Solid propylene glycol derived materials

Abstract

An energy efficient process for the rapid production of a solid metal-stabilized propylene glycol-derived material, the process comprising the step of mixing propylene glycol having a water content of up to about 50% by weight with a metal oxide and an accelerator, thereby producing an exothermic reaction, converting a liquid propylene glycol feedstock to the solid metal-stabilized propylene glycol-derived material. The invention also relates to a solid metal-stabilized propylene glycol derived material and to an animal feed composition comprising the solid metal-stabilized propylene glycol derived material.

Description

Technical Field

[0001] This invention relates to a method for producing solid propylene glycol-derived materials, and to solid metal-stabilized propylene glycol-derived materials produced by this method. The invention also relates to animal feed compositions comprising solid metal-stabilized propylene glycol-derived materials. Background Technology

[0002] Propylene glycol (IUPAC name: propane-1,2-diol) is a viscous, colorless liquid, almost odorless, with a slightly sweet taste, and soluble in water. Its chemical formula is CH3CH(OH)CH2OH.

[0003] Commercially, propylene glycol is primarily produced from food-grade propylene oxide. Manufacturers use a non-catalytic high-temperature process at 200°C to 220°C or a catalytic method at 150°C to 180°C to produce a colorless liquid in the presence of ion exchange resins or small amounts of sulfuric acid or alkali.

[0004] Propylene glycol is frequently used as a supplemental energy source (glucose precursor) in ruminant nutrition and also as an oral treatment for ruminant ketosis, where a negative energy balance in early lactation leads to low glucose levels, inducing the liver to compensate by converting body fat, resulting in various health conditions such as displaced abomasum. High doses (>500 g / day) of propylene glycol can be toxic to dairy cows due to the toxic compounds produced during its metabolism in the rumen and elsewhere, and therefore must usually be administered orally in liquid form. Clinical symptoms of toxic doses of propylene glycol include depression, ataxia, and excessive salivation, as well as abnormal, malodorous, and foul-smelling breath and feces in dairy cows. However, wetting with propylene glycol also presents problems due to its viscous nature.

[0005] Therefore, the toxicity and side effects of propylene glycol limit its maximum oral dose for use as an energy supplement and to reduce the risk of ketosis in dairy cows. However, the side effects of propylene glycol are related to the susceptibility of individual dairy cows, so it is important to consider signs of toxicity when administering propylene glycol; therefore, the maximum feeding level of propylene glycol is 500 g per cow per day.

[0006] When used as a supplemental energy source, propylene glycol is believed to increase the molar ratio of rumen propionate and hepatic gluconeogenesis in dairy cows, leading to elevated serum glucose and decreased serum non-esterified fatty acids (NEFA) and β-hydroxybutyrate (BHBA). Therefore, gavage administration of propylene glycol during the transition period is beneficial for alleviating postpartum NEB in dairy cows. However, as mentioned above, feeding levels and methods can affect the effectiveness of propylene glycol administration.

[0007] As an alternative to liquid lavage fluids, products in which liquid propylene glycol is absorbed onto solid carriers such as cellulose or silica can also be used as feed. For example, Chung et al. demonstrated that feeding propylene glycol in dry form (65% propylene glycol and 35% silica as carriers) in a total mixed ration (TMR) also reduced plasma BHBA concentrations. (Chung YH, Brown NE, Martinez CM, Cassidy TW, Varga GA Effects of rumen-protected choline and dry propylene glycol on feed intake and blood parameters for Holstein dairy cows in early lactation) J. Dairy Sci. 2009;92:2729–2736. doi: 10.3168 / jds.2008-1299).

[0008] However, the same amount of propylene glycol is more effective as a top dress (500 g / day of biscuit powder, a dried baking byproduct, mixed with dried propylene glycol) than when added to the total mixed ration (TMR). Therefore, the method of application appears to be important for the metabolic response of propylene glycol in dairy cows, as dispensing propylene glycol as an oral lavage solution or as a separate feed concentrate elicits a better response than mixing it into the TMR (Bjerre-Harpøth V., Storm AC, Eslamizad M., Kuhla B., Larsen M. Effect of propylene glycol on adipose tissue mobilization inpostpartum over-conditioned Holstein cows). J. Dairy Sci. 2015;98:8581–8596.doi: 10.3168 / jds.2014-8606).

[0009] However, liquid propylene glycol is not easily used as a top dressing due to its viscous nature and its negative impact on the taste and texture of animal feed. Furthermore, the silica required for solid carriers containing dry propylene glycol is expensive and has no nutritional value. In addition, regular or daily drenching with liquid propylene glycol is inconvenient or impractical due to the labor required.

[0010] Furthermore, neither liquid propylene glycol nor propylene glycol on a silica carrier can prevent fermentation in the rumen. More specifically, both forms will rapidly ferment in the rumen into large amounts of carbon dioxide gas (forming carbonic acid when dissolved in rumen fluid) and volatile fatty acids, namely acetic acid, propionic acid, and butyric acid (of which only propionic acid / propionic ester is a glucose precursor). This means that most of the product fed to the cow is not converted into glucose, and there is also a risk of increased rumen acidification leading to subacute rumen acidosis (SARA), reduced feed intake, and exacerbation of other metabolic disorders.

[0011] US4,680,315 describes a mixture comprising propylene glycol and magnesium oxide and / or magnesium peroxide as a solid carrier. The mixture is described as solid propylene glycol used in dietary products for calves, piglets, and lambs, as well as in other pharmaceutical compositions for veterinary use. A method for preparing the product is also described, comprising spraying propylene glycol onto the carrier.

[0012] GB2153669 discloses a feed concentrate containing propylene glycol bound to a solid carrier. A method for preparing the product is also described, comprising spraying propylene glycol onto the carrier.

[0013] The purpose of this invention is to overcome at least some of the problems of the prior art. Summary of the Invention

[0014] The applicant has developed an energy-saving process to rapidly convert viscous liquid propylene glycol into solid, particulate, metal-stabilized materials, such as powders, granules, etc. The only byproduct of this process is water released as vapor. The applicant has also developed novel solid propylene glycol-derived materials.

[0015] In a first aspect, the present invention relates to a method for producing solid metal-stabilized propylene glycol derivatives, comprising: Propylene glycol is combined with a metal oxide and an accelerator, wherein the water content of the propylene glycol is at most about 50% by weight, and An exothermic reaction occurs, converting liquid propylene glycol into a solid, metal-stabilized propylene glycol derivative.

[0016] In any embodiment, the water content of propylene glycol is up to about 30% by weight.

[0017] In any embodiment, the water content of propylene glycol is up to about 25% by weight.

[0018] In any embodiment, the water content of propylene glycol is from about 5% by weight to about 30% by weight.

[0019] In any embodiment, the water content of propylene glycol is from about 10% by weight to about 25% by weight.

[0020] In any embodiment, the metal oxide is selected from group 1A metal oxides, group 2A metal oxides, transition metal oxides, and combinations thereof.

[0021] In any embodiment, the metal oxide is a calcium oxide.

[0022] In any embodiment, the purity of the calcium oxide is at least about 75%.

[0023] In any embodiment, the metal oxide optionally comprises a metal hydroxide and / or a metal carbonate.

[0024] In any embodiment, the accelerator includes a propylene glycol acidifier.

[0025] In any embodiment, the acidifier is selected from inorganic acids, and / or organic acids, and / or combinations thereof.

[0026] In any embodiment, the inorganic acid is selected from phosphoric acid, sulfuric acid, hydrochloric acid and / or combinations thereof.

[0027] In any embodiment, the organic acid is selected from amino acids such as methionine and / or lysine, amino acid analogs or amino acid derivatives such as methane hydroxy analogs (MHA), alkyl carboxylic acids, hydroxyalkyl carboxylic acids, lactic acid, propionic acid, fatty acids, their salts and / or combinations thereof.

[0028] In any embodiment, the fatty acid is a short-chain, medium-chain, or long-chain saturated or unsaturated fatty acid, or a mixture thereof.

[0029] In any embodiment, the fatty acid is selected from palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid and / or combinations thereof.

[0030] In any embodiment, the method further includes the step of combining an inorganic salt with propylene glycol, a metal oxide, and a accelerator.

[0031] In any embodiment, the inorganic salt is selected from calcium hydroxide, calcium carbonate, one or more calcium phosphates, calcium sulfate, magnesium hydroxide, magnesium carbonate, one or more magnesium phosphates, magnesium sulfate, or combinations thereof.

[0032] In any embodiment, the method further includes the step of combining additional feed components with propylene glycol, metal oxides, and promoters.

[0033] In any embodiment, the additional feed components are selected from vitamins, minerals, trace elements, proteins, carbohydrates, oils, choline and choline salts, betaine and betaine salts, phospholipids / lecithin, metal salts, yeast, flavoring agents, coloring agents, or mixtures thereof.

[0034] In any embodiment, the oil is selected from vegetable base oils rich in ω-3 and / or ω-6 fatty acids, olive oil, rapeseed oil, canola oil, palm oil, sunflower seed oil, linseed oil, flax seed oil, coconut oil, sunflower seed oil, soybean oil, fish oil, etc., or combinations thereof.

[0035] In any embodiment, propylene glycol is partially replaced by glycerol.

[0036] If desired, the method of the present invention may include heating the reaction vessel and / or the reaction mixture and / or the raw materials and / or the reaction products.

[0037] The method of the present invention may further include the following steps: after the exothermic reaction is completed, flavoring and / or coloring and / or drying and / or heating and / or steam treatment and / or granulation and / or other steps or any combination of these steps on the reaction product.

[0038] Raw materials, with or without additional feed components, can be combined and mixed in any order or sequence using any type of equipment. For example, during the process, additional feed components can be added to the raw materials or to the reaction products in any order or sequence using any type of equipment.

[0039] The process used in the method of the present invention can be a batch process, a continuous process, a semi-batch process, a semi-continuous process, a manual process, an automatic process, a semi-automatic process, or any variation of these process types on any scale.

[0040] Therefore, the present invention provides a method for producing solid metal-stabilized propylene glycol derivatives, the method comprising the steps of: combining acidic propylene glycol or a propylene glycol-water mixture with a metal oxide (e.g., calcium oxide), wherein the water content of the propylene glycol is up to about 50% by weight, thereby generating an exothermic reaction, wherein solid propylene glycol derivatives are produced.

[0041] Therefore, the present invention relates to a method for producing a calcium salt of propylene glycol, the method comprising the steps of: combining propylene glycol with calcium oxide and at least one acid, wherein the water content of the propylene glycol is up to about 50%, selecting the combination of propylene glycol with the acid and calcium oxide and the amount of the acid and calcium oxide to produce an exothermic reaction, thereby providing a calcium salt of propylene glycol in the form of a solid, calcium-stable propylene glycol derivative.

[0042] The present invention also relates to novel solid propylene glycol derivative materials produced according to the method, which can be used as animal feed.

[0043] Therefore, the present invention also provides a method for rapidly producing animal feed compositions (e.g., feed or feed supplements), the method comprising the steps of: combining propylene glycol with calcium oxide and optionally a metal hydroxide and at least one accelerator, wherein the water content of the propylene glycol is up to about 50% by weight, and selecting the combination ratio of propylene glycol and calcium oxide and the amount of calcium oxide to produce an exothermic reaction to produce animal feed or feed supplements, wherein the accelerator is selected from inorganic acids, organic acids and / or other components as described above and combinations thereof. The inorganic acids and organic acids may be as described above.

[0044] Therefore, the method of the present invention provides a way to convert viscous liquid propylene glycol, which is a glucose precursor, into an easy-to-use rumen-protected animal feed or animal feed supplement by reacting propylene glycol with calcium oxide and an accelerator (e.g., an acid, such as phosphoric acid or sulfuric acid) to produce feed or supplements quickly and energy-efficiently.

[0045] The present invention also relates to solid metal-stabilized propylene glycol derivatives produced according to the method of the present invention.

[0046] In a second aspect, the present invention relates to solid metal-stabilized propylene glycol-derived materials comprising propylene glycol and a metal salt for stabilizing propylene glycol.

[0047] Therefore, a solid metal-stabilized propylene glycol derivative material is provided, comprising: Propylene glycol of about 20% to about 80% by weight, and About 5% by weight to about 40% by weight of metal or combination of metals.

[0048] In one embodiment, the solid metal-stabilized propylene glycol-derived material product comprises about 30% to about 70% by weight of propylene glycol.

[0049] In any embodiment, the solid metal-stabilized propylene glycol derivative product comprises about 5% to about 60% by weight of propylene glycol.

[0050] In any embodiment, the solid metal-stabilized propylene glycol derivative product comprises about 5% to about 40% by weight of a metal or a combination of metals.

[0051] In any embodiment, the metal is part of a metal salt comprising inorganic metal salts and / or organometal salts.

[0052] In any embodiment, the metal in the metal salt includes Group 1A, Group 2A, or transition metals, or combinations thereof.

[0053] In any embodiment, the inorganic salt includes phosphate, sulfate, or chloride salt, or combinations thereof.

[0054] In any embodiment, the inorganic salt includes phosphates, such as, but not limited to, calcium phosphate [Ca3(PO4)2] or dicalcium phosphate [CaHPO4], or sulfates, such as calcium sulfate [CaSO4], or combinations of these salts.

[0055] In any embodiment, the organic salt comprises an amino acid (e.g., methionine and / or lysine) salt, an amino acid analog / derivative (e.g., methionine hydroxy analog (MHA)) salt, an alkyl carboxylate, a hydroxyalkyl carboxylate, a lactate, a propionate, a fatty acid salt, or a combination thereof.

[0056] In any embodiment, the fatty acid is a short-chain, medium-chain, or long-chain saturated or unsaturated fatty acid, or a mixture thereof.

[0057] In any embodiment, the fatty acid is selected from palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, or combinations thereof.

[0058] In any embodiment, the organic salt includes monoester salts and / or diester salts.

[0059] In any embodiment, the solid metal-stabilized propylene glycol derivative further comprises an inorganic salt.

[0060] In any embodiment, the inorganic salt is selected from calcium hydroxide, calcium carbonate, one or more calcium phosphates, calcium sulfate, magnesium hydroxide, magnesium carbonate, one or more magnesium phosphates, magnesium sulfate, or combinations thereof.

[0061] In any embodiment, the solid metal-stabilized propylene glycol derivative further comprises one or more additional feed components selected from vitamins, minerals, trace elements, proteins, carbohydrates, oils, choline and choline salts, betaine and betaine salts, phospholipids / lecithin, metal salts, yeast, flavoring agents, coloring agents, or combinations thereof.

[0062] In any embodiment, the oil is selected from vegetable base oils rich in ω-3 and / or ω-6 fatty acids, olive oil, rapeseed oil, canola oil, palm oil, sunflower seed oil, flaxseed oil, coconut oil, sunflower seed oil, soybean oil, fish oil, etc., or combinations thereof.

[0063] In any embodiment, propylene glycol is partially replaced by glycerol.

[0064] In any embodiment, up to 50% by weight of propylene glycol is replaced by glycerol.

[0065] In another embodiment, the invention extends to animal feed compositions comprising solid propylene glycol-derived materials as defined above.

[0066] In any embodiment, the animal feed composition is a pelleted feed composition.

[0067] In any embodiment, the pelleted feed composition comprises powder, powder, or pellets.

[0068] In any embodiment, the propylene glycol or the combination of propylene glycol and glycerol in the feed composition is at least partially protected from fermentation in the rumen.

[0069] By being stabilized by a metal, the solid propylene glycol material of this invention is largely protected from fermentation in the rumen. Feed compositions formed from solid metal-stabilized propylene glycol material largely bypass the rumen and reach the acidic abomasum, where it is released as the powder dissolves in the acidic fluid of the abomasum. The propylene glycol is then transported to the liver, where it is efficiently and enzymatically converted to glucose. Therefore, feed compositions formed from solid metal-stabilized propylene glycol material provide an efficient / economical method for providing energy to dairy cows. Consequently, dairy cows can be more easily protected from metabolic disorders such as subclinical ketosis, subacute rumen acidosis (SARA), etc., and have beneficial effects on overall health and safety, such as improved physical condition, fertility, milk production, etc.

[0070] As mentioned above, liquid propylene glycol products are typically administered to dairy cows via oral gavage or feeding via liquid delivery devices. However, this viscous liquid is not easily or effectively fed to dairy cows. In contrast, the solid, metal-stabilized propylene glycol glucose precursor material of the present invention can be easily and effectively fed to dairy cows via a robotic system. Therefore, propylene glycol-based glucose precursors in powder, granule, or other forms can now be selectively fed to farm ruminants according to their needs. Consequently, appropriate doses can be administered to the animals, and overdosing is more easily avoided.

[0071] Therefore, compared to simply feeding ruminants liquid, free-fermentable, unprotected propylene glycol or liquid based on cellulose or silica materials, the present invention provides ruminants with a better supply of targeted energy.

[0072] Definitions and general preferences All publications, patents, patent applications and other references mentioned herein are incorporated herein by reference in their entirety, as if each individual publication, patent or patent application were explicitly and individually cited as a reference and its contents were quoted in full.

[0073] As used herein, unless otherwise specified, the following terms are intended to have the following meanings, in addition to any broader (or narrower) meaning that may be enjoyed in the art: Unless the context otherwise requires, the singular as used herein shall be understood to include the plural, and vice versa. The terms “a” or “an” used in relation to an entity shall be understood to refer to one or more of that entity. Therefore, the terms “a” or “an,” “one or more,” and “at least one” are used interchangeably herein.

[0074] As used herein, the term “comprise” or variations thereof, such as “comprises” or “comprising”, should be understood to mean including any of the stated wholes (e.g., features, elements, characteristics, properties, method / process steps, or limitations) or groups of wholes (e.g., features, elements, characteristics, properties, method / process steps, or limitations), but not excluding any other wholes or groups of wholes. Therefore, as used herein, the term “comprise” is inclusive or open-ended and does not exclude additional, unlisted wholes or method / process steps. Detailed Implementation

[0075] The "solid propylene glycol derivative material" of the present invention includes materials in the form of powder, powder, granules, flakes, particles, fragments, and combinations thereof. Typically, a method for producing the solid propylene glycol derivative material of the present invention includes the following steps: combining acidic propylene glycol or a propylene glycol-water mixture with a metal oxide (e.g., calcium oxide), wherein the water content of the propylene glycol is at most about 50% by weight, thereby generating an exothermic reaction, wherein the solid propylene glycol derivative material is produced.

[0076] The propylene glycol used in the method of this invention is liquid propylene glycol produced by any method known in the art. The water content of the propylene glycol is sufficient to produce an exothermic reaction, typically up to about 50% by weight. Typically, the water content of the propylene glycol is about 10% to 25% (w / w). This water content may include water present in the added acid or combination of acids (e.g., hydrated phosphoric acid and / or sulfuric acid, which are added to the liquid propylene glycol to acidify it). If desired, the method may also include a prior step of adding the required amount of water to the propylene glycol to achieve the desired exothermic reaction and the desired physical properties of the reaction products.

[0077] In this specification, the term "metal oxide" generally refers to oxides of Group 1A metals, Group 2A metals, transition metals, and combinations thereof. Preferred metal oxides are calcium oxides. Metal oxides are typically in powder form and have a purity of at least 75% (w / w), and may include, for example, one or more metal oxides and hydroxides or carbonates as impurities. Various factors affect the desired amount of calcium oxide. These may include the purity and particle size of the calcium oxide, the reactivity of the calcium oxide, the amount of other oxides or salts present in the calcium oxide, and the amount of water present in the propylene glycol. The reactivity of the calcium oxide will be determined by the splitting state of the calcium oxide particles; the purer and finer the material, the stronger its reactivity. The purity of the calcium oxide used in the methods of this invention is typically higher than about 75% (w / w).

[0078] Preferably, the calcium oxide will be a fine powder with a purity of about 85% to 100% (w / w), more preferably about 90% to 100% (w / w).

[0079] To control the exothermic reaction that occurs when a metal oxide reacts with acidified liquid propylene glycol, the metal oxide (e.g., calcium oxide) may be combined with a metal hydroxide salt (e.g., calcium hydroxide or magnesium hydroxide) or a metal carbonate (e.g., calcium carbonate or magnesium carbonate). For example, the metal oxide may be combined with a predetermined amount of calcium hydroxide and / or calcium carbonate or other metal hydroxides or carbonates to control the rate and / or magnitude of the exothermic reaction. Therefore, in the context of this specification, the terms calcium oxide or metal oxide include, within their scope, oxides containing hydroxides and / or carbonates, i.e., metal oxides may (optionally) contain metal hydroxides and / or metal carbonates.

[0080] Various factors can affect the required amount of calcium oxide. These can include the purity and particle size of the calcium oxide, the reactivity of the calcium oxide, the amount of other oxides or salts present in the calcium oxide, and the amount of water and / or acid present in the propylene glycol.

[0081] The method of the present invention uses one or more promoters to drive an exothermic reaction. More specifically, the promoter may be a material that undergoes an exothermic reaction with a metal oxide and / or metal hydroxide (if present), which, in combination with propylene glycol, provides heat to convert propylene glycol into a solid product, wherein propylene glycol exists as a bystander supporting the solid product or as part of forming a new solid product or chemical entity.

[0082] Accelerators can be selected as needed. In one embodiment, the accelerator is an acidifier of propylene glycol to achieve an exothermic reaction of sufficient strength to produce a solid material. In one embodiment, propylene glycol is acidified with an acid or a salt of an acid. The acid can be, for example, an inorganic acid or an organic acid or a combination of acids. Inorganic acids can be selected from phosphoric acid, sulfuric acid, and hydrochloric acid. Inorganic salts can be included, such as calcium hydroxide, calcium carbonate, calcium phosphate, calcium sulfate, magnesium hydroxide, magnesium carbonate, magnesium phosphate, magnesium sulfate, or combinations thereof. Organic acids can be selected from amino acids, such as methionine and / or lysine, amino acid analogs or amino acid derivatives, such as methane hydroxy analogs (MHA), alkyl carboxylic acids, hydroxyalkyl carboxylic acids, lactic acid, propionic acid, fatty acids, any salts of these, and combinations thereof. Fatty acids can be, for example, selected from short-chain, medium-chain, or long-chain saturated or unsaturated fatty acids, such as palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and combinations thereof. The organic acid can be selected from methionine, methionine hydroxy analogue (MHA), lysine, its salts, and mixtures thereof. The amount of acid required is determined by the amount and purity of the other components so that the combination of components achieves the desired exothermic reaction.

[0083] When phosphoric acid is used as an acidifying agent in the method of the present invention, and a mixture of calcium oxide or metal oxide and metal hydroxide with water and propylene glycol is used, the exothermic reaction is generated by the reaction of calcium oxide with water, but also by the reaction of inorganic acid with oxide and / or hydroxide. In this case, the additional reaction (depending on the reagent ratio) leads to the formation of inorganic metal salts (e.g., calcium phosphate and / or dicalcium phosphate). In this case, propylene glycol can also be loaded onto the inorganic salt matrix generated as a support.

[0084] If an organic acid, such as palmitic acid, is used as a promoter, the additional reaction is the formation of organometallic salts, such as amino acids, amino acid analogs / derivatives, alkylcarboxylic acids, hydroxyalkylcarboxylic acids, lactic acid, propionic acid, fatty acid salts, or combinations thereof. For example, when palmitic acid is used, calcium palmitate can form a solid component in the product, on which propylene glycol can be supported as a carrier. Propylene glycol can exist as an unreacted bystander supported on a solid organic salt, or it can react at least partially with the organic acid to form monoesters and / or diesters, depending on the proportions of the reagents.

[0085] Any suitable accelerators added to react exothermically with metal oxides / hydroxides and / or propylene glycol to obtain a solid product are therefore included within the scope of this invention, wherein propylene glycol exists as an observer and / or as part of a new chemical entity loaded on the solid product.

[0086] Depending on the desired outcome, the accelerator can be added in different amounts at any stage of the reaction, and as mentioned above, the accelerator can be one or more substances that are highly reactive to calcium oxide or calcium hydroxide (if present), which is formed in the reaction of the starting calcium oxide with water in a water-propylene glycol mixture, and may or may not be reactive to the starting propylene glycol.

[0087] The amount of acid and water present will determine the amount reacting with calcium oxides and the amount of water evaporated due to the exothermic reaction between calcium oxides, acid, and water. The amount of water discharged during the exothermic reaction is also affected by various factors, such as impurities in the water, altitude above sea level, ambient temperature, temperature of the mixing container, and heat loss of the system.

[0088] As needed, the methods and feed materials of the present invention may include other additional feed components. Any material compatible with the reaction conditions of the present invention and that will be, or will produce, suitable animal feed materials may be used as an additional feed component. Therefore, the present invention allows for the manipulation or adjustment of chemical properties by adding supplements or mixtures of supplements to provide products whose individual components meet the specific requirements of their intended use (e.g., regulatory approval for individual components and / or nutritional value or desired chemical and / or physical properties for an intended application in animal nutrition applications). Additional feed components may be selected from vitamins, minerals, trace elements, proteins, carbohydrates, oils, choline and choline salts, betaine and betaine salts, phospholipids / lecithin, metal salts, yeast, flavoring agents, coloring agents, or mixtures thereof. Oils may be selected from vegetable-based oils rich in ω-3 and / or ω-6 fatty acids, olive oil, rapeseed oil, canola oil, palm oil, sunflower oil, flaxseed oil, coconut oil, sunflower oil, soybean oil, fish oil, etc., or combinations thereof.

[0089] If necessary, propylene glycol in the method of the present invention may be partially replaced by a glucose precursor (e.g., glycerol), for example, up to 50% by weight of propylene glycol may be replaced by glycerol.

[0090] Therefore, the method of the present invention can be carried out in the presence of an accelerator and / or other additional feed components, which will provide, for example, phosphates, sulfates, or chlorides, or organic components such as organic acids or their salts in the propylene glycol-derived material. The propylene glycol-derived material will be suitable for use as animal feed or for use in animal feed.

[0091] Optionally, during or after the reaction, the promoter and / or additional feed components may be added in a single or multiple streams, or in combination with the feedstock propylene glycol.

[0092] The method of the present invention can be implemented in various ways as needed. For example, raw materials can be combined and mixed in any order or sequence using any type of equipment. The method can also be implemented as a batch process, a continuous process, a semi-batch process, a semi-continuous process, a manual process, an automatic process, a semi-automatic process, or any variation of these process types at any scale.

[0093] Some of the products can also be recycled back into the reaction vessel on a continuous basis.

[0094] The reaction vessel and / or reaction mixture or raw materials may optionally be heated, for example when the reaction vessel is cold and / or the raw materials have been stored at low temperature.

[0095] The method may include the following steps: after the exothermic reaction is completed, flavoring and / or drying and / or heating and / or steam treatment and / or granulation and / or other further processing steps on the reaction product.

[0096] The solid products produced in this invention are granular or powdered materials and can be animal feed on their own, or optionally, combined with other animal feed components to serve as fortifying components or nutrient materials in animal feed.

[0097] The invention will now be described by way of example only with reference to the following non-limiting embodiments: Example General method: Propylene glycol (99.9%) liquid, water, and either phosphoric acid (H3PO4, 85%, aqueous solution) or sulfuric acid (H2SO4, 98%) were placed in a 100 mL container. The liquids were mixed using a metal temperature probe, and the temperature of each liquid mixture was recorded. In each experiment, pre-weighed calcium oxide (94%) powder, with reactivity tested, was rapidly added to the liquid mixture in one go. The resulting mixture was thoroughly and rapidly mixed, and then allowed to stand for reaction. The temperature of the mixture was recorded every 30 seconds, and the highest reaction temperature for each corresponding reaction time was also recorded. After reaching the highest temperature in each reaction, the reaction products were mixed using a temperature probe. In the case of powdered products, the powder was transferred to a storage container, and the weight and physical appearance of the product were recorded.

[0098] It was found that, in the examples shown in Table 1, adding an acid such as phosphoric acid (H3PO4, 85%, aqueous solution) or sulfuric acid (H2SO4, 98%) in a suitable proportion to the propylene glycol-water mixture feedstock provided a rapid and intense exothermic reaction with calcium oxide, resulting in the conversion of the propylene glycol liquid into a powdered material. Table 1 summarizes the details and observations of a series of experiments conducted with propylene glycol, which demonstrated particulate products such as powders, granules, etc.

[0099] Table 1 Experiment using propylene glycol-water mixture, phosphoric acid, and calcium oxide as raw materials .

[0100]

[0101] *Calcium oxide (CaO): 94.0%, calcium carbonate (CaCO3): 3.9%, magnesium oxide (MgO): 0.5%, silicon oxide (SiO2): 0.8%, aluminum oxide (Al2O3): 0.8%, calcium sulfate (CaSO4): 0.05%.

[0102] Subsequent experiments were conducted in which L-lysine powder and / or methionine hydroxy analogue (calcium salt) powder or DL-methionine powder were added to the propylene glycol-water-phosphate mixture before the addition of calcium oxide powder. The same general procedure as described in the PG PHOS experiments in Table 1 was followed, except that additional feed component powders were added to the propylene glycol-water-phosphate liquid mixture to form a suspension, which was mixed in each experiment before the addition of calcium oxide powder.

[0103] The experimental results for obtaining free-flowing powders or powdery substances are summarized in Table 2.

[0104] Table 2 Using a propylene glycol-water mixture, phosphoric acid, and L-lysine and / or methionine hydroxy analogs, calcium salts (Ca-MHA). Experiments using DL-methionine and calcium oxide as starting materials .

[0105]

[0106] *Calcium oxide (CaO): 94.0%, calcium carbonate (CaCO3): 3.9%, magnesium oxide (MgO): 0.5%, silicon oxide (SiO2): 0.8%, aluminum oxide (Al2O3): 0.8%, calcium sulfate (CaSO4): 0.05%.

[0107] Additional small-scale experiments were conducted to determine the optimal raw material ratios based on the selected raw materials shown in Table 3 as examples, which resulted in the formation of granular propylene plus glycerol-based composite products.

[0108] Following the same general procedure as described in the PG PHOS experiment summarized in Table 1, a liquid mixture of propylene glycol and animal feed grade glycerol (as opposed to propylene glycol alone) and phosphoric acid and calcium oxide were used as raw materials.

[0109] The results of this set of experiments are summarized in Table 3, in which free-flowing powders or powders were obtained.

[0110] Table 3 Experiment using a mixture of propylene glycol-glycerol-water, phosphoric acid, and calcium oxide as raw materials .

[0111]

[0112] *Calcium oxide (CaO): 94.0%, calcium carbonate (CaCO3): 3.9%, magnesium oxide (MgO): 0.5%, silicon oxide (SiO2): 0.8%, aluminum oxide (Al2O3): 0.8%, calcium sulfate (CaSO4): 0.05%.

[0113] **Industrial / Animal Feed Grade Glycerin, Glycerin: 83.5%, Water: 12.1%, a dark yellow viscous liquid.

[0114] Subsequently, prior to the addition of calcium oxide powder, additional small-scale experiments were conducted by adding lysine or a methionine hydroxy analog (calcium salt), or both powders, to the propylene glycol-glycerol-water-phosphate mixture. The same general procedure as described in the PG PHOS experiments shown in Table 1 was followed, except that additional feed component powder was added to the propylene glycol-glycerol-water-phosphate liquid mixture to form a suspension, which was then mixed in each experiment prior to the addition of calcium oxide powder.

[0115] Table 4 summarizes the experimental results for obtaining free-flowing powders or powdery substances.

[0116] Table 4 With propylene glycol-glycerol-water mixture, phosphoric acid and L-lysine and / or methionine hydroxy analogs, calcium salts (Ca- Experiments using MHA and calcium oxide as raw materials .

[0117]

[0118] *Calcium oxide (CaO): 94.0%, calcium carbonate (CaCO3): 3.9%, magnesium oxide (MgO): 0.5%, silicon oxide (SiO2): 0.8%, aluminum oxide (Al2O3): 0.8%, calcium sulfate (CaSO4): 0.05%.

[0119] **Industrial / Animal Feed Grade Glycerin, Glycerin: 83.5%, Water: 12.1%, a dark yellow viscous liquid.

[0120] As mentioned above, acids other than phosphoric acid or sulfuric acid (inorganic and / or organic acids) can be used as acidifying agents to provide the corresponding calcium salts of these acids. The formulation may or may not contain additional feed components, such as amino acids.

[0121] equivalent The foregoing description presents in detail the presently preferred embodiments of the invention. Based on this description, many modifications and variations in practice will arise for those skilled in the art. These modifications and variations are intended to be included in the appended claims.

Claims

1. A method for producing solid metal-stabilized propylene glycol derivatives, comprising: Propylene glycol is combined with a metal oxide and an accelerator, wherein the water content of the propylene glycol is at most about 50% by weight, and An exothermic reaction is generated to convert liquid propylene glycol into solid propylene glycol derivatives.

2. The method according to claim 1, wherein the metal oxide is selected from group 1A metal oxides, group 2A metal oxides, transition metal oxides, and combinations thereof.

3. The method according to claim 1 or 2, wherein the metal oxide optionally comprises a metal hydroxide and / or a metal carbonate.

4. The method according to any one of the preceding claims, wherein the metal oxide is a calcium oxide.

5. The method according to claim 4, wherein the purity of the calcium oxide is at least about 75%.

6. The method according to any one of the preceding claims, wherein the accelerator comprises a propylene glycol acidifier.

7. The method according to claim 6, wherein the acidifying agent is selected from inorganic acids or salts, and / or organic acids or salts, and / or combinations thereof.

8. The method according to claim 7, wherein the inorganic acid is selected from phosphoric acid, sulfuric acid, hydrochloric acid and / or combinations thereof, and / or the organic acid is selected from amino acids, amino acid analogs or amino acid derivatives, alkyl carboxylic acids, hydroxyalkyl carboxylic acids, lactic acid, propionic acid, fatty acids, their salts and / or combinations thereof; the amino acid may include methionine and / or lysine, and the amino acid analog or amino acid derivative may include methionine hydroxy analog (MHA).

9. The method according to claim 8, wherein the inorganic acid is a fatty acid, and is a short-chain, medium-chain, or long-chain saturated or unsaturated fatty acid or a mixture thereof.

10. The method of claim 9, wherein the fatty acid is selected from palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid and / or combinations thereof.

11. The method according to any one of claims 1 to 10, further comprising the following step: Additional feed components are combined with propylene glycol, metal oxides, and promoters, said additional feed components being selected from vitamins, minerals, trace elements, proteins, carbohydrates, oils, choline and choline salts, betaine and betaine salts, phospholipids / lecithin, metal salts, yeast, flavoring agents, coloring agents, or combinations thereof.

12. The method according to any one of claims 1 to 11, wherein the propylene glycol is partially replaced by glycerol.

13. The method of claim 12, wherein up to 50% by weight of propylene glycol is replaced by glycerol.

14. The method according to any one of the preceding claims, wherein the acidifying agent is an acid, the metal oxide is a calcium oxide, and the method produces a calcium salt of propylene glycol in the form of a solid, calcium-stable propylene glycol derivative.

15. A solid metal-stabilized propylene glycol derivative material, comprising: Propylene glycol of about 20% to about 80% by weight, and About 5% by weight to about 40% by weight of metal or combination of metals.

16. The solid metal-stabilized propylene glycol derivative material according to claim 15, wherein the metal is part of an inorganic and / or organometallic salt.

17. The solid metal-stabilized propylene glycol derivative material according to claim 15 or 16, wherein the metal in the metal salt comprises a group 1A, a group 2A, or a transition metal or a combination thereof.

18. The solid metal-stabilized propylene glycol derivative material according to claim 16 or 17, wherein the inorganic metal salt comprises a phosphate, sulfate, or chloride metal salt or a combination thereof.

19. The solid metal-stabilized propylene glycol derivative material according to any one of claims 15 to 18, wherein the organometal salt comprises one or more metal salts of amino acids, amino acid analogs / derivatives, alkyl carboxylic acids, hydroxyalkyl carboxylic acids, lactic acid, propionic acid, fatty acids, or combinations thereof; the amino acid may include methionine and / or lysine, and the amino acid analog / derivative may include methionine hydroxy analog (MHA).

20. The solid metal-stabilized propylene glycol derivative material according to any one of claims 15 to 19 further comprises additional feed components, said additional feed components being selected from vitamins, minerals, trace elements, proteins, carbohydrates, oils, choline and choline salts, betaine and betaine salts, phospholipids / lecithin, metal salts, yeast, flavoring agents, coloring agents, or combinations thereof.

21. The solid metal-stabilized propylene glycol derivative material according to any one of claims 15 to 20, wherein the propylene glycol is partially replaced by glycerol.

22. An animal feed composition comprising a metal-stabilized solid propylene glycol derivative material according to any one of claims 15 to 21.

23. The animal feed composition according to claim 22, wherein the animal feed composition is a specific feed composition.

24. The animal feed composition according to claim 23, wherein the animal feed composition is a powder, granule or pellet.

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