STORAGE STABLE MIXTURES, METHODS FOR IMPROVING COMPOUND RETENTION, AND USE OF Rice SHEET AND / OR Rice FRANT

Abstract

The present invention relates to storage stable mixtures, methods of improving compound retention and the use of rice husk and / or rice bran in enhancing compound retention, in particular to improved formulations of propylene glycol mononitrates and derivatives thereof, and the production of such formulations.

Description

[0001] This application is a divisional application of Chinese Patent Application No. 201880081353.5 (PCT / EP2018 / 085205) with a filing date of December 17, 2018. Technical Field

[0002] The present invention relates to storage-stable mixtures comprising propylene glycol mononitrate and its derivatives, as well as the production and use of such forms. Background Art

[0003] The temperature of the air surrounding the earth is rising, a process known as global warming. One of the main focuses for reducing this warming effect is to reduce the amount of greenhouse gases emitted into the atmosphere. Greenhouse gases are emitted from several different natural and artificial sources; however, the two most significant sources are the agricultural industry and the fossil fuel industry. In agriculture, ruminants, especially cattle, are major contributors to biogenic methane formation, and it is estimated that preventing methane formation by ruminants would almost stabilize the methane concentration in the atmosphere.

[0004] It has been reported that 1,3-propylene glycol mononitrate (hereinafter referred to as propylene glycol mononitrate, or PDMN) and its derivatives are very effective in reducing methane formation in ruminants without affecting microbial fermentation in a manner harmful to the animals (WO2012 / 084629).

[0005] However, it has been found that under conventional storage conditions, especially when absorbed onto standard carrier systems commonly used in the feed industry, propylene glycol mononitrate and its derivatives cannot be effectively retained. In addition, it has been found that incorporating propylene glycol mononitrate absorbed on silica into a standard feed premix even further reduces the storage stability of the said standard feed premix. However, for the feed industry, the lack of retention of the active substance in the conventional product form is highly undesirable, because accordingly, without undue burden (i.e., complex packaging, analysis of the active substance content before use, or over-dosing), appropriate dosing is not possible. In addition, all of these methods increase significant additional use costs, which are not easily acceptable to the end user.

[0006] Therefore, there is a continuing need for such product forms and methods that overcome the above problems by enabling storage over a period of time without significant loss of the active substance (i.e., propylene glycol mononitrate or its derivatives). Summary of the Invention

[0007] Surprisingly, it has now been found that adding rice husk (also known as paddy husk) and / or rice bran to propylene glycol mononitrate in the following forms: in solution form in propylene glycol or in powder formulation form of propylene glycol mononitrate absorbed on silica, and after incorporating the powder formulation into a mineral premix, significantly increases the retention of propylene glycol mononitrate.

[0008] Accordingly, in a first aspect, the present invention relates to a storage-stable mixture (I), said storage-stable mixture (I) comprising:

[0009] (1) a compound of formula (I)

[0010]

[0011] wherein

[0012] n is an integer from 1 to 15,

[0013] R 1 is selected from the group consisting of: H, C 1 -C 6 alkyl, phenyl, -OH, -NH 2 , -CN, -COOH, -O(C═O)R 8 , -NHC(═O)R 8 , SO 2 NHR 8 , and -ONO 2 , and

[0014] R 8 is C 1 -C 6 alkyl, phenyl, pyridyl (such as preferably 2-pyridyl)

[0015] provided that when n > 3, the hydrocarbon chain may be interrupted by -O- or -NH-, and

[0016] (2) rice husk and / or rice bran.

[0017] In all embodiments of the present invention, particularly preferred compounds of formula (I) are those wherein n is an integer between 3 and 9 and R 1 is OH, COOH or -ONO 2 provided that if n is 4, the hydrocarbon chain may be interrupted by –NH-, for example especially a compound of formula R 1 -(CH 2 ) 2 -NH-(CH 2 ) 2 -ONO 2 Even more preferred are compounds of formula (I) wherein n is an integer between 3 and 9, and R1 is OH, COOH or -ONO 2 。

[0018] Even more advantageous compounds of formula (I) according to the invention are propylene glycol mononitrate (CAS No.: 100502-66-7), 9-nitrooxynonanol, 5-nitrooxypentanoic acid (CAS 74754-56-6), 6-nitrooxyhexanoic acid (CAS 74754-55-5), bis(2-hydroxyethyl)amine dinitrate (CAS20830-49-3), 1,4-bis-nitrooxybutane (CAS 3457-91-8) and 1,5-bis-nitrooxypentane (CAS 3457-92-9). The most preferred compound of formula (I) to be used according to the invention is propylene glycol mononitrate.

[0019] In a preferred embodiment, based on the total weight of the storage-stable mixture (I), the amount of the compound of formula (I) in the storage-stable mixture (I) is at least 0.1% by weight, more preferably at least 0.25% by weight, and most preferably at least 0.5% by weight. More preferably, based on the total weight of the storage-stable mixture (I), the amount of the compound of formula (I) in the storage-stable mixture (I) is selected from the range of 0.1 to 40% by weight, most preferably from the range of 0.25 to 25% by weight, for example in the range of 0.5 to 20% by weight. Other suitable ranges include 0.1 to 10% by weight, 0.25 to 10% by weight, 0.1 to 5% by weight and 0.25 to 5% by weight.

[0020] In another preferred embodiment, based on the total weight of the storage-stable mixture (I), the amount (in total) of rice husk and / or rice bran in the storage-stable mixture (I) is at least 10% by weight, more preferably at least 15% by weight, and most preferably at least 20% by weight. More preferably, based on the total weight of the storage-stable mixture (I), the amount of rice husk and / or rice bran in the storage-stable mixture (I) is selected from the range of 10 to 95% by weight, most preferably from the range of 15 to 95% by weight, for example in the range of 20 to 95% by weight.

[0021] As used herein, the term "storage-stable" means that the retention of the compound of formula (I) in the mixture according to the invention is improved as compared to the corresponding mixture without rice husk and / or rice bran. Preferably, the retention is improved by at least 10%, more preferably at least 20%, and most preferably at least 30% as compared to the corresponding mixture without any rice husk and / or rice bran.

[0022] In all embodiments of the present invention, the weight ratio (w / w) of rice husk and / or rice bran (in total) to the compound of formula (I) is preferably at least 1, preferably at least 5, more preferably at least 10, most preferably at least 25, for example at least 50.

[0023] Even more advantageously, in all embodiments of the present invention, the weight ratio (w / w) of rice husk and / or rice bran (in total) to the compound of formula (I) ranges from 200:1 to 1:1 (i.e., 200 parts of rice husk and / or rice bran relative to 1 part of the compound of formula (I) to 1 part of rice husk and / or rice bran relative to 1 part of the compound of formula (I)), more preferably in the range of 150:1 to 5:1, and most preferably in the range of 100:1 to 25:1. Other suitable ranges are 100:1 to 10:1, 100:1 to 15:1, 100:1 to 30:1, or 100:1 to 35:1.

[0024] In an advantageous embodiment, the compound of formula (I) is incorporated into the storage mixture (I) in the form of a solution in an edible solvent.

[0025] Accordingly, the present invention also relates to a storage-stable mixture (I), which is a storage-stable mixture (1-L) and contains

[0026] (b1) a liquid preparation (A L ), which contains

[0027] (i) the compound of formula (I)

[0028]

[0029] wherein

[0030] n is an integer from 1 to 15;

[0031] R 1 is selected from the group consisting of: H, C 1 -C 6 alkyl, phenyl, -OH, -NH 2 , -CN, -COOH, -O(C═O)R 8 , -NHC(═O)R 8 , SO 2 NHR 8 , and -ONO 2 ; and

[0032] R 8 is C 1 -C 6 alkyl, phenyl, pyridyl (such as preferably 2-pyridyl); provided that when n > 3, the hydrocarbon chain may be interrupted by -O- or -NH-, and

[0033] (ii) An edible solvent, and

[0034] (b2) Rice husk and / or rice bran.

[0035] As used herein, the term "liquid preparation" refers to a preparation (i.e., a solution in which the compound of formula (I) is completely dissolved) that is liquid at ambient temperature (i.e., about 22 °C).

[0036] The term "edible solvent" refers to an oil commonly used in feed applications that is suitable for dissolving the compound of formula (I). Preferred edible solvents for use in the liquid preparations according to the invention are propylene glycol, low erucic acid rapeseed oil, corn oil, rapeseed oil, sunflower oil, medium-chain triglycerides (MCT), soybean oil, water and glycerol, and mixtures thereof. The most preferred edible solvents for use in the liquid preparations according to the invention are propylene glycol and water and any mixtures thereof.

[0037] In the liquid preparation according to the invention, the amount of the compound of formula (I) is preferably selected from the range of 1 to 50% by weight, more preferably from the range of 5 to 40% by weight, most preferably from the range of 10 to 30% by weight, for example in the range of 10 to 25% by weight, based on the total weight of the liquid preparation.

[0038] Based on the total weight of the storage-stable mixture (1-L), the amount of the liquid preparation (A L ) in the storage-stable mixture (1-L) is preferably at least 5% by weight, more preferably at least 10% by weight. More preferably, based on the total weight of the storage-stable mixture (1-L), the amount of the liquid preparation (A L ) in the storage-stable mixture (1-L) is selected from the range of 5 to 85% by weight, most preferably from the range of 5 to 60% by weight, for example in the range of 5 to 50% by weight.

[0039] Based on the total weight of the storage-stable mixture (1-L), the amount of rice husk and / or rice bran (in total) in the storage-stable mixture (1-L) is preferably at least 20% by weight, more preferably at least 30% by weight, most preferably at least 40% by weight. More preferably, based on the total weight of the storage-stable mixture (1-L), the amount of rice husk and / or rice bran (in total) in the storage-stable mixture (1-L) is selected from the range of 20 to 95% by weight, most preferably from the range of 30 to 95% by weight, for example in the range of 40 to 95% by weight.

[0040] Based on the total weight of the liquid preparation, the amount of the edible solvent in the liquid preparation according to the invention is preferably selected in the range of 50 to 99% by weight, more preferably in the range of 60 to 95% by weight, most preferably in the range of 70 to 90% by weight, for example in the range of 75 to 90% by weight.

[0041] In a particularly advantageous embodiment, the liquid formulation (A L ) consists essentially of (i) a compound of formula (I) and (ii) an edible solvent.

[0042] A very specific liquid formulation according to the invention is the liquid formulation (A L ), which is a liquid formulation (B L ) consisting essentially of:

[0043] (i) 5 to 25% by weight of propylene glycol mononitrate, based on the total weight of the liquid formulation, and

[0044] (ii) at least 75% by weight of propylene glycol or water, preferably propylene glycol, based on the total weight of the powder formulation.

[0045] The term "liquid formulation consisting essentially of" means that the sum of all weight percentages of the listed components of the liquid formulation adds up to 100% by weight (i.e., the amount of the edible solvent is adjusted accordingly), provided, however, that the presence of minor amounts of impurities or water (moisture) in the liquid formulation according to the invention is not excluded, for example, present in an amount of less than 7% by weight, preferably less than 5% by weight, more preferably less than 3% by weight, and the impurities / water (moisture) are introduced via the corresponding raw materials or methods used.

[0046] In another advantageous embodiment, the compound of formula (I) in the storage-stable mixture (I) is used in the form of a powder formulation comprising the compound of formula (I) and silica.

[0047] Accordingly, the present invention also relates to a storage-stable mixture (I), which is a storage-stable mixture (1-S) comprising:

[0048] (a1) a powder formulation (A), the powder formulation (A) comprising

[0049] (i) a compound of formula (I)

[0050]

[0051] wherein

[0052] n is an integer from 1 to 15,

[0053] R 1 is selected from the group consisting of: H, C 1 -C 6 alkyl, phenyl, -OH, -NH 2 , -CN, -COOH, -O(C═O)R 8 , -NHC(═O)R 8 , SO 2NHR 8 and -ONO 2 and

[0054] R 8 is C 1 -C 6 alkyl, phenyl, pyridyl (such as preferably 2-pyridyl) provided that when n > 3, the hydrocarbon chain may be interrupted by -O- or -NH-, and

[0055] (ii) silica, and

[0056] (a2) rice husk and / or rice bran.

[0057] Using a powder formulation instead of a liquid formulation further improves the retention of the compound of formula (I).

[0058] Based on the total weight of the storage-stable mixture (1-S), the amount of the powder formulation (A) in the storage-stable mixture (1-S) is preferably at least 1% by weight, more preferably at least 5% by weight. More preferably, based on the total weight of the storage-stable mixture (1-S), the amount of the powder formulation (A) in the storage-stable mixture (1-S) is selected in the range of 1 to 85% by weight, most preferably in the range of 5 to 60% by weight, for example in the range of 5 to 50% by weight.

[0059] Based on the total weight of the storage-stable mixture (1-S), the amount (in total) of rice husk and / or rice bran in the storage-stable mixture (1-S) is preferably at least 10% by weight, more preferably at least 15% by weight, most preferably at least 20% by weight. More preferably, based on the total weight of the storage-stable mixture (1-S), the amount (in total) of rice husk and / or rice bran in the storage-stable mixture (1-S) is selected in the range of 10 to 99% by weight, most preferably in the range of 15 to 95% by weight, for example in the range of 20 to 95% by weight.

[0060] The weight ratio (w / w) of rice husk and / or rice bran to the powder formulation in the storage-stable formulation (1-S) is preferably selected in the range of 50:1 to 1:10, preferably in the range of 50:1 to 1:5, more preferably in the range of 40:1 to 1:2, most preferably in the range of 30:1 to 1:1 or 20:1 to 1:1. Other advantageous ratios include 15:1 to 1:1 or 10:1 to 1:1.

[0061] As used herein, the term "powder formulation" refers to a solid formulation in the form of a free-flowing powder (i.e., a free-flowing powder).

[0062] In the powder preparation according to the present invention, the amount of silica is generally selected from the range of 25% to 90% by weight, such as the range of 30% to 90% by weight, 35% to 90% by weight or 40% to 90% by weight. Further preferred amounts include 60 to 85% by weight and 70 to 85% by weight.

[0063] In all embodiments of the present invention, the powder preparation (A) is preferably the powder preparation (B), and the powder preparation (B) contains

[0064] (i) Based on the total weight of the powder preparation, at least 0.1% by weight of the compound of formula (I), and

[0065] (ii) Based on the total weight of the powder preparation, at least 25% by weight of silica, and

[0066] (iii) Based on the total weight of the powder preparation, 0% to 40% by weight of edible oil.

[0067] The term "edible oil" refers to oils commonly used in feed applications. Preferred edible oils to be used in the powder preparation according to the present invention are propylene glycol, low erucic acid rapeseed oil, corn oil, rapeseed oil, sunflower oil, medium-chain triglycerides (MCT), soybean oil, water and glycerol, and mixtures thereof. The most preferred edible oil to be used in the powder preparation according to the present invention is propylene glycol or water.

[0068] The powder preparation according to the present invention may also contain a small amount of conventional additives, which are commonly used in the preparation of powder preparations for feed applications.

[0069] Therefore, in another embodiment, the present invention relates to a powder preparation (B), and the powder preparation (B) is a powder preparation (C), and the powder preparation (C) further contains (iv) based on the total weight of the preparation, 0% to 10% by weight of additives.

[0070] The powder preparation according to the present invention is generally prepared by the following method: in the method, the compound of formula (I) is optionally diluted in edible oil and further optionally mixed with one or more additives, and sprayed onto silica or mixed with silica. Preferably, the powder preparation according to the present invention is prepared by dissolving the compound of formula (I) in edible oil, preferably at ambient temperature (i.e., about 22 °C) or slightly elevated temperature (up to 40 °C) before spraying onto silica or mixing the resulting solution with silica.

[0071] Alternatively, a powder preparation according to the present invention can be prepared by the following method: In the method, the compound of formula (I), optionally in the presence of edible oil and further optionally mixed with one or more additives, is diluted in an organic solvent suitable for preparing feed products (such as dichloromethane), and then the dilution is sprayed onto silica or mixed with silica, and thereafter the organic solvent is evaporated.

[0072] In a particularly advantageous embodiment, the powder preparation according to the present invention is an adsorbate.

[0073] For the purposes of the present invention, an adsorbate is in particular a preparation in which at least 10% by weight, in particular at least 20% by weight, preferably at least 30% by weight, particularly preferably at least 40% by weight, in particular at least 50% by weight of the components to be adsorbed (i.e. all components of the adsorbate excluding silica, i.e. the compound of formula (I), and optionally edible oil and additives) are present in the internal pore volume of the silica. The internal pore volume of the carrier can be determined as the void volume by the DPB (dibutyl phthalate) method DIN 53601.

[0074] Particularly preferably, an adsorbate is given in which at least 60% by weight, preferably at least 70% by weight, in particular at least 80% by weight of the adsorbate is present in the internal pore volume of the silica.

[0075] Silica is a well-known carrier material in the feed and food industries and refers to white microspheres of amorphous silica (also known as silica) and can be available in a variety of particle sizes. A particularly suitable silica to be used in the powder preparation according to the present invention is amorphous precipitated silica, such as Ibersil D-250 from the IQE Group, Sipernat 2200 from Evonik, or Tixosil 68 from Solvay, Zeofree 5170 from J.M. Huber Cooperation or Newsil C50 from Quechen Silicon Chemical Co Ltd.

[0076] Preferably, the average particle size D(v,0.5) of the silica used for the powder preparation according to the present invention is > 200 μm. More preferably, the particle size of the silica is selected from the range of 200 μm to 400 μm, most preferably from the range of 250 μm to 380 μm, even more preferably from the range of 300 μm to 360 μm.

[0077] The particle sizes given herein were measured by a Malvern Master Sizer 2000 in accordance with the recommendations for particle size analysis by the laser diffraction method (laser diffraction light scattering) outlined in ISO 13320-1. During this laser diffraction measurement, a focused laser beam passes through the particles. The particles scatter light at angles inversely proportional to their size. The angular intensity of the scattered light is then measured by a series of photosensitive detectors. The plot of scattered intensity versus angle is the main source of information used to calculate the particle size. To measure the silica according to the present invention, a dry powder feeder (Malvern Scirocco) was used.

[0078] Advantageously, the silica used in the powder formulation according to the present invention also exhibits a pH in the range of from pH 6 to 8.5 (measured as a 1% suspension in distilled water), for example preferably in the range of from pH 7 to 8.

[0079] As used herein, the term 'additive' refers to additives commonly used in the preparation of powder formulations for feed applications. Preferred additives to be used in the powder formulation according to the present invention are thickeners, such as in particular gums or cellulose derivatives, such as xanthan gum, karaya gum and / or ethyl cellulose.

[0080] A particularly advantageous powder formulation according to the present invention is powder formulation (A), which is a powder formulation (D) consisting essentially of:

[0081] (i) from 1% to 25% by weight, based on the total weight of the powder formulation, of a compound of formula (I), and

[0082] (ii) at least 20% by weight, based on the total weight of the powder formulation, of silica, and

[0083] (iii) from 5% to 45% by weight, based on the total weight of the formulation, of edible oil, and

[0084] (iv) from 0% to 10% by weight, based on the total weight of the powder formulation, of an additive.

[0085] An even more advantageous powder formulation according to the present invention is powder formulation (A), which is a powder formulation (E) consisting essentially of:

[0086] (i) from 2% to 20% by weight, based on the total weight of the powder formulation, of a compound of formula (I), and

[0087] (ii) at least 25% by weight, based on the total weight of the powder formulation, of silica, and

[0088] (iii) Based on the total weight of the powder formulation, 10% to 45% by weight of edible oil, and

[0089] (iv) Based on the total weight of the powder formulation, 0% to 10% by weight of additives.

[0090] A particularly preferred powder formulation according to the present invention is powder formulation (A), and the powder formulation (A) is a powder formulation (F) consisting essentially of the following:

[0091] (i) Based on the total weight of the powder formulation, 2% to 15% by weight of the compound of formula (I), and

[0092] (ii) Based on the total weight of the powder formulation, at least 40% by weight of silica, and

[0093] (iii) Based on the total weight of the powder formulation, 20% to 40% by weight of edible oil, and

[0094] (iv) Based on the total weight of the powder formulation, 0% to 5% by weight of additives.

[0095] In all embodiments of the present invention, the compound of formula (I) preferably has a boiling point below 250 °C at 760 Torr, preferably in the range between 100 °C and 200 °C at 760 Torr.

[0096] The compound of formula (I) is known and commercially available or can be prepared analogously to the methods disclosed, for example, in WO2012 / 084629.

[0097] A particularly advantageous compound of formula (I) to be used in the powder formulation according to the present invention is a compound in which n is an integer between 3 and 9, and R 1 is OH, COOH or -ONO 2 , provided that if n is 4, the hydrocarbon chain may be interrupted by -NH-, such as especially a compound of formula R 1 -(CH 2 ) 2 -NH-(CH 2 ) 2 -ONO 2 . Even more preferably, the compound of formula (I) is one in which n is an integer between 3 and 9, and R 1 is OH, COOH or -ONO 2。

[0098] Even more advantageous compounds of formula (I) for use in the powder formulations according to the invention are propylene glycol mononitrate (CAS No.: 100502-66-7), 9-nitrooxynonanol, 5-nitrooxypentanoic acid (CAS 74754-56-6), 6-nitrooxyhexanoic acid (CAS 74754-55-5), bis(2-hydroxyethyl)amine dinitrate (CAS 20830-49-3), 1,4-bis-nitrooxybutane (CAS 3457-91-8) and 1,5-bis-nitrooxypentane (CAS 3457-92-9). The most preferred compound of formula (I) for use in the powder formulations according to the invention is propylene glycol mononitrate.

[0099] A very specific powder formulation according to the invention is powder formulation (A), which is a powder formulation (G) consisting essentially of:

[0100] (i) from 2% to 15% by weight of propylene glycol mononitrate, based on the total weight of the powder formulation, and

[0101] (ii) at least 45% by weight of silica, based on the total weight of the powder formulation, and

[0102] (iii) from 20% to 40% by weight of propylene glycol, based on the total weight of the powder formulation.

[0103] The term "powder formulation consisting essentially of" means that the sum of all weight percentages of the listed components of the powder formulation adds up to 100% by weight (i.e., the amount of silica is adjusted accordingly), provided, however, that the presence of minor amounts of impurities or water (moisture) in the powder formulations according to the invention cannot be excluded, for example, in amounts of less than 7% by weight, preferably less than 5% by weight, more preferably less than 3% by weight, said impurities / water (moisture) being introduced via the corresponding raw materials or methods used and not added separately.

[0104] The powder formulations (A) to (G) having all the preferred options and definitions given herein can be additionally coated with conventional coatings in the art (such as waxes or fats). If present, such coatings are generally applied in amounts of from 5% to 50% by weight, based on the total weight of the powder form. Advantageously, the coating comprises a wax and / or a fat having a dropping point of from 30 °C to 85 °C.

[0105] As used herein, the dropping point of a material refers to the temperature (in °C) at which the material begins to melt under standard conditions. Thus, the material is heated for a long time until the heating changes the state of matter from solid to liquid. The dropping point is the temperature at which the first drop is released from the material. The determination of the dropping point is carried out as described in the standard specification DIN ISO 2176.

[0106] Particularly suitable waxes for use as coatings in the context of the present invention include organic compounds consisting of long alkyl chains; natural waxes (vegetable waxes, animal waxes), which are usually esters of fatty acids and long-chain alcohols; and synthetic waxes, which are long-chain hydrocarbons lacking functional groups.

[0107] Particularly suitable fats for use as coatings in the context of the present invention include a variety of compounds that are soluble in organic solvents and substantially insoluble in water, such as hydrogenated fats (or saturated fats), which are usually triesters of glycerol and fatty acids. Suitable fats can have a natural or synthetic origin. Unsaturated (poly)fats can be hydrogenated to obtain hydrogenated (saturated) fats.

[0108] Preferred examples of waxes and fats for use as coatings according to the present invention are glyceryl monostearate, carnauba wax, candelilla wax, sugarcane wax, palmitic acid, hydrogenated cottonseed oil, hydrogenated palm oil, and hydrogenated rapeseed oil, and mixtures thereof.

[0109] In a preferred embodiment, the powder formulations (A) to (G) having all the preferences and definitions given herein are not coated.

[0110] The term "rice husk and / or rice bran" according to the present invention refers to the outer shell of rice. Rice bran is a by-product obtained from the rice milling process, particularly during the conversion of brown rice to white rice. Rice husk (paddy husk) refers to the hard protective layer of the grain, which can be removed from the raw grain during the milling process and can also be used as rice husk powder or flour. Both rice husk and rice bran can be obtained from rice mills.

[0111] It is well known that the storage-stable mixtures (I), (1-L), and (1-S) according to the present invention and having all the definitions and preferences given herein can contain additional active substances and / or feed ingredients and / or edible oils conventionally used in the feed industry and / or feed products.

[0112] Thus, in another embodiment, the present invention relates to a storage-stable mixture (I) having all the definitions and preferences given herein, which is a storage-stable mixture (II) further comprising at least one active ingredient and / or feed ingredient and / or edible oil.

[0113] In another embodiment, the present invention relates to a storage-stable mixture (1-L) having all the definitions and preferences given herein, which storage-stable mixture (1-L) is a storage-stable mixture (2-L) further comprising (b3) at least one active ingredient and / or feed ingredient and / or (b4) edible oil.

[0114] In another embodiment, the present invention relates to a storage-stable mixture (1-S) having all the definitions and preferences given herein, said storage-stable mixture (1-S) being a storage-stable mixture (2-S), said storage-stable mixture (2-S) further comprising (a3) at least one active ingredient and / or feed ingredient and / or (a4) edible oil.

[0115] In a particularly advantageous embodiment, the storage-stable mixture (1-S) is a storage-stable mixture (3-S), said storage-stable mixture (3-S) comprising the following:

[0116] (a1) a powder preparation (A), (B), (C), (D), (E), (F) or (G), and

[0117] (a2) rice husk and / or rice bran, and

[0118] (a3) an active ingredient and / or feed ingredient, and optionally

[0119] (a4) edible oil.

[0120] In a particularly preferred embodiment, the active ingredient is selected from the group consisting of water-soluble and / or fat-soluble vitamins, trace and / or macro minerals, amino acids, and mixtures thereof.

[0121] Particularly suitable fat-soluble vitamins according to the present invention include vitamin A, vitamin D3, vitamin E and vitamin K (e.g. vitamin K3). Particularly suitable water-soluble vitamins include vitamin B12, biotin and choline, vitamin B1, vitamin B2, vitamin B6, niacin, folic acid and pantothenates (e.g. D-calcium pantothenate), and mixtures thereof.

[0122] Particularly suitable trace minerals according to the present invention include manganese (e.g. in the form of manganese oxide), zinc (e.g. in the form of zinc oxide), iron (e.g. in the form of ferrous sulfate), copper (e.g. in the form of copper sulfate), iodine (e.g. in the form of sodium iodide), selenium and cobalt, and mixtures thereof.

[0123] Particularly suitable macro minerals according to the present invention include calcium (e.g. in the form of limestone and calcium ions (calcium hydrogen phosphate, calcium pyrophosphate or calcium triphosphate), magnesium, phosphorus and sodium (e.g. in the form of sodium chloride), and mixtures thereof.

[0124] In a particularly preferred embodiment, the at least one feed ingredient is selected from the group consisting of roughage and concentrate, and mixtures thereof.

[0125] In a particularly advantageous embodiment according to the invention, the storage-stable mixture (1-S) according to the invention is a premix (1A) consisting essentially of components (a1) and (a2).

[0126] In another preferred embodiment, the storage-stable mixture (1-S) is a premix (1B) consisting essentially of:

[0127] (a1) Based on the total weight of the premix, at least 5% by weight, preferably 5% to 85% by weight, most preferably 5% to 60% by weight of a powder preparation (A), (B), (C), (D), (E), (F) or (G), and

[0128] (a2) Based on the total weight of the premix, at least 10% by weight, preferably 15% to 95% by weight, most preferably 40% to 95% by weight of rice husk and / or rice bran.

[0129] In another preferred embodiment, the storage-stable mixture (2-S) according to the invention is a premix (2A) which consists essentially of (a1) to (a3) and optionally (a4), and wherein (a3) is an additional active ingredient selected from the group consisting of water-soluble and / or fat-soluble vitamins, trace and / or macro minerals, amino acids, and mixtures thereof, provided that the sum of components (a1) to (a4) is 100% by weight.

[0130] In another preferred embodiment, the storage-stable mixture (2-S) is a premix (2B) consisting essentially of:

[0131] (a1) Based on the total weight of the premix, at least 5% by weight, preferably 5% to 20% by weight, most preferably 10% to 15% by weight of a powder preparation (A), (B), (C), (D), (E), (F) or (G), and

[0132] (a2) Based on the total weight of the premix, at least 10% by weight, preferably 15% to 70% by weight, most preferably 20% to 50% by weight of rice husk and / or rice bran, and

[0133] (a3) Based on the total weight of the premix, at least 5% by weight, preferably 20% to 80% by weight, most preferably 40% to 70% by weight of an active ingredient selected from the group consisting of water-soluble and / or fat-soluble vitamins, trace and / or macro minerals, amino acids, and mixtures thereof, and

[0134] (a4) Based on the total weight of the premix, 0% to 15% by weight, preferably 0% to 10% by weight, most preferably 0% to 5% by weight of edible oil.

[0135] It should be noted that in addition to all the preferred options given herein, particularly preferred edible oils for use in the storage-stable mixtures according to the invention are also corn oil, rapeseed oil, sunflower oil, low-erucic rapeseed oil or soybean oil and mixtures thereof, for example most preferably soybean oil.

[0136] As used herein, the term "premix" refers to a preferably homogeneous mixture of the listed ingredients, which are typically used to facilitate the uniform dispersion of the active ingredient into a larger mixture.

[0137] The term "premix consisting essentially of" means that the sum of all weight percentages of the listed ingredients of the premix adds up to 100% by weight, provided, however, that the presence of small amounts of impurities or water (moisture) in the powder formulation according to the invention cannot be excluded, for example present in an amount less than 7% by weight, preferably less than 5% by weight, more preferably less than 3% by weight, and the impurities / water (moisture) are introduced via the corresponding raw materials or methods used, rather than added separately.

[0138] All of the above-disclosed premixes can be used as such or mixed with feed products.

[0139] In addition, all of the above-disclosed premixes can be used in the production of feed products.

[0140] It is well known that the storage-stable mixture (1) according to the invention can also be a feed product.

[0141] Thus, in another preferred embodiment, the storage-stable mixture (2-S) according to the invention is a feed product (2a) consisting essentially of (a1) to (a3) and optionally (a4), and wherein (a3) is (a3 / 1) at least one additional active ingredient selected from the group consisting of water-soluble and / or fat-soluble vitamins, trace and / or macro minerals, amino acids, and mixtures thereof, and (a3 / 2) at least one feed ingredient selected from the group consisting of roughage and concentrate.

[0142] In another preferred embodiment, the storage-stable mixture (2-S) is a feed product (2b) consisting essentially of the following:

[0143] (a1) Based on the total weight of the feed product, at least 0.001% by weight, preferably from 0.001% to 10% by weight, most preferably from 0.001% to 5% by weight of powder preparations (A), (B), (C), (D), (E), (F) or (G), and

[0144] (a2) Based on the total weight of the feed product, at least 1% by weight, preferably from 1% to 20% by weight, most preferably from 1% to 10% by weight of rice husk and / or rice bran, and

[0145] (a3 / 1) Based on the total weight of the feed product, at least 0.1% by weight, preferably from 0.5% to 20% by weight, most preferably from 0.5% to 10% by weight of at least one active ingredient selected from the group consisting of water-soluble and / or fat-soluble vitamins, trace and / or macro minerals, amino acids, and mixtures thereof, and

[0146] (a3 / 2) Based on the total weight of the feed product, at least 5% by weight, preferably from 10% to 95% by weight, preferably from 20% to 90% by weight of at least one feed ingredient selected from the group consisting of roughage and concentrate feed and mixtures thereof, and

[0147] (a4) Based on the total weight of the feed product, 0% to 15% by weight, preferably 0% to 10% by weight, most preferably 0% to 5% by weight of at least one edible oil.

[0148] The terms "roughage" (also known as forage) and "concentrate feed" are well known to those skilled in the art. Roughage mainly consists of cellulosic materials such as plant stems and leaves (such as hay), introduced grasses, native grasses, green roughage, rice straw, leaves, etc.; and crude fiber (such as brewery by-products). Concentrate feed usually consists of conventional components such as mainly protein, starch and fat. Thus, concentrate feed components include, for example but not limited to, cereals such as corn, wheat, barley, rye, oats, wheat flour, etc.; oil meals such as soybean meal, sunflower oil meal, etc.; feeds of animal origin such as fish meal, meat and bone meal, animal oils (such as beef tallow, lard, bone oil, etc.).

[0149] In another embodiment, the present invention also relates to the use of rice husk and / or rice bran for enhancing the retention of a compound of formula (I) according to the present invention and having all the definitions and preferred options given herein.

[0150] In another embodiment, the present invention also relates to the use of rice husk and / or rice bran for enhancing the retention of a compound of formula (I) in a powder preparation,

[0151]

[0152] wherein

[0153] n is an integer from 1 to 15,

[0154] R 1 is selected from the group consisting of: H, C 1 -C 6 alkyl, phenyl, -OH, -NH 2 、-CN, -COOH, -O(C=O)R 8 、-NHC(=O)R 8 、SO 2 NHR 8 , and -ONO 2 , and

[0155] R 8 is C 1 -C 6 alkyl, phenyl, pyridyl (such as preferably 2-pyridyl) provided that when n>3, the hydrocarbon chain may be interrupted by -O- or -NH-, and the powder formulation comprises:

[0156] (i) a compound according to formula (I), and

[0157] (ii) silica.

[0158] Accordingly, the present invention also relates to the use of rice husk and / or rice bran for enhancing the retention (i.e., reducing evaporation) of the compound of formula (I) in the powder formulations according to the present invention, for example, especially in powder formulations (A), (B), (C), (D), (E), (F) or (G). Preferably, the retention rate is at least 70%, preferably at least 80%, most preferably at least 90%, for example, especially at least 95%.

[0159] In another embodiment, the present invention relates to a method for improving the retention (i.e., reducing evaporation) of the compound of formula (I), the method comprising mixing the compound of formula (1) with rice husk and / or rice bran. Preferably, the weight ratio (w / w) of rice husk and / or rice bran to the compound of formula (I) is at least 1, preferably at least 5, more preferably at least 10, most preferably at least 25, for example at least 50, as described above. Even more preferably, the weight ratio (w / w) of rice husk and / or rice bran to the compound of formula (I) is selected from the range of 200:1 to 1:1 (i.e., 200 parts of rice husk and / or rice bran relative to 1 part of the compound of formula (I) to 1 part of rice husk and / or rice bran relative to 1 part of the compound of formula (I)), more preferably from the range of 150:1 to 5:1, most preferably from the range of 100:1 to 25:1. Other suitable ranges are 100:1 to 10:1, 100:1 to 15:1, 100:1 to 30:1 or 100:1 to 35:1.

[0160] Accordingly, the present invention relates to a method for improving the retention of a compound of formula (I) in a powder formulation,

[0161]

[0162] wherein

[0163] n is an integer from 1 to 15,

[0164] R 1 is selected from the group consisting of: H, C 1 -C 6 alkyl, phenyl, -OH, -NH 2 , -CN, -COOH, -O(C═O)R 8 , -NHC(═O)R 8 , SO 2 NHR 8 , and -ONO 2 , and

[0165] R 8 is C 1 -C 6 alkyl, phenyl, pyridyl (such as preferably 2-pyridyl) provided that when n > 3, the hydrocarbon chain may be interrupted by -O- or -NH-, and the powder formulation comprises:

[0166] (i) a compound according to formula (I), and

[0167] (ii) silica,

[0168] The method comprises mixing the powder formulation with rice husk and / or rice bran.

[0169] Accordingly, in another embodiment, the present invention relates to a method for improving the retention (i.e., reducing evaporation) of a compound of formula (I) in a powder formulation according to the present invention, such as especially in powder formulations (A), (B), (C), (D), (E), (F) or (G), the method comprising mixing the powder formulation with rice husk and / or rice bran. In a preferred embodiment, the weight ratio (w / w) of rice husk and / or rice bran (in total) to the powder formulation is selected from the range of 50:1 to 1:5, preferably from the range of 40:1 to 1:2, most preferably from the range of 30:1 to 1:1 or 20:1 to 1:1, because these formulations are particularly suitable for effectively retaining the compound of formula (I) during storage.

[0170] In another embodiment, the present invention also relates to a method for improving the retention (i.e., reducing evaporation) of a compound of formula (I) according to the present invention, said method comprising the step of preparing a mixture or premix according to the present invention having all the definitions and preferred options given herein. Preferably, the mixture exhibits a retention rate of at least 80%, preferably at least 85%, most preferably at least 90%, for example particularly at least 95%.

[0171] In another embodiment, the present invention relates to a method for improving the retention (i.e., reducing evaporation) of a compound of formula (I) in a powder formulation according to the present invention, such as particularly in powder formulations (A), (B), (C), (D), (E), (F) or (G), said method comprising the step of preparing a mixture or premix according to the present invention having all the definitions and preferred options given herein. Preferably, the mixture / premix exhibits a retention rate of at least 80%, preferably at least 85%, most preferably at least 90%, for example particularly at least 95%.

[0172] As used herein, the term "retention" means the retention of a compound of formula (I) having all the definitions and preferred options given herein during a storage time of at least 4 weeks (re-closed (i.e., the bag has been rolled twice for sealing and then fixed with a clip) PE or aluminum bag; 25 °C; 50% relative humidity (r.H.)).

[0173] In another advantageous embodiment, the present invention relates to a method for enhancing the retention of a compound of formula (I) according to the present invention and having all the definitions and preferred options given herein in a feed product, said method comprising the step of adding / introducing a mixture according to the present invention having all the definitions and preferred options given herein together with / into the feed product.

[0174] In another advantageous embodiment, the present invention relates to a method for enhancing the retention of a compound of formula (I) having all the definitions and preferred options given herein in a feed product in a powder formulation according to the present invention, said method comprising the step of adding / introducing a mixture according to the present invention having all the definitions and preferred options given herein together with / into the feed product.

[0175] In another embodiment, the present invention relates to a method for enhancing the storage stability of a feed product comprising a compound of formula (I) or a powder formulation according to the present invention, such as in particular powder formulations (A), (B), (C), (D), (E), (F) or (G), said method comprising the step of adding rice husk and / or rice bran to said feed composition. Preferably, the weight ratio (w / w) of rice husk and / or rice bran (in total) to the powder formulation is selected from the range of 50:1 to 1:5, preferably from the range of 40:1 to 1:2, most preferably from the range of 30:1 to 1:1 or 20:1 to 1:1, because these formulations are particularly suitable for effectively retaining the compound of formula (I) during storage.

[0176] Advantageously, in all methods and uses according to the present invention, the weight ratio (w / w) of rice husk and / or rice bran to the compound of formula (I) is at least 1, preferably at least 5, more preferably at least 10, most preferably at least 25. Even more preferably, the weight ratio (w / w) of rice husk and / or rice bran (in total) to the compound of formula (I) is selected from the range of 200:1 to 1:1 (i.e., 200 parts of rice husk and / or rice bran relative to 1 part of the compound of formula (I) to 1 part of rice husk and / or rice bran relative to 1 part of the compound of formula (I)), more preferably from the range of 150:1 to 5:1, most preferably from the range of 100:1 to 25:1, such as 100:1 to 30:1 or 100:1 to 35:1.

[0177] Furthermore, preferably, in all uses and methods according to the present invention, the retention rate after at least 4 weeks is at least 80%, preferably at least 85%, most preferably at least 90%, especially at least 95%.

[0178] Preferably, the amount of the mixture according to the present invention in the feed product is selected such that the amount of the compound of formula (I) is in the range of 0.01 g / kg of feed product to 50 g / kg of feed product, preferably in the range of 0.02 g / kg of feed product to 25 g / kg of feed product, most preferably in the range of 1 g / kg of feed product to 10 g / kg of feed product.

[0179] The term "feed product" particularly refers to ruminant feed compositions as well as feed additives.

[0180] It is well known that all the definitions and preferences of rice husk and / or rice bran, powder formulations, compound of formula (I), active substances and / or feed ingredients and edible oils etc. as given herein also apply to the mixtures, premixes, feed products, uses and methods according to the present invention as described above.

[0181] The present invention is illustrated by the following examples. All temperatures are given in °C and all parts and percentages are by weight. Examples

[0182] General Information

[0183] A) HPLC method

[0184] Agilent 1260 Infinity high performance liquid chromatography system, using an Aquasil C18, 150×3 mm, 3 μm column, and detection was carried out at 210 nm. The column oven was set at 23 °C, and the autosampler was not temperature controlled. The mobile phase consisted of mobile phase A (940 mL Milli-Q-water + 60 mL acetonitrile + 1 mL methanesulfonic acid) and mobile phase B (800 mL Milli-Q-water + 200 mL acetonitrile + 1 mL methanesulfonic acid), and these mobile phase A and mobile phase B were used in a gradient mode (0 min: 0% B, 15 min: 0% B, 15.5 min: 100% B, 21 min: 100% B, 21.5 min: 0% B, 25 min: 0% B (= end of run)), with a flow rate of 0.4 mL / min.

[0185] B) Powder formulation containing propylene glycol mononitrate (PF-PDMN)

[0186] At room temperature, with gentle stirring, 80 g of a 20 wt% propylene glycol solution of propylene glycol mononitrate (PDMN) was added to 80 g of silica (Newsil C50) placed on a beaker. After stirring for 5 minutes, the adsorption was completed, and a free-flowing powder was obtained.

[0187] C) Liquid formulation containing propylene glycol mononitrate in propylene glycol (PG-PDMN)

[0188] 20 g of propylene glycol mononitrate and 80 g of propylene glycol were mixed with gentle stirring until a clear solution was obtained.

[0189] Example 1: Retention of PDMN in PF-PDMN Mixed with Different Organic Carriers

[0190] 10 g of PF-PDMN and 90 g of the organic carrier outlined in Table 1 were mixed in a swing mixer (64 revolutions per minute) for 10 min, passed through a 2 mm sieve, and mixed again for 10 min to obtain a homogeneous mixture (100 g batch). Then, 10 g of the corresponding mixture was stored in a re-closed PE bag under a controlled atmosphere (50% r.H) at 25 °C for 1 month. After that, the remaining content of PDMN was determined by HPLC. The results (as relative concentrations with respect to an initial value set as 100%) are listed in Table 1.

[0191] Table 1: Retention of PDMN in PF-PDMN according to various organic carriers

[0192] Number Inorganic Carrier Retention Rate [%] Invention 1 Rice Husk 89 Reference 1 <![CDATA[Modified starch ＊ > 48

[0193] Sodium octenyl succinate starch (“OSA - starch”)

[0194] As can be obtained from Table 1, the use of rice husks according to the present invention results in improved retention of the active substance compared to other organic carriers commonly used in the feed industry.

[0195] Example 2: Retention of PDMN in Premixes Containing Different Carriers

[0196] In a comparative test, 80 g of a mineral premix (composed of vitamins (Rovimix AD31000 / 200 (0.1 wt%) and Rovimix E 50Ads (1 wt%)), minerals (92.9 wt%) and PF - PDMN (6 wt%)) was mixed with 20 g of rice bran or kieselgur, and then stored in a re - closed PE bag under a controlled atmosphere (50% rH) at 25 °C for 3 months. Thereafter, the remaining content of PDMN was determined by HPLC. The results (as relative concentrations with respect to an initial value set at 100%) are listed in Table 2.

[0197] Table 2: Retention of PDMN in premixes containing different carriers

[0198] Number Mineral Premix Inorganic Carrier Retention Rate Invention 2 80 wt% Rice Bran 20 wt% 71％ Reference 2 80 wt% Diatomaceous Earth (Kieselgur) 20 wt% 66％

[0199] It can be seen that adding rice bran to a mineral premix containing PF - PDMN significantly improves the retention rate of PDMN compared to another carrier commonly used in the feed industry.

[0200] Example 3: Retention of PDMN in PF-PDMN Mixed with Rice Husk in Different Proportions

[0201] PF - PDMN and rice husks were mixed in the weight ratios outlined in Table 3 in a Shaker - Mixer (64 revolutions per minute) for 10 minutes, sieved through a 2 - mm sieve, and mixed for another 10 minutes to obtain a homogeneous mixture (50 g per batch). Then two samples (5 g each) were stored in a re - closed PE bag under a controlled atmosphere (60% r.H) at 25 °C for 2 months. Thereafter, the remaining content of PDMN was determined by HPLC. The results (as relative concentrations with respect to an initial value set at 100%) are listed in Table 3.

[0202] Table 3: Retention of PDMN in PF - PDMN mixed with rice husks in different ratios

[0203] Number Proportion [%] Retention Rate [%] Invention 3 90 / 10 98 Invention 4 50 / 50 92 Invention -5 30 / 70 98

[0204] As can be seen from Table 3, the use of rice husks according to the present invention results in improved retention of the active substance over a wide concentration range.

[0205] Example 4: Retention of PDMN in PG-PDMN Mixed with Rice Husk in Different Proportions

[0206] The rice husks were weighed and placed into PE bags. Then, the corresponding amount of a 20 wt% solution of PDMN in propylene glycol (as outlined in Table 4) was sprayed into the bags using a compressed air gun at a pressure of 0.5 bar (50 g batches). After that, the bags were sealed and manually mixed. Then, the rice husk / PG-PDMN mixture was transferred to a 400 ml flask and mixed in a Shaker-Mixer (64 revolutions per minute) for 10 minutes to obtain a homogeneous mixture. Then, two samples (5 g each) of the respective mixtures were stored in re-closed PE bags for 2 months under a controlled atmosphere (60% r.H) at 25 °C. After that, the remaining content of PDMN was determined by HPLC. The results (as relative concentrations with respect to an initial value set as 100%) are listed in Table 4.

[0207] Table 4: Retention rate of PDMN in PG-PDMN mixed with rice husks in different ratios

[0208] Number Proportion [%] Retention Rate [%] Invention 6 10 / 90 92 Invention 7 30 / 70 93 Invention -8 50 / 50 93

[0209] It can be concluded from Table 4 that the use of rice husks according to the present invention also results in a significant increase in the retention rate in the absence of a silica carrier over a wide concentration range.

Claims

1. A storage-stable mixture, which comprises (i) A compound of formula (I) wherein n is an integer from 1 to 15; R 1 selected from the group consisting of: H, C 1 -C 6 alkyl, phenyl, -OH, -NH 2 , -CN, -COOH, -O(C=O)R 8 , -NHC(=O)R 8 , SO 2 NHR 8 , and -ONO 2 ; and R 8 is C 1 -C 6 alkyl, phenyl, pyridyl (such as preferably 2-pyridyl); provided that when n > 3, the hydrocarbon chain may be interrupted by -O- or -NH-, and (ii) Rice husk and / or rice bran.

2. The storage-stable mixture according to claim 1, wherein the ratio (w / w) of the rice husk and / or rice bran to the compound of formula (I) is at least 1, preferably at least 5, more preferably at least 10, and most preferably at least 25.

3. The storage-stable mixture according to claim 1 or 2, which comprises (b1) A liquid preparation, the liquid preparation comprising (i) A compound of formula (I), and (ii) An edible solvent, preferably propylene glycol or water, and (b2) Rice husk and / or rice bran.

4. The storage-stable mixture according to claim 1 or 2, which comprises (a1) A powder preparation, the powder preparation comprising (i) A compound of formula (I), and (ii) Silicon dioxide, and (a2) Rice husk and / or rice bran.

5. The storage-stable mixture according to any one of claims 1 to 4, characterized in that the compound according to formula (I) is 1,3-propanediol mononitrate.

6. The storage-stable mixture according to claim 4 or 5, characterized in that the weight ratio of the rice husk and / or rice bran to the powder preparation is selected from the range of 50:1 to 1:5, preferably the range of 40:1 to 1:2, and most preferably the range of 30:1 to 1:1 or 20:1 to 1:

1.

7. The storage-stable mixture according to any one of claims 4 to 6, wherein the powder preparation consists essentially of the following components: (i) Based on the total weight of the powder preparation, 2% to 20% by weight of the compound of formula (I), and (ii) Based on the total weight of the powder preparation, at least 25% by weight of silicon dioxide, and (iii) Based on the total weight of the powder preparation, 10% to 45% by weight of edible oil, and (iv) Based on the total weight of the powder preparation, 0% to 10% by weight of additives.

8. The storage-stable mixture according to claim 7, wherein the edible oil in the powder preparation is selected from the group consisting of propylene glycol, low erucic acid rapeseed oil, corn oil, rapeseed oil, sunflower oil, medium-chain triglycerides (MCT), water and glycerol, and mixtures thereof, preferably propylene glycol and water.

9. The storage-stable mixture according to any one of claims 4 to 8, wherein the powder preparation consists essentially of the following components: (i) Based on the total weight of the powder preparation, 2% to 15% by weight of 1,3-propanediol mononitrate, and (ii) Based on the total weight of the powder preparation, at least 45% by weight of silicon dioxide, and (iii) Based on the total weight of the powder preparation, 20% to 40% by weight of propylene glycol.

10. The storage mixture according to any one of claims 3 to 9, wherein the mixture is a premix consisting essentially of (b1) and (b2) or a premix consisting essentially of (a1) and (a2).

11. The storage mixture according to any one of claims 4 to 10, wherein the mixture is a premix further comprising the following: (a3) An active ingredient selected from the group consisting of water-soluble and / or fat-soluble vitamins, trace and / or macro minerals, amino acids, and mixtures thereof, and optionally (a4) An edible oil, provided that the sum of the amounts of components (a1) to (a4) is 100% by weight.

12. The storage mixture according to any one of claims 4 to 11, wherein the mixture is a feed product further comprising the following: (a3 / 1) An active ingredient selected from the group consisting of water-soluble and / or fat-soluble vitamins, trace and / or macro minerals, amino acids, and mixtures thereof, and (a3 / 2) A feed ingredient selected from roughage and concentrate, and optionally (a4) An edible oil.

13. Use of rice husk and / or rice bran for enhancing the retention of the compound of formula (I), wherein n is an integer from 3 to 9, R 1 selected from the group consisting of: -OH, -COOH, and -ONO 2 provided that when n > 3, the hydrocarbon chain may be interrupted by -O- or -NH- provided that the ratio (w / w) of the rice husk and / or rice bran to the compound of formula (I) is at least 1, preferably at least 5, more preferably at least 10, and most preferably at least 25.

14. A method for improving the retention of the compound of formula (I), wherein n is an integer from 3 to 9, R 1 selected from the group consisting of -OH, -COOH and -ONO 2 , provided that when n>3, the hydrocarbon chain may be interrupted by -O- or -NH- the method comprising mixing the compound of formula (I) with rice husk and / or rice bran, provided that the ratio (w / w) of the rice husk and / or rice bran to the compound of formula (I) is at least 1, preferably at least 5, more preferably at least 10, and most preferably at least 25.

15. The use according to claim 14 or the method according to claim 15, wherein the retention rate after at least 4 weeks is at least 80%, preferably at least 85%, most preferably at least 90%, for example especially at least 95%.

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