A kind of production method that promotes selenium activation rate in the selenium mineral powder
Technical field
The present invention relates to a kind of production method that promotes selenium activation rate in the selenium mineral powder.
Technical background
Selenium belongs to rare elements, only accounts for 1/10 of earth crustal mass
6, and in the earth's crust serious skewness, so there are the low selenium in more than 40 countries and regions and scarce selenium in the whole world.Selenium is the essential trace element of animal and human's body, and the selenium content deficiency is brought out various diseases easily, will have a strong impact on the healthy of people, affects the development of livestock industry.The county of China 72% (city) belongs to low or scarce selenium area, from Heilungkiang, there is scarce selenium in various degree Inner Mongol, Gansu, Qinghai to areas such as Sichuan, people's Keshan disease, Kaschin-Beck disease once occured, and causes the white muscle disease of livestock and poultry popular.In order to satisfy the human body selenium intake, explore the method for good health and a long life, people are seeking a safe and effective benefit selenium approach always.And use selenium fertilizer, transform by Crop, inorganic selenium is become organoselenium, from food chain realize human-body safety to mend selenium be an effective benefit selenium by way of.
The present both at home and abroad production method of selenium fertilizer generally adopts Sodium Selenite to carry out after the technical finesse foliage-spray as raw material or root is used.Utilize Sodium Selenite as the foliage fertilizer of selenium source, easily run off, spray inhomogeneously, easily the crop part is damaged, simultaneously environment is also caused certain pollution effect.And root is executed also very easily loss, causes the loss of selenium.
Bestowing favour is described as Chinese selenium all, and according to the geological prospecting measuring and calculating, only Enshi City selenium ore reserves reaches more than 50 hundred million tons, and containing the selenium grade is 230-6300mg/kg.Contain selenium yeath and bone coal outcrop area be 850 square kilometres, be divided into north and south two bands, 2,500,000,000 tons of total reservess, selenium 500-5500 gram that contains per ton is up to 84 kilograms, the highest 178.8ppm of Selenium in Soil, average 19.11ppm.Other county also has abundant selenium ore resources in the state.And domestic other most areas lacks selenium, does not have selenium ore resources source, even if the some places part contains selenium, selenium content is also very low in its rock, can not reach the grade of exploitation selenium fertilizer, does not possess the condition of producing selenium fertilizer.Bestow favour and but have advantageous selenium ore resources advantage.
Yet the selenium content in the selenium ore deposit of bestowing favour is also astable.The people such as Xiao Benjian mention two river fishing dyke selenium ore deposits grade of bestowing favour in " bestow favour rich selenium resources of medicinal plant and development and use countermeasure " and contain the selenium grade at 230-6300mg/kg, it is inhomogeneous that this explanation selenium ore deposit selenium content in different carbonolytes distributes, for the relatively stable of selenium of controlling in the selenium fertilizer should be taked relative technical measures.
In addition, the water soluble selenium in the selenium ore deposit is lower.Bright people's (the mineral journal that waits in Korean, the 1st phase of the 27th volume March in 2007) to the analysis of selenium form in the carbonolyte in the fishing dyke of bestowing favour, no matter be yeath, or the variform of selenium distributes and sees in the siliceous shale, easily water soluble selenium absorbed by crops is relatively low, therefore should take technical measures to impel the selenium of different shape in the selenium ore deposit to be conducive to the easy absorbing state selenium of crop industralization for improving crop to the absorption of selenium in the selenium ore deposit, could realize release and the utilization of selenium.There is water soluble selenium to account for full selenium 8--10% in the general selenium mineral powder
From the above, these characteristics in selenium ore deposit of bestowing favour cause fertile production of selenium to exist selenium content to be difficult to control, the not high disadvantage of product water soluble selenium has become fertile gordian technique and the bottleneck problem of producing of selenium, for utilizing selenium ore resources production selenium fertilizer and applying and brought very large impact.
Chinese invention patent utilizes the selenium ore deposit to produce selenium fertile (CN02128368.0) and mentions that the activating technology of the selenium in the selenium ore deposit adopts single activator ammonia treatment to improve the content of water soluble selenium, and water soluble selenium can only reach 20%.
Add in a kind of Special Se-contg. mineral fertilizer (CN98100068.1) patent a selenium minerals not explanation be where to add selenium minerals, the technical finesse measure of its selenium minerals is not described simultaneously yet.
Summary of the invention
The activating process deficiency that the objective of the invention is water soluble selenium absorbed by crops in the method for existing selenium ore deposit production selenium fertilizer is carried out improved, a kind of active selenium mineral powder of highly water-soluble selenium is provided, aspect activation, has had larger improvement and water-soluble aspect that larger lifting has been arranged.
A kind of production method that promotes selenium activation rate in the selenium mineral powder of the present invention is characterized in that comprising following steps: the ore deposit pre-treatment of a. selenium: dry by crusher in crushing in the selenium ore deposit, and control moisture content is 15% and total selenium 300mg/Kg;
B. selenium mineral powder unslaked lime is processed: with the unslaked lime that adds in the selenium mineral powder, be ground into 80 purpose selenium mineral powders again;
C. charging reaction: with KH
2PO
4, NH
4HCO
3, potassium permanganate, be dissolved in 60 ℃ of hot water, mix; Add again hydrogen peroxide, mix; Spraying is advanced in the selenium mineral powder;
D. windrow activation: the selenium mineral powder after will feeding in raw material is put into reaction tank, and the control temperature is at 60 ℃-70 ℃; When temperature began to descend, whole reaction was end, got active selenium mineral powder.
A kind of production method that promotes selenium activation rate in the selenium mineral powder of the present invention, it is characterized in that comprising following steps: the ore deposit pre-treatment of a. selenium: the product of bestowing favour contains the above selenium ore deposit of selenium 300mg/Kg and just is broken into the 10mm size by jaw crusher, enter 70 ℃ of hotblast stove cartridge type baker oven dry, moisture control gets the selenium mineral powder of total selenium 300mg/Kg 15%;
B. unslaked lime selenium mineral powder unslaked lime processing: will add 10%(w/w in the selenium mineral powder) mixes, and is broken into 80 purpose selenium mineral powders through raymond grinding powder again;
C. charging reaction: in the thermostatic mixer dissolver, add respectively fertilizer grade KH
2PO
4, fertilizer grade NH
4HCO
3, potassium permanganate, add-on is the 4%(w/w of selenium mineral powder), 5%(w/w) and 2%(w/w); Be dissolved in selenium mineral powder amount 20%(w/w) 60 ℃ of hot water in, mix; The 1.5%(w/w that adds again the selenium mineral powder amount after the dissolving) hydrogen peroxide mixes; Spraying enters in the selenium mineral powder, controls selenium mineral powder at moisture content 35%, and stirs;
D. windrow activation: the selenium mineral powder after will feeding in raw material is put into reaction tank, 60 ℃-70 ℃ of temperature of reaction, because unslaked lime will be emitted heat after absorbing water, will be according to the temperature timely turning cooling of situation of rising in reaction tank, the control temperature is at 60 ℃-70 ℃, and the reaction times is 24 hours; When temperature began to descend, whole reaction was end, got active selenium mineral powder.
A kind of production method that promotes selenium activation rate in the selenium mineral powder of the present invention adopts unslaked lime to adjust pH value is finished selenium under the slight alkalinity environment release, simultaneously the selenium element Ca of insoluble attitude
2+Replace, be conducive to the release of the selenium of chemical combination attitude, be conducive to transform to water soluble selenium; Fertilizer grade KH
2PO
4And NH
4HCO
3, mainly in the Crop process, play collaborative, promoter action, simultaneously K
+Play displacement and discharge the selenium element.The main selenium of the different shape in the selenium mineral powder that promotes transforms to the water soluble selenium direction; Potassium permanganate and hydrogen peroxide mainly increase simple substance attitude selenium to oxide side to conversion, improve its water soluble selenium content.
The invention has the beneficial effects as follows and utilize the selenium ore resources preparation of bestowing favour abundant, produce environment friendly and pollution-free, safety non-toxic, can replace Sodium Selenite to be used for farm crop and increase selenium, also can be used as the raw material of producing the selenium Chemical Mixed Fertilizer, that the selenium ore resources of realizing bestowing favour takes full advantage of, for vast scarce selenium district and low selenium district and the area that produces secondary selenium agricultural-food provide a kind of valency cheap and good-quality selenium source.
A kind of production method that promotes selenium activation rate in the selenium mineral powder of the present invention, the selenium mineral powder of producing has that simple, the water-soluble lifting of production technique is large, the activation rate advantages of higher, the raw material of providing convenience in selenium-enriched fertilizer production as a kind of selenium mineral powder of high motility rate has preferably prospect simultaneously in the production of selenium-enriched food and rich selenium industrialization.
Embodiment
The present invention is further illustrated below in conjunction with embodiment:
Example 1: does not wait in the selenium ore deposit proportionately general height of ore deposit reason, generally just divide to store up by grade and put, by above (namely containing what milligram pure seleniums in the per kilogram selenium ore deposit) the selenium ore deposit of the reasonably combined one-tenth of its grade 300mg/Kg, the selenium ore deposit just is broken into into the 10mm size by jaw crusher and enters hotblast stove cartridge type baker, about 70 ℃ oven dry of temperature control, detect moisture control and about 15%, be advisable, get 2 tons in selenium ore deposit and add 100Kg just is broken into the 10mm size through jaw crusher unslaked lime.Being broken into 80 purpose selenium mineral powders through just broken selenium ore deposit and unslaked lime through raymond grinding powder.In the thermostatic mixer dissolver, add respectively fertilizer grade KH
2PO
4Amount is 20Kg, fertilizer grade NH
4HCO
3Amount is 20Kg for 20Kg, potassium permanganate amount, be dissolved in the about 60 ℃ of hot water of 400Kg, mix, spraying is advanced in the selenium mineral powder, and control selenium mineral powder moisture content about 35%, and stir, enter reaction tank and process 60 ℃-70 ℃ of temperature of reaction, because unslaked lime will be emitted heat after absorbing water, will be according to the timely turning of thermometer temperature rising situation speed cooling in reaction tank, control temperature 60 C-70 ℃, the whole reaction times is about 24 hours.When temperature began to descend, whole reaction was end, got active selenium mineral powder.
2, example 2: does not wait in the selenium ore deposit proportionately general height of ore deposit reason, generally just divide to store up by grade and put, by above (namely containing what milligram pure seleniums in the per kilogram selenium ore deposit) the selenium ore deposit of the reasonably combined one-tenth of its grade 300mg/Kg, the selenium ore deposit just is broken into the 10mm size by jaw crusher, enter hotblast stove cartridge type baker, about 70 ℃ oven dry of temperature control, control moisture content is advisable about 15%, gets 2 tons in selenium ore deposit and adds 120Kg just is broken into the 10mm size through jaw crusher unslaked lime.Being broken into 80 purpose selenium mineral powders through just broken selenium ore deposit and unslaked lime through raymond grinding powder.In the thermostatic mixer dissolver, add respectively fertilizer grade KH
2PO
4Amount is 40Kg, fertilizer grade NH
4HCO
3Amount is 30Kg for 40Kg, potassium permanganate amount, hydrogen peroxide 20Kg, and allow former three be dissolved in the about 60 ℃ of hot water of 450Kg, dissolve complete adding hydrogen peroxide, mixing spraying advances in the selenium mineral powder, and control selenium mineral powder moisture content about 35%, and stir, entering reaction tank processes, 60 ℃-70 ℃ of temperature of reaction, because unslaked lime will be emitted heat after absorbing water, will be according to the timely turning cooling of thermometer temperature rising situation speed in reaction tank, control temperature 60 C-70 ℃, the whole reaction times is about 24 hours.When temperature began to descend, whole reaction was end, got active selenium mineral powder.
Example 3: does not wait in the selenium ore deposit proportionately general height of ore deposit reason, generally just divide to store up by grade and put, by above (namely containing what milligram pure seleniums in the per kilogram selenium ore deposit) the selenium ore deposit of the reasonably combined one-tenth of its grade 300mg/Kg, the selenium ore deposit just is broken into into the 10mm size by jaw crusher and enters hotblast stove cartridge type baker, about 70 ℃ oven dry of temperature control, control moisture content is advisable about 15%, gets 2 tons in selenium ore deposit and adds 140Kg just is broken into the 10mm size through jaw crusher unslaked lime.Being broken into 80 purpose selenium mineral powders through just broken selenium ore deposit and unslaked lime through raymond grinding powder.In the thermostatic mixer dissolver, add respectively fertilizer grade KH
2PO
4Amount is 60Kg, fertilizer grade NH
4HCO
3Amount is 30Kg for 60Kg, potassium permanganate amount, hydrogen peroxide 20Kg, and allow former three be dissolved in the about 60 ℃ of hot water of 450Kg, dissolve complete adding hydrogen peroxide, allow four to become the mixed solution even spraying and advance in the selenium mineral powder, and control selenium mineral powder moisture content about 35%, and stir, entering reaction tank processes, 60 ℃ of temperature of reaction--70 ℃, because unslaked lime will be emitted heat after absorbing water, will be according to the timely turning cooling of thermometer temperature rising situation speed in reaction tank, control temperature 60 C-70 ℃, the whole reaction times is about 24 hours.When temperature began to descend, whole reaction was end, got active selenium mineral powder.
Example 4: does not wait in the selenium ore deposit proportionately general height of ore deposit reason, generally just divide to store up by grade and put, by above (namely containing what milligram pure seleniums in the per kilogram selenium ore deposit) the selenium ore deposit of the reasonably combined one-tenth of its grade 300mg/Kg, the selenium ore deposit just is broken into into the 10mm size by jaw crusher and enters hotblast stove cartridge type baker, about 70 ℃ oven dry of temperature control, control moisture content is advisable about 15%, gets 2 tons in selenium ore deposit and adds 160Kg just is broken into the 10mm size through jaw crusher unslaked lime.Being broken into 80 purpose selenium mineral powders through just broken selenium ore deposit and unslaked lime through raymond grinding powder.In the thermostatic mixer dissolver, add respectively fertilizer grade KH
2PO
4Amount is 70Kg, fertilizer grade NH
4HCO
3Amount is 40Kg for 80Kg, potassium permanganate amount, hydrogen peroxide 30Kg, and allow former three be dissolved in the about 60 ℃ of hot water of 500Kg, dissolve complete adding hydrogen peroxide, allow four to become the mixed solution even spraying and advance in the selenium mineral powder, and control selenium mineral powder moisture content about 35%, and stir, entering reaction tank processes, 60 ℃ of temperature of reaction--70 ℃, because unslaked lime will be emitted heat after absorbing water, will be according to the temperature timely turning cooling of situation speed of rising in reaction tank, control temperature 60 C-70 ℃, the whole reaction times is about 24 hours.When temperature began to descend, whole reaction was end, got active selenium mineral powder.
Example 5: does not wait in the selenium ore deposit proportionately general height of ore deposit reason, generally just divide to store up by grade and put, by above (namely containing what milligram pure seleniums in the per kilogram selenium ore deposit) the selenium ore deposit of the reasonably combined one-tenth of its grade 300mg/Kg, the selenium ore deposit just is broken into into the 10mm size by jaw crusher and enters hotblast stove cartridge type baker, about 70 ℃ oven dry of temperature control, control moisture content is advisable about 15%, gets 2 tons in selenium ore deposit and adds 180Kg just is broken into the 10mm size through jaw crusher unslaked lime.Being broken into 80 purpose selenium mineral powders through just broken selenium ore deposit and unslaked lime through raymond grinding powder.In the thermostatic mixer dissolver, add respectively fertilizer grade KH
2PO
4Amount is 70Kg, fertilizer grade NH
4HCO
3Amount is 40Kg for 100Kg, potassium permanganate amount, hydrogen peroxide 30Kg, and allow former three be dissolved in the about 60 ℃ of hot water of 500Kg, and dissolve complete adding hydrogen peroxide, the mixed solution even spraying is advanced in the selenium mineral powder, and control selenium mineral powder moisture content about 35%.And stir, enter reaction tank and process 60 ℃ of temperature of reaction--70 ℃, because unslaked lime will be emitted heat after absorbing water, will be according to the temperature timely turning of the situation speed cooling of rising in reaction tank, control temperature 60 C-70 ℃, the whole reaction times is about 24 hours.When temperature began to descend, whole reaction was end, got active selenium mineral powder.
Example 6: does not wait in the selenium ore deposit proportionately general height of ore deposit reason, generally just divide to store up by grade and put, by above (namely containing what milligram pure seleniums in the per kilogram selenium ore deposit) the selenium ore deposit of the reasonably combined one-tenth of its grade 300mg/Kg, the selenium ore deposit just is broken into into the 10mm size by jaw crusher and enters hotblast stove cartridge type baker, about 70 ℃ oven dry of temperature control, detect moisture control with thermometer and about 15%, be advisable, get 2 tons in selenium ore deposit and add 200Kg just is broken into the 10mm size through jaw crusher unslaked lime.Being broken into 80 purpose selenium mineral powders through just broken selenium ore deposit and unslaked lime through raymond grinding powder.In the thermostatic mixer dissolver, add respectively fertilizer grade KH
2PO
4Amount is 80Kg, fertilizer grade NH
4HCO
3Amount is 40Kg for 100Kg, potassium permanganate amount, hydrogen peroxide 30Kg, and allow former three be dissolved in the about 60 ℃ of hot water of 550Kg, and dissolve complete adding hydrogen peroxide, the mixed solution even spraying is advanced in the selenium mineral powder, and control selenium mineral powder moisture content about 35%.And stir, enter reaction tank and process 60 ℃ of temperature of reaction--70 ℃, because unslaked lime will be emitted heat after absorbing water, will be according to the temperature timely turning of the situation speed cooling of rising in reaction tank, control temperature 60 C-70 ℃, the whole reaction times is about 24 hours.When temperature began to descend, whole reaction was end, got active selenium mineral powder.The active selenium mineral powder drying of above gained moisture is measured its water soluble selenium content less than 20%, and data are listed in table 1
Full selenium, water soluble selenium content in table 1 selenium mineral powder and the active selenium mineral powder