A new type of feed to replace corn

Abstract

This invention belongs to the field of animal feed technology, specifically relating to a novel feed to replace corn. The feed comprises cassava flour, dried sugar residue, sprayed corn husks, bis(2-carboxyethyl)germanium sesquioxide-chitosan graft compound, N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide, soybean molasses, expanded urea, limestone powder, a compound enzyme preparation, and sodium chloride. In preparation, cassava flour, dried sugar residue, sprayed corn husks, two modified compounds, expanded urea, limestone powder, and sodium chloride are premixed. Preheated soybean molasses is added and mixing continues. After conditioning, granulation, cooling, and vibrating sieving, the mixture is then sprayed onto the surface of the sieved pellets and dried. This invention, through the synergistic effect of two newly designed modified compounds, significantly improves the energy utilization efficiency of non-grain feed ingredients, can completely replace corn, reduces feed costs, and has good palatability.

Description

Technical Field

[0001] This invention belongs to the field of animal feed technology, and specifically relates to a novel feed that can replace corn. Background Technology

[0002] Corn, as a major energy source for livestock and poultry feed, typically accounts for 60% to 70% of compound feed, and its price fluctuations directly impact the economic benefits of the livestock industry. In recent years, with the rapid development of animal husbandry, my country's demand for feed grains has continued to grow, and the shortage of corn has become increasingly prominent, becoming a key factor restricting feed grain security and controlling breeding costs. To alleviate structural contradictions related to grain and promote the diversification of feed resources, developing new energy feeds that can replace corn has become an urgent technical challenge for the industry.

[0003] Currently, scholars both domestically and internationally have conducted extensive research on corn substitution technologies. Existing substitution schemes mainly fall into two categories: one is using cereals such as wheat, sorghum, and barley as substitutes; however, these raw materials contain anti-nutritional factors such as non-starch polysaccharides, limiting the substitution ratio and requiring the addition of specialized enzymes; the other is utilizing unconventional feed resources, such as agricultural by-products like cassava, dried sugar residue, and sprayed corn husks. Studies have shown that winged bean tubers can serve as a complete substitute for corn in ruminant diets and can improve rumen fermentation characteristics. When crude glycerol is used to replace corn in fattening lambs, it does not affect production performance at appropriate addition levels and can be used as a cost-optimizing alternative. Corn ethanol by-products, such as high-protein dried distillers' grains and their solubles, can also partially replace corn and improve animal production performance.

[0004] Despite some progress in existing research, the application of unconventional feed ingredients still faces numerous technical bottlenecks. These ingredients typically contain anti-nutritional factors, exhibit significant fluctuations in nutritional value, and suffer from poor palatability and low digestibility. In particular, the efficient degradation of lignocellulose in non-grain ingredients remains a challenge, hindering improvements in energy utilization efficiency. The National Key Research and Development Program project, "Development and Product Creation of New Energy Feed Resources to Replace Corn," has established a complete innovation system encompassing "microbial enzyme tools - grain replacement technology - diet application," achieving corn savings of 15% to 30% in some scenarios. However, current technologies have not yet solved the problem of efficient removal of anti-nutritional factors from non-grain ingredients, nor the synergistic improvement of energy utilization efficiency. There is an urgent need to develop novel functional additives to overcome these technical bottlenecks. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a novel feed alternative to corn, characterized by comprising the following components in parts by weight: 25-40 parts cassava flour, 15-30 parts dried sugar residue, 100-300 parts sprayed corn husks, 50-150 parts bis(2-carboxyethyl)germanium sesquioxide-chitosan graft, 5-30 parts N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide, 50-200 parts soybean molasses, 20-100 parts expanded urea, 10-100 parts limestone powder, 5-50 parts compound enzyme preparation, and 1-10 parts sodium chloride. The compound enzyme preparation comprises cellulase, xylanase, acidic protease, and pectinase; the mass ratio of cellulase, xylanase, acidic protease, and pectinase is 3:2:1:1.

[0006] According to a preferred embodiment of the present invention, the preparation steps of the novel feed to replace corn include: S1. Premix cassava flour, dried sugar residue, sprayed corn husks, bis(2-carboxyethyl)germanium sesquioxide-chitosan graft, N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide, expanded urea, limestone powder, and sodium chloride; add preheated soybean molasses and continue mixing to obtain the mixed material. S2. The mixed materials are prepared at 80-85℃ and granulated to obtain granulated feed pellets; the granulated feed pellets are placed in a cooling dryer and cooled to room temperature to obtain cooled feed pellets; the cooled feed pellets are vibrated and screened to obtain screened feed pellets; the compound enzyme preparation is sprayed onto the surface of the screened feed pellets to obtain sprayed feed pellets; the sprayed feed pellets are dried.

[0007] In this invention, the preparation process of the novel feed alternative to corn integrates nutrition and function through synergistic optimization. In the raw material premixing stage, solid components such as cassava flour, dried sugar residue, and sprayed corn husks are uniformly mixed. After adding preheated molasses, the thermal viscosity of the molasses promotes intergranular bonding, forming a uniform matrix. The conditioning process is carried out at a suitable temperature, where the molasses further softens the fiber structure, enhancing the material's plasticity and facilitating subsequent pelleting. After pelleting, the material is cooled and dried to stabilize the pellet structure and avoid nutrient loss due to high temperatures. The key innovation lies in the post-addition strategy of the enzyme preparation: the cooled pelleted feed is first vibrated and sieved to remove powder and broken particles, obtaining clean, sieved pellets. Then, a compound enzyme preparation is uniformly sprayed onto the surface of the sieved pellets, ensuring that enzyme activity is not affected by the high temperature of pelleting and preventing enzyme loss during the sieving process. The sprayed pellets are then dried a second time, allowing the enzyme preparation to be stably loaded into the pores on the pellet surface, efficiently decomposing cellulose and xylan in the animal's digestive tract and improving feed utilization. Throughout the process, the introduction of grafts and active ingredients enhances the bioavailability and functionality of the feed through molecular-level mechanisms. The "screening before spraying" process design balances production efficiency and product activity, making the feed significantly superior to traditional formulas in terms of nutritional balance, digestibility, and palatability, thus achieving efficient application as a substitute for corn.

[0008] According to a preferred embodiment of the present invention, in step S1, the preheating temperature of the preheated soybean molasses is 40-45°C.

[0009] According to a preferred embodiment of the present invention, in step S2, the modulation time is 3-5 min; the granulation temperature is 75-80℃.

[0010] According to a preferred embodiment of the present invention, the preparation method of the bis(2-carboxyethyl)germanium sesquioxide-chitosan graft comprises: A1, mixing 8-12 parts by weight of chitosan with 40-60 parts by weight of acetic acid solution, stirring at room temperature; adjusting the pH, filtering, and drying to obtain dried chitosan; redissolving the dried chitosan in 40-60 parts by weight of acetic acid solution to obtain an acetic acid solution of chitosan; dissolving 4-6.5 parts by weight of bis(2-carboxyethyl)germanium sesquioxide in 15-25 parts by weight of N,N-dimethylformamide, and adding... Add 2-3.5 parts of N,N'-dicyclohexylcarbodiimide and 1-2 parts of 4-dimethylaminopyridine, and activate in an ice-water bath to obtain an activated solution; mix the activated solution with an acetic acid solution of chitosan, heat to room temperature, continue stirring, and continue heating to 58-62℃ for reaction; after the reaction is complete, cool to room temperature, filter, and obtain filtrate; mix the filtrate with anhydrous ethanol under stirring, let stand, and filter to obtain a solid; wash the solid successively with anhydrous ethanol and acetone to obtain the washed product; dry the washed product under vacuum.

[0011] In this invention, the preparation of the bis(2-carboxyethyl)germanium sesquioxide-chitosan graft begins with the acidic dissolution and activation of chitosan. Chitosan is dissolved in acetic acid solution at room temperature to form a stable soluble chitosan acetate. At this point, the solution is in a suitable acidic environment, ensuring that the amino groups in the chitosan molecules remain protonated. The dissolved chitosan solution is then adjusted to pH 7-8 with an alkaline substance, causing chitosan to precipitate. After drying, free chitosan base is obtained and redispersed in acetic acid solution to form a homogeneous solution. Simultaneously, bis(2-carboxyethyl)germanium sesquioxide is dissolved in the same solvent, and the coupling agent N,N'-dicyclohexylcarbodiimide and the catalyst 4-dimethylaminopyridine are added. Under low-temperature conditions, the carboxyl groups are activated to generate a highly reactive O-acylisourea intermediate. After the activated solution is mixed with the chitosan solution and heated, the amino groups on the chitosan molecules and the carboxyl groups on the germanium sesquioxide undergo nucleophilic substitution under the action of a catalyst, forming stable amide bonds and achieving functionalized grafting. This process needs to be sustained for a sufficient time to ensure a high grafting rate, allowing the germanium sesquioxide molecules to be uniformly anchored on the chitosan backbone, forming a hierarchical structure. After the reaction, the insoluble byproduct dicyclohexylurea is removed by cooling and filtration. The filtrate is then poured into anhydrous ethanol to precipitate the grafted product. The product is washed repeatedly with ethanol and acetone to remove unreacted substances and impurities, and finally dried under low-temperature vacuum conditions to obtain a pure graft. This graft combines the biocompatibility of chitosan with the activity of germanium groups, providing efficient adsorption and sustained-release functions for feed. Its structural stability stems from the strong linkage of amide bonds and the formation of a porous network.

[0012] According to a preferred embodiment of the present invention, in step A1, the pH is adjusted to 7-8; the temperature is then increased to 58-62°C for a reaction time of 24-30 hours.

[0013] According to a preferred embodiment of the present invention, in step A2, the temperature of vacuum drying is 38-42°C.

[0014] According to a preferred embodiment of the present invention, the preparation method of N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide comprises: B1, cooling 4.5-7 parts by weight of 4-methyl-1,2,3-thiadiazole-5-carboxylic acid, 40-60 parts by weight of anhydrous dichloromethane and 2.5-4 parts by weight of triethylamine in an ice-water bath; adding dropwise 3.5-5 parts by weight of a solution of tervapotranilyl chloride dissolved in 12-18 parts by weight of anhydrous dichloromethane while stirring, and stirring the reaction after the addition is complete to obtain a mixed anhydride solution; adding 2.5-4.5 parts by weight of furfurylamine and... A mixture of 15-25 parts anhydrous dichloromethane was added dropwise to a mixed acid anhydride solution. After the addition was complete, the mixture was stirred at room temperature. B2. After the reaction was complete, distilled water was added, and the mixture was transferred to a separatory funnel to separate the organic phase. The aqueous phase was extracted with dichloromethane, and the organic phases were combined. The organic phases were washed with hydrochloric acid solution, saturated sodium bicarbonate solution, and saturated sodium chloride solution, and dried over anhydrous sodium sulfate. The mixture was filtered to obtain a filtrate. The filtrate was concentrated under reduced pressure at 38-42℃ to obtain a crude product. The crude product was purified by silica gel column chromatography, and the fraction containing the target product was collected and concentrated under reduced pressure at 38-42℃.

[0015] In this invention, the synthesis of N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide is based on an amidation reaction using a mixed anhydride method. 4-Methyl-1,2,3-thiadiazole-5-carboxylic acid reacts with tervapotranilyl chloride in an organic solvent at low temperature to form a highly reactive mixed anhydride intermediate. This intermediate effectively activates the carboxyl group, lowering the energy barrier for subsequent reactions. Furfurylamine, acting as a nucleophile, is slowly added dropwise to the mixed anhydride solution, resulting in nucleophilic substitution at room temperature. This causes the carboxyl group of the thiadiazole ring to combine with the amino group of furfurylamine, forming the target amide bond. Sufficient reaction time is required to ensure directional intermolecular bonding and avoid side reactions. After the reaction, the system undergoes hydrolysis, liquid-liquid extraction, and multi-stage extraction to separate the organic and aqueous phases, effectively removing acidic byproducts. The organic phase is then washed with acid and alkali, dried, and concentrated to obtain the crude product. The crude product was purified by chromatography, utilizing the separation capability of silica gel columns based on differences in molecular polarity to precisely collect the target product fraction. This fraction was then concentrated at low temperature to obtain a high-purity final product. The synergistic effect of the thiadiazole ring and furan group in this molecular structure endows it with significant biological activity, enhancing the antioxidant and anti-stress properties of feed. Its synthetic route is highly efficient, and byproducts are controllable, meeting the safety requirements for food-grade raw materials.

[0016] According to a preferred embodiment of the present invention, in step B1, the temperature is cooled to 0-5°C; the reaction is stirred at room temperature for 8-10 hours.

[0017] According to a preferred embodiment of the present invention, in step B2, the extraction is performed 3-4 times.

[0018] Compared with the prior art, the present invention has the following beneficial effects: (1) This invention optimizes the functional performance of feed in the animal digestive tract through the molecular synergistic effect of bis(2-carboxyethyl)germanium sesquioxide-chitosan graft and N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide. The bis(2-carboxyethyl)germanium sesquioxide-chitosan graft forms a hierarchical porous structure through amide bond grafting. Its chitosan skeleton enhances the affinity for the intestinal mucosa, while the germanium group provides stable coordination sites, effectively improving the adsorption performance and sustained-release efficiency of feed in the intestine and improving the local concentration distribution of nutrients. The thiadiazole ring and furan ring of N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide synergistically enhance the antioxidant capacity, reduce oxidative stress in the intestinal environment by clearing residual oxidative free radicals in the feed, and provide a stable microenvironment for the intestinal microbiota.

[0019] (2) This invention makes full use of non-grain resources such as cassava flour, dried sugar residue, and sprayed corn husks, and reduces corn dependence through scientific formulation, thus significantly optimizing the feed cost structure. Cassava flour provides a high starch energy source, dried sugar residue improves palatability and supplements organic acids, and the usable fiber in sprayed corn husks is decomposed into short-chain fatty acids by compound enzyme preparations and converted into energy that can be absorbed by animals; soybean molasses serves as a natural binder, improves pelleting strength, and provides functional oligosaccharides; expanded urea supplements non-protein nitrogen, limestone powder regulates rumen pH, and sodium chloride maintains electrolyte balance.

[0020] (3) This invention optimizes the preparation process to maximize the efficacy of active ingredients and improve the overall performance of the feed. Heat-stable components (cassava flour, dried sugar residue, sprayed corn husks, etc.) are pre-prepared and granulated to prevent the compound enzyme preparation from becoming inactive at high temperatures. The enzyme preparation is added after cooling to ensure the retention of the activity of cellulase, xylanase, acidic protease, and pectinase. After vibrating screening, the pelleted feed exhibits uniform particle size and significantly improved palatability. Detailed Implementation

[0021] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention. Example

[0022] This embodiment provides a method for preparing a novel feed alternative to corn: Preparation of bis(2-carboxyethyl)germanium sesquioxide-chitosan graft: Step A1: Mix 10g of chitosan with 50g of acetic acid solution and stir at room temperature for 30 minutes to dissolve. At this point, the pH of the solution is 4.5. Then, adjust the pH to 7.2 with 1mol / L sodium hydroxide solution to precipitate the chitosan. Filter the solution, wash the precipitate with 20g of distilled water, and dry it in a vacuum drying oven at 40℃ to constant weight to obtain dried chitosan. Redissolve the dried chitosan in 50g of acetic acid solution and stir until completely dissolved to obtain an acetic acid solution of chitosan. Dissolve 5.2g of bis(2-carboxyethyl)germanium sesquioxide in 20g of N,N-dimethylformamide, add 2.8g of N,N'-dicyclohexylcarbodiimide and 1.5g of 4-dimethylaminopyridine, and activate in an ice-water bath for 1 hour to obtain an activated solution. Mix the activated solution with the acetic acid solution of chitosan, heat to room temperature, continue stirring for 2 hours, and then heat to 60℃ for 27 hours.

[0023] Step A2: After the reaction is complete, cool to room temperature, filter to remove insoluble dicyclohexylurea, and obtain filtrate; under stirring, slowly pour the filtrate into 500g of anhydrous ethanol, let stand for 2 hours, and then filter to obtain solid; wash the solid three times each with 50g of anhydrous ethanol and 50g of acetone, and filter after each wash to obtain the washed product; place the washed product in a vacuum drying oven and dry at 40℃ to constant weight to obtain bis(2-carboxyethyl)germanium sesquioxide-chitosan graft, i.e., compound A.

[0024] Preparation of N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide: Step B1: Add 5.8g of 4-methyl-1,2,3-thiadiazole-5-carboxylic acid, 50g of anhydrous dichloromethane, and 3.2g of triethylamine to a reaction flask and cool to 3°C in an ice-water bath. While stirring, slowly add a solution of 4.2g of pentanoyl chloride dissolved in 15g of anhydrous dichloromethane over 30 minutes. After the addition is complete, continue stirring at 3°C ​​for 1 hour to obtain a mixed anhydride solution. Mix 3.4g of furfurylamine and 20g of anhydrous dichloromethane, stir to dissolve, and slowly add to the above mixed anhydride solution. Control the reaction temperature not to exceed 10°C during the addition. After the addition is complete, remove the ice-water bath and stir the reaction at room temperature for 9 hours.

[0025] Step B2: After the reaction is complete, 50g of distilled water is added to quench the reaction. The mixture is then transferred to a separatory funnel to separate the organic phase. The aqueous phase is extracted three times with 30g of dichloromethane. The organic phases are combined and washed twice each with 30g of 1mol / L hydrochloric acid solution, 30g of saturated sodium bicarbonate solution, and 30g of saturated sodium chloride solution. The mixture is then dried overnight with anhydrous sodium sulfate. The desiccant is removed by filtration, and the filtrate is concentrated under reduced pressure at 40℃ to remove the solvent, yielding the crude product. The crude product is purified by silica gel column chromatography with petroleum ether and ethyl acetate in a volume ratio of 3:1. The fraction containing the target product is collected and concentrated to dryness under reduced pressure at 40℃ to obtain N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide, i.e., compound B.

[0026] Preparation of novel feed alternatives to corn: Step S1: Weigh 29g of cassava flour, 22g of dried sugar residue, 200g of sprayed corn husks, 100g of the above-prepared bis(2-carboxyethyl)germanium sesquioxide-chitosan graft, 18g of the above-prepared N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide, 60g of expanded urea, 55g of limestone powder, and 5.5g of sodium chloride, and premix them in a mixer for 5 minutes; weigh 125g of soybean molasses and heat it to 42℃ to improve its fluidity; add the preheated soybean molasses to the mixer and continue mixing for 12 minutes to obtain the mixed material.

[0027] Step S2: The mixed materials are prepared at 82℃ for 4 minutes, and then granulated in a pellet mill at 78℃ to achieve a pellet diameter of 4mm. The granulated feed pellets are then cooled to room temperature and the moisture content is reduced to below 12%, resulting in cooled feed pellets. The cooled feed pellets are then vibrated and sieved to remove powder, resulting in sieved feed pellets. 28g of a compound enzyme preparation is evenly sprayed onto the surface of the sieved feed pellets to obtain sprayed feed pellets. The compound enzyme preparation consists of 10.96g of cellulase, 8.52g of xylanase, 4.26g of acidic protease, and 4.26g of pectinase. The sprayed feed pellets are dried at 40℃ until the moisture content is below 12%, then weighed and packaged to obtain the finished product of a new type of energy feed that replaces corn. Example

[0028] The difference between this embodiment and Example 1 lies in the preparation of the bis(2-carboxyethyl)germanium sesquioxide-chitosan graft: Step A1: Mix 12g of chitosan with 60g of acetic acid solution and stir at room temperature for 30 minutes to dissolve. At this point, the pH of the solution is 4.8. Then, adjust the pH to 7.0 with 1mol / L sodium hydroxide solution to precipitate the chitosan. Filter the solution, wash the precipitate with 20g of distilled water, and dry it in a vacuum drying oven at 40℃ to constant weight to obtain dried chitosan. Redissolve the dried chitosan in 60g of acetic acid solution and stir until completely dissolved to obtain a chitosan acetic acid solution. Dissolve 6.5g of bis(2-carboxyethyl)germanium sesquioxide in 25g of N,N-dimethylformamide, add 3.5g of N,N'-dicyclohexylcarbodiimide and 2g of 4-dimethylaminopyridine, and activate in an ice-water bath for 1 hour to obtain an activated solution. Mix the activated solution with the chitosan acetic acid solution, heat to room temperature, continue stirring for 2 hours, and then heat to 62℃ and react for 30 hours.

[0029] Step A2: After the reaction is complete, cool to room temperature, filter to remove insoluble dicyclohexylurea, and obtain filtrate; under stirring, slowly pour the filtrate into 600g of anhydrous ethanol, let stand for 2 hours, filter to obtain solid; wash the solid three times each with 60g of anhydrous ethanol and 60g of acetone, filter after each wash to obtain washed product; place the washed product in a vacuum drying oven and dry at 42℃ to constant weight to obtain bis(2-carboxyethyl)germanium sesquioxide-chitosan graft, i.e., compound A.

[0030] Preparation of N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide: Step B1: Add 7g of 4-methyl-1,2,3-thiadiazole-5-carboxylic acid, 60g of anhydrous dichloromethane, and 4g of triethylamine to a reaction flask and cool to 2°C in an ice-water bath. While stirring, slowly add 5g of pentanoyl chloride dissolved in 18g of anhydrous dichloromethane over 30 minutes. After the addition is complete, continue stirring at 2°C for 1 hour to obtain a mixed anhydride solution. Mix 4.5g of furfurylamine and 25g of anhydrous dichloromethane, stir to dissolve, and slowly add to the above mixed anhydride solution. During the addition, control the reaction temperature to not exceed 10°C. After the addition is complete, remove the ice-water bath and stir the reaction at room temperature for 10 hours.

[0031] Step B2: After the reaction is complete, 60g of distilled water is added to quench the reaction. The mixture is then transferred to a separatory funnel to separate the organic phase. The aqueous phase is extracted four times with 40g of dichloromethane. The organic phases are combined and washed twice each with 40g of 1mol / L hydrochloric acid solution, 40g of saturated sodium bicarbonate solution, and 40g of saturated sodium chloride solution. The mixture is then dried overnight with anhydrous sodium sulfate. The desiccant is removed by filtration, and the filtrate is concentrated under reduced pressure at 42℃ to remove the solvent, yielding the crude product. The crude product is purified by silica gel column chromatography with petroleum ether and ethyl acetate in a volume ratio of 3:1. The fraction containing the target product is collected and concentrated to dryness under reduced pressure at 42℃ to obtain N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide, i.e., compound B.

[0032] Preparation of novel feed alternatives to corn: Step S1: Weigh 40g of cassava flour, 15g of dried sugar residue, 300g of sprayed corn husks, 150g of the above-prepared bis(2-carboxyethyl)germanium sesquioxide-chitosan graft, 30g of the above-prepared N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide, 100g of expanded urea, 100g of limestone powder, and 10g of sodium chloride, and premix them in a mixer for 5 minutes; weigh 200g of soybean molasses and heat it to 45℃ to improve its fluidity; add the preheated soybean molasses to the mixer and continue mixing for 15 minutes to obtain the mixed material.

[0033] Step S2: The mixed materials are prepared at 85℃ for 5 minutes, and then granulated in a pellet mill at 80℃ to a pellet diameter of 5mm. The granulated feed pellets are then cooled to room temperature and the moisture content is reduced to below 12% to obtain cooled feed pellets. The cooled feed pellets are then vibrated and sieved to remove powder, resulting in sieved feed pellets. 50g of a compound enzyme preparation is evenly sprayed onto the surface of the sieved feed pellets to obtain sprayed feed pellets. The compound enzyme preparation consists of 21.43g of cellulase, 14.29g of xylanase, 7.14g of acidic protease, and 7.14g of pectinase. The sprayed feed pellets are dried at 40℃ until the moisture content is below 12%, then weighed and packaged to obtain the finished product of a new type of energy feed to replace corn. Example

[0034] The difference between this embodiment and Example 1 lies in the preparation of the bis(2-carboxyethyl)germanium sesquioxide-chitosan graft: Step A1: Mix 8g of chitosan with 40g of acetic acid solution and stir at room temperature for 30 minutes to dissolve. At this time, the pH of the solution is 4.2. Then, adjust the pH to 7.5 with 1mol / L sodium hydroxide solution to precipitate chitosan. Filter, wash the precipitate with 20g of distilled water, and dry it in a vacuum drying oven at 40℃ to constant weight to obtain dried chitosan. Redissolve the dried chitosan in 40g of acetic acid solution and stir until completely dissolved to obtain an acetic acid solution of chitosan. Dissolve 4g of bis(2-carboxyethyl)germanium sesquioxide in 15g of N,N-dimethylformamide, add 2g of N,N'-dicyclohexylcarbodiimide and 1g of 4-dimethylaminopyridine, and activate in an ice-water bath for 1 hour to obtain an activated solution. Mix the activated solution with the acetic acid solution of chitosan, heat to room temperature, continue stirring for 2 hours, and then heat to 58℃ for 24 hours.

[0035] Step A2: After the reaction is complete, cool to room temperature, filter to remove insoluble dicyclohexylurea, and obtain filtrate; under stirring, slowly pour the filtrate into 400g of anhydrous ethanol, let stand for 2 hours, and then filter to obtain solid; wash the solid three times each with 40g of anhydrous ethanol and 40g of acetone, and filter after each wash to obtain the washed product; place the washed product in a vacuum drying oven and dry at 38℃ to constant weight to obtain bis(2-carboxyethyl)germanium sesquioxide-chitosan graft, i.e., compound A.

[0036] Preparation of N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide: Step B1: Add 4.5g of 4-methyl-1,2,3-thiadiazole-5-carboxylic acid, 40g of anhydrous dichloromethane, and 2.5g of triethylamine to a reaction flask and cool to 0°C in an ice-water bath. While stirring, slowly add a solution of 3.5g of pentanoyl chloride dissolved in 12g of anhydrous dichloromethane over 30 minutes. After the addition is complete, continue stirring at 0°C for 1 hour to obtain a mixed anhydride solution. Mix 2.5g of furfurylamine and 15g of anhydrous dichloromethane, stir to dissolve, and slowly add to the above mixed anhydride solution. Control the reaction temperature not to exceed 10°C during the addition. After the addition is complete, remove the ice-water bath and stir the reaction at room temperature for 8 hours.

[0037] Step B2: After the reaction is complete, 40g of distilled water is added to quench the reaction. The mixture is then transferred to a separatory funnel to separate the organic phase. The aqueous phase is extracted three times with 25g of dichloromethane. The organic phases are combined and washed twice each with 25g of 1mol / L hydrochloric acid solution, 25g of saturated sodium bicarbonate solution, and 25g of saturated sodium chloride solution. The mixture is then dried overnight with anhydrous sodium sulfate. The desiccant is removed by filtration, and the filtrate is concentrated under reduced pressure at 38℃ to remove the solvent, yielding the crude product. The crude product is purified by silica gel column chromatography with petroleum ether and ethyl acetate in a volume ratio of 3:1. The fraction containing the target product is collected and concentrated to dryness under reduced pressure at 38℃ to obtain N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide, i.e., compound B.

[0038] Preparation of novel feed alternatives to corn: Step S1: Weigh 25g of cassava flour, 30g of dried sugar residue, 100g of sprayed corn husks, 50g of the above-prepared bis(2-carboxyethyl)germanium sesquioxide-chitosan graft, 5g of the above-prepared N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide, 20g of expanded urea, 10g of limestone powder, and 1g of sodium chloride, and premix them in a mixer for 5 minutes; weigh 50g of soybean molasses and heat it to 40℃ to improve its fluidity; add the preheated soybean molasses to the mixer and continue mixing for 10 minutes to obtain the mixed material.

[0039] Step S2: The mixed materials are prepared at 80℃ for 3 minutes, and then granulated in a pellet mill at 75℃ to achieve a pellet diameter of 3mm. The granulated feed pellets are then cooled to room temperature and the moisture content is reduced to below 12%, resulting in cooled feed pellets. The cooled feed pellets are then vibrated and sieved to remove powder, resulting in sieved feed pellets. 5g of a compound enzyme preparation is evenly sprayed onto the surface of the sieved feed pellets to obtain sprayed feed pellets. The compound enzyme preparation consists of 2.14g of cellulase, 1.43g of xylanase, 0.71g of acidic protease, and 0.72g of pectinase. The sprayed feed pellets are dried at 38℃ until the moisture content is below 12%, then weighed and packaged to obtain the finished product of a new type of energy feed that replaces corn.

[0040] Comparative Example 1 The difference between this comparative example and Example 1 is that, in step S1, bis(2-carboxyethyl)germanium sesquioxide-chitosan graft material is not added, but 100g of corn flour is added instead. The remaining components and amounts are the same as in Example 1.

[0041] Comparative Example 2 The difference between this comparative example and Example 1 is that N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide is not added in step S1, but 18g of corn flour is added instead. The remaining components and amounts are the same as in Example 1.

[0042] Comparative Example 3 The difference between this comparative example and Example 1 is that, in step S1, bis(2-carboxyethyl)germanium sesquioxide-chitosan graft and N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide are not added, but 118g of corn flour is added instead, and the remaining components and amounts are the same as in Example 1.

[0043] The performance of the novel feed alternatives to corn provided in the above embodiments and comparative examples was tested using the following methods: One hundred and twenty Duroc-Landrace-Large White crossbred pigs of similar weight and good health were selected, with an initial weight of approximately 60 kg. They were randomly divided into six groups: Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 3, with four replicates per group and five pigs per replicate (half male and half female). The experiment was conducted in a closed pigsty, with free access to dry feed and duckbill waterers. Vaccinations were administered according to a standard immunization schedule. The pre-trial period was 7 days, and the formal trial period was 60 days. During the experiment, the health status of the pigs was observed daily, and feed intake and diarrhea were recorded.

[0044] Each pig was weighed on an empty stomach at the beginning and end of the experiment, and the initial and final weights were recorded to an accuracy of 0.1 kg.

[0045] The average daily weight gain is calculated based on the weighing results. Average daily weight gain (g / d) = total weight gain during the test period (kg) × 1000 / number of test days (d).

[0046] Record the amount of feed added and the amount of feed left over for each repetition every day, and calculate the average daily feed intake. Average daily feed intake (kg / d) = total feed intake during the experimental period (kg) / number of experimental days (d).

[0047] Feed conversion ratio = average daily feed intake (kg / d) / average daily weight gain (kg / d).

[0048] Observe and record the diarrhea status of each pig daily. Diarrhea rate % = total number of diarrhea episodes per group / (total number of pigs per group × number of days in the experiment) × 100%.

[0049] Experimental data were analyzed using SPSS software for one-way ANOVA and Duncan's method for multiple comparisons. Results are expressed as mean ± standard deviation.

[0050] The performance test data above are shown in Table 1.

[0051] Table 1 Performance Test Results

[0052] As can be seen from the above, in Examples 1-3, the simultaneous addition of bis(2-carboxyethyl)germanium sesquioxide-chitosan graft and N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide resulted in average daily weight gains of 875 g / d, 863 g / d, and 850 g / d, respectively, with feed conversion ratios of 2.78, 2.84, and 2.85, and diarrhea rates of 2.1%, 2.4%, and 2.3%, respectively. These results were significantly better than those of Comparative Example 1 (average daily weight gain 787 g / d, feed conversion ratio 3.13, diarrhea rate 3.8%) and Comparative Example 2 (average daily weight gain 80 g / d), which only added a single modified compound. The average daily weight gain was 2 g / d, feed conversion ratio was 3.04, and diarrhea rate was 3.5%, which is far superior to the control group 3 (average daily weight gain 740 g / d, feed conversion ratio 3.34, and diarrhea rate 4.6%) without any added modified compounds. This indicates that there is a significant synergistic effect between the two modified compounds. By adding them together, the technical problems of low energy utilization, poor intestinal health leading to high diarrhea rate, and poor feed conversion efficiency in existing alternative corn feeds can be effectively solved. The growth performance is comparable to or even better than that of corn without adding corn, while significantly reducing the incidence of diarrhea. This provides a feasible solution for the efficient utilization of non-grain resources.

Claims

1. A novel feed alternative to corn, characterized in that, The product comprises the following components in parts by weight: 25-40 parts cassava flour, 15-30 parts dried sugar residue, 100-300 parts sprayed corn husks, 50-150 parts bis(2-carboxyethyl)germanium sesquioxide-chitosan graft, 5-30 parts N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide, 50-200 parts soybean molasses, 20-100 parts expanded urea, 10-100 parts limestone powder, 5-50 parts compound enzyme preparation, and 1-10 parts sodium chloride, wherein the compound enzyme preparation is composed of cellulase, xylanase, acidic protease, and pectinase.

2. The novel feed alternative to corn according to claim 1, characterized in that, The preparation steps of the novel feed to replace corn include: S1. Premix cassava flour, dried sugar residue, sprayed corn husks, bis(2-carboxyethyl)germanium sesquioxide-chitosan graft, N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide, expanded urea, limestone powder, and sodium chloride; add preheated soybean molasses and continue mixing to obtain the mixed material. S2. The mixed materials are prepared at 80-85℃ and granulated to obtain granulated feed pellets; the granulated feed pellets are placed in a cooling dryer and cooled to room temperature to obtain cooled feed pellets; the cooled feed pellets are vibrated and screened to obtain screened feed pellets; the compound enzyme preparation is sprayed onto the surface of the screened feed pellets to obtain sprayed feed pellets; the sprayed feed pellets are dried.

3. The novel feed alternative to corn according to claim 2, characterized in that, In step S1, the preheating temperature of the preheated soybean molasses is 40-45℃.

4. The novel feed alternative to corn according to claim 2, characterized in that, In step S2, the modulation time is 3-5 min; the granulation temperature is 75-80℃.

5. The novel feed alternative to corn according to claim 1, characterized in that, The preparation method of the bis(2-carboxyethyl)germanium sesquioxide-chitosan graft includes: A1. By weight, mix 8-12 parts of chitosan with 40-60 parts of acetic acid solution and stir at room temperature; adjust the pH, filter, and dry to obtain dried chitosan; redissolve the dried chitosan in 40-60 parts of acetic acid solution to obtain an acetic acid solution of chitosan; dissolve 4-6.5 parts of bis(2-carboxyethyl)germanium sesquioxide in 15-25 parts of N,N-dimethylformamide, add 2-3.5 parts of N,N'-dicyclohexylcarbodiimide and 1-2 parts of 4-dimethylaminopyridine, and activate in an ice-water bath to obtain an activated solution; mix the activated solution with the acetic acid solution of chitosan, heat to room temperature, continue stirring, and continue heating to 58-62℃ for reaction; A2. After the reaction is complete, cool to room temperature and filter to obtain filtrate; mix the filtrate with anhydrous ethanol under stirring, let stand and filter to obtain solid; wash the solid with anhydrous ethanol and acetone in sequence to obtain washed product; dry the washed product under vacuum.

6. The novel feed alternative to corn according to claim 5, characterized in that, In step A1, adjust the pH to 7-8; continue heating to 58-62℃ for a reaction time of 24-30 hours.

7. The novel feed alternative to corn according to claim 5, characterized in that, In step A2, the vacuum drying temperature is 38-42℃.

8. The novel feed alternative to corn according to claim 1, characterized in that, The preparation method of the N-(furan-2-ylmethyl)-4-methyl-1,2,3-thiadiazole-5-carboxamide includes: B1. By weight, 4.5-7 parts of 4-methyl-1,2,3-thiadiazole-5-carboxylic acid, 40-60 parts of anhydrous dichloromethane, and 2.5-4 parts of triethylamine are cooled in an ice-water bath; while stirring, 3.5-5 parts of a solution of pentanoyl chloride dissolved in 12-18 parts of anhydrous dichloromethane are added dropwise. After the addition is complete, the mixture is stirred to obtain a mixed anhydride solution; 2.5-4.5 parts of furfurylamine and 15-25 parts of anhydrous dichloromethane are mixed and added dropwise to the mixed anhydride solution. After the addition is complete, the mixture is stirred to react at room temperature. B2. After the reaction is complete, add distilled water and transfer to a separatory funnel to separate the organic phase. Extract the aqueous phase with dichloromethane, combine the organic phases, and wash the organic phases with hydrochloric acid solution, saturated sodium bicarbonate solution, and saturated sodium chloride solution. Dry with anhydrous sodium sulfate. Filter to obtain the filtrate. Concentrate the filtrate under reduced pressure at 38-42℃ to obtain the crude product. Purify the crude product by silica gel column chromatography, collect the fraction containing the target product, and concentrate it under reduced pressure at 38-42℃.

9. The novel feed alternative to corn according to claim 8, characterized in that, In step B1, the mixture is cooled to 0-5°C and stirred at room temperature for 8-10 hours.

10. The novel feed alternative to corn according to claim 8, characterized in that, In step B2, the extraction is performed 3-4 times.

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