cm (22°C)

[0074] Reference Test: A 6-liter polyethylene (PE) wide-neck container with a sealed lid was filled with 3018 mL (corresponding to 2947 g) of liquid cow waste of the composition described above (see 1.1). The container was then sealed. A hole was drilled in the lid of the wide-neck container, and a sealed gas storage bag (nominal volume 5.6 L) was connected to it to collect the released gas. This structure prevented atmospheric oxygen from entering the wide-neck container. The mixture was stored for exactly 156 days without stirring or agitation at a temperature of 23 ± 1°C, a pressure of 960–980 hPa, and an altitude of 493 m above sea level (NHN). At regular intervals, the full storage bag was replaced, the volume of the stored gas was determined volumetrically, and the gas composition was analyzed by gas chromatography.

[0075] During the experiment, the gas storage bags were changed after 3, 16, 59, 73, 86, 99, 108, 115, 122, 128, 135, 142, 149 and 156 days, the volume of collected gas was determined volumetrically and the composition of the gas was measured by gas chromatography.

[0076] 1.3 result: The resulting gas volumes of methane and carbon dioxide are shown in Table 1 below (see also Figure 1 - methane and CO2 emissions chart from Example 1). These results refer to 1,000 kg of liquid cow waste per different test.

[0077] [Table 1]

[0078] The values ​​in the table indicate the time period, and the values ​​in parentheses are the cumulative values ​​over the entire study period. The chart is shown as Figure 1.

[0079] 1.4 Summary of results: Methane emissions: After 156 days of storage, 7871 mL of methane gas was released in the reference experiment (Sample 1) in association with 1,000 kg of liquid cow waste. By adding 8.86 g of calcium cyanamide in the form of calcium cyanamide-containing composition 1 (Sample 2), which corresponds to a composition containing 2.93 kg of calcium cyanamide or a molar concentration of 16.1 mol of calcium cyanamide per cubic meter of liquid cow waste, these emissions can be reduced by 99.7% to 23 mL of methane gas. CO2 emissions: A similar situation emerges here: after 156 days of storage, 1853 mL of CO2 gas was released in the reference experiment (Sample 1) in relation to 1,000 kg of slurry. By adding 8.86 g of calcium cyanamide in the form of calcium cyanamide-containing composition 1 (Sample 2), which corresponds to a composition containing 2.93 kg of calcium cyanamide or a molar concentration of 16.1 mol of calcium cyanamide per cubic meter of liquid cow waste, these emissions can be reduced by 97.9% to 39 mL of CO2 gas.

[0080] Example 2 Reducing methane and CO2 emissions from liquid cow waste 2.1 component: Fresh liquid cow waste (= farm waste for fertilizer): - From a dairy barn (Obing region, Bavaria) - No dilution with rinse water, wash water or similar water - No stable rugs - taken from the preliminary chamber of the discharge channel in the direction of the slurry pit - Analysis: Total nitrogen: 0.48% by weight Ammonium (NH4): 0.22% by weight (equivalent to 0.17% NH4 nitrogen) Nitrate nitrogen: < 20mg / kg Dry matter: 10.30% by weight pH value: 6.8(24°C) Conductivity: 18.5mS / cm(24°C)

[0081] Composition containing calcium cyanamide (Composition 2): - Calcium cyanamide: 67.7% by weight - Calcium oxide: 13.2% by weight - Calcium hydroxide: 3.2% by weight - Free carbon: 13.3% by weight - Water 2.6% by weight

[0082] Fertilizer "Calcium cyanamide" as listed in Article 3(a) of Regulation (EC) No. 2003 / 2003 of the European Parliament and of the Council of 13 October 2003 on fertilizers.

[0083] 2.2 Testing Procedure: A 6-liter polyethylene (PE) wide-neck container with a sealable lid was filled with 3090 mL (corresponding to 3032 g) of liquid cow waste of the composition described above (see 2.1). Then, 4.25 g of Composition 2 (corresponding to a composition containing 1.38 kg of calcium cyanamide or 11.6 mol of calcium cyanamide per cubic meter of liquid cow waste) was added and stirred. After stirring, the pH and conductivity of the mixture were measured, and the wide-neck container was immediately sealed. A hole was drilled in the lid of the wide-neck container, into which a sealed gas storage bag (nominal volume 5.6 liters) was connected to collect the released gas. This structure prevented atmospheric oxygen from entering the wide-neck container, thereby preventing atmospheric CO2 from distorting the measurement results. The mixture was stored for exactly 156 days without stirring or agitation at a temperature of 23±1°C, a pressure of 960-980 hPa, and an altitude of 493 m above sea level (NHN). At regular intervals, the full storage bag was replaced, the volume of the stored gas was determined volumetrically, and the gas composition was analyzed by gas chromatography.

[0084] Measurements after stirring: pH value: 7.5 (24°C) Conductivity: 18.9 mS / cm (24°C)

[0085] Reference Test: A 6-liter polyethylene (PE) wide-neck container with a sealed lid was filled with 3038 mL (corresponding to 2981 g) of liquid cow waste of the composition described above (see 2.1). The container was then sealed. A hole was drilled in the lid of the wide-neck container, and a sealed gas storage bag (nominal volume 5.6 liters) was connected to it to collect the released gas. This structure prevented atmospheric oxygen from entering the wide-neck container. The mixture was stored for exactly 156 days without stirring or agitation at a temperature of 23 ± 1°C, a pressure of 960–980 hPa, and an altitude of 493 m above sea level (NHN). At regular intervals, the full storage bag was replaced, the volume of the stored gas was determined volumetrically, and the gas composition was analyzed by gas chromatography.

[0086] During the experiment, the gas storage bags were changed after 7, 44, 57, 70, 79, 89, 96, 103, 110, 117, 127, 141 and 156 days, the volume of collected gas was determined volumetrically and the composition of the gas was measured by gas chromatography.

[0087] 2.3 result: The resulting gas volumes of methane and carbon dioxide are shown in Table 2 below (see also Figure 2 - methane and CO2 emissions chart from Example 2). These results refer to 1,000 kg of liquid cow waste per different test.

[0088] [Table 2]

[0089] The values ​​in the table indicate the time period, and the values ​​in parentheses are the cumulative values ​​over the entire study period. The chart is shown in Figure 2.

[0090] 2.4 Summary of results: Methane emissions: After 156 days of storage, 4416 mL of methane gas was released in the reference experiment (Sample 1) in association with 1,000 kg of liquid cow waste. By adding 4.25 g of calcium cyanamide in the form of calcium cyanamide-containing composition 2 (Sample 2), which corresponds to a composition containing 1.38 kg of calcium cyanamide or a molar concentration of 11.6 mol of calcium cyanamide per cubic meter of liquid cow waste, these emissions can be reduced by 99.4% to 25 mL of methane gas. CO2 emissions: A similar situation emerges here: after 156 days of storage, 1043 mL of CO2 gas was released in the reference experiment (Sample 1) in association with 1,000 kg of cow slurry. By adding 4.25 g of calcium cyanamide in the form of calcium cyanamide-containing composition 2 (Sample 2), which corresponds to a composition containing 1.38 kg of calcium cyanamide or a molar concentration of 11.6 mol of calcium cyanamide per cubic meter of liquid cow waste, these emissions can be reduced by 97.1% to 30 mL of CO2 gas.

[0091] Example 3 - Comparison with hydrogen cyanamide solution Reducing methane and CO2 emissions from liquid cow waste 3.1 component: Fresh liquid cow waste (= farm waste for fertilizer): - From a dairy barn (Obing region, Bavaria) - No dilution with rinse water, wash water or similar water - No stable rugs - taken from the preliminary chamber of the discharge channel in the direction of the slurry pit - Analysis: Total nitrogen: 0.42% by weight Ammonium (NH4): 0.23% by weight (equivalent to 0.18% NH4 nitrogen) Nitrate nitrogen: < 20mg / kg Dry matter: 9.69% by weight pH value: 7.5(23°C) Conductivity: 18.0mS / cm(23°C)

[0092] Composition containing hydrogen cyanamide (Composition 3): - Hydrogen cyanamide: 50.2% by weight - Water: 49.8% by weight

[0093] 3.2 Testing Procedure: A 6-liter polyethylene (PE) wide-neck container with a tight-fitting lid was filled with 3030 mL (corresponding to 2979 g) of liquid cow waste of the composition described above (see 3.1). Then, 2.98 g of Composition 3 (corresponding to a composition containing 0.983 kg of hydrogen cyanamide or 12.2 mol of hydrogen cyanamide per cubic meter of liquid cow waste) was added and stirred. After stirring, the pH and conductivity of the mixture were measured, and the wide-neck container was immediately sealed. A hole was drilled in the lid of the wide-neck container, into which a sealed gas storage bag (nominal volume 5.6 liters) was connected to collect the released gas. This structure prevented atmospheric oxygen from entering the wide-neck container, thereby preventing atmospheric CO2 from distorting the measurement results. The mixture was stored for exactly 150 days without stirring or agitation at a temperature of 23±1°C, a pressure of 960-980 hPa, and an altitude of 493 m above sea level (NHN). At regular intervals, the full storage bag was replaced, the volume of the stored gas was determined volumetrically, and the gas composition was analyzed by gas chromatography.

[0094] Measurements after stirring: pH value: 7.5 (23°C) Conductivity: 18.0 mS / cm (23°C)

[0095] Reference Test: A 6-liter polyethylene (PE) wide-neck container with a sealed lid was filled with 3075 mL (corresponding to 3023 g) of liquid cow waste of the composition described above (see 3.1). The container was then sealed. A hole was drilled in the lid of the wide-neck container, and a sealed gas storage bag (nominal volume 5.6 liters) was connected to it to collect the released gas. This structure prevented atmospheric oxygen from entering the wide-neck container. The mixture was stored for exactly 150 days without stirring or agitation at a temperature of 23 ± 1°C, a pressure of 960–980 hPa, and an altitude of 493 m above sea level (NHN). At regular intervals, the full storage bag was replaced, the volume of the stored gas was determined volumetrically, and the gas composition was analyzed by gas chromatography.

[0096] During the experiment, the gas storage bags were changed after 11, 57, 66, 78, 88, 95, 106, 120, 137 and 150 days, the volume of collected gas was determined volumetrically and the composition of the gas was measured by gas chromatography.

[0097] 3.3 result: The resulting gas volumes of methane and carbon dioxide are shown in Table 3 below (see also Figure 3 - methane and CO2 emissions chart from Comparative Example 3). These results refer to 1,000 kg of liquid cow waste per different test.

[0098] [Table 3]

[0099] The values ​​in the table indicate the time period, and the values ​​in parentheses are the cumulative values ​​over the entire study period. The chart is shown as Figure 3.

[0100] 3.4 Summary of results: Methane emissions: After 150 days of storage, 1931 mL of methane gas was released in the control experiment (Sample 1) in association with 1,000 kg of liquid cow waste. By adding 2.98 g of hydrogen cyanamide in the form of Composition 3 (Sample 2), which corresponds to a composition containing 0.983 kg of hydrogen cyanamide or a concentration of 12.2 mol of hydrogen cyanamide per cubic meter of liquid cow waste, these emissions could only be reduced by 82.9%, to 330 mL. Also, significant methane formation could be measured already after 78 days of storage. CO 2 Emission: After 150 days of storage, 330 mL of CO2 gas was released in association with 1,000 kg of liquid cow waste in the reference experiment (Sample 1). By adding 2.98 g of hydrogen cyanamide in the form of Composition 3 (Sample 2), which corresponds to a composition containing 0.983 kg of hydrogen cyanamide or a concentration of 12.2 mol of hydrogen cyanamide per cubic meter of liquid cow waste, these emissions could only be reduced by 78.2%, to 72 mL.

[0101] Compared to Example 2, in which similar concentrations of substances were added as a composition containing calcium cyanamide, the gas emissions in the Comparative Example are significantly higher in absolute terms for both methane and CO. Furthermore, gas emissions resume after a very short time in Example 3, and after 78 days of storage, significant methane emissions can be measured, whereas in Example 2, no significant gas emissions could be detected after 156 days of storage.

[0102] Example 4 Use of a composition containing calcium cyanamide as a fermentation stopper or inhibitor of the anaerobic fermentation of liquid cow waste during storage and as an inhibitor of the microbial decomposition of organic matter in farm waste for fertilizer

[0103] 4.1 component: Fresh liquid cow waste (= farm waste for fertilizer): - From a dairy barn (Obing region, Bavaria) - No dilution with rinse water, wash water or similar water - No stable rugs - taken from the preliminary chamber of the discharge channel in the direction of the slurry pit - Analysis: Total nitrogen: 0.48% by weight Ammonium (NH4): 0.22% by weight (equivalent to 0.17% NH4 nitrogen). Nitrate nitrogen: < 20mg / kg Dry matter: 10.30% by weight pH value: 6.8(24°C) Conductivity: 18.5mS / cm(24°C)

[0104] Composition containing calcium cyanamide (Composition 1): - Calcium cyanamide: 44.0% by weight - Calcium nitrate: 11.1% by weight - Calcium hydroxide: 13.4% by weight - Calcium carbonate: 10.0% by weight - Free carbon: 10.0% by weight - Magnesium carbonate: 2.3% by weight - Water: 9.2% by weight

[0105] Fertilizer "Calcium cyanamide containing nitrates" as listed in Article 3(b) of A.1. Nitrogen fertilizers of Regulation (EC) No. 2003 / 2003 of the European Parliament and of the Council of 13 October 2003 on fertilizers.

[0106] 4.2 Testing Procedure: In a 6-liter polyethylene (PE) wide-neck container with a hermetically sealed lid, 3058 mL (corresponding to 3001 g) of liquid cow waste of the composition described above (see 4.1) was added. The wide-neck container was then sealed. A hole was drilled in the lid of the wide-neck container, and a sealed gas storage bag (nominal volume 5.6 liters) was connected to it to collect the released gas. This structure prevented atmospheric oxygen from entering the wide-neck container, thereby preventing atmospheric CO2 from distorting the measurement results. The mixture was stored for exactly 110 days without stirring or agitation at a temperature of 23 ± 1°C, a pressure of 960–980 hPa, and an altitude of 493 m above sea level (NHN). During the experiment, the gas storage bags were changed after 7, 44, 57, 70, 79, 89, 96, 103 and 110 days, the volume of collected gas was determined volumetrically and the composition of the gas was measured by gas chromatography.

[0107] On day 110 of the experiment, the container was placed in a glove box and flushed with nitrogen until the oxygen concentration reached 0.1% by volume. The container's lid was unscrewed, and 6.60 g of Composition 1 (2.16 kg of calcium cyanamide or 11.9 mol of calcium cyanamide per cubic meter of liquid cow waste) was added and stirred. The container's lid was then immediately screwed back on and tightened. The wide-neck container was then sealed and connected to a gas storage bag (nominal volume: 5.6 liters). The contents were then stored without stirring or agitation at a temperature of 23±1°C, a pressure of 960-980 hPa, and an altitude of 493 m above sea level (NHN).

[0108] After a further 7, 17, 31 and 46 days (corresponding to 117, 127, 141 and 156 days in the total period), the gas storage bag was replaced, the volume of stored gas was determined volumetrically and the gas composition was analysed by gas chromatography.

[0109] Reference Test: A 6-liter polyethylene (PE) wide-neck container with a sealed lid was filled with 3038 mL (corresponding to 2981 g) of liquid cow waste of the composition described above (see 4.1). The wide-neck container was then sealed. A hole was drilled in the lid of the wide-neck container, and a sealed gas storage bag (nominal volume 5.6 liters) was connected to it to collect the released gas. This structure prevented atmospheric oxygen from entering the wide-neck container. The mixture was stored for exactly 156 days without stirring or agitation at a temperature of 23 ± 1°C, a pressure of 960-980 hPa, and an altitude of 493 m above sea level (NHN). At regular intervals, the full storage bag was replaced, the volume of the stored gas was determined volumetrically, and the gas composition was analyzed by gas chromatography.

[0110] During the experiment, the gas storage bags were changed after 7, 44, 57, 70, 79, 89, 96, 103, 110, 117, 127, 141 and 156 days, the volume of collected gas was determined volumetrically and the composition of the gas was measured by gas chromatography.

[0111] 4.3 result: The resulting gas volumes of methane and carbon dioxide are shown in Table 4 below (see also Figure 4 - methane and CO2 emissions chart from Example 4). These results refer to 1,000 kg of liquid cow waste per different test.

[0112] [Table 4]

[0113] The values ​​in the table indicate the time period, and the values ​​in parentheses are the cumulative values ​​over the entire study period. The chart is shown in Figure 4.

[0114] 4.4 Summary of results: Methane emissions: After 156 days of storage, 4416 mL of methane gas was released per 1,000 kg of liquid cow waste in the reference experiment (Sample 1). The course of methane release in Sample 2 was similar to that of Sample 1 until Day 110. On Day 110, the addition of 6.60 g of calcium cyanamide to Sample 2 in the form of Composition 1 containing calcium cyanamide, corresponding to a calcium cyanamide composition containing 2.16 kg or a molar concentration of 11.9 mol of calcium cyanamide per cubic meter of liquid cow waste, immediately and permanently stopped methane release for the duration of the experiment. Within 46 days of the addition of calcium cyanamide in the form of Composition 1, only 2 mL of methane was released. CO2 emissions: A similar situation emerges here. After 156 days of storage, 1,043 mL of CO2 gas was released in association with 1,000 kg of liquid cow waste in the reference experiment (Sample 1). The course of CO2 release in Sample 2 was similar to that of Sample 1 until Day 110. On Day 110, the addition of 6.60 g of calcium cyanamide to Sample 2 in the form of Composition 1 containing calcium cyanamide, corresponding to a composition containing 2.16 kg of calcium cyanamide or a molar concentration of 11.9 mol of calcium cyanamide per cubic meter of cow slurry, immediately and permanently stopped CO2 release for the duration of the experiment. Within 46 days of the addition of calcium cyanamide in the form of Composition 1, only 3 mL of CO2 was released.

[0115] Summary of the results of Examples 1 to 4 Addition of 2.93 kg of calcium cyanamide per cubic meter of liquid cow waste in the form of Composition 1 reduced methane emissions by 99.7% and CO2 emissions by 97.9% after 156 days of storage compared to the control experiment. Addition of 1.38 kg of calcium cyanamide per cubic meter of liquid cow waste in the form of Composition 2 using a similar procedure and storage period produced very similar results: methane emissions were reduced by 99.4% and CO2 emissions by 97.1%. In contrast, addition of 0.983 kg of hydrogen cyanamide solution per cubic meter of liquid cow waste in the form of Composition 3, which has very similar substance concentrations compared to Examples 2 and 4, reduced methane emissions by only 82.9% and CO2 emissions by 78.2% after 150 days of storage compared to the control experiment. Furthermore, it has been shown that in cases where liquid cow waste emits large amounts of methane and CO2, this emission can be substantially stopped by contacting 2.16 kg of calcium cyanamide in the form of Composition 1 with each cubic meter of liquid cow waste at once. Thus, from the time of addition and over the next 46 days, only 2 mL of methane and 3 mL of CO2 are emitted per 1,000 kg of liquid cow waste, compared to 1,872 mL of methane and 372 mL of CO2 emitted per 1,000 kg of liquid cow waste in the control experiment.

[0116] The absolute amount of gases such as methane and carbon dioxide that can be released from farm waste for fertilizer depends on several factors: - Types and origins of farm waste for fertilizer - retention time, temperature and oxygen supply in the form of fresh air to the farm waste for fertiliser before removal in the collection channel - Nutrient content in animal faeces as a result of feed composition for animals kept on farms

[0117] This is evident from Examples 1 to 4. Although the same type and origin of freshly recovered fertilizer-grade farm waste was used in all of these examples, the amount of methane and carbon dioxide emitted varied between the references.

[0118] Example 5 Reducing methane and CO2 emissions from liquid cow waste 5.1 component: Fresh liquid cow waste (= farm waste for fertilizer): - From a dairy barn (Obing region, Bavaria) - No dilution with rinse water, wash water or similar water - No stable rugs - taken from the preliminary chamber of the discharge channel in the direction of the slurry pit - Analysis: Total nitrogen: 0.43% by weight Ammonium (NH4): 0.17% by weight (equivalent to 0.13% NH4 nitrogen). Nitrate nitrogen: < 20mg / kg Dry matter: 9.87% by weight pH value: 7.0(15°C) Conductivity: 20.1mS / cm(15°C)

[0119] Composition containing calcium cyanamide (Composition 1): - Calcium cyanamide: 44.0% by weight - Calcium nitrate: 11.1% by weight - Calcium hydroxide: 13.4% by weight - Calcium carbonate: 10.0% by weight - Free carbon: 10.0% by weight - Magnesium carbonate: 2.3% by weight - Water: 9.2% by weight

[0120] Fertilizer "Calcium cyanamide containing nitrates" as listed in Article 3(b) of A.1. Nitrogen fertilizers of Regulation (EC) No. 2003 / 2003 of the European Parliament and of the Council of 13 October 2003 on fertilizers.

[0121] Composition containing calcium cyanamide (Composition 2): - Calcium cyanamide: 67.7% by weight - Calcium oxide: 13.2% by weight - Calcium hydroxide: 3.2% by weight - Free carbon: 13.3% by weight - Water 2.6% by weight

[0122] Fertilizer "Calcium cyanamide" as listed in Article 3(a) of Regulation (EC) No. 2003 / 2003 of the European Parliament and of the Council of 13 October 2003 on fertilizers.

[0123] Composition containing calcium cyanamide (Composition 4): - Calcium cyanamide: 97.2% by weight - Calcium oxide: 2.3% by weight - Calcium carbonate: 0.4% by weight - Water: 0.1% by weight

[0124] Composition containing calcium hydroxide (Composition 5): - Calcium hydroxide: 99.8% by weight - Water: 0.2% by weight

[0125] Composition containing calcium carbonate (Composition 6): - Calcium carbonate: 99.9% by weight - Water: 0.1% by weight

[0126] 5.2 Testing Procedure: Composition 1: A 6-liter polyethylene (PE) wide-neck container with a tight-fitting lid was filled with 3008 mL (corresponding to 2976 g) of liquid cow waste of the composition described above (see 5.1). Then, 6.55 g of Composition 1 (corresponding to a composition containing 2.18 kg of calcium cyanamide or 12.0 mol of calcium cyanamide per cubic meter of liquid cow waste) was added and gently mixed. After mixing, the pH and conductivity of the mixture were measured, and the wide-neck container was immediately sealed. A hole was drilled in the lid of the wide-neck container, and a sealed gas storage bag (nominal volume 5.6 liters) was connected to it to collect the released gas. This structure prevented atmospheric oxygen from entering the wide-neck container, thereby preventing atmospheric CO2 from distorting the measurement results. The mixture was stored for exactly 170 days without stirring or agitation at a temperature of 23±1°C, a pressure of 960-980 hPa, and an altitude of 493 m above sea level (NHN). At regular intervals, the full storage bag was replaced, the volume of the stored gas was determined volumetrically, and the gas composition was analyzed by gas chromatography.

[0127] Measurements after stirring: pH value: 7.1 (22°C) Conductivity: 20.4 mS / cm (22°C)

[0128] Composition 2: 2995 mL (corresponding to 2963 g) of liquid cow waste of the composition described above (see 5.1) was added to a 6-liter polyethylene (PE) wide-neck container with a tight-fitting lid. 4.15 g of Composition 2 (corresponding to a composition containing 1.39 kg of calcium cyanamide or 11.7 mol of calcium cyanamide per cubic meter of liquid cow waste) was then added and gently mixed. After mixing, the pH and conductivity of the mixture were measured, and the wide-neck container was immediately sealed. A hole was drilled in the lid of the wide-neck container, and a sealed gas storage bag (nominal volume 5.6 liters) was connected to it to collect the released gas. This structure prevented atmospheric oxygen from entering the wide-neck container, thereby preventing atmospheric CO2 from distorting the measurement results. The mixture was stored for exactly 170 days without stirring or agitation at a temperature of 23±1°C, a pressure of 960-980 hPa, and an altitude of 493 m above sea level (NHN). At regular intervals, the full storage bag was replaced, the volume of the stored gas was determined volumetrically, and the gas composition was analyzed by gas chromatography.

[0129] Measurements after stirring: pH value: 7.3 (22°C) Conductivity: 20.5 mS / cm (22°C)

[0130] Composition 4: A 6-liter polyethylene (PE) wide-neck container with a tight-fitting lid was filled with 3033 mL (corresponding to 3001 g) of liquid cow waste of the composition described above (see 5.1). Then, 3.00 g of Composition 4 (corresponding to a composition containing 0.99 kg of calcium cyanamide or 12.0 mol of calcium cyanamide per cubic meter of liquid cow waste) was added and thoroughly mixed. After mixing, the pH and conductivity of the mixture were measured, and the wide-neck container was immediately sealed. A hole was drilled in the lid of the wide-neck container, and a sealed gas storage bag (nominal volume 5.6 liters) was connected to it to collect the released gas. This structure prevented atmospheric oxygen from entering the wide-neck container, thereby preventing atmospheric CO2 from distorting the measurement results. The mixture was stored for exactly 170 days without stirring or agitation at a temperature of 23±1°C, a pressure of 960-980 hPa, and an altitude of 493 m above sea level (NHN). At regular intervals, the full storage bag was replaced, the volume of the stored gas was determined volumetrically, and the gas composition was analyzed by gas chromatography.

[0131] Measurements after stirring: pH value: 7.1 (22°C) Conductivity: 20.2 mS / cm (22°C)

[0132] Composition 5: 3044 mL (corresponding to 3012 g) of liquid cow waste of the composition described above (see 5.1) was added to a 6-liter polyethylene (PE) wide-neck container with a tight-fitting lid. 1.51 g of Composition 5 (corresponding to a composition containing 0.50 kg of calcium hydroxide or 6.7 mol of calcium hydroxide per cubic meter of liquid cow waste) was then added and gently mixed. After mixing, the pH and conductivity of the mixture were measured, and the wide-neck container was immediately sealed. A hole was drilled in the lid of the wide-neck container, and a sealed gas storage bag (nominal volume 5.6 liters) was connected to it to collect the released gas. This structure prevented atmospheric oxygen from entering the wide-neck container, thereby preventing atmospheric CO2 from distorting the measurement results. The mixture was stored for exactly 170 days without stirring or agitation at a temperature of 23±1°C, a pressure of 960-980 hPa, and an altitude of 493 m above sea level (NHN). At regular intervals, the full storage bag was replaced, the volume of the stored gas was determined volumetrically, and the gas composition was analyzed by gas chromatography.

[0133] Measurements after stirring: pH value: 7.3 (22°C) Conductivity: 20.2 mS / cm (22°C)

[0134] Composition 6: A 6-liter polyethylene (PE) wide-neck container with a sealed lid was filled with 2997 mL (corresponding to 2965 g) of liquid cow waste of the composition described above (see 5.1). Then, 1.48 g of Composition 6 (corresponding to a composition containing 0.49 kg of calcium carbonate or 4.9 mol of calcium carbonate per cubic meter of liquid cow waste) was added and gently stirred. After stirring, the pH and conductivity of the mixture were measured, and the wide-neck container was immediately sealed. A hole was drilled in the lid of the wide-neck container, and a sealed gas storage bag (nominal volume 5.6 liters) was connected to it to collect the released gas. This design prevented atmospheric oxygen from entering the wide-neck container, thereby preventing atmospheric CO2 from distorting the measurement results. The mixture was stored for exactly 170 days without stirring or agitation at a temperature of 23±1°C, a pressure of 960-980 hPa, and an altitude of 493 m above sea level (NHN). At regular intervals, the full storage bag was replaced, the volume of the stored gas was determined volumetrically, and the gas composition was analyzed by gas chromatography.

[0135] Measurements after stirring: pH value: 7.1 (22°C) Conductivity: 20.2 mS / cm (22°C)

[0136] 5.3 result: The resulting methane and carbon dioxide gas volumes are shown in Tables 5 to 10 below (see also Figures 5 to 10 - methane and CO2 emissions charts from Example 5). These results refer to 1,000 kg of liquid cow waste per different test.

[0137] [Table 5]

[0138] The values ​​in the table indicate the time period, and the values ​​in parentheses are the cumulative values ​​over the entire study period (see Figure 5).

[0139] [Table 6]

[0140] The values ​​in the table indicate the time period, and the values ​​in parentheses are the cumulative values ​​over the entire study period (see Figure 6).

[0141] [Table 7]

[0142] The values ​​in the table indicate the time period, and the values ​​in parentheses are the cumulative values ​​over the entire study period (see Figure 7).

[0143] [Table 8]

[0144] The values ​​in the table indicate the time period, and the values ​​in parentheses are the cumulative values ​​over the entire study period (see Figure 8).

[0145] [Table 9]

[0146] The values ​​in the table indicate the time period, and the values ​​in parentheses are the cumulative values ​​over the entire study period (see Figure 9).

[0147] 5.4 Summary of results: Methane emissions: After 170 days of storage, 4933 mL of methane gas associated with 1,000 kg of liquid cow waste was released in the control experiment (sample 1). By adding 6.55 g of calcium cyanamide in the form of Composition 1 containing calcium cyanamide, which corresponds to 2.18 kg of Composition 1 containing calcium cyanamide or a concentration of 12.0 mol of calcium cyanamide per cubic meter of liquid cow waste, these emissions can be reduced by 99.7% to 16 mL of methane gas. By adding 4.15 g of calcium cyanamide in the form of calcium cyanamide-containing composition 2, which corresponds to a calcium cyanamide-containing composition of 1.39 kg or a concentration of 11.7 mol of calcium cyanamide per cubic meter of liquid cow waste, these emissions can be reduced by 99.8% to 11 mL of methane gas. By adding 3.00 g of calcium cyanamide in the form of calcium cyanamide-containing composition 4, which corresponds to 0.99 kg of calcium cyanamide-containing composition or a concentration of 12.0 mol of calcium cyanamide per cubic meter of liquid cow waste, these emissions can be reduced by 53.2% to 2311 mL of methane gas. After 97 days of storage, only 67 mL of methane was released, corresponding to 2245 mL or a 97.1% reduction in methane gas. The majority of the methane gas was released during the subsequent storage period. - Adding 1.51 g of calcium hydroxide in the form of calcium hydroxide-containing composition 5, which corresponds to 0.50 kg of calcium hydroxide-containing composition or a molar concentration of 6.7 mol of calcium hydroxide per cubic meter of liquid cow waste, increases emissions by 37.7% to 6791 mL of methane gas. By adding 1.48 g of calcium carbonate in the form of composition 6, which corresponds to a composition containing 0.49 kg of calcium carbonate or a concentration of 4.9 mol of calcium carbonate per cubic meter of liquid cow waste, these emissions can be reduced by 6.5% to 4613 mL of methane gas.

[0148] CO2 emissions: A similar situation emerges here: after 170 days of storage, 1067 mL of CO2 gas associated with 1000 kg of liquid cow waste was released in the reference experiment (sample 1). By adding 6.55 g of calcium cyanamide in the form of composition 1 containing calcium cyanamide, which corresponds to a composition containing 2.18 kg of calcium cyanamide or a concentration of 12.0 mol of calcium cyanamide per cubic meter of liquid cow waste, these emissions can be reduced by 96.2% to 41 mL of CO2 gas. By adding 4.15 g of calcium cyanamide in the form of composition 2 containing calcium cyanamide, which corresponds to a composition containing 1.39 kg of calcium cyanamide or a concentration of 11.7 mol of calcium cyanamide per cubic meter of liquid cow waste, these emissions can be reduced by 97.2% to 30 mL of CO2 gas. By adding 3.00 g of calcium cyanamide in the form of calcium cyanamide-containing composition 4, which corresponds to a calcium cyanamide-containing composition of 0.99 kg or a concentration of 12.0 mol of calcium cyanamide per cubic meter of liquid cow waste, these emissions can be reduced by 76.7% to 249 mL of CO2 gas. - Adding 1.51 g of calcium hydroxide in the form of calcium hydroxide containing composition 5, which corresponds to 0.50 kg of calcium hydroxide containing composition or a molar concentration of 6.7 mol of calcium hydroxide per cubic meter of liquid cow waste, increases emissions by 27.6% to 1361 mL of CO2 gas. By adding 1.48 g of calcium carbonate in the form of composition 6, which corresponds to a composition containing 0.49 kg of calcium carbonate or a concentration of 4.9 mol of calcium carbonate per cubic meter of liquid cow manure, these emissions can be reduced by 15.5% to 902 mL of CO2 gas.

[0149] Summary of Results from Examples 1-5 The absolute amount of gases such as methane and carbon dioxide that can be released from farm waste for fertilizer depends on several factors: - Types and origins of farm waste for fertilizer - retention time, temperature and oxygen supply in the form of fresh air to the farm waste for fertiliser before removal in the collection channel - The content of nutrients in animal feces as a result of the feed composition for animals kept on farms.

[0150] This is evident from Examples 1 to 5. Although the same type and origin of freshly recovered fertilizer-grade farm waste was used in all of these examples, the amount of methane and carbon dioxide emitted varied between the references.

[0151] Addition of 2.93 kg of calcium cyanamide per cubic meter of liquid cow waste in the form of Composition 1 and contact in Example 1 reduced methane emissions by 99.7% and CO2 emissions by 97.9% after 156 days of storage compared to the control experiment. Addition of 1.38 kg of calcium cyanamide per cubic meter of liquid cow waste in the form of Composition 2 and contact in Example 2 using a similar procedure and storage period produced very similar results, reducing methane emissions by 99.4% and CO2 emissions by 97.1%.

[0152] These results were confirmed at longer storage times in Example 5. Addition and contact of 2.18 kg of calcium cyanamide per cubic meter of liquid cow waste in the form of Composition 1 reduced methane emissions by 99.7% and CO2 emissions by 96.2% after 170 days of storage compared to the control experiment. Addition and contact of 1.39 kg of calcium cyanamide per cubic meter of liquid cow waste in the form of Composition 2 reduced methane emissions by 99.8% and CO2 emissions by 97.2% after 170 days of storage.

[0153] In contrast, the addition of 0.983 kg of hydrogen cyanamide solution per cubic meter of liquid cow waste in the form of composition 3, a substance concentration very similar to that in examples 2, 4 and 5, only reduces methane emissions by 82.9% and CO2 emissions by 78.2% after 150 days of storage compared to the reference experiment.

[0154] Furthermore, it has been shown that in cases where liquid cow waste emits large amounts of methane and CO2, this emission can be substantially stopped by contacting 2.16 kg of calcium cyanamide in the form of Composition 1 with each cubic meter of liquid cow waste at once. Thus, from the time of addition and over the next 46 days, only 2 mL of methane and 3 mL of CO2 are emitted per 1,000 kg of liquid cow waste, compared to 1,872 mL of methane and 372 mL of CO2 emitted per 1,000 kg of liquid cow waste in the control experiment.

[0155] However, although the added mass concentration of calcium cyanamide was the same as for compositions 1 and 2 in Example 5, adding 0.99 kg of calcium cyanamide per cubic meter of liquid cow waste prior to contact in the form of composition 4 containing a low ratio of calcium oxide (2.3 wt%) and calcium carbonate (0.4 wt%) showed a significantly shorter period of reduced methane and CO2 emissions.

[0156] Similarly, Example 5 shows that adding 0.50 kg of calcium hydroxide per cubic meter of liquid cow waste in the form of Composition 5 and subsequent contact actually increases methane and CO2 emissions compared to the control experiment after 170 days of storage, while adding 0.49 kg of calcium carbonate per cubic meter of liquid cow waste in the form of Composition 6 in a similar setup only slightly reduces methane and CO2 emissions. Even more surprisingly, the effective methane and CO2 emission reductions were Contains calcium cyanamide and a combination of calcium oxide / calcium hydroxide and / or calcium carbonate By adding Composition 1 or 2, the effect lasts for 156 days and 170 days.

[0157] The volumes of gases released in the control experiments from Examples 1-5 show that after 150-170 days of storage of liquid cow waste, 4.2-5.9 times more methane is released than CO2. The molar volume (V m), methane is emitted in 1.5 to 2.1 times greater quantities by mass than CO2. According to the IPCC / AR5, which uses a 100-year base year, methane has a global warming potential (IPCC AR5) of 28. This means that within the first 100 years of its release, one kilogram of methane contributes 28 times more to the greenhouse effect than one kilogram of CO2 (Source: Wikipedia). Therefore, according to the present invention, a significant contribution can be made to reducing greenhouse gas emissions without significantly increasing the nitrogen content in farm waste for fertilizer.

Claims

1. 1. A treatment method for reducing methane and / or carbon dioxide emissions from farm waste for fertilizer, selected from liquid waste in storage, manure slurry, and biogas fermentation residue, said treatment method comprising: a) providing a storage tank for said farm waste for fertilization having a volume X; b) filling the storage tank with the fertilizer farm waste in an amount equal to at least 5% by volume of the volume X of the storage tank; c) adding a composition comprising calcium cyanamide to the holding tank and contacting the composition with the fertilizer farm waste, wherein the composition is added to the fertilizer farm waste in an amount of 0.5 to 8 kg per cubic meter of fertilizer farm waste; A processing method comprising the processing step of:

2. 2. The method of claim 1, wherein the addition of the composition is carried out before, during or after the first loading of farm waste for fertilizer.

3. adding the composition i) once after or during the initial addition of a first portion of farm waste for fertilization to said holding tank; or ii) in multiple increments, after each partial filling of the storage tank; or iii) Once after or during the complete filling of said storage tank with farm waste for fertilizer.

3. The method according to claim 1 or 2, characterized in that:

4. 4. The method according to any one of claims 1 to 3, characterized in that the storage tank for farm waste for fertilizer is an open storage tank or a closed storage tank.

5. 5. The method according to claim 1, wherein the storage temperature of the farm waste for fertilizer is between 0 and 60°C.

6. 6. The method according to claim 1, wherein the composition contains 10 to 100% by weight of calcium cyanamide.

7. 7. The method according to any one of claims 1 to 6, characterized in that the composition is added to the farm waste for fertilization as a solid or as a suspension.

8. 8. The method according to any one of claims 1 to 7, characterized in that the composition is added to the farm waste for fertilizer in an amount of 0.5 to 6 kg per cubic meter of farm waste for fertilizer.

9. 1. Use of a composition comprising calcium cyanamide for reducing methane and / or carbon dioxide emissions from farm waste for fertilizer use selected from liquid waste, manure slurry and biogas fermentation residues stored in a storage tank, wherein the composition is used in an amount of 0.5 to 8 kg per cubic meter of farm waste for fertilizer use.

10. 1. Use of a composition comprising calcium cyanamide as a fermentation stopper or inhibitor of the anaerobic fermentation of farm waste for fertilizer selected from liquid waste, manure slurry and biogas fermentation residues stored in a storage tank and / or as an inhibitor of the microbial decomposition of organic substrates in the farm waste for fertilizer to reduce methane and / or carbon dioxide emissions, wherein the composition is used in an amount of 0.5 to 8 kg per cubic meter of farm waste for fertilizer.

11. Use according to claim 9 or 10, characterized in that the composition contains 10 to 100% by weight of calcium cyanamide.

12. The composition comprises: a) 25 to 95% by weight of calcium cyanamide; b) 5 to 40% by weight of at least one compound selected from the group consisting of magnesium carbonate, magnesium bicarbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium bicarbonate, calcium oxide and calcium hydroxide, or a mixture thereof; c) up to 20% by weight of at least one nitrate selected from the group consisting of sodium nitrate, potassium nitrate, magnesium nitrate and calcium nitrate, or a mixture thereof; d) up to 15% by weight of free carbon, charcoal or graphite; e) up to 10% by weight of water 11. Use according to claim 9 or 10, characterized in that it comprises

13. The composition comprises: a) 50-80% by weight of calcium cyanamide; b) 5 to 25% by weight of at least one compound selected from the group consisting of magnesium carbonate, magnesium bicarbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium bicarbonate, calcium oxide and calcium hydroxide, or a mixture thereof; c) 1 to 15% by weight of free carbon, charcoal or graphite; d) up to 10% by weight of water 11. Use according to claim 9 or 10, characterized in that it comprises

14. The composition comprises: a) 35-55% by weight of calcium cyanamide; b) 15 to 35% by weight of at least one compound selected from the group consisting of magnesium carbonate, magnesium bicarbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium bicarbonate, calcium oxide and calcium hydroxide, or a mixture thereof; c) 1 to 20% by weight of at least one nitrate selected from the group consisting of sodium nitrate, potassium nitrate, magnesium nitrate, and calcium nitrate, or a mixture thereof; d) 1 to 15% by weight of free carbon, charcoal or graphite; e) up to 10% by weight of water 11. Use according to claim 9 or 10, characterized in that it comprises

15. Use according to any one of claims 9 to 14, characterized in that the composition is used in the form of a solid or a suspension.

16. Use according to any one of claims 9 to 15, characterized in that the composition is used in an amount of 0.5 to 6 kg per cubic meter of farm waste for fertilizer.

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