RU2803942C2 - Method of reducing gases emission from on-farm fertilizers - Google Patents

Abstract

FIELD: environmental protection.

SUBSTANCE: invention relates to the use of a composition for reducing the release of environmentally harmful climatic gases methane and/or carbon dioxide from on-farm fertilizers during their storage. The method includes the following steps: a) providing a reservoir for storing on-farm fertilizer, b) filling the storage reservoir with on-farm fertilizer, the amount of which is at least 5 vol.% of the volume of the tank, and c) introducing a composition containing from 10 to 100 wt.% calcium cyanamide, into a storage tank and bringing it into contact with on-farm fertilizer. Filling the storage tank with on-farm fertilizer at step b) and introducing the composition containing calcium cyanamide into the storage tank at step c) is carried out in any sequence or simultaneously.

EFFECT: reduction in emissions of greenhouse gases into the atmosphere without significantly increasing the nitrogen content in local fertilizer.

14 cl, 9 dwg, 9 tbl, 5 ex

Description

The present invention relates to a method for reducing the emission of environmentally harmful climatic gases methane and carbon dioxide from on-farm fertilizers during their storage. The present invention also relates to the use of a composition for preventing or reducing the release of environmentally harmful climatic gases methane and carbon dioxide from on-farm fertilizers during their storage.

In the Federal Republic of Germany, on-farm fertilizers are those that are subject to fertilizer-related legislation and standards. In particular, when using and putting into circulation on-farm fertilizers, the Fertilizer Act, the Fertilizer Ordinance, the Fertilizer Products Ordinance and the EU Regulations in their current versions are subject to compliance.

For example, the current Decree on Fertilizers regulates the amount and time of application of on-farm fertilizers. Accordingly, on-farm fertilizers should not be applied to agricultural land during prohibited periods of time, which, depending on the type of soil and crop, amount to several months a year. As a result, agricultural enterprises containing livestock are forced to have sufficient storage facilities for (semi-)liquid manure without bedding, slurry, livestock waste, bedding manure, and the like. In accordance with current legislation, on-farm fertilizers must be kept for at least 150 days.

US 2002/0121117 A1 and US 2014/0311200 A1 describe the use of calcium-cyanamide compositions to reduce the release of unpleasant odors from (semi-)liquid manure. Such unpleasant odors are caused, for example, by sulfur-containing compounds or ammonia.

(Semi)liquid manure without bedding, slurry, livestock waste, bedding manure and the like as on-farm fertilizers have long been of great importance for agriculture. However, due to the significant number of farm animals kept in a limited space, in particular when kept in stalls, such on-farm fertilizers are formed in large quantities and in concentrated form. When storing these on-farm fertilizers, many unresolved problems arise. For example, during the storage of on-farm fertilizers, environmentally harmful climatic gases methane (CH ₄ ) or carbon dioxide (CO ₂ ) are formed due to the processes of aerobic and anaerobic fermentation, as well as microbial decomposition of organic substances in on-farm fertilizers.

Thus, in 2016 in Germany, agriculture accounted for about 59% of all methane emissions. This year, the turnover of on-farm fertilizers (storage and application of (semi-)liquid manure without litter and solid manure) amounted to 19.2% of total methane emissions in German agriculture. The maximum share of methane from on-farm fertilizers comes from cattle excrement and, to a lesser extent, pig excrement. Other animal groups (eg poultry, donkeys, horses) make up a negligible share (https://www.umweltbundesamt.de/daten/land-forstwirtschaft/beitrag-der-landwirtschaft-zu-den-treibhausgas#textpart-1).

A similar picture regarding emissions of climate-harmful gases is observed during the storage of fermentation residues taken from biogas plants. These fermentation residues, which can also be used as on-farm fertilizers, emit climatically harmful gases when stored openly.

Many previous attempts have been made to overcome these problems. Thus, a number of solutions have already been created to reduce the emission of climate-harmful gases from on-farm fertilizers. Opportunities for reducing emissions are numerous and effective in different areas of agricultural production. Without pretense of completeness, the following events can be mentioned here:

- measures taken in the livestock building, e.g. exhaust air purification, use of (semi-)open spaces with low emissions, measures to improve hygiene;

- covering (semi)liquid manure without bedding in containers with straw chaff, granulate or floating films;

- the use of on-farm fertilizer application methods accompanied by low emissions, for example, direct incorporation of on-farm fertilizers into the soil;

- separation of on-farm fertilizers into solid and liquid phases to improve the possibility of transportation;

- modern and adapted feeding strategies using low-protein, multi-phase feed.

The release of harmful gases into the environment during the storage of on-farm fertilizers can be successfully prevented by using closed storage containers, capturing the resulting gases and subsequent treatment or removal of the gases. However, equipment costs are associated with significant amounts.

Therefore, the present invention is based on the object of providing a method for reducing the emission of gases, such as methane and/or carbon dioxide, from on-farm fertilizers during storage, which would be cost-effective and, in addition, would not impair the intended use of on-farm fertilizer as a fertilizer agent in agriculture.

This problem is solved by the method according to paragraph 1 of the claims, as well as by application in accordance with paragraphs 9 and 10 of the claims. Preferred embodiments of the invention are given in the dependent claims of the invention.

Therefore, according to the first embodiment, a method for reducing the release of methane (CH ₄ ) and/or carbon dioxide (CO ₂ ) from on-farm fertilizer during storage is the subject of the present invention, which includes the following steps:

a) ensuring the availability of a tank for storing on-farm fertilizer with a volume of X,

b) filling the storage tank with on-farm fertilizer, the amount of which is at least 5 vol. % of the volume X of the tank,

c) introducing a composition containing calcium cyanamide (CaNCN) into a storage tank and bringing it into contact with on-farm fertilizer.

In this case, it is essential to use calcium cyanamide, and not another cyanamide. Calcium cyanamide (CaNCN, CAS [156-62-7]), the calcium salt of cyanamide (CH ₂ N ₂ , GAS [420-04-2]), has long been known as a component and active substance for fertilizer. For example, in technical calcium cyanamide and nitrate-containing calcium cyanamide, which are approved as fertilizers in Europe, calcium cyanamide is contained as the main essential component. These are used as a soil-reactive fertilizer for many crops such as corn, potatoes and rice.

According to the present invention, on-farm (local) fertilizer means fertilizer in accordance with § 2, paragraphs (1), (2), (3), (4) and (5) of the Fertilizer Law (Fertilizer Law of January 9, 2009, Federal Gazette of Laws I, pp. 54, 136), last amended by Article 1 of the Law of May 5, 2017 (Federal Journal of Laws I, p. 1068). Thus, on-farm fertilizers according to the present invention are formed or produced:

a) as animal excretions:

aa) when keeping animals for food production

or

bb) for other keeping of animals in agriculture or

b) as plant substances in the context of plant production or agriculture,

as well as when mixed with each other or after aerobic or anaerobic treatment.

Consequently, the concept of “on-farm fertilizers” also includes, in particular:

- solid manure: on-farm fertilizer from animal excretions, also containing bedding, in particular straw, sawdust, peat or other material of plant origin, added for the maintenance of animals, or mixed with feed residues in which the dry matter content exceeds 15%;

- (semi)liquid manure without bedding: on-farm fertilizer from any animal excretions, also with a small amount of bedding or feed residues or water additives, the dry matter content of which does not exceed 15%;

- slurry: on-farm fertilizer from animal excretions, which is a mixture of urine, washed small components of feces or litter and water; slurry may contain small amounts of feed residues, as well as washing water and condensate;

- fermentation residues for biogas: on-farm fertilizer from residues resulting from the fermentation of organic substances of both plant and animal origin in biogas plants.

The method according to the invention is particularly well suited for reducing the emission of methane and/or carbon dioxide from liquid on-farm fertilizers, in particular from (semi-)liquid manure, slurry and/or digestion residues.

Unexpectedly, it turned out that a composition containing calcium cyanamide can very effectively reduce the release of climate-harmful methane (CH ₄ ) and hydrocarbon dioxide (CO ₂ ) from on-farm fertilizers during storage. It was found (see examples) that compositions containing calcium cyanamide in an amount of 1.38 kg per 1 m ³ of on-farm fertilizer already 24 hours after administration can significantly reduce the release of methane and carbon dioxide.

Accordingly, the use of a composition containing calcium cyanamide to reduce the release of methane and/or carbon dioxide from on-farm fertilizer when stored in a tank is also the subject of this invention.

Methane and carbon dioxide are odorless gases. For environmental reasons, it is advisable to limit or completely eliminate the release of these gases.

Compositions containing calcium cyanamide have been used for a long time as a fertilizer. However, such fertilizer was used separately from on-farm fertilizer, since the application of on-farm fertilizer is carried out within the time limits prescribed by law, which differ from the recommended time limits for applying compositions containing calcium cyanamide. Thus, to date there has been no reduction in emissions of climate-damaging gases.

By carrying out the research underlying the invention, it was shown that when storing on-farm fertilizer treated with a composition containing calcium cyanamide, no residues are formed that could be considered harmful when used in fertilizers. Therefore, the on-farm fertilizer treated according to the present invention can be used directly as a fertilizer.

It is of particular importance that on-farm fertilizer treated in this way does not additionally undergo significant changes in nitrogen content. This fact is especially noticeable when comparing the fertilizers used. For example, the EU-approved fertilizer containing calcium cyanamide, namely nitrate-containing calcium cyanamide, is usually applied in an amount of 400 kg per hectare (ha). With this application, total nitrogen in the amount of 79.2 kg/ha is introduced into the soil sown with forage grasses or arable land.

For on-farm fertilizer, the standard amount applied to soil sown with forage grasses or to arable land is up to 30 m ³ /ha. The average total nitrogen content in (semi-)liquid bedding-free cattle manure is about 0.40% (see also example 1), which, when applied at 30 m ³ /ha, provides a total nitrogen of 120 kg/ha. If, according to the present invention, a composition containing calcium cyanamide is introduced into the on-farm fertilizer in an amount of 2.93 kg/m ³ of on-farm fertilizer (see example 1), then the proportion of total nitrogen in the treated on-farm fertilizer increases only to 0.46%. Thus, when applying on-farm fertilizer, the added total nitrogen increases by only 18 kg per hectare of soil sown with forage grasses or arable land. Consequently, the total amount of on-farm nitrogen fertilizer per hectare will be essentially the same. As a result, on-farm fertilizer and commonly used nitrogen fertilizers, which have a different effect from on-farm fertilizer, can be applied in constant amounts throughout the year without the risk of excessive nitrogen input. Thus, the use of a composition containing calcium cyanamide, introduced according to the invention into on-farm fertilizer, differs markedly in terms of total nitrogen introduced from a conventional fertilizer containing calcium cyanamide.

The method according to the invention is characterized in that only by adding a composition containing calcium cyanamide to the storage tank and bringing the composition into contact with on-farm fertilizer is the gas emission from on-farm fertilizer reduced. Thus, according to the present invention, steps b) and c) can be carried out independently of their sequence. Therefore, the introduction of the composition in step c) can be done before, during or after the first filling of the reservoir with on-farm fertilizer. If the introduction must be carried out before the first filling, then this introduction is carried out well in advance of contact with on-farm fertilizer. In this case, a period of time of less than one day is considered to be in advance.

The introduction of the composition in step c) can be carried out into a completely empty tank or into a tank that is not completely emptied, namely if there is residual fertilizer content in it. It is essential that the reservoir is filled or filled with on-farm fertilizer in an amount of at least 5 vol. % of its capacity. As a result, sufficient mixing of the composition with on-farm fertilizer is ensured for the effect of the composition.

It is optimal that during or after the introduction of a composition containing calcium cyanamide into on-farm fertilizer located in a storage tank, this suspension and on-farm fertilizer are mixed, in particular if the contents of the tank are circulated by a paddle mixer or a pump with mixer. In this case, a composition containing calcium cyanamide is introduced into the reservoir when it contains at least 5 vol. % of on-farm fertilizer and mixed. After this, the subsequent introduction of on-farm fertilizer is permissible. Upon completion of the addition of on-farm fertilizer, the mixture is re-mixed in the tank. In this case, the reservoir can be partially or completely filled.

Paddle mixers driven by a tractor or electric motor are suitable for circulating on-farm fertilizer in the tank. Paddle mixers mounted on the tank wall or built-in mixers with a submersible electric motor, as well as tractor-mounted retractable, articulated and tower paddle mixers that are placed in the tank along with on-farm fertilizer, have proven themselves especially well. Also suitable for circulating on-farm fertilizer in the tank are mixing nozzles placed on pressure pumps, in particular, mixing pumps driven by an electric motor or tractor with long shafts and a mixing nozzle or centrifugal pumps with a scoop device.

According to a preferred embodiment of the invention, the composition can be administered in step c) once or in portions. It is particularly preferred that the composition be administered:

i) once after or during the first introduction of the first portion of on-farm fertilizer into the tank or

ii) in portions after each partial filling of the tank, or

iii) once after or during the complete filling of the tank with on-farm fertilizer.

Thus, it is possible to apply the composition containing calcium cyanamide during or after partial or complete filling of the reservoir. It is also advantageous that during or after the administration of the composition containing calcium cyanamide, the contents of the reservoir are circulated, in particular by means of a paddle mixer or a mixing pump.

It should be noted that when keeping livestock, on-farm fertilizer is continuously formed and collected in a tank filled to at least 5 vol. %. In this case, it is possible to add a composition containing calcium cyanamide before, during or after continuous filling of the reservoir with on-farm fertilizer. Also in this case, it is advisable for the on-farm fertilizer to circulate in the reservoir during and after the introduction of the composition containing calcium cyanamide.

In addition, it is advisable that the introduction of the composition containing calcium cyanamide be carried out in portions before, during or after continuous or portion filling of the reservoir with on-farm fertilizer. It is also advantageous for the on-farm fertilizer to be circulated in a storage tank during or after administration of the calcium cyanamide-containing composition.

The composition containing calcium cyanamide is introduced into open and closed storage tanks containing on-farm fertilizer. Closed storage tanks are considered to be tanks or containers with a tent roof or concrete cover. Open tanks or storage containers do not contain structural ceilings.

It should be noted that the method according to the invention can be carried out in storage tanks of various modifications. The size of the tank is also not decisive. So the volume X can have any reasonable value, in particular, X means the volume measured in m ³ , which is, in particular, [0.001 m ³ ≤ X ≤ 20,000 m ³ ]. preferably 0.1 m ³ ≤ X ≤ 10,000 m ³ , more preferably 1 m ³ ≤ X ≤ 10,000 m ³ , especially preferably from 10 m ³ ≤ X ≤ 10,000 m ³ .

The method also differs in that the composition containing calcium cyanamide is introduced into a tank containing on-farm fertilizer, and the temperature of the on-farm fertilizer in the storage tank is from 0 to 60°C. The method can be used in winter and summer conditions for on-farm fertilizers that were formed directly during the fermentation process or are located in a tank or reservoir for post-fermentation after the biogas production process.

According to the present invention, a composition containing calcium cyanamide is used in a method for reducing the release of methane and/or carbon dioxide from on-farm fertilizer during its storage.

The exposure time of a composition containing calcium cyanamide to on-farm fertilizer to reduce the emission of methane and/or carbon dioxide according to the invention is preferably at least 24 hours, more preferably over 30 days, even more preferably over 40 days, in particular over 50 days. However, the storage duration can be noticeably longer and be, for example, up to 150 days or, if desired, over 150 days.

According to the invention, as a result of the introduction of a composition containing calcium cyanamide, the reduction in the emission of methane and/or carbon dioxide from on-farm fertilizers can be, in particular, at least 30%, preferably at least 40%, preferably at least 50%, preferably at least 60%, preferably at least 70% and particularly preferably at least 80% (compared to untreated on-farm fertilizers).

Therefore, the use of a composition containing calcium cyanamide to reduce the emission of methane and/or carbon dioxide from on-farm fertilizer during storage in a tank is the subject of the present invention.

In addition, during the research it was found that the introduction of a composition containing calcium cyanamide can be carried out at any time during storage (see examples). It turned out that the introduction of the composition, even after several weeks of storage of on-farm fertilizer, ensures a reduction in the emission of methane and carbon dioxide. Therefore, the use of a composition containing calcium cyanamide as a fermentation interrupter or an inhibitor of aerobic fermentation of on-farm fertilizer and/or an inhibitor of microbial decomposition of organic matter in on-farm fertilizer during its storage in a storage tank is the subject of the present invention.

Preferably, for use according to the invention or in the method according to the invention, a composition is used that contains from 10 to 100 wt. % calcium cyanamide (wt.% of the composition). Particularly preferred is a composition containing at least 20 wt. %, preferably at least 25 wt. %, preferably at least 30 wt. %, preferably at least 35 wt. %, preferably at least 40 wt. %, preferably at least 45 wt. %, preferably at least 50 wt. %, preferably at least 60 wt. %, and up to 100 wt. %, in particular up to 95 wt. %, in particular up to 80 wt. %, in particular up to 55 wt. %, calcium cyanamide (based on composition).

In the context of this invention, wt. % should be understood as the mass amount of an ingredient or group of ingredients in relation to a composition whose ingredients constitute 100 wt. %.

According to another embodiment of the invention, calcium cyanamide can be applied to the support material. The support material may be an agriculturally inert material, an agriculturally approved auxiliary material, or a fertilizer. Calcium carbonate and/or related substances or mineral fertilizers are particularly preferred as the support material according to the present invention. Such support materials may be obtained from industrial processes and contain a proportion of free carbon, coal or graphite. It is possible that calcium cyanamide is used in a mixture with other ingredients.

It is particularly preferred to use for use according to the invention or in the method according to the invention a composition containing:

a) calcium cyanamide,

b) at least one compound from the group consisting of carbonates, oxides and hydroxides, in particular from the group consisting of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide or mixtures thereof, and

c) preferably, if necessary, free carbon, coal or graphite.

Contents of other ingredients or support materials may vary. Preferably, the composition may contain at least one compound from the group consisting of carbonates, oxides or hydroxides, in particular from the group consisting of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and hydroxide calcium and mixtures thereof, wherein the amount of at least one compound from the group of carbonates, oxides and hydroxides or mixtures thereof is at least 5 wt. %, preferably at least 10 wt. %, preferably at least 15 wt. %, preferably at least 20 wt. % and at the same time no more than 50 wt. %, in particular, not more than 40 wt. %, in particular, not more than 35 wt. %, in particular, not more than 25 wt. % (wt.% relative to the composition).

The content of free carbon, coal or graphite in the composition can be up to 15 wt. % (relative to the composition).

In addition, the composition may contain, for technological reasons, up to 10 wt. % water (relative to composition).

It is particularly preferred for use according to the invention or in the method according to the invention to use a composition containing:

a) 25 – 96 wt. % calcium cyanamide,

b) 5 – 40 wt. % of at least one compound from the group consisting of carbonates, oxides or hydroxides, in particular from the group consisting of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide or mixtures thereof (relative to the composition).

It is also preferable to use for use according to the invention or in the method according to the invention a composition containing:

a) 25 – 95 wt. % calcium cyanamide,

b) 5 – 40 wt. % of at least one compound from the group consisting of carbonates, oxides and hydroxides, in particular from the group consisting of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide or mixtures thereof,

c) up to 15 wt. % free carbon, coal or graphite,

d) up to 10 wt. % water

(in relation to composition).

According to another preferred embodiment of the use according to the invention or the method according to the invention, a composition containing:

a) 60 - 95 wt. % calcium cyanamide,

b) 5 – 25 wt. % of at least one compound from the group consisting of carbonates, oxides and hydroxides, in particular from the group consisting of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide or mixtures thereof,

c) up to 15 wt. % free carbon, coal or graphite,

d) up to 10 wt. % water

(in relation to composition).

In the studies underlying the invention it was found that, in particular, a composition containing calcium cyanamide, and 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, hydroxide magnesium, calcium carbonate, calcium bicarbonate, calcium oxide and calcium hydroxide or mixtures thereof provide very good reductions in methane and/or carbon dioxide emissions from on-farm fertilizers. This fact is unexpected, since, for example, calcium carbonate alone does not have this effect or calcium hydroxide alone additionally affects the release of these gases (see example 5).

In this case, it is also particularly preferable to use a composition containing:

a) calcium cyanamide and,

b) at least one compound from the group consisting of carbonates, oxides or hydroxides, in particular from the group consisting of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide or calcium hydroxide or mixtures of them,

to reduce the release of methane and/or carbon dioxide from on-farm fertilizer when stored in a tank, which is the subject of the present invention.

Particularly preferable is the use of a composition characterized by the potential to reduce the emission of methane and/or carbon dioxide from on-farm fertilizers by at least 4.0 liters of methane and/or carbon dioxide per 1 kg of on-farm fertilizer when stored for at least 150 days.

In addition, these studies revealed a minimum amount of 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 , calcium hydroxide or mixtures thereof, which must be contained to ensure long-term methane reduction. For example, it has been established that the composition must contain a minimum of at least 5 wt. %, compounds 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, calcium hydroxide or mixtures thereof to ensure a sustainable reduction in methane emissions. If this minimum indicator is not reached, then after approximately 100 days an increase in methane emissions is noted (see example 5).

Thus, according to another preferred embodiment of the use according to the invention or the method according to the invention, a composition comprising:

a) 60 - 95 wt. % calcium cyanamide,

b) 5 – 25 wt. % of at least one compound from the group consisting of carbonates, oxides or hydroxides, in particular from the group consisting of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide or mixtures thereof,

c) up to 15 wt. % free carbon, coal or graphite,

d) up to 10 wt. % water

(in relation to composition).

As a result of the use of such a composition, the emission of methane and/or carbon dioxide can be very effectively reduced or almost completely eliminated. Therefore, according to another preferred embodiment of the use according to the invention or the method according to the invention, a composition consisting of:

a) 60 - 95 wt. % calcium cyanamide,

b) 10 – 25 wt. % of at least one compound from the group consisting of carbonates, oxides or hydroxides, in particular from the group consisting of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide or mixtures thereof,

c) up to 15 wt. % free carbon, coal or graphite,

d) up to 10 wt. % water

(in relation to composition).

It is also preferable to provide that the composition does not contain another compound which is, in particular, approved as a fertilizer. It is particularly preferred that the composition does not contain urea. Urea contains nitrogen in the amount of 46.6 wt. % and, therefore, a significant increase in the nitrogen content in on-farm fertilizer is possible, which contradicts the objective of this invention.

According to another preferred embodiment, it can also be provided that the composition additionally contains 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.

Thus, for use according to the invention or in the method according to the invention, a composition containing:

a) calcium cyanamide,

b) at least one compound from the group consisting of carbonates, oxides and hydroxides, in particular from the group consisting of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide or mixtures 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 mixtures,

d) preferably free carbon, coal or graphite.

The amount of nitrates may vary, and the composition may contain up to 20 wt. % nitrates. Preferably, the composition may contain 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, wherein the amount of nitrates is not more than 20 wt. %, preferably no more than 15 wt. %, preferably no more than 10 wt. %, preferably no more than 5 wt. %, preferably at least 1 wt. % (relative to the composition).

Particularly preferably can be used for use according to the invention or in the method according to the invention a composition containing:

a) 25 - 95 wt. % calcium cyanamide,

b) 5 – 40 wt. % of at least one compound from the group consisting of carbonates, oxides or hydroxides, in particular from the group consisting of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide or mixtures thereof,

c) up to 20 wt. % 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 wt. % free carbon, coal or graphite,

e) up to 10 wt. % water

(in relation to composition).

According to a particularly preferred embodiment of the use according to the invention or the method according to the invention, a composition containing:

a) 50 - 80 wt. % calcium cyanamide,

b) 5 – 25 wt. % of at least one compound from the group consisting of carbonates, oxides or hydroxides, in particular from the group consisting of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide or mixtures thereof,

c) 1 - 15 wt. % free carbon, coal or graphite,

d) up to 10 wt. % water

(in relation to composition).

According to an alternative preferred embodiment of the use according to the invention or the method according to the invention, a composition containing:

a) 35 - 55 wt. % calcium cyanamide,

b) 15 – 35 wt. % of at least one compound from the group consisting of carbonates, oxides or hydroxides, in particular from the group consisting of magnesium carbonate, magnesium hydrogen carbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium hydrogen carbonate, calcium oxide and calcium hydroxide or mixtures thereof,

c) 1 - 20 wt. % of at least one nitrate from the group of sodium nitrate, potassium nitrate, magnesium nitrate and calcium nitrate or mixtures thereof,

d) 1 – 15 wt. % free carbon, coal or graphite,

e) up to 10 wt. % water

(in relation to composition).

Particularly preferably in the method according to the invention and for the use according to the invention can be used as a composition containing calcium cyanamide, technical calcium cyanamide, calcium cyanamide or nitrate-containing calcium cyanamide according to Regulation (EC) No 2003/2003 of the European Parliament and of the Council of 13 October 2003 on fertilizers.

The composition according to the invention can be used both for the use according to the invention and in the method according to the invention in different forms and adapted to the needs of the user. Thus, the compositions described here can be used in the form of a solid, in particular in the form of a powder, granulate or suspension, in particular a suspension of these solids.

The total amount of calcium cyanamide-containing composition used can also vary both during use according to the invention and in the method according to the invention within relatively wide limits. Thus, it was found that the composition can be used in quantities from 0.5 to 10 kg per 1 m ³ of on-farm fertilizer, in particular, from 1.0 to 10 kg per 1 m ³ of on-farm fertilizer, in particular, from 1.0 to 8 kg per 1 m ³ of on-farm fertilizer, particularly preferably from 1.0 to 6 kg per 1 m ³ of on-farm fertilizer, very particularly preferably from 1.0 to 5 kg per 1 m ³ of on-farm fertilizer. It is significant that the composition contains calcium cyanamide, in particular in the amounts specified herein. Therefore, preferably the composition may be each of the above compositions. Regardless, the composition may contain additional ingredients.

Examples

Example 1

Reduction of methane and CO ₂ emissions from (semi-)liquid livestock manure

1.1 Substances used

Fresh (semi)liquid, bedding-free cattle manure (= on-farm fertilizer):

- from a housing for dairy cattle (Community Obing, Bavaria),

- without dilution with rinsing water, cleaning water or similar water,

- without bedding,

- taken from the settling chamber of the drain channel running in the direction of the buried container for (semi-)liquid manure without bedding,

- analyzed substances: total nitrogen: 0.40 wt. %,

ammonium (NH ₄ ): 0.13 wt. % (corresponds to 0.10% ammonium nitrogen),

nitrate nitrogen: < 20 mg/kg,

dry matter: 11.93 wt. %,

pH: 7.4 (13 ⁰ C),

electrical conductivity: 19.5 mS/cm (13°C)

Composition containing calcium cyanamide (composition 1):

- calcium cyanamide: 44.0 wt. %

- calcium nitrate: 11.1 wt. %

- calcium hydroxide: 13.4 wt. %

- calcium carbonate: 10.0 wt. %

free carbon: 10.0 wt. %

- magnesium carbonate: 2.3 wt. %

- water: 9.2 wt. %

fertilizer: “nitrate-containing calcium cyanamide” according to A.1,

nitrogen fertilizer No. 3 (b) according to Regulation (EC) No. 2003/2003 of the European Parliament and of the Council of 13 October 2003 on fertilizer products.

1.2 Conducting experiments

3024 ml (corresponding to 2953 g) of (semi-)liquid bedding-free cattle manure of the described composition (see 1.1) was placed in a wide-mouth polyethylene container with a capacity of 6 liters with a tight-fitting lid. Then 8.86 g of composition 1 (corresponding to 2.93 kg of calcium cyanamide-containing composition or 16.1 mol of calcium cyanamide per 1 m ³ of (semi-)liquid bedding-free cattle manure) was added and mixed. After mixing, the pH and electrical conductivity of the mixture were measured, then the wide-mouth container was immediately tightly closed. A hole was made in the lid of the wide-neck container, to which a gas accumulation bag (nominal volume 5.6 liters) was connected through a seal, through which the volume of released gas was captured. With this design, air oxygen could not penetrate into the wide-mouth container. In this way, the measurement results were not distorted by carbon dioxide from the air. The mixture was kept strictly for 156 days without stirring or moving at a temperature of 23 ± 1 ° C and an air pressure of 960 to 980 hPa at an elevation of 493 m above sea level. The filled gas storage bag was periodically replaced, the volume of accumulated gas was measured, and the composition of the gas was analyzed using gas chromatography.

Indicators measured after mixing:

pH: 7.5 (22°C)

Electrical conductivity: 19.8 mS/cm (22°C).

Control experience:

3018 ml (corresponding to 2947 g) of (semi-)liquid bedding-free cattle manure of the described composition (see 1.1) was placed in a wide-mouth polyethylene container with a capacity of 6 liters with a tight-fitting lid. Then the wide-mouth container was tightly closed. A hole was made in the lid of the wide-neck container, to which a gas accumulation bag (nominal volume 5.6 liters) was connected through a seal, through which the volume of released gas was captured. With this design, air oxygen could not penetrate into the wide-mouth container. The mixture was kept strictly for 156 days without stirring or moving at a temperature of 23 ± 1 ° C and an air pressure of 960 to 980 hPa at an elevation of 493 m above sea level. The filled gas storage bag was periodically replaced, the volume of accumulated gas was determined, and the composition of the gas was analyzed using gas chromatography.

During the experiments, the gas accumulation package was replaced after 3, 16, 59, 73, 86, 99, 108, 115, 122, 128, 135, 142, 149 and 156 days, the volume of captured gas was determined and the composition of the gas was measured using gas chromatography.

1.3. results

The volumes of methane and carbon dioxide produced are shown in Table 1 below (see also Fig. 1: graphical representation of methane and CO ₂ emissions from example 1). The results refer to 1000 kg of (semi-)liquid livestock manure for each experimental option.

Table 1

Volumes of gas generated per 1000 kg of (semi-)liquid bedding-free cattle manure

Duration of experience
[day] Sample 1
(control) Sample 2
(track 1) Methane
[ml] _CO2
[ml] Methane
[ml] _CO2
[ml] 3 95
[95] 291
[291] 2
[2] 4
[4] 16 65
[160] 52
[343] 2
[4] 16
[20] 59 88
[248] 27
[370] 1
[5] 3
[23] 73 324
[572] 54
[424] 2
[7] 2
[25] 86 401
[973] 89
[513] 2
[9] 2
[27] 99 592
[1565] 95
[608] 2
[eleven] 0
[27] 108 564
[2129] 104
[712] 2
[13] 2
[29] 115 651
[2780] 124
[836] 1
[14] 2
[31] 122 756
[3536] 147
[983] 1
[15] 0
[31] 128 833
[4369] 169
[1152] 1
[16] 1
[32] 135 934
[5303] 190
[1342] 2
[18] 2
[34] 142 985
[6288] 205
[1547] 2
[20] 1
[35] 149 876
[7164] 181
[1728] 2
[22] 2
[37] 156 707
[7871] 125
[1853] 1
[23] 2
[39]

The indicators refer to the time period; the indicators in brackets are cumulative indicators for the entire period of the experiment. A graphical representation is shown in Fig. 1.

1.4. Summary of results

● Methane release

After 156 days of storage, the control experiment (sample 1) released 7871 ml of methane per 1000 kg of (semi)liquid bedding-free cattle manure. After the introduction of 8.86 g of calcium cyanamide in the form of calcium cyanamide-containing composition 1 (sample 2), which corresponds to 2.93 kg of calcium cyanamide-containing composition or a quantitative concentration of the substance equal to 16.1 mol of calcium cyanamide per 1 m ³ of (semi) liquid bedding-free manure, it became possible to reduce these emissions by 99.7% to 23 ml of methane.

● CO ₂ release

A similar picture takes place here. After 156 days of storage, the control experiment (sample 1) released 1835 ml of CO ₂ per 1000 kg of cattle waste. After the introduction of 8.86 g of calcium cyanamide in the form of calcium cyanamide-containing composition 1 (sample 2), which corresponds to 2.93 kg of calcium cyanamide-containing composition or a quantitative concentration of the substance equal to 16.1 mol of calcium cyanamide per 1 m ³ of (semi) liquid bedding-free manure, it became possible to reduce these emissions by 97.9% to 39 ml of CO ₂ .

Example 2

Reduction of methane and CO ₂ emissions from (semi-)liquid livestock manure

2.1 Substances used

Fresh (semi)liquid, bedding-free cattle manure (= on-farm fertilizer):

- from a housing for dairy cattle (Community Obing, Bavaria),

- without dilution with rinsing water, cleaning water or similar water,

- without bedding,

- taken from the settling chamber of the drain channel running in the direction of the buried container for (semi-)liquid manure without bedding,

- analyzed substances: total nitrogen: 0.48 wt. %,

ammonium (NH ₄ ): 0.22 wt. % (corresponds to 0.17% ammonium nitrogen),

nitrate nitrogen: < 20 mg/kg,

dry matter: 10.30 wt. %,

pH: 6.8 (24 °C),

electrical conductivity: 18.5 mS/cm (24 °C)

Composition containing calcium cyanamide (composition 2):

- calcium cyanamide: 67.7 wt. %

- calcium oxide: 13.2 wt. %

- calcium hydroxide: 3.2 wt. %

- free carbon: 13.3 wt. %

- water: 2.6 wt. %

fertilizer: “nitrate-containing calcium cyanamide” according to A.1.

Nitrogen fertilizer No. 3 (a) according to Regulation (EC) No. 2003/2003 of the European Parliament and of the Council of 13 October 2003 on fertilizer products.

2.2 Conducting experiments

3090 ml (corresponding to 3032 g) of (semi-)liquid bedding-free cattle manure of the described composition (see 2.1) was placed in a wide-mouth polyethylene container with a capacity of 6 liters with a tight-fitting lid. Then 4.25 g of composition 2 (corresponding to 1.38 kg of calcium cyanamide-containing composition or 11.16 mol of calcium cyanamide per 1 m ³ of (semi-)liquid bedding-free cattle manure) was added and mixed. After mixing, the pH and electrical conductivity of the mixture were measured, then the wide-mouth container was immediately tightly closed. A hole was made in the lid of the wide-neck container, to which a gas accumulation bag (with a nominal volume of 5.6 liters) was connected through a seal, through which the volume of released gas was captured. With this design, air oxygen could not penetrate into the wide-mouth container. In this way, the measurement results were not distorted by carbon dioxide from the air. The mixture was kept strictly for 156 days without stirring or moving at a temperature of 23 ± 1 ° C and an air pressure of 960 to 980 hPa at an elevation of 493 m above sea level. The filled gas storage bag was periodically replaced, the volume of accumulated gas was determined, and the composition of the gas was analyzed using gas chromatography.

Indicators measured after mixing:

pH: 7.5 (24 °C)

Electrical conductivity: 18.9 mS/cm (24 °C).

Control experience:

3038 ml (corresponding to 2981 g) of (semi-)liquid bedding-free cattle manure of the described composition (see 2.1) was placed in a wide-mouth polyethylene container with a capacity of 6 liters with a tight-fitting lid. Then the wide-mouth container was tightly closed. A hole was made in the lid of the wide-neck container, to which a gas accumulation bag (nominal volume 5.6 liters) was connected through a seal, through which the volume of released gas was captured. With this design, air oxygen could not penetrate into the wide-mouth container. The mixture was kept strictly for 156 days without stirring or moving at a temperature of 23 ± 1 ° C and an air pressure of 960 to 980 hPa at an elevation of 493 m above sea level. The filled gas storage bag was periodically replaced, the volume of accumulated gas was determined, and the composition of the gas was analyzed using gas chromatography.

During the experiments, the gas accumulation package was replaced after 7, 44, 57, 70, 79, 89, 96, 103, 110, 117, 127, 141 and 156 days, the volume of captured gas was determined and the composition of the gas was measured using gas chromatography.

2.3. results

The volumes of methane and carbon dioxide produced are shown in Table 2 below (see also Fig. 2: graphical representation of methane and CO ₂ emissions from example 2). The results refer to 1000 kg of (semi-)liquid livestock manure for each experimental option.

table 2

Volumes of gas generated per 1000 kg of (semi-)liquid bedding-free cattle manure.

Duration of experience
[day] Sample 1
(control) Sample 2
(track 2) Methane
[ml] _CO2
[ml] Methane
[ml] _CO2
[ml] 7 70
[70] 118
[118] 2
[2] 6
[6] 44 eleven
[81] 5
[123] 3
[5] 5
[eleven] 57 101
[182] 15
[138] 1
[6] 2
[13] 70 244
[426] 31
[169] 2
[8] 2
[15] 79 190
[616] 26
[195] 2
[10] 2
[17] 89 331
[947] 58
[253] 2
[12] 2
[19] 96 416
[1363] 94
[347] 2
[14] 1
[20] 103 544
[1907] 153
[500] 2
[16] 2
[22] 110 637
[2544] 171
[671] 2
[18] 2
[24] 117 691
[3235] 198
[769] 1
[19] 1
[25] 127 714
[3949] 168
[937] 2
[21] 1
[26] 141 261
[4210] 58
[995] 2
[23] 2
[28] 156 206
[4416] 48
[1043] 2
[25] 2
[thirty]

The indicators refer to the time period; the indicators in brackets are cumulative indicators for the entire period of the experiment. A graphical representation is shown in Fig. 2.

2.4. Summary of results

● Methane release

After 156 days of storage, the control experiment (sample 1) released 4416 ml of methane per 1000 kg of (semi)liquid bedding-free cattle manure. After the introduction of 4.25 g of calcium cyanamide in the form of calcium cyanamide-containing composition 2 (sample 2), which corresponds to 1.38 kg of calcium cyanamide-containing composition or a quantitative concentration of the substance equal to 11.6 mol of calcium cyanamide per 1 m ³ of (semi) liquid bedding-free manure, it became possible to reduce these emissions by 99.4% to 23 ml of methane.

● CO ₂ release

A similar picture takes place here. After 156 days of storage, the control experiment (sample 1) released 1043 ml of CO ₂ per 1000 kg of cattle waste. After the introduction of 4.25 g of calcium cyanamide in the form of calcium cyanamide-containing composition 2 (sample 2), which corresponds to 1.38 kg of calcium cyanamide-containing composition or a quantitative concentration of the substance equal to 11.6 mol of calcium cyanamide per 1 m ³ of (semi) liquid bedding-free manure, it became possible to reduce these emissions by 97.1% to 30 ml of CO ₂ .

Example 3 Comparative example using hydrogen cyanamide solution

Reduction of methane and CO ₂ emissions from (semi-)liquid livestock manure

3.1 Substances used

Fresh (semi)liquid, bedding-free cattle manure (= on-farm fertilizer):

- from a housing for dairy cattle (Community Obing, Bavaria),

- without dilution with rinsing water, cleaning water or similar water,

- without bedding,

- taken from the settling chamber of the drain channel running in the direction of the buried container for (semi-)liquid manure without bedding,

- analyzed substances: total nitrogen: 0.42 wt. %,

ammonium (NH ₄ ): 0.23 wt. % (corresponds to 0.18% ammonium nitrogen),

nitrate nitrogen: < 20 mg/kg,

dry matter: 9.69 wt. %,

pH: 7.5 (23 ⁰ C),

electrical conductivity: 18.0 mS/cm (23 °C).

Hydrogen cyanamide-containing composition (composition 3):

- hydrogen cyanamide: 50.2 wt. %

- water: 49.8 wt. %

3.2 Conducting experiments

3030 ml (corresponding to 2979 g) of (semi-)liquid bedding-free cattle manure of the described composition (see 3.1) was placed in a wide-mouth polyethylene container with a capacity of 6 liters with a tight-fitting lid. Then 2.98 g of composition 3 (corresponding to 0.983 kg of hydrogen cyanamide-containing composition or 12.2 mol of hydrogen cyanamide per 1 m ³ of (semi-)liquid bedding-free cattle manure) was added and mixed. After mixing, the pH and electrical conductivity of the mixture were measured, then the wide-mouth container was immediately tightly closed. A hole was made in the lid of the wide-neck container, to which a gas accumulation bag (with a nominal volume of 5.6 liters) was connected through a seal, through which the volume of released gas was captured. With this design, air oxygen could not penetrate into the wide-mouth container. In this way, the measurement results were not distorted by carbon dioxide from the air. The mixture was kept strictly for 150 days without stirring or moving at a temperature of 23 ± 1 ° C and air pressure from 960 to 980 hPa at an elevation of 493 m above sea level. The filled gas storage bag was periodically replaced, the volume of accumulated gas was determined, and the composition of the gas was analyzed using gas chromatography.

Indicators measured after mixing:

pH: 7.5 (23°C)

Electrical conductivity: 18.0 mS/cm (23°C).

Control experience:

3075 ml (corresponding to 3023 g) of (semi-)liquid bedding-free cattle manure of the described composition (see 3.1) was placed in a wide-mouth polyethylene container with a capacity of 6 liters with a tight-fitting lid. Then the wide-mouth container was tightly closed. A hole was made in the lid of the wide-neck container, to which a gas accumulation bag (nominal volume 5.6 liters) was connected through a seal, through which the volume of released gas was captured. With this design, air oxygen could not penetrate into the wide-mouth container. The mixture was kept strictly for 150 days without stirring or moving at a temperature of 23 ± 1°C and air pressure from 960 to 980 hPa at an elevation of 493 m above sea level. The filled gas storage bag was periodically replaced, the volume of accumulated gas was determined, and the composition of the gas was analyzed using gas chromatography.

During the experiments, the gas accumulation package was replaced after 11, 57, 66, 78, 88, 95, 106, 120, 137 and 150 days, the volume of captured gas was determined and the composition of the gas was measured using gas chromatography.

3.3. results

The volumes of methane and carbon dioxide produced are shown in the following table 3 (see also Fig. 3: graphical representation of methane and CO ₂ emissions from comparative example 3). The results refer to 1000 kg of (semi-)liquid livestock manure for each experimental option.

Table 3

Volumes of gas generated per 1000 kg of (semi-)liquid bedding-free cattle manure

Duration of experience
[day] Sample 1
(control) Sample 2
(track 3) Methane
[ml] _CO2
[ml] Methane
[ml] _CO2
[ml] eleven 41
[41] 31
[31] 2
[2] 4
[4] 57 44
[85] 6
[37] 3
[5] 8
[12] 66 325
[410] 38
[75] 4
[9] 2
[14] 78 319
[729] 35
[110] 12
[21] 3
[17] 88 375
[1104] 66
[176] 29
[50] 6
[23] 95 444
[1548] 100
[276] 43
[93] 9
[32] 106 296
[1844] 43
[319] 59
[152] 14
[46] 120 67
[1911] 7
[326] 66
[218] 17
[63] 137 17
[1928] 2
[328] 38
[256] 7
[70] 150 3
[1931] 2
[330] 13
[269] 2
[72]

The indicators refer to the time period; the indicators in brackets are cumulative indicators for the entire period of the experiment.

A graphical representation is shown in Fig. 3.

3.4. Summary of results

● Methane release

After 150 days of storage, the control experiment (sample 1) released 1931 ml of methane per 1000 kg of (semi)liquid bedding-free cattle manure. After introducing 2.08 g of hydrogen cyanamide in the form of composition 3 (sample 2), which corresponds to 0.983 kg of a composition containing hydrogen cyanamide or a quantitative concentration of the substance equal to 12.2 mol of hydrogen cyanamide per 1 m ³ of (semi-)liquid litterless manure, it became possible reduction of these secretions by only 82.9% to 330 ml. In addition, after 78 days. storage, significant methane formation was noted.

● CO ₂ emissions

After 150 days of storage, the control experiment (sample 1) released 330 ml of CO ₂ per 1000 kg of cattle waste. After introducing 2.98 g of hydrogen cyanamide in the form of composition 3 (sample 2), which corresponds to 0.983 kg of a composition containing hydrogen cyanamide or a quantitative concentration of the substance equal to 12.2 mol of hydrogen cyanamide per 1 m ³ of (semi-)liquid manure without bedding, it became possible reduce these secretions by only 78.2% to 72 ml

Compared to example 2, in which a comparable amount of the substance was added, but in the form of a hydrogen cyanamide-containing composition, in the comparative example, the gas emissions of both methane and CO ₂ were significantly higher in absolute terms. In addition, after a much shorter time, gas emissions resumed; in example 3, a noticeable release of methane was measured after 78 days of storage; in example 2, after 156 days of storage, no significant release of gases was noted.

Example 4

The use of a composition containing calcium cyanamide as an interrupter or inhibitor of anaerobic fermentation of (semi)liquid manure and as an inhibitor of microbial decomposition of organic matter in local fertilizer during its storage

4.1 Substances used

Fresh (semi)liquid, bedding-free cattle manure (= on-farm fertilizer):

- from a housing for dairy cattle (Community Obing, Bavaria),

- without dilution with rinsing water, cleaning water or similar water,

- without bedding,

- taken from the settling chamber of the drain channel running in the direction of the buried container for (semi-)liquid manure without bedding,

- analyzed substances: total nitrogen: 0.48 wt. %,

ammonium (NH ₄ ): 0.22 wt. % (corresponds to 0.17% ammonium nitrogen),

nitrate nitrogen: < 20 mg/kg,

dry matter: 10.30 wt. %,

pH: 6.8 (24 °C),

electrical conductivity: 18.5 mS/cm (24°C)

Composition containing calcium cyanamide (composition 1):

- calcium cyanamide: 44.0 wt. %

- calcium nitrate: 11.1 wt. %

- calcium hydroxide: 13.4 wt. %

- calcium carbonate: 10.0 wt. %

- free carbon: 10.0 wt. %

- magnesium carbonate: 2.3 wt. %

- water: 9.2 wt. %

Fertilizer: “nitrate-containing calcium cyanamide” according to A.1.

Nitrogen fertilizer No. 3 (b) according to Regulation (EC) No. 2003/2003 of the European Parliament and of the Council of 13 October 2003 on fertilizer products.

4.2 Conducting experiments

3058 ml (corresponding to 3001 g) of (semi-)liquid bedding-free cattle manure of the described composition (see 4.1) was placed in a wide-mouth polyethylene container with a capacity of 6 liters with a tight-fitting lid. Then the wide-mouth container was tightly closed. A hole was made in the lid of the wide-neck container, to which a gas accumulation bag (with a nominal volume of 5.6 liters) was connected through a seal, through which the volume of released gas was captured. With this design, air oxygen could not penetrate into the wide-mouth container. In this way, the measurement results were not distorted by carbon dioxide from the air. The mixture was kept strictly for 110 days without stirring or moving at a temperature of 23 ± 1 ° C and an air pressure of 960 to 980 hPa at an elevation of 493 m above sea level. During the experiment, the gas accumulation package was replaced after 7, 44, 57, 70, 79, 89, 96, 103 and 110 days, the volume of accumulated gas was determined and the composition of the gas was measured using gas chromatography.

On the 110th day of the experiment, the container was placed in a storage box, also called the “hot chamber,” and purged with nitrogen until the oxygen content in the “hot chamber” was less than 0.1 vol. %. The lid of the container was then unscrewed and 6.60 g of composition 1 (corresponding to 2.16 kg of calcium cyanamide-containing composition or 11.9 mol of calcium cyanamide per m ³ of (semi-)liquid, bedding-free cattle manure) was added and mixed. After this, the lid was immediately screwed back on, the wide-mouth container was tightly closed, a gas storage bag (nominal volume 5.6 l) was attached and stored without stirring or moving at a temperature of 23 ± 1 ⁰ C and an air pressure of 960 to 980 hPa at an elevation of 493 m above sea level.

After the next 7, 17, 31 and 46 days, which corresponds to 117, 127, 141 and 156 days of total duration, the gas storage bags were replaced, the volume of accumulated gas was determined and the composition of the gas was analyzed using gas chromatography.

Control experience:

3038 ml (corresponding to 2981 g) of (semi-)liquid bedding-free cattle manure of the described composition (see 4.1) was placed in a wide-mouth polyethylene container with a capacity of 6 liters with a tight-fitting lid. Then the wide-mouth container was tightly closed. A hole was made in the lid of the wide-neck container, to which a gas accumulation bag (nominal volume 5.6 liters) was connected through a seal, through which the volume of released gas was captured. With this design, air oxygen could not penetrate into the wide-mouth container. The mixture was kept strictly for 156 days without stirring or moving at a temperature of 23 ± 1°C and air pressure from 960 to 980 hPa at an elevation of 493 m above sea level. The filled gas storage bag was periodically replaced, the volume of accumulated gas was determined, and the composition of the gas was analyzed using gas chromatography.

During the experiments, the gas accumulation package was replaced after 7, 44, 57, 70, 79, 89, 96, 103, 110, 117, 127, 141 and 156 days, the volume of captured gas was determined and the composition of the gas was measured using gas chromatography.

4.3. results

The volumes of methane and carbon dioxide produced are shown in the following table 4 (see also Fig. 4: graphical representation of methane and CO ₂ emissions from example 4). The results refer to 1000 kg of (semi-)liquid livestock manure for each experimental option.

Table 4

Volumes of gas generated per 1000 kg of (semi-)liquid bedding-free cattle manure

Duration of experience
[day] Sample 1
(control) Sample 2
(Composition 1 was used from day 110) Methane
[ml] _CO2
[ml] Methane
[ml] _CO2
[ml] 7 70
[70] 118
[118] 70
[70] 113
[113] 44 eleven
[81] 5
[123] 12
[82] 5
[118] 57 101
[182] 15
[138] 61
[143] 10
[128] 70 244
[426] 31
[169] 208
[351] 22
[150] 79 190
[616] 26
[195] 177
[528] 21
[171] 89 331
[947] 58
[253] 270
[798] 38
[209] 96 416
[1363] 94
[347] 332
[1130] 59
[268] 103 544
[1907] 153
[500] 490
[1620] 115
[383] 110 637
[2544] 171
[671] 576
[2196] 152
[535] 117 691
[3235] 198
[769] 2
[2198] 2
[537] 127 714
[3949] 168
[937] 0
[2198] 0
[537] 141 261
[4210] 58
[995] 0
[2198] 0
[537] 156 206
[4416] 48
[1043] 0
[2198] 1
[538]

The indicators refer to the time period; the indicators in brackets are cumulative indicators for the entire period of the experiment.

A graphical representation is shown in Fig. 4.

4.4. Summary of results

● Methane release

After 156 days of storage, the control experiment (sample 1) released 4416 ml of methane per 1000 kg of (semi)liquid bedding-free cattle manure. The dynamics of methane release in sample 2 was similar to sample 1 before the 110th day. After the introduction of 6.60 g of calcium cyanamide in the form of calcium cyanamide-containing composition 1 on the 110th day to sample 2, which corresponds to 2.16 kg of calcium cyanamide-containing composition or quantitative concentration of the substance equal to 11.9 2 mol calcium cyanamide per 1 m ³ of (semi)liquid litter-free manure, methane emissions immediately stopped and did not resume during subsequent experiments. 46 days after the administration of calcium cyanamide in the form of composition 1, only 2 ml of methane was released.

● CO ₂ release

A similar picture takes place here. After 156 days of storage, the control experiment (sample 1) released 1043 ml of CO ₂ per 1000 kg of (semi)liquid bedding-free cattle manure. The dynamics of CO ₂ release in sample 2 was similar to sample 1 up to the 110th day. After the introduction of 6.60 g of calcium cyanamide in the form of composition 1 containing calcium cyanamide on the 110th day to sample 2, which corresponds to 2.16 kg of calcium cyanamide containing composition or quantitative concentration of the substance equal to 11.9 mol of calcium cyanamide per 1 m ³ of (semi)liquid litter-free manure, the release of CO ₂ immediately stopped and did not resume during subsequent experiments. For 46 days after the introduction of calcium cyanamide in the form of composition 1, only 3 ml of CO ₂ was released.

Generalization of the results obtained in examples 1 – 4.

As a result of the introduction of 2.93 kg of calcium cyanamide in the form of composition 1 per 1 m ³ of (semi)liquid litterless manure and subsequent contact after storage for 156 days, the following decreases: methane release by 97.9%, CO ₂ release by 97, 9% versus control experience. A very similar result is achieved with similar operations and a similar storage duration after the introduction of 1.38 kg of calcium cyanamide in the form of a composition of 2 per 1 m ³ of (semi-)liquid manure without bedding. Methane emissions are reduced by 99.4%, CO ₂ emissions by 97.1%. On the contrary, with the introduction of 0.983 kg of hydrogen cyanamide solution in the form of composition 3 per 1 m ³ of (semi-)liquid litterless manure, which corresponds to a very similar quantitative concentration of the substance compared to examples 2 and 4, after 150 days of storage, methane emissions decreased by only 82. 9%, CO ₂ release - only 78.2% compared to the control experiment. It will be shown below that when 2.16 kg of calcium cyanamide is introduced and brought into contact in the form of a composition of 1 per 1 m ³ of (semi)liquid litterless manure at a time when methane and CO ₂ are actively released from the (semi)liquid litterless manure, this release practically stops. Thus, from the moment of introduction of the composition and 46 days after that, only 2 ml of methane and 3 ml of CO ₂ were released per 1000 kg of (semi)liquid litterless manure, while in the control experiment this was 1872 ml of methane and 372 ml of CO ₂ per 1000 kg (semi)liquid manure without bedding.

The absolute amount of gases released, such as methane and carbon dioxide, from on-farm fertilizers is determined by several factors:

- type and origin of on-farm fertilizer,

- duration of exposure, temperature and influx of oxygen in the form of fresh air into on-farm fertilizer in the collection channel until the moment of extraction,

- nutrient content in animal excretions as a consequence of the composition of livestock feed.

This is shown in Examples 1 – 4. Although fresh on-farm fertilizer of the same type and origin was consistently applied in these examples, the amounts of methane and carbon dioxide released varied between control samples.

Example 5

Reduced methane and CO ₂ emissions from (semi)liquid manure without litter

cattle

5.1 Substances used

Fresh (semi)liquid, bedding-free cattle manure (= on-farm fertilizer):

- from a housing for dairy cattle (Community Obing, Bavaria),

- without dilution with rinsing water, cleaning water or similar water,

- without bedding,

- taken from the settling chamber of the drain channel running in the direction of the buried container for (semi-)liquid manure without bedding,

- analyzed substances: total nitrogen: 0.43 wt. %,

ammonium (NH ₄ ): 0.17 wt. % (corresponds to 0.13% ammonium nitrogen),

nitrate nitrogen: < 20 mg/kg,

dry matter: 9.87 wt. %,

pH: 7.0 (15°C),

electrical conductivity: 20.1 mS/cm (15°C)

Hydrogen cyanamide-containing composition (composition 1):

- calcium cyanamide: 44.0 wt. %

- calcium nitrate: 11.1 wt. %

- calcium hydroxide: 13.4 wt. %

- calcium carbonate: 10.0 wt. %

- free carbon: 10.0 wt. %

- magnesium carbonate: 2.3 wt. %

- water: 9.2 wt. %.

Fertilizer: “nitrate-containing calcium cyanamide” according to A. 1.

Nitrogen fertilizer No. 3 (b) according to Regulation (EC) No. 2003/2003 of the European Parliament and of the Council of 13 October 2003 on fertilizer products.

Composition containing calcium cyanamide (composition 2):

- calcium cyanamide: 67.7 wt. %

- calcium oxide: 13.2 wt. %

- calcium hydroxide: 3.2 wt. %

- free carbon: 13.3 wt. %

- water: 2.6 wt. %

Fertilizer: “nitrate-containing calcium cyanamide” according to A.1,

Nitrogen fertilizer No. 3 (a) according to Regulation (EC) No. 2003/2003 of the European Parliament and of the Council of 13 October 2003 on fertilizer products.

Composition containing calcium cyanamide (composition 4):

- calcium cyanamide: 97.2 wt. %

- calcium oxide: 2.3 wt. %

- calcium carbonate: 0.4 wt. %

- water: 0.1 wt. %

Calcium hydroxide containing composition (composition 5):

- calcium hydroxide: 99.8 wt. %

- water: 0.2 wt. %.

Calcium carbonate containing composition (composition 6):

- calcium carbonate: 99.9 wt. %

- water: 0.1 wt. %.

5.2 Conducting experiments

Composition 1:

3008 ml (corresponding to 2976 g) of (semi-)liquid bedding-free cattle manure of the described composition (see 5.1) was placed in a wide-mouth polyethylene container with a capacity of 6 liters with a tight-fitting lid. Then 6.55 g of composition 1 (corresponding to 2.18 kg of calcium cyanamide-containing composition or 12.0 mol of calcium cyanamide per 1 m ³ of (semi-)liquid bedding-free cattle manure) was added and mixed thoroughly. After stirring, the pH and electrical conductivity of the mixture were measured, then the wide-mouth container was immediately tightly closed. A hole was made in the lid of the wide-neck container, to which a gas accumulation bag (with a nominal volume of 5.6 liters) was connected through a seal, through which the volume of released gas was captured. With this design, air oxygen could not penetrate into the wide-mouth container. In this way, the measurement results were not distorted by carbon dioxide from the air. The mixture was kept strictly for 170 days without stirring or moving at a temperature of 23 ± 1°C and air pressure from 960 to 980 hPa at an elevation of 493 m above sea level. The filled gas storage bag was periodically replaced, the volume of accumulated gas was determined, and the composition of the gas was analyzed using gas chromatography.

Indicators measured after mixing:

pH: 7.1 (22°C),

electrical conductivity: 20.4 mS/cm (22°C).

Composition 2:

2995 ml (corresponding to 2963 g) of (semi-)liquid bedding-free cattle manure of the described composition (see 5.1) were placed in a wide-mouth polyethylene container with a capacity of 6 liters with a tight-fitting lid. Then 4.15 g of composition 2 (corresponding to 1.39 kg of calcium cyanamide-containing composition or 11.7 mol of calcium cyanamide per 1 m ³ of (semi-)liquid bedding-free cattle manure) was added and mixed thoroughly. After stirring, the pH and electrical conductivity of the mixture were measured, then the wide-mouth container was immediately tightly closed. A hole was made in the lid of the wide-neck container, to which a gas accumulation bag (with a nominal volume of 5.6 liters) was connected through a seal, through which the volume of released gas was captured. With this design, air oxygen could not penetrate into the wide-mouth container. In this way, the measurement results were not distorted by carbon dioxide from the air. The mixture was kept strictly for 170 days without stirring or moving at a temperature of 23 ± 1 ° C and air pressure from 960 to 980 hPa at an elevation of 493 m above sea level. The filled gas storage bag was periodically replaced, the volume of accumulated gas was determined, and the composition of the gas was analyzed using gas chromatography.

Indicators measured after mixing:

pH: 7.3 (22 °C),

electrical conductivity: 20.5 mS/cm (22 °C).

Composition 4:

3033 ml (corresponding to 3001 g) of (semi-)liquid bedding-free cattle manure of the described composition (see 5.1) was placed in a wide-mouth polyethylene container with a capacity of 6 liters with a tight-fitting lid. Then 3.00 g of composition 4 (corresponding to 0.99 kg of calcium cyanamide-containing composition or 12.0 mol of calcium cyanamide per 1 m ³ of (semi-)liquid bedding-free cattle manure) was added and mixed thoroughly. After stirring, the pH and electrical conductivity of the mixture were measured, then the wide-mouth container was immediately tightly closed. A hole was made in the lid of the wide-neck container, to which a gas accumulation bag (with a nominal volume of 5.6 liters) was connected through a seal, through which the volume of released gas was captured. With this design, air oxygen could not penetrate into the wide-mouth container. In this way, the measurement results were not distorted by carbon dioxide from the air. The mixture was kept strictly for 170 days without stirring or moving at a temperature of 23 ± 1°C and air pressure from 960 to 980 hPa at an elevation of 493 m above sea level. The filled gas storage bag was periodically replaced, the volume of accumulated gas was determined, and the composition of the gas was analyzed using gas chromatography.

Indicators measured after mixing:

pH: 7.1 (22°C),

electrical conductivity: 20.2 mS/cm (22°C).

Composition 5:

3044 ml (corresponding to 3012 g) of (semi-)liquid bedding-free cattle manure of the described composition (see 5.1) was placed in a wide-mouth polyethylene container with a capacity of 6 liters with a tight-fitting lid. Then 1.51 g of composition 5 (corresponding to 0.50 kg of calcium hydroxide-containing composition or 6.7 mol of calcium hydroxide per 1 m ³ of (semi-)liquid bedding-free cattle manure) was added and mixed thoroughly. After stirring, the pH and electrical conductivity of the mixture were measured, then the wide-mouth container was immediately tightly closed. A hole was made in the lid of the wide-neck container, to which a gas accumulation bag (with a nominal volume of 5.6 liters) was connected through a seal, through which the volume of released gas was captured. With this design, air oxygen could not penetrate into the wide-mouth container. In this way, the measurement results were not distorted by carbon dioxide from the air. The mixture was kept strictly for 170 days without stirring or moving at a temperature of 23 ± 1 ° C and an air pressure of 960 to 980 hPa at an elevation of 493 m above sea level. The filled gas storage bag was periodically replaced, the volume of accumulated gas was determined, and the composition of the gas was analyzed using gas chromatography.

Indicators measured after mixing:

pH: 7.3 (22°C),

electrical conductivity: 20.2 mS/cm (22°C).

Composition 6:

2997 ml (corresponding to 2965 g) of (semi-)liquid bedding-free cattle manure of the described composition (see 5.1) was placed in a wide-mouth polyethylene container with a capacity of 6 liters with a tight-fitting lid. Then 1.48 g of composition 6 (corresponding to 0.49 kg of calcium carbonate-containing composition or 4.9 mol of calcium carbonate per 1 m ³ of (semi-)liquid bedding-free cattle manure) was added and mixed thoroughly. After stirring, the pH and electrical conductivity of the mixture were measured, then the wide-mouth container was immediately tightly closed. A hole was made in the lid of the wide-neck container, to which a gas accumulation bag (with a nominal volume of 5.6 liters) was connected through a seal, through which the volume of released gas was captured. With this design, air oxygen could not penetrate into the wide-mouth container. In this way, the measurement results were not distorted by carbon dioxide from the air. The mixture was kept strictly for 170 days without stirring or moving at a temperature of 23 ± 1 ° C and air pressure from 960 to 980 hPa at an elevation of 493 m above sea level. The filled gas storage bag was periodically replaced, the volume of accumulated gas was determined, and the composition of the gas was analyzed using gas chromatography.

Indicators measured after mixing:

pH: 7.1 (22°C),

electrical conductivity: 20.2 mS/cm (22°C).

5.3 Results

The resulting volumes of methane and carbon dioxide are presented in the following tables 5 - 9 (see also figures 5 - 9: graphical representation of methane and CO ₂ emissions according to example 5). The results refer to 1000 kg of (semi-)liquid, bedding-free cattle manure per experimental variant.

Table 5

Volumes of gas generated per 1000 kg of (semi)liquid bedding-free cattle manure; comparison of the control sample with composition 1 containing calcium cyanamide.

Duration of experience
[day] Sample 1
(control) Sample 2
(track 1) Methane
[ml] _CO2
[ml] Methane
[ml] _CO2
[ml] 6 88
[88] 113
[113] 7
[7] 31
[31] 32 13
[101] 7
[120] 1
[8] 2
[33] 57 122
[223] 21
[141] 2
[10] 1
[34] 71 471
[694] 93
[234] 1
[eleven] 1
[35] 79 456
[1150] 92
[326] 1
[12] 1
[36] 88 497
[1647] 95
[421] 1
[13] 0
[36] 97 665
[2312] 94
[515] 1
[14] 2
[38] 104 425
[2737] 68
[583] 0
[14] 1
[39] 111 402
[3139] 66
[649] 0
[14] 0
[39] 118 433
[3572] 62
[711] 1
[15] 0
[39] 127 319
[3891] 82
[793] 0
[15] 1
[40] 139 364
[4255] 110
[903] 0
[15] 0
[40] 153 449
[4704] 99
[1002] 0
[15] 0
[40] 170 229
[4933] 65
[1067] 1
[16] 1
[41]

The indicators refer to the time period; the indicators in brackets are cumulative indicators for the entire period of the experiment.

Table 6

Volumes of gas generated per 1000 kg of (semi)liquid bedding-free cattle manure; comparison of the control sample with composition 2 containing calcium cyanamide.

Duration of experience
[day] Sample 1
(control) Sample 2
(track 2) Methane
[ml] _CO2
[ml] Methane
[ml] _CO2
[ml] 6 88
[88] 113
[113] 4
[4] 22
[22] 32 13
[101] 7
[120] 2
[6] 1
[23] 57 122
[223] 21
[141] 1
[7] 1
[24] 71 471
[694] 93
[234] 1
[8] 1
[25] 79 456
[1150] 92
[326] 0
[8] 1
[26] 88 497
[1647] 95
[421] 1
[9] 0
[26] 97 665
[2312] 94
[515] 1
[10] 1
[27] 104 425
[2737] 68
[583] 0
[10] 0
[27] 111 402
[3139] 66
[649] 0
[10] 0
[27] 118 433
[3572] 62
[711] 0
[10] 1
[28] 127 319
[3891] 82
[793] 0
[10] 0
[28] 139 364
[4255] 110
[903] 0
[10] 0
[28] 153 449
[4704] 99
[1002] 0
[10] 1
[29] 170 229
[4933] 65
[1067] 1
[eleven] 1
[thirty]

The indicators refer to the time period; the indicators in brackets are cumulative indicators for the entire time of the experiment (see Fig. 6).

Table 7

Volumes of gas generated per 1000 kg of (semi)liquid bedding-free cattle manure; comparison of the control sample with composition 4 containing calcium cyanamide.

Duration of experience
[day] Sample 1
(control) Sample 2
(track 4) Methane
[ml] _CO2
[ml] Methane
[ml] _CO2
[ml] 6 88
[88] 113
[113] 46
[46] 60
[60] 32 13
[101] 7
[120] 3
[49] 3
[63] 57 122
[223] 21
[141] 4
[53] 2
[65] 71 471
[694] 93
[234] 4
[57] 2
[67] 79 456
[1150] 92
[326] 2
[59] 1
[68] 88 497
[1647] 95
[421] 1
[60] 0
[68] 97 665
[2312] 94
[515] 7
[67] 2
[70] 104 425
[2737] 68
[583] 18
[85] 3
[73] 111 402
[3139] 66
[649] 68
[153] 8
[81] 118 433
[3572] 62
[711] 97
[250] 13
[94] 127 319
[3891] 82
[793] 177
[427] 18
[112] 139 364
[4255] 110
[903] 295
[722] 24
[136] 153 449
[4704] 99
[1002] 564
[1286] 47
[183] 170 229
[4933] 65
[1067] 1025
[2311] 66
[249]

The indicators refer to the time period, the indicators in brackets are cumulative indicators for the entire time of the experiment (see Fig. 7)

Table 8

Volumes of gas generated per 1000 kg of (semi-)liquid bedding-free cattle manure; comparison of the control sample with composition 5 containing calcium hydroxide.

Duration of experience
[day] Sample1
(control) Sample 2
(track 5) Methane
[ml] _CO2
[ml] Methane
[ml] _CO2
[ml] 6 88
[88] 113
[113] 125
[125] 138
[138] 32 13
[101] 7
[120] 39
[164] 15
[153] 57 122
[223] 21
[141] 124
[288] 21
[174] 71 471
[694] 93
[234] 709
[997] 136
[310] 79 456
[1150] 92
[326] 534
[1531] 121
[431] 88 497
[1647] 95
[421] 654
[2185] 149
[580] 97 665
[2312] 94
[515] 878
[3063] 136
[716] 104 425
[2737] 68
[583] 796
[3859] 108
[824] 111 402
[3139] 66
[649] 623
[4482] 108
[932] 118 433
[3572] 62
[711] 502
[4984] 85
[1017] 127 319
[3891] 82
[793] 411
[5395] 89
[1106] 139 364
[4255] 110
[903] 573
[5968] 89
[1195] 153 449
[4704] 99
[1002] 516
[6484] 84
[1279] 170 229
[4933] 65
[1067] 307
[6791] 82
[1361]

The indicators refer to the time period; the indicators in brackets are cumulative indicators for the entire time of the experiment (see Fig. 8).

Table 9

Volumes of gas generated per 1000 kg of (semi-)liquid bedding-free cattle manure; comparison of the control sample with composition 6 containing calcium carbonate.

Duration of experience
[day] Sample 1
(control) Sample 2
(track 6) Methane
[ml] _CO2
[ml] Methane
[ml] CO ₂
[ml] 6 88
[88] 113
[113] 64
[64] 35
[35] 32 13
[101] 7
[120] 13
[77] 4
[39] 57 122
[223] 21
[141] 112
[189] 12
[51] 71 471
[694] 93
[234] 356
[545] 46
[97] 79 456
[1150] 92
[326] 447
[992] 75
[172] 88 497
[1647] 95
[421] 409
[1401] 77
[249] 97 665
[2312] 94
[515] 555
[1956] 78
[327] 104 425
[2737] 68
[583] 393
[2349] 71
[398] 111 402
[3139] 66
[649] 488
[2837] 75
[473] 118 433
[3572] 62
[711] 413
[3250] 71
[544] 127 319
[3891] 82
[793] 348
[3598] 86
[630] 139 364
[4255] 110
[903] 337
[3935] 108
[738] 153 449
[4704] 99
[1002] 477
[4412] 97
[835] 170 229
[4933] 65
[1067] 201
[4613] 67
[902]

The indicators refer to the time period; the indicators in brackets are cumulative indicators for the entire time of the experiment (see Fig. 9).

5.4 Summary of results

● Methane release

After 170 days of storage, the control experiment (sample 1) released 4933 ml of methane per 1000 kg of (semi)liquid bedding-free cattle manure.

- As a result of the introduction of 6.55 g of calcium cyanamide in the form of calcium cyanamide-containing composition 1, which corresponds to 2.18 kg of calcium cyanamide-containing composition or a quantitative concentration of the substance equal to 12.0 mol of calcium cyanamide per 1 m ³ of (semi-)liquid litter-free manure cattle, it became possible to reduce these methane emissions by 99.7% to 16 ml.

- As a result of the introduction of 4.15 g of calcium cyanamide in the form of calcium cyanamide-containing composition 2, which corresponds to 1.39 kg of calcium cyanamide-containing composition or a quantitative concentration of the substance equal to 11.7 mol of calcium cyanamide per 1 m ³ of (semi-)liquid litter-free manure cattle, it became possible to reduce these methane emissions by 99.8% to 11 ml.

- As a result of the introduction of 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 quantitative concentration of the substance equal to 12.0 mol of calcium cyanamide per 1 m ³ of (semi-)liquid litter-free manure cattle, it became possible to reduce these methane emissions by 53.2% to 2311 ml. Moreover, after 97 days of storage, only 67 ml of methane was released, which at the moment corresponded to a decrease in methane by 2245 ml or 97.1%. The vast majority of methane was released during subsequent storage.

- As a result of the introduction of 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 quantitative concentration of the substance equal to 6.7 mol of calcium hydroxide per 1 m ³ of (semi-)liquid litterless manure cattle, methane emissions increased by 37.7% to 6791 ml.

- As a result of the introduction of 1.48 g of calcium carbonate in the form of calcium carbonate-containing composition 6, which corresponds to 0.49 kg of calcium carbonite-containing composition or a quantitative concentration of the substance equal to 4.9 mol of calcium carbonate per 1 m ³ of (semi-)liquid litterless manure cattle, it became possible to reduce these methane emissions by 6.5% to 4613 ml.

● CO ₂ release

A similar picture takes place here. After 170 days of storage, the control experiment (sample 1) released 1067 ml of CO ₂ per 1000 kg of (semi)liquid bedding-free cattle manure.

- As a result of the introduction of 6.55 g of calcium cyanamide in the form of calcium cyanamide-containing composition 1, which corresponds to 2.18 kg of calcium cyanamide-containing composition or a quantitative concentration of the substance equal to 12.0 mol of calcium cyanamide per 1 m ³ of (semi-)liquid litter-free manure cattle, it became possible to reduce CO ₂ emissions by 96.2% to 41 ml.

- As a result of the introduction of 4.15 g of calcium cyanamide in the form of calcium cyanamide-containing composition 2, which corresponds to 1.39 kg of calcium cyanamide-containing composition or a quantitative concentration of the substance equal to 11.7 mol of calcium cyanamide per 1 m ³ of (semi-)liquid litter-free manure cattle, it became possible to reduce CO ₂ emissions by 97.2% to 30 ml.

- As a result of the introduction of 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 quantitative concentration of the substance equal to 12.0 mol of calcium cyanamide per 1 m ³ of (semi-)liquid litter-free manure cattle, it became possible to reduce these CO ₂ emissions by 76.7% to 249 ml.

- As a result of the introduction of 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 quantitative concentration of the substance equal to 6.7 mol of calcium hydroxide per 1 m ³ of (semi-)liquid litterless manure cattle, CO ₂ emissions increased by 27.6% to 1361 ml.

- As a result of the introduction of 1.48 g of calcium carbonate in the form of calcium carbonate-containing composition 6, which corresponds to 0.49 kg of calcium carbonite-containing composition or a quantitative concentration of the substance equal to 4.9 mol of calcium carbonate per 1 m ³ of (semi-)liquid litterless manure cattle, it became possible to reduce these CO ₂ emissions by 15.5% to 902 ml.

Generalization of the results obtained in examples 1 – 5.

The absolute value of gases released, such as methane and carbon dioxide, from on-farm fertilizers is determined by several factors:

- type and origin of on-farm fertilizer,

- duration of exposure, temperature and influx of oxygen in the form of fresh air into on-farm fertilizer in the collection channel until the moment of extraction,

- nutrient content in animal excretions as a consequence of the composition of livestock feed.

This can be seen in Examples 1 – 5. Although fresh on-farm fertilizer of the same type and origin was consistently applied in these examples, the amounts of methane and carbon dioxide released varied between control samples.

As a result of the introduction of 2.93 g of calcium cyanamide in the form of composition 1 per 1 m ³ of (semi-)liquid bedding-free cattle manure and subsequent contact in example 1 after 156 days of storage, methane emissions decreased by 99.7% and CO ₂ emissions by 97.9% against the control experiment. A very similar result was obtained with a similar mode of action and a similar storage duration after the introduction of 1.38 kg of calcium cyanamide in the form of a composition 2 per 1 m ³ of (semi-)liquid bedding-free cattle manure in example 2. Methane emissions decreased by 99.4%, CO ₂ release – by 97.1%.

These results are confirmed in example 5 by even longer storage. As a result of the introduction of 2.18 kg of calcium cyanamide in the form of composition 1 per 1 m ³ of (semi-)liquid bedding-free cattle manure and subsequent contact after 170 days of storage, methane emission decreased by 99.7%, CO ₂ emission by 96 .2% versus control experience. After introducing 1.39 kg of calcium cyanamide in the form of composition 2 per 1 m ³ of (semi-)liquid bedding-free cattle manure and subsequent contact after 170 days of storage, methane emission decreased by 99.8%, CO ₂ emission - by 97, 2%.

On the contrary, with the introduction of 0.983 kg of hydrogen cyanamide solution in the form of composition 3 per 1 m ^{3 of} (semi-)liquid bedding-free cattle manure, which corresponds to a very similar quantitative concentration of the substance compared to examples 2, 4 and 5, after 150 days of storage the release decreased methane by only 82.9%, CO ₂ release by only 78.2% compared to the control experiment.

It will be further shown that as a result of introducing and bringing into contact 2.16 kg of calcium cyanamide in the form of a composition of 1 per 1 m ³ of (semi)liquid bedding-free cattle manure at the moment when the (semi-)liquid bedding-free cattle manure is actively methane and CO ₂ are released, this release practically stops. So, from the moment of introduction and for 46 days after that, only 2 ml of methane and 3 ml of CO ₂ were released per 1000 kg of (semi)liquid bedding-free cattle manure; in the control experiment this amounted to: 1872 ml of methane and 372 ml of CO ₂ per 1000 kg of (semi)liquid non-litter cattle manure.

However, with the introduction of 0.99 kg of calcium cyanamide in the form of composition 4, which corresponds to a small proportion of calcium oxide (2.3 wt. %) and calcium carbonate (0.4 wt. %) per 1 m ³ of (semi-)liquid coarse litterless manure cattle, and subsequent contact, a noticeably shorter period of reduced methane and CO ₂ release is found, although the quantitative concentration of calcium cyanamide added was equal to that in compositions 1 and 2 in example 5.

Also in example 5 it is shown that the introduction and subsequent contact of 0.50 kg of calcium hydroxide in the form of composition 5 per 1 m ³ of (semi)liquid bedding-free cattle manure after 170 days of storage even increases the release of methane and CO ₂ compared to control experience. The introduction of 0.49 kg of calcium carbonate in the form of composition 6 per 1 m ³ of (semi-)liquid bedding-free cattle manure with a similar mode of action reduces the release of methane and CO ₂ only to a small extent. What was even more unexpected was the effective reduction in methane and CO ₂ emissions that lasted 156 and 170 days after the addition of compositions 1 and 2, containing a combination of calcium cyanamide and calcium oxide/calcium hydroxide and/or calcium carbonate.

The amounts of gases released in control experiments, given in examples 1 - 5, show that after 150 - 170 days of storage of (semi)liquid bedding-free cattle manure, the volume of methane released exceeds the volume of released CO ₂ by 4.2 - 5.9 times. Taking into account the molar volume ( _Vm ), the mass of released methane exceeds the same mass of CO ₂ by 1.5 - 2.1 times. Methane has a Global Warming Potential (GWP) of 28 according to the Fifth Assessment Report of the United Nations Intergovernmental Panel on Climate Change (IPCC AR5) over 100 years. This means that 1 kg of methane during the first 100 years after its release contributes 28 times more to the greenhouse effect than 1 kg of CO ₂ (source: Wikipedia). Therefore, according to the present invention, a significant contribution to the reduction of greenhouse gas emissions into the atmosphere is achieved without significantly increasing the nitrogen content of the local fertilizer.

Claims (39)

1. A method for reducing the release of methane and/or carbon dioxide from on-farm fertilizer during its storage, including the steps: a) ensuring the availability of a tank for storing on-farm fertilizer with a capacity of X, b) filling the storage tank with on-farm fertilizer, the amount of which is at least 5 vol. % of the volume X of the tank, and c) introducing a composition containing from 10 to 100 wt. % calcium cyanamide into a storage tank and bringing it into contact with on-farm fertilizer, wherein filling the storage tank with local fertilizer in step b) and introducing a composition containing calcium cyanamide into the storage tank in step c) is carried out in any sequence or simultaneously . 2. The method according to claim 1, characterized in that the composition is introduced before, during or after the first filling of the tank with on-farm fertilizer. 3. Method according to claim 1 or 2, characterized in that the composition is introduced: i) once after or during the first introduction of the first portion of on-farm fertilizer into the storage tank or ii) in portions after each partial filling of the storage tank, or iii) once after or during the complete filling of the storage tank with on-farm fertilizer. 4. Method according to any one of paragraphs. 1-3, characterized in that the storage tank for on-farm fertilizer is an open or closed tank. 5. Method according to any one of paragraphs. 1-4, characterized in that the storage temperature of on-farm fertilizer is from 0 to 60°C. 6. Method according to any one of paragraphs. 1-5, characterized in that the composition is introduced into on-farm fertilizer in the form of a solid or suspension. 7. The method according to claim 1 or 2, characterized in that the composition is introduced into on-farm fertilizer in an amount of 0.5 to 10 kg per 1 m ³ of on-farm fertilizer. 8. Use of a composition containing from 10 to 100 wt. % calcium cyanamide, to reduce the release of methane and/or carbon dioxide from on-farm fertilizer during its storage in a tank. 9. Use of a composition containing from 10 to 100 wt. % calcium cyanamide, as an interrupter or inhibitor of anaerobic fermentation of on-farm fertilizer and/or as an inhibitor of microbial decomposition of organic matter in on-farm fertilizer during its storage in a tank. 10. Application according to claim 8 or 9, characterized in that the composition contains: a) 25–95 wt. % calcium cyanamide, b) 5–40 wt. % of at least one compound from the group: magnesium carbonate, magnesium bicarbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium bicarbonate, calcium oxide, calcium hydroxide or mixtures thereof, c) up to 20 wt. % of at least one nitrate from the group: sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate or mixtures thereof, d) up to 15 wt. % free carbon, coal or graphite, e) up to 10 wt. % water. 11. Application according to claim 8 or 9, characterized in that the composition contains: a) 50–80 wt. % calcium cyanamide, b) 5–25 wt. % of at least one compound from the group: magnesium carbonate, magnesium bicarbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium bicarbonate, calcium oxide, calcium hydroxide or mixtures thereof, c) 1-15 wt. % free carbon, coal or graphite, d) up to 10 wt. % water. 12. Application according to claim 8 or 9, characterized in that the composition contains: a) 35-55 wt. % calcium cyanamide, b) 15-35 wt. % of at least one compound from the group: magnesium carbonate, magnesium bicarbonate, magnesium oxide, magnesium hydroxide, calcium carbonate, calcium bicarbonate, calcium oxide, calcium hydroxide or mixtures thereof, c) 1-20 wt. % of at least one nitrate from the group: sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate or mixtures thereof, d) 1–15 wt. % free carbon, coal or graphite e) up to 10 wt. % water. 13. Application according to any one of paragraphs. 8–12, characterized in that the composition is used in the form of a solid or suspension. 14. Application according to any one of paragraphs. 8–13, characterized in that the composition is used in an amount from 0.5 to 10 kg per 1 m ³ of on-farm fertilizer.