CN1302774A - Powdered coal ash rich in Se and Ge elements and its application - Google Patents

Powdered coal ash rich in Se and Ge elements and its application Download PDF

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CN1302774A
CN1302774A CN00100070A CN00100070A CN1302774A CN 1302774 A CN1302774 A CN 1302774A CN 00100070 A CN00100070 A CN 00100070A CN 00100070 A CN00100070 A CN 00100070A CN 1302774 A CN1302774 A CN 1302774A
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selenium
flyash
rich
coal
flue gas
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CN1150135C (en
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赵善茂
张钊
肖大壮
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/002—Use of waste materials, e.g. slags
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/40—Fertilisers incorporated into a matrix

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Materials Engineering (AREA)
  • Pest Control & Pesticides (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

A flyash rich in Se and Ge elements is obtained from the boiler fume containing glassy flyash rich in Se and Ge through cooling and separation from a deduster. It can be used to prepare the functional glassy fertilizer with anticancer and health-care action, and is an industrial raw material to prepare Se and Ge elements.

Description

A kind of flyash and application thereof of being rich in selenium, element Ge
The invention belongs to selenium, the disorderly enriching method of germanium unit, a kind of preparation method that is rich in the flyash of selenium, element Ge of more specifically saying so.
The annual burning of world's electricity generation boiler coal is about 4,000,000,000 tons at present, wherein China is hundred million tons of 8-9, contain valuable selenium in the coal, element Ge, press selenium in the coal, the minimum average of the content of element Ge (is respectively 1.5,5ppm) calculate, the selenium that coal discharges is burnt in annual generating, the element Ge amount reaches 6000 tons/year respectively, 20000 tons/year, contain selenium in the indivedual coals of China and reach 61ppm, germanic in the brown coal up to 1000ppm, germanic colliery at 20 gram/ton coals just reaches that (Sun Yilu writes more than 46 in the identified coal, " dirt is to the harm of boiler in the coal ", P44, hydraulic and electric engineering processing industry press, version in 1993).The oxide compound major part that these valuable elements generate after boiler combustion is present in the coal ash and is not extracted, and small part enters atmosphere with flue gas, and this is very unfortunate.
The objective of the invention is from coal ash, to extract the glassiness flyash and the application thereof of being rich in selenium, element Ge.
Realize the main technical schemes of the object of the invention: when raw material burns, wherein be rich in the flue gas of the glassiness flyash of selenium, element Ge in liquid boiler, separate the flyash that promptly obtains being rich in selenium, element Ge through cooling, fly-ash separator.
The glassiness flyash that is rich in the selenium element Ge of the present invention, selenium, germanium concentration are respectively 10 and more than the 20ppm, and vitreum content is more than 50%, and xln is below 50%, and free CaO is 1-3%.
The extracting method that is rich in the flyash of selenium, element Ge of the present invention may further comprise the steps:
(1) with coal, phosphogypsum solubility promoter with comprise serpentine, Wingdale, quartz sand, rhombspar and comprise that the additive of zinc, copper, manganese, molybdenum, tin ore enters boiler simultaneously, the 40-95% lime-ash glass slip that obtains after the burning, with the flue gas of the glassiness flyash that is rich in selenium, element Ge of 5-60%, the glass slip is discharged boiler and is utilized in addition;
(2) flue gas of glassiness flyash that is rich in the selenium element Ge (1) step enters fly-ash separator successively after superheater, economizer, preheater are cooled to 190 ℃, the flyash that is rich in selenium, element Ge is separated with flue gas, and the fine coal that is rich in selenium, element Ge enters bunker;
(3) flue gas of being separated by (2) step enters atmosphere by chimney after denitration, desulfurization, defluorinate.
The described boiler of step (1) is the slag tap cyclone furnace preferably, this stove retention efficiency height, flyash is few, selenium element Ge concentration in coal ash is improved and by enrichment, described phosphogypsum fusing assistant and being selected from comprises two or more mixed ore of serpentine, Wingdale, quartz sand, rhombspar, the add-on of other additive should meet makes coal ash slag vitrifying functionalization condition, and the invention of number of patent application 99127191.2,00100008.X is seen in specific requirement.In step (1), also ore or the coal that is rich in selenium, element Ge can be in other additive, added, obtaining containing selenium, flyash that germanium concentration is higher, but the vitrified condition of coal ash slag that makes must be satisfied.
Superheater described in the step (2), economizer, preheater all are known equipment, described fly-ash separator comprises vortex dedusting, electric smoke precipitation, sack cleaner, the sack cleaner that uses of SNOX technology preferably, its efficiency of dust collection reaches 99.95%, and (Economic Commission for Europe compiles, " summary of experience of discharged nitrous oxides control techniques ", Electricity Department environmental protection office, Xian Thermal Power Engineering Research Institute is published, 1994, the 161-162 page or leaf).Because selenium, element Ge generate SeO after boiler combustion 2And GeO, and SeO 2Be sublimed into gas at 330 ℃ and 710 ℃ respectively with GeO, therefore selenium more than 99% and element Ge are discharged with the flue gas that contains flyash in coal and the additive, being frozen into solid at 190 ℃ enters in the flyash, to contain selenium by fly-ash separator, the glassiness flyash of element Ge separates with flue gas, selenium in the flyash, germanium concentration can be determined by the currently known methods chemical examination, also can calculate, because the selenium in the wet bottom boiler flyash, germanium unit weight is the selenium that coal and additive are brought in, element Ge amount (measuring) sum by chemical examination, its selenium, element Ge enters the weight in the glassiness fine coal, (as the vertical cyclone furnace retention efficiency is 70-80% according to the retention efficiency of cyclone furnace, horizontal cyclone stove retention efficiency 80-90%, the retention efficiency of U.S. TRW Ltd. (US) One Space Park, Redondo Beach CA 90278 U.S.A. combustion method is 90-95%) and the efficiency of dust collection (being respectively 99% and 99.95%) of fly-ash separator calculate and try to achieve, generally speaking, element Ge exceeds many times of selenium elements in the coal.
It is molten again that the flyash that contains selenium, element Ge that step (2) is separated from fly-ash separator can partly return boiler, to obtain containing selenium, flyash that germanium concentration is higher.What of the selenium that the amount of the flyash of melt back can be optionally, germanium concentration determine, and not poison with the used catalyzer of processes such as denitration, desulfurization be principle.
The described isolated flue gas of step (3) enters atmosphere after by the combined denitration in known SNOX and the DESONOX flue gas purifying method, desulfurization, defluorinate operation, and detailed process sees that application number is 99127191.2 patent application.
The flyash that is rich in selenium, element Ge that the present invention obtains can directly be made functional glass fertilizer, also can sneak into and do composite fertilizer's use in other glass fertilizer.Owing to containing a spot of basic oxide such as CaO in the flyash that contains selenium, element Ge, therefore should be during as fertilizer with in this part oxide compound and salify, can adopt conventional acid-base neutralisation as neutralizing with dilute sulphuric acid, flyash after the neutralization grinds after drying, its fineness should meet standard (" the Chinese chemical fertilizer handbook of the glass fertilizer or the siliceous fertilizer of national regulation, P381,1992).
Method of the present invention owing to can adopt contains the method that selenium, element Ge coal of high grade are made wet bottom boiler fuel or adopted melt back, obtains containing selenium, flyash that germanium concentration is higher, and selenium, germanium concentration reach 600-1500ppm just can be used as selenium, germanium industrial raw material.Selenium, element Ge are the important materials of medicine and electronics industry, China reclaims germanium from germanic 0.006% zinc sulfide ore, abroad be from germanic 0.015% plumbous zinc ore, to reclaim germanium (king's a one-legged monster in fable chief editor, " trace element in the life science ", China Measuring Press, the P792 page or leaf, 1996), now from being rich in selenium, in the flyash of element Ge, adopt conventional method further to extract valuable selenium, element Ge, then have bigger practical value.
Fig. 1 is a schematic flow sheet of the present invention.
By shown in Figure 1, contain selenium, selenium, germanium additive 15 that germanium concentration is higher and add in proportion batching in the sulfur cycle wet bottom boiler fuel system 1, levigately enter simultaneously in company with charcoal and other additive that burning generates SeO in the boiler 2 afterwards2, GeO enters flue gas, flue gas leaves the combustion chamber, when flue gas enters boiler air preheater 3, economizer 4, temperature drops to respectively 710 ℃, below 330 ℃ the time, then GeO, SeO2Solid directly congeals into respectively, when entering SNOX technology sack cleaner 5 to 190 ℃, then the overwhelming majority solid that congealed into is mixed in the flyash or is attached to the flyash surface, deduster 5 with fall into deduster after flue gas separates below bunker, it is molten again that a wind the rich selenium germanium of part flyash being sent into sulfuric acid trap 10 by metering machine supplying powder 16 is brought the combustion chamber in; The rich selenium of another part, germanium flyash are sent into neutralising arrangement 17, and by sulfuric acid 14 neutralizations that flue gas desulfurization transforms, flyash enters processing in drying, the grinding device 18 after the neutralization, can obtain the rich selenium germanium of finished product flyash 19. Melt back flyash quantity catalyst in denitrification apparatus 8, the desulfurizer 9 is not poisoned as principle. 7 is heat exchanger among the figure, and 11 is air blast, and 12 is electricity deacidification day with fog, and 13 is the flue gas fluoride removal device, and 20 is the ammonia basin, and 21 is the water quenching granulating case.
Advantage of the present invention and effect:
The present invention obtained being rich in the selenium of variable concentrations, the nature of glass flyash of Ge element from the past as enrichment the coal ash of refuse, and this flyash can be used as functional glass fertilizer and uses. Selenium in the plant, germanium master come to derive from soil, selenium has after by plant absorbing 80% to generate seleno-amino acids with vegetable protein, therefore apply the chemical fertilizer that contains the selenium element and can make the human Organic Selenium that from meals, obtains, to prevent cancer, aging and cardiovascular disease and to the heavy metal element tangerines such as arsenic, cadmium, lead, mercury are anti-detoxication to be arranged; Organic germanium such as Ge-132, spiral shell germanium etc. are to cancer of the stomach, lung cancer, the cancer of the uterus, breast cancer, liver cancer etc. have good curative effect, (king's a one-legged monster in fable chief editor, " Trace Elements in Life Science ", China Measuring Press, 1996, P627, PP804), find that also germanium is for vascular sclerosis, cerebral hemorrhage, gastric ulcer etc. also have certain curative effect and anti-aging, anaemia (Lin Nianfeng work, " medical environment geochemistry ", P114) and to harmful heavy metal mercury, cadmium, arsenic, lead has catharsis, to zinc, calcium, selenium has the antagonism detoxication, plant there is stimulating growth, improve the quality effect, can make increasing production of rice 75% (king's a one-legged monster in fable chief editor, " Trace Elements in Life Science ", China Measuring Press, 1996, so selenium P806),, Ge element can not only stimulate plant growth, improves quality, and be human cytotoxic, control is old and feeble, heart disease, the health care element of tens kinds of diseases such as diabetes, it is 5O μ g that the daily ingestion amount of selenium is recommended by Chinese Soclety of Nutrition, for the intake proposed standard of Ge element be every day 400-3500 μ g (Zheng Jianxian compiles, " functional food ", China Light Industry Press, 1999, P316, P329); Since found on the earth contain selenium, the germanium ore is few and grade is very low, selenium, Ge element that the present invention can take full advantage of in the coal ash have more significance; Therefore method of the present invention is fairly simple, and used equipment all is known, is easy to realize industrialization, and the flyash that the present invention obtains being rich in selenium, germanium can further therefrom carry selenium, Ge element, is used for the industries such as medicine, electronics; In addition, in the flyash that contains selenium, Ge element of enrichment of the present invention, arsenic, cadmium noxious material have also been collected, make it become chemical fertilizer and change into nontoxic organo-arsenic, cadmium by crops, not only make human nontoxic edible after tool possess exuberant vitality, animal experiment has proved and has lacked arrest of development behind the arsenic, (" Trace Elements in Life Science ", and eliminated arsenic, cadmium to the pollution of environment P840).
Example 1
This example adopts the horizontal cyclone stove, and its retention efficiency is 85%; Fire coal is the Western Hills meager coal, and calorific value is 25600KJ/kg, and coal as received basis ash is 21.48%, and burning the mistake rate is 0.43%, is 5% through test flyash extraction efficiency.The character of coal sees Table 1, and the add-on and the composition of additive see Table 2.
Sulphur cycle application for a patent for invention (application number 99127191 is adopted in experiment, 2) technology, through SNOX method sack cleaner (efficiency of dust collection is 99.95%) separate obtain being rich in selenium, germanium flyash with dilute sulphuric acid in and after composition see Table 3, contain selenium, germanium flyash melt back rate 11.76%.
Example 2
This example is that example 1 obtains being rich in the practical application of the flyash of selenium, element Ge as functional glass fertilizer.
With the functional glass fertilizer that is rich in selenium, element Ge of the present invention be used for the rice field after azophoska is mixed and use as base manure.The paddy soil constituent content sees Table 4, and the rate of fertilizer application that the functional glass fertilizer of selenium element Ge is rich in NPK+ the present invention sees Table 5.Rice yield, quality situation (and with use the fertile situation of NPK separately compare) see Table 6.
As shown in Table 6, be used as functional glass fertilizer owing to use the flyash that is rich in the selenium element Ge, grain contains selenium and reaches 820 μ g/Kg, 2 times of the standards that can surpass per day for adults picked-up selenium 50～200 μ g that CFN of American Academy of Sciences recommends after people are edible, and day edible 400～500g rice can prevent that just tumour from taking place, and (Zheng Jianxian compiles, " functional foodstuff ", China Light Industry Press, 1999); The germanic 840 μ g/Kg of grain after the fertilising (and rice has only 100 μ g/Kg now), and day edible 400～500g rice can be received the effect of anticancer, anti-aging and selenosis; The flyash of the rich selenium element Ge of every Kg about 2.8Kg that can produce more food.Table 1 Xishan coal character
Title The coal composition The ash dreg chemistry becomes
Low heat value Ash Sulfur Selenium Germanium Arsenic Cadmium P 2O 5 K 2O+ Na 2O
Unit KJ/Kg ％ ％ PPm PPm PPm PPm ％ ％
Quantity 25600 21.48 1.5 1 3 9 0.1 0.10 0.964
Title The lime-ash Chemical Composition
CaO MgO SiO 2 Al 2O 3 Fe 2O 3 MnO ZnO CuO MoO 3
Unit ％ ％ ％ ％ ％ ％ ％ ％ ％
Quantity 4.02 0.18 49.19 37.63 5.95 6.45× 10 -3 6× 10 -3 7.5× 10 -3 3× 10 -3
Title The lime-ash Chemical Composition
CoO Cr 2O 3 SnO NiO V 2O 5 B 2O 3 Burn and lose (SO 3)
Unit ％ ％ ％ ％ ％ ％ ％
Quantity 5.07× 10 -3 4.4× 10 -3 1.27× 10 -3 8.9× 10 -3 0.0375 0.0129 0.43
Table 2 additive add-on and Chemical Composition
Ore The place of production Addition Kg/T coal Chemical Composition, %
CaO MgO SiO 2 Al 2O 3 Fe 2O 3 SeO 3 GeO Burn and lose
Phosphogypsum The liuyang hunan phosphorus ore generates 211.53 31.28 0.23 9.09 1.87 1.45 7.09× 10 -7 6× 10 -6 53.5
Serpentine Wooden woods is deceived in Shaanxi 140.34 0.30 39.58 40.11 0.66 5.14 1.26× 10 -5 6× 10 -4 14.11
Wingdale Funing, Hebei battalion in behaviour 43.94 53 0.66 3.00 0.63 0.44 5.7× 10 -5 8.9× 10 -4 41.5
Quartz sand Sea sand 0 - - 99.50 - - - - 0.5
Rhombspar Yingkou, Liaoning Chen Jiabao 63.57 29.50 21.10 1 0.50 1.10 5.7× 10 -5 8.9× 10 -4 46.5
In the rich selenium germanium of table 3 flyash and back chemical constitution
Flammable charcoal Vitriol Xln Vitreum SeO2?GeO ?Al 2O 3 ?CdO Solubility in citric acid oxide compound (Z)
Z ?Z ?Z ?Z ?ppm ppm ??ppm ppm P 2O 5 ?K 2O ?CaO
?1.8 ?4.5 ?40.7 ?53 ?202 ?248 ?374 ?96 ??0.5 ?0.45 ????16
* explanation: above-mentioned flyash contains selenium reserves and medical stone near table 4 paddy soil constituent content table (mg/kg)
P ?K ?Ca Mg Si Al Mn ??Zn ?Cu Mo ?Co Cr
100 ?1000 ?20000 1000 330000 71000 50 ??30 ?10 0.1 ?0.1 70
Sn ?Ni ?V Se ?Ge As Cd ??Fe ?B Hg ?C(org) 0
1 ?50 ?70 0.5 ?0.30 6 0.35 ?45000 ?10 0.5 ?40000 490000
Fertile and the rich selenium germanite glass of the NPK+ matter flyash rate of fertilizer application comparison sheet of table 5 NPK three compounds
Compound is fertile to be formed Urea Kg/Ha Monoammonium phosphate Kg/Ha Potassium oxide Kg/Ha Rich selenium storage flyash Mg/Ha The fertilizer homing rate (%) that crop transforms
Form grade N=46％ P 2O 5=57％ N=11％ K 2O=60％ SeO 2202PPm; GeO=248PPm The human excrement that grain transforms Straw, stubble, root be the field also
Fertilizer A 697 336.5(N=37) 263 0 37.35 90
Fertilizer B 697 336.5(N=37) 263 106 37.35 90
Element oxide (except N, S, the B) quantity is brought in fertilising in
The element oxide title N P 2O 5 K 2O CaO MgO FeO MnO ZnO CuO MoO 3 CoO SeO 2 GeO SiO 2
Unit Kg/Ha Kg/Ha Kg/Ha Kg/Ha Kg/Ha Kg/Ha Kg/Ha Kg/Ha g/Ha g/Ha g/Ha g/Ha Kg/Ha Kg/Ha g/Ha g/Ha
Fertilizer A 357 191.8 158 0 0 0 0 0 0 0 0 0 0 0 0 0
Fertilizer B 357 192.3 158.48 8.4 1 0.60 0.46 0.52 0.11 0.005 0.002 21.64 26.47 10
* annotate the fertile border of NPK number: N: P 2O 5: K 2O=14: ≈ was 14: 8: 6 in 7.6: 6.2.Table 6 rice yield, quality situation
Project Grain yield Grain quality
Output Amount of increase in production The selenium element Element Ge Arsenic element Cadmium element
Content Improve multiple Content Improve multiple Content Improve multiple Content Improve multiple
Kg/Ha Doubly μg/kg Doubly μg/kg Doubly μg/kg Doubly μg/kg Doubly
Fertilizer A 6000 - 200 - 100 - 110 - 32 -
Fertilizer B 6300 5 820 4.1 840 8.4 950 8.20 90 2.8

Claims (7)

1. flyash that is rich in selenium, element Ge is characterized in that rich germanium, selenium concentration respectively greater than 20 and the glassiness flyash of 10ppm, and the vitreum content of its flyash is more than 50%, and xln is below 50%, and free CaO is 1-3%.
2. the described preparation method who is rich in the flyash of selenium, element Ge of claim 1 is characterized in that preparation process may further comprise the steps:
(1) with coal, phosphogypsum solubility promoter with comprise the additive of serpentine, Wingdale, quartz sand, rhombspar and comprise that the ore of zinc, copper, manganese, molybdenum, tin enters boiler simultaneously, the 40-95% lime-ash glass slip that obtains after the burning, with the flue gas of the glassiness flyash that is rich in selenium, element Ge of 5-60%, the glass slip is discharged boiler and is utilized in addition;
(2) flue gas of glassiness flyash that is rich in the selenium element Ge (1) step enters fly-ash separator successively after superheater, economizer, preheater are cooled to 190 ℃, the flyash that is rich in selenium, element Ge is separated with flue gas, and the fine coal that is rich in selenium, element Ge enters bunker;
(3) flue gas of being separated by (2) step enters atmosphere by chimney after denitration, desulfurization, defluorinate.
3. in accordance with the method for claim 1, it is characterized in that (1) step can also add the higher ore of selenium element Ge content or coal enters boiler combustion as selenium, germanium additive, to obtain containing the higher flyash of selenium element Ge concentration.
4. in accordance with the method for claim 1, it is characterized in that partly to return melt back in (1) step boiler by the isolated flyash that is rich in selenium, element Ge of (2) step, obtaining containing selenium, flyash that element Ge concentration is higher, but the amount of returning with the technological process denitrating flue gas, the used catalyzer of desulfurization is not poisoned is principle.
5. in accordance with the method for claim 1, the add-on that it is characterized in that (1) step described fusing assistant and other additive should meet the vitrifying of coal ash slag, the functionalization condition of making.
6. the described flyash that is rich in selenium, element Ge of claim 1 is used, it is characterized in that it can be separately as functional glass fertile use or add in other glass fertilizer use as functional composite fertilizer, should adopt when the fertilizer conventional method with in the basic oxide in the flyash and salify, be finely ground to after the flyash drying after will neutralizing then and meet the fineness that glass fertilizer requires.
7. the described application of being rich in the flyash of selenium, element Ge of claim 1 is characterized in that it can be as producing selenium, element Ge industrial raw material.
CNB001000705A 2000-01-04 2000-01-04 Powdered coal ash rich in Se and Ge elements and its application Expired - Fee Related CN1150135C (en)

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CNB001000705A CN1150135C (en) 2000-01-04 2000-01-04 Powdered coal ash rich in Se and Ge elements and its application
AU23442/01A AU2344201A (en) 2000-01-04 2001-01-04 Germanium and selenium-enriched glass fertilizer and the method for producing the same
PCT/CN2001/000008 WO2001049636A1 (en) 2000-01-04 2001-01-04 Germanium and selenium-enriched glass fertilizer and the method for producing the same

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102491286A (en) * 2011-11-23 2012-06-13 安徽省思达新材料科技有限公司 Selenium extraction method of selenium-containing bone coal
CN108358732A (en) * 2018-05-28 2018-08-03 张森森 A kind of richness germanium selenium-enriched health care organic fertilizer
CN114345521A (en) * 2021-12-21 2022-04-15 中国建筑第二工程局有限公司 Preparation system for preparing floor gypsum powder from construction waste and use method of preparation system

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CN102415252B (en) * 2011-08-23 2014-02-05 南京远望富硒农产品有限责任公司 Method for preparing selenium-rich rice
CN107759349A (en) * 2017-11-24 2018-03-06 中国环境科学研究院 A kind of more nutrient composite foliage fertilizers and preparation method and application for hindering control rice Cd accumulation

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BE878884A (en) * 1978-09-29 1980-03-20 Bfg Glassgroup VITREOUS FERTILIZER AND CULTURE METHOD USING THE SAME
JPS60127286A (en) * 1983-12-09 1985-07-06 日本化学工業株式会社 Manufacture of slow release fused potassium magnesium silicate fertilizer
CN1036552A (en) * 1989-01-20 1989-10-25 淮南田家庵发电厂 Coal powder phosphorous fertilizer and production method
CN1028090C (en) * 1989-09-02 1995-04-05 石振鑫 Trace element fertilizer made from flyash and its productive method
CN1057630A (en) * 1990-06-18 1992-01-08 訾风兰 A kind of manufacture method of cinder glass
CN1107452A (en) * 1994-07-12 1995-08-30 华北电力学院 Flyash-Si-K fertilizer and its producing process

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102491286A (en) * 2011-11-23 2012-06-13 安徽省思达新材料科技有限公司 Selenium extraction method of selenium-containing bone coal
CN102491286B (en) * 2011-11-23 2015-04-08 安徽省思达新材料科技有限公司 Selenium extraction method of selenium-containing bone coal
CN108358732A (en) * 2018-05-28 2018-08-03 张森森 A kind of richness germanium selenium-enriched health care organic fertilizer
CN114345521A (en) * 2021-12-21 2022-04-15 中国建筑第二工程局有限公司 Preparation system for preparing floor gypsum powder from construction waste and use method of preparation system

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