CN101019607B - Feed additive capable of promoting animal's growth and its preparation method - Google Patents
Feed additive capable of promoting animal's growth and its preparation method Download PDFInfo
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- CN101019607B CN101019607B CN2006100097036A CN200610009703A CN101019607B CN 101019607 B CN101019607 B CN 101019607B CN 2006100097036 A CN2006100097036 A CN 2006100097036A CN 200610009703 A CN200610009703 A CN 200610009703A CN 101019607 B CN101019607 B CN 101019607B
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Abstract
The present invention relates to a preparation process of a feed additive capable of promoting growth of animal. Aimed at a present condition that animal feeding often used inorganic copper sulfate as additive faces problems of low absorptivity and utilization rate and high toxicity or the like, the feed additive capable of promoting animal's growth is prepared with chitosan and copper sulfate in 1/3-10 times the weight of chitosan as material and through mixing and reaction. The feed additive of chitosan-copper chelate has advantages in actual use of: small dosage, fast absorption, capacity of promoting animal's growth and no residue. The present invention is favorable to provide a guarantee in producing healthy, safe and green animal product, and is favorable to breeding green animal in animal husbandry, and can also reach the demand of green animal food for people. At the same time, the method described by the invention is simple with good operability and is good in application and dissemination.
Description
Technical field
The present invention relates to a kind of preparation method of feed addictive.
Background technology
Along with to the going deep into of analysis on trace, it is found that each micro-shortage or surplus in people and the animal body, can cause that all physiological function is disorderly, thereby cause disease.Research shows: copper is at the blood of human body, and brain all has existence in the liver; Be a kind of important catalyst in the human body, all contain copper in protein and the enzyme more than 30 kinds such as cytochrome oxidase, it plays earn a bare living normal development and metabolic effect; But when copper ion is excessive, can bring out cancer again, copper gets into liver cell and protein, amino acid or other materials form metal complex; It is more stable at organismic internal environment, fat-soluble height, easy and interactions such as enzyme, nucleic acid; Excessive metal ion can act on DNA, causes pernicious differentiation of cell and growth.
Trace element is divided into the trace element and the inorganic microelement of biosynthetic trace element, organic synthesis.Three's absorptivity and utilization rate are followed successively by trace element, the inorganic microelement of biosynthetic trace element, organic synthesis from high to low.Though the absorptivity of inorganic microelement and utilization rate are all extremely low; But still adopt inorganic microelement such as copper sulphate at present in the animal-breeding field as feed addictive (growth promoter); Inorganic copper sulphate exists the problem of absorption difference directly as animal growth promoting agent, and residual serious in animal body; In case the people eats the animal foodstuff that contains high residue copper sulphate, will be detrimental to health greatly; On the other hand, copper sulphate toxicity is very big, and a large amount of uses can cause the animal intestine mesentery to damage, and cause diarrhoea even cause large quantities of death, and non-absorbent part excretes with ight soil, causes environmental pollution.And copper sulphate addition in feed is big; High copper feed has strong catalysed oxidn; Even experiment showed, that excess is added anti-oxidant greatly, also can't solve the problem of oxidation of feed; Especially all the more so in summer, therefore the high copper feed utmost point is not suitable for using as animal feed additive.Though the amino acid copper chelate has certain advantage as biology feed additive with respect to inorganic microelement; But this chelate does not have the ability of defence disease; Exist not enough in actual use; A kind ofly not only do not have toxic and side effect, a biology feed additive that also has outstanding defence disease ability simultaneously with regard to available and have at present through simple preparation method.
Summary of the invention
Use inorganic copper sulphate to exist absorptivity and utilization rate is low, toxicity is big, residual serious problem in the body to present animal feeding as additive; The present invention provide a kind of consumption few, absorb fast, promote growth of animal, noresidue, do not have any toxicity, and can restrain the feed addictive and the preparation method of the defective of the defence disease ability that the amino acid copper chelate had.A kind of feed addictive that promotes growth of animal, said additive are the chitosan copper chelate, it be with shitosan and the copper sulphate that accounts for 1/3 to 10 times of chitosan mass be raw material mix and react after be prepared from.Its a kind of method for preparing the chitosan copper chelate may further comprise the steps successively: 0.3～0.7g shitosan is joined in the container that fills 50ml water; In container, add the copper sulphate that accounts for chitosan mass 1/3～3/4 then; Abundant mixing; The pH of control solution is 5.5～6.5, reacts 0.2～1 hour, obtains the chitosan copper chelate.Its another kind of preparation method may further comprise the steps successively: it is in 0.1～2% the acetic acid that the 0.5g shitosan is joined 25～50ml, percent by volume, mixes and places 0.5～5h, becomes the chitosan gum liquid solution; Other gets the copper sulphate that accounts for 1～10 times of amount of chitosan mass and puts in 5～10ml water copper sulphate is disperseed, and then the chitosan gum liquid solution is poured in the container that fills copper sulphate, promptly becomes the chitosan copper chelate.
Chitosan copper chelate according to the invention belongs to biologic product, can be used as in the control of promoter that green feed additive is applied to growth of animal or relevant disease.Shitosan ((1; 4)-and 2-acetamido-2-deoxidation-callose) have another name called chitin, for white or amorphous, the translucent solid of canescence, be a kind of natural biological high molecular polymer; It also is unique trona polysaccharide of finding so far; Itself have following 4 characteristics: 1 biological stability is high: comprise mechanical strength, optics, electrical properties and 120 ℃ do not rupture with interior strand etc.; 2 bioavailabilities are high: with body good compatibility is arranged; The ability of 3 defence diseases is strong: antibiotic, antiviral, strengthen beneficial bacterium in the intestines, and suppress harmful bacterium, the activating cell immunity strengthens humoral immunity, removes interior free yl, reduces cholesterol, and reducing blood lipid has the effect of prevention and treatment disease; 4 have good chelating property.Simultaneously; The raw material chitin of shitosan extensively is present in crab shell, shrimp shell, insect, the mushroom; Be one of the abundantest natural polymer of occurring in nature, annual nature synthetic quantity reaches tens tons more than, so the raw materials used shitosan wide material sources of the present invention.Shitosan according to the invention also is widely used at medical domain simultaneously, and therefore, chitosan copper will be brought into play double effect in body, for instructing production practices also with significant.In current internal feed, copper class additive is main with copper sulphate, and the research of biological copper (chelate of shitosan and copper ion) simultaneously only limits to minor amount of water equality drawback again; Pass through the method for the invention; The biological copper that the rate that can be absorbed and utilization rate are all high, the noresidue in vivo of biological copper, avirulence; And can not cause any environmental pollution, and chitosan copper chelate according to the invention has the ability of good defence disease.Experimental verification; Consumption is few in actual use, absorption is fast for chitosan copper chelate according to the invention, promote growth of animal, noresidue;, green animal product healthy, safety for producing provides certain guarantee; Therefore product according to the invention helps the breed of animal husbandry green animal, can satisfy the demand of people to green animal food.The method of the invention is simple, workable simultaneously, is beneficial to and applies.
Description of drawings
Fig. 1 be in the specific embodiment one adsorption time to the influence curve figure of chelatropic reaction, Fig. 2 be in the specific embodiment one the pH value to the influence curve figure of chelatropic reaction.
The specific embodiment
The specific embodiment one: this embodiment is said to promote that the feed addictive of growth of animal is the chitosan copper chelate, it be with shitosan and the copper sulphate that accounts for 1/3 to 10 times of chitosan mass be raw material mix and react after be prepared from.
Said feed addictive is the chitosan copper chelate; Its preparation process may further comprise the steps successively: 0.3～0.7g shitosan is joined in the container that fills 50ml water; In container, add the copper sulphate that accounts for chitosan mass 1/3～3/4 then, abundant mixing, the pH of control solution is 5.5～6.5; Reacted 0.2～1 hour, and obtained the chitosan copper chelate.
Because chlorion can suppress the combination of metal ion, sulfate ion can promote to combine, so the present invention adopts copper sulphate and chitosan solution to react.During test, get shitosan and be 0.5g for four parts, join respectively in the glass container of capacity greater than 50ml, add water 50ml more respectively, because shitosan is water-soluble hardly, therefore, it is in water, and the shitosan of white still is sunken to the bottom of water.Then, the copper sulphate of 0.25g, 0.50g, 0.75g, 1g is joined in the above-mentioned glass container, and put into shaking table 30 minutes～1 hour, carry out abundant mixing.Can be observed through range estimation; In first container, copper sulphate and white chitosan reaction can not see white shitosan in the sediment; The substitute is blue chitosan copper chelate and be sunken to container bottom, supernatant has nattier blue copper-bath a little for clarification; In second container, copper sulphate and white chitosan reaction can not see white shitosan in the sediment, the substitute is blue chitosan copper chelate and are sunken to container bottom, and solution is not for clarifying nattier blue copper-bath of (muddiness is arranged slightly); In the 3rd container; Copper sulphate and white chitosan reaction; Can not see the shitosan of white in the sediment, the substitute is blue chitosan copper chelate and be sunken to container bottom, top solution is not for clarifying the nattier blue copper-bath of color burn of (muddiness); In the 4th container; Copper sulphate and white chitosan reaction; Can not see the shitosan of white in the sediment, the substitute is blue chitosan copper chelate and be sunken to container bottom, top solution is not for clarifying the nattier blue copper-bath of color burn of (more muddy).Get 25 milliliters of ammoniacal liquor buffer solutions that add 10 milliliters of pH=10 of above-mentioned solution respectively.When containing 0.25g copper sulphate in the above-mentioned chitosan solution; The slow liquor color constant (purpose is the content of copper ion in the test solution) of ammoniacal liquor that adds 10 milliliters of pH=10; Be light blue and under equal conditions contain the slow liquor color of ammoniacal liquor that 0.5g copper sulphate adds 10 milliliters of pH=10, color is deepened gradually after containing 0.75g copper sulphate and adding ammoniacal liquor.Infer that thus the mass ratio that shitosan and copper sulphate fully react possibly be 2: 1.Reaction solution to contain 0.25g copper sulphate is done blank solution, and using spectrophotometer is survey in 580 o'clock three kinds of solution absorbency values in addition at wavelength, is respectively 0.073; 0.288,0.628, the deducibility copper ion is excessive; And on this basis, with the increase of copper sulphate amount, solution becomes gets muddy gradually; Analysis has the part shitosan to dissociate out again, so adsorption rate also so to some extent descends.So from data analysis, the best in quality proportioning of this kind preparation method's shitosan and copper sulphate is 2: 1.
The effects the influence of adsorption time to chelatropic reaction, and trace figure is as shown in Figure 1.Can find out by Fig. 1, along with the increase of adsorption time, Cu
2+Chelation percent increases, and at preceding 30 minutes, absorption speed was very fast, and the rate of adsorption slows down subsequently.This is because along with the increase of adsorption time, on the shitosan-NH2 with-OH and Cu
2+All formed chelate, shitosan is to Cu
2+Absorption reach capacity.
PH influences the topmost factor of suction-operated, The effects the influence of pH value to chelatropic reaction, it is as shown in Figure 2 that it influences the result.More researcher thinks that pH can influence the function of the avtive spot on the shitosan.When pH is lower than 3, too much H
+Can make in the shitosan-NH
2Change into-NH
+ 3, to Cu
2+Absorption cause inhibitory action, when surpassing certain pH, Cu
2+Can form deposition, inorganic agent was lost efficacy.Therefore, along with the increase of the addition of copper sulphate, the pH of solution also decreases, and shitosan also reduces the adsorption equilibrium of copper ion, and the low adsorption equilibrium of equilibrium adsorption capacity of copper ion is tending towards desorb rather than absorption; Under nearly neutrallty condition, promptly pH5～6 o'clock can comparatively fast reach balance, and adsorbance also can reach maximum.
The specific embodiment two: this embodiment is with the specific embodiment one difference; Gained chitosan copper chelate is put into 60～90 ℃ of baking ovens dries; Obtain dry chitosan copper chelate, dry chitosan copper chelate helps storing, transports and uses.During actual the use, can use the dry chitosan copper chelate of 1～10mg, or in daily ration, add 0.1～1.0% dry chitosan copper chelate that accounts for gross mass and calculate by the per kilogram the weight of animals.
The specific embodiment three: this embodiment cooperates interpolation to use the demand that can satisfy animal protein; Again can be antibiotic, the insect antimicrobial peptide of antivirus action; Purpose is; On prophylactic basis, satisfy the production demand that makes fast growth of animal, can satisfy the demand of people again the pollution-free green animal foodstuff of safety.Said scheme does; In the specific embodiment one described additive, added insect protein; The mass ratio of chitosan copper chelate and insect protein is 1: 50～1: 500, during preparation, only need said chitosan copper chelate simply be mixed getting final product in said ratio with insect protein.Said insect protein can be the yellow meal worm antibacterial protein, also can be other insect protein.Add a certain amount of insect antimicrobial peptide in the scheme according to the invention and help preventing and treating the generation of Animal diseases, also satisfied the demand of growth of animal albumen.
The specific embodiment four: this embodiment is that with the specific embodiment three differences the mass ratio that the consumption of said chitosan copper chelate mixes with the fly maggot antibacterial protein when using is 1: 140～1: 180.During actual the use, can by the forage protein of equivalent need addition to calculate to carry out, or after using chitosan copper chelate according to the invention directly in daily ration interpolation account for the fly maggot antibacterial protein of its quality 14～18%.
The specific embodiment five: this embodiment is that with the specific embodiment three differences the mass ratio that the consumption of said chitosan copper chelate mixes with the earthworm antibacterial protein when using is: 1: 50～1: 500.During actual the use, can by the forage protein of equivalent need addition to calculate to carry out, or after using chitosan copper chelate according to the invention directly in daily ration by the amount interpolation earthworm antibacterial protein of animal 0.5g/kg body weight.
The specific embodiment six: this embodiment and the specific embodiment one difference be, it is to be that raw material carries out being prepared from after the hybrid reaction with shitosan with the copper sulphate that accounts for 1～10 times of chitosan mass.Its preparation process may further comprise the steps successively: it is in 0.1～2% the acetic acid that the 0.5g shitosan is joined 25～50ml, percent by volume, mixes and places 0.5～5h, becomes the chitosan gum liquid solution; Other gets the copper sulphate that accounts for 1～10 times of amount of chitosan mass and puts in 5～10ml water copper sulphate is disperseed, and then the chitosan gum liquid solution is poured in the container that fills copper sulphate, promptly becomes the chitosan copper chelate.
During experiment, using the shitosan of 0.5g to join 25～50ml percent by volume is in 0.1～2% acetic acid, after mixing and placing 0.5～5h, promptly becomes the chitosan gum liquid solution; Get the copper sulphate of 0.5g, 1g, 1.5g, 2g, 2.5g, 3g, 3.5g, 4g, 4.5g, 5g in addition respectively, be respectively put in the water of 5～10ml, the purpose that adds water is that copper sulphate is disperseed, and helps reaction.Afterwards the chitosan gum liquid solution is poured in the container that fills copper sulphate, finds that the shitosan in all containers all with copper ion chelatropic reaction has completely taken place.Ratio between said shitosan of this embodiment and the copper sulphate and the specific embodiment one said ratio differ greatly; This is because shitosan is dissolved in and has processed colloidal solution in the acetum; This colloidal solution has increased the surface area that shitosan contacts with copper sulphate; Therefore increase the touch opportunity of shitosan and copper ion, thereby increased the mass ratio between copper sulphate and the shitosan.
The specific embodiment seven: this embodiment is with the specific embodiment six differences; After obtaining the chitosan copper chelate,, filter or squeeze out redundant moisture then, put in 60～90 ℃ of baking ovens its taking-up; Oven dry, pulverizing are dry chitosan copper chelate.During actual the use, can use 0.1～1mg chitosan copper chelate, or in daily ration, add 0.01～0.1% the chitosan copper chelate that accounts for gross mass and calculate by the per kilogram the weight of animals.
The specific embodiment eight: this embodiment is that with the specific embodiment one, two, three, four, five, six, seven differences the viscosity number of said shitosan is 500 * 10
-3～100000 * 10
-3Pms, its preparation process is followed successively by:
A. impurity process such as decalcification: at first,, be immersed in 2～5 times of volumes, mass percent and be in 0.5～2% the hydrochloric acid solution with the fly maggot skin of 1 times of volume; The container that this mixture will be housed then places 25～50 ℃ of water-baths, behind immersion and the continuous stirring 4～6h, from water-bath, takes out this container; Naturally the cooling after, hydrochloric acid solution is poured out, use in the clear water washing container chitin to pH as neutrality after; Filter with stainless (steel) wire, be placed on then in 60～100 ℃ of drying bakers and dry;
B. take off the process of residual protein: it is in 2～6% the sodium hydroxide solution that the chitin of 1 times of volume after will drying is immersed in 2～5 times of volumes, mass percent; The container that this mixture will be housed then places 25～50 ℃ water-bath, behind immersion and the continuous stirring 4～6h, from water-bath, takes out this container; Naturally after the cooling; Sodium hydroxide solution is poured out, use in the clear water washing container chitin to pH as neutrality after, filter with stainless (steel) wire; Be placed on then in 60～100 ℃ of drying bakers and dry, can obtain the higher chitin of purity;
C. with the gained chitin join splendid attire account for 3～5 times of amounts of chitin volume, mass concentration is to carry out deacetylation in the container of 40～55% sodium hydroxide solution; Then said container is placed in 60-65 ℃ the water-bath and heats 2～6h, promptly can obtain viscosity number is 500 * 10
-3～100000 * 10
-3The shitosan of pms.
The object of the invention is to introduce a kind of chitosan copper chelate and preparation method thereof, and shitosan can be chosen the raw material of any wide material sources, and is not limited to the shitosan that from the fly maggot skin, extracts described in this embodiment.With regard to shitosan itself its adsorptivity influenced by many-side.At first be deacetylation, the chitosan molecule chain is made up of Glucosamine chain link and acetamido glucose chain link, and degree of deacetylation characterizes the percentage that amino amido glucose chain link accounts for chain link.Viscosity is high more, and amino density is also just big more on the strand.Because shitosan is with-NH to the absorption of copper ion
2For adsorption site, thus adsorbance improve with the raising of viscosity, so the present invention to recommend to use viscosity number be 500 * 10
-3～100000 * 10
-3The shitosan of pms, but this can not limit the protection domain of scheme according to the invention.Next is the time, shitosan when absorption takes place preceding 20 minutes, and the rate of adsorption is very fast, and the rate of adsorption slows down subsequently.PH through evidence chelating copper-bath itself meets requirement of experiment basically in addition, reacts also more abundant under the room temperature, does not therefore stress temperature conditions, i.e. expression reaction at room temperature in the technical scheme of the present invention.The copper sulphate that the present invention uses in experimentation is anhydrous cupric sulfate or the copper sulphate that contains five crystallizations water; But be not limited to this in actual use; That is to say that all copper sulphate can realize purpose according to the invention by said method, so all should be within protection scope of the present invention.
Be the effect that the said scheme of application of the present invention is had when being used to use below.
Divide four groups with the chicken of 7 ages in days is young, every group each 100, what each group was fed all is identical feed and trace element, and first, second and third group is fed the fish meal of adding same ratio in the feed, does not add fish meal in the 4th group.
First group is blank control group: do not add any additive relevant with copper in the feed;
Second group is control group: add anhydrous cupric sulfate in the feed, add anhydrous cupric sulfate 250～400mg in the per kilogram feed;
The 3rd group is chitosan copper chelate group, in feed, adds the chitosan copper chelate, adds chitosan copper chelate 5mg in the per kilogram feed;
The 4th group adds fly maggot antibacterial protein (peptide) group for the chitosan copper chelate; Except that in feed, adding the chitosan copper chelate identical with the 3rd group of ratio, interpolation fly maggot antibacterial protein (peptide) or the earthworm protein (peptide) identical in feed also with the ratio of fish meal in the first three groups.
(1) detection can know that the content of copper is organized high 6.7 times in the effluent of second group of pig than third and fourth to effluent.
(2) compare after feeding one month:
Control group and blank control group be average weight gain 17% relatively;
Chitosan copper chelate group and blank control group be average weight gain 20% relatively;
The chitosan copper chelate adds fly maggot antibacterial protein (peptide) or earthworm protein (peptide) group compares average weight gain 25% with blank control group.
Analysis result: chitosan copper chelate group and anhydrous cupric sulfate group be difference more to some extent; Use the chitosan copper chelate and add fly maggot antibacterial protein (peptide) group; Effect and uses the content of copper in the animal effluent of chitosan copper chelate lower more, therefore more helps environmental protection.
Claims (2)
1. preparation method that can promote the feed addictive of growth of animal; It is characterized in that said feed addictive is the chitosan copper chelate; Its preparation process may further comprise the steps successively: it is in 0.1～2% the acetic acid that the 0.5g shitosan is joined 25～50ml, percent by volume; Mixing is also placed 0.5～5h, becomes the chitosan gum liquid solution; Other gets the copper sulphate that accounts for 1～10 times of amount of chitosan mass and puts in 5～10ml water copper sulphate is disperseed, and then the chitosan gum liquid solution is poured in the container that fills copper sulphate, promptly becomes the chitosan copper chelate;
The viscosity number of said shitosan is 500 * 10
-3～100000 * 10
-3Pms, its preparation process is followed successively by:
A. impurity process such as decalcification: at first,, be immersed in 2～5 times of volumes, mass percent and be in 0.5～2% the hydrochloric acid solution with the fly maggot skin of 1 times of volume; The container that this mixture will be housed then places 25～50 ℃ of water-baths, behind immersion and the continuous stirring 4～6h, from water-bath, takes out this container; Naturally the cooling after, hydrochloric acid solution is poured out, use in the clear water washing container chitin to pH as neutrality after; Filter with stainless (steel) wire, be placed on then in 60～100 ℃ of drying bakers and dry;
B. take off the process of residual protein: it is in 2～6% the sodium hydroxide solution that the chitin of 1 times of volume after will drying is immersed in 2～5 times of volumes, mass percent; The container that this mixture will be housed then places 25～50 ℃ water-bath, behind immersion and the continuous stirring 4～6h, from water-bath, takes out this container; Naturally after the cooling; Sodium hydroxide solution is poured out, use in the clear water washing container chitin to pH as neutrality after, filter with stainless (steel) wire; Be placed on then in 60～100 ℃ of drying bakers and dry, can obtain the higher chitin of purity;
C. with the gained chitin join splendid attire account for 3～5 times of amounts of chitin volume, mass concentration is to carry out deacetylation in the container of 40～55% sodium hydroxide solution; Then said container is placed in 60-65 ℃ the water-bath and heats 2～6h, promptly can obtain viscosity number is 500 * 10
-3～100000 * 10
-3The shitosan of pms.
2. the preparation method who promotes the feed addictive of growth of animal according to claim 1; It is characterized in that taking out gained chitosan copper chelate, filter or squeeze out redundant moisture, put in 60～90 ℃ of baking ovens; Oven dry, pulverizing are dry chitosan copper chelate.
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| CN103918935B (en) * | 2014-04-25 | 2016-06-08 | 隋丽梅 | A kind of pet food additives |
| CN113563492B (en) * | 2021-08-16 | 2022-12-02 | 中北大学 | Molecular type low-ester copper pectin and preparation method thereof |
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| Title |
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| 刘秉钺等.壳聚糖-铜络合物在抗菌纸上的应用.《中华纸业》.2004,第25卷(第4期),第1.1节. * |
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