CN1255041C - Method for preparing feedstuff additive of chitosan - Google Patents

Method for preparing feedstuff additive of chitosan Download PDF

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Publication number
CN1255041C
CN1255041C CNB2004100360268A CN200410036026A CN1255041C CN 1255041 C CN1255041 C CN 1255041C CN B2004100360268 A CNB2004100360268 A CN B2004100360268A CN 200410036026 A CN200410036026 A CN 200410036026A CN 1255041 C CN1255041 C CN 1255041C
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China
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crust amine
molecular weight
oligosaccharide
crust
polysaccharide
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CN1600146A (en
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李向群
刘有利
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Abstract

The present invention relates to a method for preparing a chitinamine feed additive, which belongs to the technical field of feed additives. The chitinamine having the molecular weight larger than 30000 obtained by a chemical degradation method, a physical degradation method and a biological degradation method is continuously degraded by a biological catalysis method or a chemical degradation method into oligosaccharide, oligosaccharide and polysaccharide, and then the oligosaccharide, the oligosaccharide and the polysaccharide are compounded to prepare the chitinamine feed additive having the molecular weight of 200 to 30000, or the oligosaccharide, the oligosaccharide and the polysaccharide prepared by a chemical degradation method, a physical degradation method and a biological degradation method are directly compounded to prepare the chitinamine feed additive having the molecular weight of 200 to 30000. The method of the present invention is easy to prepare the chitinamine feed additive having the compound properties of the oligosaccharide, the oligosaccharide and the polysaccharide in a large scale, poisonous and harmful components are not added in the compound preparation process, and the present invention is suitable for preparing safe fowl and poultry products by green safe feed.

Description

A kind of preparation method of crust amine feed addictive
(1) technical field
The present invention relates to a kind of preparation method of crust amine feed addictive, belong to field of feed additive technology.
(2) background technology
Along with the raising day by day of China joined WTO and living standards of the people, the safety problem of the security of feed and the livestock products that cause thus is subjected to people's attention day by day.The theory of feed safety instant food safety is just accepted by increasing people.Because the mankind do not notice that the lesson that security brought of feed is very deep, economical and social everyway are caused very serious consequence in the actual life.Crust amine feed addictive, belong to efficient, multifunctional feed additive of new generation, it is compared with normal diet additive commonly used, possess many superiority, the existing good nutritional properties of this product can improve rate of body weight gain and the output capacity of animal, and the immunologic function of raising animal and the effect of the general level of the health are arranged again, it is few that animal is fallen ill in feeding process, can reduce a large amount of epidemic prevention expenses; It is compared with antibiotic, significant advantage be do not develop immunity to drugs, drug residue free in the animal products, fundamentally solved the people and foreign trade department misgivings, and possessed the medicament residue of reduction and animal wastes deodorization animal products.The farming and animal husbandry scientific and technological achievement is used on the true border of this achievement, although application is animal husbandry, but final service object is still human, improve the human beings'health life-span upward thereby be converted into, the incidence of disease to various diseases such as early prevention cancer, cardiovascular and cerebrovasculars has obvious effects, has increased the practical rank value of this achievement.
The crust amine feed addictive of different molecular weight section antibacterial disease-resistant, strengthen aspect effect differences such as immunity of organisms, aid digestion, growth promotion, reduction cholesterol and adsorbent drug be residual.Utilizing specified molecular weight section crust amine development multifunctional feed additive is one of current problem that needs to be resolved hurrily.
At present, the preparation method that crust amine feed addictive is commonly used both at home and abroad has:
1, chemical degradation method
With the shrimp of drying, crab shell fragment with 3% salt acid soak 30h about, to not emitting till the bubble, water washes repeatedly to neutrality then, boil 1h with about 10% sodium hydroxide solution again, and the water flushing is to neutrality.Soak 1h with rare liquor potassic permanganate, 70 ℃ of-80 ℃ of water-bath 30min of oxalic acid solution are washed to neutrality, and white chitin finished product is made in 105 ℃ of oven dry, pulverizing.
Chitin is placed on is incubated 1h (100 ℃-110 ℃) in the saturated sodium hydroxide solution, then washing.Handle in aqueous slkali, washing 2-3 time repeatedly, promptly gets the higher crust amine feed addictive of deacetylation behind the whole acetates except that the dereaction generation again.
2, mechanical degradation method
The crab shell is with 10% salt acid soak 3-4 days, and washing was boiled 1-2 hour with 10% NaOH again.Liquor potassic permanganate decolouring is handled, drying, pulverize chitin.Handled 10 minutes in the ultrasonic wave, spend the night at room temperature condition.Washing again gets crust amine feed addictive.
3, biological degradation method
Shrimp shell, crab shell be with 10% salt acid soak 3-4 days, and washing was boiled 1-2 hour with 10% NaOH again.Drying is pulverized chitin, adds enzyme then and degrades.Filter, drying gets crust amine feed addictive.
The weak point of the crust amine feed addictive of above-mentioned chemical degradation method, mechanical degradation method and biological degradation method production is that the range of molecular weight distributions of products obtained therefrom crust amine is narrower, be confined in certain scope, be generally 200-2000,2000-6000 and 6000-30000, the narrower crust amine of range of molecular weight distributions when using as feed addictive, the effect instability.
(3) summary of the invention
At the deficiency of crust amine feed addictive in the prior art, technical assignment of the present invention provides a kind of preparation method of crust amine feed addictive of molecular weight distribution broad.The crust amine that this method is produced with prior art is raw material, forms the crust amine feed addictive of molecular weight distribution broad, stable effect by compound being prepared into by the different molecular weight section.
The preparation method of crust amine feed addictive of the present invention, be with oligosaccharide molecular amount 200-2000, oligosaccharides molecule amount 2000-6000 and polysaccharide molecular weight 6000-30000, respectively account for by weight percentage 0.1~95% composite 0~60 ℃ of temperature, 200~30000 crust amine feed agent of forming by the different molecular weight section.
Above-mentioned composite product can further transfer pH value to 9-10 with NaOH solution, place after 20-30 hour, the filtered and recycled sediment, sediment is extremely neutral with the clear water flushing, then in 50-70 ℃ of dryer, dry, 200~30000 crust amine feed agent of forming by the different molecular weight section.
Above-mentioned oligosaccharide molecular amount 200-2000, oligosaccharides molecule amount 2000-6000 and polysaccharide molecular weight 6000-30000 are respectively the products of chemical degradation method in the prior art, mechanical degradation method and biological degradation method.
Above-mentioned oligosaccharide molecular amount 200-2000, oligosaccharides molecule amount 2000-6000 and polysaccharide molecular weight 6000-30000, be to be raw material greater than 30000 crust amine with mean molecule quantity, the employing biological catalysis is degraded and is got, concrete grammar is as follows: with Streptomyces SP bacterial classification is biocatalyst, the batch charging coefficient of crust amine raw material (raw material volume/reactor volume) is 0.4-0.6, and Streptomyces SP bacterial classification concentration is 2.0 * 10 6~2.0 * 10 7Individual/ml, pH value 6-6.5, sealing was cultivated 3~8 days, and was oligosaccharide molecular amount 200-1500, oligosaccharides molecule amount 2000-6000 and polysaccharide molecular weight 3000-30000 with the crust amine degradation for 25 ℃-28 ℃.
Used Streptomyces SP bacterial classification CICC numbering 11010, Chinese bacterium is called streptomyces, purposes: malaga sugar isomerase.
Above-mentioned oligosaccharide molecular amount 2000-1500, oligosaccharides molecule amount 2000-6000 and polysaccharide molecular weight 6000-30000, be to be raw material greater than 30000 crust amine with mean molecule quantity, adopt chemical degradation method that the crust amine degradation is got, concrete grammar is: the hydrochloric acid solution that adds weight percent concentration 10% in crust amine raw material, the weight ratio of crust amine raw material and 10% (WT) hydrochloric acid solution is 1: 20~500, sealing, under 70 ℃-75 ℃ condition, reacted 2~5 hours, with the crust amine degradation is oligosaccharide molecular amount 200-2000, oligosaccharides molecule amount 2000-6000 and polysaccharide molecular weight 6000-30000.
Above-mentioned mean molecule quantity is the crust amine product with prior art for preparing greater than 30000 crust amine.
The preparation method of crust amine feed addictive of the present invention, the molecular weight that chemical degradation method, mechanical degradation method, biological degradation method are obtained is greater than 30000 crust amine, adopt biological catalysis or chemical degradation method to continue degraded, make it become oligosaccharides (molecular weight 200~2000); Compound sugar (molecular weight 2000-6000); Polysaccharide (molecular weight 6000-30000), then that oligosaccharides, compound sugar and polysaccharide is compound, it is become have the crust amine feed addictive that molecular weight has 200-30000.Also oligosaccharides, compound sugar, the polysaccharide of chemical degradation method, mechanical degradation method, biological degradation method production directly can be combined into the crust amine feed addictive that the molecule amount is 200-30000.
Method of the present invention is easy to the crust amine feed addictive that large-scale production has oligosaccharides, compound sugar and polysaccharide recombination property.Produce in the recombination process and do not add any poisonous, harmful components, be applicable to green safety production of fodder security animal products.
(4) specific embodiment
Embodiment 1:
1, degraded
With mean molecule quantity greater than 30000 crust amine and Streptomyces SP bacterial classification concentration 2.0 * 10 6The biocatalyst of individual/ml places reactor, pH value 6-6.5, batch charging coefficient 0.4, sealing.25 ℃-28 ℃ of cultivation temperature were cultivated 3 days, respectively took out 1/3rd compost respectively at the 3rd day, the 4th day, the 5th day, and they are respectively oligosaccharide molecular amount 200-1500, oligosaccharides molecule amount 2000-6000 and polysaccharide molecular weight 6000-30000.
2, composite
With 33.3%, 33.3%, 33.4% mixing by weight percentage of three times composts, 30 ℃ of temperature.Transfer pH value to 10 with 40% (WT) NaOH solution, place after 24 hours, the filtered and recycled sediment, with sediment repeatedly with the clear water flushing to neutrality, then in 60 ℃ of dryers, dry, promptly get 200~30000 crust amine feed agent of forming by the different molecular weight section.
Effect is as follows:
Feed 1000 of fryer with the crust amine feed addictive that embodiment 1 method is produced, the per kilogram feed adds crust amine feed agent 1 gram, 0.5 gram, 0.1 gram, comparing monthly weightening finish with control group (control group does not add crust amine feed addictive, and other are identical) increases more than 10%.
Embodiment 2:
1, degraded
Mean molecule quantity is put into reactor greater than 30000 crust amine, add 10% hydrochloric acid solution simultaneously, weight ratio 1: 100, sealing.React under 70 ℃-75 ℃ condition, respectively take out 1/3 reactant respectively at 2 hours, 2.5 hours, 3 hours, they are respectively oligosaccharide molecular amount 200-1500, oligosaccharides molecule amount 2000-6000 and polysaccharide molecular weight 6000-30000.
2, composite
25 ℃ of mixing of reactant with top three taking-ups, transfer pH value to 10 with 40% (WT) NaOH solution, place after 24 hours, filter, reclaim sediment, with sediment repeatedly with clear water flushing to neutral, then 55 ℃ of oven dry, promptly get molecular weight and be the crust amine feed addictive of 200~30000 different molecular weight section.
Use the crust amine feed addictive of embodiment 2 preparations to feed laying hen, fryer, the result shows that to chick thymus gland, spleen, the growth of the bursa of farbricius all has certain facilitation, and prompting crust amine feed addictive has the effect that strengthens immunity.
Concrete experimental technique: young 100 of 1 age in days SPF is divided into two groups at random, 50 every group, during 7 ages in days, adds 2% crust amine feed addictive in one group of feed, another group basal diet of feeding.Respectively when 14,21,28,35 ages in days every group cut open and kill 10, cut open the blood sampling of weighing before killing, separation of serum is got thymus gland, spleen, bursa of farbricius immune organ and is weighed, and it is fixing to put into 2.5% neutral formalin fixer together with liver, duodenum, jejunum, ileum, cecal tonsil.
Measure thymus gland, spleen, the bursa of farbricius index of above-mentioned sample by light microscopic method, electron microscopy, experimental result is listed among the table 1-3.
Table 1 crust amine is to the influence of SPF chick thymus index
Age in days The control group thymus index The test group thymus index
14 21 28 4.529±0.8161 5.102±0.5991 4.731±0.8041 4.787±0.5787 5.407±0.8692 5.120±0.6763
The result shows (table 1): 14 ages in days, 21 ages in days, 28 ages in days, crust amine test group thymus index mean value all is higher than control group at three different days sections.
Table 2 crust amine is to the influence of SPF chick index and spleen index
Age in days The control group index and spleen index The test group index and spleen index
14 21 28 1.266±0.2638 1.506±0.3762 1.902±0.097 1.479±0.1187 1.594±0.3441 2.182±0.235
The result shows (table 2): from numerical value, test group index and spleen index mean value all is higher than control group at three different days sections.Test group is compared with the control group index and spleen index during 14 ages in days, and difference is remarkable (P>0.05) not; But significant difference (P<0.05) when 21 ages in days, 28 ages in days.
Table 3 crust amine is to the influence of SPF chick bursa of farbricius index
Age in days Blank Test group
14 21 28 5.356±0.1925 6.293±0.713 5.674±0.9407 5.282±1.264 8.078±1.013 7.592±1.515
The result shows (table 3): test group and control group bursa of farbricius index differential not significantly (P>0.05) during 14 ages in days; Test group and control group difference all significantly (P<0.05) when 21 ages in days, 28 ages in days.
Embodiment 3:
1, with mean molecule quantity greater than 30000 crust amine and Streptomyces SP bacterial classification concentration 2.0 * 10 7The biocatalyst of individual/ml places reactor, pH value 6-6.5, batch charging coefficient 0.6, sealing.25 ℃-28 ℃ of cultivation temperature were cultivated 4 days, respectively took out 1/3rd compost respectively at the 4th day, the 5th day, the 6th day, and they are respectively oligosaccharide molecular amount 200-2000, oligosaccharides molecule amount 2000-6000 and polysaccharide molecular weight 6000-30000.
2, three times compost 5%, 47.5%, 47.5% is mixed down at 20 ℃ by weight percentage, transfer pH value to 10 with 40% (WT) NaOH solution, place after 24 hours, the filtered and recycled sediment, sediment is extremely neutral with the clear water flushing repeatedly, then in 65 ℃ of dryers, dry, promptly get 200~30000 crust amine feed agent of forming by the different molecular weight section.
Embodiment 4:
Directly be re-dubbed the crust amine feed addictive that molecular weight is 200-30000 with under 40 ℃ of oligosaccharides, compound sugar, the polysaccharide temperature of prior art chemical degradation method, mechanical degradation method, biological degradation method production, the percentage by weight of oligosaccharides, compound sugar and polysaccharide is 2%, 40% and 48%.
Effect is as follows:
Feed laying hen, meat chick with the above-mentioned crust amine of 1000ppm feed addictive, the result shows that the content of sulfadimethoxine contrasts few 2.75 times in the egg: the content of sulfadimethoxine is than few 2.14 times of contrast in the chicken; Contrast is few more than 1.43 times for chromium content in the chick meat.Prompting crust amine feed addictive has the residual function of the medicine of reduction.
Experimental technique is as follows:
1, gets 192 of high-yield egg chickens, be divided into two groups at random, 96 every group.One group at basal diet interpolation 1000ppm crust amine and 500ppm sulfadimethoxine; Two groups are added the 500ppm sulfadimethoxine at basal diet, and temperature, humidity, illumination and hygiene index meet the raising requirement of chicken in test chicken free choice feeding, the drinking-water, hen house.Experimental period is 4 days, after 4 days, chooses 10 pieces of eggs at random for every group, carries out the residual mensuration of sulfadimethoxine medicine, the results are shown in Table 4.
Table 4 crust amine is to the influence of sulfadimethoxine content in the egg
Group The content of sulfadimethoxine (ppm) in the egg
The test group control group 0.0836±0.0377 0.23±0.0640
2,50 meat chicks of 1 age in days are divided into four groups at random, after normally feeding 5 days, change feed, add the sulfadimethoxine of 1000ppm (5g/10 jin feed) and the crust amine of 1000ppm in one group of feed; Add the sulfadimethoxine of 1000ppm in two groups of feeds: add the potassium bichromate of 10ppm and the crust amine of 1000ppm in three groups of feeds; Add the potassium bichromate of 10ppm in four groups of feeds, sampling and measuring after feeding 5 days.The results are shown in Table 5-6.
Table 5 crust amine is to the influence of sulfadimethoxine content in the chicken
Group The content of sulfadimethoxine (ppm) in the fryer
The test group control group 1.693±1.049 3.624±1.7137
The result shows (table 5): the sulfadimethoxine content in the test group chicken lacks than control group, and the sulfadimethoxine content in the control group is more than two times of test group, compares significant difference (P<0.05) with control group.
Table 6 crust amine is to the influence of chromium residues in the chicken
Group The content of chromium (ppm) in the meat chick
The test group control group 1.392±1.029 2.476±1.317
The result shows (table 6): the chromium content in the test group chicken lacks than control group, and the chromium content mean value in the control group is nearly two times of test group, compares significant difference (P<0.05) with control group.

Claims (4)

1, a kind of preparation method of crust amine feed addictive, it is characterized in that oligosaccharide molecular amount 200-2000, oligosaccharides molecule amount 2000-6000 and polysaccharide molecular weight 6000-30000, respectively account for by weight percentage 0.1~95% 0~60 ℃ composite, 200~30000 crust amine feed agent of forming by the different molecular weight section.
2, the preparation method of crust amine feed addictive as claimed in claim 1, it is characterized in that describedly further transferring pH value to 9-10 after composite with NaOH solution, place after 20-30 hour, the filtered and recycled sediment, sediment is extremely neutral with the clear water flushing, then in 50-70 ℃ of dryer, dry, 200~30000 crust amine feed agent of forming by the different molecular weight section.
3, the preparation method of crust amine feed addictive as claimed in claim 1, it is characterized in that described oligosaccharide molecular amount 200-2000, oligosaccharides molecule amount 2000-6000 and polysaccharide molecular weight 6000-30000, be to be raw material greater than 30000 crust amine with mean molecule quantity, the employing biological catalysis is degraded and is got, concrete grammar is: with Streptomyces SP bacterial classification is biocatalyst, the batch charging coefficient of crust amine raw material is 0.4-0.6, and Streptomyces SP bacterial classification concentration is 2.0 * 10 6~2.0 * 10 7Individual/ml, pH value 6-6.5, sealing was cultivated 3~8 days, the crust amine degradation is got for 25 ℃-28 ℃.
4, the preparation method of crust amine feed addictive as claimed in claim 1, it is characterized in that described oligosaccharide molecular amount 2000-1500, oligosaccharides molecule amount 2000-6000 and polysaccharide molecular weight 6000-30000, be to be raw material greater than 30000 crust amine with mean molecule quantity, adopt chemical degradation method that the crust amine degradation is got, concrete grammar is: the hydrochloric acid solution that adds weight percent concentration 10% in crust amine raw material, the weight ratio of crust amine raw material and 10%WT hydrochloric acid solution is 1: 20~500, sealing, under 70 ℃-75 ℃ condition, reacted 2~5 hours, the crust amine degradation is got.
CNB2004100360268A 2004-10-27 2004-10-27 Method for preparing feedstuff additive of chitosan Expired - Fee Related CN1255041C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102835610B (en) * 2012-09-27 2013-08-28 淮阴工学院 Feed additive for broiler chickens and preparation method thereof
AU2015287703A1 (en) 2014-07-09 2017-02-16 Cadena Bio, Inc. Oligosaccharide compositions and methods for producing thereof
EP4205553A1 (en) 2015-01-26 2023-07-05 DSM Nutritional Products, LLC Oligosaccharide compositions for use animal feed and methods of producing thereof
CA2983236A1 (en) 2015-04-23 2016-10-27 Kaleido Biosciences, Inc. Glycan therapeutics and methods of treatment
CN107927422A (en) * 2017-12-04 2018-04-20 李六秀 Artificial breeding feed of oyster and preparation method thereof

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