CN113768043A - Method for reducing content of free gossypol in cottonseed meal and feed - Google Patents
Method for reducing content of free gossypol in cottonseed meal and feed Download PDFInfo
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- CN113768043A CN113768043A CN202110910970.5A CN202110910970A CN113768043A CN 113768043 A CN113768043 A CN 113768043A CN 202110910970 A CN202110910970 A CN 202110910970A CN 113768043 A CN113768043 A CN 113768043A
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- QBKSWRVVCFFDOT-UHFFFAOYSA-N gossypol Chemical compound CC(C)C1=C(O)C(O)=C(C=O)C2=C(O)C(C=3C(O)=C4C(C=O)=C(O)C(O)=C(C4=CC=3C)C(C)C)=C(C)C=C21 QBKSWRVVCFFDOT-UHFFFAOYSA-N 0.000 title claims abstract description 156
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- 229950005277 gossypol Drugs 0.000 title claims abstract description 87
- 235000012054 meals Nutrition 0.000 title claims abstract description 84
- QHOPXUFELLHKAS-UHFFFAOYSA-N Thespesin Natural products CC(C)c1c(O)c(O)c2C(O)Oc3c(c(C)cc1c23)-c1c2OC(O)c3c(O)c(O)c(C(C)C)c(cc1C)c23 QHOPXUFELLHKAS-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229930000755 gossypol Natural products 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 47
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K10/00—Animal feeding-stuffs
- A23K10/30—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms
- A23K10/37—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms from waste material
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K50/00—Feeding-stuffs specially adapted for particular animals
- A23K50/70—Feeding-stuffs specially adapted for particular animals for birds
- A23K50/75—Feeding-stuffs specially adapted for particular animals for birds for poultry
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
- A23L5/27—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
- Y02P60/87—Re-use of by-products of food processing for fodder production
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Abstract
The invention discloses a method for reducing the content of free gossypol in cottonseed meal and feed, wherein the method for reducing the content of free gossypol in cottonseed meal comprises the following steps: step S10, dissolving acid-soluble chitosan in an acid solution to obtain a chitosan solution; step S20, mixing and soaking the cottonseed meal, the chitosan solution and the non-aqueous solvent at the temperature of 60-78 ℃, and reacting to obtain a mixed material; and step S30, performing solid-liquid separation on the mixed material to obtain a cottonseed protein product. The invention uses acid solution of acid-soluble chitosan to soak cottonseed meal, and the chitosan-gossypol Schiff base is formed by the reaction of chitosan and free gossypol, so that the free gossypol in the cottonseed meal is converted into non-toxic combined gossypol, thereby greatly reducing the content of the free gossypol in the cottonseed meal, and the processed cottonseed protein product can replace fish meal and/or soybean meal in a larger proportion and is used as a protein source for feeding monogastric animals.
Description
Technical Field
The invention relates to the technical field of feed processing, in particular to a method for reducing the content of free gossypol in cottonseed meal and feed.
Background
The shortage of feed protein resources becomes a bottleneck restricting the feed industry and the development of animal production in China. Currently, the most widely used feed proteins in China are mainly fish meal and soybean meal. The fish meal has high price due to the distribution of producing areas and the monopoly of the international market; meanwhile, in recent years, the price of soybean meal has been increased dramatically. Therefore, the intensive development and utilization of the existing non-grain feed protein resources in China as a substitute for feed protein sources are urgent.
The cottonseed protein is a byproduct of cottonseed oil processing, has high crude protein content, and is an economic and effective vegetable protein source. However, the cottonseed protein contains anti-nutritional factors such as free gossypol, so that the feeding value of the cottonseed protein is limited.
The highest safety limit of free gossypol in the compound feed is given by the current feed hygiene standard (GB13078-2001) in China: the free gossypol content of the compound feed for broiler chickens and growing chickens is not higher than 100mg/kg, and the safety limit of the free gossypol in the compound feed for laying hens and growing pigs is 20mg/kg and 60mg/kg respectively. At present, the industry standard (GH/T1042-2007) of the dephenolized cottonseed protein in China provides that the free gossypol limit in the top-grade dephenolized cottonseed protein is less than or equal to 400 mg/kg. The dosage is reduced compared with free gossypol in the raw material cottonseed meal, but the requirement that monogastric animals such as broiler chickens and growing chickens eat cottonseed protein directly still cannot be met. Therefore, the development of a new process for further reducing free gossypol in cottonseed meal enables cottonseed protein to replace fish meal and soybean meal in a larger proportion, directly meets the requirements of feeding protein sources of broiler chickens and growing chickens, and has important practical significance and profound strategic significance.
Disclosure of Invention
The invention mainly aims to provide a method for reducing the content of free gossypol in cottonseed meal and feed, and aims to reduce the content of free gossypol in the cottonseed meal.
In order to achieve the purpose, the invention provides a method for reducing the content of free gossypol in cottonseed meal, which comprises the following steps:
step S10, dissolving acid-soluble chitosan in an acid solution to obtain a chitosan solution;
step S20, mixing and soaking the cottonseed meal, the chitosan solution and the non-aqueous solvent at the temperature of 60-78 ℃, and reacting to obtain a mixed material;
and step S30, performing solid-liquid separation on the mixed material to obtain a cottonseed protein product.
Optionally, in step S10, the acidic solution includes an acetic acid aqueous solution with a mass concentration of 1% to 4%; and/or the presence of a gas in the gas,
the deacetylation degree of the acid-soluble chitosan is not less than 80%.
Optionally, in step S10, the concentration of the chitosan solution is not lower than 20 g/L.
Optionally, in step S20, the soaking time is 4-20 hours; and/or the presence of a gas in the gas,
the particle size of the cottonseed meal is 40-120 meshes.
Optionally, in step S20, the volume of the chitosan solution is 3% to 10% of the volume of the non-aqueous solvent.
Optionally, in step S20, the non-aqueous solvent includes absolute ethanol or 95% ethanol solution by volume fraction.
Optionally, in step S20, 1.5-4 mL of non-aqueous solvent is added per gram of cottonseed meal.
Optionally, step S30 is followed by:
and (3) placing the solid after solid-liquid separation at 60-85 ℃ for blast drying until the water content is equal to or less than 15%, thus obtaining the cottonseed protein product.
Optionally, step S30 is followed by: the liquid phase after the solid-liquid separation is recovered and used in step S20.
In addition, the invention also provides a feed which comprises the cottonseed protein product prepared by the method for reducing the content of free gossypol in the cottonseed meal.
In the technical scheme provided by the invention, the cottonseed meal is soaked in an acid solution of acid-soluble chitosan, and the chitosan and free gossypol react to form chitosan-gossypol Schiff base, so that the free gossypol in the cottonseed meal is converted into non-toxic combined gossypol, the content of the free gossypol in the cottonseed meal is greatly reduced, and the processed cottonseed protein product can replace fish meal and/or soybean meal in a larger proportion and serves as a protein source for feeding monogastric animals.
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 some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic flow chart diagram illustrating one embodiment of a method of reducing the free gossypol content of cottonseed meal in accordance with the present invention;
FIG. 2 is a schematic flow chart of another embodiment of the method of reducing the free gossypol content of cottonseed meal according to the invention.
The objects, features, and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. 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 highest safety limit of free gossypol in the compound feed is given by the current feed hygiene standard (GB13078-2001) in China: the free gossypol content of the compound feed for broiler chickens and growing chickens is not higher than 100mg/kg, and the safety limit of the free gossypol in the compound feed for laying hens and growing pigs is 20mg/kg and 60mg/kg respectively. At present, the industry standard (GH/T1042-2007) of the dephenolized cottonseed protein in China provides that the free gossypol limit in the top-grade dephenolized cottonseed protein is less than or equal to 400 mg/kg. The dosage is reduced compared with free gossypol in the raw material cottonseed meal, but the requirement that monogastric animals such as broiler chickens and growing chickens eat cottonseed protein directly still cannot be met. Therefore, the development of a new process for further reducing free gossypol in cottonseed meal enables cottonseed protein to replace fish meal and soybean meal in a larger proportion, directly meets the requirements of feeding protein sources of broiler chickens and growing chickens, and has important practical significance and profound strategic significance.
In practice, the cottonseed protein may be treated by a variety of dephenolization processes, such as physical detoxification, chemical inactivation, microbial detoxification, and the like. The physical detoxification method is to process the cottonseed meal by means of high-temperature high-pressure cooking or strong electric field action and the like so as to destroy the molecular structure of free gossypol in the cottonseed meal, and the processing mode is not only easy to destroy other nutritional ingredients in the cottonseed meal, but also brings potential safety hazard to operators and has high danger; the microbial detoxification method has the advantages of long treatment period, high energy consumption and high difficulty in controlling the product quality, thus causing poor product quality stability; the chemical passivation method needs to adopt high-dose ferrous sulfate, easily causes excessive chemical reagent residues, influences the feeding value of the cottonseed protein, and is poor in environmental friendliness. In view of the above, the invention provides a method for reducing the content of free gossypol in cottonseed meal, which is simple to operate, safe, efficient, low in cost, high in product quality stability, free from damage and pollution to the cottonseed meal, and beneficial to development of the cottonseed meal into feed components. FIGS. 1 and 2 show an embodiment of the method of the present invention for reducing the free gossypol content of cottonseed meal.
Referring to fig. 1, the method for reducing the content of free gossypol in cottonseed meal comprises the following steps:
and step S10, dissolving the acid-soluble chitosan in the acid solution to obtain a chitosan solution.
And step S20, mixing and soaking the cottonseed meal, the chitosan solution and the non-aqueous solvent at the temperature of 60-78 ℃, and reacting to obtain a mixed material.
And step S30, performing solid-liquid separation on the mixed material to obtain a cottonseed protein product.
In the technical scheme provided by the invention, the cottonseed meal is soaked in an acid solution of acid-soluble chitosan, and the chitosan and free gossypol react to form chitosan-gossypol Schiff base, so that the free gossypol in the cottonseed meal is converted into non-toxic combined gossypol, the content of the free gossypol in the cottonseed meal is greatly reduced, and the processed cottonseed protein product can replace fish meal and/or soybean meal in a larger proportion and serves as a protein source for feeding monogastric animals.
The chitosan is classified into acid-soluble chitosan and water-soluble chitosan. The acid-soluble chitosan is favorable for fixing water-insoluble free gossypol, and the chitosan reacts with the free gossypol to generate chitosan-gossypol Schiff base, so that the dephenolizing effect is achieved.
The deacetylation degree of the acid-soluble chitosan is not less than 80%. Within the range, the higher the deacetylation degree of chitosan is, the more amino groups contained in chitosan per unit mass is, on one hand, the more the acid-soluble chitosan is easily combined with hydrogen ions in an acid solution to form a chitosan-acid salt which is easily dissolved in water, so that the solubility of chitosan in the acid solution is increased, on the other hand, under the catalytic action of a small amount of acid, the amino groups in chitosan and aldehyde groups in free gossypol molecules are more easily reacted to generate Schiff base of chitosan-gossypol, so that the 'active' aldehyde groups in gossypol molecules are blocked to form combined gossypol, and further the detoxification effect is achieved.
Acid soluble chitosan requires an acidic solution to dissolve. The higher the acidity, the greater the amount of chitosan dissolved. However, too high acidity increases acid residue, which affects the palatability of the cottonseed meal. Moreover, the formation of chitosan-gossypol Schiff base is not facilitated by too high an acidic environment. In this embodiment, the acidic solution includes an acetic acid aqueous solution with a mass concentration of 1% to 4%. Compared with other acidic solutions, acetic acid not only has strong chitosan dissolving capacity, but also is weak acid and can serve as a buffer system for reaction; in addition, even if a little acetic acid residue exists in the processed cottonseed protein product, the acetic acid can be digested and absorbed by animals, and the feeding value of the cottonseed protein product is not influenced. In conclusion, the acid environment constructed by the acetic acid aqueous solution with the mass concentration of 1-4% can ensure that the chitosan is fully dissolved, and can play a role in catalyzing the formation of the chitosan-gossypol Schiff base.
In step S10, the concentration of the chitosan solution is not lower than 20 g/L. Within this range, the higher the quality of chitosan dissolved in an aqueous acetic acid solution, the better. Therefore, the volume of the chitosan solution added into the mixed material of the ethanol and the cottonseed meal can be reduced, and the water content in the solvent is further reduced. This is because: during the process of forming chitosan-gossypol by the action of chitosan and gossypol, water is generated, and the introduction of water is not favorable for the formation of Schiff base. However, the solution in which chitosan is dissolved contains water, which requires that the volume of the chitosan solution added is as small as possible while ensuring the same amount of chitosan added. Otherwise, the conversion of free gossypol in the cottonseed meal into chitosan-gossypol is not facilitated. Based on this, the present embodiment preferably selects a chitosan solution having a concentration of not less than 20g/L, and the higher the concentration of chitosan in the solution, the better.
In step S20, the cottonseed meal is soaked in a chitosan solution-non-aqueous solvent system, and gossypol and chitosan are combined to form schiff S base. The soaking temperature is not too low, otherwise the reaction is difficult to proceed, in this embodiment, the soaking temperature is 60 to 78 ℃, preferably 65 to 75 ℃. The soaking time is 4-20 h, and the free gossypol can be fully leached within the time range; preferably, the soaking time is 5-15 h.
In order to improve the dephenolization effect, the particle size of the cottonseed meal adopted in the embodiment is 40-120 meshes, namely the cottonseed meal can pass through a 40-mesh screen but cannot pass through a 120-mesh screen, so that the cottonseed meal particles can be small enough to improve the specific surface area of the cottonseed meal particles, the gossypol can be conveniently and fully leached, the gossypol removal rate is improved, the treatment efficiency is improved, and the subsequent increase of the difficulty of solid-liquid separation caused by the undersize particles can be avoided.
In this example, a non-aqueous solvent is selected as the reaction solvent, based on the consideration that the reaction of free gossypol with chitosan in cottonseed meal is preferably carried out in a non-aqueous environment, but it should be noted that the non-aqueous solvent herein refers to a solvent containing no or little water, and not absolutely no water. Preferably, the non-aqueous solvent comprises absolute ethyl alcohol or an ethanol solution with the volume fraction of 95%, so that the requirement for reducing the water content can be met, the reaction of free gossypol and chitosan is facilitated, and compared with other solvents, the ethanol has small pollution and is easy to recover, so that the whole production process of the method is green and environment-friendly, no three-waste discharge is caused, and the boiling point of the ethanol is about 78.5 ℃, and in the subsequent wet meal drying process, the solvent can be evaporated out only by selecting the temperature below 85 ℃ for drying treatment, so that the solvent residue is avoided, and the protein component in the cottonseed protein product cannot be damaged. Further, in order to facilitate ethanol recovery and reduce energy consumption, the smaller the amount of the non-aqueous solvent is, the better the non-aqueous solvent is, in this embodiment, 1.5 to 4mL of the non-aqueous solvent is added per gram of the cottonseed meal.
Considering that the smaller the water content in the reaction system is, the better, the volume of the chitosan solution is 3% to 10% of the volume of the non-aqueous solvent in step S20.
In step S30, the solid-liquid separation method may be various, and may be filtration, suction filtration, filter pressing, centrifugation, or the like, but the present invention is not limited thereto. Through solid-liquid separation, can obtain solid and liquid phase thing, wherein the major component of solid is the wet meal, and this embodiment carries out drying process to the wet meal, reduces its water content to cottonseed protein product is preserved and is transported. Specifically, in this embodiment, the step S30 includes: and step S40, placing the solid after solid-liquid separation at 60-85 ℃ for forced air drying until the water content is equal to or less than 15%, and obtaining the cottonseed protein product.
Because the boiling point of the ethanol is about 78.5 ℃, the ethanol can be quickly evaporated by blast drying at 60-85 ℃, and because the temperature is lower than 85 ℃, the damage of high temperature to the protein in wet meal is avoided, and the feeding value of the cottonseed protein product is ensured.
Based on the foregoing embodiment, another embodiment is provided, and referring to fig. 2, in this embodiment, after step S30, the method further includes:
in step S40, the liquid phase after the solid-liquid separation is recovered and used in step S20.
Specifically, after solid-liquid separation, the liquid phase obtained by separation is recovered, the non-aqueous solvent in the liquid phase is extracted and used for soaking the cottonseed meal in the step S20 again, so that the solvent is recycled, the cost is reduced, and the environmental friendliness of the method is improved. The recovery method can refer to the existing common solvent recovery method, and is not detailed here.
In addition, the invention also provides a feed which comprises the cottonseed protein product prepared by the method for reducing the content of free gossypol in the cottonseed meal. The cottonseed protein is rich in crude protein, is used as a processing byproduct of cottonseed oil, is low in price, and the content of free gossypol in the cottonseed protein product prepared by the method is not higher than 100mg/kg, and basically meets the feed sanitation standard.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
The cottonseed meal selected in the following examples is the same raw material batch, and the content of free gossypol in the cottonseed meal is 740 mg/kg. The detection and the content detection of the free gossypol in the following examples are carried out according to the national standard GB/T13086-. Meanwhile, the deacetylation degree of chitosan in the following examples was measured according to the linear potentiometric titration method.
Example 1
Dissolving acid-soluble chitosan in an acetic acid aqueous solution to obtain a chitosan solution, wherein the concentration of the acetic acid aqueous solution is 1%; the deacetylation degree of the acid-soluble chitosan is 90%; the concentration of the chitosan solution was 30 g/L.
Taking 0.5g of mechanically crushed and sieved cottonseed meal (the grain size is controlled to be 40-120 meshes), adding 1.9mL of absolute ethyl alcohol and 0.1mL of chitosan solution, fully and uniformly mixing, then raising the temperature of the material to 70 ℃, and soaking for 15 hours to obtain a mixed material. The material was stirred slowly for 10 minutes every 1 hour during the soaking period. Filtering to remove the solvent in the mixed material, recovering, and air-drying the wet meal by blowing air at 75 ℃ until the water content is lower than 15% to obtain the deeply dephenolized cottonseed protein product.
The content of free gossypol in the product is 39mg/kg by analysis.
Example 2
Dissolving acid-soluble chitosan in an acetic acid aqueous solution to obtain a chitosan solution, wherein the concentration of the acetic acid aqueous solution is 1%; the deacetylation degree of the acid-soluble chitosan is 90%; the concentration of the chitosan solution was 28 g/L.
Taking 1000g of mechanically crushed and sieved cottonseed meal (the grain size is controlled to be 40-120 meshes), adding 4.0L of absolute ethyl alcohol and 200mL of chitosan solution, fully and uniformly mixing, then raising the temperature of the material to 75 ℃, and soaking for 6 hours to obtain a mixed material. The material was stirred slowly for 5 minutes every 1 hour during the soaking period. Filtering to remove the solvent in the mixed material, recovering, and drying the wet meal by air blast at 80 ℃ until the water content is lower than 15% to obtain the deeply dephenolized cottonseed protein product.
The content of free gossypol in the product is 45mg/kg by analysis.
Example 3
Dissolving acid-soluble chitosan in an acetic acid aqueous solution to obtain a chitosan solution, wherein the concentration of the acetic acid aqueous solution is 2%; the deacetylation degree of the acid-soluble chitosan was 86%; the concentration of the chitosan solution was 30 g/L.
Taking 1000g of mechanically crushed and sieved cottonseed meal (the grain size is controlled to be 40-120 meshes), adding 4.0L of 95% ethanol and 200mL of chitosan solution, fully and uniformly mixing, then raising the temperature of the material to 65 ℃, and soaking for 10 hours to obtain a mixed material. The material was stirred slowly for 5 minutes every 1 hour during the soaking period. Filtering the solvent in the mixed material, recovering, and drying the wet dregs by air blast at 70 ℃ until the water content is lower than 15% to obtain the deeply dephenolized cottonseed protein product.
The content of free gossypol in the material is reduced to 61.5mg/kg by analysis.
Example 4
Dissolving acid-soluble chitosan in an acetic acid aqueous solution to obtain a chitosan solution, wherein the concentration of the acetic acid aqueous solution is 1%; the deacetylation degree of the acid-soluble chitosan is 80%; the concentration of the chitosan solution was 25 g/L.
Taking 10kg of mechanically crushed and sieved cottonseed meal (the grain size is controlled to be 40-120 meshes), adding 30.0L of 95% ethanol and 2.0L of chitosan solution, fully and uniformly mixing, then raising the temperature of the material to 75 ℃, and soaking for 4 hours to obtain a mixed material. The material was stirred slowly for 5 minutes every 1 hour during the soaking period. Filtering the solvent in the mixed material, recovering, and drying the wet dregs by air blast at 70 ℃ until the water content is lower than 15% to obtain the deeply dephenolized cottonseed protein product.
The content of free gossypol in the material is reduced to 60.5mg/kg by analysis.
Example 5
Dissolving acid-soluble chitosan in an acetic acid aqueous solution to obtain a chitosan solution, wherein the concentration of the acetic acid aqueous solution is 2%; the deacetylation degree of the acid-soluble chitosan was 86%; the concentration of the chitosan solution was 25 g/L.
Taking 5kg of mechanically crushed and sieved cottonseed meal (the grain size is controlled to be 40-120 meshes), adding 18.0L of 95% ethanol and 1.0L of chitosan solution, fully and uniformly mixing, then heating the material to 70 ℃, and soaking for 8 hours. During this time, the batch was stirred slowly for 5 minutes at intervals of 1 hour. Filtering the solvent in the mixed material, recovering, and drying the wet dregs by air blast at 80 ℃ until the water content is lower than 15% to obtain the deeply dephenolized cottonseed protein product.
The content of free gossypol in the material is 72.8mg/kg by analysis.
Example 6
Dissolving acid-soluble chitosan in an acetic acid aqueous solution to obtain a chitosan solution, wherein the concentration of the acetic acid aqueous solution is 2%; the deacetylation degree of the acid-soluble chitosan was 86%; the concentration of the chitosan solution was 25 g/L.
Taking 5kg of mechanically crushed and sieved cottonseed meal (the grain size is controlled to be 40-120 meshes), adding 10L of 95% ethanol and 300mL of chitosan solution, fully and uniformly mixing, then raising the temperature of the material to 60 ℃, and soaking for 20 hours. During this time, the batch was stirred slowly for 5 minutes at intervals of 1 hour. Filtering the solvent in the mixed material, recovering, and drying the wet meal by blowing air at 85 ℃ until the water content is lower than 15% to obtain the cottonseed protein product with deep dephenolization.
The content of free gossypol in the material was 184mg/kg by analysis.
Example 7
Dissolving acid-soluble chitosan in an acetic acid aqueous solution to obtain a chitosan solution, wherein the concentration of the acetic acid aqueous solution is 4%; the deacetylation degree of the acid-soluble chitosan was 86%; the concentration of the chitosan solution was 25 g/L.
Taking 5kg of mechanically crushed and sieved cottonseed meal (the grain size is controlled to be 40-120 meshes), adding 7.5L of 95% ethanol and 1.0L of chitosan solution, fully and uniformly mixing, then raising the temperature of the material to 78 ℃, and soaking for 4 hours. During this time, the batch was stirred slowly for 5 minutes at intervals of 1 hour. Filtering the solvent in the mixed material, recovering, and drying the wet dregs by blast at 60 ℃ until the water content is lower than 15% to obtain the deeply dephenolized cottonseed protein product.
The content of free gossypol in the material was analyzed to be 74 mg/kg.
Comparative example
The cottonseed meal is treated by adopting a dephenolized cottonseed protein production process to obtain a first-grade cottonseed meal product. The method comprises the following steps:
1kg of cottonseed meal is taken, 1.5L of 90% methanol is added, and the cottonseed meal is leached for 60min at 55 ℃. After solid-liquid separation, the solid is dried by air blast at 80 ℃ until the water content is 12 percent.
The content of free gossypol in the material was determined to be 392mg/kg by analysis.
In conclusion, the method can greatly reduce the content of free gossypol in the cottonseed meal, and can process the cottonseed protein product with the content of free cotton powder lower than 100mg/kg by controlling the processing process conditions, wherein the content of the free gossypol in the cottonseed protein product is far lower than that of the free gossypol in the first-grade cottonseed meal product obtained by the existing production process of dephenolized cottonseed protein; the treatment method is green and environment-friendly, and no three wastes are discharged; compared with a physical detoxification method, the method is simpler and safer, and has higher production efficiency, short period, low energy consumption and stable product quality compared with a microbial fermentation method.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (10)
1. A method for reducing the content of free gossypol in cottonseed meal is characterized by comprising the following steps:
step S10, dissolving acid-soluble chitosan in an acid solution to obtain a chitosan solution;
step S20, mixing and soaking the cottonseed meal, the chitosan solution and the non-aqueous solvent at the temperature of 60-78 ℃, and reacting to obtain a mixed material;
and step S30, performing solid-liquid separation on the mixed material to obtain a cottonseed protein product.
2. The method of reducing the content of free gossypol in cottonseed meal as claimed in claim 1 wherein in step S10 the acidic solution comprises an aqueous solution of acetic acid at a concentration of 1% to 4% by mass; and/or the presence of a gas in the gas,
the deacetylation degree of the acid-soluble chitosan is not less than 80%.
3. The method of reducing the free gossypol content of cottonseed meal as claimed in claim 2 wherein in step S10 the concentration of the chitosan solution is not less than 20 g/L.
4. The method for reducing the content of free gossypol in cottonseed meal according to claim 1, wherein in step S20, the soaking time is 4-20 h; and/or the presence of a gas in the gas,
the particle size of the cottonseed meal is 40-120 meshes.
5. The method of reducing the free gossypol content of cottonseed meal as claimed in claim 1 wherein in step S20 the volume of the chitosan solution is between 3% and 10% of the volume of the non-aqueous solvent.
6. The method of reducing the free gossypol content of cottonseed meal as claimed in claim 1 wherein in step S20 the non-aqueous solvent comprises absolute ethanol or a 95% by volume ethanol solution.
7. The method of reducing the content of free gossypol in cottonseed meal according to claim 6 wherein in step S20, 1.5-4 mL of non-aqueous solvent is added per gram of cottonseed meal.
8. The method of reducing the free gossypol content of cottonseed meal according to claim 6, further comprising, after step S30:
and (3) placing the solid after solid-liquid separation at 60-85 ℃ for blast drying until the water content is equal to or less than 15%, thus obtaining the cottonseed protein product.
9. The method of reducing the free gossypol content of cottonseed meal as claimed in claim 1 further comprising, after step S30: the liquid phase after the solid-liquid separation is recovered and used in step S20.
10. A feed comprising a cottonseed protein product produced by the method of reducing the content of free gossypol in cottonseed meal as claimed in any one of claims 1 to 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4279811A (en) * | 1979-06-29 | 1981-07-21 | The United States Of America As Represented By The Secretary Of Agriculture | Treatment of cottonseed meals followed by extraction with certain solvents to remove gossypol |
| US4546004A (en) * | 1981-02-02 | 1985-10-08 | The Texas A&M University System | Method of producing low-gossypol cottonseed protein material |
| CN102349595A (en) * | 2011-10-28 | 2012-02-15 | 晨光生物科技集团股份有限公司 | Industrial method for improving absorption utilization rate of cottonseed protein |
| CN103461645A (en) * | 2013-08-29 | 2013-12-25 | 石河子市天成油脂有限公司 | Preparation method of cottonseed protein |
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2021
- 2021-08-09 CN CN202110910970.5A patent/CN113768043A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4279811A (en) * | 1979-06-29 | 1981-07-21 | The United States Of America As Represented By The Secretary Of Agriculture | Treatment of cottonseed meals followed by extraction with certain solvents to remove gossypol |
| US4546004A (en) * | 1981-02-02 | 1985-10-08 | The Texas A&M University System | Method of producing low-gossypol cottonseed protein material |
| CN102349595A (en) * | 2011-10-28 | 2012-02-15 | 晨光生物科技集团股份有限公司 | Industrial method for improving absorption utilization rate of cottonseed protein |
| CN103461645A (en) * | 2013-08-29 | 2013-12-25 | 石河子市天成油脂有限公司 | Preparation method of cottonseed protein |
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| NESLIHAN BEYAZIT等: "Synthesis, characterization and antioxidant activity of chitosan Schiff base derivatives bearing (-)-gossypol", 《CARBOHYDRATE POLYMERS》 * |
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