WO2020065035A1

WO2020065035A1 - Method and composition for neutralizing or reducing harmful odors or gases

Info

Publication number: WO2020065035A1
Application number: PCT/EP2019/076243
Authority: WO
Inventors: Trine Huusfeldt
Original assignee: Trine Huusfeldt
Priority date: 2018-09-27
Filing date: 2019-09-27
Publication date: 2020-04-02
Also published as: DE102018123897A1

Abstract

The invention relates to a method and compositions for use in the neutralization or reduction of harmful odors or gases, in particular gaseous ammonia (NH3) and/or gaseous hydrogen sulphide (H2S) and/or gaseous nitrogen oxide (NOx) and/or gaseous sulfur dioxide (SO2). The method is particularly suitable for avoiding environmentally harmful gas emissions in stables, installations or during the application of liquid manure to agricultural fields.

Description

Process and composition for neutralizing or reducing harmful odors or gases

Technical field:

The present invention relates to methods and compositions for use in neutralizing or reducing harmful odors or gases,

in particular of gaseous ammonia (NH ₃ ) and / or gaseous

Hydrogen sulfide (H ₂ S) and / or gaseous nitrogen oxide (NOx) and / or

gaseous sulfur dioxide (S0 ₂ ). The method is particularly suitable for

Avoidance of environmentally harmful gas emissions in stables, facilities or when spreading liquid manure on agricultural fields.

State of the art:

Agriculture and environmental protection are shaped by new challenges in terms of climate change, animal welfare and the use of natural resources. Environmentally friendly and animal-friendly processes are the most economical at the same time

Key points of a modern, competitive animal production, which also includes the aspects of climate change or sustainable environmental protection. The levels of ammonia (NH ₃ ) in the air and soil in Central Europe have remained high for many years. In this way, not even the limit values set by the individual governments are observed. A well-known environmental goal is to reduce the emissions of ammonia and other harmful gaseous substances, such as gaseous hydrogen sulfide (H ₂ S).

Ammonia is a serious problem, especially in agriculture, because a large part of the ammonia emissions in agriculture is caused by livestock, especially cattle. Another source of ammonia arises when manure is brought into fields, which is why the ammonia load is highest at the beginning of spring and in autumn after the harvest. In pig and poultry farming, on the other hand, most emissions are generated directly in the barn. The measures implemented so far, such as targeted feeding or structural changes, can only slightly reduce such emissions.

The majority of agricultural ammonia emissions come from the

Cattle farming (52 percent), pig farming (20 percent), poultry farming (9 percent) and mineral fertilizer application (15 percent). In pig farming, the majority of the emissions are generated directly in the barn, in cattle farming when storing manure and its application.

The proportion of ammonium (NH ₄ ) contained in manure in the total nitrogen (N) is around 15 percent for manure, about 50 percent for liquid manure and almost 95 percent for liquid manure. When the manure is stored and applied, the ammonium is converted to ammonia (NH ₃ ) and can escape into the atmosphere. Ammonia also emits from large agricultural livestock facilities. In the synthetic

Nitrogen fertilizers can be used especially when using ammonium-forming

Urea fertilizers or ammonium-containing AHL solutions escape larger amounts of ammonia, i.e. up to 15 percent of the total nitrogen content.

The amount of ammonia loss during spreading depends on numerous soil and weather conditions. A high pH value, a low buffer capacity, low

Soil moisture, high temperatures and wind favor ammonia outgassing.

Gaseous ammonia arises when urea or protein in the excrement of

Farm animals are decomposed. Ammonia is considered to be an indirect greenhouse gas that promotes the formation of greenhouse gases and fine dust. Under certain conditions, for example, the nitrogen contained in the ammonia in the soil can be converted into extremely climate-damaging laughing gas (nitrous oxide; N ₂ 0). Laughing gas (N ₂ 0) is a highly effective greenhouse gas, the climate impact of which is 265 times as strong as that of carbon dioxide (C0 ₂ ).

Agriculture is responsible for around 80% of nitrous oxide emissions in Germany. The main source of N ₂ 0 emissions are emissions from agricultural soils. The level of these emissions is largely determined by nitrogen management: the spreading of organic and mineral fertilizers as well as the

Incorporation of crop residues.

In animal husbandry, gaseous ammonia and gaseous are

Hydrogen sulfide is a serious problem, as these emissions have an impact on the climate in the house and thus have a significant impact on the well-being and performance of farm animals. The well-being of the animals depends crucially on the climate in the barn. Dairy cows in particular spend almost their entire life in the barn these days. Today's high

Milk production demands top performance from the metabolism of dairy cows, which is comparable to the top performance of top athletes.

In animal husbandry, the excrement is the starting substrate for the

Ammonia release, the formation potential for NH ₃ on the one hand by the type and amount the excrement, on the other hand is influenced by the extent of nitrogen conversion. In pig fattening, it can be assumed that with an average daily nitrogen intake of 55 grams, only about 30% is retained in the body, but approximately 50% is excreted primarily as urea with urine and 20% as organically bound bacterial protein with faeces (Aarnink, 1997; Arogo et al., 2001; Kirchgässner et al., 1991 a). During the ammonification, the urea is broken down into NH ₃ and C0 ₂ by hydrolytic cleavage with the aid of the catalyzing enzyme urease. Ammonification begins about 20 to 60 minutes after urine excretion (Aarnink et al., 1992) and is usually complete after two hours (Montenni & Erisman, 1998). The speed and completeness of its conversion will depend on the amount of

Urea concentration and the temperature-dependent urease activity positively influenced. The urease enzyme is contained in the faeces and leads to an increasing inoculation of surfaces with urease-active bacteria in the barn. The speed and expression of the

Ammonification depends on whether urea and urease come into contact with each other in liquid manure or on surfaces that are contaminated with feces. Previous feeding measures, measures for keeping and mucking as well as ventilation

Measures could only lead to a slight reduction in NH ₃ and H ₂ S emissions. The emissions of ammonia in animal husbandry systems continue to have an unfavorable effect on the well-being and performance of farm animals.

In the field, gaseous ammonia and other gaseous compounds contribute

Acidification and eutrophication of ecosystems, in addition it leads to the formation and release of di-nitrogen monoxide via the path of nitrogen deposition.

Hydrogen sulfide forms an explosive mixture with air and is acutely toxic in concentrations above 30 ppm to humans or other mammals. The maximum permissible workplace concentration is <5.0 ppm (DFG, 2014). In addition, H ₂ S is the cause of odors that are unpleasant for humans, which complicate the working conditions of people in such locations or rooms and thus represent a nuisance, since the odor threshold is 0.0001 to 0.03 mg / Nm ³ air.

There are limit values for the substances mentioned, which must not be exceeded. For example, the ammonia concentration in the area where calves stay should not exceed <10 ppm.

Various measures are known to at least reduce the odors in animal and human faeces caused by gaseous ammonia and gaseous hydrogen sulfide emissions. So describes the US-PS 124,041 Odor removal from faeces with the help of sulfuric acid and hydrochloric acid. US Pat. No. 705,462 describes a method for producing a fertilizer from faeces by adding phenol, calcium carbonate and silica acid.

In US Pat. No. 3,989,498, a composition is proposed for odor removal which contains glacial acetic acid and amyl alcohol. It can also contain sulfuric acid, butanedione (2,3), benzaldehyde, hydrochloric acid and copper sulfate. US Pat. No. 0127383 describes a composition consisting of a salt of lignosulfonic acid and a foam-forming surface-active substance.

DE 31 42 254 A1 describes a composition for eliminating odors, including ammonia odors using oxo acids of sulfur or phosphorus, it also being possible to use organic acids, for example formic acid, acetic acid, propionic acid, lactic acid and the like.

EP 1140 222 B1 uses an aqueous concentrated composition for cleaning and deodorization of air by atomization, which consists of fractions of certain salts of undecylenic acid and a certain oily component.

DE 31 42 254 A1 describes a thickener in which pectins are used in addition to oxo acids. The composition is not used in connection with the neutralization of gases and the use of highly esterified or highly methylated pectins is also not described.

WO 2013 041 384 A1 describes a composition in which a low-ester pectin is used in an acetic acid solution. The use of highly methylated or highly esterified pectins in a process for neutralizing or reducing harmful gas emissions is not described.

DE 24 22 574 A1 describes a water-soluble binder in which pectins are also used. The use of highly methylated or highly esterified pectins in a process for neutralizing or reducing harmful gas emissions is not described.

Representation of the invention;

Against this background, the object of the present invention is an alternative method and to provide a composition with which neutralization or reduction of harmful gases, in particular gaseous ammonia, gaseous

Hydrogen sulfide, gaseous nitrogen oxides and / or gaseous sulfur dioxide is possible. This object is achieved by a method with the features of claim 1 and the composition used therein. Preferred embodiments of the invention can be found in the subclaims.

With the aid of the method according to the invention, undesirable emissions of

gaseous ammonia (NH ₃ ), gaseous hydrogen sulfide (H ₂ S), gaseous

Nitrogen oxides (NOx) and / or gaseous sulfur dioxide (S0 ₂ ) are reduced or at least significantly reduced, which has a positive effect on the indoor climate in closed systems and on the formation of undesirable greenhouse gases (e.g. when spreading liquid manure).

To carry out the method, a composition is used which is able to neutralize or at least significantly reduce gaseous ammonia, gaseous hydrogen sulfide, gaseous nitrogen oxides and / or gaseous sulfur dioxide. The composition according to the invention comprises the following basic components: a) pectins or a mixture of pectins,

b) at least one organic acid or salts thereof.

The use of highly methylated or highly esterified pectins in the composition for neutralizing or reducing the above-mentioned gases has proven to be particularly advantageous. According to the invention, the composition comprises highly esterified or highly methylated pectins or a mixture of pectins which

comprises highly esterified and / or highly methylated pectins. This is preferably

Ratio of the highly esterified or highly methylated pectins to the low esterified or low methylated pectins in the mixture> 1: 1, preferably> 2: 1,

preferably> 3: 1.

If in the context of the present invention of organic or inorganic

Acids are spoken, their salts are always included in the scope of protection

locked in. This also applies to derivatives of such acids.

Depending on the application, the concentration ratios and the addition of other substances or substances in the composition vary. In particular, there are differences in an internal application (e.g. in stables) or in free space (e.g. when spreading liquid manure) to prevent the spread of harmful emissions or odors.

The pectin according to the invention or the mixture of pectins are plant polysaccharides or polyuronides which essentially consist of α-1,4-glycosidically and / or β-1,4-glycosidically linked D-galacturonic acid units which comprise the Form the backbone of the molecule.

The pectin therefore predominantly has the following basic structure consisting of a-D-galacturonic acid units:

The invention also includes esterified, acetylated or pectin derivatives based thereon which are based on neutral sugars.

The pectins or polysaccharides used in the composition must be able to bind water. For example, the NH ₃ taken up in the water is bound in a polymeric matrix as NH ₄₊ , which prevents emission.

Pectins which have been isolated from plant constituents, for example from plant stems, plant flowers or plant leaves, are preferably used. In a preferred variant, pectins are made from citrus fruits, from sugar beet or

Fruit stems obtained from sunflowers, preferably from the peel of apples, quinces, oranges, apricots, cherries. However, pectins from other sources, for example from vegetables such as carrots, are also included in the present invention.

The pectins which can be used according to the invention also include protopectins, modified pectins and substances, substances or compounds which act analogously to pectins and which, in connection with the neutralization of ammonia or hydrogen sulfide, achieve the same technical effect as natural pectins. These include, for example

Modifications from the existing via a-1, 4- and ß-1, 4-glycosidic bonds

Basic structure of the pectins. Pectins can also be used as preferred variants, in which the 1,2 bonds are substituted or interrupted by a neutral sugar, for example with aL-rhamnose. In addition, pectins are also included, the side chains of which are substituted with sugars, for example with arabinose, galactose or xylose. Also included are pectins in which hydroxyl groups on the C ₂ or C ₃ atom of the

Galacturon units are acetylated or substituted by other neutral sugars such as D-galactose, D-xylose, L-arabinose or L-rhamnose. In addition, esterifications, e.g. in the case of carboxy groups of polygalacturonic acid, for example esterifications with methanol. Thus, all esterified or acetylated pectin variants are also covered by the present invention, for example highly methylated or highly esterified pectins, low methylated and low-esterified pectins, pectic acids and aminopectins.

The organic acids used according to the invention, their salts or mixtures of organic acids (or their salts) preferably originate from natural sources.

Preferred organic acids are formic acid, acetic acid, propionic acid, lactic acid, and derivatives derived or modified therefrom. Furthermore, fixed

organic acids such as benzoic acid, ethylenediaminetetraacetic acid, maleic acid,

Citric acid, malonic acid, succinic acid, malic acid, adipic acid, fumaric acid and

The like can be used for the composition according to the invention.

Instead of an organic acid or in addition to an organic acid, the composition according to the invention can also contain an inorganic acid,

preferably carbonic acid, phosphoric acid, sulfuric acid, and / or hydrochloric acid. In a further variant, the organic acid or the mixture is more organic

Acids at least one inorganic acid in the composition, selected from the group consisting of carbonic acid, phosphoric acid, sulfuric acid and / or hydrochloric acid, and mixtures thereof. The invention also includes special salts of inorganic acids, for example MgSO ₄ , which are preferably used at a content of> 20 ppm NH ₃ .

In addition to the pectin or the mixture of pectins, the invention

Composition also contain other polysaccharides, such as alginates, starch or mixtures thereof, especially those that are soluble in an acidic environment. Artificial polymers can also be used. Because it is about building a polymer grid with the pectins, polysaccharides or artificial polymers, which in turn improves or supports the binding capacity of NH ₃ and the sulfur compounds and only releases them again when they are broken down by microorganisms. The composition according to the invention is preferably based entirely on

Food or biocompatible components for humans. This means that the product can also be used in organic or eco-agricultural productions.

In a preferred variant, the composition according to the invention comprises one or more of the following additional components: c) at least one inorganic acid or salts thereof,

d) additional polysaccharides,

e) modified polymers,

f) silicates (Si0 ₂ ),

g) bentonites or zeolites,

h) polyvinyl alcohol.

Preferred polysaccharides are starch, e.g. obtained from potatoes, cassava, cereals. Depending on the application, amounts of zeolite or bentonite can also be added.

In a preferred variant, the composition is aqueous

Composition, especially as an aqueous dispersion, before, with a proportion of

a) 1 to 20 wt .-% of pectin or a mixture of pectins and

b) 1 to 25% by weight of organic acid or its salts or a mixture of organic acids or their salts, and

c) a residual solvent content for 100 wt .-%, preferably water.

In a further preferred variant, the composition is aqueous

Composition, especially as an aqueous dispersion, before, with a proportion of

a) 1 to 12% by weight of pectin or a pectin mixture, optionally with additional polysaccharides (e.g. alginates or starch) and / or a thickener,

b) 1 to 25% by weight of organic acid or its salts, optionally with additional inorganic acid or its salts and mixtures of organic and / or inorganic acids (or their salts),

c) 53 to 95 wt .-% distilled / ion free or PUR water, and

d) 0 to 10% by weight of at least one foam-forming agent.

The water used is preferably distilled water or another solvent in which the pectins contained in the composition and the organic and / or inorganic acids used therein are miscible with one another. In a further embodiment, the pectins with a proportion of at least 10 wt .-%, preferably at least 15 wt .-% and the acids with at least 10 wt .-%, preferably between 15 and 25 wt .-% in the

Composition used, the remaining content for 100 wt .-% is supplemented with distilled water or another solvent.

The composition according to the invention is applied to the object to be treated in aqueous, viscous or solid form, for example by treating the object by spraying, atomizing, applying, introducing or mixing. For the treatment of interiors, for example stables for keeping livestock, it is advisable to atomize or spray the air in the room, to use washers or to apply it to the walls of the house. In addition, an application on

Soil gaps occur or are mixed into the slurry below. The composition can be introduced, for example, in straw, wood pellets or rock.

The composition according to the invention is suitable wherever gaseous ammonia, gaseous hydrogen sulfide, gaseous nitrogen oxides and / or gaseous sulfur dioxide are formed, in particular also in those objects in which unpleasant smells for people are to be eliminated. For example, plants in agriculture, especially in animal husbandry,

Industrial plants, sewage treatment plants and closed buildings, for example stables for animal husbandry, for example when fattening or keeping dairy cows, pigs, poultry, rabbits, cats, guinea pigs, dogs or horses etc. are treated.

In addition, the composition can also be applied in aqueous, solid, viscous or gaseous form outside of closed rooms, for example if the object is waste water. Waste water from a sewage treatment plant or sewage sludge as well as liquid manure or municipal or industrial waste can also be treated with the composition. The composition is preferably applied in an open or at least partially closed room, in which gas emissions, for example high ammonia or hydrogen sulfide concentrations, are to be expected, such as stables, dung, toilets or containers which transport substances containing ammonia. In stables or other premises, a special nozzle system or nebulization system is preferably used to control the atomize composition according to the invention. The device is preferably installed directly in the barn and, if necessary, can atomize the active substance composition in the room as an aerosol. For this purpose, the interior is preferably lowered by approximately 2 ° C., which increases the binding capacity of the composition for the NH ₃ -, H ₂ S, NOx and / or S0 ₂ gases.

However, the formulation according to the invention can also be applied in a basin, for example a clarifier in a sewage treatment plant. Furthermore, application of the composition in a landfill and / or an open space is also possible, for example as part of the discharge of liquid manure into a field or open-air toilets. Here, in particular, the ammonia pollution is regularly very high, so that an immediate neutralization of the ammonia in the manure can make a significant contribution to reducing the ammonia emissions and thus the indirect formation of greenhouse gases. The invention thus encompasses any application on an object, the object being a solid (including solid surfaces), a gas and / or a liquid. Viscous substances are also included, e.g. Gels or gel papers.

In the method according to the invention, the composition is preferably sprayed onto a solid substrate in the form of an aqueous dispersion. The application can also be added in a washer, with which a complete neutralization of the NH ₃ , H ₂ S, NOx and / or S0 ₂ gases and the odors can be achieved. This application is particularly suitable in all forms of stables.

In the method according to the invention, the composition is preferably sprayed onto a solid substrate in the form of an aqueous dispersion. In the

When applied, the composition can also contain an additional foam-forming agent, preferably at least one water-soluble foam-forming natural protein. This variant can be used, for example, in sewage treatment plants to retain or neutralize the NH ₃ , H ₂ S, NOX and / or S0 ₂ gases. For this purpose, the dispersion forms a sufficiently thick foam layer, which, like a sponge or film, absorbs the questionable gases and chemically neutralizes them. In a preferred variant, the composition is used in a viscous form, so that it can also be applied to vertical surfaces, for example on the walls of a stable, and adheres like a film. All conventional agents known to those skilled in the art, for example alkyl polyglycosides or conventional protein, are suitable as foam formers. Depending on the application, the proportion of foam images is between 0 and a maximum of 10% by weight of the composition, preferably less than 7.5% by weight, preferably between 1 and 5% by weight,

In a further preferred variant, the composition preferably contains a binder (also called: thickener, thickener). Thickeners are substances that are primarily able to bind water. By withdrawing

Unbound water increases the viscosity. One for each

Thickeners with a characteristic concentration add to this effect

Network effects that lead to a mostly disproportionate increase in viscosity. In this case, it is said that molecules 'communicate' with each other, and therefore disappear. Most thickeners are linear or branched macromolecules (such as polysaccharides or proteins) that can interact with each other through intermolecular interactions such as hydrogen bonds, hydrophobic interactions, or ionic relationships. Extreme thickeners are layered silicates (bentonites, hectorites) or hydrated Si0 ₂ particles, which are dispersed as particles and can bind water in their solid-like structure or can interact with each other due to the described interactions.

Preferred thickeners are guar, locust bean gum, carrageenan, cellulose ether, polyvinyl alcohol and silicates.

In one variant, a mixture of a butadiene / acrylonitrile copolymer, a polyisocyanate and an inhibitor, for example acetic acid, is preferably used. As an inhibitor, acetic acid can prevent premature reaction of the butadiene / acrylonitrile copolymers with the polyisocyanate. In addition, however, other polymers capable of binding the active components of the composition can also be used.

Through the desired binding of gaseous ammonia or gaseous

Hydrogen sulfide is also removed from malodorous substances, making the composition suitable for deodorising locations with malodorous odors. For example, open-air toilets, urinals, bridge underpasses, subway stations, sports facilities, fitness studios or stairs in hallways etc. come into consideration. In addition, it is also possible to deodorize waste containers or laboratories, in which gaseous NH ₃ , H ₂ S, NOx and / or S0 ₂ can also be formed.

In addition to and instead of a binder, the composition can also be a

Solidifying agents are added so that they act as a gel on surfaces, for example floors or walls of the object to be treated can be applied. In a further preferred embodiment, the composition is provided as a gel, granules, liquid or hardened solid for treating the object.

For example, the granules can be used in the form of small grains as a component of cat litter, as a component of baby diapers or as an additive for a barn floor. In addition, the composition can also be applied to straw, wood shavings, cat litter or other stable floor coverings.

In order to achieve sufficient strength, the person skilled in the art can, for a gel or a solid, the appropriate amounts of the suitable components of the

Determine and use the composition yourself.

The present invention preferably relates to a method for neutralizing or reducing gaseous ammonia, gaseous hydrogen sulfide, gaseous nitrogen oxides and / or gaseous sulfur dioxide in stables for keeping livestock.

As a result, the composition is particularly suitable for improving the

Barn climates for animal husbandry, especially cattle, pig husbandry,

Poultry farming etc. For example, a reduction in ammonia is clearly measurable. However, the method is also suitable for reducing the concentration of

Hydrogen sulfide, nitrogen oxides or sulfur dioxide. One has

Combination of an organic acid (or its salts) together with a mixture of highly esterified and / or highly methylated pectins for the reduction of gases in stables has been found to be particularly effective if one such

Compared to a composition with low ester pectins. Mixtures with highly esterified and / or highly methylated pectins are preferably used, in which the degree of esterification is> 50% and / or degree of methylation> 50%. Mixtures of highly esterified pectins or highly methylated pectins with low esterified or low methylated pectins are also conceivable. The proportion of highly esterified pectins or highly methylated pectins in the composition is preferably higher in the mixture than the proportion of low esterified or low methylated pectins.

By demonstrably reducing ammonia and other gases in the

Breathing atmosphere of the stables becomes well-being and ultimately that

Performance of farm animals improved. This has a particularly lasting effect on dairy farming, which is a significant source of farmers' income. Furthermore, the composition according to the invention provides important contribution to avoiding environmental emissions, which are caused, for example, by the

Cattle farming or the spreading of manure on fields. The composition according to the invention is thus suitable as a climate-effective means of reducing the emission of gases such as ammonia as an indirect greenhouse gas into the atmosphere.

Last but not least, the house climate influences the well-being and performance of the animals. The minimum required air exchange rate (required air mass flow) is based on the heat flow, water vapor and carbon dioxide balance (DIN 18910-1, 2004), whereby it is generally determined by the heat balance in the summer situation and by the water vapor balance in the winter situation . In freely ventilated stables

Minimum air rate exceeded in most cases, often by a multiple. For a number of compounds such as ammonia (NH ₃ ), methane (CH ₄ ), carbon dioxide (C0 ₂ ), dust and bio-aerosols (bacteria, viruses, fungi, pollen etc.) there are limit values that must be observed. The measurement of gas emissions, for example of gaseous ammonia (NH ₃ ) and / or gaseous hydrogen sulfide (H ₂ S) and / or gaseous nitrogen oxide (NOx) and / or gaseous sulfur dioxide (S0 ₂ ), can be determined using the following four methods, for example :

1. Measurement of the air volume flow (m ³ SY ¹ ) and the difference of the

Concentrations of the substances of interest inside and outside the

Building (mg m ³ ).

2. T racer ratio method: Controlled release of a tracer (GH ¹ ) and measurement of the concentrations of the tracer and the substances of interest inside and outside the building (mg m ³ ).

3. Measurement of the concentration of the substances of interest as well as the wind direction and wind speed in the immediate vicinity of the barn building (also called micrometeorological method).

4. Measurement of the material input in the area of the barn building with collectors (so-called passive collectors).

It is preferred to determine the emission flow from the product of the air volume flow and the difference in the gas concentration inside and outside the building, since the measurement of the air volume flow also provides a parameter for characterizing the house climate. The determination of the air volume flow of ventilated buildings is possible with different methods (e.g. accounting method, tracer method, direct Airflow measurement, indirect airflow measurement). The choice of the suitable measurement method and the determination of the individual parameters are familiar to the person skilled in the art in order to determine the effect of the composition according to the invention on the emission of NH ₃ , H ₂ S, NOX and / or S0 ₂ gases.

Against this background, the composition according to the invention is in several

Points advantageous, i.a. since they:

- consists mainly or entirely of natural ingredients and thus

is environmentally friendly,

- is harmless to humans and animals,

in animal breeding has numerous positive effects on animal fattening

(Improvement of the stable climate and disease resistance),

- has a very good biodegradability,

- the gases are permanently neutralized and not just masked,

simple and inexpensive to manufacture and easy to use in practice, can be easily disposed of or dismantled,

- Can be processed or used as fertilizer or biogas.

The present invention relates not only to a method of neutralization or

Reduction of harmful odors or of gases, in particular of gaseous ammonia (NH ₃ ) and / or gaseous hydrogen sulfide (H ₂ S) and / or gaseous nitrogen oxide (NOx) and / or gaseous sulfur dioxide (S0 ₂ ), but also a composition aimed at it , always with the individual components as described above. In particular, the composition according to the invention contains an organic acid with preferably 1 to 9 carbon atoms, preferably selected from the group consisting of acetic acid, formic acid, citric acid, lactic acid, propionic acid and derivatives modified therefrom. In addition, the composition according to the invention can comprise at least one inorganic acid, preferably phosphoric acid, sulfuric acid, carbonic acid or hydrochloric acid, instead of the organic acid or in addition to the organic acid.

The present invention also relates to the use of such a composition for neutralizing or reducing harmful gases, in particular

gaseous ammonia (NH ₃ ) and / or gaseous hydrogen sulfide (H ₂ S) and / or gaseous nitrogen oxide (NOx) and / or gaseous sulfur dioxide (S0 ₂ ) in agriculture, especially in animal husbandry, in the fish industry, in industrial plants, in Chemical or petrochemical plants, in sewage treatment plants, landfills, sewers and / or in affected closed buildings, especially in stables for animal fattening, kitchens, old people's homes, fitness studios, sports facilities, toilets or

Treatment of open spaces or other objects containing NH ₃ and / or H ₂ S, on which gaseous NH ₃ and / or gaseous H ₂ S occurs. As such, the composition according to the invention is also suitable for controlling odors caused by NH ₃ and / or H ₂ S gas, in particular in locations where unpleasant smells predominate, for example in sanitary facilities, toilets, sewers, sewage treatment plants etc. As such, the

Composition according to the invention also as a deodorant or perfume.

Brief description of the drawings:

Figure 1 describes the test results for the determination of ammonia in the stables of a rabbit farm. The experiments were carried out with adult animals (shortly before slaughter) of a rabbit breed. The log data for the example tested NH ₃ gas in the interior of the stables (black bars) and in the outside air (hatched bars) are shown over a period of 24 hours by treatment with a composition corresponding to Example 1. Also the other gases such as H ₂ S, NOx and / or S0 ₂ could be reduced (not shown).

Figure 2 shows effectiveness studies in a comparison between highly esterified, highly methylated (HM) and low esterified, low methylated (LM) pectins. Different products 1 6 are used, which include different pectin mixtures.

Degree of esterification of product 1-3: DE 20-30 (low esterification; LM)

Degree of esterification of product 4-6: DE 73 (highly esterified; HM)

Ammonia, dust, odor and physical parameters and measurements were taken in accordance with DIN 15259 in rabbit, horse and pig stables. The FTIR method was used as the measurement method, carried out by LUFA Nord-West (DE). The sampling facilities were carried out according to VDI 2066, the measurements according to DIN EN 13284-1.

The data shows that highly esterified, highly methylated pectins (DE 73; HM) have a higher efficiency than low esterified, low methylated pectins (DE 20-30; LM). The comparative data show that products 4 - 6 with high

Degree of esterification are significantly more active than products 1 - 3, which contain low-esterified pectins. The data were collected in different rabbit, horse and

Pig stables and obtained with the same application method in order to ensure the same test conditions as possible.

Figure 3 shows an example of the effectiveness of the composition based on the measurement of ammonia in animal stalls. The NH ₃ emissions were measured in different pig stables, each with 80 animals. The one labeled "left"

Animal housing served as a control. The composition according to the invention (= product) was used in the barn labeled "right". A significant reduction in NH ₃ emissions of approximately 85% was achieved.

FIG. 4 shows the effectiveness of the composition according to the invention (= product) on the gas and odor reduction of a test stall (with pigs) in comparison to a series of control measurements which were carried out with pure water. in the

Compared to the control, an effectiveness of over 90% in gas reduction is achieved if the composition according to the invention is used. The animal smell caused by pig breeding in the test stall (right stall) was clearly perceptible to humans compared to water controls. As expected, the water controls showed no odor reduction.

WAYS OF CARRYING OUT THE INVENTION:

The invention is explained in more detail in the examples below.

Example 1 :

Composition for the neutralization of NH ₃ , H ₂ S, NOx and S0 ₂ in the stable air of stables for livestock husbandry

1. 100 g of pectin (Fresh RB) is dissolved in 450 ml of preheated (40-60 ° C.) distilled water using a high-speed mixer (IKA, Eurostar 20 "high speed") and homogenized.

2. 40 g of orange peels (Cpkelco, lille skensved, DK) are slowly added to the mixture and mixed.

3. 75 ml of acetic acid (Merck, item no. 3699010, conc. 60%), 150 ml

Citric acid (Merck, item number A15729025), 5 ml sulfuric acid (Merck, Article no. 23145000, conc. 62%) are added and stirred briefly for 10 seconds. 4. The remaining water (10 ml) is added and briefly stirred for 5 seconds.

In addition to an organic acid, a pectin mixture (Fresh RB and orange peel) is used, which contains highly esterified pectins. The

Composition can be fed directly to a room air system and has been shown to reduce gaseous NH ₃ , H ₂ S, NOx and S0 ₂ in the room air. This was tested in stables for cattle farming and

Rabbit farming.

With this composition is after an analysis of 10 different

Test stalls to determine an NH ₃ , H ₂ S, NOx and S0 ₂ reduction and odor reduction between 71 and 88%. The use of a combination of a mixture of highly esterified pectins and an organic acid is therefore extremely effective.

A washer was used to treat the interior walls. The results of the study are summarized in FIG. 1. The better effectiveness of the highly esterified or highly methylated pectins compared to low-esterified or low-methylated pectins can be seen in FIG. 2.

Example 2:

Composition for neutralizing NH ₃ , H ₂ S, NOx and S0 ₂ when spreading liquid manure and on landfills

The composition according to the invention is produced here as follows:

3. 75 ml of acetic acid (Merck, item no. 3699010, conc. 60%), 150 ml

Citric acid (Merck, article number A15729025), 5 ml sulfuric acid (Merck, article number 23145000, conc. 62%) are added and stirred briefly for 10 seconds.

4. The remaining water (10 ml) is added and briefly stirred for 5 seconds. The aqueous dispersion can be sprayed directly onto the manure or before

Spreading can be mixed with the manure. Alternatively, it can be sprayed directly onto the surface of the landfill.

With this application, a gas reduction of 70-85% is achieved with a simultaneous noticeable reduction in odor.

Example 3:

Composition for neutralizing NH ₃ , H ₂ S, NOx and S0 ₂ for

Use on walls / ceilings in contaminated rooms

The composition according to the invention is produced here as follows:

1. 120 g of pectin (Genu Phresh 30) is distilled in 550 ml of preheated (40-60 ° C). Dissolve and homogenize water with a high speed mixer (IKA, Eurostar 20 "high speed").

2. 75 ml acetic acid (Merck, item no. 3699010, conc. 60%), 200 ml

Citric acid (Merck, item number A 15729025) are added and stirred briefly for 10 seconds.

3. The remaining water (55 ml) is added and briefly stirred for 5 seconds.

There is a reduction in the NH ₃ , H ₂ S, NOx and S0 ₂ emissions of

determine at least 70%.

Example 4:

Composition for neutralizing NH ₃ , H ₂ S, NOx and S0 ₂ when spreading liquid manure and on landfills to form a foam layer.

This composition according to the invention is produced as follows:

1. 120 g of pectin (Fresh RB) is distilled in 450 ml of preheated (40-60 ° C).

Dissolve and homogenize water with a high speed mixer (IKA, Eurostar 20 "high speed").

2. 200 ml of acetic acid (Merck, item no. 3699010, conc. 60%), 100 ml

Citric acid (Merck, article number A 15729025) are added and stirred briefly for 10 seconds.

3. The remaining water (55 ml) is added and stirred briefly for 5 seconds. In order to form a foam-forming gel-like mass, after adding the water, 2000 microliters of alkylopolyglucosides are added to the composition mentioned above

Foam agent added.

It can be sprayed directly onto the liquid manure or directly onto the surface of the landfill and after a short time forms a homogeneous foam that remains stable for several hours or days and the disturbing NH ₃ -, H ₂ S-, NOx- and / or S0 ₂ gases like one

Absorbs sponge and is chemically neutralized.

An odor reduction of 74-85% and a gas emission reduction of 71-91% can be achieved (see Figures 3 and 4).

The compositions according to the invention can be used with generally known pressure sprayers or foam sprayers. Alternatively, nozzle systems or nebulization systems can also be used.

Of course, the invention is not limited to that described and illustrated

Embodiments limited. Changes to the various components or replacements with technical equivalents are possible at any time, provided they remain within the scope of the claimed protection request.

Claims

Claims:

1. method for neutralizing or reducing odors or gases,

in particular gaseous ammonia (NH ₃ ) and / or gaseous

Hydrogen sulfide (H ₂ S) and / or gaseous nitrogen oxide (NOx) and / or gaseous sulfur dioxide (S0 ₂ ) by using a composition comprising the following components:

a) pectins or a mixture of pectins,

b) at least one organic acid or salts thereof, characterized in that the pectins are highly esterified or highly methylated pectins or the mixture of pectins contains highly esterified and / or highly methylated pectins.

2. The method according to claim 1, characterized in that in the

Highly esterified pectins are used, whose

Degree of esterification is> 50%.

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

Highly methylated pectins are used, whose

Degree of methylation is> 50%.

4. The method according to any one of claims 1 to 3, characterized in that the proportion of highly esterified and / or highly methylated pectins in the

Composition is greater than the proportion of low-esterified and / or low-methylated pectins.

5. The method according to any one of claims 1 to 3, characterized in that the ratio of the highly esterified or highly methylated pectins to the

low-esterified or low-methylated pectins is> 1: 1, preferably> 2: 1, preferably> 3: 1.

6. The method according to any one of claims 1 to 5, characterized in that the composition additionally contains one or more of the following components:

c) at least one inorganic acid or its salts and mixtures thereof,

d) additional polysaccharides,

e) modified polymers, f) silicates (Si0 ₂ ),

g) bentonites or zeolites,

h) polyvinyl alcohol.

7. The method according to claim 1, characterized in that with the

Composition a treatment of an object takes place, which is the object

- a solid, a gas and / or a liquid,

- waste water or sewage sludge,

- manure or waste,

- an open or at least partially closed room,

- a stable for animal husbandry,

- a pool, a landfill and / or an open space,

- a wastewater treatment plant

These and other objects, which an NH ₃ - are subjected to ₂ S-, NOx and / or S0 ₂ pollution, H or where gaseous NH _3, H ₂ S, NO x and / or S0 ₂ is produced.

8. The method according to claim 1, characterized in that the treatment of the object is carried out by spraying, atomizing, applying, introducing or mixing with the composition in aqueous, viscous or solid form.

9. The method according to any one of claims 1 to 8, characterized in that the composition is in the form of an aqueous dispersion with a proportion of a) 1 to 12% by weight of pectin or a mixture of polysaccharides and b) 1 to 25% by weight. -% of organic acid or a mixture of organic acids, and a residual content for 100% by weight of solvent, preferably water.

10. The method according to any one of claims 1 to 9, characterized in that the pectin or the mixture of pectins are obtained from citrus fruits, sugar beets or fruit stalks of sunflowers, preferably from the peels of apples, quinces, oranges, lemons, apricots, cherries.

11. The method according to any one of claims 1 to 10, characterized in that the pectin consists predominantly of aD-galacturonic acid with the following basic structure, including esterified, acetylated or pectin derivatives based thereon:

12. The method according to any one of claims 1 to 11, characterized in that the organic acid is acetic acid, formic acid, citric acid, propionic acid, lactic acid and / or derivatives modified therefrom.

13. The method according to claim 6, characterized in that as inorganic

Acid carbonic acid, phosphoric acid, sulfuric acid and / or hydrochloric acid is used in the composition.

14. The method according to any one of claims 1 to 13, characterized in that the composition additionally contains a foam-forming agent, preferably at least one water-soluble foam-forming natural protein.

15. The method according to any one of claims 1 to 14, characterized in that the composition is provided as a gel, granules, liquid or hardened solid for treating the object.

16. Composition for neutralizing or reducing gases, in particular gaseous ammonia (NH ₃ ) and / or gaseous hydrogen sulfide (H ₂ S) and / or gaseous nitrogen oxide (NOx) and / or gaseous sulfur dioxide (S0 ₂ ), comprising one or more of the Components like in one of the

Claims 1 to 15 defined.

17. Use of a composition according to claim 16 for the neutralization or reduction of gaseous ammonia (NH ₃ ) and / or gaseous

Hydrogen sulphide (H ₂ S) and / or gaseous nitrogen oxide (NOx) and / or gaseous sulfur dioxide (S0 ₂₎ in agriculture, in _particular, animal breeding, in the fishing industry, in industrial plants, in chemical plants, or petrochemical industry, in water treatment plants, Landfills, sewers and / or in affected closed buildings, especially in stables for animal fattening, kitchens, fish processing industry, gyms, sports facilities, toilets or Treatment of open spaces containing NH ₃ and / or H ₂ S, such as liquid manure spreading or outdoor toilets.