CN106801069A - Nano selenium and preparation method thereof - Google Patents

Nano selenium and preparation method thereof Download PDF

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Publication number
CN106801069A
CN106801069A CN201710046335.0A CN201710046335A CN106801069A CN 106801069 A CN106801069 A CN 106801069A CN 201710046335 A CN201710046335 A CN 201710046335A CN 106801069 A CN106801069 A CN 106801069A
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preparation
nanometer selenium
culture medium
selenium
molasses
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Inventor
吴国杰
舒绪刚
占峰
付志欢
周新华
林羽
梁月娟
邱桂雄
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GUANGZHOU TANKE BIO-TECHNOLOGY CO LTD
Zhongkai University of Agriculture and Engineering
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GUANGZHOU TANKE BIO-TECHNOLOGY CO LTD
Zhongkai University of Agriculture and Engineering
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P3/00Preparation of elements or inorganic compounds except carbon dioxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00Selenium; Tellurium; Compounds thereof
    • C01B19/02Elemental selenium or tellurium
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Microbiology (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Biotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)

Abstract

The invention discloses a preparation method of nano-selenium, which comprises the following steps: (1) adding sodium selenite and nutritive salt into the molasses hydrolysate, and sterilizing to obtain a molasses culture medium, wherein the concentration of the sodium selenite in the molasses culture medium is 0.1-1.5 mg/mL; (2) centrifuging the beer fermentation waste liquid, and repeatedly cleaning the precipitate obtained by centrifuging to obtain yeast paste; (3) mixing the yeast paste obtained in the step (2) and the molasses culture medium obtained in the step (1) according to the ratio of 1: 3-1: mixing the materials according to a mass-volume ratio of 2g/mL, and fermenting for more than 2 hours at a temperature of 25-32 ℃ to obtain a fermentation liquid; (4) and (4) carrying out centrifugal separation on the fermentation liquor obtained in the step (3) to obtain yeast, and drying and crushing the yeast to obtain the nano-selenium. The preparation method has the advantages of low cost, short period and high preparation efficiency, and the prepared nano-selenium still can show active red nano-selenium at high temperature and has good stability.

Description

A kind of nanometer selenium and preparation method thereof
Technical field
The present invention relates to selenium preparing technical field, especially a kind of nanometer selenium and preparation method thereof.
Background technology
In brewing industry, 10000t beer is often produced, it will 100t fermented waste fluids are produced, wherein rich in a large amount of eggs Bletilla vitamin, directly treatment will cause the substantial amounts of wasting of resources and environmental pollution, and developing one kind can reuse beer The method of fermented waste fluid, makes it turn waste into wealth and is significant.
Selenium is a kind of important addition element in feed addictive, with the different physiological roles such as anti-oxidant, antitumor.Selenium exists Often with+6 ,+4 in nature, based on 0, -2 four kinds of valence states, at present, and in China's feedstuff industry, because sodium selenite toxicity is high, peace Complete smaller using scope, most area has been prohibited from using;And the yeast selenium based on the seleno-amino acids of-divalent, due to battalion Value height, bioactivity is supported to be widely used well, but its cycle is long in process of production, and waste liquid is more, instrument and equipment high cost, greatly Part small enterprise is difficult to maintain, and production is difficult.
The content of the invention
Based on this, a kind of system of nanometer selenium is provided it is an object of the invention to overcome above-mentioned the deficiencies in the prior art part Preparation Method, the preparation method has low cost, and cycle is short, unit Se content is high, and waste water is few.
To achieve the above object, the technical solution used in the present invention is:A kind of preparation method of nanometer selenium, including it is as follows Step:
(1) sodium selenite, nutritive salt are added in molasses hydrolyzate, sterilizing obtains molasses culture medium, wherein, molasses training The concentration for supporting sodium selenite in base is 0.1~1.5mg/mL;
(2) beer fermentation waste liquid is centrifuged, yeast paste is obtained;
(3) step (2) gained yeast paste and step (1) gained molasses culture medium are pressed 1:3~1:The quality volume of 2g/mL Than being mixed, fermented more than 2 hours at being 25~32 DEG C in temperature, obtain zymotic fluid;
(4) step (3) gained zymotic fluid is centrifuged, obtains yeast thalline, yeast thalline is dried, powder It is broken, obtain final product the nanometer selenium.
The preparation method of nanometer selenium of the present invention, is fermented using the concentration of beer fermentation waste liquid and prepares nanometer selenium, low cost, Preparation efficiency is high, with larger economic benefit and environmental benefit.
Preferably, in step (1) the gained molasses culture medium, pol is 3~7 ° of Be '.
Sugar is to provide yeast growth metabolism one of main energy sources material, in the presence of enzyme, be oxidized discharge electronics and Hydrogen ion, plays an important role in being nanometer selenium in reduction sodium selenite.Inventor attempts finding that sugared concentration is got over by a large amount of Height, the Se content of conversion is higher, but unit yeast amount is gradually reduced, when sugar selects above-mentioned content, it is ensured that unit ferment The unification of mother's amount and the Se content of conversion.
Preferably, in step (1) the gained molasses culture medium, pol is 5 ° of Be ', and the concentration of sodium selenite is 1mg/ mL。
When pol is above-mentioned content, the unification of the Se content of unit yeast amount and conversion is may further ensure that, make list Position yeast amount and the Se content of conversion all reach highest.
The addition concentration of sodium selenite is the main factor for influenceing selenium conversion ratio, and addition concentration is higher, by sorption enhanced Nanometer selenium it is more, but yeast cells adaptability and reducing substances therein are limited, and too high selenium concentration can cause yeast thin Born of the same parents' self-dissolving is dead, and causes Se content to decline.By a large amount of trials, finding the sodium selenite of above-mentioned concentration can ensure selenium to inventor Content is higher.When sodium selenite is above-mentioned concentration, the nanometer Se content highest of conversion can reach 11470ppm.
Preferably, in step (1) the gained molasses culture medium, nutritive salt includes ammonium sulfate, vitamin liquid, described Mass percent of the ammonium sulfate in the molasses culture medium is 0.5~2.5%, and the vitamin liquid is trained in the molasses It is 0.1~1% to support the mass percent in base.Nitrogen source during the nutritive salt afterfermentation required for Yeast Growth, The nutriments such as vitamin, comprising the vitamin required for various Yeast Growths in the vitamin liquid.
Preferably, in the step (3), fermentation time is 3~12 hours.
Inventor has found in first 3 hours that unit Se content steeply rises, 3~12 in the research to fermentation time Hour plateau is raised slowly to, this is probably there is substantial amounts of a certain reducing substances in itself in yeast cells, rapid Poisonous sodium selenite is reduced to elemental selenium absorption in the cell, it is thin by yeast then due to the shortage of reducing substances Slowly be enriched to sodium selenite in cell by the growth metabolism effect of born of the same parents.
Preferably, in the step (3), the mass volume ratio of yeast paste and molasses culture medium is 1:2.5g/mL.
Yeast paste addition is more, and the culture medium cost of unit consumption is lower, but yeast paste addition is too high, can make ferment Female anoxic in the medium, causes anaerobic fermentation, and then produces alcohol, influences yield.
Preferably, in the step (3), fermented under conditions of being 4~8 in pH value.
Inventor is attempted by a large amount of, and after finding to be processed under different pH, not substantially, yeast cells is wrapped up for selenium concentration change Effect is good, the stabilization in as feed addictive, however, it was found that declining afterwards as the increase Se content of pH first increases, pH is 4~8 When Se content entire change less, required during real attenuation low, be easy to production.
Preferably, it is to be fermented 3 hours under conditions of 7, temperature is 30 DEG C in pH value in the step (3).
Temperature is one of the key factor for influenceing all kinds of enzymatic activitys in yeast, enzyme serve in growth metabolism it is key, The activities present of enzyme is different under different temperatures, and inventor is had found with the rising of temperature, the ferment after 30 DEG C by a large amount of trials Female yield dramatic decrease, and Se content reaches peak at 30 DEG C, therefore, from 30 DEG C as fermentation temperature;Consider Fermentation costs, therefore select 3 hours most preferably;Simultaneously when pH is 7, Se content highest, therefore selection pH is 7.
It is worth noting that, the supernatant that centrifugation goes out in the step (4), can reclaim, continue to be applied to molasses In the preparation of culture medium, with further reduces cost, raw material availability is improved.
Meanwhile, the present invention also provides the nanometer selenium that a kind of above-mentioned preparation method is prepared.The nanometer selenium is by yeast The active nano selenium of cell encapsulation, remains to the active red nano selenium of performance, good stability at high temperature.
Preferably, the nano granules of selenium size is 30~40nm.
Relative to prior art, beneficial effects of the present invention are:
Preparation method of the present invention prepares nanometer selenium using the concentration fermentation of beer fermentation waste liquid, and fermentation period is extremely short, and one Determine that this link that sterilizes can be saved in degree, equipment requirement and cost input are considerably reduced, while resource reutilization, is Environment alleviates pressure, turn waste into wealth, low cost, preparation efficiency it is high, more than sodium selenite Transformation efficiency is up to 90 %, highest unit Se content 11470ppm, with larger economic benefit and environmental benefit.
The preparation-obtained nanometer selenium of the present invention remains to the active red nano selenium of performance, stability at high temperature It is good, it is suitable to industrial production with application.
Brief description of the drawings
Fig. 1 is nanometer selenium real scene shooting figure of the present invention;
Fig. 2 is the broken nanometer selenium scanning electron microscope (SEM) photograph for extracting and obtaining;
Fig. 3 is yeast cells transmission electron microscope picture;
Fig. 4 is the influence figure that sugared concentration is converted to nanometer selenium;
Fig. 5 is the influence figure that sodium selenite addition is converted to nanometer selenium;
Fig. 6 is the influence figure that fermentation time is converted to nanometer selenium.
Specific embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with the drawings and specific embodiments pair The present invention is described further.
Embodiment 1
A kind of embodiment of the preparation method of nanometer selenium of the present invention, the preparation method of nanometer selenium described in the present embodiment, Comprise the following steps:
(1) sodium selenite, ammonium sulfate, vitamin are added in the molasses hydrolyzate that molasses mass percent is 10% Liquid, 121 DEG C of high-temperature sterilizations, obtains molasses culture medium;In the culture medium, pol is 5 ° of Be ', and the concentration of sodium selenite is 1mg/ ML, the mass percent of ammonium sulfate is 2.5%, and the mass percent of vitamin liquid is 0.5%;
(2) beer fermentation waste liquid is separated under low speed centrifuge, is precipitated yeast paste;
(3) step (2) gained yeast paste and step (1) gained molasses culture medium are pressed (1:2.5) the quality volume of g/mL Than being mixed, using 1mol/L salt acid for adjusting pH to 7,30 DEG C, continuing fermentation 3h are gradually heating to;Obtain zymotic fluid;
(4) thalline is obtained with 3000r/min centrifugations 5min, repeated washing washes away surface selenium salt for 3 times, is dried under high temperature, powder It is broken, obtain final product the nanometer selenium.
The nanometer selenium that the preparation method as described in the present embodiment is prepared, is the active nano selenium wrapped up by yeast cells, Granular size is 30nm.
Embodiment 2
A kind of embodiment of the preparation method of nanometer selenium of the present invention, the preparation method of nanometer selenium described in the present embodiment, Comprise the following steps:
(1) sodium selenite, ammonium sulfate, vitamin are added in the molasses hydrolyzate that molasses mass percent is 10% Liquid, 121 DEG C of high-temperature sterilizations, obtains molasses culture medium;In the culture medium, pol is 3 ° of Be ', and the concentration of sodium selenite is 0.1mg/mL, the mass percent of ammonium sulfate is 2%, and the mass percent of vitamin liquid is 0.1%;
(2) beer fermentation waste liquid is separated under low speed centrifuge, is precipitated yeast paste;
(3) step (2) gained yeast paste and step (1) gained molasses culture medium are pressed (1:2) mass volume ratio of g/mL Mixed, using 1mol/L salt acid for adjusting pH to 4, be gradually heating to 25 DEG C, continuing fermentation 2h;Obtain zymotic fluid;
(4) thalline is obtained with 3000r/min centrifugations 5min, repeated washing washes away surface selenium salt for 3 times, is dried under high temperature, powder It is broken, obtain final product the nanometer selenium.
The nanometer selenium that the preparation method as described in the present embodiment is prepared, is the active nano selenium wrapped up by yeast cells, Granular size is 40nm.
Embodiment 3
A kind of embodiment of the preparation method of nanometer selenium of the present invention, the preparation method of nanometer selenium described in the present embodiment, Comprise the following steps:
(1) sodium selenite, ammonium sulfate, vitamin are added in the molasses hydrolyzate that molasses mass percent is 10% Liquid, 121 DEG C of high-temperature sterilizations, obtains molasses culture medium;In the culture medium, pol is 7 ° of Be ', and the concentration of sodium selenite is 1.5mg/mL, the mass percent of ammonium sulfate is 0.5%, and the mass percent of vitamin liquid is 1%;
(2) beer fermentation waste liquid is separated under low speed centrifuge, is precipitated yeast paste;
(3) step (2) gained yeast paste and step (1) gained molasses culture medium are pressed (1:0.5) the quality volume of g/mL Than being mixed, using 1mol/L salt acid for adjusting pH to 8,32 DEG C, continuing fermentation 4h are gradually heating to;Obtain zymotic fluid;
(4) thalline is obtained with 3000r/min centrifugations 5min, repeated washing washes away surface selenium salt for 3 times, is dried under high temperature, powder It is broken, obtain final product the nanometer selenium.
The nanometer selenium that the preparation method as described in the present embodiment is prepared, is the active nano selenium wrapped up by yeast cells, Granular size is 35nm.
Embodiment 4
The present embodiment is using transmission electron microscope and ESEM to structure, the shape of the preparation-obtained nanometer selenium of embodiment 1~3 State and particle diameter are further observed, characterized, analyzed.
There are substantial amounts of compacted grains by around yeast cells in sign observation Fig. 3 and in kytoplasm, its yeast cells is big Small about 3~4um, wherein granular size is about 30~40nm particles, and obtaining nanometer selenium by broken extraction precipitates by scanning Electron microscopic observation, as shown in Fig. 2 its particle is about 40nm or so particles, it is consistent with the judgement in Fig. 3, dried by product Crushing obtain product be placed in air place January after (design sketch such as Fig. 1) be cerise, be the feature face of red active nano selenium Color, thus judges that the nanometer selenium prepared by this kind of method is active nano selenium.
Embodiment 5
Selection of the present embodiment to pol in nanometer selenium preparation method of the present invention, selenium addition, fermentation time is carried out Research, method of the research using unitary variant is controlled, specific data is as shown in figures 4-6.
As seen from Figure 4, pol is higher, and the Se content of conversion is higher, but yeast amount is with the increase of pol, presents first The trend subtracted after increasing, when pol is 5 ° of Be ', unit yeast amount is maximum.
As shown in Figure 5, with the increase of concentration of sodium selenite, the Se content of conversion is presented the trend for first increasing and subtracting afterwards, yeast Amount slowly declines with the increase of concentration of sodium selenite, and when the addition of sodium selenite is 1mg/mL, the nanometer selenium of conversion contains Amount highest, can reach 11470ppm, and it is unobvious that yeast amount declines again.
It will be appreciated from fig. 6 that inventor is in the research to fermentation time, find in first 3 hours, unit Se content is drastically gone up Rise, plateau was raised slowly at 3~12 hours, this is probably there is substantial amounts of a certain reproducibility thing in itself in yeast cells Matter, is rapidly being reduced to elemental selenium absorption in the cell by poisonous sodium selenite, then due to the shortage of reducing substances, leads to Slowly be enriched to sodium selenite in cell by the growth metabolism effect for crossing yeast cells.Meanwhile, the amount of dry ferment is with fermentation The increase of time has a slow downward trend, therefore fermentation time selects 3~12 hours, and now unit Se content is basically reached most Big value, and amount of yeast decline is unobvious, while the fermentation time that Fig. 6 also further illustrates the method for the invention is short Advantage.
It is last to should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected The limitation of scope is protected, although being explained in detail to the present invention with reference to preferred embodiment, one of ordinary skill in the art should Understand, technical scheme can be modified or equivalent, without deviating from the essence of technical solution of the present invention And scope.

Claims (10)

1. a kind of preparation method of nanometer selenium, it is characterised in that comprise the following steps:
(1) sodium selenite, nutritive salt are added in molasses hydrolyzate, sterilizing obtains molasses culture medium, wherein, molasses culture medium The concentration of middle sodium selenite is 0.1~1.5mg/mL;
(2) beer fermentation waste liquid is centrifuged, yeast paste is obtained;
(3) step (2) gained yeast paste and step (1) gained molasses culture medium are pressed 1:3~1:The mass volume ratio of 2g/mL enters Row mixing, ferments more than 2 hours at being 25~32 DEG C in temperature, obtains zymotic fluid;
(4) step (3) gained zymotic fluid is centrifuged, obtains yeast thalline, yeast thalline is dried, is crushed, Obtain final product the nanometer selenium.
2. the preparation method of nanometer selenium as claimed in claim 1, it is characterised in that in step (1) the gained molasses culture medium, Pol is 3~7 ° of Be '.
3. the preparation method of nanometer selenium as claimed in claim 2, it is characterised in that in step (1) the gained molasses culture medium, Pol is 5 ° of Be ', and the concentration of sodium selenite is 1mg/mL.
4. as described in any one of claims 1 to 3 nanometer selenium preparation method, it is characterised in that the nutritive salt include sulfuric acid Ammonium, vitamin liquid, mass percent of the ammonium sulfate in the molasses culture medium are 0.5~2.5%, the dimension life Mass percent of the plain nutrient solution in the molasses culture medium is 0.1~1%.
5. the preparation method of nanometer selenium as claimed in claim 1, it is characterised in that in the step (3), fermentation time is 3~ 12 hours.
6. the preparation method of nanometer selenium as claimed in claim 1, it is characterised in that in the step (3), yeast paste and molasses are trained The mass volume ratio for supporting base is 1:2.5g/mL.
7. as described in claim 1 or 5 or 6 nanometer selenium preparation method, it is characterised in that in the step (3), be in pH value Fermented under conditions of 4~8.
8. the preparation method of nanometer selenium as claimed in claim 7, it is characterised in that in the step (3), is 7, temperature in pH value To be fermented 3 hours under conditions of 30 DEG C.
9. the nanometer selenium that a kind of preparation method of the nanometer selenium as described in any one of claim 1~8 is prepared.
10. nanometer selenium as claimed in claim 9, it is characterised in that the particle diameter of the nanometer selenium is 30~40nm.
CN201710046335.0A 2017-01-22 2017-01-22 Nano selenium and preparation method thereof Pending CN106801069A (en)

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CN107758628A (en) * 2017-08-31 2018-03-06 华南农业大学 A kind of nanometer selenium for preparing the method for nanometer selenium using camellia plant water extract and being prepared
CN108522841A (en) * 2018-03-19 2018-09-14 牡丹江市艾利维亚生物科技有限公司 A kind of animals and plants nanometer selenium peptide nutrient solution and preparation method thereof
CN113396965A (en) * 2021-06-17 2021-09-17 浙江工商大学 Nutritional nano biological composite preservative, preparation method thereof and application of preservative to preservation of Taihu whitebait

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CN103667086A (en) * 2013-12-04 2014-03-26 北京大北农科技集团股份有限公司 Selenium-enriched yeast with high biomass, and additive and premix containing the same

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107758628A (en) * 2017-08-31 2018-03-06 华南农业大学 A kind of nanometer selenium for preparing the method for nanometer selenium using camellia plant water extract and being prepared
CN107758628B (en) * 2017-08-31 2020-10-09 华南农业大学 Method for preparing nano-selenium by using camellia plant water extract and nano-selenium prepared by method
CN108522841A (en) * 2018-03-19 2018-09-14 牡丹江市艾利维亚生物科技有限公司 A kind of animals and plants nanometer selenium peptide nutrient solution and preparation method thereof
CN113396965A (en) * 2021-06-17 2021-09-17 浙江工商大学 Nutritional nano biological composite preservative, preparation method thereof and application of preservative to preservation of Taihu whitebait

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