CN112851169A - Method for solidifying heavy metal elements in copper slag - Google Patents

Method for solidifying heavy metal elements in copper slag Download PDF

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CN112851169A
CN112851169A CN202110190451.6A CN202110190451A CN112851169A CN 112851169 A CN112851169 A CN 112851169A CN 202110190451 A CN202110190451 A CN 202110190451A CN 112851169 A CN112851169 A CN 112851169A
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concentration
less
copper slag
equal
copper
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王肇嘉
刘艳军
徐瑞来
李沙
李润峰
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Beijing Building Materials Academy of Sciences Research
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Beijing Building Materials Academy of Sciences Research
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/30—Mixed waste; Waste of undefined composition
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/12—Waste materials; Refuse from quarries, mining or the like
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • C04B18/141—Slags
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Civil Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mining & Mineral Resources (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention relates to the technical field of dangerous waste disposal in metallurgical industry, in particular to a method for solidifying heavy metal elements in copper slag. The method comprises the following steps: mixing copper slag, mineral substances and additives, granulating, drying and calcining; wherein SiO in the mineral substance2With Al2O3The sum of the total amount of the components is more than 50 percent, SiO2/Al2O3The ratio is more than or equal to 0.5; the additive is one or more selected from carbonate, sulfate, silicate, bentonite, montmorillonite, limestone, calcium oxide and magnesium oxide. According to the invention, specific copper slag is consolidated by a specific method, and the obtained granular matters are judged to be general solid wastes according to the heavy metal elements in the solid matter leachate prepared according to the standard leaching toxicity identification of hazardous wastes of GB5085.3-2007 'identification standard of hazardous wastes'. According to the inventionThe granular substances can replace natural sandstone aggregates, and large-scale treatment and high-added-value application of the copper slag hazardous waste are realized.

Description

Method for solidifying heavy metal elements in copper slag
Technical Field
The invention relates to the technical field of dangerous waste disposal in metallurgical industry, in particular to a method for solidifying heavy metal elements in copper slag.
Background
The copper slag is slag generated in the copper smelting process and belongs to one of non-ferrous metal slag; the waste slag discharged by adopting the reverberatory furnace method for smelting copper is reverberatory furnace copper slag, and the waste slag discharged by adopting the blast furnace for smelting copper is blast furnace copper slag. When 1 ton of copper is smelted, 10-20 tons of slag are produced by a reverberatory furnace method, and 50-100 tons of copper slag are produced by a blast furnace method. More importantly, researches show that under the influence of copper ore sources, copper slag discharged by many copper smelting enterprises contains a large amount of heavy metal elements such as arsenic, chromium, cadmium, manganese, lead, zinc, nickel, copper and the like, the content of the heavy metal elements in solid waste leachate prepared according to HJ/T299 is detected according to GB5085.3-2007 'hazardous waste identification Standard Leaching toxicity identification', the test result far exceeds the standard limit value, and the identification result is hazardous waste. In particular, the overproof arsenic which is easy to cause cancer is extremely serious.
Currently, the main disposal methods of copper slag include: producing portland cement clinker by using copper slag as an iron correcting agent instead of iron powder; copper smelting water quenched slag is used as a main raw material, and a small amount of excitant (gypsum and cement clinker) and other materials are added to produce copper slag cement through fine grinding. The copper slag is used as raw material to produce products such as plastering mortar, low-grade concrete, hollow small building blocks and the like. However, the above-mentioned treatment method does not sufficiently take into consideration the influence of leaching of heavy metals such as arsenic on groundwater, soil, plant pollution, and human health, and has a limited scale of treatment and a low added value. Therefore, a safe, large-scale and high-added-value hazardous waste treatment technology for copper slag is needed.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for consolidating heavy metal elements in copper slag, which can effectively consolidate the heavy metal elements (arsenic, cadmium, chromium, copper, manganese, nickel, lead, zinc and the like) in the copper slag, so that the content of the heavy metal elements in the treated copper slag in a solid waste leachate prepared according to HJ/T299 is detected according to GB5085.3-2007 'hazardous waste identification Standard Leaching toxicity identification', and the treated copper slag is judged to be general solid waste; it is another object of the present invention to provide a pellet.
Specifically, the invention provides the following technical scheme:
the invention provides a method for consolidating heavy metal elements in copper slag, which comprises the following steps: mixing copper slag, mineral substances and additives, granulating, drying and calcining;
wherein SiO in the mineral substance2With Al2O3The sum of the total amount of the components is more than 50 percent, SiO2/Al2O3The ratio is more than or equal to 0.5; the additive is one or more selected from carbonate, sulfate, silicate, bentonite, montmorillonite, limestone, calcium oxide and magnesium oxide.
The invention discovers that the heavy metal in the copper slag can be effectively consolidated by adopting specific mineral substances and additives, granulating, drying and then calcining and vitrifying after mixing with the copper slag.
Preferably, the weight ratio of the copper slag: minerals: 20-70% of additive: 25-70: 1 to 10.
With the consolidation system of the present invention, when the mass ratio of the copper slag to the minerals and additives is within the above range, the consolidation effect is better.
Preferably, the mineral is one or more selected from kaolinite crystal, montmorillonite crystal, albite crystal, potassium feldspar crystal, anorthite crystal, bauxite crystal mineral, sandstone crystal mineral, fly ash, diatomite, silica fume and coal gangue; the additive is one or more selected from limestone, calcium oxide, magnesium oxide, bentonite and calcium sulfate.
Preferably, the heavy metal in the copper slag is one or more selected from arsenic, cadmium, chromium, copper, manganese, nickel, lead and zinc; the concentration of arsenic is less than or equal to 2500mg/kg, the concentration of cadmium is less than or equal to 30mg/kg, the concentration of chromium is less than or equal to 300mg/kg, the concentration of copper is less than or equal to 3000mg/kg, the concentration of manganese is less than or equal to 1000mg/kg, the concentration of nickel is less than or equal to 200mg/kg, the concentration of lead is less than or equal to 3500mg/kg, and the concentration of zinc is less than or equal to 1200 mg/kg.
Preferably, the copper slag comprises the following chemical elements in percentage by mass: iron element, in the form of Fe2O3Counting by 30-75%; aluminum elementElemental and silicon elements, with SiO2+Al2O3The sum is 20-50%; the total amount of other chemical elements is 5-15% by oxide.
The consolidation method provided by the invention is particularly suitable for the copper slag, namely when the heavy metals and chemical elements in the copper slag are in the range, the consolidation effect is improved.
Preferably, the granulated material obtained after granulation has an individual particle aspect ratio of not more than 2.0 and a particle size of not more than 20 mm.
Preferably, the calcination adopts a staged temperature rise: firstly, heating from 300 ℃ to 700 ℃ at the speed of 80-100 ℃/min; then raising the temperature from 700 ℃ to 1175-1250 ℃ at the speed of 30-40 ℃/min, and keeping the temperature for 2-10 min.
Aiming at the consolidation system, when the staged temperature rise is adopted, a compact glass body protective layer is formed on the surface of material particles through a flash combustion technology, and the escape of ions which are easy to volatilize at high temperature in the particles is retarded, so that the concentration of gas-phase heavy metal ions in tail gas is effectively controlled.
As a better technical scheme of the invention, the method comprises the following steps:
(1) mixing the copper slag, the mineral substances and the additives, and ball-milling until the particles larger than 300 mu m in the mixture are less than 5 percent to obtain mixed raw materials;
(2) mixing the mixed raw material with water, uniformly stirring, and extruding and granulating to obtain a granular material with a single particle length-diameter ratio of not more than 2.0 and a particle size of not more than 20 mm;
(3) drying the granular material at 100-300 ℃, calcining, and cooling to obtain granular materials;
the calcination adopts staged temperature rise: firstly, heating from 300 ℃ to 700 ℃ at the speed of 80-100 ℃/min; then raising the temperature from 700 ℃ to 1175-1250 ℃ at the speed of 30-40 ℃/min, and keeping the temperature for 2-10 min.
Preferably, the mixed raw material comprises the following chemical elements in percentage by mass: silicon dioxide (SiO)2) 20-70% of aluminum oxide (Al)2O3) 20-50% of iron oxide (Fe)2O3) 10-30%, calcium oxide 0-10%, magnesium oxide 0-10%, sodium oxide (Na)20 to 10% of O), potassium oxide (K)2O) content is 0-10%.
Preferably, in the step (2), the amount of the water is 15-20% of the mixed raw meal.
The present invention also provides a granulate produced by the above process.
In the invention, the granular substances obtained after consolidation treatment have a porous structure and good mechanical strength and durability, can completely or massively replace natural gravels to be used for preparing concrete for buildings, heat-insulating materials and the like, and realize large-scale, resource and high-added-value application
Preferably, the aspect ratio of the single particles of the granules is less than or equal to 2.0, the surface of the granules is a dense shell with the thickness of 2 +/-0.5 mm, and the interior of the granules is of a porous microcrystal reinforced glass body structure; the granules have a barrel pressure of greater than 7.5MPa and a bulk density of less than 1100kg/m according to GB/T17431.23The water absorption is less than 3.0%.
In the invention, the granular materials can be used for preparing LC 30-LC 60 strength grade lightweight concrete and concrete with heat preservation and insulation functions, and large-scale treatment and high-added-value application are realized.
The invention has the beneficial effects that:
(1) according to GB5085.3-2007 Standard identification Standard of hazardous waste Leaching toxicity identification, the obtained granular material is determined as general solid waste according to the heavy metal elements in the solid matter leachate prepared by HJ/T299, wherein the heavy metal elements comprise, by mass, less than 3.7mg/L of arsenic element, less than 0.03mg/L of cadmium element, less than 0.08mg/L of chromium element, less than 0.01mg/L of copper element, less than 0.04mg/L of manganese element, less than 0.03mg/L of nickel element, less than 0.02mg/L of lead element and less than 0.2mg/L of zinc element.
(2) The granular substances can replace natural sandstone aggregate to prepare lightweight aggregate concrete for structures, or non-structural lightweight aggregate concrete, or heat-insulating concrete, and realize large-scale treatment and high-added-value application of hazardous copper slag waste.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.
Example 1
The embodiment provides a method for consolidating heavy metal elements in copper slag, which comprises the following steps:
(1) mixing copper slag, coal gangue and limestone according to the proportion of 20: 70: 10, grinding the mixture by using a ball mill until the particles with the particle size of more than 300 mu m in the mixture are less than 5 percent of the total weight to obtain mixed raw material;
in the copper slag, the concentration of arsenic is 69.2mg/kg (standard limit value is 5mg/kg), the concentration of cadmium is 2.5mg/kg (standard limit value is 1mg/kg), the concentration of chromium is 1.3mg/kg (standard limit value is 5mg/kg), the concentration of copper is 1059.2mg/kg (standard limit value is 100mg/kg), the concentration of nickel is 3.6mg/kg (standard limit value is 5mg/kg), the concentration of lead is 1019.8mg/kg (standard limit value is 5mg/kg), and the concentration of zinc is 240.4mg/kg (standard limit value is 100 mg/kg); judging the hazardous waste according to GB5085.3-2007 'hazardous waste identification Standard Leaching toxicity identification';
the copper slag contains iron element (Fe)2O3Mass) is more than 60 percent, and the specific test result is 66.3 percent;
in the coal gangue, SiO2With Al2O3The contents (by mass percent) are respectively 48.23 percent and 45.35 percent, and SiO2/Al2O3The ratio is 1.06; in the limestone, the content of calcium oxide is more than 50%;
(2) mixing the mixed raw material with water (the dosage is 20 percent of the mixed raw material), uniformly stirring, and preparing a granular material with the length-diameter ratio of single granules not more than 2.0 and the maximum grain diameter not more than 20mm by adopting an extruder or a pelletizing granulator;
preparing solid mixture leachate containing copper slag from the granular material according to HJ/T299, and detecting according to GB5085.3-2007 'identification Standard for hazardous waste extraction toxicity identification', wherein: the concentration of arsenic is 20.77mg/kg (standard limit is 5mg/kg), the concentration of cadmium is 0.76mg/kg (standard limit is 1mg/kg), the concentration of chromium is 0.38mg/kg (standard limit is 5mg/kg), the concentration of copper is 317.76mg/kg (standard limit is 100mg/kg), the concentration of nickel is 1.07mg/kg (standard limit is 5mg/kg), the concentration of lead is 305.95mg/kg (standard limit is 5mg/kg), and the concentration of zinc is 72.12mg/kg (standard limit is 100 mg/kg); therefore, according to the proportion in the step (1), the content of the leached heavy metal exceeds the standard requirement limit value;
(3) drying the granular material at 100-300 ℃, calcining, and cooling to obtain granular materials;
the calcination adopts staged temperature rise: firstly, heating from 300 ℃ to 700 ℃ at the speed of 100 ℃/min; then raising the temperature from 700 ℃ to 1250 ℃ at the speed of 40 ℃/min, and keeping the temperature for 10 min;
preparing a solid mixture leaching solution containing copper slag from the granular materials according to HJ/T299, and detecting according to GB5085.3-2007 'hazardous waste identification standard leaching toxicity identification', wherein: the concentration of arsenic is 0.1mg/kg (standard limit is 5mg/kg), the concentration of cadmium is less than 0.03mg/kg (standard limit is 1mg/kg), the concentration of chromium is less than 0.08mg/kg (standard limit is 5mg/kg), the concentration of copper is less than 0.01mg/kg (standard limit is 100mg/kg), the concentration of nickel is less than 0.03mg/kg (standard limit is 5mg/kg), the concentration of lead is less than 0.02mg/kg (standard limit is 5mg/kg), and the concentration of zinc is less than 0.2mg/kg (standard limit is 100 mg/kg); and comparing the leached heavy metal content with the standard required limit value to know that the heavy metal leaching value is less than the standard required limit value, and belongs to common solid waste.
This example also provides the pellets produced by the above process; the granular material is light porous granule, and has cylinder pressure of 8.3MPa and bulk density of 848kg/m according to GB/T17431.23The water absorption rate in 1 hour was 3.42%.
In the embodiment, the LC30 strength-grade lightweight concrete is prepared from the granules, the 3d compressive strength is 22.8MPa, the 7d compressive strength is 31.2MPa, and the 28d compressive strength is 38.4MPa, so that the granules can be widely applied as structural lightweight aggregate concrete, and large-scale disposal and high-added-value application are realized.
Example 2
The embodiment provides a method for consolidating heavy metal elements in copper slag, which comprises the following steps:
(1) mixing copper slag, coal gangue, calcium oxide and magnesium oxide (mass ratio is 4: 6) according to a ratio of 45: 51: 4, grinding the mixture by using a ball mill until the particles with the particle size of more than 300 mu m in the mixture are less than 5 percent of the total weight to obtain mixed raw material;
in the copper slag, the concentration of arsenic is 69.2mg/kg (standard limit value is 5mg/kg), the concentration of cadmium is 2.5mg/kg (standard limit value is 1mg/kg), the concentration of chromium is 1.3mg/kg (standard limit value is 5mg/kg), the concentration of copper is 1059.2mg/kg (standard limit value is 100mg/kg), the concentration of nickel is 3.6mg/kg (standard limit value is 5mg/kg), the concentration of lead is 1019.8mg/kg (standard limit value is 5mg/kg), and the concentration of zinc is 240.4mg/kg (standard limit value is 100 mg/kg); judging the hazardous waste according to GB5085.3-2007 'hazardous waste identification Standard Leaching toxicity identification';
the copper slag contains iron element (Fe)2O3Mass) is more than 60 percent, and the specific test result is 66.3 percent;
in the coal gangue, SiO2With Al2O3The contents (by mass percent) are respectively 56.2 percent and 25.4 percent, and SiO2/Al2O3The ratio is 2.21;
(2) mixing the mixed raw material with water (the dosage is 18 percent of the mixed raw material), uniformly stirring, and preparing a granular material with the length-diameter ratio of single granules not more than 2.0 and the maximum grain diameter not more than 20mm by adopting an extruder or a pelletizing granulator;
preparing solid mixture leachate containing copper slag from the granular material according to HJ/T299, and detecting according to GB5085.3-2007 'identification Standard for hazardous waste extraction toxicity identification', wherein: the concentration of arsenic is 33.23mg/kg (standard limit is 5mg/kg), the concentration of cadmium is 1.21mg/kg (standard limit is 1mg/kg), the concentration of chromium is 0.60mg/kg (standard limit is 5mg/kg), the concentration of copper is 508.41mg/kg (standard limit is 100mg/kg), the concentration of nickel is 1.72mg/kg (standard limit is 5mg/kg), the concentration of lead is 489.51mg/kg (standard limit is 5mg/kg), and the concentration of zinc is 115.40mg/kg (standard limit is 100 mg/kg); therefore, according to the proportion in the step (1), the content of the leached heavy metal exceeds the standard requirement limit value;
(3) drying the granular material at 100-300 ℃, calcining, and cooling to obtain granular materials;
the calcination adopts staged temperature rise: firstly, heating up from 300 ℃ to 700 ℃ at the speed of 95 ℃/min; then raising the temperature from 700 ℃ to 1225 ℃ at the speed of 38 ℃/min, and keeping the temperature for 8 min;
preparing a solid mixture leaching solution containing copper slag from the granular materials according to HJ/T299, and detecting according to GB5085.3-2007 'hazardous waste identification standard leaching toxicity identification', wherein: the concentration of arsenic is 3.5mg/kg (standard limit is 5mg/kg), the concentration of cadmium is less than 0.03mg/kg (standard limit is 1mg/kg), the concentration of chromium is less than 0.08mg/kg (standard limit is 5mg/kg), the concentration of copper is less than 0.01mg/kg (standard limit is 100mg/kg), the concentration of nickel is less than 0.03mg/kg (standard limit is 5mg/kg), the concentration of lead is less than 0.02mg/kg (standard limit is 5mg/kg), and the concentration of zinc is less than 0.2mg/kg (standard limit is 100 mg/kg); and comparing the leached heavy metal content with the standard required limit value to know that the heavy metal leaching value is less than the standard required limit value, and belongs to common solid waste.
This example also provides the pellets produced by the above process; the granular material is light porous granule, and has cylinder pressure strength of 16.8MPa and bulk density of 950kg/m according to GB/T17431.23The water absorption rate in 1 hour was 2.21%.
In the embodiment, the LC50 strength-grade lightweight concrete is prepared from the granules, the 3d compressive strength is 32.1MPa, the 7d compressive strength is 44.5MPa, and the 28d compressive strength is 58.6MPa, so that the granules can be widely applied as structural lightweight aggregate concrete, and large-scale disposal and high-added-value application are realized.
Example 3
The embodiment provides a method for consolidating heavy metal elements in copper slag, which comprises the following steps:
(1) mixing copper slag, coal gangue and bentonite according to a proportion of 59: 40: 1, grinding the mixture by using a ball mill until the particles with the particle size of more than 300 mu m in the mixture are less than 5 percent of the total weight to obtain mixed raw material;
in the copper slag, the concentration of arsenic is 69.2mg/kg (standard limit value is 5mg/kg), the concentration of cadmium is 2.5mg/kg (standard limit value is 1mg/kg), the concentration of chromium is 1.3mg/kg (standard limit value is 5mg/kg), the concentration of copper is 1059.2mg/kg (standard limit value is 100mg/kg), the concentration of nickel is 3.6mg/kg (standard limit value is 5mg/kg), the concentration of lead is 1019.8mg/kg (standard limit value is 5mg/kg), and the concentration of zinc is 240.4mg/kg (standard limit value is 100 mg/kg); judging the hazardous waste according to GB5085.3-2007 'hazardous waste identification Standard Leaching toxicity identification';
the copper slag contains iron element (Fe)2O3Mass) is more than 60 percent, and the specific test result is 66.3 percent;
in the coal gangue, SiO2With Al2O3The contents (by mass percent) are respectively 59.0 percent and 23.6 percent, and SiO2/Al2O3The ratio is 2.50;
(2) mixing the mixed raw material with water (the dosage is 17 percent of the mixed raw material), uniformly stirring, and preparing a granular material with the length-diameter ratio of single granules not more than 2.0 and the maximum grain diameter not more than 20mm by adopting an extruder or a pelletizing granulator;
preparing solid mixture leachate containing copper slag from the granular material according to HJ/T299, and detecting according to GB5085.3-2007 'identification Standard for hazardous waste extraction toxicity identification', wherein: the arsenic concentration is 40.85mg/kg (standard limit is 5mg/kg), the cadmium concentration is 1.49mg/kg (standard limit is 1mg/kg), the chromium concentration is 0.74mg/kg (standard limit is 5mg/kg), the copper concentration is 624.92mg/kg (standard limit is 100mg/kg), the nickel concentration is 2.11mg/kg (standard limit is 5mg/kg), the lead concentration is 601.69mg/kg (standard limit is 5mg/kg), and the zinc concentration is 141.85mg/kg (standard limit is 100 mg/kg); therefore, according to the proportion in the step (1), the content of the leached heavy metal exceeds the standard requirement limit value;
(3) drying the granular material at 100-300 ℃, calcining, and cooling to obtain granular materials;
the calcination adopts staged temperature rise: firstly, heating from 300 ℃ to 700 ℃ at the speed of 90 ℃/min; then heating from 700 ℃ to 1200 ℃ at the speed of 34 ℃/min, and keeping for 6 min;
preparing a solid mixture leaching solution containing copper slag from the granular materials according to HJ/T299, and detecting according to GB5085.3-2007 'hazardous waste identification standard leaching toxicity identification', wherein: the concentration of arsenic is 4.2mg/kg (standard limit is 5mg/kg), the concentration of cadmium is less than 0.03mg/kg (standard limit is 1mg/kg), the concentration of chromium is less than 0.08mg/kg (standard limit is 5mg/kg), the concentration of copper is less than 0.01mg/kg (standard limit is 100mg/kg), the concentration of nickel is less than 0.03mg/kg (standard limit is 5mg/kg), the concentration of lead is less than 0.02mg/kg (standard limit is 5mg/kg), and the concentration of zinc is less than 0.2mg/kg (standard limit is 100 mg/kg); and comparing the leached heavy metal content with the standard required limit value to know that the heavy metal leaching value is less than the standard required limit value, and belongs to common solid waste.
This example also provides the pellets produced by the above process; the granular material is light porous granule, and has a cylinder pressure of 17.9MPa and a bulk density of 1050kg/m according to GB/T17431.23The water absorption rate in 1 hour was 1.03%.
In the embodiment, the LC60 strength grade lightweight concrete is prepared from the granules, the 3d compressive strength is 42.1MPa, the 7d compressive strength is 54.1MPa, and the 28d compressive strength is 71.2MPa, so that the granules can be widely applied as structural lightweight aggregate concrete, and large-scale disposal and high-added-value application are realized.
Example 4
The embodiment provides a method for consolidating heavy metal elements in copper slag, which comprises the following steps:
(1) mixing copper slag, coal gangue and calcium sulfate according to a ratio of 70: 25: 5, grinding the mixture by using a ball mill until the particles with the particle size of more than 300 mu m in the mixture are less than 5 percent of the total weight to obtain mixed raw material;
in the copper slag, the concentration of arsenic is 69.2mg/kg (standard limit value is 5mg/kg), the concentration of cadmium is 2.5mg/kg (standard limit value is 1mg/kg), the concentration of chromium is 1.3mg/kg (standard limit value is 5mg/kg), the concentration of copper is 1059.2mg/kg (standard limit value is 100mg/kg), the concentration of nickel is 3.6mg/kg (standard limit value is 5mg/kg), the concentration of lead is 1019.8mg/kg (standard limit value is 5mg/kg), and the concentration of zinc is 240.4mg/kg (standard limit value is 100 mg/kg); judging the hazardous waste according to GB5085.3-2007 'hazardous waste identification Standard Leaching toxicity identification';
the copper slag contains iron element (Fe)2O3Mass) is more than 60 percent, and the specific test result is 66.3 percent;
in the coal gangue, SiO2With Al2O3The contents (by mass percent) are respectively 59.0 percent and 23.6 percent, and SiO2/Al2O3The ratio is 2.50;
(2) mixing the mixed raw material with water (the dosage is 16 percent of the mixed raw material), uniformly stirring, and preparing a granular material with the length-diameter ratio of single granules not more than 2.0 and the maximum grain diameter not more than 20mm by adopting an extruder or a pelletizing granulator;
preparing solid mixture leachate containing copper slag from the granular material according to HJ/T299, and detecting according to GB5085.3-2007 'identification Standard for hazardous waste extraction toxicity identification', wherein: the arsenic concentration is 48.46mg/kg (standard limit is 5mg/kg), the cadmium concentration is 1.76mg/kg (standard limit is 1mg/kg), the chromium concentration is 0.88mg/kg (standard limit is 5mg/kg), the copper concentration is 741.43mg/kg (standard limit is 100mg/kg), the nickel concentration is 2.50mg/kg (standard limit is 5mg/kg), the lead concentration is 713.87mg/kg (standard limit is 5mg/kg), and the zinc concentration is 168.29mg/kg (standard limit is 100 mg/kg); therefore, according to the proportion in the step (1), the content of the leached heavy metal exceeds the standard requirement limit value;
(3) drying the granular material at 100-300 ℃, calcining, and cooling to obtain granular materials;
the calcination adopts staged temperature rise: firstly, heating from 300 ℃ to 700 ℃ at the speed of 85 ℃/min; then raising the temperature from 700 ℃ to 1175 ℃ at the speed of 30 ℃/min, and keeping the temperature for 5 min;
preparing a solid mixture leaching solution containing copper slag from the granular materials according to HJ/T299, and detecting according to GB5085.3-2007 'hazardous waste identification standard leaching toxicity identification', wherein: the concentration of arsenic is 5.8mg/kg (standard limit is 5mg/kg), the concentration of cadmium is less than 0.03mg/kg (standard limit is 1mg/kg), the concentration of chromium is less than 0.08mg/kg (standard limit is 5mg/kg), the concentration of copper is less than 0.01mg/kg (standard limit is 100mg/kg), the concentration of nickel is less than 0.03mg/kg (standard limit is 5mg/kg), the concentration of lead is less than 0.02mg/kg (standard limit is 5mg/kg), and the concentration of zinc is less than 0.2mg/kg (standard limit is 100 mg/kg); and comparing the leached heavy metal content with the standard required limit value to know that the heavy metal leaching value is less than the standard required limit value, and belongs to common solid waste.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. The method for consolidating heavy metal elements in copper slag is characterized by comprising the following steps: mixing copper slag, mineral substances and additives, granulating, drying and calcining;
wherein SiO in the mineral substance2With Al2O3The sum of the total amount of the components is more than 50 percent, SiO2/Al2O3The ratio is more than or equal to 0.5; the additive is one or more selected from carbonate, sulfate, silicate, bentonite, montmorillonite, limestone, calcium oxide and magnesium oxide.
2. The method according to claim 1, wherein the weight ratio of the copper slag: minerals: 20-70% of additive: 25-70: 1 to 10.
3. The method according to claim 1 or 2, wherein the mineral substance is one or more selected from kaolinite crystal, montmorillonite crystal, albite crystal, potassium feldspar crystal, anorthite crystal, bauxite crystal mineral, sandstone crystal mineral, fly ash, diatomite, silica fume, coal gangue; the additive is one or more selected from limestone, calcium oxide, magnesium oxide, bentonite and calcium sulfate.
4. The method according to any one of claims 1 to 3, wherein the heavy metal in the copper slag is one or more selected from arsenic, cadmium, chromium, copper, manganese, nickel, lead and zinc; the concentration of arsenic is less than or equal to 2500mg/kg, the concentration of cadmium is less than or equal to 30mg/kg, the concentration of chromium is less than or equal to 300mg/kg, the concentration of copper is less than or equal to 3000mg/kg, the concentration of manganese is less than or equal to 1000mg/kg, the concentration of nickel is less than or equal to 200mg/kg, the concentration of lead is less than or equal to 3500mg/kg, and the concentration of zinc is less than or equal to 1200 mg/kg.
5. The method according to any one of claims 1 to 4, wherein the copper slag comprises the following chemical elements in percentage by mass: iron element, in the form of Fe2O3Counting by 30-75%; aluminum element and silicon element, with SiO2+Al2O3The sum is 20-50%; the total amount of other chemical elements is 5-15% by oxide.
6. A process according to any one of claims 1 to 5, wherein the particulate material obtained after granulation has an individual particle aspect ratio of not more than 2.0 and a particle size of not more than 20 mm.
7. The method according to any one of claims 1 to 6, wherein the calcination is carried out by stepwise temperature rise: firstly, heating from 300 ℃ to 700 ℃ at the speed of 80-100 ℃/min; then raising the temperature from 700 ℃ to 1175-1250 ℃ at the speed of 30-40 ℃/min, and keeping the temperature for 2-10 min.
8. The method of claim 1, comprising the steps of:
(1) mixing the copper slag, the mineral substances and the additives, and ball-milling until the particles larger than 300 mu m in the mixture are less than 5 percent to obtain mixed raw materials;
(2) mixing the mixed raw material with water, uniformly stirring, and extruding and granulating to obtain a granular material with a single particle length-diameter ratio of not more than 2.0 and a particle size of not more than 20 mm;
(3) drying the granular material at 100-300 ℃, calcining, and cooling to obtain granular materials;
the calcination adopts staged temperature rise: firstly, heating from 300 ℃ to 700 ℃ at the speed of 80-100 ℃/min; then raising the temperature from 700 ℃ to 1175-1250 ℃ at the speed of 30-40 ℃/min, and keeping the temperature for 2-10 min.
9. The method of claim 8, wherein the mixed raw meal comprises the following chemical elements in percentage by mass: 20-70% of silicon dioxide, 20-50% of aluminum oxide, 10-30% of ferric oxide, 0-10% of calcium oxide, 0-10% of magnesium oxide, 0-10% of sodium oxide and 0-10% of potassium oxide.
10. A granular material produced by the method according to any one of claims 1 to 9.
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