CN113261614A - Methionine hydroxy analogue-calcium phosphate and its feed preparation and preparation method - Google Patents
Methionine hydroxy analogue-calcium phosphate and its feed preparation and preparation method Download PDFInfo
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Abstract
The invention belongs to the technical field of animal feed preparation, and particularly relates to a methionine hydroxy analogue-calcium phosphate salt, a feed preparation and a preparation method thereof. The preparation method comprises mixing methionine hydroxy analogue with concentration of 10-95 wt% with calcium hydrogen phosphate for reaction, and drying to obtain methionine hydroxy analogue-calcium phosphate; the mol ratio of the methionine hydroxy analogue to the calcium hydrophosphate is 1: 1-20. In the method, the calcium hydrophosphate is used as a calcium source for converting the methionine hydroxy analogue into the methionine hydroxy analogue calcium salt and also used as a dispersant for the methionine hydroxy analogue and the calcium salt thereof, and the physical properties of the composition are changed through two aspects of chemistry and physics, so that the methionine hydroxy analogue-calcium phosphate salt which has good fluidity, uniform color, no agglomeration and stable properties and is beneficial to storage and use is obtained.
Description
Technical Field
The invention belongs to the technical field of animal feed preparation, and particularly relates to a methionine hydroxy analogue-calcium phosphate salt, a feed preparation and a preparation method thereof.
Background
D, L-2-hydroxy-4-methylthiobutyric acid (MHA) is also called methionine hydroxy analogue and is mainly used as a feed additive to supplement methionine. MHA has started to be used in animal husbandry as early as the fifties of the last century and has been proven by feed, animal and pet manufacturing companies to be a source of methionine with excellent properties. Despite the many advantages of MHA, there are also 1) strong corrosive and pungent odors that are inconvenient to store, transport, use, necessitating the use of expensive dedicated liquid feed systems; 2) the viscosity is very high, and the materials are not easy to be uniformly mixed in the feed premix; 3) a large amount of heat is released when meeting water, so that the feed is heated, fermented and rancid in the storage and transportation process; the acidity is very high, the pH value is about 1, and the feed additive is easy to generate acid-base reaction with other components in the feed or the premixed feed, and can damage the nutrient components in the feed. The prior art generally solves the problems by reacting with calcium salt to generate methionine hydroxy analogue calcium salt or adsorbing and drying with inert carrier to achieve solidification and dispersion. For example, Chinese patent CN02137790.1 discloses adding calcium oxide or calcium hydroxide into a mixing dryer, and then adding methionine hydroxy analogue solution in small dosage continuously, so that neutralization reaction occurs to generate methionine hydroxy analogue calcium salt. Chinese patent CN104356035A discloses that methionine hydroxy analogue and one or more of calcium hydroxide, calcium oxide and calcium carbonate are used as reaction raw materials, ammonium bisulfate is introduced as reaction catalyst, and methionine hydroxy analogue calcium salt is obtained by reaction.
According to the method, solid methionine hydroxy analogue calcium salt prepared by directly reacting MHA with calcium sources such as calcium hydroxide and calcium carbonate is adopted to realize solidification of liquid MHA, and the method has the advantage of providing calcium element at the same time.
Chinese patent CN1094562640A discloses that 2-hydroxy-4-methylthiobutyronitrile is hydrolyzed to obtain 2-hydroxy-4-methylthiobutyramide, the 2-hydroxy-4-methylthiobutyramide is reacted with alcohol to prepare 2-hydroxy-4-methylthiobutyric acid or the amide is directly hydrolyzed to 2-hydroxy-4-methylthiobutyric acid (MHA), the 2-hydroxy-4-methylthiobutyric acid ester or 2-hydroxy-4-methylthiobutyric acid is extracted by methylene chloride or methyl isobutyl ketone, inert carriers such as silicon dioxide and zeolite powder are added, and then the mixture is dried to obtain solid 2-hydroxy-4-methylthiobutyric acid ester or 2-hydroxy-4-methylthiobutyric acid with dispersion fluidity. According to the method, inert substances such as silicon dioxide and zeolite powder are used as carriers, an organic solvent is used as a dispersing agent, a methionine hydroxyl analogue carrier powder product with dispersion fluidity is obtained, certain acidity of MHA is kept, more inert carriers are used, the effective content of MHA is greatly reduced, the carriers such as the additionally added silicon dioxide cannot provide effective nutrient substances for animals, the cost performance of the product is relatively reduced, the organic solvents such as dichloromethane and methyl tert-butyl ketone are used in the reaction process, the production risk and the cost are greatly increased, and the method is not beneficial to large-area popularization and use.
The calcium dihydrogen phosphate (MCP) is an excellent high-efficiency phosphate feed additive, has high phosphorus content and high water solubility, is a supplement for phosphorus and calcium of animals, has the highest biological value in feed-grade phosphate, is particularly suitable for aquatic animals such as fish, shrimps and crabs, and has the utilization rate of phosphorus in the calcium dihydrogen phosphate up to about 96 percent and the utilization rate of phosphorus in calcium hydrogen phosphate (DCP) only up to 50 percent; monocalcium phosphate (MDCP) is a eutectic compound of monocalcium phosphate (MCP) and calcium hydrophosphate (DCP), and is a feed additive combining water-soluble phosphate and citrate-soluble phosphate, wherein monocalcium phosphate is water-soluble phosphate and accounts for about 60 percent, and researches show that the absorption rate of the effective components of the feed additive to animals is much better than that of DCP (more than 75 percent). At present, DCP is mainly added in China, and the DCP has low requirements on the grade of required phosphorite, so that qualified feed-grade DCP can be produced at most low and medium grade, and the cost is lower; in addition, although the resources of the Chinese phosphorite are rich, most of the China phosphorite belongs to middle-low grade lean ores, so that the direct preparation of the MDCP or MCP with higher water-soluble phosphorus content and better biological absorptivity is directly limited by the phosphorite resources.
At present, MDCP is prepared by further processing DCP, but most of DCCP is obtained by carrying out secondary incomplete reaction on phosphoric acid solution and calcium hydrophosphate, and the content of water-soluble phosphorus is relatively increased. For example, chinese patent CN1463614A discloses that phosphoric acid with a concentration of 20-60% is obtained by using a thermal phosphoric acid dilution or a wet phosphoric acid and thermal phosphoric acid blending method, and then the phosphoric acid is mixed with calcium hydrogen phosphate or calcium phosphate-rich acid for reaction, and the obtained material is dried and sieved to finally obtain feed-grade mono-di-calcium phosphate. Chinese patent CN1155513C discloses a powdered feed grade mono-dicalcium phosphate prepared by mixing and reacting 40-60% defluorinated solution of phosphoric acid, water or calcium hydrophosphate with semi-finished calcium hydrophosphate, wherein the content of water-soluble phosphorus in the product is 40-70%. The method still utilizes the phosphoric acid and calcium hydrophosphate to further react to prepare MDCP, but still needs phosphoric acid with higher concentration to participate in the reaction, and is only an economic compromise scheme relative to the direct production of MCP with higher quality, and the problem of the demand for high-quality phosphoric acid is not substantially solved.
In summary, the current MHA curing technology has the disadvantages of: since MHA contains more dimers and oligomers, and undergoes a neutralization reaction with calcium hydroxide and the like to generate intense heat, local overheating and incomplete reaction are easily caused, and thus solid methionine hydroxy analogue calcium salt with local coking, agglomeration and poor fluidity is easily obtained. And inert carriers such as organic solvents, silicon dioxide and the like are adopted for adsorption and drying, more inert carriers are used, the effective content of MHA is greatly reduced, the additionally added carriers such as silicon dioxide and the like cannot provide effective nutrient substances for animals, the cost performance of the product is relatively reduced, organic solvents such as dichloromethane, methyl tert-butyl ketone and the like are used in the reaction process, the production risk and the cost are greatly increased, and the large-area popularization and use are not facilitated. In addition, in the aspect of improving the ratio of water-soluble phosphorus in DCP and the bioavailability, the prior art mainly adopts a method for further reacting high-concentration phosphoric acid and DCP to generate MDCP, high-quality phosphoric acid and phosphate ore are still needed, the problem of high production cost of MDCP and MCP caused by the deficiency of high-quality phosphate ore and the like is not solved, the nutrient contents of methionine, phosphorus and calcium in feed preparations or complete feeds in the prior art need to be calculated and repeatedly added in many ways, and the calculation and adding processes are complicated.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a feed preparation, in which hydroxy methionine analogue and calcium dihydrogen phosphate can be directly added at a proper proportion at one time according to the nutritional amount of methionine, phosphorus and calcium required in the feed preparation, so as to avoid multi-way calculation and repeated addition, and be simple, efficient and convenient. And can be directly mixed with basic feed to obtain complete feed.
The preparation method of the feed preparation comprises the following steps:
(1) hydrolyzing 10-95 wt% of methionine hydroxy analogue to obtain methionine hydroxy analogue monomer, wherein the hydrolysis mode is one or combination of heating dilution hydrolysis, high-temperature high-pressure hydrolysis, acid hydrolysis, microwave radiation and ultrasonic radiation;
(2) mixing the obtained methionine hydroxy analogue monomer with calcium hydrogen phosphate for reaction, and drying to obtain methionine hydroxy analogue-calcium phosphate;
(3) mixing the obtained methionine hydroxy analogue-calcium phosphate with other nutrient elements and/or carriers required by feeding object to prepare into feed preparation.
Wherein, the mol ratio of the methionine hydroxy analogue to the calcium hydrophosphate is determined by one-time calculation according to the nutrient contents of methionine, phosphorus and calcium required in different feed preparations.
Preferably, the molar ratio of the methionine hydroxy analogue to the calcium hydrophosphate is 1: 1-20; preferably 1: 1-10; more preferably 1: 1-3; more preferably 1: 1-1.5.
Further, in the step (2), in the mixed reaction, acid is added for catalysis. Acetic acid which is helpful for dissolving the DCP is added in the reaction process to obviously promote the reaction, and similarly, hydrochloric acid, nitric acid, phosphoric acid and other compounds which are used for promoting the dissolution of the DCP are added as catalysts to accelerate the reaction.
More preferably, the acid is one or more of acetic acid, hydrochloric acid, nitric acid, phosphoric acid and citric acid; more preferably acetic acid, citric acid.
Further, in the step (2), the mixing reaction is carried out for 0.5-72h at the temperature of 25-105 ℃.
Further, the feed preparation is mixed with a basic feed to prepare a complete feed.
In particular, the basal feed is routinely recognized by those skilled in the art, such as protein feed, energy feed, roughage, and the like.
Further, monocalcium phosphate may also be used instead of the calcium hydrogen phosphate.
The invention aims to provide a preparation method of methionine hydroxy analogue-calcium phosphate, which solves the problems that in the prior art, a large amount of organic solvent, zeolite powder and the like are additionally used for curing liquid hydroxy methionine as a dispersing agent or a carrier, or calcium hydroxide is used for directly neutralizing and curing to easily cause local coking, caking, agglomeration and poor fluidity of products; meanwhile, another purpose of the present application is to provide an economical secondary reaction method to increase the water-soluble phosphorus content of the existing cheap and easily available DCP product, and to achieve the improvement of the bioavailability and economic value without using phosphoric acid.
In the preparation method, the main chemical reactions are as follows:
the preparation method of the methionine hydroxy analogue-calcium phosphate salt comprises the following steps: mixing 10-95 wt% methionine hydroxy analogue with calcium hydrogen phosphate for reaction, and drying to obtain methionine hydroxy analogue-calcium phosphate; the mol ratio of the methionine hydroxy analogue to the calcium hydrophosphate is 1: 1-20.
Preferably, the molar ratio of the methionine hydroxy analogue to the calcium hydrogen phosphate is 1: 1-10; more preferably 1: 1-3; more preferably 1: 1-1.5.
Preferably, the concentration of the methionine hydroxy analogue is 10-88 wt%.
In particular, high concentrations of MHA (e.g., 88% concentration of commercial MHA) are responsible for the reaction to form MHA due to the presence of more anhydrides, dimers and oligomers in the ester form2Ca has certain obstruction and can be easily adsorbed to the surface of the product to cause agglomeration of the product and poor flowability. Therefore, before the composition is prepared, MHA is pretreated by a certain physical and chemical means, dimers and oligomers in MHA are converted into MHA monomers as much as possible, and then the MHA monomers are reacted with DCP to prepare the composition. Preferably, the methionine hydroxy analogue is hydrolyzed by one or more of heating dilution hydrolysis, high temperature and high pressure hydrolysis, acid hydrolysis, microwave radiation and ultrasonic radiation before the mixing reaction.
Specifically, the methionine hydroxy analogue solution is separately pretreated before the reaction to reduce the dimer and/or oligomer contained therein; the pretreatment refers to a process of converting oligomers in the methionine hydroxy analogue into monomers as much as possible by using a combination of one or more means including simple dilution heat hydrolysis (60-105 ℃), dilution and acid heat hydrolysis (0.1-2% MHA molar equivalent of strong acid such as sulfuric acid, hydrochloric acid, etc.), heat pressure hydrolysis (above 105 ℃, above 0.1 MPa), microwave radiation, ultrasonic radiation, etc.
Preferably, in the mixed reaction, acid is added for catalysis. Acetic acid which is helpful for dissolving the DCP is added in the reaction process to obviously promote the reaction, and similarly, hydrochloric acid, nitric acid, phosphoric acid and other compounds which are used for promoting the dissolution of the DCP are added as catalysts to accelerate the reaction.
More preferably, the acid is one or more of acetic acid, hydrochloric acid, nitric acid, phosphoric acid and citric acid; more preferably acetic acid, citric acid.
Preferably, the mixing reaction is carried out at 25-105 ℃ for 0.5-72 h.
In certain embodiments, the methionine hydroxy analog-calcium phosphate salt is prepared by: mixing the methionine hydroxy analogue and calcium hydrophosphate in the presence of water, carrying out heat preservation reaction for 0.5-72h at the temperature of 25-105 ℃, drying and removing water after the reaction is finished, and obtaining the methionine hydroxy analogue-calcium phosphate with uniform chroma, no agglomeration and agglomeration phenomenon, good dispersion fluidity and effective water-soluble phosphorus/total phosphorus ratio of 30-95 wt%.
Further, the reaction may be carried out using monocalcium phosphate instead of the calcium hydrogen phosphate.
The present invention also provides a methionine hydroxy analogue-calcium phosphate salt prepared by the above-mentioned method for preparing methionine hydroxy analogue-calcium phosphate salt. The calcium hydrogen phosphate is used as a calcium source for converting the methionine hydroxy analogue into the methionine hydroxy analogue calcium salt, and also used as a dispersant for the methionine hydroxy analogue and the calcium salt thereof, and the physical properties of the composition are changed through two aspects of chemistry and physics, so that the methionine hydroxy analogue-calcium phosphate salt which has good fluidity, uniform color, no agglomeration and stable property and is beneficial to storage and use is obtained. The effective water-soluble phosphorus accounts for 30-95 wt%.
Furthermore, the effective water-soluble phosphorus proportion is converted according to the actual amount of calcium hydrogen phosphate which can effectively participate in the reaction, namely, calcium hydrogen phosphate with the same molar amount as the methionine hydroxyl analogue is used as the effective water-soluble phosphorus proportion, the surplus carrier which is not considered to participate in the reaction is used, and the water-soluble phosphorus index which is considered to be carried by the carrier part is deducted.
Further, the mol ratio of the methionine hydroxy analogue to the calcium hydrophosphate is 1: 1-20; preferably 1: 1-10; more preferably 1: 1-3; more preferably 1: 1-1.5.
The invention aims to provide a feed preparation prepared by the preparation method for preparing the feed preparation, wherein the feed preparation can be a pig feed preparation or a broiler feed preparation, the composition can be directly prepared according to the addition ratio of phosphate to methionine in different animal premixes, and the necessary addition amounts of methionine, phosphorus and calcium required by the premixes are met at one time while the hydroxymethionine-calcium phosphate composition which is good in fluidity, free of agglomeration and high in bioavailability is provided.
Preferably, the feed preparation is a pig feed preparation, and the molar ratio of the methionine hydroxy analogue to the calcium hydrogen phosphate is 1: 10-11; or the feed preparation is a broiler feed preparation, and the mol ratio of the methionine hydroxyl analogue to the calcium hydrophosphate is 1: 3-4.
In the embodiment of the invention, the numerical values such as the measurement unit 'mass' and 'concentration' do not contain data errors caused by operation errors and instrument errors, even though the data errors caused by the operation errors and the instrument errors are still in the numerical values of the technical scheme of the invention.
The invention has the beneficial effects that
In the preparation method of the methionine hydroxy analogue-calcium phosphate composition provided by the invention, calcium hydrogen phosphate is simultaneously used as a calcium source for converting the methionine hydroxy analogue into the methionine hydroxy analogue calcium salt and also used as a dispersant for the methionine hydroxy analogue and the calcium salt thereof, and the physical properties of the composition are changed through two aspects of chemistry and physics, so that the solid methionine hydroxy analogue-calcium phosphate composition which has good fluidity, uniform color, no agglomeration and stable properties and is beneficial to storage and use is obtained.
According to the methionine hydroxy analogue-calcium phosphate composition prepared by the preparation method of the methionine hydroxy analogue-calcium phosphate composition, part of calcium hydrophosphate is converted into calcium dihydrogen phosphate with higher bioavailability, and the ratio analysis of water-soluble phosphorus shows that the ratio of effective water-soluble phosphorus in the composition after reaction is improved by about 2-8 times compared with that of water-soluble phosphorus in a raw material DCP, and the ratio of the effective water-soluble phosphorus is close to that of water-soluble phosphorus in MDCP and MCP, so that the biological value and the economic value of the calcium hydrophosphate are greatly improved.
The preparation method of the methionine hydroxy analogue-calcium phosphate composition skillfully utilizes the combined reaction of the methionine hydroxy analogue and calcium hydrophosphate in the feed additive, and prepares the calcium hydroxy methionine-calcium phosphate composition with good flowing dispersibility and effective water-soluble phosphorus ratio close to MDCP and MCP without adding extra dispersant or high-quality phosphoric acid.
In the preparation method of the feed preparation provided by the invention, the prepared methionine hydroxy analogue-calcium phosphate composition can be directly used for the combination of hydroxy methionine calcium and calcium phosphate salt added in the premix, and hydroxy methionine and calcium phosphate salt with proper proportion are added at one time, so that multi-party calculation and repeated addition are avoided, and the preparation method is simple, efficient and convenient.
Detailed Description
The examples are given for the purpose of better illustration of the invention, but the invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.
In the embodiment of the invention, the apparent water-soluble phosphorus proportion refers to a direct ratio of the water-soluble phosphorus content and the total phosphorus content obtained by product analysis, and the effective water-soluble phosphorus proportion is calculated according to the actual calcium hydrogen phosphate amount which can effectively participate in the reaction, namely, the equivalent molar amount of calcium hydrogen phosphate of methionine hydroxyl analogue is used as the effective water-soluble phosphorus proportion (see a chemical reaction formula below), the surplus is regarded as a carrier which does not participate in the reaction, and the water-soluble phosphorus index which is regarded as the carrier part is deducted. When the calcium hydrophosphate and the methionine hydroxyl analogue are fed according to the ratio of 1:1, the two indexes are the same and are not distinguished.
In the embodiment of the invention, the chemical equation of the reaction is as follows:
in the embodiment of the invention, DCP (calcium hydrophosphate) is 99 wt% type I and is sourced from Tianbao animal nutrition science and technology, Inc.
Example 1(105 ℃, 10%, 0.5h, 1:1)
34.1g of MHA (88 wt%, 0.2mol) are transferred into a 500ml glass beaker, stirred on and diluted to about 10% concentration with 270ml of pure water, in the form of a light brown clear solution having a pH of 2.5; heating the system to 105 ℃, adding 34.7g of DCP 0.2mol, keeping the temperature, stirring and reacting for 0.5h to obtain an off-white suspension. Removing excessive water to obtain off-white pasty fluid, transferring to a tray, and drying at 105 deg.C to obtain white solid powder 57.8g, with uniform chromaticity and good fluidity. However, the product is slightly sticky after being placed in contact with air for 4 hours at room temperature, and the fluidity of the product is poor.
The water-soluble phosphorus content of the product obtained by analysis is 34.55% (total phosphorus: 8.74%, water-soluble phosphorus: 3.02%), which is improved by about 2 times compared with 11.53% (total phosphorus: 17.08%, water-soluble phosphorus: 1.97%) of the water-soluble phosphorus in the raw material DCP. Obviously, because MHA is relatively acidic and not very acidic, and DCP has very low solubility in water, the reaction driving force is weak, the reaction is carried out in a heterogeneous phase, and the degree of reaction in a short time is still limited. Although the unreacted MHA is adsorbed and dispersed by DCP (and the converted MCP), it is apparent that the current unreacted MHA is too much, and thus the fluidity thereof is not stable.
Example 2(85 ℃, 20%, 1.5h, 1:1.2)
Transferring 34.1g of MHA (88 wt%, 0.2mol) into a 500ml four-neck flask, starting stirring, adding 120ml of pure water to dilute the mixture to about 20% concentration, wherein the system is brown clear liquid and the pH value is 2.5; heating to 85 ℃, adding 41.3g of DCP 0.24mol, and keeping the temperature to react for 1.5h to obtain an off-white suspension. Removing excessive water to obtain an off-white pasty fluid, transferring the off-white pasty fluid to a tray, drying at 105 ℃ to obtain 61.8g of a white solid powder product, wherein the yield is 98.63%, the obtained solid has uniform chromaticity, good fluidity and no agglomeration and agglomeration phenomenon, and the product is placed in the air at room temperature for 4 hours without obvious changes in appearance and fluidity.
The apparent water-soluble phosphorus content of the product obtained by analysis is 35.07% (total phosphorus: 10.72%, water-soluble phosphorus: 3.76%), and is 50.30% in terms of the mol number of the effective DCP participating in the reaction (based on the mol number of MHA), which is improved by nearly 4 times compared with 11.53% (total phosphorus: 17.08%, water-soluble phosphorus: 1.97%) of the water-soluble phosphorus in the raw material DCP.
Example 3(75 ℃, 20%, 3h, 1:1.5)
Transferring 34.1g of MHA (88 wt%, 0.2mol) into a 500ml four-neck flask, starting stirring, adding 120ml of pure water to dilute the mixture to about 20% concentration, wherein the system is brown clear liquid; heating to 75 ℃, adding 0.3mol of 51.8g of DCP, and reacting for 3 hours under the condition of heat preservation to obtain light grey white suspension. Removing excessive water to obtain offwhite pasty fluid, transferring the offwhite pasty fluid to a tray, and drying at 105 ℃ to obtain 71.14g of white solid powder product with yield of 99.08%, uniform product chromaticity, good fluidity and no agglomeration. The product is placed in the air for 4 hours at room temperature, and the appearance and the fluidity are not obviously changed.
The apparent water-soluble phosphorus content of the obtained product is 45.14% (total phosphorus: 12.14%, water-soluble phosphorus: 5.48%) in analysis, the effective water-soluble phosphorus content is 61.98%, and the effective water-soluble phosphorus content is improved by about 5 times compared with 11.53% (total phosphorus: 17.08%, water-soluble phosphorus: 1.97%) in the raw material DCP.
From examples 2 and 3, it can be seen that the control of the temperature, the concentration of MHA, the reaction time and the ratio of DCP to MHA in a certain range is helpful for the conversion of MHA to MHA2-Ca and the conversion of DCP to MCP in the composition, so as to obtain a product with more stable fluidity and improved water-soluble phosphorus content. It is however clear that there are chemically preferred combinations of the above parameters in order to obtain the best conversion efficiency, but that further attempts have been made to provide preferred conditions which are at the same time economically satisfactory in view of production, for which purpose parameters such as temperature, MHA concentration and reaction time length are used.
Example 4(25 ℃, 20%, 36h, 1:1.5)
Transferring 34.1g of MHA (88 wt%, 0.2mol) into a 500ml four-neck flask, starting stirring, adding 120ml of pure water to dilute the mixture to about 20% concentration, wherein the system is brown clear liquid; at room temperature (about 25 ℃), 51.6g of 0.3mol of DCP is added, and the mixture is stirred and reacted for 36 hours under the condition of heat preservation, thus obtaining light grey white suspension. Removing excessive water to obtain off-white pasty fluid, transferring the off-white pasty fluid to a tray, and drying at 105 ℃ to obtain 70.22g of white solid powder product, wherein the white solid powder product has uniform chroma, good fluidity and no agglomeration and agglomeration phenomenon, and the product is placed in the air at room temperature for 6 hours, and has no obvious change in appearance and fluidity.
The apparent water-soluble phosphorus content of the obtained product is 33.47% (total phosphorus: 12.40%, water-soluble phosphorus: 4.15%) in analysis, the effective water-soluble phosphorus content is 44.43%, and the effective water-soluble phosphorus content is improved by about 3 times compared with 11.53% (total phosphorus: 17.08%, water-soluble phosphorus: 1.97%) of the water-soluble phosphorus in the raw material DCP.
Example 5(25 ℃, 88%, 72h, 1:1.5)
Transferring 34.1g MHA (88 wt%, 0.2mol) into a 500ml glass beaker, adding 51.6g DCP 0.24mol, stirring and mixing uniformly by a glass rod to obtain a brown-white slurry mixture, sealing, standing at 25 ℃, curing and reacting for 72h, stirring and mixing uniformly at intervals of 12-24h, drying and crushing the product after the reaction to obtain 68.92g of white powdery solid, and the white powdery solid has uniform chroma, good fluidity and no agglomeration. The product is placed in the air for 6 hours at room temperature, and the appearance and the fluidity are not obviously changed.
The apparent water-soluble phosphorus content of the obtained product is 42.81% (total phosphorus: 12.17%, water-soluble phosphorus: 5.21%) through analysis, the effective water-soluble phosphorus content is 58.45%, and the effective water-soluble phosphorus content is improved by about 4 times compared with 11.53% (total phosphorus: 17.08%, water-soluble phosphorus: 1.97%) of the water-soluble phosphorus in the raw material DCP.
Example 6(45 ℃, 88%, 24h, 1:1.5)
Transferring 34.1g MHA (88 wt%, 0.2mol) into a 500ml glass beaker, adding 0.3mol of 51.6g DCP, stirring and mixing uniformly by a glass rod to obtain a brown-white slurry mixture, sealing, standing at 45 ℃, curing and reacting for 24h, stirring and mixing uniformly at intervals of 4-8h, drying and crushing the product after the reaction to obtain 69.68g of white powdery solid, and having uniform chroma, good fluidity and no agglomeration. The product is placed in the air for 6 hours at room temperature, and the appearance and the fluidity are not obviously changed.
The apparent water-soluble phosphorus content of the obtained product is 43.21% (total phosphorus: 12.08%, water-soluble phosphorus: 5.22%) by analysis, the effective water-soluble phosphorus content is 59.06% by conversion, and the effective water-soluble phosphorus content is improved by about 4 times compared with 11.53% (total phosphorus: 17.08%, water-soluble phosphorus: 1.97%) of the water-soluble phosphorus in the raw material DCP.
From examples 4-6, it can be seen that, on the whole, optimization of the conditions of the preparation process of the composition can obtain a product with an apparent water-soluble phosphorus content of more than 40% and an effective water-soluble phosphorus content of approximately 60%, and the product has uniform chromaticity, good fluidity, no agglomeration and an increase of about 3-4 times of the content of the water-soluble phosphorus in DCP.
Example 7(85 ℃, 20%, 3h, 1:1, plus catalysis)
Transferring 34.1g of MHA (88 wt%, 0.2mol) into a 500ml four-neck flask, starting stirring, adding 120ml of pure water to dilute the mixture to about 20% concentration, wherein the system is brown clear liquid; heating to 75 ℃, adding 34.4g of DCP 0.2mol, simultaneously adding 8g of glacial acetic acid, and reacting for 3 hours under the condition of heat preservation to obtain light grey white suspension. Removing excessive water to obtain off-white pasty fluid, transferring the off-white pasty fluid to a tray, and drying at 105 ℃ to obtain 58.4g of white solid powder product with uniform chroma, good fluidity and no agglomeration. The product is placed in the air for 6 hours at room temperature, and the appearance and the fluidity are not obviously changed.
The water-soluble phosphorus content of the product obtained by analysis is 71.99% (total phosphorus: 8.64%, water-soluble phosphorus: 6.22%), which is improved by about 6 times compared with 11.53% (total phosphorus: 17.08%, water-soluble phosphorus: 1.97%) of the water-soluble phosphorus in the raw material DCP.
Example 8(75 ℃, 20%, 1.5h, 1:1.5, hydrolysis with sulfuric acid for 1.5h)
Transferring 34.1g MHA (88 wt%, 0.2mol) into a 500ml glass beaker, starting stirring, adding 120ml pure water to dilute to about 20% concentration, adding 2g sulfuric acid (75 wt%), stirring and hydrolyzing at 85 ℃ for 1.5h, monitoring the content of dimer and polymer by HPLC to reduce to about 3.75 wt%, adding 51.6g DCP 0.3mol, and reacting at 75 ℃ for 1.5h to obtain light grey white suspension. Removing excessive water to obtain off-white pasty fluid, transferring the off-white pasty fluid to a tray, and drying at 105 ℃ to obtain 69.74g of white solid powder product with uniform chroma, good fluidity and no agglomeration. The product is placed in the air for 6 hours at room temperature, and the appearance and the fluidity are not obviously changed.
The product obtained by analysis has an apparent water-soluble phosphorus content of 44.33% (total phosphorus: 12.52%, water-soluble phosphorus: 5.55%), a reduced effective water-soluble phosphorus content of 60.73%, and an effective water-soluble phosphorus content which is about 5 times higher than 11.53% (total phosphorus: 17.08%, water-soluble phosphorus: 1.97%) of the water-soluble phosphorus in the raw material DCP.
From the comparison of example 3 and example 8 above, it is clear that after pretreatment, 20% concentration MHA and DCP reacted at 75 ℃ for 1.5h, which is equivalent or slightly superior to that of the non-pretreated MHA, for 3 h.
Example 9(85 ℃, 44%, 1.5h, 1:3)
Preparation of hydroxy methionine-calcium phosphate composition added in premix for broiler chickens
Transferring 34.1g MHA (88 wt%, 0.2mol) into a 500ml glass beaker, starting stirring, adding 35ml pure water to dilute the mixture to about 44% concentration, wherein the system is brown clear liquid; heating to 75 ℃, adding 103.2g of DCP 0.6mol, reacting for 1.5h under heat preservation, drying to remove water, transferring to 105 ℃ and drying to obtain 112.6g of white solid powder product with uniform chroma, good fluidity and no agglomeration. The product is placed in the air for 6 hours at room temperature, and the appearance and the fluidity are not obviously changed.
The apparent water-soluble phosphorus content of the product obtained by analysis is 23.76% (total phosphorus: 14.52%, water-soluble phosphorus: 3.45%), the effective water-soluble phosphorus content is 59.75%, and the effective water-soluble phosphorus content is improved by about 5 times compared with 11.53% (total phosphorus: 17.08%, water-soluble phosphorus: 1.97%) of the water-soluble phosphorus in the raw material DCP.
Example 10(75 ℃, 20%, 1.5h, 1:10)
Preparation of a premix-added hydroxymethionine-calcium phosphate composition for swine
Transferring 341gMHA (88 wt%, 2mol) into a 5L reaction kettle, starting stirring, adding 1200ml of pure water to dilute the mixture to about 20% concentration, wherein the system is brown clear liquid; heating to 75 ℃, adding 3442g of DCP 20mol, and reacting for 1.5h under heat preservation to obtain light grey white suspension. The suspension is sent to spray drying (105 ℃), and 3174g of white solid powder product is obtained, which has uniform chroma, good fluidity and no agglomeration. The product is placed in the air for 6 hours at room temperature, and the appearance and the fluidity are not obviously changed.
The apparent water-soluble phosphorus content of the product obtained by analysis is 16.33% (total phosphorus: 16.11%, water-soluble phosphorus: 2.33%), the effective water-soluble phosphorus content is 92.69%, and the effective water-soluble phosphorus content is improved by about 8 times compared with 11.53% (total phosphorus: 17.08%, water-soluble phosphorus: 1.97%) of the water-soluble phosphorus in the raw material DCP.
Example 11(MHA + MDCP, 75 ℃, 20%, 1h, 1:2)
Transferring 34.1g MHA (88 wt%, 0.2mol) into a 500ml glass beaker, starting stirring, adding 120ml pure water to dilute the mixture to about 20% concentration, wherein the system is brown clear liquid; heating to 75 ℃, adding 57.3g of MDCP (total phosphorus 21.64 wt%, 0.4mol (calculated by P)), keeping the temperature and reacting for 1h to obtain light grey white suspension, drying to remove water, transferring out and drying at 105 ℃ to obtain 87.0g of white solid powder product with uniform chroma, good fluidity and no agglomeration. The product is placed in the air for 6 hours at room temperature, and the appearance and the fluidity are not obviously changed.
The water-soluble phosphorus content of the obtained product was 80.88% (total phosphorus: 14.24%, water-soluble phosphorus: 11.52%) which was improved by about 17% compared with 63.68% (total phosphorus: 21.64%, water-soluble phosphorus: 13.78%) of the raw material MDCP.
The range requirements for water soluble phosphorus in DCP, MDCP, MCP products can be derived from relevant standards, see table 1 below.
TABLE 1 Water soluble phosphorus content requirement for different calcium phosphates
From examples 1 to 10, it can be seen that the water-soluble phosphorus content of the composition obtained after the reaction is greatly improved compared with that of the raw material DCP before the reaction, and even if the apparent water-soluble phosphorus content of the composition obtained in examples 3, 5, 6, 7 and 8 is improved to more than 40%, the requirement of MDCP products on the water-soluble phosphorus content is basically met, and from examples 7 and 11, the effective water-soluble phosphorus content of the composition after the reaction reaches or is close to that of MCP, which shows that the effective conversion of DCP and MHA is high, and the remarkable improvement of the water-soluble phosphorus content is beneficial to the absorption and utilization of phosphorus and calcium in the products by animals, so that the aim of improving the bioavailability of DCP by the invention is achieved.
In addition, it is clear from the examples that the compositions are obtained predominantly from the reaction of MHA with DCP, predominantly by conversion of MHA with DCP to MHA2Ca and MCP, but the conversion of the reaction (effective reaction mass in MHA molar amount, conversion scale 0 when 11% water-soluble phosphorus is used as reference, conversion 100% 91% water-soluble phosphorus) is in the range of 30% to 100%, and is mainly centered around 50-60%, as estimated by the index of effective water-soluble phosphorus content.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. A method for preparing a feed formulation, characterized in that the preparation method comprises the steps of:
(1) hydrolyzing 10-95 wt% of methionine hydroxy analogue to obtain methionine hydroxy analogue monomer, wherein the hydrolysis mode is one or combination of heating dilution hydrolysis, high-temperature high-pressure hydrolysis, acid hydrolysis, microwave radiation and ultrasonic radiation;
(2) mixing the obtained methionine hydroxy analogue monomer with calcium hydrogen phosphate for reaction, and drying to obtain methionine hydroxy analogue-calcium phosphate;
(3) mixing the obtained methionine hydroxy analogue-calcium phosphate with other nutrient elements and/or carriers required by feeding objects to prepare a feed preparation;
wherein, the mol ratio of the methionine hydroxy analogue to the calcium hydrophosphate is determined by one-time calculation according to the nutrient contents of methionine, phosphorus and calcium required in different feed preparations.
2. The method according to claim 1, wherein the molar ratio of said methionine hydroxy analogue to said calcium hydrogen phosphate is 1: 1-20.
3. The method according to claim 1, wherein the feed preparation is mixed with a basal feed to prepare a complete feed.
4. A method of preparation according to any one of claims 1 to 3, characterized in that dicalcium phosphate is used instead of said dicalcium phosphate.
5. A method for producing a methionine hydroxy analog-calcium phosphate salt, comprising: mixing 10-95 wt% methionine hydroxy analogue with calcium hydrogen phosphate for reaction, and drying to obtain methionine hydroxy analogue-calcium phosphate; the mol ratio of the methionine hydroxy analogue to the calcium hydrophosphate is 1: 1-20.
6. The method according to claim 5, wherein the molar ratio of said methionine hydroxy analogue to said calcium hydrogen phosphate is 1: 1-10.
7. The method according to claim 5 or 6, wherein the methionine hydroxy analogue is hydrolyzed by one or more of dilution hydrolysis by heating, hydrolysis at high temperature and pressure, hydrolysis by adding acid, microwave irradiation, and ultrasonic irradiation; and/or in the mixed reaction, adding acid for catalysis.
8. The method according to claim 5 or 6, wherein the mixing reaction is carried out at 25 to 105 ℃ for 0.5 to 72 hours.
9. The methionine hydroxy analogue-calcium phosphate salt prepared by the preparation method according to any one of claims 3 to 8, wherein the effective water-soluble phosphorus content is 30 to 95 wt%.
10. The feed preparation prepared by the preparation method of claim 1, wherein the feed preparation is a pig feed preparation, and the mol ratio of the methionine hydroxy analogue to the calcium hydrophosphate is 1: 10-11; or the feed preparation is a broiler feed preparation, and the mol ratio of the methionine hydroxyl analogue to the calcium hydrophosphate is 1: 3-4.
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