CN116998603A - Efficient micromolecular organic acidulant and preparation method thereof - Google Patents

Efficient micromolecular organic acidulant and preparation method thereof Download PDF

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Publication number
CN116998603A
CN116998603A CN202311028478.0A CN202311028478A CN116998603A CN 116998603 A CN116998603 A CN 116998603A CN 202311028478 A CN202311028478 A CN 202311028478A CN 116998603 A CN116998603 A CN 116998603A
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CN
China
Prior art keywords
acidulant
acid
chitosan
organic acidulant
adsorbent
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Pending
Application number
CN202311028478.0A
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Chinese (zh)
Inventor
张昌荣
姬长存
邢良勇
高长江
吕国晓
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Shandong Qilu Zhongmu Biotechnology Co ltd
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Shandong Qilu Zhongmu Biotechnology Co ltd
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Priority to CN202311028478.0A priority Critical patent/CN116998603A/en
Publication of CN116998603A publication Critical patent/CN116998603A/en
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K20/00Accessory food factors for animal feeding-stuffs
    • A23K20/10Organic substances
    • A23K20/105Aliphatic or alicyclic compounds
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K20/00Accessory food factors for animal feeding-stuffs
    • A23K20/10Organic substances
    • A23K20/163Sugars; Polysaccharides
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K20/00Accessory food factors for animal feeding-stuffs
    • A23K20/20Inorganic substances, e.g. oligoelements
    • A23K20/28Silicates, e.g. perlites, zeolites or bentonites
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K40/00Shaping or working-up of animal feeding-stuffs
    • A23K40/10Shaping or working-up of animal feeding-stuffs by agglomeration; by granulation, e.g. making powders
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K40/00Shaping or working-up of animal feeding-stuffs
    • A23K40/30Shaping or working-up of animal feeding-stuffs by encapsulating; by coating
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K50/00Feeding-stuffs specially adapted for particular animals
    • A23K50/30Feeding-stuffs specially adapted for particular animals for swines
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23KFODDER
    • A23K50/00Feeding-stuffs specially adapted for particular animals
    • A23K50/60Feeding-stuffs specially adapted for particular animals for weanlings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/00272-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof

Abstract

The invention relates to a high-efficiency small-molecule organic acidulant and a preparation method thereof, wherein the acidulant comprises the following components in parts by mass: 30-100 parts of small molecular organic acid, 15-35 parts of adsorbent, 10-20 parts of modified chitosan and 1-5 parts of auxiliary agent; wherein the modified chitosan is obtained by reacting 4-ethoxycarbonyloxy-3, 5-dimethoxy benzoic acid with chitosan; the adsorbent is hydroxylated montmorillonite. The preparation method of the modified chitosan comprises the following steps: s1, mixing chitosan, 4-ethoxycarbonyloxy-3, 5-dimethoxy benzoic acid and an activating agent, and heating and stirring to react to obtain a crude product; s2, dialyzing and freeze-drying the crude product to obtain the modified chitosan. The high-efficiency small-molecule organic acidulant has strong slow release performance, realizes lasting effect, is beneficial to the growth and development of livestock and poultry, and solves the problems existing in the existing products.

Description

Efficient micromolecular organic acidulant and preparation method thereof
Technical Field
The invention relates to the technical field of feeds, in particular to a high-efficiency small-molecule organic acidulant and a preparation method thereof.
Background
The acidulant is a widely applied feed additive, and the component plays an important role in improving the feeding condition of livestock and poultry.
The acidulant can reduce the pH value of the digestive system of livestock and poultry, acidify the gastrointestinal tract, promote digestion, improve nutrient absorption and conversion, can directly participate in-vivo energy metabolism, and has no residue, drug resistance and toxic or side effect. Meanwhile, the acidulant also has the effects of fresh feed, sterilization and mildew prevention, palatability improvement, secondary pollution reduction, maintenance of the nutritional value of the feed and prolongation of the storage time of the feed. The acidulant can also help young animals establish healthy flora balance (control harmful bacteria in the digestive tract), inhibit and neutralize digestive tract pathogenic bacteria, promote gastrointestinal development and immune response, promote healthy growth of intestinal villi, stimulate animal immune system and prevent disease from entering from the mouth. In addition, the acid preparation also has the function of astringing, can protect liver and heart vessels, reduce the formation of harmful metabolites, reduce the burden of toxin decomposition of the liver, improve the health condition of animals and exert the maximum potential.
However, the small molecular organic acid component is easy to lose in the processing, storage and use processes, is easy to react with alkaline substances in the feed, reduces the nutritive value in the feed, and cannot effectively ensure the stability and effect of the product; the rapid release of acidic substances causes the mutation of the pH value in animals, and can damage oral mucosa, affect the palatability of feed and affect the secretion of gastric acid and pepsin of animals. Therefore, the existing organic acidulant products still have more problems, and the demands of the market are difficult to meet.
In view of the foregoing, there is a need to develop a new technical solution to solve the problems in the prior art.
Disclosure of Invention
Based on the above, the invention provides a high-efficiency small-molecule organic acidulant and a preparation method thereof. The invention adopts the micromolecular organic acid and the adsorbent as the core structure, the modified chitosan as the shell structure, the compatibility among the components is good, the stability of the product is effectively improved, the product is easier to store, the high-efficiency micromolecular organic acidating agent has stronger slow release performance, the lasting effect is realized, the growth and development of livestock and poultry are facilitated, and the problems existing in the existing product are solved.
The invention aims to provide a high-efficiency small-molecule organic acidulant which comprises the following components in parts by weight:
wherein,
the modified chitosan is obtained by reacting 4-ethoxycarbonyloxy-3, 5-dimethoxy benzoic acid with chitosan;
the adsorbent is hydroxylated montmorillonite.
Further, the preparation method of the modified chitosan comprises the following steps:
s1, mixing chitosan, 4-ethoxycarbonyloxy-3, 5-dimethoxy benzoic acid and an activating agent, and heating and stirring to react to obtain a crude product;
s2, dialyzing and freeze-drying the crude product to obtain the modified chitosan.
Further, in the step S1, the temperature of the heating and stirring reaction is 30-50 ℃ and the time is 5-10h.
Further, the mass ratio of the chitosan to the 4-ethoxycarbonyloxy-3, 5-dimethoxy benzoic acid is 1 (0.5-5).
Further, the preparation method of the adsorbent comprises the following steps:
mixing montmorillonite powder with glucose, performing ball milling treatment, and purifying to obtain the adsorbent.
According to the invention, the montmorillonite and the glucose are mixed for ball milling treatment, so that the specific surface area of montmorillonite powder can be further increased, the appearance is improved, and the organic acid micromolecule is better adsorbed; in addition, in the ball milling process, glucose is tightly adhered to the surface of montmorillonite powder, so that the friction force among particles is increased, on the other hand, the energy in a ball milling tank is increased along with the increase of the ball milling time and the temperature, and part of hydroxyl groups on the surface of glucose molecules are fallen off and connected with unsaturated cations in montmorillonite, so that the montmorillonite has more surface hydroxyl groups, and the compatibility and the adsorption capacity of the adsorbent are further enhanced.
Further, the small molecule organic acid is selected from one or more of formic acid, propionic acid, acetic acid, citric acid and fumaric acid.
Further, the high-efficiency small-molecule organic acidulant comprises the following components in parts by weight:
further, the auxiliary agent is one or more selected from inorganic salts, dispersants, film forming agents, antioxidants, binders and preservatives.
The invention also provides a preparation method of the high-efficiency small-molecule organic acidulant, which comprises the following steps:
uniformly mixing small molecular organic acid, an adsorbent and an auxiliary agent, and adding the mixture into a granulator for granulation to obtain a nuclear structure; spraying modified chitosan on the surface of the core structure, and drying to obtain the high-efficiency micromolecular organic acidating agent.
The invention has the following beneficial effects:
1. the high-efficiency small-molecule organic acidulant provided by the invention adopts small-molecule organic acid such as formic acid, acetic acid and propionic acid as components, and has the effects of promoting digestion of livestock and poultry, inhibiting growth of pathogenic bacteria in stomach and intestine (crop), keeping health of livestock and poultry, reducing use of medicines and eliminating ammonia odor of livestock and poultry houses.
2. The efficient micromolecular organic acidulant has a core-shell structure, wherein the core structure comprises an adsorbent, and the adsorbent is prepared by mixing montmorillonite powder and glucose and performing ball milling treatment, has larger specific surface area and more active functional groups, so that more micromolecular organic acid can be adsorbed, and the stability is higher; the modified chitosan grafted with 4-ethoxycarbonyloxy-3, 5-dimethoxy benzoic acid has the advantages that a large number of phenoxy, alkoxy, ester groups and other structures are introduced into the modified chitosan, so that the polarity of the chitosan is improved, the acidulant product has more ideal slow-release function, and the acidulant effect can be permanently effective; in addition, hydrogen bonds are easily formed between various oxygen-containing functional groups in the core structure and the shell structure, so that a synergistic effect is generated, the stability of the product is further enhanced through intermolecular forces, and the shelf life is prolonged.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the following examples are set forth. The starting materials, reactions and workup procedures used in the examples are those commonly practiced in the market and known to those skilled in the art unless otherwise indicated.
The words "preferred," "more preferred," and the like in the present disclosure refer to embodiments of the present disclosure that may provide certain benefits in some instances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
It should be understood that, except in any operating examples, or where otherwise indicated, quantities or all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention.
The chitosan in the examples of the present invention was purchased from Shandong Seiya chemical Co., ltd.
The auxiliary agent in the embodiment of the invention is sodium alginate.
In the embodiment of the invention, "parts" refer to parts by weight.
The preparation method of the modified chitosan in the embodiment of the invention comprises the following steps:
s1, dissolving chitosan in 2% acetic acid solution, then adding an absolute ethyl alcohol solution of 4-ethoxycarbonyloxy-3, 5-dimethoxy benzoic acid and an activating agent (the mass ratio of chitosan, 4-ethoxycarbonyloxy-3, 5-dimethoxy benzoic acid, EDC, HCl and NHS is 8:8:8.3:1, and the mass ratio of chitosan, acetic acid solution and absolute ethyl alcohol is 1:49:25), and stirring and reacting for 6 hours at 40 ℃ to obtain a crude product;
s2, performing distilled water dialysis and freeze drying on the crude product to obtain the modified chitosan.
The preparation method of the adsorbent in the embodiment of the invention comprises the following steps:
mixing montmorillonite powder and glucose with the mass ratio of 1:5, adding the mixture into a ball mill for ball milling treatment for 10 hours, wherein the ball material ratio is 5:1, the rotating speed is 400rpm, and filtering, washing and drying the mixture to obtain the adsorbent.
Example 1
The efficient micromolecular organic acidulant comprises the following components in parts by weight:
the preparation method of the high-efficiency small-molecule organic acidulant comprises the following steps:
uniformly mixing small molecular organic acid, adsorbent and auxiliary agent according to the parts by weight, and adding into a granulator for granulating to obtain a nuclear structure; spraying modified chitosan on the surface of the core structure, and drying to obtain the high-efficiency micromolecular organic acidating agent.
Example 2
The efficient micromolecular organic acidulant comprises the following components in parts by weight:
the preparation method of the high-efficiency small-molecule organic acidulant comprises the following steps:
uniformly mixing small molecular organic acid, adsorbent and auxiliary agent according to the parts by weight, and adding into a granulator for granulating to obtain a nuclear structure; spraying modified chitosan on the surface of the core structure, and drying to obtain the high-efficiency micromolecular organic acidating agent.
Example 3
The efficient micromolecular organic acidulant comprises the following components in parts by weight:
the preparation method of the high-efficiency small-molecule organic acidulant comprises the following steps:
uniformly mixing small molecular organic acid, adsorbent and auxiliary agent according to the parts by weight, and adding into a granulator for granulating to obtain a nuclear structure; spraying modified chitosan on the surface of the core structure, and drying to obtain the high-efficiency micromolecular organic acidating agent.
Comparative example 1
The difference between this comparative example and example 1 is that: the modified chitosan was replaced with unmodified chitosan, and other components and preparation methods were the same as in example 1.
Comparative example 2
The difference between this comparative example and example 1 is that: in the preparation method of the modified chitosan, 4-ethoxycarbonyloxy-3, 5-dimethoxybenzoic acid was replaced with lauric acid, and other components and preparation methods were the same as in example 1.
Test case
Performance tests were performed on the small molecule organic acidulant samples prepared in examples 1-3 and comparative examples 1-2.
The testing method comprises the following steps:
stability test:
the small molecule organic acidulant samples prepared in examples 1-3 and comparative examples 1-2 were left to stand for 3 months at 40 ℃ + -2 ℃ and 75% + -5% RH, and then the appearance of the samples was examined and evaluated.
Growth promoting performance test:
50 weaned pigs with similar batches, similar weight and good health condition are randomly divided into 5 groups of 10 pigs for test. The conventional commercial piglet feed is adopted as the feed, and 2kg/t of the small molecular organic acidulant prepared in the examples 1-3 or the comparative examples 1-2 is added into each group of feed, and after 30 days of feeding, the average weight of each group is measured.
The test results are shown in Table 1.
TABLE 1 Performance test results
According to the table 1, the high-efficiency small-molecule organic acidulant prepared by the embodiment of the invention has strong stability and good slow release property, can effectively improve the digestion and absorption levels of livestock and poultry, improves the gastrointestinal tract environment, and realizes a good weight increasing effect; and the comparative examples 1-2 with the modified chitosan can reduce the compatibility and stability of the acidulant product, and the slow release effect is not ideal enough, so that the effect is difficult to take effect for a long time, and the weight gain effect of piglets is poor. In conclusion, the invention has good application prospect.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.

Claims (9)

1. The efficient small-molecule organic acidulant is characterized by comprising the following components in parts by weight:
wherein,
the modified chitosan is obtained by reacting 4-ethoxycarbonyloxy-3, 5-dimethoxy benzoic acid with chitosan;
the adsorbent is hydroxylated montmorillonite.
2. The efficient small molecular organic acidulant of claim 1, wherein the preparation method of the modified chitosan comprises the following steps:
s1, mixing chitosan, 4-ethoxycarbonyloxy-3, 5-dimethoxy benzoic acid and an activating agent, and heating and stirring to react to obtain a crude product;
s2, dialyzing and freeze-drying the crude product to obtain the modified chitosan.
3. The efficient small molecular organic acidulant of claim 2, wherein in step S1, the temperature of the heating and stirring reaction is 30-50 ℃ for 5-10h.
4. The efficient micromolecular organic acidulant as claimed in claim 2, wherein the mass ratio of the chitosan and the 4-ethoxycarbonyloxy-3, 5-dimethoxy benzoic acid is 1 (0.5-5).
5. The efficient small molecule organic acidulant of claim 1, wherein the preparation method of the adsorbent comprises the following steps:
mixing montmorillonite powder with glucose, performing ball milling treatment, and purifying to obtain the adsorbent.
6. The efficient small molecule organic acidulant of claim 1, wherein the small molecule organic acid is selected from one or more of formic acid, propionic acid, acetic acid, citric acid, fumaric acid.
7. The efficient small-molecule organic acidulant of claim 6, wherein the efficient small-molecule organic acidulant comprises the following components in parts by weight:
8. the efficient small molecule organic acidulant of claim 1, wherein the auxiliary agent is selected from one or more of inorganic salts, dispersants, film formers, antioxidants, binders, preservatives.
9. The method for preparing the efficient small molecular organic acidulant as claimed in any one of claims 1 to 8, which comprises the following steps:
uniformly mixing small molecular organic acid, an adsorbent and an auxiliary agent, and adding the mixture into a granulator for granulation to obtain a nuclear structure; spraying modified chitosan on the surface of the core structure, and drying to obtain the high-efficiency micromolecular organic acidating agent.
CN202311028478.0A 2023-08-16 2023-08-16 Efficient micromolecular organic acidulant and preparation method thereof Pending CN116998603A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109393205A (en) * 2018-11-20 2019-03-01 界首市芙乐园农业发展有限公司 A kind of preparation method of the fodder acidulant for aquaculture

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109393205A (en) * 2018-11-20 2019-03-01 界首市芙乐园农业发展有限公司 A kind of preparation method of the fodder acidulant for aquaculture

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