CN103408351B - Polysaccharide composition and preparation method thereof - Google Patents
Polysaccharide composition and preparation method thereof Download PDFInfo
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- CN103408351B CN103408351B CN201310285412.XA CN201310285412A CN103408351B CN 103408351 B CN103408351 B CN 103408351B CN 201310285412 A CN201310285412 A CN 201310285412A CN 103408351 B CN103408351 B CN 103408351B
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Abstract
The invention discloses a polysaccharide composition and a preparation method thereof, wherein the composition mainly comprises the following components in percentage by mass: 0.5-15 parts of sodium selenite; 5-50 parts of xylo-oligosaccharide; 1-30 parts of chitosan; 5-50 parts of trehalose; 2-60 parts of organic acid and 50-300 parts of water; the primary product of the composition is a dark red viscous liquid, the pH value is 4-6, and no precipitate is generated after the composition is diluted by water. The preparation method adopts the composition of the invention in percentage by mass and the following processes: dissolving sodium selenite in water at normal temperature and pressure, dissolving chitosan and organic acid in water, adding sodium selenite water solution into chitosan solution, stirring for 8 hr, and standing for 24 hr to obtain solution A; dissolving xylo-oligosaccharide and trehalose in water to obtain solution B; and then uniformly mixing the solution A and the solution B, and standing for 24 hours to obtain the polysaccharide composition.
Description
Technical field
The present invention relates to agricultural fertilizer technology, be specially a kind of polysaccharide composition and preparation method thereof.Said composition is characterised in that several kinds of mineral elements such as being rich in xylo-oligosaccharide, chitosan, trehalose and nanometer selenium.
Background technology
Promoting the use of of chemical pesticide and chemical fertilizer, has played huge promoter action to agriculture production, especially to aspects such as the prevention and control of plant diseases, pest control of farm crop, raising crop yield per unit.But, a large amount of life-time service of chemical pesticide and inorganic chemical fertilizer, its negative impact is also more and more significant.Cause harmful organism to develop immunity to drugs on the one hand, along with consumption is increasing, formed vicious cycle, caused environmental pollution; On the other hand, excessively use fertilizer and pesticide, Agro-ecology balance is done great damage, make soil deterioration, agricultural byproducts and livestock product pesticide residue severe overweight, nutritive element is unbalance, and interior quality declines, and the mankind healthy brought to serious threat.The mankind need to take in various nutritive elements every day to keep fit and normal physiological function from meals.In human body, the intake of various nutritive elements is not enough, will cause function of human body to decline even ill, supplements corresponding nutritive element and can improve the health level of human body, and then eliminate associated conditions.Therefore, Development of Novel fertilizer, agricultural chemicals, substitute traditional chemical pesticide and chemical fertilizer, enriches crop alimentary element, become the inexorable trend of modern agricultural development.
Selenium is a kind of important trace element of needed by human, and human body lacks selenium can cause many diseases, and wherein cancer, Keshan disease are just relevant with scarce selenium.And China is the country that lacks selenium, more than 70% region area is to belong to the big and medium-sized cities such as scarce selenium, few selenium area, particularly North China, northeast and northwest all to belong to and lack selenium area, does not reach every day everyone more than 40 micrograms standard and mend selenium level in food.Therefore, many benefit selenium products and selenium-enriched fertilizer are constantly released.But, only with regard to current agricultural selenium-enriched fertilizer, be mostly simple with regard to mending selenium, to mend selenium, can not meet disease control, soil remediation and the multiple needs such as degeneration-resistant of crop.
Summary of the invention
For the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is that a kind of polysaccharide composition and preparation method thereof is provided.Said composition is rich in the several kinds of mineral elements such as xylo-oligosaccharide, chitosan, trehalose and nanometer selenium, bestow farm crop, not only can significantly improve the selenium content of crop and fruit thereof, and can prevent and treat the disease that crop is caused by mushroom, improvement soil, promotes growth, improves resistance and the drought-resistant ability of crop, increase output, improve quality; This preparation method adopts normal temperature and pressure to produce, and technique is simple, easy to operate, is applicable to suitability for industrialized production.
The technical scheme that the present invention solves described composition technical problem is, designs a kind of polysaccharide composition, and the massfraction that it is characterized in that said composition forms and is mainly: 0.5～15 part of Sodium Selenite; 5～50 parts of xylo-oligosaccharides; 1～30 part of chitosan; 5～50 parts of trehaloses; 50～300 parts, organic acid 2-60 part and water; Wherein, purity >=95% of xylo-oligosaccharide; Deacetylation >=85% of chitosan; Organic acid is the combination of one or more arbitrary proportions in acetic acid, citric acid or xitix; The first batch of newly-designed products of said composition is scarlet thick liquid, and pH is 4～6, nothing precipitation after dilute with water.
The technical scheme that the present invention solves described preparation method's technical problem is, design a kind of preparation method of polysaccharide composition, this preparation method adopts the massfraction of polysaccharide composition of the present invention to form and following technique: at normal temperatures and pressures, (1), first Sodium Selenite is dissolved in water, just chitosan and organic acid are dissolved in water again, after all dissolving, sodium selenite aqueous solution is added in chitosan and aqueous solutions of organic acids, and constantly stir 8 hours, pH value≤5 that keep solution, standing 24 hours, make A solution; (2), xylo-oligosaccharide is dissolved in water together with trehalose,, after all dissolving, make B solution; (3), A solution is mixed and stirred with B solution, standing 24 hours, make described polysaccharide composition.
Compared with prior art, preparation method's normal temperature and pressure of the present invention is produced, and technique is simple, easy to operate, pollution-free, and less energy-consumption is easy to promote, and is applicable to suitability for industrialized production.Polysaccharide composition result of use of the present invention is obvious, not only when making crop and fruit thereof be rich in organic selenium and other trace elements, realize low toxicity efficient, reduce chemical pesticide consumption, alleviate environmental pressure, and can strengthen anti-adversity and the diseases and insect pests resistance of plant, photosynthesis strengthens, for high crop yield stable yields has been established important foundation, can also improve soil, reduce soil compaction simultaneously.It is easy to use various that the polysaccharide composition of nanometer selenium is rich in the present invention, after dilution, both can be used as foliage-spray, also can root executes to chase after and water; The stoste use of can dressing seed, can sneak into organic base manure and use together, also can adopt to make pulvis after conventional drying and use.
Embodiment
Below in conjunction with embodiment, further narrate the present invention.
The polysaccharide composition (abbreviation composition) of the present invention's design, is characterized in that the massfraction composition of said composition is mainly: 0.5～15 part of Sodium Selenite; 5～50 parts of xylo-oligosaccharides; 1～30 part of chitosan; 5～50 parts of trehaloses; 50～300 parts, organic acid 2-60 part and water.
For further enriching the nutritive element of farm crop, increase kind and the content of crop trace element, improve the quality of crop, the demand that adapts to extraordinary plant husbandry, the further feature of the present composition is: said composition also comprises at least one in the following substance that massfraction forms: 0.5～3 part of 1～20 part of element Ge, 1～20 part of zinc element, 1～5 part of manganese element, 1～5 part of boron or molybdenum element.
The massfraction preferred group of the present composition becomes: 1～15 part of Sodium Selenite; 5～50 parts of xylo-oligosaccharides; 1～30 part of chitosan; 5～50 parts of trehaloses; Organic acid 2-60 part; 1～20 part of germanium dioxide; 1～20 part of zinc acetate; 1～10 part of manganous acetate, 1～10 part of boric acid; 50～200 parts, 1～5 part of ammonium molybdate and water.
Purity >=95% of the described xylo-oligosaccharide of the present composition;
Deacetylation >=85% of chitosan;
Organic acid can be the combination of one or more arbitrary proportions of acetic acid, citric acid or xitix;
Element Ge derives from germanium dioxide or organic germanium;
Zinc element derives from zinc acetate or chelated zinc;
Manganese element derives from manganous acetate or Chelated Manganese;
Boron derives from boric acid;
Molybdenum element derives from ammonium molybdate.
This composition is red thick liquid, and pH is 4～6, nothing precipitation after dilute with water.Bestow after farm crop, not only can improve the selenium and other trace elements content of crop, but also can prevent and treat Micobial Disease, improve photosynthesis, improve degeneration-resistant, the drought-resistant ability of plant; Bestow in soil and can improve soil, increase fertility of land; Can be mixed with acid agrichemical while spraying for the page, and can improve drug effect.
Xylo-oligosaccharide claims again wood oligose, be by 2～7 wood sugars with β-Isosorbide-5-Nitrae glycosidic link oligose that is formed by connecting, its main component is xylo-bioses and xylotriose.Typical xylo-oligosaccharide raw materials for production have hardwood, corn cob, straw, bagasse, rice hulls, beer saccharification grain and wheat bran.As new resource food, after people is edible, can optionally promote the proliferation activity of intestinal bifidobacteria and milk-acid bacteria, suppress harmful bacteria growth, improve enteric microorganism environmental functional, its bifidobacterium factor functional is 10-20 times of other polymerization carbohydrate.Agriculturally, xylo-oligosaccharide can excite plant to produce the disease resistance materials such as phenols, plant protecting chemical, improves the activity of relevant disease-resistant enzyme; As biological pesticide, xylo-oligosaccharide good water solubility, toxicological harmless, free from environmental pollution, life-time service do not cause that plant produces the advantages such as special disease resistance, using dosage be low; As its crop of nutritive substance cultivation agriculture, it can regulate and control crop growth, improve the output of fruit, simultaneously by affect the absorption of soil microorganisms flora raising farm crop to elements such as nitrogen potassium.
Trehalose is the nonreducing sugar consisting of with 1,1-glycosidic link two glucose molecules, is a kind of safe and reliable natural glucide, and its most peculiar function is its biological characteristics.In many organisms, trehalose not only exists with free sugar form, but also as the integral part of various glycolipids.Recent research shows, many species, under poor environment (as arid, high temperature, freezing etc.) condition, can be resisted external influence by trehalose synthesis in control agent.Trehalose is the material that a kind of stress situation that environmental change is formed has high resistance, is also a kind of typical stress metabolite in organism.Under various severe environment, also still can bring into play good provide protection to biomacromolecules such as the microbial film of species, protein and nucleic acid.Up-to-date research shows, ectogenic trehalose has the good nonspecific provide protection to organism and biomacromolecule equally.Due to the profound meaning of trehalose to life protection, therefore there is people trehalose to be called to " sugar of life ".The biological characteristics of this excellence of trehalose, bestows after farm crop the present composition just, makes farm crop have the excellent anti-adversity such as drought-resistant, low temperature resistant, high temperature resistant.
Chitosan, is the product of the de-N-ethanoyl of chitin, and chemical name is Chitosan (1-4)-2-amino-B-D glucose, is the crust that is mainly derived from Crustacean.The premium propertiess such as the biological functionality of this natural polymer of chitosan and consistency, blood compatibility, security, microbic resolvability are by all trades and professions extensive concern, in the applied research of the numerous areas such as medicine, food, chemical industry, makeup, water treatment, METAL EXTRACTION and recovery, biochemistry and biomedical engineering, have obtained major progress.Chitosan, in agricultural production application, can not only make crop growing state good, robust plant, and photosynthesis strengthens, and aspect resistance, disease and insect resistance, is also showing positive effect, has and stablizes and significant the effect of increasing income.In addition, chitosan also improves and has larger meaning the improvement of crop quality and food value and economic worth.On the other hand, chitosan can be used as plant-growth regulator, promotes crop yield to improve, and also can be used as soil improvement agent and for gathering in the crops the fresh-keeping etc. of rear agricultural-food, and especially it is suppressing becoming gradually aspect Plant diseases the focus of people's research.Large quantity research shows, chitosan can inducing plant produce the resistance of wide spectrum, strengthen plant self-defence ability, suppress the growth of various plants pathogenic micro-organism, and it is nontoxic and can be microbiological deterioration, to environment, can not produce pollution.This likely plays an important role it in agriculture production as a kind of novel environment friendly agricultural.The more important thing is, chitosan is the high molecular polymer with positive charge, there is stronger reducing power, also this reducing power of chitosan just, the plasma selenium that makes Sodium Selenite in this composition after chitosan absorption, parcel, chelating and progressively reduction generates simple substance nanometer selenium or/and selenium chitosan, and selenium element can fully be disperseed in composition.Chitosan also has good film forming properties, can make the beneficiating ingredient of the present composition be adsorbed on preferably blade face, branches and tendrils, cane, the seed-coat of plant, absorbs, and have slow releasing function for plant.
Selenium is a kind of trace element of needed by human, participates in body metabolism endoperoxide and iodine, regulates the level of iodine and the level of free radical in organism, can enhancing body diseases prevention, resistance against diseases.Though mend selenium, can effectively prevent and treat various diseases, between the nutrition dosage of inorganic selenium and toxicity dose, scope is narrow, to such an extent as to people are studying the efficient selenium product of low toxicity always for many years.Up-to-date research shows, organoselenium absorbs the aspects such as efficiency, hypotoxicity and is all better than inorganic selenium at height, and red nanometer selenium is more better than organoselenium in many aspects, demonstrates the efficient feature of low toxicity.Research shows, per os medium lethal dose (LD_50) organoselenium of small white mouse, selenium chitosan, nanometer selenium are improved to 2.3 times, 6.3 times and 7.5 times than inorganic selenium compound respectively.In agricultural application field, nanometer selenium, selenium chitosan have efficient absorption utility and good biological organic transformation performance equally, plant will change in the organoselenium form bodies such as selenium-L-glutamic acid, selenocystein, selenium-methyl selenium-halfcystine after absorbing nano-selenium element, become the plant of being rich in organoselenium; With respect to traditional use inorganic selenium mode, nanometer selenium both can greatly reduce the consumption of selenium element, reduced costs, and can alleviate the harm that inorganic selenium element causes environment such as surface water, underground water and soils again; For remaining in crop and fruit surface thereof and the inner not yet inorganic selenium of organic transformation, the hypotoxicity of nanometer selenium, selenium chitosan has more very important safe meaning.
Element Ge, although be at present not yet clearly the necessary trace element of human body, a kind of human body beneficial element really, many glossy ganodermas with special healthy functions, ginseng etc., its special healthy functions it is believed that relevant with the content of its germanium.Research shows, the almost non-toxic property of organic germanium, have and bring out self Interferon, rabbit, increase nk cytoactive, activation phagocytic cell, promotes body to produce antitumor, anti-ageing biological action, as a kind of important nutritive element, former health ministry has been listed organic germanium in the new resource food list of formal production, and has been widely used in the various fields such as beverage, food and health care.Therefore, the extraordinary fertilizer that use contains element Ge, make farm crop and fruit thereof contain element Ge and by the biological process of plant, realize the organic transformation of element Ge, and then for people provide new wholesome food, will being one of effective selection of new special agricultural.
Zinc is composition or the coenzyme of the large enzyme of human body six, 200 kinds of metalloenzyme, and general metabolism is played to wide application, is described as " flowers of life " by people.Meanwhile, zinc element is also necessity trace element of plant-growth, therefore, uses the fertilizer that contains zinc element, improves the zinc content of farm crop and fruit thereof, not only can Promoting plant growth, and people's health is had important practical significance.
What is more important, aspect biological activity, selenium and germanium have synergy, and selenium element and zinc element also have synergy.The present composition organically combines red nano selenium, organic germanium and organic zinc, make farm crop and fruit thereof can increase the content of selenium, germanium, zinc simultaneously, after making people edible, can supplement these three kinds of trace elements simultaneously, and can effectively bring into play three's synergistic effect, for the mankind's health contributes.
The present invention has designed the preparation method of described composition simultaneously, this preparation method adopts the massfraction of nanometer selenium polysaccharide composition of the present invention to form and following technique: at normal temperatures and pressures, (1), first Sodium Selenite is dissolved in water, just chitosan and organic acid are dissolved in water again, after all dissolving, sodium selenite aqueous solution is added in chitosan solution, and constantly stir 8 hours, keep pH value≤5 of solution, then standing 24 hours, make A solution; (2), xylo-oligosaccharide is dissolved in water together with trehalose,, after all dissolving, make B solution; (3), A solution, B solution are mixed, and stir, standing 24 hours, make described polysaccharide composition.For accelerating the nanometer process of selenium element, in B liquid, can add part xitix.
The present composition increases or adjusts while having new component, and its preparation method is done corresponding adjustment.
The present composition is according to design, also can comprise at least one in the following substance that massfraction forms: 1～5 part of 1～20 part of element Ge, zinc element 1～20,1～10 part of manganese element, 1～10 part of boron or molybdenum element.In preparation B solution process, described substance is dissolved in water together with trehalose with xylo-oligosaccharide.But when substance element Ge is germanium dioxide, must first germanium dioxide be dissolved in potassium hydroxide solution, then use after the pH value of this solution being adjusted to 5.5 left and right with organic acid.
The present composition is when design and contain described substance simultaneously: when 0.5～3 part of 1～20 part of element Ge, zinc element 1～20,1～5 part of manganese element, 1～5 part of boron or molybdenum element, its preparation method as previously mentioned, is dissolved in water together with trehalose with xylo-oligosaccharide when preparation B solution.
Compared with prior art, preparation method of the present invention is that normal temperature and pressure is produced, and technique is simple, easy to operate, pollution-free, and less energy-consumption is easy to promote, and is applicable to suitability for industrialized production.
The present composition is scarlet thick liquid, and pH value is 5～5.5.This is a kind of basic product, according to different purposes, utilizes this basic product, can prepare different secondary products.
The present invention does not address part and is applicable to prior art.
Provide specific embodiments of the invention below.These embodiment, only for further concrete narration the present invention, do not limit the protection domain of the application's claim.
Embodiment 1
Design a kind of polysaccharide composition, its material by following massfraction forms: 0.5 part of Sodium Selenite; 2 parts of chitosans; 5 parts of xylo-oligosaccharides; 5 parts of trehaloses; 1 part of organic germanium (Ge-132); 1 part of zinc acetate; 1 part of manganous acetate; 1 part of boric acid; 0.5 part of ammonium molybdate; 4 parts of citric acids; 50 parts, 1 part, xitix and water.Its preparation method is:
1, under normal temperature and pressure, first Sodium Selenite is added to 2 parts of dissolvings of water, more just chitosan and citric acid add 30 parts of dissolvings of water, after all dissolving, sodium selenite aqueous solution is added in chitosan solution, and constantly stir 8 hours, and keep pH value≤5 of solution, then standing 24 hours, make A solution;
2, xylo-oligosaccharide, trehalose, organic germanium, manganous acetate, zinc acetate, boric acid, ammonium molybdate are added together with xitix to 18 parts of water dissolution, after all dissolving, make B solution;
3, A solution is mixed with B solution, stir, standing 24 hours, make described polysaccharide composition.
Embodiment 2
Design a kind of polysaccharide composition, its material by following massfraction forms: 5 parts of Sodium Selenites; 10 parts of chitosans; 30 parts of xylo-oligosaccharides; 30 parts of trehaloses; 15 parts of germanium dioxides; 28 parts, potassium hydroxide; 10 parts of zinc acetates; 5 parts of manganous acetates; 5 parts of boric acid; 35 parts of citric acids; 200 parts, 5 parts, xitix and water.Its preparation method is:
1, under normal temperature and pressure, first Sodium Selenite is added to 10 parts of dissolvings of water, more just chitosan and 20 parts of citric acids add 90 parts of dissolvings of water, after all dissolving, sodium selenite aqueous solution is added to chitosan solution, and constantly stir 8 hours, and keep pH value≤5 of solution, then standing 24 hours, make A solution;
2, potassium hydroxide is dissolved in to 100 parts of water, then add germanium dioxide to be stirred to after whole dissolvings, add again xylo-oligosaccharide, trehalose, zinc acetate, manganous acetate, boric acid after adding 15 parts of citric acids, 5 parts of dissolution of ascorbic acid, after all dissolving, make B solution;
3, A liquid, B liquid mixed and stirred, standing 24 hours, making described polysaccharide composition.
Embodiment 3
Design a kind of polysaccharide composition, its material by following massfraction forms: 10 parts of Sodium Selenites; 20 parts of chitosans; 15 parts of xylo-oligosaccharides; 15 parts of trehaloses; 20 parts of organic germaniums; 20 parts of zinc acetates; 35 parts of acetic acid; 10 parts, xitix; 200 parts, water.Its preparation method is:
1, under normal temperature and pressure, first Sodium Selenite is added to 30 parts of dissolvings of water, more just chitosan and acetic acid add 100 parts of dissolvings of water, after all dissolving, sodium selenite aqueous solution added to chitosan solution and constantly stir 8 hours, and pH value≤5 that keep solution, then standing 24 hours, make A solution;
2, xylo-oligosaccharide, trehalose, organic germanium, zinc acetate are added together with xitix to 70 parts of water dissolution, after all dissolving, make B solution;
3, A liquid, B liquid mixed and stirred, standing 24 hours, making described polysaccharide composition.
Embodiment 4
Design a kind of polysaccharide composition, its material by following massfraction forms: 15 parts of Sodium Selenites; 30 parts of chitosans; 50 parts of xylo-oligosaccharides; 50 parts of trehaloses; 50 parts of acetic acid; 10 parts, xitix; 300 parts, water.Its preparation method is:
1, under normal temperature and pressure, first Sodium Selenite is added to 40 parts of dissolvings of water, more just chitosan and acetic acid add 200 parts of dissolvings of water, after all dissolving, sodium selenite aqueous solution added to chitosan solution and constantly stir 8 hours, and pH value≤5 that keep solution, then standing 24 hours, make A solution;
2, xylo-oligosaccharide, trehalose are added together with xitix to 60 parts of water dissolution, after all dissolving, make B solution;
3, A liquid, B liquid mixed and stirred, standing 24 hours, making described polysaccharide composition.
Embodiment 5
Design a kind of polysaccharide composition, its material by following massfraction forms: 1 part of Sodium Selenite; 5 parts of chitosans; 25 parts of xylo-oligosaccharides; 25 parts of trehaloses; 2 parts of organic germaniums (Ge-132); 2 parts of zinc acetates; 1 part of manganous acetate; 1 part of boric acid; 1 part of ammonium molybdate; 10 parts of citric acids; 100 parts, water.Its preparation method is:
1, under normal temperature and pressure, first Sodium Selenite is added to 5 parts of dissolvings of water, more just chitosan and citric acid add 50 parts of dissolvings of water, after all dissolving, sodium selenite aqueous solution added to chitosan solution and constantly stir 8 hours, and pH value≤5 that keep solution, then standing 24 hours, make A solution;
2, xylo-oligosaccharide, trehalose, organic germanium, manganous acetate, zinc acetate, boric acid are added together with ammonium molybdate to 45 parts of water dissolution, after all dissolving, make B solution;
3, A liquid, B liquid mixed and stirred, standing 24 hours, making described polysaccharide composition.
Claims (1)
1. a polysaccharide composition, is characterized in that being comprised of the material of following massfraction: 1 part of Sodium Selenite; 5 parts of chitosans; 25 parts of xylo-oligosaccharides; 25 parts of trehaloses; 2 parts of Ge-132; 2 parts of zinc acetates; 1 part of manganous acetate; 1 part of boric acid; 1 part of ammonium molybdate; 10 parts of citric acids; 100 parts, water;
Its preparation method is:
1) under normal temperature and pressure, first Sodium Selenite is added to 5 parts of dissolvings of water, more just chitosan and citric acid add 50 parts of dissolvings of water, after all dissolving, sodium selenite aqueous solution added to chitosan solution and constantly stir 8 hours, and pH value≤5 that keep solution, then standing 24 hours, make A solution;
2), xylo-oligosaccharide, trehalose, Ge-132, manganous acetate, zinc acetate, boric acid are added to 45 parts of water dissolution together with ammonium molybdate,, after all dissolving, make B solution;
3) A liquid, B liquid mixed and stirred, standing 24 hours, making described polysaccharide composition.
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| CN104609947A (en) * | 2015-01-04 | 2015-05-13 | 咸阳三精科工贸有限公司 | Organic water-soluble fertilizer containing organic acid and chitosan and preparation method thereof |
| CN105294251B (en) * | 2015-10-26 | 2019-01-11 | 潘灿平 | Chitosan functionalized nano selenium compound bacterium enzyme system and its preparation method and application |
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| CN109279964A (en) * | 2018-11-09 | 2019-01-29 | 安徽帝元生物科技有限公司 | A kind of zinc fertilizer and the preparation method and application thereof |
| CN109504722A (en) * | 2018-11-29 | 2019-03-22 | 烟台固特丽生物科技股份有限公司 | A kind of method that amylorrhexis prepares chitosan oligosaccharide chelated selenium |
| CN112209762A (en) * | 2019-07-12 | 2021-01-12 | 山东金必来生物科技有限公司 | Macroelement water-soluble fertilizer containing microbial metabolite |
| CN111470897A (en) * | 2020-03-13 | 2020-07-31 | 江苏徐淮地区淮阴农业科学研究所 | Selenium-rich high-calcium rice foliar fertilizer and preparation method and application thereof |
| CN112778048A (en) * | 2021-01-22 | 2021-05-11 | 北部湾大学 | Liquid selenium fertilizer rich in marine active ingredients and preparation method thereof |
| CN114230686B (en) * | 2021-12-22 | 2022-05-31 | 众合发(北京)生物科技发展有限公司 | Preparation process, device and application of selenized chitosan oligosaccharide |
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