CN108911795A - A method of magnesium silico-calcium fertilizer is produced using mineral hot furnace melting asbestos tailings - Google Patents
A method of magnesium silico-calcium fertilizer is produced using mineral hot furnace melting asbestos tailings Download PDFInfo
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- CN108911795A CN108911795A CN201811071447.2A CN201811071447A CN108911795A CN 108911795 A CN108911795 A CN 108911795A CN 201811071447 A CN201811071447 A CN 201811071447A CN 108911795 A CN108911795 A CN 108911795A
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- ball
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- ball mill
- asbestos tailings
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Classifications
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D3/00—Calcareous fertilisers
- C05D3/04—Calcareous fertilisers from blast-furnace slag or other slags containing lime or calcium silicates
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/006—Starting from ores containing non ferrous metallic oxides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Fertilizers (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of methods using mineral hot furnace melting asbestos tailings production magnesium silico-calcium fertilizer, and asbestos tailings are entered ball mill ball milling with addition of graphite first；With 2.4% that charcoal amount is mineral quantity, mass percent；The graphite that phosphorus content is 85% is selected to match carbon；Ball mill discharges material ball milling to 100 mesh；The above material is subjected to pressure ball using dry type ball press, sphere size is between 30~100mm；Mine heat furnace smelting is added by charging system in sphere, molten condition keeps 30min, pours out the slag liquid in furnace；Enter ball mill after slag liquid slow cooling and be milled down to 150 mesh, the magnetic separator that material passes through 0.4T first during discharging selects iron, cobalt, nickel, and then material sieves powder by the rotary screen of 150 mesh, and for oversize as special tailing, carry out crome metal selects operation；Raw material of the screenings of rotary screen as secondary and micro-element fertilizers, may be directly applied to farmland as pulvis, use after can also being granulated as secondary and micro-element fertilizers.
Description
Technical field
The present invention relates to a kind of methods using mineral hot furnace melting asbestos tailings production magnesium silico-calcium fertilizer.
Background technique
Asbestos are important raw mineral materials during the development of the national economy.Asbestos fecund is born in serpentine mineral band, every life
One ton of asbestos is produced, 40 tons of tailing waste thing serpentinite is generated.Asbestos tailings because rich in the heavy metals such as Cr, nickel, cobalt, copper, iron,
It is serious for the harm of environment and animals and plants, it is typical danger wastes, originates in Altun and Kun Lun Mountain in Xinjiang
The fractions of the domestic asbestos tailings of Qarkilik County are as in the table below：
According to above table it is found that serpentine is a kind of hydrosilicate mineral of magnesium.Its chemical composition is 3MgO
2SiO2·2H2O or MgO [Si4O10](OH)8, the content of beary metal among asbestos tailings is big, larger for the harm of soil.
Consulting literatures（1）Tan Zhuhong, Zheng Shuilin were the 3rd phase in 2007《Chinese non-metallic mineral industry guide》Upper announcement
Among entitled " asbestos tailings status and research of utilization progress " paper, there is content below to state：" China's asbestos tailings
Accumulating amount is big, causes greatly to pollute to environment.Since the 1990s, synthesis of China scientific worker to asbestos tailings
Using some researchs have been carried out, so far, although the application prospect of some exploration projects is good, in terms of industrialized utilization but
Be make slow progress, or even efficient industrialization comprehensive utilization truly not yet " content statement；（2）Wu Chunxiang, Song Peng
Journey, Sun Hongjuan, Peng Tongjiang were the 4th phase in 2014《Chinese non-metallic mineral industry guide》Entitled " chrysotile and the tail of upper announcement
Among ore resources research on utilization progress " paper, there is content below to state：" chrysotile tailing belongs to Industrial Solid Waste, although right
It is more deep that valuable component extracts research, but in addition to Gansu acthar and Xinjiang are according to the progress pilot scale of the industry park Bu Lake is gulped down, also not
Carry out industrialized production, and production technology have it is to be solved, such as the dirt to instrument, environment of volatilization, sulfuric acid of ammonium hydroxide
The problems such as dye." content statement；（3）Su Qingping, imperial Xiao Ling were the 1st phase in 2009《Mineral products comprehensive utilization》On magazine
Have among entitled " harm and comprehensive Utilization Ways of the asbestos tailings " paper announced " containing not selecting largely in asbestos tailings
Tiny staple fiber, these staple fiber balloonings, causes the destruction of air quality.Recently as high-temperature plasma
The development of technology, the developed countries such as Italy, France develop asbestos high temperature crystal technology, and asbestos are useless at high temperature
Object is melted, and is no longer presented threadiness, and is converted into wear-resisting, corrosion resistant glass ceramics " content statement.
By above document statement it is found that there is presently no the process introduction for producing fertilizer using asbestos tailings,
Also without the process introduction of heavy metal among removal asbestos tailings.
Summary of the invention
The purpose of the present invention is to provide a kind of method using mineral hot furnace melting asbestos tailings production magnesium silico-calcium fertilizer, energy
It is enough that asbestos tailings are effectively treated, turn waste into wealth.
The object of the present invention is achieved like this, a kind of side using mineral hot furnace melting asbestos tailings production magnesium silico-calcium fertilizer
Asbestos tailings are entered ball mill ball milling with addition of graphite first by method；With 2.4% that charcoal amount is mineral quantity, mass percent；It selects
The graphite that phosphorus content is 85% matches carbon；Ball mill discharges material ball milling to 100 mesh；By the above material using dry type ball press into
Row pressure ball, sphere size is between 30~100mm；Mine heat furnace smelting is added by charging system in sphere, molten condition is kept
30min pours out the slag liquid in furnace；Enter ball mill after slag liquid slow cooling and be milled down to 150 mesh, material passes through first during discharging
The magnetic separator of 0.4T selects iron, cobalt, nickel, and then material sieves powder by the rotary screen of 150 mesh, and oversize is carried out as special tailing
Crome metal selects operation；Raw material of the screenings of rotary screen as secondary and micro-element fertilizers can be applied directly as pulvis
In farmland, used after can also being granulated as secondary and micro-element fertilizers.
Inventor is according to metallurgical principles and the anti-principle of mechanical force and chemical, in conjunction with the mineralogy feature of serpentinite, discovery benefit
With asbestos tailings powder, it is incorporated graphitic carbon, milling processing is carried out in ball mill, during this, graphitic carbon can be enable
It is uniformly distributed among the powder of asbestos tailings, the granularity of powder is controlled in 100 mesh, in this course, mechanical force
Learning adverse effect can promote the crystal structure among asbestos tailings that distortion of lattice occurs, and the serpentinite crystallization water of part is dehydrated
Reaction, by these mixtures, pelletizing, production become the pelletizing containing reducing agent carbon, then pelletizing are added on dry type ball press
Mineral hot furnace is melted, in melting process, the heavy metal Cr among carbon and asbestos tailings, Cd, Ni, Co, Mo between pelletizing
And iron oxide is reacted, and realizes the metallization of these metal oxides, then after melting and reducing, by the slag night of thawing
Mineral hot furnace is poured out, after slow cooling processing, the slag night of melting solidifies out into block-like mineral, and secondary mineral are crushed and are removed
After metal, by secondary mineral dust to 150 mesh, just become the solubility in citric acid slow release fertilizer that can be absorbed by plants.
Technical principle of the invention is based on innovative point below：
1) it is allowed to first with graphitic carbon as the oxide of iron and the oxide of heavy metal among reducing agent reduction asbestos tailings
Achieve the purpose that metallization.
2) to reach this purpose, asbestos tailings addition graphitic carbon is subjected to ball milling, the layer structure of graphite, in ball first
During mill, play the role of grinding aid, the difficulty of ball milling is reduced, while by the operation of ball mill, by graphite-phase to equal
Even is dispersed among material.
3) crystallization water in the operation process of ball mill, due to the effect of mechano-chemical reation, among asbestos tailings
It is partially completed dehydration, this is contributed for subsequent in mine heat furnace smelting reduction melting electric consumption.
4) it by the raw material pressure ball after milling, is added among mineral hot furnace, carries out energization smelting, since graphitic carbon can be uniform
Be distributed among furnace charge, and it is foundation that the additional amount of graphitic carbon, which is according to reducing heavy metal and iron oxide, so mine is hot
Reduction reaction in furnace can metallize the heavy metal among asbestos tailings, become metal droplet, disperse is at slag night
Centre, the heavy metal Pb harmful for environment vaporize after restoring first since its vapour pressure is lower, enter back into dust pelletizing system,
As dedusting ash, during this, de- splicer's skill of serpentinite is realized first.
5) after keeping the autoreduction reaction of 30min after melting, the slag night of melting is poured out into rear slow cooling, after preventing metallization
Heavy metal secondary oxidation.
6) after the fusion reduction reaction of above-mentioned mineral hot furnace, the fiber among serpentinite becomes the mineral group of recrystallization
It knits, eliminates harm of the asbestos fibre for environment.
7) SiO equally under the molten condition of mineral hot furnace, among mineral2, the crystal structures such as MgO, CaO send out at high temperature
Raw crystal transfer, becomes the simple crystal structure of structure.
8) mineral after slow cooling are crushed, then to ball milling in ball mill to 150 mesh, so that mineralogical composition therein,
As the solubility in citric acid fertilizer component that can be absorbed by plants.
9) after ball mill has gone out, by raw material enter magnetic field strength be 0.4T belt feeder magnetic separation system, the iron of metallization,
Nickel, cobalt have magnetic separation, are separated first by the magnetic field magnetic separation of 0.4T, and Cr metallic particles is sieved in the screening system of subsequent 150 mesh
It sub-elects, the purpose of the removing heavy metal element of asbestos tailings has been achieved, has reached the Fertilizer Transformed mesh of the elements such as calcium and magnesium silicon
's.
10) it is enriched the dedusting ash of Pb, is utilized as lead raw materials for metallurgy.
Key chemical reaction of the invention is as follows：
MgO[Si4O10](OH)8→3MgO·2SiO2+2H2O (mechano-chemical reation in ball mill)
3MgO·2SiO2→3MgO+2SiO2（Local reaction [the old auspicious data atlas 653 of family within the scope of 1898 DEG C of mineral hot furnace
Page]）
MgO·SiO2（s）→MgO·SiO2（l）（1577 DEG C of humite liquefaction reaction temperature [the old auspicious data atlas page 653 of family]）
MgO·SiO2（s）→MgO（s）+SiO2（s）（Decomposition reaction under solid-state, 25~1898 DEG C of reaction temperature）
αSiO2（s）→βSiO2（l）（The crystal transfer of silica under high temperature reacts, fertilizer efficiency reaction）
Cr2O3+3C→2Cr+3CO（The metallization reduction reaction of chromium）
Fe2O3+3C→2Fe+3CO（The metallization reduction reaction of iron）
FeO+C→Fe+CO（The metallization reduction reaction of iron）
NiO+C→Ni+CO（The metallization reduction reaction of nickel）
CoO+C→Co+CO（The metallization reduction reaction of cobalt）
MnO+C→Mn+CO（The metallization reduction reaction of manganese）
De- lead reaction process therein is as follows：
327.3 DEG C of the fusing point of lead, 1744 DEG C of boiling point, density 11.34g/cm3, 885 DEG C of PbO fusing point.Lead oxide and carbon and CO
Following reaction occurs:
PbO(l)+C=Pb(g) + CO(g)
ΔG0= 252700-247.92T
It is 746 DEG C from reaction starting temperature known to above formula.
PbO(l)+CO=Pb(g)+CO2(g)
ΔG0=86150-76.92T
It is calculated by above formula and knows that reaction starting temperature is 847 DEG C.From above-mentioned reaction, lead oxide is very easy to by carbon or CO
It is reduced into lead.So the lead among asbestos tailings enters dedusting ash after restoring, removed from raw material centre.
It is therein carried out with carbon according to the main reaction of reducing metal chromium, nickel, iron, cobalt it is excessive with addition of, it is contemplated that graphite electrode
Influence for smelting, with addition of coefficient be 1.2, it is of the invention with 2.4% that charcoal amount is mineral quantity（Selecting phosphorus content is 85%
Graphite matches carbon）.
Specific embodiment
The present invention is produced as example explanation with Ruoqiang Holy Land science and technology.
1) asbestos tailings are entered into ball mill ball milling with addition of graphite first；With 2.4% that charcoal amount is mineral quantity, quality percentage
Than；The graphite that phosphorus content is 85% is selected to match carbon；
2) ball mill discharges material ball milling to 100 mesh；
3) the above material is subjected to pressure ball using dry type pressure ball, sphere size is between 30~100mm；
4) mine heat furnace smelting is added by charging system in sphere, detects the CO between the concentration of flue gas, molten condition is kept
30min pours out the slag liquid in furnace；
5) enter ball mill after slag liquid slow cooling and be milled down to 150 mesh, the magnetic separator that material passes through 0.4T first during discharging select iron,
Cobalt, nickel, then material sieves powder by the rotary screen of 150 mesh, and for oversize as special tailing, carry out crome metal selects operation；
6）Raw material of the screenings of rotary screen as secondary and micro-element fertilizers, may be directly applied to farmland as pulvis, can also
It is used using after being granulated as secondary and micro-element fertilizers.
Claims (1)
1. a kind of method using mineral hot furnace melting asbestos tailings production magnesium silico-calcium fertilizer, it is characterised in that：First by asbestos tail
Mine enters ball mill ball milling with addition of graphite；With 2.4% that charcoal amount is mineral quantity, mass percent；Selecting phosphorus content is 85% stone
Ink matches carbon；Ball mill discharges material ball milling to 100 mesh；The above material is subjected to pressure ball, sphere size using dry type ball press
Between 30~100mm；Mine heat furnace smelting is added by charging system in sphere, molten condition keeps 30min, pours out in furnace
Slag liquid；Enter ball mill after slag liquid slow cooling and be milled down to 150 mesh, the magnetic separator that material passes through 0.4T first during discharging select iron,
Cobalt, nickel, then material sieves powder by the rotary screen of 150 mesh, and for oversize as special tailing, carry out crome metal selects operation；
Raw material of the screenings of rotary screen as secondary and micro-element fertilizers, may be directly applied to farmland as pulvis, can also be granulated
It is used afterwards as secondary and micro-element fertilizers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2018110341180 | 2018-09-05 | ||
| CN201811034118 | 2018-09-05 |
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| Publication Number | Publication Date |
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| CN108911795A true CN108911795A (en) | 2018-11-30 |
| CN108911795B CN108911795B (en) | 2021-06-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201811071447.2A Active CN108911795B (en) | 2018-09-05 | 2018-09-14 | Method for producing magnesium-silicon-calcium fertilizer by melting asbestos tailings in submerged arc furnace |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111410576A (en) * | 2020-03-16 | 2020-07-14 | 华南理工大学 | Method for realizing asbestos tailing detoxification and recycling by using activation and co-reduction method |
| CN113578518A (en) * | 2021-05-21 | 2021-11-02 | 若羌县圣地石棉尾料再利用科技开发有限公司 | Method for removing heavy metal by serpentine magnetization |
| CN114380626A (en) * | 2021-06-10 | 2022-04-22 | 若羌县圣地石棉尾料再利用科技开发有限公司 | Preparation method for extracting medium-trace element fertilizer by using asbestos tailings |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111410576A (en) * | 2020-03-16 | 2020-07-14 | 华南理工大学 | Method for realizing asbestos tailing detoxification and recycling by using activation and co-reduction method |
| CN113578518A (en) * | 2021-05-21 | 2021-11-02 | 若羌县圣地石棉尾料再利用科技开发有限公司 | Method for removing heavy metal by serpentine magnetization |
| CN114380626A (en) * | 2021-06-10 | 2022-04-22 | 若羌县圣地石棉尾料再利用科技开发有限公司 | Preparation method for extracting medium-trace element fertilizer by using asbestos tailings |
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