阅读说明：本技术 一种提高种鸭蛋品质的改性层状铝硅酸盐及其制备方法和应用 (Modified layered aluminosilicate for improving quality of breeding duck eggs and preparation method and application thereof ) 是由 李焰 邓凡 罗玉和 岳稳 黄玥琦 吴琼 潘浩哲 张林城 李状伟 邱龙新 于 2021-10-22 设计创作，主要内容包括：本发明公开了一种提高种鸭蛋品质的改性层状铝硅酸盐及其制备方法和应用。该制备方法包括以下步骤：分离纯化、调整pH值、杂糅柱撑、复配陈化制得改性层状铝硅酸盐。本发明提供的改性层状铝硅酸盐,是以酿酒酵母细胞壁水解产物作为有机改性剂,采用高温高压法,为提纯后的层状铝硅酸盐晶层添加柱撑。本发明通过对天然层状铝硅酸盐提纯改性,制成一种多位点、多孔道的新型层状铝硅酸盐产品,并添加于种鸭饲粮中,能够减少种鸭采食霉变饲粮后对种鸭蛋品质的影响,将改性层状铝硅酸盐开发成一种有效的抗生素替抗产品,在种鸭生产中发挥作用。(The invention discloses modified layered aluminosilicate for improving the quality of breeding duck eggs and a preparation method and application thereof. The preparation method comprises the following steps: separating and purifying, adjusting the pH value, carrying out mixed column supporting, compounding and aging to obtain the modified layered aluminosilicate. The modified layered aluminosilicate provided by the invention takes saccharomyces cerevisiae cell wall hydrolysate as an organic modifier, and adds a column support to a purified layered aluminosilicate crystal layer by adopting a high-temperature and high-pressure method. According to the invention, the natural layered aluminosilicate is purified and modified to prepare a novel layered aluminosilicate product with multiple sites and multiple channels, and the novel layered aluminosilicate product is added into feed for breeding ducks, so that the influence of the breeding ducks on the quality of eggs of the breeding ducks after eating the mildewed feed can be reduced, and the modified layered aluminosilicate is developed into an effective antibiotic substitute product which plays a role in the production of the breeding ducks.)

1. A preparation method of modified layered aluminosilicate for improving the quality of breeding duck eggs is characterized by comprising the following steps:

(1) separation and purification: crushing and rolling montmorillonite raw ore, adding hydrogen peroxide for soaking, performing suction filtration, sieving and washing, adding water into a system to prepare slurry, centrifuging, separating and removing associated impurities of the raw ore to obtain purified raw pulp with the montmorillonite content of more than 90%;

(2) adjusting the pH value: adding 380ml of 350-acetic acid solution into every 1kg of purified raw stock, sealing and acidifying at constant temperature, adding 130g of 120-acetic acid calcium carbonate for neutralization, centrifuging, removing supernatant, drying, standing and cooling to room temperature, fully grinding, and sieving with a 200-mesh sieve to obtain layered aluminosilicate powder;

(3) the mixed mixture column support: adding 120-200g of saccharomyces cerevisiae cell wall hydrolysate into 1kg of layered aluminosilicate powder by a gradient dilution method, and stirring the mixed flour in a stirring pool for 1-1.2h at the constant temperature of 80-85 ℃ under the condition of 1.5-3.8 atmospheric pressures;

(4) compounding and aging: adding 30-100g of glucose oxidase in every 1kg of mixed layered aluminosilicate in a gradient manner, stirring the mixed layered aluminosilicate, aging, drying, and sieving to obtain the modified layered aluminosilicate.

2. The preparation method of the modified layered aluminosilicate for improving the quality of the breeding duck eggs, according to claim 1, is characterized in that in the step (1), 1kg of montmorillonite raw ore is crushed and rolled to 5-40 meshes, 2-5L of hydrogen peroxide is added for soaking for 30-40min, and then the obtained product is subjected to suction filtration, sieving and water washing, and water is added into a system to prepare slurry with the solid content of 8-15%.

3. The method for preparing modified layered aluminosilicate for improving the quality of duck eggs as claimed in claim 1, wherein in step (1) and step (2), the centrifugation rotation speed is 10000-.

4. The preparation method of the modified layered aluminosilicate for improving the quality of the breeding duck eggs, according to claim 3, wherein in the step (2), the temperature of the constant-temperature closed acidification is 60-65 ℃, and the time is 2-2.5 h.

5. The method for preparing modified layered aluminosilicate for improving the quality of duck eggs as claimed in claim 1, wherein in the steps (2) and (4), the temperature for drying is 100-105 ℃ and the time is 2-2.5 h.

6. The method for preparing a modified layered aluminosilicate for improving the quality of duck eggs, as claimed in claim 1, wherein in step (4), the temperature of the mixing and kneading is 50 ℃, the time of mixing and kneading is 1-1.2h, and the aging time is 48 h.

7. The modified layered aluminosilicate obtained by the production method according to any one of claims 1 to 6.

8. The use of the modified layered aluminosilicate of claim 7, wherein the modified layered aluminosilicate is added to a feed for a breeding duck for feeding the breeding duck.

Technical Field

The invention relates to the technical field of aluminosilicate, in particular to modified layered aluminosilicate for improving the quality of duck eggs and a preparation method and application thereof.

Background

The growth environment of waterfowls such as laying ducks and the like is humid, the feed is stored improperly or the daily management of a house is not good, harmful flora such as mold and the like are easily bred, the quality of the feed is greatly reduced, gastrointestinal tract mucous membrane barriers and liver metabolic capacity of the poultry are damaged, and the growth and the egg laying performance of the poultry are influenced. In order to prevent and control pathogen development, antibiotics are added to the diet for a long time, so that the flora resistance genes are accumulated, the drug resistance level is increased, and a series of problems of food safety, environmental sanitation and the like are caused.

The layered aluminosilicate is a layered aluminosilicate mineral with a porous structure, and has the effects of high water absorption, high bacteria attachment, high binding detoxification and the like after being improved by methods such as physical stripping purification, chemical hybrid pillaring and the like. The modified layered aluminosilicate with proper amount is added into the feed, and the strong grabbing and attaching effect of the modified layered aluminosilicate can be utilized to absorb moisture and inhibit bacteria, so that the content of harmful bacteria and toxins in the feed is reduced; the health level of the intestinal tract of the livestock and the poultry can be improved by improving the expression of the intestinal mucosa nutrient transport carrier, promoting the growth of intestinal villi, regulating and controlling the intestinal flora and the like; or promoting the proliferation of T lymphocytes and macrophages to improve the immune response efficiency of the organism; besides, the expression level of the tight junction protein can be increased, the apoptosis can be slowed down, and the oxidation resistance and the damage repair capacity can be enhanced. At present, the modified layered aluminosilicate has related researches on the aspects of feed additives and intestinal protection and resistance substitution of animals such as pigs, cattle, chickens and the like, but the production application and the resistance substitution performance of waterfowls such as laying ducks and the like are not reported.

Although the natural layered hydrated aluminosilicate has the property of adsorbing mycotoxin due to the microstructure, the action effect of the natural layered aluminosilicate has limitation because the internal surface structure of the aluminosilicate has strong hydrophilicity, a thin water film usually exists to occupy interlayer domains under the replacement action of a large number of exchangeable cations between the layers, a small number of residual sites absorb hydrophilic molecules together with hydrogen bonds in water, the adsorption action is extremely unstable, and the hydrophobic substances cannot be effectively adsorbed. Therefore, the raw materials must be modified to enhance the adsorption capacity of the raw materials on mycotoxins, improve the protection capacity of the raw materials on digestive and reproductive systems of breeding poultry and weaken the capturing performance of the raw materials on nutrients.

Disclosure of Invention

The invention aims to provide a modified layered aluminosilicate for improving the quality of breeding duck eggs and a preparation method and application thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of modified layered aluminosilicate for improving the quality of breeding duck eggs comprises the following steps:

(1) separation and purification: crushing and rolling montmorillonite raw ore, adding hydrogen peroxide for soaking, performing suction filtration, sieving and washing, adding water into a system to prepare slurry, centrifuging, separating and removing associated impurities of the raw ore to obtain purified raw pulp with the montmorillonite content of more than 90 percent, wherein the particle size range of the purified raw pulp is 80-200 meshes;

(2) adjusting the pH value: adding 380ml of 350-acetic acid solution into every 1kg of purified raw stock, sealing and acidifying at constant temperature, adding 130g of 120-acetic acid calcium carbonate to neutralize to the pH value of 5-7, centrifuging, removing supernatant, drying, standing and cooling to room temperature, fully grinding, and sieving with a 200-mesh sieve to obtain layered aluminosilicate powder;

(3) the mixed mixture column support: adding 120-200g of saccharomyces cerevisiae cell wall hydrolysate into 1kg of layered aluminosilicate powder by a gradient dilution method, and stirring the mixed flour in a stirring pool for 1-1.2h at the constant temperature of 80-85 ℃ under the condition of 1.5-3.8 atmospheric pressures; ensuring that the cell wall hydrolysate of the saccharomyces cerevisiae is fully contacted with the layered aluminosilicate powder, and expanding the interlayer domain of the layered aluminosilicate crystal through the connection of the pillared at the inner surface sites;

(4) compounding and aging: adding 30-100g of glucose oxidase in a gradient manner into every 1kg of layered aluminosilicate after the mixed kneading, stirring the mixed kneading, aging, enabling about 60% of the glucose oxidase to be stably coated in a layered aluminosilicate framework after the mixed kneading, releasing at a fixed point in an intestinal tract through the change of a pH value, playing a role in maintaining the stable state of intestinal flora and protecting the complete form of intestinal villus while not influencing the adsorption of mould, and finally drying and sieving to prepare the modified layered aluminosilicate.

Preferably, in the step (1), 1kg of montmorillonite raw ore is crushed and rolled to 5-40 meshes, 2-5L of hydrogen peroxide is added for soaking for 30-40min, and then the slurry with the solid content of 8-15% is prepared by carrying out suction filtration, sieving and water washing.

Preferably, in the step (1) and the step (2), the centrifugation rotation speed is 10000-12000r/min, and the centrifugation time is 10-15 min.

Preferably, in the step (2), the temperature of the constant-temperature closed acidification is 60-65 ℃, and the time is 2-2.5 h.

Preferably, in the step (2) and the step (4), the drying temperature is 100-105 ℃, and the time is 2-2.5 h.

Preferably, in the step (4), the temperature of the mixing and kneading process is 50 ℃, the time of the mixing and kneading process is 1-1.2 hours, and the aging time is 48 hours.

The modified layered aluminosilicate provided by the invention takes saccharomyces cerevisiae cell wall hydrolysate as an organic modifier, and adds a column support to a purified layered aluminosilicate crystal layer by adopting a high-temperature and high-pressure method. About 1kg of the modified layered aluminosilicate contains: 855g of purified layered aluminosilicate, 120g of saccharomyces cerevisiae cell wall hydrolysate and 25g of glucose oxidase.

The invention has the beneficial effects that: according to the invention, the natural layered aluminosilicate is purified and modified to prepare a novel layered aluminosilicate product with multiple sites and multiple channels, and the novel layered aluminosilicate product is added into feed for breeding ducks, so that the influence of the breeding ducks on the quality of eggs of the breeding ducks after eating the mildewed feed can be reduced, and the modified layered aluminosilicate is developed into an effective antibiotic substitute product which plays a role in the production of the breeding ducks.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.

FIG. 1 is an electron microscope scan of a naturally layered aluminosilicate;

FIG. 2 is an electron microscope scan of a modified layered aluminosilicate provided in example 1 of the present invention;

fig. 3 is an XRD diffractogram of the modified layered aluminosilicate provided in example 1 of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The saccharomyces cerevisiae cell wall hydrolysate used in the examples of the present invention was purchased from xuzhou seifu bio ltd, cat # seqi XBB 4; glucose oxidase was purchased from Zhengzhou Meilidun commercial and trade Co., Ltd, information No. 151841309.

Example 1

Preparation of modified layered aluminosilicate

(1) Separation and purification: crushing and rolling 1kg of montmorillonite raw ore for 15min, adding 3.5L hydrogen peroxide, soaking for 300min to remove organic matters and other harmful impurities, and then performing suction filtration and sieving to remove large-particle impurities; washing with deionized water once, adding deionized water into the system according to a proportion, preparing slurry with the solid content of 10% by using a strong stirring device and matching with a customized stirring pool, centrifuging for 10min at 10000r/min by using a high-speed horizontal centrifuge, and separating and removing associated impurities of raw ores to obtain purified raw pulp with the montmorillonite content of more than 90%;

(2) adjusting the pH value: adding 350ml of hydrochloric acid solution into 1kg of purified raw stock, carrying out closed acidification for 2h at a constant temperature of 60 ℃, adding 120g of calcium carbonate for neutralization, centrifuging for 10min at 10000r/min, removing supernatant, drying for 2h at 105 ℃, standing and cooling to room temperature, fully grinding, and sieving with a 200-mesh sieve to obtain layered aluminosilicate powder;

(3) the mixed mixture column support: adding 150g of saccharomyces cerevisiae cell wall hydrolysate into 1kg of purified and neutralized layered aluminosilicate powder by a gradient dilution method, stirring and mixing the saccharomyces cerevisiae cell wall hydrolysate in a stirring pool for 1-1.2 hours at a constant temperature of 80-85 ℃ under the condition of 3 atmospheric pressures, ensuring that the saccharomyces cerevisiae cell wall hydrolysate is fully contacted with the layered aluminosilicate powder, and connecting a column support through an inner surface site to expand the interlayer domain of a layered aluminosilicate crystal layer;

(4) compounding and aging: adding 45g of glucose oxidase in a gradient manner into 1kg of layered aluminosilicate after the mixed dough is stirred at 50 ℃ for 1-1.2h, and then aging for 48h, so that about 60% of glucose oxidase can be stably coated in a layered aluminosilicate framework after the mixed dough is expanded, and through the change of pH value, the glucose oxidase can be released at a fixed point in an intestinal tract to play a role, so that the glucose oxidase can play a role in maintaining the stable state of intestinal flora and protecting the complete form of intestinal villus while not affecting the adsorption of the mould, and finally drying for 2h at 105 ℃ and sieving with a 200-mesh sieve to obtain the modified layered aluminosilicate.

Microstructural characterization of the modified layered aluminosilicate prepared in this example

The microstructure characterization of the modified layered aluminosilicate was analyzed by scanning electron microscopy (SEM, Zeiss-Supra55) and X-ray diffraction (XRD, D8ADVANCE) techniques. As can be seen from fig. 1 and 2, compared with the natural layered aluminosilicate, the modified layered aluminosilicate subjected to organic-inorganic composite modification has the characteristics of loose, flat and large-area lamellar layers in a natural stacking state, and as can be seen from fig. 3, the mesoporous scattering phenomenon of the modified layered aluminosilicate is obvious, indicating that many pores exist between the layers; the half-height peak width is larger than that of natural layered aluminosilicate.

Example 2

Preparation of modified layered aluminosilicate

(1) Separation and purification: crushing and rolling 1kg of montmorillonite raw ore for 20min, adding 3.5L hydrogen peroxide, soaking for 40min to remove organic matters and other harmful impurities, and performing suction filtration and sieving to remove large-particle impurities; washing with deionized water once, adding deionized water into the system according to a proportion, preparing slurry with the solid content of 10% by using a strong stirring device and matching with a customized stirring pool, centrifuging for 15min at 12000r/min through a high-speed horizontal centrifuge, separating and removing associated impurities of raw ores, and obtaining purified raw pulp with the montmorillonite content of more than 90%;

(2) adjusting the pH value: adding 380ml of hydrochloric acid solution into 1kg of purified raw stock, carrying out closed acidification at a constant temperature of 65 ℃ for 2.5h, adding 130g of calcium carbonate for neutralization, centrifuging at 12000r/min for 10min, removing supernatant, drying at 100 ℃ for 2.5h, standing, cooling to room temperature, fully grinding, and sieving with a 200-mesh sieve to obtain layered aluminosilicate powder;

(3) the mixed mixture column support: adding 150g of saccharomyces cerevisiae cell wall hydrolysate into 1kg of purified and neutralized layered aluminosilicate powder by a gradient dilution method, stirring and mixing the layered aluminosilicate powder in a stirring pool for 1.2h at a constant temperature of 85 ℃ under the condition of 3 atmospheric pressures, ensuring that the saccharomyces cerevisiae cell wall hydrolysate is fully contacted with the layered aluminosilicate powder, and connecting a column support through an inner surface site to expand an interlayer region of a layered aluminosilicate crystal;

(4) compounding and aging: adding 45g of glucose oxidase in a gradient manner into 1kg of layered aluminosilicate after the mixed dough is mixed at 50 ℃, stirring the mixed dough for 1.2h, and then aging for 48h, so that about 60% of glucose oxidase can be stably coated into a layered aluminosilicate framework after the mixed dough is expanded, and through the change of pH value, the glucose oxidase can be released at a fixed point in the intestinal tract to play a role, so that the glucose oxidase can play a role in maintaining the stable state of intestinal flora and protecting the complete form of intestinal villus while not affecting the adsorption of the mould, and finally drying for 2.5h at 100 ℃ and sieving with a 200-mesh sieve to obtain the modified layered aluminosilicate.

Example 3

Preparation of modified layered aluminosilicate

(1) Separation and purification: crushing and rolling 1kg of montmorillonite raw ore for 18min, adding 3.5L hydrogen peroxide, soaking for 35min to remove organic matters and other harmful impurities, and then performing suction filtration and sieving to remove large-particle impurities; washing with deionized water once, adding deionized water into the system according to a proportion, preparing slurry with the solid content of 10% by using strong stirring equipment and matching with a customized stirring pool, centrifuging for 12min at 11000r/min through a high-speed horizontal centrifuge, separating and removing associated impurities of raw ores, and obtaining purified raw pulp with the montmorillonite content of more than 90%;

(2) adjusting the pH value: adding 365ml of hydrochloric acid solution into 1kg of purified raw stock, carrying out sealed acidification at a constant temperature of 625 ℃ for 2h, adding 150g of calcium carbonate for neutralization, centrifuging at 10000r/min for 15min, removing supernatant, drying at 105 ℃ for 2h, standing, cooling to room temperature, fully grinding, and sieving with a 200-mesh sieve to obtain layered aluminosilicate powder;

(3) the mixed mixture column support: adding 150g of saccharomyces cerevisiae cell wall hydrolysate into 1kg of purified and neutralized layered aluminosilicate powder by a gradient dilution method, stirring and mixing the mixture in a stirring pool for 1h at a constant temperature of 82 ℃ under the condition of 3 atmospheric pressures, ensuring that the saccharomyces cerevisiae cell wall hydrolysate is fully contacted with the layered aluminosilicate powder, and expanding the interlayer domain of the layered aluminosilicate crystal through an inner surface site connecting column support;

(4) compounding and aging: adding 45g of glucose oxidase in a gradient manner into 1kg of layered aluminosilicate after the mixed kneading at 50 ℃, stirring the mixed kneading for 1h, and then aging for 48h, so that about 60% of the glucose oxidase can be stably coated into the layered aluminosilicate framework after the mixed kneading, and through the change of the pH value, the glucose oxidase can be released at a fixed point in the intestinal tract to play a role, so that the effects of maintaining the stable state of intestinal flora and protecting the complete form of intestinal villus are achieved while the adsorption of the mould by the glucose oxidase is not influenced, and finally, drying for 2h at 100 ℃ and sieving with a 200-mesh sieve to obtain the modified layered aluminosilicate.

Example 4

Application of modified layered aluminosilicate

1. Test feed

The basic feed is corn-soybean meal type, and the mildewed basic feed is prepared by replacing 5% of corn in the basic feed with natural mildewed corn. The experimental diet is powder. Liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) is adopted to determine the content of mycotoxins such as aflatoxin B1(AFB1), Zearalenone (ZEN) and Deoxynivalenol (DON) in the mildew basic diet, and the content is shown in Table 1.

TABLE 1 mycotoxin assay in mildew basal diet

2. Test design and feeding management

2.1 design of the experiment

448 healthy Longyan sheldrake of 110 days old (50% of the first-birth days old) are randomly divided into 7 groups (CK, M1, M2, M3, M4, CC and KK), each group has 8 repetitions, and each repetition has 8 repetitions. KK is blank group, and basal diet is used for feeding; CK is a mildewed corn group and is fed with mildewed basic feed; m1, M2, M3 and M4 are modified layered aluminosilicate test groups, and 0.05%, 0.10%, 0.15% and 0.20% of modified layered aluminosilicate are respectively added into a mildew basic diet; CC is antibiotic group, and 0.04% chlortetracycline is added into the basic moldy diet. Pre-run period 7d, run period 35 d. The experimental design is shown in table 2.

TABLE 2 test design

2.2 Breeding management

The production test is carried out in a Shanma duck stock ground in Longyan city. All the experimental ducks adopt a single-layer online cage culture management mode, and 8 ducks are bred in each cage. Feeding twice in the afternoon. During the test period, the drinking water is taken freely, and the natural ventilation condition is kept. The eggs are picked up once every morning before feeding, and sprayed at 09:00 and 14:00 for 15 min. The immunization program is operated according to the conventional program of the mountain Ma duck stock farm in Longyan city.

2.3 method for measuring quality of eggs

Egg quality measurements were performed weekly. Repeatedly extracting 3 duck eggs with weight close to the average egg weight, wiping the surfaces of the duck eggs clean, measuring the transverse diameter and the longitudinal diameter by using a vernier caliper, and measuring the color of the eggshell by using an eggshell color measuring instrument; measuring the eggshell strength by using an eggshell strength measuring instrument; measuring the concentrated egg white height of three uniform equidistant points between the yolk edge and the concentrated egg white edge by using an egg white height measuring instrument, and taking an average value to be accurate to 0.01 mm; measuring the color of the yolk by using a Roche colorimetric fan; measuring the thicknesses of the blunt end, the sharp end and the middle part of the eggshell by using an eggshell thickness measuring instrument, and taking an average value to be accurate to 0.01 mm; accurately weighing the weight of eggs, the weight of eggshells, the weight of yolks and the like by using an electronic scale to be 0.01 g; calculating the egg-shape index as longitudinal diameter/transverse diameter

2.4 data processing and analysis data are expressed as "mean ± sd", one-way anova using SPSS 26.0 software, and differences between groups were examined using Duncan's multiple comparison method, with P <0.05 as significant difference.

3. Influence of modified layered aluminosilicate on quality of breeding duck eggs

TABLE 3 influence of adding different levels of modified layered aluminosilicates to the diet on the quality of Longyan mountain Ma duck eggs (1-35 days)

Note: the data shoulder marks of the same row have no letters or contain the same letters to indicate that the difference is not significant (P >0.05), and different lower case letters to indicate that the difference is significant (P < 0.05).

As can be seen from Table 3, the concentrated proteins of the M1, M2 and M4 groups are significantly higher than those of the antibiotics group, and the modified layered aluminosilicate with a certain proportion can enhance the fresh-keeping and transportation capacities of duck eggs; in the whole view, the proportion of meat spot eggs can be obviously reduced by adding the modified layered aluminosilicate, and the proportion of blood spots is close to that of antibiotics by adding the M4 group of 0.2 percent of the modified layered aluminosilicate, so that the modified layered aluminosilicate prepared by the invention can improve the qualified rate of hatching eggs, achieves a certain anti-substitution effect and has positive significance for guaranteeing food safety.

The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.