CN107518175A - A kind of feed addictive coating aliphatic acid copper and preparation method thereof and a kind of feed - Google Patents
A kind of feed addictive coating aliphatic acid copper and preparation method thereof and a kind of feed Download PDFInfo
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- CN107518175A CN107518175A CN201610498210.7A CN201610498210A CN107518175A CN 107518175 A CN107518175 A CN 107518175A CN 201610498210 A CN201610498210 A CN 201610498210A CN 107518175 A CN107518175 A CN 107518175A
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Abstract
The invention provides a kind of feed addictive to be coated aliphatic acid copper, including core and the coating for being coated on core surfaces, and the core includes aliphatic acid copper, and the coating includes water-soluble coating and the enteric coating for being coated on the core surfaces successively.Coating aliphatic acid copper provided by the invention, aliphatic acid copper and the oxygen in air are separated by coating material, avoid the oxidation of aliphatic acid copper, while feed addictive provided by the invention coating aliphatic acid copper dosage is few, and high-copper can be substituted.
Description
Technical field
The invention belongs to field of feed additive technology, and in particular to a kind of feed addictive coating aliphatic acid copper and its system
Preparation Method and a kind of feed.
Background technology
Report that high-copper is added in daily ration over more than 70 years of growth promoting function to pig first from nineteen fifty-five Barber, largely
Scientific experiment card adds 200-250ppm (with Cu using cupric sulfate pentahydrate or copper sulfate monohydrate in pig feed2+Meter) can significantly it carry
High daily gain in pigs simultaneously improves the price of deed, and this effect is highly stable, reliable, is that antibiotic is irreplaceable.Added in daily ration
During 250ppm, 0-60kg suckling piglet daily gain and feed conversion rate can improve 10% or so, even as high as 27.2%;Addition
During 200ppm, 0-60kg suckling piglet daily gain and feed conversion rate, which improve, may only have 5-6%, when adding below 150ppm,
0-60kg suckling piglet daily gain and feed conversion rate, which improves, may only have 2-3%;For 60-100kg pig, 150ppm high-copper
Also there is good growth-promoting effect.In general, addition uses cupric sulfate pentahydrate in daily ration, grows up in recent years
Basic copper chloride, when reaching identical effect, copper dosage can reduce by 20%, i.e. 0-60kg piglets apply basic copper chloride
190ppm is (with Cu2+Meter) when can obtain 250ppm (with Cu2+Meter) CuSO45H2Effect the same O.In any case, the whole world is produced per year
1000000000 tons of feeds, hundred million tons of pig feeds of 2-3 are there are about, 45,000,000 tons of copper are there are about over 70 years and are consumed by pig feed, still, due to suckling piglet
Nutrition only needs 5-8ppm copper, and 1,000,000 tons or so are about only needed altogether over 70 years, that is to say, that 98% copper, over 70 years altogether about
44000000 tons in line to cause serious pollution into environment.
First, Cu in the pig liver produced using high-copper grain2+12-48mg/kg (in terms of dry), reaches as high as 120mg/
Kg, this to eating pork liver Chinese harm it is extremely serious.
As the Cu in soil2+When being accumulated to 100ppm, edaphon can be dead because of albuminous degeneration, soil hardening, fertility
Decline, crop failure.If herbage copper content is exceeded, easily cattle and sheep are caused to be poisoned, ox maximal tolerance dose 100ppm, sheep is
25ppm.For pig farm, because high-copper excrement makes microorganism reduction in manure pit and increase stool odor.
The water source of Cu-W ore deposit, because copper is very big to aquatic toxicity, when reaching concentration 0.5ppm, 35-100% original
Raw fresh plant is dead, thus water body self-purification ability declines, water quality deterioration, can cause fishes and shrimps dead when serious.High-copper cultivation is tight
The ecosystem is destroyed again!Japanese Scientists point out to use 80ppm copper in long-term daily ration, and contaminated soil will no longer after 23 years
With cultivability.
Although copper is the indispensable nutrient of the mankind, requirement very little, 0-6 month babies, 0.4- is needed daily
6mg, 6-10 year children, 0.7-2mg is needed daily, adult only needs 2mg daily, and almost all of food and drinking water source is all contained
Copper, the situation that copper lacks seldom occur.
But if intake copper is excessive, the autologous protection mechanism of body is that the copper of excess is being absorbed into group by vomitting
Excreted before knitting, this toxic reaction is referred to as " acute high doses of copper poisoning ";Long-term non-Poisoning intake copper content is too high
Food can cause chronic copper poisoning, have a strong impact on health, such as cause hemolytic anemia, liver renal failure, shock, stupor.Non-
Often rare suffers from the heredity diseases such as Wilson's disease (can not be from internal discharge copper) OR gate creutzfeldt jakob disease (can not absorb copper in vivo)
The crowd of disease, entail dangers to life.
Although obvious symptom will not occur for chronicity accumulation property copper slow poisoning, it can progressively cause human immunity energy
Power declines, and the inducement of many chronic diseases (such as hypertension, diabetes, cancer, Parkinson's disease, rheumatism),
At least, people's state of an illness with these diseases can be constantly aggravated, accelerates the development process of these chronic diseases.Therefore, forbid feeding
High-copper is very urgent.
The content of the invention
In view of this, the technical problem to be solved in the present invention be to provide a kind of feed addictive coating aliphatic acid copper and its
Preparation method and a kind of feed, feed addictive coating aliphatic acid copper dosage provided by the invention is few, and can substitute height
Copper.
The invention provides a kind of feed addictive to be coated aliphatic acid copper, including core and is coated on the core surfaces
Coating, the core includes aliphatic acid copper, the coating include the water-soluble coating for being coated on the core surfaces successively and
Enteric coating.
Preferably, the aliphatic acid copper is selected from copper formate, copper acetate, propionic acid copper, copper butyrate, valeric acid copper, caproic acid copper, enanthic acid
Copper, cupric octoate, n-nonanoic acid copper, capric acid copper, undecanoic acid copper, lauric acid/dodecanoic acid copper, tridecanoic acid copper, tetradecylic acid copper, pentadecanoic acid copper, hexadecylic acid
Copper, heptadecanoic acid copper, stearic acid copper, nonadecanoic acid copper, 20 sour copper, heneicosoic acid copper, behenic acid copper, tricosanic acid copper, 20
Tetracid copper, neocerotic acid copper, cerinic acid copper, carboceric acid copper, octacosanoic acid copper, motanic acid copper, triacontanoic acid copper, linoleic acid
Copper, copper oleate, leukotrienes copper, CLA copper, arachidonic acid copper, eicosapentaenoic acid copper, docosahexaenoic acid copper,
Erucic acid copper, tangerine acid copper, rape acid copper, 16 monoenoic acid copper, positive heptadecenoic acid copper, 18 dienoic acid copper, 18 single diluted acid copper,
18 diluted acid copper, palmitoleic acid copper, behenic acid copper, eicosatetraenoic acid copper, clupanodonic acid copper, arachidic acid
One or more in the eight carbon-trienic acid copper of copper, cis- 6,9,12- bis- ten eight carbon-trienic acid copper and cis- 9,12,15- 20.
Preferably, it is fine to be selected from hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl for the material of the water-soluble coating
Tie up element, PVP, polyvinyl alcohol, pulullan polysaccharide, chitosan, polyethylene glycol 200, polyethylene glycol 400, poly- second two
Alcohol 600, PVOH 800, PVOH 1000, polyethylene glycol 2000, Macrogol 3000, Macrogol 4000 and polyethylene glycol
One or more in 5000;
The material of the enteric coating is selected from polyacrylic acid resin, HPMCP, acetic acid
Hydroxypropyl methyl cellulose, succinate ethyl butyrate, Glyceryl tributyrate, shellac, PVAP, fiber
Element and its derivative, cellulose acetate phthalate, 1,2,4- benzenetricarboxylic acid cellulose acetates, 1,2,4- benzenetricarboxylic acid hydroxypropyls
Ylmethyl cellulose, acetate succinate cellulose, acetate succinate hydroxypropyl cellulose, methacrylate, methacrylic acid,
Acrylate, butyl acrylate, acroleic acid resin, ethyl cellulose, triacetin, propionate, poly- vinyl propionate
Ester, polyvinyl acetate, poly- vinyl butyrate, carboxylic acid vinyl ester polymer, vinyl acrylate, vinylpyrrolidone and carboxylic acid
In the polymer of vinyl acetate, vinyl ester polymer, vinyl methacrylate and its polymer and o- benzoic acid ethyl ester
It is one or more of.
Preferably, the mass ratio of the coating material and the core is (0.1~20):100.
Present invention also offers a kind of preparation method of feed addictive coating aliphatic acid copper, comprise the following steps:
Coating material is coated in granular core surfaces, obtains feed addictive coating aliphatic acid copper, the core bag
Include aliphatic acid copper.
Preferably, comprise the following steps:
A dried after) white carbon is mixed with the maltodextrin aqueous solution, obtain the white carbon hard particles containing maltodextrin;
B) by the white carbon hard particles adsorptive liquid aliphatic acid copper containing maltodextrin, core is obtained;
C water-soluble coating material solution) is sprayed in the core surfaces, drying obtains the fat of water-soluble coating material coating
Fat acid copper;
D) in the aliphatic acid copper surface spraying or infiltration enteric-coating material solution of the water-soluble coating material coating, do
System, obtain feed addictive coating aliphatic acid copper.
Preferably, comprise the following steps:
A) water-soluble coating material, suitable quantity of water, maltodextrin and solid fatty acid copper are mixed, obtains mixture;
By the mixture successively through granulation, bake, throw circle after, obtain core;
B) in high-pressure agitated vessels, removing air is vacuumized after putting into enteric-coating material, is held to the high-pressure stirring
Liquid gas is imported in device, is stirred, obtains enteric coating liquefaction gas solution;
C) water-soluble coating material solution is sprayed in the core surfaces, drying obtains the fat of water-soluble coating material coating
Fat acid copper;
D) aliphatic acid copper by the water-soluble coating material coating is put into vacuum rake dryer, and sky is removed in vacuum
Gas, the enteric coating liquefaction gas solution is imported, is stirred, feed addictive coating fat is obtained after liquid gas volatilization
Sour copper;
The step a) and step b) limits without order.
Preferably, the aliphatic acid copper is prepared as follows:
Grease is mixed with alkali metal hydroxide after carrying out saponification, then mix with copper sulfate solution, carried out instead
Should, obtain aliphatic acid copper.
Preferably, the grease be selected from perilla herb oil, sunflower oil, olive oil, corn oil, three-coloured amaranth oil, soya-bean oil, peanut oil,
One or more in sesame oil, rapeseed oil, cotton benevolence oil, palm oil, lard, butter, chicken fat, coconut oil, fish oil and rice bran oil.
Present invention also offers a kind of feed, including above-mentioned feed addictive coating aliphatic acid copper or above-mentioned preparation method system
Standby feed addictive coating aliphatic acid copper, with Cu2+Meter, addition concentration of the coating aliphatic acid copper in the feed are
0.1~12500mg/kg.
Preferably, the feed be used for feeding pig, turkey, chicken, duck, goose, black-bone chicken, quail, pigeon, ox, horse, sheep, dog,
Ermine, deer, cat, donkey, rabbit, fish, shrimp, crab, shellfish, tortoise, soft-shelled turtle, snake or yellow eel;
The feed is mixed feed, mixed fodder, concentrated feed, mineral trace element premixed feed, vitamin
Premixed feed, compound premixed feed, expanded pellet diet, substitute breast milk or customized feed.
Compared with prior art, the invention provides a kind of feed addictive to be coated aliphatic acid copper, including core and bag
The coating of core surfaces is overlying on, the core includes aliphatic acid copper, and the coating includes being coated on the core surfaces successively
Water solubility coating and enteric coating.Coating aliphatic acid copper provided by the invention, by coating material by aliphatic acid copper and air
Oxygen separate, avoid the oxidation of aliphatic acid copper, while feed addictive provided by the invention coating aliphatic acid copper dosage is few,
And high-copper can be substituted.
Embodiment
The invention provides a kind of feed addictive to be coated aliphatic acid copper, including core and is coated on the core surfaces
Coating, the core includes aliphatic acid copper, the coating include the water-soluble coating for being coated on the core surfaces successively and
Enteric coating.
Feed addictive provided by the invention includes core, wherein, the core includes aliphatic acid copper.In the present invention,
The aliphatic acid copper is selected from copper formate, copper acetate, propionic acid copper, copper butyrate, valeric acid copper, caproic acid copper, enanthic acid copper, cupric octoate, n-nonanoic acid
Copper, capric acid copper, undecanoic acid copper, lauric acid/dodecanoic acid copper, tridecanoic acid copper, tetradecylic acid copper, pentadecanoic acid copper, hexadecylic acid copper, heptadecanoic acid copper, 18
Sour copper, nonadecanoic acid copper, 20 sour copper, heneicosoic acid copper, behenic acid copper, tricosanic acid copper, tetracosanoic acid copper, neocerotic acid
Copper, cerinic acid copper, carboceric acid copper, octacosanoic acid copper, motanic acid copper, triacontanoic acid copper, copper linoleate, copper oleate, flax
Sour copper, CLA copper, arachidonic acid copper, eicosapentaenoic acid copper, docosahexaenoic acid copper, erucic acid copper, tangerine acid copper,
Rape acid copper, 16 monoenoic acid copper, positive heptadecenoic acid copper, 18 dienoic acid copper, 18 single diluted acid copper, 18 diluted acid copper,
Palmitoleic acid copper, behenic acid copper, eicosatetraenoic acid copper, clupanodonic acid copper, arachidic acid copper, cis- 6,9,12- bis-
It is one or more in 18 carbon-trienic acid copper and cis- 9,12,15- bis- ten eight carbon-trienic acid copper.Preferably capric acid copper, lauric acid/dodecanoic acid
One or more in copper, stearic acid copper and copper oleate.
The present invention is not specifically limited to the source of the aliphatic acid copper, can be general commercially available, can also voluntarily make
It is standby.In the present invention, it is preferred to the preparation of aliphatic acid copper is carried out as follows:
Grease is mixed with alkali metal hydroxide after carrying out saponification, then mix with copper sulfate solution, carried out instead
Should, obtain aliphatic acid copper.
The present invention mixes with alkali metal hydroxide first by grease and carries out saponification, wherein, the aliphatic acid is preferred
For perilla herb oil, sunflower oil, olive oil, corn oil, three-coloured amaranth oil, soya-bean oil, peanut oil, sesame oil, rapeseed oil, cotton benevolence oil, palm
One or more in oil, lard, butter, chicken fat, coconut oil, fish oil and rice bran oil.
Wherein, the aliphatic acid composition of soya-bean oil:About 51% linoleic acid, 29% oleic acid, the sour and a small amount of C14 of 7% linseed
~C22 saturated fatty acids form
Peanut oil (peanut oil) is yellowish transparent, and color and luster is limpid, and fragrant, flavour is tasty, is that one kind is easier
The edible oil of digestion.Peanut oil (wherein containing oleic acid 41.2%, linoleic acid 37.6%) containing unrighted acid more than 80%.In addition
Also contain palmitic acid, the saturated fatty acid such as stearic acid and arachidic acid 19.9%.
For the composition of aliphatic acid because of the influence of weather conditions, the sunflower oil that cold district produces contains oleic acid in sunflower oil
15% or so, linoleic acid 70% or so;The sunflower oil of warm area production contains oleic acid 65% or so, linoleic acid 20% or so.
The human consumption of sunflower oil leads 96.5%.
The aliphatic acid composition of sesame oil:Palmitic acid, stearic acid, oleic acid, linoleic acid, eicosanoic acid, leukotrienes are different fragrant
6 kinds of aliphatic acid relative scales do not have difference in the sesame oil of type, are respectively:Palmitic acid 8.39%~9.37%, stearic acid
4.69%~5.55%, oleic acid 35.74%~38.28%, linoleic acid 45.99%~48.99%, eicosanoic acid 0.48%~
0.79%, leukotrienes 0.47%~0.56%.But content of fatty acid gap is obvious, light odor type sesame oil aliphatic acid definitely contains
Highest is measured, next to that Luzhou-flavor, not odor type.Wherein palmitic acid, oleic acid and linoleic acid difference are maximum.
The primary chemical composition of olive oil is fatty acid glycerine fat and non-glycerol fat composition.Glyceride is mainly by saturated fat
Sour (accounting for 12.1%~18.3%) and unrighted acid (accounting for 81.1%~87.4%), linoleic acid (4.6%~13.2%) are sub-
Sesame oil acid (0.28%~1.7%) and positive heptadecenoic acid (0.1%~0.3%).Unsaponifiable matter in the non-glycerol fat of olive oil
Very low (0.3%~1.4%).
0.4-1.0% containing arachidic acid in rapeseed oil, oleic acid 14-19%, linoleic acid 12-24%, erucic acid 31-55%, flax
Sour 1-10%.
In cottonseed oil aliphatic acid composition be 45% linoleic acid, 3% oleic acid, 20% palmitic acid, 21% myristic acid and a small amount of
Stearic acid, arachidic acid composition.
Aliphatic acid composition is 43% palmitic acid in palm oil, 41% oleic acid, 10% linseed oleic acid, 3% myristic acid,
3% stearic acid.40~47 DEG C of fusing point, iodine number 32~35, saponification number 190~202.
The aliphatic acid composition of corn oil is general more stable, and linoleic acid content is 55%~60%, and oleic acid content 25%~
30%, palmitoleic acid 10%~12%, stearic acid 2%~3%, linolenic acid content is few (less than 2%), other as myristic acid,
The content of fatty acid such as palmitoleic acid, arachidic acid are atomic or are not present.
The aliphatic acid composition of rice bran oil:Oleic acid 38-52%, linoleic acid 29-42%, the sour 0.5-1.8% of fiber crops, palmitic acid 12-
18%th, stearic acid 1.0-3.0%, phytosterol 3.0-4.5%.
The aliphatic acid composition (%) of lard:Myristic acid 3, palmitic acid 24, stearic acid 18, oleic acid 42, linoleic acid 9, hexadecylene
Acid 3.Lard is white or pale yellow waxy solid, not soluble in water, is dissolved in chloroform, carbon disulfide.The aliphatic acid contained in lard
Species have C16:0、C18:0、C14:0、C16:1、C18:2、C18:3、C22:0 (" C " expression carbon, Cm:" m " in n represents carbon
Atom number, " n " represent aliphatic acid double bond number).
Unsaturated fatty acid content is 93.707%, wherein linolenic acid content highest in perilla herb oil, is 60.752%, sub- oil
Acid and oleic acid content are respectively 15.761% and 17.194%;The total content of vitamin E is 500.9mg/kg in perilla herb oil;Purple perilla
Oily proportion is 0.9288, refraction index 1.4817, acid value 2.9mg/g, iodine value 1980g/kg, saponification number 190.7mg/
G, unsaponifiable matter 0.6%, moisture and volatile matter content 0.07%, peroxide value 3.7mmol/kg.
The aliphatic acid composition of evening primrose oil:Containing a variety of aliphatic acid, mainly including linoleic acid (linoleicacid), γ-Asia
Numb acid (γ-linolenic acid), oleic acid (oleic acid), palmitic acid (palmitic acid), stearic acid (stearic
Acid), cis- 6,9,12- bis- ten eight carbon-trienic acids (cis-6,9,12-octadecatrienoic acid), cis- 9,12,15-
28 carbon-trienic acid (cis-9,12,15-octadecatrienoic acid).
Tallow acid composition is hexadecylic acid (C16:0) 27-29%;Stearic acid (C18:0) 24-29%;Tetradecylic acid (C14:
0) 2.0-2.5%, oleic acid 43-45%, linoleic acid 2-5%.
Chicken fat contains laurate, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, palmitoleic acid (C16:1)、
Oleic acid (C18:1), eicosenoic acid (C20:1), linoleic acid (C18:2), leukotrienes (C18:3).
Coconut oil contains octanoic acid, capric acid, laurate, myristic acid, palmitic acid, stearic acid, oleic acid.
Fish oil contains:Aliphatic acid C14:0、C14:1、C15:0、C16:1、C18:3、C18:2、C18:1、C18:0、C20:5、
C20:4、C20:1、C20:0、C22:6、C22:5.(" C " represents carbon, Cm:" m " in n represents carbon atom number, and " n " represents fat
Fat acid double bond number)
The alkali metal hydroxide is preferably sodium hydroxide or potassium hydroxide.
The present invention is not specifically limited to the specific method of the saponification, and well known to a person skilled in the art saponification
Reaction.
After saponification terminates, reaction product is mixed with copper sulfate solution, specifically:
Reaction product is poured into copper-bath and reacted, obtains aliphatic acid copper.
Feed addictive provided by the invention is also coated on the coating of the core surfaces, and the coating is included successively
It is coated on water-soluble coating and the enteric coating of the core surfaces.In the present invention, the enteric-coating material is preferably poly-
Acrylic resin, HPMCP, hydroxypropylmethylcellulose acetate methylcellulose, succinate butyric acid second
Ester, Glyceryl tributyrate, chitosan, shellac, PVAP, water-insoluble cellulose and its derivative, neighbour
Cellulose acetate phthalate, 1,2,4- benzenetricarboxylic acid cellulose acetates, 1,2,4- benzenetricarboxylic acid hydroxypropyl methyl celluloses, amber
Amber acid cellulose acetate, acetate succinate hydroxypropyl cellulose, methacrylate, methacrylic acid, acrylate, acrylic acid
Butyl ester, acrylic resin, ethyl cellulose, triacetin, propionate, polyvinyl proprionate, polyvinyl acetate,
Poly- vinyl butyrate, carboxylic acid vinyl ester polymer, vinyl acrylate, vinylpyrrolidone and vinyl carboxylates polymer,
Vinyl ester polymer, vinyl methacrylate and its polymer and o- benzoic acid ethyl ester, hydrogenated fat, stearic acid list
It is sweet fat, laurate monoglyceride, stearic acid, rice bran wax, higher aliphatic acid polyol ester, glycerol stearate adipate polyester, advanced
One or more in fatty polyol polyester and polyglycerol fatty acid ester.Wherein, the enteric coating aliphatic acid copper is not
Water is dissolved in, the oxygen that can completely cut off in air, the enteric coating hardness is high, and Mohs' hardness is preferably 2~8, more preferably 3~
6, also, 80-90 DEG C of high temperature extrusion of the enteric coating granulator of resistance to feed granules.
The water-soluble coating material is preferably hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, poly-
Ethylene ratio pyrrolidone, polyvinyl alcohol, pulullan polysaccharide, polyethylene glycol 200, polyethylene glycol 400, Macrogol 600, PVOH
800th, PVOH 1000, polyethylene glycol 2000, Macrogol 3000, Macrogol 4000, one kind in polyethylene glycol 5000 or
It is a variety of.
In the present invention, the mass ratio of the coating material and the core is (0.1~20):100, be preferably (1~
10):100.
Present invention also offers a kind of preparation method of feed addictive coating aliphatic acid copper, comprise the following steps:
Coating material is coated in granular core surfaces, obtains feed addictive coating aliphatic acid copper, the core bag
Include aliphatic acid copper.
Specifically, the method for preparing feed addictive coating aliphatic acid copper comprises the following steps:
A dried after) white carbon is mixed with the maltodextrin aqueous solution, obtain the white carbon hard particles containing maltodextrin;
B) by the white carbon hard particles adsorptive liquid aliphatic acid copper containing maltodextrin, core is obtained;
C water-soluble coating material solution) is sprayed in the core surfaces, drying obtains the fat of water-soluble coating material coating
Fat acid copper;
D) in the aliphatic acid copper surface spraying or infiltration enteric-coating material solution of the water-soluble coating material coating, do
System, obtain feed addictive coating aliphatic acid copper.
The present invention is dried after 40-80 mesh particle white carbons are mixed with the maltodextrin aqueous solution first, obtains pasting containing malt
The carbon black hard particles of essence.
Wherein, maltodextrin is preferably 3wt%~10wt% relative to the accounting of white carbon..
Then, by the white carbon hard particles adsorptive liquid aliphatic acid copper containing maltodextrin, core is obtained.
Specially:Under the conditions of certain temperature, by the white carbon hard particles absorbing fats acid copper containing maltodextrin,
Obtain loading the silica particles of aliphatic acid copper, i.e. core.Wherein, the temperature conditionss are 50-90 DEG C.
After obtaining core, water-soluble coating material solution is sprayed in the core surfaces, drying obtains water-soluble coating material
Expect the aliphatic acid copper of coating.
Wherein, the material of the water-soluble coating is selected from hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl fiber
Element, PVP, polyvinyl alcohol, pulullan polysaccharide, chitosan, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol
600th, PVOH 800, PVOH 1000, polyethylene glycol 2000, Macrogol 3000, Macrogol 4000 and polyethylene glycol 5000
In one or more.
Then, it is molten in the aliphatic acid copper surface spraying or infiltration enteric-coating material of the water-soluble coating material coating
Liquid, it is drying, obtain feed addictive coating aliphatic acid copper.
The present invention is not specifically limited to the method for the spraying and infiltration, and well known to a person skilled in the art method to be
Can.
The enteric-coating material solution is preferably the ethanol solution of the enteric-coating material containing 3wt%~20wt%.
Wherein, the enteric-coating material is selected from polyacrylic acid resin, HPMCP, vinegar
Sour hydroxypropyl methyl cellulose, succinate ethyl butyrate, Glyceryl tributyrate, shellac, PVAP, fibre
Dimension element and its derivative, cellulose acetate phthalate, 1,2,4- benzenetricarboxylic acid cellulose acetates, 1,2,4- benzenetricarboxylic acid hydroxyls
Propyl methocel, acetate succinate cellulose, acetate succinate hydroxypropyl cellulose, methacrylate, metering system
Acid, acrylate, butyl acrylate, acroleic acid resin, ethyl cellulose, triacetin, propionate, poly- propionic acid second
Alkene ester, polyvinyl acetate, poly- vinyl butyrate, carboxylic acid vinyl ester polymer, vinyl acrylate, vinylpyrrolidone and carboxylic
Polymer, vinyl ester polymer, vinyl methacrylate and its polymer and o- benzoic acid ethyl ester of vinyl acetate
Middle one or more.
In above-mentioned preparation method, the mass ratio of the coating material and the core is (0.1~20):100, be preferably
(1~10):100.
In the present invention, it is described prepare feed addictive coating aliphatic acid copper method can also be:
A) water-soluble coating material, suitable quantity of water, maltodextrin and solid fatty acid copper are mixed, obtains mixture;
By the mixture successively through granulation, bake, throw circle after, obtain core;
B) in high-pressure agitated vessels, removing air is vacuumized after putting into enteric-coating material, is held to the high-pressure stirring
Liquid gas is imported in device, is stirred, obtains enteric coating liquefaction solution;
C) water-soluble coating material solution is sprayed in the core surfaces, drying obtains the fat of water-soluble coating material coating
Fat acid copper;
D) aliphatic acid copper by the water-soluble coating material coating is put into vacuum rake dryer, and sky is removed in vacuum
Gas, the enteric coating liquefaction gas solution is imported, is stirred, feed addictive coating fat is obtained after liquid gas volatilization
Sour copper;
The step a) and step b) limits without order.
In the present invention, the core is prepared as follows:
The aqueous solution, maltodextrin and aliphatic acid copper of water-soluble coating material are mixed, obtain mixture.
Specifically, first fully dissolving water-soluble coating material with water, the aqueous solution for obtaining water-soluble coating material is standby;
Fully stirred evenly with aliphatic acid copper with maltodextrin again.
Wherein, the mass ratio of the maltodextrin, water-soluble coating material, water and aliphatic acid copper is preferably:(5~50):
(0.001~10):(1~10):100, more preferably (10~40):(0.01~5):(2~8):100.
Wherein, the water-soluble coating material be selected from sodium carboxymethylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose,
Hydroxypropyl methyl cellulose, polyethylene glycol, polyvinyl alcohol, polypyrrole alkanone, chitosan, pulullan polysaccharide, polyethylene glycol 200,
Polyethylene glycol 400, Macrogol 600, PVOH 800, PVOH 1000, polyethylene glycol 2000, Macrogol 3000, poly- second two
One or more in alcohol 4000 and polyethylene glycol 5000,
After obtaining mixture, by the mixture successively through granulation, bake, throw circle after, obtain core;
The present invention is not specifically limited to the method for being granulated baking and throwing circle, and well known to a person skilled in the art side
Method.The obtained core is preferably sized to 60~100 mesh.
Then, the aqueous solution of water-soluble coating material is sprayed in the core surfaces, drying, obtains water-soluble coating material
The aliphatic acid copper of coating;
Wherein, the water-soluble coating material be selected from sodium carboxymethylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose,
Hydroxypropyl methyl cellulose, polyethylene glycol, polyvinyl alcohol, polypyrrole alkanone, pulullan polysaccharide, chitosan, polyethylene glycol 200,
Polyethylene glycol 400, Macrogol 600, PVOH 800, PVOH 1000, polyethylene glycol 2000, Macrogol 3000, poly- second two
One or more in alcohol 4000 and polyethylene glycol 5000.
In the present invention, the enteric coating liquefaction gas solution is prepared as follows:
In high-pressure agitated vessels, removing air is vacuumized after putting into enteric-coating material, to the high-pressure agitated vessels
Middle importing liquid gas, stirring, obtains enteric coating solution;
Wherein, the enteric-coating material be preferably polyacrylic resin, HPMCP,
Hydroxypropylmethylcellulose acetate methylcellulose, succinate ethyl butyrate, Glyceryl tributyrate, chitosan, shellac, polyvinyl alcohol acetic acid benzene two
Formic acid esters, water-insoluble cellulose and its derivative, cellulose acetate phthalate, 1,2,4- benzenetricarboxylic acid acetate fibers
Element, 1,2,4- benzenetricarboxylic acid hydroxypropyl methyl celluloses, acetate succinate cellulose, acetate succinate hydroxypropyl cellulose, first
Base acrylate, methacrylic acid, acrylate, butyl acrylate, acrylic resin, ethyl cellulose, triacetin,
Propionate, polyvinyl proprionate, polyvinyl acetate, poly- vinyl butyrate, carboxylic acid vinyl ester polymer, vinyl
Ester, the polymer of vinylpyrrolidone and vinyl carboxylates, vinyl ester polymer, vinyl methacrylate and its poly-
Compound and o- benzoic acid ethyl ester, hydrogenated fat, stearic acid monoglyceride, laurate monoglyceride, stearic acid, rice bran wax, higher aliphatic
One in acid polyol ester, glycerol stearate adipate polyester, higher fatty acids polyol polyester and polyglycerol fatty acid ester
Kind is a variety of.
The liquid gas is selected from liquefied petroleum gas, normal butane, high-purity isobutane, propane, dimethyl ether, 1,1,1,2- tetra-
Fluoroethane, sulfur hexafluoride, monochloro methane or carbon dioxide.
The present invention is not specifically limited to the preparation order of enteric coating liquefaction gas solution and core.
Then, the aliphatic acid copper by the water-soluble coating material coating is put into vacuum rake dryer, and vacuum is removed
Air is removed, the enteric coating liquefaction gas solution is imported, is stirred, obtains being coated aliphatic acid copper after liquid gas volatilization;
Specifically, the aliphatic acid copper of water-soluble coating material coating obtained above is put into high voltage bearing vacuum rake type
In drying machine, air is removed in vacuum, imports enteric coating solution made of liquid gas, after stirring 10-30 minutes, side stirring is beaten
Valve opening door, allow liquid gas to enter compressor, then become liquid gas and recycled into high-pressure bottle, be to rake type drier
During negative pressure, compressor valve is led in closing, then opens rake type drier exhaust-valve, releases product, obtains feed addictive coating
Aliphatic acid copper.
Wherein, the mass ratio of the coating material and the core is (0.1~20):100, be preferably (1~10):100.
In the present invention, the aliphatic acid copper used in above-mentioned preparation method can be general commercially available, can also voluntarily prepare.
In the present invention, the preparation of aliphatic acid copper is preferably carried out as follows:
Grease is mixed with alkali metal hydroxide after carrying out saponification, then mix with copper sulfate solution, carried out instead
Should, obtain aliphatic acid copper.
The present invention mixes with alkali metal hydroxide first by grease and carries out saponification, wherein, the aliphatic acid is preferred
For perilla herb oil, sunflower oil, olive oil, corn oil, three-coloured amaranth oil, soya-bean oil, peanut oil, sesame oil, rapeseed oil, cotton benevolence oil, palm
One or more in oil, lard, butter, chicken fat, coconut oil, fish oil and rice bran oil.The alkali metal hydroxide is preferably
Sodium hydroxide or potassium hydroxide.
The present invention is not specifically limited to the specific method of the saponification, and well known to a person skilled in the art saponification
Reaction.
After saponification terminates, reaction product is mixed with copper sulfate solution, specifically:
Reaction product is poured into copper-bath and reacted, obtains aliphatic acid copper.
Present invention also offers a kind of feed, wherein, including above-mentioned feed addictive coating aliphatic acid copper or above-mentioned preparation
Feed addictive coating aliphatic acid copper prepared by method, with Cu2+Meter, addition of the coating aliphatic acid copper in the feed are dense
Spend for 0.1~12500mg/kg, preferably 3~50mg/kg.
In the present invention, the feed be used for feeding pig, turkey, chicken, duck, goose, black-bone chicken, quail, pigeon, ox, horse, sheep,
Dog, ermine, deer, cat, donkey, rabbit, fish, shrimp, crab, shellfish, tortoise, soft-shelled turtle, snake or yellow eel;
The feed is mixed feed, mixed fodder, concentrated feed, mineral trace element premixed feed, vitamin
Premixed feed, compound premixed feed, expanded pellet diet, substitute breast milk or customized feed.
Coating aliphatic acid copper provided by the invention, by two-layered coating material by the oxygen in aliphatic acid copper and air every
Open, avoid the oxidation of aliphatic acid copper, while feed addictive provided by the invention coating aliphatic acid copper dosage is few, and can be with
Substitute high-copper.
For a further understanding of the present invention, aliphatic acid is coated to feed addictive provided by the invention with reference to embodiment
Copper and preparation method thereof and feed are illustrated, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
In N2Under protection, by 1000kg palm oils, under stirring and heating, 10% NaOH solution 1330kg is continuously added
To its space saponification, when the water surface is there is no during the grease of floating, 6.8~7.2, reaction solution is transparent molten for now pH value control
After liquid, it is 1173kg to add 35.5% cupric sulfate pentahydrate solution, obtains upper strata water-insoluble aliphatic acid copper, separation, discards glycerine
And Na2SO4The aqueous solution, obtain palm oil resin acid copper low melting point solid 1061kg and (contain Cu2+10%).
Embodiment 2
In N2Under protection, by 1000kg lards, under stirring and heating, 10% 1330kg pairs of NaOH solution is continuously added
Its space saponification, when the water surface is there is no during the grease of floating, now pH value control is 6.8~7.2, the transparent solution of reaction solution
Afterwards, add 35.5% cupric sulfate pentahydrate solution be 1173kg, obtain upper strata water-insoluble aliphatic acid copper, separation, discard glycerine with
Na2SO4The aqueous solution, obtain lard resin acid copper low melting point solid 1062kg and (contain Cu2+10%).
Embodiment 3
In N2Under protection, by 1000kg palm oils, lard, under stirring and heating, 10% NaOH solution is continuously added
1330kg is to its space saponification, and when the water surface is there is no during the grease of floating, now pH value control is in 6.8~7.2, reaction solution
After clear solution, it is 1173kg to add 35.5% cupric sulfate pentahydrate solution, obtains upper strata water-insoluble aliphatic acid copper, separation, abandons
Remove glycerine and Na2SO4The aqueous solution, obtain fatty acid copper low melting point solid 1063kg and (contain Cu2+10%).
Embodiment 4
In N2Under protection, by 1000kg coconut oil, under stirring and heating, 10% NaOH solution 1130kg is continuously added
To its space saponification, when the water surface is there is no during the grease of floating, 6.8~7.2, reaction solution is transparent molten for now pH value control
After liquid, it is 1173kg to add 35.5% cupric sulfate pentahydrate solution, obtains upper strata water-insoluble aliphatic acid copper, separation, discards glycerine
And Na2SO4The aqueous solution, obtain coconut fatty acid copper low melting point solid 1064kg and (contain Cu2+10%).
Embodiment 5
In N2Under protection, by 1000kg perilla herb oils, under stirring and heating, 50% NaOH solution 350kg is continuously added
To its space saponification, when the water surface is there is no during the grease of floating, 6.8~7.2, reaction solution is transparent molten for now pH value control
After liquid, it is 1533kg to add 35.5% cupric sulfate pentahydrate solution, obtains upper strata water-insoluble aliphatic acid copper, separation, discards glycerine
And Na2SO4The aqueous solution, obtain purple perilla fatty acid copper low melting point solid 1065kg and (contain Cu2+10%).
Embodiment 6
The particle white carbon saturation of 10000kg40-120 mesh is adsorbed to the 6% maltodextrin aqueous solution, drying is contained
The 5% hard silica particles of maltodextrin are standby.
Embodiment 7
40kg pulullan polysaccharides are dissolved in 960kg deionized waters and form the transparent aqueous solution.
Embodiment 8
100kg polyacrylic resins, Glyceryl tributyrate 8kg are dissolved in 892kg ethanol and form transparent polyacrylic acid tree
Fat ethanol coating solution.
Embodiment 9
The hard white carbons of 500kg that the palm oil resin acid copper 500kg embodiments 6 that embodiment 1 produces are produced while hot
Grain absorption, obtain 1000kg load palm oil resin acid copper silica particles.
Embodiment 10
The hard silica particles of 500kg that the lard resin acid copper 500kg embodiments 6 that embodiment 2 produces are produced while hot
Absorption, obtain 1000kg load lard resin acid copper silica particles.
Embodiment 11
The hard hard charcoals of 500kg that the lard palm oil resin acid copper 500kg embodiments 6 that embodiment 3 produces are produced while hot
Black granular absorption, obtain 1000kg load lard palm oil resin acid copper silica particles.
Embodiment 12
The hard white carbons of 500kg that the coconut fatty acid copper 500kg embodiments 6 that embodiment 4 produces are produced while hot
Grain absorption, obtain 1000kg load coconut fatty acid copper silica particles.
Embodiment 13
The hard white carbons of 500kg that the purple perilla fatty acid copper 500kg embodiments 6 that embodiment 5 produces are produced while hot
Grain absorption, obtain 1000kg load purple perilla fatty acid copper silica particles.
Embodiment 14
By the load palm oil resin acid copper silica particles 500kg that embodiment 9 produces, side stirring becomes in agitator is dried
The pulullan polysaccharide aqueous solution 50kg that spraying spraying embodiment 7 produces, while negative pressure of vacuum removes water, obtains containing 0.4% coating
Material pulullan polysaccharide palmitic acid fatty acid copper particle 502kg.
Embodiment 15
By the load lard resin acid copper silica particles 500kg that embodiment 10 produces, side stirring becomes spray in agitator is dried
Spray painting applies the pulullan polysaccharide aqueous solution 50kg that embodiment 7 produces, while negative pressure of vacuum removes water, obtains containing 1% coating material
Pulullan polysaccharide lard resin acid copper particle 502kg.
Embodiment 16
The load lard palm oil resin acid copper silica particles 500kg that embodiment 11 produces is stirred on side in agitator is dried
Mix and become the pulullan polysaccharide aqueous solution 100kg that spraying spraying embodiment 7 produces, while negative pressure of vacuum removes water, obtains containing 0.8%
Coating material pulullan polysaccharide lard palmitic acid fatty acid copper particle 504kg.
Embodiment 17
By the load coconut fatty acid copper silica particles 500kg that embodiment 12 produces, side stirring becomes in agitator is dried
The pulullan polysaccharide aqueous solution 100kg that spraying spraying embodiment 7 produces, while negative pressure of vacuum removes water, obtains containing 0.8% coating
Material pulullan polysaccharide coconut fatty acid copper particle 504kg.
Embodiment 18
By the load purple perilla fatty acid copper silica particles 500kg that embodiment 13 produces, side stirring becomes in agitator is dried
The pulullan polysaccharide aqueous solution 200kg that spraying spraying embodiment 7 produces, while negative pressure of vacuum removes water, obtains containing 1.57% bag
Clothing material pulullan polysaccharide purple perilla fatty acid copper particle 508kg.
Embodiment 19
The pulullan polysaccharide coating load palm oil resin acid copper silica particles 500kg that embodiment 14 is produced is in seed-coating machine
The polyacrylic resin ethanol coating solution 100kg that middle spraying spraying embodiment 8 produces, is obtained containing enteric-coating material 2.11%
Palm oil resin acid copper 510.8kg.
Embodiment 20
The pulullan polysaccharide coating load lard resin acid copper silica particles 500kg that embodiment 15 is produced is in seed-coating machine
The polyacrylic resin ethanol coating solution 100kg that spraying spraying embodiment 8 produces, obtains the pig containing enteric-coating material 2.11%
Fatty acid copper 510.8kg.
Embodiment 21
The pulullan polysaccharide coating load lard palm oil resin acid copper silica particles 500kg that embodiment 16 produces is being wrapped
The polyacrylic resin ethanol coating solution 200kg that spraying spraying embodiment 8 produces in clothing machine, obtains containing enteric-coating material
4.22% lard palm oil resin acid copper 521.6kg.
Embodiment 22
The pulullan polysaccharide coating load coconut fatty acid copper silica particles 500kg that embodiment 17 is produced is in seed-coating machine
The polyacrylic resin ethanol coating solution 400kg that middle spraying spraying embodiment 8 produces, is obtained containing enteric-coating material 8.44%
Coconut fatty acid copper 543.2kg.
Embodiment 23
The pulullan polysaccharide coating load purple perilla fatty acid copper silica particles 500kg that embodiment 18 is just produced is being coated
The polyacrylic resin ethanol coating solution 400kg that spraying spraying embodiment 8 produces in machine, obtains containing enteric-coating material 8.44%
Purple perilla fatty acid copper 543.2kg.
Embodiment 24
The palm oil resin acid copper 700kg that embodiment 1 is produced is adsorbed with 300kg powder white carbon while hot, is made and is easy to make
Contain the feed addictive 1000kg of 70% palm oil resin acid copper.
Embodiment 25
The lard resin acid copper 700kg that embodiment 2 is produced is adsorbed with 300kg powder white carbon while hot, is made easy to use
The feed addictive 1000kg containing 70% lard resin acid copper.
Embodiment 26
The lard palm oil resin acid copper 700kg that embodiment 3 is produced is adsorbed with 300kg powder white carbon while hot, is made just
In the feed addictive 1000kg containing 70% lard palm oil resin acid copper used.
Embodiment 27
The coconut fatty acid copper 700kg that embodiment 4 is produced is adsorbed with 300kg powder white carbon while hot, is made and is easy to make
Contain the feed addictive 1000kg of 70% coconut fatty acid copper.
Embodiment 28
The purple perilla fatty acid copper 700kg that embodiment 5 is produced is adsorbed with 300kg powder white carbon while hot, is made and is easy to make
Contain the feed addictive 1000kg of 70% purple perilla fatty acid copper.
Embodiment 29
The a collection of 42 age in days piglet 108 being in a good state of health is chosen, is randomly divided into six groups, every group of three repetitions, each
6 pigs are repeated, male and female half and half, feeds contain 70% 430 grams of palm oil resin acid copper feed additive containing what embodiment 24 produced successively
(Cu2+30ppm), 200 grams of (Cu of pulullan polysaccharide coating palmitic acid fatty acid copper feed additive that embodiment 14 produces2+20ppm)、
50.5 grams of (Cu of enteric coating palm oil resin acid copper feed additive that embodiment 19 produces2+5ppm), the water sulfuric acid of control group (1) five
1000 grams of (Cu of copper2+250ppm), 600 grams of (Cu of control group (2) cupric sulfate pentahydrate2+150ppm, control group (3) cupric sulfate pentahydrate 40
Gram (Cu2+10ppm), other feed ingredients are consistent, and formula is as shown in table 1, and rearing conditions are consistent.
Other feed ingredient formulas of the embodiment 29 of table 1
Feeding one month, test beginning counterpoise, last counterpoise, daily gain, feedstuff-meat ratio and the diarrhea rate of six groups of piglets, test result
As shown in table 2, table 2 is the performance test results of the embodiment of the present invention 29.
The performance test results of 2 embodiment of the present invention of table 29
A, b, c represent level of difference, and letter is identical, represents no significant difference (P>0.05);It is alphabetical different, indicate
Significant difference (P<0.05);There are two letters different, indicate pole significant difference (P<0.01).
As shown in Table 2, palm oil resin acid copper, pulullan polysaccharide coating palm oil resin acid copper, enteric coating palm oil resin acid
Three kinds of palm oil resin acid copper-bases of copper limit low copper (Cu2+5-30ppm) group and copper sulphate high-copper (Cu2+250ppm) group all achieves ratio
Low copper (the Cu of copper sulphate2+Growth Results 10ppm) organized, wherein, daily gain copper (Cu lower than copper sulphate2+10ppm) component you can well imagine
High 5.3% (P>0.05), 8.7% (P>0.05), 15.5% (P<0.01), 11.5% (P<0.05), palm oil resin acid copper, Pu Lu
Blue more sweet tablet palm oil grease acid copper, three kinds of palm oil resin acid copper group daily gains levels of enteric coating palm oil resin acid copper and high-copper
No significant difference (the P of group>0.05) there are, but successively increase trend, palm oil resin acid copper, pulullan polysaccharide coating palm oil grease
Sour copper increases trend successively than uncoated palm oil resin acid copper;Palm oil resin acid copper, pulullan polysaccharide coating palm oil resin acid
Three kinds of copper, enteric coating palm oil resin acid copper palm oil resin acid copper-bases limit low copper (Cu2+5-15ppm) group and high-copper (Cu2+
250ppm) feed conversion rate copper (the Cu lower than copper sulphate of group2+10ppm) 2.1% (P is respectively increased in group>0.05), 4.1% (P>
0.05), 9.2% (P<0.05), 7.7% (P<0.05), three kinds of palm oil resin acid copper group feeds of enteric coating palm oil resin acid copper
Transform level does not have significant difference (P with high-copper group>0.05).
Illustrate palm oil resin acid copper, pulullan polysaccharide coating palm oil resin acid copper, three kinds of enteric coating palm oil resin acid copper
The alternative high-copper of palm oil resin acid copper, palm oil resin acid copper, pulullan polysaccharide coating palm oil resin acid copper and cupric sulfate pentahydrate
1000 grams of (Cu2+150ppm) quite, copper dosage is also larger, and only enteric coating palm oil resin acid copper could replaced truly
For high-copper.
Embodiment 30
The a collection of 42 age in days piglet 108 being in a good state of health is chosen, is randomly divided into six groups, every group of three repetitions, each
6 pigs of repetition, male and female half and half, feed contain 70% 573 grams of lard resin acid copper feed additive containing what embodiment 25 produced successively
(Cu2+40ppm), 350.5 grams of (Cu of pulullan polysaccharide coating lard resin acid copper feed additive that embodiment 15 produces2+
35ppm), 52 grams of (Cu of enteric coating lard resin acid copper feed additive that embodiment 20 produces2+5ppm), the water of control group (1) five
1000 grams of (Cu of copper sulphate2+250ppm), 600 grams of (Cu of control group (2) cupric sulfate pentahydrate2+150ppm, the water sulfuric acid of control group (3) five
40 grams of (Cu of copper2+10ppm), other feed ingredients are consistent, and formula is as shown in table 3, and rearing conditions are consistent,
Other feed ingredient formulas in the embodiment 30 of table 3
Feeding one month, test beginning counterpoise, last counterpoise, daily gain, feedstuff-meat ratio and the diarrhea rate of six groups of piglets, test result
As shown in table 4,
Table 4 is the performance test results of the embodiment of the present invention 30.
A, b, c represent level of difference, and letter is identical, represents no significant difference (P>0.05);It is alphabetical different, indicate
Significant difference (P<0.05);There are two letters different, indicate pole significant difference (P<0.01).
As shown in Table 4, lard resin acid copper, pulullan polysaccharide coating lard resin acid copper, three kinds of enteric coating lard resin acid copper
Lard resin acid copper-base limits low copper (Cu2+5-15ppm) group and copper sulphate high-copper (Cu2+250ppm) group all achieves lower than copper sulphate
Copper (Cu2+Growth Results 10ppm) organized, wherein, daily gain copper (Cu lower than copper sulphate2+10ppm) group is respectively increased -1.1%
(P>0.05), 12.9% (P<0.01), 14.0% (P<0.01), 10.1% (P<0.05), pulullan polysaccharide coating lard resin acid
Copper (Cu2+35ppm), enteric coating lard resin acid copper (Cu2+5ppm) two boar fatty acid copper group daily gains level and high-copper group
(Cu2+There is no significant difference (P 250ppm)>0.05) there are, but successively increase trend, enteric coating lard resin acid copper, Propiram
More sweet tablet pig fat acid copper have extremely notable growth (P than uncoated lard resin acid copper<0.01);Lard resin acid copper, Propiram
More sweet tablet oil lard acid copper, the boar fatty acid copper-base of enteric coating lard resin acid copper three limit low copper (Cu2+5-15ppm) group and height
Copper (Cu2+250ppm) feed conversion rate copper (the Cu lower than copper sulphate of group2+10ppm) -3.6% (P is respectively increased in group<0.05)、
8.3% (P<0.05), 8.3% (P<0.05), 6.7% (P<0.05), pulullan polysaccharide coating lard resin acid copper, enteric coating pig
The boar fatty acid copper group feed conversion rate of fatty acid copper three is horizontal not to have significant difference (P with high-copper group>0.05) it is, uncoated
Lard resin acid copper compares the low copper (Cu of copper sulphate2+10ppm) there is negative effect in daily gain and feed conversion rate, it is impossible to substitute high
Copper.
Illustrate that pulullan polysaccharide coating lard resin acid copper, the boar fatty acid copper of enteric coating lard resin acid copper two are alternative
High-copper.Uncoated lard resin acid copper can not substitute high-copper.
Embodiment 31
It is young 108 to choose a collection of 42 ages in days that are in a good state of health, is randomly divided into six groups, every group of three repetitions, Mei Gechong
Multiple 6 pigs, male and female half and half, feed contain 70% lard palm oil resin acid copper feed additive 287 containing what embodiment 26 produced successively
Gram (Cu2+20ppm), 505 grams of (Cu of pulullan polysaccharide coating lard palm oil resin acid copper feed additive that embodiment 16 produces2+
50ppm), 52 grams of (Cu of enteric coating lard palm oil resin acid copper feed additive that embodiment 21 produces2+5ppm), control group
(1) 1000 grams of (Cu of cupric sulfate pentahydrate2+250ppm), 600 grams of (Cu of control group (2) cupric sulfate pentahydrate2+150ppm, control group (3)
40 grams of (Cu of cupric sulfate pentahydrate2+10ppm), other feed ingredients are consistent, and formula is as shown in table 5, and rearing conditions are consistent,
Other feed ingredient formulas of the embodiment 31 of table 5
Feeding one month, test beginning counterpoise, last counterpoise, daily gain, feedstuff-meat ratio and the diarrhea rate of 6 groups of piglets, test result
As shown in table 6,
The performance test results of 6 embodiment of the present invention of table 31.
A, b, c represent level of difference, and letter is identical, represents no significant difference (P>0.05);It is alphabetical different, indicate
Significant difference (P<0.05);There are two letters different, indicate pole significant difference (P<0.01).
As shown in Table 6, lard palm oil resin acid copper, pulullan polysaccharide coating lard palm oil resin acid copper, enteric coating pig
The boar oil palm fatty acid copper-base of oil palm fatty acid copper three limits low copper (Cu2+5-50ppm) group and copper sulphate high-copper (Cu2+
250ppm) group all achieves copper (Cu lower than copper sulphate2+Growth Results 5ppm) organized, wherein, daily gain copper lower than copper sulphate
(Cu2+10ppm) 4.4% (P is respectively increased in group>0.05), 14.5% (P<0.01), 15.96% (P<0.01), 11.5% (P<
0.05), pulullan polysaccharide lard coating palm oil resin acid copper (Cu2+50ppm), enteric coating lard palm oil resin acid copper (Cu2+
5ppm) two boar oil palm fatty acid copper group daily gains are horizontal does not have significant difference (P with high-copper group>0.05) have, but successively
Increase trend, lard palm oil resin acid copper, pulullan polysaccharide are coated lard palm oil resin acid copper than uncoated lard palm oil
Resin acid copper increases trend successively;Lard palm oil resin acid copper, pulullan polysaccharide coating lard palm oil resin acid copper, enteric coating pig
The brown lard palmitic acid fatty acid copper-base of three kinds of oil palm fatty acid copper limits low copper (Cu2+5-15ppm) group and high-copper (Cu2+250ppm) group
Feed conversion rate copper (Cu lower than copper sulphate2+10ppm) group is respectively increased 1.0%(P<0.05), 8.7%(P<0.05)、9.2
%(P<0.05), 8.2%(P<0.05), pulullan polysaccharide coating lard palm oil resin acid copper, enteric coating lard palm oil resin acid copper two
Boar oil palm fatty acid copper group feed conversion rate is horizontal not to have significant difference (P with high-copper group>0.05).
Illustrate pulullan polysaccharide coating lard palmitic acid fatty acid copper, the boar oil palm of enteric coating lard palm oil resin acid copper three
The alternative high-copper of fatty acid copper, the also high (Cu of pulullan polysaccharide coating lard palmitic acid fatty acid copper copper consumption2+50ppm), lard palm fibre
Palmitic acid fatty acid copper effect is undesirable, with copper sulphate high-copper (Cu2+150ppm) quite, the low copper (Cu of copper sulphate2+5ppm) group is without aobvious
Write sex differernce (P>0.05).
Embodiment 32
The a collection of 42 age in days piglet 108 being in a good state of health is chosen, is randomly divided into six groups, every group of three repetitions, each
6 pigs of repetition, male and female half and half, feed contain 70% 215 grams of coconut fatty acid copper feed additive containing what embodiment 27 produced successively
(Cu2+15ppm), 50.5 grams of (Cu of pulullan polysaccharide coating coconut fatty acid copper feed additive that embodiment 17 produces2+
5ppm), 55 grams of (Cu of enteric coating coconut fatty acid copper feed additive that embodiment 22 produces2+5ppm), the water of control group (1) five
1000 grams of (Cu of copper sulphate2+250ppm), 600 grams of (Cu of control group (2) cupric sulfate pentahydrate2+150ppm, the water sulfuric acid of control group (3) five
40 grams of (Cu of copper2+10ppm), other feed ingredients are consistent, and formula is as shown in table 7, and rearing conditions are consistent,
Other feed ingredient formulas of the embodiment 32 of table 7
Feeding one month, test beginning counterpoise, last counterpoise, daily gain, feedstuff-meat ratio and the diarrhea rate of 6 groups of piglets, test result
As shown in table 8,
The performance test results of 8 embodiment of the present invention of table 32
A, b, c represent level of difference, and letter is identical, represents no significant difference (P>0.05);It is alphabetical different, indicate
Significant difference (P<0.05);There are two letters different, indicate pole significant difference (P<0.01).
As shown in Table 8, coconut fatty acid copper, pulullan polysaccharide coating coconut fatty acid copper, enteric coating coconut fatty acid
Three kinds of coconut fatty acid copper-bases of copper limit low copper (Cu2+5-15ppm) group and high-copper (Cu2+250ppm) group, which all achieves, compares copper sulphate
Low copper (Cu2+Growth Results 10ppm) organized, wherein, daily gain copper (Cu lower than copper sulphate2+10ppm) group is respectively increased
2.9%(P>0.05), 4.2%(P>0.05), 15.3%(P<0.01), 10.7%(P<0.05), coconut fatty acid copper (Cu2+15ppm), Propiram
More sweet tablet coconut oil resin acid copper (Cu2+5ppm) two kinds of coconut fatty acid copper group daily gains levels and high-copper cupric sulfate pentahydrate 600
Gram (Cu2+150ppm) group is suitable, without significant difference(P>0.05);Coconut fatty acid copper, pulullan polysaccharide coating coconut oil, intestines
Three kinds of coconut fatty acid copper-bases of molten coating coconut fatty acid copper limit low copper (Cu2+5-15ppm) group and high-copper (Cu2+250ppm) group
Feed conversion rate copper (Cu lower than copper sulphate2+10ppm) group is respectively increased -2.6%(P>0.05), 1.0%(P>0.05)、
8.3%(P<0.05), 6.2%(P<0.05), coconut fatty acid copper, pulullan polysaccharide coating coconut fatty acid two kinds of coconut fatty acids of copper
Copper group feed conversion rate is horizontal and high-copper group is in negative growth(P>0.05), show that the two has oxidation deterioration tendency.
Illustrate pulullan polysaccharide coating coconut fatty acid copper, the alternative high-copper of enteric coating coconut fatty acid copper, Pu Lu
Blue more sweet tablet coconut oil resin acid copper only have copper sulphate high-copper (Cu2+Effect 150ppm), uncoated coconut fatty acid copper are several
There is no growth-promoting effect, opposite feed conversion rate has negative effect, it is impossible to substitutes high-copper.
Embodiment 33
The a collection of 42 age in days piglet 108 being in a good state of health is chosen, is randomly divided into six groups, every group of three repetitions, each
6 pigs of repetition, male and female half and half, feed contain 70% purple perilla fatty acid copper feed additive 502 containing what example 24 produced successively
Gram (Cu2+35ppm), 102 grams of (Cu of pulullan polysaccharide coating purple perilla fatty acid copper feed additive that example 14 produces2+
10ppm), 55 grams of (Cu of enteric coating purple perilla fatty acid copper feed additive that example 19 produces2+5ppm), control group (1) five
1000 grams of (Cu of brochanite2+250ppm), 600 grams of (Cu of control group (2) cupric sulfate pentahydrate2+150ppm, the water sulphur of control group (3) five
Sour 40 grams of (Cu of copper2+10ppm), other feed ingredients are consistent, and formula is as shown in table 9, and rearing conditions are consistent,
Other feed ingredient formulas of the embodiment 33 of table 9
Feeding one month, test beginning counterpoise, last counterpoise, daily gain, feedstuff-meat ratio and the diarrhea rate of 6 groups of piglets, test result
As shown in table 10,
The performance test results of 10 embodiment of the present invention of table 33
A, b, c represent level of difference, and letter is identical, represents no significant difference (P>0.05);It is alphabetical different, indicate
Significant difference (P<0.05);There are two letters different, indicate pole significant difference (P<0.01).
As shown in Table 10, two kinds of pulullan polysaccharide coating purple perilla fatty acid copper, enteric coating purple perilla fatty acid copper coatings are purple
Fatty acid copper-base of reviving limits low copper (Cu2+5-10ppm) group and high-copper (Cu2+250ppm) group all achieves copper (Cu lower than copper sulphate2+
Growth Results 10ppm) organized, wherein, daily gain is than low copper (Cu2+10ppm) group is respectively increased 15.2%(P<0.01)、
8.6%(P<0.05), 11.1%(P<0.05), pulullan polysaccharide coating purple perilla fatty acid copper (Cu2+10ppm) than copper sulphate high-copper (Cu2+
It is 150ppm) good(P<0.05), not coated purple perilla fatty acid copper (Cu2+35ppm) daily gain is but with feed conversion rate all than five water sulphur
Sour 40 grams of (Cu of copper2+It is 10ppm) poor, difference poor -6.42%(P<0.05), -26.2%(P<0.01), including pulullan polysaccharide coating purple perilla
Fatty acid copper (Cu2+10ppm) group, pig regularity is also poor, may due in perilla herb oil unrighted acid linolenic acid content height exist
Processing storing process in there occurs oxidation deterioration and further make feed oxide go bad cause, purple perilla fatty acid copper, Propiram are more
Three kinds of sweet tablet purple perilla fatty acid copper, enteric coating purple perilla fatty acid copper purple perilla fatty acid copper-bases limit low copper (Cu2+5-15ppm) group
With high-copper (Cu2+250ppm) feed conversion rate copper (the Cu lower than copper sulphate of group2+10ppm) group is respectively increased -26.2%(P<0.01)、
2.1%(P>0.05), 8.2%(P<0.05), 6.7%(P<0.05)。
Illustrate that two kinds of pulullan polysaccharide coating purple perilla fatty acid copper, enteric coating purple perilla fatty acid copper purple perilla fatty acid copper are equal
Alternative high-copper, the fatty acid copper of the high grease production of this unsaturated fatty acid content of purple perilla fatty acid copper must be coated with place
Reason, it is preferably most reliable with enteric coating purple perilla fatty acid copper.
In summary, fatty acid copper, coating fatty acid copper (Cu2+It 5-15ppm) can reach copper sulphate high-copper (Cu2+150-
Effect 250ppm), but the fatty acid copper for not being coated with processing is very unstable, and replacement high-copper effect is very unreliable, is coated with fatty acid
The fatty acid copper of the alternative high-copper of copper, preferably water-insoluble enteric-coating material coating.
Equally, we use sunflower oil, olive oil, corn oil, three-coloured amaranth oil, soya-bean oil, peanut oil, sesame oil, rapeseed oil, cotton
Benevolence oil, butter, chicken fat, fish oil, rice bran oil obtain fatty acid copper or coating fatty acid oil copper;
Equally, we chicken, turkey, duck, goose, black-bone chicken, quail, pigeon, ox, horse, sheep, dog, ermine, deer, cat, donkey, rabbit,
Fish, shrimp, crab, shellfish, tortoise, snake, the feed applications coating fatty acid oil copper of yellow eel can also obtain preferable growth-promoting effect and good
Production performance.
Embodiment 34
It is standby that 100kg pulullan polysaccharides are dissolved in into formation clear solution in 1900kg water.
Embodiment 35
300kg maltodextrins and 700kg capric acid copper (commercially available) are stirred, embodiment 34 is sprayed while stirring and gives birth to
The pulullan polysaccharide aqueous solution 180kg of production, paste thick liquid is formed, is dried to and does very likely, be granulated with granulator, be dried to ninety percent again
It is dry, throw round formed after spherical granules with circle-throw movement machine and thoroughly dry, in seed-coating machine, then the sprayed on membrane pulullan polysaccharide aqueous solution
60kg, drying, obtain the hard particles coating capric acid of the 60-120 mesh pulullan polysaccharide overlay films of the copper of fatty acids containing maltodextrin
Copper 1012kg, containing Cu2+10.825%.
Embodiment 36
200kg maltodextrins and 800kg lauric acid/dodecanoic acids copper (commercially available) are stirred, spray embodiment 34 while stirring
The pulullan polysaccharide aqueous solution 140kg of production, paste thick liquid is formed, is dried to and does very likely, be granulated with granulator, be dried to ninety percent again
It is dry, throw round formed after spherical granules with circle-throw movement machine and thoroughly dry, in seed-coating machine, then the sprayed on membrane pulullan polysaccharide aqueous solution
60kg, drying, obtain the hard particles coating 12 of the 60-120 mesh pulullan polysaccharide overlay films of the copper of fatty acids containing maltodextrin
Sour copper 1010kg, containing Cu2+10.891%.
Embodiment 37
100kg maltodextrins and 900kg stearic acids copper (commercially available) are stirred, spray embodiment 34 while stirring
The pulullan polysaccharide aqueous solution 100kg of production, paste thick liquid is formed, is dried to and does very likely, be granulated with granulator, be dried to ninety percent again
It is dry, throw round formed after spherical granules with circle-throw movement machine and thoroughly dry, in seed-coating machine, then the sprayed on membrane pulullan polysaccharide aqueous solution
50kg, drying, obtain the hard particles coating 18 of the 60-120 mesh pulullan polysaccharide overlay films of the copper of fatty acids containing maltodextrin
Sour copper 1007.5kg, containing Cu2+9.004%.
Embodiment 38
500kg maltodextrins and 500kg copper oleates (commercially available) are stirred, embodiment 34 is sprayed while stirring and gives birth to
The pulullan polysaccharide aqueous solution 180kg of production, paste thick liquid is formed, is dried to and does very likely, be granulated with granulator, be dried to ninety percent again
It is dry, thoroughly dried with round formed after spherical granules of Throwing circular knitting machines throwing is thrown, in seed-coating machine, then sprayed on membrane pulullan polysaccharide is water-soluble
Liquid 60kg, drying, obtain the hard particles coating oil of the 60-120 mesh pulullan polysaccharide overlay films of the copper of fatty acids containing maltodextrin
Sour copper 1012kg, containing Cu2+5.010%.
Embodiment 39
It is empty that removing is vacuumized in high-pressure agitated vessels, after input polyacrylic resin 30kg, tributyrin 0.5kg
Gas, importing liquid gas monochloro methane 650kg, fully to form uniform coating liquid gas molten for dissolving coating material under agitation
Liquid.60-120 mesh capric acid copper hard particles 1012kg made of embodiment 35 is put into high voltage bearing vacuum rake dryer
In, air is removed in vacuum, imports Coating Solution made of liquid gas, after stirring 10-30 minutes, valve is opened in side stirring, is allowed
Liquid gas enters compressor, then becomes liquid gas and recycled into high-pressure bottle, when to rake type drier being negative pressure, closes
Close and lead to compressor valve, then open rake type drier exhaust-valve, release product, obtain enteric coating capric acid copper 1042.5kg,
Containing Cu2+10.51%.
Embodiment 40
In high-pressure agitated vessels, input HPMCP 20kg, tributyrin
Removing air is vacuumized after 0.2kg, importing liquid gas monochloro methane 680kg, fully dissolving coating material is formed under agitation
Even coating open country liquefied gas solution.60-120 mesh laurate copper hard particles 1010kg made of embodiment 36 is put into resistance to
In the vacuum rake dryer of high pressure, air is removed in vacuum, imports Coating Solution made of liquid gas, stirs 10-30 minutes
Afterwards, valve is opened in side stirring, allows liquid gas to enter compressor, then is become liquid gas and recycled into high-pressure bottle, is arrived
When rake type drier is negative pressure, compressor valve is led in closing, then opens rake type drier exhaust-valve, is released product, is obtained intestines
Molten coating laurate copper 1030.2kg, containing Cu2+10.68%.
Embodiment 41
In high-pressure agitated vessels, after input polyvinyl alcohol acetate phthalate ester 18kg, tributyrin 0.4kg
Removing air is vacuumized, importing liquid gas monochloro methane 560kg, fully dissolving coating material forms uniform bag under agitation
Clothing open country liquefied gas solution.60-120 mesh stearic acid copper hard particles 1007.5kg made of embodiment 37 is put into high pressure resistant
Vacuum rake dryer in, be removed in vacuum air, import Coating Solution made of liquid gas, after stirring 10-30 minutes, side
Valve is opened in stirring, allows liquid gas to enter compressor, then is become liquid gas and recycled into high-pressure bottle, is done to rake
When dry machine is negative pressure, compressor valve is led in closing, then opens rake type drier exhaust-valve, is released product, is obtained enteric coating
Stearic acid copper 1025.9kg, containing Cu2+8.84%.
Embodiment 42
In high-pressure agitated vessels, input polyacrylic resin 18kg, HPMCP
Removing air is vacuumized after 20kg, tributyrin 0.8kg, it is abundant under agitation to import liquid gas monochloro methane 860kg
Dissolving coating material, which is formed, is uniformly coated wild liquefied gas solution.By hard of 60-120 mesh copper oleate made of embodiment 38
Grain 1012kg is put into high voltage bearing vacuum rake dryer, and air is removed in vacuum, and it is molten to import coating made of liquid gas
Liquid, after stirring 10-30 minutes, valve is opened in side stirring, allows liquid gas to enter compressor, then become liquid gas to high pressure-volume
Being recycled in device, when to rake type drier being negative pressure, compressor valve is led in closing, then opens rake type drier exhaust-valve,
Product is released, enteric coating copper oleate 1050.8kg is obtained, containing Cu2+4.83%.
Equally, we use copper formate, copper acetate, propionic acid copper, copper butyrate, valeric acid copper, caproic acid copper, enanthic acid copper, cupric octoate, nonyl
Sour copper, undecanoic acid copper, tridecanoic acid copper, tetradecylic acid copper, pentadecanoic acid copper, hexadecylic acid copper, heptadecanoic acid copper, nonadecanoic acid copper, 20 sour copper,
Heneicosoic acid copper, behenic acid copper, tricosanic acid copper, tetracosanoic acid copper, neocerotic acid copper, cerinic acid copper, carboceric acid copper,
Octacosanoic acid copper, motanic acid copper, triacontanoic acid copper, copper linoleate, leukotrienes copper, CLA copper, arachidonic acid copper, two
The sour copper of ten carbon 5 alkene acids (EPA), the sour copper of docosahexaenoic acid (DHA), erucic acid copper, tangerine acid copper, rape acid copper obtain coating fat
Fat acid copper.
Embodiment 43
The a collection of 42 age in days piglet 108 being in a good state of health is chosen, is randomly divided into six groups, every group of three repetitions, each
6 pigs are repeated, male and female half and half, feed the enteric coating capric acid copper (Cu produced containing embodiment 39 successively2+10.51%) feed adds
76 grams of (Cu of agent2+8ppm), the pulullan polysaccharide coating capric acid copper (Cu that embodiment 35 produces2+10.825%) feed addictive 185
Gram (Cu2+20ppm), capric acid copper (Cu2+15.5%) 129 grams of (Cu are organized2+20ppm), 1000 grams of control group (1) cupric sulfate pentahydrate
(Cu2+250ppm), 600 grams of (Cu of control group (2) cupric sulfate pentahydrate2+40 grams of 150ppm, control group (3) cupric sulfate pentahydrate (Cu2+
10ppm), other feed ingredients are consistent, and formula is as shown in table 11, and feed is placed 30 days and carried out again through 80-90 DEG C of high temperature granulating
Feeding experiment, rearing conditions are consistent,
Other feed ingredient formulas of the embodiment 43 of table 11
Feeding one month, test beginning counterpoise, last counterpoise, daily gain, feedstuff-meat ratio and the diarrhea rate of six groups of piglets, test result
As shown in table 12, table 12 is the performance test results of the embodiment of the present invention 43.
The performance test results of 12 embodiment of the present invention of table 43
A, b, c represent level of difference, and letter is identical, represents no significant difference (P>0.05);It is alphabetical different, indicate
Significant difference (P<0.05);There are two letters different, indicate pole significant difference (P<0.01).
As shown in Table 12, enteric coating capric acid copper (Cu2+8ppm), pulullan polysaccharide coating capric acid copper (Cu2+20ppm), the last of the ten Heavenly stems
Sour copper (Cu2+20ppm), high-copper (Cu2+250ppm), high-copper (Cu2+150ppm) than low copper (Cu2+10ppm) daily gain is respectively increased
14.2% (P<0.01), 4.7% (P>0.05), 2.1% (P>0.05), 11.0% (P<0.01), 4.5% (P>0.05);Feed
Conversion ratio copper (Cu lower than copper sulphate2+10ppm) 5.2% (P is respectively increased in group>0.05), -0.5% (P>0.05), -2.1% (P>
0.05), 1.0% (P>0.05), -1.6% (P>0.05).
Illustrate that only enteric coating capric acid copper can substitute high-copper, untreated capric acid copper, pulullan polysaccharide coating capric acid copper are only
Copper (Cu lower than copper sulphate2+10ppm) group is slightly better, and untreated capric acid copper is far below enteric coating capric acid copper group and high-copper (Cu2 +250ppm), also than high-copper (Cu2+It is poor 150ppm) to organize, and illustrates that feed is already oxidised by the storage of 30 days, uncoated capric acid copper
It is rotten, even if being coated through pulullan polysaccharide, due to the most of coating of high-temperature steam dissolved destruction of pelletizing, exposed capric acid copper
Oxidation deterioration, this two groups of feed conversion rates copper (Cu lower than copper sulphate2+It is also poor 10ppm) to organize, and also illustrates two groups of feed oxide degree
Copper (Cu lower than copper sulphate2+10ppm) high, nutritive loss is more.
Enteric coating capric acid copper is due to having completely cut off oxygen, and feed oxide degree of metamorphism is low, and nutritive loss is few, thus feed turns
Rate is high, and weightening pole is significantly higher than other groups, than copper sulphate high-copper (Cu2+2.9% 250ppm) is also improved, feed conversion rate improves
6.15%, the dosage (Cu of copper2+8ppm) there was only copper sulphate high-copper (Cu2+250ppm) 3.2%, illustrate enteric coating capric acid copper not
It is only capable of substituting high-copper, effect is more preferable, and feed stored by 30 days, and effect is still very stable, it was demonstrated that enteric coating capric acid copper is
A kind of reliable and stable feedstuff additive product.
Embodiment 44
The a collection of 42 age in days piglet 108 being in a good state of health is chosen, is randomly divided into six groups, every group of three repetitions, each
6 pigs are repeated, male and female half and half, feed the enteric coating laurate copper (Cu produced containing embodiment 40 successively2+10.68%) feed adds
Add 46.8 grams of (Cu of agent2+5ppm), the pulullan polysaccharide coating lauric acid/dodecanoic acid copper (Cu that embodiment 36 produces2+10.891%) feed adds
Add 92 grams of (Cu of agent2+10ppm), lauric acid/dodecanoic acid copper (Cu2+13.5%) 296 grams of (Cu of feed addictive group2+40ppm), control group (1)
1000 grams of (Cu of cupric sulfate pentahydrate2+250ppm), 600 grams of (Cu of control group (2) cupric sulfate pentahydrate2+150ppm, the water of control group (3) five
40 grams of (Cu of copper sulphate2+10ppm), other feed ingredients are consistent, and formula is as shown in table 13, feed through 80-90 DEG C of high temperature granulating, and
To place 45 days and carry out feeding experiment again, rearing conditions are consistent,
Other feed ingredient formulas in the embodiment 44 of table 13
Feeding one month, test beginning counterpoise, last counterpoise, daily gain, feedstuff-meat ratio and the diarrhea rate of six groups of piglets, test result
As shown in table 4,
Table 14 is the performance test results of the embodiment of the present invention 44
A, b, c represent level of difference, and letter is identical, represents no significant difference (P>0.05);It is alphabetical different, indicate
Significant difference (P<0.05);There are two letters different, indicate pole significant difference (P<0.01).
As shown in Table 14, enteric coating laurate copper (Cu2+5ppm), pulullan polysaccharide coating laurate copper (Cu2+
5ppm), laurate copper (Cu2+40ppm), high-copper (Cu2+250ppm), high-copper (Cu2+150ppm) than low copper (Cu2+10ppm) increase day by day
15.9% (P is respectively increased again<0.01), 6.4% (<P0.05), 3.0% (P>0.05), 11.1% (P<0.01), 5.9% (P>
0.05);Feed conversion rate copper (Cu lower than copper sulphate2+10ppm) 7.0% (P is respectively increased in group>0.05)、0(P>0.05)、-
1.5% (P>0.05), 3.5% (P>0.05), -1.5% (P>0.05).
Illustrate enteric coating laurate copper (Cu2+It can 5ppm) substitute copper sulphate high-copper (Cu2+250ppm), pulullan polysaccharide
It is coated laurate copper (Cu2+10ppm) alternative copper sulphate high-copper (Cu2+150ppm), untreated sour bay copper is far below enteric bag
Clothing laurate copper group and high-copper (Cu2+250ppm) group, also than high-copper (Cu2+150ppm) and pulullan polysaccharide is coated laurate copper
Group is poor, illustrate feed by the storage of 45 days, and uncoated laurate copper is already oxidised to go bad, enteric coating laurate copper due to every
Oxygen absolutely, feed oxide degree of metamorphism is low, nutritive loss is few, thus feed conversion rate is high, and weightening pole is significantly higher than other groups,
Than copper sulphate high-copper (Cu2+2.9% 250ppm) is also improved, feed conversion rate improves 4.3%, the dosage (Cu of copper2+5ppm) only
Copper sulphate high-copper (Cu2+250ppm) 2%, illustrate that enteric coating laurate copper can not only substitute high-copper, effect is more preferable, and feed passes through
Store within 45 days, effect is still very stable, it was demonstrated that enteric coating laurate copper is a kind of reliable and stable feedstuff additive product.
Embodiment 45
It is young 108 to choose a collection of 42 ages in days that are in a good state of health, is randomly divided into six groups, every group of three repetitions, Mei Gechong
Multiple 6 pigs, male and female half and half, the enteric coating stearic acid copper (Cu produced containing embodiment 41 is fed successively2+8.84%) feed adds
113 grams of (Cu of agent2+10ppm), the pulullan polysaccharide coating copper stearate (Cu that embodiment 37 produces2+9.004%) feed addictive
333 grams of (Cu2+30ppm), copper stearate (Cu2+10.0%) 300 grams of (Cu of feed addictive group2+30ppm), the water of control group (1) five
1000 grams of (Cu of copper sulphate2+250ppm), 600 grams of (Cu of control group (2) cupric sulfate pentahydrate2+150ppm, the water sulfuric acid of control group (3) five
40 grams of (Cu of copper2+10ppm), feed is through 80-90 DEG C of high temperature, granulation, and places 15 days and carry out feeding experiment again, other feed ingredients
Unanimously, formula is as shown in Table 15, and rearing conditions are consistent,
Other feed ingredient formulas of the embodiment 45 of table 15
Feeding one month, test beginning counterpoise, last counterpoise, daily gain, feedstuff-meat ratio and the diarrhea rate of 6 groups of piglets, test result
As shown in table 16,
The performance test results of 16 embodiment of the present invention of table 45
A, b, c represent level of difference, and letter is identical, represents no significant difference (P>0.05);It is alphabetical different, indicate
Significant difference (P<0.05);There are two letters different, indicate pole significant difference (P<0.01).
As shown in Table 16, enteric coating stearate acid copper (Cu2+10ppm), pulullan polysaccharide coating copper stearate (Cu2+
30ppm), copper stearate (Cu2+30ppm), high-copper (Cu2+250ppm), high-copper (Cu2+150ppm) than low copper (Cu2+10ppm) day
14.4% (P is respectively increased in weightening<0.01), 7.92% (P<0.05), 2.02% (P>0.05), 10.3% (P>0.05)、
3.68% (P>0.05);Feed conversion rate copper (Cu lower than copper sulphate2+10ppm) 6.6% (P is respectively increased in group<0.05), 2.0%
(P>0.05), -3.1% (P>0.05), 1.5% (P>0.05), 0.5% (P>0.05).
Illustrate only enteric coating copper stearate Cu2+It can 10ppm) substitute high-copper (Cu2+250ppm), pulullan polysaccharide bag
Clothing copper stearate (Cu2+It can 30ppm) substitute high-copper (Cu2+150ppm), untreated copper stearate copper (Cu lower than copper sulphate2+
10ppm) group is slightly better, and daily gain only improves 2.02% (P>0.05), far below enteric coating copper stearate group and high-copper
(Cu2+250ppm), also than high-copper (Cu2+It is poor 150ppm) to organize, moreover, the low copper (Cu of feed conversion rate copper sulphate2+10ppm) group is gone back
Low 3.1%, illustrate the storage that feed passes through 15 days, uncoated copper stearate is in Cu2+Oxidation deterioration is had started under ionic catalysis,
Even if being coated through pulullan polysaccharide, due to the most of coating of high-temperature steam dissolved destruction of pelletizing, (Cu2+30ppm) it can not still reach
To enteric coating copper stearate Cu2+Effect 10ppm), illustrate that feed granulating process causes the copper stearate of exposed part also oxygen
Change rotten.
Enteric coating copper stearate will not cause feed oxide to go bad due to having completely cut off oxygen, and nutritive loss is few, thus raise
Expect high conversion rate, be significantly higher than other groups, than copper sulphate high-copper (Cu2+5.18% 250ppm) is also improved, the dosage (Cu of copper2+
10ppm) there was only copper sulphate high-copper (Cu2+250ppm) 4%, illustrate that enteric coating copper stearate can not only substitute high-copper, effect is more
Good, feed stored by 15 days, and effect is still very stable, it was demonstrated that enteric coating copper stearate is a kind of reliable and stable feed
Additive product.
Embodiment 46
The a collection of 42 age in days piglet 108 being in a good state of health is chosen, is randomly divided into six groups, every group of three repetitions, each
6 pigs of repetition, male and female half and half, the enteric coating copper oleate (Cu produced containing embodiment 42 is fed successively2+4.83%) feed adds
125 grams of (Cu of agent2+6ppm), the pulullan polysaccharide coating copper oleate (Cu that embodiment 38 produces2+5.010%) feed addictive 800
Gram (Cu2+40ppm), copper oleate (Cu2+10.0%) 400 grams of (Cu of feed addictive2+40ppm), control group (1) cupric sulfate pentahydrate
1000 grams of (Cu2+250ppm), 600 grams of (Cu of control group (2) cupric sulfate pentahydrate2+150ppm, 40 grams of control group (3) cupric sulfate pentahydrate
(Cu2+10ppm), other feed ingredients are consistent, and formula is as shown in table 17, and feed places 3 days again through 80-90 DEG C of high temperature, granulation
Feeding experiment is carried out, rearing conditions are consistent,
Other feed ingredient formulas of the embodiment 46 of table 17
Feeding one month, test beginning counterpoise, last counterpoise, daily gain, feedstuff-meat ratio and the diarrhea rate of 6 groups of piglets, test result
As shown in table 18,
The performance test results of 18 embodiment of the present invention of table 46
A, b, c represent level of difference, and letter is identical, represents no significant difference (P>0.05);It is alphabetical different, indicate
Significant difference (P<0.05);There are two letters different, indicate pole significant difference (P<0.01).
As shown in Table 18, enteric coating copper oleate (Cu2+6ppm), pulullan polysaccharide coating copper oleate (Cu2+40ppm), it is oily
Sour copper (Cu2+40ppm), high-copper (Cu2+250ppm), high-copper (Cu2+150ppm) than low copper (Cu2+10ppm) daily gain is respectively increased
12.4% (P<0.01), 1.6% (P>0.05), -3.23% (P>0.05), 10.1% (P<0.05), 4.31% (P>0.05);Raise
Expect conversion ratio copper (Cu lower than copper sulphate2+10ppm) 7.2% (P is respectively increased in group<0.05), -2.6% (P>0.05), -8.7% (P
<0.01), 4.6% (P>0.05), 0.5% (P>0.05).
Illustrate only enteric coating copper oleate Cu2+It could 6ppm) substitute high-copper (Cu2+250ppm), i.e., usage amount is up to Cu2 +40ppm, pulullan polysaccharide coating copper oleate (Cu2+40ppm) also only copper (Cu lower than copper sulphate2+10ppm) organize slightly better, day
Weightening only improves 1.6% (P>0.05), feed conversion rate has copper (Cu lower than copper sulphate2+10ppm) poor -2.6% (P>0.05), say
Bright pulullan polysaccharide is coated copper oleate in feed granulating, as long as high-temperature steam, extruding somewhat destroy pulullan polysaccharide coating,
Unrighted acid can be oxidized quickly to become sour and causes oxidation chain reaction, the nutriment further destroyed in feed, makes
Feed conversion rate declines, thus pulullan polysaccharide coating copper oleate can not substitute high-copper, it is impossible to as feed addictive
Untreated copper oleate (Cu2+A 40ppm) copper (Cu lower than copper sulphate2+10ppm) group daily gain reduce on the contrary-
3.23% (P>0.05), low -8.7% (P of feed conversion rate<0.05), illustrate uncoated copper oleate in feed manufacturing accumulating
Unsaturated fat pinolenic acid can be in Cu in journey2+Oxidative rancidity, and cause oxidation chain reaction quickly, further breaks under ionic catalysis
Nutriment in bad feed, feed conversion rate is set to decline -8.7% (P<0.01), Cu2+Dosage more high oxidation is faster, and feed becomes
Matter is faster;Not to mention high-copper is substituted, uncoated copper oleate either daily gain or feed conversion rate are all far below high-copper
(Cu2+250ppm), high-copper (Cu2+It is 150ppm) two groups, farther to be less than enteric coating copper oleate group.Thus, uncoated copper oleate root
Originally high-copper can not be substituted, cannot function as feed addictive at all.
Enteric coating copper oleate will not cause feed oxide to go bad due to having completely cut off oxygen, and nutritive loss is few, thus feed
High conversion rate, it is significantly higher than other groups, than copper sulphate high-copper (Cu2+2.45% 250ppm) is also improved, the dosage (Cu of copper2+
6ppm) there was only copper sulphate high-copper (Cu2+250ppm) 2.4%, illustrate that enteric coating copper oleate can not only substitute high-copper, effect is more
Good, feed stored by 3 days, and effect is still very stable, it was demonstrated that enteric coating copper oleate is that a kind of reliable and stable feed adds
Add agent product.
Equally, we chicken, turkey, duck, goose, black-bone chicken, quail, pigeon, ox, horse, sheep, dog, ermine, deer, cat, donkey, rabbit,
Fish, shrimp, crab, shellfish, tortoise, snake, the feed applications enteric coating aliphatic acid copper of yellow eel can also obtain preferable growth-promoting effect and good
Good production performance;
In summary, only enteric coating aliphatic acid copper (Cu2+It 5-15ppm) can reach copper sulphate high-copper (Cu2+150-
Effect 250ppm), high-copper can be substituted completely, even if feed stores 3-60 days, because enteric coating has blocked and aliphatic acid
Copper contacts, will not autoxidation become sour, will not also cause feed oxide to go bad, be a kind of reliable and stable feed addictive production
Product, therefore, only water-insoluble enteric-coating material is coated, and has the enteric coating aliphatic acid copper of certain degree of hardness could conduct
Feed addictive, replacement high-copper that can be truly.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of feed addictive is coated aliphatic acid copper, it is characterised in that including core and is coated on the core surfaces
Coating, the core include aliphatic acid copper, and the coating includes water-soluble coating and the intestines for being coated on the core surfaces successively
Molten coating.
2. feed addictive according to claim 1 is coated aliphatic acid copper, it is characterised in that the aliphatic acid copper is selected from first
Sour copper, copper acetate, propionic acid copper, copper butyrate, valeric acid copper, caproic acid copper, enanthic acid copper, cupric octoate, n-nonanoic acid copper, capric acid copper, undecanoic acid copper,
Lauric acid/dodecanoic acid copper, tridecanoic acid copper, tetradecylic acid copper, pentadecanoic acid copper, hexadecylic acid copper, heptadecanoic acid copper, stearic acid copper, nonadecanoic acid copper, 20
Sour copper, heneicosoic acid copper, behenic acid copper, tricosanic acid copper, tetracosanoic acid copper, neocerotic acid copper, cerinic acid copper, 27
Sour copper, octacosanoic acid copper, motanic acid copper, triacontanoic acid copper, copper linoleate, copper oleate, leukotrienes copper, CLA copper, flower
Raw tetraenoic acid copper, eicosapentaenoic acid copper, docosahexaenoic acid copper, erucic acid copper, tangerine acid copper, rape acid copper, 16 monoenoic acids
Copper, positive heptadecenoic acid copper, 18 dienoic acid copper, 18 single diluted acid copper, 18 diluted acid copper, palmitoleic acid copper, 22 carbon
Sour copper, eicosatetraenoic acid copper, clupanodonic acid copper, arachidic acid copper, cis- 6,9,12- bis- ten eight carbon-trienic acid copper and
One or more in cis- 9,12,15- bis- ten eight carbon-trienic acid copper.
3. feed addictive according to claim 1 is coated aliphatic acid copper, it is characterised in that the material of the water-soluble coating
Material is selected from hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, PVP, polyvinyl alcohol, Pu Lu
Blue polysaccharide, chitosan, polyethylene glycol 200, polyethylene glycol 400, Macrogol 600, PVOH 800, PVOH 1000, poly- second two
One or more in alcohol 2000, Macrogol 3000, Macrogol 4000 and polyethylene glycol 5000;
The material of the enteric coating is selected from polyacrylic acid resin, HPMCP, acetic acid hydroxypropyl
Ylmethyl cellulose, succinate ethyl butyrate, Glyceryl tributyrate, shellac, PVAP, cellulose and
Its derivative, cellulose acetate phthalate, 1,2,4- benzenetricarboxylic acid cellulose acetates, 1,2,4- benzenetricarboxylic acid hydroxypropyl first
Base cellulose, acetate succinate cellulose, acetate succinate hydroxypropyl cellulose, methacrylate, methacrylic acid, propylene
It is acid esters, butyl acrylate, acroleic acid resin, ethyl cellulose, triacetin, propionate, polyvinyl proprionate, poly-
Vinyl acetate, poly- vinyl butyrate, carboxylic acid vinyl ester polymer, vinyl acrylate, vinylpyrrolidone and generating vinyl carboxylate
It is a kind of in polymer, vinyl ester polymer, vinyl methacrylate and its polymer and o- benzoic acid ethyl ester of ester
It is or several.
4. feed addictive according to claim 1 is coated aliphatic acid copper, it is characterised in that the coating material with it is described
The mass ratio of core is (0.1~20):100.
5. a kind of preparation method of feed addictive coating aliphatic acid copper, it is characterised in that comprise the following steps:
Coating material is coated in granular core surfaces, obtains feed addictive coating aliphatic acid copper, the core includes fat
Fat acid copper.
6. preparation method according to claim 5, it is characterised in that comprise the following steps:
A dried after) white carbon is mixed with the maltodextrin aqueous solution, obtain the white carbon hard particles containing maltodextrin;
B) by the white carbon hard particles adsorptive liquid aliphatic acid copper containing maltodextrin, core is obtained;
C water-soluble coating material solution) is sprayed in the core surfaces, drying obtains the aliphatic acid of water-soluble coating material coating
Copper;
It is D drying) in the aliphatic acid copper surface spraying or infiltration enteric-coating material solution of the water-soluble coating material coating,
Obtain feed addictive coating aliphatic acid copper.
7. preparation method according to claim 5, it is characterised in that comprise the following steps:
A) water-soluble coating material, water, maltodextrin and solid fatty acid copper are mixed, obtains mixture;
By the mixture successively through granulation, bake, throw circle after, obtain core;
B) in high-pressure agitated vessels, removing air is vacuumized after putting into enteric-coating material, into the high-pressure agitated vessels
Liquid gas is imported, stirring, obtains enteric coating liquefaction gas solution;
C) water-soluble coating material solution is sprayed in the core surfaces, drying obtains the aliphatic acid of water-soluble coating material coating
Copper;
D) aliphatic acid copper by the water-soluble coating material coating is put into vacuum rake dryer, and air is removed in vacuum,
The enteric coating liquefaction gas solution is imported, is stirred, feed addictive coating aliphatic acid is obtained after liquid gas volatilization
Copper;
The step a) and step b) limits without order.
8. preparation method according to claim 5, it is characterised in that the aliphatic acid copper is made as follows
It is standby:
Grease is mixed with alkali metal hydroxide after carrying out saponification, then mixed with copper sulfate solution, reacted, obtained
To aliphatic acid copper.
9. preparation method according to claim 8, it is characterised in that the grease is selected from perilla herb oil, sunflower oil, olive
Oil, corn oil, three-coloured amaranth oil, soya-bean oil, peanut oil, sesame oil, rapeseed oil, cotton benevolence oil, palm oil, lard, butter, chicken fat, coconut
One or more in oil, fish oil and rice bran oil.
10. a kind of feed, it is characterised in that including the feed addictive coating aliphatic acid copper or right described in Claims 1 to 4
It is required that feed addictive coating aliphatic acid copper prepared by the preparation method described in 5~9, with Cu2+Meter, the coating aliphatic acid copper exist
Addition concentration in the feed is 0.1~12500mg/kg.
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CN109511786A (en) * | 2019-01-04 | 2019-03-26 | 重庆威迪特药业有限责任公司 | A kind of feed addictive and preparation method thereof containing zinc oxide |
CN111685239A (en) * | 2020-01-19 | 2020-09-22 | 浙江农林大学 | Copper monolaurate feed additive and preparation method thereof |
CN114099458A (en) * | 2020-08-31 | 2022-03-01 | 河北征宇制药有限公司 | Coated florfenicol particle, preparation method and application thereof |
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