Liquid complex acidifying agent and use thereof

Abstract

This application provides a liquid composite acidifier and its application. The first aspect of this application provides a liquid composite acidifier comprising formic acid, hydroxymethionine, and water. The liquid composite acidifier further includes at least one of phosphoric acid, lactic acid, and propionic acid. The liquid composite acidifier provided in this application is prepared by adding formic acid and hydroxymethionine to water. The formic acid and hydroxymethionine components have a synergistic effect, which can increase feed intake in livestock and poultry, especially weaned piglets, promoting growth, inhibiting common intestinal bacteria such as Escherichia coli and Salmonella, and providing an additional effective source of methionine. The liquid composite acidifier of this application is carrier-free, has a high acid content, and strong functionality. It can be used as a feed acidifier and also for adjusting the pH of drinking water.

Description

Technical Field

[0001] This application relates to the field of feed additive technology, specifically to a liquid compound acidifier and its application. Background Technology

[0002] This application is a divisional application of the invention patent application with application number 202311032842.0, application date August 16, 2023, entitled "Liquid composite acidifier, preparation method of liquid composite acidifier and application".

[0003] The use of high acid-binding ingredients such as limestone powder in feed exacerbates the impact on the digestion of weaned piglets. It is necessary to reduce the acid-binding capacity of feed by acidifying agents, reduce the neutralization of gastric acid by feed, improve the digestion of crude protein in the gastrointestinal tract, inhibit the growth of pathogens, improve the intestinal microbiota, and improve the health of animals.

[0004] Currently, most acidifiers added to feed are solid acidifiers, which have carriers and low total acid content of active ingredients, affecting feed bulk density and impacting feed production and formulation design. Escherichia coli and Salmonella are common pathogens in the intestines of weaned piglets; inhibiting their growth can effectively promote animal growth. Summary of the Invention

[0005] The first aspect of this application provides a liquid composite acidifier comprising formic acid, hydroxymethionine and water, and the liquid composite acidifier further comprising at least one of phosphoric acid, lactic acid and propionic acid.

[0006] The liquid compound acidifier provided in this application is a mixture of formic acid and hydroxymethionine with water. The formic acid and hydroxymethionine components work synergistically to increase feed intake in livestock, especially weaned piglets, promoting growth, while also inhibiting common intestinal bacteria such as Escherichia coli and Salmonella, and providing an additional effective source of methionine. This liquid compound acidifier is carrier-free, has a high acid content, and strong functionality; it can be used as a feed acidifier or to adjust the pH of drinking water.

[0007] Each component in the liquid compound acidifier provided in this application is listed in the "Catalogue of Feed Additive Varieties (2013)" (Announcement No. 2425 of the Ministry of Agriculture of the People's Republic of China).

[0008] In some optional embodiments of the first aspect of this application, the mass ratio of formic acid to hydroxymethionine is 0.1 to 10.

[0009] In some optional embodiments of the first aspect of this application, the mass ratio of formic acid to hydroxymethionine is 0.5 to 5.

[0010] In some optional embodiments of the first aspect of this application, the mass ratio of formic acid to hydroxymethionine is 0.75 to 2.5.

[0011] In some optional embodiments of the first aspect of this application, the liquid composite acidifier further includes a surfactant.

[0012] In some optional embodiments of the first aspect of this application, the surfactant is selected from either polyoxyethylene sorbitan fatty acid ester or polyoxyethylene ricinoleate glycerol.

[0013] In some optional embodiments of the first aspect of this application, the liquid composite acidifier further comprises phosphoric acid, lactic acid and propionic acid, and the mass ratio of hydroxymethionine, formic acid, phosphoric acid, lactic acid and propionic acid is 30~32:40~41:1~6:3~8:2~7.

[0014] In some optional embodiments of the first aspect of this application, the liquid composite acidifier further includes glyceryl laurate, wherein the mass fraction of glyceryl laurate in the liquid composite acidifier is 0.5% to 2.5%.

[0015] In some optional embodiments of the first aspect of this application, the liquid composite acidifier further includes plant essential oils, wherein the mass fraction of the plant essential oils in the liquid composite acidifier is 0.5% to 2.5%.

[0016] The second aspect of this application provides the application of the liquid composite acidifier of the first aspect of this application in piglet feed.

[0017] The third aspect of this application provides the application of the liquid composite acidifier of the first aspect of this application in acidified drinking water.

[0018] The fourth aspect of this application provides a method for preparing the liquid composite acidifier of the first aspect of this application, comprising:

[0019] Weigh the raw material components of the liquid composite acidifier, which include formic acid, hydroxymethionine, glyceryl laurate, and water;

[0020] Heat and stir the formic acid until the temperature of the formic acid rises to 30°C to 40°C;

[0021] Add glyceryl laurate to formic acid that has been heated to the target temperature to obtain a first mixture and stir the first mixture for 5 min to 15 min;

[0022] The remaining raw material components are added to the first mixture and stirred until homogeneous to obtain a liquid composite acidifier.

[0023] In some optional embodiments of the fourth aspect of this application, the stirring speed of the stirring operation is 120 rpm to 150 rpm. Detailed Implementation

[0024] The technical solutions of this application will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0025] The features and exemplary embodiments of various aspects of the present invention will now be described in detail. To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are only configured to explain the present invention and are not configured to limit the present invention. For those skilled in the art, the present invention can be practiced without some of these specific details. The following description of the embodiments is merely intended to provide a better understanding of the present invention by illustrating examples of the invention.

[0026] It should be noted that, in this document, relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising..." does not exclude the presence of additional identical elements in the process, method, article, or apparatus that includes said element.

[0027] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0028] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0029] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0030] Furthermore, the technical features involved in the different embodiments of this application described below can be combined with each other as long as they do not conflict with each other.

[0031] The first aspect of this application provides a liquid composite acidifier comprising formic acid, hydroxymethionine, and water.

[0032] The liquid compound acidifier provided in this application is a mixture of formic acid and hydroxymethionine with water. The formic acid and hydroxymethionine components work synergistically to increase feed intake in livestock, especially weaned piglets, promoting growth, while also inhibiting common intestinal bacteria such as Escherichia coli and Salmonella, and providing an additional effective source of methionine. This liquid compound acidifier is carrier-free, has a high acid content, and strong functionality; it can be used as a feed acidifier or to adjust the pH of drinking water.

[0033] Each component in the liquid compound acidifier provided in this application is listed in the "Catalogue of Feed Additive Varieties (2013)" (Announcement No. 2425 of the Ministry of Agriculture of the People's Republic of China).

[0034] In some optional embodiments of the first aspect of this application, the mass ratio of formic acid to hydroxymethionine is 0.1 to 10.

[0035] In some optional embodiments of the first aspect of this application, the mass ratio of formic acid to hydroxymethionine is 0.5 to 5.

[0036] In some optional embodiments of the first aspect of this application, the mass ratio of formic acid to hydroxymethionine is 0.75 to 2.5.

[0037] In some optional embodiments of the first aspect of this application, the liquid composite acidifier further includes a surfactant.

[0038] In some optional embodiments of the first aspect of this application, the surfactant is selected from either polyoxyethylene sorbitan fatty acid ester or polyoxyethylene ricinoleate glycerol.

[0039] In some optional embodiments of the first aspect of this application, the liquid composite acidifier further includes at least one of phosphoric acid, lactic acid, and propionic acid.

[0040] In some optional embodiments of the first aspect of this application, the liquid composite acidifier further comprises phosphoric acid, lactic acid and propionic acid, and the mass ratio of hydroxymethionine, formic acid, phosphoric acid, lactic acid and propionic acid is 30~32:40~41:1~6:3~8:2~7.

[0041] In some optional embodiments of the first aspect of this application, the liquid composite acidifier further includes glyceryl laurate, wherein the mass fraction of glyceryl laurate in the liquid composite acidifier is 0.5% to 2.5%.

[0042] In some optional embodiments of the first aspect of this application, the liquid composite acidifier further includes plant essential oils, wherein the mass fraction of the plant essential oils in the liquid composite acidifier is 0.5% to 2.5%.

[0043] The second aspect of this application provides the application of the liquid composite acidifier of the first aspect of this application in piglet feed.

[0044] The third aspect of this application provides the application of the liquid composite acidifier of the first aspect of this application in acidified drinking water.

[0045] The fourth aspect of this application provides a method for preparing the liquid composite acidifier of the first aspect of this application, comprising:

[0046] Weigh the raw material components of the liquid composite acidifier, which include formic acid, hydroxymethionine, glyceryl laurate, and water;

[0047] Heat and stir the formic acid until the temperature of the formic acid rises to 30°C to 40°C;

[0048] Add glyceryl laurate to formic acid that has been heated to the target temperature to obtain a first mixture and stir the first mixture for 5 min to 15 min;

[0049] The remaining raw material components are added to the first mixture and stirred until homogeneous to obtain a liquid composite acidifier.

[0050] In some optional embodiments of the fourth aspect of this application, the stirring speed of the stirring operation is from 120 rpm to 150 rpm.

[0051]

Example

[0052] To make the inventive objectives, technical solutions, and beneficial technical effects of this application clearer, the following detailed description is provided in conjunction with embodiments. However, it should be understood that the embodiments of this application are merely for illustrative purposes and not for limiting the application, and the embodiments are not limited to those given in the specification. Unless otherwise specified, the experimental conditions in the embodiments are conventional conditions or conditions recommended by material or equipment suppliers.

[0053] I. Mass fraction of each component and proportional relationship between components in the acidifying agents of different embodiments and comparative examples

[0054] Table 1

[0055]

[0056] Comparative Examples B1 to B3 were purchased from a feed additive company in Shandong Province and were commercially available products.

[0057] II. Determination of the properties of acidifying agents in the examples and comparative examples

[0058] 2.1 Total acid content test;

[0059] The total acid content was determined according to Method II of GB 12456-2021 "Determination of Total Acidity in Food"—pH meter potentiometric titration method. The total acid content was expressed as lactic acid (g / 100mL), and the results are shown in Table 2 below:

[0060] Table 2

[0061]

[0062] 2.2 Acid strength test;

[0063] Acid-binding capacity refers to the ability of a diet to bind acid, that is, the amount of H+ required to lower the pH of a certain amount of feed sample to 4. The acid-binding capacity of an acidifier is tested as follows: Take 50g of feed, add 100mL of deionized water, mix well, and measure the pH. Titrate the pH to 4 using 1mol / L hydrochloric acid, and record the volume of hydrochloric acid consumed, V0. Take 50g of feed containing a certain amount of acidifier, add 100mL of deionized water, mix well, and measure the pH. Titrate the pH to 4 using 1mol / L hydrochloric acid, and record the volume of hydrochloric acid consumed, V1. Calculate the ABC-4 (mEqH+ / kg) of the acidifier using the following formula:

[0064] ABC-4 (mEqH+ / kg) = (V0-V1) (L) * HCl concentration (1 mol / L) / acidifier mass (kg) * 1000

[0065] The experimental results are shown in Table 3 below:

[0066] Table 3

[0067]

[0068] A higher acid-binding power value indicates a stronger affinity for acid, which is detrimental to feed. Since the acidifier in this application provides acid, its acid-binding power is negative, and a smaller value indicates that the acidifier provides more acid. 2.3 Inhibition Zone Test; The inhibition zone test reflects the acidifier's ability to inhibit common pathogens. The experimental method is as follows: Prepare MHA agar medium, and spread 100 μL of activated bacterial solution onto the plate. Immerse small round filter paper discs (6 mm in diameter) in different acidifier solutions (solid acidifier dissolved 1:5, liquid composite acidifier diluted 1:5). Place the small round filter paper discs on the surface of the MHA agar plate, invert it, and incubate it in a 35℃±2℃ incubator for 16–18 hours. Measure the diameter of the inhibition zone using calipers (round to the nearest integer, unit: mm). The selected pathogens included: enteroaggregative Escherichia coli, enteropathogenic Escherichia coli, hemorrhagic Escherichia coli O157:H7, enterotoxigenic Escherichia coli, enterohemorrhagic Escherichia coli, enteroinvasive Escherichia coli, Shigella typhimurium, Salmonella enterica subspecies cholerae, and Salmonella enterica subspecies enteritis serotype. The results of the inhibition zone experiment are shown in Table 4 below.

[0069] Table 4

[0070]

[0071] 2.4 Application Experiment of Acidified Drinking Water

[0072] The liquid composite acidifier provided in this application also has the ability to acidify drinking water. The drinking water acidification capacity refers to the volume (µL) of acidifier required to lower the pH of 1L of tap water to 4, as shown in Table 5 below:

[0073] Table 5

[0074]

[0075] 2.5 Wetting properties

[0076] The wetting performance test method is as follows: The feed was crushed and sieved to collect feed particles with a diameter of 0.4-0.6 mm. These particles were then pressed into tablets with a thickness of 5 mm using a tableting machine. 20 μL of liquid composite acidifying agent (from Examples A1, D1, and D2) was accurately added to the center of the tablet. The time it took for all the liquid to penetrate into the tablet was calculated, which is the wetting time (s). The results are shown in Table 6 below.

[0077] Table 6

[0078]

[0079] As shown in Table 6 above, adding surfactants to liquid composite acidifiers can enhance their wetting properties, thereby allowing them to be better adsorbed by feed particles and improving the uniformity of mixing of liquid composite acidifiers in feed.

[0080] III. Preparation Method

[0081] Method 1: A method in which the acidifier contains glyceryl laurate (used to prepare the liquid composite acidifier of Example C1).

[0082] Step 1: Weigh each component in sequence;

[0083] Step 2: Add formic acid to a heated and stirred container, and heat the formic acid to 30°C to 40°C;

[0084] Step 3: Add glyceryl laurate to the container and stir, that is, add glyceryl laurate to formic acid that has been raised to the target temperature to obtain the first mixture and stir the first mixture for 10 minutes to form a homogeneous liquid;

[0085] Step 4: Pour the remaining raw materials into the container in sequence and stir to obtain the finished liquid composite acidifier.

[0086] Method 2: A method in which the acidifier does not contain glyceryl laurate (e.g., the liquid composite acidifier used to prepare Example C2).

[0087] Step 1: Weigh each component in sequence;

[0088] Step 2: Pour each group of raw materials into a container in sequence and stir to obtain the finished liquid composite acidifier.

[0089] Comparative method: A method in which the acidifier contains glyceryl laurate (used to prepare the liquid composite acidifier of Example C1, after which glyceryl laurate was added).

[0090] Step 1: Weigh each component in sequence;

[0091] Step 2: Add all ingredients except glyceryl laurate into the container and stir.

[0092] Step 3: Add glyceryl laurate to the container and stir until a homogeneous liquid is formed to obtain the finished liquid composite acidifier.

[0093] After preparing 1L of liquid composite acidifier according to the corresponding preparation method, record the preparation time (min).

[0094] The stirring speed in each method was varied from 120 rpm to 150 rpm. The experimental results are shown in Table 7 below:

[0095] Table 7

[0096]

[0097] Therefore, when preparing a liquid composite acidifier with raw material components including formic acid, hydroxymethionine, glyceryl laurate and water, the method of first heating the formic acid, then adding glyceryl laurate to the heated formic acid and mixing, and finally adding other components, can greatly reduce the preparation time of the liquid composite acidifier.

[0098] IV. Examples and Comparative Analysis

[0099] 4.1 Example Group A:

[0100] Example A group includes Examples A1 to A3, which explore the ratio of formic acid to hydroxymethionine;

[0101] Example A2 had the highest formic acid content, followed by A1, and A3 had the lowest formic acid content. From the total acid content test, a higher formic acid content indicates a greater acid content. From the acid-binding power results, a higher formic acid content and a higher formic acid to hydroxymethionine ratio resulted in a lower acid-binding power value and weaker acid binding force, which is more beneficial for optimizing feed performance. From the inhibition zone test analysis, a larger inhibition zone diameter is better. The ranking of antibacterial abilities against various Escherichia coli and Salmonella strains was: Example A2 had a stronger antibacterial ability than Example A1, and Example A1 had a stronger antibacterial ability than Example A3.

[0102] Liquid compound acidifiers containing formic acid and hydroxymethionine have significant advantages over commercially available solid acidifiers in inhibiting bacteria, especially Escherichia coli and Salmonella. Liquid acidifiers containing formic acid and hydroxymethionine exhibit a substantial reduction in feed acidity and a significant increase in acid content, thus effectively reducing feed acidity, minimizing the neutralization of stomach acid by feed, improving gastrointestinal digestion of crude protein, inhibiting the growth of pathogens, improving the intestinal microbiota, enhancing animal health, and effectively promoting animal growth.

[0103] 4.2 Example B Group:

[0104] Example B group includes Examples B1 to B2, which investigate the performance of a liquid composite acidifier containing formic acid, hydroxymethionine, phosphoric acid, lactic acid, and propionic acid. From the total acid content test, the acid content of Examples B1 to B4 significantly exceeded that of commercially available solid acidifiers (Comparative Examples B1 to B3). From the acid-holding capacity test results, the acid-holding capacity of Examples B1 to B4 was lower than that of commercially available solid acidifiers (Comparative Examples B1 to B3), indicating that Examples B1 to B4 provided more acid.

[0105] The inhibition zone test showed that the addition of phosphoric acid, lactic acid, and propionic acid to the liquid composite acidifier enhanced the antibacterial effect against various Escherichia coli and various Salmonella species compared to Examples A1 to A2, which only contained formic acid and hydroxymethionine, resulting in an increase in the diameter of the inhibition zone.

[0106] 4.3 Comparative Example A:

[0107] Comparative Example A includes Comparative Examples A1 to A3, which are mainly used to investigate the synergistic effect of formic acid, hydroxymethionine, phosphoric acid, lactic acid and propionic acid in liquid composite acidifier. The experimental results can be compared with those of Example B and Example A.

[0108] Comparative Example A can be compared with Example A1, and Comparative Example A1 can be compared with Example B1. In Comparative Examples A1 to A3, the liquid composite acidifiers in each comparative example lack one of phosphoric acid, lactic acid, or propionic acid. From the results of the total acid content and acid-binding capacity tests, the total acid content and acid-binding capacity of Comparative Examples A1 to A3 are relatively close to the results of Example B1. However, the inhibition zone test shows that when the liquid composite acidifier lacks any one of phosphoric acid, lactic acid, or propionic acid, the antibacterial ability of the liquid composite acidifier is generally lower than that of all liquid composite acidifiers containing all three. Comparing Comparative Example A with Example A1, the total acid content and acid-binding capacity of Comparative Example A are relatively close to the results of Example A1. However, the inhibitory effects of each comparative example in Comparative Example A on various Escherichia coli and Salmonella strains were generally weaker than those of Example A1. Therefore, the five components of the liquid composite acidifier—formic acid, hydroxymethionine, phosphoric acid, lactic acid, and propionic acid—have a synergistic effect in inhibiting various Escherichia coli and Salmonella strains, and their inhibitory effects are stronger than those of liquid composite acidifiers containing only formic acid and hydroxymethionine, or those containing formic acid and hydroxymethionine plus any two of phosphoric acid, lactic acid, and propionic acid.

[0109] 4.4 Example C:

[0110] Example C group includes Example C1 and Example C2. The performance of the liquid composite acidifier, which contains formic acid, hydroxymethionine, phosphoric acid, lactic acid, and propionic acid, was investigated by adding glyceryl laurate or plant essential oil.

[0111] Compared with Example B1, the total acid content and acid-binding power are similar. However, the results of the inhibition zone test show that after adding glyceryl laurate or plant essential oil, the antibacterial effects of this application example against various Escherichia coli and various Salmonella were significantly enhanced compared with Example B1.

[0112] 4.5 Example D:

[0113] Example D group includes Example D1 and Example D2. It investigates the effect of adding a surfactant on the wetting properties of a liquid composite acidifier.

[0114] As can be seen from the wetting performance experiment in section 2.5 above, the addition of surfactant can increase the wetting performance of the composite acid liquid composite acidifier, thereby allowing it to be better adsorbed by feed particles and improving the mixing uniformity of the liquid composite acidifier in the feed.

[0115] The above description is only a specific embodiment of this application, but the protection scope of this application is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the protection scope of this application.

Claims

1. A liquid composite acidifier, characterized in that, It contains formic acid, hydroxymethionine and water, and the liquid composite acidifier further includes at least one of phosphoric acid, lactic acid and propionic acid.

2. The liquid composite acidifier according to claim 1, characterized in that, The mass ratio of formic acid to hydroxymethionine is 0.1 to 10.

3. The liquid composite acidifier according to claim 2, characterized in that, The mass ratio of formic acid to hydroxymethionine is 0.5 to 5.

4. The liquid composite acidifier according to claim 3, characterized in that, The mass ratio of formic acid to hydroxymethionine is 0.75 to 2.

5.

5. The liquid composite acidifier according to claim 1, characterized in that, The liquid composite acidifier also includes surfactants.

6. The liquid composite acidifier according to claim 5, characterized in that, The surfactant is selected from either polyoxyethylene sorbitan fatty acid ester or polyoxyethylene ricinoleate glycerol.

7. The liquid composite acidifier according to claim 1, characterized in that, The liquid composite acidifier further includes phosphoric acid, lactic acid and propionic acid, and the mass ratio of hydroxymethionine, formic acid, phosphoric acid, lactic acid and propionic acid is 30~32:40~41:1~6:3~8:2~7.

8. The liquid composite acidifier according to claim 7, characterized in that, The liquid composite acidifier also includes glyceryl laurate, and the mass fraction of glyceryl laurate in the liquid composite acidifier is 0.5% to 2.5%.

9. The liquid composite acidifier according to claim 7, characterized in that, The liquid composite acidifier also includes plant essential oils, and the mass fraction of the plant essential oils in the liquid composite acidifier is 0.5% to 2.5%.

10. The application of a liquid composite acidifier as described in any one of claims 1 to 9 in piglet feed.

11. The application of a liquid composite acidifier as described in any one of claims 1 to 9 in acidified drinking water.

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