CN105668527A - Method for preparing red selenium - Google Patents
Method for preparing red selenium Download PDFInfo
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- CN105668527A CN105668527A CN201610206279.8A CN201610206279A CN105668527A CN 105668527 A CN105668527 A CN 105668527A CN 201610206279 A CN201610206279 A CN 201610206279A CN 105668527 A CN105668527 A CN 105668527A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract
The invention discloses a method for preparing red selenium. The method for preparing the red selenium comprises the following steps: adding a reducing agent into a solution containing tetravalent selenium or/and hexavalent selenium, controlling temperature of a reaction process to be 0-60 DEG C, controlling reaction rate to enable reaction to be finished within 1-2 hours, carrying out solid-liquid separation to obtain elemental selenium, and drying, so that the red selenium is obtained. The method disclosed by the invention has the advantages that aims such as atmospheric pressure reduction and high reduction yield are realized, required reaction conditions are simple, reaction process is short, and required reagents and equipment are respectively common wet metallurgy industrial equipment, and industrial production application can be easily realized on the whole; fewer reagents are used in the invention, production cost is low, and product stability is good; namely the red selenium with a good research prospect in the biological medicine field is obtained by carrying out one-step reduction on industrial selenium-containing wastewater in a simple and low-cost way.
Description
Technical field
The invention belongs to field of hydrometallurgy, it relates to a kind of method preparing red selenium.
Background technology
Selenium is a kind of dissipated metal element, it has unique photoelectric characteristic, piezoelectric effect and thermoelectric effect, it is widely used in electronics chemical industry, photoelectric material, the fields such as metallurgical industry, its special biochemical action, make selenium also receive people at biological and field of medicaments to pay close attention to greatly, owing to selenium is the important element of composition multiple amino acids, bioprotein synthesis and organism daily activity in play an important role, existing medical research shows: selenium has multiple physiological function in human body, as participated in the composition of Selenoperoxidase, lipid in Cell protection film is from the destruction of peroxidation, thus protect cardiovascular and cardiac muscle health, in addition, promptly detoxify after the harmful elements such as selenium is still effective at present heavy metal element lead, toxic element arsenic are poisoning medicament.
The selenium that current medicine industry uses can be divided into two kinds: inorganic selenium simple substance and organic selenium compounds. Organic selenium compounds has bioavailability height, bioresorbable height, biological activity in vivo advantages of higher, but it has to produce and requires with deposit strict, absorbs the shortcomings such as operating speed is slow in medical procedure; It is fast that inorganic selenium has absorption rate, the advantages such as instant effect, but its problem such as biological activity and bio-toxicity perplexs inorganic selenium use clinically always. Now there are some researches show, the selenium simple substance bio-toxicity of tripartite and monoclinic form is little, but its bioresorbable and biological activity are all very low, it is difficult to be used to pharmaceutical industries, and without the red selenium simple substance bio-toxicity of brilliant type far below compounds such as selenates, and bioresorbable and biological activity are far above the selenium simple substance of tripartite or monoclinic form, there is good biological medicine research prospect.
The preparation of current reactive red selenium mainly concentrates on the hot method of solvent/water, reductive agent many employings glucose, xitix, saccharan, bioprotein or bacterium etc., these method shortcomings are that reaction process all needs the temperature of more than 100 DEG C and corresponding reaction pressure, reductive agent owing to adopting is the reductive agent of week reduction, its long reaction time (8-90 hour), reaction yield low (single preparation amount tens milligrams to and gram between), reaction process operational condition harsh; As adopted protein or bacterium etc. for method of reducing, in addition it is also necessary to special gnotobasis is as operational condition. More than producing the method having reactive red selenium, after large-scale application, production cost is all very surprising, is not suitable for application.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, it is provided that a kind of speed of response is fast, reaction yield big, be suitable for the reactive red selenium production technique of large-scale commercial production.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is:
Prepare a method for red selenium, containing tetravalence selenium or/and the solution of hexavalent selenium adds reductive agent, the temperature of control reaction process is 0-60 DEG C, and control speed of reaction makes reaction complete in 1-2h, obtains selenium simple substance after solid-liquid separation, namely obtains red selenium after dry.
Above-mentioned method, it is preferable that, the reductive agent of standard oxidationreduction potential lower than selenium simple substance standard oxidationreduction potential elected as by described reductive agent.
Above-mentioned method, it is preferable that, described reductive agent be selected from hydrazine hydrate, sulfurous gas, sulphite, hydroborates, glucose, xitix, concentrated hydrochloric acid any one.
Above-mentioned method, preferably, described containing tetravalence selenium or/and the solution of hexavalent selenium be metallurgical process processes selenic acid mud, containing selenium waste residue, containing the Se solution obtained after selenium flue dust, in chemical process manually by acid or alkaline solution will selenium simple substance dissolve aftertreatment after the Se solution for preparing. Above-mentioned method, it is preferable that, described tetravalence selenium is selenous acid or selenite.
Above-mentioned method, it is preferable that, described hexavalent selenium is selenic acid or selenate.
Above-mentioned method, it is preferable that, in reaction process, the control method behaviour work of speed of reaction is dripped and is added or peristaltic pump drips and adds; In reaction process, the control method of temperature is water jacket loop temperature-control, water-bath temperature control or negative pressure temperature control.
Above-mentioned method, it is preferable that, the temperature of described drying is not higher than 80 DEG C.
The present invention by after carrying out big quantity research and experimental verification many times to selenium reduction process thermodynamics and kinetics, under finding low temperature (temperature is less than 60 DEG C) condition, the selenium (tetravalence or sexavalence) of high-valence state can be reduced agent and directly be reduced to red selenium simple substance, the thermodynamic stability height of red selenium simple substance under this temperature condition, black granules of selenium can not be converted into, after temperature of reaction is higher than 60 DEG C, the red selenium that reduction produces can be changed into the grey selenium simple substance of crystal habit gradually. And by control reduction reaction speed, reaction was completed in 1-2 hour, the red selenium crystal grain of generation is impelled to grow, suppress nucleation excessive velocities to avoid red selenium product specific surface area excessive, reduce it be heated or under oxidizing condition, be changed into the possibility of black selenium and selenium oxide, and then improve red selenium product rate.
Compared with prior art, it is an advantage of the current invention that:
(1) present invention achieves normal pressure reduction, the reduction objects such as output is big, required reaction conditions is simple, reaction flow process reagent short, required and equipment are common hydrometallurgy industrial equipments, and entirety is very easy to realize suitability for industrialized production application.
(2) reagent used of the present invention is less, and production cost is low, and product stability is good.
(3) method of the present invention adopts the mode of simple low cost to obtain having at biomedicine field the red selenium of good research prospect from industrial containing a step reduction selenium waste water.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction detection figure of the embodiment of the present invention 1 reduzate.
Fig. 2 is the scanning electronic microscope detection figure of the embodiment of the present invention 1 reduzate.
Embodiment
Unless otherwise defined, the implication that all technical terms and the those skilled in the art hereinafter used understand usually is identical. Technical term used herein is the object in order to describe specific embodiment, is not be intended to limit the scope of the invention.
Apart from special instruction, all ingredients used in the present invention, raw material are can commodity commercially or can by the obtained product of known method.
For the ease of understanding the present invention, hereafter in conjunction with preferred embodiment, the present invention will be done more comprehensively, describe meticulously, but protection scope of the present invention will be not limited to following specific embodiment.
Embodiment 1:
A method for the red selenium of preparation of the present invention, comprises following concrete steps:
By Sodium Selenite (Na2SeO3) dissolve with ultrapure water, selenium content in solution is made to be 10g/L, then get 500mL sodium selenite solution and put into four-hole bottle, adopt solution temperature in ice-water bath control reaction process to be 0 DEG C, lead to into technical grade sulfur dioxide gas (gas flow rate is 1.5L/min) simultaneously, react and filter after 1 hour, detection filtrate remains selenium content, by filter residue drying 20 hours at 30 DEG C, namely obtain red selenium product, it is 99.68% by calculating selenium reduction ratio. The X-ray diffraction detection of reduzate selenium is schemed as shown in Figure 1, scanning electronic microscope detection is schemed as shown in Figure 2, and it is the red selenium without sizing that the XRD figure of Fig. 1 demonstrates product, does not have tripartite or the selenium simple substance of other crystalline substance types completely, product thing mutually equal in product. It is that spherical particle reunion is formed that the Electronic Speculum figure of Fig. 2 demonstrates product, has the characteristics such as specific surface area is big, product particle surface groove isoreactivity contact is many.
Embodiment 2:
A method for the red selenium of preparation of the present invention, comprises following concrete steps:
By Sodium Selenite (Na2SeO3) dissolve with ultrapure water, selenium content in solution is made to be 10g/L, then get 500mL sodium selenite solution and put into four-hole bottle, solution temperature in water-bath control reaction process is adopted to be 40 DEG C, lead to into technical grade sulfur dioxide gas (gas flow rate is 2L/min) simultaneously, reacting and filter after 1 hour, in 30 DEG C of dryings, namely filter residue is obtained red selenium product for 20 hours, selenium reduction ratio is 99.83%.
Embodiment 3:
A method for the red selenium of preparation of the present invention, comprises following concrete steps:
By sodium selenate (Na2SeO4) dissolve with ultrapure water, selenium content in solution is made to be 10g/L, getting 100mL sodium selenate solution adds in four-hole bottle, adopting solution temperature in water-bath control reaction process to be 60 DEG C, drip and add concentrated hydrochloric acid 50mL, the control reaction times is 2 hours, filter, filter residue is drying 10 hours at 50 DEG C, obtain the red selenium product of biological activity, and selenium reduction ratio is 99.79%.
Embodiment 4:
A method for the red selenium of preparation of the present invention, comprises following concrete steps:
By Sodium Selenite (Na2SeO3) dissolve with ultrapure water, selenium content in solution is made to be 15g/L, add a certain amount of sodium hydroxide, make the initial pH of sodium selenite solution be 10, get 100mL and put into four-hole bottle, then adopt peristaltic pump to drip and add analysis pure water conjunction hydrazine, adopting water-bath Systematical control temperature of reaction system to be 20 DEG C, react after 2 hours, filtration, filter residue be drying 8 hours at 60 DEG C, namely obtaining red selenium, selenium reduction ratio is 99.23%.
Embodiment 5:
A method for the red selenium of preparation of the present invention, comprises following concrete steps:
(adopt oxidation acid leaching technical finesse containing selenium coal fly ash to metallurgical process process containing the solution obtained after selenium flue dust, containing plasma selenium concentration in leach liquor is 28g/L, in leach liquor, hydrogen ion concentration is 3mol/L, the solution obtained after the impurity removal process such as peroxidation sulphur removal, calcium precipitation) in artificial dripping add S-WAT, control temperature of reaction is 0 DEG C, reacts and filters after 2 hours, and filter residue was in 40 DEG C of dryings 20 hours, products therefrom is red selenium simple substance, and selenium reduction ratio is 98.33%.
Embodiment 6:
A method for the red selenium of preparation of the present invention, comprises following concrete steps:
Selenium tellurium mixing waste (is adopted leaching with sodium hydroxide by the solution getting 100mL process selenium tellurium mixing waste acquisition, the mode of calcium precipitation is utilized to remove arsonium ion, solution is regulated to be the tellurium in neutral postprecipitation solution, again by acidify solution, solution now contains the plasma selenium of 2.1g/L) put into four-hole bottle, then peristaltic pump drips and adds analytical pure glucose, water-bath Systematical control temperature of reaction system is adopted to be 50 DEG C, react and filter after 2 hours, filter residue is drying 20 hours at 30 DEG C, and selenium reduction ratio reaches 98.71%.
Embodiment 7:
A method for the red selenium of preparation of the present invention, comprises following concrete steps:
(selenic acid mud adopts pressure oxidation to leach containing the selenium aqueous solution to get 200mL, what kerosin desulfurization obtained after processing contains the selenium aqueous solution) add S-WAT 30g, control temperature of reaction is 25 DEG C, react and filter after 1 hour, by filter residue drying 10 hours at 50 DEG C, reach 99.79% through calculating selenium reduction ratio.
To sum up, present invention achieves from the red selenium obtaining having at biomedicine field good research prospect containing the reduction of normal pressure the selenium aqueous solution, reduction output is big, and product stability is good; Required reaction conditions is simple, reaction flow process reagent short, required and equipment are common hydrometallurgy industrial equipments, and entirety is very easy to realize suitability for industrialized production application.
Claims (8)
1. prepare the method for red selenium for one kind, it is characterised in that, containing tetravalence selenium or/and hexavalent selenium solution in add reductive agent, the temperature of control reaction process is 0-60 DEG C, control speed of reaction makes reaction complete in 1-2h, obtains selenium simple substance after solid-liquid separation, namely obtains red selenium after dry.
2. the method for claim 1, it is characterised in that, the reductive agent of standard oxidationreduction potential lower than selenium simple substance standard oxidationreduction potential elected as by described reductive agent.
3. method as claimed in claim 2, it is characterised in that, described reductive agent be selected from hydrazine hydrate, sulfurous gas, sulphite, hydroborates, xitix, concentrated hydrochloric acid and glucose any one.
4. the method for claim 1, it is characterized in that, described containing tetravalence selenium or/and the solution of hexavalent selenium be metallurgical process processes selenic acid mud, containing selenium waste residue, containing the Se solution manually prepared after selenium compound is dissolved aftertreatment by acid, alkali in the Se solution obtained after selenium flue dust or chemical process.
5. the method for claim 1, it is characterised in that, described tetravalence selenium is selenous acid or selenite.
6. the method for claim 1, it is characterised in that, described hexavalent selenium is selenic acid or selenate.
7. the method for claim 1, it is characterised in that, in reaction process, the control method behaviour work of speed of reaction is dripped and is added or peristaltic pump drips and adds.
8. method as described in item as arbitrary in claim 1-7, it is characterised in that, the temperature of described drying is not higher than 80 DEG C.
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| CN201610206279.8A CN105668527A (en) | 2016-04-05 | 2016-04-05 | Method for preparing red selenium |
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| CN201610206279.8A CN105668527A (en) | 2016-04-05 | 2016-04-05 | Method for preparing red selenium |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107352514A (en) * | 2017-08-25 | 2017-11-17 | 云南核度生物产业发展有限公司 | A kind of preparation method of high-purity nm selenium |
| CN114618415A (en) * | 2022-01-27 | 2022-06-14 | 昆明理工大学 | Preparation method of hexagonal selenium crystal/amorphous selenium simple substance |
Citations (5)
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| JPS54120226A (en) * | 1978-03-11 | 1979-09-18 | Furukawa Electric Co Ltd:The | Recovering method for copper and selenium from copper electrolysis anode slime |
| CN1184776A (en) * | 1997-05-06 | 1998-06-17 | 合肥经济技术学院 | Method for preparing active and elementary selenium |
| CN101759159A (en) * | 2009-12-24 | 2010-06-30 | 暨南大学 | Method for manufacturing nano-selenium in liquid phase and obtained nano-selenium thereof |
| CN102363522A (en) * | 2011-11-21 | 2012-02-29 | 郴州雄风稀贵金属材料股份有限公司 | Technology for extracting selenium from low-grade selenium-containing material |
| CN104525224A (en) * | 2014-12-31 | 2015-04-22 | 中国地质大学（武汉） | Preparation method for single crystal selenium nanorod visible light catalytic material and use thereof |
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2016
- 2016-04-05 CN CN201610206279.8A patent/CN105668527A/en active Pending
Patent Citations (5)
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| JPS54120226A (en) * | 1978-03-11 | 1979-09-18 | Furukawa Electric Co Ltd:The | Recovering method for copper and selenium from copper electrolysis anode slime |
| CN1184776A (en) * | 1997-05-06 | 1998-06-17 | 合肥经济技术学院 | Method for preparing active and elementary selenium |
| CN101759159A (en) * | 2009-12-24 | 2010-06-30 | 暨南大学 | Method for manufacturing nano-selenium in liquid phase and obtained nano-selenium thereof |
| CN102363522A (en) * | 2011-11-21 | 2012-02-29 | 郴州雄风稀贵金属材料股份有限公司 | Technology for extracting selenium from low-grade selenium-containing material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107352514A (en) * | 2017-08-25 | 2017-11-17 | 云南核度生物产业发展有限公司 | A kind of preparation method of high-purity nm selenium |
| CN114618415A (en) * | 2022-01-27 | 2022-06-14 | 昆明理工大学 | Preparation method of hexagonal selenium crystal/amorphous selenium simple substance |
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Application publication date: 20160615 |
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