CN108911795B - Method for producing magnesium-silicon-calcium fertilizer by melting asbestos tailings in submerged arc furnace - Google Patents
Method for producing magnesium-silicon-calcium fertilizer by melting asbestos tailings in submerged arc furnace Download PDFInfo
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- CN108911795B CN108911795B CN201811071447.2A CN201811071447A CN108911795B CN 108911795 B CN108911795 B CN 108911795B CN 201811071447 A CN201811071447 A CN 201811071447A CN 108911795 B CN108911795 B CN 108911795B
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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
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- 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
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- 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
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- 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
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- 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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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
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- 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 method for producing a magnesium-silicon-calcium fertilizer by melting asbestos tailings in a submerged arc furnace, which comprises the following steps of firstly adding graphite into the asbestos tailings, and then feeding the mixture into a ball mill for ball milling; the carbon content is 2.4 percent of the mineral content by mass percent; selecting graphite with 85% carbon content for carbon matching; the ball mill is used for ball-milling the materials to 100 meshes and discharging the materials; pressing the materials by a dry ball press, wherein the size of the ball is 30-100 mm; adding the spheres into an ore furnace through a feeding system for smelting, keeping the molten state for 30min, and pouring out slag liquid in the furnace; slowly cooling the slag liquid, grinding the slag liquid into 150 meshes in a ball mill, selecting iron, cobalt and nickel from the materials by a 0.4T magnetic separator in the discharging process, screening the materials by a 150-mesh rotary screen, and taking oversize materials as special tailings to perform the selection operation of metal chromium; the undersize of the drum sieve is used as a raw material of the medium trace element fertilizer, can be directly applied to farmlands as powder, and can also be used as the medium trace element fertilizer after granulation.
Description
Technical Field
The invention relates to a method for producing a magnesium-silicon-calcium fertilizer by melting asbestos tailings in a submerged arc furnace.
Background
Asbestos is an important mineral raw material in the national economic construction process. Asbestos is produced in serpentine mineral belt, and 40 tons of tailing waste serpentine are produced every one ton of asbestos. The asbestos tailings are typical dangerous wastes because of being rich in heavy metals such as Cr, nickel, cobalt, copper, iron and the like, and are serious in harm to the environment and animals and plants, and the components of the asbestos tailings which are originally produced in Aljinshan and Kunlun mountain in Qiang county in Xinjiang are partially shown in the following table:
from the above table, serpentine is a hydrous silicate mineral of magnesium. The chemical composition of the material is 3 MgO.2SiO2·2H2O or MgO [ Si ]4O10](OH)8And the asbestos tailings have high heavy metal content and great harm to soil.
In the middle of the paper entitled "current situation of asbestos tailings and research progress of resource utilization" published in "the journal of non-metal mining industry" of china, 2007 3 rd of the consulting literature (1), santo zhu hong, zheng shui lin, there are the following contents: "the asbestos tailings in China are accumulated in large quantities, and cause great pollution to the environment. Since the 90 s of the 20 th century, Chinese scientists have made some research on the comprehensive utilization of asbestos tailings, but so far, although some development projects have good application prospects, the industrial utilization is slow in progress, and even no content expression of high-efficiency industrial comprehensive utilization in the true sense exists; (2) the intermediate of the paper entitled "research progress on resource utilization of chrysotile and tailings" published in "journal of non-metallic mineral industry in china" 2014 4 of Wuchunxiang, Song Peng Cheng Juan, Peng Tong Jiang, has the following content: the chrysotile tailings belong to industrial solid wastes, although valuable components are deeply extracted and researched, the industrial production is not carried out except the pilot plant test in the industry park of Aksai Gansu and Bulack Xinjiang Yigul, and the production process needs to be solved, such as the volatilization of ammonia water and the pollution of sulfuric acid to instruments and environment
Dyeing and the like. "is expressed in terms of content; (3) the subject of the publication of the journal of mineral comprehensive utilization of Suqingping and Longxiao in No. 1 of 2009 is that asbestos tailings contains a large amount of unselected asbestos tailings
Fine short fibers, which drift with the wind, cause damage to the atmospheric quality. In recent years, with the development of high-temperature plasma technology, high-temperature crystallization technology of asbestos waste has been developed in developed countries such as italy and france, and the technology is described as a content of converting asbestos waste into wear-resistant and corrosion-resistant glass ceramic without melting at high temperature and then taking on a fibrous form.
The above documents show that no technological method for producing fertilizer by using asbestos tailings is introduced at present, and no technological method for removing heavy metals in asbestos tailings is introduced.
Disclosure of Invention
The invention aims to provide a method for producing a magnesium-silicon-calcium fertilizer by melting asbestos tailings in a submerged arc furnace, which can effectively treat the asbestos tailings and change waste into valuable.
The invention aims to realize the method for producing the magnesium-silicon-calcium fertilizer by melting asbestos tailings in the submerged arc furnace, firstly adding graphite into the asbestos tailings and then feeding the mixture into a ball mill for ball milling; the carbon content is 2.4 percent of the mineral content by mass percent; selecting graphite with 85% carbon content for carbon matching; the ball mill is used for ball-milling the materials to 100 meshes and discharging the materials; pressing the materials by a dry ball press, wherein the size of the ball is 30-100 mm; adding the spheres into an ore furnace through a feeding system for smelting, keeping the molten state for 30min, and pouring out slag liquid in the furnace; slowly cooling the slag liquid, grinding the slag liquid into 150 meshes in a ball mill, selecting iron, cobalt and nickel from the materials by a 0.4T magnetic separator in the discharging process, screening the materials by a 150-mesh rotary screen, and taking oversize materials as special tailings to perform the selection operation of metal chromium; the undersize of the drum sieve is used as a raw material of the medium trace element fertilizer, can be directly applied to farmlands as powder, and can also be used as the medium trace element fertilizer after granulation.
The inventor finds that the asbestos tailing powder is mixed with graphite carbon and ground in a ball mill according to a metallurgical principle and a mechanochemical inverse principle and by combining with the mineralogical characteristics of serpentine, the graphite carbon can be uniformly distributed among the asbestos tailing powder in the process of grinding in the ball mill, the particle size of the powder is controlled to be 100 meshes, in the process, the mechanochemical inverse effect can promote the crystal structure in the asbestos tailing to generate lattice distortion, partial serpentine crystal water generates dehydration reaction, the mixture is pelletized on a dry type ball press to produce pellets containing reducing agent carbon, then the pellets are added into a submerged arc furnace to be melted, in the melting process, the carbon among the pellets reacts with heavy metals Cr, Cd, Ni, Co, Mo and iron oxide in the asbestos tailing to realize the metallization of the metal oxides, and pouring the melted slag out of the ore furnace after melting reduction, solidifying the melted slag into blocky mineral after slow cooling treatment, crushing and removing metals from the secondary mineral, and then pulverizing the secondary mineral to 150 meshes to obtain the citric acid-soluble slow-release fertilizer capable of being absorbed by plants.
The technical principle of the invention is based on the following innovation points:
1) firstly, graphite carbon is used as a reducing agent to reduce the oxides of intermediate iron and heavy metals in asbestos tailings, so that the aim of metallization is fulfilled.
2) In order to achieve the purpose, graphite carbon is added into the asbestos tailings for ball milling, the layered structure of graphite plays a role of a grinding aid in the ball milling process, the ball milling difficulty is reduced, and meanwhile, graphite is relatively uniformly dispersed among materials through the operation of a ball mill.
3) In the operation process of the ball mill, due to the action of mechanochemical reaction, the crystal water in the asbestos tailings partially completes dehydration reaction, which contributes to the reduction of smelting power consumption in the following smelting in a submerged arc furnace.
4) The milled raw materials are pressed into balls and added into the middle of the submerged arc furnace for electrified smelting, because graphite carbon can be uniformly distributed in the middle of furnace materials, and the addition amount of the graphite carbon is based on reduction of heavy metal and iron oxide, the reduction reaction in the submerged arc furnace can metalize the heavy metal in the middle of asbestos tailings to form metal droplets which are dispersed in the middle of slag liquid, and the heavy metal Pb which is harmful to the environment is vaporized after being reduced firstly due to lower steam pressure and then enters a dust removal system to form dust, and in the process, the deleading process of the serpentine is realized firstly.
5) After 30min of self-reduction reaction after melting, pouring out the molten slag and slowly cooling to prevent secondary oxidation of the metallized heavy metal.
6) After the melting reduction reaction of the submerged arc furnace, the fibers in the middle of the serpentine become recrystallized mineral tissues, and the harm of asbestos fibers to the environment is eliminated.
7) SiO in the middle of the ore in the molten state in the submerged arc furnace2And the crystal structures of MgO, CaO and the like are subjected to crystal form conversion at high temperature to form a crystal structure with a simple structure.
8) And crushing the slowly cooled minerals, and then ball-milling the crushed minerals into 150 meshes in a ball mill, so that the mineral components in the crushed minerals become citrate-soluble fertilizer components capable of being absorbed by plants.
9) After the ball mill is discharged, the raw materials enter a belt conveyor magnetic separation system with the magnetic field intensity of 0.4T, the metalized iron, nickel and cobalt are subjected to magnetic separation, the metalized iron, nickel and cobalt are firstly subjected to magnetic separation by the magnetic field of 0.4T, and Cr metal particles are screened out by a subsequent 150-mesh screening system, so that the purpose of removing heavy metal elements from asbestos tailings is achieved, and the purpose of fertilizing calcium, magnesium, silicon and other elements is achieved.
10) The dust collected with the enriched Pb is used as the raw material for smelting lead.
The key chemical reactions of the invention are as follows:
MgO[Si4O10](OH)8→3MgO·2SiO2+2H2o (mechanochemical reaction in ball mill)
3MgO·2SiO2→3MgO+2SiO2(local reaction in the submerged arc furnace 1898 ℃ C. [ Chen Jia Xiang data atlas 653 p.)]）
MgO·SiO2（s）→MgO·SiO2（l）(reaction temperature of liquefaction of stevensite 1577 ℃ [ Chenxiang data atlas 653 page)]）
MgO·SiO2（s）→MgO（s）+SiO2（s）(decomposition reaction in solid state at a reaction temperature of 25 to 1898 ℃ C.)
αSiO2（s）→βSiO2（l）(Crystal transformation reaction of silicon dioxide at high temperature, fertilizer efficiency reaction)
Cr2O3+3C → 2Cr +3CO (reduction of chromium by metallization)
Fe2O3+3C → 2Fe +3CO (reduction of iron by metallization)
FeO + C → Fe + CO (iron metallization reduction reaction)
NiO + C → Ni + CO (reduction of nickel)
CoO + C → Co + CO (cobalt metal reduction reaction)
MnO + C → Mn + CO (metallization reduction reaction of manganese)
The deleading reaction process comprises the following steps:
melting point of lead is 327.3 ℃, boiling point is 1744 ℃, and density is 11.34g/cm3PbO has a melting point of 885 ℃. The lead oxide reacts with carbon and CO as follows:
PbO(l)+C=Pb(g) + CO(g)
ΔG0= 252700-247.92T
from the above formula, the reaction temperature was 746 ℃.
PbO(l)+CO=Pb(g)+CO2(g)
ΔG0=86150-76.92T
The initial reaction temperature was 847 ℃ as calculated from the above formula. From the above reaction, it is known that lead oxide is very easily reduced to lead by carbon or CO. Therefore, the lead in the middle of the asbestos tailings enters into the dedusting ash after being reduced, and is removed from the middle of the raw material.
The carbon is excessively added according to the main reaction of reducing metal chromium, nickel, iron and cobalt, the influence of a graphite electrode on smelting is considered, the addition coefficient is 1.2, and the carbon addition amount of the invention is 2.4% of the mineral amount (the graphite carbon with the carbon content of 85% is selected).
Detailed Description
The invention is illustrated by the production of the boehmeria technology.
1) Firstly, adding graphite into asbestos tailings, and then feeding the asbestos tailings into a ball mill for ball milling; the carbon content is 2.4 percent of the mineral content by mass percent; selecting graphite with 85% carbon content for carbon matching;
2) the ball mill is used for ball-milling the materials to 100 meshes and discharging the materials;
3) pressing the materials into balls by adopting dry-type ball pressing, wherein the size of each ball is 30-100 mm;
4) adding the spheres into a submerged arc furnace through a feeding system for smelting, detecting CO between the concentrations of the flue gas, keeping the molten state for 30min, and pouring out slag liquid in the furnace;
5) slowly cooling the slag liquid, grinding the slag liquid into 150 meshes in a ball mill, selecting iron, cobalt and nickel from the materials by a 0.4T magnetic separator in the discharging process, screening the materials by a 150-mesh rotary screen, and taking oversize materials as special tailings to perform the selection operation of metal chromium;
6) the undersize of the drum sieve is used as a raw material of the medium trace element fertilizer, can be directly applied to farmlands as powder, and can also be used as the medium trace element fertilizer after granulation.
Claims (1)
1. A method for producing a magnesium-silicon-calcium fertilizer by melting asbestos tailings by a submerged arc furnace is characterized by comprising the following steps: firstly, adding graphite into asbestos tailings, and then feeding the asbestos tailings into a ball mill for ball milling; the carbon content is 2.4 percent of the mineral content by mass percent; selecting graphite with 85% carbon content for carbon matching; the ball mill is used for ball-milling the materials to 100 meshes and discharging the materials; pressing the materials by a dry ball press, wherein the size of the ball is 30-100 mm; adding the spheres into an ore furnace through a feeding system for smelting, keeping the molten state for 30min, and pouring out slag liquid in the furnace; slowly cooling the slag liquid, grinding the slag liquid into 150 meshes in a ball mill, selecting iron, cobalt and nickel from the materials by a 0.4T magnetic separator in the discharging process, screening the materials by a 150-mesh rotary screen, and taking oversize materials as special tailings to perform the selection operation of metal chromium; the undersize of the drum sieve is used as a raw material of the medium trace element fertilizer, can be directly applied to farmlands as powder, and can also be used as the medium trace element fertilizer after granulation.
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| CN201811034118 | 2018-09-05 |
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| CN108911795B true CN108911795B (en) | 2021-06-22 |
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| CN111410576B (en) * | 2020-03-16 | 2023-01-31 | 纽博恩(佛山)科技有限公司 | 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 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5420035A (en) * | 1977-07-16 | 1979-02-15 | Chichibu Cement Kk | Production of asbestos cement board having smooth surface |
| CN1097408A (en) * | 1994-04-22 | 1995-01-18 | 西南工学院 | A kind of production method of mineral fertilizer containing natural magnesium and purposes |
| CN101942562A (en) * | 2010-04-26 | 2011-01-12 | 张夫道 | Harmless treatment technology of main metal tailings |
| CN103540768A (en) * | 2013-10-18 | 2014-01-29 | 左晓娟 | Integrated serpentine nickel element smelting process |
| CN103694001A (en) * | 2013-12-20 | 2014-04-02 | 华南理工大学 | Method for preparing mineral fertilizer by using serpentine |
| CN106365915A (en) * | 2016-09-10 | 2017-02-01 | 上海大学 | Method for preparing silicon-magnesium-phosphorus-potassium composite fertilizer from serpentine |
| CN106733068A (en) * | 2016-10-19 | 2017-05-31 | 中信重工机械股份有限公司 | The recovery method of nickel chromium triangle metal in a kind of metallurgical tailings |
-
2018
- 2018-09-14 CN CN201811071447.2A patent/CN108911795B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5420035A (en) * | 1977-07-16 | 1979-02-15 | Chichibu Cement Kk | Production of asbestos cement board having smooth surface |
| CN1097408A (en) * | 1994-04-22 | 1995-01-18 | 西南工学院 | A kind of production method of mineral fertilizer containing natural magnesium and purposes |
| CN101942562A (en) * | 2010-04-26 | 2011-01-12 | 张夫道 | Harmless treatment technology of main metal tailings |
| CN103540768A (en) * | 2013-10-18 | 2014-01-29 | 左晓娟 | Integrated serpentine nickel element smelting process |
| CN103694001A (en) * | 2013-12-20 | 2014-04-02 | 华南理工大学 | Method for preparing mineral fertilizer by using serpentine |
| CN106365915A (en) * | 2016-09-10 | 2017-02-01 | 上海大学 | Method for preparing silicon-magnesium-phosphorus-potassium composite fertilizer from serpentine |
| CN106733068A (en) * | 2016-10-19 | 2017-05-31 | 中信重工机械股份有限公司 | The recovery method of nickel chromium triangle metal in a kind of metallurgical tailings |
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