CN110904333A - Method for discharging serpentine magnesium extraction tailings without solid waste - Google Patents

Method for discharging serpentine magnesium extraction tailings without solid waste Download PDF

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CN110904333A
CN110904333A CN201911249240.4A CN201911249240A CN110904333A CN 110904333 A CN110904333 A CN 110904333A CN 201911249240 A CN201911249240 A CN 201911249240A CN 110904333 A CN110904333 A CN 110904333A
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aluminum
serpentine
silicon
calcium
magnesium extraction
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CN110904333B (en
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卢惠民
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Beijing Oufei Jintai Technology Co Ltd
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Beijing Oufei Jintai Technology Co Ltd
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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
    • C22B1/242—Binding; Briquetting ; Granulating with binders
    • 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
    • C22B21/00—Obtaining aluminium
    • C22B21/02—Obtaining aluminium with reducing
    • 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
    • C22B21/00—Obtaining aluminium
    • C22B21/06—Obtaining aluminium refining
    • C22B21/068—Obtaining aluminium refining handling in vacuum
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • C22B26/22—Obtaining magnesium
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/04—Refining by applying a vacuum
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention provides a method for discharging serpentine magnesium extraction tailings without solid waste, belonging to the field of mineral solid waste utilization. The invention makes full use of the tailings of extracting magnesium from serpentine, and the whole process has no discharge of tailings and is fully utilized; according to the invention, the serpentine magnesium extraction tailings are used as raw materials for producing the aluminum-silicon-calcium alloy, the reduction temperature (1500-1800 ℃) can be reduced due to the high content of calcium oxide in the serpentine magnesium extraction tailings, the generated scum is used for preparing the serpentine magnesium extraction tailings by using serpentine magnesium extraction, the aluminum-silicon-calcium alloy is further subjected to vacuum distillation to obtain metal calcium, and the rest aluminum-silicon alloy can be used as a serpentine magnesium extraction reducing agent. The whole process flow provided by the invention obtains metal magnesium, metal calcium and aluminum-silicon alloy, valuable elements in the serpentine magnesium extraction tailings are comprehensively utilized, and the whole process belongs to a green circulation process.

Description

Method for discharging serpentine magnesium extraction tailings without solid waste
Technical Field
The invention relates to the technical field of mineral solid waste utilization, in particular to a method for discharging serpentine magnesium extraction tailings without solid waste.
Background
China has a large amount of serpentine which reaches the level of hundreds of millions of tons and is a good raw material for producing metal magnesium, and China also has a large amount of laterite-nickel ore, the gangue mineral of which is serpentine and is also a good raw material for smelting magnesium. Therefore, when the serpentine and the laterite-nickel ore are used for refining magnesium metal, a large amount of tailings are generated. At present, the tailings have no good treatment method and are not beneficial to recycling of resources.
The invention patent 201710512597.1 discloses a method for discharging magnesium metal and byproducts from nickel-containing serpentine ore by vacuum thermal reduction, and although magnesium metal can be obtained from magnesium silicate minerals, a large amount of tailings generated become solid waste and seriously affect the environment.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for discharging serpentine magnesium extraction tailings without solid waste. The invention realizes the method for discharging no solid waste of the serpentine magnesium extraction tailings, obtains metallic calcium and aluminum-silicon alloy in the whole process flow, comprehensively utilizes valuable elements, and is a green circulation process.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a serpentine magnesium extraction tailings solid-free discharge method, which comprises the following steps:
mixing serpentine magnesium extraction tailings, an aluminum-containing material, a reducing agent, a binder and water, and then briquetting to obtain pellets, wherein the reducing agent comprises bituminous coal and petroleum coke;
carrying out reduction reaction on the pellets to obtain aluminum-silicon-calcium alloy liquid and scum, wherein the scum is used for extracting magnesium from serpentine to prepare serpentine magnesium extraction tailings;
mixing the aluminum-silicon-calcium alloy liquid with a refining agent for refining to obtain an aluminum-silicon-calcium alloy;
and carrying out vacuum distillation on the aluminum-silicon-calcium alloy to obtain metal calcium and aluminum-silicon alloy.
Preferably, the pellet comprises the following components in percentage by weight: 30-60% of serpentine magnesium extraction tailings, 20-30% of aluminum-containing materials, 20-40% of reducing agents, 5-8% of binders and 4-6% of water, wherein the sum of the mass percentages of the components is 100%.
Preferably, the mass ratio of the bituminous coal to the petroleum coke is 8: 2-6: 4.
Preferably, the fixed carbon content of the bituminous coal is 40-60%, and the fixed carbon content of the petroleum coke is 80-90%.
Preferably, the pelletizing is further dried, wherein the drying is performed at 100-150 ℃ until the mass percentage of water in the pellets is not more than 1%.
Preferably, the temperature of the reduction reaction is 1500-1800 ℃ and the time is 2-3 h.
Preferably, the vacuum degree of the vacuum distillation is 0.5-20 Pa, the temperature is 1000-1300 ℃, and the time is 2-5 h.
Preferably, the aluminum-containing material is one or more of fly ash, coal gangue, andalusite, bauxite, kyanite and kaolin.
Preferably, the briquetting pressure is 20-30 MPa.
The invention also provides a method for discharging serpentine magnesium extraction tailings without solid waste, which comprises the following steps: mixing serpentine magnesium extraction tailings, an aluminum-containing material, a reducing agent, a binder and water, and then briquetting to obtain pellets, wherein the reducing agent comprises bituminous coal and petroleum coke; carrying out reduction reaction on the pellets to obtain aluminum-silicon-calcium alloy liquid and scum, wherein the scum is used for extracting magnesium from serpentine to prepare serpentine magnesium extraction tailings; mixing the aluminum-silicon-calcium alloy liquid with a refining agent for refining to obtain an aluminum-silicon-calcium alloy; and carrying out vacuum distillation on the aluminum-silicon-calcium alloy to obtain metal calcium and aluminum-silicon alloy. The invention provides a novel method for discharging serpentine magnesium extraction tailings without solid waste, which makes full use of the serpentine magnesium extraction tailings, and the whole process has no tailings discharge and is fully utilized; according to the invention, the serpentine magnesium extraction tailings are used as raw materials for producing the aluminum-silicon-calcium alloy, the reduction temperature (1500-1800 ℃) can be reduced due to the high content of calcium oxide in the serpentine magnesium extraction tailings, the generated scum is used for preparing the serpentine magnesium extraction tailings by using serpentine magnesium extraction, the aluminum-silicon-calcium alloy is further subjected to vacuum distillation to obtain metal calcium, and the remaining aluminum-silicon alloy can also be used as a serpentine magnesium extraction reducing agent. The whole process flow provided by the invention obtains metal magnesium, metal calcium and aluminum-silicon alloy, valuable elements in the serpentine magnesium extraction tailings are comprehensively utilized, and the whole process belongs to a green circulation process. The data of the embodiment shows that the chemical components of the aluminum-silicon alloy obtained by the discharge method provided by the invention comprise 35-50 wt% of Al, 40-60 wt% of Si, 3-20 wt% of Fe and 0.001-0.005 wt% of Ca, and the purity of the obtained metal calcium reaches 99.5-99.9%.
Drawings
FIG. 1 is a flow chart of the method for discharging serpentine magnesium extraction tailings without solid waste.
Detailed Description
The invention provides a serpentine magnesium extraction tailings solid-free discharge method, which comprises the following steps:
mixing serpentine magnesium extraction tailings, an aluminum-containing material, a reducing agent, a binder and water, and then briquetting to obtain pellets, wherein the reducing agent comprises bituminous coal and petroleum coke;
carrying out reduction reaction on the pellets to obtain aluminum-silicon-calcium alloy liquid and scum, wherein the scum is used for extracting magnesium from serpentine to prepare serpentine magnesium extraction tailings;
mixing the aluminum-silicon-calcium alloy liquid with a refining agent for refining to obtain an aluminum-silicon-calcium alloy;
and carrying out vacuum distillation on the aluminum-silicon-calcium alloy to obtain metal calcium and aluminum-silicon alloy.
The invention mixes the serpentine magnesium extraction tailings, aluminum-containing materials, a reducing agent, a binder and water and then briquettes to obtain pellets, wherein the reducing agent comprises bituminous coal and petroleum coke. In the invention, the aluminum-containing material is preferably one or more of fly ash, coal gangue, andalusite, bauxite, kyanite and kaolin.
In the invention, the pellet preferably comprises the following components in percentage by weight: 30-60% of serpentine magnesium extraction tailings, 20-30% of aluminum-containing materials, 20-40% of reducing agents, 5-8% of binders and 4-6% of water, wherein the sum of the mass percentages of the components is 100%. The type of the binder is not particularly limited in the present invention, and any binder known to those skilled in the art may be used.
In the invention, the serpentine magnesium extraction tailings, the aluminum-containing material and the reducing agent are preferably independently ground into powder with the particle size of less than 1mm and then used.
In the invention, the mass ratio of the bituminous coal to the petroleum coke is preferably 8: 2-6: 4.
In the invention, the fixed carbon content of the bituminous coal is preferably 40-60%, and the fixed carbon content of the petroleum coke is preferably 80-90%. In the invention, the sum of the fixed carbon contents in the bituminous coal and the petroleum coke is preferably 93-95% of the theoretical requirement for complete reduction reaction.
In the invention, the briquetting is preferably made into pellets in a briquetting machine, and the briquetting pressure is preferably 20-30 MPa.
In the invention, the pelletizing is preferably carried out by drying, and the drying is preferably carried out at 100-150 ℃ until the mass percentage of water in the pellets is not more than 1%.
After the pellets are obtained, the pellets are subjected to reduction reaction to obtain aluminum-silicon-calcium alloy liquid and scum, and the scum is used for extracting magnesium from serpentine to prepare the serpentine magnesium extraction tailings.
In the invention, the temperature of the reduction reaction is preferably 1500-1800 ℃, more preferably 1550-1600 ℃, and the time is preferably 2-3 h. The invention uses the serpentine magnesium extraction tailings which contain a large amount of calcium oxide, so the temperature of the reduction reaction is low. In the present invention, the reduction reaction is preferably carried out in an AC or DC ore-thermal arc furnace.
In the invention, the yield of the scum is preferably 2-5%, and the main components of the scum comprise 50-60 wt% of MgO and SiO220～30wt％，CaO 5～10wt％，Al2O35～10wt％。
After the reduction reaction is finished, the invention preferably discharges the aluminum-silicon-calcium alloy liquid from the aluminum outlet ladle at regular intervals. In the present invention, the regular intervals are preferably 2 to 3 hours.
After the aluminum-silicon-calcium alloy liquid is obtained, the aluminum-silicon-calcium alloy liquid and a refining agent are mixed for refining to obtain the aluminum-silicon-calcium alloy. In the invention, because the aluminum-silicon-calcium alloy liquid contains a certain amount of non-metallic impurities, a refining agent is added into the ladle to remove slag. The type and amount of the refining agent are not particularly limited in the present invention, and conventional techniques of those skilled in the art may be used.
In the invention, the refining preferably comprises vacuum filtration deslagging, mixing and ingot casting after dilution in sequence to obtain the aluminum-silicon-calcium alloy. In the present invention, the aluminum-silicon-calcium alloy preferably includes the following components: 30-45 wt% of aluminum, 20-40 wt% of silicon, 20-45 wt% of calcium, 1-10 wt% of iron, and the balance of other elements contained in the raw materials entering the aluminum-silicon-calcium alloy through refining.
After the aluminum-silicon-calcium alloy is obtained, the aluminum-silicon-calcium alloy is subjected to vacuum distillation to obtain metal calcium and the aluminum-silicon alloy. In the invention, the vacuum degree of the vacuum distillation is preferably 0.5-20 Pa, the temperature is preferably 1000-1300 ℃, and the time is preferably 2-5 h. In the invention, the aluminum-silicon-calcium alloy is preferably crushed into fragments with the particle size of less than or equal to 10cm, and then the fragments are placed into a vacuum distillation tank for vacuum distillation. In the invention, after the vacuum distillation is finished, calcium is distilled out and condensed into solid calcium metal, and the rest material is aluminum-silicon alloy. In the present invention, the aluminum-silicon alloy preferably includes the following components: 35-50 wt% of Al, 40-60 wt% of Si, 3-20 wt% of Fe, 0.001-0.005 wt% of Ca, and the balance of other elements contained in the raw materials entering the aluminum-silicon-calcium alloy through refining. In the invention, the aluminum-silicon alloy is preferably recycled for serpentine magnesium extraction tailings.
FIG. 1 is a flow chart of the method for discharging serpentine magnesium extraction tailings without solid waste.
In order to further illustrate the present invention, the following will describe the method for discharging serpentine magnesium extraction tailings without solid waste in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
The method for discharging the serpentine magnesium extraction tailings used in the embodiment of the invention comprises the following steps:
and mining to obtain blocky serpentine ores with the maximum blockiness of 30 cm. The main ore mineral in the serpentine ore is serpentine and contains a small amount of olivine and chromium spinel, and the metal minerals include magnetite, hematite, chromite, pentlandite and chalcopyrite. The chemical composition is shown in table 1.
TABLE 1 serpentine chemical composition
MgO Al2O3 CaO Fe2O3 FeO Mn SiO2 Ni
35.54 0.64 3.36 5.23 1.47 0.048 37.17 0.22
Cr Co P S K20 Na2O TFe H2O
0.12 0.015 0.0022 0.0009 0.055 0.097 4.80 0.48
A1200-ton production line for producing magnesium metal by treating 2 ten thousand tons of serpentine in construction year comprises the following specific production processes: firstly, serpentine and lime are crushed to about 5 cm by a PE400 x 600 jaw crusher, and then the crushed serpentine, lime and silicon-aluminum alloy powder (the chemical components of the silicon-aluminum alloy powder are Al 25-50 wt%, Si 40-60 wt%, Fe 10-20 wt%, and the silicon-aluminum-iron alloy is discharged by an Inmunoquan gangue carbon thermal reduction method and ground into 120 meshes) and fluorite powder (chemical reagent grade, CaF) are added into a phi 1.5 x 5.7 type ball mill according to the mixture ratio298 percent purity and-80 meshes) are mixed and ground to 120 meshes, 50 percent of serpentine, 40 percent of additive lime (chemical grade, 98 percent purity and-80 meshes) and 10 percent of total amount of silicon-aluminum alloy and catalyst fluorite powder. The ground mixture enters a GF520 dry powder ball press machine to be pressed into balls, the long diameter is 3 cm, and the short diameter is 2 cm. Dry ball feedingAnd (3) putting the magnesium into a vacuum continuous production induction heating magnesium reduction furnace, vacuumizing by 10Pa, heating power by 1000kW, temperature by 1200 ℃, and keeping the temperature of each furnace for 4 hours. Feeding and discharging slag under vacuum condition, and keeping vacuum state and constant temperature heating state in the furnace. The magnesium reduction furnace is provided with two magnesium crystallizers, and crude magnesium is periodically and alternately discharged (3 groups). The mixed slag discharged from the furnace is in a block shape, is crushed to micron level by a double-roll crusher, enters a dry magnetic separator, and has the magnetic field intensity of 8000-12000 gauss to obtain ferronickel alloy particles, and the chemical analysis of the finally obtained tailings, namely the serpentine magnesium extraction tailings, is shown in table 2.
TABLE 2 serpentine magnesium extraction tailings chemistry
Serial number CaO Fe2O3 Al2O3 SiO2 MgO
1 65.73 2.12 7.61 18.46 6.08
2 61.69 13.45 4.39 17.44 3.03
3 61.47 2.04 8.83 20.29 5.47
As can be seen from the results of X-ray diffraction analysis of the tailings, the tailings are mainly 2 CaO. SiO2And a small amount of 12CaO 7Al2O3And (4) forming.
Example 1
The serpentine magnesium extraction tailings and aluminum-containing material fly ash are used as raw materials, bituminous coal and petroleum coke are used as reducing agents, the serpentine magnesium extraction tailings are 40%, the aluminum-containing material is 30%, the bituminous coal and the petroleum coke are 20%, and 5% of binder and 5% of water are added. The fixed carbon content of bituminous coal is 40%, the fixed carbon content of petroleum coke is 90%, and the material mixing ratio of bituminous coal and petroleum coke is 8: 2.
The production steps are as follows:
1. respectively grinding the serpentine magnesium extraction tailings fly ash, the reducing agent bituminous coal and the petroleum coke into powder with the granularity of less than 1 mm; all materials are uniformly mixed in a mixer. The mixed materials are made into pellets in a briquetting machine, and the briquetting pressure is 20 MPa; drying and dehydrating the prepared pellets at 100 ℃, wherein the water content is required to be not more than 1%.
2. And (3) adding the dried pellets into an alternating current ore thermal arc furnace, wherein the temperature in the furnace is 1500 ℃, and the reduction reaction time is 3 hours.
3. And discharging the aluminum-silicon-calcium alloy liquid from the aluminum outlet to the ladle at regular intervals (at intervals of 3 hours). Because the alloy contains a certain amount of non-metallic impurities, a refining agent is added into the ladle to remove slag. Adding a refining agent into a ladle, carrying out vacuum filtration for deslagging, mixing, diluting, and then carrying out ingot casting to obtain the aluminum-silicon-calcium alloy, wherein the aluminum-silicon-calcium alloy comprises the following components: aluminium 30 wt%, silicon 40 wt%, calcium 25 wt%, iron 5 wt%, and the balance of other elements contained in the raw materials which are introduced into the aluminum-silicon-calcium alloy by melting. At this stage, in addition to the production of Al-Si-Ca alloy, 2% of dross is produced, containing 50% of MgO and 50% of SiO as main components220％，CaO 5％，Al2O310 percent. The scum returns to the serpentine magnesium extraction process.
Crushing the aluminum-silicon-calcium alloy block into fragments with the granularity less than or equal to 10cm, putting the fragments into a vacuum distillation tank, heating the fragments to 1000 ℃ under the condition that the vacuum degree is 20Pa, and carrying out vacuum distillation for 5 hours; keeping the vacuum degree at 20Pa in the vacuum distillation process; after vacuum distillation is finished, calcium is distilled out and condensed into solid metal calcium, the rest material is aluminum-silicon alloy (Al-50Si), the purity of the metal calcium reaches 99.9%, and the aluminum-silicon alloy comprises the following main chemical components: 40 wt% of Al, 50 wt% of Si, 5 wt% of Fe, 0.001wt% of Ca0, and the balance of other elements contained in the raw materials entering the aluminum-silicon-calcium alloy through refining. Aluminum-silicon alloy is used as a reducing agent to be reused in serpentine magnesium extraction tailings.
Example 2
The serpentine magnesium extraction tailings and aluminum-containing material coal gangue are used as raw materials, bituminous coal and petroleum coke are used as reducing agents, 50% of the serpentine magnesium extraction tailings, 20% of aluminum-containing materials and 20% of bituminous coal and petroleum coke are added, and 6% of binder and 4% of water are added. The fixed carbon content of bituminous coal is 40%, the fixed carbon content of petroleum coke is 90%, and the material mixing ratio of bituminous coal and petroleum coke is 6: 4.
The production steps are as follows:
1. respectively grinding the serpentine magnesium extraction tailings fly ash, the reducing agent bituminous coal and the petroleum coke into powder with the granularity of less than 1 mm; all materials are uniformly mixed in a mixer. The mixed materials are made into pellets in a briquetting machine, and the briquetting pressure is 30 MPa; drying and dehydrating the prepared pellets at 150 ℃ until the water content is not more than 1 percent.
2. And (3) adding the dried pellets into an alternating current ore thermal arc furnace, wherein the temperature in the furnace is 1800 ℃, and the reduction reaction time is 2 hours.
3. And discharging the aluminum-silicon-calcium alloy liquid from the aluminum outlet to the ladle at regular intervals (2 hours). Because the alloy contains a certain amount of non-metallic impurities, the alloy needs to be added into a ladleAnd removing slag of the refining agent. Adding a refining agent into the ladle, carrying out vacuum filtration for deslagging, mixing, diluting, and then carrying out ingot casting to obtain the aluminum-silicon-calcium alloy, wherein the aluminum-silicon-calcium alloy comprises the following components in percentage by weight: 40 wt% of aluminum, 25 wt% of silicon, 30 wt% of calcium, 8 wt% of iron and the balance of other elements contained in the raw materials which are smelted into the aluminum-silicon-calcium alloy. At this stage, 5% of dross, including 60 wt% of MgO and 60 wt% of SiO, is produced in addition to the Al-Si-Ca alloy230wt％，CaO 5wt％，Al2O35 wt%. The scum returns to the serpentine magnesium extraction process.
Crushing the aluminum-silicon-calcium alloy block into fragments with the granularity less than or equal to 10cm, putting the fragments into a vacuum distillation tank, heating the fragments to 1300 ℃ under the condition that the vacuum degree is 0.5Pa, and carrying out vacuum distillation for 4 hours; the vacuum degree is kept at 0.5Pa in the vacuum distillation process; after vacuum distillation is finished, calcium is distilled out and condensed into solid metal calcium, the rest material is aluminum-silicon alloy (Al-50Si), the purity of the metal calcium reaches 99.9%, and the aluminum-silicon alloy comprises the following main chemical components: 45 wt% of Al, 53 wt% of Si, Fewt 12%, 0.001wt% of Ca0, and the balance of other elements contained in raw materials entering the aluminum-silicon-calcium alloy through refining, wherein the aluminum-silicon alloy is used as a reducing agent to be reused in serpentine magnesium extraction tailings.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (9)

1. A method for discharging serpentine magnesium extraction tailings without solid waste is characterized by comprising the following steps:
mixing serpentine magnesium extraction tailings, an aluminum-containing material, a reducing agent, a binder and water, and then briquetting to obtain pellets, wherein the reducing agent comprises bituminous coal and petroleum coke;
carrying out reduction reaction on the pellets to obtain aluminum-silicon-calcium alloy liquid and scum, wherein the scum is used for extracting magnesium from serpentine to prepare serpentine magnesium extraction tailings;
mixing the aluminum-silicon-calcium alloy liquid with a refining agent for refining to obtain an aluminum-silicon-calcium alloy;
and carrying out vacuum distillation on the aluminum-silicon-calcium alloy to obtain metal calcium and aluminum-silicon alloy.
2. The discharge method as claimed in claim 1, wherein the pellets comprise the following components in percentage by weight: 30-60% of serpentine magnesium extraction tailings, 20-30% of aluminum-containing materials, 20-40% of reducing agents, 5-8% of binders and 4-6% of water, wherein the sum of the mass percentages of the components is 100%.
3. The discharging method according to claim 1 or 2, wherein the mass ratio of the bituminous coal to the petroleum coke is 8: 2 to 6: 4.
4. The discharging method according to claim 1 or 2, wherein the bituminous coal has a fixed carbon content of 40 to 60% and the petroleum coke has a fixed carbon content of 80 to 90%.
5. The discharging method as claimed in claim 1, wherein the pelletizing is followed by drying, wherein the drying is performed at 100-150 ℃ until the mass percentage of water in the pellets does not exceed 1%.
6. The discharge method according to claim 1, wherein the temperature of the reduction reaction is 1500-1800 ℃ and the time is 2-3 h.
7. The discharging method according to claim 1, wherein the vacuum degree of the vacuum distillation is 0.5-20 Pa, the temperature is 1000-1300 ℃, and the time is 2-5 h.
8. The discharge method according to claim 1, wherein the aluminum-containing material is one or more of fly ash, coal gangue, andalusite, bauxite, kyanite and kaolin.
9. The discharge method according to claim 1, wherein the briquetting pressure is 20 to 30 MPa.
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CN105331806A (en) * 2015-10-05 2016-02-17 杭州碧清环保科技有限公司 Pellets manufactured through magnesium smelting waste and manufacturing method of pellets
CN108342585A (en) * 2018-03-13 2018-07-31 东北大学 A kind of method of comprehensive utilization of magnesium-smelting reduction slag
KR20180097855A (en) * 2017-02-24 2018-09-03 주식회사 텍사리소스 Non-roasting Pellet Composition Prepared By Using Melted Iron slags and Melted Iron Process By-products, and Pellet Preparation Method

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* Cited by examiner, † Cited by third party
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CN103451450A (en) * 2013-09-25 2013-12-18 会理瑞志镍镁矿业有限责任公司 Method for comprehensively utilizing serpentine containing nickel
CN105331806A (en) * 2015-10-05 2016-02-17 杭州碧清环保科技有限公司 Pellets manufactured through magnesium smelting waste and manufacturing method of pellets
KR20180097855A (en) * 2017-02-24 2018-09-03 주식회사 텍사리소스 Non-roasting Pellet Composition Prepared By Using Melted Iron slags and Melted Iron Process By-products, and Pellet Preparation Method
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